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 and a plurality of outer shells each provided to the outside of the inner core and substantially composed of silver bromide or silver iodobromide.
• a silver iodobromide emulsion which is an object of the invention have 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 orthodox process therefor is to improve the quantum efficiency of a silver halide used.
• the observation of solid state physics and the like have positively been adopted.
• such an emulsion comprises the so-called normal crystal grains each having both of the (100) and (111) planes in various ratios. It is well-known that a high sensitization may be achieved by making use of the above-mentioned normal crystal grains.
• 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; 'Joumal of Photographic Science', No. 24, p. 198, 1976; and the like each describe, respectively, that a development activity is increased or a high sensitization is realized by making use of multilayered type silver halide grains applied with a plurality of shells on the outside of the inner cores of the grains.
• West German Patent No. 2,932,650; Japanese Patent O.P.I. Publication Nos. 2417/1976. 17436/1976 and 11927/1977; and the like describe the respective silver halide grains each provided with a covering layer through a halogen substitution so as to serve as the outermost layer of the silver halide grain.
• These silver halide grains are practically unable to serve as any negative type emulsion, because a fixing time may be shortened thereby, however, to the contrary, a development may be thereby inhibited, so that a satisfactory sensitivity may not be obtained.
• 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 an outermost shell containing silver iodide of 0 to 10 mol%, a highly iodide-containing shell provided inside the outermost shell, of which silver iodide content is at least 6 mol% higher than that of the outermost shell, and an intermediate shell provided therebetween the silver iodide content of the intermediate shell being at least 3 mol% higher than that of the outermost shell, and at least 3 mol% lower that of the high iodide-containing shell.
• 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.
• the volume of an outermost shell is preferably from 4 to 70% of a whole grain and, more preferably, from 10 to 50% thereof.
• the volume of a highly iodide-containing shell is preferably 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 an intermediate shell is preferably from 5 to 60% of a whole grain and, more preferably, from 20 to 55% thereof.
• Such highly iodide-containing shell is allowed to be at least one part of an inner core and, more preferably, a separate inner shell is made present inside the highly iodide-containing shell.
• the iodide content of such an 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 such an inner core is preferably from 0.05 to 0.8um and, more preferably, from 0.05 to 0.4 ⁇ m.
• the iodide content of a 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 mon- odispere type.
• 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:
• a multilayered color light-sensitive material having the features mentioned in the Item (7), it is desired that a 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.
• a 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 3.0um; and the configuration thereof may be any one of an octahedron, a cube, a sphere, a flat plate and the like and, more preferably, an octahedron.
• an inner shell and a highly iodide-containing shell may be the same, or the such inner shell may separately be provided to the inside of the highly iodide-containing shell.
• An inner shell and a highly iodide-containing shell, the highly iodide-containing shell and an intermediate shell, and the intermediate shell and the outermost shell are allowed to be adjacent to each other; and, in addition, it is also allowed that 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 be any one of a monolayered shell having a uniform composition, a group of the shells which comprises a plurality of shells each having a uniform composition and changes its composition stepwise, a continuous shell which changes its composition continuously in its arbitrary shell, and the combination thereof.
• the above-mentioned highly iodide-containing shell and intermediate shell may be used plurally or in only a pair.
• the inner cores of the silver halide grains of the invention can be prepared in such a process as described in, for example, P. Glafkides, 'Chimie et Physique Photographique', published by Paul Mon- tel, 1967; G.F. Duffin, 'Photographic Emulsion Chemistry', published by The Focal Press, 1966; V.L. Zelikman et al, 'Making and Coating Photographic Emuision', published by The Focal Press, 1964; and the like.
• Such processes include any one of an acid method process, a neutral method process, an ammonia method process and the like.
• a single-jet precipitation process, a double-jet precipitation process or the combination thereof may also be applied to make a reaction of a soluble silver salt on a soluble halide.
• the so-called reverse precipitation process in which grains may be formed in presence of silver ions in excess.
• the so-called 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.
