EP0298321B1 - Farbphotographisches Silberhalogenidmaterial - Google Patents

Farbphotographisches Silberhalogenidmaterial Download PDF

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Publication number
EP0298321B1
EP0298321B1 EP19880110100 EP88110100A EP0298321B1 EP 0298321 B1 EP0298321 B1 EP 0298321B1 EP 19880110100 EP19880110100 EP 19880110100 EP 88110100 A EP88110100 A EP 88110100A EP 0298321 B1 EP0298321 B1 EP 0298321B1
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EP
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Prior art keywords
group
aromatic
aliphatic
hydrogen atom
general formula
Prior art date
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EP19880110100
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English (en)
French (fr)
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EP0298321A3 (en
EP0298321A2 (de
Inventor
Masakazu Fuji Photo Film Co. Ltd. Morigaki
Nobuo Fuji Photo Film Co. Ltd. Seto
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Publication of EP0298321A3 publication Critical patent/EP0298321A3/en
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3003—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
    • 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
    • G03C7/392—Additives
    • G03C7/39296—Combination of additives
    • 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
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • 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
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G03C7/39284—Metallic complexes

Definitions

  • the present invention relates to a silver halide color photographic light-sensitive material which exhibits excellent fastness to light, heat and humidity and exhibits less formation of stain.
  • dye images are formed by a reaction of dye image forming coupler(s) (hereinafter simply referred to as coupler(s)) and an oxidation product of the color developing agent formed as the result of development.
  • coupler(s) dye image forming coupler(s)
  • an oxidation product of the color developing agent formed as the result of development for a multicolor photographic material, a combination of a yellow coupler, a cyan coupler, and a magenta coupler is usually used.
  • the quality of photographic images obtained from silver halide color photographic materials is not permanent and degrades during preservation with the lapse of time.
  • color photographs when they are exposed to light for a long period of time or preserved under conditions of high temperature and high humidity, color fading or discoloration of dye images and discoloration of the white background ordinarily occur and the color images degrade. This degradation of the color image is a fatal defect for recording materials.
  • color fading preventing agents there are known, for example, hydroquinones, hindered phenols, tocopherols, chromans, coumarans, and the compounds formed by etherifying the phenolic hydroxy groups of these compounds as described in U.S. Patents 3,935,016, 3,930,866, 3,700,455, 3,764,337, 3,432,300, 3,573,050 and 4,254,216, British Patents 2,066,975 and 1,326,889, Japanese Patent Publication No. 30462/76.
  • These compounds may have the effect of preventing color fading and discoloration of dye images, but since the effect is yet insufficient for meeting the customers' requirement for high image quality and the use of these compounds changes the hue, forms fogs, causes poor dispersibility, and causes fine crystals after coating silver halide emulsions, overall excellent effects for color photography have not yet been obtained by the use of these compounds.
  • EP-0-0255722 and EP-A-0258662 which are comprised in the state of the art according to Art. 54(3) EPC disclose a silver halide color photographic material comprising a compound satisfying the following formula (I), (II) or (III) and a color fading agent.
  • a silver halide color photographic material comprising a support having thereon at least one silver halide emulsion layer, wherein the silver halide color photographic material contains
  • the above described object is also accomplished by a method for producing color images which comprises imagewise exposing a silver halide color photographic material containing at least one dye image forming coupler and subjecting the photographic material exposed to a color photographic processing in the presence of the above compounds of (1) and (2).
  • the present invention also provides a color photographic print comprising a reflective support having thereon at least one of a layer containing a yellow image-forming dye, a layer containing a magenta image-forming dye and a layer containing again image-forming dye, said photographic print having at least one layer containing the above compounds of (1) and (2).
  • the compounds of (1) and (2) may be incoporated in at least one hydrophilic colloidal layer in the photographic material. It is preferred that the compounds are incorporated in a silver halide emulsion layer, and it is more preferred that the compounds are incorporated in a silver halide emulsion layer containing a magenta coupler.
  • the occurrence of color stain caused by the components of processing solutions remaining in the photographic material after development processing can be markedly prevented, and prevention from degradation of color image and occurrence of yellow stain of the white background during preservation for a long period of time can be achieved.
  • the degree of prevention from degradation of color image and occurrence of yellow stain of the white background is extremely high and such effects can not be expected from combinations of hitherto known color fading preventing agents.
  • At least one compound selected from compounds represented by the general formula (I) or (II) and at least one compound represented by the general formula (III) are employed together.
  • aliphatic group represents a straight chain, branched chain or cyclic alkyl, alkenyl or alkynyl group and these groups may be substituted with a substituent.
  • aromatic group as used in the present invention may be a carbocyclic series aromatic group (examples for R 1' R 2 , B or R include a phenyl group, a naphthyl group), or a heterocyclic series aromatic group (examples for R 1' R 2 , B or R include a furyl group, a thienyl group, a pyrazolyl group, a pyridyl group, an indolyl group) and the group may be a monocyclic series or condensed ring series (e.g., a benzofuryl group, a phenanthridinyl group). Furthermore, these aromatic rings may have a substituent.
  • heterocyclic group used in the present invention represents a group having a 3-membered to 10-membered ring having carbon atom(s), oxygen atom(s), nitrogen atom(s), or sulfur atom(s) as nucleus- forming atoms, the heterocyclic ring itself may be a saturated ring or an unsaturated ring (examples for R 1' R 2 , B or R include a chromanyl group, a pyrrolidyl group, a pyrrolinyl group, a morpholinyl group), and further the ring may be substituted with a substituent.
  • X in the general formula (I) represents a group capable of being released upon a reaction of A with an aromatic amine developing agent and preferably represents a group connected to A through an oxygen atom, a sulfur atom or a nitrogen atom (e.g., a 3-pyrazolyloxy group, a 3H-1,2,4-oxadiazolin-5-oxy group, an aryloxy group, an alkoxy group, an alkylthio group, an arylthio group, a substituted N-oxy group) or a halogen atom.
  • a in the general formula (I) represents a group capable of reacting with an aromatic amine developing agent to form a chemical bond.
  • Such groups includes a group containing an atom of low electron density, for example, When X is a halogen atom, n represents 0.
  • L represents a single bond, an alkylene group, -O-, -S-, (e.g., a carbonyl group, a sulfonyl group, a sulfinyl group, an oxycarbonyl group, a phosphonyl group, a thiocarbonyl group, an aminocarbonyl group, a silyloxy group).
  • Y has the same meaning as Y defined in the general formula (II), and Y' has the same meaning as defined for Y Y and Y' may be the same or different.
  • R' and R which may be the same or different, each represents -L"'-R o .
  • R o has the same meaning as defined for R 1 .
  • R'" represents a hydrogen atom, an aliphatic group (e.g., a methyl group, an isobutyl group, a tert-butyl group, a vinyl group, a benzyl group, an octadecyl group, a cyclohexyl group), an aromatic group (e.g., a phenyl group, a pyridyl group, a naphthyl group), a heterocyclic group (e.g., a piperidinyl group, a pyranyl group, a furyl group, a chromanyl group), an acyl group (e.g., an acetyl group, a benzoyl group), or an aliphatic or aromatic sulfonyl group (e.g., a methanesulfonyl group, a benzenesulfonyl group).
  • an aromatic group e.g., a methyl
  • L', L" and L"' which may be the same or different each represents -O-, -S- or
  • A is preferably a divalent group represented by
  • R 1 has the same meaning as R 1 defined in the general formula (I);
  • Link represents a single bond or - O-;
  • Ar represents an aromatic group provided that it does not become a group useful as a photographic reducing group such as a hydroquinone derivative or a catechol derivative, as a result of reaction with an aromatic amine developing agent;
  • R a , R b and R e which may be the same or different, each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a carboxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, an acylamino group, a sulfonamido group, an acyl group, an aliphatic or aromatic sulfonyl group, an alkoxycarbonyl group, a
  • the groups or rings in the formula (I) to (IV) and (I-a) to (I-b) may be substituted with a substituent such as groups recited for R a , R b and R e , and/or a halogen atom.
