EP0371338A1 - Lichtempfindliches photographisches Silberhalogenidmaterial - Google Patents

Lichtempfindliches photographisches Silberhalogenidmaterial Download PDF

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Publication number
EP0371338A1
EP0371338A1 EP89121214A EP89121214A EP0371338A1 EP 0371338 A1 EP0371338 A1 EP 0371338A1 EP 89121214 A EP89121214 A EP 89121214A EP 89121214 A EP89121214 A EP 89121214A EP 0371338 A1 EP0371338 A1 EP 0371338A1
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EP
European Patent Office
Prior art keywords
silver halide
sensitive material
photographic light
material according
grain
Prior art date
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.)
Granted
Application number
EP89121214A
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English (en)
French (fr)
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EP0371338B1 (de
Inventor
Yuichi Ohashi
Norihiko Sakata
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Filing date
Publication date
Priority claimed from JP63290676A external-priority patent/JPH0810318B2/ja
Priority claimed from JP1156049A external-priority patent/JP2820154B2/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0371338A1 publication Critical patent/EP0371338A1/de
Application granted granted Critical
Publication of EP0371338B1 publication Critical patent/EP0371338B1/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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium
    • 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
    • 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
    • G03C1/10—Organic substances
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—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
    • 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
    • G03C2001/03582—Octahedral grains

Definitions

  • the present invention relates to a silver halide photographic light-sensitive material and, more particularly, to a silver halide photographic light-sensitive material having high sensitivity and producing low fog and a high maximum image density.
  • the present invention also relates to a silver halide photographic light-sensitive material having a small variation over time in sensitivity and fog during its storage.
  • Basic properties required for a photographic silver halide emulsion are high sensitivity, low fog, and fine grains.
  • Patents 2,518,698, 3,201,254, 3,411,917, 3,779,777, and 3,930,867 are disclosed in, e.g., JP-B-57-33572 ("JP-B-" means examined Japanese patent publication), JP-B-58-1410, and JP-A-57-179835 ("JP-A-" means unexamined published Japanese patent application). Techniques of improving storage stability of an emulsion subjected to reduction sensitization are disclosed in JP-A-57-82831 and JP-A-60-178445.
  • 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. nuclation, ripening, and precipitation substeps. These steps are sometimes performed not in the above-mentioned order but in a reverse order or repeatedly.
  • At least one type of compounds represented by formulas [I], [II], and [III] can be added in any step from grain formation to coating processes of a monodisperse silver halide emulsion.
  • the compound is preferably added in the grain formation process of silver halide grains, and more preferably, during precipitation of the grains.
  • reduction sensitization is performed in the presence of the compound during precipitation of the monodisperse silver halide grains.
  • the reduction sensitization can be performed during any of nucleation as the initial stage of grain formation, physical ripening, and precipitation. Although the reduction sensitization is normally performed prior to chemical sensitization (preferably gold-plus-sulfur sensitization), it can be performed after the chemical sensitization if necessary.
  • the reduction sensitization is preferably performed before the chemical sensitization so as not to produce an undesired fog.
  • the reduction sensitization is most preferably performed during precipitation of silver halide grains.
  • "precipitation” means a state in which silver halide grains are being grown and precipitated by physical ripening or addition of water-soluble silver salt and water-soluble alkali halide.
  • the method of performing the reduction sensitization during the precipitation includes a method in which the reduction sensitization is performed while addition of silver salt and alkali halide is temporarily stopped during precipitation and then precipitation is further continued.
  • the reduction sensitization employed in the present invention can be selected from a method of adding a known reducing agent in 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. These methods can be used in a combination of two or more thereof.
  • a method of adding a reduction sensitizer is preferable because the level of reduction sensitization can be precisely adjusted.
  • the reduction sensitizer are stannous salt, amines and polyamines, a hydrazine derivative, formamidinesulfinic acid, a silane compound, and a borane compound.
  • the reduction sensitizer for use in the present invention can be selected from these known compounds, and the compounds can be used singly or in a combination of two or more thereof.
  • Preferable compounds of the reduction sensitizer are stannous chloride, thiourea dioxide, and dimethylamineborane.
  • An addition amount of the reduction sensitizer depends on emulsion manufacturing conditions and therefore must be selected to satisfy the conditions. A preferable addition amount falls within the range of 10- 7 to 10- 3 per mol of a silver halide.
  • the reduction sensitizer is used as a solution dissolved in water or a solvent, e.g., glycols, ketones, esters, or amides, and the solution can be added during grain formation, or before or after chemical sensitization.
  • the reduction sensitizer can be added in any step of emulsion manufacturing process, it is most preferably added during grain precipitation.
  • the reduction sensitizer is preferably added at an arbitrary timing during grain formation though it can be added in a reaction vessel beforehand.
  • the 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 the aqueous solution.
  • a method of adding a solution of the reduction sensitizer several times or continuously adding it over a long time period as grain formation progresses is also preferable.
  • R, R 1 , and R 2 each present 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', and R 2 includes aromatic group of single-ring or condensed-ring.
  • the aromatic group 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', 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.
