EP0170164A2 - Matériau photographique couleur à l'halogénure d'argent sensible à la lumière - Google Patents

Matériau photographique couleur à l'halogénure d'argent sensible à la lumière Download PDF

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Publication number
EP0170164A2
EP0170164A2 EP85108995A EP85108995A EP0170164A2 EP 0170164 A2 EP0170164 A2 EP 0170164A2 EP 85108995 A EP85108995 A EP 85108995A EP 85108995 A EP85108995 A EP 85108995A EP 0170164 A2 EP0170164 A2 EP 0170164A2
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Prior art keywords
group
sensitive material
light
atom
general formula
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EP85108995A
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German (de)
English (en)
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EP0170164A3 (en
EP0170164B1 (fr
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Toshio Kawagishi
Kiyoshi Nakazyo
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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
    • G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
    • G03C7/3005—Combinations of couplers and photographic additives
    • G03C7/3008—Combinations of couplers having the coupling site in rings of cyclic compounds and photographic additives
    • G03C7/301—Combinations of couplers having the coupling site in pyrazoloazole rings and photographic additives

Definitions

  • This invention relates to a silver halide color photographic light-sensitive material and, more particularly, to a silver halide color photographic light-sensitive material having improved color reproducibility and color image fastness.
  • silver halide color photographic light-sensitive materials silver halide emulsions and so-called dye forming couplers (hereinafter merely referred to as couplers) capable of reacting with an oxidation product of an aromatic primary amine developing agent are often employed.
  • couplers dye forming couplers
  • a combination of a yellow coupler, a cyan coupler and a magenta coupler is usually employed in color photographic light-sensitive materials.
  • 5-pyrazolone type couplers widely used as magenta couplers have serious problems in color reproduction, since they show a side absorption around 430 nm and show a poor toe cut of absorption on the longer wavelength side.
  • Magenta dyes obtained by coupling this type of coupler with an oxidation product of an aromatic primary amine developing agent do not have a side absorption around 430 nm as an ethyl acetate solution, and provide a very pure magenta color with a good toe cut of absorption on the longer wavelength side.
  • An object of the present invention is to provide a silver halide color photographic light-sensitive material having an improved color reproducibility which is attained by forming a magenta color image with a good hue and a sharp toe cut of absorption on the longer wavelength side using a pyrazoloazole type coupler.
  • Another object of the present invention is to provide a silver halide color photographic light-sensitive material having an improved color image fastness using a pyrazoloazole coupler.
  • a silver halide color photographic light-sensitive material which comprises a support having thereon at least one silver halide emulsion layer containing dispersed therein at least one magenta coupler represented by the following general formula (I):
  • Figures 1 and 2 show absorption spectra of magenta color dyes.
  • the absorption spectrum for Comparative Example 2 almost overlaps that of Comparative Example 3 on the shorter wavelength side with respect to the absorption maximum.
  • A, B and D almost overlap one another on the shorter wavelength side with respect to the absorption maximum.
  • a dimer or a higher polymer means two or more groups represented by the general formula (I) are present in each molecule, including bis derivatives and polymer couplers.
  • the polymer couplers may be homopolymers comprising one or more monomers having the moiety represented by the general formula (I) (preferably having an ethylenically unsaturated group) or may be copolymers of at least one such monomer with at least one ethylenically unsaturated monomer which does not couple with an oxidation product of an aromatic primary amine developing agent and, therefore, does not form a color dye.
  • Examples of compounds represented by the general formula (I) include 1H-imidazo[1,2-b]pyrazoles and 1H-pyrazolo[1,5-b][1,2,4]triazoles, which are respectively represented by the following general formulae (III) and (IV). Of these, those compounds which are represented by the general formula (IV) are particularly preferable.
  • R 1 , R 2 and R 6 each represents a hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom, etc.), an alkyl group (e.g., a methyl group, a propyl group, a t-butyl group, a trifluoromethyl group, a tridecyl group, a 3-(2,4-di-t-amylphenoxy)propyl group, a 2-dodecyloxyethyl group, a 3-phenoxypropyl group, a 2-hexylsulfonylethyl group, a cyclopentyl group, a benzyl group, etc.), an aryl group (e.g., a phenyl group, a 4-t-butylphenyl group, a 2,4-di-t-amylphenyl group, a 4-tetradecanamidophenyl group, etc.
  • R 1 , R 2 , R 6 or X represents a divalent group to form a bis derivative
  • such divalent group includes a substituted or unsubstituted alkylene group (e.g., a methylene group, an ethylene group, a 1,10- decylene group, etc.), a substituted or unsubstituted phenylene group (e.g., a 1,4-phenylene group, a 1,3-phenylene group, etc.), or -NHCO-R 7 -CONH- (wherein R 7 represents a substituted or unsubstituted alkylene or phenylene group).
  • a substituted or unsubstituted alkylene group e.g., a methylene group, an ethylene group, a 1,10- decylene group, etc.
  • a substituted or unsubstituted phenylene group e.g., a 1,4-phenylene group, a 1,3-phenylene
  • the linking group represented by R 1 , R 2 or R 6 includes an alkylene group (a substituted or unsubstituted alkylene group, e.g., a methylene group, an ethylene group, a 1,10-decylene group, -CH 2 CH 2 OCH 2 CH 2 -, etc.), a phenylene group (a substituted or unsubstituted phenylene group, e.g., a 1,4-phenylene group, a 1,3-phenylene group, etc.), -NHCO-, -CONH-, -O-, -OCO-, or an aralkylene group (e.g., etc.) alone or in combination thereof.
