EP0170164B1 - 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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EP0170164B1
EP0170164B1 EP85108995A EP85108995A EP0170164B1 EP 0170164 B1 EP0170164 B1 EP 0170164B1 EP 85108995 A EP85108995 A EP 85108995A EP 85108995 A EP85108995 A EP 85108995A EP 0170164 B1 EP0170164 B1 EP 0170164B1
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Prior art keywords
group
sensitive material
light
general formula
atom
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German (de)
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EP0170164A3 (en
EP0170164A2 (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 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.
  • US ⁇ A ⁇ 3725067 and US-A-3061432 describe photographic materials comprising magenta couplers.
  • US ⁇ A ⁇ 3676137 and GB-A-2067301 describe the use of high boiling organic solvents to introduce magenta couplers into photographic materials.
  • 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): wherein R' and R 2 , which may be the same or different, each represents a hydrogen atom or a substituent, X represents a hydrogen atom or a group capable of being eliminated on coupling with an oxidation product of an aromatic primary amine developing agent, Z represents a nitrogen atom or-CR s where R 6 represents a hydrogen atom or a substituent, and the coupler may form a dimer or higher polymer at R', R 2 , R 6 or X ; together with at least one high boiling organic solvent represented by the following general formula (II): wherein R 3 , R 4 and R 5 , which may be the same or different, each represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group
  • 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 (1) 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.
  • the substituent includes a halogen atom, an alkyl group, an aryl group, a heterocyclic groupo, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy group, an acylamino group, an anilino group, a ureido group, an imido group, a sulfamoylamino group, a carbamoylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido
  • X represents a hydrogen atom or a group capable of being eliminated upon coupling with an aromatic primary amine developing agent which includes a halogen atom, a carboxy group, or an another coupling-off group bound to the carbon atom in the coupling position through an oxygen atom, a nitrogen atom or a sulfur atom.
  • R', R 2 , R 6 or X also may be a divalent group to form a bis derivative.
  • R 1 , R2or R 6 represents a bond or a linking group through which the moiety represented by the general formula (III) or (IV) and an ethylenically unsaturated group are bound to each other.
  • R', R 2 and R 6 each represents a hydrogen atom, a halogen atom (e.g., a chlorine atom, or a bromide atom) an alkyl group (e.g., a methyl group, a propyl group, a t-butyl group, a trifluro- methyl 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, or a benzyl group) an aryl group (e.g., a phenyl group, a 4-t-butylphenyl group, a 2,4-di-t-amylphenyl group, or a tetradecanamidophenyl group) a hal
  • R', 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, or-CH2CH2-0-CHzCH2-), a substituted or unsubstituted phenylene group (e.g., a 1,4-phenylene group, a 1,3-phenylene group, 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, or-CH2CH2-0-CHzCH2-
  • a substituted or unsubstituted phenylene group e.g., a 1,4
  • the linking group represented by R', 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 or -CH 2 CH 2 0CH 2 CH 2 -), a phenylene group (a substituted or unsubstituted phenylene group, e.g., a 1,4-phenylene group, a 1,3-phenylene group, -NHCO-, -CONH-, -O-, -OCO-, or an aralkylene group 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 or -CH 2 CH 2 0CH 2 CH 2 -
  • a phenylene group a substituted or unsubstituted pheny
  • 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 aromatically primary amine developing agent and therefore do not form a color dye include acrylic acid, a-chloroacylic acid, a-alacrylic acids (e.g., methacrylic acid), 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 ⁇ -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 or an eicosyl group, and the cycloalkyl group represented by R 3 , R 4 or R 6 can be, for example,
  • the aryl group represented by R 3 , R 4 or R 5 can be a phenyl group or a naphthyl group, the alkenyl group represented by R 3 , R 4 or R 5 can be a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a decenyl group, a dodecenyl group or an octadecenyl group.
  • alkyl, cycloalkyl, aryl and alkenyl groups may also have one or more substituents.
