EP0368304B1 - Méthode de préparation d'une émulsion photographique à l'halogénure d'argent - Google Patents

Méthode de préparation d'une émulsion photographique à l'halogénure d'argent Download PDF

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Publication number
EP0368304B1
EP0368304B1 EP89120772A EP89120772A EP0368304B1 EP 0368304 B1 EP0368304 B1 EP 0368304B1 EP 89120772 A EP89120772 A EP 89120772A EP 89120772 A EP89120772 A EP 89120772A EP 0368304 B1 EP0368304 B1 EP 0368304B1
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Prior art keywords
silver halide
emulsion
mol
grains
silver
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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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EP89120772A
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German (de)
English (en)
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EP0368304A1 (fr
Inventor
Mikio Fuji Photo Film Co. Ltd. Ihama
Yuuji Fuji Photo Film Co. Ltd. Kume
Hiroshi Fuji Photo Film Co. Ltd. Takehara
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP63283929A external-priority patent/JPH02130545A/ja
Priority claimed from JP30582588A external-priority patent/JPH02150837A/ja
Priority claimed from JP1026565A external-priority patent/JP2514707B2/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0368304A1 publication Critical patent/EP0368304A1/fr
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Publication of EP0368304B1 publication Critical patent/EP0368304B1/fr
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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
    • G03C1/015—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
    • G03C1/06—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
    • G03C1/0051—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
    • G03C1/0051—Tabular grain emulsions
    • G03C2001/0055—Aspect ratio of tabular grains in general; High aspect ratio; Intermediate aspect ratio; Low aspect ratio
    • 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
    • G03C2001/0152—Desalting
    • 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
    • G03C2001/0357—Monodisperse emulsion
    • 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 having a high sensitivity and a low fogging density, as well as a method of preparing a silver halide color light-sensitive material.
  • U.S. Patent 2,448,060 discloses that the sensitivity of an emulsion can be increased by adding a palladium compound and ascorbic acid to the emulsion after sulfur sensitization and before coating of the emulsion.
  • U.S. Patent 2,598,079 discloses that especially the low-intensity sensitivity of an emulsion can be increased by adding a palladium compound to the emulsion after gold-plus-sulfur sensitization and before coating of the emulsion.
  • Patents 2,472,627, 2,472,631, 2,566,245, and 2,566,263 disclose that the storage stability of a photosensitive material at high temperatures and high humidities can be improved by adding a palladium compound to the emulsion after chemical sensitization of the emulsion.
  • British Patent 1,351,309 discloses the addition of a noble metal salt in an amount of 3 x 10 ⁇ 7 to 3 x 10 ⁇ 5 mol per mol of silver halide during the formation of silver halide grains (during conversion).
  • U.S. Patent 4,092,171 discloses that a high sensitivity can be obtained and that the storage stability can be improved by adding an organic phosphinic acid complex of a palladium compound to an emulsion.
  • JP-A-61-67845 discloses a method of manufacturing a silver halide emulsion, in which monodisperse core/shell type silver halide grains having different silver iodide contents in the portions near the surface and the inside thereof are chemically ripened in the presence of at least one member of a chalcogen sensitizer, a gold sensitizer, and a water-soluble palladium salt.
  • JP-A-62-212641 discloses a method of manufacturing a silver halide emulsion, in which silver halide grains having an (nnl) face are chemically sensitized in the presence of at least one member of a chalcogen sensitizer, a gold sensitizer, and a compound of a Group VIII of the periodic table.
  • JP-A-48-87825 discloses that the sensitivity is increased while the gradation is reduced by adding a reducing agent in a process of forming silver halide grains.
  • JP-B-58-1410 discloses that the sensitivity is increased without reducing the gradation by adding a reducing agent in a process of forming silver halide grains and then adding an oxidizing agent before the silver halide grains reach their final size.
  • the above object is achieved by a method of manufacturing a silver halide photographic emulsion, wherein a palladium compound is added in an amount of 5 x 10 ⁇ 5 mol to 1 x 10 ⁇ 3 mol per mol of silver halide after a grain formation step and before a desalting step.
  • the present invention also refers to a method of manufacturing a silver halide color light-sensitive material using the above prepared silver halide emulsion. It is preferred to subject the silver halide grains to a reduction sensitization in the grain formation step.
  • a process of manufacturing a silver halide emulsion is roughly divided into grain formation, desalting, chemical sensitization, and coating steps.
  • the grain formation step is further classified into e.g. nucleation, ripening, and precipitation. These steps are not necessarily performed in the above-mentioned order. For example, grain formation and chemical sensitization are simultaneously performed, or chemical sensitization is repeatedly performed.
  • “To add a palladium compound after a grain formation step and before a desalting step” means that the palladium compound is added during a time interval from the time at which the addition of the silver salt solution is completed in the grain formation step to the time at which the desalting step is started.
  • the palladium compound can be added simultaneously with completion of the addition of the silver salt solution or added at an arbitrary time after completion of the addition of the silver salt solution and before the desalting step.
  • the total amount of the palladium compound can be added at once, can be divided and added several times, or can be continuously added over a predetermined time.
  • the emulsion may be ripened after the addition of the palladium compound and before the desalting step or left to stand at a high temperature for a long time period after the addition of the palladium compound and before the desalting step.
  • the palladium compound is added in an amount of 5 x 10 ⁇ 5 mol to 1 x 10 ⁇ 3 mol per mol of silver halide.
  • the palladium compound is added in an amount of 1 x 10 ⁇ 4 mol to 5 x 10 ⁇ 4 mol per mol of silver halide. If the amount is less than 1 x 10 ⁇ 5 mol the effect of the present invention cannot be obtained. If the amount is more than 1 x 10 ⁇ 3 mol, other problems occurs.
  • a palladium compound means a divalent or tetravalent palladium salt.
  • the palladium compound is preferably represented by R2PdX6 or R2PdX4 wherein R represents hydrogen, an alkali metal atom, or a ammonium group and X represents halogen, e.g., chlorine, bromine, or iodine. More specifically, K2PdCl4, (NH4)2PdCl6, Na2PdCl4, or (NH4)2PdCl4 is preferable.
  • PdCl2, PdCl2 ⁇ 2H2O, Pd(NH3)4Cl2, (NH3)2PdCl2, PdI2, Pd(OH)2, Pd(SO4), Pd(NO3)2, Na2Pd(NO3)4, or (NH3)2PdCl4 can be used, a water-soluble palladium compound is preferable. Most preferably, these palladium compounds are used in combination with thiocyanate ions in a molar amount of not less than five times that of the palladium compound.
  • the conditions for adding the palladium compound are arbitrary.
  • the temperature may be 30°C to 80°C, and preferably, 40°C to 70°C.
  • the pH and the pAg may have arbitrary values.
  • the pH is preferably 4 to 10.
  • the above palladium compound is most preferably added after groin formation of the silver halide grains, which have been subjected to a reduction sensitization in the groin formation step, and before the desalting step.
