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
  • G03C1/035—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
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/03535—Core-shell grains
• • 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
  • G03C2001/03558—Iodide content

Definitions

• This invention relates to a silver halide photographic light sensitive material containing negative type silver halide grains each having an inner core substantially comprising silver bromide or silver iodobromide surrounded by a plurality of outer shells each substantially composed of silver bromide or silver iodobromide.
• High-speed emulsions such as a silver iodobromide emulsion containing silver iodide in an amount of from 0 to 10 mol% of the emulsion to satisfy the above-mentioned requirements are known.
• the well-known methods include, for example, an ammonia method, a neutral method, an acid method in which the conditions of pH and pAg values are controlled, and a precipitation method such as a single-jet or double-jet method.
• a silver iodobromide emulsion which is provided by the invention has been studied so as to control not only the crystal habits and grain distribution but also the iodide content distribution in an individual silver halide grain.
• the most conventional process is to improve the quantum efficiency of the silver halide used.
• studies have been made of solid state physics and the like.
• the silver halide emulsions suitably used in high speed photographic films include a silver iodobromide emulsion comprising polydispersed type twinned crystal grains.
• silver iodobromide emulsions each containing tabular shaped twinned crystal grains are disclosed in, for example, Japanese Patent O.P.I. Publication No. 113927/1983 and others.
• Japanese Patent O.P.I. Publication No. 22408/1978; Japanese Patent Examined Publication No. 13162/1968; 'Journal of Photographic Science', No. 24, p. 198, 1976; and the like each describe, respectively, that development activity is increased or high sensitization is realized by making use of multilayered type silver halide grains applied with a plurality of shells around the inner cores of the grains.
• DE-A-3310609 discloses a silver halide photographic material comprising silver halide grains provided with iodobromide grains having an average iodide content of at least 12 mol%.
• the grains comprise at least 3 different iodobromide phases, each having a different iodide content.
• the external phase preferably has an average iodide content of between 5 and 13 mol percent of the average content of the entire grain; the second phase preferably contains between 15 and 25 mol percent and the innermost phase preferably has a content of between 30 and 70 mol percent.
• color light-sensitive materials each having an ISO speed of 1000 or over have recently been introduced. It is, however, usual that as such a light-sensitive material shows improved sensitivity, it deteriorates in terms of graininess and sharpness.
• the present invention seeks to provide a negative type silver halide photographic light-sensitive material which is high in sensitivity, excellent in the correlation between sensitivity and fog, wide in the exposure range, and excellent in both graininess and image sharpness.
• a negative type silver halide photographic material comprising silver halide grains of a core-shell structure which consists of an inner core essentially consisting of silver bromide or silver iodobromide and a plurality of shells, essentially consisting of silver bromide or silver iodobromide, wherein each of the silver halide grains comprises (a) an outermost shell containing silver iodide of 0 to 10 mol%, (b) a highly iodide-containing shell provided inside the outermost shell, of which silver iodide content is from 6 to 40 mol% and is at least 6 mol% higher than that of the outermost shell, and (c) an intermediate shell provided between the shells (a) and (b) the
• the expression, 'substantially comprising -----' means that the above-mentioned silver halide grains are allowed to contain such a silver halide other than silver bromide or silver iodide as silver chloride and, more particularly, means that the content thereof is desirably not more than 1 mol% if it is silver chloride, provided that the content thereof does not disturb the advantages of the invention.
• compositions according to the invention satisfy the following criteria:
• the shells have an iodide content as follows:
• the volume of the outermost shell preferably comprises from 4 to 70% of the whole grain and, more preferably, from 10 to 50% thereof.
• the volume of the highly iodide-containing shell preferably comprises from 10 to 80% of a whole grain and, more preferably, from 20 to 50% and, further preferably, from 20 to 45% thereof.
• the volume of the intermediate shell preferably comprises from 5 to 60% of a whole grain and, more preferably, from 20 to 55% thereof.
• the highly iodide-containing shell may comprise at least one part of an inner core and, more preferably, a separate inner shell is present inside the highly iodide-containing shell.
• the iodide content of the inner shell is preferably from 0 to 40 mol% and, more preferably, from 0 to 10 mol% and, further preferably, from 0 to 6 mol%.
• the grain size of the inner core is preferably from 0.05 to 0.8 ⁇ m and, more preferably, from 0.05 to 0.4u.m.
• the iodide content of the whole grain is preferably from 1 to 20 mol% and, more preferably, from 1 to 15 mol% and, further preferably, from 2 to 12 mol%.
• the grain size distribution is allowed to be either one of the polydisperse type and the monodispere type.
• the variation coefficient of such grain size distribution is preferably not more than 20% in a monodispersed emulsion and, more preferably, not more than 15%. Such a variation coefficient will be defined as follows to measure a monodispersibility:
• the multilayered arrangement is made of not less than three emulsion layers comprising three kinds of light-sensitive layers; a blue-sensitive layer, a red-sensitive layer and a green-sensitive layer; and at least one emulsion layer thereof contains the silver halide grains relating to the invention or the above-mentioned desirable silver halide grains.
• the grain size of a silver halide grain (which is defined as a length of one side of a cube having the same volume as that of the silver halide grain) is preferably from 0.1 to 3.0 ⁇ m: and the configuration thereof may be, for example, an octahedron, a cube, a sphere, or a flat plate and, most preferably, an octahedron.
• the inner shell may be the highly iodide-containing shell, or there may be both an inner shell and a highly iodide-containing shell.
• the inner shell and the highly iodide-containing shell, the highly iodide-containing shell and the intermediate shell, and the intermediate shell and the outermost shell may be adjacent to each other; or, optionally another shell comprising at least one layer having an arbitrary composition (hereinafter called an arbitrary shell) may be interposed between the above-mentioned shells.