• a pAg value is varied in accordance with a reaction temperature and the kinds of silver halide solvents when an inner core is prepared, and is preferably from 2 to 11. It is also preferred to use a silver halide solvent, because a grain-forming time may be shortened. Such a silver halide solvent as those of ammonia or thioether which is well-known 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.
• a single shell or a plurality of arbitrary shells may be interposed between a highly iodide-containing shell comprising silver halide grains and an intermediate shell.
• Such highly iodide-containing shells may be provided in such a process as that a desalting step is applied, if necessary, to the resulted 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 applied.
• the halogen substitution process may be applied in the manner, for example, 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.
• it is desired, in this process to adjust the concentration of an aqueous iodide compound solution to 10. 2 mol% or lower and then to add the solution by taking a time for not shorter than ten minutes.
• the processes of newly coating a silver halide over to an inner core include, for example, the so-called double-jet precipitation process and controlled double-jet precipitation process each in which an aqueous halide solution and an aqueous silver nitrate solution are simultaneously added.
• 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.
• a pAg value is varied in accordance with a reaction temperature and the kinds and the amount of silver halide solvents used. The same conditions as those for the case of the above-mentioned inner core are preferably applied to this case.
• a pAg value is desirably from 7 to 11.
• a double-jet precipitation process and a controlled double-jet precipitation process are preferred more than others.
• the intermediate shells of the silver halide grains of the invention may be provided in such a manner 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 having 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 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.
• the arbitrary shells may be interposed singly or plurally, if required, between an inner core and a highly iodide-containing shell, the highly iodide-containing shell and an intermediate shell, and the intermediate shell and the outermost shell, respectively; and it is allowed not necessarily to interpose such an arbitrary shell.
• the above-mentioned arbitrary shells may be provided in the same processes as in the case of providing the aforementioned highly iodide-containing shell.
• an ordinary desalting may also be carried out in the course of providing the adjacent shell, if required, or 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 obtained in such a method as 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- ⁇ 3 (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 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; a flocculation method; and the like.
• 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 such an optical sensitizer as cyanine or merocyanine dyes including, for example, zeromethine, monomethine, dimethine, trimethine and the like.
• cyanine or merocyanine dyes including, for example, zeromethine, monomethine, dimethine, trimethine and the like.
• a combination of spectrally sensitizing dyes is often used parti cularly for a supersensitization.
• An emulsion is also allowed to 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 of light but capable of displaying supersensitizing characteristics.
• spectrally sensitizing dyes a dye having no spectrally sensitizing characteristic in itself or a substance substantially incapable of absorbing any visible rays of light but capable of displaying supersensitizing characteristics.
• the above-mentioned technics may be optionally selected in accordance with a wavelength region, sensitivity and the like to which a sensitization is to be applied and with the purpose and use of a light-sensitive material.
• the core/shell type silver halide crystals of the invention may also be treated in various chemical sensitization processes applicable to ordinary type emulsions.
• the chemical sensitization may be carried out in such a process as described in, for example, H. Frieser. 'Die Grundlagen der Photographische Pro- zesse mit Silberhalogeniden', Akademische Verlagsgesselschaft, 1968, pp. 675-734. Namely, there may be used, independently or in combination, a sulfur sensitization process using therein a compound or active gelatin containing sulfur capable of reacting on silver ions; a reduction sensitization process using therein a reducible substance; a noble-metal sensitization process using therein 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, 2,410,689, 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 silane compound and the like may be used. They typically include those described in U.S. Patent Nos.
• a gold complex salt and besides the metal complex salts of the VIII group of the periodic table such as platinum. iridium, palladium and the like may 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 in a combination of not less than two of the above-mentioned chemical sensitization processes.
• An amount of silver to be coated is not limited but preferably from not less than 1000mg/m 2 to not more than 15000mg/m 2 and, more preferably, from not less than 2000mg/m 2 to not more than 10000mg/m 2 .
• the light-sensitive layers each containing the above-mentioned grains may be present on both sides of a support.
• each of the shells of the core/shell type emulsions of the invention various kinds of dopants may be doped.
• the inner dopants thereof onclude, for example, silver, sulfur, iridium, gold, platinum, osmium, rhodium, tellurium, selenium, cadmium, zinc, lead, thallium, iron, antimony, bismuth, arsenic and the like.
