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
  • G03C7/3835—Heterocyclic compounds with two heterocyclic rings the nuclei containing only nitrogen as hetero atoms four nitrogen 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
  • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
  • G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
  • G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
  • G03C7/30529—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution having the coupling site in rings of cyclic compounds

Definitions

• the present invention relates to a method for processing a silver halide color photographic material and, more particularly, to a method for processing a silver halide color photographic material, which can increase photographic speed, improve gradation (gamma) and heighten color density of the developed image.
• a process for forming color image which comprises developing a silver halide color photographic material using a developer containing an aromatic primary amine in the presence of a magenta coupler of the lH-pyrazolo[1,5-b]-1,2,4-triazole or IH-pyrazolo[5,1-c]-1,2,4-triazole type which is characterized by having a substituted or unsubstituted alkyloxy, aryloxy, or heterocyclic oxy group at the 6- position.
• color developing agents of the aromatic primary amine type which have been oxidized with exposed silver halides as oxidants react with couplers to produce indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine and their analogous dyes, thus forming color images.
• a magenta color image is formed by using couplers of a 5-pyrazolone, cyanoacetophenone, indazolone, pyrazolobenzimidazole or pyrazolotriazole type.
• magenta couplers described in the foregoing patent specifications also have such undesirable properties that when mixed with a silver halide emulsion in a condition that they are dispersed in a hydrophilic protective colloid like gelatin, some of them provide only unsatisfactory color images, some of them have low solubility in high boiling organic solvents, some of them are difficult to synthesize, some of them have relatively low coupling activity in an ordinary developer, and that some of them provide dyes of extremely poor fastness to light.
• couplers have advantages in that they are excellent in color reproducibility, can be synthesized with ease, and can be readily converted to socalled two-equivalent couplers by introducing a split-off group to a coupling active site, thus achieving reduction of the amount of silver to be used.
• a coupling split-off group - (X) is such a group as to give facility in synthesizing the resulting coupler, e.g., a halogen atom, an alkylthio group, an arylthio group, etc.
• a problem that such couplers are somewhat inferior to 5-pyrazolone magenta couplers in respect to sensitivity and gradation (gamma).
• couplers having an aryloxy group as a coupling split-off group can afford a means for solving the above-described problem.
• the aryloxy group-releasing couplers suffer from disadvantages that they are obtained in such a low yield as to be unsuitable for large-scaled synthesis and that they have low stability.
• pyrazoloazoles described in the above-cited U.S. Patent 3,725,067 have similar defects.
• a primary object of the present invention is to solve the above-described problems and to provide a magenta coupler having higher sensitivity and improved gradation (gamma).
• the above-described object is attained with a process for forming color image, which comprises developing a silver halide photographic material using a developer containing an aromatic primary amine in the presence of at least one of couplers represented by the following formulae (I) and (II): wherein R, represents an alkyl group, an aryl group, or a heterocyclic group; R 2 represents a hydrogen atom or a substituent group; and X represents a hydrogen atom or a coupling split-off group: wherein R, and X have the same meanings as in the formula (I), respectively; and R 2 represents an alkyl group or an aryl group, an alkylthio group, an arylthio group, or a heterocyclic thio group.
• R represents an alkyl group such as methyl group, ethyl group, isopropyl group, t-butyl group, trifluoromethyl group, phenylmethyl group, methoxyethyl group, 2-phenoxyethyl group, 2-methylsulfonylethyl group, 2-hydroxyethyl group, 3,3,3-trifluoropropyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 3-oxobutyl group, or the like; an aryl group such as phenyl group, 4-methylphenyl group, 4-t-butylphenyl group, 4-acylaminophenyl group, a 4- halogenophenyl group, a 4-alkoxyphenyl group, or the like; or a heterocyclic group such as a 2-furyl group, 2-thienyl group, 2-pyrimidyl
• R2 represents a hydrogen atom, an halogen atom (e.g., chlorine atom, bromine atom, etc.), an alkyl group [including substituted alkyl groups such as a sulfonamido-substituted alkyl group (e.g., sul- fonamidomethyl group, I-sulfonamidoethyl group, 2-sulfonamidoethyl group, I-methyl2-sulfonamidoethyl group, 3-sulfonamidopropyl group, etc.), an acylamino-substituted alkyl group (e.g., acylaminomethyl group, I-acylaminoethyl group, 2-acylaminoethyl group, 1-methyl-2-acylaminoethyl group, 3-acylaminopropyl, etc.), a sulfonamido-substituted phenylalkyl group (e
• ethoxy group 2-methoxyethoxy group, 2-dodecylethoxy group, 2-methanesul- fonylethoxy group. etc.
• an aryloxy group e.g., phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, etc.