  • suitable substituents for the alkyl, cycloalkyl and alkenyl groups include a halogen atom (e.g., a fluorine atom, or a chlorine atom), an alkoxy group (e.g., a methoxy group, an ethoxy group, or a butoxy group), an aryl group (e.g., a phenyl group, a tolyl group, or a naphthyl group), an aryloxy group (e.g., a phenoxy group), an alkenyl group or an alkoxycarbonyl group, and examples of substituents for aryl group include an alkyl group, in addition to those for the alkyl, cycloalkyl and alkenyl group described above.
  • R 3 , R 4 and R 5 include a tolyl group, a 2-ethylhexyl group, a 7-methyloctyl group, a cyclohexyl group, and a straight chain alkyl group containing 8 to 18 carbon atoms).
  • high boiling organic solvents means those organic solvents which have a boiling point of 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 0.05:1 to 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 or di-2-ethylhexyl phthalate), amide type solvents (e.g., N,N-diethyldodecanamide), fatty acid ester type solvents, benzoate type solvents and phenolic solvents (e.g., 2,5-di-tert-amylphenol).
  • phthalate type solvents e.g., dibutyl phthalate or di-2-ethylhexyl phthalate
  • amide type solvents e.g., N,N-diethyldodecanamide
  • fatty acid ester type solvents e.g., benzoate type solvents
  • phenolic solvents e.g., 2,5-di-tert-amylphenol
  • 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 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 or low boiling organic solvents 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 or butyl acetate), ethyl propionate, sec-butyl alcohol, methyl isobutyl ketone, ⁇ -ethoxyethyl acetate or methyl Cellosolve acetate may be allowed to coexist in the phosphoric ester type coupler solvent before dissolving the coupler in the coupler solvent.
  • 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 (11) may be added thereto.
  • the mixing ratio of other coupler solvents to the high boiling organic solvents represented by the general formula (11) 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 Wais, The Macromolecular Chemistry of Gelatin, Academic Press (1964).
  • any of silver bromide, silver bromiodide, 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 urn 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 surface 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 Photographique, Paul Montel (1967), G. F. Duffin, Photographic Emulsion Chemistry, The Focal Press (1966), V. L. Zelikman et al., and Making and Coating Photographic Emulsions, The Focal Press (1964). 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 pAq 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, 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 or rhodanines
  • reduction sensitization using a reductive substance e.g., stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid or silane compounds
  • noble metal sensitization using compounds of noble metals e.g., complex salts of the Group VIII metals such as Pt, Ir, or Pd, as well as gold complex salts
  • noble metals e.g., complex salts of the Group VIII metals such as Pt, Ir, or Pd, 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, nitrobenz- imidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles or mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes (e.g., triazainden
  • 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 or sensitization).
  • 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 or sensitization).
  • 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 or a 3-pyrazolidone, 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 hemioxanol 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 or a thiobarbituric acid nucleus, 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.
  • aninostilbene 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 or azaindene compounds may be incorporated.
  • 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 or an aminophenol derivative) 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 or an aminophenol derivative
  • magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolo[5,1-c][1,2,4]triazole couplers, pyrazolopyrazole couplers, pyrazolotetrazole couplers, or open chain acylacetonitrile couplers
  • suitable yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides or pivaloylacetanilides)
  • suitable cyan couplers include naphthol couplers and phenol couplers.
  • non-diffusible 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 or chromium acetate
  • aldehydes e.g., formaldehyde, glyoxal or glutaraldehyde
  • N-methylol compounds e.g., dimethylolurea or methyloldimethylhydantoin
  • dioxane derivatives e.g. 2,3-dihydroxydioxane
  • active vinyl compounds e.g., 1,3,5-triacryloyl-hexahydro-s-triazine or 1,3- vinylsulfonyl-2-propanol
  • active halogen compounds e.g., 2,4-dichloro-6-hydroxy-s-triazine
  • mucohalogeic acids e.g., mucochloric acid or mucophenoxychloric acid
  • the light-sensitive material according to the present invention contains a dye or an ultraviolet light absorbent, 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 or ascorbic acid derivatives, 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 and 3,352,681), 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.