  • Reduction sensitization is performed during the grain formation step of a silver halide emulsion means that a reduction sensitization is performed during nucleation, ripening, or precipitation. Reduction sensitization may be performed during nucleation or physical ripening in the initial stage of grain formation, or during precipitation. Most preferably, the reduction sensitization is performed during precipitation of the silver halide grains.
  • the method of performing the reduction sensitization during precipitation includes a method in which the reduction sensitization is performed while the 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 in which the reduction sensitization is performed while the precipitation is temporarily stopped and then the grains are further precipitated.
  • the reduction sensitization can be selected from a method in which a known reducing agent is added to the silver halide emulsion, a method called “silver ripening” in which precipitation or ripening is performed in a low-pAg atmosphere at a pAg of 1 to 7, and a method called "high-pH ripening” in which precipitation or ripening is performed in a high-pH atmosphere at a pH of 8 to 11.
  • these methods can be performed in a combination of two or more thereof.
  • a method of adding a reduction sensitizer is preferable since the level of reduction sensitization can be finely adjusted.
  • reduction sensitizers are a stannous salt, amines and polyamines, a hydrazine derivative, formamidine sulfinic acid, a silane compound, and a borane compound. In the present invention, these known compounds can be used singly or in a combination of two or more thereof.
  • Preferred reduction sensitizers are stannuous chloride, thiourea dioxide, and dimethylamineborane.
  • the addition amount of the reduction sensitizer must be properly selected since it depends on the emulsion manufacturing conditions. The addition amount is preferably 10 ⁇ 8 to 10 ⁇ 3 mol per mol of silver halide. Ascorbic acid or its salts can be preferably used as a reduction sensitizer.
  • this reduction sensitizer is used in an amount of 5 x 10 ⁇ 5 to x 10 ⁇ 1, preferably 5 x 10 ⁇ 4 to 1 x 10 ⁇ 2, and most preferably, 1 x 10 ⁇ 3 to 1 x 10 ⁇ 2 mol per mol of silver halide.
  • the reduction sensitizer can be dissolved in water, alcohols, glycols, ketones, esters, and amides and then added during grain formation.
  • the reduction sensitizer can be added in a reaction vessel beforehand, it is preferably added at an arbitrary time during grain formation.
  • the reduction sensitizer may be added to an agueous solution of a water-soluble silver salt or water-soluble alkali halide, and grain formation may be performed by using these solutions.
  • a method in which a solution of the reduction sensitizer is added several times or continuously added as grain formation progresses is also preferable.
  • the present inventors have studied in detail the effects of the addition timing and addition amount of a palladium compound on, e.g. the sensitivity and the fogging density of a prepared emulsion, and have found that the best results can be obtained when a predetermined amount or more of a palladium compound is added before the desalting step. Although a preferable effect can also be obtained when the palladium compound is added after the desalting step and before chemical sensitization, this effect is inferior to that obtained when the compound is added before the desalting step.
  • a preferable effect is obtained by a silver halide photographic emulsion manufactured by performing a reduction-sensitization in the grain formation step and chemical sensitization in the presence of a palladium compound in an amount of 1 x 10 ⁇ 4 mol or more per mol of silver halide.
  • the reduction sensitization can be performed during nucleation or physical ripening in the initial stages of grain formation, and precipitation. Most preferably, the reduction sensitization is performed during precipitation of the silver halide grains.
  • the terms "during precipitation” and "reduction sensitization” are defined as described above.
  • the silver halide emulsion subjected to the reduction-sensitization is desalted and then chemically sensitized in the presence of a palladium compound in an amount of 1 x 10 ⁇ 4 mol or more per mol of a silver halide. More preferably, chemical sensitization is performed in the presence of 2 x 10 ⁇ 4 mol or more of the palladium compound. In this case, the upper limit is 5 x 10 ⁇ 3 mol. More preferably, chemical sensitization is performed in the presence of 1 x 10 ⁇ 3 mol or less of the palladium compound.
  • chemical sensitization is performed by using, together with the palladium compound, thiocyanate ions in a molar amount of five times or more that of the palladium compound.
  • the expression "chemical sensitization in the presence of a palladium compound” beans that a palladium compound is added and chemical sensitization at a high temperature is performed.
  • Chemical sensitization is preferably performed at a temperature or 45°C or more, and more preferably, at 50°C or more.
  • Chemical sensitization is preferably performed for five minutes or more, and more preferably, 10 to 120 minutes.
  • a sulfur sensitization method using an active gelatin or a compound containing sulfur capable of reacting with silver e.g., thiosulfate, thioureas, mercapto compounds, and rhodanines
  • a reduction sensitization method using a reducing agent e.g., stannous salt, amines, a hydrazine derivative, formamidine sulfinic acid and a silane compound
  • a noble metal sensitization method using a noble metal compound e.g., gold complex salt and complex salts of Group VII metals of the periodic table, e.g., Pt and Ir
  • the most preferable method is a combination of sulfur sensitization and gold sensitization (this is also called “gold-plus-sulfur sensitization”) or a combination of sulfur sensitization, reduction sensitization, and gold sensitization.
  • Chemical sensitization in the presence of a palladium compound is performed within pH and pAg ranges to be described later.
  • a silver halide photographic emulsion which is desalted and then chemically sensitized in the presence of a palladium compound in an amount of 1 x 10 ⁇ 4 to 5 x 10 ⁇ 3 mol per mol of a silver halide can achieve a higher sensitivity and a lower fogging density than those of an emulsion to which no palladium compound is added.
  • the sensitivity of this emulsion tends to vary in accordance with sedimentation conditions in the desalting step.
  • the resulting sensitivity of this emulsion is lower than that of an emulsion to which is added a palladium compound before the desalting step.
  • At least one compound selected from compounds represented by formulae (I), (II), and (III) below is used in a process of manufacturing a silver halide emulsion subjected to reduction sensitization: (I) R-SO2S-M (II) R-SO2S-R1 (III) RSO2S-L m -SSO2-R2 wherein R, R1, and R2 may be the same or different and represent an aliphatic, aromatic, or heterocyclic group, M represents a cation, L represents a divalent bonding group, and m represents 0 or 1.
  • the compounds represented by formula (I), (II), or (III) may be a polymer containing a divalent group derived from a structure represented by formula (I), (II), or (III) as a repeating unit. If possible, R, R1, R2, and L may be bonded to form a ring.
  • R, R1, and R2 are aliphatic groups, it is a saturated or unsaturated, straight-chain, branched, or cyclic aliphatic hydrocarbon group, and preferably, alkyl having 1 to 22 carbon atoms or alkenyl or alkynyl having 2 to 22 carbon atoms. These groups may 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.
  • alkynyl group examples are propargyl and butynyl.
  • An aromatic group of R, R1, and R2 is preferably a monocyclic or condensation ring aromatic group and preferably has 6 to 20 carbon atoms.
