EP0264954B1 - Matériau photographique à l'halogénure d'argent ayant une structure spécifique - Google Patents

Matériau photographique à l'halogénure d'argent ayant une structure spécifique Download PDF

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Publication number
EP0264954B1
EP0264954B1 EP19870115593 EP87115593A EP0264954B1 EP 0264954 B1 EP0264954 B1 EP 0264954B1 EP 19870115593 EP19870115593 EP 19870115593 EP 87115593 A EP87115593 A EP 87115593A EP 0264954 B1 EP0264954 B1 EP 0264954B1
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Prior art keywords
group
silver halide
silver
photographic material
grains
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German (de)
English (en)
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EP0264954A2 (fr
EP0264954A3 (en
Inventor
Shunichi Fuji Photo Film Co. Ltd. Aida
Hiroyuki Fuji Photo Film Co. Ltd. Yamagami
Shinpei Fuji Photo Film Co. Ltd. Ikenoue
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • G03C1/0051—Tabular grain emulsions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/22—Methine and polymethine dyes with an even number of CH groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/26—Polymethine chain forming part of a heterocyclic ring
    • 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
    • G03C1/28—Sensitivity-increasing substances together with supersensitising substances
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium

Definitions

  • This invention relates to a silver halide photographic material comprising a support having thereon at least one light-sensitive silver halide emulsion layer containing chemically and spectrally sensitized silver halide grains.
  • the basic properties required for photographic silver halide emulsions are high sensitivity, low fogging, fine graininess, and high development activity.
  • Silver halides include silver fluoride, silver chloride, silver bromide, and silver iodide.
  • silver fluoride is not used in photographic emulsions due to its high solubility in water, and combinations of the remaining three silver halides have been intensively studied for improving the basic properties of the emulsions.
  • Moisar have disclosed that mixed silver halide emulsions containing silver halide cores covered by layers of different silver halides (specifically, a silver bromide core, a first layer composed of silver bromoiodide containing 1 mol % of silver iodide, and an outer layer composed of silver bromide) shows increased light sensitivity without reduced development activity (Japanese Patent Publication No. 13,162/68 corresponding to Brit. Pat. 1,027,146).
  • Koitabashi et al have disclosed that photographically desirable properties such as improved covering power can be obtained by forming a thin outer layer (hereinafter referred to as shell) of 0.01 to 0.1 ⁇ m in thickness on core grains containing a comparatively low content of silver iodide (Japanese Patent Applicatio (OPI) No. 154,232/82 corresponding to U.S. Pat. 4,444,877 (the term "OPI” as used herein means an "unexamined published Japanese patent application)).
  • shell a thin outer layer of 0.01 to 0.1 ⁇ m in thickness on core grains containing a comparatively low content of silver iodide
  • the common technical concept in these patents is to adjust development activity and light sensitivity by increasing the iodide content in the core portion as much as possible, while decreasing the iodide content in the shell portion.
  • EP-A-0147854 discloses a silver halide photographic light-sensitive material having one silver halide emulsion layer on a support wherein chemically and spectrally sensitized silver halide grains have a silver halide core comprising 10 to 45 mol% of silver iodide surrounded by a shell with a composition of the part very near the surface which can contain 5 mol% of silver iodide.
  • a silver halide photographic material comprising a support having thereon at least one light-sensitive silver halide emulsion layer containing chemically and spectrally sensitized silver halide grains having a silver halide core comprising at least one portion comprising 10 to 40 mol % of silver iodide, substantially surrounded by a silver halide shell portion containing less silver iodide than the average silver iodide content of the core, and the silver halide of the surface region containing at least 5 mol % of silver iodide, said surface region being the portion between the surface of the silver halide grains and 5 nm in depth of the grains from the surface of the shell portion, characterized in that the silver halide grains are spectrally sensitized by at least one sensitizing dye selected from the group consisting of dyes represented by formula (I) or (II): wherein Z1 and Z2 each represents an atomic group necessary for forming the same or different, substituted or unsubsti
  • the silver halide content of the surface portion is analysed by XPS (X-ray photoelectron spectroscopy).
  • the XPS method used for analyzing the iodide content in the surface of silver halide grains is described in Junichi Aihara et al. Denshi no Bunko (Spectroscopy of Electrons), Kyoritsu Library 16 (Kyoritsu Shuppan, 1978).
  • a standard method of XPS is to use Mg-K ⁇ as exciting X-rays and measure the intensity of photoelectrons of iodide (I) and silver (Ag) (usually I-3d 5/2 and Ag-3d 5/2 ) released from silver halide grains of a suitable sample form.
  • the content of iodide can be determined by using a calibration curve of the intensity ratio of photoelectrons from iodide (I) to those from silver (Ag) (intensity (I)/intensity (Ag)), prepared by using several standard samples having known iodide contents.
  • the XPS must be performed after decomposing gelatin adsorbed on the surface of silver halide grains, for example, with protease to remove it.
  • the contents of silver iodide in the core portion and shell portion can be measured by X-ray diffractiometry. Examples of applying the X-ray diffractiometry to silver halide grains are described in H. Hirsch; Journal of Photographic Science , 10 , p.129 et seq.
  • a standard measuring method is to use Cu as a target and determine the diffraction curve of a (220) crystal face of silver halide using K ⁇ rays of Cu as a radiation source (tube voltage: 40 KV; tube current: 60 mA).
  • a radiation source tube voltage: 40 KV; tube current: 60 mA.
  • it is necessary to confirm the measuring accuracy by properly selecting the width of the slit (e.g., diverging slit or receiving slit), the time constant of the apparatus, the scanning speed of goniometer, and the recording speed using a standard sample such as silicon.
  • Curves of diffraction intensity versus diffraction angle obtained with (220) crystal face of silver halide using K ⁇ rays of Cu are grouped into two types: one type containing a diffraction peak corresponding to the higher iodide content layer containing 10 to 45 mol % of silver iodide and a diffraction peak corresponding to the lower iodide content layer distinctly separated from each other; and the other type containing two overlapping peaks not distinctly separated from each other.
  • the above-described lower iodide content layer and higher iodide content layer of the silver halide grains to be used in the present invention may or may not be distinctly separated from each other.
  • the EPMA method (Electron-Probe Micro Analyzer method) can also be used to determine whether a particular silver halide emulsion is an emulsion in accordance with the present invention or an emulsion containing the above-described two kinds of silver halide grains.
  • a sample is prepared having well-dispersed silver halide grains that do not come into contact with each other, and it is irradiated with electron beams.
  • X-ray analysis by electron beam excitation permits elemental analysis of an extremely small portion.
  • This method permits determination of the halide compositions of individual grains by determining the intensity of the characteristic X-rays emitted by silver and iodine.
  • Confirmation of the halide composition of at least 50 grains according to the EPMA method is generally sufficient to determine whether a particular emulsion is an invention emulsion, which is preferably as uniform as possible in iodide contents among grains.
  • the relative standard deviation is preferably not more than about 50 %, more preferably not more than about 35 %, particularly preferably not more than about 20 %.
  • the core portion contains a silver halide having a higher iodide content, the average iodide content being between about 10 mol % and 40 mol % which is the solid solution limit, preferably between about 15 and 40 mol %, more preferably between about 20 and 40 mol %.
  • the optimum iodide content in the core portion is between about 20 and 40 mol % or between 30 and 40 mol %, depending upon the process for preparing the core grains.
  • the silver halide other than silver iodide may be at least one of silver bromide, silver chloride and silver chlorobromide, preferably with at least about 50 mol%, more preferably with at least about 60 mol% of silver bromide.
  • the average iodide content of the shell portion is less than that of the core portion, and the shell portion contains silver halide containing preferably from 0 to about 10 mol%, more preferably up to about 5 mol%, of silver iodide.
  • the shell portion contains silver halide containing preferably from 0 to about 10 mol%, more preferably up to about 5 mol%, of silver iodide.
  • In the shell portion at least one of silver bromochloride, silver chloride and silver bromide is contained.
  • the distribution of silver iodide in the shell portion may be uniform or non-uniform.
  • the grains used in the present invention contain an average of about 5 mol % or more, preferably about 7 mol % to 15 mol %, of silver iodide in the grain surface portion measured according to the XPS method, and it may be more than or the same as the average silver iodide content in the shell portion.
  • any off silver chloride, silver chlorobromide, and silver bromide may be used, with the content of silver bromide being preferably at least 40 mol %, more preferably at least 60mol %.
  • the effects of the present invention are remarkable when the total content of silver iodide is about 7 mol % or more.
  • the total silver iodide content is more preferably about 9 mol % or more, particularly preferably about 12 mol % to 21 mol %.
  • the size of silver halide grains to be used in the present invention are not particularly limited, but are preferably about 0.4 ⁇ m or more, more preferably about 0.6 ⁇ m to 2.5 ⁇ m.
  • the silver halide grains used in the present invention may have a regular form ("normal crystal grains") such as hexahedral, octahedral, dodecahedral, and tetradecahedral, or an irregular form, such as spherical, pebble-like shape or tabular.
  • regular crystal grains such as hexahedral, octahedral, dodecahedral, and tetradecahedral
  • an irregular form such as spherical, pebble-like shape or tabular.
  • the face ratio of (111) face can be determined by Kubelka-Munk's dye adsorption method. In this method, a dye is selected which preferentially adsorbs on either the (111) face or (100) face, and which associates on the (111) face in a spectrally differentiable state from that on (100) face. The thus selected dye is added to an emulsion to be measured, and the spectrum for an amount of the dye added is studied in detail to determine the face ratio of the (111) face.