• the above-mentioned arbitrary shell may suitably be a monolayered shell having a uniform composition, a plurality of shells each having a uniform composition with a stepwise change in composition from shell to shell, a continuous shell which changes its composition gradually in its arbitrary shell, and the combination thereof.
• the above-mentioned highly iodide-containing shell and intermediate shell may be used together as a pair or a plurality of layers may be employed.
• Iodide content will be represented by I.
• Subscripts denote the order of shells.
• the inner cores of the silver halide grains of the invention can be prepared by a process as described in, for example, P. Glafkides, 'Chimie et Physique Photographique', published by Paul Montel, 1967; G.F. Duffin, 'Photographic Emulsion Chemistry', published by The Focal Press, 1966; V.L. Zelikman et al, 'Making and Coating Photographic Emulsion', published by The Focal Press, 1964; Such processes typically include an acid method process, a neutral method process, and an ammonia method process. Further, a single-jet precipitation process, a double-jet precipitation process or the combination thereof may also be applied to cause the reaction between a soluble silver salt and a soluble halide.
• the reverse precipitation process may be employed in which grains may be formed in presence of silver ions in excess.
• the controlled double-jet precipitation process a version of the double-jet precipitation processes, may also be applied for keeping a pAg value of a silver halide produced in a liquid phase. According to this process, a silver halide emulsion regular in crystal form and nearly uniform in grain size may be prepared.
• the A pAg value varies in accordance with the reaction temperature and the kinds of silver halide solvents in the preparation of an inner core, and is preferably from 2 to 11. It is also preferred to use a silver halide solvent, because the grain-forming time may be reduced.
• a silver halide solvent such as ammonia or thioether may be used.
• Inner cores may be used in a flat plate, sphere or twinned crystal system and also in the form of an octahedron, cube, tetradecahedron or the mixed forms thereof.
• the above-mentioned processes may also advantageously be used to introduce arbitrary shells, highly iodide-containing shells, intermediate shells or the outermost shells, because new renucleation will not occur and each silver halide grain is uniformly coated in these processes.
• a single shell or a plurality of arbitrary shells may be interposed between the highly iodide-containing shell comprising silver halide grains and the intermediate shell.
• Such highly iodide-containing shells may be provided by a process including a desalting step, if necessary, applied to the resultant inner shell or the inner shell provided with an arbitrary shell and an ordinary halogen substitution process a silver halide coating process or the like is then performed.
• the halogen substitution process may be performed for example, such that, after an inner core is formed, an aqueous solution mainly comprising an iodide compound (preferably, potassium iodide), which is preferably not higher than 10% in concentration, is added.
• an iodide compound preferably, potassium iodide
• This processes are more particularly described in, for example, U.S. Patent Nos. 2,592,250 and 4,075,020; Japanese Patent O.P.I. Publication No. 127549/1980; and the like.
• the processes for providing a coating of a silver halide an inner core include, for example, the double-jet precipitation process and controlled double-jet precipitation process, in which, in each case, an aqueous halide solution and an aqueous silver nitrate solution are simultaneously added. More specifically, the processes are described in detail in, for example, Japanese Patent O.P.I. Publication Nos. 22408/1978 and 14829/1983; Japanese Patent Examined Publication No. 13162/1968; 'Journal of Photographic Science', No. 24,198, 1976; and the like.
• the pAg value is varied in accordance with the reaction temperature and the nature and the amount of silver halide solvents used. The same conditions as those for the case of the above-mentioned inner core are appropriate to this case.
• a pAg value of from 7 to 11 is preferred.
• a double-jet precipitation process or a controlled double-jet precipitation process is preferred.
• the intermediate shells, of the silver halide grains of the invention may be prepared such that a highly iodide-containing shell is arranged onto the surface of a grain containing the above-mentioned highly iodide-containing shells and the inner shells, or, if required, the highly iodide-containing shell is provided thereon with a single or plurality of arbitrary shells and, to the outside of the above-mentioned grain, a silver halide a halogen composition different from those of the highly iodide-containing shells is further coated in a double-jet or controlled double-jet precipitation process or the like.
• the aforementioned process for preparing highly iodide-containing shell may similarly serve as the above-mentioned processes.
• the outermost shell of the silver halide grains of the invention may be provided in such a manner that an intermediate shell is provided to the surface of a grain containing the above-mentioned intermediate shells, the highly iodide-containing shells and the inner core or, if required, the intermediate shell provided thereon with a single or plurality of arbitrary shells and, to the outside of the above-mentioned grain, a silver halide having a halogen composition different from those of the highly iodide-containing shells and the intermediate shells is further coated in a double-jet or controlled double-jet precipitation process or the like.
• Any number of arbitrary shells may optionally be interposed if required, between the inner core and the highly iodide-containing shell, and/or between the highly iodide-containing shell and an intermediate shell, and/or the intermediate shell and the outermost shell.
• the above-mentioned arbitrary shells may be prepared by the same processes as employed to prepare the aforementioned highly iodide-containing shell.
• an ordinary desalting process may be performed to prepare the adjacent shell.
• such shells may be continuously formed without carrying out any desalting.
• Structural characteristics of the silver halide grains of the invention such as the iodide content of each coated shell of the silver halide grains may be determined by such methods as that described in, for example, J.I. Goldstein and D.B. Williams, 'X-Ray Analyses in TEM/ATEM', Scanning Electron Microscopy, 1977, vol. 1, LIT Research Institute, p. 651, March, 1977; 'Annual Meeting of SPSTJ '84', p 49-51 (1984); 'The International East-West Symposium on the Factors Influencing Photographic Sensitivity (1984)', c-60-c-63 (1984); Japanese Patent O.P.I. Publication No. 143331/1985 and Japanese Patent O.P.I. Publication No. 143332.
