EP0377463A2 - Farbphotographisches Silberhalogenidmaterial - Google Patents

Farbphotographisches Silberhalogenidmaterial Download PDF

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Publication number
EP0377463A2
EP0377463A2 EP90100163A EP90100163A EP0377463A2 EP 0377463 A2 EP0377463 A2 EP 0377463A2 EP 90100163 A EP90100163 A EP 90100163A EP 90100163 A EP90100163 A EP 90100163A EP 0377463 A2 EP0377463 A2 EP 0377463A2
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Prior art keywords
group
silver halide
nucleus
photographic material
color photographic
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French (fr)
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EP0377463A3 (en
EP0377463B1 (de
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Yasushi Fuji Photo Film Co. Ltd. Nozawa
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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
    • 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
    • G03C7/3041—Materials with specific sensitometric characteristics, e.g. gamma, density

Definitions

  • This invention relates to a silver halide color photographic material. More particularly the invention relates to a silver halide color photographic material which provides excellent high-fidelity color reproducibility of primary colors and neutral tints with high chroma.
  • Multi-layer silver halide color photographic materials generally comprise a red-sensitive silver halide emulsion layer containing a nondiffusing cyan dye image forming coupler, a green-sensitive silver halide emulsion layer containing a nondiffusing magenta dye image forming coupler and a blue-sensitive silver halide emulsion layer containing a nondiffusing yellow dye image forming coupler. These layers are laminated onto a support such as a cellulose ester support or a polyester support.
  • JP-A-50-2537 discloses that the interlaminar restraining effect is increased and chroma is improved by adding couplers which are reacted with the oxidation products of developing agents in p-phenylenediamine color developing solutions to release restrainers.
  • color photographic materials have some disadvantages related to color reproducibility.
  • One of them is that the colors of hue between blue and green (e.g., greenish blue, bluish green, etc) differ from the hue of the actual object. For example, blue is not always clearly distinguishable from green.
  • U.S. Patent 3,672,898 discloses a method wherein the spectral sensitivity distributions of the blue-sensitive, green-sensitive and red-sensitive silver halide emulsions are limited to certain ranges.
  • Another object of the present invention is to provide a silver halide color photographic material which provides excellent high-fidelity color reproducibility of primary colors and neutral tints, particularly those colors between blue and green with high color chroma.
  • a silver halide color photographic material comprising at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer, at least one blue-sensitive emulsion layer, and at least one yellow filter layer provided on a support, wherein the relationship between the sensitivity (S4 80 of the green-sensitive silver halide emulsion layer to monochromatic light of 480 nm and the sensitivity (SB 80) of the blue-sensitive silver halide emulsion layer to monochromatic light of 480 nm is in the range of 0.85 ⁇ ⁇ 0.2, when measured after the silver halide color photographic material having ISO sensitivity of S is uniformly exposed to white light of 2/S lux'sec and the optical density of the yellow filter layer at peak wavelength is 1.0 or above.
  • Figure 1 is a graph showing the spectral characteristics of blue, green and red filters for use in the measurement of density.
  • the determination and definition of S4 80 and S4 80 will be described in detail below.
  • the ISO sensitivity of color photographic materials is determined according to the method described in ISO 5800-1979 (E).
  • a photographic material to be tested with an exposure amount of 2x1/S lux ⁇ sec for a period of the same exposure time as in the determination of ISO sensitivity is uniformly exposed by using a light source of the same relative spectral energy as that used for the determination of ISO sensitivity of a color photographic material having ISO sensitivity of S.
  • the test is carried out inside a room under such conditions that the temperature is 20 ⁇ 5°C and the relative humidity is 60 ⁇ 10%.
  • the photographic material to be tested is left to stand under the above conditions for at least one hour and then used.
  • the photographic material is exposed by changing the illuminance with monochromatic light of 500 nm within one hour after uniform exposure.
  • monochromatic light of 500 nm As the exposure device, those of the non-intermittent exposure illuminance scale type, etc., are used as in the measurement of ISO sensitivity.
  • the change of illuminance is made through a light modulator such as an optical wedge.
  • the term "monochromatic light of 480 nm" as used herein refers to light in which the peak wavelength of relative spectral energy is 480 ⁇ 2 nm with a half width of not more than 20 nm.
  • the monochromatic light can be obtained by combining a conventional light source for exposure such as a tungsten lamp with a commercially available interference filter.
  • Photographic sensitivities, S4 80 and S4 80 can be calculated by the following formulae: wherein lux ⁇ sec an lux ⁇ sec represent each exposure amount which give a density of minimum density (after uniform exposure) +0.6.
  • emulsions containing sensitizing amounts of supersensitizing agents and cyanine dye forming J-associated material see JP-A-1-223441
  • suitable sensitizing dyes can be selected, or various filter layers can be introduced.
  • silver halide emulsions used for the blue-sensitive emulsion layer of the present invention are of a monodisperse system.
  • Monodisperse silver halide grains have good graininess and give an image having excellent sharpness when the size range causes little light scattering.
  • Monodisperse silver halide grains are described, for example, in JP-A-54-48521, JP-A-54-99419, JP-A-56-16124, JP-A-56-78831, U.S. Patent No. 4,444,877, JP-A-57-182730, JP-A-58-49938, JP-A-58-37635, U.S. Patent No.
  • an emulsions wherein the amount of ultra-tabular (ultra-plate form) silver halide grains having a diameter of at least 5 times the thickness of grain, accounts for at least 50% of the total projected area of the total grains.
  • Spectral sensitization is preferably carried out with methine dyes, etc.
  • methine dyes etc.
  • conventional sensitizing dyes cyanine dyes forming a J-associated material are particularly preferred.
  • Silver halide emulsions used in the green-sensitive emulsion layer of the present invention can be spectral-sensitized by any conventional method.
  • suitable dyes which can be used in the present invention include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • particularly useful dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes. These dyes may have any nucleus which is conventionally applied to the cyanine dyes as a basic heterocyclic nucleus.
  • nucleus examples include a pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus; nucleui formed by fusing an alicyclic hydrocarbon ring with any of the above-described heterocyclic nucleui; and nuclei formed by fusing an aromatic hydrocarbon ring with the above-described heterocyclic nucleui such as an indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzthiazole nucleus, naphothiazole nucleus, benzselenazole nucleus, benzimidazole nucleus and quinoline nucleus
  • Merocyanine dyes or complex merocyanine dyes may have nuclei having a keto-methylene structure.
  • nuclei include five-membered to six-membered heterocyclic nuclei such as a pyrazoline-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus.
  • useful sensitizing dyes include those described in German Patent No. 929,080, U.S. Patent Nos. 2,231,658, 2,493,748, 2,503,776, 2,519,001, 2,912,323, 3,656,959, 3,672,897, 3,694,217, 4,025,349 and 4,046,572.
  • U.K. Patent No. 1,242,588, JP-B-44-14030 (the term "JP-B" as used herein means an "examined Japanese patent publication") and JP-B-52-24844.
