EP0369491B1 - Methode zur Herstellung einer Silberhalogenidemulsion - Google Patents

Methode zur Herstellung einer Silberhalogenidemulsion Download PDF

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Publication number
EP0369491B1
EP0369491B1 EP19890121452 EP89121452A EP0369491B1 EP 0369491 B1 EP0369491 B1 EP 0369491B1 EP 19890121452 EP19890121452 EP 19890121452 EP 89121452 A EP89121452 A EP 89121452A EP 0369491 B1 EP0369491 B1 EP 0369491B1
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EP
European Patent Office
Prior art keywords
silver halide
emulsion
grain
silver
layer
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP19890121452
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English (en)
French (fr)
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EP0369491A1 (de
Inventor
Seiji C/O Fuji Photo Film Co. Ltd Yamashita
Shunji C/O Fuji Photo Film Co. Ltd Takada
Shigeru C/O Fuji Photo Film Co. Ltd Shibayama
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP63291966A external-priority patent/JP2505262B2/ja
Priority claimed from JP1015520A external-priority patent/JP2519794B2/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0369491A1 publication Critical patent/EP0369491A1/de
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Publication of EP0369491B1 publication Critical patent/EP0369491B1/de
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/015—Apparatus or processes for the preparation of emulsions
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/07—Substances influencing grain growth during silver salt formation
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers
    • G03C2005/3007—Ascorbic acid
    • 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
    • G03C2200/00—Details
    • G03C2200/59—R-SO2SM compound
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains

Definitions

  • the present invention relates to a method of manufacturing a silver halide photographic emulsion for providing a light-sensitive material with high sensitivity and low fogging density.
  • the present invention also relates to a method of manufacturing a silver halide photographic emulsion for providing a light-sensitive material whose sensitivity and fogging density do not vary much upon storage.
  • Basic properties required for photographic silver halide emulsion are high sensitivity, low fogging density, and fine graininess.
  • Patents 2,518,698, 3,201,254, 3,411,917, 3,779,777, and 3,930,867 are described in JP-B-57-33572 and JP-B-58-1410 ("JP-B-" means examined Japanese patent application).
  • JP-B- means examined Japanese patent application.
  • conventional reduction sensitizers are enumerated, and ascorbic acid is included therein.
  • a compound such as thiourea dioxide is considered to be preferable, and thiourea dioxide, silver ripening, and hydrazine are exemplified. Therefore, preferable properties of an ascorbic acid compound as a reduction sensitizer have not been yet found. Improvements are also disclosed in JP-A-57-179835 ("JP-A-" means unexamined published Japanese patent application).
  • the conventional techniques of reduction sensitization do not satisfy a recent demand for high sensitivity and high image quality of a photographic light-sensitive material. This is because, firstly, variations in sensitivity and fogging density are large when a light-sensitive material containing an emulsion subjected to reduction sensitization is stored. Secondly, an increase in sensitivity obtained by reduction sensitization is insufficient.
  • the above objects of the present invention are achieved by performing reduction sensitization by using at least one of ascorbic acid and its derivatives in an amount of 1 x 10- 3 to 1 x 10- 2 mol per mol of a silver halide in the presence of at least one of compounds represented by formulas (I), (II), and (III).
  • R, R 1 , and R 2 can be the same or different and represent an aliphatic group, an aromatic group, or a heterocyclic group
  • M represents a cation
  • L represents a divalent bonding group
  • m represents 0 or 1, in a process of manufacturing a silver halide emulsion, and by a color light-sensitive material comprising a transparent support having thereon at least one light-sensitive silver halide emulsion layer, wherein 50 weight percent or more of silver halide grains contained in the emulsion layer are the silver halide grains constituting the silver halide emulsion manufactured by the above method.
  • Compounds represented by formulas (I) to (III) can be polymers containing divalent groups derived from structures represented by formulas (I) to (III) as repeating units.
  • Process of manufacturing silver halide emulsions are roughly classified into, e.g., grain formation, desalting, chemical sensitization, and coating steps. Grain formation is further classified into e.g. nucleation, ripening, and precipitation substeps. These steps are performed not in the above-mentioned order but in a reverse order or repeatedly.
  • “To perform reduction sensitization in a process of manufacturing silver halide emulsions” means that reduction sensitization can be basically performed in any step. The reduction sensitization can be performed during nucleation or physical ripening in the initial stage of grain formation, during precipitation, or before or after chemical sensitization.
  • the reduction sensitization is perferably performed before the chemical sensitization so as not to produce an undesired fog.
  • the reduction sensitization is most perferably performed during precipitation of silver halide grains.
  • the method of performing the reduction sensitization during precipitation includes a method of performing the reduction sensitization while silver halide grains are grown by physical ripening or addition of a water-soluble silver salt and a water-soluble alkali halide and a method of performing the reduction sensitization while grain precipitation is temporarily stopped and then precipitating grains.
  • ascorbic acid and its derivative are as follows.
  • ком ⁇ онент compounds in a process of manufacturing a silver halide emulsion of the present invention, they can be dispersed directly in an emulsion, or can be dissolved in a solvent or solvent mixture of, e.g., water, methanol, and ethanol and then added in the manufacturing process.
  • the ascorbic acid compound of the present invention is used in an amount much larger than a preferable addition amount of a conventional reduction sensitizer.
  • JP-B-57-33572 describes "an amount of a reducing agent normally does not exceed 0.75 x 10- 2 milli equivalent amount (8 x 10- 4 mol/AgX mol) per gram of silver ions.
  • An amount of 0.1 to 10 mg (10- 7 to 10- s mol/AgX mol for ascorbic acid) per kg of silver nitrate is effective in many cases" (reduced values are calculated by the present inventors).