• the water-soluble salts or complex salts thereof may be made coexist therewith when forming each of the shells.
• a hydrophilic colloid ordinarily used in a silver halide emulsion may also be used.
• hydrophilic colloids there are not only a gelatin regardless of the lime-or acid-treated but also the following; namely, a gelatin derivative including, for example, those prepared through a reaction of gelatin on either one of an aromatic sulfonyl chloride, acid chloride, acid anhydride, isocyanate or 1,4-diketone, 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 is allowed to further contain various kinds of additives ordinarily 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 mercap- tothiazole, a mercaptobenzthiazole, a mercaptobenzimidazole and a mercaptothiadiazole; a triazole, e.g., an aminotriazole, a benzotriazole and a nitrobenzotriazole; a tetrazole, e.g., a mercaptotetrazole, particularly including 1-phenyl-5-mercaptotetrazole and the like; a mercaptopyrimidine; a mercaptotriazine, e.g., a thiok
• the photographic emulsion layers and the other hydrophilic colloidal layers thereof are allowed to 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, methyloldimethylhydantoine and the like; a dioxane derivative such as 2,3-dihydroxydioxane and the like; an active vinyl compound such as 1,3,5-triacryloyl-hexahydro-S-triazine, 1,3- - vinylsulfonyl-2-propanol and the like; an active halide such as 2,4-dichloro-6-hydroxy-S-triazine
• the photographic emulsion layers and the other hydrophilic colloidal layers thereof are allowed to contain the dispersed matters of a water- insoluble or hardly soluble synthetic polymer with the purposes of improving the dimensional stability thereof and the like.
• the polymers may be used the polymers, 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, styrene and the like; 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-unsaturated dicarboxylic acid, hydroxyalkyl (metha)acrylate, sulfoalkyl (metha)-acrylate, styrenesulfonic acid or the like.
• alkyl (metha)acrylate alkoxyalkyl (metha)acrylate, glycidyl (metha)acrylate, (metha)-acrylamide, a vinyl ester such as vinyl acetate
• the silver halide photographic light-sensitive materials relating to the invention are also allowed to contain, if required, a development accelerator such as benzyl alcohol, a polyoxyethylene compound and the like; an image stabilizer such as those of 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 and the like
• an image stabilizer such as those of 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
• the surfactants which are allowed to be contained therein there may use a coating aid, a permeability improving agent 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.
• the antistatic agents there may effectively use 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, and the like.
• the matting agents include, for example, a polymethacrylic acid methyl, a polystyrene, an alkalisoluble 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, an alkylvinylether-maleic acid copolymer and the like.
• 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 are different from each other in 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, heat processable light-sensitive materials, and the like. 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 relating to the invention to a color photographic light-sensitive material, the silver halide emulsion is to 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 crystals and having been prepared to be red-, green-and blue -sensitive, respectively.
• the above-mentioned materials include, for example, the magenta couplers such as that of 5-pyrazolone, pyrazolobenzimidazole, pyrazolotriazole, cyanoacetylcoumaran, open- chained acylacetonitrile or the like; the yellow couplers such as that of acylacetoamide (e.g., a ben- zoylacetanilide and a pivaloylacetanilide) or the like; and the cyan couplers such as that of naphthol, phenol or the like.
• magenta couplers such as that of 5-pyrazolone, pyrazolobenzimidazole, pyrazolotriazole, cyanoacetylcoumaran, open- chained acylacetonitrile or the like
• the yellow couplers such as that of acylacetoamide (e.g., a ben- zoylacetanilide and a pivalo
• the above-mentioned couplers are desired to be the non-diffusible ones each having, in the molecules thereof, a hydrophobic group that is 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 are also allowed to contain, besides 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.
• the undermentioned well-known anti-discoloring agent may jointly be used, and color image stabilizers may also be used independently or in combinaton.
• anti-discoloring agents include, for example, a hydroquinone derivative, a gallic acid derivative, a p-alkoxyphenol, a p-oxyphenol derivative, a bisphenol and the like.