  • tabular grains are preferred. Grains having a thickness of not more than about 0.5 ⁇ m, a diameter of about 0.6 ⁇ m or more, and an aspect ratio of about 2 or more, preferably about 3 to 10, account for particularly preferably at least about 50 % of the total projected area of silver halide grains present in one and the same layer.
  • the definition of average aspect ratio and a method for its measurement are specifically described in Japanese Patent Application (OPI) Nos. 113,926/83, 113,930/83 and 113,934/83.
  • the emulsions used in the present invention may have a broad grain size distribution, but emulsions with a narrow grain size distribution are preferred. Particularly in emulsions containing normal crystal grains, monodisperse emulsions in which about 90 % (by weight or number) of the total silver halide grains have grain sizes within ⁇ 40 %, more preferably ⁇ 30 %, of the average grain size are preferred.
  • the silver halide grains of the material of present invention may be prepared by combining proper processes selected from various conventional processes.
  • any of an acidic process, a neutral process or an ammoniacal process may be selected and, as for reacting a soluble silver salt with a soluble halide salt, any of a one sided-mixing process, a simultaneous mixing process or their combination, can be used.
  • simultaneous mixing process a process in which the pAg in the liquid phase in which silver halide is formed is kept constant, i.e., a controlled double jet process, may be employed.
  • a simultaneous mixing process a triple jet process in which soluble halide salts with different compositions (for example, soluble silver salt, soluble bromide salt, and soluble iodide salt) are independently added may also be used.
  • silver halide solvents such as ammonia, a rhodanate, a thiourea, a thioether or an amine, may be properly selected for use.
  • Core grains desirably have a narrow grain size distribution, and the monodisperse core emulsions described above are particularly preferred. Whether the halide composition of individual core grains is uniform or not can be determined by the technique of X-ray diffraction and the EPMA method described above. Grains with uniform halide composition give a narrow and sharp diffraction peak width in X-ray diffraction.
  • Japanese Patent Publication No. 21,657/74 discloses two processes for preparing core grains with uniform halide composition among grains.
  • One process is a double jet process in which a solution is prepared by dissolving 5 g of inert gelatin and 0.2 g of potassium bromide in 700 ml of distilled water and, while stirring the solution, simultaneously adding 1 l of an aqueous solution containing dissolved therein 52.7 g of potassium bromide and 24.5 g of potassium iodide, and 1 l of an aqueous solution containing dissolved therein 100 g of silver nitrate. These two solutions are simultaneously added to the stirred solution at an equal and constant rate in about 80 min, then water is added thereto to make the total amount 3 l.
  • silver bromoiodide grains containing 25 mol % of silver iodide are obtained.
  • silver bromoiodide grains have been found to have a comparatively sharp iodide distribution curve by X-ray diffractiometry.
  • Another process is a rash addition process wherein an aqueous solution is prepared by dissolving 33 g of inert bone gelatin, 5.4 g of potassium bromide, and 4.9 g of potassium iodide in 500 ml of distilled water and, while stirring the aqueous solution at 70°C, 125 ml of an aqueous solution containing 12.5 g of silver nitrate is added at once to obtain comparatively uniform silver bromoiodide grains containing 40 mol % of silver iodide.
  • Japanese Patent Application (OPI) No. 16,124/81 discloses that uniform silver bromoiodide grains can be obtained by keeping the pAg of a protective colloid-containing solution with a silver bromoiodide emulsion containing silver bromoiodide having a silver iodide content of 15 to 40 mol % at 1 to 8.
  • uniform silver bromoiodide can also be prepared by a process of accelerating the rate of addition of an aqueous solution of a water soluble halide as disclosed in Japanese Patent Publication No. 36,890/73 (corresponding to U.S. Patent 3,650,757) by Iris and Suzuki, or by a process of increasing the concentrations of added solutions to develop silver bromoiodide grains as disclosed in U.S. Patent 4,242,445 to Saito. These processes give particularly preferable results.
  • the process of Irie et al is a process of preparing photographic, slightly soluble inorganic crystals by double decomposition reaction through simultaneous addition of almost equal amounts of two or more aqueous solutions of inorganic salts in the presence of a protective colloid.
  • the Saito's process is a process of preparing silver halide crystals by simultaneously adding two or more aqueous solutions of inorganic salts in the presence of a protective colloid, in which the concentrations of the aqueous solutions of inorganic salts to be reacted are increased to such a degree that new crystal nuclei are scarcely produced during the crystal growth period.
  • Silver iodide in the core portion may be transferred into the shell portion upon addition of an aqueous solution of a water-soluble bromide salt and an aqueous solution of a water-soluble silver salt according to the double jet process.
  • the amount and distribution of silver iodide in the shell portion can be controlled by adjusting the pAg during the addition or using a silver halide solvent.
  • an aqueous solution of a mixture of a water-soluble bromide and a water-soluble iodide and an aqueous solution of a water-soluble silver salt may be added according to the double jet process, or an aqueous solution of a water-soluble bromide, an aqueous solution of water-soluble iodide, and a water-soluble silver salt may be added according to the triple jet process.
  • an aqueous solution containing a water-soluble iodide can be added, or 0.1 ⁇ m or smaller silver iodide fine grains or silver halide fine grains having a high silver iodide content can be added after formation of the grains.
  • the shell may be formed around the core grains without further treatment after core formation, but it is preferred to form the shell after washing the core emulsion to desalt the core grains.
  • Shell formation may be conducted according to various processes known in the field of silver halide photographic materials, with a simultaneous mixing process being preferred.
  • the above-described process of Irie et al and the Saito's process are preferred for preparing emulsions having grains with a distinct layered structure.
  • the necessary shell thickness varies depending upon grain sizes. Large grains of 1.0 ⁇ m or larger are preferably covered by a shell of 0.1 ⁇ m or more in thickness, while small grains not larger than 1.0 ⁇ m are preferably covered by a shell of 0.05 ⁇ m or more in thickness.
  • the ratio of silver in the core portion to that in the shell portion is preferably in the range of from about 1:5 to 5:1, more preferably about 1:5 to 3:1, most preferably about 1:5 to 2:1.
  • cadmium salts zinc salts, lead salts, thallium salts, iridium salts or the complex salts thereof, rhodium salts or the complex salts thereof, iron salts or the complex salts thereof, may be present during the formation or physical ripening of silver halide grains.
  • the silver halide emulsion used in the present invention is chemically sensitized by a sulfur-containing silver halide solvent. Chemical sensitization can be conducted according to the processed described in, for example, H. Frieser, Die Unen der Photographischen Sawe mit Silberhalogeniden pp. 675 - 734 (Akademische Verlagsgesellschaft, 1986).
  • Sulfur sensitization is conducted with a solvent selected from the group consisting of thiocyanates, thioethers represented by formula (IV), thione compounds represented by formula (V) and mercapto compounds represented by formula (VI).
  • gelatin As a protective colloid used in the preparation of an emulsion of silver halide grains in accordance with the present invention, or as a binder for hydrophilic colloidal layers, gelatin is advantageously used. However, other hydrophilic colloids can be used as well.
  • proteins such as gelatin derivatives, graft polymers of gelatin and other high polymers, albumin or casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethylcellulose or cellulose sulfate; sugar derivatives such as sodium alginate or starch derivatives; and various synthetic hydrophilic macromolecular substances such as homopolymers or copolymers (e.g., polyvinyl alcohol, partially acetallized polyvinyl alcohol, poly-n-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole or polyvinyl pyrazole) can be used.
  • polyvinyl alcohol partially acetallized polyvinyl alcohol, poly-n-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole or polyvinyl pyrazole
  • gelatin acid-processed gelatin or enzyme-processed gelatin as described in Bull. Soc. Sci. Phot. Japan , No. 16, p. 30 (1966) may be used, as well as lime-processed gelatin, a gelatin hydrolyzate or an enzyme-decomposed product.
  • the photographic emulsions used in the present invention are spectrally sensitized by at least one sensitizing dye selected from the group consisting of dyes represented by formula (I) or (II).
  • any of the nuclei ordinarily used as basic hetero ring nuclei in cyanine dyes can be used. That is, 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 or a pyridine nucleus; those in which these nuclei are fused with an alicyclic hydrocarbon ring; and those in which these nuclei are fused with an aromatic ring, i.e., an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphth
  • the merocyanine dyes or complex merocyanine dyes can contain a ketomethylenen nucleus, including 5- or 6-membered hereto ring nuclei such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thio-oxazolidine-2,4-dione nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, a thiobarbituric acid nucleus, etc.
  • a ketomethylenen nucleus including 5- or 6-membered hereto ring nuclei such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thio-oxazolidine-2,4-dione nucleus,
  • sensitizing dyes may be used alone or in combination.
  • a combination of sensitizing dyes is often employed, particularly for the purpose of supersensitization. Typical examples thereof are described in U.S. Pats. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769,301, 3,814,609, 3,837,862, 4,026,707, British Pat. 1,344,281, 1,507,803, Japanese Patent Publication Nos. 4,936/68, 12,375/78, and Japanese Patent Application (OPI) Nos. 110,618/77, 109,925/77.
  • a dye which itself does not have a spectrally sensitizing effect or a substance which substantially does not absorb visible light and which shows a supersensitizing effect may be incorporated to an emulsion together with the sensitizing dye.
  • sensitizing dyes of formula (I) or (II) may be used alone or as a combination thereof.
  • Z1 and Z2 each represents atomic group necessary for forming the same or different, substituted or unsubstituted 5- or 6-membered, nitrogen-containing hetero rings, such as a thiazoline ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, a selenazoline ring, a selenazole ring, a benzoselenazole ring, a naphthoselenazole ring, an oxazole ring, a benzoxazole ring, a naphthoxazole ring, a benzimidazole ring, a naphthoimidazole ring, a pyridine ring, a quinoline ring, an indolenine ring or an imidazo (4,5-b)quinoxaline ring.