  • Patent 2,487,850 describes that "a tin compound can be used as a reduction sensitizer in an addition amount of 1 x 10- 7 to 44 x 10 -6 mol".
  • JP-A-57-179835 describes that it is suitable to add about 0.01 mg to about 2 mg of thiourea dioxide or about 0.01 mg to about 3 mg of stannous chloride per mol of a silver halide.
  • a preferable addition amount of the ascorbic acid compound used in the present invention depends on factors such as a grain size and a halogen composition of an emulsion, a temperature, a pH, and a pAg in emulsion preparation.
  • the addition amount is selected from a range of, preferably, 5 x 10- s mol to 1 x 10- 1 mol, more preferably, 5 x 10- 4 mol to 1 x 10- 2 mol, and most preferably, 1 x 10- 3 mol to 1 x 10- 2 mol per mol of a silver halide.
  • the ascorbic acid compound of the present invention can be added at any timing in an emulsion manufacturing process, it is most preferably added during grain precipitation.
  • the ascorbic acid compound is preferably added at an arbitrary timing in grain formation though it can be added in a reaction vessel beforehand.
  • a reduction sensitizer can be added in an aqueous solution of a water-soluble silver salt or water-soluble alkali halide to perform grain formation by using this aqueous solution.
  • a method of adding a solution of the reduction sensitizer several times or continuously adding it over a long time period during grain growth is also preferable.
  • a method of performing reduction sensitization by using the ascorbic acid compound of the present invention is superior to a conventional reduction sensitization method in sensitivity, fogging density, and age stability, it is sometimes more preferable to use the method of the present invention in combination with another reduction sensitization method. In this case, however, it is preferred that the other method is used as merely an auxiliary means of reduction sensitization and a main means of reduction sensitization is performed by the ascorbic acid compound.
  • a method to be used in combination with the method of the present invention can be selected from a method of adding a known reducing agent to a silver halide emulsion, a method called silver ripening in which precipitating or ripening is performed in a low-pAg atmosphere of a pAg of 1 to 7, and a method called high-pH ripening in which precipitating or ripening is performed in a high-pH atmosphere of a pH of 8 to 11.
  • a method of adding a reduction sensitizer is preferable because the level of reduction sensitization can be precisely adjusted.
  • reduction sensitizer for example, stannous salt, amines and polyamines, a hydrazine derivative, formamidinesulfinic acid, a silane compound, and a borane compound are known.
  • the ascorbic acid compound can provide superior results to those obtained by the above known reduction sensitizers.
  • reduction sensitization by using the ascorbic acid compound in a process of manufacturing a silver halide emulsion is performed in the presence of at least one compound selected from compounds represented by formulas (I), (II), and (III) during the manufacturing process.
  • R, R 1 , and R 2 can be the same or different and represent an aliphatic group, an aromatic group, or a heterocyclic group
  • M represents a cation
  • L represents a divalent bonding group
  • m represents 0 or 1.
  • R 1 and R 2 each represent an aliphatic group, it is a saturated or unsaturated, straight-chain, branched or cyclic aliphatic hydrocarbon group and is preferably alkyl having 1 to 22 carbon atoms or alkenyl or alkinyl having 2 to 22 carbon atoms. These groups can have a substituent group.
  • alkyl examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl, and t-butyl.
  • alkenyl examples are allyl and butenyl.
  • alkinyl examples are propargyl and butynyl.
  • An aromatic group of R, R 1 , and R 2 includes aromatic group of single-ring or condensed-ring and preferably has 6 to 20 carbon atoms. Examples of such an aromatic group are phenyl and naphthyl. These groups can have substituent group.
  • a heterocyclic group of R, R l , and R 2 includes a 3- to 15-membered ring having at least one element of nitrogen, oxygen, sulfur, selenium, and tellurium and at least one carbon atom, preferably, a 3- to 6-membered ring.
  • heterocyclic group examples include pyrrolidine, piperidine, pyridine, tetrahydrofurane, thiophene, oxazole, thiazole,, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tellur- azole, triazole, benzotriazole, tetrazole, oxadiazole, and thiadiazole.
  • R, R 1 , and R 2 are an alkyl group (e.g., methyl, ethyl, and hexyl), an alkoxy group (e.g., methoxy, ethoxy, and octyloxy), an aryl group (e.g., phenyl, naphthyl, and tolyl), a hydroxyl group, a halogen atom (e.g., fluorine, chlorine, bromine, and iodine), an aryloxy group (e.g. phenoxy), an al- kylthio group (e.g., methylthio and butylthio), an arylthio group (e.g.
  • an alkyl group e.g., methyl, ethyl, and hexyl
  • an alkoxy group e.g., methoxy, ethoxy, and octyloxy
  • an aryl group e.g.,
  • phenylthio an acyl group (e.g. acetyl, propionyl, butyryl, and valeryl), a sulfonyl group (e.g. methyl sulfonyl and phenylsulfonyl), an acylamino group (e.g., acetylamino and benzaoylamino), a sulfonylamino group (e.g., methanesulfonylamino and benzenesul- fonylamino), an acyloxy group (e.g., acetoxy and benzoxy), carboxyl, cyano, sulfo, amino, -S0 2 SM (M represent a monovalent cation), and -S0 2 R'.
  • acyl group e.g. acetyl, propionyl, butyryl, and valeryl
  • a sulfonyl group
  • a divalent bonding group represented by L includes an atom or an atom group containing at least one of C, N, S, and O.
  • L are alkylene, alkenylene, alkynylene, arylene, -O-, -S-, -NH-, -CO-, and -S0 2 -. These divalent group can be used singly or in a combination of two or more thereof.
  • L represent divalent aliphatic group or a divalent aromatic group.