  • aromatic groups are phenyl and naphthyl. These groups can have a substituent group.
  • a heterocyclic group of R, R1, and R2 is a 3-to 15-membered ring having at least one element of nitrogen, oxygen, sulfur, selenium, and tellurium, and at least one carbon atom.
  • the heterocyclic group are pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tellurazole, triazole, benzotriazole, tetrazole, oxadiazole, and thiadiazole.
  • R, R1, and R2 are alkyl (e.g., methyl, ethyl, and hexyl), alkoxy (e.g., methoxy, ethoxy, and octyloxy), aryl (e.g., phenyl, naphtyl, and tolyl), hydroxy, halogen (e.g., fluorine, chlorine, bromine, and iodine), aryloxy (phenoxy), alkylthio (methylthio and butylthio), arylthio (phenylthio), acyl (acetyl, propionyl, butyryl, and valeryl), sulfonyl (methyl sulfonyl and phenylsulfonyl), acylamino (e.g., acetylamino and benzoylamino), sulfonylamino (e.g., methanesulfon
  • Examples of the divalent bonding group represented by L are an atom or atom group including at least one member selected from the group consisting of C, N, S, and O. More specifically, L is one or a combination of two or more of alkylene, alkenylene, alkinylene, arylene, -O-, -S-, -NH-, -CO-, and -SO2-.
  • L is preferably a divalent aliphatic group or a divalent aromatic group.
  • divalent aromatic group of L are phenylene and napthylene.
  • These substituent groups may further have the above-mentioned substituent groups.
  • 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 guanidyl group.
  • the compound represented by formula (I), (II), or (III) is a polymer
  • examples of its repeating unit are as follows. These polymers may be a homopolymer or a copolymer with another copolymerizable monomer.
  • the compound represented by formula (I), (II), or (III) is preferably added in an amount of 1 x 10 ⁇ 7 to 1 x 10 ⁇ 1 mol per mol of silver halide.
  • the addition amount is more preferably 1 x 10 ⁇ 6 to 1 x 10 ⁇ 2 mol/molAg and most preferably 1 x 10 ⁇ 5 to 1 x 10 ⁇ 3 mol/molAg.
  • a conventional method of adding an additive in a photographic emulsion can be adopted to add the compounds represented by formulas (I) to (III) in a process of manufacturing silver halide emulsions.
  • 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 the photographic properties, and then added as a solution.
  • the compound represented by formula (I), (II), or (III) can be added at any time in a manufacturing process, e.g., during grain formation of the silver halide emulsion or before or after chemical sensitization.
  • the compound is preferably added before or during reduction sensitization.
  • Reduction sensitization is preferably performed in the presence of the thiosulfonic acid compound during the silver halide grain formation step.
  • the compound can be added in a reaction vessel beforehand, it is preferably added at an arbitrary time during grain formation.
  • the 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 the 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 silver halide of any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride can be used in a photographic emulsion layer of the photographic light-sensitive material used in the present invention.
  • the preferable silver halide is silver iodobromide, or silver chlorobromide containing 30 mol% or less of silver iodide, or silver bromide, or silver bromochloride.
  • the silver halide grains to be used in the present invention can be selected from regular crystals not including a twined crystal face and grains having twined crystals described in Japan Photographic Society ed., "Silver Salt Photographs, Basis of Photographic Industries", (Corona Co., P. 163) such as single twined crystals including one twined crystal face, parallel multiple twined crystals including two or more parallel twined crystal faces, and non-parallel multiple twined crystals including two or more non-parallel twined crystal faces in accordance with its application.
  • Grains including two or more types of faces e.g., tetradecahedral grains having both (100) and (111) faces, grains having both (100) and (110) faces, and grains having both (111) and (110) faces can be selectively used in accordance with the application.
  • the grains of the silver halide may be fine grains having a grain size of 0.1 ⁇ m or less or large grains having a projected surface area diameter of 10 ⁇ m.
  • the emulsion may 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, can be used in the present invention.
  • 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 jet 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 generated by the silver halide is 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.
  • Tabular grains having an aspect ratio of 3 or more can also be used in the present invention.
  • Tabular grains 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 spectrally sensitizing efficiency of a sensitizing dye can be advantageously improved as described in detail in U.S. Patent 4,434,226.
  • Tabular grains are preferably used in the method of the present invention.
  • tabular grains in which grains having aspect ratios of 3 to 8 occupy 50% or more of the total projected surface area are preferable.
  • the crystal structure may be uniform, may have different halogen compositions inside and outside the crystal, or may be a 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 may be bonded by an epitaxial junction, or a compound other than silver halide such as silver rhodanate or zinc oxide may be bonded.
  • the silver halide emulsion prepared in the present invention preferably has a distribution or structure of a halogen composition in its grain.
  • a typical example is a core-shell type or double structured grains having different halogen compositions in the interior and surface layer of the grains 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 the core portion is sometimes identical to or sometimes different from that of the entire grains with a shell. More specifically, while the core portion is cubic, the grains with a shell are sometimes cubic or sometimes octahedral.
  • the core portion is octahedral
  • the grains with a shell are sometimes cubic or sometimes octahedral.
  • the core portion is comprised of clear regular grains
  • the grains of the shell are sometimes slightly deformed or sometimes do not have any definite shape.
  • a simple double structure but a triple structure as disclosed in JP-A-60-222844 or a multilayered structure of more layers can be formed, or a thin film of silver halide having a different composition can be formed on the surface of the core-shell double structure grains.
  • junction structure In order to give a structure inside the grains, grains having not only the above surrounding structure but a so-called junction structure can be made. Examples of such grains are disclosed in, e.g., JP-A-59-133540, JP-A-58-108526, EP 199290A2, JP-B-58-24772, and JP-A-59-16254. Crystals to be bonded having a composition different from that of the host crystals can be produced and bonded to an edge, corner, or face portion of the host crystals. Such junction crystals can be formed regardless of whether the host crystals have 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 may be high at the core portion and low at the shell portion or vice versa.
  • the silver iodide content may be high in the host crystals and relatively low in the junction crystals or vice versa.
  • the boundary portion between different halogen compositions may be clear or unclear due to a crystal mixture formed by a composition difference.
  • a continuous structure change may be positively made.
  • the silver halide emulsion for use in the present invention can be subjected to a treatment for rounding the grains as disclosed in, e.g., EP-0096727B1 and EP-0064412B1 or a treatment of modifying the surface of the grains 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 the application.
  • a silver halide solvent can be effectively used to promote ripening.
  • an excessive amount of halogen ions is 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.
  • the 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 in separate steps together with a halide and a silver salt.
  • ripening agent other than halide ions examples include ammonium, an amine compound and a thiocyanate such as an alkali metal thiocyanate, especially sodium or potassium thiocyanate and ammonium thiocyanate.
