EP0909979B1 - Silberhalogenidemulsion - Google Patents

Silberhalogenidemulsion Download PDF

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Publication number
EP0909979B1
EP0909979B1 EP98119401A EP98119401A EP0909979B1 EP 0909979 B1 EP0909979 B1 EP 0909979B1 EP 98119401 A EP98119401 A EP 98119401A EP 98119401 A EP98119401 A EP 98119401A EP 0909979 B1 EP0909979 B1 EP 0909979B1
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EP
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Prior art keywords
grain
silver
emulsion
grains
silver halide
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EP98119401A
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English (en)
French (fr)
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EP0909979A2 (de
EP0909979A3 (de
Inventor
Katsuhiko Suzuki
Hiromoto Ii
Sadayasu Ishikawa
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Konica Minolta Inc
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Konica Minolta Inc
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051—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
    • G03C1/015—Apparatus or processes for the preparation of emulsions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/16—Methine and polymethine dyes with an odd number of CH groups with one CH group
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups
    • 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
    • G03C2001/0056—Disclocations
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/015—Apparatus or processes for the preparation of emulsions
    • G03C2001/0153—Fine grain feeding method
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials

Definitions

  • the present invention relates to a silver halide emulsion improved in sensitivity, pressure resistance and processability.
  • JP-A 63-220238 and 1-102547 disclose techniques for improving photographic characteristics through the introduction of dislocation lines.
  • JP-A means an unexamined published Japanese Patent Application
  • JP-A 3-175440 discloses a technique of allowing dislocation lines to be concentrated at the edge of tabular grains to improve sensitivity and reciprocity law failure characteristics.
  • JP-A 6-27564 discloses a technique of restricting dislocation lines to fringe portions of tabular grains to improve sensitivity and pressure resistance.
  • a means for introducing dislocation lines is to introduce iodide ions, forming a gap or misfit of the crystal lattice.
  • the presence of the high iodide containing layer with the grain is contemplated to be related to deterioration of photographic performance, such as sensitivity loss due to closely localized lattice defects, lowered pressure resistance and deterioration in processability due to iodide ions released at development.
  • FR-A-2 516 264 discloses a photographic product consisting of a support and at least one photosensible emulsion layer formed from a dispersing medium and tabular grains of silver iodobromide, characterized in that at least 50 % of the total projected surface of the silver iodobromide grains is formed of tabular grains having two principle surfaces parallelly opposed to each other, with a thickness of at least of 0.5 ⁇ m, a diameter of at least 0.6 ⁇ m, the grain diameter being defined as the diameter of a circle, the surface of which equals the grain projected surface, and a mean form index, defined as the relation of the grain diameter to its thickness, which is higher than 8:1, at least one part of these silver iodobromide tabular grains comprising a central area located between their main surfaces, containing a lower proportion of iodine than at least one peripheral portion, which is also located between the principal surfaces.
  • Fig. 1 is an electronmicrograph of a silver halide grain having a silver iodide border.
  • Figs. 2 and 3 illustrate variation of the silver iodide content within a silver halide grain in the direction from the center to the edge.
  • Effects of the present invention are supposed to be attributable mainly to reduction of a high iodide containing layer formed at the time of introducing dislocation lines without lowering the dislocation line introducing efficiency and also to its synergistic effect with grain monodispersity, shallow electron trapping centers and reduction sensitization.
  • the essential of the present invention is that the position of photographic performance deteriorating factors which are concurrently produced with the dislocation lines, is not limited, as in the prior art, but the photographic performance deteriorating factors themselves are reduced.
  • dislocation lines are closely introduced and abrupt variation in silver iodide content produced when introducing the dislocation lines is prevented.
  • the silver iodide content is gradually and continuously varied overall the grain, resulting in close dislocation lines.
  • abrupt variation in the silver iodide content, which is produced along with introduction of the dislocation lines can not be prevented.
  • a silver halide emulsion according to the invention comprises grains in a tabular form (hereinafter, denoted simply as tabular grains).
  • the tabular grains are crystallographically classified as twinned crystals.
  • the twinned crystal is a silver halide crystal having one or more twin planes within the grain. Classification of the twinned crystal form is detailed in Klein & Moisar, Photographishe Korrespondenz, Vol.99, p.100, and ibid Vol.100, p.57.
  • the tabular grains according to the invention are preferably ones having two or more twin planes parallel to the major faces.
  • the twin planes can be observed with a transmission electron microscope, for example, according to the following manner.
  • a coating sample is prepared by coating a silver halide emulsion on a support so that the major faces of tabular silver halide grains are oriented substantially parallel to the support.
  • the sample is cut using a diamond cutter to obtain an approximately. 0.1 ⁇ m thick slice.
  • the twin plane can then be observed with a transmission electron microscope.
  • the spacing between twin planes can be determined according to the following manner. Thus, 1,000 tabular grains exhibiting a cross-section perpendicular to the major faces are selected through transmission electron microscopic observation of the slice and the shortest twin plane spacing of each grain is measured to obtain an arithmetic average thereof.
  • the average twin plane spacing is preferably 0.01 to 0.05 ⁇ m, and more preferably 0.013 to 0.025 ⁇ m.
  • the twin plane spacing can be controlled by selecting an optimal combination of parameters affecting supersaturation at nucleation, such as the gelatin concentration, the kind of gelatin, the temperature, the iodide ion concentration, pBr, pH, the ion supplying rate and the stirring rate. Details of the supersaturation parameter can be referred to, for example, in JP-A 63-92924 and 1-213637.
  • the thickness of the silver halide grains according to the invention can be determined in the following manner.
  • the silver halide grains are subjected to metal deposition, along with latexes for reference from the direction oblique to the grains and electronmicrographs are taken.
  • the shadow length is measured from the electronmicrograph, and the grain thickness can be determined by reference to the latex shadow length.
  • the average grain thickness (d) is defined as di when the product of the frequency (ni) of grain with a thickness (di) and di 3 (i.e., ni x di 3 ) is maximal (with the significant figure being three, and the last digit being rounded off).
  • the number of measured grains is 600 or more at random.
  • the average thickness of the silver halide grains according to the invention is preferably 0.05 to 1.5 ⁇ m, and more preferably 0.07 to 0.50 ⁇ m.
  • the grain size of the silver halide grains according to the invention is represented in terms of an equivalent circle diameter of the projected area of the silver halide grain (i.e., the diameter of a circle having an area equivalent to the projected area of the grain).
  • the tabular grains according to the invention are those having an aspect ratio (or a ratio of grain diameter to grain thickness) of 5 or more and accounting for at least 50% of the total grain projected area, and preferably are those having a 6 to 80 aspect ratio and accounting for at least 60% of the total grain projected area.
  • the grain diameter can be determined by viewing silver halide grains with an electron microscope and measuring the projected area.
  • the average grain diameter (r) is defined as ri when the product of the frequency (ni) of grain with a diameter (ri) and ri 3 (i.e., ni x ri 3 ) is maximal, in which at least 6000 randomly selected grains, are subjected to measurement.
  • the average grain diameter is preferably 0.1 to 5.0 ⁇ m, and more preferably 0.2 to 2.5 ⁇ m.
  • the silver halide emulsion according to the invention is preferably a monodispersed emulsion.
  • the monodispersed emulsion according to the invention has preferably 25% or less of the grain diameter distribution width.
  • the tabular grains according to the invention may be comprised of a core and a shell covering the core.
  • the shell may be formed of one or more layers.
  • the halide composition of the core and shell can optionally be selected.
  • the silver iodide content of the core or shell is preferably 5 mol% or less, and more preferably 3 mol% or less.
  • the core preferably accounts for 1 to 60%, based on the total silver amount, and more preferably 4 to 40%.
  • the average overall iodide content of the tabular grains of the invention is preferably not more than 10 mol%, more preferably not more than 7 mol%, and still more preferably not more than 4 mol%.
