EP0270078B1 - Matériau photographique couleur à l'halogénure d'argent et épreuve photographique couleur - Google Patents

Matériau photographique couleur à l'halogénure d'argent et épreuve photographique couleur Download PDF

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Publication number
EP0270078B1
EP0270078B1 EP19870117764 EP87117764A EP0270078B1 EP 0270078 B1 EP0270078 B1 EP 0270078B1 EP 19870117764 EP19870117764 EP 19870117764 EP 87117764 A EP87117764 A EP 87117764A EP 0270078 B1 EP0270078 B1 EP 0270078B1
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EP
European Patent Office
Prior art keywords
group
color photographic
silver halide
represented
color
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EP19870117764
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German (de)
English (en)
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EP0270078A3 (en
EP0270078A2 (fr
Inventor
Yukio Fuji Photo Film Co. Ltd. Aogaki
Yuzo Fuji Photo Film Co. Ltd. Toda
Nobuhiko Fuji Photo Film Co. Ltd. Minagawa
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • G03C7/32—Colour coupling substances
    • G03C7/3225—Combination of couplers of different kinds, e.g. yellow and magenta couplers in a same layer or in different layers of the photographic material
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/795—Photosensitive materials characterised by the base or auxiliary layers the base being of macromolecular substances

Definitions

  • the present invention relates to a silver halide color photographic material and a color photographic print, and more particularly to a color photographic print suitable for use as, for example, an ID card, a cashing card or a telephone card.
  • Conventional silver halide color photographic materials comprise a silver halide emulsion layer containing a cyan color forming coupler, a silver halide emulsion layer containing a magenta color forming coupler and a silver halide emulsion layer containing a yellow color forming coupler coated on various kinds of supports.
  • EP-A-0 162 328 discloses a silver halide color photographic light-sensitive material having a good color formability, color reproducibility, image preservability and color balance, said material comprising a support and red-sensitive, green-sensitive and blue-sensitive light-sensitive layers formed on the support.
  • a transparent plastic film for example, a cellulose triacetate film, a polyethylene terephthalate film or a vinyl resin film
  • a reflective support for example, baryta coated paper, synthetic paper, polyethylene laminated paper, a plastic sheet containing a white pigment, a glass plate or a metal plate (for example, an aluminium plate having an anodized surface) may be employed.
  • a white pigment be incorporated into a plastic material or that a white pigment containing layer is provided on a surface of a plastic material in order to particularly improve the whiteness of the supports.
  • EP-A-0 065 329 discloses a surface-treated polyvinyl chloride material which may contain pigments including an adhering hydrophilic layer containing a mixture of a hydrophilic colloid binder, gelatin in particular, and dispersed colloidal silica.
  • the surface-treated polyvinyl chloride material is particularly suitable for use in identification document production.
  • a silver halide color photographic material comprising a reflective support composed of a vinyl chloride resin containing a white pigment and having thereon in an appropriate order at least one red-sensitive silver halide emulsion layer containing a cyan color forming coupler represented by the general formula (1) or (2) shown below, at least one green-sensitive silver halide emulsion layer containing a magenta color forming coupler represented by the general formula (3) or (4) shown below, and at least one blue-sensitive silver halide emulsion layer containing a yellow color forming coupler represented by the general formula (5) shown below wherein R1, R4 and R5 each represents an aliphatic group, an aromatic group, a heterocyclic groups an aromatic amino group or a heterocyclic amino group; R2 represents an aliphatic group; R3 and R6 each represents a hydrogen atom, a halogen atom, an aliphatic groups an aliphatic oxy group or an acylamino group; R1, R4 and R5 each represents an
  • a color photographic print comprising a reflective support composed of a vinyl chloride resin containing a white pigment and having thereon in an appropriate order at least one emulsion layer containing a cyan dye obtained by a reaction of a cyan color forming coupler represented by the general formula (1) or (2) shown below with an oxidation product of an aromatic primary amine developing agent, at least one emulsion layer containing a magenta dye obtained by a reaction of a magenta color forming coupler represented by the general formula (3) or (4) shown below with an oxidation product of an aromatic primary amine developing agent, and at least one emulsion layer containing a yellow dye obtained by a reaction of a yellow color forming coupler represented by the general formula (5) shown below with an oxidation product of an aromatic primary amine developing agent wherein R1, R4 and R5 each represents an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic
  • CD oxidation product of an aromatic primary amine developing agent
