EP0097720B1 - Verfahren zur herstellung einer silberhalidemulsion - Google Patents

Verfahren zur herstellung einer silberhalidemulsion Download PDF

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Publication number
EP0097720B1
EP0097720B1 EP83900062A EP83900062A EP0097720B1 EP 0097720 B1 EP0097720 B1 EP 0097720B1 EP 83900062 A EP83900062 A EP 83900062A EP 83900062 A EP83900062 A EP 83900062A EP 0097720 B1 EP0097720 B1 EP 0097720B1
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EP
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Prior art keywords
silver halide
silver
ring
sensitization
emulsion
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EP83900062A
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English (en)
French (fr)
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EP0097720A4 (de
EP0097720A1 (de
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Hideki Takiguchi
Toshifumi Iijima
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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
    • G03C1/015—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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03529—Coefficient of variation
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03535—Core-shell grains
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03564—Mixed grains or mixture 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
    • G03C2200/00—Details
    • G03C2200/06—Additive

Definitions

  • This invention relates to a light-sensitive silver halide photographic emulsion, more particularly to a method for sensitizing a silver halide emulsion including silver halide grains mainly comprising silver iodobromide, and a silver halide photographic emulsion sensitized by the aforementioned method.
  • silver halides for photography there has been utilized a variety of silver halides such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide, but as silver halides for high-sensitive photography, the silver iodobromide has been used to obtain high-sensitive emulsions.
  • the most orthodox method for obtaining photographic performances such as high sensitivity and low fog mentioned above is to improve the quantum efficiency of the silver halide.
  • Researches, in which the quantum efficiency is calculated theoretically and the influence of grain size distribution is studied, are described, for example, on page 91 of "Interactions between Light and Materials for Photographic Applications" contributed in a preliminary text for lectures at Tokyo Symposium regarding the advancement of photography in 1980.
  • it is predicted that preparing a monodispersed emulsion of a narrow grain size distribution would improve the quantum efficiency.
  • the monodispersed emulsion can be theoretically presumed to be advantageous.
  • the silver halide emulsion manufactured under such conditions comprises the so-called regular crystal grains having faces (100) and faces (111) in various ratios, and these grains have any configuration of cube, octahedron and tetradecahedron.
  • octahedral grains The characteristics of octahedral grains are described in, e.g., "Journal of Photographic Science", Volume 14, pages 181 to 184 (1966), and Volume 16, pages 102 to 113 (1968), “Photographische Korrespondenz), Volume 106, pages 149 to 160 (1970) and “Nippon Shashin Gakkai Journal", Volume 42, pages 112 to 121 (1979). It can be supposed from these reports that the chemical sensitization of the tetradecahedral grains is predominantly advanced on the faces (111), and that tetradecahedral grains are considered to have the same characteristics as in the octahedral grains. From our research it has been found that tetradecahedral grains have indeed similar properties to those of octahedral grains.
  • a hydroxyazaindene compound is well known in the art, as a stabilizer for a photographic emulsion because it has the ability to inhibit chemical ripening by a sulphur-containing compound. Therefore, the azaindene compound has been used with the aim of terminating a sulphur sensitization reaction and/or preventing the occurrence of fog in the course of a manufacturing process, a storage step or a development processing. Also, it has been known that this compound increases photographic sensitivity. For example, U.K. Patent No.
  • 1,315,755 describes that the inherent sensitivity of the silver halide is higher than by the conventional method, when in gold-sulphur sensitization of the silver halide emulsion, the azaindene is added prior to the sulphur sensitization, and at the same time or subsequently a monovalent gold complex salt compound including sulphur is also added, followed by ripening.
  • the sensitization method without the azaindene is applied to the silver halide emulsion, a sufficient effect cannot be obtained.
  • JP-A-63914/1975 and DE-A-2,419,798 disclose that when a monodispersed silver halide cubic grain emulsion in which the molar percentage of silver bromide is 80% or more, is sulphur sensitized and the hydroxytetrazaindene compound is then added thereto, the sensitivity increases.
  • these publications also describe that crystalline grains other than cubes, e.g. octahedral grains and platelike grains substantially surrounded with the faces (111) decrease rather than increase in sensitivity, or even if it increases, it is only a little.
  • JP-A-77223/1976 and U.S. Patent No. 4,078,937 it is disclosed that if the silver halide grains in a sulphur sensitized silver halide photographic emulsion have an average grain size of 0.5 pm or less, the sensitivity increases on condition that a particular hydroxytetrazaindene compound is added thereto.