• an acylamino group e.g., acetamido group, benzamido group, tetradecanamido group, a-(2,4-di-t-amylphenoxy)butylamido group, -y-(3-t-butyl-4-hydroxyphenoxy)butylamido group, a-(4-(4-hydrox- yphenylsulfonyl)phenoxy ⁇ decanamido group, etc.), an anilino group (e.g., phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecanamidoanilin
• R'2 represents a substituted alkyl group such as a sulfonamido-substituted alkyl group (e.g., sul- fonamidomethyl group, I-sulfonamidoethyl group, 2-sulfonamidoethyl group, I-methyl-2-sulfonamidoethyl group, 3-sulfonamidopropyl group, etc.) an acylamino-substituted alkyl group (e.g., acylaminomethyl group, I-acylaminoethyl group, 2-acylaminoethyl group, I-methyl-2-acylaminoethyl group, 3-acylaminopropyl group, etc.), a sulfonamido-substituted phenylalkyl group (e.g., p-sulfonamidophenylmethyl group, p-sul- fonamid
• X represents a hydrogen atom, a halogen atom (e.g., chlorine atom, bromine atom, iodine atom, etc.), a carboxyl group, a group linked through an oxygen atom (e.g., acetoxy group, propanoyloxy group, benzoyloxy group, 2,4-dichlorobenzoyloxy group, ethoxyoxaloyloxy group, pyruvoyloxy group, cin- namoyloxy group, phenoxy group, 4-cyanophenoxy group, 4-methanesulfonamidophenoxygroup, 4- methanesulfonylphenoxy group, a-naphthoxy group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group, 2-phenethyloxy group, 2-phenoxyethoxy group, 5-phenyltetrazoly
• R 1 , R 2 , or R' 2 represents a substituted or unsubstituted alkylene group (e.g., methylene group, ethylene group, 1,10-decylene group, -CH 2 CH 2 -O-CH 2 CH-, etc.), or a substituted or unsubstituted phenylene group - (e.g., 1,4-phenylene group, 1,3-phenylene group, etc.) and X represents a divalent group obtained by converting any of the above-cited monovalent groups into the corresponding divalent group at a proper position.
• R 1 , R 2 , or R' 2 represents a substituted or unsubstituted alkylene group (e.g., methylene group, ethylene group, 1,10-decylene group, -CH 2 CH 2 -O-CH 2 CH-, etc.), or a substituted or unsubstituted phenylene group - (e.g., 1,4-phenylene group,
• a linkage group represented by R,, R2, or R'2 includes groups formed by connecting some groups selected from substituted or unsubstituted alkylene groups (e.g., methylene group, ethylene group, 1,10-decylene group, -CH 2 CH 2 OCH 2 CH 2 -, etc.), substituted or unsubstituted phenylene groups (e.g., 1,4-phenylene group, 1,3-phenylene group, etc.), -NHCO-, -CONH-, -O-, -OCO-, and aralkylene groups
• substituted or unsubstituted alkylene groups e.g., methylene group, ethylene group, 1,10-decylene group, -CH 2 CH 2 OCH 2 CH 2 -, etc.
• substituted or unsubstituted phenylene groups e.g., 1,4-phenylene group, 1,3-phenylene group, etc.
• linkage groups include and the like.
• the vinyl group may further have a substituent group.
• substituent groups include a hydrogen atom, a chlorine atom, and a lower alkyl group containing I to 4 carbon atoms (e.g., methyl group, ethyl group, etc.).
• a monomer having a moiety represented by the foregoing general formula (I) or (II) may form a copolymer together with a non-color-forming ethylenic monomer which is not coupled with an oxidation product of an aromatic primary amine developing agent.
• non-color-forming ethylenic monomers which are not coupled with-an oxidation product of an aromatic primary amine developing agent
• acrylic acid a-chloroacrylic acid
• a-alkylacrylic acids e.g., methacrylic acid, etc.
• esters and amides derived from acrylic acids as described above e.g., acrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and p-hydroxy methacrylate
• non-color-forming ethylenic unsaturated monomers can be used in combination with two or more thereof.
• a combination of n-butyl acrylate with methyl acrylate, that of styrene with methacrylic acid, that of methacrylic acid with acrylamide, that of methyl acrylate with diacetoneacrylamide, and the like can be employed.
• non-color-forming ethylenic unsaturated monomers to be copolymerized with water-insoluble solid monomer couplers can be so selected as to exert a favorable influence upon physical properties and/or chemical properties of the resulting copolymers, such as solubility, compatibility with binders of photographic colloidal compositions, e.g., gelatin, flexibility, thermal stability, and so on.
• the polymer couplers which can be used in the present invention may be either water-soluble or water-insoluble. However, particularly preferred are polymer coupler latexes.
• magenta couplers which can be used in the present invention are illustrated below. However, the invention is not intended to be construed as being limited to these specific examples. Unless otherwise indicated, all fractions of constituent monomers in the polymer couplers instanced below are by weight.
• a general process for synthesizing the couplers of the present invention is described below. Some of the inventors have disclosed in Japanese Patent Application (OPI) No. 197688/85 a process for synthesizing 1H-pyrazolo-[1,5-b]-1,2,4-triazoles which have a hydrogen atom or an alkyl group at the 6-position.
• the couplers of the present invention (formula (I)) can be synthesized in basically the same manner as those described above except that different starting materials are used. The synthesis scheme is illustrated below.
• R,, R 2 and X have the same meanings as in the foregoing formula (I), respectively; and R' represents an alkyl group or an aryl group.