  • Examples of the heterocyclic group are rings of pyrrolidine, piperidine, pyridine, tetrahydrofurane, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tellurazole, triazole, benzotriazole, tetrazole, oxadiazole, and thiadiazole. 3- to 6-membered ring is preferred.
  • R, R , 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 alkylthio 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., phenyl
  • 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 benzaoylmino), a sulfonylamino group (e.g., methanesul- fonylamino and benzenesulfonylamino), 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 linking group represented by L includes an atom or an atom group containing at least one of C, N, S, and O.
  • Examples of L are alkylene, alkenylene, alkynylene, arylene, -0-, -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.
  • linking groups can have further substituent group above-mentioned.
  • M is preferably a metal ion, an ammonium ion, or an organic cation.
  • the metal ion are a lithium ion, a sodium ion, and a potassium ion.
  • organic cation are an organic ammonium ion (e.g., tetramethylammonium, and tetrabutylammonium), an organic phosphonium ion (e.g. tetraphenylphosphonium), and a guanidinium ion.
  • Each of the above polymers can be a homopolymer or a copolymer with another copolymerizable monomer.
  • Thiosulfonic acid compounds represented by formulas [1], [II], and [III] can be easily synthesized by methods described or cited in JP-A-54-1019; British Patent 972,211; "Journal of Organic Chemistry", Vol. 53, PP. 396 (1988); and "Chemical Abstracts", Vol. 59, 9776e.
  • a preferable addition amount of a compound represented by formula [I], [II], or [III] is 10- 7 to 10 -1 mol per mol of a silver halide.
  • the addition amount is more preferably 10- 6 to 10- 2 and most preferably 10- 5 to 10- 3 mol per mol of a silver halide.
  • a conventional method of adding an additive in a photographic emulsion can be adopted to add thiosulfonic acid compounds represented by formulas [I] to [III] in manufacturing process.
  • a water-soluble compound can be added in the form of an aqueous solution having an arbitrary concentration.
  • a water-insoluble or hardly water-soluble 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.
  • a compound represented by formula [I], [II], or [III] can be added at any timing during manufacturing process such as 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 while water-soluble silver salt and alkali halide are added.
  • 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 as grain formation progresses is also preferable.
  • a thiosulfonic acid compound most preferable in the present invention is represented by formula [I].
  • ascorbic acid and its derivative are as follows.
  • the above ascorbic acid compounds in a process of manufacturing a silver halide emulsion of the present invention, they may be dispersed directly in an emulsion.
  • the ascorbic acid compound may be dissolved in a single solvent or solvent mixture of, e.g., water, methanol, and ethanol and then added during 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 (8 x 10- 4 mol/AgX mol) per gram of silver ions.
  • An amount of 0.1 to 10 mg (10 -7 to 10- 5 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, an emulsion preparation temperature, a pH, and a pAg.
  • the addition amount is selected within the range of, preferably, 5 x 10- 5 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.
  • the ascorbic acid compound 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 ascorbic acid compound several times or continuously adding it over a long time period as grain precipitation progresses 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, fog, and storage stability. In accordance with other conditions, however, it is sometimes more preferable to use the ascorbic acid compound with another reduction sensitization method. In this case, however, it is preferred that the other reduction sensitization method is used as merely an auxiliary means of reduction sensitization and the ascorbic acid compound is used as a main reduction sensitization.
  • the other sensitization method combined with the method using the ascorbic acid compound can be selected from a method of adding another known reduction sensitizer to a silver halide emulsion, a method called silver ripening of precipitating or ripening in a low-pAg atmosphere of a pAg of 1 to 7, and a method called high-pH ripening of precipitating or ripening in a high-pH atmosphere of a pH of 8 to 11.
  • a method of adding another reduction sensitizer is generally preferable because the level of reduction sensitization can be precisely adjusted.
  • 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 is performed by using the ascorbic acid compound in a process of manufacturing a silver halide emulsion. Also, the reduction sensitization is preferably performed in the presence of at least one compound selected from compounds represented by formulas [I], [III], and [III].
  • a monodisperse silver halide emulsion means an emulsion in which silver halide grains falling within the grain size region ranging from -20% to +20% of a maximum grain size r occupies 60% or more, preferably, 70% or more, and most preferably, 80% or more of a total silver halide grain weight.
  • the maximum grain size r is defined as a grain size r which maximizes a product value of [n' x (r') 3 ], wherein n' denotes a frequency of a grain having a grain size r'.
  • the value of r (the number of significant digits are 3, and the least significant digit is rounded) is equal to a grain size for giving a maximum value of a volume frequency curve.
  • the grain size is a diameter in the case of a spherical silver halide grain and is a sphere-equivalent diameter in the case of a grain having a shape other than a sphere.
  • a silver halide which can be used in combination with a light-sensitive material of the present invention can have any composition containing a component selected from the group consisting of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride.
  • a preferable silver halide is silver iodobromide containing 30 mol% or less of silver iodide, silver bromide, or silver chlorobromide.
  • a silver halide grain which can be used in the monodisperse silver halide emulsion of the present invention can be selected from a regular crystal not including a twined crystal plane and grain including a twined crystal plane 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 comprising (100) faces, an octahedral grain comprising (111) faces, and a dodecahedral grain comprising (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 comprising both (100) and (111) faces, a grain comprising both (100) and (110) faces, and a grain comprising both (111) and (110) faces can be selectively used in accordance with an application.