  • alkylene group a substituted or unsubstituted alkylene group, e.g., a methylene group, an ethylene group, a 1,10-decylene group, -CH 2 CH 2 OCH 2 CH 2 -, etc.
  • the ethylenically unsaturated group in the vinyl monomer includes those which have other substituents than are represented by the general formulae (III) and (IV).
  • Preferred substituents are a hydrogen atom, a chlorine atom or a lower alkyl group containing 1 to 4 carbon atoms.
  • Illustrative examples of ethylenically unsaturated monomers which do not couple with an oxidation product of an aromatic primary amine developing agent and therefore do not form a color dye include acrylic acid, a-chloroacrylic acid, a-alacrylic acids (e.g., methacrylic acid, etc.), esters or amides derived from these acrylic acids (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, lautyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and 8-hydroxymethacrylate),
  • couplers represented by the general formula (III) or (IV) are illustrated below. However, the present invention is not to be construed as being limited at all to the couplers set forth below.
  • the reason for limiting the total number of carbon atoms of the substituents represented by R 3 , R 4 and R 5 in the general formula (II) to 12 to 60 is that the improved effects of the present invention are reduced when the total is outside this range.
  • the solubility of coupler is so reduced that, in some cases, the coupler forms a precipitate, thus the total number of carbon atoms of more than 60 is not preferable.
  • the alkyl group represented by R 3 , R 4 or R 5 may be either a straight chain alkyl group or a branched chain alkyl group, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, etc.
  • the cycloalkyl group represented by R 3 , R 4 or R 5 can be,
  • the aryl group represented by R 3 , R 4 or R 5 can be a phenyl group, a naphthyl group, etc.
  • the alkenyl group represented by R 3 , R 4 or R 5 can he a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a decenyl group, a dodecenyl group, an octadecenyl group, etc.
  • These alkyl, cycloalkyl, aryl and alkenyl groups may also have one or more substituents.
  • substituents for the alkyl, cycloalkyl and alkenyl groups include a halogen atom (e.g., a fluorine atom, a chlorine atom, etc.), an alkoxy group (e.g., a methoxy group, an ethoxy group, a butoxy group, etc.), an aryl group (e.g., a phenyl group, a tolyl group, a naphthyl group, etc.), an aryloxy group (e.g., a phenoxy group, etc.), an alkenyl group, an alkoxycarbonyl group, etc., and examples of substituents for the aryl group include an alkyl group, etc., in addition to those for the alkyl, cycloalkyl and alkenyl group described above.
  • substituents for the aryl group include an alkyl group, etc., in addition to those for the alkyl, cycloalkyl and alkenyl
  • R 3 , R 4 and R 5 include a tolyl group, a 2-ethylhexyl group, a 7-methyloctyl group, a cyclohexyl group, a straight chain alkyl group containing 8 to 18 carbon atoms, etc.
  • high boiling organic solvents means those organic solvents which have a boiling point of about 175°C or above at atmospheric pressure.
  • the high boiling organic solvent represented by the general formula (II) may be used in any amount depending upon the kind and the amount of magenta coupler represented by the general formula (I).
  • the ratio of the high boiling organic solvent to magenta coupler is preferably about 0.05:1 to about 20:1 by weight.
  • the high boiling organic solvent to be used in the present invention represented by the general formula (II) may be used in combination with other conventionally known high boiling organic solvents as long as the objects of the present invention can be achieved.
  • solvents examples include phthalate type solvents (e.g., dibutyl phthalate, di-2-ethylhexyl phthalate, etc.), amide type solvents (e.g., N,N-diethyldodecanamide), fatty acid ester type solvents, benzoate type solvents, phenolic solvents (e.g., 2,5-di-tert-amylphenol, etc.), etc.
  • Dyes derived from a coupler must have a preferable hue for color reproduction. Specifically, the color region of the main absorption is in a suitable range, and a distinct color dye with less unnecessary absorption is desirable.
  • the pattern of the absorption spectrum of the dye on, particularly, the longer wavelength side greatly influences the distinctness of color. The smaller the difference between the wavelength at which the absorption is 50%, 10% or 2% of the maximum absorption and the wavelength at which the absorption is maximal, the sharper the hue. Dyes with such sharp hue provide a distinct color dye with less color stain not only when used alone but when used together with other dyes with different hues.
  • the phrase "toe cut of absorption" can be expressed quantitatively in terms of the above-described 10% or 2% absorption wavelength width, etc.
  • magenta couplers and the high boiling organic solvents in accordance with the present invention can be dispersed and incorporated into at least one hydrophilic organic colloidal layer constituting a photographic light-sensitive layer.
  • the high boiling organic solvents represented by the general formula (II) generally have an extremely good solubility for the couplers of the present invention.
  • other coupler solvents such as phthalic ester type coupler solvents, low boiling organic solvents, etc., may be used in combination.
  • a low boiling organic solvent having a boiling point of about 30 to about 150°C such as a lower alkyl acetate (e.g., ethyl acetate, butyl acetate, etc.), ethyl propionate, sec-butyl alcohol, methyl isobutyl ketone, B-ethoxyethyl acetate, methyl Cellosolve acetate, etc.
  • a lower alkyl acetate e.g., ethyl acetate, butyl acetate, etc.
