EP0326853B1 - Emulsions photographiques à l'halogénure d'argent et procédé pour les préparer - Google Patents

Emulsions photographiques à l'halogénure d'argent et procédé pour les préparer Download PDF

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Publication number
EP0326853B1
EP0326853B1 EP19890100764 EP89100764A EP0326853B1 EP 0326853 B1 EP0326853 B1 EP 0326853B1 EP 19890100764 EP19890100764 EP 19890100764 EP 89100764 A EP89100764 A EP 89100764A EP 0326853 B1 EP0326853 B1 EP 0326853B1
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EP
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Prior art keywords
silver
grains
silver halide
emulsion
mol
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Expired - Lifetime
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EP19890100764
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German (de)
English (en)
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EP0326853A1 (fr
Inventor
Shigeharu Urabe
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP63007853A external-priority patent/JPH07104569B2/ja
Priority claimed from JP785288A external-priority patent/JPH01183644A/ja
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Publication of EP0326853A1 publication Critical patent/EP0326853A1/fr
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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
    • G03C1/06—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
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/047—Proteins, e.g. gelatine derivatives; Hydrolysis or extraction products of proteins
    • G03C2001/0473—Low molecular weight gelatine

Definitions

  • the present invention relates to light-sensitive silver halide emulsions comprising a dispersion medium and silver halide grains useful in the field of photography and, in particular, those comprising silver halide grains containing a dispersion medium and silver iodide, as well as to a process for preparing the same.
  • silver iodobromide grains which are generally used in the field of photography contain silver iodide in the silver bromide crystal lattice of the grain in a soluble limit amount or less, or in an amount of iodide content of about 40 mol% or less.
  • the iodide content in the silver iodobromide emulsions has the following advantages (1) and disadvantages (2).
  • silver iodide may uniformly be distributed throughout the grains formed, or alternatively, if addition of bromide is reduced or stopped in the course of the formation of the grains while addition of iodide only is continued, a silver iodide shell or silver iodide-rich silver iodobromide shell may be formed on the outer surface (shell) of the grains.
  • JP-A-58-113927 (the term "JP-A" as used herein means an "unexamined published Japanese patent application") corresponding to U.S.
  • Patent 4,434,226 mentions a silver halide emulsion wherein tabular silver iodobromide grains having a thickness of less than 0.5 ⁇ m, a diameter of 0.6 ⁇ m or more and a mean aspect ratio of 8/1 or more account for at least 50% of the total projected area of the grains therein, in which the tabular silver iodobromide grains have first and second parallel main surface planes which face each other and a center region extending between the two main planes. The silver iodide content in the center region is lower than that in at least one region which also extends between the two main planes and which is crosswise displaced.
  • JP-A-59-99433 mentions a silver halide emulsion containing silver halide grains, in which tabular silver halide grains having an aspect ratio of 5 or more account for 10% (by number) of the silver halide grains.
  • the grains contain silver iodide in the inside site by 80 mol% of the silver amount of the total grains from the center of the grains in the major axis or minor axis direction of the grains (inside iodine-rich phase).
  • the silver iodide content is varied in different sites in one grain (especially the content is varied between the inside and the outside of the grain), so as to obtain a better photographic characteristic.
  • JP-A-60-14331 mentions a silver halide photographic emulsion containing silver halide grains with a distinct layered structure, in which the grains are composed of a core part containing from 10 to 45 mol% of silver iodide and a shell part having 5 mol% or less silver iodide and have a mean silver iodide content of 7 mol% or more.
  • JP-A-61-245151 corresponding to EP 202784A mentions a silver halide emulsion containing silver halide grains having a multi-layered structure with a different silver iodide content in the respective layers, in which the silver iodide content in the outermost layer is 10 mol% or less, a silver iodide-rich layer having a higher silver iodide content than the outermost layer by 6 mol% or more is provided inside the outermost layer, and a interlayer having an intermediate silver iodide content is provided between the outermost layer and the silver iodide-rich layer.
  • the silver iodide content is varied in different sites in one grain (especially the content is varied between the inside and the outside of one grain), so as to obtain a better photographic characteristic.
  • silver halide grains having a completely uniform silver iodobromide phase and the grains are those in which the above-mentiond microscopic silver iodide distribution is completely uniform.
  • the microscopic silver iodide distribution in silver iodobromide grains can be observed by a cooling type transmission electron microscope.
  • the silver halide grains where the silver iodide distribution is completely uniform, which are provided by the present invention, could not be obtained by any conventional technical means.
  • the object of the present invention is to provide a negative type silver halide emulsion which has a high sensitivity with less fog, which has improved graininess and sharpness-covering power and which is excellent in storability and pressure-resistance.
  • the object of the present invention has been met by a silver halide photographic emulsion comprising a dispersion medium and silver halide grains, which is characterized in that the silver halide grains include a silver halide phase containing 3 mol% or more of silver iodide, the microscopic non-uniformity caused by the silver iodide being such that the silver halide grains exhibit at most two lines at an interval of 0.2 ⁇ m in the direction perpendicular to the lines when observed by a transmission electron microscope, and the emulsion contains at least 60 wt.% of the said silver halide grains.
  • the present invention further provides a process for preparing the above silver halide photographic emulsion comprising the steps of
  • Fig. 1 is a photograph taken by a transmission electron microscope at a magnification of 50,000 times.
  • Fig. 1 shows the crystal structure of conventional tabular silver halide grains where the iodine distribution in the silver iodobromide phase is not completely uniform.
  • Fig. 2 is an outline to typically show one embodiment of the process of preparing the emulsion of the present invention, in which fine silver halide grains are fed from the mixer vessel as provided outside the reactor vessel.
  • the interval between the respective stripes in the pattern is extremely fine and small or is or the order of 100 ⁇ or less and the stripes are extremely microscopically non-uniform.
