EP0709725B1 - Emulsions photographiques aux halogénures d'argent ayant une désensibilisation par le colorant réduite - Google Patents

Emulsions photographiques aux halogénures d'argent ayant une désensibilisation par le colorant réduite Download PDF

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EP0709725B1
EP0709725B1 EP19950420278 EP95420278A EP0709725B1 EP 0709725 B1 EP0709725 B1 EP 0709725B1 EP 19950420278 EP19950420278 EP 19950420278 EP 95420278 A EP95420278 A EP 95420278A EP 0709725 B1 EP0709725 B1 EP 0709725B1
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Prior art keywords
core
silver
emulsion according
shell
halide
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EP0709725A1 (fr
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Didier Jean Kodak-Pathe Martin
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Kodak Pathe SA
Eastman Kodak Co
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Kodak Pathe SA
Eastman Kodak Co
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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
    • 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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain

Definitions

  • the present invention concerns a silver halide emulsion, and more particularly a silver halide emulsion which resolves the problem of desensitisation which can be caused by the spectral sensitising dye.
  • Silver halide photographic emulsions have a natural photosensitivity region which is limited to ultraviolet, violet and blue. In order to obtain an acceptable colour rendering, it is necessary to use compounds which have the property of being adsorbed on the silver halide grains and making these grains sensitive to a wavelength region extending, in the visible spectrum, beyond the intrinsic photosensitivity region of the silver halides.
  • the photosensitivity of the emulsion depends on the quantity of spectral sensitisers adsorbed on the silver halide grains. It increases with the increase in the quantity of spectral sensitising dyes up to a maximum sensitivity value. Beyond this maximum, when the quantity of spectral sensitising dyes is increased a reduction in sensitivity is observed.
  • the quantity of dye which enables maximum sensitivity to be obtained may vary according to the spectral sensitising dye and the size, shape or composition of the halide grains.
  • the effect of the spectral sensitisers may therefore be reversed.
  • this reversed effect known as desensitisation, appears when the quantity of sensitisers adsorbed on the surface of the halide grains exceeds a certain threshold.
  • this desensitisation appears as soon as the spectral sensitiser covers 50% of the surface of the silver halide grains.
  • emulsions can be chemically sensitised in the presence of one or more compounds of sulphur, gold and/or selenium in order to increase the overall sensitivity of the photosensitive products obtained. Examples of chemical sensitising compounds were described in Research Disclosure, No 308119, December 1989, Section III.
  • the object of the present invention is to obtain an emulsion having high sensitivity whilst eliminating the problem of dye desensitisation.
  • the photographic emulsion according to the invention has improved sensitivity which results from increasing the quantity of spectral sensitisers adsorbed on the silver halide grains without causing dye desensitisation.
  • the photographic emulsion of the present invention consists of silver halide grains comprising a central zone (the core) consisting of at least two silver halides and an outer zone (the shell) having a silver halide composition different from the composition of the central zone, characterised in that
  • the proportion of at least one of the halides forming the core decreases continuously between the centre of the grains and the core/shell interface so that the difference between the molar percentage of each of the silver halides between the centre of the grain and the core/shell interface is at least 10%, the percentages being calculated from the total number of moles of silver halides constituting the core.
  • the silver halide emulsion forming the core of the invention comprises at least two silver halides chosen from amongst silver chloride, bromide and iodide.
  • the process for preparing such decreasing-profile emulsions consists of precipitating successive regions having different silver halide compositions whilst simultaneously introducing a solution of a silver salt and a solution of alkali metal halide(s), hereinafter referred to as "halide solution” or “halide jet” containing one or more alkaline halides.
  • halide solution a solution of alkali metal halide(s)
  • halide jet containing one or more alkaline halides.
  • the process according to the invention is characterised in that, during the precipitation of the core, a halide solution is used which comprises at least two different halides, the concentrations of which are caused to vary inversely, between initial values and predetermined final values. These variations are preferably practically linear.