  • the silver halide emulsion according to the invention preferably comprises mainly silver iodobromide, and may further comprise other halide, such as chloride.
  • Means for forming the tabular grains according to the invention include a variety of methods known in the art. Thus, single jet addition, controlled double jet addition and controlled triple jet addition can be employed individually or in combination. To obtain highly monodispersed grains, it is important to control the pAg in the grain forming liquid phase, so as to fit the growth rate of silver halide grains.
  • the pAg is to be in the range of 7.0 to 11.5, preferably 7.5 to 11.0, and more preferably 8.0 to 10.5.
  • the flow rate can be selected by referring to JP-A 54-48521 and 58-49938.
  • a silver halide solvent known in the art such as ammonia, thioethers and thiourea may be employed in forming the tabular grains.
  • the tabular grains according to the invention may be grains forming latent images mainly on the grain surface or ones forming latent images mainly in the grain interior.
  • the tabular grains are prepared in the presence of a dispersing medium, i.e., in an aqueous solution containing a dispersing medium.
  • a dispersing medium i.e., in an aqueous solution containing a dispersing medium.
  • the aqueous solution containing a dispersing medium is an aqueous solution in which a protective colloid is formed with gelatin or other compounds capable of forming a hydrophilic colloid (or materials capable forming a binder), and preferably an aqueous solution containing a colloidal protective gelatin.
  • Gelatins used as a protective colloid include alkali-processed gelatin and acid processed gelatin. Preparation of the gelatin is detailed in A. Veis, "The Macromolecular Chemistry of Gelatin", Academic Press (1964).
  • hydrophilic colloids usable as a protective colloid other than gelatin include gelatin derivatives; graft polymers of gelatin and other polymers; proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfuric acid ester; saccharine derivatives such as sodium alginate and starch derivatives; and synthetic hydrophilic polymeric materials such as homopolymers or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacryl amide, polyvinyl imidazole, and polyvinyl pyrazole.
  • gelatin having a jelly strength of at least 200, as defined in
  • the tabular grain emulsion of the invention can be desalted to remove unnecessary soluble salts.
  • the emulsion can also be desalted during grain growth, as described in JP-A 60-138538. Desalting can be conducted according to the method described in Research Disclosure (hereinafter, also denoted as RD) 17643, Section II.
  • the noodle washing method by gelling gelatin and the flocculation method using inorganic salts, anionic surfactants (e.g., polystylenesulfonate) or gelatin derivatives (e.g., acylated gelatin, carbamoyl-modified gelatin).
  • anionic surfactants e.g., polystylenesulfonate
  • gelatin derivatives e.g., acylated gelatin, carbamoyl-modified gelatin.
  • the average silver iodide content of a silver halide grain group can be determined by the EPMA (or Electron Probe Micro Analyzer) method.
  • EPMA Electron Probe Micro Analyzer
  • Characteristic X-ray intensities of silver and iodine which are radiated from individual grains are measured to determine the silver iodide content of each grain. At least 50 grains are subjected to measurement and their average value is determined.
  • distribution of the iodide content is preferably uniform among grains.
  • the relative standard deviation thereof i.e., a standard deviation of the silver iodide content of grains/average value x 100%, is preferably 30% or less, and more preferably 20% or less.
  • At least 50% of the projected area of total silver halide grains is accounted for by tabular grains requiring the condition that the silver iodide content gradually and continuously varies laterally outwardly from the center to the edge of the grain.
  • the said condition can be measured by the EPMA method using beam with a narrow diameter. The condition is further detailed below.
  • a line is drawn on the major face from the center vertically to the edge.
  • Measuring points are set along the line at intervals of 5 to 15% of the line length and the iodide content at each of the points is measured in the direction vertical to the major face, i.e., the iodide content is measured with respect to a cylyndrical portion with a spot diameter of an electron beam and a grain thickness.
  • the spot diameter of the electron beam must be narrowed to 40 nm or less. Taking into account possible damage of a sample, the measurement needs to be made at a temperature of not higher than -100° C. Measurement at each point is to be made over a period of 30 sec.
  • the variation in iodide content between two measuring points is shown as a difference of an iodide content (mol%) between the two points divided by the distance (nm) between the said two points.
  • the variation when the iodide content increases or decreases outwardly from the center, the variation is represented respectively as a positive or negative value.
  • the iodide content variation in the direction of from the center to the edge of the grain is within the range of -0.03 mol%/nm and +0.03 mol%/nm, it is defined that the iodide content gradually and continuously varies outwardly from the grain center to the grain edge.
  • the iodide content variation is preferably within the range of -0.01 mol%/nm and +0.02 mol%/nm, and more preferably within the range of 0.00 mol%/nm and 0.01 mol%/nm.
  • Tabular grains in which the iodide content varies gradually and continuously, are to account for preferably at least 70%, and more preferably at least 90% of the total grain projected area.
  • Halide composition of the tabular grain surface can be determined by the XPS (X-ray Photoelectron Spectroscopy) method.
  • the XPS method is known as a technique for measuring the iodide content of the surface of silver halide grains, as disclosed in JP-A 2-24188.
  • X-ray irradiation destroys a sample so that the iodide content of the outermost surface can not be accurately determined.
  • the inventors of the present invention succeeded in accurately determining the iodide content of the surface by cooling the sample to a temperature at which no destruction of the sample occurred.
  • the procedure of the XPS method employed in the invention is as follows. To an emulsion is added a 0.05% by weight proteinase aqueous solution and stirred at 45° C for 30 min. to degrade the gelatin. After centrifuging and sedimenting the emulsion grains, the supernatant is removed. Then, distilled water is added thereto and the grains are redispersed. The resulting solution is coated on the mirror-finished surface of a silicon wafer to prepare a sample. Using the thus prepared sample, measurement of the surface iodide was conducted using the XPS method.
  • the sample in the measuring chamber was cooled to -110 to -120° C, exposed to X-rays of Mg-K ⁇ line generated at an X-ray source voltage of 15 kV and an X-ray source current of 40 mA and measured with respect to Ag3d5/2, Br3d and I3d3/2 electrons. From the integrated intensity of a measured peak which has been corrected with a sensitivity factor, the halide composition of the surface can be determined.
  • the interior of the grain is referred to as the internal region within the grain to a depth of 50 ⁇ or more from the outermost surface.
  • the silver iodide content of the grain surface is preferably higher than the average overall silver iodide content.
  • the ratio of silver iodide content of grain surface/average silver iodide content is preferably between 1.1 and 8, and more preferably between 1.3 and 5.
  • the silver halide emulsion according to the invention is characterized in that at least 50% of the total grain projected area is accounted for by tabular grains having at least 30 dislocation lines per grain in the fringe portion.
  • the grains having at least 30 dislocation lines per grain in the fringe portion preferably account for at least 60%, and more preferably at least 70% of the total grain projected area.
  • the dislocation lines in tabular grains can be directly observed by means of transmission electron microscopy at a low temperature, for example, in accordance with methods described in J.F. Hamilton, Phot. Sci. Eng. 11 (1967) 57 and T. Shiozawa, Journal of the Society of Photographic Science and Technology of Japan, 35 (1972) 213.
  • Silver halide tabular grains are taken out from an emulsion while ensuring to not apply such a pressure as to cause dislocation in the grains, and are placed on a mesh for electron microscopy.
  • the sample is observed via transmission electron microscopy, while cooled to prevent the grain from being damaged (e.g., printing-out) by the electron beams.
  • the expression "having dislocation lines in the fringe portion” means that the dislocation lines are present in the vicinity of peripheral portions of the tabular grain or in the vicinity of the edges or corners of the grain. More concretely, when the tabular grain is viewed vertically to its major face and the length of a line connecting the center of the major face and the corner of the grain is represented as L, the fringe portion means an outer region other than an inner region bounded by lines connecting points at a distance of 0.50L from the center on the line connecting the center and each of the corners. In this case, the center of the major face is referred to as the center of gravity of the major face.