  • the total number of carbon atoms included in the compound per se is preferably at least 13, and the more the carbon atoms present, the more preferred.
  • the total number of carbon atoms is usually not more than 13 in order to render the compounds water soluble.
  • the compound used according to the present invention does not decompose during development processing in order to attain the objects of the present invention.
  • M represents an atom or an atomic group forming an inorganic salt (e.g., a salt of Li, Na, K, Ca, Mg, ammonium) or an organic salt (e.g., a salt of triethylamine, methylamine), wherein R 15 and R 16 , which may be the same or different, each represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, wherein R 15 and R 16 may be connected to each other to form a 5- membered to 7-membered ring; R 17 , R 18 , R 20 , and R 21 , which may be the same or different, each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aliphatic or aromatic sulfonyl group, a ureido group, or a urethane group, provided that at least
  • the group in which the sum of Hammet's ⁇ values with respect to the -S0 2 M group is at least 0.5 is preferred to better achieve the effect of the present invention.
  • the total number of carbon atoms of the compound is that which provides the compound non-diffusible.
  • the total number of carbon atoms is that which renders the compound water soluble.
  • the compounds represented by the general formula (I), (II) or (III) can be synthesized according to the methods as described in EP 0,230,048A2, 0,258,662A2, and 0,255,722A2 and Japanese Patent Application (OPI) No. 229145/87 or methods analogous thereto.
  • the aliphatic group, aromatic group and heterocyclic group represented by R 30 , R 31 or R 35 each has the same meaning as defined for the aliphatic group, aromatic group and heterocyclic in the general formula (I), (II) or (III).
  • R 32 , R 33 and R 34 which may be the same or different, each represents a straight chain, branched chain or cyclic alkyl group (e.g., a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a benzyl group, an octyl group, a cyclohexyl group, a hexadecyl group), an alkenyl group (e.g., a vinyl group, an allyl group), an aryl group (e.g., a phenyl group, a p-methylphenyl group, a 2-chlorophenyl group, a 3-methoxyphenyl group, a 2,4-dimethoxyphenyl group, a 4-hexadecyloxyphenyl group, a 3-pentadecylphenyl group, a 4-bromophenyl group, a naphthyl group
  • R 41 represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, or (wherein R 32 , R 33 , and R34 each has the same meaning as defined in the general formula (IV);
  • R 42 , R 43 , R 44 , R 45 and R 46 which may be the same or different, each represents a hydrogen atom, -W-R 31 , an aliphatic group, an aromatic group, a heterocyclic group, a diacylamino group, a halogen atom, an aliphatic or aromatic sulfonyl group, an aliphatic or aromatic sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a ureido group, a urethane
  • the 5-membered to 7-membered ring described above may be a monocyclic ring, a condensed ring, a spiro ring, or a bicyclo ring, and the resulting condensed ring may be an alicyclic ring, an aromatic ring, a heterocyclic ring, or a heteroaromatic ring, and these rings may be substituted with one or more substituents.
  • R' 41 has the same meaning as R 35 defined in the general formula (IV), and R' 41 may be connected with R 41 or R 42 to form a 5-membered to 7-membered ring same as defined for R 41 .
  • R 50 represents an aliphatic group, a heteroaromatic group, a heterocyclic group
  • R 51 represents a hydrogen atom, an aliphatic group, a heteroaromatic group or a heterocyclic group
  • R 35 has the same meaning as defined in the general formula (IV), and R 50 and R 51 or R 50 and R 35 may be connected to each other to form a 5-membered to 7-membered ring which is the same as defined above for R 41 .
  • R 41 to R 46 each has the same meaning as defined in the general formula (IV-a), R' 41 and R' 42 to R' 46 each has the same meaning as defined for R 41 and R 42 to R 46 respectively, and each group may be connected to each other to form a 5-membered to 7-membered ring which is the same as defined in the general formula (IV-a);
  • R 47 represents an aliphatic group, an aromatic group or a heterocyclic group;
  • R 61 to R 64 which may be the same or different, each represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group;
  • R s5 and R 66 which may be the same or different, each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an acyl amino group, or wherein E 1 represents a non-metall
  • the total number of carbon atoms of the compound is that which provides the compound non-diffusible.
  • the total number of carbon atoms is that which renders the compound water soluble.
  • the organic metal complex which can be used in the present invention is characterized by containing copper, cobalt, nickel, palladium or platinum, as the central metal, and have at least one organic ligand having a bidentate or more conformation.
  • nickel is particularly preferred.
  • atom coordinated to the central metal a nitrogen atom, a sulfur atom, an oxygen atom or a phosphorous atom is preferred.
  • organic metal complexes used in the present invention particularly preferred complexes are represented by the following general formula (V-a), (V-b), (V-c) or (V-d): wherein M represents copper, cobalt, nickel, palladium or platinum; R 80 and R' 80 , which may be the same or different, each represents a hydrogen atom, an alkyl group, an aryl group or a hydroxy group, wherein R 80 and R' 80 may be connected to each other; R 81 , R 82 , R 83 , R' 81 , R' 82 and R' 83 , which may be the same or different, to each represents a hydrogen atom, an alkyl group or an aryl group, wherein R 82 and R 83 or R' 82 and R' 83 may be connected to each other to form an aromatic ring or a 5-membered to 8-membered ring; R 84 , R 85 , R' 84 and R' 85 , which may be the same or
  • an alkyl group or an alkyl moiety preferably has from 1 to 25 carbon atoms, and an aryl group or an aryl moiety preferably has from 6 to 25 carbon atoms.
  • organic color fading preventing agents and the organic metal complexes used in the present invention are set forth below.
  • the compounds for use in the present invention which have low molecular weight or are easily soluble in water may be added to at least one processing solution such as a color developing solution, a bleaching solution, fixing solution, a blixing solution, water for washing and a stabilizing solution and carried over into the color photographic material during development processing of the color photographic material.
  • a processing solution such as a color developing solution, a bleaching solution, fixing solution, a blixing solution, water for washing and a stabilizing solution
  • the compounds are usually dissolved in a high-boiling point solvent (an oil) having a boiling point of at least 170°C at atmospheric pressure or a low-boiling point solvent, or a mixture of the above described oil and low-boiling solvent, and the solution is dispersed by emulsification in an aqueous solution of a hydrophilic colloid such as gelatin.
  • a high-boiling point solvent an oil having a boiling point of at least 170°C at atmospheric pressure or a low-boiling point solvent, or a mixture of the above described oil and low-boiling solvent
  • the compounds for use in the present invention described above are preferably soluble in the high-boiling organic solvent.
  • the particle size of the emulsified dispersion particles of the compounds is preferably from 0.05 ⁇ m to 0.5 ⁇ m, particularly preferably from 0.1 ⁇ m to 0.3 ⁇ m.
  • the compounds for use in the present invention be co-emulsified with coupler(s) to achieve the effects of the present invention.
  • the ratio of oil/coupler is preferably from 0.00 (containing no oil) to 2.0 by weight ratio.
  • Each amount of the above described compounds of (1) and (2) is from 1 x1 0-2 mol to 10 mols, preferably from 3x10- 2 mols to 5 mols per mol of the coupler in the same layer.
  • the molar ratio of the amount of the compound(s) of (1) to that of the compound(s) of (2) is preferably from 0.1 to 10.