  • octahedral grains having a (111) face and tetradecahedral grains having both of a (100) face and a (111) face in one grain are particularly preferable.
  • the silver halide grains may be fine grains having a grain size of 0.1 u.m or less or large grains having a projected surface area diameter of 10 I lm.
  • two or more types of monodisperse silver halide emulsions manufactured in the presence of a thiosulfonic acid compound represented by formula [I], [II], or [III] and having different maximum-frequency grain sizes can be mixed in the same layer or independently coated on different layers.
  • two or more types of polydisperse silver halide emulsions or monodisperse emulsions other than that of the present invention can be mixed in an amount of half or less, and preferably, 30 wt% or less with respect to a total weight of silver halide grains.
  • the photographic emulsions for use in the present invention can be prepared using the 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 the photographic emulsion", Focal Press, 1964.
  • the described method is, for example, an acid method, a neutralization method, and an ammonia method.
  • a single mixing method, a double mixing method, or a combination thereof can be used as a system for reacting a soluble silver salt and a soluble halide.
  • 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 in which the silver halide is generated 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.
  • grains having a desired grain size can be obtained by performing nucleation and precipitation by a double jet method while a pAg is maintained constant and a supersaturation degree is held so as not to cause re-nucleation.
  • an aqueous potassium iodobromide-gelatin solution and an aqueous ammonium silver nitrate solution are preferably added to an aqueous gelatin solution containing silver halide grains while an addition speed is changed as a function of a time.
  • an addition speed is changed as a function of a time.
  • a high monodisperse silver halide emulsion can be prepared. This method is described in detail in, e.g., "Photographic Science and Engineering", Vol. 6, PP. 159 to 165 (1962); “Journal of Photographic Science", Vol. 12, PP. 242 to 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", P. 131, (1930); Gutoff, "Photographic Theory 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.
  • Tabular grains are preferable as an emulsion of the present invention.
  • tabular grains in which grains having an aspect ratio of 3 to 8 occupy 50% or more of a total projected surface area are preferred.
  • Monodisperse tabular grains can be manufactured by, e.g., the following method. That is, a fine grain tabular silver iodobromide emulsion can be prepared by a double jet method in which equimolar amounts of an aqueous silver nitrate solution and an aqueous solution mixture of potassium bromide and potassium iodide are added.
  • a pAg is so controlled as to maintain a tabular shape and not to cause re-necleation. More specifically, the pAg is preferably 9 to 7.
  • a crystal structure may be uniform, may have different halogen compositions in its interior and on its surface, or may be a layered structure. These emulsion grains are dislosed in, e.g., British Patent 1,027,146, U.S. Patents 3,505,068 and 4,444,877, and Japanese Patent Application 58-248469.
  • a silver halide layers having a different composition each other may be epitaxially bonded, or a compound other than a silver halide such as a silver rhodanide or a lead oxide may be bonded.
  • the silver halide emulsion of the present invention preferably has a distribution or structure of a halogen composition in its grain.
  • a typical example is a coreshell 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 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 a silver halide having a different composition can be formed on the surface of a core-shell double structure grain.
  • a structured grain can be obtained not only by giving the above surrounding structure on the core but also by giving a so-called junction structure.
  • Examples of such a grain of junction structure 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 junction crystal 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 on the host crystal 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 rocksalt 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 with a silver halide.
  • a silver iodide concentration may have any distribution.
  • the silver iodide content may be high at a core portion and low at a shell portion or vice versa.
  • the silver iodide content may be high in a host crystal and relatively low in a junction crystal or vice versa.
  • a boundary portion between different halogen compositions may be clear or unclear due to forming a mixed crystal.
  • a continuous structural change may be positively made in the boundary portion.
  • 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 or a treatment of modifying the surface of a grain as disclosed in DE-2306447C2 and JP-A-60-221320.
  • the silver halide emulsion according to the present invention is preferably used as a surface latent image type. It can be also used, however, as an internal latent image type emulsion by selecting a developing solution or development conditions as disclosed in JP-A-59-133542. In addition, a shallow internal latent image type emulsion covered with a thin shell can be effective 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 halide solution into a reaction vessel.
  • other ripening agents can be used. In this case, a total amount of these other 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. Alternatively, the ripening agents can be added independently in the step of adding a halide and a silver salt.
  • Examples of the ripening agent other than the halogen ion are ammonium, an amine compound and a thiocyanate such as an alkali metal thiocyanate (especially sodium thiocyanate or potassium thiocyanate), and ammonium thiocyanate.
  • the present invention it is very important to perform chemical sensitization, typically sulfur sensitization or gold sensitization. Photographic properties of grains doped with 1 x 10- 4 mol/mol Ag of multivalent metal ions are significantly improved when chemical sensitization is performed. A portion at which the chemical sensitization is performed differs depending on the composition, structure, or shape of an emulsion grain or an application of the emulsion. A chemical sensitized nucleus is embedded either in a deep portion 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 sensitized 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. Alternatively, 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 sensitization 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 of the present invention can contain various compounds in order to prevent fogging during manufacture, storage, or a photographic process 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); mer- captopyrimidines; mercaptotriadines; a thioketo compound such as oxadrinthione; azaindenes, e.g., triazain- denes, te
  • the photographic emulsion used in the present invention can be spectrally sensitized by, e.g., methine dyes.
