EP0302528B1 - Procédé pour la préparation d'un matériau photographique à l'halogénure d'argent - Google Patents

Procédé pour la préparation d'un matériau photographique à l'halogénure d'argent Download PDF

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Publication number
EP0302528B1
EP0302528B1 EP88112876A EP88112876A EP0302528B1 EP 0302528 B1 EP0302528 B1 EP 0302528B1 EP 88112876 A EP88112876 A EP 88112876A EP 88112876 A EP88112876 A EP 88112876A EP 0302528 B1 EP0302528 B1 EP 0302528B1
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Prior art keywords
silver halide
face
grains
plane
producing
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German (de)
English (en)
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EP0302528A3 (en
EP0302528A2 (fr
Inventor
Hiroyuki Mifune
Shunji Takada
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP62197741A external-priority patent/JPH07119936B2/ja
Priority claimed from JP62219983A external-priority patent/JPH0782211B2/ja
Priority claimed from JP62219984A external-priority patent/JPH0782212B2/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0302528A2 publication Critical patent/EP0302528A2/fr
Publication of EP0302528A3 publication Critical patent/EP0302528A3/en
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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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes

Definitions

  • This invention relates to a process for producing a silver halide photographic emulsion comprising regularly shaped silver halide grains.
  • Silver halide emulsions used in silver halide photographic materials are usually subjected to chemical sensitization using a sulfur sensitizer, a selenium sensitizer, a reduction sensitizer, a noble metal sensitizer, either alone or in combination, for the purpose of obtaining a desired sensitivity and gradation.
  • sulfur sensitizers, selenium sensitizers and noble metal sensitizers are important.
  • silver halide emulsions are spectrally sensitized with sensitizing dyes so as to exhibit sensitivity to light of longer wavelengths to which silver halides are by nature substantially insensitive.
  • a spectral sensitization sensitivity S ⁇ (at a wavelength ⁇ ) obtained by addition of a sensitizing dye can be determined according to the equation: wherein S°400 and S400 represent the photographic sensitivity of the spectrally non-sensitized emulsion and that of the spectrally sensitized emulsion, respectively, at a wavelength of 400 nm; ⁇ r represents a relative quantum efficiency; and A ⁇ and A400 represent percent absorption at a wavelength of ⁇ and 400 nm, respectively.
  • a chemical sensitization technique is desired which provides a high sensitivity silver halide emulsion without causing reduction of inherent sensitivity due to a dye, as is encountered in using a developer having low solubility.
  • chemical sensitization nuclei i.e., positions where a latent image is to be formed
  • the reduction of inherent sensitivity due to the dye should be suppressed even when the silver halide is developed with a general developer of low solubility.
  • the conventional techniques including the method of Simson et al., rarely have referred to possibility of isolating latent image specks from an adsorbed dye as well as controllability of the position of the chemical sensitization nuclei where a latent image is to be formed.
  • JP-A-61-133941, JP-A-59-9153, JP-A-58-28738 and JP-A-62-7040 also refer to the addition of a sensitizing dye at the time of chemical sensitization.
  • JP-A refers to a "published unexamined Japanese patent application”.
  • JP-A-61-311131 describes control of positions of development centers, i.e., positions of chemical sensitization, and particularly formation of development centers, i.e., chemical sensitization nuclei, on a (111) plane.
  • the dye is employed without being accurately evaluated for its adsorption selectivity, and halogen conversion is chiefly used here.
  • JP-A-62-152330 teaches the use of a compound called a "CR compound" in order to form a development center on the top of octahedral or tetradecahedral normal crystals having a (111) plane, that is, on a plane other than the (111) plane.
  • EP-A-0 097 790 discloses the preparation of octahedral or tetradecahedral silver bromoiodide grains whose surface area is bounded by (111) crystal faces to at least 5 %, whereby the grains are chemically gold/sulphur sensitized in the presence of a nitrogen-containing silver complexing compound.
  • Object of this invention is to provide a process for preparing a high sensitivity silver halide emulsion, which includes chemical sensitization and spectral sensitization under control.
  • the object of the invention can be accomplished by a process for producing a silver halide photographic emulsion comprising regularly shaped silver halide grains comprising a (111) face and a (100) face comprising adding a spectral sensitizing dye capable of selectively adsorbing onto the (111) face of the grains to the emulsion, and then subjecting the emulsion to chemical sensitization using at least one sulfur compound to preferentially form chemically sensitized nuclei on the (100) face of the grains, whereby the dye is used in an amount greater than that required for entirely covering the (111) face and whereby 60% or more of fine silver specks formed by development are formed on the (100) face.
  • the invention further provides a process for producing a silver halide photographic emulsion comprising regularly shaped silver halide grains comprising a (111) face and a (100) face, comprising the steps of
  • Figures 1 and 2 are electron micrographs (magnification: ⁇ 15,600) of silver halide crystal grains in Samples 1 and 2 prepared in Example 1, respectively.
  • the normal silver halide grains contained in the silver halide emulsion layer produced by the process of the present invention are crystals having substantially no stacking fault of twin plane.
  • the silver halide grains have both (111) plane and (100) plane on which a latent image is preferentially formed, and the grains may have a high index of (h, k, l) plane such as (331) plane, (210) plane, (321) plane and (211) plane.
  • the normal silver halide grains generally have an average grain size of from 0.1 to 6 ⁇ m, preferably from 0.1 to 4 ⁇ m, more preferably from 0.2 to 3 ⁇ m, and the grains are generally contained in an amount of at least 50%, preferably 60% or more, particularly preferably 75% or more, based on the total projected area of silver halide grains contained in the silver halide emulsion layer.
  • the grains are spectrally sensitized with a spectral sensitizing dye selectively adsorbed more on one plane than on the other plane, generally the amount of the dye adsorbed on the one surface being least 60%, preferably 70% or more and particularly preferably 75% or more, based on the total amount of the dye adsorbed on both planes.
  • chemical sensitization nuclei i.e., positions where a latent image is formed, are formed apart from most of an adsorbed dye under rigid control.
  • the inventors have found that this can be accomplished by the following two methods.
  • Method (B) requires a chemical sensitizer capable of selectively sensitizing the (100) plane, while method (A) permits the use of any kind of chemical sensitizers as described in Research Disclosure , Nos. 17643 and 13716. It is preferable to use a chemical sensitizer selectively sensitizing the (100) plane.
  • a dye which is easily adsorbed on planes other than the (111) plane or a dye which is evenly adsorbed on all planes may be added, if desired, in combination with the above-described dye for selective adsorption onto the (111) plane before or after or during the chemical sensitization.
  • a sensitizing dye to be used should be evaluated for its selective adsorption on a particular plane of silver halide grains, and also the indices of planes of silver halide grains should be considered. Based on these results and taking advantage thereof, chemical sensitization nuclei (i.e., positions where a latent image is to be formed) are formed at a limited position under control to thereby obtain an excellent light-sensitive silver halide emulsion having been spectrally sensitized.
  • chemical sensitization is effected selectively on a (100) plane while a (111) plane is covered more positively with a sensitizing dye whose adsorption selectivity has been judged, thus providing a highly refined technique.
  • method (A) requires a compound which chemically sensitizes a (100) plane selectively
  • method (A) permits the use of any kind of chemical sensitizers to preferentially form a latent image at positions other than a (111) plane.
  • a chemical sensitizer is added after a (111) plane occupying 40% or more of the silver halide grain surface is covered with a sensitizing dye which is adsorbed selectively on the (111) plane among other planes. Therefore, formation of effective chemical sensitization nuclei on the (111) plane is inhibited, while effective chemical sensitization nuclei are formed preferentially on uncovered or less covered planes other than the (111) plane, for example, a (100) plane. As a result, a latent image can be formed in a limited position.