• the suitable methods of removing the above-mentioned materials typically include, for example, a noodle washing method usually applied to an ordinary type emulsion; a dialysis method; a sedimentation method utilizing an inorganic salt, an anionic surfactant, such an anionic polymer as a polystyrene sulfonic acid, or such a gelatin derivative as an acylated or carbamoylated gelatin; and a flocculation method.
• the core/shell type silver halide grains of the invention can be optically sensitized to a desired wavelength region, and there is no special limitation to the optical sensitization methods.
• the grains may be optically sensitized by making use, independently or in combination, of an optical sensitizer such as cyanine or merocyanine dyes suitably including, for example, zero-methine, monomethine, dimethine, and trimethine.
• an optical sensitizer such as cyanine or merocyanine dyes suitably including, for example, zero-methine, monomethine, dimethine, and trimethine.
• a combination of spectrally sensitizing dyes is often used particularly for a supersensitization.
• An emulsion may contain, as well as the above-mentioned spectrally sensitizing dyes, a dye having no spectrally sensitizing characteristic in itself or a substance substantially incapable of absorbing any visible rays off light but capable of displaying super-sensitizing characteristics.
• spectrally sensitizing dyes a dye having no spectrally sensitizing characteristic in itself or a substance substantially incapable of absorbing any visible rays off light but capable of displaying super-sensitizing characteristics.
• the core/shell type silver halide crystals of the invention may also be treated by various chemical sensitization processes applicable to ordinary type emulsions.
• the chemical sensitization may be carried out by a process such as that described in, for example, H. Frieser, 'Die Grundlagen der Photographische mit Silberhalogeniden', Akademische Verlagsges- selschaft, 1968, pp. 675-34. Namely, there may be used, independently or in combination, a sulfur sensitization process employing a compound or active gelatin containing sulfur capable of reacting with silver ions: a reduction sensitization process employing a reducible substance; a noble-metal sensitization process employing gold and other noble-metal compounds; and the like.
• a thiosulfate, a thiourea, a thiazole, a rhodanine and other compounds may be used. They typically include those described in U.S. Patent Nos. 1,574,944, 2,410,589, 2,278,947, 2,728,668, 3,656,955, 4,032,928 and 4,067,740.
• a stannous salt, an amine, a hydrazine derivative, a formamidine sulfinic acid, a a silane compound may suitably be used. They typically include those described in U.S. Patent Nos.
• a gold complex salt and the metal complex salts of the VIII group of the periodic table such as platinum, iridium, and palladium may suitably be used. They typically include those described in U.S. Patent Nos. 2,399,083 and 2,448,060: British Patent No. 618,061; and the like.
• the silver halide grains of the invention may be treated by a combination of two or more of the above-mentioned chemical sensitization processes.
• the amount of silver to be coated is not limited but is preferably in the range of from 1000mg/m 2 to 15000mg/m 2 and, more preferably, from 2000mg/m 2 to 1 OOOOmg/m2.
• the light-sensitive layers each containing the above-mentioned grains may be present on both sides of a support.
• the inner dopants include, for example, silver, sulfur, iridium, gold, platinum, osmium, rhodium, tellurium, selenium, cadmium, zinc, lead, thallium, iron, antimony, bismuth, and arsenic.
• the water-soluble salts or complex salts thereof may be used in combination with the dopants when forming each of the shells.
• a hydrophilic colloid ordinarily used in a silver halide emulsion may also be used.
• examples include gelatin, whether lime- or acid-treated and also the following; namely, a gelatin derivative including, for example, those prepared through a reaction of gelatin on any one of an aromatic sulfonyl chloride, acid chloride, acid anhydride, isocyanate or 1,4-diketone, such as described in U.S. Patent No.
• a gelatin derivative prepared by a reaction of gelatin on a trimellitic acid anhydride such as described in U.S. Patent No. 3,118,766: a gelatin derivative prepared by a reaction of gelatin on an organic acid having an active halogen, such as described in Japanese Patent Examined Publication No. 5514/1964; a gelatin derivative prepared by a reaction of gelatin on an aromatic glycidyl ether, such as described in Japanese Patent Examined Publication No. 26845/1967; a gelatin derivative prepared by a reaction of gelatin on a maleimide, maleaminic acid or unsaturated aliphatic diamide and the like, such as described in U.S. Patent No.
• the silver halide photographic emulsions each containing the core/shell type silver halide grains of the invention may further contain various kinds of additives ordinary used according to the purposes.
• the above-mentioned additives include, for example, a stabilizer and an antifoggant such as an azole or an imidazole, e.g., a benzothiazolium salt, a nitroindazole, a nitrobenzimidazole, a chlorobenzimidazole, a bromobenzimidazole, a mercaptothiazole, a mercaptobenzthiazole, a mercaptobenzimidazole and a mercap- tothiadiazole; a triazole.
• an antifoggant such as an azole or an imidazole, e.g., a benzothiazolium salt, a nitroindazole, a nitrobenzimidazole, a chlorobenzimidazole, a bromobenzimidazole, a mercaptothiazole, a mercaptobenzthiazole, a mercaptobenzimidazole
• a tetrazole e.g., a mercaptotetrazole, particularly including 1-phenyl-5-mercaptotetrazole and the like; a mercaptopyrimidine; a mercaptotriazine, e.g., a thioketo compound including oxazolinethione; an azaindene, e.g., a triazaindene, a tetraazaindene, particularly including a 4-hydroxy substituted-(1,3,3a,7)tetraazaindene, and a pentaazaindene benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, an imidazolium salt, a tetrazolium salt, and a polyhydroxy compound.
