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
  • 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

Definitions

• the present invention relates to a silver halide multilayer reversal color photographic material, comprising a support having coated thereon a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, wherein at least one of these emulsion layers is comprised of a plurality of sublayers of differing photographic sensitivity.
• a certain layer e.g., a red-sensitive layer
• a green-sensitive layer upon another layer; e.g., a green-sensitive layer
• red-sensitive layer When a photographic material is exposed to green monochromatic light, its red-sensitive layer also responds to the light because of imperfections in the spectral sensitivity distribution. Such a phenomenon lowers the green color saturation. However, response of the red-sensitive layer to green monochromatic light to such an extent that perceivable gradation is produced takes place only in its high sensitivity sublayer or in both its high sensitivity sublayer and its medium sensitivity sublayer because the responsivity of the red-sensitive layer to green monochromatic light is considerably lower.
• the photographic material comprises at least one emulsion layer having two or three sublayers, which have different photographic sensitivities but the same spectral sensitivities, wherein the sublayer, which is made of a silver halide emulsion having a low iodine content, contains 40 to 80% by weight, preferably 45 to 70% by weight, of the total silver ions in the emulsion layer.
• the iodine content of the sublayer having a low iodine content is by at least 0.3 mole %, preferably by 0.5 to 3.0 mole %, lower than the iodine content of the sublayer having a high iodine content.
• the sublayer having a low iodine content comprises silver halide having a halide composition containing 0.5 to 5.7, preferably 1.5 to 4.5, mole % iodide, while the sublayer having a high iodine content comprises silver halide having a halide composition containing 0.8 to 6, preferably 2.0 to 5.0 mole % iodide.
• the silver halide emulsion layer having a low iodine content may have one sublayer or two sublayers.
• emulsions to form them may have the same iodine content or different ones. If the emulsions have different iodine contents, it is desirable that the emulsion having higher sensitivity has a lower iodine content.
• the present invention is embodied in a silver halide multilayer reversal color photographic material which has three emulsion layers, a blue-sensitive, a green-sensitive and a red-sensitive, silver halide emulsion layer. Further at least one of the emulsion layers consists of two or three sublayers differing in photographic sensitivity.
• the material of the present invention is improved in blue, red and green saturations.
• an increase in saturation of e.g., green color leads to a decrease in saturation of e.g., red color
• the photographic material of this invention provides a clear reversal color image of high color purities.
• the most preferred layer to be employed in this invention as the layer in which its high sensitivity sublayer and its low sensitivity sublayer differ in their iodine contents is a green-sensitive layer or a red-sensitive layer.
• silver halides which may be present in the silver halide emulsions of this invention include silver iodobromide and silver iodochlorobromide.
• the mean grain size of the silver halide grains in the photographic emulsions, wherein diameters of spherical or nearly spherical grains and edge lengths of cubic grains are employed as grain size, which are averaged on the basis of the projection area method, is not particularly limited. However, a mean grain size of 3 p m or less is preferable.
• the grain size distribution may be narrow or broad.
• the silver halide grains in the photographic emulsions of this invention may have a regular crystal form such as a cube or an octahedron, an irregular crystal form such as a sphere, or a plate, or a composite form thereof.
• a mixture of various crystal forms of silver halide grains may also be present.
• the interior and the surface of the silver halide grains may differ, or the silver halide grains may be uniform throughout. Further, either silver halide grains which form a latent image predominantly at the surface of the grains, or silver halide grains which mainly form a latent image inside the grains can be used.
• Photographic emulsions to be employed in this invention can be made using methods as described in, for example, P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), G. F. Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966) or V. L. Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1964).
• the acid process, the neutral method or the ammonia process may be employed.
• a method for reacting a water-soluble silver salt with a water-soluble halide a single jet method, a double jet method, or a combination thereof may be employed.
• a method wherein silver halide grains are produced in the presence of excess silver ions can be employed in this invention.
• the so-called controlled double jet method in which the pAg of the liquid phase wherein silver halide grains are to be precipitated is maintained constant, may also be employed in this invention.
• Two or more silver halide emulsions separately produced may be used in the form of a mixture.
• cadmium salts zinc salts, thallium salts, iridium salts or complexes, rhodium salts or complexes, iron salts or complexes may be present.
• the removal of the soluble salts from the silver halide emulsion is, in general, carried out after the formation of the silver halide or after physical ripening.