  • the position where a latent image is to be formed can be limited more strictly by using the dye in an amount greater than that required for covering the (111) plane or by using a small amount of a dye which is adsorbed selectively on other planes in combination.
  • the position where most of the dye is adsorbed and the position where a latent image is to be formed can be separated on the surface of silver halide grains, a large quantity of a dye can be used and a number of common developers having small solubility can be employed without being accompanied by development delay as encountered in the case of shallow internal latent image type grains to thereby obtain a high sensitivity silver halide emulsion.
  • At least 40%, preferably at least 60%, more preferably at least 80% of the grain surface is occupied by a (111) plane, with the surface area occupied by a (100) plane preferably ranging from about 5 to about 20%.
  • the surface of silver halide grains is composed of a (100) plane, a (111) plane, and a (110) plane and, in most cases, composed of a (100) plane and a (111) plane.
  • the plane ratio can be obtained by directly observing an electron micrograph taken of a carbon replica of silver halide grains.
  • the method described in Nippon Kagaku Kaishi , No. 6, 942 (1984) can be adopted, which utilizes the fact that anhydro-3,3′-bis(sulfobutyl)-9-methylthiacarbocyanine hydroxide pyridinium salt gives a reflective spectrum markedly differing depending on the plane on which it is adsorbed. That is, the reflective spectra of a thick emulsion layer containing the above-described dye in varied amounts are obtained and evaluated using Kubelka-Munk's formula to obtain the ratios of the (100) plane and the (111) plane.
  • the position where a latent image is formed can be discriminated as follows.
  • a light-sensitive material composed of a support coated with a silver halide emulsion is exposed to light at an exposure of from (a) an exposure corresponding to (maximum density - minimum density) ⁇ 1/2 of a characteristic curve of a silver image obtained when exposed for 1 second and developed with a developer "MAA-1" (produced by Eastman Kodak Co., Ltd.) at 20°C for 10 minutes to (b) an exposure 1,000 times that exposure.
  • the exposed material is then developed with an arresting developing solution having the following formulation at 20°C for 10 minutes.
  • the development time, the pH of the developing solution, and the amount of a surface active agent used should be varied depending on the grain size or halogen composition of the silver halide grains so that fine silver spots indicating development centers may be observed easily.
  • Arresting Developing Solution Formulation Metol 0.45 g Ascorbic Acid 3.0 g Borax 5.0 g KBr 1.0 g Surface Active Agent (cetyl trimethylammonium chloride) 0.2 g Water to make
  • the pH of the developing solution can be slightly elevated with a sodium hydroxide aqueous solution or the development time is extended.
  • the surface active agent in the arresting developer serves to set the developed silver which is apt to extend in the form of filaments into masses so as to facilitate judgment of the position of the developed silver.
  • the development is stopped with a 5 wt% aqueous solution of glacial acetic acid and, without effecting fixation, subjected to enzymatic decomposition using pronase to recover silver halide grains. Thereafter, a small amount of the material is placed on a micromesh of an electron microscope. After carbon is vacuum evaporated thereon to prevent formation of print-out silver, the developed material is fixed with a fixing solution, and a carbon replica thereof is prepared. The position of remaining developed silver, i.e., the position where a latent image is formed, is observed under an electron microscope.
  • the phrase "capable of preferentially forming a latent image on the (100) plane" as used herein means that a major proportion, e.g., 60% or more, preferably 70% or more, particularly preferably 75% or more, of the fine silver specks formed by the above-described arrested development is formed on the (100) plane. It is the best that all of the fine silver specks are formed on the (100) plane. A few fine silver specks may, however, be formed on the (111) plane in a proportion of less than 40% and preferably less then 30%.
  • the compound capable of chemically sensitizing the (100) plane selectively which can be used in method (B) can be selected as follows.
  • emulsion comprising tetradecahedral pure silver bromide grains having (111) and (100) planes in an equal proportion is prepared.
  • the emulsion is chemically sensitized with a compound under examination to the degree optimum for 1 second exposure and then subjected to the above-described determination of the latent image position.
  • An illustrative example for the selection of the chemical sensitizer will be given in Example 1.
  • the compound capable of chemically sensitizing the (100) plane selectively mainly includes sulfur sensitizers.
  • sulfur sensitizers include organic chemical sensitizers, such as thioureas, rhodanines, oxazolidines, polysulfides and selenoureas.
  • Noble metal sensitizers such as gold, platinum, palladium and iridium, can also be used.
  • unstable sulfur compounds such as conventional thiosulfates can be used, and particularly preferably in the presence of the above-described dye which is adsorbed more on the (111) plane than on the (100) plane.
  • the sensitizing dye which is selectively adsorbed onto a (111) plane instead of a (100) plane of silver halide grains can be determined by the following three methods.
  • Octahedral silver bromide grains composed of (111) planes and cubic silver bromide grains composed of (100) planes are prepared (silver bromide may be replaced by silver iodobromide or silver chlorobromide).
  • the surface area of each of these grains is obtained from the respective electron micrograph, and both grains are mixed together to prepare a silver halide emulsion at such a mixing ratio that the area of the (111) plane and that of the (100) plane are equal.
  • methine dyes that are photographically useful and also preferred in the present invention, those giving different absorption spectra depending on whether they are adsorbed on a (111) plane or a (100) plane can be evaluated for their selectivity in adsorption between these two planes from their absorption spectra. That is, the absorption spectrum of a dye adsorbed on each of the cubic grains and the octahedral grains is obtained in advance, and the absorption spectrum of the dye when added to the above-prepared mixed emulsion is then determined, whereby the plane on which the dye begins to be selectively adsorbed can be judged from the absorption peak wavelength.
  • the plane on which the dye begins to be adsorbed can be quantitatively determined from the resulting spectrum according to the method described in the above-cited Nippon Kagaku Kaishi , No. 6, 942 (1984).
  • Octahedral silver bromide grains and cubic silver bromide grains greatly differing in grain size are mixed so as to have the (111) and (100) planes at an equal area ratio.
  • a dye is added to the resulting mixed emulsion and adsorbed thereon.
  • the emulsion is then separated into the octahedral grains and the cubic grains, and the amount of the dye in each separated emulsion is quantitatively determined.
  • Example 2 An example illustrating this method is given in Example 2.
  • Octahedral silver bromide grains and cubic silver bromide grains are mixed so as to have the (111) planes and (100) planes in equal proportions.
  • the silver bromide may be replaced by silver iodobromide or silver chlorobromide.
  • the sensitivity of the octahedral grains should be remarkably lower than that of the cubic grains, so that only the cubic grains will contribute to the photographic sensitivity of the mixed emulsion.
  • the octahedral grains are doped with rhodium. Even if a dye is adsorbed on such rhodium-doped octahedral grains to any high degree, spectral sensitization due to the dye does not occur. It is not until the dye is adsorbed onto the cubic grains.that spectral sensitivity due to the dye is imparted to the mixed emulsion.
  • the cubic grains begin to adsorb the dye to acquire spectral sensitivity after the saturation of the octahedral grains is reached.
  • a given amount of the added dye being taken as b
  • the amount of the dye added to the mixed emulsion which affords the same sensitivity as that obtained with b is taken as a.
  • the dye of the amount a is added to the mixed emulsion, the amount of the dye on the cubic grains and that on the octahedral grains can be quantitatively obtained as (b/2) and (a - b/2), respectively.