  • the dye used for this purpose 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 a 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 contained.
  • 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 condensation of an alicyclic hydrocarbon ring to each of the above nuclei; and a nucleus obtained by condensation of an aromatic hydrocarbon ring to each of the above nuclei, e.g., an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxadole nucleus, a naphthooxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a be
  • a 5- or 6-membered heterocyclic nucleus having a ketomethylene structure e.g., a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be contained.
  • 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 and 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. The dye can also be 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, a part of the above compound can be added before chemical sensitization and the remaining portion is added thereafter. Further, 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 of the above dye can be 4 x 10- 6 to 8 x 10- 3 mol per mol of a silver halide.
  • a silver halide grains has a preferable size of 0.2 to 1.2 u.m, an addition amount of about 5 x 10- 5 to 2 x 10- 3 mol is more effective.
  • 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 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 coupler are 5-pyrazolone and pyrazoloazole compounds. Most preferable examples of the compound are described in, e.g., U.S. Patents 4,310,619 and 4,351,897, EP 73,636, U.S. Patents 3,061,432 and 3,752,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, and U.S. Patents 4,500,630 and 4,540,654.
  • a cyan coupler examples include phenol and naphthol couplers.
  • Preferable examples of the coupler are 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 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 also preferably used in the present invention.
  • Preferable 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-60-184243, 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.
  • the couplers for use in this invention can be introduced in the light-sensitive materials by various known dispersion methods.
  • phthalic esters e.g., dibutylphthalate, dicyclohexyl- phthalate, di-2-ethylhexylphthalate, decylphthalate, bis(2,4-di-t-amylphenyl)phthalate, bis(2,4-di-t-amylphenyl)isophthlate, and bis(1,1-diethylpropyl)phthalate; esters of phosphoric acid or phosphonic acid, e.g., triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, tri-2-ethyl- hexylphosphate, tridodecylphosphate, tributoxyethylphosphate, trich
  • 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 an auxiliary solvent.
  • Typical examples of the auxili solvent are ethyl acetate, butyl acetate, ethyl propionate, methylethylketone, cyclohexanone, 2-ethoxyethylacetate, and dimethylformamide.
  • the present invention can be applied to any light-sensitive material, it is preferably applied to various color light-sensitive materials.
  • Typical examples of the color light-sensitive 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 can be applied to light-sensitive materials having various structures and to light-sensitive materials having combinations of various layer structures and special color materials.
  • Typical examples are: light-sensitive materials, in which a coupling speed and diffusibility of a color coupler 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-59-58147, 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 same-color-sensitive layer is divided into two or more layers, as disclosed in JP-B-49-15495 and U.S.
  • Patent 3843469 and light-sensitive materials, in which an arrangement of high-and low-sensitivity layers or an arrangement of 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 of this invention can be processed for development by the ordinary processes as described, for example, in above-described Research Disclosure, No. 17643, pages 28 to 29 and ibid., No. 18716, page 651, left column to right column.
  • a color developer used in developing of the light-sensitive material of the present invention is, preferably, an aqueous alkaline solution containing, as a main component, color developing agent of an aromatic primary amine-series.
  • the color developing agent an aminophenol-series compound is effective.
  • a p-phenylenediamine-series compound is preferably used.
  • Typical examples of the p-phenylenediamine-series compound are 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-,e-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ 3-methoxyethylaniline, and sulfates, hydrochlorides and p-toluenesulfonates thereof. These compounds can be used in a combination of two or more thereof in accordance with applications.
  • the color developer solution 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 solution can also contain a preservative such as hydroxylamine, diethylhydroxylamine, a hydrazine sulfite, a phenyl- semicarbazide, 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 solution 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 developer solution and the black-and-white developer solution is generally 9 to 12.
  • a replenishment amount of the developer solution depends on a color photographic light-sensitive material to be processed for development, it is generally 3 liters or less per m 2 of the light-sensitive material.
  • the replenishment amount can be decreased to be 500 m or less by decreasing a bromide ion concentration in a replenishing solution.
  • a contact area of the developer solution in a processing tank with air is preferably decreased in order to prevent evaporation and oxidation of the solution.
  • the replenishment amount can be also decreased by using a means capable of suppressing an accumulation amount of bromide ions in the developer solution.
  • a 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 of the developer solution and using the color developing agent at a high concentration.
  • the photographic emulsion layer is generally subjected to bleaching after color development.
  • the bleaching can be performed either simultaneously with fixing (bleach-fixing) or independently thereof.
  • bleach-fixing can be performed after bleaching.
  • the processing can be performed in a bleach-fixing bath having two continuous tanks, wherein fixing can be performed before bleach-fixing, or bleaching can 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; a nitro compound.