• a tetrazole e.g., a mercaptotetrazole, particularly including 1-phenyl-5-mercapto
• the photographic emulsion layers and the other hydrophilic colloidal layers thereof may contain inorganic or organic hardeners, independently or in combination, which include, for example, a chromium salt such as chrome alum, chromium acetate and the like; an aldehyde such as formaldehyde, glyoxal, glutaric aldehyde and the like; a N-methylol compound such as dimethylolurea and methyloldimethylhydantoine; a dioxane derivative such as 2,3-dihydroxydioxane; an active vinyl compound such as 1,3,5-triacryloyl-hexahydro-S-triazine, and 1,3-vinylsulfonyl-2-propanol; an active halide such as 2,4-dichloro-6-hydroxy-S-triazine; a mucohalogen acid such as mu
• the photographic emulsion layers and the other hydrophilic colloidal layers thereof may contain the dispersed matters of a water-insoluble or slightly soluble synthetic polymer in order to improve the dimensional stability thereof, for example.
• Polymers may also be used, independently or in combination, including, for example, alkyl (metha)acrylate, alkoxyalkyl (metha)acrylate, glycidyl (metha)acrylate, (metha)-acrylamide, a vinyl ester such as vinyl acetate, acrylonitrile, olefin, and styrene; or the polymers each having the monomer-components each comprising a combination of the above-mentioned dispersed matters and acrylic acid, methacrylic acid, a,,6-unsaturateddicarboxylic acid, hydroxyalkyl (metha) acrylate, sulfoalkyl (metha)acrylate and styrenesulfonic acid.
• the silver halide photographic light-sensitive materials relating to the invention may also contain, if required, a development accelerator such as benzyl alcohol, a polyoxyethylene compound; an image stabilizer such as a chroman, coumaran, bisphenol or phosphorous acid ester; a lubricant such as a wax, glycerides of a higher fatty acid, the higher alcohol esters of a higher fatty acid and the like; a development regulator; a developing agent; a plasticizer; and a bleaching agent.
• a development accelerator such as benzyl alcohol, a polyoxyethylene compound
• an image stabilizer such as a chroman, coumaran, bisphenol or phosphorous acid ester
• a lubricant such as a wax, glycerides of a higher fatty acid, the higher alcohol esters of a higher fatty acid and the like
• a development regulator such as benzyl alcohol, a polyoxyethylene compound
• an image stabilizer such as a chro
• a coating aid for a processing liquid or the like, a defoaming agent or various materials of the anion, cation, non-ion or amphoteric type for controlling various physical properties of the light-sensitive materials.
• a coating aid for a processing liquid or the like, a defoaming agent or various materials of the anion, cation, non-ion or amphoteric type for controlling various physical properties of the light-sensitive materials.
• antistatic agents there may effectively be used a diacetyl cellulose, a styrene perfluoroalkylsodium maleate copolymer, an alkali salt of the reaction products of a styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid.
• the matting agents include, for example, a polymethacrylic acid methyl, a polystyrene, an alkali-soluble polymer and the like.
• a colloidal silica oxide may also be used.
• the latexes to be added for improving the physical properties of layers include, for example, a copolymer of an acrylic ester, a vinyl ester or the like and a monomer having the other ethylene group.
• the gelatin plasticizers include, for example, glycerol and a glycol compound.
• the thickening agents include, for example, a styrene-sodium maleate copolymer, and an alkylvinylether-maleic acid copolymer.
• the emulsions each having the silver halide grains of the invention may be provided with a wide latitude, if they are prepared by mixing at least two emulsions which have different average grain size and sensitivity.
• the core/shell type silver halide emulsions relating to the invention may effectively be applied to the photographic light-sensitive materials for various applications such as a general black-and-white photography, X-ray photography, color photography, infrared photography, microphotography, silver dye bleach photographic process, reversal photography, diffusion transfer photographic process, high contrast photography, photothermography and heat processable light sensitive materials. Inter alia, they are particularly suitable for a high speed color light-sensitive material.
• the silver halide emulsion When applying a core/shell type silver halide emulsion of the invention to a color photographic light-sensitive material, the silver halide emulsion should be treated in such a process as usually applied to a color light-sensitive material as well as with the materials therefor.
• cyan, magenta and yellow couplers are contained in the emulsions each having the aforementioned Dcrystais and having been prepared to be red-, green- and blue-sensitive, respectively.
• the above-mentioned materials include, for example, the magenta couplers such as 5-pyrazolone, pyrazolobenzimidazole, pyrazolotriazole, cyanoacetylcoumaran, and open-chained acylacetonitrile; the yellow couplers such as acylacetoamide (e.g., a benzoylacetanilide and a pivaloylacetanilide; and the cyan couplers such as naphthol and phenol.
• the above-mentioned couplers are preferably the non-diffusible ones each having, in the molecules thereof, a hydrophobic group that is the so-called ballast group.
• the couplers may be of either 4- or 2-equivalent per silver ion. They may also be colored couplers capable of displaying a color-compensation effect or couplers capable of releasing a development inhibitor while a development is being carried out, (which are called 'non-coloration DIR couplers').
• the above-mentioned emulsions may also contain, in addition to the DIR couplers, a non-coloration DIR coupling compound which is capable of producing a colorless coupling reaction products and also releasing a development inhibitor.
• anti-discoloring agents and color image stabilisers may optionally be used alone or in combination.
• anti-discoloring agents include, for example, a hydroquinone derivative, a gallic acid derivative, a p-alkoxyphenol, a p-oxyphenol derivative, and a bisphenol.
• the hydrophilic layers thereof may contain a UV absorbing agent such as a benzotriazole compound substituted by an aryl group, a 4-thiazolidone compound, a benzophenone compound, a cinnamic acid ester compound, a butadiene compound, a benzoxazole compound, or a UV absorptive polymer. It is also possible for such UV absorbing agents to be included in above-mentioned hydrophilic colloidal layers.