  • a first object of this invention is to provide a method by which a monodispersed emulsion including silver halide grains of octahedral or tetrahedral crystals having faces (111) is noticeably sensitized, scarcely producing a photographic fog
  • a second object of this invention is to provide a silver halide photographic emulsion having a high sensitivity obtained by such a chemical sensitization method.
  • the invention provides a method for preparing a silver halide emulsion which comprises subjecting the silver halide emulsion including core-shell type silver halide grains substantially composed of silver iodobromide to a gold-sulphur sensitization or gold-selenium sensitization by use of a gold sensitizer and sulphur or selenium sensitizer, characterized in that the silver halide grains are octahedral or tetradecahedral crystals each having faces (111); the coefficient of variation regarding a grain size distribution of the silver halide grains is 0.18 or less; and the sensitization is carried out in the presence of a nitrogen-containing heterocyclic compound capable of forming a complex with silver or a silver ion.
  • This invention is based on the discovery that when the silver halide grains contained in the silver halide emulsion are monodispersed core-shell type silver iodobromide grains comprising octahedral or tetradecahedral crystals each having (111) faces, and when the ratio between the selenium sensitizer and gold sensitizer or the ratio between the sulphur sensitizer and gold sensitizer is controlled in a certain range in the presence of the nitrogen-containing heterocyclic compound which forms the complex with silver in an amount sufficient to cover the grains, a noticeably high sensitization can be accomplished.
  • This invention removes the disadvantage that when the known gold-sulphur sensitization or gold-selenium sensitization is used for the octahedral or tetradecahedral silver iodobromide grains, the silver sulphide nuclei are easily produced on the faces (111) and many light-sensitive nuclei are formed on one silver iodobromide grain, which fact prevents the increase in the quantum efficiency.
  • the effect of this invention can be procured by constituting the silver iodobromide grains in the form of the core-shell type in the monodispersed emulsion, and intentionally controlling a light-sensitive nucleus-forming reaction on the (111) faces in the presence of the nitrogen-containing heterocyclic compound capable of producing the complex with silver or a silver ion.
  • the effect of this invention cannot be obtained, because the cubic silver halide grains allow light-sensitive nuclei to be more easily and selectively formed on the vertices of each cube than on the faces (100) thereof.
  • the effect of the sensitization is not so great.
  • the core-shell type monodispersed octahedral or tetradecahedral silver iodobromide emulsion is gold-sulphur sensitized or gold-selenium sensitized in the absence of any nitrogen-containing heterocyclic compound, the effect of the sensitization is also small.
  • the quantum efficiency will increase and the gold-sulphur sensitization or gold-selenium sensitization will also increase, but due to the added iodine, lattice defects increase and thus the number of silver ions between lattices also increase. Further, the iodine atoms which are present on the surfaces of the crystals serve to restrain the gold-sulphur sensitization or gold-selenium sensitization reaction.
  • the influence of the iodine atoms, on the surfaces, during chemical sensitization can be weakened by using core-shell grains to reduce the content of the silver iodide on the faces, but use of these grains is not effective against the increase in the lattice defects and the augmentation in the silver ions between the lattices and cannot control the crystal habit dependency of the chemical sensitization reaction.
  • the nitrogen-containing heterocyclic compound serves to reduce the amount of the silver ions between the lattices to a level necessary for the chemical sensitization reaction by forming a complex with the silver ion on the surfaces thereby controlling the chemical sensitization reaction so that effective light-sensitive nuclei may be produced in a small amount, but the compound cannot prevent the restraining effect on the chemical sensitization reaction by the iodine atoms on the surfaces.
  • the core-shell type octahedral or tetradecahedral silver iodobromide emulsion is gold-sulphur sensitized or gold-selenium sensitized in the presence of a nitrogen-containing heterocyclic compound, good results can be expected, and the degree of sensitization obtained is more remarkable than anticipated, because of a synergistic effect which could not be predicted.
  • a feature of this invention is that the reaction of forming the nuclei for the chemical sensitization is controlled by taking the above-mentioned technical constitution and the combination effect of the gold-sulphur or gold-selenium sensitization is obtained more remarkably than in the conventional one.
  • the nitrogen-containing heterocyclic compound is added at the end of the sulphur sensitization in order to control silver ions on and near the surfaces of the silver halide grains and to thereby improve the efficiency of latent image formation. Therefore, this invention is different from these in technique.
  • JP-A-77223/1976 and U.S. Patent No. 4,078,937 disclose a method in which a specific hydroxytetrazaindene compound is added to an emulsion of a sulphur sensitized silver halide the average grain size of which is not in excess of 0.5 pm, in order to increase the sensitivity of the silver halide emulsion.