  • divalent aromatic group of L are phenylene and naphthylene.
  • M is preferably a metal ion or an organic cation.
  • the metal ion are a lithium ion, a sodium ion, and a potassium ion.
  • the organic cation are an ammonium ion (e.g., ammonium, tetramethylammonium, and tetrabutylammonium), a phosphonium ion (e.g. tetraphenylphosphonium), and a guanidil group.
  • Each of the above polymers can be a homopolymer or a copolymer with another copolymerizable monomer.
  • a compound represented by formula (I), (II), or (III) is preferably added in an amount of 10- 7 to 10- 1 mol per mol of a silver halide.
  • the addition amount is more preferably 10- 6 to 10- 2 mol/molAg and most preferably 10 -5 to 10- 3 mol/molAg.
  • a conventional method of adding an additive in a photographic emulsion can be adopted to add compounds represented by formulas (I) to (III) in a manufacturing process.
  • a water-soluble compound can be added in the form of an aqueous solution having an arbitrary concentration, and a water-insoluble or water- retardant compound is dissolved in an arbitrary organic solvent such as alcohols, glycols, ketones, esters, and amides, which is miscible with water and does not adversely affect photographic properties, and then added as a solution.
  • Acompound represented by formula (I), (II), or (III) can be added at any timing in a manufacturing process, e.g., during grain formation of a silver halide emulsion or before or after chemical sensitization.
  • the compound is preferably added before or during reduction sensitization.
  • the compound is most preferably added during grain precipitation.
  • the compound can be added in a reaction vessel beforehand, it is preferably added at an arbitrary timing during grain formation.
  • a compound represented by formula (I), (II), or (III) can be added in an aqueous solution of a water-soluble silver salt or water-soluble alkali halide to perform grain formation by using the aqueous solution.
  • a method of adding a solution of a compound represented by formula (I), (II), or (III) several times or continuously adding it over a long time period during grain formation is also preferable.
  • a compound most preferable in the present invention is represented by formula (I).
  • Asilver halide of any of silver bromide, silver iodobromide, silver iodochlorobromide, silverchlorobromide, and silver chloride can be used in a photographic emulsion layer of a photographic light-sensitive material used in the present invention.
  • a preferable silver halide is silver iodobromide, silver bromide, or silver chlorobromide containing 30 mol% or less of silver iodide.
  • Asilver halide grain to be used in the present invention can be selected from a regular crystal not including a twined crystal face and those described in Japan Photographic Society ed., "Silver Salt Photographs, Basis of Photographic Industries", (Corona Co., P. 163) such as a single twined crystal including one twined crystal face, a parallel multiple twined crystal including two or more parallel twined crystal faces, and a non-parallel multiple twined crystal including two or more non-parallel twined crystal faces, in accordance with its application.
  • a cubic grain consisting of (100) faces, an octahedral grain consisting of (111) faces, and a dodecahedral grain consisting of (110) faces disclosed in JP-B-55-42737 and JP-A-60-222842 can be used.
  • a grain including two or more types of faces e.g., a tetradecahedral grain having both (100) and (111) faces, a grain having both (100) and (110) faces, and a grain having both (111) and (110) faces can be selectively used in accordance with an application.
  • the grain of a silver halide can be a fine grain having a grain size of 0.1 microns or less or a large grain having a projected surface area diameter of 10 microns.
  • An emulsion can be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution.
  • a so-called monodisperse silver halide emulsion having a narrow size distribution i.e., in which 80% or more (the number or weight of grains) of all grains fall within the range of ⁇ 30% of an average grain size.
  • two or more types of monodisperse silver halide emulsions having different grain sizes can be coated in a single layer or overlapped in different layers in emulsion layers having substantially the same color sensitivity.
  • two or more types of polydisperse silver halide emulsions or a combination of monodisperse and polydisperse emulsions can be mixed or overlapped.
  • the photographic emulsions for use in the present invention can be prepared by using methods described in, for example, P. Glafkides, "Chimie et Physique Photographique", Paul Montel, 1967; Duffin, “Photographic Emulsion Chemistry", Focal Press, 1966; and V.L. Zelikman et al., “Making and Coating Photographic Emulsion", Focal Press, 1964. That is, the photographic emulsion can be prepared by, e.g., an acid method, a neutralization method, and an ammonia method. Also, as a system for reacting a soluble silver salt and a soluble halide, a single mixing method, a double mixing method, or a combination thereof can be used.
  • a so-called back mixing method for forming silver halide grains in the presence of excessive silver ions can be used.
  • a so-called controlled double jet method wherein the pAg in the liquid phase, where the silver halide is generated, kept at a constant value can be used. According to this method, a silver halide emulsion having a regular crystal form and almost uniform grain sizes is obtained.
  • the silver halide emulsion containing the above-described regular silver halide grains can be obtained by controlling the pAg and pH during grain formation. More specifically, such a method is described in "Photographic Science and Engineering", Vol. 6, 159-165 (1962); “Journal of Photographic Science”, Vol. 12, 242-251 (1964); U.S. Patent 3,655,394, and British Patent 1,413,748.
  • a tabular grain having an aspect ratio of 3 or more can also be used in the present invention.
  • the tabular grain can be easily prepared by methods described in, for example, Cleve, "Photography Theory and Practice", (1930), P. 131; Gutoff, "Photographic Science and Engineering", Vol. 14, PP. 248 to 257, (1970); and U.S. Patents 4,434,226, 4,414,310, 4,433,048 and 4,439,520 and British Patent 2,112,157.
  • covering power and a color sensitizing efficiency of a sensitizing dye can be advantageously improved as described in detail in U.S. Patent 4,434,226.
  • the tabular grains are preferably used in the emulsion of the present invention.