  • the inventors have chosen dyes which are adsorbed more easily on a (111) plane than on a (100) plane in accordance with the above-described three methods of determination.
  • Such dyes are preferably chosen from among methine dyes.
  • methine dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes, with cyanine dyes, merocyanine dyes and complex merocyanine dyes being particularly useful.
  • nuclei commonly utilized in cyanine dyes as basic heterocyclic nuclei can be present in these dyes.
  • Such nuclei include a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus; the above-enumerated nuclei to which an alicyclic hydrocarbon ring has been fused; and the above-enumerated nuclei to which an aromatic hydrocarbon ring has been fused, e.g., an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothi
  • Merocyanine dyes or complex merocyanine dyes can contain 5- to 6-membered heterocyclic nuclei having a ketomethylene structure, e.g., a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus or a thiobarbituric acid nucleus.
  • a ketomethylene structure e.g., a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus or a thiobarbituric acid nucleus.
  • the dye to be used in the present invention can be chosen from conventional compounds, such as those recited in Research Disclosure , No. 17643, 23, IV (December, 1978) or those described in the publications cited therein.
  • Typical examples of these methine dyes which can be used preferably are cyanine dyes, and more particularly thiocyanine dyes, selenacyanine dyes, quinocyanine dyes, thiaquinocyanine dyes, selenaquinocyanine dyes.
  • More preferred cyanine dyes include benzothiacyanines, benzoselenacyanines and benzothiaselenacyanines each having a halogen substituent (e.g., a chlorine atom) at the 5-position thereof; thiaquinocyanines or selenaquinocyanines having, on one side thereof, a thiazole or selenazole ring substituted with a halogen atom at the 5-position thereof; and quinocyanines.
  • a halogen substituent e.g., a chlorine atom
  • Particularly preferred among them are those forming J-aggregates on silver halide grains.
  • the amount of these sensitizing dyes is preferably at least an amount enough to saturate the (111) plane and not more than an amount that saturates all of the (111) and (100) planes.
  • the silver halide which can be used in the present invention may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver iodide, and silver chloride, with silver bromide, silver iodobromide, silver iodochlorobromide, and silver chlorobromide being particularly preferred.
  • the silver chloride content is preferably 50 mol% or less.
  • the pAg preferably ranges from 6 to 11, more preferably 7 to 10, most preferably 7 to 9.5, and the temperature from 40 to 95°C, more preferably 50 to 85°C.
  • the amount of the chemical sensitizers such as a sulfur sensitizer and a gold sensitizer ranges from 10 ⁇ 8 to 10 ⁇ 3 mol, preferably from 10 ⁇ 7 to 10 ⁇ 4 mol, per mol of silver halide.
  • any known compound such as a chloroaurate and a potassium aurothiocyanate, may be employed.
  • the individual silver halide grains may be homogeneous throughout the crystal structure or may have a layered structure composed of an outer shell and a core having different halogen compositions. Further, the grains may be fused type crystals composed of an oxide crystal (e.g., PbO) and a silver halide crystal (e.g., silver chloride) or epitaxially grown crystals, e.g., silver bromide grains on which silver chloride, silver iodobromide and, silver iodide, is epitaxially grown.
  • an oxide crystal e.g., PbO
  • a silver halide crystal e.g., silver chloride
  • epitaxially grown crystals e.g., silver bromide grains on which silver chloride, silver iodobromide and, silver iodide, is epitaxially grown.
  • the silver halide grains in photographic emulsions may have any size distribution or may be monodisperse.
  • the term "monodispersion” as used herein means a dispersion system in which 90% of the grains fall within a size range of 60%, preferably 40%, of the number average particle size.
  • the term "number average particle size” as used herein means the number average diameter of the projected area of silver halide grains.
  • the photographic emulsion of the present invention can be prepared by known techniques as described, e.g., in P. Glafkides, Chemie et Physique Photographique (Paul Montel, 1967), G.F. Duffin, Photographic Emulsion Chemistry (The Focal Press, 1966), and V.L. Zelikman et al., Making and Coating Photographic Emulsion (The Focal Press, 1964).
  • the emulsion can be prepared by any of an acid process, a neutral process, an ammonia process, and the like.
  • the reaction between a soluble silver salt and a soluble halogen salt can be carried out by any of a single jet method, a double jet method and, a combination thereof, A reverse mixing method may also be adopted, in which grains are formed in the presence of excess silver ions. Further, a controlled double jet method, in which a pAg of a liquid phase where silver halide grains are formed is maintained constant, may also be used. According to the controlled double jet method, an emulsion of grains having a regular crystal form and a nearly uniform grain size can be obtained.
  • Two or more silver halide emulsions separately prepared may be used as a mixture.
  • 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, an iron salt or a complex salt thereof may be present in the system.
  • addition of an iridium salt, a rhodium salt or an iron salt is preferred.
  • the amount of these compounds may be either small or large depending on the end use.
  • silver halide solvents may be used.
  • the silver halide solvents include ammonia, potassium thiocyanate, and thioethers or thione compounds described in US-A-3,271,157 and JP-A-51-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717 and JP-A-54-155828.
  • the photographic emulsion can contain various compounds.
  • Such compounds include azoles, such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, and benzimidazoles (particularly nitro- or halogen-substituted azoles); heterocyclic mercapto compounds, e.g., mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), and mercaptopyrimidines; the above-enumerated heterocyclic mercapto compounds having a water-soluble group, e.g., a carboxyl group, a sulfo group; thioketo compounds, e.g., oxazolinethione; aza
  • sensitizing dyes other than the above-described spectrally sensitizing dyes in accordance with the present invention may be added to the photographic emulsion immediately before coating.
  • Such sensitizing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, oxonol dyes and hemioxonol dyes.
  • Specific examples of these sensitizing dyes are described, e.g., in P. Glafkides, Chimie Photographique , Chapters 35 to 41 (Paul Montel, 2nd Ed., 1957), F.M. Hamer, The Cyanine and Related Compounds (Interscience), U.S. Patents 2,503,776, 3,459,553 and 3,177,210, and Research Disclosure , Vol. 176, 17643, 23-IV (December, 1978).
  • the hydrophilic colloidal layers of the photographic material produced according to the present invention may contain various water-soluble dyes as filter dyes or for prevention of irradiation or for other purposes.
  • water-soluble dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes, with oxonol dyes, hemioxonol dyes and merocyanine dyes being particularly useful.
  • the photographic emulsion layers or other hydrophilic colloidal layers can further contain organic. or inorganic hardening agents.
  • the hardening agents include chromates (e.g., chromium alum, chromium acetate), aldehydes (e.g., formaldehyde, glyoxal, glutaraldehyde), N-methylol compounds (e.g., dimethylolurea, methyloldimethylhydantoin), dioxane derivatives (e.g., 2,3-dihydroxydioxane), active vinyl compounds (e.g., 1,3,5-triacryloylhexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol), active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine), mucohalogenic acids (e.g., mucochloric acid, mucophenoxychlor
  • the photographic emulsion layers or other hydrophilic colloidal layers of the photographic materials may furthermore contain various surface active agents as coating aids or antistatic agents or for improvement of lubrication, improvement of emulsifying dispersibility, prevention of adhesion, improvement of photographic characteristics (e.g., acceleration of development, increase of contrast, and increase of sensitivity).
  • various surface active agents as coating aids or antistatic agents or for improvement of lubrication, improvement of emulsifying dispersibility, prevention of adhesion, improvement of photographic characteristics (e.g., acceleration of development, increase of contrast, and increase of sensitivity).
