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
  • G03C7/32—Colour coupling substances
  • G03C7/36—Couplers containing compounds with active methylene groups
  • G03C7/38—Couplers containing compounds with active methylene groups in rings
  • G03C7/381—Heterocyclic compounds
  • G03C7/382—Heterocyclic compounds with two heterocyclic rings
  • G03C7/3825—Heterocyclic compounds with two heterocyclic rings the nuclei containing only nitrogen as hetero atoms
• • 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
  • G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
  • G03C7/3885—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor characterised by the use of a specific solvent

Definitions

• the present invention relates to a silver halide color photographic light-sensitive material having an excellent processing stability and improved graininess.
• the pyrazoloazole magenta couplers significantly improve the reproducibility of red color while there exists such a problem that a density of a dye image is liable to vary by change of processing conditions, in particular, pH change of a developer.
• the primary object of the invention is to provide a silver halide color photographic light-sensitive material having an improved processing stability and graininess.
• the secondary object of the invention is to provide a light-sensitive material capable of providing a dye image having a stable color density against change of processing conditions, in particular, pH change of a developer.
• a silver halide color photographic light-sensitive material comprising a support and provided thereon plural light-sensitive layers including at least one green-sensitive layer, wherein the at least one green-sensitive layer contains a magenta coupler represented by Formula M-I and a compound represented by Formula A-I: wherein Z represents a group of non-metal atoms necessary to form a nitrogen-containing heterocycle which may have a substituent; X represents a hydrogen atom or a group which can be released by a reaction with an oxidation product of a color developing agent; and R represents a hydrogen atom or a substituent; Formura A-I H O ( ⁇ J) ⁇ C O O Y wherein J represents a divalent organic group; and Y represents an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkynyl group, a cycloalkenyl group and a heterocyclic group.
• M-I magenta coupler represented by Formula M-I and
• the examples of the substituent represented by R are an alkyl group, an aryl group, an anilino group, an acylamino group, a sulfonamide group, an alkylthio group, an arylthio group, an alkenyl group, a cycloalkyl group, a halogen atom, a cycloalkenyl group, an alkynyl group, a heterocyclic group, a sulfonyl group, a sulfinyl group, a phosphonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclicoxy group, a siloxy group, an acyloxy group, a carbamoyloxy group, an amino group, an alkylamino group, an imido group, an ureido group,
• the respective groups represented by R are as follows: the alkyl group has preferably 1 to 32 carbon atoms and may be linear or branched; the aryl group is preferably phenyl; the examples of the acylamino group are alkylcarbonylamino and arylcarbonylamino; the examples of the sulfonamide group are alkylsufonylamino and arylsulfonylamino; the alkyl and aryl components in the alkylthio and arylthio groups may be the same as the above alkyl and aryl groups; the alkenyl group has preferably 2 to 32 carbon atoms and may be linear or branched; the cycloalkyl and cycloalkenyl groups each have preferably 3 to 12, more preferably 5 to 7 carbon atoms; the examples of the sulfonyl group are alkylsulfonyl and arylsulfonyl; the examples of the sulfinyl
• the examples of the group represented by X are a halogen atom, an alkoxy group, an aryloxy group, a heterocyclicoxy group, an acyloxy group, a sulfonyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyloxalyloxy group, an alkoxyoxalyoxy group, an alkylthio group, an arylthio group, a heterocyclicthio group, an alkoxythiocarbonylthio group, an acylamino group, a sulfonamide group, a nitrogen-containing heterocycle having a bonding site at the nitrogen atom, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a carboxyl group, wherein R1′ and Z′ are the same groups as those defined for R and Z in Formula M-I, respectively, and R2′ and R3′ each represent a hydrogen atom, an aryl group,
• the nitrogen-containing heterocycles formed by Z and Z′ are a pyrazole ring, an imidazole ring, a triazole ring and a tetrazole ring, and may have the same substituents as those defined for R.
• magenta coupler represented by M-I are represented by the following Formulae M-II to M-VII: wherein R1 to R8 and X represent the same groups as those defined for R and X in Formula M-I, respectively.
• magenta coupler represented by Formula M-I is represented preferably by the following Formula M-VIII: wherein R1, X and Z1 represent the same groups as those defined for R, X and Z in Formula M-I, respectively.
• magenta couplers represented by Formulae M-II to M-VII preferable are those represented by Formula M-II.
• the substituents for the rings formed by Z in Formula M-I and Z1 in Formula M-VIII and the groups represented by R2 to R6 in Formula M-II to M-VI are represented preferably by the following Formula M-IX: Formura M-IX - R1 - SO2 - R2 wherein R1 represents an alkylene group and R2 represents an alkyl group, a cycloalkyl group or an aryl group.
• R1 or R2 has preferably at least one acid group. This acid group is preferably a carboxylic group or a sulfonic group, more preferably a carboxylic group or a salt thereof.