  • ethyl propionate sec-butyl alcohol
  • methyl isobutyl ketone methyl isobutyl ketone
  • B-ethoxyethyl acetate methyl Cellosolve acetate, etc.
  • the coupler of the present invention may be dissolved in the low boiling organic solvent described above, then the high boiling organic solvent represented by the general formula (II) may be added thereto.
  • the mixing ratio of other coupler solvents to the high boiling organic solvents represented by the general formula (II) is in the range of about 0.1 to 10, preferably about 0.2 to 5 by weight.
  • the dispersing technique using a polymer described in, for example, Japanese Patent Publication No. 39853/76 and Japanese Patent Application (OPI) No. 59943/76 may be employed in combination.
  • couplers have an acid group such as a carboxylic acid group or a sulfonic acid group, they may be introduced into the hydrophilic colloid layer as an alkaline aqueous solution.
  • gelatin As a binder or protective colloid which can be used for emulsion layers or interlayers of the light-sensitive material of the present invention, gelatin is advantageously used. However, other hydrophilic colloids may be used alone or in combination with gelatin.
  • gelatin which can be used in the present invention, either lime-processed gelatin or acid- processed gelatin may be used. Detailed descriptions on preparation of gelatin are given in Arser Nais, The Macromolecular Chemistry of Gelatin, Academic Press (1964).
  • any of silver bromide, silver bromoiodide, silver chlorobromoiodide, silver chlorobromide, and silver chloride may be used as the silver halide.
  • a preferred silver halide is silver bromoiodide containing 15 mol% or less silver iodide, particularly 2 mol% to 12 mol% silver iodide.
  • the silver halide grains in the photographic emulsion are not particularly limited as to mean particle size (particle diameter with respect to spherical or approximately spherical particles, and edge length with cubic particles; presented in terms of an average based on projected area), with particle size of about 3 ⁇ m or less being preferable.
  • the particle size distribution can be either narrow or broad.
  • Silver halide grains in the photographic emulsion may be in a regular crystal form such as a cubic or octahedral form, in an irregular crystal form such as a spherical or platy form, or in a mixed form thereof, or may comprise a mixture of grains in different forms.
  • an emulsion in which superplaty silver halide grains having a diameter-to-thickness ratio of about 5:1 or more account for 50% or more of the total projected area may also be used.
  • the silver halide grains may have an inner portion and a surfafe layer different from each other in phase composition.
  • silver halide grains of the type forming latent images mainly on the surface thereof and grains of the type forming latent images mainly within them may be used.
  • the photographic emulsion which can be used in the present invention can be prepared by the processes described in P. Glafkides, Chimie et Physique Photo- graphique, Paul Montel (1967), G.F. Duffin, Photographic Emulsion Chemistry, The Focal Press (1966), V.L. Zelikman et al., Making and Coating Photographic Emulsions, The Focal Press (1964), etc. That is, any of an acidic process, a neutral process, and an ammoniacal process can be used.
  • any of reacting a soluble silver salt with a soluble halide salt any of the single jet mixing method, double jet mixing method and a combination thereof may be employed.
  • a process of forming grains in the presence of excess silver ion can be employed as well.
  • a process called a controlled double jet process wherein the pAg in the liquid phase in which the silver halide is formed is kept constant can be employed.
  • This process provides a silver halide emulsion containing silver halide grains of a regular crystal form having an approximately uniform particle size.
  • Two or more silver halide emulsions separately prepared may be mixed for use.
  • cadmium salts zinc salts, lead salts, thallium salts, iridium salts or the complex salts thereof, rhodium salts or the complex salts thereof, iron salts or the complex salts thereof, etc., may also be present.
  • Silver halide emulsions are usually subjected to chemical sensitization.
  • This chemical sensitization can be conducted according to the processes described in, for example, H. Frieser, Die Unen der Photo- graphischen Liste Too mit Silberhalogeniden, Akademische Verlagsgesellschaft (1968), pp. 675-734.
  • sulfur sensitization using active gelatin or sulfur-containing compounds capable of reacting with silver e.g., thiosulfates, thioureas, mercapto compounds, rhodanines, etc.
  • reduction sensitization using a reductive substance e.g., stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, etc.
  • noble metal sensitization using compounds of noble metals e.g., complex salts of the Group VIII metals such as Pt, Ir, Pd, etc., as well as gold complex salts
  • noble metals e.g., complex salts of the Group VIII metals such as Pt, Ir, Pd, etc., as well as gold complex salts
  • Various compounds for the purpose of preventing formation of fog or stabilizing photographic properties may be incorporated in the photographic emulsion used in the present invention during the steps of producing, or during storage or processing of, light-sensitive materials. That is, many compounds known as antifoggants or stabilizers such as azoles (e.g., benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenz- imidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzo- triazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), etc.); mercaptopyrimidines; mercapto- triazines; thioketo compounds such as oxazolinethione; azaindenes (e.g.
  • the photographic light-sensitive material of the present invention may contain in its photographic emulsion layers or other hydrophilic colloidal layers various surfactants for various purposes such as improvement of coating properties, antistatic properties, slipping properties, emulsion dispersibility, antiadhesion properties, and photographic properties (for example, development acceleration, realization of contrasty tone, sensitization, etc.).
  • various surfactants for various purposes such as improvement of coating properties, antistatic properties, slipping properties, emulsion dispersibility, antiadhesion properties, and photographic properties (for example, development acceleration, realization of contrasty tone, sensitization, etc.).