  • multivalent anions such as sodium sulfate, an anionic surfactant, an anionic polymer (e.g., polystyrene sulfonic acid, or a gelatin derivative (e.g., aliphatic acylated gelatin, aromatic acylated gelatin, or aromatic carbamoylated gelatin)
  • an anionic polymer e.g., polystyrene sulfonic acid, or a gelatin derivative (e.g., aliphatic acylated gelatin,
  • An emulsion manufactured according to the method of the present invention is subjected to chemical sensitization after it is desalted.
  • Chemical sensitization is preferably performed at 45°C or more, and more preferably, at 50°C or more.
  • Chemical sensitization is preferably performed for five minutes or more, and more preferably for ten minutes or more.
  • a sulfur sensitization method using active gelatin or a compound containing sulfur which can react with silver e.g., thiosulfate, thioureas, mercapto compounds, and rhodanines
  • a selenium sensitization method e.g., a reduction sensitization method using a reducing substance (e.g., a primary tin salt, amines, a hydrazine derivative, formamidine-sulfinic acid, and a silane compound)
  • a noble metal sensitization method using a noble metal compound in addition to a gold complex salt, a complex salt of Pt or Ir
  • the sulfur sensitization method, the selenium sensitization method, or the sensitization method using a gold complex salt is preferably used singly or in a combination of two or more thereof to perform chemical sensitization.
  • the most preferable chemical sensitization is a combination of sulfur sensitization and gold sensitization (also called as gold-plus-sulfur sensitization).
  • Chemical sensitization is performed at a pH of 4 or more, preferably, 5 or more, and most preferably 6 or 6.5 or more.
  • the upper limit of the pH is 9 or less, and preferably, 8.5 or less.
  • Chemical sensitization is normally performed at a pAg of 6 to 10, and preferably, 7 to 9.
  • the photographic emulsion for use in the present invention can contain various compounds in order to prevent fogging during the 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, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, and mercaptotetrazoles (especially, 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriadines; a thioketo compound such as oxadrinthione; azaindenes, e.g., triazaindenes,
  • the photographic emulsion for use in the present invention can be spectrally sensitized with, e.g., methine dyes.
  • the dyes are a cyanine dye, merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye, and hemioxonol dye.
  • the most effective dyes are a cyanine dye, a merocyanine dye, and a complex merocyanine dye. In these dyes, any nucleus normally used as a basic heterocyclic nucleus in cyanine dyes can be used.
  • nucleus examples include a 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 indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole 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 may contain, in addition to the sensitizing dye, a dye not having a spectral sensitizing effect or a substance substantially not absorbing visible light and having supersensitization.
  • the dye can be added in the emulsion at any time 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 time during silver halide grain formation.
  • the addition amount may be 4 x 10 ⁇ 6 to 1 x 10 ⁇ 2 mol per mol of silver halide. More preferably, when the silver halide grain size is 0.2 to 1.2 ⁇ m, an addition amount of about 5 x 10 ⁇ 5 to 6 x 10 ⁇ 3 mol is more effective.
  • Additives are described in Research Disclosures, Item 17643 (Dec. 1978) and Item 18716 (Nov. 1979) and they are summarized in the following table.
  • Additives RD No.17643 RD No.18716 1. Chemical sensitizers page 23 page 648, right column 2. Sensitivity increasing agents do 3. Spectral sensitizers, super sensitizers pages 23-24 page 648, right column to page 649, right column 4. Brighteners page 24 5. Antifoggants and stabilizers pages 24-25 pages 24-25 page 649, right column 6. Light absorbent, filter dye, ultraviolet absorbents pages 25-26 page 649, right column to page 650, left column 7. Stain preventing agents page 25, right column page 650, left to right columns 8. Dye image stabilizer page 25 9. Hardening agents column page 26 page 651, left 10. Binder page 26 do 11. Plasticizers, lubricants page 27 page 650, right column 12. Coating aids, surface active agents pages 26-27 do 13. Antistatic agents page 27 do
  • various color couplers can be used in the light-sensitive material. Specific examples of these couplers are described in above-described Research Disclosure, No. 17643, VII-C to VII-G as patent references.
  • a yellow coupler Preferred examples of a yellow coupler are described in, e.g., U.S. Patents 3,933,501, 4,022,620, 4,326,024, and 4,401,752, JP-B-58-10739, and British Patents 1,425,020 and 1,476,760.
  • magenta couplers are 5-pyrazolone and pyrazoloazole compounds, and more preferably, compounds described in, e.g., U.S. Patents 4,310,619 and 4,351,897, EP 73,636, U.S. Patents 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-34659, and U.S. Patents 4,500,630 and 4,540,654.
  • Examples of a cyan coupler are phenol and naphthol couplers, and preferably, those described in, e.g., U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011, and 4,327,173, West German Patent Application (OLS) No. 3,329,729, EP 121,365A, U.S. Patents 3,446,622, 4,333,999, 4,451,559, and 4,427,767, and EP 161,626A.
  • OLS West German Patent Application
  • a colored coupler for correcting additional, undesirable absorption of a colored dye are those described in Research Disclosure No. 17643, VII-G, U.S. Patent 4,163,670, JP-B-57-39413, U.S. Patents 4,004,929 and 4,138,258, and British Patent 1,146,368.
  • a coupler capable of forming colored dyes having proper diffusibility are those described in U.S. Patent 4,366,237, British Patent 2,125,570, EP 96,570, and West German Patent Application (OLS) No. 3,234,533.
  • Couplers releasing a photographically useful residue upon coupling are preferably used in the present invention.
  • DIR couplers i.e., couplers releasing a development inhibitor are described in the patents cited in the above-described Research Disclosure No. 17643, VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, and U.S. Patent 4,248,962.
  • a coupler imagewise releasing a nucleating agent or a development accelerator upon development are those described in British Patent 2,097,140, 2,131,188, and JP-A-59-157638 and JP-A-59-170840.
  • Examples of a coupler which can be used in the light-sensitive material prepared according to the present invention are competing couplers described in, e.g., U.S. Patent 4,130,427; poly-equivalent couplers described in, e.g., U.S. Patents 4,283,472, 4,338,393, and 4,310,618; DIR redox compound or DIR coupler releasing couplers described in, e.g., JP-A-60-185950 and JP-A-62-24252; couplers releasing a dye which turns to a colored form after being released described in EP 173,302A; bleaching accelerator releasing couplers described in, e.g., RD. Nos. 11449 and 24241 and JP-A-61-201247; and a ligand releasing coupler described in, e.g., U.S. Patent 4,553,477.
  • the couplers for use in this invention can be introduced in the light-sensitive materials by various known dispersion methods.
  • a high-boiling organic solvent to be used in the oil-in-water dispersion method and having a boiling point of 175°C or more at normal pressure examples include phthalic esters (e.g., dibutylphthalate, dicyclohexylphthalate, di-2-ethylhexylphthalate, decylphthalate, bis(2,4-di-t-amylphenyl)phthalate, bis(2,4-di-t-amylphenyl)isophthalate, and bis(1,1-diethylpropyl)phthalate), phosphates or phosphonates (e.g., triphelphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, tri-2-ethylhexylphosphate, tridodecylphosphate, tributyoxyethylphosphate, trichloropropylphosphate, and
  • An organic solvent having a boiling point of about 30°C or more, and preferably, 50°C to about 160°C can be used as a co-solvent.