• the substituent X may be introduced from the start as shown above, or the synthesis may be conducted using the compound wherein X is a hydrogen atom as a starting material and various substituents for X may be introduced after synthesis of the skeleton as described hereinafter.
• the 1H-pyrazolo[5,1-c]-1,2,4-triazole couplers can be synthesized using 3-alkoxy (or aryloxy)-5-hydrazinopyrazoles as a starting material according to the method described in Japanese Patent Publication No. 30895/73.
• the polymer couplers can be synthesized using a solution polymerization process or an emulsion polymerization process.
• the solution polymerization can be carried out using the processes described in U.S. Patent 3,451,820 and Japanese Patent Application (OPI) No. 28745/83.
• a monomer coupler having the moiety represented by the formula (I) and a non-color-forming ethylenic monomer e.g., acrylic acid, a-chloroacrylic acid, alacrylic acid such as methacrylic acid, or an ester or amide derived from such an acrylic acid (e.g., acrylamide, n-butyl acrylamide, n-butyl methacrylate, methyl methacrylate, ethyl methacrylate, etc.)
• a soluble organic solvent e.g., dioxane, methyl cellosolve, etc.
• polymerization can be initiated at a proper temperature (about 30 to 100°C) through formation of free radicals by applying thereto a physical means such as UV irradiation, high energy irradiation, or the like, or by applying chemical means such as use of initiators (e.g., persulfates, hydrogen peroxide
• the polymer After completion of the polymerization reaction, the polymer can be isolated by extract the product into an organic organic solvent, concentrating the product, or pouring the product into water.
• the emulsion polymerization can be effected using the method described in U.S. Patent 3,370,952.
• Linking an oxygen atom can be effected using a process as described, e.g., in U.S. Patent 3,926,631 and Japanese Patent Application (OPI) No. 70817/82.
• a 4-equivalent coupler having the matrix nucleus of the present invention is converted to a dye in a manner as in Example I described below, and the resulting dye is hydrolyzed in the presence of an acid catalyst to convert it into a ketone derivative.
• the ketone derivative is subjected to hydrogenation using a Pd-on-carbon catalyst, reduction with a Zn-acetic acid mixture, or reduction with sodium borohydride, to thereby synthesize a 7-hydroxyl derivative.
• the thus obtained product is allowed to react with a halide to yield an intended coupler to which an oxygen atom is linked.
• Linking a nitrogen atom is divided roughly into three groups. Processes falling into the first group involve, as described in U.S. Patent 3,419,391, nitrosifying the coupling active site of a coupler with an appropriate nitrosifying agent, reducing the nitroso group by a suitable process (for example, a hydrogenation process using a catalyst like Pd-on-carbon or a chemical reduction process using stannous chloride or so on), and then allowing the resulting 7-amino compound to react with a halide to yield predominantly the amide compound.
• a suitable process for example, a hydrogenation process using a catalyst like Pd-on-carbon or a chemical reduction process using stannous chloride or so on
• Processes falling into the second group involve, as described in U.S. Patent 3,725,067, halogenating the 7-position of a coupler with an appropriate halogenating agent such as sulfuryl chloride, chlorine gas, bromine, N-chlorosuccinimide, N-bromosuccinimide, or the like, and then replacing the halogen with a nitrogen-containing hetero ring in the presence of an appropriate base catalyst such as triethylamine, sodium hydroxide, diazabicyclo[2,2,2]octane, anhydrous potassium carbonate, etc. according to the process described in Japanese Patent Publication No. 45135/81, thus the coupler which is linked to a nitrogen atom at the 7-position beinq synthesized.
• an appropriate halogenating agent such as sulfuryl chloride, chlorine gas, bromine, N-chlorosuccinimide, N-bromosuccinimide, or the like
• an appropriate base catalyst such as triethylamine, sodium hydroxide
• Processes falling into the third group are effective in introducing a 67r or 10 ⁇ -electron system aromatic nitrogen-containing hetero ring to a coupler at the 7-position and involve, as described in Japanese Patent Publication No. 36577/82, adding 2 moles or more of a 6w-or low-electron system aromatic nitrogen-containing hetero ring to I mole of a 7-halogenated coupler synthesized in the course of the second group process described above and heating the mixture at a temperature of from 50°C to 150°C without using any solvent.
• aprotic polar solvent such as dimethylformamide, sulfolane, hexamethylphosphotriamide, or so on to introduce the aromatic nitrogen-containing heterocyclic group to the 7-position of the coupler via the nitrogen atom.
• Couplers substituted by an aromatic mercapto or heterocyclic mercapto group at the 7-position can be synthesized using the process described in U.S. Patent 3,227,554, which involves dissolving an arylmercap- tane, a heterocyclic mercaptane, or a disulfide corresponding thereto in a halogenated hydrocarbon solvent, converting the mercaptane or disulfide into a sulfenyl chloride with chlorine or sulfuryl chloride, and then adding the sulfenyl chloride a 4-equivalent coupler dissolved in an aprotic solvent.
• reaction product was extracted with ethyl acetate and recrystallized from a mixed solvent of n-hexane and ethyl acetate to give 8.0 g of (VII) in a 72.4% yield. Melting Point 170-172°C.