  • the light-sensitive material of the present invention may contain a polyalkylene oxide or its ether, ester or amine derivative, a thioether compound, a thiomorpholine, a quaternary ammonium salt compound, a urethane derivative, a urea derivative, an imidazole derivative, a 3-pyrazolidone, etc., for the purpose of enhancing sensitivity or contrast or for accelerating development.
  • the photographic light-sensitive material of the present invention may contain in its photographic emulsion layer or other hydrophilic colloidal layer a dispersion of a water-insoluble or slightly water-soluble synthetic polymer for improving dimensional stability, etc.
  • Photographic emulsions used in the present invention may be spectrally sensitized with methine dyes or the like.
  • Dyes which can be used 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. In these dyes, any nuclei ordinarily used as basic hetero ring nuclei in cyanine dyes can be present.
  • 5- or 6-membered hetero ring nuclei such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, a thiobarbituric acid nucleus, etc.
  • ketomethylene structure- containing nuclei may be used as ketomethylene structure- containing nuclei.
  • sensitizing dyes may be used alone or in combination.
  • sensitizing dyes is often employed particularly for the purpose of supersensitization.
  • a dye which itself is not sensitizing or a substance which substantially does not absorb visible light and which shows a supersensitizing effect may be incorporated together with the sensitizing dye.
  • aminostilbene compounds substituted with a nitrogen-containing hetero ring for example, those described in U.S. Patents 2,933,390 and 3,635,721
  • aromatic organic acid-formaldehyde condensates for example, those described in U.S. Patent 3,743,510
  • cadmium salts for example, those described in U.S. Patent 3,743,510
  • the present invention may also be applied to a multilayered, multicolor photographic material comprising a support having thereon at least two layers with different spectral sensitivity.
  • Multilayered natural color photographic materials usually comprise a support having thereon at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer, and at least one blue-sensitive emulsion layer. The order of these layers may be optionally selected as the case demands.
  • the red-sensitive emulsion layer usually contains a cyan dye forming coupler, the green-sensitive emulsion layer a magenta dye forming coupler and the blue-sensitive emulsion layer a yellow dye forming coupler. However, in some cases, different combinations may be employed.
  • other dye forming couplers i.e., compounds capable of forming color dyes by oxidative coupling with an aromatic primary amine developing agent (e.g., a phenylenediamine derivative, an aminophenol derivative, etc.) in color development processing, may be used together with the coupler represented by the foregoing general formula (I).
  • an aromatic primary amine developing agent e.g., a phenylenediamine derivative, an aminophenol derivative, etc.
  • magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolo[5,1-c][1,-2,4]triazole couplers, pyrazolopyrazole couplers, pyrazolotetrazole couplers, open chain acylacetonitrile couplers, etc.
  • suitable yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides, etc.), etc.
  • suitable cyan couplers include naphthol couplers and phenol couplers.
  • nondiffusible couplers having a hydrophobic group called a ballast group or polymerized couplers are advantageous.
  • the couplers may be either 4-equivalent type or 2- equivalent type with respect to silver ion.
  • Colored couplers having a color correcting effect or couplers capable of releasing a development inhibitor upon development (called DIR couplers) may also be incorporated.
  • non-color-forming DIR coupling compounds capable of forming a colorless coupling reaction product and releasing a development inhibitor may also be incorporated.
  • Couplers of the present invention and the above-described couplers may of course be used in one and the same layer, or the same compound may be present in two or more different layers for attaining properties required for light-sensitive materials.
  • the photographic light-sensitive material of the present invention may contain an organic or inorganic hardener in its photographic emulsion layers or other hydrophilic colloidal layers.
  • an organic or inorganic hardener in its photographic emulsion layers or other hydrophilic colloidal layers.
  • chromium salts e.g., chromium alum, chromium acetate, etc.
  • aldehydes e.g., formaldehyde, glyoxal, glutaraldehyde, etc.
  • N-methylol compounds e.g., dimethylolurea, methyloldimethylhydantoin, etc.
  • dioxane derivatives e.g., 2,3-dihydroxydioxane, etc.
  • active vinyl compounds e.g., 1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.
  • the light-sensitive material according to the present invention contains a dye, an ultraviolet light absorbent, etc., in its hydrophilic colloidal layer, they may be mordanted with a cationic polymer or the like.
  • the light-sensitive material of the present invention may contain hydroquinone derivatives, aminophenol derivatives, ascorbic acid derivatives, etc., as color fog preventing agents.
  • the light-sensitive material of the present invention may contain in its hydrophilic colloidal layer an ultraviolet light absorbent.
  • an ultraviolet light absorbent for example, aryl group- substituted benzotriazole compounds (e.g., those described in U.S. Patent 3,533,794), 4-thiazolidone compounds (e.g., those described in U.S. Patents 3,314,794, 3,352,681, etc.), benzophenone compounds (e.g., those described in Japanese Patent Application (OPI) No. 2784/71), cinnamic ester compounds (e.g., those described in U.S. Patents 3,705,805 and 3,707,375), butadiene compounds (e.g., those described in U.S.
  • Patent 4,045,229), and benzoxidol compounds may be used.
  • Ultraviolet light absorbing couplers e.g., a-naphtholic and cyan dye forming couplers
  • ultraviolet light absorbing polymers etc.
  • These ultraviolet light absorbents may be mordanted in a specific layer.
  • the light-sensitive material of the present invention may contain a water-soluble dye as a filter dye or for various purposes such as prevention of irradiation.
  • a water-soluble dye as a filter dye or for various purposes such as prevention of irradiation.
