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
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/07—Substances influencing grain growth during silver salt formation
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/08—Sensitivity-increasing substances
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/0051—Tabular grain emulsions
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/0051—Tabular grain emulsions
  • G03C2001/0055—Aspect ratio of tabular grains in general; High aspect ratio; Intermediate aspect ratio; Low aspect ratio
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/0051—Tabular grain emulsions
  • G03C2001/0058—Twinned crystal
• • 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
  • G03C2001/0357—Monodisperse emulsion
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/08—Sensitivity-increasing substances
  • G03C2001/0854—Indium

Definitions

• This invention relates to a silver halide photographic emulsion applicable to a silver halide photographic light-sensitive material and, particularly, to a silver halide photographic emulsion having improved in sensitivity and graininess.
• a silver halide grain As is aimed at making sensitivity and image quality higher have so far been developed in progress by the art.
• JP OPI Publication Japanese Patent Publication Open to Public Inspection
• the surface area of the former tabular-shaped silver halide grain becomes larger than that of the latter when both silver halide grains have each the same volume. Therefore, the former silver halide grain has such an advantage that a more higher sensitivity can be provided, because more sensitizing dyes can be adsorbed to the surface of the former.
• JP OPI Publication No. 63-92942/1988 discloses a technique in which a core having a high silver iodide content is contained inside a tabular-shaped silver halide grain; JP OPI Publication No. 63-151618/1988 discloses a technique in which a hexahedral tabular-shaped silver halide grain is used; and JP OPI Publication No. 63-163451/1988 discloses a technique in which a tabular-shaped silver halide grain is so used as to have a ratio of a grain thickness to the farthest distance from and to the twinned crystal surfaces of not higher than 5. These techniques show each the effects on sensitivity and graininess.
• JP OPI Publication Nos. 61-160739/1986 and 62-260137/1987 disclose each the techniques in which a polyvalent metal salt such as those of lead and cadmium is added; and JP OPI Publication No. 1-121844/1989 discloses a technique in which an iron compound is doped in a narrow band-gapped layer comprising a grain having a multilayered structure.
• JP OPI Publication Nos. 2-20852/1990, 2-20853/1990, 2-20854/1990, 2-222653/1990 and 2-224545/1990 discloses the technique in which a polyvalent metal and a novel ligand are used in combination.
• Another object of the invention is to provide a silver halide photographic emulsion capable of providing a silver halide photographic light-sensitive material excellent in latent image preservability.
• the silver halide grains applicable to the invention comprise substantially silver bromide and/or silver iodobromide.
• substantially comprise silver bromide and/or silver iodobromide --- herein means that it may also contain other silver halides than silver bromide or silver iodobromide, such as silver chloride, provided that the effects of the invention shall not be spoiled.
• the content thereof is preferably not more than 1 mol%.
• the silver halide grains to be contained in a silver halide photographic emulsion of the invention may have either such a regular crystal form as a cube, an octahedron and a tetradecahedron, or such an irregular crystal form as the spherical form and a tabular form.
• these grains those having any ratio of ⁇ 100 ⁇ plane to ⁇ 111 ⁇ plane may be used.
• twinned crystal herein means a silver halide crystal having one or more twinned crystal planes in a grain.
• the classification of the twinned crystal forms is detailed in, for example, A Report made by Klein and Moisar in "Photographishe Korrespondenz", Vol. 99, p.99 and, ibid., Vol. 100, p. 57.
• an average aspect ratio of the thickness of a tabular-shaped grain to a grain size thereof is to be preferably less than 5, more preferably within the range of not less than 1.1 to less than 4.5 and, particularly not less than 1.2 to less than 4.
• the above-mentioned average aspect ratio can be obtained by averaging the ratios of the grain sizes of the whole tabular-shaped grains to the thicknesses thereof.
• the diameter of a silver halide grain is indicated by the projected area thereof converted into a circular form, (i.e., the diameter of a circle having the same projected area as that of the grain).
• the diameter thereof is to be preferably within the range of 0.1 to 5.0 ⁇ m, more preferably 0.2 to 4.0 ⁇ m and, particularly 0.3 to 3.0 ⁇ m.
• any one of those may be used, such as a polydisperse type emulsion having a relatively wide grain-size distribution and a monodisperse type emulsion having a relatively narrow grain-size distribution.