• Magenta dye images produced from the magenta couplers to be employed in the present invention are enhanced in fastness to light by a combined use with color image stabilizers represented by the following formula: wherein R, o represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group; R,,, R 12 , R 14 , and R 15 each represents a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an acylamino group, an alkoxycarbonyl group, or a sulfonamido group; and R,3 represents an alkyl group, a hydroxyl group, an aryl group, or an alkoxy group, provided that R, o and R,, may combine with each other to form a 5-or 6-membered ring or a methylenedioxy ring, and that R 13 and R, 4 may combine with each other to form a 5-membered hydrocarbon ring.
• the couplers of the present invention are incorporated in a silver halide color photographic material.
• the couplers of the present invention may be incorporated in a light-sensitive material or may be added to a color developing bath.
• a suitable content of the coupler in the light-sensitive material ranges from 2 - 1 10- 3 mole to 5 x 10-' mole, preferably from 1 X 10-z mole to 5 x 10- 1 mole, per mole of silver halide.
• the coupler is a polymeric coupler, its amount is so adjusted that the amount of the color-forming moiety falls into the above-described range.
• a suitable amount of the coupler to be added to a color developing agent ranges from 0.001 mole to 0.1 mole, preferably from 0.01 mole to 0.05 mole, per liter of the bath containing the same.
• the pyrazoloazole couplers of the present invention can be introduced into a light-sensitive material using various known methods of dispersing.
• the dispersion can be effected by a solid dispersion method, an alkaline dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method.
• couplers are dissolved in either a high boiling organic solvent having a boiling point of 175°C or above or a so-called auxiliary solvent having a low boiling point, or in a mixture of these solvents and then dispersed finely into an aqueous medium like water or an aqueous gelatin solution in the presence of a surface active agent.
• Suitable examples of high boiling organic solvents are described in, for example, U.S. Patent 2,322,027, and so on.
• the dispersion may be accompanied by phase inversion. Further, the auxiliary solvent used may be removed from the dispersion or decreased in content therein through distillation, noodle washing, ultrafiltration, or so on, if desired, in preference to coating of the dispersion.
• high boiling organic solvents which can be used include phthalic acid esters (e.g., dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, etc.), phosphoric or phosphonic acid esters (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenylphosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate, tributoxyethyl phosphate, trich- loropropyl phosphate, di-2-ethylhexylphenyl phosphate, etc.), benzoic acid esters (e.g., 2-ethyl-hexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxy benzoate, etc.
• auxiliary solvents organic solvents having a boiling point of from about 30°C or more, preferably from 50°C to about 160°C, can be used, with typical examples including ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and so on.
• Silver halide emulsion which can be employed in the present invention include not only a silver chloride emulsion and a silver bromide emulsion but also mixed silver halide emulsions.
• Typical examples of mixed silver halides which can be used include silver chlorobromide, silver chloroiodobromide and silver iodobromide.
• silver chloroiodobromide, silver iodochloride, or silver iodobromide each having an iodide content of 3 mole% or less silver chloride, silver bromide, and silver chlorobromide are more preferred.
• the interior and the surface of the silver halide grain may differ, the silver halide grain may have such a multiphase structure as to have epitaxial faces, or the silver halide grain may be uniform throughout.
• the silver halide grains of the above-described kinds may be present as a mixture.
• a means grain size of the silver halide grains employed in the present invention refers to a grain diameter in case of grains which are spherical or approximately spherical in shape, while it refers to an edge length in case of cubic grains, and in both cases, it is represented by a mean value based on the projected area of the grains) ranges preferably from 0.1 micron to 2 microns, particularly preferably from 0.15 micron to I micron.
• the distribution of the grain size may be either narrow or broad.
• a so-called monodispersed silver halide emulsion having a grain size distribution so narrow that at least 90%, preferably at least 95%, of the grains fall within the range of ⁇ 40% of the number or weight average grain size can be used.
• monodispersed silver halide emulsions having substantially the same color sensitivity but differing in grain size can be coated in a single layer as a mixture, or they can be coated separately in a multilayer.
• two or more polydispersed silver halide emulsions or a combination of monodispersed and polydispersed emulsions may be coated as a mixture or separately in a multilayer.
• the silver halide grains to be employed in the present invention may have a regular crystal form such as that of a cube, an octahedron, a dodecahedron, or a tetradecahedron, or an irregular crystal form, such as that of the sphere or so on. Also, the grains may have a composite form of these crystal forms. Moreover, the grains may have a tabular form in which a grain diameter is greater than a grain thickness by a factor of 5 or more, particularly 8 or more. Emulsions in which such tabular grains account for 50% or more of the total projected area of the grains may be employed in this invention. Emulsions which contain silver halide grains having various kinds of crystal forms as a mixture may be employed. These various kinds of emulsions may be either those which form a latent image predominantly at the surface of the grain (surface latent image type) or those which mainly form a latent image inside the grains (internal latent image type).
• photographic emulsions can be prepared using various methods as described, e.g., in P. Grafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), G.F. Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), V.L. Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966), and so on. More specifically, any processes, e.g., the acid process, the neutral process, the ammoniacal process, and so on, can be employed.
• a method in which silver halide grains are produced in the presence of excess silver ions (the so-called reverse mixing method) can be employed.