  • Typical examples of the bleaching agent are a fs'ricyanide; a dichromate; an organic complex salt of iron (III) or cobalt (III), e.g., a complex salt of iron (III) or cobalt (II) with an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycoletherdiaminetetraacetic acid, or a complex salt with 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,
  • an iron (III) complex salt with aminopolycarboxylic acid such as an iron (III) complex salt with ethylenediaminetetraacetic acid, and a persulfate are preferred because they can increase a processing speed and prevent an environmental contamination.
  • the iron (III) complex salt with aminopolycarboxylic acid is effective in both the bleaching solution and bleach-fixing solution.
  • the pH of the bleaching solution or the bleach-fixing solution using the iron (III) complex salt with 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.
  • Examples of the effective bleaching accelerator are described in the following patent specifications: compounds having a mercapto group or a disulfide group described in, e.g., U.S. Patent 3,893,858, West German Patent Nos.
  • 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-53-124424, JP-A-53-141623 and JP-A-53-28426, and Research Disclosure No. 17,129 (July, 1978); a thiazolidine derivative described in JP-A-50-140129; thiourea derivatives described in JP-B-45-8506, JP-A-52-20832 and JP-A-53-32735, and U.S.
  • Patent 3,706,561 iodides described in West German Patent No. 1,127,715 and JP-A-58-16235; polyoxyethylene compounds described in West German Patent Nos. 966,410 and 2,748,430; a polyamine compound described in JP-B-45-8836; compounds described in JP-A-49-42434, JP-A-49-59644, JP-A-53-94927, JP-A-54-35727, JP-A-55-26506 and JP-A-58-163940; and a bromide ion.
  • a compound having a mercapto group or a disulfide group is preferable because it has a good accelerating effect.
  • the fixing agent examples include a thiosulfate, a thiocyanate, a thioether-series compound, a thiourea and a large amount of an iodide.
  • a thiosulfate, especially, ammonium thiosulfate can be used in a widest range of applications.
  • a sulfite, a bisulfite or a carbonyl bisulfite adduct is preferred.
  • the silver halide color photographic light-sensitive material of the present invention is normally subjected to washing with water and/or stabilizing steps after desilvering.
  • An amount of water used in the washing step can be arbitrarily determined over a broad range depending on the properties of the light-sensitive material (e.g., a property determined by used substance such as a coupler), the application of the material, the temperature of the water, the number of water tanks (the number of stages), a 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 proliferate and floating substances produced by the bacteria can be undesirably attached to the light-sensitive material.
  • a method of decreasing calcium and magnesium ions can be very effectively utilized, as described in Japanese Patent Application No. 61-131632.
  • a germicide such as an isothiazolone compound and thiabendazole described in JP-A-57-8542, a germicide of chlorine-series 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 of the present invention 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 to 45 C, and preferably, 30 seconds to 5 minutes at 25 to 40 C.
  • the light-sensitive material of the present invention 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 subsequently to washing.
  • An example thereof is the case in which a stabilizing bath containing formalin and a surface-active agent is used as a final bath of the color light-sensitive material for photographing.
  • various chelating agents and antifungal agents can be added also in the stabilizing bath.
  • An overflow liquid produced upon replenishment of the washing and/or stabilizing solution can be reused in another step such as a desilvering step.
  • the silver halide color light-sensitive material of the present invention can contain a color developing agent in order to simplify processing for development and increase the processing speed.
  • a color developing agent in order to simplify processing for development and increase the processing speed.
  • various precursors of the color developing agent are an indoaniline-series compound described in U.S. Patent 3,342,597; Schiff base compounds described in U.S. Patent 3,342,599 and Research Disclosure Nos. 14,850 and 15,159; an aldol compound described in Research Disclosure No. 13,924; a metal complex salt described in U.S. Patent 3,719,492; and a urethane-series compound described in JP-A-53-135628.
  • the silver halide color light-sensitive material of the present invention can 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 to 50 C. Although a normal solution temperature is 33 to 38 C, processing can be accelerated at a higher temperature to shorten a processing time, or quality of image and/or stability of a processing solution can be improved at a lower temperature.
  • processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or U.S. Patent 3,674,499 can be performed.
  • the silver halide light-sensitive material of the present invention can also be applied to heat 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.
  • 60 g of gelatin and 900 m of water were added to a stainless reaction vessel having a volume of 4 1, and equal volume of an aqueous silver nitrate solution and an aqueous solution mixture of potassium bromide and potassium iodide were added to the vessel maintained at 60 C, thereby preparing a silver iodobromide emulsion to serve as a core.
  • equal volume of an aqueous silver nitrate solution and an aqueous potassium bromide solution were added to cover the core with silver bromide, thereby preparing a core/shell type silver iodobromide emulsion.
  • a pAg was kept at 8.6 for first 10 minutes, at 8.3 for following 80 minutes, and at 7.3 for last 20 minutes.
  • the emulsion was subjected to a normal desalting/washing process and then redispersed at a temperature of 40 C, a pAg of 8.9, and a pH of 6.3, thereby preparing an emulsion Em-101.
  • the prepared emulsion comprises octahedral grains having a (111) face with a maximum grain size of 0.6 ⁇ m and an average Agl content (prescription value) of 5 mol%.
  • a weight of a silver halide falling within the grain size region ranging from -20% to +20% of a maximum grain size was 75% of a total silver halide grain weight.