• the hydrophilic layers thereof may contain such a UV absorbing agent 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, a UV absorptive polymer, and the like. It is also allowed that such UV absorbing agents may be fixed into the above-mentioned hydrophiiic .coiioidai layers.
• the hydrophilic layers thereof are allowed to contain a water-soluble dyestuff to serve as a filter dyestuff or with the various purposes of preventing an irradiation and the like.
• Such dyes as mentioned above include, for example, an oxonol, hemioxonol, styryl, merocyanine, cyanine or azo dye.
• the hemioxonal dyes and the merocyanine dyes are particularly useful:
• the light-sensitive materials of the invention are allowed to contain such anticolor-fogging agent as a hydroquione derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative and the like.
• 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 layer arrangement order may be freely selected according to the necessity. It is a usual 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 occasion demands.
• the photographic emulsion layers and other hydrophilic colloidal layers thereof may be coated on the support or other layers thereof in various well-known coating methods such as a dip- coating method, a roller-coating method, a curtain- coating method, an extrusion-coating method and the like.
• coating methods such as a dip- coating method, a roller-coating method, a curtain- coating method, an extrusion-coating method and the like.
• the advantageous methods thereof are described in, for example, U.S. Patent Nos. 2,681,294, 2,761,791 and 3,526,528.
• the supports of the above-mentioned photographic light-sensitive materials include, for example, a baryta paper, a polyethylene-coated paper, a synthetic polypropylene paper, a glass plate, a cellulose acetate film, a cellulose nitrate film, a polyvinyl acetal film, a polypropylene film, a polyester film such as a polyethyleneterephthalate film, a polystyrene film, and the Iike, each of which is ordinarily used and may suitably be selected according to the purposes of using the photographic light-sensitive materials.
• the above-mentioned supports may also be sublayered, if occasion demands.
• 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 in any well-known process being normally used.
• a black-and-white developer is an alkaline solution containing such a developing agent as a hydroxybenzene, an aminophenol, an aminobenzene or the like and, beside the above, it is also allowed to contain a sulfite, carbonate, bisulfite, bromide or iodide each produced with an alkali metal salt.
• a developing agent as a hydroxybenzene, an aminophenol, an aminobenzene or the like
• a sulfite, carbonate, bisulfite, bromide or iodide each produced with an alkali metal salt.
• a development is made with a black-and-white developer at first, and a white-light exposure is applied or a treatment is made in a bath containing a fogging agent, and further a color-development is made with an alkaline developer containing a color developing agent.
• a typical example of such processes is that, after color-developing, a bleach-fixing is made and, if required, a washing and a stabilizing are then made; and the other example thereof is that, after color-developing, a bleaching and a fixing are separately made and, if required, a washing and a stabilizing are further made.
• a color developer comprises an aqueous alkaline solution containing a color developing agent.
• the color developing agents include, for example, such a well-known aromatic primary amine developer as a phenylenediamine, e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethyl aniline, 4-amino-N-ethyl-N-,8-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 4-amino-3-methyl-N-ethyl-N-,B-methoxyethylaniline, and the like.
• the color developers are also allowed to contain a pH buffer, an antifoggant and the like, besides the above. They may further contain, if required, 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, an oxidation inhibitor and the like.
• the photographic emulsion layers are ordinarily bleached after they were color-developed. Such bleaching process may be carried out either simultaneously with or separately from a fixing process.
• the bleaching agents for this purpose include, for example, the compounds of such a poly-valent metal as iron (III), cobalt (IV), chromium (VI), copper (11) and the like; a peroxy acid, a quinone, a nitroso compound, and the like.
• a bleaching or bleach-fixing liquid with various additives as well as the bleaching accelerators such as those described in, for example, U.S. Patent Nos. 3,042,520 and 3,241,966, Japanese Patent Examined Publication Nos. 8506/1967 and 8836/1967, and the like; the thiol compounds such as those described in, for example, Japanese Patent O.P.I. Publication No. 65732/1978.