• the alkylene group represented by R1 is a linear or branched alkylene group which has preferably 2 or more, more preferably 3 to 6 carbon atoms in its linear structure.
• the cycloalkyl group represented by R2 is preferably 5 to 6-membered.
• R and R1 are preferably the groups represented by Formula M-X: wherein R9, R10 and R11 each represent the same groups as those defined for R, provided that two of R9, R10 and R11 may combine to form a saturated or unsaturated ring such as cycloalkane, cycloalkene and heterocycle and that R9 or R11 may combine with this ring to form a bridged hydrocarbon residue.
• substituents represented by Formula M-X preferable is (i) the one in which at least two of R9 to R11 are alkyl groups, or (ii) the one in which at least one of R9 to R11 is a hydrogen atom and the remaining two combine to form a cycloalkyl group.
• R and R1 are preferably those represented by Formula M-XI: Formura M-XI R12 - CH2 - wherein R12 is the same group as that defined for R.
• R12 is preferably a hydrogen atom or an alkyl group.
• magenta couplers usable in the invention are described in Japanese Patent Application No. 9791/1986.
• magenta couplers can be synthesized by the methods described in Journal of the Chemical Society, Perkin I (1977), pp. 2047 to 2052, U.S. Patent No. 3,725,067, Japanese Patent O.P.I. Publication No. 99437/1984, 42045/1983, 162548/1984, 171956/1984, 33552/1985, 43659/1985, 172982/1985 and 190779/1985.
• the preceding magenta couplers are added normally in an amount of 1 x 10 ⁇ 3 to 1 mol, preferably 1 x 10 ⁇ 2 to 8 x 10 ⁇ 1 mol per mol of silver halide, and may be used in combination with other couplers.
• the examples of the divalent organic group represented by J are an alkylene group, an alkenylene group, a cycloalkylene group, a carbonyl group, a carbonyloxy group, an allylene group and a heterocyclic group, each of which may have a substituent.
• the above group is preferably an arylene group, more preferably a phenylene group.
• the alkyl, cycloalkyl, aryl, alkenyl, alkynyl and cycloalkenyl groups represented by Y each have preferably 1 to 32 carbon atoms and may have a substituent.
• the alkyl, alkenyl and alkynyl groups may be either linear or branched.
• the heterocyclic group represented by Y is preferably a nitrogen-containing heterocyclic group such as pyrrolyl, pyrazolyl, imidazolyl, pyridyl, pyrrolinyl, imidazolidinyl, imidazolinyl, piperadinyl and piperidinyl, each of which may have a substituent.
• magenta coupler represented by Formula M-I (hereinafter referred to as Magenta coupler M-I) and the compound represented by Formula A-I (hereinafter referred to as Compound A-I) are incorporated into at least one of the green-sensitive layers.
• Magenta coupler M-I and Compound A-I can be added by a known method; Magenta coupler M-I and Compound A-I are dissolved singly or in combination in a mixed solvent of a high boiling solvent such as dibutyl phthalate and tricresyl phosphate and a low boiling solvent such as butyl acetate and propionic acid; the solution is dispersed in a gelatin solution containing a surfactant with a high-speed rotary mixer, a colloid mill or an ultrasonic apparatus; and the dispersion is added to an emulsion, or the gelatinized dispersion is cut into pieces, rinsed and then added to an emulsion.
• a high boiling solvent such as dibutyl phthalate and tricresyl phosphate
• a low boiling solvent such as butyl acetate and propionic acid
• Magenta coupler M-I and Compound A-I are added to a silver halide emulsion after dispersing them separately by the above dispersion method, and the dispersion containing both compounds is added to an emulsion.
• the amount of Compound A-I is preferably 0.01 to 10 g, more preferably 0.1 to 3.0 g per gram of Magenta coupler M-I.
• Compound A-I may be employed either alone or in combination.
• the silver halide emulsions used in the invention may be conventional ones.
• the silver halide emulsions can be chemically sensitized by conventional methods, and can be spectrally sensitized to a prescribed wavelength region with a sensitizing dye,
• the silver halide emulsion may contain such an additive as antifoggant and a stabilizer.
• Gelatin is preferably used as a binder.
• the emulsion layers and other hydrophilic colloidal layers may be hardened and contain a plasticizer an a latex.
• a colored coupler a competitive coupler and a compound which releases by a coupling reaction with an oxidation product of a development agent such photographically significant fragments as a development accelerator, a bleaching accelerator, a developing agent, a silver halide solvent, a toning agent, a hardener, a fogging agent, an antifoggant, a chemical sensitizer, a spectral sensitizer and a desensitizer.
• auxiliary layers such as a filter layer, an anti-hallation layer and an anti-irradiation layer.
• These layers and/or the emulsion layers may contain a dye which can be removed from the light-sensitive material or bleached during development.
