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
  • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
  • G03C7/30541—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the released group
  • G03C7/30552—Mercapto

Definitions

• This invention relates to a silver halide photographic material, more particularly to a silver halide color photographic material having improved photographic characteristics and keeping quality.
• DIR compounds which release development restrainers upon reaction with the oxidation product of color developing agents.
• incorporating these DIR compounds in emulsions is effective for enhancing the sharpness of color image by the edge effect and further for improving the fidelity of color reproduction by the interimage effect.
• the conventional DIR compounds have the disadvantage that development restrainers released during color development diffuse from photographic materials into the developing solution which will eventually exhibit a development inhibiting action in the presence of accumulated restrainers.
• JP-A As used herein means an "unexamined published Japanese patent application”
• JP-A-58-205150 JP-A-60-218644
• JP-A-60-221750 JP-A-61-11743
• the methods described in these patents are based on using couplers that exhibit a development inhibiting action when leaving groups are eliminated from the coupling site of a coupler and which, when released into the developing solution, will be decomposed into compounds that cause no adverse effects on the photographic performance of the light-sensitive material in which they are used.
• An object, therefore, of the present invention is to provide a color light-sensitive material that achieves good sharpness and high fidelity of color reproduction and which also is improved in storage stability.
• This object of the present invention can be attained by a silver halide photographic material containing a compound of the following formula (I) which is capable of releasing a development restrainer upon reaction with the oxidation product of a developing agent: where Cp is a coupler residue that is capable of entering into a coupling reaction with the oxidation product of a color developing agent; TIME is a timing group bound to Cp at the coupling site; l is 0 or 1; R1 is -X-Y or a substituent; R2 is a substituent when R1 is -X-Y, and it is -X-Y when R1 is a substituent; X is a linkage group; and Y is a hydrolyzable group.
• Cp is a coupler residue that is capable of entering into a coupling reaction with the oxidation product of a color developing agent
• TIME is a timing group bound to Cp at the coupling site
• l is 0 or 1
• R1 is -X-Y
• the coupler residue represented by Cp in the general formula (I) may either be a residue that generates a yellow, magenta or cyan dye or a residue that generates a substantially colorless product.
• Typical examples of the yellow coupler residue represented by Cp are described in U.S. Patent Nos. 2,298,443, 2,407,210, 2,875,057, 3,048,194, 3,265,506, 3,447,928, and Farbkuppler ein Literaturuversiecht Agfa Mitannon (Band II), pp. 112-126, 1961, etc.
• acyl acetanilides such as benzoyl acetanilide and pivaloyl acetanilide are preferred.
• magenta coupler residue represented by Cp are described in U.S. Patent Nos. 2,369,489, 2,343,703, 2,311,182, 2,600,788, 2,908,573, 3,062,653, 3,152,896, 3,519,429, 3,725,067, 4,540,654, JP-A-59-162548, Agfa Mitannon (Band II), ibid , pp. 126-156, 1961, etc.
• pyrazolones and pyrazoloazoles e.g. pyrazoloimidazole and pyrazolotriazole
• cyan coupler residue represented by Cp are described in U.S. Patent Nos. 2,367,531, 2,423,730, 2,474,293, 2,772,162, 2,395,826, 3,002,836, 3,034,892, 3,041,236, 4,666,999 and Agfa Mitteilung (Band II), ibid , pp. 156-175, 1961.
• phenols and naphthols are preferred.
• Typical examples of the coupler residue represented by Cp which forms a substantially colorless product are described in U.K. Patent No. 861,138, U.S. Patent Nos. 3,632,345, 3,928,041, 3,958,993, 3,961,959, etc.
• cyclic carbonyl compounds are preferred.
• Typical examples of the timing group represented by TIME include those which release photographically useful groups by an intramolecular nucleophilic substitution reaction as described in U.S. Patent No. 4,248,962 and JP-A-57-56837, as well as those which release photographically useful groups by an electron transfer reaction along conjugated chains as described in JP-A-56-114946 and JP-A-57-154243.
• timing group is described in JP-A-57-188035, JP-A-58-98728, JP-A-59-206834, JP-A-60-7429, JP-A-60-214358, JP-A-50-225844, JP-A-60-229030, JP-A-60-233649, JP-A-60-237446 and JP-A-60-237447.
• Preferred examples of the yellow coupler residue represented by Cp in the general formula (I) are represented by the following general formulas (II) and (III): where R3 and R4 each represents an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group or a halogen atom, with the alkyl, cycloalkyl, aryl and heterocyclic group being optionally bound via at least one member of the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom; the alkyl, cycloalkyl, aryl and hetero ring may also be bound via one or more of the following bonding groups, namely, acylamino, carbamoyl, sulfonamido, sulfamoyl, sulfamoylcarbonyl, carbonyloxy, oxycarbonyl, ureido, thioureido, thioamide, sulfone, sulf
• the alkyl, cycloalkyl, aryl and hetero ring may further contain one or more of the following substituents, namely, a halogen atom, nitro, cyano, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, carboxy, sulfo, sulfamoyl, carbamoyl, acylamino, ureido, urethane, sulfonamido, hetero ring, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylamino, anilino, hydroxyl, imido, acyl, etc.