  • Typical examples of the co-solvent are ethyl acetate, butyl acetate, ethyl propionate, methylethylketone, cyclohexanone, 2-ethoxyethylacetate, and dimethylformamide.
  • Steps and effects of a latex dispersion method and examples of a loadable latex are described in, e.g., U.S. Patent 4,199,363 and West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.
  • a silver halide color light-sensitive material which comprises at least one blue-sensitive silver halide emulsion layer containing a yellow coupler, at least one green-sensitive silver halide emulsion layer containing a magenta coupler, and at least one red-sensitive silver halide emulsion layer containing a cyan coupler on a support
  • at least one of the emulsion layers contains a silver halide photographic emulsion manufactured by performing addition of palladium compound in amount of 5 x 10 ⁇ 5 mol to 1 x 10 ⁇ 3 mol per mol of silver halide after a grain formation step and before a desalting step.
  • 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 present invention When the present invention is used to prepare a material for color photographing, the present invention can be applied to light-sensitive materials having various structures and to light-sensitive materials having combinations of layer structures and special color materials.
  • Typical examples are light-sensitive materials in which a coupling speed of a color coupler or diffusibility is combined with a layer structure, as disclosed in, e.g., JP-B-47-49031, JP-B-49-3843, JP-B-50-21248, JP-A-59-38147, JP-A-59-60437, JP-A-60-227256, JP-A-61-4043, JP-A-61-43743, and JP-A-61-42657; light-sensitive materials in which a single color-sensitive layer is divided into two or more layers, as disclosed in JP-B-49-15495 and U.S.
  • Patent 3,843,469 and light-sensitive materials, in which an arrangement of high- and low-sensitivity layers or layers having different color sensitivities is defined, as disclosed in JP-B-53-37017, JP-B-53-37018, JP-A-51-49027, JP-A-52-143016, JP-A-53-97424, JP-A-53-97831, JP-A-62-200350, and JP-A-59-177551.
  • the color photographic light-sensitive materials prepared by this invention can be processed by 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.
  • a color developer used in developing of the light-sensitive material is preferably an aqueous alkaline solution containing an aromatic primary amine-based color developing agent as a main component.
  • an aromatic primary amine-based color developing agent as a main component.
  • an aminophenol-based compound is effective, a p-phenylenediamine-based compound is preferably used.
  • Typical examples of the p-phenylenediamine-based compound are 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyehtylaniline, and sulfates, hydrochlorides and p-toluenesulfonates thereof. These compounds can be used in a combination of two or more thereof in accordance with the applications.
  • the color developer contains a pH buffering agent such as a carbonate, a borate or a phosphate of an alkali metal, and a development restrainer or antifoggant such as a bromide, an iodide, a benzimidazole, a benzothiazole or a mercapto compound.
  • a pH buffering agent such as a carbonate, a borate or a phosphate of an alkali metal
  • a development restrainer or antifoggant such as a bromide, an iodide, a benzimidazole, a benzothiazole or a mercapto compound.
  • the color developer may also contain a preservative such as hydroxylamine, diethylhydroxylamine, a hydrazine sulfite, a phenylsemicarbazide, triethanolamine, a catechol sulfonic acid or a triethylenediamine(1,4-diazabicyclo[2,2,2]octane); an organic solvent such as ethyleneglycol or diethyleneglycol; a development accelerator such as benzylalcohol, polyethyleneglycol, a quaternary ammonium salt or an amine; a dye forming coupler; a competing coupler; a fogging agent such as sodium boron hydride; an auxiliary developing agent such as 1-phenyl-3-pyrazolidone; a viscosity imparting agent; and a chelating agent such as an aminopolycarboxylic acid, an aminopolyphosphonic acid, an alkylphosphonic acid or a phosphonocarboxylic acid.
  • chelating agent examples include ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid and ethylenediamine-di(o-hydroxyphenylacetic acid), and salts thereof.
  • black-and-white development is performed and then color development is performed.
  • black-and-white developer well-known black-and-white developing agents, e.g., a dihydroxybenzene such as hydroquinone, a 3-pyrazolidone such as 1-phenyl-3-pyrazolidone, and an aminophenol such as N-methyl-p-aminophenol can be used singly or in a combination of two or more thereof.
  • the pH of the color and black-and-white developers is generally 9 to 12.
  • the replenishment amount of the developer depends on the color photographic light-sensitive material to be processed, it is generally 3 liters or less per m2 of the light-sensitive material.
  • the replenishment amount can be decreased to be 500 ml less by decreasing the bromide ion concentration in the replenishing solution.
  • the contact area of the processing tank with air is preferably decreased to prevent evaporation and oxidation of the solution upon contact with air.
  • the replenishment amount can be decreased by using a means capable of suppressing an accumulation amount of bromide ions in the developer.
  • the color development time is normally set between 2 to 5 minutes.
  • the processing time can be shortened by setting a high temperature and a high pH and using the color developing agent at a high concentration.
  • the photographic emulsion layer is generally subjected to bleaching after color development.
  • the bleaching may be performed either simultaneously with fixing (bleach-fixing) or independently thereof.
  • bleach-fixing may be performed after bleaching.
  • processing may be performed in a bleach-fixing bath having two continuous tanks, fixing may be performed before bleach-fixing, or bleaching may be performed after bleach-fixing, in accordance with applications.
  • the bleaching agent are a compound of a multivalent metal such as iron (III), cobalt (III), chromium (VI) and copper (II); a peroxide; a quinone; and a nitro compound.
  • Typical examples of the bleaching agent are a ferricyanide; a dichromate; an organic complex salt of iron (III) or cobalt (III), e.g., a complex salt of an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, and 1,3-diaminopropanetetraacetic acid, and glycoletherdiaminetetraacetic acid, or a complex salt of citric acid, tartaric acid or malic acid; a persulfate; a bromate; a permanganate; and a nitrobenzene.
  • an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, and 1,3-dia
  • an iron (III) complex salt of aminopolycarboxylic acid such as an iron (III) complex salt of ethylenediaminetetraacetic acid, and a persulfate are preferred because they can increase the processing speed and prevent an environmental contamination.
  • the iron (III) complex salt of aminopolycarboxylic acid is effective in both the bleaching and bleach-fixing solutions.
  • the pH of the bleaching or bleach-fixing solution using the iron (III) complex salt of aminopolycarboxylic acid is normally 5.5 to 8. In order to increase the processing speed, however, processing can be performed at a lower pH.
  • a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath, if necessary.
  • Effective examples of the bleaching accelerator are compounds having a mercapto group or a disulfide group described in, e.g., U.S. Patent 3,893,858, West German Patents 1,290,812 and 2,059,988, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-28426, and Research Disclosure No.