  • nonionic surface active agents such as saponin (steroid type), alkylene oxide derivatives (e.g., polyethylene glycol, polyethylene glycol/polypropylene glycol condensation products, polyethylene glycol alkyl ethers or alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, silicon-polyethylene oxide adducts), glycidol derivatives (e.g., alkenylsuccinic polyglycerides, alkylphenyl polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars; anionic surface active agents containing an acid group (e.g., carboxyl, sulfo, phospho, sulfate and phosphate groups), such as alkylcarboxylates, alkyl sulfonates, alkylbenzenesul
  • an acid group e.g.
  • the photographic emulsion layers may contain, for example, polyalkylene oxides or derivatives thereof (e.g., ethers, esters and amides), thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives and 3-pyrazolidones.
  • polyalkylene oxides or derivatives thereof e.g., ethers, esters and amides
  • thioether compounds e.g., thiomorpholines
  • quaternary ammonium salt compounds e.g., urethane derivatives, urea derivatives, imidazole derivatives and 3-pyrazolidones.
  • the photographic layers in the present invention can contain color image-forming couplers, i.e., compounds capable of developing a color upon oxidative coupling with an aromatic primary amine developing agent, such as phenylenediamine derivatives, aminophenol derivatives, and so on.
  • color image-forming couplers i.e., compounds capable of developing a color upon oxidative coupling with an aromatic primary amine developing agent, such as phenylenediamine derivatives, aminophenol derivatives, and so on.
  • magenta-forming couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, and open chain acylacetonitrile couplers.
  • Yellow-forming couplers include acylacetamide couplers (e.g., benzoylacetanilides and pivaloylacetanilides).
  • Cyan-forming couplers include naphthol couplers and phenol couplers.
  • Couplers that are nondiffusible due to a hydrophobic group called a ballast group are preferred.
  • the couplers may be either 2-equivalent or 4-equivalent to a silver ion.
  • the photographic materials may further contain colored couplers having a color correction effect, couplers capable of releasing a development inhibitor on development (“DIR couplers”), or colorless DIR coupling compounds which produce a colorless coupling reaction product and release a development inhibitor.
  • the photographic material can contain known color fog inhibitors, e.g., hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives and ascorbic acid derivatives.
  • known color fog inhibitors e.g., hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives and ascorbic acid derivatives.
  • the hydrophilic colloidal layers of the photographic material can contain an ultraviolet absorbent, such as benzotriazole compounds substituted with an aryl group (e.g., those described in US-A-3,533,794), 4-thiazolidone compounds (e.g., those described in US-A-3,314,794 and 3,352,681), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic esters (e.g., those described in US-A-3,705,805 and 3,707,375), butadiene compounds (e.g., those described in US-A-4,045,229), and benzoxidol compounds (e.g., those described in US-A-3,700,455).
  • an ultraviolet absorbent such as benzotriazole compounds substituted with an aryl group (e.g., those described in US-A-3,533,794), 4-thiazolidone compounds (e.g., those described in US-A-3,314,
  • UV absorbing couplers e.g., ⁇ -naphthol type cyan couplers
  • ultraviolet absorbing polymers may also be employed. A specific layer may be mordanted with these ultraviolet absorbents.
  • the dye image stabilizers may be used either individually or in combination of two or more thereof.
  • the known discoloration inhibitors include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-hydroxyphenol derivatives and bisphenol derivatives.
  • the photographic materials produced according to the present invention can contain other various known additives, such as brightening agents, desensitizers, plasticizers, slip agents, matting agents, oils and mordants.
  • additives such as brightening agents, desensitizers, plasticizers, slip agents, matting agents, oils and mordants. Specific examples of useful additives are described in Research Disclosure , No. 17643, 22-31 (December, 1978).
  • the present invention is applicable to various color and black-and-white silver halide photographic materials, including color positive films, color papers, color negative films, color reversal materials (some containing couplers and some not), light-sensitive materials for plate-making (e.g., lith films), light-sensitive materials for cathode ray tube displays, X-ray films (especially for direct or indirect photographing), light-sensitive materials for a colloid transfer process, a silver salt diffusion transfer process, a dye transfer process, a silver dye bleach process, a print-out paper process or a heat development process.
  • color positive films e.g., lith films
  • light-sensitive materials for cathode ray tube displays e.g., lith films
  • X-ray films especially for direct or indirect photographing
  • light-sensitive materials for a colloid transfer process e.g., a silver salt diffusion transfer process, a dye transfer process, a silver dye bleach process, a print-out paper process or a heat development process.
  • the light exposure for obtaining a photographic image can be effected in a usual manner.
  • Any of known light sources including infrared light can be used, for example, natural light (sunlight), a tungstem lamp, a fluorescent lamp, a mercury lamp, a xenon arc lamp, a carbon arc lamp, a xenon flash lamp, a cathode ray tube flying spot, a light-emitting diode, a laser beam (e.g., a gas laser, a YAG laser, a dye laser or a semiconductor laser).
  • the exposure may also be effected using light emitted from a fluorescent substance excited by electron beams, X-rays, ⁇ -rays or ⁇ -rays.
  • the exposure time ranges from 1/1,000 to 1 second as is usually employed for photographing with cameras.
  • a shorter exposure time e.g., 10 ⁇ 6 to 10 ⁇ 4 seconds is also employable with a xenon flash lamp or a cathode ray tube, or a longer exposure may also be used.
  • the spectral composition of light for exposure can be controlled by the use of a color filter.
  • the photographic materials can be subjected to development processing according to known methods using known processing solutions as described, e.g., in Research Disclosure , No. 17643, 28-30. Depending on purposes, either of black-and-white photographic processing for forming a silver image or color photographic processing for forming a color image can be applied.
  • Embodiment (II) according to the present invention will be described in greater detail below.
  • the selective chemical sensitization of the (100) plane can be carried out in the same manner as described with respect to embodiment (I).
  • Determination of a dye which is selectively adsorbed more onto a (100) plane than on a (111) plane of silver halide grains and a dye which is selectively adsorbed more onto a (111) plane than on a (100) plane as used in method (A) can also be carried out in the same manner as described in embodiment (I).
  • the dye to be used here for selective adsorption onto a (100) plane can preferably be selected from methine dyes including cyanine dyes and merocyanine dyes, more preferably from cyanine dyes.
  • methine dyes including cyanine dyes and merocyanine dyes, more preferably from cyanine dyes.
  • Particularly preferred are benzoxacyanine, benzimidacyanine, benzoxaimidacyanine, benzoxathiacyanine, benzimidathiacyanine, benzoxaselenacyanine, benzimidaselenacyanine; and benzothiacyanine, benzoselenacyanine or benzothiaselenacyanine, each of which may have a substituent other than halogen atoms at the 5-position of the benzene nucleus.
  • Particularly preferred of these dyes are those forming J-aggregates on the surface of silver halide grains.
  • the dye to be used here for selective adsorption onto a (111) plane instead of a (100) plane preferably includes cyanine dyes, more preferably thiacyanine dyes, selenacyanine dyes, quinocyanine dyes, thiaquinocyanine dyes and selenaquinocyanine dyes.
  • These dyes for selective adsorption either onto the (100) plane or onto the (111) plane are used in an amount of from 1 ⁇ 10 ⁇ 7 to 2 ⁇ 10 ⁇ 3 mol, preferably from 1 ⁇ 10 ⁇ 6 to 1 ⁇ 10 ⁇ 3 mol, per mol of silver.
  • the amount of the former dye is preferably at least an amount sufficient for saturating the (100) planes and not more than an amount for saturating all the (100) planes and the (111) planes.
  • the amount of the latter dye is preferably at least an amount enough to saturate the (111) planes.
  • Silver halide to be used in embodiment (II) may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver iodide and silver chloride, with silver bromide, silver iodobromide, silver iodochlorobromide, and silver chlorobromide being particularly preferred.
  • the bromine content is preferably 50 mol% or more, more preferably 70 mol% or more.
  • the iodine content is preferably 38 mol% or less, more preferably 20 mol% or less.
  • the chlorine content is preferably 50 mol% or less, more preferably 30 mol% or less.
  • Embodiment (III) according to the present invention will be described in greater detail below.