  • the sensitizing dyes may be used either alone or in combination. Combinations of sensitizing dyes are often used for the purpose of supersensitization. Typical examples of such combinations are described in U.S. Patent Nos. 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 and 4,026,707, U.K. Patent Nos. 1,344,281 and 1,507,803, JP-B-43-4936, JP-B-53-12375, JP-A-52-110618 and JP-A-52-109925.
  • emulsions may contain a dye which itself does not have a spectral sensitizing effect or a substance which does not substantially absorb visible light, but has a supersensitization activity.
  • dyes or substances include aminostyryl compounds substituted by a nitrogen containing heterocyclic group (see. e.g., those described in U.S. Patent Nos. 2,933,390 and 3,635.721 aromatic organic acid-formaldehyde condensates (see e.g., those described in U.S. Patent No. 3,743,510), cadmium salts and azaindene compounds.
  • the combinations described in U.S. Patent Nos. 3,615,613, 3,615,641, 3,617,295 and 3,635,721 are particularly preferred.
  • sensitizing dyes used in the green-sensitive emulsion layer of the present invention contain at least one sensitizing dye represented by the following general formulae (S-1) to (S-VI).
  • Z 1 and Z 2 each represent an appropriate atomic group for the formation of a nucleus originating from tellurazole nucleus, benztellurazole nucleus, naphthotellurazole nucleus, quinoline nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzthiazole nucleus, naphthothiazole nucleus, benzselenazole nucleus or naphthoselenazole nucleus; R' and R 2 each represent an alkyl group, preferably at least one of R' and R 2 is an alkyl group substituted by sulfo group or carboxyl group; L 1 represents methine group; X 1 represents an anion; and n' represents 0 or 1 provided that when an inner salt is formed, n 1 is 0.
  • Z 3 and Z 4 each represent an appropriate atomic group for the formation of a nucleus originating from tellurazole nucleus, benztellurazole nucleus, naphthotellurazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzimidazole nucleus, naphthoimidazole nucleus, oxazolidine nucleus, oxazole nucleus, thiazolidine nucleus or selenazolidine nucleus; R 3 and R 4 have the same definition as R 1 and R 2 ; L 2 , L 3 and L 4 have the same defination as L 1 ; X 2 has the same meaning as in X 1 ; and n 2 has the same meaning as n 1 .
  • Z 5 represents an appropriate atomic group for the formation of a nucleus originating from tellurazole nucleus, benztellurazole nucleus, naphthotellurazole nucleus, benzthiazole nucleus, naphthothiazole nucleus, benzselenazole nucleus, naphthoselenazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, quinoline nucleus, pyridine nucleus, thiazole nucleus or pyrrolidine nucleus; Z 6 represents an appropriate atomic group for the formation of a nucleus originating from rhodanine nucleus, 2-thioxoox- azolidine nucleus or thiohydantoin nucleus; and R 6 represents an alkyl group.
  • Z 7 represents an appropriate atomic group for the formation of a nucleus originating from tellurazole nucleus, benztellurazole nucleus, naphthotellurazole nucleus, oxazole nucleus, oxazolidine nucleus, isoxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, thiazolidine nucleus, selenazolidine nucleus, benzthiazole nucleus, naphthothiazole nucleus, benzimidazole nucleus, naphthoimidazole nucleus, pyrrolidine nucleus or tetrazole nucleus;
  • Z 8 represents an appropriate atomic group for the formation of a nucleus originating from rhodanine nucleus, thiohydantoin nucleus, pyrazolone nucleus, thiobarbituric acid nucleus, pyrazolone nucleus
  • Z 9 represents an appropriate atomic group for the formation of a nucleus originating from tellurazole nucleus, benztellurazole nucleus, naphthotellurazole nucleus, thiazolidine nucleus or selenazolidine nucleus;
  • Z 10 and Z" each represent an appropriate atomic group for the formation of a nucleus originating from rhodanine nucleus; and
  • R S has the same meaning as R 6 .
  • Z 12 and Z 13 each represent an appropriate atomic group for the formation of a nucleus originating from oxazolidine nucleus, oxazole nucleus, benzoxazole nucleus, naphthooxazole nucleus, thiazolidine nucleus, thiazole nucleus, benzthiazole nucleus, naphthothiazole nucleus, selenazolidine nucleus, selenazole nucleus, benzselenazole nucleus, naphthoselenazole nucleus, tellurazole nucleus, benztellurazole nucleus or naphthotellurazole nucleus; R 9 and R 10 have the same as R 1 and R 2 ; L 7 , L 8 , L 9 and L 10 have the same meaning as L 1 ; X 3 and X 4 have the same meaning as X 1 ; n 3 and n 4 have the same meaning as n 1 ; W represents
  • R 1 , R 2, R 3, R 4 , R 5, R 6 , R 7 , R 8 , R 9 and R 10 are each preferably hydrogen atom, an unsubstituted alkyl group having not more than 18 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, octadecyl), a substituted alkyl group having not more than 18 carbon atoms (examples of substituent groups include carboxyl group, sulfo group, cyano group, halogen (e.g., fluorine, chlorine, and bromine), hydroxyl group, and alkoxycarbonyl group having not more than 8 carbon atoms (e.g., methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, and benzyloxycarbonyl), an alkoxy group having not more than 8 carbon atoms (e
  • an unsubstituted alkyl group e.g., methyl, and ethyl
  • a sulfoalkyl group e.g., 2-sulfoethyl, 3-sulfopropyl, and 4-sulfobutyl
  • alkali metals capable of forming a salt with R' , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R g , R 9 or R' o .
  • alkali metals are particularly preferred.
  • organic compounds pyridines and amines are preferred.
  • nuclei formed by Z', Z 2 , Z 3 , Z 4 , 2 5 , Z 7 , Z 9 , Z' 2 and Z' 3 include thiazole nuclei such as thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-di-methylthiazole, and 4,5-diphenylthiazole; benzthiazole nuclei such as benzthiazole, 4-chlorobenzthiazole, 5- chlorobenzthiazole, 6-chlorobenzthiazole, 5-nitrobenz- thiazole, 4-methylbenzthiazole, 5-methylbenzthiazole, 6-methylbenzthiazole, 5-bromobenzthiazole, 6-bromobenzthiazole, 5-iodobenzthiazole, 5-phenylbenzthiazole, 5-methoxybenzthiazole, 6-methoxybenzthiazole, 5-ethoxybenzthiazole, 5-ethoxycarbonylbenzthiazole, 5-carboxybenzthiazole, 5-phenethy
  • nuclei formed by Z 6 , Z 8 , Z 10 and Z11 examples include 2-pyrazoline-5-one, pyrazolidine-3,5-dione, imidazoline-5-one, hydantoin, 2- or 4-thiohydantoin, 2-iminooxazolidine-4-one, 2-oxazoline-5-one, 2-thiooxazolidine-2,4-dione, isoxazoline-5-one, 2-thiazoline-4-one, thiazolidine-4-one, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indane-1,3-dione, barbituric acid and 2-thiobarbituric acid.
  • substituent groups attached to the nitrogen atoms which constitute members of the nuclei include hydrogen atom, an alkyl group having from 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, more preferably 1 to 4 carbon atoms (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, and octadecyl), a substituted alkyl group (e.g., an aralkyl group such as benzyl, and 2-phenylethyl), a hydroxyalkyl group (e.g., 2-hydroxyethyl, and 3-hydroxypropyl), a carboxyalkyl group (e.g., 2-carboxyethyl, 3-carboxypropyl, and 4-carboxybutyl, carboxymethyl), an alkoxyalkyl group (e.g., 2-methoxye
  • L 1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 7 , L 8 , L 9 and L IO each represent a methine group which may be optionally substituted by a substituted or unsubstituted alkyl group (e.g., methyl, and ethyl), a substituted or unsubstituted aryl group (e.g., phenyl) or halogen (e.g., chlorine, and bromine).
  • the methine groups may combine together to form a ring or may form a ring together with auxochrome.
  • the anion represented by X', X 2 , X 3 and X 4 may be any of an inorganic anion or an organic anion.
  • anions include halogen anions (e.g., fluorine ion, chlorine ion, bromine ion, and iodine ion), substituted arylsulfonate ions (e.g., p-toluenesulfonate ion, and p-chlorobenzenesulfonate ion), aryldisul- fonate ions (e.g., 1,3-benzenesulfonate ion, 1,5-naphthalenedisulfonate ion, and 2,6-naphthalenedisulfonate ion), alkylsulfate ions (e.g., methylsulfate ion), sulfate ions, thiocyanate ions, perchlorate ions, tetraflu
  • Particularly preferred examples of the dyes include the following compounds.
  • red-sensitive emulsion layer green-sensitive emulsion layer