  • the extremely fine stripe patterns indicates the non-uniformity of the silver iodide distribution in the grains, which may be clarified by various methods. More directly, when the tabular grains are annealed under the condition that the iodide ion may move in the silver halide crystals (for example, at 250°C for 3 hours), the stripe patterns are lost. From this fact, non-uniformity may be concluded.
  • the nuclei may be polydispersed or monodispersed, but they are more preferably monodispersed.
  • the "monodispersed nuclei" as herein referred to have the same meaning as mentioned above.
  • the silver halide grains may have a uniform grain size
  • a method of varying or properly controlling the adding speed of the silver nitrate or aqueous alkali halide solution in accordance with the growing speed of the silver halide grains formed for example, as described in British Patent 1,535,016 and JP-B-48-36890 (the term "JP-B" as referred to herein means an "examined Japanese patent publication") and JP-B-52-16364, and a method of varying the concentration of the aqueous solutions to be added, for example, as described in US-A-4,242,445 and JP-A-55-158124 are preferably employed, so that the grains may rapidly be grown within a range not exceeding the critical persaturation degree for the reaction system.
  • an aqueous silver salt solution and an aqueous halide solution are added to a reactor vessel having a dispersion medium-containing aqueous solution therein with efficient stirring.
  • fine silver halide grains having a small grain size may be added to the reactor vessel, in place of adding the aqueous silver salt solution and the aqueous halide solution thereto, and the fine grains may optionally subsequently be ripened in the reactor vessel for nucleation. This will be mentioned hereunder for the method of growing the grain nuclei.
  • the size of the fine silver halide grains to be added in the method is preferably 0.1 ⁇ m or less, more preferably 0.06 ⁇ m or less, especially preferably 0.03 ⁇ m or less.
  • the method for preparation of the fine silver halide grains for use in the method will be mentioned in detail in the item of "growth of grains" to follow.
  • the fine silver halide grains have an extremely high solubility as the grain size thereof is extremely fine. Thus, they are rapidly dissolved immediately after being added to the reactor vessel to be decomposed to the constituting silver ion and halide ion. Accordingly, they are deposited on a slight amount of the fine grains as introduced into the reactor vessel to form nuclei grains.
  • silver halide solvents may be used, if desired, which will be mentioned hereinafter.
  • the nucleation temperature is preferably 50°C or higher, more preferably 60°C or higher.
  • the fine silver halide grains may be added to the reactor vessel all at once or they may be gradually and continuously added thereto. In the latter case of continuous addition, the flow rate of the grains to be added may be constant or this may be accelerated over the course of time.
  • a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, or an iron salt or a complex salt thereof may be incorporated into the reaction system.
  • An aqueous halide solution and an aqueous silver solution are fed into the mixer from the top and bottom open mouths through feeding ducts while the mixer is rapidly rotated so that the solutions are rapidly blended and reacted together (when the mixer has, the separating disc, the aqueous halide solution and the aqueous silver salt solution as fed into the two rooms are diluted with the aqueous colloid as filled in each room, and these are rapidly blended and reacted near the outlet slits of the mixer), whereby the silver halide grains formed by the reaction are expelled out into the aqueous colloid in the reactor vessel because of the centrifugal force formed by rotation of the mixer and the grains are grown in the colloid in the reactor vessel.
  • the problem of the non-uniform silver iodide distribution in the grains formed can not be overcome at all by this method, and the grains formed are observed by a cooling type transmission electron microscope to have regular ring-like stripe patterns which indicate the non-uniform distribution of silver iodide in the grains.
  • JP-B-55-10545 mentions a technique of improving the local distribution of the ion concentrations so as to prevent the non-uniform growth of grains.
  • a mixer filled with an aqueous colloid is provided in the inside of a reactor vessel filled with an aqueous colloid is provided in the inside of a reactor vessel filled with an aqueous colloid, an aqueous halide solution and an aqueous silver halide solution are separately fed into the mixer through feeding ducts so that the reaction solutions are rapidly and vigorously stirred and blended by the lower stirring blades (turbine blades) as equipped in the mixer to form and grow silver halide grains.
  • JP-A-62-99751 mentions a photographic element containing silver bromide and silver iodobromide tabular grains having a mean diameter range of from 0.4 to 0.55 ⁇ m and an aspect ratio of 8 or more
  • JP-A-62-115435 mentions the same element with the same grains having a mean grain size of from 0.2 to 0.55 ⁇ m.
  • US-A-2,246,938 mentions a method of growing coarse grains in an emulsion by blending coarse grains on which nothing has been adsorbed and fine grains on which nothing has also been adsorbed or by gradually adding a fine grains-containing emulsion to a coarse grains-containing emulsion.
  • the same silver iodobromide emulsion is divided into two parts, ammonia is added to one part to ripen and then the other part is blended therewith or gradually added thereto. Accordingly, this method is quite different from the process of the present invention for growing silver iodide-containing tabular grains.
  • this U.S. Patent is silient on the limitation of the silver iodide content in the silver halide grains formed. The silver iodide content in the grains formed in the example is only 2.6 mol%.
  • JP-A-57-23932 mentions a method of growing silver halide grains, in which a fine grains-containing emulsion as prepared in the presence of a growth inhibitor is washed with water by decantation and re-dispersed. The resulting emulsion is again re-dissolved, and the solution thus prepared is added to the emulsion containing fine grains to be grown, whereby the fine grains are grown after dissolution thereof.
  • fine grains having a smaller grain size are advantageously be obtained, but the re-dissolution of the fine grains in the reactor vessel is interfered with by the growth inhibitor.
  • JP-A-57-23932 is silent on the halogen composition of the fine grains. In the example thereof, fine grains of pure silver bromide only are illustrated. Accordingly, the invention of JP-A-57-23932 should be said quite different from the present invention which relates to growth of silver iodide-containing tabular grains.