• the so-called controlled double jet method in which the pAg of the liquid phase where silver halide grains are to be precipitated is maintained constant may be employed. According to this method, silver halide emulsions having a regular crystal form and an almost uniform grain size can be obtained.
• the emulsions used in the present invention are, in general, those that are subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in these steps are described in Research Disclosure, No. 17643 and ibid. , No. 18716, and the relevant parts therein are listed in the following Table.
• color couplers may be used in the present invention, and specific examples thereof are described in the patent specifications referred to in the aforesaid Research Disclosure, No. 17643, VII-C through G.
• Important dye-forming couplers are those capable of forming three primary colors (of yellow, magenta, and cyan) in a subtractive color process by color development, and specific examples of nondiffusible four-equivalent or two-equivalent couplers which may be used in the present invention are described in the patent specifications referred to in Research Disclosure, No. 17643, VII-C and D.
• other couplers as mentioned below may also preferably be used in the present invention.
• yellow couplers which may be used in the present invention are hydrophobic acylacetamide type couplers having a ballast group. Specific examples thereof are described, for example, in U.S. Patents 2,407,210, 2,875,057, and 3,265,506. Two-equivalent yellow couplers are particularly preferably used in the present invention; and typical examples thereof are oxygen atom-releasing type yellow couplers as described in U.S. Patents 3,408,194, 3,447,928, 3,933,501, and 4,022,620; and nitrogen atom-releasing type yellow couplers as described in Japanese Patent Publication No. 10739/83, U.S. Patents 4,401,752 and 4,326,024, Research Disclosure , No.
• a-Pivaloylacetanilide type couplers are good in fastness, especially to light, of the formed dyes; and, on the other hand, a-benzoylacetanilide type couplers are high in color density of the formed dyes.
• Magenta couplers which may be used in combination with the pyrazoloazole type coupler in the present invention are ballast group-containing hydrophobic indazolone type or cyanoacetyl type couplers, preferably 5-pyrazolone type or pyrazoloazole type couplers.
• the 5-pyrazolone type couplers those whose 3- position is substituted by an arylamino group or an acylamino group are preferred because of hue and color density of the formed dyes.
• Typical examples of these couplers are described in U.S. Patents 2,311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896, and 3,936,015.
• ballast group-containing 5-pyrazolone type couplers as described in European Patent 73,636 are preferred because they provide a high color density.
• cyan couplers which can be used in the present invention
• hydrophobic and diffusion-resistant naphthol type and phenol type couplers are exemplified.
• Typical examples thereof include naphthol type couplers as described in U.S. Patent 2.474,293 and preferably oxygen atom-releasing type two-equivalent naphthol type couplers as described in U.S. Patents 4,052,212, 4,146,396, 4,228,233 and 4,296,200, etc.
• Specific examples of phenol type couplers are described in U.S. Patents 2,369,929, 2,801,171, 2,772,162 and 2,895,826, etc.
• Cyan couplers capable of forming cyan dyes fast to humidity and temperature are preferably used in the present invention.
• Typical examples thereof include phenol type cyan couplers having an alkyl group more than a methyl group at the meta-position of the phenol nucleus as described in U.S. Patent 3,772,002, 2,5-diacylamino-substituted phenol type couplers as described in U.S. Patents 2,772,162, 3,758,308, 4,126,396, 4,334,011 and 4,327,173, West German Patent Application (OLS) No.
• phenol type couplers having a phenylureido group at the 2-position thereof and an acylamino group at the 5-position thereof as described in U.S. Patents 3,446,622, 4,333,999, 4,451,559 and 4,427,767, etc.
• cyan couplers of the naphthol type having a sulfonamido group or an amido group, etc. at the 5-position thereof as described in Japanese Patent Application (OPI) Nos. 237448/85, 153640/86 and 145557/86 are also preferably employed in the present invention because of excellent fastness of color images formed therefrom.
• couplers capable of forming appropriately diffusible dyes can be used together in order to improve graininess.
• Specific examples of such types of magenta couplers are described in U.S. Patent 4,366,237 and British Patent 2,125,570, etc. and those of yellow, magenta and cyan couplers are described in European Patent 96,570 and West German Patent Application (OLS) No. 3,234,533, etc.
• Dye forming couplers and the above described special couplers may form polymers including dimers or more.
• Typical examples of polymerized dye forming couplers are described in U.S. Patents 3,451,820 and 4,080,211, etc.
• Specific examples of polymerized magenta couplers are described in British Patent 2,102,173 and U.S. Patent 4,367,282, etc.
• Couplers capable of releasing a photographically useful residue during the course of coupling can also be employed preferably in the present invention.
• Specific examples of useful DIR couplers capable of releasing a development inhibitor are described in the patents cited in Research Disclosure, No. 17643 - (December, 1978), "VII-F" as mentioned above.
• the color photographic materials of the present invention may be developed by means of a conventional develop ing means as described, for example, in the aforesaid Research Disclosure, NO. 17643, pp. 28-29 and ibid., No. 18716, page 651, from left-hand column to right-hand column.
• the color photographic light-sensitive material of the present invention is generally subjected to washing or stabilization.