  • tabular grains in which grains having aspect ratios of 3 to 8 occupy 50% or more of a total projected surface area are preferable.
  • a crystal structure can be uniform, can have different halogen compositions inside and outside a crystal, orcan be layered structure.
  • These emulsion grains are disclosed in, e.g., British Patent 1,027,146, U.S. Patents 3,505,068 and 4,444,877, and Japanese Patent Application No. 58-248469.
  • a silver halide having different compositions can be bonded by an epitaxial junction, or a compound other than a silver halide such as silver rhodanate or zinc oxide can be bonded.
  • the silver halide emulsion of the present invention preferably has a distribution or structure of a halogen composition in its grain.
  • a halogen composition in its grain.
  • Atypical example is a core-shell type or double structured grain having different halogen compositions in the interior and surface layer of the grain as disclosed in, e.g., JP-B-43-13162, JP-A-61-215540, JP-A-60-222845, and JP-A-61-75337.
  • the shape of a core portion is sometimes identical to or sometimes different from that of the entire grain with a shell. More specifically, while the core portion is cubic, the grain with a shell is sometimes cubic or sometimes octahedral.
  • the grain with a shell is sometimes cubic or sometimes octahedral.
  • the core portion is a clear regular grain, the grain with a shell is sometimes slightly deformed or sometimes does not have any definite shape.
  • a simple double structure buta triple structure as disclosed in JP-A-60-222844 or a multilayered structure of more layers can be formed, or a thin layer of a silver halide having a different composition can be formed on the surface of a core-shell double structure grain.
  • a grain having not only the above surrounding structure but a so-called junction structure can be made.
  • Examples of such a grain are disclosed in, e.g., JP-A-59-133540, JP-A-58-108526, EP 199290A2, JP-B-58-24772, and JP-A-59-16254.
  • a crystal bonded having a composition different from that of a host crystal can be produced and bonded to an edge, corner, or face portion of the host crystal.
  • Such a junction crystal can be formed regardless of whether the host crystal has a homogeneous halogen composition or a core-shell structure.
  • the junction structure can be naturally made by a combination of silver halides.
  • the junction structure can be made by combining a silver salt compound not having a rock salt structure, e.g., silver rhodanate or silver carbonate, with a silver halide.
  • a non-silver salt compound such as PbO can also be used as long as the junction structure can be made.
  • the silver iodide content can be high at a core portion and low at a shell portion or vice versa.
  • the silver iodide content can be high in a host crystal and relatively low in a junction crystal or vice versa.
  • a boundary portion between different halogen compositions can be clear or unclear due to a crystal mixture formed by a composition difference.
  • a continuous structure change can be positively made.
  • the silver halide emulsion for use in the present invention can be subjected to a treatment for rounding a grain as disclosed in, e.g., EP-0096727BI and EP-0064412BI ora a treatment of modifying the surface of a grain as disclosed in DE-2306447C2 and JP-A-60-221320.
  • the silver halide emulsion for use in the present invention is preferably of a surface latent image type.
  • An internal latent image type emulsion can be used by selecting a developing solution or development conditions as disclosed in JP-A-59-133542.
  • a shallow internal latent image type emulsion covered with a thin shell can be used in accordance with an application.
  • a solvent for silver halide can be effectively used to promote ripening.
  • an excessive amount of halogen ions are supplied in a reaction vessel in order to promote ripening. Therefore, it is apparent that ripening can be promoted by only supplying a silver halide solution into a reaction vessel.
  • another ripening agent can be used.
  • a total amount of these ripening agents can be mixed in a dispersion medium in the reaction vessel before a silver salt and a halide are added therein, or they can be added in the reaction vessel together with one or more halides, a silver salt or a deflocculant.
  • the ripening agents can be added singly in step of adding a halide and a silver salt.
  • ripening agent other than the halogen ion examples include ammonia, an amine compound and a thiocyanate such as an alkali metal thiocyanate, especially sodium or potassium thiocyanate and ammonium thiocyanate.
  • a portion to be subjected to the chemical sensitization differs in accordance with the composition, structure, or shape of an emulsion grain or an application of the emulsion. That is, a chemical sensitization nucleus is embedded either inside a grain or in a shallow portion from the grain surface or formed on the surface of a grain. Although the present invention is effective in any case, the chemical sensitization nucleus is most preferably formed in a portion near the surface. That is, the present invention is more effective in the surface latent image type emulsion than in the internal latent image type emulsion.
  • Chemical sensitization can be performed by using active gelatin as described in T.H. James, "The Theory of the Photographic Process", 4th ed., Macmillan, 1977, PP. 67 to 76.
  • chemical sensitization can be performed at a pAg of 5 to 10, a pH of 5 to 8 and a temperature of 30 to 80°C by using sulfur, selenium, tellurium, gold, platinum, palladium or irridium, or a combination of a plurality of these sensitizers as described in Research Disclosure Vol. 120, No. 12,008 (April, 1974), Research Disclosure Vol. 34, No. 13,452 (June, 1975), U.S.
  • Chemical sensitization is optimally performed in the presence of a gold compound and a thiocyanate compound, a sulfur-containing compound described in U.S. Patents 3,857,711, 4,266,018 and 4,054,457 or a sulfur-containing compound such as a hypo, thiourea compound and a rhodanine compound.
  • Chemical sensitization can also be performed in the presence of a chemical sensitization assistant.
  • An example of the chemical assistant is a compound known to suppress fogging and increase sensitivity in the chemical sensitization process such as azaindene, azapyridazine, and azapyrimidine.
  • Examples of a chemical sensitization assistant modifier are described in U.S. Patents 2,131,038, 3,411,914, 3,554,757, JP-A-58-126526 and G.F. Duffin, "Photographic Emulsion Chemistry", PP. 138 to 143.