  • Ultra-violet light absorbing couplers e.g., a-naphtholic and cyan dye forming couplers
  • ultraviolet light absorbing polymers may also be used. 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 or bisphenols.
  • 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- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylanilien, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline or 4-amino-3-methyl-N-ethyl-N-(3-methoxyethylaniline).
  • phenylenediamines e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline
  • 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 or diethylene glycol), a development accelerator (e.g., polyethylene glycol, a quaternary ammonium salt or an amine), 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 or an antioxidant.
  • pH buffers such as alkali metal sulfites, carbonates, borates or phosphates, development inhibitor
  • Color developed photographic emulsion layers are usually bleached. Bleaching may be conducted separately or simultaneously with fixing.
  • Compounds of polyvalent metals such as iron (111), cobalt (III), chromium (VI) or copper (II), peracids, quinones or nitroso compounds, can be used as bleaching agents.
  • ferricyanates, dichromates, organic complex salts of iron (111) or cobalt (111) such as complex salts with an aminopolycarboxylic acid (e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid or 1,3-diamino-2-propanoltetraacetic acid) or an organic acid (e.g., citric acid, tartaric acid, or maleic acid); persulfates, permanganates or nitrosophenol; may be used.
  • aminopolycarboxylic acid e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid or 1,3-diamino-2-propanoltetraacetic acid
  • organic acid e.g., citric acid, tartaric acid, or maleic acid
  • persulfates e.g., citric acid, tartaric acid, or maleic acid
  • 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 or polycarbonate, and papers coated or limited with a baryta layer or an a-olefin polymer (for example, polyethylene or polypropylene).
  • 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 and titanium phosphate. 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.
  • plastic film For example, polyolefin, polyester, polyacrylate, polyvinyl acetate, polystyrene, butadiene-styrene copolymer or polycarbonate, can be used as the laminating plastic film.
  • polyethylene terephthalate, vinyl alcohol-ethylene copolymer and polyethylene 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 (5-7) 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 inventioon 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 ml 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 (5-24) for Sample F, Compound (S-7) for Sample G, di-2-ethyl-hexyl 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.
  • a layer of gelatin containing black colloidal silver is provided.
  • This layer had a silver/coupler ratio of 17.0 and a silver coverage of 0.9 g/m 2 .
  • This layer had a silver 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 .
  • This layer had a silver coverage of 0.30 g/m 2 .
  • a layer of gelatin containing yellow colloidal silver is provided.
  • This layer had a silver/coupler ratio of 13.0 and a silver coverage of 0.9 g/m 2 .
  • This layer had a silver coverage of 0.6 g/m 2 .
  • 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 - tertamylphenoxyacetamido)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

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Claims (20)

1. Matériau photosensible pour photographie en couleur à l'halogénure d'argent comprenant un support portant au moins une couche d'émulsion à l'halogénure d'argent contenant, dispersé dans la couche, au moins un coupleur magenta représenté par la formule générale (I) suivante:
Figure imgb0309
dans laquelle R' et R2, qui peuvent être identiques ou différents, représentent chacun un atome d'hydrogène ou un substituant, X représente un atome d'hydrogène ou un groupe capable d'être éliminé au couplage avec le produit d'oxydation d'un développateur amine primaire aromatique, Z représente un atome d'azote ou CR6, où R6 représente un atome d'hydrogène ou un substituant, et le coupleur magenta peut former un dimère ou un polymère supérieur en R', R2, R6 ou X; ainsi qu'au moins un solvant organique à haut point d'ébullition représenté par la formule générale (II):
Figure imgb0310
dans laquelle R3, R4 et R5, qui peuvent être identiques ou différents, représentent chacun un groupe alkyle, un groupe cycloalkyle, un groupe alcényle ou un groupe aryle, sous réserve que le nombre total d'atomes de carbone dans les groupes représentés par R3, R4, et R5 soit de 12 à 60, avec la condition que, quand Z dans la formule générale (I) représente CR6, le solvant organique représenté par la formule générale (II) ne soit pas le phosphate de triphényle, le phosphate de tricrésyle, le phosphate de trioctyle et le phosphate de dioctyle et de butyle.