  • Em-114 was prepared following the same procedures as for Em-101 except that a stirring speed was reduced to be 500 rpm after 50 minutes in Table 1-1.
  • the prepared emulsion comprised grains with a maximum grain size of 0.6 / lm and had an average Agl content (prescription value) of 5 mol%.
  • a weight of a silver halide falling within the grain size region ranging from -20% to +20% of a maximum grain size was 65% of a total silver halide grain weight.
  • Emulsions as comparative examples were prepared as follows.
  • Em-121 was prepared following the same procedures as for Em-101 except that during core formation, aqueous solutions of silver nitrate and potassium halide were added such that addition amounts were maintained constant per unit time and a maximum grain size was adjusted to equal to that of Em-101.
  • the prepared emulsion had a maximum grain size of 0.6 ⁇ m and an average Agl content (prescription value) of 5 mol%.
  • a weight of a silver halide falling within the grain size region ranging from -20% to +20% of the maximum grain size was 55% of a total silver halide grain weight.
  • Em-102 to Em-113 of the present invention and the emulsions Em-101, Em-114, and Em-121 to Em-133 prepared as described above were optimally subjected to gold-plus-sulfur sensitization by using sodium thiosulfate and chloroauric acid to prepare emulsions.
  • Emulsion and protective layers in amounts as listed in Table 1-5 were coated on triacetylcellulose film supports having undercoating layers.
  • the processed samples were subjected to density measurement by using a green filter.
  • the obtained photographic performance results are listed in Table 1-6.
  • 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: available from Fuji Photo Film Co. Ltd.).
  • Sensitivities were compared using density at a point from a fog 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-101 is 100 (100 for both 1/100" and 1 ").
  • the maximum density Dmax is represented as a relative density assuming that Dmax of the sample using Em-101 is 100.
  • Em-201 which is perfectly identical to Em-101 was prepared following the same procedures as in Example 1.
  • Em-210 was prepared following the same procedures as for Em-201 except that a stirring speed was reduced to be 500 rpm after 50 minutes in Table 1-1.
  • the prepared emulsion had a maximum grain size of 0.6 u.m and an average Agl content (prescription value) of 5 mol%.
  • a weight of a silver halide falling within the grain size region ranging from -20% to +20% of a maximum grain size was 65% of a total silver halide grain weight.
  • Emulsions as comparative examples were prepared as follows.
  • Em-217 was prepared following the same procedures as for Em-201 except that during core formation, aqueous solutions of silver nitrate and potassium halide were added such that addition amounts thereof were maintained constant per unit time and a maximum grain size was adjusted to equal to that of Em-201.
  • the prepared emulsion had a maximum grain size of 0.6 ⁇ m and an average Agl content (prescription value) of 5 mol%.
  • a weight of a silver halide falling within the grain size region ranging from -20% to + 20% of the maximum grain size was 55% of a total silver halide grain weight.
  • Em-201 to Em-223 of the present invention and the comparative examples were optimally subjected to gold-plus-sulfur sensitization by using sodium thiosulfate and chloroauric acid to prepare emulsions.
  • Samples 201 to 223 of this example were prepared following the same procedures as in Example 1 except that the emulsions Em-201 to Em-223 were used instead of the emulsion Em-101. Subsequently, sensitometry was performed following the same procedures as in Example 1 except that an exposure time was changed from "1 sec. and 1/100 sec.” to "10 sec. and 1/100 sec.” The obtained results are summarized in Table 2-5.
  • Table 2-6 shows the results represented by relative sensitivities assuming that the sensitivity of the sample 201 obtained before storage is 100.
  • a plurality of layers having the following compositions were coated on an undercoated triacetylcellulose film support to prepare a multilayered color light-sensitive material 301.
  • Numerals corresponding to the respective components indicate coating amounts in units of g/m 2 .
  • Coating amounts of a silver halide and colloid silver are represented by a silver amount.
  • a coating amount of a sensitizing dye is represented in units of mols per mol of a silver halide in the same layer.
  • Percentages of gains falling within the grain size region ranging from -20% to +20% of the maximum grain size were 73% in the emulsion I; 70% in the emulsion II; and 66% in the emulsion III.
  • the emulsions I to III were optimally subjected to gold-plus-sulfur sensitization by using sodium thiosulfate and chloroauric acid.
  • Samples 302 to 305 were prepared following the same procedures as for the sample 301 except that the above emulsions were replaced with emulsions produced by adding thiosulfonic acid compounds and reduction sensitizers as shown in Table 3-1 (A) during grain formation as in the case of Em-102 to Em-113.
  • the processed samples were subjected to density measurement by using red, green, and blue filters. The obtained results are shown in Table 3-1.
  • the results of photographic performance are represented by relative sensitivities of the red-, green-, and blue-sensitive layers assuming that the sensitivities of the sample 301 are each 100.
  • the color development process was performed at 38 °C in accordance with the following process steps.
  • Samples 401 to 404 were prepared following the same procedures as for the sample 301 in Example 3.
  • Em-204 to Em-206 were used to prepare the monodisperse silver iodobromide emulsions I to III for use in the layers 4, 7, and 10, respectively, and thiosulfonic acid compounds and a reduction sensitizer L-ascorbic acid were added to the emulsions as shown in Table 4-1-(A).