  • US-A-3,317,322 and 3,206,313 mention a method of forming a core/shell grains-containing silver halide emulsion having a high internal sensitivity, in which a silver halide grain emulsion containing chemically sensitized core grains having a mean grain size of at least 0.8 ⁇ m is blended with another silver halide grain emulsion containing not chemically sensitized silver halide grains having a mean grain size of 0.4 ⁇ m or less. The resulting mixture is ripened so a to form shells over the cores.
  • the method disclosed relates to the preparation of internal latent image-forming type grains having a high internal sensitivity. In the examples of these U.S.
  • JP-A-58-113927 mentions (page 207) that "Silver, bromide and iodide may be introduced initially or during the growing stage of the grains in the form of fine silver halide grains as suspended in a dispersion medium. Concretely, silver bromide, silver iodide and/or silver iodobromide grains may be introduced for the purpose.” However, it is quite silent on the technique of growing tabular grains by addition of only a fine grains-containing emulsion to a reactor vessel without feeding aqueous solutions of silver salt and halide(s) thereto.
  • JP-A-62-124500 mentions an example of growing host grains in a rector vessel from previously prepared extremely fine grains (about 0.02 ⁇ m) as put in the reactor vessel.
  • the fine grains used therein are silver bromide grains, and this reference relates to growth of normal crystalline grains. Accordingly, this is quite different from the present invention.
  • tabular grains which are to be nuclei or cores are previously put in the reactor vessel and an emulsion containing previously prepared fine grains having a small grain size is added to the reactor vessel, whereby the fine grains are dissolved by Ostwald ripening and are deposited on the nuclei or cores existing in the reactor vessel so that the nuclei or cores are grown to the intended tabular grains.
  • the halide composition of the previously prepared fine grains is to have the same silver iodide content as that in the intended tabular grains to be finally obtained, which is silver iodobromide, silver chloroiodobromide or silver iodochloride.
  • silver halide solvents to be used for this purpose there may be mentioned water-soluble bromides, water-soluble chlorides, thiocyanates, ammonia, thioethers and thioureas.
  • the temperature of growing the tabular grains is 50°C or higher, preferably 60°C or higher, more preferably 70°C or higher.
  • the fine grains-containing emulsion may be added hereto all at a once, or alternatively, the emulsion may be divided into parts which are added one by one to the reactor vessel.
  • the fine grains-containing emulsion is fed into the reactor vessel at a constant flow rate, and more preferably, at an accelerated flow rate.
  • fine silver halide crystal grains necessary for growing the silver halide crystal grains are added to the reactor vessel, without adding silver ion and halide ion(s) (containing iodide ion) in the form of respective aqueous solutions thereto (like the known conventional means) to cause Ostwald ripening because of the high solubility of the said fine grains, whereby the core nuclei existing in the reactor vessel are grown to the intended tabular grains.
  • the reaction stage in the reaction system depends upon the speed of the dissolution of the fine grains as fed to release silver ion and halide ion(s) in the reactor vessel, but not the growing speed of the tabular grains to be finally obtained.
  • the fine grains to be added are desired to have a possibly minimum grain size.
  • silver halide grains having a smaller grain size have a higher solubility, so that these would be extremely unstable to cause Ostwald ripening by themselves. As a result, the grain size of the grains would increase.
  • T.H. James The Theory of the Photographic Process , 4th Ed. refers to a Lippman emulsion as an example of fine grains and mentions that the mean grain size of the grains is 0.05 ⁇ m. Preparation of fine grains having a grain size of 0.05 ⁇ m or less is possible, but if obtained, the grains would be unstable and would easily undergo Ostwald ripening. As a result, the grain size of the resulting grains is increase. The Ostwald ripening may be prevented to some degree by adsorbing something to the fine grains, which, however would decrease the dissolution speed and is therefore contrary to the intended object of the present invention.
  • the concentration of the protective colloid is 1% by weight or more, preferably 2% by weight or more.
  • silver gelatin When gelatin is used, silver gelatin is formed from silver ion and gelatin and this gives a silver colloid by photolysis and pyrolysis. Accordingly, the silver nitrate solution and the protective colloid it is better that be blended immediately before use.
  • extremely fine grains having a small grain size may directly be fed into the reactor vessel, whereupon the dissolution speed of the fine grains is high so that the growing speed of the tabular grains in the reactor vessel is advantageously high.
  • silver halide solvents are no longer indispensable, but silver halide solvents may of course be used also in the method of the present invention, if desired, for the purpose of further accelerating the growing speed or for any other purposes.
  • the description for the aforesaid Method (1) may be referred to.
  • the feeding speed of silver ion and halide ion(s) to the reactor vessel may freely be controlled. These may be fed thereto at a constant speed, or preferably the feeding speed may be accelerated.
  • the means of accelerating the feeding speed is mentioned in JP-B-48-36890 and 52-16364.
  • the description for the aforesaid Method (1) may be referred to.
  • the reaction temperature in the mixer vessel may advantageously be 60°C or lower, preferably 50°C or lower, more preferably 40°C or lower.
  • a low molecular weight gelatin a synthetic high molecular compound having a protective colloidal action on silver halide grains or other natural high molecular compounds than gelatin are preferably used as a binder, since general gelatin would easily solidify at such a low temperature.
  • Examples of high molecular compounds having a protective colloidal action on silver halide grains which can be used in the present invention include the following compounds.
  • the longer the enzyme-decomposing time the lower the molecular weight of the decomposed gelatins.
  • a general gelatin is heated and hydrolyzed under a low pH (pH of from 1 to 3) or high pH (pH of from 10 to 12) atmosphere.
  • the concentration of the protective colloid to be added to the mixer vessel in Method (A) is 0.2% by weight or more, preferably 1% by weight or more, more preferably 2% by weight or more.