2. Le matériau photosensible de la revendication 1, caractérisé en ce que ledit coupleur représenté par la formule générale (I) est un 1H-imidazo[1,2-b]pyrazole ou un 1H-pyrazolo[1,5-b][1,2,4]triazole.
3. Le matériau photosensible de la revendication 1, caractérisé en ce que ledit coupleur représenté par la formule générale (I) a la formule générale (III) ou (IV):
Figure imgb0311
dans lesquelles R1, R2, et R6, qui peuvent être identiques ou différents, représentent chacun un atome d'hydrogène, un atome d'halogène, un groupe alkyle, un groupe aryle, un groupe hétérocyclique, un groupe cyano, un groupe alcoxy, un groupe aryloxy, un groupe oxyhétérocyclique, un groupe acyloxy, un groupe carbamyloxy, un groupe silyloxy, un groupe sulfonyloxy, un groupe acylamino, un groupe anilino, un groupe uréido, un groupe imido, un groupe sulfamylamino, un groupe carbamylamino, un groupe alkylthio, un groupe arylthio, un groupe thiohétérocyclique, un groupe alcoxycarbonylamino, un groupe aryloxycarbonylamino, un groupe sulfonamido, un groupe carbamyle, un groupe acyle, un groupe sulfamyle, un groupe sulfonyle, un groupe sulfinyle, un groupe alcoxycarbonyle, ou un groupe aryloxy- carbonyle, et X représente un atome d'hydrogène, un atome d'halogène, un groupe carboxy, ou un autre groupe séparable au couplage lié à l'atome de carbone en position de couplage par un atome d'oxygène, un atome d'azote ou un atome de soufre, ou R', R2, R6 ou X peuvent aussi être un groupe divalent formant un dérivé bis ou une liaison ou un groupe de liaison avec un groupe éthyléniquement insaturé.
4. Le matériau photosensible de la revendication 3, caractérisé en ce que R', R2 et R6 représentent chacun un atome d'hydrogène, un atome de chlore, un atome de brome, un groupe méthyle, un groupe propyle, un groupe t-butyle, un groupe trifluorométhyle, un group tridécyle, un groupe 3-(2,4-di-t-amyl- phénoxy)propyle, un groupe 2-dodécyloxyéthyle, un groupe 3-phénoxypropyle, un groupe 2-hexyl- sulfonyléthyle, un groupe cyclopentyle, un groupe benzyle, un groupe phényle, un groupe 4-t-butyl- phényle, un groupe 2,4-di-t-amylphényle, un groupe 4-tétradécanamidophényle, un groupe 2-furyle, un groupe 2-thiényle, un groupe 2-pyrimidinyle, un groupe 2-benzothiazolyle, un groupe cyano, un groupe méthoxy, un groupe éthoxy, un groupe 2-méthoxyéthoxy, un groupe 2-dodécyloxyéthoxy, un groupe 2-méthanesulfonyléthoxy, un groupe phénoxy, un groupe 2-méthylphénoxy, un groupe 4-t-butylphénoxy, un groupe 2-benzimidazolyloxy, un groupe acétoxy, un groupe hexadécanoyloxy, un groupe N-phényl- carbamyloxy, un groupe N-éthylcarbamyloxy, un groupe triméthylsilyloxy, un groupe dodécylsulfonyloxy, un groupe acétamido, un groupe benzamido, un groupe tétradécanamido, un groupe a-(2,4-di-t-amylphénoxy)butyramido, un groupe y-(3-t-butyl-4-hydroxyphénoxy)butyramido, un groupe a-[4-(4-hydroxyphénylsulfonyl)phénoxy]décanamido, un groupe phénylamino, un groupe 2-chloroanilino, un groupe 2-chloro-5-tétradécanamidoanilino, un groupe 2-chloro-5-dodécyloxycarbonylanilino, un groupe N-acétylanilino, un groupe 2-chloro-5-[a-(3-t-butyl-4-hydroxyphénoxy)dodécanamido]anilino, un groupe phényluréido, un groupe méthyluréido, un groupe N,N-dibutyluréido, un groupe N-succinimido, un