  • the above publications disclose neither the particular combination of features nor the effects of this invention anywhere, and, in all the examples of the publications, the hydroxytetrazaindene compound is added after chemical ripening. Probably for this reason, the effect of the sensitization by the above method depends on the average grain size, and the particular crystal habit of the silver halide grains is not selected. Accordingly, the inventions disclosed in these publications are different from this invention in technique.
  • US ⁇ A ⁇ 3,317,322 discloses the use of core-shell type grains in silver halide emulsions.
  • the specification of U.K. Patent No. 1,315,755 discloses a method in which after the azaindene compound has been added, a monovalent gold complex salt compound including sulphur is added to carry out a gold-sulphur sensitization, but it does not refer to the crystal structure of the silver halide grains, the core-shell structure or the like anywhere. Therefore, this invention is not anticipated by the instant literature.
  • the silver halide composition preferably comprises substantially silver iodobromide including 0.5 to 15 mol% of silver iodide, but it may include silver chloride in an amount that the object of the invention is still achieved.
  • the morphology of the silver halide grains is octahedral substantially formed with faces (111), or tetradecahedral formed with the faces (111) and faces (100). There is no limit to the diameters of these grains.
  • the ratio between the faces (111) and faces (100) is not limited to a specific range, but the percentage of the faces (111) is generally at least 5% of the whole surface area of the grains.
  • the percentage of the silver halide grains with the required features is preferably 50% or more, more preferably 70% or more.
  • the emulsion in which the silver halide grains substantially comprise the silver halide grains with the required features is most preferred.
  • a so-called monodispersed emulsion is employed in which coefficient of variation of the grain size distribution of the silver halide grains contained in the silver halide emulsion is 0.18 or less.
  • the method is based on the concept that gold-selenium sensitization or gold-sulphur sensitization is controlled by covering the silver halide surfaces with the nitrogen-containing heterocyclic compound capable of forming a complex with silver or a silver ion, but it seems that when a polydispersed emulsion is used, the distribution of a grain surface area is large, and it is thus difficult to efficiently cover the grain surfaces.
  • the uniformity of the size of the silver halide grains included in the silver halide emulsion can be represented by a value obtained by dividing the standard deviation S of a grain size distribution by the average grain size (diameter) r, i.e. the coefficient of variation of the grain diameter distribution, as shown by the following formula (1):
  • the average grain diameter referred to here means an average value of diameters obtained by converting projected images of the silver halide grains into circular images having the same areas, and it can be defined as r by the following formula, when each grain diameter is r, and the number of the grains of radius r, is n ; .
  • the grain diameter r can be measured in various ways usually used in the art for the aforesaid purpose. Typical methods are described in Loveland, "Analytical Method of Grain Diameter", A.S.T.M. Symposium on Light Microscopy, pages 94 to 122 (1955), and Mies and James, “Theory Of Photographic Process", 3rd Edition, Volume 2, McMillan Co., Ltd. (1966).
  • the emulsion with a coefficient of variation of 0.18 or less will be referred to as a monodispersed emulsion.
  • the silver halide emulsion can be prepared by the use of methods described in, for example, P. Glafkides, "Chimie et Physique Photographique”, Paul Montel Co., Ltd. (1967); G. F. Duffin, "Photographic Emulsion Chemistry", The Focal Press (1966); and V. L. Zelikman, "Making and Coating Photographic Emulsion", The Focal Press (1964). That is to say, the silver halide emulsion may be prepared by an acidic method, a neutral method or an ammonia method, and the soluble silver salt may be reacted with a soluble halogen salt to an injection mixing process, a simultaneous mixing process or a combination thereof.
  • An example of the aforesaid simultaneous mixing process is a method of constantly maintaining a pAg in a liquid phase in which the silver halide is produced, i.e. the so-called controlled double-jet method.
  • the core-shell type silver halide grains have a grain structure comprising two or more layers which differ in the content of silver iodide, and it is preferred that a portion nearer the surface has a smaller silver iodide content, as compared with an inner portion of the grain.
  • the surface-near portion referred to above means an outer portion of the grain which ranges from 0.001 to 0.1 pm in thickness from the surface.
  • the difference between the respective silver iodide contents in the outer portion and the inner layers is preferably 5 mol % or more.
  • the lower the silver iodide content in the outer portion is, the better, and it is preferred that the outer portion substantially comprises silver bromide.
  • An emulsion including such silver halide grains can provide a high sensitization efficiency and is especially suitable for obtaining a surface latent image type emulsion.
  • the transition from the layer having the higher silver iodide content to the layer having the lower content thereof may be bounded by a sharp or gradual transition.
  • the distribution of the silver iodide in the aforementioned silver halide grains can be detected by a variety of physical measurements, for example, by measuring luminescence at low temperature, as described in Annual Congress Lecture Summary Bulletin in 1981 published by Nippon Shashin Gakkai.