  • 17129 July, 1978; a thiazolidine derivative described in JP-A-50-140129; thiourea derivatives described in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735, and U.S.
  • the compound having a mercapto group or disulfide group is preferable because it has a significant accelerating effect.
  • the most preferable compounds are those described in U.S.
  • Patent 3,893,858 West German Patent 1,290,812, and JP-A-53-95630.
  • a compound described in U.S. Patent 4,552,834 is also preferable.
  • These bleaching accelerators may be added in the light-sensitive material. These bleaching accelerators are effective especially in bleach-fixing of a photographic color light-sensitive material.
  • the fixing agent examples include a thiosulfate, a thiocyanate, a thioether-based compound, a thiourea and a large amount of an iodide.
  • a thiosulfate especially an ammonium thiosulfate, can be used in a wide range of applications.
  • a sulfite, a bisulfite or a carbonyl bisulfite adduct is preferred.
  • the photographic light-sensitive material prepared by the present invention is normally subjected to washing and/or stabilizing steps after desilvering.
  • the amount of water used in the washing step can be arbitrarily determined over a broad range in accordance with the properties (e.g., a property determined by an used material such as coupler) of the light-sensitive material, the application of the material, the temperature of the water, the number of water tanks (the number of stages), the replenishing scheme representing a counter or forward current, and other conditions.
  • the relationship between the amount of water and the number of water tanks in a multi-stage counter-current scheme can be obtained by a method described in "Journal of the Society of Motion Picture and Television Engineers", Vol. 64, PP. 248 - 253 (May, 1955).
  • the amount of water used for washing can be greatly decreased. Since washing water stays in the tanks for a long period of time, however, bacteria multiply and floating substances may be undesirably attached to the light-sensitive material.
  • a method of decreasing calcium and magnesium ions can be effectively utilized, as described in JP-A-61-131632.
  • a germicide such as an isothiazolone compound and cyabendazole described in JP-A-57-8542, a chlorine-based germicide such as chlorinated sodium isocyanurate, and germicides such as benzotriazole described in Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents", Eiseigijutsu-Kai ed., “Sterilization, Antibacterial, and Antifungal Techniques for Microorganisms", and Nippon Bokin Bokabi Gakkai ed., “Cyclopedia of Antibacterial and Antifungal Agents".
  • the pH of the water for washing the photographic light-sensitive material is 4 to 9, and preferably, 5 to 8.
  • the water temperature and the washing time can vary in accordance with the properties and applications of the light-sensitive material. Normally, the washing time is 20 seconds to 10 minutes at a temperature of 15°C to 45°C, and preferably, 30 seconds to 5 minutes at 25°C to 40°C.
  • the light-sensitive material can be processed directly by a stabilizing solution in place of washing. All known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can be used in such stabilizing processing.
  • Stabilizing is sometimes performed, further, subsequently to said washing.
  • An example is a stabilizing bath containing formalin and a surface-active agent to be used as a final bath of the photographic color light-sensitive material.
  • Various chelating agents or antifungal agents can also be added in the stabilizing bath.
  • An overflow solution produced upon washing and/or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.
  • the silver halide color light-sensitive material prepared by the present invention may contain a color developing agent in order to simplify processing and increase the processing speed.
  • a color developing agent for this purpose, various precursors of a color developing agent are preferably used.
  • the precursor are an indoaniline-based compound described in U.S. Patent 3,342,597, Schiff base type compounds described in U.S. Patent 3,342,599, and Research Disclosure Nos. 14,850 and 15,159, an aldol compound described in RD No. 13,924, a metal salt complex described in U.S. Patent 3,719,492, and a urethane-based compound described in JP-A-53-135628.
  • the silver halide color light-sensitive material may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary.
  • Typical examples of the compound are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.
  • Each processing solution in the present invention is used at a temperature of 10°C to 50°C. Although the normal processing temperature is 33°C to 38°C, processing may be accelerated at a high temperature to shorten the processing time, or image quality or stability of a processing solution may be improved at a lower temperature. In order to save silver for the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or U.S. Patent 3,674,499 may be performed.
  • the silver halide light-sensitive material prepared according to the present invention can also be applied to thermal development light-sensitive materials described in, e.g., U.S. Patent 4,500,626, JP-A-60-133449, JP-A-59-218443, JP-A-61-238056, and EP 210.660A2.
  • 1,000 ml of an aqueous solution containing 40 g of gelatin and 0.2 g of KBr were strongly stirred at 75°C.
  • 208 ml of an aqueous silver nitrate solution (containing 1.46 g of AgNO3) and 208 ml of an aqueous KBr solution (containing 1.1 g of KBr) were simultaneously added to the resultant solution over 17 minutes.
  • the silver potential of the resultant solution was adjusted to -25 mV with respect to a saturated calomel electrode, and 0.6 mg of thiourea dioxide were added in the form of an aqueous solution.
  • the flow rates of the aqueous silver nitrate solution were adjusted to 1 ml/min and 19 ml/min at the initial and final stages, respectively, maintaining the silver potential of the reaction solution at -25 mV.
  • the resultant solution was ripened for 10 minutes and then desalted by a flocculation method. 43 g of gelatin were added, the pH was adjusted to 6.9 and pAg was adjusted to 8.0 at 40°C, thereby obtaining a yield of 700 g.
  • Em-A 3.0 x 10 ⁇ 3 mol/molAg of potassium thiocyanate, 3.0 x 10 ⁇ 5 mol/molAg of sodium thiosulfate, and 1.2 x 10 ⁇ 6 mol/molAg of potassium chloroaurate were added and the mixture was stirred at 60°C for 40 minutes to perform chemical sensitization, thereby preparing Em-A.
  • the prepared emulsion consisted of monodisperse octahedral grains having an average circle-equivalent diameter of 0.60 ⁇ m and a variation coefficient of a circle-equivalent diameter of 9%.
  • Em-B was prepared following the same procedures as for Em-A except that 4 x 10 ⁇ 4 mol/molAg of (NH4)2PdCl4 and 2 x 10 ⁇ 3 mol/molAg of potassium thiocyanate were added over three minutes from 20 minutes after addition of the aqueous silver nitrate solution at the second stage was started to 10 minutes before it was finished.
  • Em-C was prepared following the same procedures as for Em-A except that 4 x 10 ⁇ 4 mol/molAg of (NH4)2PdCl4 and 2 x 10 ⁇ 3 mol/molAg of pottasium thiocyanate were added 10 minutes before a chemical sensitizer was added in chemical sensitization.
  • Em-A was dissolved at 40°C, and 4 x 10 ⁇ 4 mol/molAg of (NH4)2PdCl4 and 2 x 10 ⁇ 3 mol/molAg of potassium thiocyanate were added to the solution. The resultant mixture was stirred for 30 minutes to prepare Em-D.