  • the final values of the concentration in the halide solution used for the core are preferably equal to the concentrations of said halides in the halide solution at the start of precipitation of the shell immediately adjacent to the core.
  • the core of the silver halide grains of the emulsions of the invention preferably consists of silver bromoiodide, silver chloroiodide or silver chlorobromoiodide with a molar percentage of silver iodide which decreases between the centre of the grains and the core/shell interface.
  • the silver bromoiodide core is precipitated whilst linearly decreasing the concentration of iodide and linearly increasing the concentration of bromide in the halide jet consisting of alkaline iodide and alkaline bromide.
  • the iodide content in the grain varies from a maximum value at the centre of the grain to a zero value at the core/shell interface.
  • the shell which may consist of one or more silver halides other than iodide, is then precipitated.
  • the overall quantity of silver iodide in the core is, within the framework of the invention, between 10 and 30% molar with respect to the total number of moles of silver halide contained in the core, and this proportion of iodide can vary between 36% at the centre of the grain and 0% at the core/shell interface.
  • the shell of the grains constituting the emulsion may be formed by one or more layers having identical or different silver halide compositions. According to one embodiment, this shell does not contain any silver iodide.
  • the ratio of the number of moles of silver halide constituting the core to the number of moles of silver halide constituting the shell is between 0.2 and 2.
  • the core of the grains is formed by silver bromoiodide
  • the shell of the grains is formed by silver bromide
  • the core/shell molar ratio is 0.5.
  • the grains may have different morphologies, for example tabular, octahedral (faces 111), cubo-octahedral or cubic (faces 100).
  • the grains are cubo-octahedral with a size of between 0.1 and 3.0 ⁇ m, and preferably 0.3 and 2.0 ⁇ m.
  • the thioureas which can be used in the present invention are tetrasubstituted thioureas of formula: in which each R 1 , R 2 , R 3 and R 4 group represents either separately a hydrogen atom, an alkyl, cycloalkyl or carbocyclic or heterocyclic aryl radical, or an aralkyl radical, or R 2 -R 3 , R 3 -R 4 or R 4 -R 1 are combined to represent a heterocycle with 5 to 7 linkages, provided that at least one of the R 1 , R 2 , R 3 or R 4 groups contains or is a nucleophilic group of the carboxylic, sulphinic, sulphonic, hydroxamic, mercapto, sulphonamido or primary or secondary amino group.
  • the radicals R 1 , R 2 , R 3 and R 4 which contain a nucleophilic group are, for example, chosen from amongst -COOH, -CH 2 COOH, C 2 H 4 COOH, -CH 2 SO 2 H, -CH 2 SO 3 H, -C 2 H 4 SO 2 H, -C 2 H 4 NHOH, -C 2 H 4 SH, -(CH 2 ) 2 NHSO 2 CH 3 , -C 2 H 4 NHCH 3 and the corresponding salts.
  • the preferred thioureas are the 1,1,3,3-tetrasubstituted 2-thioureas of formulae:
  • the thioureas may be synthesised using the method described in US patent 4,810,626.
  • One method for example, consists of reacting an aliphatic monoaminocarboxylic acid with a dialkylthiocarbamoyl halide.
  • the quantities of thioureas may be between 10 -6 and 10 -1 mmole per mole of silver halide and preferably between 10 -4 and 10 -2 mmole per mole of silver halide.
  • the gold (I) compounds containing no labile sulphur atom are compounds which are sufficiently stable to be used in the photographic emulsions without causing undesirable secondary reactions.
  • the gold (I) compounds must not contain a labile sulphur atom which would react with the silver present in the medium so as to form silver sulphide, which would interfere with the chemical sensitisation of the emulsion.
  • the gold (I) compounds must be easily dispersable in the aqueous compositions used in photography.
  • the gold (I) compounds which may be used within the scope of the invention were described in US patents 5 049 484 and 5 049 485.
