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 color reproduction in a silver halide reversal color photographic material.
• this invention intends to improve upon color reproducibility through exercising an interimage effect in an improved condition.
• a green-sensitive layer upon another layer; e.g., a green-sensitive layer, is intended and for this purpose, iodine contents in emulsions of the whole constituent layers of-the red-sensitive layer are increased, and the interimage effect fromt the green-sensitive layer upon the red-sensitive layer is reduced to result in lowering of the saturation of green color-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.
• the difference in iodine content between the emulsion having a high iodine content and the emulsion having a low iodine content is controlled to at least 0.3 mole % or more, preferably within the range of 0.5 mole % to 3.0 mole %.
• the emulsion which forms a silver halide emulsion layer having a low iodine content has the halide composition of the silver halide being 0.5 to 5.7, preferably 1.5 to 4.5, mole % iodide, while the emulsion which forms a silver halide emulsion layer having a high iodine content has the halide composition of the silver halide being 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 constituent layer or two constituent layers. In case of two constitutent layers, emulsions to form them may have the same iodine content or different ones. "If the emulsions have different iodine contents, .it is desirable to let the emulsion having higher sensitivity have a lower iodine content.
• the present invention is embodied in a silver halide multilayer reversal color photographic material which has three kinds of, that is, a blue-sensitive, a green-sensitive and a red-sensitive, silver halide emulsion layer.
• at least one of the emulsion layess forms a group consisting of two or three emulsion layers differing in photographic sensitivity, with the emulsion layer group containing silver in its high sensitivity constituent layer or in combination of its high sensitivity constituent layer and its inter- mediate sensitivity constituent layer in such an amount that it comprises 40 to 80% of the total silver amount in the emulsion layer group.
• This invention makes it possible to obtain simultaneous improvements in blue, red and greeen saturations. It may safely be said that this invention is epochal, taking into account that conventional methods have been attended by, e.g., such a side effect that increase in saturation of, e.g., green color brings about an inevitable-decrease in saturation of, e.g., red color. Therefore, using the photographic material of this invention makes it feasible to provide a clear reversal color image of high color purities.
• the most suitable layer to be employed in this invention as the layer in which its high sensitivity constituent layer and its low sensitivity constituent layer are made to differ in iodine contents is a green-sensitive layer or a red-sensitive layer from the standpoint of the magnitude of the effect attained.
• silver halides which may be present in the silver halide emulsions of this invention include silver iodobromide and silver iodochlorobromide.
• 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 that of a cube or an octahedron, an irregular crystal form such as that of a sphere, a plate or so on, or a composite form thereof.
• a mixture of various crystal forms of silver halide grains may be also 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 of the kind which form latent image predominantly at the surface of the grains, or silver halide grains of the kind which mainly form 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), V.L.Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1964), and so on. Namely, the acid process, the neutral method, the ammonia process and so on may be employed. As for methods 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 in which silver halide grains are produced in the presence of excess silver ion can be employed in this invention.
• the so-called controlled double jet method in which the pAg of the liquid phase in which silver halide grains are to be precipitated is maintained constant, may be also employed in this invention.
• silver halide emulsions having a regular crystal form and a nearly uniform grain size that is, the so-called monodisperse emulsions can be obtained.
• Two or more of silver halide emulsions made separately may be used in the form of a mixture.
• cadimium salts zinc salts, thallium salts, iridium salts or complexes, rhodium salts or complexes, iron salts or complexes and/or the like may be present.
• 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., sodoum 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, an aromatic carbamoylated gelation or the like).
• a sedimenting agent such as a polyvalent anion-containing inorganic salt (e.g., sodoum sulfate), an anionic surface active agent or an anionic polymer (e
• the silver halide emulsion of this invention can be a so-called un-after-ripened emulsion (e.g., a primitive emulsion), that is to say, a chemically unsensitized emulsion.
• a chemically unsensitized emulsion e.g., a chemically unsensitized emulsion.
• Chemical sensitization can be carried out using processes described in P. Glafkides, supra, V.L.Zelikman et al, supra or H. Frieser, Die Gründlagen der Photographischen Too mit Silverhaloqeniden, Akademische Verlagsfesell- schaft (1968).
• sulfur sensitization using compounds containing surfur capable of reacting with silver ion or active gelatin, reduction sensitization using reducing materials, sensitization-with gold or other noble metal compounds and so on can be employed individually or as a combination-thereof.