  • the outer portion of each grain includes 0 to 4 mol % of silver iodide and the inner portion includes 2 to 15 mol % of silver iodide.
  • the silver halide composition other than the aforementioned silver iodide is mainly silver bromide, but silver chloride may be employed so long as it does not impair the effect of this invention, and this limit is typically less than approximately 1 mol %.
  • the silver halide emulsion may include a mixture of octahedral and tetradecahedral grains.
  • the core-shell type silver halide grains included in the silver halide emulsion can be prepared by covering, with a shell, a core comprising a monodispersed silver halide grain.
  • Monodispersed cores of appropriate size can be manufactured by the double-jet method, while maintaining pAg at a constant level.
  • the monodispersed silver halide emulsion can be prepared by a method disclosed in JP-A-48521/1979.
  • the emulsion is manufactured by adding an aqueous potassium iodide-gelatin solution and an aqueous ammoniacal silver nitrate solution to an aqueous gelatin solution including silver halide seed crystals, with an addition rate varied as a function of time.
  • the variation in the addition rate pH, pAg, temperature and the like, it is possible to obtain high-grade monodispersed silver halide grains.
  • a cadmium salt zinc salt, lead salt, thallium salt, iridium salt, any one of their complex salts, rhodium salt or its complex salt.
  • the nitrogen-containing heterocyclic compounds used in this invention may be, e.g., a pyrazole ring, pyrimidine ring, 1,2,4-triazole ring, 1,2,3-triazole ring, 1,3,4-thiadiazole ring, 1,2,3-thiadiazole ring, 1,2,4-thiadiazole ring, 1,2,5-thiadiazole ring, 1,2,3,4-tetrazole ring, pyridazine ring, 1,2,3-triazine ring, 1,2,4-triazine ring, 1,3,5-triazine ring, benzotriazole ring, benzimidazole ring, benzothiazole ring, quinoline ring, benzoxazole ring, benzoselenazole ring, naphthothiazole ring, naphthoimidazole ring, rhodanine ring, thiohydantoin ring, oxazole ring
  • Preferred nitrogen-containing heterocyclic compounds have an azaindene ring, and azaindene compounds having hydroxy groups as substituent groups, e.g. hydroxytriazaindene, tetrahydroxy- azaindene and hydroxypentazaindene compounds are particularly preferred.
  • the heterocyclic rings may have substituent groups other than hydroxy.
  • substituent groups include an alkyl group, alkylthio group, amino group, hydroxyamino group, alkylamino group, dialkylamino group, arylamino group, carboxy group, alkoxycarbonyl group, halogen atom, acylamino group, cyano group and mercapto group.
  • the amount of nitrogen-containing heterocyclic compound to be added varies extensively with the size of the silver halide grains, composition, ripening condition and the like, but the compound is required to be added in such an amount as to enable the formation of from 3/1o to 10 molecular layers on the surface of each silver halide grain. This amount can be adjusted by the control of an adsorption equilibrium condition in accordance with a variation of a pH and/or temperature at the time of ripening.
  • the nitrogen-containing heterocyclic compound can be used together with a sensitizing dye at the time of the gold-sulphur sensitization or gold-selenium sensitization of this invention.
  • the nitrogen-containing heterocyclic compound and the sensitizing dye are added in a total amount such as to enable the formation of from 3 /io to 10 molecular layers on the surface of each silver halide grain, but it is preferred that the amount of the sensitizing dye does not exceed 70% of the amount required to form a single molecular layer on the surface of the silver halide grain.
  • the amount of the nitrogen-containing heterocyclic compound necessary for the formation of the single molecular layer can be determined by a drawn adsorption isotherm, but, for example, when the silver iodobromide emulsion grains comprising octahedral grains of 0.65 11 m in diameter are covered with 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, the required amount is approximately 210 mg/Ag mol. Therefore, an area occupied by this compound is approximately 30nm 2 per molecule. For other grains different in diameter, the amount of the compound may be found by an appropriate calculation, taking the value of the above example as a standard.
  • the nitrogen-containing heterocyclic compounds used in this invention are preferably colorless.
  • the addition of the nitrogen-containing heterocyclic compound to the emulsion can be carried out in the form of a solution where it is dissolved in a suitable solvent (e.g., water or an aqueous alkaline solution) which has no harmful influence on the photographic emulsion.
  • a suitable solvent e.g., water or an aqueous alkaline solution
  • the compound may exist in the emulsion at the time of the gold-sulphur sensitization or gold-selenium sensitization, and it is preferred that the compound is added thereto at the time of or before the addition of a sulphur sensitizer or selenium sensitizer.