  • these gold (I) compounds have the following structure: in which R 1 , R 2 and R 3 are each separately a hydrogen atom, or an alkyl, alkylene, alkyloxy, aryl or amino group, substituted or otherwise, and X is an anion.
  • the quantity of gold (I) compounds which may be added to a silver halide emulsion is between 10 -6 and 10 -1 mmol/mol of silver and preferably between 10 -4 and 10 -2 mmol/mol of silver.
  • the thioureas and gold (I) compounds are, according to the invention, such that the molar ratio between the quantity of sulphur contained in the thiourea and the quantity of gold (I) is between 1 and 4 and preferably 2 and 3.
  • the compounds described above may be used alone or in combination with conventional sensitising agents known for the chemical sensitisation of photographic emulsions.
  • the thioureas and gold (I) compounds may be added to the silver halide emulsion together or separately and at different stages of the sensitisation of the emulsion.
  • the addition of these chemical sensitisers to the emulsion may be effected in the presence of a solvent for silver halides such as thioethers or thiocyanates.
  • the conditions for sensitising the silver halide grains are not particularly limited when the compounds described here are used.
  • the pH is generally between 1 and 9, and preferably between 5 and 7, and the pAg is generally between 5 and 12 and preferably between approximately 7 and 10.
  • the silver halide grains may be sensitised at a temperature between approximately 30 and 90°C, and it is preferred to use a temperature between approximately 35 and 70°C.
  • the silver halide emulsion can be spectrally sensitised with spectral sensitising dyes and in accordance with the chromating methods as described for example in Research Disclosure, December 1989, No 308119, Section IV (hereinafter referred to as Research Disclosure).
  • These dyes may for example be cyanine, merocyanine, composite cyanine, composite merocyanine and hemioxodol dyes.
  • the dyes which are particularly useful belong to the merocyanine class.
  • These dyes contain, as a heterocyclic core, any core generally used in cyanine dyes.
  • the spectral sensitising dyes are added to the emulsion after the chemical sensitisation stage.
  • the emulsions of the present invention may be used in colour photographic products of different types, such as negative, positive or reversal photographic products.
  • the colour photographic products comprise, in a conventional manner, at least three elements which are respectively blue-, green- and red-sensitive and which supply respectively the yellow, magenta and cyan components of the subtractive synthesis of the colour image.
  • Colour photographic products generally comprise a support carrying at least one blue-sensitive silver halide emulsion layer with which a yellow dye forming coupler is associated, at least one green-sensitive silver halide emulsion layer with which a magenta dye forming coupler is associated, and at least one red-sensitive silver halide emulsion layer with which a cyan dye forming coupler is associated.
  • the support may be any suitable support used with photographic products.
  • Conventional supports comprise polymer films, paper (including polymer-coated paper), glass and metal.
  • Research Disclosure Section XVII supplies details concerning supports and auxiliary layers for photographic products.
  • the silver halide emulsions of the invention and other layers on the photographic products of this invention may contain, as a vehicle, hydrophilic colloids, used alone or in combination with other polymer substances (for example latexes).
  • Suitable hydrophilic substances comprise natural substances such as proteins, protein derivatives, cellulose derivatives, for example cellulose esters, gelatin, for example gelatin treated with a base (cattle bone or tanned gelatin) or gelatin treated with an acid (pigskin gelatin), gelatin derivatives, for example acetylated gelatin, phthylated gelatin, etc, polysaccharides such as dextran, gum arabic, zein, casein, pectin, collagen derivatives, collodion, agar-agar and albumin.
  • Surfactants may be incorporated in a layer of photographic emulsion or in another hydrophilic colloidal layer as a coating additive to prevent the accumulation of static charges, to improve the lubrication properties, to improve the dispersion of the emulsion, to prevent adhesion and to improve the photographic characteristics such as rapid access development, or increase in contrast or sensitisation.
  • the photographic emulsion of the present invention may contain dye image forming couplers, that is to say compounds capable of reacting with an oxidation product of an aromatic amine (generally a primary amine) to form a dye.