groupe 3-benzylhydantoïnyle, un groupe 4-(2-éthylhexanoylamino)phtalimido, un groupe N,N-dipropylsulfamyl- amino, un groupe N-méthyl-N-décylsulfamylamino, un groupe méthylthio, un groupe octylthio, un groupe tétradécylthio, un groupe 2-phénoxyéthylthio, un groupe 3-phénoxypropylthio, un groupe 3-(4-t-butylphénoxy)propylthio, un groupe phénylthio, un groupe 2-butoxy-5-t-octylphénylthio, un groupe 3-penta- décylphénylthio, un groupe 2-carboxyphénylthio, un groupe 4-tétradécanamidophénylthio, un groupe 2-benzothiazolylthio, un groupe méthoxycarbonylamino, un groupe tétradécyloxycarbonylamino, un groupe phénoxycarbonylamino, un groupe 2,4-di-tert-butylphénoxycarbonylamino, un groupe méthanesulfon- amido, un groupe hexadécanesulfonamido, un groupe benzènesulfonamido, un groupe p-toluènesulfon- amido, un groupe octadécanesulfonamido, un groupe 2-méthyloxy-5-t-butylbenzènesulfonamido, un groupe N-éthylcarbamyle, un groupe N,N-dibutylcarbamyle, un groupe N-(2-dodécyloxyéthyl)carbamyle, un groupe N-méthyl-N-dodécylcarbamyle, un groupe N-[3-(2,4-di-tert-amylphénoxy)propyl]carbamyle, un groupe acétyle, un groupe (2,4-di-tert-amylphénoxy)acétyl, un groupe benzoyle, un groupe N-éthyl- sulfamyle, un groupe N,N-dipropylsulfamyle, un groupe N-(2-dodécyloxyéthyl)sulfamyle, un groupe N-éthyl-N-dodécylsulfamyle, un groupe N,N-diéthylsulfamyle, un groupe méthanesulfonyle, un groupe octanesulfonyle, un groupe benzènesulfonyle, un groupe toluènesulfonyle, un groupe octanèsulfinyle, un groupe dodécylsulfinyle, un groupe phénylsulfinyle, un groupe méthoxycarbonyle, un groupe butyloxy- carbonyle, un groupe dodécylcarbonyle, un groupe octadécylcarbonyle, un groupe phényloxycarbonyle, ou un groupe 3-pentadécyloxycarbonyle, et X représente un atome d'hydrogène, un atome de chlore, un atome de brome, un atome d'iode, un groupe carboxyle, un groupe acétoxy, un groupe propanoyloxy, un groupe benzoyloxy, un groupe 2,4-dichlorobenzoyloxy, un groupe éthoxyoxaloyloxy, un groupe pyruvinyloxy, un groupe cinnamoyloxy, un groupe phénoxy, un groupe 4-cyanophénoxy, un groupe méthanesulfonamidophénoxy, un groupe 4-méthanesulfonylphénoxy, un groupe a-naphtoxy, un groupe pentadécylphénoxy, un groupe benzyloxycarbonyloxy, un groupe éthoxy, un groupe 2-cyanoéthoxy, un groupe benzyloxy, un groupe 2-phénéthyloxy, un groupe 2-phénoxyéthoxy, un groupe 5-phényltétra- zolyloxy, un groupe 2-benzothiazolyloxy, un groupe benènesulfonamido, un groupe N-éthyltoluènesulfon- amido, un groupe heptafluorobutanamido, un groupe 2,3,4,5,6-pentafluorobenzamido, un groupe octanesulfonamido, un groupe p-cyanophényluréido, un groupe N,N-diéthylsulfamylamino, un groupe 1-pipéridyle, un groupe 5,5-diméthyl-2,4-dioxo-3-oxazolidinyle, un groupe 1-benzyléthoxy-3-hydantoïnyle, un groupe 2N-1,1-dioxo-3[2H]-oxo-1,2-benzoisothiazolyle, un groupe 2-oxo-1,2-dihydro-1-pyridinyle, un groupe imidazolyle, un groupe pyrazolyle, un groupe 3,5-diéthyl-1,2,4-triazol-1-yle, un groupe 5- ou 6-bromobenzotriazol-1-yle, un groupe 5-méthyl-1,2,3,4-triazol-1-yle, un groupe benzimidazolyle, un groupe 3-benzyl-1-hydantoïnyle, un groupe 1-benzyl-5-hexadécyloxy-3-hydantoïnyle, un groupe 5-méthyl-1-tétra- zolyle, un groupe 4-méthoxyphénylazo, un groupe 4-pivaloylaminophénylazo, un groupe 