  • the dislocation lines are localized only in the fringe portion of the grain.
  • the tabular grains having dislocation lines only in the fringe portion account for preferably at least 60%, and more preferably at least 70% of the total grain projected area.
  • the region in which the dislocation lines are localized is preferably an outer region other than an inner region bounded by lines connecting points at a distance of 0.70L (and more preferably 0.80L) from the center.
  • the dislocation lines are directed substantially outwardly from the center to the outer surface (side face), but often snakes.
  • the introduction of the dislocation lines into the tabular grains can be performed using any of the several well-known methods, including addition of an iodide ion containing aqueous solution such as a potassium iodide aqueous solution and a silver salt aqueous solution by the double jet method, addition of an iodide ion solution alone, addition of a fine iodide-containing silver halide grain emulsion, and addition of an iodide ion releasing agent described in JP-A 6-11781.
  • an iodide ion containing aqueous solution such as a potassium iodide aqueous solution and a silver salt aqueous solution by the double jet method
  • addition of an iodide ion solution alone addition of a fine iodide-containing silver halide grain emulsion
  • an iodide ion releasing agent described in JP-A 6-11781.
  • the iodide ion releasing agent is a compound capable of releasing an iodide ion upon reaction with a base or a nucleophilic agent, represented by the following formula: R 1 -I in which R 1 is a univalent organic group.
  • R 1 is preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a heterocyclic group, an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group or a sulfamoyl group.
  • R 1 is preferably an organic group having 30 or less carbon atoms, more preferably 20 or less carbon atoms, and still more preferably 10 or less carbon atoms.
  • R1 is preferably substituted with a substituent. The substituent may be further substituted.
  • Preferred examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a heterocyclic group, an acyl group, an acyloxy group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group or a sulfamoyl group, alkoxy group, an aryloxy group, an amino group, an acylamino group, a ureido group, urethane group, a sulfonylamino group, sulfinyl group, a phosphoric acid amido group, an alkylthio group, a cyano group, sulfo group, carboxy group, a hydroxy group and a nitro group.
  • the iodide ion releasing agent, R 1 -I is preferably iodoalkanes, an iodoalcohol, an iodocarboxylic acid, an iodoamide and their derivatives, and more preferably an iodoamide and an iodoalcohol including their derivatives.
  • Iodoamides substituted by a heterocyclic group is still more preferred, and particularly, a(iodoacetoamido)-benzenesulfonate is most preferred.
  • a nucleophilic agent preferably employed hydroxide ion, sulfite ion, thiosulfate ion, a sulfinate salt, a carboxylic acid salt, ammonia, amines, alcohols, ureas, thioureas, phenols, hydrazines, sulfides or hydroxamic acids. Of these are preferred hydroxide ion and sulfite ion.
  • the emulsion of the invention was prepared using the iodide ion releasing agent with adjusting conditions for releasing an iodide ion.
  • Preferred iodide ion releasing reaction condition are as follows. In the iodide ion releasing reaction during preparation of the emulsion according to the invention, at least 50% of the iodide ion releasing agent added can releases iodide ions preferably within 30 to 180 sec.
  • the iodide ion releasing rate can be measured by monitoring the pAg during reaction.
  • the iodide ion releasing amount can be determined from the pAg employing a calibration curve which was previously prepared using an aqueous soluble iodide such as KI.
  • the iodide ion releasing rate can be controlled with an iodide ion releasing agent, an adding amount of a nucleophilic agent and its concentration, a molar ratio of the iodide ion releasing agent to the nucleophilic agent, a pH and a temperature.
  • the reaction temperature is preferably not higher than 40° C, and more preferably not higher than 35° C.
  • the pBr is preferably not more than 1.50, more preferably not more than 1.30, and still more preferably nit more than 1.10.
  • the addition amount of the iodide ion releasing agent is preferably not more than 3.5 mol%, more preferably not more than 1.5 mol%, and still more preferably not more than 1.0 mol%, based on total silver amount after completing grain growth.
  • the iodide ion releasing reaction is performed preferably at a pH of 9.0 to 12.0, and more preferably 10.0 to 11.0.
  • the molar amount of the nucleophilic agent is preferably 0.25 to 2.0, more preferably 0.50 to 1.5, and still more preferably 0.80 to 1.2 times the iodide ion releasing agent amount, and the pH is preferably 8.5 to 10.5, and more preferably 9.0 to 10.0.
  • the nucleophilic agent is added preferably after starting addition of the iodide ion releasing agent, and more preferably after completing addition of the iodide ion releasing agent.
  • the dislocation line introducing position refers to the portion at which the iodide ion is introduced into the grain.
  • the silver halide emulsion according to the invention comprises tabular grains each having an aspect ratio of 5 or more and further having 30 or more dislocation lines in the fringe portion, in which the silver iodide content gradually and continuously varied in the direction of from the center of the grain to the grain edge.
  • the tabular grains preferably account for at least 30%, more preferably at least 40%, and still more preferably 50% of the total grain projected area.
  • tabular grains each having a silver iodide border preferably account for less than 20% of the total projected area of silver halide grains.
  • the tabular grains having the silver iodide border account for more preferably less than 15%, still more preferably less than 10%, still furthermore preferably less than 5%, and optimally 0% of the total grain projected area. In this case, at least 600 grains needs to be observed.
  • the silver iodide border which is a term defined in the present invention, can be observed in the same manner as for the dislocation lines.
  • the silver iodide border is defined as a border line portion of a width of several nm to several 10 nm, which is observed, by TEM, near the dislocation line introducing position and has a form similar to that of the periphery of the grain.
  • the iodide content at this portion measured by the EPMA method is 8 to 15 mol%.
  • it is a high silver iodide containing phase, which is concurrently produced at the time of introducing the dislocation lines.
  • the ratio of electron beam transmission to scattering is different from other portions, enabling them to be observed by TEM.
  • An exemplary example of the silver iodide border is shown in Fig 1.
  • the tabular silver halide grains each contain at least a polyvalent metal compound in the fringe portion. Allowing the polyvalent metal compound to be occluded within the grain is called metal-doping or doping.
  • the metal-doping is a known technique in the photographic art. It is reported by Leubner that doping an iridium complex into silver halide forms an electron trapping center (The Journal of Photographic Science Vol.31, 93, 1983).
  • a metal compound used in metal-doping is called a metal dopant or simply a dopant.
  • one or more metal dopants can be occluded at any position within the grain.
  • One preferred embodiment is to allow one or more polyvalent metal compounds to be contained in the fringe portion of the tabular grains.
  • metal dopant examples include compounds of metals, such as Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Cd, Sn, Ba, Ce, Eu, W, Re, Os, Ir, Pt, Hg, Tl, Pd, Bi and In.
  • a metal compound to be doped is selected preferably from simple salts and complex salts.
  • a six-coordinate complex In the case of metal complex salts, a six-coordinate complex, a five-coordinated complex, a four-coordinated complex and a two-coordinated complex are preferred, and an octahedral six-coordinate complex or a planar four-coordinate complex is more preferred.
  • the complex may be a single nucleus complex or poly-nucleus complex.
  • Examples of a ligand constituting the complex include CN - , CO, NO 2 - , 1,10-phenthroline, 2,2'-bipyridine, SO 3 - , ethylenediamine, NH 3 , pyridine, H 2 O, NCS - , NCO - , NO 3 - , SO 4 2- , OH-, CO 3 2- , SSO 3 2- , N 3 - , S 2 - , F - , Cl - , Br - and I - .
  • Preferred examples of the metal compound to be doped include K 4 Fe(CN) 6 , K 3 Fe(CN) 6 , Pb(NO 3 ) 2 , K 2 IrCl 6 , K 3 IrCl 6 , K 2 IrBr 6 and InCl 3 .
  • Concentration distribution of the metal dopant within the grain can be determined by gradually dissolving the grain from the surface to the interior and measuring the dopant content at each portion. The following method is exemplarily explained below.