  • alkyl phthalates e.g., dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, dimethoxyethyl phthalate
  • phosphoric acid esters e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctylbutyl phosphate, monophenyl-p-tert-butylphenyl phosphate
  • citric acid esters e.g., tributyl acetylcitrate
  • benzoic acid esters e.g., octyl benzoate
  • alkylamides e.g., diethyllaurylamide, dibutyllaurylamide
  • fatty acid esters e.g., dibutoxyethyl succinate, diethyl a
  • the low-boiling solvent which can be used as an auxiliary solvent in the case of incorporating the above described compounds used according to the present invention into the color photographic material preferably is an organic solvent having a boiling point of from about 30°C to about 150°C at atmospheric pressure and examples thereof include lower alkyl acetates (e.g., ethyl acetate, isopropyl acetate, butyl acetate), ethyl propionate, methanol, ethanol, secondary butyl alcohol, cyclohexanol, fluorinated alcohol, ethyl isobutyl ketone, ⁇ 3-ethoxyethyl acetate, methyl cellosolve acetate, acetone, methylacetone, acetonitrile, dioxane, dimethylformamide, dimethylsulfoxide, chloroform, cyclohexane.
  • lower alkyl acetates e.g., ethyl acetate, is
  • an oily solvent for additives such as coupler(s), (including a solvent which is solid at room temperature, such as wax), as well as a latex polymer can be used.
  • Additives themselves, such as a coupler, a color mixing preventing agent, an ultraviolet light absorbing agent, may be used as an oily solvent for dissolving the compounds for use in the present invention.
  • latex polymers produced by using monomers such as acrylic acid, methacrylic acid, esters of these acids (e.g., methyl acrylate, ethyl acrylate, butyl methacrylate), acrylamide, methacrylamide, vinyl esters (e.g., vinyl acetate, vinyl propionate) acrylonitrile, styrene, divinylbenzene, vinyl alkyl ethers (e.g., vinyl ethyl ether), maleic acid esters (e.g., maleic acid methyl ester), N-vinyl-2-pyrrolidone, N-vinylpyridine, 2-vinylpyridine, and 4-vinylpyridine, singly or as a mixture of two or more.
  • monomers such as acrylic acid, methacrylic acid, esters of these acids (e.g., methyl acrylate, ethyl acrylate, butyl methacrylate), acrylamide, methacrylamide, vinyl esters (e
  • a surface active agent is usually used and examples of the surface active agent include saponin, sodium alkylsulfosuccinate, sodium alkylbenzenesulfonate.
  • the compounds used according to the present invention described above can be used in combination with a yellow coupler, a magenta coupler, or a cyan coupler. In these cases, it is particularly preferred, to achieve the effects of the present invention, to use the compounds in combination with a magenta coupler.
  • the coupler which is used in combination with the above described compounds may be 4-equivalent or 2-equivalent for silver ions, and also may be in the form of a polymer or an oligomer. Furthermore, the couplers which are used in combination with the above described compounds may be used singly or as a mixture of two or more kinds thereof.
  • Couplers which can be preferably used in the present invention are those represented by the following general formula (C-I), (C-II), (M-I), (M-II) or (Y); wherein, R 1' R 4 , and R 5 each represents an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group; R 2 represents an aliphatic group; R 3 and R 6 each represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, or an acylamino group; R 5 ' represents a hydrogen atom, or a group represented by R 5 defined above; R 7 and R 9 each represents a substituted or unsubstituted phenyl group; R 8 represents a hydrogen atom, an aliphatic acyl group, an aromatic acyl group, an aliphatic sulfonyl group, or an aromatic sulfonyl group; R 10 represents a hydrogen
  • R 2 and R 3 or R 5 and R 6 may be connected to each other to form a 5-membered, 6-membered, or 7-membered ring.
  • the coupler represented by the above described formula may form a dimer or a higher polymer through R 1' R 2 , R 3 or Y 1 ; R 4 , R 5 , R 6 or Y 2 ; R 7 , R s , R 9 or Y 3 ; R 10 , Za, Zb or Y 4 ; or Q or Y 5 .
  • the aliphatic group described above is a straight chain, branched chain or cyclic alkyl, alkenyl, or alkynyl group.
  • magenta couplers represented by the general formulae (M-I) and (M-II) are illustrated below.
  • the cyan couplers represented by the general formula (C-I) or (C-II) can be synthesized by the following known methods.
  • the cyan couplers represented by the general formula (C-I) can be synthesized by the methods as described in U.S. Patents 2,423,730 and 3,772,002, and the cyan couplers represented by the general formula (C-II) can be synthesized by the methods as described in U.S. Patents 2,895,826, 4,333,999 and 4,327,173.
  • magenta couplers represented by the general formula (M-I) can be synthesized by the methods as described in Japanese Patent Application (OPI) Nos. 74027/74 and 74028/74, Japanese Patent Publication Nos. 27930/73 and 33846/78, U.S. Patent 3,519,429. Also the magenta couplers represented by the general formula (M-II) can be synthesized by the methods as described in U.S. Patent 3,725,067 and Japanese Patent Application (OPI) Nos. 162548/74, 171956/74 and 33552/85.
  • the yellow couplers represented by the general formula (Y) can be synthesized by the methods as described in Japanese Patent Application (OPI) No. 48541/79, Japanese Patent Publication No. 10739/83, U.S. Patent 4,326,024, Research Disclosure, No. 18053.
  • Each of these couplers is generally incorporated into a silver halide emulsion layer in an amount of from 2x10- 3 mol to 5x1 0-1 mol, and preferably from 1x10- 2 mol to 5x1 0-1 mol per mol of silver in the layer.
  • the compounds used according to the present invention are preferably employed in combination with the coupler represented by the general formula (C-I), (C-II), (M-I) or (M-II), more particularly with the magenta coupler represented by the general formula (M-I) or (M-II) in order to achieve the effects of the present invention.
  • magenta coupler represented by the general formula (M-II) wherein Za represents -N , Z b represents a substituted methine group and Y 4 represents a chlorine atom in combination with the compound represented by the general formula (I-c) wherein Z 1 represents an atomic group necessary to form a 2-pyrazoline ring, the effect of improving light-fastness of magenta dye is relatively small in comparison with cases using other compounds of the general formula (I-C).
  • the color photographic material according to the present invention contains dye(s) and ultraviolet light absorbing agent(s) in the hydrophilic colloid layer(s) thereof, these additives may be mordanted for example, by a cationic polymer.
  • the color photographic material according to the present invention may further contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, as a color fog preventing agent.
  • the color photographic material according to the present invention may contain ultraviolet light absorbing agent(s) in the hydrophilic colloid layer as described above.
  • the ultraviolet light absorbing agents include aryl group-substituted benzotriazole compounds (e.g., those as described in U.S. Patent 3,533,794), 4-thiazolidone compounds (e.g., those as described in U.S. Patents 3,314,794 and 3,352,681), benzophenone compounds (e.g., those as described in Japanese Patent Application (OPI) No. 2784/71), cinnamic acid ester compounds (e.g., those as described in U.S.
  • Patents 3,705,805 and 3,707,375 include butadiene compounds (e.g., those as described in U.S. Patent4,045,229), and bisphenol derivatives (e.g., those as described in U.S. Patent 3,700,455).
  • ultraviolet light absorptive couplers e.g., a-naphtholic cyan dye forming couplers
  • ultraviolet light absorptive polymers may be used as ultraviolet light absorbing agents. These ultraviolet light absorbing agents may be mordanted in a specific layer.
  • the color photographic material according to the present invention may contain water-soluble dyes as filter dyes or for irradiation prevention or other various purposes in the hydrophilic colloid layers.