• the washing step is, in general, carried out using two or more tanks according to the countercurrent washing method for the purpose of saving water.
• the stabilizing step mention may be made of a multistage countercurrent stabilization processing which is to be carried out in place of the washing step, as described in Japanese Patent Application (OPI) No. 8543/82.
• OPI Japanese Patent Application
• a countercurrent bath having 2 to 9 tanks is required.
• To the stabilizing bath used in the present invention are added various kinds of compounds in order to stabilize the developed images.
• Typical examples of such additives include various buffering agents for adjusting the pH of the film to a proper value (ranging, e.g., from 3 to 8), such as those prepared by combining properly acids and alkalis selecting from borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, and the like , and formaldehyde.
• a proper value ranging, e.g., from 3 to 8
• the stabilizing bath may further contain a water softener (e.g., inorganic phosphoric acids, aminopolycarboxylic acids, organic phosphoric acids, aminopolyphosphonic acids, phosphonocarboxylic acids, or so on), a fertilizer (e.g., benzisothiazolinone, isothiazolone, 4-thiazolinebenzimidazole, halogenated phenols, or so on), a surface active agent, a fluorescent whitening agent, a hardener, and other various kinds of additives, if desired.
• a water softener e.g., inorganic phosphoric acids, aminopolycarboxylic acids, organic phosphoric acids, aminopolyphosphonic acids, phosphonocarboxylic acids, or so on
• a fertilizer e.g., benzisothiazolinone, isothiazolone, 4-thiazolinebenzimidazole, halogenated phenols, or so on
• ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosulfate, and the like are added to the stabilizing bath in order to control the pH of the processed film.
• the present invention can be applied to various kinds of color photographic materials.
• Representatives of such materials are color negative films for general use or motion picture use, color reversal films for slide use or television use, color paper, color positive films, color reversal paper, and so on.
• the whole amount of the emulsion dispersion was added to 100 g of a silver chlorobromide emulsion having a bromide content of 50 mole% (containing 6.5 g of silver), and 10 ml of a 2% aqueous solution of 2,4-dihydroxy-6-chloro-s-triazine sodium salt was further added thereto as a hardener.
• the thus prepared composition was coated on a paper support laminated with polyethylene on both the sides thereof in such an amount that the silver coverage was 200 rng/rn*.
• a gelatin layer was provided on the coated layer to prepare a sample. This sample is referred to as Sample A.
• emulsion dispersions were prepared in the same manner as described above except that the magenta coupler was replaced by 15.2 g of Coupler (8), 14.3 g of Coupler (15), and 10.0 g of Coupler (29), respectively and that the amount of tri(2-ethylhexyl) phosphate was altered to 19 ml, 17 ml, and 16 ml, respectively.
• These emulsion dispersions each was mixed with the same amount of the same silver chlorobromide emulsion as described above and coated on the same support at the same silver coverage as described above. The thus obtained samples were referred to as Sample B, Sample C, and Sample D, respectively.
• a comparative sample was prepared in the same manner as described above except that 8.9 g of the following compound, was used as the magenta coupler and that tri(2-ethylhexyl) phosphate was used in an amount of 18 instead of 20 ml.
• Samples A to D and the comparative sample were subjected to 1000 C.M.S. wedge exposure and the processed using the following processing solutions.
• the couplers of the present invention are superior in both sensitivity and gradation to the coupler having an alkyl group at the 6-position. This is attributable to introduction of an alkoxy group or an aryloxy group at the 6-position, whereby the coupling activity is enhanced and the color-forming efficiency is improved.
• a first layer (undermost layer) to a seventh layer (uppermost layer) were coated in sequence on a paper support laminated with polyethylene on both sides thereof to prepare color photographic materials E, F and G.
• each third layer in which an emulsion dispersion of magenta coupler and a silver halide emulsion were contained were prepared in the same manner as in Example I.
• the couplers of the present invention can contribute to attainment of photographic characteristics with less fluctuation by short-time development.
• High activity and high color-forming efficiency of which the couplers of the present invention are possessed as compared with those of conventional pyrazoloazole couplers are advantageous in designing photographic materials.
• the couplers of the present invention are found to have excellent properties.
• the whole amount of the emulsion dispersion was added to 100 g of a silver chlorobromide emulsion having a bromide content of 30 mole% (containing 6.5 g of silver), and 10 ml of a 2% aqueous solution of 2,4-dihydroxy-6-chloro-s-triazine sodium salt was further added thereto as a hardener.
• the thus prepared composition was coated on a paper support laminated with polyethylene on both the sides thereof in such an amount that a silver coverage was 200 mg/m 2 .
• a gelatin layer was provided on the coated layer to prepare a sample. This sample is referred to as Sample I-(A).
• Comparative Sample (I) was prepared in the same manner as described above except that 8.9 g (16.8 mmol) of the following Comparative Compound (I): (described in European Patent Application No. 176,804A) was used as the magenta coupler and that tri(2-ethylhexyl) phosphate was used in an amount of 18 ml instead of 20 ml.