  • blue-sensitive emulsion layer refer to silver halide emulsion layers which are reacted with red light, green light and blue light to form cyan dye image, magenta dye image and yellow dye image, respectively. They do not contain a donor layer exhibiting multi-layer effect as described in JP-A-54-118245 and JP-A-61-34541 which correspond to U.S. Patents 4,306,015 and 4,705,744, respectively.
  • the red-sensitive emulsion layer and the green-sensitive emulsion layer are usually sensitive to blue light. Accordingly it is necessary to provide the yellow filter layer above these layers to prevent blue light from reaching the red-sensitive and green-sensitive emulsion layers.
  • the optical density of the yellow filter layer at peak wavelength should be at least 1.0, preferably 1.2 or above, more preferably 1.4 or above.
  • Colloidal silver grains, yellow colored magenta couplers and nondiffusing yellow organic dyes can be used as the yellow filter.
  • a density of the yellow filter is naturally depending on a colloidal silver halide grain, a yellow colored magenta coupler, a light absorption property and used amount of nondiffusing yellow organic dyes.
  • a filter layer which has the same composition and coated amount as of the yellow filter layer in the silver halide color photographic material according to the present invention, is coated exclusively on a transparent support thereby obtaining a density as a correspondence.
  • the yellow colored magenta couplers can be introduced into the yellow filter of the present invention by conventional methods for introducing couplers into silver halide emulsion layers such as the method described in U.S. Patent No. 2,322,027.
  • a solvent such as an alkyl phthalate (e.g., dibutyl phthalate, and dioctyl phthalate), a phosphoric ester (e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, and dioctyl butyl phosphate), a citric ester (e.g., tributyl acetyl- citrate), a benzoic ester (e.g., octyl benzoate), an alkylamides (e.g., diethyllaurylamide), a fatty acid ester (e.g., dibutoxyethyl succinate, and dioctyl
  • a solvent
  • the resulting solutions are dispersed in a hydrophilic colloid.
  • a hydrophilic colloid If desired, mixtures of the above-described high-boiling organic solvents and the above-described low-boiling organic solvents can be used.
  • dispersion methods using polymers such as those described in JP-B-51-39853 and JP-A51-59943 can be used.
  • the yellow colored magenta couplers in the form of an aqueous alkaline solution can be introduced into a hydrophilic colloid when they have an acid radical such as carboxylic acid or sulfonic acid.
  • the nondiffusing yellow organic dyes which may be used in the present invention can be arbitrarily selected from among conventional dyes. Dyes represented by the following general formula (I) are particularly preferred.
  • R, and R 2 may be the same or different and selected from a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, hydroxyl group, carboxyl group, a substituted amino group, a carbamoyl group, a sulfamoyl group, nitro group or an alkoxycarbamoyl group;
  • R 3 and R 4 may be the same or different and selected from a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, an acyl group or a sulfonyl group, and R 3 and R 4 may be combined together to form a 5-membered or 6-membered ring; and X and Y may be the same or different and are electron attractive groups.
  • Particularly preferred examples of the dyes include the following compounds.
  • the yellow filter containing the organic dye used in the present invention can be prepared by conventional methods.
  • the yellow filter can be prepared in the same manner as the methods for introducing the above-described yellow colored magenta couplers.
  • the organic dyes are water-soluble, the dyes in the form of an aqueous alkaline solution can be introduced into hydrophilic colloid.
  • the yellow filter layer of the present invention can be prepared in the same manner as the methods using colloidal silver. The amounts of colloidal silver, the yellow colored magenta coupler and the organic dye can be controlled so as to give a desired optical density.
  • the above-described yellow dyes provide not only a means for lowering the amount of silver by allowing the use of yellow colloidal silver to be omitted, but also have a unique sensitizing effect.
  • the yellow dyes have such sharp light absorption characteristics that effective light is transmitted to the green-sensitive and red-sensitive silver halide emulsion layer without allowing the light to be absorbed. Accordingly, the dyes favor an increase in the sensitivity of the lower layers.
  • theyellow dye filter can prevent physical development. Such physical development is often caused by adjoining colloidal silver.
  • there ⁇ is an advantage that high-sensitivity emulsions can be used for the blue-sensitive and green-sensitive layers without adverse effect, the emulsions having been sufficiently after-ripened.
  • Emulsions having a narrow grain size distribution are preferably used in the present invention, though emulsions having a wide grain size distribution can be used.
  • a monodisperse emulsion can be used having such a grain size distribution that grains which account for 90% (by weight or in terms of the number of grains) of the total silver halide grains of each emulsion, have a grain size within ⁇ 40% of the mean grain size, preferably within ⁇ 30% of the mean grain size.
  • Twin grains are preferably used. It is preferred that the grains contain at least 30%, preferably at least 50%, more preferably at least 70% (in terms of projected area), of tabular (plate-form) grains having two or more parallel twin planes.
  • Emulsions having a clear layered structure are preferably used in the present invention. They can be prepared by choosing appropriate methods from among various methods known in the field.
  • core grains are prepared by an acid process, neutral process or ammonia process.
  • a soluble silver salt and a soluble halogen salt can be reacted in accordance with a single jet process, double jet process or a combination thereof.
  • a type of the double jet process there can be used a controlled double jet process in which the pAg value in the liquid phase, in which silver halide is formed, is maintained constant.
  • a triple jet process e.g., a soluble silver salt, a soluble bromine salt and a soluble iodine salt in which soluble halogen salts having different compositions are independently added.
  • Solvents such as ammonia, a Rhodan salt, thiourea, thioether and an amine for silver halide may be used during the course of preparative the core. Emulsions having a narrow grain size distribution are preferred as core grains. A monodisperse core emulsion is particularly preferred. It is desirable to use an emulsion in which individual grains are uniform in halogen composition, particularly iodine content at the stage of a core.
  • halogen compositions of individual grains is uniform or not can be determined using X-ray diffraction or EPMA.
  • the halogen composition of core grains is uniform, the diffraction breadth of X-ray diffraction is narrow and the peak is sharp.
  • Uniform silver iodobromide can be obtained by allowing silver iodobromide grains to be grown by a method wherein the addition rate is accelerated with time as disclosed in Irie and Suzuki's JP-B-48-36890, or a method wherein addition concentration is increased with time as disclosed in U.S. Patent No. 4,242,445 after the seed crystal of silver iodobromide having a high silver iodide content is prepared. These methods give particularly good results.
  • aqueous solutions of inorganic salts to be reacted are added at a given addition rate or higher, but at an addition rate Q which is not higher than an addition rate proportional to the total surface area of poorly soluble inorganic salt crystals during the course of growth in a method for preparing the poorly soluble inorganic crystal by a double composition reaction in which two or more aqueous inorganic salt solutions are simultaneously added by about equal amounts in the presence of a protective colloid.