  • examples of such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Oxonol dyes, hemioxonol dyes and merocyanine dyes are particularly useful of these dyes.
  • Color image stabilizers used in the present invention may be employed as a combination of two or more thereof.
  • Suitable known dye stabilizers include, for example, hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-hydroxyphenol derivatives, bisphenols, etc.
  • the photographic processing of the layers composed of photographic emulsion used in the present invention can be conducted by any known process and using known processing solutions described in, for example, Research Disclosure, 176, pages 28 to 30.
  • the processing temperature is usually between about 18 and about 50°C. However, temperatures lower than about 18°C or higher than about 50°C may be employed.
  • Suitable fixing solutions are those which have the same formulation as are ordinarily employed.
  • Organic sulfur compounds which are known to function as fixing agents can be used as well as thiosulfates and thiocyanates.
  • the fixing solution may contain a water-soluble aluminum salt as a hardener.
  • Color developers generally comprise an alkaline aqueous solution containing a color developing agent.
  • Suitable color developing agents include known primary aromatic amine developing agents such as phenylenediamines (e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-B-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-B-hydroxyethylanilien, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 4-amino-3-methyl-N-ethyl-N-ß-methoxyethylaniline, etc.).
  • phenylenediamines e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylan
  • the color developer may further contain pH buffers such as alkali metal sulfites, carbonates, borates or phosphates, development inhibitors or antifogging agents such as bromides, iodides, and organic antifogging agents and, if necessary, a water softener, a preservative (e.g., hydroxylamine), an organic solvent (e.g., benzyl alcohol, diethylene glycol, etc.), a development accelerator (e.g., polyethylene glycol, a quaternary ammonium salt, an amine, etc.), a dye forming coupler, a competitive coupler, a fogging agent (e.g., sodium borohydride), an auxiliary developing agent (e.g., 1-phenyl-3-pyrazolidone), a viscosity imparting agent, a polycarboxylic acid type chelating agent, an antioxidant, etc.
  • pH buffers such as alkali metal sulfites, carbonates, borates or
  • Color developed photographic emulsion layers are usually bleached. Bleaching may be conducted separately or simultaneously with fixing.
  • Compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI), copper (II), etc., peracids, quinones, nitroso compounds, etc., can be used as bleaching agents.
  • ferricyanates, dichromates, organic complex salts of iron (III) or cobalt (III) such as complex salts with an aminopolycarboxylic acid (e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, etc.) or an organic acid (e.g., citric acid, tartaric acid, maleic acid, etc.); persulfates, permanganates; nitrosophenol; etc., may be used.
  • aminopolycarboxylic acid e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, etc.
  • organic acid e.g., citric acid, tartaric acid, maleic acid, etc.
  • persulfates e.g., permanganates
  • potassium ferricyanate iron (III) sodium ethylenediaminetetraacetate
  • iron (III) ammonium ethylenediaminetetraacetate are particularly useful.
  • Iron (III) ethylenediaminetetraacetates are useful in both an independent bleaching solution and a monobath bleach-fixing solution.
  • the color photographic emulsion layer in accordance with the present invention forming the dye image layer is coated on a flexible support such as a synthetic resin film, paper or cloth usually used for photographic light-sensitive materials.
  • a flexible support such as a synthetic resin film, paper or cloth usually used for photographic light-sensitive materials.
  • Useful flexible supports include films composed of semisynthetic or synthetic high polymers such as cellulose nitrate, cellulose acetate butyrate, polystyrene, polyethylene terephthalate, polycarbonate, etc., and papers coated or liminated with a baryta layer or an a-olefin polymer (for example, polyethylene, polypropylene, etc.).
  • the support may be colored with a dye or a pigment, or may be blackened for intercepting light.
  • a white pigment is desirably added to the support or to a laminate layer.
  • Suitable white pigments include titanium dioxide, barium sulfate, zinc oxide, zinc sulfide, calcium carbonate, antimony trioxide, silica white, alumina white, titanium phosphate, etc. Of these, titanium dioxide, barium sulfate and zinc oxide are particularly useful.
  • the surface of the support is generally subbed for improving adhesion to a photographic emulsion layer or the like.
  • the support surface may be subjected to a corona discharge treatment, a UV light irradiation, or a flame treatment before or after the subbing treatment.
  • polymer laminated paper is often used as support.
  • a synthetic resin film containing a white pigment incorporated therein provides photographic images with particularly excellent saturation and expression in the dark areas as well as improved smoothness, glossiness and sharpness, thus being particularly preferred.
  • polyethylene terephthalate or cellulose acetate is particularly useful as the synthetic resin material, and barium sulfate or titanium oxide as the white pigment.
  • the surface and the back of the photographic material of the present invention may be laminated with plastic film.
  • plastic film Polyolefin, polyester, polyacrylate, polyvinyl acetate, polystyrene, butadiene-styrene copolymer, polycarbonate, etc.
  • Polyethylene terephthalate, vinyl alcohol-ethylene copolymer, polyethylene, etc. are particularly useful.
  • magenta dye obtained by reacting illustrative Coupler (M-6) with the following developing agent in the presence of ammonium persulfate and potassium sulfate was dissolved in an equal weight of illustrative Compound (S-7) using ethyl acetate as assistant solvent. After evaporating off the ethyl acetate, the visible absorption spectrum of this dye solution was measured.