  • dye image forming couplers that is to say compounds capable of reacting with an oxidation product of an aromatic amine (generally a primary amine) to form a dye.
  • Non-diffusible couplers containing a ballast group are desirable. It is possible to use either couplers with four equivalents or couplers with two equivalents.
  • couplers enabling the colours to be corrected, or couplers releasing a development inhibiter in the course of development referred to as a DIR coupler).
  • the photographic products of the invention may contain, inter alia, optical brighteners, anti-fogging compounds, surfactants, plasticisers, lubricants, hardening agents, stabilising agents, or absorption and/or diffusion agents as described in Sections V, VI, VIII, XI, XII and XVI of the above-mentioned Research Disclosure.
  • optical brighteners anti-fogging compounds
  • surfactants plasticisers
  • lubricants lubricants
  • hardening agents stabilising agents
  • absorption and/or diffusion agents as described in Sections V, VI, VIII, XI, XII and XVI of the above-mentioned Research Disclosure.
  • the methods of adding these various compounds and the coating and drying methods are described in Sections XIV and XV of the same Research Disclosure.
  • the products of the invention after being exposed, undergo photographic processing to develop the latent silver image and a colour image, in the presence of a coupler, which, in certain cases, may be incorporated in the photographic product.
  • the photographic products are then washed and processed in a stabilising bath.
  • This reducing compound oxidises and its oxidised form reacts with the coupler to form a dye.
  • These compounds are chosen from amongst the aromatic primary amines such as paraphenylene diamines, aminophenols, etc. These compounds may be used alone or in a mixture, or with auxiliary developers.
  • This bath may in addition contain a stabiliser such as sulphites, a buffer such as carbonates, boric acid, borates or alkanolamines.
  • an AgBrI cubo-octahedral emulsion of the core/shell type is prepared as follows:
  • nucleation is effected at 60°C and at a pH of 5.1 by introducing, over 70 seconds by the double jet method, a 0.5 M solution of AgNO 3 and a 0.5 M solution of NaBr.
  • the flow of AgNO 3 is constant and the flow of NaBr is adjusted so that the pAg remains equal to 9. (The pAg is the reciprocal of the logarithm of the silver ion concentration in the vessel.)
  • the AgBr shell is then formed by introducing a solution of AgNO 3 , 2M and a solution of NaBr, 2M at 60°C using the double jet method over 43 minutes.
  • the flow of AgNO 3 is constant and the flow of NaBr is adjusted so that the pAg remains constant and equal to 9. 6.67 moles of AgBr are precipitated.
  • a control emulsion with cubo-octahedral grains is obtained, having a core of AgBrI with a uniform iodide content of 18% molar and an AgBr shell.
  • the total iodide content of the grains is 3% molar.
  • the emulsion obtained above has a grain size of approximately 1.2 ⁇ m.
  • Example 1 The operating method of Example 1 is repeated except, during the core precipitation step, the iodide concentration in the halide jet decreases linearly over time between an initial concentration of 36% and a final concentration of 0%. Conversely, the bromide concentration varies linearly between 64% at the start of the precipitation and 100% at the end of the precipitation of the core.
  • the emulsion thus obtained consists of silver halide grains of the core/shell type with an iodide content in the core which gradually reduces to a nil value at the interface.
  • the core/shell molar ratio is 0.5 with an iodide content in the core of 18%, the total iodide content being 6%.
  • the mean size of the grains is 1.16 ⁇ m.
  • Example 2 The emulsion of Example 2 is chemically sensitised by means of the gold (I) compound of formula (A) (0.73 mg/mol Ag) and the thiourea of formula (B) (0.83 mg/mol Ag) in the presence of sodium thiocyanate (150 mg/mol Ag) in accordance with the method described below.
  • the chemical sensitisers are added to the emulsion maintained at 40°C, the pH being adjusted to 6.4 and the pAg to 8.25.
  • the emulsion After introduction of the chemical sensitisers, the emulsion is maintained at 70°C for 25 min.