  • the concentrations of aqueous solutions of inorganic salts to be reacted are increased in such a proportion that there is no significants formation of new crystal nucleus during the course of crystal growth.
  • the core emulsion is washed with water to carry out desilverization and then a shell is formed, though a shell can be formed on the core grains as formed.
  • the shell is formed by a double jet process, though the formation of the shell can be carried out by various conventional methods known in the field.
  • pl, pAg and stirring conditions are important factors. In addition thereof, it is important to determine the amount of protective collide when the low iodine layer is grown. It is desirable that the iodine layer is grown in the presence of compounds such as spectral sensitizing dyes, anti-fogging agents and stabilizers which are allowed to be adsorbed by the silver halide. Furthermore, it is effective that fine grains of silver halide are added in place of water-soluble silver salts and water-soluble alkali metal halides when a low iodine layer is formed.
  • silver halide grains having a clear layer structure means that substantially two or more areas having different halogen compositions exist within a grain wherein the central part of the grain forms a core and the outer part thereof forms a shell.
  • substantially two ore more areas means that there may optionally exist a third area (e.g., a layer existing between the central core part and the outermost shell part) in addition to the core and the shell.
  • a third area optionally exists in such a range that the forms of two peaks corresponding to the high iodine layer and the low iodine layer are not substantially effected by the third layer when X-ray diffraction patterns are determined.
  • silver halide grains having substantially two clear layer structures are grains in which there exist a core having a high iodine content, an intermediate part and a shell having a low iodine content; an X-ray diffraction pattern shows that there exist two peaks and one minimum part between these two peaks; the intensity of diffraction corresponding to the high iodine part is in the range of from 1/10 to 3/1, preferably 1/5 to 3/1, more preferably 1/3 to 3/1 of that corresponding to the low iodine part; and the minimum part is 90% or below, preferably 80% or below, particularly 70% or below of the smaller peak of the two peaks.
  • the grain has a similar structure to that described above.
  • silver halides having different compositions may be joined to each other by epitaxial joining, or silver halides may be joined to a compound such as silver rhodanide or lead oxide.
  • Grains having various crystal forms can be used, or the mixtures of grains having different crystal forms can be used.
  • the emulsion layers of the present invention contain two equivalent type couplers.
  • A represents a residue of a coupler which releases (LINK) n -B by the coupling reaction with the oxidant of an aromatic primary developing agent
  • LINK represents a group which is attached to the coupling active site of A and is capable of releasing B after it is released from A by the coupling reaction
  • X is a substituted or unsubstituted aliphatic group having from 1 to 4 carbon atoms wherein the substituent group has not more than 3 carbon atoms and is selected from the group consisting of an alkoxy group, an alkoxycarbonyl group, hydroxyl group, an acylamino group, a carbamoyl group, a sulfonyl group, a sulfonamido group, a sulfamoyl group, an amino group, an acylamino group, cyano group,a ureido group, an acyl group and an alkylthio group or X, is a substituted phenyl group wherein the substituent group has not more than 3 carbon atoms and is selected from the group consisting of hydroxyl group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, a sulfonyl group, a sulf
  • the residues of the couplers, represented by A in the formula (I) include residues of couplers, which form dyes (e.g., yellow, magenta, cyan dyes, etc.) by the coupling reaction with the oxidants of aromatic primary amine developing agents and residues of couplers, which give coupling reaction products having substantially no absorption in the region of visible light.
  • dyes e.g., yellow, magenta, cyan dyes, etc.
  • Examples of yellow dye image forming coupler residues represented by A include coupler residues (residues of couplers) such as pivaloylacetanilide type, benzoylacetanilide type, malonic diester type, malondiamide type, benzoylmethane type, benzthiazolylacetamide type, molonic ester monoamide type, benzthiazolyl acetate type, benzoxazolylacetamide type, benzoxazolyl acetate type, malonic diester type, benzmimidazolylacetamide type and benzimidazolyl acetate type residues; coupler residues derived from heterocyclic ring-substituted acetamides or heterocyclic ring-substituted acetates such as those described in U.S.
  • Patent No. 3,841,880 coupler residues derived from cylacetamides such as those described in U.S. Patent No. 3,770,446, U.K. Patent No. 1,459,171, West German (OLS) 2,503,099, JP-A-50-139738 and Research Disclosure No. 15737; and heterocyclic ring type coupler residues such as those described in U.S. Patent No. 4,046,574.
  • magenta dye image forming coupler residues represented by A include residues having 5-oxo-2-pyrazoline nucleus, pyrazolo[1,5-a]benzimidazole nucleus, pyrazoloimidazole nucleus, pyrazolotriazole nucleus or pyrazolotetrazole nucleus and cyanoacetophenone type residues.
  • Preferred examples of cyan dye image forming coupler residues include residues having a phenol nucleus or a-naphthol nucleus.
  • the couplers have substantially the same effect as DIR couplers, even though a dye is substantially not formed after they release restrainers by the coupling reaction with the oxidants of developing agents.
  • Other examples of the residues represented by A include those described in U.S. Patent Nos. 4,052,213, 4,088,491, 3,632,345, 3,958,993 and 3,961,959.
  • the group A may also be residues of polymer couplers such as those described in U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282 and U.K. Patent No. 2,102,173.
  • Examples of the group X include methyl, ethyl, propyl, butyl, methoxyethyl, ethoxyethyl, isobutyl, allyl, dimethylaminoethyl, propargyl, chloroethyl, methoxycarbonylmethyl, methylthioethyl, 4-hydroxyphenyl, 3-hydroxyphenyl, 4-sulfamoylphenyl, 3-sulfamoylphenyl, 4-carbamoylphenyl, 3-carbamoylphenyl, 4-dimethylaminophenyl, 3-acetamidophenyl, 4-propaneamido, 4-methoxyphenyl, 2-hydroxyphenyl, 2,5-dihydroxyphenyl, 3-methoxycarbonylaminophenyl, 3-(3-methylureido)phenyl, 3-(3-ethylureido)phenyl; 4-hydroxyethoxyphenyl and
  • Examples of the group X 2 include hydrogen atom, methyl, ethyl, benzyl, n-propyl, i-propyl, n-butyl, i-butyl, cyclohexyl, fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxymethyl, hydroxyethyl, hydroxyl, methoxy, ethoxy, butoxy, allyloxy, benzyloxy, methylthio, ethylthio, methoxycarbonyl, ethoxycarbonyl, acetamido, propaneamido, butaneamido, oc- taneamido, benzamido, dimethylcarbamoyl, methylsulfonyl, methylsulfonamido, phenylsulfonamido, dimethylsulfamoyl, acetoxy, ureido, 3-methylureid
  • the groups represented by formulae (Ila) to (Ilp) are preferred.
  • the groups represented by the formulae (Ila), (IIb), (Ili), (Ilj), (Ilk) and (IIl) are particularly preferred.
  • Examples of the group represented by B in the formula (I') include the following groups.
  • couplers which are used in the present invention include, but are not limited to, the following compounds.
  • the compounds represented by the formula (I) can be prepared according to the methods described in U.S. Patent Nos. 4,174,966, 4,183,752, 4,421,845 and 4,447,563, and JP-A-54-145135, JP-A-57-151944, JP-A-57-154234, JP-A-57-188035, JP-A-58-98728, JP-A-58-162949, JP-A-58-209736, JP-A-58-209737, JP-A-58-209738 and JP-A-58-209740.
  • the compounds having the formula (I') are incorporated in at least one layer of the silver halide material, i.e., at least one of the silver halide emulsion layers, the intermediate layers, the filter layers (yellow filter layer, magenta filter layer, etc.), the undercoat layer, the antihalation layer, the protective layer and other auxiliary layers of the photographic material. It is preferred that the compounds are incorporated in a sensitive silver halide layer or a sensitive layer adjacent thereto, particularly a layer containing the emulsion grains of the present invention or a layer sensitive to the same color as the layers and adjacent to the layers.