  • a silver halide emulsion which can be used in embodiment (III) contains substantially normal crystal grains, with at least about 60%, preferably at least about 65%, more preferably at least about 70%, of the surface of the substantially normal crystal grains being composed of a (100) plane.
  • the area occupied by a (111) plane is preferably not more than about 40%, more preferably not more than about 35%.
  • the silver halide to be used here may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver iodide and silver chloride, with silver bromide, silver iodobromide, silver iodochlorobromide and silver chlorobromide being particularly preferred.
  • the bromine content is preferably 50 mol% or more, more preferably 70 mol% or more.
  • the iodine content is preferably 38 mol% or less, more preferably 20 mol% or less.
  • the chlorine content is preferably 50 mol% or less, more preferably 30 mol% or less.
  • the area proportions of (100) planes and (111) planes of the resulting emulsion were found to be 52% and 48%, respectively, as determined in accordance with the method described in Nippon Kagaku Kaishi , No. 6, 942 (1984).
  • Each of the chemical sensitizers shown in Table 1 below was added to the emulsion in an amount indicated, and the emulsion was subjected to chemical ripening at 60°C for 60 minutes.
  • Samples 1 to 8 were exposed to light for 1 second through an optical wedge and developed with a developer "MAA-1" produced by Eastman Kodak Co., Ltd. at 20°C for 10 minutes.
  • each of the samples was uniformly exposed to light at an exposure 100 times as exposure which provided a midpoint density of the characteristic curve obtained by the above-described development with "MAA-1", i.e., (D max - fog) ⁇ 1/2 , and then was developed with an arresting developer having the same formulation as described above at 20°C for 10 minutes. After the development was stopped with a 5 wt% aqueous solution of acetic acid, the emulsion layer was removed from the coating by decomposing with pronase, and undeveloped silver halide grains were removed therefrom to prepare a carbon replica.
  • MAA-1 midpoint density of the characteristic curve obtained by the above-described development with "MAA-1"
  • an arresting developer having the same formulation as described above at 20°C for 10 minutes.
  • Electron micrographs taken of Samples 1 and 2 are shown in Figures 1 and 2, respectively.
  • the chemical sensitizers in the present invention formed developed silver specks on the (100) plane to the corner edges, while sodium thiosulfate formed developed silver specks on the (111) plane.
  • the site where the chemical sensitizer selectively forms chemical sensitization nuclei where a latent image is to be formed can be judged.
  • a monodisperse emulsion of octahedral silver iodobromide grains (iodine content: 1 mol%) having a grain size of 2 ⁇ m and a monodisperse emulsion of cubic silver iodobromide grains (iodine content: 1 mol%) having a grain size of 0.5 ⁇ m were prepared.
  • the two emulsions were mixed to prepare a mixed emulsion having (111) planes and (100) planes in equal proportions.
  • the mixed emulsion was spectrally sensitized with each of the sensitizing dyes shown in Table 2 at a pH of 6.5, a pAg of 8 and a temperature of 60°C for 30 minutes, the dye being added in an amount of 10 ⁇ 10 ⁇ 5 mol per mol of silver iodobromide which corresponded to an amount covering about 20% of the total surface area of silver iodobromide grains, taking the surface area of the grains being 0,7 nm2 (70 ⁇ 2) per molecule.
  • the thus-sensitized emulsion was filtered through a filter having a pore size of 0.8 ⁇ m, and the amount of the adsorbed dye in the filtrate (emulsion of cubic grains) was determined.
  • the ratio of the amount of the dye adsorbed to the cubic grains or the octahedral grains to the amount of the dye added is shown in Table 2.
  • Example 2 The same tetradecahedral silver bromide emulsion as used in Example 1 was chemically sensitized with a sulfur sensitizer as shown in Table 3 at 60°C for 60 minutes.
  • a sensitizing dye D-8 used in the invention, in an amount of 3 ⁇ 10 ⁇ 4 mol per mol of silver bromide.
  • (4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene) was added thereto as a stabilizer in an amount of 3 ⁇ 10 ⁇ 3 mol per mol of silver bromide, and the same coating aid, thickener and hardening agent as used in Example 1 were further added.
  • the resulting coating composition was coated on a cellulose acetate film support simultaneously with a gelatin protective layer.
  • the resulting samples were designated as Samples 10 to 14.
  • a monodisperse tetradecahedral silver iodobromide emulsion (iodine content: 2 mol%, grain size: about 0.6 ⁇ m) composed of 38% of a (100) plane and 62% of a (111) plane was prepared in the same manner as described in Example 1, except for maintaining the grain formation system at a pAg of 8.1. After water washing and desalting, the emulsion was adjusted to a pH of 6.5 and a pAg of 8.5.
  • Emulsions A, B, C and D The resulting emulsion was divided into four portions, designated as Emulsions A, B, C and D.
  • Emulsion A was chemically sensitized with sodium thiosulfate, chloroauric acid and potassium thiocyanate at 60°C for 60 minutes, and then a sensitizing dye used in the invention (D-8) and two kinds of sensitizing dyes having the formulae shown below were added thereto in amounts of 3.5 ⁇ 10 ⁇ 4 mol, 1 ⁇ 10 ⁇ 5 mol, and 1 ⁇ 10 ⁇ 4 mol, each per mol of silver.
  • Emulsion B was chemically sensitized with a sulfur sensitizer, S-2, chloroauric acid and potassium thiocyanate, and the same three dyes as used for Emulsion A were then added thereto.
  • Emulsion C was added D-8, and the emulsion was chemically sensitized with sodium thiosulfate, chloroauric acid, and potassium thiocyanate at 60°C for 60 minutes. Then, the two other dyes were added thereto.
  • Emulsion D was added D-8, and the emulsion was chemically sensitized with S-2, chloroauric acid, and potassium thiocyanate at 60°C for 60 minutes. Then, the two other dyes were added thereto.
  • Couplers C-6 and C-7
  • dispersing oils Oil-1 and Oil-2
  • an antifoggant (1-(m-sulfophenyl)-5-mercaptotetrazole monosodium salt
  • a stabilizer (4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene).
  • the same coating aid, thickener and hardening agent as used in Example 1 were further added thereto.
  • the resulting coating composition was coated on a cellulose acetate film support together with a gelatin protective layer.
  • the resulting sample was exposed to light through an optical wedge and a yellow filter and subjected to color development processing according to the procedure shown below at 38°C.
  • the site for latent image formation was predominantly formed on the plane other than the (111) plane, i.e., the (100) plane, and the emulsion had high sensitivity.
  • Emulsions A and D as prepared in Example 4 were treated in the same manner as in Example 4, except for replacing D-8 with D-17, D-18 or D-20, and tested in the same manner as in Example 4. As a result, Emulsion D proved more highly sensitive than Emulsion A in each case.
  • Emulsion E and Emulsion F comprising core/shell grains both having a silver iodide content of 10 mol% and each having a grain size of 0.7 ⁇ m and 1.5 ⁇ m, respectively.
  • Emulsion E grains were composed of 20% of a (100) plane and 80% of a (111) plane, while Emulsion F grains were composed of 15% of a (100) plane and 85% of a (111) plane, both being monodisperse tetradecahedra close to octahedra.
  • Emulsions E and F After adjustment to a pH of 6.3 and a pAg of 8.9, each of Emulsions E and F was divided into two portions, designated as Emulsions E-1 and E-2 and Emulsions F-1 and F-2, respectively.
  • Emulsion E-1 was chemically sensitized with sodium thiosulfate and chloroauric acid, and Dyes I, II and III were added thereto.
  • Dye II corresponding to D-8
  • the emulsion was sensitized with sodium thiosulfate and chloroauric acid, and Dyes I and III were then added thereto.
  • Emulsion F-1 was chemically sensitized with sodium thiosulfate and chloroauric acid, and Dye IX was then added thereto.
  • Emulsion F-2 was added Dye IX (corresponding to D-2) and the emulsion was then chemically sensitized with a sulfur sensitizer, S-3, and chloroauric acid.
  • a multilayer color light-sensitive material having a layer structure described below was prepared using Emulsion E-1 in the fifth layer and Emulsion F-1 in the twelfth layer or using Emulsion E-2 in the fifth layer and Emulsion F-2 in the twelfth layer.
  • the resulting samples were designated as Sample 20 and Sample 21, respectively.
  • the processing solutions used in the development processing had the same formulations as used in Example 4.