2-hydroxy-4-propanoylphénylazo, un groupe phénylthio, un groupe 2-carboxyphénylthio, un groupe 2-méthoxy-5-t-octylphénylthio, un groupe 4-méthanesulfonylphénylthio, un groupe 4-octanesulfonamidophénylthio, un groupe 2-butoxyphénylthio, un groupe 2-(2-hexanesulfonyléthyl)-5-tert-octylphénylthio, un groupe benzylthio, un groupe 2-cyanoéthylthio, un groupe 1-éthoxycarbonyltridécylthio, un groupe 5-phényl-2,3,4,5-tétrazolylthio, un groupe 2-benzothiazolylthio, un groupe 2-dodécylthio-5-thiophénylthio ou un g rou pe-phényl-3-dodécyl-1,2,4-triazolyl-5-th io.
5. Le matériau photosensible de la revendication 3, caractérisé en ce que ledit groupe divalent est un groupe alkylène substitué ou insubstitué, un groupe phénylène substitué ou insubstitué ou un groupe -NHCOR7CONH- où R7 représente un groupe alkylène ou phénylène substitué ou insubstitué.
6. Le matériau photosensible de la revendication 5, caractérisé en ce que ledit groupe divalent est un groupe méthylène, un groupe éthylène, un groupe 1,10-décylènes un groupe -CH2CH2-O-CH2-, un groupe 1,4-phénylène, un groupe 1,3-phénylène, ou un groupe
Figure imgb0312
7. Le matériau photosensible de la revendication 3, caractérisé en ce que ledit groupe de liaison représenté par R', R2 ou R6 est un groupe alkylène substitué ou insubstitué, un groupe phénylène substitué ou insubstitué, -NHCO-, -CONH-, -0-, -OCO- ou un groupe aralkylène.
8. Le matériau photosensible de la revendication 7, caractérisé en ce que ledit groupe de liaison est un groupe méthylène, un groupe éthylène, un groupe 1,10-décylène, un groupe―CH2CH2―O―CH2CH2―, un groupe 1,4-phénylène, un groupe 1,3-phénylène,
Figure imgb0313
seul ou en combinaison.
9. Le matériau photosensible de la revendication 1, caractérisé en ce que ledit polymère supérieur est un homopolymère comprenant un ou plusieurs monomères ayant l'unité représentée par la formule générale (I) ou un copolymère d'au moins un monomère ayant l'unité représentée par la formule générale (1) et d'au moins un monomère éthyléniquement insaturé qui ne se couple pas avec un produit d'oxydation d'un développateur amine primaire aromatique.
10. Le matériau photosensible de la revendication 9, caractérisé en ce que ledit monomère éthyléniquement insaturé est l'acide acrylique, l'acide a-chloroacrylique, l'acide méthacrylique, l' acrylamide, le n-butylacrylamide, le t-butylacrylamide, le diacétoneacrylamide, le méthacrylamide, l'acrylate de méthyle, l'acrylate d'éthyle, l'acrylate de n-propyle, l'acrylate de n-butyle, l'acrylate de t-butyle, l'acrylate d'isobutyle, l'acrylate de 2-éthylhexyle, l'acrylate de n-octyle, l'acrylate de lauryle, le méthacrylate de méthyle, le méthacrylate d'éthyle, le méthacrylate de n-butyle, le méthacrylate de β-hydroxyméthyle, le méthylènedibisacrylamide, l'acétate de vinyle, le propionate de vinyle, le laurate de vinyle, l'acrylonitrile, le méthacrylonitrile, le styrène et ses dérivés, le vinyltoluène, le divinylbenzène, la vinylacétophénone, le sulfostyrène, l'acide itaconique, l'acide citraconique, l'acide crotonique, le chlorure de vinylidène, l'éther de vinyle et d'éthyle, l'acide maléique, l'anhydride maléique, les esters maléiques, la N-vinylpyrrolidone, la N-vinylpyridine ou la 2- ou 4-vinylpyridine.