• Comparative Sample (2) was prepared using 8.9 g of the following Comparative Compound (2): (described in European Patent Application No. 176,804A)
• a blue-sensitive emulsion was prepared by adding a blue-sensitive dye illustrated below to a silver chlorobromide emulsion (having a bromide content of 50 mol% and containing Ag in an amount of 70 g of per kg of the emulsion) in an amount of 2.25 x 10- 4 mole per mole of silver chlorobromide.
• the emulsion dispersion and the silver chlorobromide emulsion was mixed with each other, and gelatin was further added thereto in such an amount as to adjust concentrations of the ingredients to values set forth in Table 5.
• a coating composition for the first layer was prepared.
• Coating compositions for the second to seventh layers were prepared in a similar manner as described above.
• I-oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardener.
• Spectral sensitizers employed in the respective emulsion layers are illustrated below.
• the following dyes were incorporated in the emulsion layers as their respective irradiation preventing dyes.
• the compositions were simultaneously coated to prepare a multilayered silver halide color photographic material.
• Various coating compositions for the third layer were prepared using the couplers represented by the formula (I) or (II) of the present invention and the comparative couplers as the magenta coupler and changing the formulation variously as shown in Table 6. Using these coating compositions respectively, multilayered color photographic materials were prepared and referred to as Samples II-A to II-N.
• the sensitivity is a relative value, taking the sensitivity of Sample II-A, and Sample E attained by 1.5 minutes' development as 100 (comparison was carried out using samples having the same volume).
• the gradation (-y) is expressed in terms of a slope of the characteristic curve in the straight line portion corresponding to the density range of from 0.6 to 2.0.
• the maximum density means a maximum density of magenta dye image.
• Example 8 For the purpose of sensitometry evaluation, the samples prepared in Example 4, Samples II-A to II-N, were subjected to wedge exposure in a conventional manner and processed according to the following processing steps using processing solutions having formulations described below. The results obtained are shown in Table 8.
• the sensitivity is a relative value, taking the sensitivity of Samples II-A, and II-E attained by 30 seconds' development as 100.
• the gradation ( ⁇ ) is expressed in terms of a slope of the characteristic curve in the straight line portion corresponding to the density range of from 0.6 to 2.0.
• Gamma values in parentheses are slopes of individual straight line portions because image densities did not go up to 2.0 under such conditions.
• the maximum density means a maximum density of magenta dye image.
• the Samples II-B to 11-D and 11-F to II-N in which the couplers of the present invention were incorporated had enhanced sensitivity and improved gradation and provided high color density of the developed image.
• Second Layer (antihalation layer):
• Samples III-B to III-N were prepared in the same manner as Sample III-A, or III-A 2 except that the comparative magenta coupler (*15) was replaced by an equimolar amount of each of Couplers (6), (8), (10), - (17), (26), (28), (30), (31), (36), (37), (42), (44), and (45).
• These samples III-A to III-N were subjected to wedge exposure in a conventional manner and then processed according to the following processing steps using processing solutions having the formulations described below. The thus obtained sensitometric samples were examined for photographic characteristics, and the results obtained are shown in Table 9.
• the gradation (y) is a slope of the characteristic curve in the straight line portion corresponding to the density range of 0.6 to 2.0.
• the maximum density means a maximum density of magenta dye image.
• Samples III-B to III-N in which the couplers of the present invention are employed had improved gradation ( ⁇ ) and produced high color density of the developed image.
• Second Layer (Gelatin interlaver):
• Emulsion (b) 2,5-Di-t-octylhydroquinone was dissolved in a mixture of 100 ml of dibutyl phthalate and 100 ml of ethyl acetate. The solution and I kg of a 10% gelatin aqueous solution were stirred at a high speed to prepare an emulsion (referred to as Emulsion (b)). A 2 kg portion of Emulsion (b) was mixed with a 1.5 kg portion of 10% gelatin, and the mixture was coated in a dry thickness of I micron.
• Emulsion (c) A 500 g portion of Emulsion (c) was mixed with a I kg portion of a red-sensitive silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin and having an iodide content of 4 mol%). The mixture was coated in a dry thickness of I micron (silver coverage: 0.5 g/m 2 ).
• Emulsion (c) was mixed with a I kg portion of a red-sensitive silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin and having an iodide content of 2.5 mol%), and the mixture was coated in a dry thickness of 2.5 microns (silver coverage: 0.8 g/m 2 ).
• Emulsion (b) was mixed with a I kg portion of 10% gelatin, and the mixture was coated in a dry thickness of I micron.
• Emulsion (d) An emulsion was prepared in the same manner as the emulsion for the 3rd layer except that Comparative Magenta Coupler (I) (in Sample IV-A,) or Comparative Magenta Coupler (2) (in Sample IV-A 2 ) was used in place of the cyan coupler. This emulsion was referred to as Emulsion (d).
• Emulsion (d) A 300 g portion of Emulsion (d) was mixed with a I kg portion of a green-sensitive silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin and having an iodide content of 3 mol%), and the mixture was coated in a dry thickness of 2.0 microns (silver coverage: 0.7 g/m 2 ).
• Emulsion (d) A 1000 g portion of Emulsion (d) was mixed with a I kg portion of a green-sensitive silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin and having an iodide content of 2.5 mol%), and the mixture was coated in a dry thickness of 2.0 microns (silver coverage: 0.7 g/m 2 ).