• a monodisperse type emulsion is preferably used.
• an amount of silver halide by weight contained within the range of ⁇ 20% of an average grain size r is to be preferably not less than 60% of the whole silver halide grain by weight, more preferably not less than 70% and particularly not less than 80% thereof.
• an average grain size r is herein defined as a grain size ri obtained when maximizing a product ni x ri3 wherein ni represents a frequency of grains having a grain size ri (and, the significant figures are three and the figure of the lowest column is rounded).
• a grain size herein means a diameter obtained when the projected image of a silver halide grain is converted into a circular image having the same area.
• the above-mentioned grain size can be obtained in the following manner for example.
• a subject grain is magnified 10,000 to 70,000 times by an electron microscope; the magnified grain image is photographed; and the printed grain size or the projected area thereof is practically measured, (provided, the number of the subject grains are not less than 1,000 grains at random.)
• Grain size distribution(%) (Standard deviation/Average grain size) x 100
• a highly monodisperse type emulsion preferably applicable to the invention has a grain size distribution of not more than 20% and preferably not more than 15%.
• the silver iodide content thereof is to be within the range of, preferably not less than 0.1 mol% to not more than 15 mol%, more preferably not less than 5 mol% to not more than 12 mol% and particularly not less than 6 mol% to not more than 10 mol%, in terms of an average silver iodide content of the whole silver halide grain.
• the silver halide composition of the silver halide grains relating to the invention shall be no special limitation. It is therefore allowed that the silver halide composition inside a grain may substantially be uniform, may also be continuously varied, or may be of the so-called core/shell type. For achieving a sensitization effectively, a core/shall type silver halide grain is used. In this case, the grains are to be provided inside with a highly silver iodide containing phase having a silver iodide content of preferably not less than 8 mol%, more preferably within the range of 10 to 45 mol% and particularly 20 to 40 mol%.
• the outermost layer thereof is formed of a silver iodide containing phase having a silver iodide content less than that of the highly silver iodide containing phase.
• the silver iodide content thereof is preferably not more than 10 mol%, more preferably not more than 6 mol% and particularly within the range of 0 to 4 mol%.
• the interlayer is to have a silver iodide content within the range of preferably 10 to 22 mol% and more preferably 12 to 20 mol%.
• the differences of the silver iodide contents between the outermost layer and the interlayer and between the interlayer and the highly silver iodide containing phase are each preferably not less than 6 mol% and more preferably not less than 10 mol%.
• the volume of the outermost layer is preferably within the range of preferably 4 to 70% of the whole grain and more preferably 10 to 50 mol%.
• the volume of the highly silver iodide containing phase is preferably within the range of preferably 10 to 80% of the whole grain and more preferably 20 to 50 mol%.
• the volume of the interlayer is preferably within the range of preferably 5 to 60% of the whole grain and more preferably 20 to 55 mol%.
• the above-mentioned phases may be substantially any single phases having a uniform composition, the group consisting of plural phases having uniform compositions each variable stepwise, any continuous phases having the compositions continuously variable in any one of the phases, or the combination of the above-mentioned phases.
• the silver halide grains applicable to the silver halide photographic emulsions of the invention in the following manner.
• An aqueous solution containing protective colloid and seed grains are put in a reaction chamber in advance and, if required, silver ions, halogen ions or silver halide fine grains are supplied thereto, and the seed grains are grown up to be crystallized thereby.
• the seed grains can be prepared in a single-jet method or a controlled double-jet method of which has been well-known in the art.
• the silver halide thereof is substantially comprised of silver bromide or silver iodobromide.
• the seed grains may be either of the regularly crystallized forms such as a cube, an octahedron and a tetradecahedron, or of the irregularly crystallized forms such as a spherical form and a tabular form.
• the regularly crystallized forms such as a cube, an octahedron and a tetradecahedron
• the irregularly crystallized forms such as a spherical form and a tabular form.
• those having any ratio of ⁇ 100 ⁇ plane to ⁇ 111 ⁇ plane may be used. It is also allowed to use those having a complex of the above-mentioned crystal forms or those having a mixture of variously crystallized grains.
• twinned crystal silver halide grains having two ⁇ 111 ⁇ twinned planes parallel to each other.
• a variety of methods well-known in the art can be used.