• a UV absorbing agent such as a benzotriazole compound substituted by an aryl group, a 4-thiazolidone compound, a benzophenone compound, a cinnamic acid ester compound, a butadiene compound, a benzoxazole compound, or a UV absorptive polymer. It is also possible for such UV absorbing agents to be included in above-mentioned hydrophilic colloidal layers.
• the hydrophilic layers thereof may contain a water-soluble dyestuff to serve as a filter dyestuff or for another purpose such as preventing irradiation.
• Such dyes as mentioned above include, for example, an oxonol, hemioxonol, styryl, merocyanine, cyanine or azo dye.
• an oxonol, hemioxonol, styryl, merocyanine, cyanine or azo dye include, for example, an oxonol, hemioxonol, styryl, merocyanine, cyanine or azo dye.
• the hemioxonol dyes and the merocyanine dyes are particularly useful.
• the light-sensitive materials of the invention may contain an anticolor-fogging agent such as a hydroquione derivative, an aminophenol derivative, a gallic acid derivative or an ascorbic acid derivative.
• an anticolor-fogging agent such as a hydroquione derivative, an aminophenol derivative, a gallic acid derivative or an ascorbic acid derivative.
• This invention may also be applied to a multilayered multicolor photographic light-sensitive material comprising a support bearing thereon at least two light-sensitive layers having different spectral sensitivity from each other.
• a multilayered color photographic material is provided, on the support thereof, with at least one each of red-, green- and blue-sensitive emulsion layers, respectively.
• the layers may be arranged in any order, as appropriate. It is usual for the combination to contain cyan forming couplers in a red-sensitive emulsion layer, magenta forming couplers in a green-sensitive emulsion layer and yellow forming couplers in a blue-sensitive emulsion layer, however, a different combination may also be adopted, if necessary.
• the photographic emulsion layers and other hydrophilic colloidal layers thereof may be coated on the support or other layers thereof by various well-known coating methods such as a dip-coating method, a roller-coating method, a curtain-coating method or an extrusion-coating method.
• various well-known coating methods such as a dip-coating method, a roller-coating method, a curtain-coating method or an extrusion-coating method.
• the preferred methods are described in, for example, U.S. Patent Nos. 2,681,294, 2,761,791 and 3,526,528.
• the support of the above-mentioned photographic light-sensitive materials may be, for example, baryta paper, polyethylene-coated paper, synthetic polypropylene paper, glass plate, cellulose acetate film, cellulose nitrate film, polyvinyl acetal film, polypropylene film, polyester film such as polyethylenetereph- thalate film or polystyrene film, each of which is ordinarily used and may suitably be selected according to the intended use of the photographic light-sensitive materials.
• the above-mentioned supports may also be sublayered, if required.
• the photographic light-sensitive materials containing the core/shell type silver halide emulsions relating to the invention may be exposed to light and, after then, developed by any conventional process.
• a black-and-white developer is an alkaline solution containing a developing agent such as a hydroxybenzene, an aminophenol or an aminobenzene and, in addition, it may also contain a sulfite, carbonate, bisulfite, bromide or iodide of an alkali metal salt.
• a developing agent such as a hydroxybenzene, an aminophenol or an aminobenzene
• it may also contain a sulfite, carbonate, bisulfite, bromide or iodide of an alkali metal salt.
• the above-mentioned photographic light-sensitive material is for color photographic use, it may be color developed by any convention color developing process. In a reversal process, the development is performed using a black-and-white developer followed by exposure to white-light or a treatment in a bath containing a fogging agent, and further a color- development is made with an alkaline developer containing a color developing agent.
• a developing agent such as a
• a typical example of such a process is that, after color- development, a bleach-fixing is made and, if required, followed by washing and a stabilizing process; another example thereof is that, after color-developing, bleaching and fixing are separately performed and, if required, washing and a stabilizing process are further performed.
• a color developer comprises an aqueous alkaline solution containing a color developing agent.
• the color developing agents include, for example, well-known aromatic primary amine developers such as a phenylenediamine, e.g..
• the color developers may also additionally contain a pH buffer and/or an antifoggant. They may also further contain, if required, any one of: a water softener, a preserver, an organic solvent, a development accelerator, a dye forming coupler, a competing coupler, a fogging agent, an auxiliary developer, a thickener, a polycarboxylic acid chelating agent, and an oxidation inhibitor.
• the photographic emulsion layers are ordinarily bleached after they are color-developed.
• the bleaching process may be carried out either simultaneously with the fixing process, or independently.
• the bleaching agents for this purpose include, for example, the compounds of a polyvalent metal such as iron (III), cobalt (IV), chromium (VI) or copper (II) or a peroxy acid, a quinone, or a nitroso compound.
• a silver iodide emulsion EM-1 was prepared so as to contain silver iodide in an amount of 4 mol% thereof.
• Both Solutions of E-1 and B-1 were added to Solution A-1 in a double-jet precipitation method, at 40° C, by making use of a mixing stirrer described in Japanese Patent O.P.I. Publication Nos. 92523/1982 and 92524/1982. While the double-jet precipitation method was being applied, the pAg and pH value thereof and the rates of addition of both Solutions of E-1 and B-1 were controlled as shown in Table 1. The pAg and pH values were controlled by adjusting the flow rates of both Solutions F-1 and H-1 by making use of a roller-tube pump capable of changing flow rates.
• the resultant matter was desalted and washed by a conventional method and dispersed in an aqueous solution containing 125g of ossein gelatin. An aggregate amount of the dispersed matter was then adjusted with distilled water to 4,800ml.
• 'grain size' means a length of one side of a cube which is equivalent to a grain in volume.