  • magenta dye formed from the 5-pyrazolone type coupler does not show a great change in the absorption spectrum when dissolved in the phosphoric ester type solvent of the present invention and when dissolved in dibutyl phthalate
  • magenta dye formed from the pyrazoloazole type coupler of the present invention shows a greatly improved toe cut of the absorption spectrum on the longer wavelength side when dissolved in the phosphoric ester solvent of the present invention in comparison with the result obtained when it is dissolved in dibutyl phthalate.
  • magenta dye formed from the pyrazoloazole type coupler used in the present invention has no side absorption on the shorter wavelength side
  • the absorption spectrum of this magenta dye dissolved in the phosphoric ester solvent of the present invention is found to be suited for improving the color reproducibility of a color photograph.
  • the visual absorption spectrum was measured using an automatic recording spectrophotometer, Model 340, made by Hitachi, Ltd.
  • This emulsion dispersion was added to 100 g of a silver chlorobromide emulsion containing 50 mol% Br (containing 6.55 g of Ag), 10 m ⁇ of a 2% solution of 2,4-dihydroxy-6-chloro-s-triazine sodium salt (hardener) was added thereto, and the resulting mixture was coated in a silver amount of 200 mg/m 2 on a paper support laminated on both sides with polyethylene, followed by providing a gelatin layer thereon to prepare a sample. This sample was designated Sample A.
  • Samples B, C and D were prepared in the same manner as described above except for using illustrative Compound (S-7), di-2-ethylhexyl phthalate, and 2,4-di-tert-pentylphenol, respectively, in place of illustrative Compound (S-24).
  • Sample E was prepared using the-following comparative coupler in place of Coupler (M-6) used in Example 1 and illustrative Compound (S-24) as a solvent.
  • the high boiling phosphoric ester solvent of the present invention represented by the general formula (II) gives the pyrazoloazole type coupler of the present invention desirable spectral absorption characteristics as magenta color forming agent for subtractive color photography, i.e., less absorption on the longer wavelength side (600 nm and longer), no side absorption as is different from known pyrazolone type couplers, and less absorption on the shorter wavelength side, thus giving preferred spectral absorption curve for color reproduction.
  • a first layer (lowermost layer) to a seventh layer (uppermost layer) were coated as shown in Table I below on a paper laminated with polyethylene on both sides to prepare Color Photographic Light-Sensitive Materials F to J.
  • the coating solutions for forming the respective emulsion layers were prepared according to the procedures described in Example 2.
  • Coupler (M-6) is used as a magenta coupler and Compound (S-24) for Sample F, Compound (S-7) for Sample G, di-2-ethylhexyl phthalate for Sample H and 2,4-di-tert-pentylphenol for Sample I are used as a solvent in the 3rd layer.
  • Comparative Coupler (A) is used as a magenta coupler and Compound (S-24) is used as a solvent in the 3rd layer.
  • Samples F and G provided distinct images having high saturation.
  • Samples H, I and J provided images having low saturation, and Samples H and I gave violet tone, which is disadvantageous with respect to color reproduction.
  • Samples F to J prepared in Example 3 were exposed in the same manner as described in Example 2 using a B-G-R three color separation filter, and processed in the same manner.
  • the thus obtained samples were subjected to three week fading test using a fluorescent lamp fading apparatus (15,000 lux). The results thus obtained are shown in Table II below.
  • a multilayered color light-sensitive material comprising a cellulose triacetate film support having provided thereon in sequence the layers having the following formulations was prepared.
  • the thus obtained sample was subjected to gradation exposure using a 4,800°K white light, then to the following development processing, followed by sensitometry using a densitometer fitted with a status M filter.
  • the development processing was conducted at 38°C as follows.
  • This layer had a silver/coupler ratio of 17.0 and a silver coverage of 0.9 g/ m 2 .
  • High Speed Red-Sensitive Emulsion Layer A layer of gold and sulfur sensitized high speed silver iodobromide emulsion having a silver iodide content of 3.5 mol% and an average grain size of about 0.6 um and incorporated with the same sensitizing dye and cyan coupler emulsion as in the 3rd Layer.
  • This layer had a silver coverage of 0.4 g/m 2 .
  • 5th Layer Gelatin Interlayer 6th Layer: Interlayer
  • This layer had a silver coverage of 0.03 g/m 2 and a gelatin coverage of 0 . 4 g/ m 2 .
  • This layer had a silver/coupler ratio of 15.0 and a silver coverage of 0.50 g/ m 2 .
  • High Speed Green-Sensitive Emulsion Layer A layer of gold and sulfur sensitized high speed silver iodobromide emulsion having a silver iodide content of 2.6 mol% and an average grain size of about 0.9 ⁇ m and incorporated with the same sensitizing dye and magenta coupler emulsion as in the 7th layer described above.
  • This layer had a silver coverage of 0.30 g/m 2 .
  • 9th Layer Gelatin Interlayer
  • Yellow Filter Layer A layer of gelatin containing yellow colloidal silver.
  • This layer had a silver/coupler ratio of 13.0 and a silver coverage of 0 . 9 g/ m 2 .
  • High Speed Blue-Sensitive Emulsion Layer A layer of gold and sulfur sensitized high speed silver iodobromide emulsion layer having a silver iodide content of 2.6 mol% and an average grain size of about 1.0 ⁇ m and incorporated with the same yellow coupler emulsion as in 11th Layer described above.
  • This layer had a silver coverage of 0.6 g/ m 2 .