  • the samples 402 to 404 are the same as the sample 401 except for this point.
  • each sample using the emulsion of the present invention had good storage stability.
  • the samples 301 to 305 were exposed following the same procedures as in Example 3 and processed as follows by using an automatic developing machine.
  • 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 the concentrations of calcium and magnesium to be 3 mg/L or less. Subsequently, 20 mg/L of of sodium isocyanuric acid dichloride 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 samples 302 to 305 of the present invention provided the good results as in Example 3 after they were subjected to the above processing.
  • Example 4 The sample 401 of the comparative example and the sample 402 to 404 of the present invention obtained in Example 4 were exposed following the same procedures as in Example 4 and then processed by using an automatic developing machine.
  • a processing method and compositions of the processing solutions were the same as those in Example 5.
  • the samples 402 to 404 of the present invention provided the good results as in Example 4 after they were subjected to the above processing.
  • Example 3 The samples 301 to 305 of Example 3 were exposed following the same procedures as in Example 3 and processed as follows by using an automatic developing machine.
  • 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 the concentrations of calcium and magnesium to be 3 mg/L or less. Subsequently, 20 mg/L of of sodium isocyanuric acid dichloride 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 samples 302 to 305 of the present invention provided the good results as in Example 3 after they were subjected to the above processing.
  • Example 4 The sample 401 of the comparative example and the samples 402 to 404 of the present invention obtained in Example 4 were exposed following the same procedures as in Example 4 and then processed by using an automatic developing machine.
  • a processing method and compositions of processing solutions are the same as those in Example 7.
  • the samples 402 to 404 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 triacetylcellulose film support to prepare a sample 901 as a multilayer color light-sensitive material.
  • Numerals corresponding to the respective components indicate coating amounts in units of g/m 2 except that the silver halide and colloid silver are represented in a silver-converted coating amount, and that 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. Structures of the used compounds are listed in Table D to be presented later.
  • the emulsions A to H are silver iodobromide emulsions.
  • An average Agl content and the like of these emulsions are listed in Table below.
  • Samples 902 to 905 were prepared following the same procedures as for the sample 901 except that the emulsion of the layer 9 was replaced with an emulsion obtained by adding thiosulfonic acid compounds and reduction sensitizers during grain formation as in the case of Em-102 to Em-113.
  • Photographic properties are represented by the sensitivity of a green-sensitive layer as a relative sensitivity assuming that the sensitivity of the sample 901 is 100.
  • sample 1001 A plurality of layers having the following compositions were coated on an undercoated cellulose triacetate film support to prepare sample 1001 as a multilayer color light-sensitive material.
  • compositions of Light-Sensitive Layers are Compositions of Light-Sensitive Layers:
  • the coating amounts of a silver halide and colloid silver are represented in units of g/m 2 of silver, those of couplers, additives, and gelatin are represented in units of g/m 2 , and that of sensitizing dyes is represented by the number of mols per mol of the silver halide in the same layer.
  • n-butyl-p-hydroxybenzoate ditto, about 1,000 ppm
  • 2-phenoxyethanol ditto, about 1,000 ppm
  • Samples 1002 to 1004 were prepared following the same procedures as for the sample 1001 except that the emulsion of the layer 10 was replaced with an emulsion prepared by adding thiosulfonic acid compounds and a reduction sensitizer L-ascorbic acid during grain formation as in the case of Em-204 to Em-206.
  • Photographic properties are represented by the sensitivity of a green-sensitive layer as a relative sensitivity assuming that the sensitivity of the sample 1001 is 100.
  • Example 3 The samples 301 to 305 of Example 3 and Samples 901 to 905 of Example 9 were exposed following the same procedures as in Example 3, 9 and processed as follows by using an automatic developing machine. As a result, it was confirmed that the samples according to the present invention provided the good effects similar to the result obtained in Example 3 and Example 9.
  • compositions of the processing solution are summarized below.
  • Tap water was supplied to a mixed-bed column filed 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 the concentrations of calcium and magnesium to be 3 mg/L or less. Subsequently, 20 mg/L of sodium isocyanuric acid dichloride 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.

