Classifications

• • 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
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/0051—Tabular grain emulsions
  • G03C2001/0055—Aspect ratio of tabular grains in general; High aspect ratio; Intermediate aspect ratio; Low aspect ratio
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/03535—Core-shell grains
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/03558—Iodide content
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/0357—Monodisperse emulsion

Definitions

• the present invention relates to a silver halide light-sensitive color photographic material, specifically to a silver halide light-sensitive photographic material having high sensitivity, excellent graininess and improved storage stability.
• Japanese Patent O.P.I. Publication No. 92942/1988 discloses tabular silver halide grains having therein a core of high AgI;
• Japanese Patent O.P.I. Publication No. 163451 discloses tabular hexagonal grains;
• Japanese Patent O.P.I. Publication No. 163451/1988 discloses tabular silver halide grains having an aspect ratio of not less than 5.
• the object of the invention is to provide a silver halide light-sensitive color photographic material having an improved sensitivity, graininess and storage stability.
• a silver halide light-sensitive color photographic material comprising a support and provided thereon at least one silver halide emulsion layer, wherein at least one of the emulsion layers contains core/shell type tabular silver halide grains comprising: a) a ratio of monodispersed grains of not less than 70% in terms of the number of the grains; b) an average aspect ratio (diameter/thickness) of not less than 1 and less than 5; and the portion having a silver iodide content of not less than 15.3 mol % in the core.
• most of the tabular silver halide grains are hexagonal and the degree of monodispersion of the grains is less than 20%.
• the tabular grain is defined by the grain having two major faces parallel to each other.
• Tabular silver halide grains of the invention have an average diameter/thickness ratio (aspect ratio) of not less than 1 and smaller than 5, preferably not less than 1 and smaller than 4, more preferably not less than 1 and smaller than 3.
• the average aspect ratio is obtained by averaging the aspect ratios of all silver halide grains.
• the diameter of a tabular silver halide grain which is represented by the diameter of a circle having the same area as that of the projected major face of the grain, is preferably 0.1 to 5.0 ⁇ m, more preferably 0.2 to 4.0 ⁇ m, most preferably 0.3 to 3.0 ⁇ m.
• the silver halide emulsion according to the invention is monodispersed.
• the monodispersed silver halide emulsion is defined by the silver halide emulsion containing 60% by weight or more of the silver halide grains with the sizes falling within the range of 80 to 120% of the average grain size d.
• the above weight percentage is preferably not less than 65%, more preferably not less than 70% of all silver halide grains.
• the average grain size d is defined by a diameter d i in which the product of d i 3 and the number thereof n i is maximized.
• n i represents the frequency of grains having the grain-size d i .
• the significant figure is calculated down to the third decimal place and the fourth digit is rounded to the nearest whole number.
• the grain diameters can be calculated by taking an electron microphotograph of a grain (x 10,000 to 50,000) and measuring the projected area of more than 1,000 grains selected arbitrarily on this photograph.
• the silver halide emulsion used in the invention preferably has a degree of monodispersion of lower than 20%, more preferably lower than 18%, most preferably lower than 15%, wherein the degree of monodispersion is defined by the following formula: ##EQU1##
• the numerical ratio of the tabular silver halide grains to all silver halide grains contained in the silver halide emulsion of the invention can be calculated by counting the number of grains on an electron microphotograph of the emulsion.
• the number of the tabular grains accounts for not less than 70%, preferably not less than 75%, more preferably not less than 80% of the total silver halide grains.
• the tabular silver halide grains have mainly the hexagonal major faces.