• Emulsion (b) A I kg portion of Emulsion (b) was mixed with a I kg portion of 10% gelatin, and the mixture was coated in a dry thickness of 0.5 micron.
• An emulsion containing yellow colloidal silver was coated in a dry thickness of I micron.
• Emulsion (e) A 1000 g portion of Emulsion (e) was mixed with a I kg portion of a blue-sensitive silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin and having iodide content of 2.5 mol%), and the mixture was coated in a dry thickness of 3 microns (silver coverage: I.I g/m 2 ).
• Emulsion (a) was mixed with 10% gelatin water, and coating aids, and the mixture was coated in a dry thickness of 2 microns.
• a 10% gelatin aqueous solution containing a fine grain emulsion in which the individual grain surfaces were fogged (grain size: 0.06 micron, I mol% silver iodobromide emulsion) was so coated as to have a dry thickness of 0.8 micron and a silver coverage of 0.1 g/m 2 .
• Samples IV-B to IV-P were prepared in the same manner as the Sample IV-A, or IV-A 2 except that Comparative Magenta Coupler (1) or (2) was replaced by an equimolar amount of each of Couplers (6), (8), (10), (17), (26), (28), (30), (31), (36), (37), (42), (44), (45), (49), and (51), respectively.
• the gradation y) is a slope of the characteristic curve in the straight line portion corresponding to the density range of 0.6 to 20.
• the maximum density means a maximum density of magenta dye image.
• Samples IV-B to IV-P in which the couplers of the present invention are employed had improved gradation (y) and produced high color density of the developed image.
• a gelatin layer containing black colloidal silver is provided.
• a layer containing a silver iodobromide emulsion (having an iodide content of 5 mol% and a silver coverage of 1.6 g/m 2 ), 4.5 x 10 -4 mol/mol silver of Sensitizing Dye I, 1.5 x 10 -4 mol/mol silver of Sensitizing Dye II, 0.04 mol/mol silver of Coupler EX-I, 0.003 mol/mol silver of Coupler EX-3, and 0.0006 mol/mol silver of Coupler EX-9.
• a layer containing a silver iodobromide emulsion (having an iodide content of 10 mol% and a silver coverage of 1.4 g/m 2 ), 3 x 10 -4 mol/mol silver of Sensitizing Dye I, I x 10 -4 mol/mol silver of Sensitizing Dye II, 0.002 mol/mol silver of Coupler EX-I, 0.02 mol/mol silver of Coupler EX-2, and 0.0016 mol/mol of Coupler EX-3.
• a layer containing a silver iodobromide emulsion (having an iodide content of 4 mol% and a silver coverage of 1.2 g/m 2 ), 5 x 10 -4 mol/mol silver of Sensitizing Dye III, 2 x 10 -4 mol/mol silver of Sensitizing Dye IV, and 0.05 mol/mol silver of Comparative Magenta Coupler (I) or (2).
• a layer containing a silver iodobromide emulsion (having an iodide content of 8 mol% and a silver coverage of 1.3 g/m 2 ), 3 x 10 -4 mol/mol silver of Sensitizing Dye III, 1.2 ;TS 10;S-;S4 mol/mol silver of Sensitizing Dye IV, and 0.017 mol/mol silver of Comparative Magenta Coupler (I) or (2).
• a layer containing a silver iodobromide emulsion (having an iodide content of 6 mol% and a silver coverage of 0.7 g/m 2 , 0.25 mol,/mol silver of Coupler EX-4, and 0.015 mol/mol silver of Coupler EX-5.
• a gelatin layer containing silver iodobromide (having an iodide content of I mol% and a mean grain size of 0.07 micron and a silver coverage of 0.5 g/m 2 ) and an emulsion dispersion of UV Light Absorbent UV-I.
• a gelatin layer containing polymethyl methacrylate particles (having a diameter of about 1.5 microns).
• Gelatin Hardener H-I and a surface active agent were incorporated in each of the foregoing layers.
• Samples V-B to V-P were prepared in the same manner Sample V-A, or V-A 2 except that Comparative Magenta Coupler (I) or (2) was replaced by an equimolar amount of each of Couplers (6), (8), (10), (17), (26), (28), (30), (31), (36), (37), (42), (44), (45), (49), and (51), respectively.
• These Samples V-A to V-P were subjected to wedge exposure in a conventional manner and then processed according to the following processing steps using processing solutions having the formulations described below.
• compositions of the processing solutions used were as follows.
• the sensitivity is expressed in terms of a relative value of a reciprocal of an exposure required for providing a density of fog +0.2, taking the sensitivity of Sample V-A, as 100.
• the couplers of the present invention have less dependence of sensitivity, gradation and maximum density upon color development time and can exhibit photographic characteristics with smaller fluctuation by short-time development as compared with the conventional couplers having an alkyl group at the 6-position.
• the couplers of the present invention possesses higher activity and higher color-forming efficiency as compared with the conventional pyrazoloazole couplers, they are advantageous in designing photographic materials.
• the couplers of the present invention are found to have excellent properties.

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• 1986
  • 1986-11-25 EP EP19860116345 patent/EP0226849B1/de not_active Expired
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