  • the photographic emulsion for use in the present invention can contain various compounds in order to prevent fogging during manufacture, storage, or a photographic treatment of the light-sensitive material or to stabilize photographic properties.
  • the compound known as an antifoggant or stabilizer are azoles, e.g., benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimida- zoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiaziazoles, amino- triazoles, benzotriazoles, nitrobenzotriazoles, and mercaptotetrazoles (especially, 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriadines; a thioketo compound such as oxadrinthione; azaindenes, e.g., triazainden
  • the photographic emulsion for use in the present invention can be spectrally sensitized with, e.g., methine dyes.
  • the dye to be used are a cyanine dye, merocyanine dye, a composite cyanine dye, a composite merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye, and hemioxonol dye.
  • Most effective dyes are those belonging to a cyanine dye, a merocyanine dye, and a composite merocyanine dye. In these dyes, any nucleus normally used as a basic heterocyclic nucleus in cyanine dyes can be used.
  • nucleus examples include pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, and a pyridine nucleus; a nucleus obtained by condensing an alicyclic hydrocarbon ring to each of the above nuclei; and a nucleus obtained by condensing an aromatic hydrocarbon ring to each of the above nuclei, e.g., an in- dolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxadole nucleus, a naphthooxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a
  • a 5- or 6-membered heterocyclic nucleus e.g., a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be used as a nucleus having a ketomethylene structure.
  • sensitizing dyes can be used singly or in a combination of two or more thereof.
  • a combination of the sensitizing dyes is often used especially in order to perform supersensitization.
  • Typical examples of the combination are described in U.S. Patents 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769,301, 3,814,609, 3,837,862, 4,026,707, British Patents 1,344,281 and 1,507,803, JP-B-43-4936 and JP-B-53-12375, and JP-A-52-110618 and JP-A-52-109925.
  • the emulsion can contain, in addition to the sensitizing dye, a dye not having a spectral sensitizing effect or a substance substantially not absorbing visible light, having supersensitization.
  • the dye can be added in the emulsion at any timing conventionally known to be effective in emulsion preparation. Most ordinarily, the dye is added after completion of chemical sensitization and before coating. However, the dye can be added at the same time as a chemical sensitizer to simultaneously perform spectral sensitization and chemical sensitization as described in U.S. Patents 3,628,969 and 4,225,666, added before chemical sensitization as described in JP-A-58-113928, or added before completion of silver halide grain precipitation to start spectral sensitization. In addition, as described in U.S. Patent 4,225,666, the above compound can be separately added such that a portion of the compound is added before chemical sensitization and the remaining portion is added thereafter. That is, as described in U.S. Patent 4,183,756, the compound can be added at any timing during silver halide grain formation.
  • An addition amount can be 4 x 10- s to 8 x 10- 3 mol per mol of a silver halide. More preferably, when a silver halide grain size is preferable size i.e. 0.1 to 1.2 f..lm, an addition amount of about 5 x 10- 5 to 2 x 10- 3 mol is more effective.
  • the couplers for use in this invention can be introduced in the light-sensitive materials by various known dispersion methods.
  • the present invention can be applied to various color light-sensitive materials.
  • the material are a color negative film for a general purpose or a movie, a color reversal film for a slide or a television, color paper, a color positive film, and color reversal paper.
  • the color photographic light-sensitive materials of this invention can be processed by the ordinary processes as described, for example, in the above-described Research Disclosure, No. 17643, pages 28 to 29 and ibid., No. 18716, page 651, left to right columns.
  • Double twined crystal grains comprising silver iodobromide and having an average iodide content of 24 mol% and a average sphere-equivalent diameter of 0.8 ⁇ m were used as seed crystals to form an emulsion in an aqueous gelatin solution by a controlled double jet method, the emulsion comprising twined crystal grains comprising silver iodobromide and having an average sphere-equivalent diameter of 1.2 ⁇ m, in which a core/shell ratio was 1 : 2, a shell iodide content was 2 mol%, and an average iodide content was 10 mol%.
  • the emulsion was subjected to a normal desalting/washing step and redispersed under conditions of 40°C, a pAg of 8.9, and a pH of 6.3, thereby preparing an emulsion Em-1.
  • Thiosulfonic acid compounds 1-2,1-6, and 1-16 listed in Table A were individually added in a reaction vessel in addition amounts listed in Table 1-1, one minute before shell formation was started, to perform grain formation, thereby preparing emulsions Em-2 to Em-4.
  • Em-1 to Em-12 of the present invention and comparative examples prepared as described above were subjected to optimal gold-plus-sulfur-sensitization by using sodium thiosulfate and chloroauric acid, thereby preparing emulsions.
  • Emulsion and protective layers in amounts as listed in Table 1-4 were coated on triacetylcellulose film supports having undercoating layers.
  • compositions of processing solutions used in the above steps were as follows.
  • a light source was adjusted at a color temperature of 4,800°K by using a filter, and blue light was extracted by using a blue filter(BPN42 (tradename): available from Fuji Photo Film Co. Ltd.).
  • Sensitivities were compared at a point from a fogging density by an optical density of 0.2. The sensitivities are listed as relative sensitivities assuming that the sensitivity of a sample using the emulsion Em-1 is 100 (100 for both 1/100" and 10"). Each fogging density was a value with respect to a non-exposed portion and the same for both 1/100" and 10").
  • each emulsion of the present invention had low fogging density and high sensitivity (especially with low intensity).
  • the prepared emulsions were optimally subjected to chemical sensitization by gold-plus-sulfur to prepare emulsions 13 to 24 as listed in Table 2-1.