  • Em-E was prepared following the same procedures as for Em-A except that 4 x 10 ⁇ 4 mol/molAg of (NH4)2PdCl4 and 2 x 10 ⁇ 3 mol/molAg of potassium thiocyanate were added two minutes after addition of the aqueous silver nitrate solution at the second stage was finished and stirred for eight minutes, and then the solution mixture was desalted by a flocculation method.
  • Em-F was prepared following the same procedures as for Em-A except that 4 x 10 ⁇ 4 mol/molAg of (NH4)2Cl4 and 2 x 10 ⁇ 3 mol/molAg of potassium thiocyanate were added immediately before desalting was performed by the flocculation method.
  • Emulsion layer of Em-A to Em-F and protective layer were coated in amounts as listed in Table 1 on triacetylcellulose film supports having undercoating layers, thereby preparing samples.
  • Densities of the developed samples were measured using a green filter.
  • Color Developing Solution (g) Diethylenetriaminepentaacetic Acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic Acid 3.0 Sodium Sulfite 4.0 Potassium Carbonate 30.0 Potassium Bromide 1.4 Potassium Iodide 1.5 mg Hydroxylamine Sulfate 2.4 4-(N-Ethyl-N- ⁇ -hydroxyethylamino)-2-methylaniline Sulfate 4.5 Water to make 1.0 l pH 10.05
  • 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 anion exchange resin (Amberlite IR-400) to set the concentrations of calcium and magnesium to be 3 mg/l or less. Subsequently, 20 mg/l of sodium dichloroisocyanurate and 1.5 g/l of sodium sulfate were added. The pH of the solution fell within the range of 6.5 to 7.5.
  • the sensitivity is represented by the relative value of the reciprocal of the exposure amount in units of lux/sec at a fogging density of 0.2.
  • Em-C1, Em-C2, Em-E4, and Em-E5 were prepared following the same procedures as for Em-C and Em-E, respectively, except that the time required for flocculation was changed. These emulsions were coated, exposed, and developed following the same procedures as described above, thereby obtaining the results shown in Table 4.
  • Table 4 Comparison of Sensitivity/Fogging Density of Em-C to Em-E Emulsion No. Time Required for Flocculation Relative Sensitivity Fogging Density Em-C1 Short 132 0.38 Em-C2 Long 118 0.33 Em-E4 Short 135 0.18 Em-E5 Long 135 0.18
  • aqueous solution containing gelatin and KBr was maintained at 40°C, and an aqueous silver nitrate solution (containing 32.7 g of AgNO3) and a halogen solution (containing 24.9 g of KBr and 1.3 g of KI) were added to the solution over four minutes under constant stirring. After an aqueous solution containing KBr and gelatin was added, the resultant mixture was heated up to 70°C, and an aqueous solution containing 6 mg of dimethylamineborane and an aqueous solution containing 100 mg of compound 1-2 listed in Table A were simultaneously added.
  • an aqueous silver nitrate solution (containing 152.3 g of AgNO3) and an aqueous halogen solution (containing 5.3 wt% of KI with respect to KBr) were added over 32.1 minutes.
  • the silver potential of the reaction solution was maintained at 0 mV with respect to a saturated calomel electrode.
  • an aqueous silver nitrate solution (containing 7.2 g AgNO3) and an aqueous NaCl solution (containing 6.7 g of NaCl) were added over 1.5 minutes.
  • the resultant mixture was desalted by a flocculation method five minutes after the addition was finished.
  • Gelatin was added and the pH was adjusted to 6.9 and the pAg was adjusted to 8.0 at 40°C.
  • This emulsion consisted of tabular grains having an average thickness of 0.13 ⁇ m, an average circle-equivalent diameter of 0.68 ⁇ m, a variation coefficient of a circle-equivalent diameter of 28%, and an aspect ratio of 5.2.
  • Em-H was prepared following the same procedures as for Em-G except that 1 x 10 ⁇ 5 mol/molAg of (NH4)2PdCl4 and 5 x 10 ⁇ 5 mol/molAg of potassium thiocyanate were added 30 seconds after addition of silver nitrate was finished, and the resultant mixture was stirred for five minutes and desalted by the flocculation method.
  • Em-I was prepared following the same procedures as for Em-G except that 5 x 10 ⁇ 5 mol/molAg of (NH4)2PdCl4 and 2.5 x 10 ⁇ 4 mol/molAg of potassium thiocyanate were added 30 seconds after addition of silver nitrate was finished, and the resultant mixture was stirred for five minutes and desalted by the flocculation method.
  • Em-J was prepared following the same procedures as for Em-G except that 1 x 10 ⁇ 4 mol/molAg of (NH4)2PdCl4 and 5 x 10 ⁇ 4 mol/molAg of potassium thiocyanate were added 30 seconds after addition of silver nitrate was finished, and the resultant mixture was stirred for five minutes and desalted by the flocculation method.
  • Em-K was prepared following the same procedures as for Em-G except that 4 x 10 ⁇ 4 mol/molAg of (NH4)2PdCl and 2 x 10 ⁇ 3 mol/molAg of potassium thiocyanate were added 30 seconds after addition of silver nitrate was finished, and the resultant mixture was stirred for five minutes and desalted by the flocculation method.
  • Em-L was prepared following the same procedures as for Em-I except that 5 x 10 ⁇ 4 mol/molAg of (NH4)2PdCl4 and 2.5 x 10 ⁇ 3 mol/molAg of potassium thiocyanate were added ten minutes before the chemical sensitizer was added in chemical sensitization.
  • a coating aid and a hardener were added to Em-G to Em-L and the resultants were coated on cellulose film bases in a Ag coating amount of 2 g/m2.
  • the exposed coated emulsion was developed at 20°C for ten minutes by using the following surface developer (MAA-1).
  • the sensitivity of an obtained emulsion is represented by the relative value of the reciprocal of the exposure amount required to obtain an optical density of a fogging density plus 0.1.
  • Layers having the following compositions were formed on an undercoated triacetylcellulose film support, thereby preparing a sample as a multilayered color light-sensitive material.
  • the coating amount of a silver halide and colloid silver are represented in units of g/m2 of silver, that of couplers, additives, and gelatin is represented in units of g/m2, and that of a sensitizing dye is represented by the number of mols per mol of 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 for emulsion Cpd-3 (0.07 g/m2) and a surfactant Cpd-4 (0.03 g/m2) were added as coating aids to each layer.
  • Samples in which Em-G, Em-H, Em-I, Em-J, Em-K, and Em-L prepared in Example 2 were used in the layer 12, are designated samples 301, 302, 303, 304, 305, and 306, respectively.
  • compositions of the process solutions will be presented below.
  • 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 strongly basic anion exchange resin (Amberlite IR-400) to set calcium and magnesium ion concentrations to be 3 mg/l or less. Subsequently 20 mg/l of sodium dichloroisocyanurate and 1.5 g/l 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 strongly basic anion exchange resin
  • the sensitivity is represented by the relative value of the reciprocal of the exposure amount for giving a density higher than a fogging density by 1.0 with respect to a characteristic curve of a yellow image.