• a single-jet method, double-jet method and a triple-jet method may be used in combination. It is also allowed to use a method for controlling a pAg and a pH so as to meet the silver halide growing rate, in a liquid phase in which silver halide is produced.
• a silver halide photographic emulsion of the invention can also be prepared in any one of an acidic method, a neutral method and an ammoniacal method.
• halide ions and silver ions may be mixed up at the same time or one of them may also be mixed in the other. It is also allowed that, while taking the critical silver halide crystal growing rate into consideration, halide ions and silver ions are added gradually or at the same time while controlling the pH and pAg thereof in a mixing chamber, so that the silver halide crystals may be grown up. It is further allowed that, in any step for preparing silver halide, the silver halide composition of grains may be varied in a conversion method. It is still further allowed that halide ions and silver ions are formed into silver halide fine grains and the fine grains are supplied to a mixing chamber.
• a silver halide photographic emulsion of the invention it is allowed to make present a well-known silver halide solvent such as ammonia, thioether and thiourea.
• a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt (including the complex salts thereof), a rhodium salt (including the complex salts thereof) and an iron salt (including the complex salts thereof) may be so added as to contain the above-mentioned metal elements inside and/or on the grain surfaces. It is also allowed that a reduction-sensitization nuclei may be provided inside and/or on the grain surfaces by putting them in a suitable reducible atmosphere.
• the silver halide grains to be contained in a silver halide emulsion of the invention may be those capable of forming a latent image mainly on the surfaces thereof or mainly inside thereof.
• unnecessary soluble salts may be removed from a silver halide photographic emulsion of the invention or may be contained as they are in the emulsion.
• the salts may be removed in the method described in, for example, Research Disclosure (hereinafter abbreviated to RD), No. 17643, Paragraph 11.
• the indium compounds to be contained in a silver halide photographic emulsion of the invention may be monovalent, divalent or trivalent. Among them, a trivalent one is preferable, because it is readily available and stable.
• halide an oxide, a sulfide, a nitride and a hydroxide
• indium compounds such as a sulfate, a nitrate, an oxalate, a halogenocomplex salt, an organic indium compound and an indium acid salt.
• InCl3 ⁇ nH2O (NH4)3 ⁇ [InF6] InBr3 ⁇ nH2O K3InCl6 ⁇ 2H2O InI3 ⁇ nH2O (NH4)2 ⁇ [InCl5(H2O)] In2O3 (CH3)4NInCl4 In2S3 [C5H5N ⁇ HCl]3InCl4 InN (NH4)2InBr5 ⁇ H2O In(OH)3 ⁇ nH2O K3InBr6 ⁇ 2H2O In2(SO4)3 ⁇ nH2O (CH3)4NInBr4 In(NO3)3 ⁇ 3H2O In In2(CrO4)3 ⁇ 6H2O)
• a method for adding the additive generally well-known in the art to the silver halide photographic emulsion it is allowed to use a method for adding the additive generally well-known in the art to the silver halide photographic emulsion.
• these compounds are dissolved in advance in a suitable organic solvent typified by an alcohol or in water and the solution thereof is then added in.
• a method for dispersing a spectrally sensitizing dye such a dispersion method as described in, for example, JP Application No. 4-714/1990 can be used.
• a metal complex of the invention is added in an amount exceeding the solubility thereof in an aqueous system without substantially having any organic solvent and/or any surfactant, so that the resulting solution is dispersed mechanically in solid fine grains having a grain size of not larger than 1 ⁇ m and the resulting dispersion is then added to the silver halide photographic emulsion of the invention.
• the indium compound may be added at the point of time in the course of carrying out any one of the preparing steps for a silver halide photographic emulsion. However, it may be added preferably within the period from a step for forming grains to the point of time before starting a chemically sensitizing step and more preferably at the point of time before completing the growth of silver halide grains.
• a solution containing the indium compound is directly added in the silver halide photographic emulsion.
• the indium compound is added in advance to an aqueous solution containing halide ions, an aqueous solution containing silver ions or a solution containing silver halide fine grains.
• a solution containing the indium compound may be added instantly or may also be added continuously by making use of any arbitrary function.