  • First Layer Antihalation Layer Black colloidal silver 0.2 g-Ag/m2 Gelatin 1.3 g/m2 Colored coupler, C-1 0.06 g/m2 Ultraviolet absorbent, UV-1 0.1 g/m2 Ultraviolet absorbent, UV-2 0.2 g/m2 Dispersing oil, Oil-1 0.01 g/m2 Dispersing oil, Oil-2 0.01 g/m2 Second Layer: Intermediate Layer Silver bromide fine grains (mean grain size: 0.07 ⁇ m) 0.15 g-Ag/m2 Gelatin 1.0 g/m2 Colored coupler, C-2 0.02 g/m2 Dispersing oil, Oil-1 0.1 g/m2 Third Layer: First Red-Sensitive Emulsion Layer Silver iodobromide emulsion (silver iodide: 2 mol%, mean grain size: 0.3 ⁇ m) 0.4 g-Ag/m2 Gelatin 0.6 g/m2 Sensitizing Dye I
  • Each of the layers additionally contained a surface active agent as a coating aid.
  • a monodisperse emulsion of octahedral silver iodobromide grains (iodine content: 1 mol%) having a grain size of 2 ⁇ m and a monodisperse emulsion of cubic silver iodobromide grains (iodine content: 1 mol%) having a grain size of 0.5 ⁇ m were prepared.
  • the two emulsions were mixed to prepare a mixed emulsion having (111) planes and (100) planes in equal proportions.
  • the mixed emulsion was spectrally sensitized with each of the sensitizing dyes shown in Table 6 at a pH of 6.5, a pAg of 8.4 and a temperature of 60°C for 30 minutes, the dye being added in an amount of 10 ⁇ 10 ⁇ 5 mol per mol of silver iodobromide which corresponded to an amount covering about 20% of the total surface area of silver iodobromide grains, taking the surface area of the grains as 0,7 nm2 (70 ⁇ 2) per molecule.
  • the thus-sensitized emulsion was filtered through a filter having a pore size of 0.8 ⁇ m, and the amount of the adsorbed dye in the filtrate (emulsion of cubic grains) was determined.
  • the ratio of (a) the amount of the dye adsorbed to the cubic grains or the octahedral grains to (b) the amount of the dye added is shown in Table 6.
  • Table 6 Dye Ratio of Dye Adsorbed Based on Added Dye On Cubic Grains (%) On Octahedral Grains (%) E-14 ca. 100 ca. 0 E-1 98 2 E-2 ca. 100 ca. 0 E-3* 75 25 E-7 ca. 100 ca. 0 E-11 ca. 100 ca.
  • the tetradecahedral silver bromide emulsion as prepared in Example 1 was chemically sensitized with a sulfur sensitizer as shown in Table 7 at 60°C for 60 minutes. Then, E-2 was added thereto in an amount of 3 ⁇ 10 ⁇ 4 mol per mol of silver bromide.
  • a stabilizer (4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene; 4 ⁇ 10 ⁇ 3 mol/mol AgBr) and the same coating aid, thickener and hardening agent as used in Example 1 were further added to the emulsion.
  • the resulting coating composition was coated on a cellulose acetate film support together with a gelatin protective layer.
  • the resulting light-sensitive materials were designated as Samples 22 to 26.
  • Emulsions A, B, C and D as prepared in Example 4 were used.
  • Emulsion A was chemically sensitized with sodium thiosulfate, chloroauric acid, and potassium thiocyanate at 60°C for 60 minutes, and then E-1 and D-2 were added thereto in an amount of 2.5 ⁇ 10 ⁇ 4 mol and 2.0 ⁇ 10 ⁇ 4 mol, respectively, each per mol of silver.
  • Emulsion B was chemically sensitized with S-2, chloroauric acid, and potassium thiocyanate, and the same amounts of the same dyes as used above were then added thereto.
  • Emulsion C was first added to Emulsion C, and the emulsion was chemically sensitized with sodium thiosulfate, chloroauric acid, and potassium thiocyanate at 60°C for 60 minutes. Then, E-1 was added thereto.
  • Emulsion D-2 was first added to Emulsion D, and the emulsion was chemically sensitized with S-2, chloroauric acid, and potassium thiocyanate at 60°C for 60 minutes. Then, E-1 was added thereto.
  • Couplers C-1, C-11, C-13 and C-15
  • dispersing oils Oil-1 and Oil-2
  • an antifoggant (1-(m-sulfophenyl)-5-mercaptotetrazole monosodium salt
  • a stabilizer (4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene).
  • the same coating aid, thickener and hardening agent as used in Example 1 were further added thereto.
  • the resulting coating composition was coated on a cellulose acetate film support together with a gelatin protective layer.
  • Example 8 The resulting sample was exposed to light through an optical wedge and a yellow filter and subjected to color development processing according to the same procedure as in Example 4. The results obtained are shown in Table 8, in which the sensitivity is relatively expressed taking that of Emulsion A as a standard (100). Further, the site of a latent image formation was examined in the same manner as in Example 7 and the results are also shown in Table 8.
  • a tetradecahedral silver bromide emulsion was prepared in the same manner as in Example 1, except for maintaining the pAg of the grain formation system at 7.8.
  • the surface of the silver bromide grains was found to be composed of 67% of a (100) plane and 33% of a (111) plane.
  • the emulsion was chemically sensitized with a sulfur sensitizer as shown in Table 9 at 60°C for 60 minutes. Then, a sensitizing dye, D-8, was added to the emulsion in an amount of 3 ⁇ 10 ⁇ 4 mol per mol of silver bromide. A stabilizer (4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene; 4 ⁇ 10 ⁇ 3 mol/mol AgBr) and the same coating aid, thickener and hardening agent as used in Example 1 were further added thereto. The resulting coating composition was coated on a cellulose acetate film support together with a gelatin protective layer. The resulting light-sensitive materials were designated as Samples 27 to 31.
  • a monodisperse tetradecahedral silver iodobromide emulsion (iodine content: 2 mol%, grain size: about 0.6 ⁇ m) having 65% of a (100) plane and 35% of a (111) plane was prepared in the same manner as in Example 10. After washing with water and desalting, the emulsion was adjusted to a pH of 6.5 and a pAg of 8.5. The emulsion was divided into four portions, designated as Emulsions G, H, I and J.
  • Emulsion G was chemically sensitized with sodium thiosulfate, chloroauric acid, and potassium thiocyanate at 60°C for 60 minutes, and then D-8, E-13 and E-20 were added thereto in an amount of 2.5 ⁇ 10 ⁇ 4 mol, 1 ⁇ 10 ⁇ 5 mol, and 1.0 ⁇ 10 ⁇ 4 mol, respectively, each per mol of silver.
  • Emulsion H was chemically sensitized with S-2, chloroauric acid, and potassium thiocyanate, and then the same amounts of the same dyes as added to Emulsion G were added thereto.
  • Emulsion I was first added to Emulsion I, and the emulsion was sensitized with sodium thiosulfate, chloroauric acid, and potassium thiocyanate at 60°C for 60 minutes. E-13 and E-20 were then added to the emulsion.
  • Emulsion J was chemically sensitized with S-2, chloroauric acid, and potassium thiocyanate at 60°C for 60 minutes. E-13 and E-20 were then added thereto.
  • Couplers C-6 and C-7
  • dispersing oils Oil-1 and Oil-2
  • an antifoggant (1-(m-sulfophenyl)-5-mercaptotetrazole monosodium salt; 2 ⁇ 10 ⁇ 4 mol/mol silver halide
  • a stabilizer (4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene; 3 ⁇ 10 ⁇ 3 mol/mol silver halide)
  • the resulting coating composition was coated on a cellulose acetate film support together with a gelatin protective layer to prepare a light-sensitive material.
  • Couplers and dispersing oils used in this example were the same as used in Example 6.
  • Emulsions G and J as prepared in Example 11 were treated in the same manner as in Example 11, except for replacing D-8 with D-17, D-18 or D-20, and tested in the same manner as in Example 11.
  • Emulsion J proved more highly sensitive than Emulsion G in any case.
  • Silver bromide was grown as an outer shell on seed crystals of silver iodobromide having an iodine content of 18 mol% to prepare a monodisperse emulsion containing tetradecahedral core/shell grains having a silver iodide content of 4.5 mol% and a mean grain size of 0.8 ⁇ m and composed of 72% of a (100) plane and 28% of a (111) plane.
  • the resulting emulsion was designated as Emulsion K.
  • Emulsion K After adjusting the pH to 6.3 and the pAg to 8.5, Emulsion K was divided into four portions, designated as K-1, K-2, K-3 and K-4.
  • Emulsion K-1 was chemically sensitized with sodium thiosulfate, chloroauric acid, and potassium thiocyanate, and then E-1, E-11 and D-2 were added thereto.
  • Emulsion K-2 was chemically sensitized with S-3, chloroauric acid, and potassium thiocyanate, and then E-1, E-11 and D-2 were added thereto.
  • D-2 was first added to Emulsion K-3, and the emulsion was chemically sensitized with sodium thiosulfate, chloroauric acid and potassium thiocyanate. Thereafter, E-1 and E-11 were added to the emulsion.
  • D-2 was first added to Emulsion K-4, and the emulsion was chemically, sensitized with S-3, chloroauric acid and potassium thiocyanate. Thereafter, E-1 and E-11 were added thereto.
  • Emulsions K-2, K-3 and K-4, and particularly K-3 and K-4 formed developed silver specks on (100) planes
  • Emulsion K-1 formed developed silver specks on the entire surface of the grains, and particularly on corners of the grains, i.e., on (111) planes.
  • a multilayer color light-sensitive material was prepared having the same layer structure as described in Example 6, except for replacing the emulsion of the ninth layer with Emulsion K-1, K-2, K-3 or K-4.
  • the resulting samples were designated as Samples 32, 33, 34 and 35, respectively.