  • the concentration thereof is 0.2% by weight or more, preferably 1% by weight ore more, more preferably 2% by weight or more.
  • the concentration of the aqueous protective colloid solution in the reactor vessel in previous preparation of the fine silver halide grains is 0.2% by weight or more, preferably 1% by weight or more, more preferably 2% by weight or more.
  • spectral sensitizing dyes for use in the present invention, there are generally methine dyes, which include, for example, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • methine dyes include, for example, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • merocyanine dyes or complex merocyanine dyes can be applied 5-membered or 6-membered heterocyclic nuclei such as pyrazolin-5-one nuclei, thiohydantoin nuclei, 2-thiooxazolidine-2,4-dione nuclei, thiazolidine-2,4-dione nuclei, rhodanine nuclei or thiobarbituric acid nuclei, as nuclei having a ketomethylene structure.
  • 5-membered or 6-membered heterocyclic nuclei such as pyrazolin-5-one nuclei, thiohydantoin nuclei, 2-thiooxazolidine-2,4-dione nuclei, thiazolidine-2,4-dione nuclei, rhodanine nuclei or thiobarbituric acid nuclei, as nuclei having a ketomethylene structure.
  • the amount of the sensitizing dye to be added to the silver halide emulsion being prepared can not be indiscriminately determined, and depends upon the kind of the additives added to the emulsion or the amount of the silver halide therein. However, it may be almost the same as that to be used in the preparation of conventional emulsions by conventional methods.
  • the amount of the sensitizing dye to be added may be from 0.001 to 100 mmol, preferably from 0.01 to 10 mmol, per mol of silver halide.
  • the sensitizing dye is added to the emulsion before or after chemical ripening thereof.
  • the sensitizing dye is most preferably added to the emulsion during chemical ripening or before chemical ripening (for example during formation of the grains or during physical ripening of the grains formed).
  • the emulsion of the present invention may further contain, together with the sensitizing dye, a dye having no spectral sensitizing action by itself or a material which does not substantially absorb visible lights but shows supersensitizing action.
  • a dye having no spectral sensitizing action by itself may contain a nitrogen-containing heterocyclic group-substituted aminostyryl compound (for example, as described in US-A-2,933,390 and 3,635,721), an aromatic organic acid/formaldehyde condensation product (for example, as described in US-A-3,743,510), a cadmium salt or an azaindene compound for the purpose.
  • a nitrogen-containing heterocyclic group-substituted aminostyryl compound for example, as described in US-A-2,933,390 and 3,635,721
  • an aromatic organic acid/formaldehyde condensation product for example, as described in US-A-3,743,510
  • the silver halide emulsion of the present invention is generally chemically sensitized.
  • chemical sensitization for example, the method described in H. Frieser, Die Unen der Photographischen Sawe mit Silberhalogeniden (published by Akademische Verlagsgesellschaft, 1968), pages 675 to 734 may be employed.
  • a sulfur sensitization method using a sulfur-containing compound capable of reacting with active gelatin or silver e.g., thiosulfates, thioureas, mercapto compounds, rhodanines
  • a reduction sensitization method using a reducing substance e.g., stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds
  • a noble metal sensitization method using a noble metal compound e.g., gold complexes, as well as complexes of metals belonging to Group VIII of the Periodic Table such as platinum, iridium or palladium
  • a noble metal compound e.g., gold complexes, as well as complexes of metals belonging to Group VIII of the Periodic Table such as platinum, iridium or palladium
  • the photographic emulsion of the present invention can contain various compounds for the purpose of preventing of photographic materials and for the purpose of stabilizing the photographic property of the materials.
  • various compounds which are known as an anti-foggant or stabilizer can be added for the above purposes, which compounds include azoles, such as benzothiazolium salts, nitroindazoles, traizoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted derivatives); heterocyclic mercapto compounds, such as mercapthothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the heterocyclic mercapto compounds having a water-soluble group such as carboxyl group or sulfone group; thioketo compounds, such as oxazolinethi
  • the anti-foggant or stabilizer is generally added to the emulsion after chemical sensitization thereof, and more preferably, it is added thereto in the course of chemical ripening of the emulsion or at any time selected from prior to the beginning of chemical ripening of the emulsion. Specifically, it may be added to the emulsion at any time in the course of the formation of the silver halide grains of the emulsion, for example, during the course of addition of the silver salt solution, or after addition of the solution and before beginning of chemical ripening of the emulsion, or during the course of chemical ripening of the emulsion (preferably within the time of 50% from the beginning of chemical ripening, more preferably within the time of 20% therefrom).
  • the emulsion of the present invention may be applied to any of mono-layered and multi-layered photographic materials having one or more layers in the form of any desired layer constitution.
  • the emulsion of the present invention may be applied to a silver halide multi-layer color photographic material, which has a multi-layered structure composed of laminates of binder and silver halide grains-containing layers, for the purpose of separately recording blue light, green light and red light, and the respective emulsion layers comprise two of a high sensitive layer and a low sensitive layer.
  • a silver halide multi-layer color photographic material which has a multi-layered structure composed of laminates of binder and silver halide grains-containing layers, for the purpose of separately recording blue light, green light and red light
  • the respective emulsion layers comprise two of a high sensitive layer and a low sensitive layer.
  • the high sensitive layer and the low sensitive layer may be arranged reversely.
  • the silver halide emulsion of the present invention may be applied to color photographic materials as mentioned above, and it may further be applied to other mono-layered or multi-layered photographic materials having one or more emulsion layers, such as X-ray photographic materials, picture-taking black-and-white photographic materials, photographic materials for photomechanical process and printing photographic papers.