• an indium compound is to be added in an amount within the range of preferably not less than 1.0x10 ⁇ 8 mols to not more than 1.0x10 ⁇ 1 mols per mol of silver halide grain used, more preferably not less than 1.0x10 ⁇ 7 mols to not more than 1.0x10 ⁇ 2 mol and most preferably not less than 1.0x10 ⁇ 6 mols to not more than 1.0x10 ⁇ 3 mols.
• the optimum conditions can be selected and, about the conditions other than the above, the well-known processing conditions may be referred to, for example, JP OPI Publication Nos. 61-6643/1986, 61-14630/1986, 61-112142/1986, 62-157024/1987, 62-18556/1987, 63-92942/1988, 63-151618/1988, 63-163451/1988, 63-220238/1988 and 63-311244/1988.
• a silver halide photographic emulsion of the invention can be applied preferably to a silver halide color photographic light-sensitive material.
• an additive applicable thereto can be added in such a dispersion method as described in, for example, RD 308119, p. 1007, paragpraph XIV.
• a color photographic light-sensitive material is prepared by making use of a silver halide photographic emulsion of the invention, such a support as described in, for example, RD 17643, p. 28, RD 18716, pp. 647-648 and RD 308119, p. 1009, paragraph XVII can be used.
• auxiliary layer as a filter layer and an interlayer each described in, for example, the foregoing RD 308119, paragraph VII-K may be provided.
• a color photographic light-sensitive material applied with a silver halide photographic emulsion of the invention may have various layer arrangements such as a normal layer arrangement, an inverse layer arrangement and a unit layer arrangement each described in, for example, RD 308119, paragraph VII-K.
• a silver halide photographic emulsion of the invention can preferably be applied to a variety of color photographic light-sensitive materials typified by a color negative film for general or movie use, a color reversal film for slide or TV use, a color paper, a color positive film and a color reversal paper.
• a color photographic light-sensitive material applied with a silver halide photographic emulsion of the invention can be developed in such an ordinary method as described in, for example, the foregoing RD 17643, pp.28-29, RD 18716, p. 615 and RD 308119, paragraph XIX.
• Monodispersed silver iodobromide octahedral grains were prepared by making use of monodispersed silver iodobromide regular crystal seed emulsion (of 0.0775 mols in terms of silver content) having an average size (i.e., a side length converted into a cube having the same volume) of 0.28 ⁇ m, a silver iodide content (in a uniform composition) of 2 mol% and a size distribution of 18.9% and the following three kinds of solutions.
• the silver iodobromide regular crystal seed emulsion was added to Solution A1 and, while keeping the resulting solution at 40°C and stirring it, Solution B1 was acceleratingly added thereto at the same flow rate by taking 150 minutes.
• the pH and pAg thereof were controlled by making use of an aqueous acetic acid solution and an aqueous potassium bromide solution as shown in Table 1.
• a desalting treatment was carried out in an ordinary method and 56 g of ossein gelatin was then added. After that, the pH and EAg thereof were adjusted (at 40°C) to be 6.0 and 100mV, so that Em-A was prepared.
• Em-A was proved to be comprised of monodispersed octahedral grains (containing iodine of 2 mol%) having an average grain size of 1.0 ⁇ m.
• Table 1 Amount of silver added 0% ⁇ 10% ⁇ 100% pH 9.0 ⁇ 9.0 ⁇ 8.0 pAg 9.7 ⁇ 9.7 ⁇ 10.5
• Em-B was prepared in the same manner as in Em-A, except that the following solution was used in place of Solution B1 used for preparing Em-A. From the result of observing Em-B through a scanning electron microscope, Em-B was proved to be comprised of monodispersed octahedral grains (containing iodine of 4.4 mol%) having an average grain size of 1.0 ⁇ m. However, in the preparation, the adding rate and the pAg were adjusted a little so as to inhibit the small grain production and to uniform the final grain configuration to be octahedral.
• Em-C and Em-D were each prepared in the same manner as in Em-A, except that Solution B1 used for preparing Em-A was replaced by Solutions B1-1 and B1-2 as shown in Table 2, respectively.
• Em-C and Em-D were each proved to be comprised of monodispersed octahedral grains (containing iodine of 4.5 mol% in Em-C and 6 mol% in Em-D) having an average grain size of 1.0 ⁇ m, respectively.
• the adding rate and the pAg were adjusted a little so as to inhibit the small grain production and to uniform the final grain configuration to be octahedral.