11. Le matériau photosensible de la revendication 1, caractérisé en ce que ledit coupleur représenté par la formule générale (1) est:
Figure imgb0314
Figure imgb0315
Figure imgb0316
Figure imgb0317
Figure imgb0318
Figure imgb0319
Figure imgb0320
Figure imgb0321
Figure imgb0322
Figure imgb0323
Figure imgb0324
Figure imgb0325
Figure imgb0326
Figure imgb0327
Figure imgb0328
Figure imgb0329
Figure imgb0330
Figure imgb0331
Figure imgb0332
Figure imgb0333
Figure imgb0334
Figure imgb0335
Figure imgb0336
Figure imgb0337
Figure imgb0338
Figure imgb0339
Figure imgb0340
Figure imgb0341
Figure imgb0342
Figure imgb0343
Figure imgb0344
Figure imgb0345
Figure imgb0346
Figure imgb0347
Figure imgb0348
Figure imgb0349
Figure imgb0350
Figure imgb0351
Figure imgb0352
Figure imgb0353
Figure imgb0354
Figure imgb0355
Figure imgb0356
Figure imgb0357
Figure imgb0358
Figure imgb0359
Figure imgb0360
Figure imgb0361
Figure imgb0362
Figure imgb0363
Figure imgb0364
12. Le matériau photosensible de la revendication 1, caractérisé en ce que ledit solvant représenté par la formule générale (II) a un point d'ébullition supérieur ou égal à 175°C à pression atmosphérique.
13. Le matériau photosensible de la revendication 1, caractérisé en ce que lesdits groupe alkyle, groupe cycloalkyle, et groupe alcényle représentés par R3, R4 et R5 sont chacun substitués par au moins un des substituants: atome d'halogène, groupe alcoxy, groupe aryle, groupe aryloxy, groupe alcényle et groupe alcoxycarbonyle.
14. Le matériau photosensible de la revendication 1, caractérisé en ce que ledit groupe aryle représenté par R3, R" et R5 est substitué par au moins un des substituants: atome d'halogène, groupe alcoxy, groupe aryloxy, groupe alcényle, groupe alcoxycarbonyle et groupe alkyle.
15. Le matériau photosensible de la revendication 1, caractérisé en ce que R3, R4 et R5, qui peuvent être identiques ou différents, représentent chacun un groupe méthyle, un groupe éthyle, un groupe propyle, un groupe butyle, un groupe pentyle, un groupe hexyle, un groupe heptyle, un groupe octyle, un groupe nonyle, un groupe décyle, un groupe undécyle, un groupe dodécyle, un groupe tridécyle, un groupe tétradécyle, un groupe pentadécyle, un groupe hexadécyle, un groupe heptadécyle, un groupe octadécyle, un groupe nonadécyle, un groupe eicosyle, un groupe 2-éthylhexyle, un groupe 7-méthyloctyle, un groupe cyclopentyle, un groupe cyclohexyle, un groupe butényle, un groupe pentényle, un groupe hexényle, un groupe heptényle, un groupe octényle, un groupe décényle, un groupe dodécényle, un groupe octédécényle, ou ces groupes substitués par au moins un des substituants: un atome de fluor, un atome de chlore, un groupe méthoxy, un groupe éthoxy, un groupe butoxy, un groupe phényle, un groupe tolyle, un groupe naphtyle, et un groupe phénoxy.