  • water-soluble dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes. In these dyes, oxonol dyes, hemioxonol dyes, and merocyanine dyes are useful.
  • gelatin is advantageously used but other hydrophilic colloids can be used alone or together with gelatin.
  • gelatin lime-treated gelatin or acid-treated gelatin can be used in the present invention. Details of the production of gelatin are described in Arther Weiss, The Macromolecular Chemistry of Gelatin, published by Academic Press, 1964.
  • any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride is used as the silver halide.
  • the average grain size (the grain size being defined as the diameter of the grains when the grain has a spherical or a nearly spherical form and as the length of the edge when the grain has a cubic form, and being averaged based on the projected area of the grains) of the silver halide grians in the photographic emulsions but it is preferred that the grain size be not more than 2 f..lm.
  • the grain size distribution may be narrow or broad, but a monodispersed silver halide emulsion having a coefficient of variation of not more than 15% is preferred.
  • the silver halide grains in the photographic emulsion layers may have a regular crystal form such as cubic, octahedral, oran irregular crystal form such as spherical, tabular, or may have a composite form of these crystal forms. Also, a mixture of grains having various crystal forms may be used. Of these emulsions, the use of a photographic emulsion of regular crystal form is preferred.
  • a silver halide emulsion wherein tabular silver halide grains having a diameter/thickness ratio of at least 5 accounts for at least 50% of the total projected area of the silver halide grains may be used in the present invention.
  • the silver halide grains used in the present invention may have a composition or structure inside the grain which is different from that on the surface layer thereof. Also, the silver halide grains may be of the type that latent images are formed mainly on the surface thereof or of the type that latent images are formed mainly in the interior thereof.
  • a cadmium salt a zinc salt, a thallium salt, a lead salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof, may exist in the system.
  • Silver halide emulsions are usually chemically sensitized.
  • the silver halide emulsions used in the present invention can further contain various kinds of compounds for preventing the occurrence of fog or for stabilizing photographic performance during the production, storage and/or photographic processing of color photographic materials.
  • examples of such compounds include the compounds known as antifoggants or stabilizers such as azoles (e.g., benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (in particular, 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes (e.g.
  • the present invention can be applied to multilayer multicolor photographic materials having at least two photographic emulsion layers each having different spectral sensitivity on a support.
  • a multilayer natural color photographic material usually has at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer on a support.
  • the disposition order of these photographic emulsion layers can be optionally selected according to the purpose for which the photographic material is used.
  • a red-sensitive emulsion layer contains a cyan-forming coupler
  • a green-sensitive emulsion layer contains a magenta-forming coupler
  • a blue-sensitive emulsion layer contains a yellow-forming coupler.
  • Other combinations may be used, if desired.
  • the support used in the present invention there are those conventionally employed in photographic light-sensitive materials, for example, cellulose nitrate films, cellulose acetate films, cellulose acetate butyrate films, cellulose acetate propionate films, polystyrene films, polyethylene terephthalate films, polycarbonate films, laminates of these films, thin glass films, papers.
  • Paper coated with baryta or an ⁇ -olefin polymer in particular, a polymer of an ⁇ -olefin having 2 to 10 carbon atoms, such as polyethylene, polypropylene, ethy- lenebutene copolymer, and a support such as a plastic film, having a roughened surface for improving the adhesion with other polymers as described in Japanese Patent Publication No. 19068/72 give good results. Also, a resin hardenable by the irradiation of ultraviolet rays can be used.
  • a transparent support or an opaque support may be used.
  • a colored transparent support containing dyes or pigments can also be used.
  • an opaque support used in the present invention there are papers which are opaque by themselves and transparent films which were opacified by the incorporation of dyes or pigments such as titanium oxide. Also, a plastic film surface-treated by the method as described in Japanese Patent Publication No. 19068/72 and further papers or plastic films rendered completely light shielding by the addition of carbon black, dyes, can be used.
  • a subbing layer is usually provided on the support. Furthermore, for improving the adhesive property, a pretreatment such as a corona discharging treatment, an ultraviolet irradiation treatment, a flame treatment, may be applied to the surface of the support.
  • a pretreatment such as a corona discharging treatment, an ultraviolet irradiation treatment, a flame treatment, may be applied to the surface of the support.
  • color photographic light-sensitive material which can be used for making the color photograph according to the present invention
  • an ordinary color photographic light-sensitive material in particular, a color photographic light-sensitive material for color print is preferred
  • color photographic light-sensitive materials of color photographic systems in particular, color diffusion transfer photographic systems as described in U.S. Patents 3,227,550, 3,227,551 and 3,227,552, and U.S. Preliminary Published Patent B351,673, may be used.
  • Color photographic development processing fundamentally includes the steps of color development, bleaching and fixing. In this case, two steps of bleaching and fixing may be performed by one step (bleach-fixing).
  • the color development processing step may include, if necessary, various steps of pre-hardening, neutralization, first development (black-and-white development), image stabilization, washing with water.
  • the processing temperature is generally 18°C or more, and preferably in the range from 20°C to 60°C. In particular, recently the range of from 30°C to 60°C is used.
  • a color developing solution is an aqueous alkaline solution containing an aromatic primary amine color developing agent and having a pH of at least 8, preferably from 9 to 12.
  • a water washing process is usually performed, but a simple so-called “stabilization process” may be substituted in place of the waterwashing process substantially without employing a water washing step.
  • aromatic primary amine color developing agent Preferred examples of the aromatic primary amine color developing agent are p-phenylenediamine derivatives and specific examples thereof are described below:
  • these p-phenylenediamine derivatives may be in the form of salts thereof, such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates.
  • salts thereof such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates.
  • the above described compounds are described, for example, in U.S. Patents 2,193,015, 2,552,241, 2,566,271, 2,592,364, 3,656,950 and 3,698,525.
  • the amount of the aromatic primary amine color developing agent is from about 0.1 g to about 20 g, and preferably from about 0.5 g to about 10 g per liter of color developing solution.
  • the color developing solution used in the present invention may contain hydroxylamines as conventionally known.
  • the processing temperature of the color developing solution is preferably from 30°C to 50°C, and more preferably from 33°C to 42°C.
  • the amount of a replenisher for the color developing solution is from 30 ml to 2,000 ml, and preferably from 30 ml to 1,500 ml per square meter of color photographic material.
  • the amount of the replenisher is, however, preferably as low as possible from the viewpoint of reducing the amount of waste liquid.
  • the amount thereof is preferably not more than 2.0 mi/liter, and more preferably not more than 0.5 ml/liter.
  • a color developing solution containing no benzyl alcohol is most preferred.
  • the time for color development is preferably within 2 minutes and 30 seconds, more preferably from 10 seconds to 2 minutes and 30 seconds, and most preferably from 45 seconds to 2 minutes.
  • the compounds of (1) and (2) may be applied to a silver halide color photographic material after imagewise exposure.
  • the application can be conducted by incorporating the compounds into at least one of color photographic processing solutions such as a developing solution, a bleaching solution, a fixing solution, a blixing solution, water for washing or water specifically provided for applying the compounds to the photographic material, or a stabilizing solution. It is also possible to incorporate these compounds separately into two or more solution.
  • the compounds are preferably contained in a developing solution. It is also possible to apply the compounds after developing process using an aqueous solution containing the compounds.
  • Each concentration of the compounds (1) and (2) in the processing solution is preferably from 1 x 10 -5 to 1 moi/f, and the molar ratio of the concentration of the compound (1) to that of compound (2) is from 0.1 to 10.