  • each emulsion of the present invention had high sensitivity and low fogging density.
  • the prepared emulsions were coated following the same procedures as in Example 1 to perform a sensitometry test.
  • the sensitometry test was performed following the same procedures as in Example 1 except that the emulsions added with the red- or green-sensitive dyes were exposed by using a yellow filter (SC-52 (tradename): available from Fuji Photo Film Co. Ltd.) in place of the blue filter used in Example 1 and the emulsions added with the blue-sensitive dye were exposed without using a filter.
  • Table 3-2 shows sensitivities of Em-28 to Em-33 as relative sensitivities assuming that sensitivities of Em-25, Em-26, and Em-27 are 100 with respect to ten-sec and 1/100-sec exposures (Each fogging density is a value with respect to a non-exposed portion and was the same for both 1/100" and 10").
  • each emulsion of the present invention had high sensitivity and low fogging density even after it was subjected to spectral sensitization.
  • a plurality of layers having the following compositions were coated on an undercoated triacetylcellulose film support to prepare a sample as a multilayer color light-sensitive material.
  • Numerals corresponding to the respective components indicate coating amounts in units of g/m 2 .
  • a coating amount of silver halide is represented in unit of g/m 2 of silver.
  • a coating amount of the sensitizing dye is represented in units of mols per mol of the silver halide in the same layer.
  • a gelatin hardener H-1 and/or a surfactant were added to each layer.
  • Samples 401 to 403 were prepared following the same procedures as the above described sample except that the silver iodobromide emulsions I, II, and III in the layers 5, 9, and 13, respectively, were changed.
  • the processed samples were subjected to density measurement by using red, green, and blue filters. The obtained results are shown in Table 4-1.
  • the results of photographic properties are represented by relative sensitivities of the red-, green-, and blue-sensitive layers assuming that the sensitivity of the sample 401 is 100.
  • the color development process was performed at 38°C in accordance with the following process steps.
  • the emulsions of the present invention has an effect of increasing the sensitivity with almost no increase in fogging density.
  • Tap water was supplied to a mixed-bed column filled with an H type strongly acidic cation exchange resin (Amberlite IR-120B: available from Rohm & Haas Co.) and an OH type basic anion exchange resin (Amberlite IR-400) to set the concentrations of calcium and magnesium to be 3 mg/f or less. Subsequently, 20 mg/f of sodium isocyanuric acid dichloride and 0.15 g/f of sodium sulfate were added. The pH of the solution fell within the range of 6.5 to 7.5.
  • H type strongly acidic cation exchange resin Amberlite IR-120B: available from Rohm & Haas Co.
  • Amberlite IR-400 OH type basic anion exchange resin
  • the samples 402 and 403 of the present invention provided the good results as in Example 4 after they were subjected to the above processing.
  • Tap water was supplied to a mixed-bed column filled with an H type strongly acidic cation exchange resin (Amberlite IR-120B: available from Rohm & Haas Co.) and an OH type basic anion exchange resin (Amberlite IR-400) to set the concentrations of calcium and magnesium to be 3 mg/f or less. Subsequently, 20 mg/f of sodium isocyanuric acid dichloride and 0.15 g/f of sodium sulfate were added. The pH of the solution fell within the range of 6.5 to 7.5.
  • H type strongly acidic cation exchange resin Amberlite IR-120B: available from Rohm & Haas Co.
  • Amberlite IR-400 OH type basic anion exchange resin
  • the samples 402 and 403 of the present invention provided the good results as in Example 4 after they were subjected to the above processing.
  • a plurality of layers having the following compositions were coated on an undercoated cellulose triacetate film support to prepare a sample as a multilatered color light-sensitive material.
  • the amounts are represented in units of g/m 2 .
  • the coated amounts of a silver halide and colloid silver are represented in units of g/m 2 of silver, and that of sensitizing dyes is represented by the number of mols per mol of the silver halide in the same layer.
  • Samples 701 to 703 were prepared following the same procedures as for the above sample except that the silver iodobromide emulsions I, II, and III in the layers 5, 10, and 16, respectively, were changed.
  • the processed samples were subjected to density measurement by using red, green, and blue filters. The obtained results are shown in Table 7-1.
  • the results of photographic properties are represented by relative sensitivities of the red-, green-, and blue-sensitive layers assuming that the sensitivity of the sample 701 is 100.
  • the emulsions of the present invention have an effect of increasing the sensitivity with almost no increase in fogging density.
  • the samples 702 and 703 using the emulsions of the present invention provided good photographic properties.
  • a plurality of layers having the following compositions were coated on an undercoated triacetylcellulose film support to prepare a sample as a multilayered color light-sensitive material.
  • the coated amount of a silver halide and colloid silver are represented in units of g/m 2 of silver, that of couplers, additives, and gelatin is represented in units of g/m 2 , and that of sensitizing dye is represented by the number of mols per mol of the silver halide in the same layer.
  • Symbols representing additives have the following meanings. Note that if an additive has a plurality of effects, only one of the effects is shown.
  • a stabilizer Cpd-3 (0.07 g/m 2 ) for an emulsion and a surfactant Cpd-4 (0.03 g/m 2 ) were added as coating aids to each layer.
  • Em-201 An emulsion Em-201 was prepared following the same procedures as for Em-1 in Example 1 except that the average sphere-equivalent diameter of a seed crystal was 0.5 ⁇ m and therefore the average sphere-equivalent diameter of a final grain was 0.75 ⁇ m.
  • a thiosulfonic acid compound and a reduction sensitizer were added in amounts listed in Table 8-1 to Em-201 following the same procedures as in Example 1, thereby preparing emulsions 202 to 207.
  • the emulsions 201 to 207 prepared as described above were optimally subjected to gold-plus-sulfur-sensitization by using a sodium thiosulfate and chloroauric acid.