  • the molar ratio of the sensitising dyes (I)/(II) is 3/1.
  • the quantity of spectral sensitising dyes is such that the coverage of the grains is 55%, the coverage of the grain by the dye being defined as the surface area of the grain covered by the dye compared with the total surface of the grain, expressed as a percentage. This percentage is determined from the molecular dimension of the dye when it is adsorbed on the grain (the impression of the dye) and from the surface area of the grain.
  • the chemically and spectrally sensitised emulsion is coated on a cellulose triacetate support with a silver content of 0.807 g/m 2 , a gelatin content of 3.23 g/m 2 and coupler (C1) with a content of 1.05 g/m 2 .
  • This emulsion layer is covered with a gelatin top layer (2.15 g/m 2 ) containing a hardening agent.
  • the sample thus obtained is exposed by means of a Kodak sensitometer equipped with a lamp with a colour temperature of 5500°K for 1/100 seconds.
  • the sensitometer is fitted with a Wratten 9 filter.
  • the desensitisation by the dye ( ⁇ ) is assessed by means of the difference between the intrinsic sensitivity of the emulsion and the sensitivity of the same emulsion spectrally sensitised to the optimum extent.
  • Intransic sensitivity means the sensitivity of the emulsion before spectral sensitisation. This intrinsic sensitivity is determined on a sample obtained from the emulsion chemically sensitised according to the method described above, which is exposed at 365 nm and processed using the Kodak Flexicolor C41 R process. The sensitivity as defined above is measured.
  • the granularity is the granularity normalised by the contrast, that is to say the granularity measured for a maximum contrast.
  • the contrast ( ⁇ ) is determined by the slope of the sensitometric curve measured between Dmin + 0.4 and Dmin + 1.4.
  • the CSDP emulsion of Example 2 is processed as described in Example 3 except that the chemical sensitisation is effected by means of sodium thiosulphate pentahydrate (0.70 mg/mol Ag) and potassium tetrachloroaurate (0.47 mg/mol Ag) in the presence of sodium thiocyanate (150 mg/mol Ag) and acetamidophenyltetramercaptol (50 mg/mol) which acts as an anti-fogging agent. After introduction of the chemical sensitisers, the emulsion is maintained at 70°C for 25 min.
  • the emulsion is then coated, exposed and developed according to the method of Example 3.
  • Example 2 The CSDP emulsion of Example 2 is processed as described in Example 3 except that the chemical sensitisation is effected by means of sodium thiosulphate pentahydrate (1.3 mg/mol Ag) and potassium tetrachloroaurate (0.43 mg/mol Ag).
  • the emulsion After introduction of the chemical sensitisers, the emulsion is maintained at 70°C for 25 min.
  • the emulsion is then coated, exposed and developed according to the method of Example 3.
  • the CSDP emulsion of Example 2 is processed as described in Example 3 except that the chemical sensitisation is effected by means of sodium thiosulphate pentahydrate (0.09 mg/mol Ag) and a gold (I) compound of formula Na 3 [Au(S 2 O 3 ) 3 ]2H 2 O (0.65 mg/mol Ag) in the presence of sodium thiocyanate (150 mg/mol Ag) and acetamidophenyltetramercaptol (50 mg/mol), which acts as an anti-fogging agent.
  • the emulsion After introduction of the chemical sensitisers, the emulsion is maintained at 70°C for 25 min.
  • the emulsion is then coated, exposed and developed according to the method of Example 3.
  • the addition of sulphur is effected by means of the thiosulphate and the gold (I) compound, which contains labile sulphur atoms.
  • the CSDP emulsion of Example 2 is processed as described in Example 3 except that the chemical sensitisation is effected by means of sodium thiosulphate pentahydrate (0.73 mg/mol Ag) and a gold (I) compound of formula Na 3 [Au(S 2 O 3 ) 3 ]2H 2 O (0.60 mg/mol Ag).
  • the addition of sulphur is effected by means of the thiosulphate and the gold (I) compound, which contains labile sulphur atoms.