Claims (20)

  1. Procédé pour produire une émulsion photographique d'halogénure d'argent, comprenant des grains d'halogénure d'argent de forme régulière comprenant une face (111) et une face (100) comprenant l'addition d'un colorant sensibilisateur spectral capable de s'adsorber sélectivement sur la face (111) des grains de l'émulsion et ensuite la sensibilisation chimique de l'émulsion en utilisant au moins un composé soufré pour former préférentiellement des germes sensibilisés chimiquement sur la face (100) des grains, le colorant étant utilisé en quantité supérieure à celle nécessaire pour couvrir entièrement la face (111) et 60% ou plus des grains fins d'argent formés par développement étant formés sur la face (100).
  2. Procédé pour produire une émulsion photographique d'halogénure d'argent selon la revendication 1, dans lequel la face (111) occupe au moins 40% de la surface des grains, ou bien la face (100) occupe plus de 60% de la surface des grains.
  3. Procédé pour produire une émulsion photographique d'halogénure d'argent selon la revendication 1, dans lequel le procédé comprend l'addition d'un colorant sensibilisateur spectral capable de s'adsorber sélectivement plus sur la face (100) que sur la face (111) pendant ou après la sensibilisation chimique.
  4. Procédé pour produire une émulsion photographique d'halogénure d'argent selon la revendication 2, dans lequel ladite face (111) occupe au moins 60% de la surface desdits grains de forme régulière.
  5. Procédé pour produire une émulsion photographique d'halogénure d'argent selon la revendication 4, dans lequel ladite face (111) occupe au moins 80% de la surface desdits grains de forme régulière et ladite face (100) occupe de 5 à 20% de la surface desdits grains de forme régulière.
  6. Procédé pour produire une émulsion photographique d'halogénure d'argent selon la revendication 1, dans lequel le colorant sensibilisateur spectral capable de s'adsorber sélectivement sur la face (111) est une cyanine, une mérocyanine ou une mérocyanine complexe.
  7. Procédé pour produire une émulsion photographique d'halogénure d'argent selon la revendication 6, dans lequel le colorant de cyanine est une thiocyanine, une sélénacyanine, une quinocyanine, une thiaquinocyanine ou une sélénaquinocyanine.
  8. Procédé pour produire une émulsion photographique d'halogénure d'argent selon la revendication 7, dans lequel ledit colorant de cyanine est choisi parmi une benzothiacyanine, une benzosélénacyanine ou une benzothiasélénacyanine, substituées chacune par un halogène en position 5 ; une thiaquinocyanine ou une sélénaquinocyanine, comprenant chacune un noyau thiazole ou sélénazole substitué par un halogène en position 5 ; et une quinocyanine.
  9. Procédé pour produire une émulsion photographique d'halogénure d'argent selon la revendication 1, dans lequel ledit colorant sensibilisateur est présent en quantité suffisante pour saturer ladite face (111) et au plus suffisante pour saturer lesdites faces (111) et (100).
  10. Procédé pour produire une émulsion photographique d'halogénure d'argent selon la revendication 3, dans lequel le colorant sensibilisateur spectral capable de s'adsorber sélectivement sur la face (100) est un colorant sensibilisateur dans lequel ledit colorant sensibilisateur est choisi parmi les benzoxacyanines, les benzimidacyanines, les benzoxaimidacyanines, les benzoxathiacyanines, les benzimidathiacyanines, les benzoxasélénacyanines, les benzimidasélénacyanines, les benzothiacyanines ayant un substituant autre qu'un halogène en position 5, les benzosélénacyanines ayant un substituant autre qu'un halogène en position 5 et les benzothiasélénacyanines ayant un substituant autre qu'un halogène en position 5.
  11. Procédé pour produire une émulsion photographique d'halogénure d'argent selon la revendication 1, dans lequel le colorant sensibilisateur spectral capable de s'adsorber sélectivement sur la face (111) est présent en quantités de 1 x 10⁻⁷ à 2 x 10⁻³ mole/mole d'halogénure d'argent.
  12. Procédé pour produire une émulsion photographique d'halogénure d'argent selon la revendication 3, dans lequel le colorant sensibilisateur spectral capable de s'adsorber sélectivement sur la face (100) est présent en quantités de 1 x 10⁻⁷ à 2 x 10⁻³ mole/mole d'halogénure d'argent.
  13. Procédé pour produire une émulsion photographique d'halogénure d'argent selon la revendication 1, dans lequel le composé soufré est un thiosulfate, une thiourée, une rhodanine, une oxazolidine ou un polysulfure.
  14. Procédé pour produire une émulsion photographique d'halogénure d'argent selon la revendication 13, dans lequel le composé soufré est présent en quantité de 1 x 10⁻⁸ à 1 x 10⁻³ mole/mole d'halogénure d'argent.
  15. Procédé pour produire une émulsion photographique d'halogénure d'argent comprenant des grains d'halogénure d'argent de forme régulière comprenant une face (111) et une face (100), comprenant les étapes suivantes :
    (a) on ajoute un colorant sensibilisateur spectral capable de s'adsorber sélectivement dans une plus grande mesure sur la face (111) que sur la face (100),
    (b) on soumet ladite émulsion à la sensibilisation chimique en utilisant un composé soufré choisi parmi les thiourées, les rhodanines, les oxazolidines et les polysulfures et
    tel que les germes sensibilisés chimiquement soient formés de préférence sur la face (100) des grains, dans lequel
    (i) la face (111) occupe au moins 40% de la surface des grains ou bien la face (100) occupe plus de 60% de la surface des grains et dans lequel
    (ii) ladite étape d'addition (b) est effectuée pendant ou après ladite étape (a).
  16. Procédé pour produire une émulsion photographique d'halogénure d'argent selon la revendication 15, dans lequel le composé soufré est présent en quantité de 1 x 10⁻⁸à 1 x 10⁻³ mole/mole d'halogénure d'argent.
  17. Procédé pour produire une émulsion photographique d'halogénure d'argent selon la revendication 15, dans lequel ladite face (111) occupe au moins 60% de la surface desdits grains de forme régulière.
  18. Procédé pour produire une émulsion photographique d'halogénure d'argent selon la revendication 15, dans lequel les germes sensibilisés chimiquement sur la face (100) constituent 60% ou plus de tous les germes sur le grain.
  19. Procédé pour produire une émulsion photographique d'halogénure d'argent selon la revendication 15, dans lequel le colorant sensibilisateur spectral est une cyanine, une mérocyanine ou une mérocyanine complexe.
  20. Procédé pour produire une émulsion photographique d'halogénure d'argent selon la revendication 17, dans lequel la face (111) occupe au moins 80% de la surface desdits grains de forme régulière et dans lequel la face (100) occupe de 5 à 20% de la surface des grains de forme régulière.
EP88112876A 1987-08-07 1988-08-08 Procédé pour la préparation d'un matériau photographique à l'halogénure d'argent Expired - Lifetime EP0302528B1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP62197741A JPH07119936B2 (ja) 1987-08-07 1987-08-07 ハロゲン化銀写真感光材料
JP197741/87 1987-08-07
JP219983/87 1987-09-02
JP62219983A JPH0782211B2 (ja) 1987-09-02 1987-09-02 ハロゲン化銀写真感光材料
JP219984/87 1987-09-02
JP62219984A JPH0782212B2 (ja) 1987-09-02 1987-09-02 ハロゲン化銀写真感光材料