  • Samples 801 to 804 were prepared following the same procedures as for the above sample except that the silver iodobromide emulsions I, II, and III in the layers 4, 8, and 14, respectively, were changed.
  • the processed samples were subjected to density measurement by using red, green, and blue filters.
  • the results of photographic properties are compared by using relative sensitivities of the red-, green-, and blue-sensitive layers assuming that the sensitivity of the sample 801 is 100.
  • the samples 803 and 804 of the present invention had higher sensitivity and lower fogging density than the samples 801 and 802 of the comparative example.
  • a fogging density of the sample 802 was significantly increased while its sensitivity was decreased.
  • the samples 803 and 804 of the present invention had photographic properties better than those of the comparative examples 801 and 802.
  • R, R l , R 2 , M, and m in formulas (I), (II), and (III) are as described before.
  • a tabular grain means a grain having a plurality of parallel twinned crystal faces and a tabular shape regardless of its aspect ratio.
  • a grain having no twinned crystal face and having an aspect ratio of 2 or more is also included in the tabular grain.
  • the latter grain includes a rectangular parallelepiped grain as reported in A. Mignot et al., "Journal of Cryst. Growth", Vol. 23, P. 207 (1974).
  • an aspect ratio means a ratio of a diameter of a silver halide grain with respect to its thickness. That is, the aspect ratio is a value obtained by dividing the diameter of each silver halide grain by its thickness.
  • the diameter means a diameter of a circle having an area equal to a projected area of a grain upon observation of a silver halide emulsion by a microscope or electron microscope. Therefore, when the aspect ratio is 3 or more, the diameter of a circle is three times or more the thickness of a grain.
  • An average aspect ratio is obtained as follows. That is, 1,000 silver halide grains of the emulsion are extracted at random to measure their aspect ratios, tabular grains corresponding to 50% of a total projected area are selected from those having larger aspect ratios, and a number-average of aspect ratios of the selected tabular grains is calculated. A number-average of a diameter or thickness of the tabular grains used to calculate the average aspect ratio is defined as an average grain size or average grain thickness, respectively.
  • An example of an aspect ratio measuring method is a method of photographing a transmission electron micrograph by a replica technique to obtain a circle-equivalent diameter and a thickness of each grain. In this case, the thickness is calculated from the length of a shadow of the replica.
  • the average aspect ratio of the tabular silver halide grains reduction-sensitized by the ascorbic acid compound is 3.0 or more, preferably, 3 to 20, more preferably, 4 to 15, and most preferably, 5 to 10.
  • a ratio of a projected area occupied by tabular silver halide grains with respect to all silver halide grains is 50% or more, preferably, 70% or more, and more preferably, 85% or more.
  • Asilver halide photographic light-sensitive material having good sharpness can be obtained by using such an emulsion.
  • the sharpness is good because a degree of light scattering caused by an emulsion layer using the above emulsion is much smaller than that of a conventional emulsion layer. This can be easily confirmed by an experiment method ordinarily used by those skilled in the art.
  • the reason why the light scattering degree of an emulsion layer using the tabular silver halide emulsion is small is not clear. It can be assumed, however, that a major surface of the tabular silver halide emulsion grain is oriented parallel to the surface of a support.
  • the average grain diameter of the tabular silver halide grains reduction-sensitized by the ascorbic acid compound is 0.2 to 10.0 f..lm, preferably, 0.3 to 5.0 f..lm, and more preferably, 0.4 to 3.0 ⁇ m.
  • the average grain thickness is preferably 0.5 ⁇ m or less.
  • the average grain size is 0.4 to 3.0 ⁇ m
  • the average grain thickness is 0.5 ⁇ m or less
  • the aspect aspect ratio is 5 to 10
  • 80% or more of a total projected area of all silver halide grains are occupied by tabular grains.
  • the tabular silver halide grains reduction-sensitized by the ascorbic acid compound may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. More preferable examples are silver bromide, silver iodobromide having 20 mol% or less of silver iodide, and silver chloroiodobromide and silver chlorobromide having 50 mol% or less of silver chloride and 2 mol% or less of silver iodide. In a mixed silver halide, a composition distribution may be uniform or localized.
  • the tabular silver halide emulsion of the present invention can be prepared by, for example, forming a seed crystal having 40% (weight) or more of tabular grains in a comparatively-high-pAg atmosphere in which a pBr is 1.3 or less, and simultaneously adding silver and halogen solutions to grow the seed crystal while the pBr value is maintained substantially the same level. In this grain growth step, it is preferred to add the silver and halogen solutions so that no new crystal nucleus is generated.
  • the size of emulsion grains can be adjusted, for example, by adjusting a temperature, selecting the type or quality of a solvent, and controlling addition rates of silver salts and halides used in grain formation.
  • Samples 1101 to 1110 of multilayered color light-sensitive material having the same layer arrangement as that of Example 4 were prepared following the same procedures as in Example 4 except that the silver iodobromide emulsions I, II, and III of the layers 5, 9, and 13 were changed as shown in Table 9-2. Note that in addition to the emulsions listed in Table 9-2, the sensitizing dyes of the dye groups 1, 2, and 3 of Example 3 were added to the layers 5, 9, and 13, respectively, in the same amounts as those in Example 3.
  • aqueous solution obtained by dissolving 30 g of inactive gelatin and 6 g of potassium bromide in 1 f of distilled water was stirred at 75°C, and 35 cc of an aqueous solution containing 5.0 g of silver nitrate and 35 cc of an aqueous solution containing 3.2 g of potassium bromide and 0.98 g of potassium iodide were added to the resultant solution each at a rate of 70 cc/min for 30 seconds. Thereafter, the pAg of resultant solution increased to 10 to perform ripening for 30 minutes, thereby preparing a seed emulsion.