• the light-sensitive material may contain a formalin scavenger, a fluorescent bleaching agent, a matting agent, a lubricant, an image stabilizer, a surfactant, an anti-fogging agent, a development accelerator, a development retarder and a bleaching accelerator.
• the examples of the support are polyethylene-laminated paper, a polyethylene terephthalate film, baryta paper and a cellulose triacetate film.
• a dye image can be obtained by processing an exposed light-sensitive material by conventional methods.
• the amounts of ingredients are given by g/m2 unless otherwise indicated.
• the amounts of silver halide and colloidal silver are converted to the amounts of silver,
• a multilayer color photographic light-sensitive material (Sample No. 1) was prepared by providing on a cellulose triacetate film support the layers of the following constitutions in sequence from the support.
• 1st Layer Anti-halation layer (HC-1) Black colloidal silver 0.20 UV absorber (UV-1) 0.20 Colored coupler (CC-1) 0.05 Colored coupler (CM-1) 0.05 High boiling solvent (Oil-1) 0.20 Gelatin 1.5
• 2nd Layer Intermediate layer (IL-1) UV absorber (UV-1) 0.01 High boiling solvent (Oil-1) 0.01 Gelatin 1.5
• 3rd Layer Low-speed red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-1) 0.8 Silver iodobromide emulsion (Em-2) 0.8 Sensitizing dye (SD-1) 2.5 x 10 ⁇ 4 (mol per mol silver) Sensitizing dye (SD-2) 2.5 x 10 ⁇ 4 (mol per mol silver) Sensitizing dye (SD-3)
• a coating aid Su-2
• a dispersion aid Su-3
• hardeners H-1 and H-2
• a stabilizer ST-1
• antifoggants AF-1, AF-2
• the grain size distribution is defined by the following equation:
• Samples No. 2 to 14 were prepared in the same manner as in Sample No.1, except that the magenta couplers in the 6th and 7th layers were replaced as shown in Table 1 and that Compounds A-I were added to the 6th and 7th layers.
• Table 1 Sample No. 6th layer 7th layer Coupler Compound [A-I] Coupler Compound [A-I] No. Amount No. Amount No. Amount No. Amount No.
• Amount 1 (Comparison) M-A 0.1 - - M-A 0.18 - - M-B 0.2 2 (Comparison) M-4 0.2 - - M-4 0.12 - - 3 (Comparison) M-57 0.2 - - M-57 0.1 - - 4 (Invention) M-4 0.2 A-16 0.1 M-A 0.18 - - 5 (Invention) M-4 0.2 A-16 0.1 M-4 0.12 A-16 0.05 6 (Invention) M-4 0.2 A-17 0.1 M-4 0.12 A-17 0.05 7 (Invention) M-4 0.2 A-2 0.1 M-4 0.12 A-2 0.05 8 (Invention) M-4 0.22 A-24 0.15 M-4 0.12 A-13 0.05 9 (Invention) M-1 0.2 A-12 0.1 M-1 0.12 A-12 0.05 10 (Invention) M-5 0.2 A-19 0.12 M-5 0.12 A-19 0.06 11 (Invention) M-10 0.2 A-18 0.1 M-10 0.12 A-18 0.05 12 (Invention)
• RMS value was determined by a standard deviation of a variation of a density, which was observed when scanning a portion of 250 ⁇ m2 on a magenta dye image having the density of the minimum density + 0.5 with a Sakura microdensitometer (model PDM-5, Type AR, manufactured by Konica Corp), and expressed by a value relative to that of Sample No. 1, which was set at 100.
• Processing stability was evaluated by varying pH of the developer from 10.0 to 10.4 and observing a variation of a gamma value on the characteristic curve of a magenta dye image.
• the samples of the invention are significantly improved in graininess and processing stability.
• Example 2 Each sample was exposed in the same manner as in Example 1 and subjected to the following processing, in which pH of the developer was varied from 10.0 to 10.4 to evaluate processing stability in the same manner as in Example 1.
• Processing Temperature Time Color developer 34.7 ⁇ 0.3°C 45 sec Bleach-fixing 34.7 ⁇ 0.5°C 50 sec Stabilizing 30 to 34°C 90 sec Drying 60 to 80°C 60 sec Color developer Pure water 800 ml
• Potassium chloride 2 g N-ethyl-N- ⁇ -methanesulfonamidethyl-3-methyl-4-aminoaniline sulfate 5 g
• Sodium tetrapolyphosphate 2 g Potassium carbonate 30 g Potassium sulfite 0.2 g
• Fluorescent bleaching agent (4,4-diaminostilbene disulfonic acid derivative) 1 g Water was added to make a total quantity 1l

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• 1989
  • 1989-10-12 JP JP26393889A patent/JPH03126031A/ja active Pending
• 1990
  • 1990-10-09 EP EP90119366A patent/EP0422595A1/fr not_active Withdrawn

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