• the removal can be effected using the noodle washing method which comprises gelling the gelatin or using a sedimentation process (thereby causing flocculation in the emulsion) taking advantage of a sedimenting agent such as a polyvalent anion- containing inorganic salt (e.g., sodium sulfate), an anionic surface active agent or an anionic polymer (e.g., polystyrene sulfonic acid), or a gelatin derivative (e.g., an aliphatic acylated gelatin, an aromatic acylated gelatin or an aromatic carbamoylated gelatin.
• a sedimenting agent such as a polyvalent anion- containing inorganic salt (e.g., sodium sulfate), an anionic surface active agent or an anionic polymer (e.g., polyst
• the removal of soluble salts from the silver halide emulsion may be omitted.
• the silver halide emulsion of this invention can be a so-called unripened emulsion (e.g., a primitive emulsion), which is a chemically unsensitized emulsion.
• a primitive emulsion e.g., a primitive emulsion
• Chemical sensitization can be carried out using processes described in P. Glafkides, supra, V. L. Zelikman et al, supra or H. Frieser, Die Unen der Photographischen mit Silberhalogeniden, Akademische Verlagsgesellschaft (1968).
• sulfur sensitization using compounds containing sulfur capable of reacting with silver ions or active gelatin, reduction sensitization using reducing materials, sensitization with gold or other noble metal compounds can be employed individually or as a combination thereof.
• suitable sulfur sensitizers which can be used include thiosulfates, thioureas, thiazoles, rhodanines and other sulfur-containing compounds.
• Specific examples of sulfur sensitizers are described in U.S. Patents 1,574,944; 2,410,689; 2,278,947; 2,728,668; 3,656,955; 4,032,928 and 4,067,740.
• reducing sensitizers include stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, saline compounds and specific examples of these sensitizers are described in U.S. Patents 2,487,850; 2,419,974; 2,518,698; 2,983,609; 2,983,610; 2,694,637; 3,930,867 and 4,054,458.
• Group VIII metal complexes such as those of platinum, iridium or palladium, other than gold metal complexes, can be employed for the purpose of sensitization with a noble metal. Specific examples of these metal complexes are disclosed in U.S. Patents 2,399,083 and 2,448,060; and British Patent 618,061.
• the photographic emulsions to be employed in this invention can contain a wide variety of compounds for purposes of preventing fogging or stabilizing photographic functions during production, storage or processing.
• azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro or halogen substituted ones); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above-described heterocyclic mercapto compounds containing water soluble groups such as carboxylic group or sulfonyl group; thioketo compounds such as oxazoline thione; azaindenes such as tetraazaindenes (especially 4-hydroxy substituted (1,3,3
• the photographic emulsion layers or other hydrophilic colloidal layers of the photographic material of this invention can contain dispersions of water insoluble or slightly soluble synthetic polymers for the purpose of improving the dimensional stability.
• the photographic emulsion layers or other hydrophilic colloidal layers of the photographic material of this invention can contain inorganic or organic hardeners.
• specific examples of the hardener which can be employed include chromium salts (e.g., chrome alum, chromium acetate), aldenydes (e.g.
• N-methylol compounds e.g., dimethylol urea, methylol dimethylhydantoin
• dioxane derivatives e.g., 2,3 - dihydroxydioxane
• active vinyl-containing compounds e.g., 1.3.5 - triacryloyl - hexahydro - S - triazine, 1,3 - vinylsulfonyl - 2 - propanol
• active halogen-containing compounds e.g., 2,4 - dichloro - 6 - hydroxy - S - triazine
• mucohalogenic acids e.g., mucochloric acid, mucophenoxychloric acid.
• Such hardeners may be added. individually or in a combination of two or more thereof.
• the photographic material of this invention may contain as a color fog preventing agent a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative or an ascorbic acid derivative.
• color fog preventing agent examples include those described in U.S. Patents 2,360,290; 2,336,327; 2,403,721; 2,418,613; 2,675,314; 2,701,197; 2,728,659; 2,732,300 and 2,735,365: published unexamined Japanese Patent Applications 92988/'75, 92989/'75, 93928/'75,110337/'75 and 146235/'77: and published examined Japanese Patent Application 23813/'75.
• Hydrophilic colloidal layers of the photographic material of this invention may contain an ultraviolet absorbing agent.