  • additives to be added to the silver halide emulsion of the present invention such as binder, chemical sensitizer, spectral sensitizer, stabilizer, gelatin hardening agent, surfactant, antistatic agent, polymer latex, mat agent, color coupler, ultraviolet absorbent, anti-fading agent and dye, as well as supports for the emulsion-having photographic materials, the coating method, the light-exposing method and the developing method are not specifically limited, and for example, the descriptions of Research Disclosure , Vol. 176, Item 17643 (RD-17643), ibid ., Vol. 187, Item 18716 (RD-18716) and ibid ., Vol. 225, Item 22534 (RD-22534) may be referred to.
  • the color couplers for use in the present invention are preferably non-diffusible as having a ballast group or being polymerized.
  • 2-Equivalent couplers in which the coupling active position is substituted by a coupling-releasing group are more preferred than 4-equivalent couplers where a hydrogen atom is in the coupling active position, because the amount of silver to be coated may be reduced.
  • couplers capable of forming a colored dye with a pertinent diffusibility colorless couplers, DIR couples capable of releasing a development inhibitor by a coupling reaction, or couplers capable of releasing a development accelerator by a coupling reaction may also be used.
  • yellow couplers for use in the present invention there are oil-protect type acylacetamide couplers as the typical examples. Specific examples thereof are described in US-A-2,407,210, 2,875,057 and 3,265,506.
  • 2-equivalent yellow couplers are preferably used, and specific examples of these yellow couplers are the oxygen atom-releasing type yellow couplers described in US-A-3,408,194, 3,447,928, 3,933,501 and 4,022,620, and the nitrogen atom-releasing type yellow couplers described in JP-B-58-10739, US-A-4,401,752 and 4,326,024, RD-18053 (April, 1979), GB-B-1,425,020, DE-A-Nos.
  • ⁇ -pivaloylacetanilide couplers are excellent in fastness, in particular, light fastness of the colored dyes formed, while ⁇ -benzoylacetanilide couplers are excellent in coloring density.
  • magenta couplers for use in the present invention there are oil-protect type indazolone or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolones or pyrazolotriazoles.
  • pyrazoloazole couplers such as 5-pyrazolones or pyrazolotriazoles.
  • 5-pyrazolone couplers those substituted by an arylamino or acylamino group at the 3-position thereof are preferred from the viewpoint of the hue and coloring density of the colored dyes formed. Specific examples of these couplers are described in US-A-2,311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896 and 3,936,015.
  • the nitrogen atom-releasing groups described in US-A-4,310,619and the arylthio groups described in US-A-4,351,897 are especially preferred.
  • the 5-pyrazolone magenta couplers having a ballast group described in EP-B-73,636 give high coloring density.
  • the pyrazoloazole couplers there may be mentioned the pyrazolobenzimidazoles described in US-A-3,061,432, preferably the pyraozolo[5,1-c][1,2,4]triazoles described in RD-24220 (June, 1984)and JP-A-60-33552, and the pyrazolopyrazoles described in RD-24230 (June, 184) and JP-A-60-43659.
  • the imidazo[1,2-b]pyrazoles described in US-A-4,500,630 are preferred because of the small yellow side-absorption of the colored dye and the sufficient light-fastness thereof.
  • the pyraozolo[1,5-b][1,2,4]triazoles described in US-A-4,540,654 are especially preferred.
  • cyan couplers for use in the present invention there are oil-protect type naphthol couplers.
  • the couplers there be mentioned the naphthol couplers described in US-A-2,474,293, preferably the oxygen atom-releasing 2-equivalent naphthol couplers described in US-A-4,052,212, 4,146,396, 4,228,233 and 4,296,200.
  • Specific examples of phenol couplers which may be used in the present invention are described in US-A-2,369,929, 2,801,171, 2,772,162 and 2,895,826.
  • Cyan couplers having high fastness to humidity and temperature are preferably used in the present invention and specific examples of these cyan couplers include the phenol cyan couplers having an alkyl group of 2 or more carbon atoms at the meta-position of the phenol nucleus described in US-A-3,772,002; the 2,5-diacylamino-substituted phenol cyan couplers described in US-A-2,772,162, 3,758,308, 4,126,396, 4,334,011 and 4,327,173, DE-A-.
  • the naphthol cyan couplers having a sulfonamido or amido group at the 5-position of the naphthol nucleus described in JP-A-59-93605, 59-264277 and 59-268135 are also excellent in the fastness of the color image formed therefrom, and these may preferably be used in the present invention.
  • couplers giving colored dyes having a proper diffusibility together with the aforesaid color couplers, the graininess of the color images formed can be improved.
  • magenta couplers of this type are described in US-A-4,366,237 and GB-B-2,125,570, and specific examples of yellow, magenta and cyan couplers of this type are described in EP-B-96,570 and DE-A-. 3,234,533.
  • the dye-forming couplers and the above-mentioned particular couplers for use in the present invention may form dimers or higher polymers.
  • Typical examples of the polymerized dye-forming couplers are described in US-A-3,451,820 and 4,080,211.
  • specific examples of the polymerized magenta couplers are described in GB-B-2,102,173, US-A-4,367,282 and JP-A-60-75041 and 60-113596.
  • So-called DIR couplers capable of releasing a development inhibitor along with coupling may also be used in the present invention.
  • the color developer for use in development of the photographic materials of the present invention is preferably an aqueous alkaline solution consisting essentially of an aromatic primary amine developing agent.
  • an aromatic primary amine developing agent As the color developing agent for the developer, p-phenylenediamine compounds are preferably used, although aminophenol compounds are useful.
  • the silver halide color photographic materials are of the present invention generally rinsed in water and/or stabilized, after being desilvered.
  • the amount of the water to be used in the rinsing step can be set in a broad range, in accordance with the characteristic of the photographic material being processed (for example, depending upon the raw material components, such as the coupler and so on) or the use of the material, as well as the temperature of the rinsing water, the number of the rinsing tanks (the number of the rinsing stages), the replenishment system of normal current or countercurrent and other various kinds of conditions.