  • a stable method of manufacturing a silver halide photographic emulsion can be achieved.
  • a stabilized method of manufacturing a silver halide photographic emulsion subjected to a reduction sensitization in the grain formation step can be achieved.

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Claims (13)

  1. Procédé de fabrication d'une émulsion photographique d'halogénure d'argent, dans lequel on ajoute un composé de palladium en quantité de 5.10⁻⁵ à 1.10⁻³ mole par mole d'halogénure d'argent après l'étape de formation des grains et avant l'étape d'élimination des sels.
  2. Procédé selon la revendication 1, caractérisé en ce que les grains d'halogénure d'argent sont soumis à une sensibilisation par réduction dans l'étape de formation des grains.
  3. Procédé selon la revendication 1, caractérisé en ce que ledit composé de palladium est ajouté en quantité de 1.10⁻⁴ à 5.10⁻⁴ mole par mole d'halogénure d'argent.
  4. Procédé selon la revendication 1, caractérisé en ce que ledit composé de palladium est représenté par la formule R₂PdX₆ ou R₂PdX₄, dans laquelle R représente un atome d'hydrogène, un atome de métal alcalin ou un groupe ammonium et X représente un atome d'halogène.
  5. Procédé selon la revendication 4, caractérisé en ce que ledit composé de palladium est utilisé en combinaison avec des ions thiocyanates en quantité molaire de pas moins de cinq fois celle dudit composé de palladium.
  6. Procédé selon la revendication 1, caractérisé en ce que l'on utilise dans le procédé de fabrication d'une émulsion d'halogénure d'argent sensibilisée par réduction au moins un composé choisi parmi les composés représentés par les formules (I), (II) et (III) :



            (I)   R-SO₂S-M





            (II)   R-SO₂S-R¹





            (III)   RSO₂S-Lm-SSO₂-R²



    dans lesquelles R, R¹ et R² peuvent être identiques ou différents et représentent chacun un groupe aliphatique, un groupe aromatique ou un groupe hétérocyclique, M représente un cation, L représente un groupe divalent de liaison et m est égal à 0 ou 1,
    dans lequel les composés représentés par les formules (I) à (III) peuvent être des polymères contenant comme motifs récurrents des groupes divalents dérivés de structures représentées par les formules (I) à (III) et si possible R, R¹, R² et L peuvent être reliés les uns aux autres pour former un cycle.
  7. Procédé selon la revendication 6, caractérisé en ce que l'on utilise un composé représenté par la formule (I).
  8. Procédé selon la revendication 6, caractérisé en ce que l'on utilise 1.10⁻⁶ à 1.10⁻² mole des composés représentés par les formules (I), (II) ou (III) par mole d'argent.
  9. Procédé selon la revendication 1, caractérisé en ce que l'émulsion de l'halogénure d'argent comprend des grains réguliers d'halogénure d'argent.
  10. Procédé selon la revendication 1, caractérisé en ce que ladite émulsion d'halogénure d'argent est une émulsion d'halogénure d'argent monodispersée ayant une distribution granulométrique dans laquelle pas moins de 80 % de tous les grains sont dans les limites à ± 30 % de la dimension moyenne de grain, le pourcentage représentant le nombre ou le poids des grains.
  11. Procédé selon la revendication 1, caractérisé en ce que ladite émulsion d'halogénure d'argent comprend des grains tabulaires d'halogénure d'argent ayant un rapport d'aspect de pas moins de 3.
  12. Procédé selon la revendication 1, caractérisé en ce que pas moins de 50 % de la surface projetée totale de l'émulsion d'halogénure d'argent sont occupés par des grains tabulaires ayant des rapports d'aspect de 3 à 8.
  13. Procédé de fabrication d'un matériau photosensible en couleur à l'halogénure d'argent qui comprend sur un support au moins une couche d'émulsion d'halogénure d'argent sensible au bleu contenant un coupleur au jaune, au moins une couche d'émulsion d'halogénure d'argent sensible au vert contenant un coupleur au magenta et au moins une couche d'émulsion d'halogénure d'argent sensible au rouge contenant un coupleur pour cyan, dans lequel on utilise dans l'une au moins desdites couches d'émulsions une émulsion photographique d'halogénure d'argent préparée par le procédé selon l'une quelconque des revendications 1 à 12.
EP89120772A 1988-11-11 1989-11-09 Méthode de préparation d'une émulsion photographique à l'halogénure d'argent Expired - Lifetime EP0368304B1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP63283929A JPH02130545A (ja) 1988-11-11 1988-11-11 ハロゲン化銀写真乳剤およびこれを用いる写真材料
JP283929/88 1988-11-11
JP305825/88 1988-12-02
JP30582588A JPH02150837A (ja) 1988-12-02 1988-12-02 ハロゲン化銀写真乳剤
JP26565/89 1989-02-07
JP1026565A JP2514707B2 (ja) 1989-02-07 1989-02-07 ハロゲン化銀写真乳剤の製造方法

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EP0368304A1 EP0368304A1 (fr) 1990-05-16
EP0368304B1 true EP0368304B1 (fr) 1994-02-16

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JPH05197059A (ja) * 1992-01-20 1993-08-06 Konica Corp ハロゲン化銀写真感光材料
US5415992A (en) * 1993-11-30 1995-05-16 Eastman Kodak Company Heat stabilized silver chloride photographic emulsions containing phosphine compounds
US5443947A (en) * 1993-11-30 1995-08-22 Eastman Kodak Company Heat stabilized silver chloride photographic emulsions containing thiosulfonate/sulfinate compounds
US5399479A (en) * 1993-12-16 1995-03-21 Eastman Kodak Company Photographic element exhibiting improved speed and stability
US5411855A (en) * 1993-12-16 1995-05-02 Eastman Kodak Company Photographic element exhibiting improved speed and stability
EP0693707B1 (fr) * 1994-07-21 2001-06-20 Eastman Kodak Company Elément photographique à l'halogénure d'argent sensible à la lumière
DE69517372T2 (de) 1994-08-26 2001-02-15 Eastman Kodak Co., Rochester Tafelkornemulsionen mit verbesserter Sensibilisierung
US5763154A (en) * 1996-08-07 1998-06-09 Eastman Kodak Company Palladium chemical sensitizers for silver halides
EP0838720B1 (fr) * 1996-10-23 2003-04-16 Eastman Kodak Company Procédé de sensibilisation d'une émulsion photographique à l'halogénure d'argent
US5759760A (en) * 1997-06-04 1998-06-02 Eastman Kodak Company Aqueous solid particle dispersions in chemical sensitization

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BE490866A (fr) * 1948-08-31
JPS5827486B2 (ja) * 1977-06-03 1983-06-09 富士写真フイルム株式会社 ハロゲン化銀写真乳剤

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