  • the compounds having the formula (I') can be added to the photographic material in the same manner as coupler dispersion method described hereinafter.
  • the compounds are used in an amont of 10- 6 to 10- 3 mol/m 2 , preferably 3 x 10 -6 to 5 x 10 -4 mol/m 2 and more preferably 5 x 10 -6 to 2x 10- 4 mol/m 2 .
  • the compound which cleaves the restrainer by the reaction of said compound with the oxidant of a developing agent and then the reaction of the resulting cleaved compound with another one molecule of the oxidant of the developing agent can be represented by the following general formula [I"] A -P-Z [(]
  • A represents a coupling component capable or reacting with the oxidants of color developing agents and a component capable of releasing the -P-Z group by reaction with the oxidants of the color developing agents;
  • Z represents a development restrainer whose diffusion can be freely chosen (preferably Z is a restrainer whose ability as the restrainer is rapidly deactivated when it flows out into developing agents);
  • -P-Z represents a group which forms a restrainer through the reaction with the oxidants of the developing agents after cleavage from the group A .
  • Restrainers represented by Z include restrainers described in Research Disclosure No. 17643 (December 1978), preferably mercaptotetrazole, selenotetrazole, mercaptobenzthiazole, selenobenzthiazole, mercaptobenzoxazole, selenobenzoxazole, mercaptobenzimidazole, selenobenzimidazole, benztriazole, mercaptotriazole, mercaptooxadiazole, mercaptothiadiazole and derivatives thereof.
  • Preferred examples of the restrainers include those represented by the following general formulas.
  • R 11 and R 1 are each an alkyl group, an alkoxy group, an acylamino group, a halogen atom, an alkoxycarbonyl group, a thiazolylideneamino group, an aryloxycarbonyl group, an acyloxy group, a carbamoyl group, an N-alkylcarbamoyl group, an N,N-dialkylcarbamoyl group, nitro group, anamino group, an N-arylcarbamoyloxy group, a sulfamoyl group, a sulfonamido group, an N-alkylcar- bamoyloxy group, a ureido group, hydroxyl group, an alkoxycarbonylamino group, an aryloxy group, an alkylthio group, an arylthio group, an anilino group, an aryl group, an imid
  • R13, Ri4, R 15 , R 11 and R 17 are each an alkyl group, an aryl group or a heterocyclic group.
  • the alkyl group represented by R 11 to R 17 may be a substituted or unsubstituted, linear or cyclic alkyl group.
  • substituent groups include halogen, nitro group, cyano group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a carbamoyl group, hydroxyl group, an alkanesulfonyl group, an arylxulfonyl group, an alkylthio group and an arylthio group.
  • the aryl group represented by R 11 to R 17 may be optionally be substituted.
  • substituent groups include an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, nitro group, an amino group, a sulfamoyl group, hydroxyl group, a carbamoyl group, an aryloxycarbonylamino group, an alkoxycarbonylamino group, an acylamino group, cyano group and a ureido group.
  • the heterocyclic group represented by R 11 to R 17 may be a 5-membered or 6-membered, monocyclic or condensed ring containing a nitrogen atom, oxygen atom or sulfur atom as the hetero-atom.
  • the heterocyclic group include pyridyl group, quinolyl group, furyl group, benzthiazolyl group, oxazolyl group, imidazolyl group, thiazolyl group, triazolyl group, benztriazolyl group, imido group and oxazine group. These groups may optionally be substituted by one or more substituent groups already described above for the aryl group.
  • the number of carbon atoms of R 11 or R 12 2 is 1 to 20, more preferably 7 to 20.
  • the sum total of carbon atoms of each of R 13 to R 17 is 1 to 20, more preferably 4 to 20.
  • Examples of these compounds include, but are not limited to, the compounds having the following formulas.
  • the above-described restrainer-releasing compounds can be added to the silver halide emulsion layers or the non-sensitive intermediate layers of the silver halide color photographic material.
  • the restrainer-releasing compounds should be used in an amount of 10- 6 to 10- 3 mol/m 2 , preferably 5x10 -6 to 3x10-4 mol/m2 .
  • the photographic material is thin-layered.
  • the thickness thereof from the surface of the support to the surface of the protective layer is preferably not more than 23 ⁇ m, more preferably not more than 18 ⁇ m.
  • tubular (plate-form) silver halide grains having an average aspect ratio of not lower than 5 and good light transmission or monodisperse silver halide grains having a grain size within which light in the region of visible light is scarcely scattered.
  • color couplers can be used in the present invention. Specific examples thereof include those couplers described in the Patent Specifications cited in the Research Disclosure (RD) No. 17643, VII-C to G.
  • yellow couplers include those described in U.S. Patent Nos. 3,933,501, 4,022,620, 4,326,024 and 4,401,752, JP-B-58-10739, U.K. Patent Nos. 1,425,020 and 1,476,760, U.S. Patent Nos. 3,973,968, 4,314,023 and 4,511,649, and European Patent 249,473A.
  • 5-Pyrazolone compounds and pyrazoloazole compounds are preferred as magenta couplers. Particularly preferred compounds are described in U.S. Patent Nos. 4,310,619 and 4,351,897, European Patent 73,636, U.S. Patent Nos. 3,061,432 and 3,725,064, Research Disclosure No. 2422 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, JP-A-60-185951, U.S. Patent Nos. 4,500,630, 4,540,654 and 4,556,630.
  • Cyan couplers include phenol couplers and naphthol couplers.
  • Preferred examples of cyan couplers include those compounds described in U.S. Patent Nos. 4,052,212, 4,146,396, 4,228,238, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011 and 4,327,173, West German Patent Laid-Open No. 3,329,729, European Patent Nos. 121,365A and 249,453A, U.S. Patent Nos. 3,446,622, 4,333,999, 4,753,871, 4,451,559, 4,427,767, 4,690,889, 4,254,212 and 4,296,199, and JP-A-61-42658.
  • Colored couplers for correcting the unnecessary absorption of color forming dyes include those described in Research Disclosure No. 17643, item VII-G, U.S. Patent 4,163,670, JP-B-57-39413, U.S. Patent Nos. 4,004,929 and 4,138,258 and U.K. Patent No. 1,146,368. It is preferred that there are used couplers for correcting the unnecessary absorption of color forming dyes by fluorescent dye released during coupling, described in U.S Patent No. 4,774,181, or couplers having, as an eliminable group, a dye precursor group capable of forming a dye by the reaction with developing agent such as those described in U.S. Patent No. 4,777,120.
  • couplers whose color forming dyes are properly diffusing there are preferred those couplers described in U.S. Patent No. 4,366,237, U.K. Patent 2,125,670, European Patent No. 96,570 and West German Patent Laid-Open No. 3,234,533.
  • Couplers which release photographically useful residues by coupling are preferably used in the present invention.
  • DIR couplers which release a restrainer include those decribed in Patent Specifications cited in the afore-mentioned Research Disclosure (RD) No. 17643, item VII-F, JP-A-60-184248, JP-A-63-37346 and U.S. Patent No. 4,782,012 in addition to the compounds represented by the general formula (I).
  • couplers which release imagewise a nucleating agent or a development accelerator during development there are preferred the compounds described in U.K. Patent Nos. 2,097,140 and 2,131,188, JP-A-59-157638 and JP-A-59-170840.
  • couplers which can be used in the photographic material of the present invention include couplers which release a dye capable of restoring its color to the original one after elimination such couplers are described in European Patent No. 173,302A.
  • Other useful couplers include releasing bleaching accelerators such as those described in JP-A-61-201247; couplers releasing ligands such as those described in U.S. Patent No. 4,553,477; couplers releasing leuco dyes such as those described in JP-A-63-75747; and couplers releasing fluorescent dyes such as those described in U.S. Patent No. 4,774,181.