• Emulsion EM-2 was prepared, by using the following 5 kinds of solution, in such a process that the above-mentioned Emulsion EM-1 was used as a seed emulsion to which silver iodobromide shells each having a silver iodide content of 2 mol% were provided.
• Both Solutions of E-2 and B-2 were added to Solution A-2 in a double-jet precipitation method, at 40 C, by making use of a mixing stirrer described in Japanese Patent O.P.I. Publication Nos. 92523/1982 and 92524/1982, by taking a time for 32.5 minutes at a minimum so as not to produce any small grains during the addition thereof.
• the pAg and pH value thereof and the adding rates of both Solutions of E-2 and B-2 were controlled as shown in Table 2.
• the pAg and pH values were controlled by adjusting the flow rates of Solutions F-2, G-2 and B-2 by making use of a roller-tube pump capable of changing flow rates.
• the resultant matter was desalted and washed by a conventional process, and was dispersed in an aqueous solution containing 128.6g of ossein gelatin. An aggregate amount thereof was then adjusted to 3,000ml with distilled water.
• Emulsion EM-3 was prepared, by using the following 5 kinds of solution, in such a process that the above-mentioned Emulsion EM-2 was used as a seed emulsion to which silver iodobromide shells each having a silver iodide content of 2.6 mol% were provided.
• Both Solutions of E-3 and B-3 were added to Solution A-3 in a double-jet precipitation method, at 40° C, by making use of a mixing stirrer described in Japanese Patent O.P.I. Publication Nos. 92523/1982 and 92524/1982, by taking a time for 56.5 minutes at a minimum so as not to produce any small grains during the addition thereof.
• the pAg and pH values and the rates of addition of both Solutions of E-3 and B-3 were controlled as shown in Table 3.
• the pAg and pH values were controlled by adjusting the flow rates of Solutions F-3, G-3 and B-3 by making use of a roller-tube pump capable of changing flow rates.
• the resultant matter was desalted and washed by a conventional process, and was dispersed in an aqueous solution containing 128.1g of ossein gelatin. After then, an aggregate amount thereof was adjusted to 3,000mi with distilled water.
• Emulsion EM-4 was prepared, by using the following 7 kinds of solutions, in such a process that the above-mentioned Emulsion EM-3 was used as a seed emulsion to which a highly iodide-containing shell, an intermediate shell and the outermost shell were provided.
• Both Solutions of E-4 and B-4 were added to Solution A-4 in a double-jet precipitation method, at 50° C, by making use of a mixing stirrer described in Japanese Patent O.P.I. Publication Nos. 92523/1982 and 92524/1982, by taking a time for 46.6 minutes.
• Solution B-4 Solution C-4 was added thereto.
• Solution D-4 was added thereto and after 25.5 minutes, the addition of Solution D-4 was completed.
• the pAg and pH values and the rates of addition of the solutions of E-4, B-4, C-4 and D-4 were controlled as shown in Table-8.
• the pAg and pH values were controlled by adjusting the flow rates of Solutions F-4 and G-4 by making use of a roller-tube pump capable of changing flow rates.
• the resultant matter was desalted and washed by a conventional method and was dispersed in an aqueous solution containing 127g of ossein gelatin. After then, the resulted dispersed matter was adjusted to an aggregate amount of 3,000ml with distilled water.
• the resultant emulsion was an excellent monodispersed emulsion of 1.60 ⁇ m in average grain size and of 11 % in the variation coefficient of grain size distribution.
• the emulsion EM-4 is a core/shell type silver iodobromide emulsion having the silver iodide contents of 15 mol%, 5 mol% and 0.3 mol% in the order arranged from the inside of each grain. (i.e.,
• the emulsions, EM-5, EM-6, EM-7, EM-8 and EM-9, were prepared in the same manner as in (1-4) of the above-mentioned preparation example, except that they employed the 7 kinds of solutions described in (1-4) of the preparation example and added KBr, KI and 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene in the amounts designated in Tables 4, 5, 6 and 7, respectively.
• the resultant emulsions were monodispersed emulsions each of 1.60u.m in average grain size and their variation coefficients of grain size distribution were 17%, 15%, 12%, 16% and 16%, respectively.
• the emulsions, EM-10 through EM-26, were prepared in the same manner as in (1-4) of the Preparation Example 1, except that the 7 kinds of solutions designated in the Preparation Example 1 and, KBr, KI and 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene were used in the amounts designated in Tables 4, 5, 6 and 7, respectively.
• emulsions were monodispersed, having an average grain size of 1.60 ⁇ m and the variation coefficients of the grain size distributions of 10%, 10%, 11%, 12%, 13%, 18%, 19%, 35%, 39%, 10%, 11%, 11%. 11%, 12%, 12%, 12% and 13%, respectively.
• the emulsions, EM-28 and EM-29 were prepared in the same manner as in (1-4) of the Preparation Example 1, except that the 7 kinds of solutions designated in the Preparation 'Example 1 and, KBr, KI, and 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene were used in the amounts designated in Tables 4, 5, 6 and 7, respectively.
• Emulsion EM-27 was prepared in such a manner that the pAg and pH values and rates of addition thereof were changed to those designated in Table-9 in the course of the mixation thereof; and the Emulsion EM-30 and 31 were also prepared as shown in Table-10.
• the above-mentioned emulsions were monodispersed, having the average grain size of 1.6 ⁇ m and the variation coefficients of the grain size distributions of 9%, 18%, 19%, 32% and 34%, respectively.