  • a silver halide tabular grain emulsion Prior to determination of the content of the polyvalent compound, a silver halide tabular grain emulsion is subjected to the following pre-treatment. To about 30 ml of the emulsion is added 50 ml of a 0.2% actinase aqueous solution and stirred continuously at 40° C for 30 min. to perform degradation of the gelatin. This procedure is repeated five times. After centrifuging, washing is repeated five times with 50 ml of methanol, two times with 50 ml of 1N nitric acid solution and five times with ultra-pure water, and after centrifuging, only tabular grains are separated.
  • a surface portion of the resulting tabular grains is dissolved with aqueous ammonia or pH-adjusted ammonia (in which the concentration of ammonia or the pH is varied according to the kind of silver halide and the dissolution amount).
  • aqueous ammonia or pH-adjusted ammonia in which the concentration of ammonia or the pH is varied according to the kind of silver halide and the dissolution amount.
  • the outermost surface portion of silver bromide grains can be dissolved to an extent of about 3% from the surface, using 20 ml of 10% aqueous ammonia per 2 g of silver bromide grains.
  • the amount of dissolved silver bromide can be determined in the following manner.
  • the solution After dissolving, the solution is subjected to centrifuging to separate any remaining silver bromide grains and the amount of silver contained in the resulting supernatant can be determined with a high frequency induction plasma mass-spectrometer (ICP-MS), a high frequency induction plasma emission spectral analyzer (ICP-AES) or an atomic absorption spectrometer.
  • ICP-MS high frequency induction plasma mass-spectrometer
  • ICP-AES high frequency induction plasma emission spectral analyzer
  • an atomic absorption spectrometer From the difference in the content of the polyvalent metal compound between the surface-dissolved silver bromide grains and the undissolved silver bromide grains, the amount of the polyvalent metal compound present in about the grain surface of 3% (i.e., it means that silver halide corresponding to about 3% of the total silver amount is dissolved from the surface).
  • a measuring sample is diluted by 100 times with ultra-pure water and the silver content thereof is measured with the ICP-AES method or atomic absorption method.
  • the tabular grains is washed with ultra-pure water and the content of the polyvalent metal compound in the internal direction of the grain can be determined by repeating the dissolution of the grain surface in the same manner as described above.
  • the metal doped in the peripheral region of the tabular grain can be determined by a combination of the ultra-thin slice preparation method aforementioned and the above-described metal determination.
  • the metal dopant occluded in the tabular grains is preferably 1x10 -9 to 1x10 -4 mol, and more preferably 1x10 -8 to 1x10 -5 mol per mol of silver halide.
  • the ratio of the amount of the metal dopant occluded in the peripheral region to that occluded in the central region of the major face is preferably not less than 5, more preferably not less than 10, and still more preferably not less than 20.
  • the metal dopant can be occluded by adding, to the substrate grains, a fine silver halide grain emulsion which has previously metal-doped.
  • the metal is doped preferably in an amount of 1x10 -7 to 1x10 -1 mol, and more preferably 1x10 -5 to 1x10 -3 mol per mol of fine silver halide grains.
  • the fine grain emulsion is prepared by using a halide solution containing the metal dopant.
  • the halide composition of the fine silver halide grains may be any one of silver bromide, silver iodide, silver iodobromide, silver chlorobromide and silver iodochlorobromide, and preferably is the same as that of the substrate grains.
  • the fine silver halide grains containing a metal dopant are deposited on the substrate grains at any time after completing fine grain formation and before starting chemical sensitization, and preferably at a time after completion of desalting and before starting chemical sensitization.
  • the fine grains are deposited with the metal dopant onto the most active portion of the substrate grain, through adding a fine grain emulsion to the substrate grain emulsion in the state of a low salt concentration. As a result, the fine grains can effectively be deposited onto the peripheral region including the corner and edge of the tabular grains.
  • the fine silver halide grains are not coagulated or adsorbed directly onto the substrate grains, but when the fine silver halide grains are concurrently present with the substrate grains, the fine grains are dissolved and recrystalized onto the substrate grains.
  • the fine grains can not be observed and any epitaxially protruded portion is not observed on the substrate grainy surface.
  • the fine silver halide grains are added preferably in an amount of 1x10 -7 to 0.5 mol, and more preferably 1x10 -5 to 1x10 -1 mol per mol of the substrate grains.
  • the physical ripening condition to deposit the fine silver halide grains is optionally selected at 30 to 70° C and over a period of 10 to 60 min.
  • At least a part of the tabular grains contained in the silver halide emulsion according to the invention internally contain reduction sensitization center.
  • the statement "internally contain reduction sensitization center” means having fine silver nucleus formed by reduction sensitization in the interior of the grain, and this accomplished by subjecting to reduction sensitization treatment before completing silver halide grain growth.
  • the interior of the grain an inner portion of 90% or less of the grain volume and preferably 70% or less, and still more preferably 50% or less.
  • the reduction sensitization is conducted by adding a reducing agent to a silver halide emulsion or a reaction mixture for growing grains.
  • the silver halide emulsion or mixture solution is subjected to ripening or grain growth at a pAg of 7 or less, or at a pH of 7 or more.
  • the method of adding a reducing agent is preferred.
  • a preferable reducing agent are cited thiourea dioxide, ascorbic acid or its derivative, and a stannous salt.
  • the addition amount thereof is preferably 10 -8 to 10 -2 mol, and more preferably 10 -6 to 10 -4 mol per mol of silver halide.
  • a silver salt preferably aqueous soluble silver salt.
  • aqueous silver salt is preferably silver nitrate.
  • Ripening at a high pH is conducted by adding an alkaline compound to a silver halide emulsion or reaction mixture solution for growing grains.
  • the alkaline compound are usable sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and ammonia.
  • an alkaline compound other than ammonia is preferably employed because of lowering an effect of ammonia.
  • the silver salt or alkaline compound may be added instantaneously or over a period of a given time. In this case, it may be added at a constant rate or accelerated rate. It may be added dividedly in a necessary amount. It may be made present in a reaction vessel prior to the addition of aqueoussoluble silver salt and/or aqueous-soluble halide, or it may be added to an aqueous halide solution to be added. It may be added apart from the aqueous-soluble silver salt and halide.
  • Silver halide grains contained in the emulsion according to the invention preferably contain a silver chalcogenide nucleus containing layer in the interior of the grain.
  • the silver chalcogenide nucleus containing layer is located preferably in an outer region other than an inner region of 50% (more preferably 70%) of the grain volume.
  • the silver chalcogenide nucleus containing layer may be or not in contact with the grain surface.
  • the silver chalcogenide nucleus contained in the silver chalcogenide nucleus containing layer is definitely distinguished from a chalcogenide chemical sensitization nucleus, in a point that it forms a latent image forming center or not.
  • the silver chalcogenide nucleus is lower in electron trapping capability than the chemical sensitization nucleus.
  • the silver chalcogenide nucleus meeting such requirements can be formed according to a method described later.
  • the silver chalcogenide nucleus containing layer is located preferably in the outside of the dislocation line introducing portion.
  • the silver chalcogenide nucleus can be formed by adding a compound capable of releasing a chalcogen ion.
  • the silver chalcogenide nucleus is preferably a silver sulfide nucleus, silver selenide nucleus and silver telluride nucleus, and more preferably a silver sulfide nucleus.
  • the compound capable of releasing a chalcogen ion is preferably a compound capable of releasing a sulfide ion, a selenide ion or a telluride ion.
  • Preferred examples of the compound capable of releasing a sulfide ion include a thiosulfonic acid compound, a disulfide compound, a thiosulfate, a sulfide, a thiocarbamate compound, thioformaldehyde compound and a rhodanine compound.
  • the compound capable of releasing a selenide ion is preferably a compound known as a selenium sensitizer.