• Em-E, Em-F, Em-G and Em-H were each prepared in the same manner as in Em-A, Em-B, Em-C and Em-D, except that lead nitrate was added, in an amount of 1.0x10 ⁇ 4 mols per mol of silver based on the whole silver content, to Solution A1, respectively.
• Em-I, Em-J, Em-K and Em-L were each prepared in the same manner as in Em-E, Em-F, Em-G and Em-H, except that lead nitrate was replaced by indium (III) chloride, respectively.
• Em-E through Em-L From the results of observing Em-E through Em-L through a scanning type electron microscope, they were each proved to be monodisperse type octahedral grains having an average grain size of 1.0 ⁇ m, respectively.
• Em-A A part of Em-A was heated up to 50°C and dissolved. Sensitizing dyes (A) and (B) were added thereto in the amounts of 100 mg and 90 mg per mol of silver halide, respectively. The resulting mixture was then adsorbed for 15 minutes. Further, sodium thiosulfate pentahydrate, chloroauric acid and ammonium thiocyanate were added thereto in the amounts of 3.5x10 ⁇ 6 mols, 1.0x10 ⁇ 6 mols and 4.0x10 ⁇ 4 mols per mol of silver halide, respectively.
• Emulsion-1 was prepared.
• Sensitizing dyes (A) and (B) were also used for preparing Emulsion-13.
• Emulsion-2 through Emulsion-12 were each prepared in the same manner as in Emulsion-1, except that Em-A was replaced by Em-B through Em-L, respectively.
• Coated samples 101 through 112 were each prepared by coating the resulting Emulsion-1 through Emulsion-3 on a subbed triacetyl cellulose support in accordance with the following coating formulas and the resulting coated samples were then dried up.
• Layer 1 A green-sensitive silver halide emulsion layer
• Emulsion An amount of silver coated 2.5 g/m2 Magenta coupler (M-1) 0.01 mols/mol of Ag Colored magenta coupler (CM-1) 0.005 mols/mol of Ag DIR compound (D-1) 0.0002 mols/mol of Ag HBS-I (Tricresyl phosphate, TCP) 0.22 g/m2
• Emulsified dispersion of yellow colloidal silver and 2,5-di-t-octyl hydroquinone, and H-I Sodium 2,4-dichloro-6-hydroxy-s-triazine
• the resulting coated samples 101 through 112 were each exposed wedgewise to green light, they were processed in the following processing steps. And, the characteristic curves thereof were made out. Then, the fog density, relative sensitivity and RMS graininess of each sample were each obtained.
• the relative sensitivity was indicated by a value relative to the reciprocal of an exposure quantity capable of giving a density of a fog density + 0.1; and the RMS graininess was indicated by a value relative to the value of the standard deviation of a density obtained when scanning a dye image having a density of a fog density + 0.4 through a microdensitometer having a circular-shaped scanning aperture of 25 ⁇ m.
• composition of the processing solutions used in the processing steps were as follows.
• Core/shell type silver iodobromide twinned crystal grains having a low aspect ratio were prepared by making use of monodispersed spherical silver bromide twinned crystal grains having an average grain size of 0.3 ⁇ m and a grain-size distribution of 16.8% (of which the proportion of two parallel twinned crystals was 89% in number) for serving as the seed grains, and the following solutions.
• a fine-grained emulsion comprising gelatin of 3% by weight and silver iodide grains (having an average grain size of 0.04 ⁇ m)
• a fine-grained emulsion comprising gelatin of 3% by weight and silver iodobromide grains (having a silver iodide content of 1 mol% and an average grain size of 0.04 ⁇ m)
• the procedures for preparing Solutions D2 and E2 were as follows.
• Solution A2 was kept at 70°C, pAg 7.8 and pH 7.2 in a reaction chamber and, while stirring well, a seed emulsion in an amount equivalent to 0.286 mols was added thereto. Thereafter, Solutions B2, C2 and D2 were each acceleratingly added up so that a proportion of silver added could be 78% by taking 140 minutes in a triple-jet method at a flow rate necessary to make the silver halide composition shown in Table 4. Successively, Solution E2 was added in a proportion of 28% equivalent to the amount of silver added, by taking 10 minutes. The resulting emulsion was further ripened for 10 minutes.
