EP0170164B1 - Lichtempfindliches farbphotographisches Silberhalogenidmaterial - Google Patents

Lichtempfindliches farbphotographisches Silberhalogenidmaterial 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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French (fr)
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EP0170164A3 (en
EP0170164A2 (de
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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. Lichtempfindliches farbphotographisches Silberhalogenidmaterial, das einen Träger mit wenigstens einer Silberhalogenidemulsionsschicht darauf umfaßt, welche darin dispergiert wenigstens einen Purpurkuppler, dargestellt durch die folgende allgemeine Formel I
Figure imgb0226
worin R' und R2, die gleich oder verschieden sein können, jeweils ein Wasserstoffatom oder einen Substituenten bedeuten, X ein Wasserstoffatom oder eine Gruppe, die beim Kuppeln mit einem Oxidationsprodukt eines primären aromatischen Aminentwicklungsmittels abgespalten werden kann, bedeutet, Z ein Stickstoffatom oder CR6 bedeutet, worin R6 ein Wasserstoffatom oder ein Substituent bedeutet, wobei der Purpurkuppler ein Dimer oder ein höheres Polymer bei R1, R2, R6 oder X bilden kann, zusammen mit wenigstens einem hochsiedenden organischen Lösungsmittel, dargestellt durch die folgende allgemeine Formel II
Figure imgb0227
worin R3, R4 und R5, die gleich oder verschieden sein können, jeweils eine Alkylgruppe, eine Cycloalkylgruppe, eine Alkenylgruppe oder eine Arylgruppe bedeuten, wobei die Gesamtzahl der Kohlenstoffatome in den Gruppen der Substituenten R3, R4 und R5 12 bis 60 beträgt, mit der Maßgabe, daß wenn Z in der allgemeinen Formel I CR6 bedeutet, das organische Lösungsmittel der allgemeinen Formel II nicht Triphenylphosphat, Tricresylphosphat, Trioctylphosphat und Dioctylbutylphosphat ist, enthält.
2. Lichtempfindliches Material nach Anspruch 1, worin der Kuppler der allgemeinen Formel I 1H-Imid- azo[1,2-b]pyrazol oder 1H-Pyrazolo[1,5-b][1,2,4]triazol ist.
3. Lichtempfindliches Material nach Anspruch 1, worin der Kuppler der allgemeinen Formel I die allgemeine Formel III oder IV
Figure imgb0228
besitzt, worin R1, R2 und R6, die gleich oder verschieden sein können, jeweils ein Wasserstoffatom, ein Halogenatom, eine Alkylgruppe, eine Arylgruppe, eine heterocyclische Gruppe, eine Cyanogruppe, eine Alkoxygruppe, eine Aryloxygruppe, eine heterocyclische Oxygruppe, eine Acyloxygruppe, eine Carbamoyloxygruppe, eine Silyloxygruppe, eine Sulfonyloxygruppe, eine Acylaminogruppe, eine Anilinogruppe, eine Ureidogruppe, eine Imidogruppe, eine Sulfamoylaminogruppe, eine Carbamoylaminogruppe, eine Alkylthiogruppe, eine Arylthiogruppe, eine heterocyclische Thiogruppe, eine Alkoxycarbonylaminogruppe, eine Aryloxycarbonylaminogruppe, eine Sulfonamidogruppe, eine Carbamoylgruppe, eine Acylgruppe, eine Sulfamoylgruppe, eine Sulfonylgruppe, eine Sulfinylgruppe, eine Alkoxycarbonylgruppe oder eine Aryloxycarbonylgruppe bedeuten und X ein Wasserstoffatom, ein Halogenatom, eine Carboxygruppe oder eine andere Abkupplungsgruppe, die an das Kohlenstoffatom in der Kupplungsposition durch ein Sauerstoffatom, ein Stickstoffatom oder ein Schwefelatom gebunden ist, bedeutet oder R1, R2, R6 oder X ebenfalls eine zweiwertige Gruppe sein können, die ein Bisderivat oder eine Bindung oder eine Bindungsgruppe zu einer ethylenisch ungesättigten Gruppe bildet.