• substituents namely, a halogen atom, nitro, cyano, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, ary
• R3 and R4 When more than one each of R3 and R4 is present, two or more R3's or R4's may be the same or different.
• magenta coupler residue represented by Cp in the general formula (I) are those represented by the following general formulas (IV), (V), (VI) and (VII): where R3 and R4 are the same as defined for R3 and R4 in the general formulas (II) and (III).
• Preferred examples of the cyan coupler residue represented by Cp in the general formula (I) are those represented by the following general formulas (VIII), (IX) and (X): where R3 and R4 are the same as defined for R3 and R4 in the general formulas (II) and (III).
• R5 and X are the same as defined for R5 and X in the general formula (XI);
• R7 is an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, an alkoxy group, an aryloxy group, a heterocycloxy group, an alkylamino group, a dialkylamino group or an anilino group;
• R8 and R9 which may be the same or different each represents an alkoxycarbonyl group, a carbamoyl group, an acyl group, a cyano group, a formyl group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, an ammoniumyl group or
• TIME useful in the present invention include, but are not limited to, those which are represented by the following general formulas (XV), (XVI) and (XVII): where X is the atomic group necessary to form an optionally substituted benzene or naphthalene ring; Y is -O-, -S- or and is bound at the coupling site to the coupler residue represented by Cp in the general formula (I); R11, R12 and R13 are each a hydrogen atom, an alkyl group or an aryl group; and which is substituted in the position ortho or para to Y is bound to the sulfur atom in the development restraining group; where Y, R11 and R12 are each the same as defined in the general formula (XV); R14 may be a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfonyl group, an alkoxycarbonyl group or a heterocyclic group; and R15 may be a hydrogen atom
• the timing group TIME is bound via Y to the coupling site of the coupler residue represented by Cp in the general formula (I), or via to the sulfur atom in the development restraining group.
• Timing group that releases a development restraining group by an intramolecular nucleophilic substitution reaction is represented by the following general formula (XVII): where Nu is a nucleophilic group having an electron-rich oxygen, sulfur or nitrogen atom and it is bound at the coupling site to the coupler residue represented by Cp in the general formula (I); E is an electrophilic group having an electron-lean carbonyl, thiocarbonyl, phosphinyl or thiophosphinyl group and it is bound to the sulfur atom in the development restraining group; X is a bonding group that sterically relates Nu and E and which, after Nu is released from the coupler residue represented by Cp in the general formula (I), undergoes an intramolecular nucleophilic reaction involving the formation of a 3- to 7-membered ring to thereby release a development restrainer.
• Nu is a nucleophilic group having an electron-rich oxygen, sulfur or nitrogen atom and it is bound at the coupling
• Examples of the substituents represented by R1 and R2 in the general formula (I) include a hydrogen atom and a halogen atom, as well as groups such as nitro, cyano, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, carboxyl, sulfo, sulfamoyl, carbamoyl, acylamino, ureido, urethane, sulfonamido, hetero ring, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylamino, anilino, hydroxyl, imido and acyl.
• a hydrogen atom, an alkyl group and an aryl group are preferred.
• X represents a simple bond, alkylene, cycloalkylene, phenylene, alkenylene, -O-, -S- (where R13 may be a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group) or combinations of these groups.
• R13 may be a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group
• alkylene, and combinations of these groups are preferred.
• Examples of the hydrolyzable group represented by Y in the general formula (I) include -COOR16, -OCOR16, -OSO2R16 and with -COOR16 being preferred.
• Examples of the group represented by R16 include an alkyl group (e.g. methyl, ethyl, propyl, isopropyl, butyl, sec-butyl or hexyl), a cycloalkyl group (e.g. cyclopentyl or cyclohexyl), an aryl group (e.g. phenyl or naphthyl), and a heterocyclic group (e.g. pyridinyl, imidazolyl or pyrrolyl).
• alkyl group e.g. methyl, ethyl, propyl, isopropyl, butyl, sec-butyl or hexyl
• a cycloalkyl group e.g. cyclopentyl or
• These groups may have substituents such as a halogen atom, nitro, cyano, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, carboxyl, sulfo, sulfamoyl, carbamoyl, acylamino, ureido, urethane, sulfonamido, hetero ring, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylamino, anilino, hydroxyl, imido and acyl.
• An alkyl group and an aryl group are preferred as R16.
• a preferred example of the compound of the general formula (I) is the one represented by the following general formula (I'): where Cp, TIME, X, l, R2 and R16 have the same meanings as defined in the general formula (I).