• the pH and pAg were controlled to be the values shown in Table 4, by adding an aqueous potassium bromide solution and an aqueous acetic acid solution to the reaction chamber. After completing the grain formation, the grains were washed in an ordinary method and the pH and pAg thereof were adjusted to be 5.8 and 8.06 at 40°C, respectively.
• the resulting emulsion was an low-aspect monodispersed twinned crystal emulsion having a grain size (i.e., a 1.0 ⁇ m-diameter converted into that of a sphere) equivalent to the 1.18 ⁇ m-diameter of a circle having an average projected area, a grain size distribution of 8.6%, an aspect ratio of 1.3 and a proportion of the grains having two parallel twinned-crystal planes of 86% in number.
• Em-M The resulting emulsion is named Em-M.
• Em-N was prepared in the same manner as in Em-M, except that lead nitrate was added, to Solution B2, in an amount of 1.0x10 ⁇ 4 mols per mol of silver, that corresponded to the standard set by the silver content of the grains already formed.
• Em-O was prepared in the same manner as in Em-N, except that lead nitrate was replaced by indium (III) nitrate.
• Em-P was prepared in the same manner as in Em-M, except that indium nitrate was added, to Solution E2, in an amount of 1x10 ⁇ 4 mols per mol of silver, that corresponded to the standard set by the silver content of the grains already formed.
• Em-Q was prepared in the same manner as in Em-M, except that indium nitrate was added, to the halide solution used when preparing Solution E2, in an amount of 1x10 ⁇ 4 mols per mol of silver, that corresponded to the standard set by the silver content of the grains already formed.
• Em-R was prepared in the same manner as in Em-M, except that, after completing the grain growth, indium nitrate was added in an amount equivalent to 1x10 ⁇ 4 mols per mol of silver and then the emulsion was ripened for 30 minutes before starting a desalting step.
• Em-M From the results of observing the resulting Em-N through Em-R through a scanning type electron microscope, all of the emulsions were each proved to be a low aspect-ratio monodispersed twinned crystal emulsions having the same grain-size, grain size distribution, aspect ratio, proportion of the grains having two parallel twinned crystal planes as in Em-M.
• Em-M A part of Em-M was heated up to 50°C and dissolved. Sensitizing dyes (A) and (B) were each added thereto in the amounts of 110 mg and 100 mg per mol of silver halide, respectively. The resulting mixture was then adsorbed for 15 minutes. Further, sodium thiosulfate pentahydrate, chloroauric acid and ammonium thiocyanate were each added thereto in the amounts of 3.5x10 ⁇ 6 mols, 1.0x10 ⁇ 6 mols and 4.0x10 ⁇ 4 mols per mol of silver halide, respectively. After the resulting mixture was ripened for 120 minutes, 4-hydroxy-6-methyl-(1,3,3a,7)-tetrazaindene was added as a stabilizer and was then cooled down and solidified, so that Emulsion-13 was prepared.
• Emulsion-14 through Emulsion-18 were each prepared in the same manner as in Emulsion 13, except that Em-M was replaced by Em-N through Em-R, respectively.
• Em-M was heated up to 60°C and was then dissolved.
• the pAg of the resulting solution was adjusted to be 9.5.
• indium nitrate in an amount equivalent to 1.0x10 ⁇ 4 mols per mol of silver was added.
• the resulting emulsion was treated in the same manner as in Emulsion-13, so that Emulsion-19 was prepared.
• Emulsion-20 was prepared in the same manner as in Emulsion-19, except that indium nitrate was not added.
• Multilayer-coated samples 201 through 208 were each prepared in the following formulas for the multilayer-coated samples by making use of the Emulsion-13 through Emulsion-20 as the silver iodobromide emulsion I for a high-speed green-sensitive layer (Layer 9).
• the amounts of the compositions added to a silver halide photographic light-sensitive material will be indicated in terms of grams per sq.meter of the light-sensitive material, unless otherwise expressly stated.
• the silver and silver halides used therein will be indicated in terms of the silver contents thereof.
• the sensitizing dyes will be indicated in terms of mol numbers per mol of the silver halides used.