4. Lichtempfindliches Material nach Anspruch 3, worin R1, R2 und R6 jeweils ein Wasserstoffatom, ein Chloratom, ein Bromatom, eine Methylgruppe, eine Propylgruppe, eine t-Butylgruppe, eine Trifluormethylgruppe, eine Tridecylgruppe, eine 3-(2,4-Di-t-amylphenyloxy)propylgruppe, eine 2-Dodecyloxyethylgruppe, eine 3-Phenoxypropylgruppe, eine 2-Hexylsulfonylethylgruppe, eine Cyclopentylgruppe, eine Benzylgruppe, eine Phenylgruppe, eine 4-t-Butylphenylgruppe, eine 2,4-Di-t-amylphenylgruppe, eine 4-Tetradecanamidophenylgruppe, eine 2-Furylgruppe, eine 2-Thienylgruppe, eine 2-Pyrimidinylgruppe, eine 2-Benzothiazolylgruppe, eine Cyanogruppe, eine Methoxygruppe, eine Ethoxygruppe, eine 2-Methoxyethoxygruppe, eine 2-Dodecyloxyethoxygruppe, eine 2-Methansulfonylethoxygruppe, eine Phenoxygruppe, eine 2-Methylphenoxygruppe, eine 4-t-Butylphenoxygruppe, eine 2-Benzimidazolyloxygruppe, eine Acetoxygruppe, eine Hexadecanoyloxygruppe, eine N-Phenylcarbamoyloxygruppe, eine N-Ethylcarbamoyloxygruppe, eine Trimethylsilyloxygruppe, eine Dodecylsulfonyloxygruppe, eine Acetamidogruppe, eine Benzamidogruppe, eine Tetradecanamidogruppe, eine a-(2,4-Di-t-amylphenoxy)butyramido- gruppe, eine y-(3-t-Butyl-4-hydroxyphenoxy)butyramidogruppe, eine a-[4-(4-Hydroxyphenylsulfonyl)phenoxy]decanamidogruppe, eine Phenylaminogruppe, eine 2-Chloranilinogruppe, eine 2-Chlor-5-tetradecan- amidoanilinogruppe, eine 2-Chlor-5-dodecyloxycarbonylanilinogruppe, eine N-Acetylanilinogruppe, eine 2-Chlor-5-[a-(3-t-butyl-4-hydroxyphenoxy)dodecanamido]anilinogruppe, eine Phenylureidogruppe, eine Methylureidogruppe, eine N,N-Dibutylureidogruppe, eine N-Succinimidogruppe, eine 3-Benzylhydantoinylgruppe, eine 4-(2-Ethylhexanoylamino)phthalimidogruppe, eine N,N-Dipropylsulfamoylamino- gruppe, eine N-Methyl-N-decylsulfamoylaminogruppe, eine Methylthiogruppe, eine Octylthiogruppe, eine Tetradecylthiogruppe, eine 2-Phenoxyethylthiogruppe, eine 3-Phenoxypropylthiogruppe, eine 3-(4-t-Butylphenoxy)propylthiogruppe, eine Phenylthiogruppe, eine 2-Butoxy-5-t-octylphenylthiogruppe, eine 3-Pentadecylphenylthiogruppe, eine 2-Carboxyphenylthiogruppe, eine 4-Tetradecanamidophenylthiogruppe, eine 2-Benzothiazolylthiogruppe, eine Methoxycarbonylaminogruppe, eine Tetradecyloxycarbonylaminogruppe, eine Phenoxycarbonylaminogruppe, eine 2,4-Di-tert-butylphenoxycarbonylaminogruppe, eine Methansulfonamidogruppe, eine Hexadecansulfonamidogruppe, eine Benzolsulfonamidogruppe, eine p-Toluolsulfonamidogruppe, eine Octadecansulfonamidogruppe, eine 2-Methyloxy-5-t-butylbenzolsulfon- amidogruppe, eine N-Ethylcarbamoylgruppe, eine N,N-Dibutylcarbamoylgruppe, eine N-(2-Dodecyloxyethyl)carbamoylgruppe, eine N-Methyl-N-dodecylcarbamoylgruppe, eine N-[3-(2,4-Di-tert-amylphenoxy)-propyl]carbamoylgruppe, eine Acetylgruppe, eine (2,4-Di-tert-amylphenoxy)acetylgruppe, eine Benzoylgruppe, eine N-Ethylsulfamoylgruppe, eine N,N-dipropylsulfamoylgruppe, eine N-(2-dodecyloxyethyl)-sulfamoylgruppe, eine N-Ethyl-N-dodecylsulfamoylgruppe, eine N,N-diethylsulfamoylgruppe, eine Methansulfonylgruppe, eine Octansulfonylgruppe, eine Benzolsulfonylgruppe, eine Toluolsulfonylgruppe, eine Octansulfinylgruppe, eine