  • the couplers can be introduced into the photographic material of the present invention by conventional dispersion methods.
  • Examples of the high-boiling organic solvents which are suitable for use in the oil-in-water dispersion methods and have a boiling point of not lower than 175°C under atmospheric pressure include phthalic esters such as dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate and bis(1,1-diethylpropyl) phthalate; phosphoric or phosphonic esters such as triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichlor
  • Organic solvents having a boiling point of not lower than about 30 C, preferably from 50 to 160 °C can be used as co-solvents.
  • Typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.
  • the present invention can be applied to various color photographic materials. Typical examples thereof include cinema and general-purpose color negative films and reversal color films for slide and TV.
  • the photographic material of the present invention has such properties that the sum total of the layer thicknesses of the entire hydrophilic colloid layers on the side having the emulsion layers is not more than 28 ⁇ m and a layer swelling rate T i is not larger than 30 seconds.
  • layer thickness as used herein means a layer thickness measured by air conditioning at 25. C and 55% RH (two days).
  • the layer swelling rate T can be measured by conventional methods, for example, by using a swellometer described in A. Grren, et al., Photographic Science and Engineering, Vol. 19, No. 2, pages 124-129. T. is defined as the time taken to reach a saturated layer thickness which is referred to be 90% of the maximum swelling layer thickness attainable when processed with a color developing solution at 30 C for 3 min 15 sec.
  • the layer swelling rate T can be controlled by adding a hardening agent to gelatin as a binder, or by changing conditions with time after coating.
  • the swelling ratio is preferably in the range of 150 to 400%.
  • the swelling ratio can be calculated from the maximum swelling layer thickness under the conditions described above. That is, the swelling ratio can be calculated by the following equation.
  • the color photographic material of the present invention can be developed by conventional methods such as those described in RD No. 17643 (pages 28-29) and ibid. No. 18716 (page 615 left column to right column).
  • the color developing solutions which can be used in the present invention are preferably aqueous alkaline solutions prinarily composed of aromatic primary amine color developing agents.
  • Aminophenol compounds are useful as the color developing agents and p-phenylenediamine compounds are preferred as the color developing agents.
  • Typical examples thereof include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesul- fonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-Q-methoxyethylaniline and salts thereof such as sulfate, hydrochloride and p-toluenesulfonate.
  • the color developing solutions contain pH buffering agents such as alkali metal carbonates, borates and phosphates, restrainers such as bromides, iodides, benzimidazoles, benzothiazoles and mercapto compounds and anti-fogging agents.
  • pH buffering agents such as alkali metal carbonates, borates and phosphates
  • restrainers such as bromides, iodides, benzimidazoles, benzothiazoles and mercapto compounds and anti-fogging agents.
  • the color developing solutions may optionally contain preservatives such as hydroxylamine, diethylhydroxylamine, hydrazine, sulfites, phenylsemicar- apelides, triethanolamine, catecholsulfonic acids and triethylenediamine (1,4-diazabicyclo[2,2,2]octane); organic solvents such as ethylene glycol and diethylene glycol; development accelerators such as benzyl alcohol polyethylene glycol, quaternary ammonium salts and amines; fogging agents such as color forming couplers, competitive couplers and sodium boron hydride; auxiliary developing agents such as 1-phenyl-3-pyrazolidone; tackifiers; and chelating agents such as polyamino carboxylic acids, polyaminophosphonic acids, alkylphosphonic acids and phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminep
  • Black-and-white developing solutions may contain conventional developing agents such as dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone) and aminophenols (e.g., N-methyl-p-aminophenol). These developing agents may be used either alone or in combination of two or more.
  • dihydroxybenzenes e.g. hydroquinone
  • 3-pyrazolidones e.g., 1-phenyl-3-pyrazolidone
  • aminophenols e.g., N-methyl-p-aminophenol
  • the pH of the color developing solutions and the black-and-white developing solutions is generally in the range of 9 to 12.
  • the replenishment rate of these developing solutions varies depending on the types of the color photographic materials, but is usually not more than 3 per m 2 of the photographic material.
  • the replenishment rate can be reduced to 500 ml or less when the concentration of bromide ion in the replenisher is reduced.
  • the replenishment rate can be reduced by using a means for inhibiting the accumulation of bromide ion in the developing solution.
  • Color development time is generally from 2 to 5 minutes. However, the processing time can be shortened when the color developing agent is used at a higher concentration, and processing is carried out at a higher temperature and at a higher pH.
  • the photographic emulsion layer is generally bleached.
  • Bleaching may be carried out simultaneously with fixing (bleaching-fixing treatment) or they may be separately carried out.
  • a bleaching-fixing treatment may be conducted to expedite processing.
  • a bleaching-fixing bath composed of two consecutive baths may be used. Fixing may be conducted before the bleaching-fixing treatment.
  • bleaching may be conducted according to purpose. Examples of bleaching agents include compounds of polyvalent metals such as iron(III), cobalt(III), chromium(VI) and copper(II), peracids, quinones and nitro compounds.
  • bleaching agents include ferricyanates; dichromates; organic complex salts of iron(III) and cobalt(III) such as complex salts of polyaminocarboxylic acids (e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraaacetic acid) citric acid, tartaric acid, and malic acid; persulfates; bromates; permanganates; and nitrobenzenes.
  • polyaminocarboxylic acids e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diamine
  • ion(III) complex salts of polyaminocarboxylic acids such as (ethylenediaminetetraacetonato)iron(III) complex and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution.
  • iron(III) complex salts of polyaminocarboxylic acids are useful for bleaching solutions and bleaching-fixing solutions.
  • the pH of the bleaching solutions containing the iron(III) complex salts of the polyaminocarboxylic acids and the bleaching-fixing solutions containing the iron(III) complex salts is generally in the range of 5.5 to 8. A lower pH may be used to expedite processing.
  • the bleaching solution, the bleaching-fixing solution and the previous bath thereof may contain bleaching accelerators.
  • the bleaching accelerators include compounds having a mercapto group or disulfide group such as those described in U.S. Patent No. 3,893,858, West German Patent Nos. 1,290,812 and 2,059,988, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, JP-A-53-28426 and Research Disclosure No.
  • 17129 July 1978: thiazolidine derivatives such as those described in JP-A-50-140129; thiourea derivatives such as those described in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735 and U.S. Patent No. 3,706,561; iodides such as those described in West German Patent No. 1,127,715 and JP-A-58-16235; polyoxyethylene compounds such as those described in West German Patent Nos.
  • fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas and various iodides.
  • Thiosulfates are widely used as fixing agents. Particularly, ammonium thiosulfate is the most widely used. Sulfites, bisulfites and carbonyl bisulfite adducts are preferred as preservatives for the bleaching-fixing solutions.
  • the silver halide color photographic materials of the present invention will be subjected to washing and/or stabilization after desilverization.