16. Le matériau photosensible de la revendication 1, caractérisé en ce que R3, R4 et R5, qui peuvent être identiques ou différents, représentent chacun un groupe phényle, un groupe naphtyle, un groupe tolyle, ou ces groupes substitués par au moins un des substituants: atome de fluor, atome de chlore, groupe méthoxy, groupe éthoxy, groupe butoxy, groupe phénoxy et groupe alkyle.
17. Le matériau photosensible de la revendication 1, caractérisé en ce que R3, R4 et R5, qui peuvent être identiques ou différents, représentent chacun un groupe tolyle, un groupe 2-éthylhexyle, un groupe 7-méthyloctyle, un groupe cyclohexyle ou un groupe alkyle linéaire contenant 8 à 18 atomes de carbone.
18. Le matériau photosensible de la revendication 1, caractérisé en ce que ledit solvant représenté par la formule générale (II) est:
Figure imgb0365
Figure imgb0366
Figure imgb0367
Figure imgb0368
Figure imgb0369
Figure imgb0370
Figure imgb0371
Figure imgb0372
Figure imgb0373
Figure imgb0374
Figure imgb0375
Figure imgb0376
Figure imgb0377
Figure imgb0378
Figure imgb0379
Figure imgb0380
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Figure imgb0384
Figure imgb0385
Figure imgb0386
Figure imgb0387
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Figure imgb0391
19. Le matériau photosensible de la revendication 1, caractérisé en ce que ledit solvant représenté par la formule générale (II) est utilisé en combinaison avec un autre solvant à haut point d'ébullition choisi parmi les solvants du type phtalate, les solvants du type amide, les solvants du type esters d'acide gras, les solvants du type benzoate et les solvants phénoliques.
20. Le matériau photosensible de la revendication 1, caractérisé en ce que le rapport dudit solvant représenté par la formule générale (II) audit coupleur représenté par la formule générale (I) est 0,05:1 à 20:1 en poids.
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

Publications (3)

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

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EP85108995A Expired EP0170164B1 (fr) 1984-07-19 1985-07-18 Matériau photographique couleur à l'halogénure d'argent sensible à la lumière

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

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JPS6153644A (ja) * 1984-08-24 1986-03-17 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料
JPS6165245A (ja) 1984-09-06 1986-04-03 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料
JPH0746215B2 (ja) * 1985-05-01 1995-05-17 コニカ株式会社 ハロゲン化銀写真感光材料
JPS62194252A (ja) * 1986-02-20 1987-08-26 Fuji Photo Film Co Ltd カラ−画像形成方法
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
JPH0616164B2 (ja) * 1986-03-05 1994-03-02 コニカ株式会社 ハロゲン化銀カラ−感光材料
EP0236986B2 (fr) * 1986-03-07 2000-10-04 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
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
DE3750631T2 (de) * 1986-07-10 1995-02-09 Fuji Photo Film Co Ltd Farbphotographisches silberhalidmaterial.
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
EP0574090A1 (fr) 1992-06-12 1993-12-15 Eastman Kodak Company Copulants à un équivalent et colorants à pKa bas libérés
EP0686873B1 (fr) 1994-06-08 2000-04-19 Eastman Kodak Company Elément photographique couleur comprenant des agents de blocage époxy nouveaux pour copulant magenta résiduel
EP0711804A3 (fr) 1994-11-14 1999-09-22 Ciba SC Holding AG Stabilisateurs à la lumière latents
US5695921A (en) * 1995-03-31 1997-12-09 Eastman Kodak Company Photographic elements with magenta dye forming couplers and stabilizers
GB0314857D0 (en) * 2003-06-25 2003-07-30 Eastman Kodak Co Photpgraphic elements containing a de-aggregating compound, dye-forming coupler, stabilizer and solvent
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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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
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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

Also Published As

Publication number Publication date
DE3565430D1 (en) 1988-11-10
USH122H (en) 1986-09-02
EP0170164A3 (en) 1986-04-16
JPS6128948A (ja) 1986-02-08
JPH0413699B2 (fr) 1992-03-10
EP0170164A2 (fr) 1986-02-05

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