Dodecylsulfinylgruppe, eine Phenylsulfinylgruppe, eine Methoxycarbonylgruppe, eine Butyloxycarbonylgruppe, eine Dodecylcarbonylgruppe, eine Octadecylcarbonylgruppe, eine Phenyloxycarbonylgruppe oder eine 3-Pentadecyloxycarbonylgruppe bedeuten und X eine Wasserstoffatom, ein Chloratom, ein Bromatom, ein Jodatom, eine Carboxylgruppe, eine Acetoxygruppe, eine Propanoyloxygruppe, eine Benzoyloxygruppe, eine 2,4-Dichlorbenzoyloxygruppe, eine Ethoxyoxaloyloxygruppe, eine Pyruvinyloxygruppe, eine Cinnamoyloxygruppe, eine Phenoxygruppe, eine 4-Cyanophenoxygruppe, eine 4-Methansulfonamidophenoxygruppe, eine 4-Methansulfonylphenoxygruppe, eine a-Naphthoxygruppe, eine 3-Pentadecylphenoxygruppe, eine Benzyloxycarbonyloxygruppe, eine Ethoxygruppe, eine 2-Cyanoethoxygruppe, eine Benzyloxygruppe, eine 2-Phenethyloxygruppe, eine 2-Phenoxyethoxygruppe, eine 5-Phenyltetrazolyloxygruppe, eine 2-Benzothiazolyloxygruppe, eine Benzolsulfonamidogruppe, eine N-Ethyltoluolsulfonamidogruppe, eine Heptafluorbutanamidogruppe, eine 2,3,4,5,6-Pentafluorbenzamidogruppe, eine Octansulfonamidogruppe, eine p-Cyanophenylureidogruppe, eine N,N-Diethylsulfamoylaminogruppe, eine 1-Piperidylgruppe, eine 5,5-Dimethyl-2,4-dioxo-3-oxazolidinylgruppe, eine 1-Benzylethoxy-3-hydantoinylgruppe, eine 2N-1,1-Dioxo-3(2H)-oxo-1,2-Benzoisothiazolylgruppe, eine 2-0xo-1,2-dihydro-1-pyridinylgruppe, eine Imidazolylgruppe, eine Pyrazolylgruppe, eine 3,5-Diethyl-1,2,4-triazol-1-ylgruppe, eine 5- oder 6-Brombenzotriazol-1-ylgruppe, eine 5-Methyl-1,2,3,4-triazol-1-ylgruppe, eine Benzimidazolylgruppe, eine 3-Benzyl-1-hydantoinylgruppe, eine 1-Benzyl-5-hexadecyloxy-3- hydantoinylgruppe, eine 5-Methyl-1-tetrazolylgruppe, eine 4-Methoxyphenylazogruppe, eine 4-Pivaloylaminophenylazogruppe, eine 2-Hydroxy-4-propanoylphenylazogruppe, eine Phenylthiogruppe, eine 2-Carboxyphenylthiogruppe, eine 2-Methoxy-5-t-octylphenylthiogruppe, eine 4-Methansulfonylphenylthiogruppe, eine 4-Octansulfonamidophenylthiogruppe, eine 2-Butoxyphenylthiogruppe, eine 2-(2-Hexansul- fonylethyl)-5-tert-octylphenylthiogruppe, eine Benzylthiogruppe, eine 2-Cyanoethylthiogruppe, eine 1-Ethoxycarbonyltridecylthiogruppe, eine 5-Phenyl-2,3,4,5-tetrazolylthiogruppe, eine 2-Benzothiazolylthiogruppe, eine 2-Dodecylthio-5-thiophenylthiogruppe oder eine 2-Phenyl-3-dodecyl-1,2,4-triazolyl-5-thiogruppe bedeutet.
5. Lichtempfindliches Material nach Anspruch 3, worin die zweiwertige Gruppe eine substituierte oder unsubstituierte Alkylengruppe, eine substituierte oder unsubstituierte Phenylengruppe oder -NHCOR7C0NH- ist, worin R7 eine substituierte oder unsubstituierte Alkylen- oder Phenylengruppe bedeutet.
6. Lichtempfindliches Material nach Anspruch 5, worin die zweiwertige Gruppe eine Methylengruppe, eine Ethylengruppe, eine 1,10-Decylengruppe, -CH2CHz-O-CH2CH2-, eine 1,4-Phenylengruppe, eine 1,3 Phenylengruppe,
Figure imgb0229
ist.
7. Lichtempfindliches Material nach Anspruch 3, worin die Bindungsgruppe, dargestellt durch R', R2 oder R6, eine substituierte oder unsubstituierte Alkylengruppe, eine substituierte oder unsubstituierte Phenylengruppe, -NHCO-, -CONH-, -0-, -OCO- oder eine Aralkylengruppe ist.