  • a thiazoline ring such as a thiazoline ring, a thiazole ring
  • heterocyclic nuclei may be substituted.
  • substituents include a lower alkyl group (containing preferably up to 6 carbon atoms and being optionally further substituted by a hydroxy group, a halogen atom, a phenyl group, a substituted phenyl group, a carboxy group, an alkoxycarbonyl group or an alkoxy group), a lower alkoxy group (containing preferably up to 6 carbon atoms), an acylamino group (containing preferably up to 8 carbon atoms), a monocyclic aryl group, a carboxy gruop, a lower alkoxycarbonyl group (containing preferably up to 6 carbon atoms), a hydroxy gruop, a cyano group or a halogen atom.
  • Q1 represents an atomic group necessary for forming a 5- or 6-membered, nitrogen-containing ketomethylene ring such as a thiazolidin-4-one ring, a selenazolidin-4-one ring, an oxazolidin-4-one ring or an imidazolidin-4-one ring.
  • R1, R2, R3, and R4 which may be the same or different, each represents a hydrogen atom, a lower alkyl group (containing preferably up to 4 carbon atoms), a substituted or unsubstituted phenyl group, or aralkyl group; provided that when l1 represents 2 or 3 or when n represents 2 or 3, one R1 and another R1, one R2 and another R2, one R3 and another R3, or one R4 and another R4 may be linked to each other to form a 5- or 6-membered ring optionally containing an oxygen atom, a sulfur atom or a nitrogen atom.
  • R5, R6 and R7 which may be the same or different, each represents a substituted or unsubstituted alkyl or alkenyl group containing up to 10 carbon atoms which may have an oxygen atom, a sulfur atom or a nitrogen atom in the carbon chain.
  • the substituents include a sulfo group, a carboxy group, a hydroxy group, a halogen atom, an alkoxycarbonyl group, a carbamoyl group, a phenyl group, and a substituted phenyl group.
  • the hetero ring represented by Z1 or Z2 is a ring containing another substitutable nitrogen atom such as a benzimidazole ring, a naphthoimidazole ring or an imidazo[4,5-b]quinoxaline ring
  • the other nitrogen atom in the hetero ring may be substituted by, for example, an alkyl or alkenyl group containing up to 6 carbon atoms, this substituent optionally substituted by a hydroxy group, an alkoxy group or an alkoxycarbonyl group.
  • l1 and n1 each represents 0 or a positive integer of up to 3, with l1 + n1 being up to 3.
  • R5 and R1 may be connected to each other to form a 5- or 6-membered ring.
  • j1, k1, and m1 each represents 0 or 1.
  • X1 represents an acid anion such as Cl ⁇ , B r ⁇ , I-, CH3OSO3 ⁇ or
  • r1 represents 0 or 1.
  • At least one of R5, R6, and R7 more preferably represents a group substituted with a sulfo or carboxy group.
  • sensitizing dyes represented by general formula (I) the following are preferred.
  • Z11 represents an atomic group necessary for forming a nitrogen-containing, 5- or 6-membered hetero ring, including for example, hetero ring nuclei which are usually used for forming cyanines, such as thiazoline, thiazole, benzothiazole, naphthothiazole, selenazoline, selenazole, benzoselenazole, naphthoselenazole, oxazole, benzoxazole, naphthoxazole, benzimidazole, naphthoimidazole, pyridine, quinoline, pyrrolidine, indolenine or imidazo[4,5-b]-quinoxalinetetrazole.
  • hetero ring nuclei which are usually used for forming cyanines, such as thiazoline, thiazole, benzothiazole, naphthothiazole, selenazoline, selenazole, benzoselenazole, naphthoselenazole, o
  • These hetero ring nuclei may optionally be substituted.
  • substituents include a lower alkyl group (containing preferably up to 10 carbon atoms and being optionally substituted by a hydroxy group, a halogen atom, a phenyl group, a substituted phenyl group, a carboxy group, an alkoxycarbonyl gruop or an alkoxy group), a lower alkoxy group (containing preferably up to 7 carbon atoms), an acylamino group (containing preferably up to 8 carbon atoms), a monocyclic aryl group, a monocyclic aryloxy gruop, a carboxy group, a lower alkoxycarbonyl group (containing preferably up to 7 carbon atoms), a hydroxy group, a cyano group and a halogen atom.
  • Q11 represents an atomic group necessary for forming a nitrogen-containing, 5- or 6-membered ketomethylene ring such as thiazolidin-4-one, selenazolidin-4-one, oxazolidin-4-one or imidazolidin-4-one.
  • Q12 represents an atomic group necessary for forming a nitrogen-containing, 5- or 6-membered ketomethylene ring, including for example, a hetero ring nucleus capable of forming an ordinary merocyanine dye, such as rhodanine, 2-thiohydantoin, 2-selenathiohydantoin, 2-thio-oxazolidine-2,4-dione, 2-selenaoxazolidine-2,4-dione, 2-thioselenazolidine-2,4-dione, 2-selenathiazolidine-2,4-dione or 2-selenazolidine-2,4-dione.
  • a hetero ring nucleus capable of forming an ordinary merocyanine dye, such as rhodanine, 2-thiohydantoin, 2-selenathiohydantoin, 2-thio-oxazolidine-2,4-dione, 2-selenaoxazolidine-2,4-
  • hetero rings represented by Z11 , Q11, and Q12 are rings containing two or more nitrogen atoms as the hetero ring-forming atoms, such as benzimidazoles and thiohydantoins
  • the nitrogen atoms not bonded to R13, R15, and R14, respectively may be substituted.
  • substituents include alkyl or alkenyl groups containing up to 8 carbon atoms and in which a carbon atom or atoms may be substituted by an oxygen atom, a sulfur atom or a nitrogen atom, and may further be substituted, or optionally substituted monocyclic aryl groups.
  • R11 represents a hydrogen atom or an alkyl group containing up to 4 carbon atoms
  • R12 represents a hydrogen atom, a phenyl group or a substituted phenyl group (examples of the substituents being an alkyl or alkoxy group containing up to 4 carbon atoms, a halogen atom, a carboxyl group, or a hydroxyl group) or an alkyl group optionally substituted by a hydroxyl group, a carboxyl group, an alkoxy group or a halogen atom, and, when m21 represents 2 or 3, plural R12 groups may be linked to form a 5- or 6-membered ring optionally containing an oxygen atom, a sulfur atom or a nitrogen atom.
  • R13 represents substituted or unsubstitutes alkyl, alkenyl or hetero ring group containing up to 10 carbon atoms and optionally containing an oxygen atom, a sulfur atom or a nitrogen atom in the carbon chain or a hetero ring roup.
  • substituents include a sulfo group, a hydroxy group, a halogen atom, an alkoxycarbonyl group, a carbamoyl group, a phenyl group, a substituted phenyl group, and a monocyclic saturated hetero ring group.
  • R14 and R15 which may be the same or different, each has the same definition as R13, or each represents a hydrogen atom or substituted or unsubstituted monocyclic aryl group (examples of the substituents being a sulfo group, a carboxy group, a hydroxy group, a halogen atom, an alkyl, acylamino or alkoxy group containing up to 5 carbon atoms).
  • n21 0 or 1; provided that when m21 represents a positive integer of 1 to 3, R11 and R13 may be linked to form a 5- or 6-membered ring.
  • At least one of R13, R14,and R15 preferably represents a group containing a sulfo or carboxy group.
  • sensitizing dyes represented by general formula (II) the following compounds are particularly preferred.
  • R represents an aliphatic, aromatic or heterocyclic group substituted by at least one of -COOM or -SO3M
  • M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium group or a quaternary phosphonium group.
  • the sulfur-containing silver halide solvent used in the present invention may be added in any step between formation of emulsion grains and coating of the emulsion.
  • the amount of sulfur-containing silver halide solvent used in the present invention is usually from about 1.25 x 10 ⁇ 4 mol to 5.0 x 10 ⁇ 2 mol per mol of silver, and more specifically, an amount of 5.0 x 10 ⁇ 4 mol to 5.0 x 10 ⁇ 2 mol per mol of silver is preferred with respect to silver halide grains of from about 0.4 to 0.8 ⁇ m in grain size, about 2.5 x 10 ⁇ 4 to 2.5 x 10 ⁇ 2 mol per mol of silver is preferred with respect to silver halide grains of from about 0.8 to 1.6 ⁇ m in grain size, and about 1.25 x 10 ⁇ 4 to 1.25 x 10 ⁇ 3 mol per mol of silver is preferred with respect to silver halide grains of from about 1.6 to 3.5 ⁇ m in grain size.
  • sulfur-containing silver halide solvent means a silver halide solvent capable of being coordinated with the silver ion through the sulfur atom.
  • Such solvents include thiocyanates (e.g. potassium rhodanate or ammonium rhodanate), organic thioether compounds (for example, compounds described in US Pats. 3,574,628, 3,021,215, 3,057,724, 3,038,805, 4,276,374, 4,297,439, 3,704,130, Japanese Patent Application (OPI) No. 104,926/82), thione compounds (for example, tetra-substituted thioureas described in Japanese Patent Application (OPI) Nos. 82,408/78, 77,737/80 and US Pat. 4,221,863, and compounds described in Japanese Patent Application (OPI) No. 144,319/78), mercapto compounds capable of accelerating growth of silver halide grains described in Japanese Patent Application (OPI) No. 202,531/82, with thiocyanates and organic thioether compounds being particularly preferred.
  • thiocyanates e.g. potassium rhodan
  • the thioethers are represented by the general formula (IV): R16 - (S-R18) m -S-R17 (IV)
  • m represents 0 or an integer of 1 to 4.
  • R16 and R17 which may be the same or different, each represents a lower alkyl group (containing 1 to 5 carbon atoms) or a substituted alkyl group (containing a total of 1 to 30 carbon atoms), substituted for example, with -OE, -COOM, -SO3M, -NHR19, -NR19R19 (provided that the two R19 groups may be the same or different), -OR19, -CONHR19, -COOR19 or a hetero ring.
  • R19 represents a hydrogen atom, or a lower alkyl group which may further be substituted by the above-described substituent or substituents.
  • Two or more substituents may be present in the alkyl group, which may be the same or different.
  • M represents a hydrogen atom or a cation such as an alkali metal atom and an ammoniums ion.
  • R18 represents an alkylene group (containing preferably 1 to 12 carbon atoms) provided that, when m is 2 or more, the plural R18 groups may be the same or different.
  • the alkylene chain may contain one or more of -O-, -CONH- or -SO2NH-, and may be substituted by those substituents which have been described for R16 and R17.
  • R16 and R17 may be linked to form a cyclic thioether.
  • the thione compounds are represented by the general formula (V): In the above general formula, Z represents -OR24 or -SR25.
  • R20, R21, R22, R23, R24, and R25 which may be the same or different and may optionally be substituted, each represents an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a hetero ring residue (each containing preferably a total of up to 30 carbon atoms).
  • R20 and R21, R22 and R23, R20 and R22, R20 and R24, or R20 and R25 may be linked to form a 5- or 6-membered hetero ring, which may be substituted.
  • the mercapto compounds are represented by the following general formula (VI):
  • A represents an alkylene group
  • R26 represents -NH2, -NHR27, -CONHR30, -OR30, -COOM, -COOR27, -SO2NHR30, -NHCOR27 or -SM3M (containing preferably a total of up to 30 carbon atoms).
  • L represents -S ⁇ when R26 represents or represents -SM in other cases.
  • R27, R28, and R29 each represents an alkyl group
  • R30 represents a hydrogen atom or an alkyl group
  • M represents a hydrogen atom or a cation (e.g., an alkali metal ion or an ammonium ion).