• the emulsion EM-32 was prepared in the same manner as in (1-4) of the Preparation Example 1, except that the 7 kinds of solutions designed in the Preparation Example 1 and, KBr, KI and 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene were used in the amounts designated in Tables 4, 5, 6 and 7, respectively, and the pAg and pH values and rates of addition of E-4, B-4, C-4 and D-4 thereof were further changed to those designated in Table-11 during mixing; and the Emulsion EM-33 was prepared as shown in Table-12, and Emulsion EM-34 was further prepared as shown in Table-13, respectively.
• the above-mentioned emulsions were the monodispersed having the average grain size of 1.6u.m and the variation coefficients of the grain size distributions of 10%, 10% and 12%, respectively.
• the emulsions EM-35, EM-36 and EM-37 were prepared in the same manner as in (1-4) of the Preparation Example 1, except that the 7 kinds of solutions designated in the Preparation Example 1 and, KBr, KI and 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene were used in the amounts designated in Tables 4, 5, 6 and 7, respectively.
• Emulsions EM-38 and EM-39 were prepared in such a manner that the pAg and pH values and the rates of addition of E-4, B-4, C-4 and D-4 thereof were changed to those designated in Table 12 during mixing.
• the above-prepared emulsions were monodispersed having an average grain size of 1.6 ⁇ m and variation coefficients of the grain size distributions of 12%, 14%, 13%, 9% and 11 %, respectively.
• the effects on the multilayer sensitivity were examined with a multilayered color light-sensitive material having three light-sensitive layers, a blue light-sensitive layer, a green light-sensitive layer and a red light-sensitive layer.
• a material of the invention comprising a light-sensitive material having two layers, one is an emulsion-coated layer containing a coupler and the other is a protective layer.
• magenta-color forming coupler a magenta-color forming coupler was used. Namely. 1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-t-amylphenoxyacetamido)benzamido]-5-pyrazolone was used in this example to serve as the magenta color forming coupler.
• Tricresyl phosphate (TCP) was used as the high boiling solvent for dissolving the couplers.
• the couplers were oil-protect-dispersed by a conventional method.
• the silver iodobromide emulsions (EM-4 through EM-9) described in the aforementioned preparation examples were chemically sensitized by conventional method and were additionally green-color-sensitized with a green-color-sensitive spectral sensitizer.
• DNP ditertiary nonyl phenol
• DBP dibutyl- terephthalate
• each of the samples was exposed to light through a wedge in an ordinary method; and for measuring the graininess, each of the samples was exposed to light through a square wave frequency wedge; and each of them was processed in the following steps:
• the composition of the processing liquids used in the above-mentioned processing steps are shown below:
• the improvement effects on the sharpness of an image were detected by obtaining a MTF (which stands for Modulation Transfer Function) so as to compare the samples with each other with respect to the MTFs obtained when each spatial frequency is 10 lines per mm.
• MTF Modulation Transfer Function
• the standard deviation of a density value variation is obtained when scanning a dye image having a ratio of a RMS to a dye image density of Dmin. +0.8 with a micro-densitometer having a round scanning aperture of 25 urn, and 1.000 times this value is expressed as a value relative to the standard deviation value of a controlled sample regarded as a value of 100. The higher the value, the coarser the graininess. That is not preferred.
• an exposure quantity (at a logarithmic value) giving an optical density with a fog of +0.1 and an exposure quantity (at a logarithmic value) giving a maximum optical density of -0.1 is, the wider an exposure range is. It is, therefore, preferred that a difference therebetween is greater.
• the silver iodobromide emulsions (EM-4 through EM-9) described in the above-mentioned preparation examples were chemically sensitized by conventional methods so as to prepare a color photographic material comprising 9 layers including 3 kinds of light-sensitive layers, a blue light-sensitive layer, a green light-sensitive layer and a red light-sensitive layer, in the following manner.
• the emulsions EM-4 to EM-9 each chemically sensitized were changed only in a green-sensitive high speed layer that was the 5th layer. In each sample, the same and common emulsions were used in the other light-sensitive layers than the 5th layer.
• the sample was prepared by coating the aforementioned layers, in sequence, on a transparent support which comprises a sub-layered cellulose triacetate film and bears thereon an antihalation layer (containing 0.40g of black colloidal silver and 3.0g of gelatin).
• an antihalation layer containing 0.40g of black colloidal silver and 3.0g of gelatin.
• a low speed red-sensitive emulsion layer (hereinafter called an RL layer) containing 1.4g of a low speed red-sensitive silver iodobromide emulsion layer (containing silver iodide of 7 mol%) which was color-sensitized to red; 1.2g of gelatin; 0.65g of tricresyl phosphate (TCP) in which 0.8g of 1-hydroxy-4(,8-methoxyethylaminocarbonylmethoxy)-N-[ ⁇ -(2,4-di-t-amylphenoxy)butyl]-2-naphthamide [hereinafter called C-1]; 0.075g of 1-hydroxy-4-[4-(1-hydroxy-b-acetamido-3,6-disulfo-2-naphthylazojphenoxy]-N-[b-(2,4-di-t-amyl- phenoxy)-butyl-2-naphthamido.d
• a high speed red-sensitive emulsion layer (hereinafter called an RH layer) containing 1.3g of a high speed red-sensitive silver iodobromide emulsion; 1.2g of gelatin; and 0.23g of TCP in which 0.21 g of cyan coupler (C-1); and 0.02g of colored cyan coupler (CC-1) were dissolved.
• An intermediate layer (hereinafter called an IL layer) containing 0.04g of dibutyl phthalate (hereinafter called DBP) in which 0.07g of 2,5-di-t-octylhydroquinone ⁇ hereinafter called an antistaining agent (HQ-1) ⁇ were dissolved; and 0.8g of gelatin.