8. Lichtempfindliches Material nach Anspruch 7, worin die Bindungsgruppe eine Methylengruppe, eine Ethylengruppe, eine 1,10-Decylengruppe, ―CH2CH2OCH2CH2―, eine 1,4-Phenylengruppe, eine 1,3-Phenylengruppe,
Figure imgb0230
alleine oder in Kombination ist.
9. Lichtempfindliches Material nach Anspruch 1, worin das höhere Polymer ein Homopolymer ist, das ein oder mehrere Monomere mit dem Rest der allgemeinen Formel oder ein Copolymer aus wenigstens einem Monomer mit dem Rest der allgemeinen Formel mit wenigstens einem ethylenisch ungesättigten Monomer, das mit einem Oxidationsprodukt eines primären aromatischen Aminentwicklungsmittels nicht kuppelt, umfaßt.
10. Lichtempfindliches Material nach Anspruch 9, worin das ethylenisch ungesättigte Monomer Acrylsäure, a-Chloracrylsäure, Methacrylsäure, Acrylamid, n-Butylacrylamid, t-Butylacrylamid, Diacetonacrylamid, Methacrylamid, Methylacrylat, Ethylacrylat, n-Propylacrylat, n-Butylacrylat, t-Butylacrylat, Isobutylacrylat, 2-Ethylhexylacrylat, n-Octylacrylat, Laurylacrylat, Methylmethacrylat, Ethylmethacrylat, n-Butylmethacrylat, β-Hydroxymethacrylat, Methylendibisacrylamid, Vinylacetat, Vinylpropionat, Vinyllaurat, Acrylonitril, Methacrylonitril, Styrol und seine Derivate, Vinyltoluol, Divinylbenzol, Vinylacetophenon, Sulfostyrol, Itaconsäure, Citraconsäure, Crotonsäure, Vinylidenchlorid, Vinylethylether, Maleinsäure, Maleinsäureanhydrid, Maleinsäureester, N-Vinyl-2-pyrrolidon, N-Vinylpyridin oder 2- oder 4-Vinylpyridin ist.
11. Lichtempfindliches Material nach Anspruch 1, worin der Kuppler der allgemeinen Formel I
Figure imgb0231
Figure imgb0232
Figure imgb0233
Figure imgb0234
Figure imgb0235
Figure imgb0236
Figure imgb0237
Figure imgb0238
Figure imgb0239
Figure imgb0240
Figure imgb0241
Figure imgb0242
Figure imgb0243
Figure imgb0244
Figure imgb0245
Figure imgb0246
Figure imgb0247
Figure imgb0248
Figure imgb0249
Figure imgb0250
Figure imgb0251
Figure imgb0252
Figure imgb0253
Figure imgb0254
Figure imgb0255
Figure imgb0256
Figure imgb0257
Figure imgb0258
Figure imgb0259
Figure imgb0260
Figure imgb0261
Figure imgb0262
Figure imgb0263
Figure imgb0264
Figure imgb0265
Figure imgb0266
Figure imgb0267
Figure imgb0268
Figure imgb0269
Figure imgb0270
Figure imgb0271
Figure imgb0272
Figure imgb0273
Figure imgb0274
Figure imgb0275
Figure imgb0276
Figure imgb0277
Figure imgb0278
Figure imgb0279
Figure imgb0280
Figure imgb0281
12. Lichtempfindliches Material nach Anspruch 1, worin das Lösungsmittel der allgemeinen Formel II einen Siedepunkt von 175°C oder mehr bei atmosphärischem Druck besitzt.
13. Lichtempfindliches Material nach Anspruch 1, worin die Alkylgruppe, die Cycloalkylgruppe und die Alkenylgruppe in den Substituenten R3, R4 und R5 jeweils mit wenigstens einem Substituenten aus einem Halogenatom, einer Alkoxygruppe, einer Arylgruppe, einer Aryloxygruppe, einer Alkenylgruppe und einer Alkoxycarbonylgruppe substituiert sind.
14. Lichtempfindliches Material nach Anspruch 1, worin die Arylgruppe der Substituenten R3, R4 und R5 mit wenigstens einem Substituenten aus einem Halogenatom, einer Alkoxygruppe, einer Aryloxygruppe, einer Alkenylgruppe, einer Alkoxycarbonylgruppe und einer Alkylgruppe substituiert ist.