• Layer 3 A low-speed red-sensitive layer
• a silver iodobromide emulsion having an average grain-size of 0.38 ⁇ m and a silver iodide content of 8.0 mol%) 0.50 A silver iodobromide emulsion (having an average grain-size of 0.27 ⁇ m and a silver iodide content of 2.0 mol%) 0.21 Sensitizing dye (SD-1) 2.8x10 ⁇ 4 Sensitizing dye (SD-2) 1.9x10 ⁇ 4 Sensitizing dye (SD-3) 1.9x10 ⁇ 5 Sensitizing dye (SD-4) 1.0x10 ⁇ 4 Cyan coupler (C-1) 0.48 Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.020 High-boiling solvent (Oil-1) 0.53 Gelatin 1.30
• Layer 4 A medium-speed red-sensitive layer
• a silver iodobromide emulsion having an average grain-size of 0.52 ⁇ m and a silver iodide content of 8.0 mol%) 0.62
• a silver iodobromide emulsion having an average grain-size of 0.38 ⁇ m and a silver iodide content of 8.0 mol%) 0.27 Sensitizing dye (SD-1) 2.3x10 ⁇ 4 Sensitizing dye (SD-2) 1.2x10 ⁇ 4 Sensitizing dye (SD-3) 1.6x10 ⁇ 5 Sensitizing dye (SD-4) 1.2x10 ⁇ 4 Cyan coupler (C-1) 0.15 Cyan coupler (C-2) 0.18 Colored cyan coupler (CC-1) 0.030 DIR compound (D-1) 0.013 High-boiling solvent (Oil-1) 0.30 Gelatin 0.93
• Layer 5 A high-speed red-sensitive layer
• a silver iodobromide emulsion (having an average grain-size of 1.00 ⁇ m and a silver iodide content of 8.0 mol%) 0.27 Sensitizing dye (SD-1) 1.3x10 ⁇ 4 Sensitizing dye (SD-2) 1.3x10 ⁇ 4 Sensitizing dye (SD-3) 1.6x10 ⁇ 5 Cyan coupler (C-2) 0.12 Colored cyan coupler (CC-1) 0.013 High-boiling solvent (Oil-1) 0.14 Gelatin 0.91
• Layer 7 A low-speed green-sensitive layer
• a silver iodobromide emulsion having an average grain-size of 0.38 ⁇ m and a silver iodide content of 8.0 mol%) 0.61
• a silver iodobromide emulsion having an average grain-size of 0.27 ⁇ m and a silver iodide content of 2.0 mol%) 0.20 Sensitizing dye (SD-4) 7.4x10 ⁇ 5 Sensitizing dye (SD-5) 6.6x10 ⁇ 4 Magenta coupler (M-1) 0.18 Magenta coupler (M-2) 0.44 Colored cyan coupler (CM-1) 0.12 High-boiling solvent (Oil-2) 0.75 Gelatin 1.95
• Layer 8 A medium-speed green-sensitive layer
• a silver iodobromide emulsion (having an average grain-size of 0.59 ⁇ m and a silver iodide content of 8.0 mol%) 0.87 Sensitizing dye (SD-6) 2.4x10 ⁇ 4 Sensitizing dye (SD-7) 2.4x10 ⁇ 4 Magenta coupler (M-1) 0.058 Magenta coupler (M-2) 0.13 Colored cyan coupler (CM-1) 0.070 DIR compound (D-2) 0.025 DIR compound (D-3) 0.002 High-boiling solvent (Oil-2) 0.50 Gelatin 1.00
• Layer 9 A high-speed green-sensitive layer
• Silver iodobromide emulsion I 1.27 Magenta coupler (M-2) 0.084 Magenta coupler (M-3) 0.064 Colored cyan coupler (CM-1) 0.012 High-boiling solvent (Oil-1) 0.27 High-boiling solvent (Oil-2) 0.012 Gelatin 1.00
• Layer 12 A low-speed blue-sensitive layer
• a silver iodobromide emulsion having an average grain-size of 0.38 ⁇ m and a silver iodide content of 3.0 mol%) 0.22
• a silver iodobromide emulsion having an average grain-size of 0.27 ⁇ m and a silver iodide content of 2.0 mol%) 0.03
• Sensitizing dye SD-8) 4.9x10 ⁇ 4 Yellow coupler (Y-1) 0.75 DIR compound (D-1) 0.010 High-boiling solvent (Oil-2) 0.30 Gelatin 1.20
• Layer 13 A medium-speed blue-sensitive layer
• a silver iodobromide emulsion (having an average grain-size of 0.59 ⁇ m and a silver iodide content of 8.0 mol%) 0.30 Sensitizing dye (SD-8) 1.6x10 ⁇ 4 Sensitizing dye (SD-9) 7.2x10 ⁇ 5 Yellow coupler (Y-1) 0.10 DIR compound (D-1) 0.010 High-boiling solvent (Oil-2) 0.046 Gelatin 0.47
• Layer 14 A high-speed blue-sensitive layer
• a silver iodobromide emulsion (having an average grain-size of 1.00 ⁇ m and a silver iodide content of 10.0 mol%) 0.85 Sensitizing dye (SD-8) 7.3x10 ⁇ 5 Sensitizing dye (SD-9) 2.8x10 ⁇ 5 Yellow coupler (Y-1) 0.11 High-boiling solvent (Oil-2) 0.046 Gelatin 0.80