  • S S S -(1) K S C N S S S -(2) NH4SCN S S S S -(3) HO(CH2)2S(CH2)2OH S S S S -(4) HO( ⁇ CH2)6S(CH2)5S(CH2)6OH S S S -(5) HO( ⁇ CH2)2-S-(CH2)2-S-(CH2)2-OH S S S -(6) HO-(CH2)3-S-(CH2)2-S-(CH2)3-OH S S S -(7) HO( ⁇ CH2)6-S-(CH2)2-S-(CH2)6-OH S S S -(8) HO(CH2)2S(CH2)2S(CH2)2S(CH2)2OH S S S -(9) HO(CH2)2S(CH2)2O(CH2)2O(CH2)2S(CH2)2OH S S S -(10) HOOCCH2S(CH2)2SCH2COOH S S S S -(
  • azoles e.g., benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriadiazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole)); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes (such as, triazaindenes, tetrazaindenes (particularly 4-hydroxy-substituted (1,3,3a,7)tetrazaindenes) or pentazaindenes; benzenethiosulfonic acid, benzenesulfinic acid,
  • the photographic light-sensitive material of the present invention may contain in its photographic emulsion layer or layers a polyalkylene oxide or its ether, ester or amine derivative, a thioether compound, a thiomorpholine, a quaternary ammonium salt compound, a urethane derivative, a urea derivative, an imidazole derivative or a 3-pyrazolidone, for the purpose of enhancing sensitivity or contrast or for accelerating development.
  • a polyalkylene oxide or its ether, ester or amine derivative a thioether compound, a thiomorpholine, a quaternary ammonium salt compound, a urethane derivative, a urea derivative, an imidazole derivative or a 3-pyrazolidone
  • a polyalkylene oxide or its ether, ester or amine derivative a thioether compound, a thiomorpholine, a quaternary ammonium salt compound, a urethane derivative, a
  • the light-sensitive material prepared according to the present invention may contain in its hydrophilic layer a water-soluble dye as a filter dye or for various purposes such as prevention of irradiation.
  • a water-soluble dye as a filter dye or for various purposes such as prevention of irradiation.
  • Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes. Of these, oxonol dyes, hemioxonol dyes, and merocyanine dyes are particularly useful.
  • the light-sensitive material of the present invention may contain in its photographic emulsion layer or an other hydrophilic colloidal layer a brightening agent such as a stilbene, a triazine, an oxazole, or a coumarin. These may be water-soluble, and water-insoluble brightening agents may be used in the form of a dispersion.
  • a brightening agent such as a stilbene, a triazine, an oxazole, or a coumarin.
  • color image stabilizers used in the present invention may be used alone or in combination of two or more.
  • the known dye stabilizers include, for example, hydroquinone derivatives described in US Pats. 2,360,290, 2,418,613, 2,675,314, 2,702,197, 2,704,713, 7,728,659, 2,732,300, 2,735,765, 2,710,801, 2,816,028, British Pat. No. 1,363,921, gallic acid derivatives described in US Pats. 3,457,079, 3,069,262, p-alkoxyphenols described in US Pats. 2,735,765, 3,698,909, and Japanese Patent Publication Nos.
  • the light-sensitive material prepared according to the present invention may contain hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives or ascorbic acid derivatives, as color fog-preventing agents.
  • the photographic light-sensitive materials of the present invention include both black-and-white light-sensitive materials and multi-layer multi-color light-sensitive materials. They are particularly preferably used as high-speed color light-sensitive materials for photographic use.
  • Multi-layer natural color photographic materials usually contain a support having thereon at least one red-sensitive emulsion layer, one green-sensitive emulsion layer, and one blue-sensitive emulsion layer.
  • the order or these layers can be arbitrarily selected as the case demands.
  • the red-sensitive emulsion layer usually contains a cyan-forming coupler, the green-sensitive emulsion layer a magenta-forming coupler, and the blue-sensitive emulsion layer a yellow-forming coupler. In some cases, however, different combinations may be employed.
  • yellow color-forming couplers known open chain ketomethylene couplers may be used. Of these, benzoylacetanilide type and pivaloylacetanilide type compounds are advantageous. Specific examples of yellow color-forming couplers are those described in US Pats. 2,875,057, 3,265,506, 3,408,194, 3,551,155, 3,582,322, 3,725,072, 3,891,445, West German Pat. No. 1,547,868, West German Pat. Application (OLS) Nos. 2,219,917, 2,261,361, 2,414,006, British Pat. No. 1,423,020, Japanese Patent Publication No. 10,783/76, Japanese Patent Application (OPI) Nos.
  • magenta color-forming couplers pyrazolone compounds, indazolone compounds or cyanoacetyl compounds, may be used, with pyrazolone compounds being particularly advantageous.
  • useful magenta color-forming couplers are those described in US Pats. 2,600,788, 2,983,608, 3,062,653, 3,127,269, 3,311,475, 3,419,391, 3,519,429, 3,558,319, 3,582,322, 3,615,506, 3,834,908, 3,891,445, West German Pat. No. 1,810,464, West German Pat. Application (OLS) Nos. 2,408,665, 2,417,945, 2,418,959, 2,424,467, Japanese Patent Publication No.
  • phenolic compounds or naphtholic compounds may be used as cyan color-forming couplers. Specific examples thereof are described in US Pats. 2,369,929, 2,434,272, 2,474,293, 2,521,908, 2,895,826, 3,034,892, 3,311,476, 3,458,315, 3,476,563, 3,583,971, 3,591,383, 3,767,411, 4,004,929, West German Pat. Application (OLS) Nos. 2,414,830, 2,454,329, Japanese Patent Application (OPI) Nos. 59,838/73, 26,034/76, 5,055/73, 146,828/76, 69,624/77, and 90,932/77.
  • OLS Japanese Patent Application
  • couplers having a ureido group described in Japanese Patent Application (OPI) Nos. 204,545/82, 65,134/81, 33,252/73, 33,249/83 are preferably used (corresponding to U.S. Pats. 4,451,559, 4,333,999, European Pat. 73, 145A and U.S. Pat. 4,444,872, respectively).
  • the couplers may be of either 4-equivalent type or 2-equivalent type based on silver ions. Since 2-equivalent couplers are capable of more effectively utilizing silver, they are more preferred. Particularly in silver halide emulsions containing grains containing silver iodide in an average content of not less than 7 mol %, it is more advantageous to employ 2-equivalent couplers in view of photographic properties.
  • Preferred 2-equivalent couplers used in the present invention are represented by the following general formuale (Cp-1) to (Cp-9).
  • R51 to R59, Z1, Z2, Z3, Y, l, m, and p in the above general formulae (Cp-1) to (Cp-9) are described below.
  • R51 represents an aliphatic group, an aromatic group, an alkoxy group or a heterocyclic group
  • R52 and R53 which may be the same or different each represents an aromatic group or a heterocyclic gruop.
  • the aliphatic group represented by R51 preferably contains 1 to 22 carbon atoms, and may be substituted or unsubstituted, and may be in a chain form or cyclic form.
  • Substituents for an alkyl group represented by R51 include an alkoxy group, an aryloxy group, an amino group, an acylamino group and a halogen atom, which themselves may further be substituted.
  • aliphatic group represented by R51 examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isoamyl group, a tert-amyl group, a 1,1-dimethylbutyl, 1,1-dimethylhexyl, 1,1-diethylhexyl gruop, a dodecyl group, a hexadecyl group, an octadecyl group, a cyclohexyl group, a 2-methyoxyisopropyl group, a 2-phenoxyisopropyl group, 2-p-tert-butylphenoxy-isopropyl group, an ⁇ -aminoisopropyl group, an ⁇ -(diethylaminoisopropyl group,an ⁇ -(succinimido)isopropyl group, an ⁇ -(phthalimido)isopropyl group and
  • R51, R52 or R53 represents an aromatic group (particularly a phenyl group)
  • the aromatic group may be substituted, by an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an alkoxycarbonylamino group, an aliphatic amido group, an alkylsulfamoyl group, an alkylsulfonamido group, an alkyureido group or an alkyl-substituted succinimido group, containing up to 32 carbon atoms.
  • the alkyl group may contain in its chain an aromatic group such as a phenylene group.
  • the phenyl group in the aromatic group may also be substituted by an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamido group or an arylureido group, with the aryl moiety of these substituents being optionally substituted by one or more alkyl groups containing a total of 1 to 22 carbon atoms.
  • the phenyl group in the aromatic group represented by R51, R52 or R53 may further be substituted by an amino group including those substituted by a lower alkyl group or groups containing 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, a sulfo group, a nitro group, a cyano group, a thiocyano group or a halogen atom.
  • R51, R52 or R53 may represent a substituent in which a phenyl group is fused with an other ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a coumaranyl group or a tetrahydronaphthyl group. These substituents themselves may further have a substituent or substituents.
  • the alkyl moiety includes a straight or branched alkyl, alkenyl, cyclic alkyl or cyclic alkenyl group containing 1 to 32, preferably 1 to 22, carbon atoms, which may further be substituted by a halogen atom, an aryl group or an alkoxy group.
  • R51, R52 or R53 represents a heterocyclic group
  • the heterocyclic group is linked to the carbon atom of the carbonyl group in the acyl group of the ⁇ -acylacetamido group, or to the nitrogen atom of the amido group of the ⁇ -acylacetamido group, through one carbon atom contained in the ring.
  • Such hetero rings include thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolidine, imidazole, thiazole, oxazole, triazine, thiadiazine or oxazine. These may further have a substituent or substituents in the ring.
  • R55 represents a straight or branched alkyl group containing 1 to 32, preferably 1 to 22, carbon atoms (e.g., a methyl group, an isopropyl group, a tert-butyl group, a hexyl group or a dodecyl group), an alkenyl group (e.g., an allyl group), a cyclic alkyl group (e.g., a cyclopentyl group, a cyclohexyl group or a norbornyl group), an aralkyl group (e.g., a benzyl group or a ⁇ -phenylethyl group), or a cyclic alkenyl group (e.g., a cyclopentenyl group, or a cyclohexenyl group), which may further be substituted by a halogen atom, a nitro group, a cyano group, an aryl group
  • carbon atoms
  • R55 may represent an aryl group (e.g., a phenyl group or an ⁇ -or ⁇ -naphthyl group).
  • the aryl group may have one or more substituents.
  • substituents include an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, a urethane group, a sulfonamido group, a heterocyclic group, an
  • R55 may represent a heterocyclic group (for example, a 5- or 6-membered heterocyclic group or fused heterocyclic group containing a sulfur atom, an oxygen atom or a nitrogen atom as a hetero atom, such as a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group, an oxazolyl group, an imidazolyl group or a naphthoxazolyl group), a heterocyclic group substituted with a substituents for the aryl group represented by R55, an aliphatic or aromatic acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group.
  • a heterocyclic group for example, a 5- or 6-membere
  • R54 represents a hydrogen atom, a straight or branched alkyl or alkenyl group containing 1 to 32, preferably 1 to 22, carbon atoms, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group (these groups optionaly having substituents mentioned with respect to R55), an aryl group and a heterocyclic group (these optionally having substituents mentioned with respect to R55), an alkoxycarbonyl group (e.g., a methoxycarbonyl group an ethoxycarbonyl group or a stearyloxycarbonyl group), an aryloxycarbonyl group (e.g., a phenoxycarbonyl group or a naphthoxycarbonyl group), an aralkyloxycarbonyl group (e.g., a benzyloxycarbonyl group), an alkoxy group (e.g., a methoxy group; an ethoxy group or a