• suitable sulfur sensitizers which-can be used include thiosulfates, thioureas, thiazoles, rhodanines and other sulfur-contain- ing compounds-
• Specific examples of sulfur sensitizers are descrived 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, silane compounds and the like, 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, palladium, etc., 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; British Patent 618,061; and so on.
• 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), etc.
• heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, ' mercaptothiadiazoles, mercaptotetrazoles (especially l-phenyl-5-mercaptotetrazole), mercaptopyrimidines, etc.
• -the above-described heterocyclic mercapto compounds containing water soluble groups such as carboxylic group, sulfonyl group and the like
• thioketo compounds such as oxazoline thione,-etc.
• the photographic emulsion layers or other hydrophilic colloidal layers of the photographic material prepared in accordance with an embodiment of this invention can contain dispersions of water insoluble or slightly soluble synthetic polymers for the purposes of improvement in dimentional stability and so on.
• the photographic emulsion layers or other hydrophilic colloidal layers of the photographic material prepared in accordance with an embodiment of this invention can contain in organic or organic hardeners.
• specific examples of the hardener which can be employed incoude chromium salts e.g., chrome alum, chromium acetate, etc.
• aldehydes e.g.
• N-methylol compounds e.g., dimethylol urea, methylol dimethylhydantoin, etc.
• dioxane derivatives e.g., 2,3-dihydroxydixane, etc.
• active vinyl-containing compounds e.g., 1.3.5-triacryloyl-hexahydro-S-triazine, 1,3- vinylsulfonyl-2-propanol, etc.
• active halogen-containing compounds e.g., 2,4-dichloro-6-hydroxy-S-triazine, etc.
• mucohalogenic acids e.g., mucochloric acid, mucophenoxy- chloric acid, etc.
• Such hardeners may be added individually or in a combination of two or more thereof.
• the photographic material prepared in accordance with an embodiment of this invention may contain as a color fog preventing agent a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative and the like.
• 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; 2,704,713; 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: published examined Japanese Patent A ppli- cation 23813/'75: and so on.
• Hydrophilic colloidal layers of the photographic material prepared in accordance with an embodiment 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 prepared in accordance with an embodiment of this invention may contain water soluble dyes as a filter dye or for the purposes of preventing irradiation and so on.
• water soluble dyes include exonol dyes, hemi-oxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Amoong these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are used to advantage. 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 prepared in accordance with this invention are oil soluble couplers.
• polymeric couplers may be incorporated therein.
• Magenta couplers which can be used to advantage are those of 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: West German Patent Applications (OLS) 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.
• 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: Japanese Patent Applications 68978/'81, 60264/'81, 89115/'81, 109056/'81, 140667/'81, 2419/'82 and 29683/'82: and so on.
• Yellow couplers which can be used to advantage are compounds of benzoyl acetanilide type and those of pivaloyl acetaniliede 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: West German Patent Applications (OLS) 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: Japanese Patent Application 140667/'81: and so on.
• Cyan couplers which can be used to advantage are compounds of phenol type and those of 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: West German Patent Applications (OLS) 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: Japanese Patent Application 140667/'81 and so on.
• 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; 3,656,95-9; 3,6'72,897 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. Pantents 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 prepared in accordance with an embodiment 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, and so on, 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, and so on, 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, hydroxyben- senes, sulfites and so on.
• gas fog preventing agents which can be used to advantage 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, sodium sulfite and so on.
• the present invention will be explained in greater detail with reference to the following examples.
• the first laver Low sensitivity red-sensitive emulsion laver
• the second laver High sensitivity red-sensitive emulsion layer
• a 1,000 g portion of the thus made 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 ⁇ (which corresponds to a dry coverage of 0.8 g silver per square meter).
• the third layer Interlayer
• 2,5-Di-t-octylhydroquinone was dissolved in a mixture consisting of 100 cc of dibutyl phthalate and 100 cc 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 ⁇ .
• the fourth layer Low sensitivitv green-sensitive emulsion layer
• the fifth layer High sensitivity green-sensitive emulsion layer
• the sixth layer Interlayer
• 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 ⁇ .
• the seventh laver Yellow filter layer
• An emulsion containing yellow colloidal silver was coated in a layer having a dry thickness of 1 ⁇ .
• the eighth layer Low sensitivity blue-sensitive emulsion layer
• the nineth layer High sensitivity blue-sensitive emulsion layer
• the tenth layer The second protective layer
• 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 ⁇ .
• the eleventh layer The eleventh layer: The first protective layer
• 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.
• 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 DE DE8383109913T patent/DE3369203D1/de not_active Expired
  • 1983-10-04 EP EP19830109913 patent/EP0108250B1/de not_active Expired

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