  • the pBr value of the resulting emulsion was adjusted to be 2.6, and 75 g of silver nitrate and the same molar amount of potassium bromide were added thereto under the condition of an accelerated flow rate (the final flow rate was 2 times of the initial flow rate).
  • the emulsion was washed with water and re-dispersed, as in the case of the preparation of Emulsion (3-B).
  • the thus prepared tabular grains were also core/shell grains, in which the core was silver iodobromide containing 25 mol% of silver iodide and the shell was silver bromide.
  • the projected area circle-corresponding diameter of the grains was 2.6 ⁇ m and the grain thickness thereof was 0.22 ⁇ m.
  • the development procedure comprised the following steps, which were conducted at 38°C. 1. Color Development 2 min 45 sec 2. Bleaching 6 min 30 sec 3. Rinsing in Water 3 min 15 sec 4. Fixation 6 min 30 sec 5. Rinsing in Water 3 min 15 sec 6. Stabilization 3 min 15 sec
  • Nitrilotriacetic Acid Sodium Salt 1.0 g Sodium Sulfite 4.0 g Sodium Carbonate 30.0 g Potassium Bromide 1.4 g Hydroxylamine Sulfate 2.4 g 4-(N-ethyl-N- ⁇ -hydroxyethylamino)-2-methylaniline Sulfate 4.5 g Water to make 1 liter
  • Ammonium Bromide 160.0 g Aqueous Ammonia (28 wt.%) 25.0 ml Ethylenediamine-tetraacetic Acid Sodium Salt 130 g Glacial Acetic Acid 14 ml Water to make 1 liter
  • Tetrapolyphosphoric Acid Sodium Salt 2.0 g Sodium Sulfite 4.0 g Ammonium Thiosulfate (70%) 175.0 ml Sodium Brisulfite 4.6 g Water to make 1 liter
  • Emulsions (3-C) and (3-D) of the present invention had a higher sensitivity than comparative Emulsion (3-B).
  • Emulsion (1-E) obtained in Example 1 was optimally chemically sensitized by the conventional manner, using sodium thiosulfate (5.5 x 10 ⁇ 6 mol/mol Ag) , potassium chloroaurate (4.5 x 10 ⁇ 6 mol/mol Ag) and potassium thiocyanate (4.5 x 10 ⁇ 4 mol/mol Ag) .
  • the resulting emulsion was used as the emulsion for the fourth layer of the Sample No. 104 in Example 1 of JP-A-62-215271 to prepare a photographic material sample. This was processed in the manner described in Example 1 of JP-A-62-215271. As a result, the sample was proved to have a good photographic property.
  • the emulsion was used as a core emulsion, and a shell (second coat layer or outer layer) of silver bromide was formed over the core.
  • the molar ratio of first coat layer/second coat layer was 1/1.
  • the thus obtained emulsion grains were monodispersed core/shell octahedral grains having a mean projected area circle-corresponding diameter of 2.2 ⁇ m and a core silver iodide content of 25 mol%.
  • the emulsion grains were used as core grains, and 800 ml of silver nitrate solution (1.5 M of AgNO3) and 800 ml of potassium bromide solution (1.5 M of KBr) were simultaneously added thereto over a period of 80 minutes in the reactor vessel by the double jet method so as to form a silver bromide shell (second coat layer or outer layer) over the core grains.
  • the ratio of first coat layer/second coat layer was 1/1.
  • the thus prepared grains were monodispersed core/shell octahedral grains having a mean projected area circle-corresponding diameter of 2.2 ⁇ m and a silver iodide core of 25 mol%.
  • first coat layer/second coat layer was 1/1.
  • the thus obtained grains were monodispersed octahedral core/shell grains having a mean projected area circle-corresponding diameter of 2.2 ⁇ m.
  • Each of emulsions (6-A), (6-B) and (6-C) was optimally chemically sensitized with sodium thiosulfate (4.0 x 10 ⁇ 6 mol/mol Ag), potassium chloroaurate (3.0 x 10 ⁇ 6 mol/mol Ag) and potassium thiocyanate (3.0 x 10 ⁇ 4 mol/mol Ag), and the compounds mentioned below were added thereto.
  • the resulting coating composition was coated on a subbing layer-coated triacetyl cellulose film support.
  • the development procedure comprised the following steps all of which were conducted at 38°. 1. Color Development 2 min 45 sec 2. Bleaching 6 min 30 sec 3. Rinsing in Water 3 min 15 sec 4. Fixation 6 min 30 sec 5. Rinsing in Water 3 min 15 sec 6. Stabilization 3 min 15 sec
  • Nitrilotriacetic Acid Sodium Salt 1.0 g Sodium Sulfite 4.0 g Sodium Carbonate 30.0 g Potassium Bromide 1.4 g Hydroxylamine Sulfate 2.4 g 4(N-ethyl-N- ⁇ -hydroxy e thylamino)-2-methylaniline Sulfate 4.5 g Water to make 1 liter
  • Tetrapolyphosphoric Acid Sodium Salt 2.0 g Sodium Sulfite 4.0 g Ammoniumthiosulfate (70%) 175.0 ml Sodium Bisulfite 4.6 g Water to make 1 liter
  • Emulsions (6-B) and (6-C) of the present invention are extremely excellent because of the high sensitivity and low fog.
  • the samples were subjected to pressure test (bending test where the emulsion-coated films are bent).
  • pressure test bending test where the emulsion-coated films are bent.
  • Emulsion (6-A) showed extreme pressure desensitization
  • Emulsions (6-B) and (6-C) showed almost no pressure desensitization. From the test, therefore, it is noted that the pressure-resistance of the emulsions of the present invention was noticeably improved.
  • the grains were used as cores, and 400 ml of a 1.5 M aqueous silver nitrate solution and 400 ml of an aqueous halide solution containing 0.15 M potassium iodide and 1.35 M potassium bromide were simultaneously added thereto by the double jet method, whereby a silver iodobromide shell with 10 mol% of silver iodide content was formed over the core.