  • color photographic light-sensitive materials which exhibit remarkable improvement in preservability even when the composition of the processing solution is changed due to processing with a processing solution which provides a large amount of its components to the color photographic material, such as a processing solution of a running state, a processing solution of reduced amount of washing water or without employing a water washing step, a color developing solution containing substantially no benzyl alcohol, or other processing solutions which impose a burden on color development.
  • a processing solution which provides a large amount of its components to the color photographic material such as a processing solution of a running state, a processing solution of reduced amount of washing water or without employing a water washing step, a color developing solution containing substantially no benzyl alcohol, or other processing solutions which impose a burden on color development.
  • color photographs excellent in fastness of color images are obtained.
  • color photographs are obtained in which, the three color balance of a yellow dye, a magenta dye and a cyan dye is maintained and the coloration of white background is exceptionally low even when they are preserved for a long period of time.
  • a first layer (the undermost layer) to a seventh layer (the uppermost layer) as shown in Table A below were coated in this order to prepare a color photographic light-sensitive material.
  • the following dyes were used for the emulsion layers as irradiation preventing dyes.
  • compositions of the processing solutions used were as follows.
  • compositions of the processing solutions used were almost in an equilibrium state since the development processing was conducted while performing normal replenishing using an ordinary roller transport type developing solution processer.
  • a color photographic light-sensitive material (Sample G) was prepared as follows.
  • the polyethylene coating on the Layer 1 side of the support contained titanium dioxide as a white pigment and a small amount of ultramarine as a bluish dye.
  • each layer is shown below.
  • the coating amounts of the components are described in the unit of g/m 2 .
  • the coating amount is indicated in terms of a silver coating amount.
  • the compounds used for the color photographic light-sensitive material were as follows.
  • the samples thus-prepared were exposed through an optical wedge and subjected to development processing according to the following processing steps.
  • compositions for the processing solutions used were as follows.
  • magenta reflection density (stain) at the non-imaged portion of each sample thus processed was measured and then the magenta reflection density (stain) at the non-imaged portion thereof was measured again after allowing the sample to stand for 3 days at 80°C and 70% RH and after allowing the sample to stand for 80 days at room tesmperature.
  • the increase in stain from one hour after processing is shown in Table 2 below.
  • the following First layer to Fourteenth layer were coated on a paper support, both surfaces of which were laminated with polyethylene to prepare a multilayer color photographic light-sensitive material.
  • the polyethylene laminated on the First layer side of the support contained titanium dioxide as a white pigment and a small amount of ultramarine as a bluish dye.
  • composition of each layer is shown below.
  • the coating amounts of the components are described in the unit of g/m 2 .
  • the coating amount is indicated in terms of silver coating amount.
  • An aqueous solution of potassium bromide and an aqeuous solution of silver nitrate were added simultaneously to a gelatin aqueous solution containing 0.3 g/molAg of 3,4-dimethyl-1,3-thiazoiine-2-thion over about 20 minutes at 75°C while vigorously stirring, to obtain a monodispersed octahedral silver bromide emulsion having an average grain size of about 0.40 ⁇ m.
  • nucleating agent N-I-9
  • Nucleating accelerator ExZS-1
  • Example 3 The compounds used in Example 3 are illustrated below.
  • the samples thus-obtained were exposed to light through an optical wedge, and then processed according to the following Processing A.
  • compositions of the processing solutions used were as follows. (pH was adjusted with potassium hydroxide or hydrochloric acid.) (pH was adjusted with aqueous ammonia or hydrochloric acid.)
  • pure water used herein means the water produced by processing city water with an ion exchange process whereby the cation concentration and the anion concentration (except hydrogen ion and hydroxide ion) were reduced to 1 ppm or less.

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Claims (22)

1. Farbphotographisches Silberhalogenidmaterial, umfassend einen Träger mit darauf mindestens einer Silberhalogenidemulsionsschicht, worin das farbphotographische Silberhalogenidmaterial enthält:
(1) mindestens eine Verbindung, die durch die allgemeine Formel (I) oder (11) dargestellt ist, und mindestens eine Verbindung, die durch die allgemeine Formel (III) dargestellt ist, wobei jede Verbindung der Formel (I), (II) und (III) Dimere oder höhere Polymere einschließt, welche mindestens einen Bestandteil enthalten, der abgeleitet ist von den Verbindungen:
Figure imgb0634
Figure imgb0635
Figure imgb0636
worin R1 und R2 jeweils eine aliphatische Gruppe, eine aromatische Gruppe oder eine heterocyclische Gruppe darstellt; X eine Gruppe darstellt, die bei einer Reaktion von A mit einem aromatischen Aminentwicklungsmittel freigesetzt werden kann; A eine Gruppe darstellt, die mit einem aromatischen Aminentwicklungsmittel reagieren kann, um eine chemische Bindung zu bilden; n 0 oder 1 darstellt; wenn n 0 ist, Xein Halogenatom darstellt; Bein Wasserstoffatom, eine aliphatische Gruppe, eine aromatische Gruppe, eine heterocyclische Gruppe, eine Acylgruppe oder eine aliphatische oder aromatische Sulfonylgruppe darstellt; Y eine Gruppe darstellt, welche die Addition eines aromatischen Aminentwicklungsmittels an die durch die allgemeine Formel (II) dargestellte Verbindung beschleunigen kann; worin R1 und X, oder Y und R2 oder B miteinander verbunden sein können, um eine cyclische Struktur zu bilden; M ein Atom oder eine Atomgruppe, die ein anorganisches Salz oder ein organisches Salz bilden,
Figure imgb0637
Figure imgb0638