  • the emulsion After introduction of the chemical sensitisers, the emulsion is maintained at 70°C for 25 min.
  • the emulsion is then coated, exposed and developed according to the method of Example 3.
  • Example 1 The CSWP emulsion of Example 1 is processed as described in Example 3 except that the chemical sensitisation is effected by means of sodium thiosulphate pentahydrate (0.39 mg/mol Ag) and a gold (I) compound of formula Na 3 [Au(S 2 O 3 ) 3 ]2H 2 O (2.88 mg/mol Ag) in the presence of sodium thiocyanate (200 mg/mol Ag).
  • the quantity of spectral sensitising dyes (S-1) used with such an emulsion is such that the coverage of the grains is 80%. After introduction of the sensitising dyes, the emulsion is maintained at 70°C for 20 min.
  • the emulsion is then coated, exposed and developed according to the method of Example 3.
  • the CSWP emulsion of Example 1 is processed according to the method of Example 8 except that the chemical sensitisation is effected by means of the gold (I) compound of formula (A) (2.03 mg/mol Ag) and the thiourea of formula (B) (2.22 mg/mol Ag) in the presence of sodium thiocyanate (50 mg/mol Ag).
  • Examples 6 and 7 show that the use of a conventional sulphur sensitiser and a gold (I) compound containing labile sulphur atoms does not improve the dye desensitisation.

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Claims (16)

  1. Emulsion photographique constituée de grains d'halogénures d'argent comprenant une zone centrale (core) constituée d'au moins deux halogénures d'argent et une zone externe (shell) ayant une composition en halogénure d'argent différente de la composition de la core, caractérisée en ce que
    (1) le pourcentage molaire d'au moins un des halogénures d'argent de la core par rapport au nombre de moles total d'halogénures d'argent de la core est décroissant entre le centre des grains et l'interface core/shell,
    (2) la sensibilisation chimique est effectuée au moyen d'une thiourée et d'un composé d'or(I) ne contenant pas d'atome de soufre labile.
  2. Emulsion photographique selon la revendication 1 dans laquelle la thiourée correspond à la formule :
    Figure 00310001
    dans laquelle chaque groupe R1, R2, R3 et R4 représente soit séparément un atome d'hydrogène, un radical alkyle, cycloalkyle, aryle carbocyclique ou hétérocyclique, un radical aralkyle, soit R2-R3, R3-R4 ou R1-R4 sont combinés pour représenter un hétérocycle de 5 à 7 chaínons, avec la condition supplémentaire qu'au moins un des groupes R1, R2, R3 ou R4 contient ou est un groupe nucléophile de type carboxylique, sulfinique, sulfonique, hydroxamique, mercapto, sulfonamido, amino primaire ou secondaire.
  3. Emulsion selon la revendication 2 dans laquelle les groupes nucléophiles sont choisis parmi -COOH, - CH2COOH, -C2H4COOH, -CH2SO2H, -CH2SO3H, -C2H4SO2H, - C2H4NHOH, -C2H4SH, -(CH2)2NHSO2CH3, -C2H4NHCH3 ainsi que les sels d'acide correspondants.
  4. Emulsion selon la revendication 1 dans laquelle le composé d'or(I) correspond à la formule
    Figure 00320001
    dans laquelle R1, R2 et R3 sont chacun séparément un atome d'hydrogène, un groupe alkyle, alkylène, alkyloxy, aryle, amino, substitué ou non, X est un anion.
  5. Emulsion photographique selon la revendication 1, dans laquelle les quantités de thiourée et de composé d'or(I) sont telles que le rapport molaire de la quantité de Soufre contenu dans la thiourée sur la quantité d'or(I) est compris entre 1 et 4, de préférence 2 et 3
  6. Emulsion photo graphique selon la revendication 4, dans laquelle le composé d'or est
    Figure 00320002
  7. Emulsion photographique selon la revendication 2, dans laquelle la thiourée est
    Figure 00330001
  8. Emulsion photographique selon la revendication 1 dans laquelle la différence du pourcentage molaire de chacun des halogénures constituant la core entre le centre des grains et l'interface core/shell est au moins égale à 10 %.