  • R56 represents a hydrogen atom or a straight or branched chain alkyl or alkenyl group containing 1 to 32, preferably 1 to 22, carbon atoms, a cyclic alkyl group, an aralkyl group or a cyclic alkenyl group, which may be substituted by the substituents for R55.
  • R56 may represent an aryl group or a heterocyclic group, which may be substituted by the substituents for R55.
  • R56 may represent a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, a urethane group, a sulfonamido group, an arylsulfonyl group, an alkylsulfonyl group, an arylthio group, an alkylthio group, an alkylamino group, a dialkylamino group, an anilino group, an N-arylanilino group, an N-alkylanilino group, an N-acylanilino group or a hydroxyl group.
  • R56 may be substituted at any position of the benzene ring.
  • R57, R58, and R59 which may be the same or different each represents a group present ordinary 4-equivalent phenolic or ⁇ -naphtholic couplers, specifically a hydrogen atom, a halogen atom, an alkoxycarbonylamino group, an aliphatic hydrocarbon group, an N-arylureido group, an acylamino group, -O-R62 or -S-R62 (provided that R62 represents an aliphatic hydrocarbon group).
  • Plural R57 groups in the same molecule may be the same or different.
  • the aliphatic hydrocarbon group includes those which have a substituent or substituents.
  • the aryl moiety may have one or more substituent for R55.
  • R58 and R59 include aliphatic hydrocarbon groups, aryl groups, and hetero ring groups, or one of them may be a hydrogen atom.
  • the groups may have a substituent or substituents.
  • R58 and R59 may be linked to form a nitrogen-containing hetero ring nucleus.
  • the aliphatic hydrocarbon residue represented by R58 and R59 may be saturated or unsaturated, and may be in a straight chain form, a branched chain form or a cyclic form. Preferred examples thereof include an alkyl group (e.g., a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, an isobutyl group, a dodecyl group, an octadecyl group, a cyclobutyl group or a cyclohexyl group), and an alkenyl group (e.g., an allyl group or an octenyl group),
  • the aryl group represented by R58 and R59 includes a phenyl group or a naphthyl group), and the hetero ring group represented by R58 and R59 typically includes a pyridinyl group, a quinolyl group,
  • the substituents for these aliphatic hydrocarbon groups, aryl groups, and hetero ring groups include a halogen atom, a nitro group, a hydroxyl group, a carboxyl group, an amino group, a substituted amino group, a sulfo group, an alkyl group, an alkenyl group, an aryl group a heterocyclic group, an alkoxy group, an aryloxy group, an arylthio group, an arylazo group, an acylamino group, a carbamoyl group, an ester group, an acyl group, an acyloxy group, a sulfonamido group, a sulfamoyl group, a sulfonyl group or a morpholino group.
  • l represents an integer of 1 to 4
  • m represents an integer of 1 to 3
  • p represents an integer of 1 to 5.
  • preferred yellow couplers are those represented by general formula (Cp-1), in which R51 represents a t-butyl group or a substituted or unsubstituted aryl group, and R52 represents a substituted or unsubstituted aryl group; and those represented by general formula (Cp-2), in which R52 and R53 each represents a substituted or unsubstituted aryl group.
  • Preferred magenta couplers are those represented by general formula (Cp-3), in which R54 represents an acylamino group, a ureido group or an arylamino group and R55 represents a substituted aryl group; those represented by general formula (Cp-4) in which R54 represents an acylamino group, a ureido group or an arylamino group and R56 represents a hydrogen atom; and those represented by general formulae (Cp-5) and (Cp-6) in which R54 and R56 each represents a straight or branched alkyl or alkenyl group, a cyclic alkyl or aralkyl group or a cyclic alkenyl group.
  • Preferred cyan couplers are those represented by general formula (Cp-7), in which R57 represents a 2-position acylamino or ureido group, a 5-position acylamino or alkyl group, or a 6-position hydrogen or chlorine atom; and those represented by general formula (Cp-9) in which R57 represents a 5-position hydrogen atom, acylamino group, sulfonamido group or alkoxycarbonyl group, R58 represents a hydrogen atom, and R59 represents a phenyl group, an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group or a cyclic alkenyl group.
  • Z1 represents a halogen atom, a sulfo group, an acyloxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group or a heterocyclic thio group, which may be further substituted by such substituents as an aryl group (e.g., a phenyl group), a nitro group, a hydroxyl group, a cyano group, a sulfo group, an alkoxy group (e.g., a methoxy group), an aryloxy group (e.g., a phenoxy group), an acyloxy group (e.g., an acetoxy group), an acylamino group (e.g., an acetylamino group), a sulfonamido group (e.g., a methanesulfonamido group), a s
  • Z2 and Y which may be the same or different each represents a coupling-off group bonded to the coupling site through an oxygen atom, a nitrogen atom or a sulfur atom.
  • Z2 and Y are bonded to the coupling site through an oxygen atom, a nitrogen atom or a sulfur atom, these atoms are bound to an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an arylcarbonyl group or a heterocyclic group.
  • Z2 or Y represents a 5- or 6-membered ring containing the nitrogen atom to form a coupling-off group (e.g., an imidazolyl group, a pyrazolyl group, a triazolyl group or a tetrazolyl group).
  • a coupling-off group e.g., an imidazolyl group, a pyrazolyl group, a triazolyl group or a tetrazolyl group.
  • the above-described alkyl, aryl, and hetorocyclic groups contained in Z2 and Y may have substituents.
  • substituents include an alkyl group (e.g., a methyl group or an ethyl group), an alkoxy group (e.g., a methoxy group or an ethoxy group), an aryloxy group (e.g., a phenyloxy group), an alkoxycarbonyl group (e.g., a methoxycarbonyl group), an acylamino group (e.g., an acetylamino group), a carbamoyl group, an alkylcarbamoyl group (e.g., a methylcarbamoyl group or an ethylcarbamoyl group), a dialkylcarbamoyl group (e.g., a dimethylcarbamoyl group), an arylcarbamoyl group (
  • substituents include a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and a cyano group.
  • Z2 are groups which are bonded to the coupling site through a nitrogen atom or a sulfur atom
  • preferred examples of Y are a chlorine atom and groups which are bonded to the coupling site through an oxygen atom, a nitrogen atom or a sulfur atom.
  • Z3 represents a hydrogen atom or a group represented by the following general formulae (R-I), (R-II), (R-III) or (R-IV): wherein R63 represents a substituted or unsubstituted aryl or heterocyclic group; wherein R64 and R 65, which may be the same or different, each represents a hydrogen atom, a halogen atom, a carboxylic acid ester group, an amino group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsufonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, an unsubstituted or substituted phenyl or heterocyclic group; wherein W1 represents a non-metallic atomic group necessary for forming a 4-, 5- or 6-membered ring together with therein.
  • R66 and R67 which may be the same or different each represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a hydroxy group
  • R68, R69, and R70 which may be the same or different, each represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or an acyl group
  • W2 represents an oxygen atom or a sulfur atom.
  • the couplers used in the present invention may be polymers derived from coupler monomers represented by the following general formula (CI) and having repeating units represented by the general fomula (CII) or copolymers of the coupler monomer and one or more non-color forming monomers incapable of oxidatively coupling with an aromatic primary amine developing agent, and containing at least one ethylene group. Two or more of the coupler monomers may be contained in the polymer.
  • CI coupler monomers represented by the following general formula (CI) and having repeating units represented by the general fomula (CII) or copolymers of the coupler monomer and one or more non-color forming monomers incapable of oxidatively coupling with an aromatic primary amine developing agent, and containing at least one ethylene group.
  • Two or more of the coupler monomers may be contained in the polymer.
  • R' represents a hydrogen atom, a lower alkyl group containing 1 to 4 carbon atoms or a chlorine atom
  • K1 represents -CONR''-, -NR''CONR''-, -NR''COO-, -COO-, -SO2-, -CO-, -NR''CO-, -SO2NR''-, -NR''SO2-, -OCO-, -OCONR''-, -NR''-, -S-, or -O-
  • K2 represents -CONR''- or -COO-
  • R'' represents a hydrogen atom, an aliphatic group or an aryl group and, when two or more R'' groups are present in the same molecule, they may be the same or different.
  • K3 represents an unsubstituted or substituted alkylene group containing 1 to 10 carbon atoms, an aralkylene group or an unsubstituted or substituted arylene group, with the alkylene group a straight chain or branched chain group.
  • the alkylene group includes a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a decylmethylene group, etc.;
  • the aralkylene group includes a benzylidene group; and
  • the arylene group includes a phenylene group and naphthylene group.
  • Substituents for the alkylene, aralkylene, or arylene group represented by K3 include an aryl group (e.g., a phenyl group), a nitro group, a hydroxyl group, a cyano group, a sulfo group, an alkoxy group (e.g., a methoxy group), an aryloxy group (e.g., a phenoxy group), an acyloxy group (e.g., an acetoxy group), an acylamino group (e.g., an acetylamino group), a sulfonamido group (e.g., a methanesulfonamido group), a sulfamoyl group (e.g., a methylsulfamoyl group), a halogen atom (e.g., a fluorine atom, a chlorine atom or a bromine atom), a carboxy
  • Q is bonded to in formula (CI) or (CII) through any of R51 to R59, Z1 to Z3, and Y of the foregoing general formulae (Cp-1) to (Cp-9).
  • the non-color forming ethylenic monomers incapable of coupling with an oxidation product of an aromatic primary amine developing agent include acrylic acid, ⁇ -chloroacrylic acid, ⁇ -alkylacrylic acid (e.g., acrylic acid or methacrylic acid), an ester or amide derived therefrom (e.g., acrylamide, methacrylamide, t-butylacrylamide, methyl acrylate, methyl methacrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, t-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, n-octylatrylate, lauryl acrylate, and methylenebisacrylamide), a vinyl ester (e.g., vinyl acetate, vinyl propionate, and vinyl laurate),
  • non-color forming ethylenically unsaturated monomers may be used as a combination of two or more.
  • a combination of n-butyl acrylate and divinylbenzene, a combination of styrene and methacrylic acid, a combination of n-butyl acrylate and methacrylic acid may be employed.
  • the polymer couplers used in the present invention may be water-soluble or water-insoluble, with a polymer coupler latex being particularly preferable.