  • the resulting emulsion was cooled to 35°C and washed with water by the conventional flocculation method.
  • 85 g of gelatin was added and the emulsion was adjusted to have a pH of 6.2 and a pAg of 8.8.
  • the thus prepared grains were monodispersed octahedral core/shell grains having a mean projected area circle-corresponding diameter of 2.2 ⁇ m, in which the shell contained 10 mol% of silver iodide.
  • Cores having a mean projected area circle-corresponding diameter of 1.7 ⁇ m were prepared as in the case of Emulsion (7-A). 20 ml of 30 % potassium bromide was added thereto. The fine grains-containing Emulsion (1-A) of Example 1 (containing 10 mol% of silver iodide) was added in an amount of 0.6 mol as silver, with a pump, at a constant flow rate over a period of 50 minutes. Thus, core/shell grains were prepared a in the case of Emulsion (7-A). These were monodispersed octahedral core/shell grains having a mean projected area circle-corresponding diameter of 2.2 ⁇ m, in which the shell contained 10 mol% of silver iodide.
  • Silver bromide cores having a mean projected area circle-corresponding diameter of 1.7 ⁇ m were prepared as in the case of Emulsion (7-A).
  • 400 ml of an aqueous 1.5 M silver nitrate solution, 400 ml of an aqueous halide solution containing 0.15 M potassium iodide and 1.35 M potassium bromide and 200 ml of an aqueous 1 wt.% gelatin solution were simultaneously added to a strong and efficient mixer provided near the reactor vessel, by the triple jet method over a period of 50 minutes, whereupon the temperature in the mixer was kept at 35°C.
  • the ultra-fine grains thus prepared in the mixer were directly continuously introduced into the reactor vessel kept at 75°C.
  • Emulsions (7-A), (7-B) and (7-C) were optimally chemically sensitized with sodium thiosulfate (7.2 x 10 ⁇ 6 mol/mol Ag), potassium chloroaurate (5.6 x 10 ⁇ 6 mol/mol Ag) and potassium thiocyanate (5.5 x 10 ⁇ 4 mol/mol Ag).
  • photographic samples were prepared in the same manner as in Example 6. These samples were sensitometrically processed, and the photographic properties of the respective samples obtained are shown in Table 6 below.
  • Example of the Invention 7-C 350 0.15
  • seed crystal tabular silver bromide grains which are to be nuclei
  • an aqueous solution containing 150 g of silver nitrate, a potassium bromide solution containing 10 mol% of potassium iodide (the potassium bromide therein being equimolecular to silver nitrate in the solution), and 500 ml of an aqueous 3 wt% gelatin solution were added to the mixer which was provided near the reactor vessel, by the triple-jet method over a period of 55 minutes, under the condition of an accelerated flow rate (the final flow rate was 10 times of the initial flow rate).
  • the residence time of the solutions added in the mixer vessel was 10 seconds.
  • the rotation number of the stirring blades in the mixer vessel was 3000 room temperature.
  • the thus formed fine silver iodobromide grains were observed with a direct transmission electron microscope at a magnification of 20,000 times. As a result, the mean grain size was 0.03 ⁇ m.
  • the temperature of the mixer vessel was kept at 35°C, and the fine grains formed in the mixer were continuously introduced into the reactor vessel.
  • Emulsion (8-C) was tried to be prepared in the same manner as emulsion (8-B), except that the temperature in the mixer vessel was changed to 15°C. However, when the temperature in the mixer vessel was adjusted to be 15°C, the gelatin solution gelled in the mixer vessel so that fine grains were not formed therein. In order to obtain fine grains having a small grain size, it is said necessary to lower the temperature in the mixer vessel. However, when the gelatin (P-1) was used as the protective colloid, it was found that formation of fine grains was impossible at such a low temperature.
  • the low molecular weight gelatin (P-2) was used as the protective colloid, in place of the gelatin (P-1). In this case using the gelatin (P-2), no gelation occurred even at 15°C and formation of fine grains was possible.

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Claims (15)

  1. Une émulsion photographique d'halogénure d'argent comprenant un milieu dispersant et des grains d'halogénure d'argent, caractérisée en ce que les grains d'halogénure d'argent comprennent une phase d'halogénure d'argent contenant 3 mol% ou plus d'iodure d'argent, la non-uniformité microscopique provoquée par l'iodure d'argent étant telle que les grains d'halogénure d'argent présentent au plus deux lignes à un intervalle de 0,2 µm dans la dimension perpendiculaire au lignes, observées au microscope électronique à transmission, et en ce que l'émulsion contient au moins 60 % en poids desdits grains d'halogénure d'argent.
  2. Une émulsion photographique à l'halogénure d'argent selon la revendication 1, dans laquelle des grains d'halogénure d'argent tabulaires ayant un rapport d'aspect moyen supérieur à 2 rendent compte d'au moins 50 % de la surface projetée totale des grains d'halogénure d'argent.
  3. L'émulsion photographique d'halogénure d'argent selon la revendication 1, dans laquelle les grains d'halogénure d'argent n'ont pas de lignes produites par la non-uniformité microscopique de l'iodure d'argent dans les grains.
  4. L'émulsion photographique d'halogénure d'argent selon la revendication 3, dans laquelle les grains d'halogénure d'argent ont une structure noyau/enveloppe de bromure d'argent et d'iodobromure d'argent.
  5. L'émulsion photographique d'halogénure d'argent selon la revendication 4, dans laquelle les grains d'halogénure d'argent ont une structure noyau/enveloppe à trois couches de bromure d'argent et d'iodobromure d'argent.
  6. L'émulsion photogrpahique d'halogénure d'argent selon la revendication 4, dans laquelle la proportion d'iodobromure d'argent dans chaque grain est de 5 à 95 mol%.