• an ultraviolet absorbing agent for example, aryl group-substituted benzotriazole compounds, 4-thiazolidone compounds, benzophenone compounds, cinnamic acid ester compounds, butadiene compounds, benzoxazole compounds and further, ultraviolet absorbing polymers can be employed in the hydrophilic colloidal layers. These ultraviolet absorbing agents may be fixed in the hydrophilic colloidal layer to which they are added.
• the photographic material of this invention may contain water soluble dyes as a filter dye or for preventing irradiation.
• water soluble dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes.
• oxonol dyes, hemioxonal dyes and merocyanine dyes are preferably used. Specific examples of these dyes which can be used in this invention are described in British Patents 546,708; 584,609: 1,265,842 and 1,410,488: and U.S.
• Preferable couplers which can be added to hydrophilic colloidal layers of the photographic material of this invention are oil soluble couplers.
• polymeric couplers may be incorporated therein.
• Magenta couplers which can preferably be used are those of the 5-pyrazolone type, and specific examples thereof are described in U.S. Patents 2,600,788; 2,983,608; 3,062,653; 3,127,269; 3,311,476; 3,419,391; 3,519,429; 3,558,319; 3,582,322; 3,615,506; 3,834,908 and 3,891,445: West German Patent 1,810,464: DE-A-2,408,665; 2,417,945; 2,418,959 and 2,424,467: published examined Japanese Patent Application 6031/'65: published unexamined Japanese Patent Applications 20826/'76, 58922/'77, 129538/ '74, 74027/'74, 159336/'75, 42121/'77, 74028/'74, 60233/'75, 26541/'76, 55122/'78, 94752/'82 and 35858/'82: U.S.
• Patents 3,163,625, 3,211,553; 3,370,952, 3,451,820; 3,926,436; 4,080,211 and 4,128,427 British Patent 1,247,688: Research Disclosure, No. 18815 and No. 19033: and Japanese Patent Applications 68978/'81, 60264/'81, 89115/'81., 109056/'81, 140667/'81, 2419/'82 and 29683/'82.
• Yellow couplers which can be used are compounds of the benzoyl acetanilide type and those of the pivaloyl acetanilide type, and specific examples thereof are described in U.S. Patents 2,875,057; 3,265,506; 3,408,194; 3,551,155; 3,582,322; 3,725,072 and 3,891,445: West German Patent 1,547,868: DE-A-2,219,917; 2,261,361 and 2,414,006: British Patent 1,425,020: published examined Japanese Patent Application 10783/'76: published unexamined Japanese Patent Applications 26133/'72, 73147/'73, 102636/ '76, 6341/'75, 123342/'75, 130442/'75, 21827/'76, 87650/'75, 82424/'77 and 115219/'77: U.S.
• Patents 3,211,552; 3,370,952; 3,451,820; 3,926,436; 4,080,211 and 4,128,427 Research Disclosure, No. 19033 and No. 21728: and Japanese Patent Application 140667/'81.
• Cyan couplers which can be preferably used are compounds of the phenol type and the naphthol type, and specific examples thereof are described in U.S. Patents 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 and 4,004,929: DE-A-2,414,830 and 2,454,329: published unexamined Japanese Patent Applications 59838/'73, 26034/ '76, 5055/'73,146828/'76, 69624/'77 and 90932/'77: U.S. Patents 3,211,552; 3,370,952; 3,451,820; 3,926,436; 4,080,211 and 4,128,427: Research Disclosure No. 21728; and Japanese Patent Application 140667/'81.
• Photographic emulsions to be employed in this invention may be spectrally sensitized with methine dyes and others.
• sensitizing dyes which can be used include those described in German Patent 929,080: U.S. Patents 2,493,748; 2,503,776; 2,519,001; 2,912,329; 3,656,959; 3,672,897 and 4,025,349: British Patent 1,242,588: and published examined Japanese Patent Application 14030/'69.
• sensitizing dyes may be employed individually or in combination. Combinations of sensitizing dyes are often employed for the purpose of supersensitization. Typical examples of supersensitizing combinations are described in U.S. Patents 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; 3,814,609 and 4,026,707: British Patent 1,344,281: published examined Japanese Patent Applications 4936/'68 and 12375/'78: and published unexamined Japanese Patent Applications 110618/'77 and 109,925/'77.