  • the polymer coupler latex may be prepared by dissolving a hydrophilic polymer coupler obtained by polymerization of the coupler monomer in an organic solvent, and dispersing the solution to obtain a latex form or by directly dispersing the hydrophilic polymer coupler solution obtained by polymerization to obtain a latex.
  • a polymer coupler latex prepared by emulsion polymerization or layer-structure polymer coupler latex may directly be added to a gelatin-silver halide emulsion.
  • 2-equivalent magenta couplers or 2-equivalent cyan couplers are preferably used, and especially 2-equivalent magenta coupers are preferably used.
  • 2-Equivalent yellow couplers include the following examples.
  • Colored couplers can be used in the present invention, including those described in, for example, US Pats. 3,476,560, 2,521,908, 3,034,892, Japanese Patent Publication Nos. 2016/69, 22,335/63, 11,304/67, 32,461/69, Japanese Patent Application (OPI) Nos. 26,034/76, 42,121/77, and West German Patent Application (OLS) No. 2,418,959.
  • DIR couplers can be used in the present invention, including those described in, for example, US Pats. 3,227,554, 3,617,291, 3,701,783, 3,790,384, 3,632,345, West German Patent Application (OLS) Nos. 2,414,006, 2,454,301, 2,454,392, British Pat. No. 953,454, Japanese Patent Application (OPI) Nos. 69,624/77, 122,335/74, and Japanese Patent Publication No. 16,141/76.
  • compounds which release a development inhibitor according to proceeding of development may be incorporated in light-sensitive materials according to the invention, including, for example, those described in US Pats. 3,297,445, 3,379,529, West German Patent Application (OLS) No. 2,417,914, Japanese Patent Application (OPI) Nos. 15,271/77 and 9,116/78.
  • Couplers capable of releasing a development accelerator or a fogging agent according to proceeding of development as described in Japanese Patent Application (OPI) No. 150,845/82 are particularly preferably used.
  • Non-diffusible couplers capable of forming a slightly diffusible dye as described in British Pat. No. 2,083,640 are also preferably used.
  • couplers are added to emulsion layers in an amount of about 2 x 10 ⁇ 3 mol to 5 x 10 ⁇ 1 mol, preferably about 1 x 10 ⁇ 2 mol to 5 x 10 ⁇ 1 mol.
  • the light-sensitive material prepared according to the present invention may contain in its hydrophilic colloidal layer an ultraviolet light absorbent, including, for example, aryl group-substituted benzotriazole compounds (e.g., those described in US Pat. 3,533,794), 4-thiazolidone compounds (e.g., those described in U.S. Pats. 3,314,794 and 3,352,681), benzophenone compounds (e.g., those described in Japanese Patent Application (OPI) No. 2784/71), cinnamic acid esters (e.g., those described in U.S. Pats. 3,705,805 and 3,707,375), butadiene compounds (e.g., those described in US Pat.
  • an ultraviolet light absorbent including, for example, aryl group-substituted benzotriazole compounds (e.g., those described in US Pat. 3,533,794), 4-thiazolidone compounds (e.g., those described in U.S. Pats. 3,314,79
  • Ultraviolet light absorbing couplers e.g., ⁇ -naptholic cyan dye-forming couplers
  • ultraviolet ray-absorbing polymers may also be used. These ultraviolet light absorbents may be mordanted to a specific layer.
  • the layer containing the emulsion of the present invention is not particularly limited. Further, fine silver halide grains having a grain size of not more than 0.2 ⁇ m are preferably present in at least one layer adjacent to the emulsion layer.
  • any of known processes and known processing solutions may be employed.
  • the processing temperature is usually selected between 18 and 50°C. However, temperatures lower than 18°C or higher than 50°C may be employed. Any of silimer image-forming development (black-and white development) and color photographic processing (dye image-forming development) may be used depending upon purpose.
  • a color developer generally is an alkaline aqueous solution containing a color-developing agent.
  • a color-developing agent there may be used known primary aromatic amine developers such as phenylenediamines (e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethyl-aniline, 4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfoamido-ethyaniline or 4-amino-3-methyl-N-ethyl-N- ⁇ -methoxyethylaniline).
  • Color-developed photographic emulsion layers are usually bleached. Bleaching may be conducted separately or simultaneously with fixing.
  • bleaching agents compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI) or copper (II), peracids, quinones, nitroso or compounds are used, including, for example, ferricyanides, dichromates, organic complex salts of iron (III) or cobalt (III), complex salts of aminopolycarboxylic acids (e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid, or 1, 3-diamino-2-propanol-tetraacetic acid), or organic acids (e.g., citric acid, tartaric acid or malic acid), persulfates, permanganates and nitrosophenols; Of these, potassium ferricyanide, iron (III) sodium ethylenediaminetetraacetate, and iron (III) ammonium ethylenediaminete
  • Emulsions A to G containing silver bromoiodide tabular were prepared according to the process described in Japanese Patent Application (OPI) No. 209,445/87, as follows: An aqueous solution of 30 g of inert gelatin and 6 g of potassium bromide in 1 l of distilled water was stirred at 60°C, and 35 ml of an aqueous solution containing 5.0 g of silver nitrate and 35 ml of an aqueous solution containing 3.2 g of potassium bromide and 0.98 g of potassium iodide were added thereto at a flow rate of 70 ml/min for 30 s, then the solution was ripened for 30 min by raising the pAg of the solution to 10 to prepare a seed emulsion.
  • OPI Japanese Patent Application
  • emulsions D and E For preparing emulsions D and E, a part or all of the potassium iodide used in the preparation of the seed emulsion was replaced by an equimolar of potassium bromide to obtain cores having an iodide content as shown in Table 1.
  • the grain sizes of the emulsions were controlled to be the same.
  • the aspect ratios of emulsions A to G were changed by adjusting the pAg.
  • the grain sizes of silver halide in emulsions A to G were controlled to be 0.75 ⁇ m, in terms of the diameter of a sphere corresponding to the projected area of the grains. With respect to grain size distribution, emulsions A to G had a variation coefficient of diameter about 30%, thus being considered to have almost the same distribution.
  • Table 1 shows the size and iodide contents of silver halide grains in emulsions A to G.
  • XPS analysis was conducted using ESCA-750 made by Shimazu Seisakusho Ltd.
  • Mg-K ⁇ accelerating voltage: 8 kV; current: 30 mA
  • peak areas corresponding to I-3d 5/2 and Ag-3d 5/2 were determined.
  • the average silver iodide content in the surface portion of the silver halide grains was determined from the intensity ratio.
  • the silver bromoiodide tabular emulsions A to G were chemically sensitized to have optimal sensitivity for 1/100S exposure.
  • the amounts of chemically sensitizing agents (per mole of silver) used are shown in Table 2.
  • Samples 101 to 114 were prepared by changing the silver bromoiodide emulsions in the 4th, 7th, and 12th layers of the following coated stratum structure as shown in Table 3.
  • the densities of the processed samples were measured through a red filter, a green filter, and a blue filter.
  • Color development processing was conducted according to the following processing steps at 38°C. Color development 3 min 15 S Bleaching 6 min 30 S Washing with water 2 min 10 S Fixing 4 min 20 S Washing with water 3 min 15 S Stabilizing 1 min 05 S
  • the sensitivities of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer are given below, relative to taking that of sample 101 taken as 100.
  • Table 4 Sample Sensitivity of Red-sensitive Layer Sensitivity of Green-sensitive Layer Sensitivity of Blue-sensitive Layer 101 comparative sample 100 100 100 102 comparative sample 115 117 110 103 present invention 128 130 120 104 present invention 125 125 117 105 comparative sample 113 115 109 106 present invention 125 125 118 107 present invention 120 122 114 108 comparative sample 75 76 73 109 comparative sample 85 87 84 110 comparative sample 70 72 71 111 comparative sample 82 80 76 112 comparative sample 102 101 94 113 comparative sample 109 109 108 114 present invention 115 116 115
  • Comparative samples 108 to 111 were less sensitive than standard samples 101 and 112. Samples of the present invention were more sensitive than the standard samples 101 and 112 and had equal or better graininess.
  • samples stored for 3 days under conditions of 45°C and 80% RH before exposure, and fresh samples not having been subjected to such conditions were simultaneously subjected to spectrum separation exposure and developed as above.
  • Standard samples 101 and 112 suffered serious changes in spectral sensitivity distribution due to the difference of storing conditions, whereas samples of the present invention were scarcely influenced by the change in storage conditions.
  • Samples 201 to 204 were prepared by changing ExM-8 used in the 7th layer of samples 101 to 104 in Example 1 to an equimolar amount of following ExM-20.
  • ExM-20 These samples were subjected to exposure for sensitometry in the same manner as in Example 1. Sensitivities of the green-sensitive layer thus determined are shown in Table 5.
  • Table 5 Sample Sensitivity of Green-sensitive Layer 101 comparative sample 100 102 comparative sample 117 103 PRESENT INVENTION 130 104 PRESENT INVENTION 125 201 comparative sample 92 202 comparative sample 97 203 PRESENT INVENTION 102 204 PRESENT INVENTION 100
  • Octahedral monodisperse silver bromoiodide core grains containing 24 mol% of silver iodide were prepared according to the controlled double jet process in the presence of ammonia, as follows. 500 ml of an aqueous solution containing 100 g of silver nitrate and 500 ml of an aqueous solution containing KBr and KI were added to 1000 ml of an aqueous solution containing 3% of gelatin and 45 ml of 25% NH3. The reaction temperature was 70°C, and the silver potential was controlled at 10 mV, and the flow rates were accelerated so that the final flow rates became 4 times as fast as the initial flow rates.
  • the grains thus obtained were of octahedrons 1.9 ⁇ m in average diameter, and were confirmed by X-ray diffractiometry to be grains showing two peaks at diffraction angles corresponding to the lattice constant of about 22 mol% silver bromoiodide and the lattice constant of about 2 mol% silver bromoiodide and having a double structure of 12 mol % in total AgI content.
  • This emulsion was designated emulsion K.
  • Emulsions L to P shown in Table 6 were also prepared in the same manner as emulsion K except for replacing KI by an equimolar amount of KBr.
  • the finished grain size was adjusted to be 1,9 ⁇ m by controlling the addition rates of the AgNO3 aqueous solution and the KBr/KJ aqueous solution during formation of the core grains.
  • Emulsions K to P were chemically sensitized using sodium thiosulfate, potassium chloroaurate, sulfur-containing silver halide solvent SSS-1, so that they showed optimal sensitivity when subjected to 1/1000 s exposure.
  • Samples 301 to 306 were prepared by coating 1.5 g/m2 of each of emulsions K to P in place of the AgBrI emulsion used in the 12th layer of sample 101 in Example 1.
  • samples 302 and 303 of the present invention were more sensitive than the standard samples 301 and 304, and showed the same or better graininess.