Publications (3)

Publication Number Publication Date
EP0302528A2 EP0302528A2 (fr) 1989-02-08
EP0302528A3 EP0302528A3 (en) 1990-11-22
EP0302528B1 true EP0302528B1 (fr) 1994-02-23

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Application Number Title Priority Date Filing Date
EP88112876A Expired - Lifetime EP0302528B1 (fr) 1987-08-07 1988-08-08 Procédé pour la préparation d'un matériau photographique à l'halogénure d'argent

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EP (1) EP0302528B1 (fr)
DE (1) DE3887935T2 (fr)

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Publication number Priority date Publication date Assignee Title
JP2791492B2 (ja) * 1989-04-25 1998-08-27 コニカ株式会社 画像形成方法
US5310644A (en) * 1991-09-17 1994-05-10 Eastman Kodak Company Process for preparing a photographic emulsion using excess halide during nucleation
US5213944A (en) * 1991-10-17 1993-05-25 Eastman Kodak Company Nucleated high contrast photographic elements containing substituted thioureas which enhance speed and increase contrast
JPH05127290A (ja) * 1991-11-06 1993-05-25 Konica Corp ハロゲン化銀写真乳剤およびそれを用いたハロゲン化銀写真感光材料
US5254455A (en) * 1991-12-02 1993-10-19 Polaroid Corporation Silver halide emulsions spectrally sensitized to infrared radiation with novel cyanine dyes
JP3408282B2 (ja) * 1993-04-28 2003-05-19 富士写真フイルム株式会社 新規なベンゾイミダゾロカルボシアニン色素及び該色素を含有するハロゲン化銀写真感光材料
US5399477A (en) * 1994-02-25 1995-03-21 Eastman Kodak Company Silver halide photographic elements

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JPH06193447A (ja) * 1992-12-25 1994-07-12 Komatsu Ltd 内燃機関の混合気燃焼方法および完全予混合燃焼圧縮着火機関

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Publication number Priority date Publication date Assignee Title
JPS58126526A (ja) * 1981-12-19 1983-07-28 Konishiroku Photo Ind Co Ltd ハロゲン化銀乳剤の製造方法およびハロゲン化銀写真感光材料
JPS58107530A (ja) * 1981-12-21 1983-06-27 Konishiroku Photo Ind Co Ltd ハロゲン化銀乳剤およびその製造方法
JPS5950438A (ja) * 1982-09-16 1984-03-23 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真乳剤
US4463087A (en) * 1982-12-20 1984-07-31 Eastman Kodak Company Controlled site epitaxial sensitization of limited iodide silver halide emulsions
JPS60143331A (ja) * 1983-12-29 1985-07-29 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JPS6193447A (ja) * 1984-10-12 1986-05-12 Fuji Photo Film Co Ltd ハロゲン化銀写真乳剤
JPH0766156B2 (ja) * 1985-09-26 1995-07-19 オリエンタル写真工業株式会社 ハロゲン化銀写真感光材料の製造方法
DE3644223A1 (de) * 1985-12-24 1987-06-25 Fuji Photo Film Co Ltd Photoempfindliches silberhalogenid-direktpositivmaterial

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
JPH06193447A (ja) * 1992-12-25 1994-07-12 Komatsu Ltd 内燃機関の混合気燃焼方法および完全予混合燃焼圧縮着火機関

Also Published As

Publication number Publication date
DE3887935D1 (de) 1994-03-31
DE3887935T2 (de) 1994-09-08
EP0302528A3 (en) 1990-11-22
EP0302528A2 (fr) 1989-02-08

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