  • Preferred examples thereof include colloidal selenium single body, isoselenocyanates (e.g., allylisoselenocyanate)selenoureas (e.g., N,N-dimethylselenourea, N,N,N-triethylselenourea, N,N,,N-trimethyl-N-heptafluoroselenourea, N,N,N-trimethyl-N-heptafluoropropylcarbonyllselenourea, N,N,N-trimethyl-N-4-nitrophenylcarbonylselenourea), selenoketones (e.g., selenoacetoamide, N,N-dimethylselenobenzamide), selenophosphates (e.g., tri-p-triselenophosphate) and selenides (e.g., diethyl selenide, diethyl diselenide, triethylphosphine selenide).
  • Preferred compounds capable of releasing a telluride ion include telluroureas (e.g., N,N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N,N-dimethyltellurourea), phosphine tellurides (e.g., tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride), telluroamides (e.g., telluroacetoamide, N,N-dimethyltellurobenzamide), telluroketones, telluroesters and isotellurocyanates.
  • telluroureas e.g., N,N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N,N-dimethyltellurourea
  • phosphine tellurides e.g., tribut
  • chalcogen ion releasing compounds is particularly preferred a thiosulfonic acid compound represented by the following formulas [1] to [3]: [1] R-SO 2 S-M [2] R-SO 2 S-R 1 [3] RSO 2 S-Lm-SS0 2 -R 2 wherein R, R1 and R2, which may be the same or different from each other, represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group; M represents a cation; L represents a bivalent linkage group; and m is 0 or 1.
  • a compound represented by formulas [1] to [3] may be a polymer containing a bivalent repeating unit derived from these structures; and R, R 1 , R 2 an L may be combined with each other to form a ring.
  • R, R 1 and R 2 being an aliphatic group, they are a saturated or unsaturated, straight or branched, or cyclic aliphatic hydrocarbon group; preferably, an alkyl group having 1 to 22 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl, t-butyl, etc.); an alkenyl group having 2 to 22 carbon atoms (allyl, butenyl, etc.) and an alkynyl group (propargyl, butynyl etc.).
  • an alkyl group having 1 to 22 carbon atoms e.g., methyl, ethyl, propyl, butyl, pentyl
  • R, R 1 and R 2 being an aromatic group, they include a monocyclic and condensed ring, aromatic hydrocarbon groups, preferably those having 6 to 20 carbon atoms such as phenyl. These may be substituted.
  • R 1 and R 2 being a heterocyclic group, they contain at least one selected from nitrogen, oxygen, sulfur, selenium and tellurium atoms, being each 3 to 15-membered ring (preferably, 3 to 6-membered ring) having at least one carbon atom, such as pyrroridine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzooxazole, benzimidazole, selenazole, benzoselenazole, tetrazole, triazole, benzotriazole, oxadiazole and thiadiazole.
  • nitrogen, oxygen, sulfur, selenium and tellurium atoms being each 3 to 15-membered ring (preferably, 3 to 6-membered ring) having at least one carbon atom, such as pyrroridine, piperidine, pyridine, tetrahydrofuran,
  • R, R 1 and R 2 are cited an alkyl group (e.g., methyl, ethyl, hexyl etc.), alkoxy group (e.g., methoxy, ethoxy, octyloxy, etc.), aryl group (e.g., phenyl, naphthyl, tolyl etc.), hydroxy group, halogen atom (e.g., fluorine, chlorine, bromine, iodine), aryloxy group (e.g., pheoxy), alkylthio (e.g., methylthio, butylthio), arylthio group (e.g., phenylthio), acyl group (e.g., acetyl, propionyl, butylyl, valeryl etc.), sulfonyl group (e.g., methylsulfonyl, phenylsulfonyl group (e.g.,
  • a bivalent linkage group represented by L is an atom selected from C, N, S and O or an atomic group containing at least one of them. Examples thereof are an alkylene group, alkenylene group, alkynylene group, arylene group, -O-, -S-, -NH-, -CO- or -SO 2 -, or a combination thereof.
  • L is preferably a bivalent aliphatic or aromatic group.
  • aromatic group are cited phenylene group and naphthylene group. These groups may have a substituent as afore-described.
  • M is preferably a metallic ion or organic cation.
  • metallic ion are cited lithium ion, sodium ion and potassium ion.
  • organic cation are cited an ammonium ion (e.g., ammonium, tetramethyammonium, tetrabutylammonium, etc.), phosphonium ion (e.g., tetraphenylphosphonium) and guanidyl group.
  • a repeating unit thereof is as follows. These polymer may be a homopolymer or copolymer with other copolymerizing monomers.
  • the chalcogen ion releasing compound is added to form the silver chalcogenide nucleus, in an amount of 10 -8 to 10 -2 mol, and more preferably 10 -6 to 10 -3 mol per mol of silver halide.
  • the chalcogen ion releasing compound may be added instantaneously or over a period of time.
  • the compound may be added at a constant flow rate or a variable flow rate.
  • the compound may separately be added.
  • Formation of the silver chalcogenide nucleus must be completed before completing grain growth.
  • a silver chalcogenide nucleus formed after completion of the grain growth, which is incorporated as a part of chemical sensitization nuclei formed in the chemical sensitization process, does not substantially contribute to effect of the present invention.
  • a silver chalcogenide nucleus formed on the same face as in chemical sensitization does not substantially contribute to effect of the present invention.
  • the silver halide emulsion according to the invention may be added with an oxidizing agent during the preparation process.
  • the oxidizing agent used in the invention refers to a compound capable of acting metallic silver to convert to silver ions.
  • the oxidizing agent may be an organic or inorganic compound.
  • inorganic oxidizing agents are cited ozone, hydrogen peroxide and its adduct (e.g., NaBO 2 -H 2 O 2 -3H 2 O, 2NaCO 3 -3H 2 O 2 , Na 4 P 2 O 7 -2H 2 O 2 , 2Na 2 SO 4 -H 2 O 2 -H 2 O), peroxy acid salt (e.g., K 2 S 2 o 8 , K 2 C 2 O 6 , K 4 P 2 O 8 ), peroxy complex compound (e.g., K 2 [Ti(O 2 )C 2 O 4 ]3H 2 O, 4K 2 SO 4 Ti(O 2 )OHSO 4 2H 2 O, Na 3 [VO(O 2 )(C 2 O 4 ) 2 ]6H 2 O), oxy acid salt such as permanganate salt (e.g., KMnO 4 ) or chromate salt (K 2 Cr 2 O 7 ), halogen elements such as iodine and bromine,
  • organic oxidizing agent examples include a quinone such as p-quinone, organic peroxide such as peracetic acid or perbenzoic acid and a compound capable of releasing an active halogen (e.g., N-bromsucciimide, chloramine T, chloramine B).
  • a quinone such as p-quinone
  • organic peroxide such as peracetic acid or perbenzoic acid
  • a compound capable of releasing an active halogen e.g., N-bromsucciimide, chloramine T, chloramine B.
  • halogen elements e.g., N-bromsucciimide, chloramine T, chloramine B
  • iodine is particularly preferred
  • the oxidizing agent is added preferably in an amount of 1x10 -5 to 1x10 -2 mol, and more preferably 1x10 -4 to 1x10 -3 mol per mol of silver.
  • iodine is optimally added in an amount of 5x10
  • the silver halide emulsion according to the invention can be used, in an emulsion layer, singly or in combination with another silver halide emulsion.
  • the emulsion of the invention is mixedly used with other emulsion(s) in the same layer, it is preferred that plural emulsions different in average grain size are mixedly used.
  • the average grain size of an emulsion contained in each layer is preferably different from each other.
  • the average grain size of an emulsion contained in each layer is preferably close to each other.
  • the silver halide emulsion according to the invention can be applicable to any emulsion layer.
  • the emulsion according to the invention can be chemically sensitized according to the conventional method. Sulfur sensitization, selenium sensitization and a gold sensitization by use of gold or other noble metal compounds can be employed singly or in combination.
  • the emulsion can be spectrally sensitized to a wanted wavelength region by use of sensitizing dyes known in the art.