15. Lichtempfindliches Material nach Anspruch 1, worin R3, R4 und R5, die gleich oder verschieden sein können, jeweils eine Methylgruppe, eine Ethylgruppe, eine Propylgruppe, eine Butylgruppe, eine Pentylgruppe, eine Hexylgruppe, eine Heptylgruppe, eine Octylgruppe, eine Nonylgruppe, eine Decylgruppe, eine Undecylgruppe, eine Dodecylgruppe, eine Tridecylgruppe, eine Tetradecylgruppe, eine Pentadecylgruppe, eine Hexadecylgruppe, eine Heptadecylgruppe, eine Octadecylgruppe, eine Nonadecylgruppe, eine Eicosylgruppe, eine 2-Ethylhexylgruppe, eine 7-Methyloctylgruppe, eine Cyclopentylgruppe, eine Cyclohexylgruppe, eine Butenylgruppe, eine Pentenylgruppe, eine Hexenylgruppe, eine Heptenylgruppe, eine Octenylgruppe, eine Decenylgruppe, eine Dodecenylgruppe, eine Octadecenylgruppe bedeutet oder diese Gruppen mit wenigstens einem Substituenten aus einem Fluoratom, einem Chloratom, einer Methoxygruppe, einer Ethoxygruppe, einer Butoxygruppe, einer Phenylgruppe, einer Tolylgruppe, einer Naphthylgruppe und einer Phenoxygruppe substituiert sind.
16. Lichtempfindliches Material nach Anspruch 1, worin R3, R4 und R5, die gleich oder verschieden sein können, jeweils eine Phenylgruppe, eine Naphthylgruppe, eine Tolylgruppe bedeuten oder diese Gruppen mit wenigstens einem Substituenten aus einem Fluoratom, einem Chloratom, einer Methoxygruppe, einer Ethoxygruppe, einer Butoxygruppe, einer Phenoxygruppe und einer Alkylgruppe substituiert sind.
17. Lichtempfindliches Material nach Anspruch 1, worin R3, R4 und R5, die gleich oder verschieden sein können, jeweils eine Tolylgruppe, eine 2-Ethylhexylgruppe, eine 7-Methyloctylgruppe, eine Cyclohexylgruppe oder eine geradkettige Alkylgruppe mit 8 bis 18 Kohlenstoffatomen bedeuten.
18. Lichtempfindliches Material nach Anspruch 1, worin das Lösungsmittel der allgemeinen Formel II
Figure imgb0282
Figure imgb0283
Figure imgb0284
Figure imgb0285
Figure imgb0286
Figure imgb0287
Figure imgb0288
Figure imgb0289
Figure imgb0290
Figure imgb0291
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Figure imgb0295
Figure imgb0296
Figure imgb0297
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Figure imgb0299
Figure imgb0300
Figure imgb0301
Figure imgb0302
Figure imgb0303
Figure imgb0304
Figure imgb0305
Figure imgb0306
Figure imgb0307
Figure imgb0308
19. Lichtempfindliches Material nach Anspruch 1, worin das Lösungsmittel der allgemeinen Formel II in Kombination mit einem anderen hochsiedenden organischen Lösungsmittel, gewählt aus Lösungsmitteln vom Phthalattyp, vom Amidtyp, vom Fettsäurestertyp, vom Benzoattyp und phenolischen Lösungsmitteln, verwendet wird.
20. Lichtempfindliches Material nach Anspruch 1, worin das Verhältnis des Lösungsmittels der allgemeinen Formel II zu dem Kuppler der allgemeinen Formel 10,05:1 bis 20: 1, bezogen auf das Gewicht, beträgt.
EP85108995A 1984-07-19 1985-07-18 Lichtempfindliches farbphotographisches Silberhalogenidmaterial Expired EP0170164B1 (de)

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

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EP (1) EP0170164B1 (de)
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DE (1) DE3565430D1 (de)

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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 (de) * 1986-03-07 2000-10-04 Konica Corporation Verfahren zur Behandlung eines photographischen lichtempfindlichen Silberhalogenidmaterials, das eine gute Farb- und Weisswiedergabe besitzt
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
EP0599808B1 (de) * 1986-07-10 1998-10-14 Fuji Photo Film Co., Ltd. Farbphotographisches Silberhalogenidmaterial
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 (de) 1992-06-12 1993-12-15 Eastman Kodak Company 1-Äquivalentkuppler und freisetzbaren Farbstoffen mit niedrigem pKa
DE69516332T2 (de) 1994-06-08 2000-11-30 Eastman Kodak Co Farbphotographisches Element, das neue Epoxy-Abfänger für restlichen Purpurrot-Kuppler enthält
EP0711804A3 (de) 1994-11-14 1999-09-22 Ciba SC Holding AG Kryptolichtschutzmittel
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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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
JPH0413699B2 (de) 1992-03-10
EP0170164A3 (en) 1986-04-16
USH122H (en) 1986-09-02
JPS6128948A (ja) 1986-02-08
DE3565430D1 (en) 1988-11-10
EP0170164A2 (de) 1986-02-05

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