darstellt, worin R15 und R16, welche gleich oder verschieden sein können, jeweils ein Wasserstoffatom, eine aliphatische Gruppe, eine aromatische Gruppe oder eine heterocyclische Gruppe darstellt, worin R15 und R16 miteinander verbunden sein können, um einen 5-gliedrigen bis 7-gliedrigen Ring zu bilden; R17, R18, R20 und R21, welche gleich oder verschieden sein können, jeweils ein Wasserstoffatom, eine aliphatische Gruppe, eine aromatische Gruppe, eine heterocyclische Gruppe, eine Acylgruppe, eine Alkoxycarbonylgruppe, eine aliphatische oder aromatische Sulfonylgruppe, eine Ureidogruppe, oder eine Urethangruppe darstellt, vorausgesetzt, daß mindestens eines von R17 und R18 und mindestens eines von R20 und R21 jeweils ein Wasserstoffatom darstellt; R19 und R22 jeweils ein Wasserstoffatom, eine aliphatische Gruppe, eine aromatische Gruppe oder eine heterocyclische Gruppe darstellt; R19 außerdem eine Alkylaminogruppe, eine Arylaminogruppe, eine Alkoxygruppe, eine Aryloxygruppe, eine Acylgruppe, eine Alkoxycarbonylgruppe oder eine Aryloxycarbonylgruppe darstellen kann; worin mindestens zwei von R17, R18 und R19 miteinander verbunden sein können, um einen 5-gliedrigen bis 7-gliedrigen Ring zu bilden, und mindestens zwei von R20, R21 und R22 miteinander verbunden sein können, um einen 5-gliedrigen bis 7-gliedrigen Ring zu bilden; R23 ein Wasserstoffatom, eine aliphatische Gruppe, eine aromatische Gruppe oder eine heterocyclische Gruppe darstellt; R24 ein Wasserstoffatom, eine aliphatische Gruppe, eine aromatische Gruppe, ein Halogenatom, eine Acyloxygruppe oder eine aliphatische oder aromatische Sulfonylgruppe darstellt; R25 ein Wasserstoffatom oder eine alkalisch hydrolysierbare Gruppe darstellt; und R10, R11, R12, R13 und R14, welche gleich oder verschieden sein können, jeweils ein Wasserstoffatom, eine aliphatische Gruppe, eine aromatische Gruppe, eine heterocyclische Gruppe, ein Halogenatom, -SR26, -OR26,
Figure imgb0639
(worin R26 und R27, welche im Fall von -NR26R27 gleich oder verschieden sein können, jeweils ein Wasserstoffatom, eine aliphatische Gruppe, eine Alkoxygruppe oder eine aromatische Gruppe darstellen), eine Acylgruppe, eine Alkoxycarbonylgruppe, eine Aryloxycarbonylgruppe, eine aliphatische oder aromatische Sulfonylgruppe, eine aliphatische oder aromatische Sulfonamidogruppe, eine Sulfamoylgruppe, eine Ureidogruppe, eine Urethangruppe, eine Carbamoylgruppe, eine Sulfogruppe, eine Carboxygruppe, eine Nitrogruppe, eine Cyanogruppe, eine Alkoxyoxalylgruppe, eine Aryloxyoxalylgruppe, eine aliphatische oder aromatische Sulfonyloxygruppe, -P(R26)3,
Figure imgb0640
-P(OR26)3, (worin R26 die gleiche Bedeutung wie oben definiert hat), oder eine Formylgruppe darstellt; und
(2) mindestens eine Verbindung, ausgewählt aus der Gruppe bestehend aus organischen, das Verblassen der Farbe verhindernden Mitteln, die durch die allgemeine Formel (IV) dargestellt sind, und Dimeren oder höheren Polymeren, enthaltend mindestens einen Bestandteil, der abgeleitet ist von den Mitteln, organischen Metallkomplexen, die Kupfer, Cobalt, Nickel, Palladium oder Platin als Zentralmetall enthalten und mindestens einen organischen Liganden mit mindestens einem Atom haben, welches mit dem Zentralatom koordiniert, und Dimeren oder höheren Polymeren, welche mindestens einen Bestandteil enthalten, der von den Komplexen abgeleitet ist:
Figure imgb0641
worin R30 eine aliphatische Gruppe, eine aromatische Gruppe oder eine heterocyclische Gruppe darstellt; R31 ein Wasserstoffatom, eine aliphatische Gruppe, eine aromatische Gruppe, eine heterocyclische Gruppe oder
Figure imgb0642
darstellt; R32, R33 und R34, welche gleich oder verschieden sein können, jeweils eine Alkylgruppe, eine Alkenylgruppe, eine Arylgruppe, eine Alkoxygruppe, eine Alkenoxygruppe oder eine Aryloxygruppe darstellen; W -O-, -S- oder
Figure imgb0643
darstellt; R35 ein Wasserstoffatom, eine aliphatische Gruppe, eine aromatische Gruppe, eine heterocyclische Gruppe, eine Acylgruppe, eine Sulfonylgruppe, eine Sulfinylgruppe, eine Sauerstoffradikal-Gruppe (oxy-radical group) oder eine Hydroxygruppe darstellt; worin R30 und R31 oder R35 und R30 oder R31 miteinander verbunden sein können, um einen 5-gliedrigen bis 7-gliedrigen Ring zu bilden.
2. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, worin die durch die allgemeine Formel (I) oder (II) dargestellte Verbindung eine Geschwindigkeitskonstante der Reaktion zweiter Ordnung K2 (80°C) bei einer Reaktion mit p-Anisidin im Bereich von 1,0 I/Mol.s bis 1x10-5 l/Mol·s hat.
3. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, worin die durch X in der allgemeinen Formel (I) dargestellte Gruppe eine Gruppe ist, die mitAüberein Sauerstoffatom, ein Schwefelatom oder ein Stickstoffatom oder ein Halogenatom verbunden ist.
4. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, worin die durch A in der allgemeinen Formel (I) dargestellte Gruppe eine Gruppe ist, die ein Atom mit niedriger Elektronendichte enthält, ausgewählt aus
Figure imgb0644
worin L eine Einfachbindung, eine Alkylengruppe, -O-, -S-,
Figure imgb0645
Figure imgb0646
darstellt; Ydie gleiche Bedeutung wie in der allgemeinen Formel (II) definiert hat; Y' die gleiche Bedeutung wie für Y definiert hat; R' und R", welche gleich oder verschieden sein können, jeweils -L"'-R0 darstellen; Ro die gleiche Bedeutung wie für R1 definiert hat; R"' ein Wasserstoffatom, eine aliphatische Gruppe, eine aromatische Gruppe, eine heterocyclische Gruppe, eine Acylgruppe oder eine aliphatische oder aromatische Sulfonylgruppe darstellt; und L', L" und L"' jeweils -O-, -S- oder
Figure imgb0647
darstellt.
5. Farbphotographisches Silberhalogenidmaterial nach Anspruch 4, worin A
Figure imgb0648
oder
Figure imgb0649
darstellt.
6. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, worin die durch die allgemeine Formel (I) dargestellte Verbindung ausgewählt ist aus Verbindungen, die durch die folgende allgemeine Formel (I-a), (I-b), (I-c) und (I-d) dargestellt sind, und eine Geschwindigkeitskonstante der Reaktion zweiter Ordnung K2 (80°C) bei einer Reaktion mit p-Anisidin im Bereich von 1x10-1 I/Mol·s bis 1x10-5 l/Mol·s hat:
Figure imgb0650
Figure imgb0651
Figure imgb0652
Figure imgb0653
worin R1 die gleiche Bedeutung wie R1, das in der allgemeinen Formel (I) definiert ist, hat; Link eine Einfachbindung oder -0- darstellt; Ar eine aromatische Gruppe darstellt, vorausgesetzt, daß sie nicht infolge einer Reaktion mit einem Entwicklungsmittel der aromatischen Aminreihe eine als photographische reduzierende Gruppe brauchbare Gruppe wird; Ra, Rb und Rc, welche gleich oder verschieden sein können, jeweils ein Wasserstoffatom, eine aliphatische Gruppe, eine aromatische Gruppe, eine heterocyclische Gruppe, eine Alkoxygruppe, eine Aryloxygruppe, eine heterocyclische Oxygruppe, eine Carboxygruppe, eine Alkylthiogruppe, eine Arylthiogruppe, eine heterocyclische Thiogruppe, eine Aminogruppe, eine Alkylaminogruppe, eine Acylaminogruppe, eine Sulfonamidogruppe, eine Acylgruppe, eine aliphatische oder aromatische Sulfonylgruppe, eine Alkoxycarbonylgruppe, eine Sulfogruppe, eine Hydroxylgruppe, eine Acyloxygruppe, eine Ureidogruppe, eine Urethangruppe, eine Carbamoylgruppe oder eine Sulfamoylgruppe darstellen, worin Ra und Rb, oder Rb und Re miteinander verbunden sein können, um einen 5-gliedrigen bis 7-gliedrigen Heteroring zu bilden, wobei dieser Heteroring weiterhin mit einem Substituenten substituiert sein oder einen Spiroring oder einen Bicycloring bilden oder mit einem aromatischen Ring kondensiert sein kann; Z1 und Z2jeweils eine Nichtmetallatomgruppe darstellt, die erforderlich ist, um einen 5-gliedrigen bis 7-gliedrigen Heteroring zu bilden, wobei dieser Heteroring weiter mit einem Substituenten substituiert sein oder einen Spiroring oder einen Bicycloring bilden oder mit einem aromatischen Ring kondensiert sein kann.
7. Farbphotographisches Silberhalogenidmaterial nach Anspruch 6, worin die durch die allgemeine Formel (I-a), (I-b), (I-c) oder (I-d) dargestellte Verbindung eine Gesamtzahl von mindestens 13 Kohlenstoffatomen hat.
8. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, worin die durch Y in der allgemeinen Formel (II) dargestellte Gruppe ein Sauerstoffatom, ein Schwefelatom, =N-R4 oder
Figure imgb0654
worin R4, R5 und R6 jeweils ein Wasserstoffatom, eine aliphatische Gruppe, eine aromatische Gruppe, eine heterocyclische Gruppe, eine Acylgruppe oder eine aliphatische oder aromatische Sulfonylgruppe darstellt, worin R5 und R6 miteinander verbunden sein können, um eine cyclische Struktur zu bilden.
9. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, worin die durch die allgemeine Formel (IV) dargestellte Verbindung eine Verbindung ist, die durch die folgende allgemeine Formel (IV-a), (IV-b), (IV-c), (IV-d), (IV-e) oder (IV-f) dargestellt ist:
Figure imgb0655
Figure imgb0656
Figure imgb0657
Figure imgb0658
Figure imgb0659
Figure imgb0660
worin R41 ein Wasserstoffatom, eine aliphatische Gruppe, eine aromatische Gruppe, eine heterocyclische Gruppe oder
Figure imgb0661
(worin R32, R33 und R34 jeweils die gleiche Bedeutung wie in der allgemeinen Formel (IV) definiert hat) darstellt; R42, R43, R44, R45 und R46, welche gleich oder verschieden sein können, jeweils ein Wasserstoffatom, -W-R31, eine aliphatische Gruppe, eine aromatische Gruppe, eine heterocyclische Gruppe, eine Diacylaminogruppe, ein Halogenatom, eine aliphatische oder aromatische Sulfonylgruppe, eine aliphatische oder aromatische Sulfinylgruppe, eine Alkoxycarbonylgruppe, eine Aryloxycarbonylgruppe, eine Ureidogruppe, eine Urethangruppe, eine Sulfamoylgruppe, eine Carbamoylgruppe, eine Cyanogruppe, eine Nitrogruppe. eine aliphatische oder aromatische Carbonyloxygruppe, eine aliphatische oder aromatische Sulfonyloxygruppe, eine Silyloxygruppe, oder eine Imidogruppe darstellt, -W-R31 die gleiche Bedeutung wie in der allgemeinen Formel (IV) definiert hat, worin R41 und R42 miteinander verbunden sein können, um einen 5-gliedrigen bis 7-gliedrigen Ring zu bilden, oder zwei Substituenten von R42 bis R46, die in der o-Position zueinander vorliegen, miteinander verbunden sein können, um einen 5-gliedrigen bis 7-gliedrigen Ring zu bilden, oder R31 oder R35, wenn W
Figure imgb0662
darstellt, mit einer Gruppe verbunden sein können, die an der ortho-Position dazu vorhanden ist, um einen 5-gliedrigen bis 7-gliedrigen Ring zu bilden, R'41 die gleiche Bedeutung wie R35 hat, welches in der allgemeinen Formel (IV) definiert ist, worin R'41 mit R41 oder R42 verbunden sein kann, um einen 5-gliedrigen bis 7-gliedrigen Ring zu bilden, welcher der gleiche wie für R41 definiert ist, R50 eine aliphatische Gruppe, eine heteroaromatische Gruppe, eine heterocyclische Gruppe darstellt, R51 ein Wasserstoffatom, eine aliphatische Gruppe, eine heteroaromatische Gruppe oder eine heterocyclische Gruppe darstellt, und R35 die gleiche Bedeutung wie in der allgemeinen Formel (IV) definiert hat, und R50 und R51 oder R50 und R35 miteinander verbunden sein können, um einen 5-gliedrigen bis 7-gliedrigen Ring zu bilden, welcher der gleiche wie oben für R41 definiert ist.
10. Farbphotographisches Silberhalogenidmaterial nach Anspruch 9, worin die durch die allgemeine Formel (IV-a) oder (IV-f) dargestellte Verbindung eine Verbindung ist, die durch die folgende allgemeine Formel (IV-a1), (IV-a2), (IV-a3), (IV-a4), (lV-a5), (IV-a6), (IV-a7), (IV-a8) oder (IV-f1) dargestellt ist:
Figure imgb0663
Figure imgb0664
Figure imgb0665
Figure imgb0666
Figure imgb0667
Figure imgb0668
Figure imgb0669
Figure imgb0670
Figure imgb0671
worin R41 bis R46 jeweils die gleiche Bedeutung wie in der allgemeinen Formel (IV-a) definiert hat, R'41 und R'42 bis R'46 jeweils die gleiche Bedeutung wie für R41 bzw. R42 bis R46 definiert hat, und jeder Substituent mit jedem anderen verbunden sein kann, um einen 5-gliedrigen bis 7-gliedrigen Ring zu bilden, welcher der gleiche wie in der allgemeinen Formel (IV-a) definiert ist; R61 bis R64, welche gleich oder verschieden sein können, jeweils ein Wasserstoffatom, eine aliphatische Gruppe, eine aromatische Gruppe oder eine heterocyclische Gruppe darstellen; R65 und R66, welche gleich oder verschieden sein können, jeweils ein Wasserstoffatom, eine aliphatische Gruppe, eine aromatische Gruppe, eine heterocyclische Gruppe, eine Alkoxygruppe, eine Aryloxygruppe, eine Alkylthiogruppe, eine Arylthiogruppe, eine Alkylaminogruppe, eine Acylaminogruppe oder
Figure imgb0672
darstellen, worin E1 eine Nichtmetallatomgruppe darstellt, die erforderlich ist, um einen 5-gliedrigen bis 7-gliedrigen Ring zu bilden; R35 die gleiche Bedeutung wie in der allgemeinen Formel (IV-f) definiert hat; E eine Nichtmetallatomgruppe darstellt, die erforderlich ist, um einen 5-gliedrigen bis 7-gliedrigen Ring zu bilden; und R71 bis R74, welche gleich oder verschieden sein können, jeweils ein Wasserstoffatom oder eine Alkylgruppe darstellen.
11. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, worin das Zentralmetall des organischen Metallkomplexes Nickel ist.
12. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, worin der organische Metallkomplex ein Komplex ist, der durch die folgende allgemeine Formel (V-a), (V-b), (V-c) oder (V-d) dargestellt ist:
Figure imgb0673
Figure imgb0674
Figure imgb0675
Figure imgb0676
worin M Kupfer, Cobalt, Nickel, Palladium oder Platin darstellt; R80 und R'80, welche gleich oderverschieden sein können, jeweils ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe oder eine Hydroxygruppe darstellen, worin R80 und R'80 miteinander verbunden sein können; R81, R82, R83, R'81, R'82 und R'83, welche gleich oder verschieden sein können, jeweils ein Wasserstoffatom, eine Alkylgruppe oder eine Arylgruppe darstellen, worin R82 und R83 oder R'82 und R'83 miteinander verbunden sein können, um einen aromatischen Ring oder einen 5-gliedrigen bis 8-gliedrigen Ring zu bilden; R84, R85, R'84 und R'85, welche gleich oder verschieden sein können, jeweils eine Alkylgruppe, eine Arylgruppe, eine Alkylthiogruppe, eine Arylthiogruppe, eine Alkoxygruppe, eine Aryloxygruppe, eine Alkylaminogruppe oder eine Arylaminogruppe darstellen; R 86, R87, R 88, R89, R9o, R'86, R'87, R'88, R'89 und R'90, welche gleich oder verschieden sein können, jeweils ein Wasserstoffatom, eine Alkylgruppe oder eine Arylgruppe darstellen, worin mindestens einer von R86 und R87, R89 und R90, R'86 und R'87 und R'89 und R'90 miteinander verbunden sein können, um einen aromatischen Ring oder einen 5-gliedrigen bis 8-gliedrigen Ring zu bilden; X1 eine Verbindung darstellt, die an M koordinieren kann; A1, A2, A'1 und A'2, welche gleich oder verschieden sein können, jeweils ein Sauerstoffatom, ein Schwefelatom, -NR91-, eine Hydroxygruppe, eine Alkoxygruppe, eine Alkylthiogruppe oder
Figure imgb0677
darstellen;
R91 ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Hydroxygruppe oder eine Alkoxygruppe darstellt; R92 und R93, welche gleich oder verschieden sein können, jeweils ein Wasserstoffatom oder eine Alkylgruppe darstellen; und A3 und A'3 jeweils ein Sauerstoffatom, ein Schwefelatom oder-NH- darstellen.
13. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, worin das farbphotographische Material mindestens einen von einem Gelbkuppler, einem Magentakuppler und einem Cyankuppler enthält.
14. Farbphotographisches Silberhalogenidmaterial nach Anspruch 13, worin der Kuppler ausgewählt ist aus den durch die folgende allgemeine Formel (C-I), (C-II), (M-I), (M-II) oder (Y) dargestellten:
Figure imgb0678
Figure imgb0679
Figure imgb0680
Figure imgb0681
Figure imgb0682
worin R1, R4 und R5 jeweils eine aliphatische Gruppe, eine aromatische Gruppe, eine heterocyclische Gruppe, eine aromatische Aminogruppe oder eine heterocyclische Aminogruppe darstellt; R2 eine aliphatische Gruppe darstellt; R3 und Rsjeweils ein Wasserstoffatom, ein Halogenatom, eine aliphatische Gruppe, eine aliphatische Oxygruppe oder eine Acylaminogruppe darstellt; R5' ein Wasserstoffatom oder eine Gruppe, die durch das oben definierte R5 dargestellt ist, darstellt; R7 und R9 eine substituierte oder unsubstituierte Phenylgruppe darstellt; R8 ein Wasserstoffatom, eine aliphatische Acylgruppe, eine aromatische Acylgruppe, eine aliphatische Sulfonylgruppe oder eine aromatische Sulfonylgruppe darstellt; R10 ein Wasserstoffatom oder einen Substituenten darstellt; Q eine substituierte oder unsubstituierte N-Phenyl-carbamoyl-Gruppe darstellt; Za und Zb jeweils eine Methingruppe, eine substituierte Methingruppe oder =N- darstellt; und Y1, Y2, Y3 und Y5 jeweils ein Wasserstoffatom oder eine Gruppe darstellt, die bei einer Kupplungsreaktion mit dem Oxidationsprodukt eines Farbentwicklungsmittels freigesetzt werden kann, worin R2 und R3 oder R5 und R6 miteinander verbunden sein können, um einen 5-gliedrigen bis 7- gliedrigen Ring zu bilden; oder R1, R2, R3 oder Y1; R4, R5, R6 oder Y2; R7, R8, R9 oder Y3; R10, Za, Zb oder Y4; und Q oder Z5 jeweils ein Dimer oder ein höheres Polymer bilden können.
15. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, worin jede Menge der mindestens einen Verbindung von (1) und der mindestens einen Verbindung von (2) von 1 x 10-2 bis 10 Mol pro Mol des Kupplers in der gleichen Schicht beträgt.
16. Farbphotographisches Silberhalogenidmaterial nach Anspruch 15, worin das Molverhältnis der Menge der mindestens einen Verbindung von (1) und der mindestens einen Verbindung von (2) 0,1 bis 10 beträgt.
17. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, worin die Verbindung(en) von (1) und die Verbindung(en) von (2) in mindestens einer hydrophilen Kolloidschicht in dem photographischen Material eingearbeitet sind.
18. Farbphotographisches Silberhalogenidmaterial nach Anspruch 17, worin die hydrophile Kolloidschicht eine Silberhalogenidemulsionsschicht ist.
19. Verfahren zum Erzeugen von Farbbildern, welches das bildmäßige Belichten eines farbphotographischen Silberhalogendmaterials, welches mindestens einen Farbstoffbild-erzeugenden Kupplerenthält, und das Unterwerfen des belichteten photographischen Materials einerfarbphotographischen Verarbeitung in Gegenwart von mindestens einer Verbindung von (1) und mindestens einer Verbindung von (2), wie sie in Anspruch 1 definiert sind, umfaßt.
20. Verfahren nach Anspruch 19, worin die Verbindungen in mindestens einer von einer Entwicklungslösung, einer Bleichlösung, einer Fixierlösung, einer Blixierlösung, einer stabilisierenden Lösung und Waschwasser eingearbeitet sind.
21. Verfahren nach Anspruch 20, worin jede Konzentration der mindestens einen Verbindung von (1) und der mindestens einen Verbindung von (2) in der wäßrigen Verarbeitungslösung 1 x 10-5 bis 1 Mol/1 beträgt.
22. Farbphotographischer Abzug, umfassend einen reflektierenden Träger mit darauf mindestens einem von einer Schicht, enthaltend einen Farbstoff, der ein gelbes Bild erzeugt, einer Schicht, enthaltend einen Farbstoff, der ein Magentabild erzeugt, und einer Schicht, enthaltend einen Farbstoff, der ein Cyanbild erzeugt, wobei der photographische Abzug mindestens eine Schicht hat, die mindestens eine Verbindung von (1) und mindestens eine Verbindung von (2), wie sie in Anspruch 1 definiert sind, enthält.
EP19880110100 1987-06-25 1988-06-24 Farbphotographisches Silberhalogenidmaterial Expired - Lifetime EP0298321B1 (de)

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JP62158342A JPH07122745B2 (ja) 1987-06-25 1987-06-25 ハロゲン化銀カラ−写真感光材料
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JP2537088B2 (ja) * 1988-09-27 1996-09-25 富士写真フイルム株式会社 カラ―写真感光材料
US5043256A (en) * 1988-09-27 1991-08-27 Fuji Photo Film Co., Ltd. Color photographic material
JPH02220046A (ja) * 1989-02-21 1990-09-03 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
JP2618707B2 (ja) * 1989-04-24 1997-06-11 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
JP2876077B2 (ja) * 1989-07-17 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
JP2631145B2 (ja) * 1989-07-18 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および該感材を用いて得られたカラー写真
JP2876079B2 (ja) * 1989-07-21 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
JP2964009B2 (ja) * 1990-02-08 1999-10-18 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
US5298368A (en) * 1991-04-23 1994-03-29 Eastman Kodak Company Photographic coupler compositions and methods for reducing continued coupling
JP2964459B2 (ja) * 1991-06-28 1999-10-18 コニカ株式会社 ハロゲン化銀写真感光材料
JPH06175316A (ja) * 1992-12-11 1994-06-24 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料及びカラー画像形成方法
JPH07146532A (ja) * 1993-11-24 1995-06-06 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
US5601970A (en) * 1995-01-03 1997-02-11 Eastman Kodak Company Photographic elements exhibiting improved stability
JPH08202001A (ja) 1995-01-30 1996-08-09 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
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JPS5425823A (en) * 1977-07-29 1979-02-27 Konishiroku Photo Ind Co Ltd Silver halide color photographic material
JPS599657A (ja) * 1982-07-07 1984-01-19 Fuji Photo Film Co Ltd ハロゲン化銀カラ−感光材料
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EP0298321A3 (en) 1990-01-17
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EP0298321A2 (de) 1989-01-11
DE3853742T2 (de) 1995-10-05
JPS642042A (en) 1989-01-06

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