  • the sensitizing dye can be employed singly or in combination thereof. There may be incorporated, with the sensitizing dye, a dye having no spectral sensitizing ability or a supersensitizer which does not substantially absorb visible light and enhances sensitization of the dye.
  • An antifoggant and stabilizer can be added into the tabular grain emulsion.
  • Gelatin is preferably employed as a binder.
  • An emulsion layer or other hydrophilic colloid layers can be hardened with hardeners.
  • a plasticizer or a dispersion of a water-soluble or water-insoluble polymer (so-called latex) can be incorporated.
  • the silver halide emulsion according to the invention can be employed in photographic materials, and preferably in color photographic materials including a color film for general use or for cine, color paper, color reversal film, and color reversal paper.
  • a coupler in a silver halide emulsion layer of the color photographic material, can be employed.
  • a competing coupler having an effect of color correction and a compound which, upon coupling reaction with an oxidation product of a developing agent, is capable of releasing a photographically useful fragment, such as a developing accelerator, a developing agent, a silver halide solvent, a toning agent, hardener, a fogging agent, a chemical sensitizer, a spectral sensitizer and a desensitizer.
  • a filter layer, anti-halation layer or anti-irradiation layer can be provided in the photographic material relating to the invention.
  • a dye which is leachable from a processed photographic material or bleachable during processing can be incorporated.
  • a matting agent, lubricant, image stabilizer, formalin scavenger, UV absorbent, brightening agent, surfactant, development accelerator or development retarder is also incorporated into the photographic material.
  • Employed may be, as a support, polyethylene-laminated paper, polyethylene terephthalate film, baryta paper or cellulose triacetate film.
  • reaction mother liquor (Gr-1) contained in a reaction vessel was maintained at 30° C and adjusted to a pH of 1.96 with a 1N sulfuric acid aqueous solution, while stirring at a rotation speed of 400 r.p.m. with a stirring mixer apparatus described in JP-A 62-160128. Thereafter, solutions (S-1) and (H-1), each 178 ml are added by the double jet addition at a constant flow rate for a period of 1 min. to form nucleus grains.
  • solution (G-1) was added thereto and the temperature was raised to 60° C in 30 min., while the silver potential of the emulsion within the reaction vessel (which was measured with a silver ion selection electrode using a saturated silver-silver chloride electrode, as a reference electrode) was controlled at 6 mV. Subsequently, the pH was adjusted to 9.3 with an aqueous ammonia solution and after maintained for 7 min., the pH was adjusted to 6.1 with an acetic acid aqueous solution, while the silver potential was maintained at 6 mV.
  • solutions (S-1) and (H-1) described above were added by the double jet addition at an accelerated flow rate (12 times faster at the end than at the start) for a period of 37 min.
  • solution (G-2) was added and the stirring speed was adjusted to 550 r.p.m., then, 2.11 1 of solution (S-2) and solution (H-2) were added by the double jet addition at an accelerated flow rate (2 times faster at the end than at the start) for a period of 40 min., while the silver potential of the emulsion was maintained at 6 mV.
  • the emulsion was desalted according to the method described in JP-A 5-72658. Then, gelatin was further added thereto to redisperse the emulsion and the pH and pAg were adjusted to 5.80 and 8.05, respectively. The resulting emulsion was denoted as EM-1.
  • the resulting emulsion was comprised of tabular grains having an average diameter of 1.50 ⁇ m (average of equivalent circle diameter), an aspect ratio of 7.4 at 50% of the total grain projected area (i.e., 50% of the total grain projected area being accounted for tabular grains having an aspect ratio of 7.4 or more), a variation coefficient of grain diameter distribution of 15.0% and a variation coefficient of thickness of 21.2%.
  • Emulsion EM-2 was prepared in the same manner as in emulsion EM-1, except that in the growth stage, the temperature after being lowered was 55° C and subsequently the EAg was adjusted to -30 mV (pBr of 1.29). As a result of electronmicroscopic observation, it was proved that emulsion Em-2 was the same in the average diameter, aspect ratio, variation coefficient of grain diameter and variation coefficient of grain thickness as those Em-1.
  • Emulsion EM-3 was prepared in the same manner as in emulsion EM-1, except that the growth stage was conducted in the following manner. As a result of electronmicroscopic observation, it was proved that emulsion Em-3 was the same in the average diameter, aspect ratio, variation coefficient of grain diameter and variation coefficient of grain thickness of Em-1. Further, in Fig. 2 is shown the silver iodide content within the grain at a distance extending outwardly from the center to the edge of the grain. As apparent from Fig. 2, the silver iodide content abruptly varies at the points within the range of 640 to 690, and the silver iodide content variation was not less than 0.2 mol%/nm.
  • solutions (S-1) and (H-1) described above were added by the double jet addition at an accelerated flow rate (12 times faster at the end than at the start) for a period of 37 min.
  • solution (G-2) was added and the stirring speed was adjusted to 550 r.p.m., then, 2.11 l of solution (S-3) and solution (H-2) were added by the double jet addition at an accelerated flow rate (2 times faster at the end than at the start) for a period of 40 min., while the silver potential of the emulsion was maintained at 6 mV.
  • the above emulsion was prepared in the following manner. To 5000 ml of a 6.0 wt.% gelatin solution containing 0.06 mol of potassium iodide, an aqueous solution containing 7.06 mol of silver nitrate and an aqueous solution containing 7.06 mol of potassium iodide, 2000 ml of each were added over a period of 10 min., while the pH was maintained at 2.0 using nitric acid and the temperature was maintained at 40° C. After completion of grain formation, the pH was adjusted to 6.0 using a sodium carbonate aqueous solution. The finished weight of the emulsion was 12.53 kg.
  • Emulsion EM-4 was prepared in the same manner as in emulsion EM-3, except that in the growth stage, the temperature after being lowered was 55° C and subsequently the EAg was adjusted to -30 mV (pBr of 1.29). As a result of electronmicroscopic observation, it was proved that emulsion Em-4 was the same in average diameter, aspect ratio, variation coefficient of grain diameter and variation coefficient of grain thickness as those of Em-3.
  • Emulsion EM-5 was prepared in the same manner as in emulsion EM-1, except that the growth stage was conducted in the following manner. As a result of electronmicroscopic observation, it was proved that emulsion Em-5 was the same in average diameter, aspect ratio, variation coefficient of grain diameter and variation coefficient of grain thickness as those Em-1. Further, in Fig. 3 is shown the silver iodide content within the grain at a distance extending outwardly from the center to the edge of the grain. As apparent from Fig. 3, the silver iodide content variation was small and within the range of -0.03 and +0.03 mol%/nm.
  • solutions (S-1) and (H-1) described above were added by the double jet addition at an accelerated flow rate (12 times faster at the end than at the start) for a period of 37 min.
  • solution (G-2) was added and the stirring speed was adjusted to 550 r.p.m., then, 2.11 l of solution (S-3) and solution (H-2) were added by the double jet addition at an accelerated flow rate (2 times faster at the end than at the start) for a period of 40 min., while the silver potential of the emulsion was maintained at 6 mV.
  • the temperature of the reaction mixture was lowered to 40° C in 15 min.
  • solution (Z-1) containing an iodide ion releasing agent and solution (SS-1) containing a nucleophilic agent were added and the pH was adjusted to 9.3 with a potassium hydroxide aqueous solution. Then, the silver potential was adjusted to -40 mV (pBr of 1.29) with a 3N potassium bromide aqueous solution. Subsequently, after adding solution (F-1) of 407.5 g, residual solution (S-3) and (H-4) were added by the double jet addition at an accelerated flow rate (1.2 times faster at the end than at the start, and the flow rate was discontinuously varied at the time fine grains disappeared) for period of 25 min.
  • Emulsion EM-6 was prepared in the same manner as in emulsion EM-5, except that in the growth stage, the temperature after being lowered was 55° C and the EAg subsequent to the iodide ion releasing reaction was adjusted to -30 mV (pBr of 1.29). As a result of electronmicroscopic observation, it was proved that emulsion Em-6 was the same in average diameter, aspect ratio, variation coefficient of grain diameter and variation coefficient of grain thickness as those of Em-1.