• a particularly preferred example is such that R16 is an unsubstituted alkyl group.
• the compound represented by the general formula (I) may be incorporated in any layers, such as silver halide emulsion layers and/or non-light-sensitive hydrophilic colloidal layers, in a photographic material.
• the DIR coupler is incorporated in silver halide emulsion layers. More preferably, the DIR coupler of the present invention is incorporated in a red-sensitive silver halide emulsion layer and/or a blue-sensitive silver halide emulsion layer.
• the DIR couplers of the present invention may be incorporated in hydrophilic colloidal layers in a color photographic material by the following procedure: the DIR couplers, taken either individually or in combination, are dissolved in a mixture of a known high-boiling point solvent such as dibutyl phthalate, tricresyl phosphate or dinonyl phenol and a known low-boiling point solvent such as butyl acetate or propionic acid; the solution is then mixed with an aqueous gelatin solution containing a surfactant, followed by dispersion using a high-speed rotary mixer, a colloid mill or an ultrasonic disperser, with the resulting dispersion being directly added to a silver halide emulsion; alternatively, the dispersion is allowed to set, shredded into noodles, which are then washed with water and added to a silver halide emulsion.
• a known high-boiling point solvent such as dibutyl phthalate, tric
• the DIR couplers of the present invention are used in amounts that preferably range from 0.005 to 20 mol % of silver halide, more preferably from 0.01 to 10 mol % of silver halide.
• the DIR couplers of the present invention may be used either individually or as admixtures.
• any customary silver halide emulsions may be used in the photographic material of the present invention.
• Such emulsions may be chemically sensitized in the usual manner, or they may be optically sensitized with spectral sensitizers to have sensitivity in a desired wavelength region.
• Antifoggants, stabilizers, etc. may be added to silver halide emulsions.
• Gelatin is advantageously used as a binder for silver halide emulsions.
• Emulsion layers and other hydrophilic colloidal layers may be hardened.
• Plasticizers or dispersions (latices) of synthetic polymers that are either insoluble or slightly soluble in water may also be contained in emulsion layers and other hydrophilic colloidal layers.
• Couplers are used in emulsion layers in a color photographic material. Also usable are colored couplers which are capable of color correction, competing couplers, as well as those compounds which, upon coupling with the oxidation product of developing agents, release photographically useful fragments such as a development accelerator, a bleach accelerator, a developing agent, a silver halide solvent, a toning agent, a hardener, a foggant, an antifoggant, a chemical sensitizer, a spectral sensitizer and a desensitizer.
• a development accelerator a bleach accelerator, a developing agent, a silver halide solvent, a toning agent, a hardener, a foggant, an antifoggant, a chemical sensitizer, a spectral sensitizer and a desensitizer.
• the photographic material of the present invention may have a filter layer, an anti-halation layer, an anti-irradiation layer, etc. These layers and/or emulsion layers may contain dyes that will dissolve out of the photographic material during development or which are bleachable.
• the photographic material of the present invention may also contain a matting agent, a lubricant, an image stabilizer, a surfactant, an anti -color fog agent, a development accelerator, a development retarder or a bleach accelerator.
• Supports that can be used in the present invention include paper laminated with a resin such as polyethylene, a polyethylene terephthalate film, baryta paper, a triacetyl cellulose film etc.
• a resin such as polyethylene, a polyethylene terephthalate film, baryta paper, a triacetyl cellulose film etc.
• Multi-layered color photographic material (sample 1) was prepared by forming the following layers in the order written on a triacetyl cellulose film base.
• Yellow filter layer (YC-1) Gelatin layer containing yellow colloidal silver and an emulsified dispersion of 2,5-di-t-ocytlhydroquinone
• Second protective layer Gelatin layer containing polymethyl methacrylate particles (diameter, 1.5 ⁇ m) and formaldehyde scavenger (HS-1)
• a gelatin hardener (H-1) and a surfactant were also added to each layer.
• JP-B-63-27701 Compound described in JP-B-63-27701 ("JP-B" refers to an "examined Japanese patent publication)
• Samples 2 - 5 were prepared by replacing the DIR compound (D - 1) in the third and fourth layers of sample 1 with equimolar amounts of the compounds shown in Table 1 below.
• Each of the thus prepared samples 1 - 5 was divided into two lots, one of which was left to stand at 55°C for 7 days at 20% r.h. before exposure.
• the samples including the untreated lots were exposed to white light through an optical wedge and processed by the scheme shown below.
• the sensitivity of the red-sensitive layers and the fog that occurred were measured.
• the sharpness of image was also measured and the results were shown in terms of the relative values of MTF at a resolution of 30 lines/mm, with the value for sample 1 taken as 100.
• the results of the measurements are shown in Table 1 below.
• the processing solutions used in the color developing, bleaching, fixing and stabilizing steps had the following compositions.
• a basic sample was prepared by coating multiple layers in superposition on a triacetate base in the order indicated below.

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