  • 13th Layer Protective Gelatin Layer
  • each of the above-mentioned layers was additionally incorporated with:
  • control sample The thus prepared color reversal photographic light-sensitive material (control sample) is designated as Sample 1.
  • Sample 2 was prepared in the same manner as with Sample 1 except for using Coupler (M-37) of the following structure: for green-sensitive emulsion layer in place of Coupler (M-49).
  • a control sample was prepared in absolutely the same manner as with Sample 1 except for changing the coupler in the green-sensitive emulsion layer to 1-(2,4,6-trichlorophenyl)-3-[3-(2,5-di-tert-amylphenoxyacetamido)benzamido]-5-pyrazolone and changing the silver/coupler ratio to 30.0 and the coated silver amount to 1.0 g/m 2 and 0.60 g/m 2 (in 8th Layer).
  • the thus prepared sample was designated as Sample 3.
  • Sample 4 Another control sample was prepared in absolutely the same manner as with Sample 1 except for using the same coupler as that used in Sample 3 and changing the coupler solvent to di(2-ethylhexyl) phthalate. The thus obtained sample was designated as Sample 4.
  • Samples 1 to 4 were exposed through an optical wedge fitted with a B-G-R three color filter and then subjected to color reversal processing in accordance with processing prescriptions 1, 2, 3 and 4 of the following:
  • Samples 1 and 2 obtained by the combination of the coupler of the present invention and the high-boiling solvent represented by the general formula (II) of the present invention i.e., the phosphate type oil
  • the high-boiling solvent represented by the general formula (II) of the present invention i.e., the phosphate type oil
  • the phosphate type oil provided magenta color images having higher distinctness and higher saturation than that of the magenta color images provided by Control Sanples 3 and 4.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP85108995A 1984-07-19 1985-07-18 Matériau photographique couleur à l'halogénure d'argent sensible à la lumière Expired EP0170164B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP150263/84 1984-07-19
JP15026384A JPS6128948A (ja) 1984-07-19 1984-07-19 ハロゲン化銀カラ−写真感光材料

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EP0170164A2 true EP0170164A2 (fr) 1986-02-05
EP0170164A3 EP0170164A3 (en) 1986-04-16
EP0170164B1 EP0170164B1 (fr) 1988-10-05

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US (1) USH122H (fr)
EP (1) EP0170164B1 (fr)
JP (1) JPS6128948A (fr)
DE (1) DE3565430D1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0173256A2 (fr) * 1984-08-24 1986-03-05 Fuji Photo Film Co., Ltd. Matériau photographique couleur à l'halogénure d'argent
EP0177765A1 (fr) 1984-09-06 1986-04-16 Fuji Photo Film Co., Ltd. Matériau photographique couleur à l'halogénure d'argent
EP0207596A2 (fr) * 1985-05-01 1987-01-07 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière
EP0236131A2 (fr) * 1986-03-05 1987-09-09 Konica Corporation Matériau photographique couleur à l'halogénure d'argent
EP0236986A2 (fr) * 1986-03-07 1987-09-16 Konica Corporation Méthode de traitement de matériau photographique à l'halogénure d'argent sensible à la lumière ayant une bonne reproduction de couleur et de blanc
EP0261244A1 (fr) * 1986-02-20 1988-03-30 Fuji Photo Film Co., Ltd. Procede de formation d'une image couleur
EP0574090A1 (fr) 1992-06-12 1993-12-15 Eastman Kodak Company Copulants à un équivalent et colorants à pKa bas libérés
EP0686873A1 (fr) 1994-06-08 1995-12-13 Eastman Kodak Company Elément photographique couleur comprenant des agents de blocage époxy nouveaux pour copulant magenta résiduel
EP0711804A2 (fr) 1994-11-14 1996-05-15 Ciba-Geigy Ag Stabilisateurs à la lumière latents
WO2005001568A1 (fr) * 2003-06-25 2005-01-06 Eastman Kodak Company Elements photographiques contenant un composant desagregeant, un coupleur formant pigment, un stabilisant et un solvant

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62201441A (ja) * 1986-02-28 1987-09-05 Konishiroku Photo Ind Co Ltd 色再現性および退色バランスに優れたハロゲン化銀写真感光材料
JPS62203160A (ja) * 1986-03-03 1987-09-07 Konishiroku Photo Ind Co Ltd 画質および皮膜物性が改良されたハロゲン化銀写真感光材料
JPH087405B2 (ja) * 1986-03-10 1996-01-29 コニカ株式会社 新規なマゼンタカプラーを含有するハロゲン化銀写真感光材料
US5006453A (en) * 1986-07-10 1991-04-09 Fuji Photo Film Co. Ltd. Silver halide color photographic material having improved dye image stability
JP2631466B2 (ja) * 1987-04-07 1997-07-16 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
JPH01131560A (ja) * 1987-08-05 1989-05-24 Konica Corp 色再現性のすぐれたハロゲン化銀写真感光材料
JP2711452B2 (ja) * 1987-08-13 1998-02-10 コニカ株式会社 色再現性の優れたハロゲン化銀写真感光材料
JP2876075B2 (ja) * 1989-05-25 1999-03-31 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