  • the addition of the gold sensitizer may be carried out in the course of or at the end of the ripening for the sulphur or selenium sensitization.
  • the complex referred to here means a combination of two or more compounds or ions.
  • sulphur sensitizers can be used. Examples include thiosulfate, allythiocarbamidothiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate and rhodanine.
  • Sulphur sensitizers which are disclosed in U.S. Patent Nos. 1,574,944,2,410,689,2,278,947,2,728,668,3,501,313 and 3,656,955, German Patent No. 1,422,869, JP-A-24937/1981 and JP-A-45016/1980 may also be used.
  • the amount of sulphur sensitizer is such that it effectively increases the sensitivity of the emulsion.
  • This amount varies over a fairly extensive range under various conditions such as the amount of nitrogen-containing heterocyclic compound used, the pH, the temperature and the size of the silver halide grains, but about 10- 7 to about 10- 1 mol per mol of the silver halide is generally preferable.
  • selenium sensitizers may be used, which include aliphatic isoselenocyanates such as allyisoselenocyanate, selenoureas, selenoketones, selenoamides, seleno- carboxylic acids, selenoesters, selenophosphates, and selenides such as diethylselenide and diethyl diselenide.
  • aliphatic isoselenocyanates such as allyisoselenocyanate, selenoureas, selenoketones, selenoamides, seleno- carboxylic acids, selenoesters, selenophosphates, and selenides such as diethylselenide and diethyl diselenide.
  • the amount of the selenium sensitizer varies over an extensive range, but approximately 10- 7 to 10- 1 mol per mol of the silver halide is generally preferable.
  • gold sensitizers used in this invention a variety of gold compounds inclusive of ones having oxidation numbers of +1 and +3 can be employed.
  • Typical examples of the gold sensitizers include chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate and pyridyltrichlorogold.
  • the amount of the gold sensitizer is typically within the range of from about 10- 7 to 10- 1 mol per mol of the silver halide, though varying with various conditions.
  • gold nuclei and silver sulphide-gold nuclei or silver selenide-gold nuclei are produced as light-sensitive nuclei.
  • the number of these nuclei and especially the composition of the silver gold sulphide or silver gold selenide nuclei greatly influence the electron trap and development characteristics.
  • the proportion of gold sensitizer with respect to sulphur or selenium sensitizer has a great influence on the sensitization effect.
  • the proportion of the gold sensitizer with respect to the sulphur sensitizer or selenium sensitizer must be such that the ratio of gold atoms to sulphur atoms in the sulphur sensitizer which are capable of forming silver sulphide with silver ions or selenium atoms in the selenium sensitizer which are capable of forming silver selenide with the silver ions is within the range of 1:2 to 1:200.
  • the ratio of the latter to the former is within the range of 1:2 to 1:200.
  • the emulsion which undergoes the gold-sulphur sensitization or gold-selenium sensitization preferably has a pAg of 7.5 to 10.0 and a pH of 5.0 to 9.0.
  • the sensitization step can also be used with a sensitization process based on another noble metal such as platinum, palladium, iridum or rhodium, or a salt thereof.
  • another noble metal such as platinum, palladium, iridum or rhodium, or a salt thereof.
  • reducing agents are not particularly limited, but include stannous chloride, thiourea dioxide, hydrazine derivatives and silane compounds.
  • reduction sensitization is carried out while the silver halide grains grow or after the sulphur and gold sensitization has been completed.
  • the sensitizing process can also perform a noticeable spectrophotometric sensitization by using the sensitizing dye on the occasion of the gold-sulphur sensitization or gold-selenium sensitization of this invention.
  • the sensitizing dyes referred to above mean dyes which can expand the light-sensitive region of the silver halide for an electromagnetic wave into the outside of an inherent light-sensitive wave range.
  • Particular sensitizing dyes useful in this invention include cyanine dyes, merocyanine dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes and conjugate merocyanine dyes. These dyes are disclosed in, for example, F. M. Hamer, "The Cyanine Dye and Related Compounds" and C. T. H. James, "The Theory of the Photographic Process, Fourth Edition", pages 194 to 234.
  • Typical examples of the sensitizing dyes represented by the aforesaid general formula (I) used in this invention are as follows:
  • a particular limitation is not made and any procedure is applicable. For example, typically after color development, bleach-fix processing is carried out, followed, if desired, by washing and then stabilization; or after color development, bleaching and fixing are carried out separately, followed, if desired, by washing and then stabilization.
  • the silver halide photographic emulsion manufactured by the method of this invention can suitably be applied to many silver halide photographic light-sensitive materials, because it has a particularly high photographic sensitivity, less failure at high intensity and less photographic fog.