  • Emulsion EM-7 was prepared in the same manner as in emulsion EM-5, except that solutions (Z-1) and (SS-1) in the growth stage were replaced by solutions (Z-2) and (SS-2), respectively.
  • emulsion Em-7 was the same in average diameter, aspect ratio, variation coefficient of grain diameter and variation coefficient of grain thickness as those of Em-1.
  • Z-2 Sodium p-iodoacetoamidobenzenesulfonate 57.7 g Distilled water to make 1.0 l
  • SS-2) Sodium sulfite 20.0 g Distilled water to make 0.3 l
  • Emulsion EM-8 was prepared in the same manner as in emulsion EM-1, except that in the growth stage solution (K-1) was not added. As a result of electronmicroscopic observation, it was proved that emulsion Em-8 was the same in average diameter, aspect ratio, variation coefficient of grain diameter and variation coefficient of grain thickness as those of Em-1.
  • Emulsions Em-1 to Em-8 each were added with sensitizing dyes SSD-1, SSD-2 and SSD-3, while being maintained at 52° C. After ripened for 20 min., sodium thiosulfate was added thereto and were further added chloroauric acid and potassium thiocyanate. After the emulsions each were ripen until reached an optimum sensitivity-fog relationship, 1-phenyl-5-mercaptotetrazole and 4-hydroxy-6-methyl-1,3,3a,6-tetraazaindene was added to stabilize the emulsions. The addition amount of each of the sensitizing dyes, sensitizers and stabilizer and the ripening time were set so as to obtain an optimum sensitivity-fog relationship at 1/200 sec. exposure.
  • an emulsified dispersion in which a coupler MCP-1 was dissolved in ethylacetate and tricresylphosphate and dispersed in a gelatin aqueous solution, and photographic adjuvants such as a coating aid and a hardener were added to prepare a coating solution.
  • the coating solutions each were coated on a subbed cellulose triacetate film support according to the conventional manner and dried to obtain color photographic material samples 101 to 108.
  • the samples each were exposed to light at a color temperature of 5,400° K through a glass filter Y-48 (available from Toshiba) and processed according the following process.
  • a color developer, bleach, fixer and stabilizer each were prepared according to the following formulas.
  • Sensitivity and fog of processed samples each were measure using green light according to the following manner.
  • Sensitivity which was represented in terms of reciprocal of exposure necessary for giving a density of the minimum density (Dmin) plus 0.2, was shown as a relative value, based on the sensitivity of Sample 108 being 100. The more the sensitivity, the higher and more acceptable.
  • a fog increase due to pressure was evaluated by measuring an increase in density at a loaded non-exposure portion and shown as a relative value ( ⁇ Dp1), based on the density increase of Sample 108 being 100. The less this value, the less the increase in density due to pressure and the more superior in pressure resistance.
  • a sensitivity lowering due to pressure was evaluated by measuring a decrease in density at a loaded portion with a density of (Dmax-Dmin)/2 and shown as a relative value ( ⁇ Dp2), based on the density decrease of Sample 108 being 100. The less this value, the less the sensitivity lowering due to pressure and the more superior in pressure resistance.
  • Samples were also processed in shortened development of 2 min.50 sec. and developability of each sample was evaluated in terms of difference in sensitivity between development 3 min.15 sec and 2 min.50 sec. ( ⁇ S) which was shown as relative value, based on that of Sample 108 being 100.
  • Each emulsion was diluted to 5 tomes with ultra-pure water, centrifuged and redispersed in ultra-pure water.
  • the dispersion was dropped onto a 200 mesh with hydrophilic carbon supporting membrane and extra water was removed with a spin coater.
  • Electronmicrographs of about 700 grains were taken at a temperature of -130° C and a direct magnification of 8.000 to 10,000 times using a transmission electronmicroscope at an acceleration voltage of 200 kV, the proportion of grains having 30 or more dislocation lines per grain in the fringe portion and that of grains having a silver iodide border were each determined.
  • An electronmicrograph of a tabular grain having the silver iodide border is exemplarily shown in Fig. 1.
  • the silver iodide content variation from the center to the edge of the grain was measured by the EPMA method (TEM-EDS method). Measurements at 16 points on the straight line from the grain center to the edge were made at an acceleration voltage of 200 kV, a temperature of -130° C and with a spot diameter of 20 nm over a total period of 50 sec. The proportion of grains having the variation within the range of -0.03 mol%/nm and +0.03 mol%/nm, based on the grain projected area, was determined for each emulsion. Results thereof are shown in Table 1.
  • Emulsion Em-9 was prepared in the same manner as Em-7, except that the ripening process was varied as follow.
  • solution (G-1) was added and the temperature was raised to 60° C in 30 min., while the silver potential of the emulsion contained in a reaction vessel was controlled at 6 mV (measured with a silver ion selection electrode with a reference electrode of a saturated silver-silver chloride electrode) using a 2N potassium bromide solution. Thereafter, stirring was continued further 15 min. and then the pH was adjusted to 6.1 with potassium hydroxide while the silver potential was maintained at 6 mV using a 2N potassium bromide solution.
  • the resulting emulsion was comprised of tabular grains having an average diameter of 1.53 ⁇ m (average equivalent circle diameter), an aspect ratio of 7.3 at 50% of the total grain projected area (i.e., 50% of the total grain projected area being accounted for tabular grains having an aspect ratio of 7.3 or more), a variation coefficient of grain diameter distribution of 28.0.0% and a variation coefficient of thickness of 37.4%.
  • the proportion of the grains having dislocation lines, that of grains having a slow, continuous silver iodide content variation and that of grains having a silver iodide border, based on the grain projected area, are 76%, 91% and 9%, respectively.
  • a photographic material sample 109 was prepared and evaluated in the same manner as Example 1. Results are shown in Table 2. As can be seen from the results, effects of the present invention were marked in the emulsion with a narrow grain size distribution and grain thickness distribution.
  • Emulsion Em-10 was prepared in the same manner as Em-7, except that in the grain growth stage, after completing addition of a solution (S-1), solution (R-1)described below was instantaneously added and after instantaneously adding solution (T-1) described below, the temperature was lowered to 40° C. From electronmicrograph of the grains, it was proved that the resulting emulsion grains were substantially the same as Em-1.
  • R-1) Thiourea dioxide 26.6 mg Distilled water 46.6 ml
  • T-1) Sodium ethanethiosulfonate 880.1 ml Distilled water 293.4 ml
  • Emulsion Em-11 was prepared in the same manner as Em-10, except that, after completing grain growth and desalting, gelatin was added, the temperature was adjusted to 50° C, then solution (F-2) was added thereto, and ripening was conducted for 20 min.; thereafter, the temperature was lowered to 40° C and the pH and pAg were adjusted to 5.80 and 8.06, respectively.
  • F-2 Fine silver bromide grain emulsion (av. size of 0.05 ⁇ m) doped with K 2 IrCl 6 4.70 g
  • the above emulsion was prepared in the following manner. To 5000 ml of a 6.0 wt.% gelatin solution containing 0.06 mol of potassium bromide, an aqueous solution containing 7.06 mol of silver nitrate and an aqueous solution containing 7.06 mol of potassium bromide, 2000 ml of each were added over a period of 10 min., while the pH was maintained at 2.0 using nitric acid and the temperature was maintained at 40° C. After completion of grain formation, the pH was adjusted to 6.0 using a sodium carbonate aqueous solution. The finished weight of the emulsion was 12.53 kg.
  • Emulsion 12 was prepared in the same manner as Em-1, except that similarly to Em-10, after completing addition of a solution (S-1), solution (R-1)described below was instantaneously added and after instantaneously adding solution (T-1) described below, the temperature was lowered to 40° C. From electronmicrograph of the grains, it was proved that the resulting emulsion grains were substantially the same as Em-1.