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Claims (22)

  1. Un matériau photographique à l'halogénure d'argent comprenant un support portant au moins une couche d'émulsion d'halogénure d'argent sensible à la lumière contenant des grains d'halogénure d'argent sensibilisé chimiquement et spectralement ayant un noyau d'halogénure d'argent comprenant au moins une portion comprenant 10 à 40 mol % d'iodure d'argent, substantiellement entouré par une portion d'enveloppe d'halogénure d'argent contenant moins d'iodure d'argent que la teneur moyenne en iodure d'argent du noyau et l'halogénure d'argent de la région de surface contenant au moins 5 mol % d'iodure d'argent, ladite région de surface étant la portion entre la surface des grains d'halogénure d'argent et une profondeur de 5 nm dans les grains depuis la surface de la portion d'enveloppe, caractérisé en ce que les grains d'halogénure d'argent sont sensibilisés spectralement par au moins un colorant sensibilisateur choisi parmi les colorants de formule générale (I) ou(II):
    Figure imgb0149
     dans laquelle
    Z₁ et Z₂ représentent chacun un groupement atomique nécessaire pour former des hétérocycles azotés à 5 ou 6 chaînons, substitués ou non, identiques ou différents, Q₁ représente un groupement atomique nécessaire pour former un cycle cétométhylène azoté à 5 ou 6 chaînons,
    R₁, R₂, R₃ et R₄ représentent chacun un atome d'hydrogène, un groupe alkyle inférieur, un groupe phényle substitué ou non, ou un groupe aralkyle; lorsque l₁ représente 2 ou 3 ou lorsque n représente 2 ou 3, un reste R₁ et un autre R₁, un R₂ et un autre R₂, un R₃ et un autre R₃, ou un R₄ et un autre R₄ peuvent être liés l'un à l'autre pour former un cycle à 5 ou 6 chaînons contenant facultativement un atome d'oxygène, un atome de soufre ou un atome d'azote,
    R₅, R₆ et R₇ représentent chacun un groupe alkyle ou alcényle jusqu'en C₁₀ substitué ou non qui peut contenir dans la chaîne carbonée un atome d'oxygène, un atome de soufre ou un atome d'azote,
    l₁ et n₁ représentent chacun zéro ou un entier positif de 1 à 3, la somme l₁ + n₁ étant de 1 à 3, lorsque l₁ représente 1, 2 ou 3, R₅ et R₁ peuvent être reliés l'un à l'autre pour former un cycle à 5 ou 6 chaînons,
    j₁, k₁ et m₁ représentent chacun 0 ou 1,
    X₁⁻ représente un anion d'acide,
    r₁ représente 0 ou 1;
    Figure imgb0150
     dans laquelle
    Z₁₁ représente un groupement atomique nécessaire pour former un hétérocycle azoté à 5 ou 6 chaînons, substitué ou non,
    Q₁₁ représente un groupement atomique nécessaire pour former un cycle cétométhylène azoté à ou 6 chaînons,
    Q₁₂ représente un groupement atomique nécessaire pour former un cycle cétométhylène azoté à 5 ou 6 chaînons,
    R₁₁ représente un atome d'hydrogène ou un groupe alkyle jusqu'en C₄,
    R₁₂ représente un atome d'hydrogène, un groupe phényle substitué ou non ou un groupe alkyle et lorsque m₂₁ représente 2 ou 3, plusieurs groupes R₁₂ peuvent être liés pour former un cycle à 5 ou 6 chaînons contenant facultativement un atome d'oxygène, un atome de soufre ou un atome d'azote,
    R₁₃ représente un groupe alkyle ou alcényle ou hétérocyclique jusqu'en C₁₀ et substitué ou non et contenant facultativement un atome d'oxygène, un atome de soufre ou un atome d'azote dans la chaîne carbonée du groupe alkyle ou alcényle,
    R₁₄ et R₁₅ ont chacun la même définition que R₁₃, ou bien chacun représente un atome d'hydrogène ou un groupe aryle monocyclique substitué ou non,
    m₁₂ représente 0 ou un entier positif de 1 à 3,
    j₂₁ représente 0 ou 1 et n₂₁ représente 0 ou 1, lorsque m₂₁ représente un entier positif de 1 à 3, R₁₁ et R₁₃ peuvent être reliés pour former un cycle à 5 ou 6 chaînons, et en ce que les grains d'halogénure d'argent sont sensibilisés chimiquement par un solvant soufré de l'halogénure d'argent choisi parmi:
    les thiocyanates;
    les thioéthers représentés par la formule (IV):