  • the aforementioned silver halide photographic emulsion can be applied effectively to a variety of the light-sensitive materials for use in black-and-white photography, X-ray photography, color photography, infrared photography, microphotography, silver dye bleach, reversal process and diffusion transfer process.
  • Emulsion (1) An octahedral monodispersed emulsion including grains was prepared by a double jet method, in which pAg and pH were controlled, according to the procedure disclosed in JP-A-48521/1979 (the thus prepared emulsion will hereinafter be referred to as Emulsion (1)).
  • Each of the above grains had an average diameter of 0.9 11m and comprised a core of silver iodide and a shell thereon of silver bromide having an average thickness of 0.016 pm.
  • the degree of dispersion of their grain size distribution was 0.15.
  • this emulsion was divided into 9 portions, and a predetermined amount of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene (hereinafter briefly referred to as Compound (I)) was added thereto, as shown in Table 1.
  • Compound (I) 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene
  • the sensitometry of these samples was performed as follows: With regard to exposure, a 1/50 second exposure was carried out through an optical wedge by the use of a tungsten lamp (color temperature 5,400°K) and a 10- 6 second exposure was done by the use of a Zenon flash. Development was performed at a temperature of 20°C for a period of 10 minutes with the following developing solution:
  • Sensitivities each mean a reciprocal number of an exposure necessary to obtain a fog density of +0.1 and are represented with relative sensitivities, taking a value of Samples 1 and 6 as 100.
  • Emulsion (1) prepared in Example 1 was divided into 2 portions, and to these emulsions, a panchromatic sensitizing ew dye, anhydro-2,2'-di-(3-sulfopropyl)-5,5'-dichloro-9-ethylthiacarbocyanine hydroxide, was added in an amount of 140 mg/mol AgX as a methanolic solution. Then, 5 minutes after the addition, 210 mg/mol AgX of Compound (I) was added to either emulsion and the pH was adjusted to 6.5.
  • a panchromatic sensitizing ew dye anhydro-2,2'-di-(3-sulfopropyl)-5,5'-dichloro-9-ethylthiacarbocyanine hydroxide
  • Compound (11) 1-phenyl-5-mercaptotetrazole (hereinafter referred to as Compound (11)) and the following coupler dispersing solution, as well as usually used photographic additives such as a spreading agent and a hardening agent. And, triacetate bases were coated with the respective emulsions so that the amount of the silver might be 20 mg/dm 2 , followed by drying in order to prepare Sample 12 and 13.
  • the coupler dispersing solution was prepared as follows: In a mixture of 100 ml of tricresyl phosphate and 50 ml of ethyl acetate was completely dissolved 80 g of 1-hydroxy-N-[y-(2,4-di-tert-amylphenoxy- propyl)]-2-naphtho- amide, and 2 g of sorbitan monolaurate was further added thereto.
  • the resultant solution was added to 1 kg of a 10% by weight aqueous gelatin solution including 2.5 g of dodecylbenzenesulfonate, and a high-speed agitation and ultrasonic agitation followed for emulsification and dispersion, thereby preparing the desired coupler dispersing solution.
  • Example 2 The above samples were subjected to the same wedge exposure as in Example 1, and were then color developed at a temperature of 38°C for a period of 3 minutes with a color developing solution having the following composition:
  • Results are set forth in Table 2 below. As is clear from Table 2, the sample, which was prepared under conditions that the nitrogen-containing heterocyclic compound and the sensitizing dye were together present at the time of the gold-sulphur sensitization of this invention, had also a remarkably high sensitivity.
  • Emulsion (2) a tetradecahedral monodispersed emulsion including grains of 0.9 ⁇ m in average diameter was prepared by a double jet method in which a pAg and pH were controlled.
  • Each of the grains above comprised a core of silver iodobromide containing 2 mole % of silver iodide and a shell thereon of silver bromide having an average thickness of 0.016 pm.
  • the degree of dispersion of their grain size distribution was 0.14.
  • this emulsion was divided into 3 portions. One of them was processed as a control, and Compound (I) was added to each of the remainder in an amount shown in Table 3. Afterward, a pH of each emulsion was adjusted to a predetermined level.
  • Emulsion (3) In place of Emulsion (1), an emulsion (hereinafter referred to as Emulsion (3); degree of dispersion 0.15) and another emulsion (hereinafter referred to as Emulsion (4); degree of dispersion 0.14) were used.
  • Emulsion (3) above comprised core-shell type silver iodobromide grains (core ... silver iodobromide including 2 mol % of silver iodide; shell...
  • sensitization effect did not depend on the kind of sulphur sensitizer, and even a thiourea derivative sensitizer provided the same sensitization effect as in sodium thiosulfate.