  9. Emulsion photographique selon la revendication 1, dans laquelle la core est constituée de bromoiodure d'argent, de chloroiodure d'argent ou de chlorobromoiodure d'argent.
  10. Emulsion selon la revendication 8 dans laquelle la core est constituée de bromoiodure d'argent et le pourcentage molaire d'iodure d'argent dans la core, par rapport au nombre de moles total d'halogénures d'argent de la core décroít de façon continue entre le centre des grains et l'interface core/shell et la shell ne contient pas d'iodure d'argent.
  11. Emulsion photographique selon la revendication 8, dans laquelle le pourcentage molaire d'iodure d'argent global dans la core est compris entre 10 et 30 %, par rapport au nombre de moles d'halogénures d'argent total de la core.
  12. Emulsion photographique selon la revendication 8 dans laquelle la shell est constituée de plusieurs couches ayant des compositions en halogénure différentes.
  13. Emulsion photographique selon la revendication 8, dans laquelle le rapport du nombre de moles d'halogénures d'argent constituant la core sur le nombre de moles d'halogénures d'argent constituant la shell est compris entre 0,2 et 2.
  14. Emulsion selon la revendication 8 dans laquelle la core des grains est constituée de bromoiodure d'argent, la shell de bromure d'argent et le rapport molaire core/shell est égal à 0,5.
  15. Emulsion photographique selon la revendication 14 dans laquelle le pourcentage molaire d'iodure d'argent dans la core varie entre 36 % au centre et 0 % à l'interface, par rapport au nombre de moles total d'halogénures d'argent de la core.
  16. Procédé de préparation de l'émulsion photographique sensibilisée chimiquement telle que définie dans l'une quelconque des revendications précédentes, comprenant la précipitation de zones successives ayant des compositions en halogénure différentes en introduisant simultanément une solution de sel d'argent et une solution d'halogénure(s) d'un métal alcalin, le procédé étant caractérisé en ce qu'au moins pendant la précipitation de la zone centrale (core), la solution d'halogénure contient au moins deux halogénures différents dont les concentrations dans la solution d'halogénure varient de façon pratiquement linéaire entre des valeurs initiales prédéterminées et des valeurs finales qui sont égales aux concentrations de ces halogénures dans la solution d'halogénure au début de la précipitation de la zone de la shell immédiatement adjacente.
EP19950420278 1994-10-26 1995-10-13 Emulsions photographiques aux halogénures d'argent ayant une désensibilisation par le colorant réduite Expired - Lifetime EP0709725B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9413050 1994-10-26
FR9413050A FR2726376B1 (fr) 1994-10-26 1994-10-26 Emulsions photographiques aux halogenures d'argent ayant une desensibilisation par le colorant reduite

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EP0709725A1 EP0709725A1 (fr) 1996-05-01
EP0709725B1 true EP0709725B1 (fr) 2000-12-13

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EP19950420278 Expired - Lifetime EP0709725B1 (fr) 1994-10-26 1995-10-13 Emulsions photographiques aux halogénures d'argent ayant une désensibilisation par le colorant réduite

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EP (1) EP0709725B1 (fr)
DE (1) DE69519621T2 (fr)
FR (1) FR2726376B1 (fr)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5049485A (en) * 1990-11-16 1991-09-17 Eastman Kodak Company Photographic silver halide material comprising gold compound
FR2703478B1 (fr) * 1993-04-02 1995-06-02 Kodak Pathe Procédé de préparation d'émulsions photographiques présentant un niveau de voile faible.

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Publication number Publication date
DE69519621D1 (de) 2001-01-18
EP0709725A1 (fr) 1996-05-01
DE69519621T2 (de) 2001-06-13
FR2726376B1 (fr) 1998-10-16
FR2726376A1 (fr) 1996-05-03

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