US5695921A (en) * 1995-03-31 1997-12-09 Eastman Kodak Company Photographic elements with magenta dye forming couplers and stabilizers
JP2009299746A (ja) * 2008-06-11 2009-12-24 Hiroyasu Minayoshi 孔閉塞用埋込栓および該孔閉塞用埋込栓を用いた孔閉塞方法
JP2021020422A (ja) * 2019-07-30 2021-02-18 尾池工業株式会社 転写フィルム、加飾フィルム成形体、加飾フィルム成形体の製造方法、サテンめっき調製品、容器、筐体、車両用内外装部材

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US3061432A (en) * 1958-06-21 1962-10-30 Agfa Ag Pyrazolino benzimidazole color coupler
US3676137A (en) * 1969-08-27 1972-07-11 Fuji Photo Film Co Ltd Color photographic light-sensitive element containing magenta coupler and alkyl phosphate solvent
US3725067A (en) * 1970-01-15 1973-04-03 Eastman Kodak Co Silver halide emulsion containing 1-h-pyrazolo(3,2-c)-s-triazole color couplers
GB2067301A (en) * 1979-12-07 1981-07-22 Konishiroku Photo Ind Photographic material containing a high boiling solvent
EP0119741A2 (fr) * 1983-02-15 1984-09-26 Fuji Photo Film Co., Ltd. Procédé d'obtention d'images magenta dans des matériaux photographiques couleurs à l'halogénure d'argent

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JPS5525057A (en) 1978-08-10 1980-02-22 Fuji Photo Film Co Ltd Silver halide photographic material
DE3271701D1 (en) 1982-01-26 1986-07-17 Agfa Gevaert Nv Method of dispersing photographic adjuvants in a hydrophilic colloid composition

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US3061432A (en) * 1958-06-21 1962-10-30 Agfa Ag Pyrazolino benzimidazole color coupler
US3676137A (en) * 1969-08-27 1972-07-11 Fuji Photo Film Co Ltd Color photographic light-sensitive element containing magenta coupler and alkyl phosphate solvent
US3725067A (en) * 1970-01-15 1973-04-03 Eastman Kodak Co Silver halide emulsion containing 1-h-pyrazolo(3,2-c)-s-triazole color couplers
GB2067301A (en) * 1979-12-07 1981-07-22 Konishiroku Photo Ind Photographic material containing a high boiling solvent
EP0119741A2 (fr) * 1983-02-15 1984-09-26 Fuji Photo Film Co., Ltd. Procédé d'obtention d'images magenta dans des matériaux photographiques couleurs à l'halogénure d'argent

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0173256B1 (fr) * 1984-08-24 1989-03-15 Fuji Photo Film Co., Ltd. Matériau photographique couleur à l'halogénure d'argent
EP0173256A2 (fr) * 1984-08-24 1986-03-05 Fuji Photo Film Co., Ltd. Matériau photographique couleur à l'halogénure d'argent
EP0177765B1 (fr) * 1984-09-06 1990-03-14 Fuji Photo Film Co., Ltd. Matériau photographique couleur à l'halogénure d'argent
EP0177765A1 (fr) 1984-09-06 1986-04-16 Fuji Photo Film Co., Ltd. Matériau photographique couleur à l'halogénure d'argent
US4828969A (en) * 1985-05-01 1989-05-09 Konishiroku Photo Industry Co., Ltd. Silver halide photographic light-sensitive material
EP0207596A2 (fr) * 1985-05-01 1987-01-07 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière
EP0207596A3 (en) * 1985-05-01 1987-11-04 Konishiroku Photo Industry Co. Ltd. Silver halide photograhic light-sensitive material
EP0261244A4 (fr) * 1986-02-20 1989-07-27 Fuji Photo Film Co Ltd Procede de formation d'une image couleur.
EP0261244A1 (fr) * 1986-02-20 1988-03-30 Fuji Photo Film Co., Ltd. Procede de formation d'une image couleur
EP0236131A3 (en) * 1986-03-05 1989-01-25 Konishiroku Photo Industry Co. Ltd. Silver halide color photographic material
EP0236131A2 (fr) * 1986-03-05 1987-09-09 Konica Corporation Matériau photographique couleur à l'halogénure d'argent
US4968594A (en) * 1986-03-05 1990-11-06 Konishiroku Photo Industry Co., Ltd. Silver halide color photographic material
EP0236986A3 (en) * 1986-03-07 1989-05-31 Konishiroku Photo Industry Co. Ltd. Processing method of light-sensitive silver halide photographic material having good color reproducibility and whiteness
EP0236986A2 (fr) * 1986-03-07 1987-09-16 Konica Corporation Méthode de traitement de matériau photographique à l'halogénure d'argent sensible à la lumière ayant une bonne reproduction de couleur et de blanc
EP0574090A1 (fr) 1992-06-12 1993-12-15 Eastman Kodak Company Copulants à un équivalent et colorants à pKa bas libérés
EP0686873A1 (fr) 1994-06-08 1995-12-13 Eastman Kodak Company Elément photographique couleur comprenant des agents de blocage époxy nouveaux pour copulant magenta résiduel
EP0711804A2 (fr) 1994-11-14 1996-05-15 Ciba-Geigy Ag Stabilisateurs à la lumière latents
WO2005001568A1 (fr) * 2003-06-25 2005-01-06 Eastman Kodak Company Elements photographiques contenant un composant desagregeant, un coupleur formant pigment, un stabilisant et un solvant

Also Published As

Publication number Publication date
USH122H (en) 1986-09-02
DE3565430D1 (en) 1988-11-10
EP0170164A3 (en) 1986-04-16
EP0170164B1 (fr) 1988-10-05
JPH0413699B2 (fr) 1992-03-10
JPS6128948A (ja) 1986-02-08

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