  • the amount of rinsing water in the washing stage varies widely depending on the characteristics of the material (e.g., depending on materials used such as couplers), use, the temperature of rinsing water, the number of rinsing tanks (the number of stages), the replenishing system (countercurrent, direct flow) and other conditions.
  • the relationship between the amount of water and the number of rinsing tanks in the multi-stage countercurrent system can be determined by the method described in Journal of the Society of Motion Picture and Television Engineers, Vol. 64, p. 248-253 ( May 1955).
  • isothiazolone compounds thiabendazole compounds
  • chlorine-containing germicides such as sodium chlorinated isocyanurate and benztriazole
  • benztriazole such as those described in JP-A-57-8542
  • germicides such as those described in Chemistry of Germicidal Antifungal Agent, written by Hiroshi Horiguchi, Sterilization, Disinfection, Antifungal Technique, edited by Sanitary Technique Society and Antiacterial and Antifungal Cyclopedie, edited by Nippon Antibacterial Antifungal Society, can be used.
  • the pH of the rinsing water in the treatment of the photographic materials of the present invention ranges from 4 to 9, preferably 5 to 9.
  • the temperature of the rinsing water and washing time will vary depending on the characteristics of the photographic materials, use, etc., but the temperature and time of washing are generally 15 to 45 . C for 20 seconds to 10 minutes, preferably 25 to 40° C for 30 seconds to 5 minutes.
  • the photographic materials of the present invention may be processed directly with stabilizing solutions in place of the rinsing water. Such stabilizing treatment can be carried out by conventional methods such as those described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345.
  • a stabilizing treatment subsequent to the rinsing may be conducted.
  • the stabilizing treatment may be used as the final bath for the color photographic materials for photography.
  • An example thereof include a stabilizing bath containing formalin and a surfactant.
  • the stabilizing bath may contain various chelating agents and antifungal agents.
  • Overflow solution from the replenishment of rinsing water and/or stabilizing can be reused in other stages such as a desilverization stage.
  • the color developing agents may be incorporated in the silver halide color photographic materials of the present invention for the purpose of simplifying and expediting processing. It is preferred that precursors for the color developing agents are used for the incorporation thereof in the photographic materials.
  • the precursors include indoaniline compounds such as those described in U.S. Patent No. 3,342,597; Schiff base-type compounds such as those described in U.S. Patent No. 3,342,599 Research Disclosure No. 14850 and ibid., No. 15159; aldol compounds such as those described in Research Disclosure No. 13924; metal complex salts such as those described in U.S. Patent No. 3,719,492; and urethane compounds such as those described in JP-A-53-135628.
  • 1-phenyl-3-pyrazolidones may be incorporated in the silver halide color photographic materials of the present invention for the purpose of accelerating color development.
  • Typical examples of the compounds include those described in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.
  • various processing solutions are used at a temperature of 10 to 50 °C. Generally, a temperature of 33 to 38 C is used. However, it is possible that higher temperatures can be used to accelerate processing and to shorten processing time, while lower temperatures can be used to improve image quality and to improve the stability of the processing solutions. If desired, treatments using cobalt intensification or hydrogen peroxide intensification such as those described in West German Patent No. 2,226,770 and U.S. Patent No. 3,674,499 may be carried out to save silver.
  • the silver halide photographic materials of the present invention can be applied to heat-developing photosensitive materials such as those described in U.S. Patent No. 4,500,626, JP-A-60-133449, JP-A-59-218443, JP-A-61-238056, and European Patent 210,660A2.
  • Comparative sample 101 was prepered. This sample was a photographic material which has a spectral sensitive distribution similar to that disclosed in U.S. Patent No. 3,672,898 and had a low multi-layer effect.
  • the coating weights of silver halide and colloidal silver are represented by the unit of g/m 2 in terms of silver.
  • the amounts of couplers, additives and gelation are represented by the unit of g/m 2.
  • the amounts of sensitizing dyes are represented by moles per one mole of silver halide in the same layer.
  • Comparative Sample 102 was prepared by using DIR coupler to enhance the chroma of a reproduced color. This sample was prepared in the same manner as Sample 101, but with the following modifications.
  • Comparative Sample 103 in which the concentration of yellow filter layer was increased was prepared to improve blue color reproducibility. This sample was prepared in the same manner as Sample 102, except with the following modifications.
  • Comparative sample 104 was prepared in the same manner as Sample 102, except that the following modifications were made to prepare the sample 104.
  • Comparative sample 105 was prepared in the same manner as Sample 102, except that the following modifications were made to prepare the sample 105.
  • Comparative sample 106 was prepared in the same manner as Sample 102, except that the following modifications were made to prepare the sample 106.
  • Comparative sample 107 and Samples 108 and 109 representing the invention were prepared in the same manner as Samples 104 to 106 except with the following modifications were made to prepare the samples 107 to 109 respectively.
  • Sample 110 representing the invention was prepared in the same manner as Sample 109, except that the amount of the yellow colloidal silver was decreased by 30% to prepare the sample 110.
  • Sample 111 representing the invention was prepared in the same manner as Sample 109, except that nondiffusing yellow dye YD-13 in an amount of 0.17 g/m 2 was used in place of yellow colloidal silver in the tenth layer.
  • Sample 112 representing the invention was prepared in the same manner as Sample 111, except that the silver iodobromide emulsion in the twelfth layer was changed to 5 mol% of silver iodide and the average particle size to 1.7 ⁇ m.
  • Comparative sample 113 was prepared in the same manner as Sample 112, except that the following modifications were made to prepare sample 113.
  • ISO sensitivity S of each of Samples 101 to 112 and S G 480 - S B 480 after uniform exposure were determined by the above-described method.
  • Interference filter of Line double Filter, DEPIL 0.5 manufactured by Shott Glass-werre
  • DEPIL 0.5 was used to obtain monochromatic light of 480 nm.
  • Half width was 8 nm. Development was carried out in the following stages.
  • Each processing solution had the following composition.
  • Each of the Samples 101 to 112 was processed into a Leica size for camera photography. Color rendition charts (manufactured by Macbeth) were photographed and printing was made on color paper (Fuji Color Paper AGL #653-258) so that a grey sheet having an optical density of 0.7 reproduced lightness as well as hue.
  • the chroma and fidelity of Blue and the fidelity of Bluish Green were visually evaluated.
  • the comparative sample 101 shows the fidelity of Bluish Green well enough, but insufficient, and the fidelity and chroma of Blue so insufficient.
  • the comparative sample 102 shows the chroma in acceptable level, however, the fidelity of Bluish Green so worse.
  • the comparative samples 103 to 107 and 113 none of the samples satisfies requirements of the chroma and fidelity simultaneously.
  • sample 108 to 112 according to the present invention produce excellent color and satisfy all three requirements, i.e. the chloma and fidelity of Blue, and the fidelity of Bluish Green.
  • Samples 201 to 204 were prepared in the same manner as in the preparation of the Samples 109 and 111 except that equimolar amounts of the following sensitizing dyes were used in place of sensitizing dye III.