  7. L'émulsion photographique d'halogénure d'argent selon la revendication 5, dans laquelle la teneur en iodure d'argent dans la phase d'iodobromure d'argent est de 3 à 45 mol%.
  8. L'émulsion photographique d'halogénure d'argent selon la revendication 7, dans laquelle la teneur en iodure d'argent dans la phase d'iodobromure d'argent est de 5 à 35 mol%.
  9. L'émulsion photographique d'halogénure d'argent selon la revendication 8, dans laquelle la teneur en iodure d'argent dans les grains totaux d'halogénure d'argent est de 3 mol% ou plus.
  10. L'émulsion photographique d'halogénure d'argent selon la revendication 7, dans laquelle la teneur en iodure d'argent dans les grains totaux d'halogénure d'argent est de 5 mol% ou plus.
  11. L'émulsion photographique d'halogénure d'argent selon la revendication 2, dans laquelle les grains d'halogénure d'argent tabulaires ont un rapport d'aspect moyen de 3 à 20.
  12. L'émulsion photographique d'halogénure d'argent selon la revendication 1 ou 2, qui a été préparée en utilisant comme liant une gélatine de bas poids moléculaire, un composé synthétique de haut poids moléculaire ayant une action de colloïde protecteur sur les grains d'halogénure d'argent ou un composé naturel de haut poids moléculaire, sauf pour la gélatine.
  13. L'émulsion photographique d'halogénure d'argent selon la revendication 12, dans laquelle le liant est une gélatine de bas poids moléculaire.
  14. Un procédé pour préparer l'émulsion photographique d'halogénure d'argent selon la revendication 1, comprenant les étapes suivantes :
    (1) On mélange une solution aqueuse d'un sel d'argent soluble dans l'eau et une solution aqueuse d'au moins un halogénure soluble dans l'eau dans un mélangeur disposé à l'extérieur d'un récipient de réaction et
    (2) on charge dans le mélangeur une solution aqueuse de colloïde protecteur à une concentration d'au moins 1 % en poids par l'une des méthodes suivantes :
    (a) séparément;
    (b) dans la solution aqueuse du sel d'argent soluble dans l'eau ; et
    (c) dans la solution aqueuse de l'halogénure soluble dans l'eau,
    pour préparer des germes cristallins et
    (3) on mélange les germes d'halogénure d'argent avec des grains fins d'halogénure d'argent contenant de l'iodure dans le réacteur au lieu d'y ajouter des solutions aqueuses séparées d'halogénure et de sel d'argent.
  15. Un procédé pour préparer l'émulsion photographique d'halogénure d'argent selon la revendication 14, dans lequel la dimension moyenne de grains de l'émulsion d'halogénure d'argent à grains fins est de 0,1 µm ou moins, la température pendant la formation de l'émulsion d'halogénure d'argent à grains fins est de 40°C ou moins et on fait grossir les grains dans le récipient de réaction à une température de 50°C ou plus.
EP19890100764 1988-01-18 1989-01-18 Emulsions photographiques à l'halogénure d'argent et procédé pour les préparer Expired - Lifetime EP0326853B1 (fr)

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JP7853/88 1988-01-18
JP63007853A JPH07104569B2 (ja) 1988-01-18 1988-01-18 ハロゲン化銀写真乳剤
JP785288A JPH01183644A (ja) 1988-01-18 1988-01-18 ハロゲン化銀写真乳剤
JP7852/88 1988-01-18

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EP0362699A3 (fr) * 1988-10-03 1991-03-13 Eastman Kodak Company Emulsions à grains tabulaires à haut indice de forme présentant une répartition granulométrique plus étroite
JPH0769581B2 (ja) * 1988-11-08 1995-07-31 富士写真フイルム株式会社 ハロゲン化銀写真乳剤
JPH02164719A (ja) * 1988-12-19 1990-06-25 Fuji Photo Film Co Ltd ハロゲン化銀粒子の形成方法
JPH02186337A (ja) * 1989-01-13 1990-07-20 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
JP2890051B2 (ja) * 1989-09-06 1999-05-10 コニカ株式会社 ハロゲン化銀カラー写真感光材料
US5262294A (en) * 1990-02-19 1993-11-16 Konica Corporation Silver halide photographic light sensitive material
JPH03241336A (ja) * 1990-02-19 1991-10-28 Konica Corp ハロゲン化銀写真感光材料
JPH03293662A (ja) * 1990-04-12 1991-12-25 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
EP0480294B1 (fr) * 1990-10-03 1997-07-16 Konica Corporation Procédé de préparation d'émulsions photographiques à l'halogénure d'argent
JP2699223B2 (ja) * 1991-04-18 1998-01-19 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
JP2936105B2 (ja) * 1991-06-06 1999-08-23 コニカ株式会社 ハロゲン化銀乳剤の製造方法及びハロゲン化銀写真感光材料
JPH0566510A (ja) * 1991-09-06 1993-03-19 Konica Corp ハロゲン化銀写真乳剤
JP2961579B2 (ja) * 1991-11-20 1999-10-12 コニカ株式会社 ハロゲン化銀カラー写真感光材料
JP3074497B2 (ja) * 1991-12-27 2000-08-07 コニカ株式会社 色再現性に優れたハロゲン化銀カラー写真感光材料
US5320938A (en) * 1992-01-27 1994-06-14 Eastman Kodak Company High chloride tabular grain emulsions and processes for their preparation
US5360703A (en) * 1993-01-28 1994-11-01 Eastman Kodak Company Multicolor photographic elements exhibiting an enhanced characteristic curve shape
US6518008B1 (en) * 1999-01-25 2003-02-11 Eastman Kodak Company Fragmentable electron donor compounds in combination with high bromide tabular grain emulsions

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