• 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 adding rates of both Solutions of E-1 and B-1 were controlled as shown in Table1. 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 resulted matter was desalted and washed in an ordinary method and dispersed in an aqueous solution containing 125g of ossein gelatin. After then, an aggregate amount of the dispersed matter was 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 resulted matter was desalted and washed in an ordinary process, and was dispersed in an aqueous solution containing 128.6g of ossein gelatin. Afer then, an aggregate amount thereof was 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 thereof and the adding rates 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 resulted matter was desalted and washed in an ordinary process, and was dispersed in an aqueous solution containing 128.1g of ossein gelatin. Afer then, an aggregate amount thereof was adjusted to 3,000ml 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 thereof and the adding rates 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 resulted matter was desalted and washed in an ordinary process 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 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 there used 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 resulted emulsions were the monodispersed emulsions each of 1.60 ⁇ 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 the monodispersed having the average grain size of 1.60u.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 adding rates thereof were changed to those designated in Table-9 in the course of the mixation thereof; and the Emulsions EM-30 and 31 were also prepared as shown in Table-10.
• the above-mentioned emulsions were the 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 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, and the pAg and pH values and adding rates of E-4, B-4, C-4 and D-4 thereof were further changed to those designated in Table-11 in the course of the mixation thereof; 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 1.6 ⁇ 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 adding rates of E-4, B-4, C-4 and D-4 thereof were changed to those designated in Table 12 in the course of the mixation thereof.
• the above-prepared emulsions were the monodispersed having the 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 tight-sensitive material having three light-sensitive layers, a blue light-sensitive layer, a green tight-sensitive layer and a red light-sensitive layer.
• the description will be made about the case that the invention was applied to the sample 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 magent color forming coupler.
• TCP tricresyl phosphate
• the couplers were oil-protect-dispersed in an ordinary process.
• the silver iodobromide emulsions (EM-4 through EM-9) described in the afore-mentioned preparation examples were chemically sensitized in an ordinary process and were further green-color-sensitized, when they were being chemically sensitized, with a green-color-sensitive spectral sensitizer in an ordinary process.
• 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 reciprocal of a quantity of exposure which gives an optical density of fog +0.1 on a characteristic curve.
• the reciprocal numbers each are expressed as a value relative to the sensitivity of the comparative example which is regarded as the value 100.: The higher a value of such a reciprocal number is, the higher a sensitivity is. Therefore, a high reciprocal number is preferred.
• 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 which stands for 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 25a, 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 is, the more coarse a graininess is. That is not preferred.
• the sample was prepared by coating the under-mentioned layers in order 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 amount of every material to be added in light-sensitive materials is indicated by an amount per square meter, and both of a silver halide emulsion and a colloidal silver are indicated in terms of a silver content.
• 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-( ⁇ -methoxyethylaminocarbonylmethoxy)-N-[s-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide [hereinafter called C-1]; 0.075g of 1-hydroxy-4-[4-(1-hydroxy- ⁇ -acetamido-3,6-disulfo-2-naphthylazo)phenoxy]-N-[b, (2,4-di-t-amylphenoxy)butyl-2-naphthamido.dis
• 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 ct- pivaloyl-a-(1-benzyl-2-phenyl-3,5-dioxoimidazolidine-4-yl)-2'-chloro-5'-[a-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 of 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 an remarkably higher sensitivity, as compared with such a conventional core/shell type emulsion as EM-5 and EM-9 each not 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.
• the other coreishell type emulsions than those of the invention tend to broaden the grain size distribution and increase fogs, so that they may not be preferred to use, also from these points of view.
• Table-15 shows the effects of the iodide contents in highly iodide-containing shells resulted by making use of the emulsions EM-4, EM-5 and EM-9 through EM-18 of the above-mentioned Preparation Example and in the same manner as in Example 1.
• the emulsions-EM-10 through EM-15 are the examples in which the intermediate shells and the outermost shells each were made of the same while the iodide contents in the highly iodide-containing shells were varied. It is found therefrom that the higher the iodide content in a highly iodide-containing shell is, the higher the sensitivity is.
• Such 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 be less in 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 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 little, say 5%, (as in EM-33), though the emulsion may be sensitized a little, and the effects may be enjoyed more 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 an 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, are less in 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
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