• Hydrophilic colloidal layers of the photographic material of this invention can contain a so-called gas fog preventing agent for the purpose of preventing deterioration of photographic properties, e.g., lowering of developed color density, increase in color stain and fog, from being caused by harmful gases like formaldehyde.
• gas fog preventing agent for the purpose of preventing deterioration of photographic properties, e.g., lowering of developed color density, increase in color stain and fog, from being caused by harmful gases like formaldehyde.
• Suitable examples of such an agent include amines (including alkylamines, arylamines and heterocyclic amines), amides, cyclic or acyclic ureas, sulfinic acids, imides, active methylenes, hydroxybenzenes, and sulfites.
• gas fog preventing agents which can be preferably used include urea, ethylenediurea, ethyleneurea, melamine, hydantoin, allantoin, urazol, parabanic acid, biuret, glycoluril, 1-methylglycoluril, phthalimide, succinimide, benzenesulfinic acid, styrenesulfinic acid polymer, malonic acid, cyanoacetic acid, dimedone barbituric acid, semicarbazide, 5-pyrazolone type magenta couplers, acylacetanilide type yellow couplers, resorcinol, phloroglucinol, 2, 3 dihydroxynaphthalene, and sodium sulfite.
• the present invention will be explained in greater detail with reference to the following examples.
• a 500 g portion of the resulting emulsion was mixed with 1 kg of a red-sensitive, low sensitivity silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin, and having an iodine content of 3 mole %), and coated in a layer having a dry thickness of 2 um (corresponding to a dry coverage of 0.5 g silver per square meter).
• Second layer High sensitivity red-sensitive emulsion layer
• a 1 kg portion of the resulting emulsion was mixed with 1 kg of a red-sensitive, high sensitivity silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin, and having an iodine content of 3 mole %), and coated in a layer having a dry thickness of 2 um (which corresponds to a dry coverage of 0.8 g silver per square meter).
• 2,5 - Di - t - octylhydroquinone was dissolved in a mixture consisting of 100 ml of dibutyl phthalate and 100 ml of ethyl acetate, and the resulting solution was mixed with 1 kg of a 10% gelatin aqueous solution with stirring at a high speed to make an emulsion.
• a 1 kg portion of the thus made emulsion was mixed with 1 kg of a 10% gelatin aqueous solution, and coated in a layer having a dry thickness of 1 ⁇ m.
• a 1 kg portion of the emulsion used in the third layer was mixed with 1 kg of a 10% gelatin aqueous solution, and coated in a layer having a dry thickness of 1 pm.
• An emulsion containing yellow colloidal silver was coated in a layer having a dry thickness of 1 um.
• 1 kg of the emulsion employed in the third layer was mixed with 1 kg of a 10% gelatin aqueous solution, and coated in a layer having a dry thickness of 2 um.
• a 10% gelatin aqueous solution containing a chemically unsensitized fine grain emulsion (grain size: 0.15 pm, 1 mole % silver iodobromide emulsion) was coated in a layer having a dry thickness of 1 um at a dry coverage of 0.3 g/m2.
• the thus obtained multilayer coated film was named Sample A.
• Sample B was produced in the same manner as Sample A except that the iodine content in the emulsion employed in the first layer was changed to 4.0 mole % and further, the iodine content in the emulsion employed in the second layer was changed to 2.5 mole %.
• Sample C, Sample D and Sample E were produced in the same manner as Sample A except that the iodine content in the emulsion employed in the first layer was changed to 3.5 mole %, 4.5 mole % and 4.0 mole % respectively and further, the iodine content in the emulsion employed in the second layer was changed to 1.5 mole %, 2.5 mole % and 3.5 mole % respectively.
• D Max C was 3.11
• D Max M was 3.18
• Sample F was prepared in the same manner as Sample B in Example 1 except that the iodine content in the emulsion of the third layer was changed to 4.0 mole % and the iodine content in the emulsion of the fourth layer was changed to 2.5 mole %, and exposed to red light or green light through a wedge for sensitometry, followed by the above-described reversal processings.

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• 1982
  • 1982-10-05 JP JP17520182A patent/JPS5964843A/ja active Granted
• 1983
  • 1983-10-04 EP EP19830109913 patent/EP0108250B1/en not_active Expired
  • 1983-10-04 DE DE8383109913T patent/DE3369203D1/de not_active Expired

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