  • Table 6 indicates that when the emulsion which was low in the degree of dispersion, i.e. good in mono- dispersibility was subjected to gold-sulphur sensitization in the presence of the nitrogen-containing heterocyclic compound of this invention, the obtained sensitization effect was outstandingly great.
  • Emulsion (5) was a silver iodobromide emulsion (the content of silver iodide was 6 mol % and the degree of dispersion was 0.12) comprising a silver halide of octahedral crystals having an average diameter of 0.65 pm, with the silver iodide distributed uniformly in the silver halide;
  • Emulsion (6) above was a silver iodobromide emulsion (the content of silver iodide was 8 mol % and the degree of dispersion was 0.12) comprising a silver halide of octahedral crystals having an average diameter of 0.65 pm, with the cores of the crystals coated with the silver bromide shells of 0.016 pm in thickness.
  • Emulsions (5) and (6) above were then subjected to the type of sensitizations of a sulphur sensitization and gold-sulphur sensitization in the same manner as in Example 1.
  • chemical sensitizers there were employed 5.7 mg/mol AgX of sodium thiosulfate (pentahydrate), 0.62 mg/mol AgX of chloroauric acid (tetrahydrate) and 50 mg/mol AgX of ammonium thiocyanate.
  • Results obtained are set forth in Table 8 below.
  • the relative sensitivities in the table are represented with relative values, taking, as 100, sensitivities obtained by subjecting, to a 1/50 second exposure, the samples which were prepared by adding Compound (1) to the respective emulsions at addition time (3) above and by carrying out the chemical sensitization.
  • a monodispersed emulsion was prepared by the double jet method in which a pAg and pH were controlled, which monidispersed emulsion was composed of tetradecahedral grains having an average diameter of 0.9 ⁇ m and having a degree of disperse of 0.15, each of the grains comprising a cover of silver iodobromide including 10 mol% of silver iodide and a shell thereon of silver bromide having an average thickness of 0.016 pm.
  • the thus prepared emulsion was divided into 9 portions, and 3 portions of them were treated as controls; to the remainder were added compounds in amounts shown in Table 9 and their pH and pAg were adjusted to predetermined levels.
  • Example 9 The thus prepared emulsions were subjected to gold-sulphur sensitization and dye sensitization as in Example 2. The same photographic additives as in Example 2 were then added thereto, followed by coating and drying in order to prepare Samples 45 to 53. These samples were evaluated as in Example 2, and results obtained are set forth in Table 9 below:
  • Example 2 in place of Compound (I), benzotriazole was added. The obtained sensitization effect was good similarly to that of Example 2.
  • Example 2 in place of Compound (I), benzothiazole was added. The obtained sensitization effect was good similarly to that of Example 2.
  • Example 2 in place of Compound (I), benzimidazole was added. The obtained sensitization effect was good similarly to that of Example 2.

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Claims (10)

1. Verfahren zur Herstellung einer Silberhalogenidemulsion unter Gold/Schwefel- oder Gold/Selen-Sensibilisierung einer Silberhalogenidemulsion mit im wesentlichen aus Silberjodbromid bestehenden Silberhalogenidkörnchen vom Kern/Hülle-Typ mit Hilfe eines Goldsensibilisators und eines Schwefelsensibilisators oder Selensensibilisators, dadurch gekennzeichnet, daß es sich bei den Silberhalogenidkörnchen um oktaedrische oder tetradekaedrische Kristalle mit jeweils [1111-flächen handelt, die prozentuale quadratische Streuung bezüglich der Korngrößenverteilung der Silberhalogenidkörnchen 0,18 oder weniger beträgt und die Sensibilisierung in Gegenwart einer zur Bildung eines Komplexes mit Silber oder einem Silberion fähigen stickstoffhaltigen heterocyclischen Verbindung erfolgt.
2. Verfahren zur Herstellung einer Silberhalogenidemulsion nach Anspruch 1, dadurch gekennzeichnet, daß die Menge an der stickstoffhaltigen heterocyclischen Verbindung der zum Abdecken der Oberflächen der Silberhalogenidkörnchen (mit dieser Verbindung) in einer Stärke entsprechend dem 3/10-bis 10fachen einer einmolekularen Schicht (dieser Verbindung) erforderlichen Menge entspricht.
3. Verfahren zur Herstellung einer Silberhalogenidemulsion nach Ansprüchen 1 oder 2, dadurch gekennzeichnet, daß das Verhältnis der Goldatome in dem Goldsensibilisator zu den in dem Schwefelsensibilisator enthaltenen und zur Bildung von Silbersulfid mit Silberionen fähigen Schwefelatome oder zu den in dem Selensensibilisator enthaltenen und zur Bildung von Silberselen mit Silberionen fähigen Selenatome im Bereich von 1:200 bis 1:2 liegt.