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  • Physics & Mathematics (AREA)
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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP89121214A 1988-11-17 1989-11-16 Lichtempfindliches photographisches Silberhalogenidmaterial Expired - Lifetime EP0371338B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP63290676A JPH0810318B2 (ja) 1988-11-17 1988-11-17 ハロゲン化銀写真感光材料
JP290676/88 1988-11-17
JP156049/89 1989-06-19
JP1156049A JP2820154B2 (ja) 1989-06-19 1989-06-19 ハロゲン化銀写真感光材料

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0435355A1 (de) * 1989-12-28 1991-07-03 Fuji Photo Film Co., Ltd. Silberhalogenidemulsion und photographisches, lichtempfindliches, diese verwendendes Silberhalogenidmaterial
EP0495253A1 (de) * 1991-01-15 1992-07-22 Agfa-Gevaert N.V. Verfahren zur photographischen Herstellung von Silberbildern
US5399479A (en) * 1993-12-16 1995-03-21 Eastman Kodak Company Photographic element exhibiting improved speed and stability
EP0645668A1 (de) * 1993-09-28 1995-03-29 Konica Corporation Photographische Silberhalogenidemulsion und photographisches lichtempfindliches Silberhalogenidmaterial
US5411855A (en) * 1993-12-16 1995-05-02 Eastman Kodak Company Photographic element exhibiting improved speed and stability
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
EP0687948A1 (de) * 1994-06-17 1995-12-20 Konica Corporation Photographische Silberhalogenidemulsion
US5489504A (en) * 1992-06-23 1996-02-06 Konica Corporation Silver halide photographic emulsion and silver halide photographic light sensitive material applied therewith
EP0703495A1 (de) * 1994-08-30 1996-03-27 Konica Corporation Ein farbphotographisches lichtempfindliches Silberhalogenidmaterial
EP0435270B1 (de) * 1989-12-26 1997-04-09 Fuji Photo Film Co., Ltd. Verfahren zur Herstellung einer Silberiodobromid- Emulsion und diese verwendendes photographisches lichtempfindliches Silberhalogenidmaterial
EP0843209A1 (de) 1996-11-13 1998-05-20 Imation Corp. Verfahren zur Herstellung einer Silberhalogenidemulsion

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FR2169360A1 (de) * 1972-01-26 1973-09-07 Agfa Gevaert Ag
DE2824082A1 (de) * 1977-06-03 1978-12-14 Fuji Photo Film Co Ltd Photographische silberhalogenidemulsionen und das daraus hergestellte photographische silberhalogenidmaterial
US4775617A (en) * 1985-07-18 1988-10-04 Fuji Photo Film Co., Ltd. Silver halide color photographic material containing monodispersed tabular silver halide grains

Family Cites Families (1)

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EP0369424B1 (de) * 1988-11-15 1995-09-27 Fuji Photo Film Co., Ltd. Lichtempfindliches photographisches Silberhalogenidmaterial

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Publication number Priority date Publication date Assignee Title
FR2169360A1 (de) * 1972-01-26 1973-09-07 Agfa Gevaert Ag
DE2824082A1 (de) * 1977-06-03 1978-12-14 Fuji Photo Film Co Ltd Photographische silberhalogenidemulsionen und das daraus hergestellte photographische silberhalogenidmaterial
US4775617A (en) * 1985-07-18 1988-10-04 Fuji Photo Film Co., Ltd. Silver halide color photographic material containing monodispersed tabular silver halide grains

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* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 9, no. 37 (P-335)(1760) 16 February 1985, & JP-A-59 178447 (KONISHIROKU PHOTO INDUSTRY COMPANY LIMITED) 09 October 1984, *
Zeitschrift für wissenschaftliche Photographie vol. 63, no. 7-9, 1969, Berlin,DD pages 133 - 148; S.Gahler: "Benzolthiosulfonsäure und Reduktionssensibilisierung" *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0435270B1 (de) * 1989-12-26 1997-04-09 Fuji Photo Film Co., Ltd. Verfahren zur Herstellung einer Silberiodobromid- Emulsion und diese verwendendes photographisches lichtempfindliches Silberhalogenidmaterial
EP0435355A1 (de) * 1989-12-28 1991-07-03 Fuji Photo Film Co., Ltd. Silberhalogenidemulsion und photographisches, lichtempfindliches, diese verwendendes Silberhalogenidmaterial
US5368999A (en) * 1989-12-28 1994-11-29 Fuji Photo Film Co., Ltd. Silver halide emulsion and silver halide photographic light-sensitive material using the same
EP0495253A1 (de) * 1991-01-15 1992-07-22 Agfa-Gevaert N.V. Verfahren zur photographischen Herstellung von Silberbildern
US5489504A (en) * 1992-06-23 1996-02-06 Konica Corporation Silver halide photographic emulsion and silver halide photographic light sensitive material applied therewith
US5460936A (en) * 1993-09-28 1995-10-24 Konica Corporation Silver halide photographic emulsion and silver halide photographic light-sensitive material
EP0645668A1 (de) * 1993-09-28 1995-03-29 Konica Corporation Photographische Silberhalogenidemulsion und photographisches lichtempfindliches Silberhalogenidmaterial
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
US5411855A (en) * 1993-12-16 1995-05-02 Eastman Kodak Company Photographic element exhibiting improved speed and stability
US5399479A (en) * 1993-12-16 1995-03-21 Eastman Kodak Company Photographic element exhibiting improved speed and stability
EP0687948A1 (de) * 1994-06-17 1995-12-20 Konica Corporation Photographische Silberhalogenidemulsion
US5627018A (en) * 1994-06-17 1997-05-06 Konica Corporation Silver halide photographic emulsion
EP0703495A1 (de) * 1994-08-30 1996-03-27 Konica Corporation Ein farbphotographisches lichtempfindliches Silberhalogenidmaterial
US5616453A (en) * 1994-08-30 1997-04-01 Konica Corporation Silver halide light-sensitive color photographic material
EP0843209A1 (de) 1996-11-13 1998-05-20 Imation Corp. Verfahren zur Herstellung einer Silberhalogenidemulsion

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DE68925676D1 (de) 1996-03-28
DE68925676T2 (de) 1996-10-17

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