• the ratio of the major length to the minor one in the hexagonal major face is preferably not more than 2, more preferably not more than 1.8, most preferably not more than 1.5. This ratio can be calculated also by using an electron microphotograph of the silver halide emulsion.
• the tabular grains of 50% or more have preferably the hexagonal major faces.
• the tabular silver halide grains of the invention is of a core/shell type in which high content silver iodide is localized in the core of the grain.
• High content silver iodide localized in the core is identified by the average silver iodide contents J 1 and J 3 satisfying the following relationship:
• J 1 represents an average silver iodide content measured by a fluorescent X-ray spectroscopy and J 3 represents the average value of silver iodide contents measured by an X-ray microanalysis in which the contents concerned are measured at the portions far away by 80% or more of a grain radius from the center thereof.
• the high iodide portion in the grain has a silver content of higher than 15.3 mol %, preferably 18 to 45 mol %, more preferably 20 to 45 mol %, most preferably 25 to 45 mol %.
• the silver halide emulsion used in the invention can be prepared by growing monodispersed spherical seed grains prepared by the method described in Japanese Patent O.P.I. Publication No. 6643/1986 under stirring with a stirrer disclosed in Japanese Patent O.P.I. Publication No. 92523/1982, at 500 to 1200 r.p.m.
• the seed grains can be grown by any of the acid method, the neutral method and the ammonia method, or by utilizing the known methods described in Japanese Patent Publication Nos. 6643/1986, 14630/1986, 112142/1986, 157024/1987, 18556/1987, 92942/1988, 151618/1988, 1613451/1988, 220238/1988 and 311244/1988.
• Water-soluble salts may be removed by a flocculation method or a noodle washing method.
• Silver halides used in the invention are silver iodochloride and silver iodobromochloride and may be a surface latent image type or an inner latent image type.
• the silver halide grains may be chemically sensitized by conventional methods, and spectrally sensitized to a prescribed wavelength with sensitizing dyes.
• the silver halide emulsion may contain various additives such as an anti-foggant and a stabilizer.
• Gelatin is used preferably as the binder.
• Emulsion layers and other hydrophilic colloid layers may be hardened and contain a plasticizer and a latex.
• a coupler is contained in a silver halide light-sensitive emulsion layer.
• a color coupler there may be added a color coupler, a competitive coupler, and a compound capable of releasing by a coupling reaction with an oxidation product of a developing agent, various photographically useful fragments such as a development accelerator, a bleaching accelerator, a developing agent, a solvent for silver halide, a toning agent, a hardener, a fogging agent, an anti-foggant, a chemical sensitizer, a spectral sensitizer and a desensitizer.
• various photographically useful fragments such as a development accelerator, a bleaching accelerator, a developing agent, a solvent for silver halide, a toning agent, a hardener, a fogging agent, an anti-foggant, a chemical sensitizer, a spectral sensitizer and a desensitizer.
• auxiliary layers such as a filter layer, an anti-halation layer and an anti-irradiation layer.
• These layers and the silver halide emulsion layers may contain a dye which can be removed or bleached during development.
• the light-sensitive material may contain conventional additives such as a formalin scavenger, a fluorescent bleaching agent, a matting agent, a lubricant, an image stabilizer, a surfactant, an anti-foggant, a development accelerator, a development retarder and a bleaching accelerator.
• a formalin scavenger such as a formalin scavenger, a fluorescent bleaching agent, a matting agent, a lubricant, an image stabilizer, a surfactant, an anti-foggant, a development accelerator, a development retarder and a bleaching accelerator.
• the support is polyethylene-coated paper, a polyethylene terephthalate film, baryta paper or a cellulose triacetate film.
• the light-sensitive material of the invention is subjected to conventional processing after exposure.
• a comparative core/shell type emulsions was prepared according to the method described in Japanese Patent O.P.I. Publication No. 138538/1985, wherein the emulsion comprised octahedral silver iodobromide grains (average grain size: 1.3 ⁇ m, silver iodide content: 5 mol %).