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EP19900100163 1989-01-05 1990-01-04 Farbphotographisches Silberhalogenidmaterial Expired - Lifetime EP0377463B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP74689A JPH02181144A (ja) 1989-01-05 1989-01-05 ハロゲン化銀カラー写真感光材料
JP746/89 1989-01-05

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EP0377463A2 true EP0377463A2 (de) 1990-07-11
EP0377463A3 EP0377463A3 (en) 1990-11-14
EP0377463B1 EP0377463B1 (de) 1995-09-13

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Family Applications (1)

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EP19900100163 Expired - Lifetime EP0377463B1 (de) 1989-01-05 1990-01-04 Farbphotographisches Silberhalogenidmaterial

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EP (1) EP0377463B1 (de)
JP (1) JPH02181144A (de)
DE (1) DE69022252T2 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0661591A2 (de) 1993-12-29 1995-07-05 Eastman Kodak Company Photographische Elemente die Ultraviolett absorbierendes beladenes Polymerlatex enthalten
EP0695968A2 (de) 1994-08-01 1996-02-07 Eastman Kodak Company Viskositätsverminderung in einer photographischen Schmelze

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0115304A2 (de) * 1983-01-19 1984-08-08 Fuji Photo Film Co., Ltd. Multigeschichtetes lichtempfindliches farbphotographisches Silberhalogenidmaterial
GB2165058A (en) * 1984-08-08 1986-04-03 Fuji Photo Film Co Ltd Silver halide color photographic materials
JPS62177547A (ja) * 1986-01-30 1987-08-04 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料
EP0251042A2 (de) * 1986-06-28 1988-01-07 Agfa-Gevaert AG Farbfotografisches Aufzeichnungsmaterial
US4764455A (en) * 1985-08-06 1988-08-16 Fuji Photo Film Co., Ltd. Color image-forming process

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62178965A (ja) * 1986-02-03 1987-08-06 Fuji Photo Film Co Ltd ハロゲン化銀カラ−反転写真感光材料
JPS63259563A (ja) * 1986-10-18 1988-10-26 Konica Corp 粒状性及び鮮鋭性の改良された片面感光性写真感光材料

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0115304A2 (de) * 1983-01-19 1984-08-08 Fuji Photo Film Co., Ltd. Multigeschichtetes lichtempfindliches farbphotographisches Silberhalogenidmaterial
GB2165058A (en) * 1984-08-08 1986-04-03 Fuji Photo Film Co Ltd Silver halide color photographic materials
US4764455A (en) * 1985-08-06 1988-08-16 Fuji Photo Film Co., Ltd. Color image-forming process
JPS62177547A (ja) * 1986-01-30 1987-08-04 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料
EP0251042A2 (de) * 1986-06-28 1988-01-07 Agfa-Gevaert AG Farbfotografisches Aufzeichnungsmaterial

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
BRITISH JOURNAL OF PHOTOGRAPHY. vol. 131, no. 52, 28 December 1984, LONDON GB pages 1389 - 1393; G.ASHTON: "ISO 200 COLOUR NEGATIVE FILMS" *
BRITISH JOURNAL OF PHOTOGRAPHY. vol. 313, no. 21, May 1984, LONDON GB pages 536 - 538; G.ASHTON: "KONICA COLOR SR100" *
BRITISH KINEMATOGRAPHY SOUND AND TELEVISION SOCIETY JOURNAL. vol. 64, no. 7, July 1982, LONDON GB pages 338 - 343; B.DAVIES: "TWO NEW EASTMAN MOTION PICTURE COLOUR CAMERA FILMS" *
PATENT ABSTRACTS OF JAPAN vol. 12, no. 23 (P-658)(2870) 23 January 1988, & JP-A-62 177547 (KONISHIROKU PHOTO INDUSTRY) 04 August 1987, *
SMPTE JOURNAL. vol. 91, no. 12, December 1982, SCARSDALE,NEW YORK,US pages 1161 - 1170; K.J KARL ET AL.: "EASTMAN COLOR PRINT FILM 5384" *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0661591A2 (de) 1993-12-29 1995-07-05 Eastman Kodak Company Photographische Elemente die Ultraviolett absorbierendes beladenes Polymerlatex enthalten
EP0695968A2 (de) 1994-08-01 1996-02-07 Eastman Kodak Company Viskositätsverminderung in einer photographischen Schmelze

Also Published As

Publication number Publication date
DE69022252T2 (de) 1996-02-15
DE69022252D1 (de) 1995-10-19
EP0377463A3 (en) 1990-11-14
EP0377463B1 (de) 1995-09-13
JPH02181144A (ja) 1990-07-13

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