• DBP dibutyl phthalate
• HQ-1 ⁇ antistaining agent
• a low speed green-sensitive emulsion layer (hereinafter called a GL layer) containing 0.80g of a low speed silver iodobromide emulsion (containing silver iodide of 6 mol%) which was green-sensitized; 2.2g of gelatin; 0.95g of TCP in which0.8g of 1-(2,4,6-trichlorophenyl)3-[3-(2,4-di-t-amylphenoxyacetamido]-5-pyrazolone [hereinafter called a magent coupler (M-1)]; 0.15g of 1-(2,4,6-trichlophenyl)-4-(1-naphthylazo)-3-(2-chloro-5-octadecenylsuccineimidoanilino)-5-pyrazolone [herein after called a colored magenta coupler (CM-1)]; and 0.016g of the DIR compound (D-1) were dissolved.
• a high speed green-sensitive emulsion layer (hereinafter called a GH layer) containing 1.8g of a high speed green-sensitive silver iodobromide emulsion which was green-sensitized; 1.9g of gelatin; 0.25g of TCP in which 0.20g of the magenta coupler (M-1); and 0.049g of the colored magenta coupler (CM-1) were dissolved.
• a yellow filter layer (hereinafter called a YC layer) containing 0.15g of yellow colloidal silver; 0.11g of DBP in which 0.2g of the antistaining agent (HQ-1) was dissolved; and 1.5g of gelatin.
• a low speed blue-sensitive emulsion layer (hereinafter called a BL layer) containing a low speed silver iodobromide emulsion (containing silver iodide of 4 mol%) which was blue-sensitized; 1.9g of gelatin; and 0.6g of TCP in which 1.5g of «-pivaloyl- ⁇ -(1-benzyl-2-phenyl-3,5-dioxoimidazolidine-4-yl)-2'-chloro-'-[ ⁇ -dodecyloxycarbonyl)ethoxycarbonyl]acetanilide [hereinafter called Y-1] was dissolved.
• a high speed blue-sensitive emulsion layer (hereinafter called a BH layer) containing 1.0g of a high speed silver iodobromide emulsion which was color-sensitized to blue; 1.5g of gelatin; and 0.65g of TCP in which 1.30g of yellow coupler (Y-1) were dissolved.
• a protective layer (hereinafter called a PR layer) containing 2.3g of gelatin.
• the prepared multilayered color photographic material was exposed to white light through a wedge and processed in the above-mentioned processing steps.
• a green optical sensitivity was obtained therefrom by a sensitometry. (The definition of sensitivity is the same as that in the case of the above-mentioned single layer coated sample.)
• Table-14 shows the results of the fog, sensitivity, graininess, exposure range and sharpness off the single-color-sensitive coated sample as well as the results of the multilayered sample.
• the core/shell type emulsions (EM-4 and EM-7) each provided with a highly iodide-containing shell, an intermediate shell and the outermost shell in accordance with the invention are capable of displaying remarkably higher sensitivity, as compared with such conventional core/shell type emulsions as EM-5 and EM-9 neither of which were provided with any intermediate shell interposed between the outermost shell that is a low iodide-containing shell and a highly iodide-containing shell so as to contain iodide in an intermediate amount; such a core!shell type emulsion as EM-6 provided with an intermediate shell but having no reasonable difference in iodide contents between a highly iodide-containing shell and the intermediate shell; and such a core/shell type emulsion as EM-8 having no reasonable difference in iodide contents between the outermost shell and an intermediate shell.
• Table-15 shows the effects of varying the iodide content in highly iodide-containing shells, prepared using the emulsions EM-4, EM-5 and EM-9 to EM-18 of the above-mentioned Preparation Example and in the same manner as in Example 1.
• the emulsions EM-10 to EM-15 are examples in which the intermediate shells and the outermost shells each have constant iodide content while the iodide content of the highly iodide-containing shells was varied. It is found therefrom that the higher the iodide content in a highly iodide-containing shell, the better the sensitivity.
• An emulsion having an iodide content of 40 or 50 mol% in the highly iodide-containing shell thereof as EM-15 or EM-17 tends to show a reduced sensitizing effect. This is supposedly due to the fact that the grain size distribution was broadened, and it is found that the emulsions of the invention may be able to enjoy a satisfactory sensitization effect as compared with any emulsions each having the same highly iodide-containing shell, such as EM-16 and EM-18, which are other than those of the invention.
• Table-16 shows, similarly to the above, the effects of the iodide contents in the low iodide-containing shells and the intermediate shells.
• Table-17 similarly shows the effects of the grain size distribution.
• the sensitizing effects may effectively be obtained than in a monodispersed emulsion having a narrow grain size distribution.
• the emulsions each having a broader distribution are inferior, in sharpness, to the emulsions having a narrower distribution.
• the monodispersed emulsions of the invention are more preferred to serve as an emulsion excellent in sensitivity, fog and sharpness.
• Table-18 also shows the effects of varying the volume of a highly iodide-containing shell.
• the sensitizing effects of the invention is rather less when the volume of a highly iodide-containing shell is small, say 5%. (as in EM-33), though the emulsion may be sensitized a little, and the effects may be improved when using an emulsion provided with a highly iodide-containing shell having such a relatively greater volume as 12% in EM-32, 22% in EM-33 and 41% in EM-34.
• Table-19 further shows the effects of whole iodide content in the whole silver iodobromide.
• the emulsions each having a relatively higher whole iodide content such as EM-35 and EM-36, show a reduced sensitizing effect; and that the emulsions each having a relatively lower whole iodide content, such as EM-38, are poor in graininess, sharpness and exposure range; and further that it is preferable to use the emulsions of the invention of which the iodide contents are within a suitable range, so that a high sensitivity, an excellent graininess, an excellent sharpness and a broad exposure range may be obtained.

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• 1985
  • 1985-04-23 JP JP8665985A patent/JPS61245151A/ja active Granted
• 1986
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