• Comparative emulsions, Em-2, Em-3 and Em-4 each consisting of core/shell type tabular silver halide grains were prepared by the following methods:
• Inventive emulsions Em-5 to 8 were prepared by the following procedures:
• the same seed emulsion 300 g as in Em-5 was added to 5 l of an aqueous 2.0% gelatin solution, followed by stirring at 75° C. and pH 5.8.
• 2.8 l of an aqueous solution containing 337 g of silver nitrate and 2.8 l of an aqueous solution containing 188.5 g of potassium bromide and 65.8 g of potassium iodide were added at the equal flow rate by the double-jet method while maintaining pBr at 1.5.
• Em-5 The same seed emulsion 300 g as in Em-5 was added to 4.5 l of an aqueous 1.5% gelatin solution, followed by stirring at 75° C. and pH 5.8.
• 2.4 l of an aqueous solution containing 337 g of silver nitrate and 2.4 l of an aqueous solution containing 183.8 g of potassium bromide and 72.4 g of potassium iodide were added at the equal flow rate by the double-jet method while maintaining pBr at 1.8.
• Em-1 to 8 The above dispersion and 350 g (containing 40 g of silver) of Em-1 to 8 subjected to optimum sulfur sensitization, gold sensitization and green-sensitization were mixed and coated on a subbed cellulose triacetate film in a silver amount of 16 mg/dm 2 .
• composition of each processing liquid is as follows:
• Relative sensitivity is defined by a reciprocal of the exposure required to provide a density of a fog+0.1 and is a value relative to the green sensitivity of Sample No. 1, which is set at 100.
• RMS is a value obtained by multiplying by 1000 times a standard deviation for the variation of a density in scanning a density of the minimum density+0.1 with a microdensitometer having a 250 ⁇ m 2 opening for scanning, and shown by a value relative to that of Sample No. 1, which is set at 100.
• 1st layer anti-halation layer containing gelatin and black colloidal silver
• 2nd layer interlayer containing gelatin and 2,5-di-t-octylhydroquinone
• 3rd layer low speed red-sensitive silver halide emulsion layer
• 4th layer interlayer same as the 2nd layer
• 5th layer high speed red-sensitive silver halide emulsion layer
• 6th layer interlayer same as the 2nd layer
• 8th layer interlayer same as the 2nd layer
• 13th layer 1st protective layer containing silver iodobromide (AgI content: 1 mol %, average diameter: 0.07 ⁇ m) in the amount of silver coated: 0.4 g/m 2 and UV absorbers UV-1 and UV-2.
• AgI content 1 mol %, average diameter: 0.07 ⁇ m
• 2nd protective layer containing polymethyl methacrylate (diameter: 1.5 ⁇ m) and formalin scavenger (HS-1)
• gelatin hardeners(H-1) and (H-2), and a surfactant were added to each layer.
• Sensitizing dye I anhydro-5,5'-dichloro-9-ethyl-3,3'-di-(3-sulfopropyl)thiacarbocyanine hydroxide
• Sensitizing dye II anhydro-9-ethyl-3,3'-di-(3-sulfopropyl)-4,5,4',5'-dibenzothiacarbocyanine hydroxide
• Sensitizing dye III anhydro-5,5'-diphenyl-9-ethyl-3,3'-di-(3-sulfopropyl)oxycarbocyanine hydroxide
• Sensitizing dye IV anhydro-9-ethyl-3,3'-di-(3-sulfopropyl)-5,6,5',6'-dibenzoxacarbocyanine hydroxide
• Sensitizing dye V anhydro-3,3'-di-(3-sulfopropyl)-4,5-benzo-5'-methoxythiacyanine hydroxide ##STR2## Sample Nos. 9 to 16 were exposed to white light through an optical wedge, and processed in the same manner as in Example 1.
• Sensitivity and RMS granularity were evaluated for the high speed green-sensitive layers of the processed samples. The results are shown in Table 3. Sensitivity and granularity are the values relative to those of Sample No. 9, which are set at 100, respectively.
• Example 2 Light-sensitive material samples prepared in Example 2 were stored under the following two different conditions. The stored samples were processed and evaluated in the same manner as in Example 2.

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• Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Citations (6)

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• 1989
  • 1989-09-06 JP JP1232369A patent/JP2890051B2/ja not_active Expired - Lifetime
• 1990
  • 1990-09-04 EP EP19900309685 patent/EP0416881A3/en not_active Withdrawn
  • 1990-09-05 AU AU62194/90A patent/AU6219490A/en not_active Abandoned
  • 1990-09-05 CA CA002024679A patent/CA2024679A1/en not_active Abandoned
• 1992
  • 1992-03-16 US US07/851,280 patent/USH1300H/en not_active Abandoned

Patent Citations (6)

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