  • a thiosulfonic acid compound was added, and one minute after the addition, equimolar amounts of the remaining aqueous silver nitrate solution and an aqueous solution of a mixture of potassium bromide and potassium iodide having a different composition from that used in core emulsion preparation were added at an addition rate close to a critical growth rate to start shell formation.
  • the ascorbic acid compound was added one minute after shell formation was started to continue shell formation, thereby finally preparing a core/shell type silver iodobromide tabular emulsions.
  • An aspect ratio was adjusted by selecting the pAg upon core and/or shell formation.
  • the processed samples were subjected to density measurement by using red, green, and blue filters. The obtained results are summarized in Table 9-2.
  • results of photographic properties are represented by relative sensitivities of the red-, green-, and blue-sensitive layers assuming that the sensitivity of the sample 1101 is 100.
  • a response to pressure of each sample was evaluated as follows. That is, each sample was wound around a columnar rod having a diameter of 6 mm so that the emulsion surface of the sample faced inward, and held in this state for 10 seconds. Thereafter, wedge exposure was performed under the same conditions as described above for 1/100 seconds, development was performed following the same procedures as described above, and the density was measured by using a blue filter, thereby measuring fog and sensitivity of the blue-sensitive layer.
  • the sensitivity is represented by a relative value assuming that the sensitivity of the sample 1101 was 100.
  • the sharpness was evaluated by measuring the MTF of the red-sensitive layer.
  • the MTF value was measured in accordance with a method described in "The Theory of Photographic Process", 3rd, ed., Macmillan. Exposure was performed by white light, and cyan color forming density was measured by a red filter. The MTF value with respect to a spatial frequency of 25 cycle/mm at cyan colorforming density of 1.0 is used as a typical value. Larger MTF values are more preferable.
  • the color photographic light-sensitive material of the present invention has good sharpness and response to pressure while maintaining high sensitivity.
  • an emulsion having higher sensitivity and producing lower fog can be obtained by additionally using a thiosulfonic acid compound.
  • Samples 1201 to 1210 having the same layer arrangement as that of Example 7 were prepared using the emulsions prepared in Example 9 as silver bromide emulsions I, II, and III of layers 5,10, and 16, respectively.
  • the color photographic light-sensitive material according to the present invention has high sensitivity and good sharpness and response to pressure.
  • Samples 1301 to 1310 having the same layer arrangement as that of Example 8 were prepared using the emulsions 101 to 110 prepared in Example 9 as silver iodobromide emulsions I, II, and III of layers 4, 8, and 14, respectively.

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Claims (6)

1. Verfahren zum Herstellen einer Silberhalogenidemulsion, umfassend das Durchführen einer Reduktionssensibilisierung in Gegenwart von mindestens einer von den Verbindungen, die durch die Formeln (I), (11) und (111) dargestellt sind:
Figure imgb0158
Figure imgb0159
Figure imgb0160
worin R, R1 und R2, die gleich oder verschieden sein können, jeweils eine aliphatische Gruppe, eine aromatische Gruppe oder eine heterocyclische Gruppe bedeuten, M ein Kation bedeutet, Leine zweiwertige Bindungsgruppe bedeutet, und m 0 oder 1 bedeutet, und Polymeren davon, welche als wiederkehrende Einheit zweiwertige Gruppen enthalten, die von Strukturen abgeleitet sind, die durch die Formeln (I) bis (111) dargestellt sind, dadurch gekennzeichnet, daß diese Reduktionssensibilisierung unter Verwendung von Ascorbinsäure und/oder Derivaten davon in einer Menge von 1 x 10-3 bis 1 x 10-2 Mol pro Mol Silberhalogenid durchgeführt wird.
2. Verfahren nach Anspruch 1, worin die Reduktionssensibilisierung während der Ausfällung von Silberhalogenidkörnern durchgeführt wird.
3. Verfahren nach Anspruch 1, worin die Reduktionssensibilisierung unter Verwendung von Ascorbinsäure durchgeführt wird.
4. Farbphotographisches lichtempfindliches Silberhalogenidmaterial, umfassend einen Träger mit mindestens einer darauf befindlichen lichtempfindlichen Silberhalogenidemulsionsschicht, enthaltend eine Silberhalogenidemulsion, die durch das Verfahren nach Anspruch 1 hergestellt ist.
5. Farbphotographisches lichtempfindliches Silberhalogenidmaterial nach Anspruch 4, worin 50 Gew.-% oder mehr aller Silberhalogenidkörner, die in der Silberhalogenidemulsion enthalten sind, die Silberhalogenidkörner sind, welche die Silberhalogenidemulsion bilden, die durch das Verfahren von Anspruch 1 hergestellt ist.
6. Farbphotographisches lichtempfindliches Silberhalogenidmaterial nach Anspruch 4, worin mindestens 50% der gesamten projizierten Fläche aller Silberhalogenidkörner in einer Emulsionsschicht, enthaltend eine Emulsion, die durch das Verfahren nach Anspruch 1 hergestellt ist, von tafelförmigen Silberhalogenidkörnern mit einem mittleren Aspektverhältnis von nicht weniger als 3,0 eingenommen wird.
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JP2604045B2 (ja) * 1989-12-28 1997-04-23 富士写真フイルム株式会社 ハロゲン化銀乳剤及びそれを用いたハロゲン化銀写真感光材料
JP2709228B2 (ja) * 1992-01-10 1998-02-04 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
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US5415992A (en) * 1993-11-30 1995-05-16 Eastman Kodak Company Heat stabilized silver chloride photographic emulsions containing phosphine compounds
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