            R₁₆-(S-R₁₈)m-S-R₁₇   (IV)



    dans laquelle
    m représente 0 ou entier de 1 à 4,
    R₁₆ et R₁₇, qui peuvent être identiques ou différents, représentent chacun un groupe alkyle inférieur en C₁-C₅ ou un groupe alkyle substitué en C₁-C₃₀ au total, ou bien R₁₆ et R₁₇ peuvent être reliés pour former un thioéther cyclique et
    R₁₈ représente un groupe alkylène substitué ou non, avec la condition que, lorsque m est égal à, ou plus, les groupes R₁₈ peuvent être identiques ou différents;
    les composés thiones représentés par la formule (V):
    Figure imgb0151
     dans laquelle
    Z représente
    Figure imgb0152
     -OR₂₄ ou -SR₂₅,
    R₂₀, R₂₁, R₂₂, R₂₃, R₂₄ et R₂₅, qui peuvent être identiques ou différents et qui peuvent être facultativement substitués, représentent chacun un groupe alkyle, un groupe alcényle, un groupe aralkyle, un groupe aryle ou un reste hétérocyclique, ou bien
    R₂₀ et R₂₁, R₂₂ et R₂₃, R₂₀ et R₂₂, R₂₀ et R₂₄, ou R₂₀ et R₂₅ peuvent être reliés pour former un hétérocycle à 5 ou 6 chaînons, qui peut être substitué;
    et les composés mercapto représentés par la formule (VI):
    Figure imgb0153
     dans laquelle
    A représente un groupe alkylène,
    R₂₆ représente -NH₂, -NHR₂₇,
    Figure imgb0154
     -CONHR₃₀, -OR₃₀,
    -COOM, -COOR₂₇, -SO₂NHR₃₀, -NHCOR₂₇ ou -SM₃M
    L représente -S⊖ lorsque R₂₆ représente
    Figure imgb0155
     ou représente -SM dans les autres cas,
    R₂₇, R₂₈ et R₂₉ représentent chacun un groupe alkyle,
    R₃₀ représente un atome d'hydrogène ou un groupe alkyle, et
    M représente un atome d'hydrogène ou un cation.
  2. Le matériau photographique à l'halogénure d'argent selon la revendication 1, dans lequel le matériau photographique contient en outre un coupleur à 2 équivalents.
  3. Le matériau photographique à l'halogénure d'argent selon la revendication 2, dans lequel ledit coupleur à 2 équivalents est un coupleur pour magenta ou un coupleur pour cyan.
  4. Le matériau photographique à l'halogénure d'argent selon la revendication 1, dans lequel la déviation standard relative de la distribution de la teneur en iodure dans les grains est de pas plus de 50 %.
  5. Le matériau photographique à l'halogénure d'argent selon la revendication 1, dans lequel la teneur en iodure d'argent dans la portion de noyau est de 10 à 40 mol %.
  6. Le matériau photographique à l'halogénure d'argent selon la revendication 1, dans lequel la teneur en bromure d'argent dans la portion de noyau est d'au moins 50 mol %.
  7. Le matériau photographique à l'halogénure d'argent selon la revendication 1, dans lequel la portion de noyau contient en outre au moins un halogénure choisi parmi un bromochlorure d'argent et le bromure d'argent.
  8. Le matériau photographique à l'halogénure d'argent selon la revendication 1, dans lequel la teneur moyenne en iodure d'argent dans la portion d'enveloppe est de 0 à 10 mol %.
  9. Le matériau photographique à l'halogénure d'argent selon la revendication 1, dans lequel la portion d'enveloppe comprend au moins un halogénure choisi parmi le chlorure d'argent, un chlorobromure d'argent et le bromure d'argent.
  10. Le matériau photographique à l'halogénure d'argent selon la revendication 9, dans lequel la teneur en iodure d'argent est de pas plus de 5 mol %.
  11. Le matériau photographique à l'halogénure d'argent selon la revendication 1, dans lequel la teneur en iodure d'argent dans la région de surface de l'halogénure d'argent est de 7 à 15 mol %.
  12. Le matériau photographique à l'halogénure d'argent selon la revendication 11, dans lequel la teneur moyenne en iodure d'argent dans les grains d'halogénure d'argent est au moins égale à la teneur moyenne en iodure d'argent dans la portion d'enveloppe.
  13. Le matériau photographique à l'halogénure d'argent selon la revendication 1, dans lequel la portion de surface contient au moins un halogénure d'argent choisi parmi le chlorure d'argent, un chlorobromure d'argent et le bromure d'argent.
  14. Le matériau photographique à l'halogénure d'argent selon la revendication 1, dans lequel la portion de surface contient au moins 40 mol % de bromure d'argent.
  15. Le matériau photographique à l'halogénure d'argent selon la revendication 1, dans lequel la teneur totale en iodure d'argent dans les grains d'halogénure d'argent est d'au moins 7 mol %.
  16. Le matériau photographique à l'halogénure d'argent selon la revendication 15, dans lequel la teneur totale en iodure d'argent dans les grains d'halogénure d'argent est au plus de 21 mol %.
  17. Le matériau photographique à l'halogénure d'argent selon la revendication 1, dans lequel lesdits grains d'halogénure d'argent sont sous forme tabulaire.
  18. Le matériau photographique à l'halogénure d'argent selon la revendication 17, dans lequel les grains ont une épaisseur de pas plus de 0,5 µm, un diamètre d'au moins 0,6 µm et un rapport d'aspect d'au moins 2 et les grains occupent au moins 50 % de la surface projetée totale des grains d'halogénure d'argent dans l'émulsion.
  19. Le matériau photographique à l'halogénure d'argent selon la revendication 1, dans lequel l'émulsion est une émulsion monodispersée contenant des grains cristallins normaux et 90 % des grains d'halogénure d'argent dans l'intervalle de ±40 % par rapport à la dimension moyenne de grains.
  20. Le matériau photographique à l'halogénure d'argent selon la revendication 1, dans lequel les grains ayant une dimension d'au moins 1,0 µm sont recouverts par une enveloppe d'au moins 0,1 µm d'épaisseur et les grains de pas plus de 1,0 µm sont recouverts par une enveloppe d'au moins 0,05 µm.
  21. Le matériau photographique à l'halogénure d'argent selon la revendication 1, dans lequel le rapport de la teneur en argent dans la portion de noyau à celle de la portion d'enveloppe est dans la gamme de 1:5 à 5:1.
  22. Le matériau photographique à l'halogénure d'argent selon la revendication 1, dans lequel ledit solvant soufré de l'halogénure d'argent est contenu en quantité de 1,25.10⁻⁴ mol à 5,0.10⁻² mol par mol d'argent.
EP19870115593 1986-10-24 1987-10-23 Matériau photographique à l'halogénure d'argent ayant une structure spécifique Expired - Lifetime EP0264954B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP25337086A JPS63106745A (ja) 1986-10-24 1986-10-24 ハロゲン化銀写真感光材料
JP253370/86 1986-10-24

Publications (3)

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EP0264954A2 EP0264954A2 (fr) 1988-04-27
EP0264954A3 EP0264954A3 (en) 1989-02-15
EP0264954B1 true EP0264954B1 (fr) 1993-04-07

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EP19870115593 Expired - Lifetime EP0264954B1 (fr) 1986-10-24 1987-10-23 Matériau photographique à l'halogénure d'argent ayant une structure spécifique

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EP (1) EP0264954B1 (fr)
JP (1) JPS63106745A (fr)
DE (1) DE3785291T2 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2516767B2 (ja) * 1987-05-18 1996-07-24 コニカ株式会社 ハロゲン化銀写真感光材料
JP2645367B2 (ja) * 1987-06-25 1997-08-25 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及びその処理方法
DE3852916T2 (de) * 1987-09-14 1995-06-29 Konishiroku Photo Ind Photographisches lichtempfindliches Silberhalogenidmaterial.
JPH0228637A (ja) * 1988-04-11 1990-01-30 Fuji Photo Film Co Ltd ハロゲン化銀写真乳剤及びそれを用いたハロゲン化銀写真感光材料
JP2578206B2 (ja) * 1988-11-15 1997-02-05 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
JP2587288B2 (ja) * 1989-02-15 1997-03-05 富士写真フイルム株式会社 ハロゲン化銀写真感光材料及びその製造方法
EP0421453A1 (fr) * 1989-10-05 1991-04-10 Fuji Photo Film Co., Ltd. Matériau photographique couleur à l'halogénure d'argent
JP2736450B2 (ja) * 1989-10-27 1998-04-02 コニカ株式会社 高感度、高画質で階調性の優れたハロゲン化銀写真感光材料
US5240824A (en) * 1990-02-15 1993-08-31 Konica Corporation Silver halide photographic light-sensitive material having a high sensitivity and improved preservability and a process for producing the same
US5273871A (en) * 1990-10-03 1993-12-28 Konica Corporation Silver halide photographic emulsion and silver halide color photographic light-sensitive material incorporating it
EP0574090A1 (fr) 1992-06-12 1993-12-15 Eastman Kodak Company Copulants à un équivalent et colorants à pKa bas libérés
JPH07261299A (ja) * 1994-03-17 1995-10-13 Konica Corp ハロゲン化銀写真乳剤及びハロゲン化銀写真感光材料
GB9603658D0 (en) * 1996-02-21 1996-04-17 Minnesota Mining & Mfg Photographic materials with improved image tone

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4477564A (en) * 1982-04-01 1984-10-16 Minnesota Mining And Manufacturing Company Photographic silver halide emulsions, process for preparing the same and their use in color reversal films
JPS60254032A (ja) * 1983-12-29 1985-12-14 Fuji Photo Film Co Ltd 感光性ハロゲン化銀乳剤
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
DE3581367D1 (de) * 1984-11-02 1991-02-21 Ilford Ag Verfahren zur herstellung photographischer direktpositivemulsionen.
JPS61148442A (ja) * 1984-12-21 1986-07-07 Fuji Photo Film Co Ltd 熱現像感光材料
JPH0617986B2 (ja) * 1985-04-24 1994-03-09 コニカ株式会社 ハロゲン化銀写真感光材料
JPH0619507B2 (ja) * 1985-04-24 1994-03-16 コニカ株式会社 ハロゲン化銀写真感光材料
JPS62123445A (ja) * 1985-08-26 1987-06-04 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料

Also Published As

Publication number Publication date
JPS63106745A (ja) 1988-05-11
JPH0575096B2 (fr) 1993-10-19
EP0264954A2 (fr) 1988-04-27
DE3785291T2 (de) 1993-07-22
DE3785291D1 (de) 1993-05-13
EP0264954A3 (en) 1989-02-15

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