  • Emulsion Em-13 was prepared in the same manner as Em-12, except that, similarly to Em-12, after completing grain growth and desalting, gelatin was added, the temperature was adjusted to 50° C, then solution (F-2) was added thereto, and ripening was conducted for 20 min.; thereafter, the temperature was lowered to 40° C and the pH and pAg were adjusted to 5.80 and 8.06, respectively.
  • Emulsions Em-10 to Em-13 were each the same in the average grain diameter, aspect ratio, variation coefficient of grain diameter and variation coefficient of grain thickness as those of Em-1.
  • a multi-layered color photographic material Sample 407 was prepared, in which chemically and spectrally sensitized emulsion Em-7 was used in the high-speed green sensitive layer.
  • the addition amount of each compound was represented in term of g/m 2 , provided that the amount of silver halide or colloidal silver was converted to the silver amount and the amount of a sensitizing dye was represented in mol/Ag mol.
  • Emulsions d and f were prepared according to the following procedure described below.
  • Emulsions a, b, c, e, g, h and i were prepared in a manner similar to emulsions d and f.
  • a Seed Emulsion-1 was prepared in the following manner.
  • To Solution A1 maintained at 35° C and stirred with a mixing stirrer described in JP-B 58-58288 and 58-58289 were added an aqueous silver nitrate solution (1.161 mol) and an aqueous potassium bromide and potassium iodide mixture solution (containing 2 mol% potassium iodide) by the double jet method in 2 min., while keeping the silver potential at 0 mV (measured with a silver electrode and a saturated silver-silver chloride electrode as a reference electrode), to form nucleus grains. Then the temperature was raised to 60° C in 60 min.
  • seed Emulsion-1 aqueous silver nitrate solution (5.902 mol) and an aqueous potassium bromide and potassium iodide mixture solution (containing 2 mol% potassium iodide) were added by the double jet method in 42 minutes, while keeping the silver potential at 9 mV.
  • the temperature was lowered to 40° C and the emulsion was desalted according to the conventional flocculation washing.
  • the obtained seed emulsion was comprised of grains having an average equivalent sphere diameter of 0.24 ⁇ m and an average aspect ratio of 4.8. At least 90% of the total grain projected area was accounted for by hexagonal tabular grains having the maximum edge ratio of 1.0 to 2.0. This emulsion was denoted as Seed Emulsion-1
  • each of the solutions was added at an optimal flow rate so as not to cause nucleation or Ostwald ripening.
  • the emulsion desalted at 40° C by the conventional flocculation method gelatin was added thereto and the emulsion was redispersed and adjusted to a pAg of 8.1 and a pH of 5.8.
  • the resulting emulsion was comprised of tabular grains having an average size (an edge length of a cube with an equivalent volume) of 0.74 ⁇ m, average aspect ratio of 5.0 and exhibiting the iodide content from the grain interior of 2/8.5/X/3 mol%, in which X represents the dislocation line-introducing position. From electron microscopic observation, it was proved that at least 60% of the total grain projected area was accounted for by grains having 5 or more dislocation lines both in fringe portions and in the interior of the grain.
  • the silver iodide content of the surface was 6.7 mol%.
  • Silver iodobromide emulsion f was prepared in the same manner as emulsion d, except that in the step 1), the pAg, the amount of silver nitrate to be added and the SMC-1 amount were varied to 8.8, 2.077 mol and 0.218 mol, respectively; and in the step 3), the amounts of silver nitrate and SMC-1 were varied to 0.91 mol and 0.079 mol, respectively.
  • the resulting emulsion was comprised of tabular grains having an average size (an edge length of a cube with an equivalent volume) of 0.65 ⁇ m, average aspect ratio of 6.5 and exhibiting the iodide content from the grain interior of 2/9.5/X/8 mol%, in which X represents the dislocation line-introducing position. From -electron microscopic observation, it was proved that at least 60% of the total grain projected area was accounted for by grains having 5 or more dislocation lines both in fringe portions and in the interior of the grain. The silver iodide content of the surface was 11.9 mol%.
  • the thus prepared emulsions d and f were added with sensitizing dyes afore-described and ripened, and then chemically sensitized by adding triphenylphosphine selenide, sodium thiosulfate, chloroauric acid and potassium thiocyanate until relationship between sensitivity and fog reached an optimum point.
  • Silver iodobromide emulsions a, b, c, g, h, and i were each spectrally and chemically sensitized in a manner similar to silver iodobromide emulsions d and f.
  • coating aids SU-1, SU-2 and SU-3 In addition to the above composition were added coating aids SU-1, SU-2 and SU-3; a dispersing aid SU-4; viscosity-adjusting agent V-1; stabilizers ST-1 and ST-2; fog restrainer AF-1 and AF-2 comprising two kinds polyvinyl pyrrolidone of weight-averaged molecular weights of 10,000 and 1.100,000; inhibitors AF-3, AF-4 and AF-5; hardener H-1 and H-2; and antiseptic Ase-1.
  • Samples 401, 411 and 413 were each prepared in the same manner as Sample 407, except that emulsion Em-7 was respectively replaced by Em-1, Em-11 or Em-13. These samples were evaluated in the same manner as in Example 1 and there were obtained similar results to a single emulsion layer samples as shown in Tables 1 and 2. Results thereof are shown in Table 3.
  • Sample Emulsion Remarks Sensitivity ⁇ Dp1 ⁇ Dp2 ⁇ S 401 Em-1 Comp. () 179 115 188 191 407 Em-7 Inv. () 211 55 38 67 411 Em-11 Inv. () 301 36 30 57 413 Em-13 Inv. () 184 112 199 189

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Claims (6)

  1. Silberhalogenidemulsion, die Silberhalogenidkörnchen und ein Dispersionsmedium umfasst, wobei mindestens 50 % der gesamten Kornprojektionsfläche von tafelförmigen Körnchen mit einem Aspektverhältnis von 5 oder mehr eingenommen werden, wobei die tafelförmigen Körnchen des weiteren 30 oder mehr Versetzungslinien pro Korn in einem Randbereich des Korns aufweisen und wobei die tafelförmigen Körnchen jeweils Silberiodid enthalten, wobei die Schwankung des Silberiodidgehalts in Richtung vom Mittelpunkt zum Rand des Korns in einem Bereich von -0,03 Mol-%/nm bis +0,03 Mol-%/nm liegt.
  2. Silberhalogenidemulsion nach Anspruch 1, wobei die tafelförmigen Körnchen mit einer Silberiodidgrenze weniger als 20 % der gesamten Kornprojektionsfläche ausmachen.
  3. Silberhalogenidemulsion nach Anspruch 1, wobei der Variationskoeffizient der Korngrößenverteilung 25 % oder weniger und der Variationskoeffizient der Korndickeverteilung 35 % oder weniger beträgt.
  4. Silberhalogenidemulsion nach Anspruch 1, wobei mindestens 50 % der Projektionsfläche der gesamten Silberhalogenidkörnchen von tafelförmigen Körnchen mit 30 oder mehr Versetzungslinien pro Korn lediglich im Randbereich der Körnchen eingenommen wird.
  5. Silberhalogenidemulsion nach Anspruch 1, wobei mindestens ein Teil der tafelförmigen Körnchen jeweils ein Reduktionssensibilisierungszentrum im Inneren der Körnchen enthält.
  6. Silberhalogenidemulsion nach Anspruch 1, wobei mindestens ein Teil der tafelförmigen Körnchen jeweils eine mehrwertige Metallverbindung im Randbereich der Körnchen enthält.
EP98119401A 1997-10-15 1998-10-14 Silberhalogenidemulsion Expired - Lifetime EP0909979B1 (de)

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US6080537A (en) * 1998-04-28 2000-06-27 Konica Corporation Silver halide emulsion, preparation method thereof and silver halide photographic material
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US5498516A (en) * 1992-05-14 1996-03-12 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
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