4. Verfahren zur Herstellung einer Silberhalogenidemulsion nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es sich bei der stickstoffhaltigen heterocyclischen Verbindung um mindestens eine Verbindung mit einem Azainden-, Triazol-, Tetrazol-, Thiazol-, Benzothiazol-, Naphthothiazol-, Oxazol-, Benzoxazol-, Thiadiazol-, Oxadiazol- oder Selenazolring handelt.
5. Verfahren zur Herstellung einer Silberhalogenidemulsion nach Anspruch 4, dadurch gekennzeichnet, daß es sich bei der stickstoffhaltigen heterocyclischen Verbindung um eine solche mit einem Azaindenring handelt.
6. Verfahren zur Herstellung einer Silberhalogenidemulsion nach Anspruch 5, dadurch gekennzeichnet, daß es sich bei der Azaindenverbindung um eine Hydroxyazaindenverbindung mit 3-5 Stickstoffatomen am Azaindenring handelt.
7. Verfahren zur Herstellung einer Silberhalogenidemulsion nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß der Gehalt an Silberjodid in dem Silberjodbromid 0,5-15 Mol-% beträgt.
8. Verfahren zur Herstellung einer Silberhalogenidemulsion nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß der Silberjodidgehalt im Hülleteil jeden Silberhalogenidkorns vom Kern/ Hülle-Typ geringer ist als im Kernteil.
9. Verfahren zur Herstellung einer Silberhalogenidemulsion nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die Silberhalogenidemulsion zusätzlich mindestens einen Sensibilisierungsfarbstoff der allgemeinen Formel:
Figure imgb0050
worin bedeuten:
R1 und R2 jeweils eine Alkyl- oder Arylgruppe;
L1, L2 und L3 jeweils eine Methingruppe;
Z1 und Z2 jeweils diejenigen Atome oder Atomgruppen, die zur Vervollständigung eines 5- oder 6- gliedrigen heterocyclischen Rings erforderlich sind;
m und m2 jeweils 0 oder 1;
n = 0, 1 oder 2;
X ein Säureanion und
I = 1 oder 2, wobei gilt, daß im Falle, daß die Verbindung ein inneres Salz bildet, I = 1, enthält.
10. Verfahren zur Herstellung einer Silberhalogenidemulsion nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß es sich bei der stickstoffhaltigen heterocyclischen Verbindung um eine durchsichtige Substanz handelt.
EP83900062A 1981-12-19 1982-12-20 Verfahren zur herstellung einer silberhalidemulsion Expired EP0097720B1 (de)

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JPS6197648A (ja) * 1984-10-18 1986-05-16 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料
JPS61250636A (ja) 1985-04-30 1986-11-07 Fuji Photo Film Co Ltd 熱現像感光材料
JPH083621B2 (ja) 1985-07-31 1996-01-17 富士写真フイルム株式会社 画像形成方法
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JPS62178239A (ja) * 1986-01-31 1987-08-05 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料
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US5244782A (en) * 1987-08-07 1993-09-14 Fuji Photo Film Co. Ltd. Process for producing silver halide photographic emulsion
DE3887935T2 (de) * 1987-08-07 1994-09-08 Fuji Photo Film Co Ltd Verfahren zum Herstellen eines photographischen Silberhalogenidmaterials.
JPH07101291B2 (ja) * 1987-09-02 1995-11-01 富士写真フイルム株式会社 ハロゲン化銀乳剤及びその製造方法
JPH0769582B2 (ja) * 1988-06-15 1995-07-31 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
JPH07109487B2 (ja) * 1988-09-05 1995-11-22 富士写真フイルム株式会社 ハロゲン化銀写真用乳剤
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EP0562476B1 (de) 1992-03-19 2000-10-04 Fuji Photo Film Co., Ltd. Verfahren zur Herstellung einer photographischen Silberhalogenidemulsion
JP2777949B2 (ja) 1992-04-03 1998-07-23 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
DE69322429T2 (de) * 1992-04-16 1999-04-29 Eastman Kodak Co., Rochester, N.Y. Photographische Silberhalogenidemulsionen mit geringen Farbstoffsensibilisierungen und mit zugesetzten, Schleier unterdrückenden Mitteln
JPH06102613A (ja) * 1992-09-22 1994-04-15 Konica Corp ハロゲン化銀写真感光材料
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EP1691237A3 (de) 2005-02-15 2006-10-18 Fuji Photo Film Co., Ltd. Holographisches Aufzeichnungsmaterial und holographisches Aufzeichnungsverfahren

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