• a silver iodobromide emulsion (having an average grain-size of 0.08 ⁇ m and a silver iodide content of 1.0 mol%) 0.40 UV absorbent (UV-1) 0.065 UV absorbent (UV-2) 0.10 High-boiling solvent (Oil-1) 0.07 High-boiling solvent (Oil-3) 0.07 Formalin scavenger (HS-1) 0.40 Gelatin 1.31
• An alkali-soluble matting agent having an average particle size of 2 ⁇ m
• Polymethyl methacrylate having an average particle size of 3 ⁇ m
• Lubricant having an average particle size of 3 ⁇ m
• coating aids Su-1 and Su-2 Besides the above-given compositions, coating aids Su-1 and Su-2, a viscosity controller, layer hardeners H-1 and H-2, stabilizer ST-1, antifoggants AF-1 and AF-2 having a weight average molecular weights of 10,000 and 1,100,000 respectively, and antiseptic D1-1 were each added, provided that D1-1 was added in an amount of 9.4 mg/m2.
• the chemical structures of the compounds used in the samples will be shown below.
• the resulting multilayer -coated samples 201 through 208 were each cut into strips. A part of each stripped sample were exposed wedgewise to white light (for an exposure time of 1/100th sec.) and then the fog and sensitivity thereof were evaluated. Another part of each sample were exposed wedgewise to light for an exposure time of 1/100th sec.) and, after storing in the conditions of 55°C and 20%RH for 2 days, they were developed, and the preservability of the latent images were evaluated.
• the development process was carried out by making use of the processing solutions having the same formulas as in Example-1 and by taking the following processing time.
• Table 5 shows the results of the evaluation on the fog production, sensitivity, RMS graininess and latent image preservability of each green-sensitive layer.
• Sensitivity of the samples were obtained in terms of the reciprocals of an exposure quantity necessary for giving a density of a fog density+0.1, and each of the values thereof was expressed by a value relative to the sensitivity of Sample 201 obtained when exposing it to light for 1/100th sec., that was regarded as the reference value of 100.
• the fog densities were expressed by the difference between the fog density of a sample developed in an ordinary process and the fog density of the sample developed in a developing agent-free process.
• Each RMS graininess of the samples was obtained in terms of the standard deviation of the density variations produced when scanning a dye image having a density of a fog density+0.8 through a microdensitometer having an circular scanning aperture of 25 ⁇ m, and each of the resulting RMS graininess was expressed by a value relative to the value obtained from Sample 201 that was regarded as the reference value of 100.
• Each of the latent image preservability was obtained in terms of a sensitivity obtained after completing a preservation and the sensitivity value was expressed by a value relative to the sensitivity obtained by same-day developing the subject sample, that was regarded as the reference value of 100.

Landscapes

• Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Crystallography & Structural Chemistry (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=18338629

Family Applications (1)

Country Status (3)

Families Citing this family (1)

Citations (2)

Family Cites Families (5)

• 1992
  • 1992-12-21 JP JP4340610A patent/JPH06186661A/ja active Pending
• 1993
  • 1993-12-08 EP EP93119804A patent/EP0603654A3/fr not_active Withdrawn
• 1994
  • 1994-11-10 US US08/339,297 patent/USH1550H/en not_active Abandoned

Patent Citations (2)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events