  • the color photographic print according to the present invention includes a color photographic print obtained by conducting at least the step or processing the silver halide color photographic material of the present invention, after imagewise exposure, with a color developing solution containing an aromatic primary amine color developing agent, and a color photographic print obtained by adhering the above-described color photographic print (but employing a transparent support) on a reflective support composed of a vinyl chloride resin containing a white pigment.
  • the groups capable of being released represented by X1, X2, X3, X4 or X5 include those described in U.S. Patent 4,540,654, column 4, line 30 to column 5, line 24. Among them, a chlorine atom for X1 or X2, a hydrogen atom or a group capable of being released containing a sulfur atom as a releasing atom for X3 or X4 and a group capable of being released containing an oxygen atom or a nitrogen atom as a releasing atom for X5 are preferred.
  • the vinyl chloride resin which constitutes the reflective support used in the present invention is a homopolymer or copolymer containing a vinyl chloride monomer as at least one kind of monomer. It is preferred that the vinyl chloride monomer occupies at least 50% by weight of the total monomer component.
  • comonomer component examples include, for example, methyl methacrylate, vinyl acetate, acrylonitrile, a fluorinated olefin, a vinyl ether, vinyl bromide, maleic acid, dichlorobutadiene, vinyl fluoride, vinylidene fluoride, trifluorochloroethylene, tetrafluoroethylene, vinylidene chloride, styrene, butadiene and chloroprene. Two or more of these comonomer components may be employed.
  • Suitable examples of fillers include starch, wood flour, clay, calcium carbonate and bentonite.
  • Suitable examples of plasticimers include a phthalic ester (e.g., dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, butyllauryl phthalate, dilauryl phthalate, butylbenzyl phthalate), a phosphoric ester (e.g., tricresyl phosphate, trixylenyl phosphate, trioctyl phosphate), a straight chain dibasic acid ester (e.g., dioctyl adipate, dioctyl azelate, dioctyl sebacate) and butylphthalyl butylglycolate.
  • Suitable examples of stabilizers include tribasic ester (e.g., dioctyl a
  • a filler may be added in an amount of from about 20 parts to 100 parts by weight per 100 parts by weight of the resin material.
  • the white pigments which can be added to the vinyl chloride resin include, for example, titanium white, zinc white, calcium carbonate, barium sulfate, white lead, white organic pigments or dyes and brightening agents.
  • the white pigments can be employed individually or as a mixture of two or more thereof.
  • the total amount of the white pigment added is preferably from 1 part by weight to 30 parts by weight and more preferably from 5 parts by weight to 15 parts by weight per 100 parts by weight of the vinyl chloride resin material.
  • the vinyl chloride resin as used in the present invention exhibits resistance to heat deformation, preferably to at least 50°C, more preferably to at least 70°C thereby preventing a dimensional change during the drying step after preparation and development steps of light-sensitive materials or during their use.
  • the average reflectivity of the reflective support used in the present invention in a visible range is from 80 to 98%.
  • the thickness of the reflective support is preferably from 50 ⁇ m to 500 ⁇ m and more preferably from 100 ⁇ m to 300 ⁇ m.
  • a subbing treatment may be conducted in order to improve adhesion of both materials.
  • various kinds of methods are known and a suitable method can be appropriately selected therefrom.
  • a method wherein the surface of the support is etched with acetone to make a rough surface, wood flour (cellulose component) is coated to fill in a concave portion of the surface and to cover a convex portion of the surface and thereby an affinity with gelatin is provided (because of a good affinity between cellulose and protein) and then a subbing solution containing pearl essence is coated thereon as described in Japanese Patent Publication No. 3583/60, a method wherein at least one layer composed of a mixture of cellulose nitrate and a vinyl acetate-vinyl chloride copolymer is coated as a subbing agent as described in Japanese Patent Publication No.
  • EP 0065329A1 (the term "OPI" as used herein refers to a "published unexamined application"), a method wherein a straight chain polyphosphoric acid ester resin is coated on a support as described in British Patent 742,370, a method wherein a hardened gelatin subbing layer is subjected to corona discharge treatment and then a light-sensitive silver halide emulsion layer is coated as described in British Patent 1,472,854, a method wherein an epoxidated rubbery polymer and a film-forming unsaturated polyester are coated as subbing agents as described in British Patent 1,179,563, a method wherein first a solution of an isobutyl methacrylate polymer dissolved in a solvent which does not affect the vinyl chloride polymer and then a usual subbing layer composed of gelatin and cellulose nitrate is coated thereon as described in U.S.
  • Patent 2,388,817 and a method wherein a subbing solution having the composition shown below is coated on a support as described in U.S. Patent 2,483,966.
  • Composition of Subbing Solution Parts by Weight Cellulose Nitrate (nitrogen content 11%) 5.0 to 7.0 Acetone 40.0 to 50.0 Methyl Ethyl Ketone 9.0 to 10.0 Methanol 25.0 to 35.0 Dioctyl Phosphate 2.5 to 4.2 Ethanol 0.0 to 3.5
  • a development inhibitor releasing compound (DIR compound) is added to the color photographic light-sensitive material according to the present invention for the purpose of further improving the sharpness.
  • Suitable DIR compounds include DIR couplers as described in U.S. Patents 3,933,500, 4,187,100 and 4,477,563, British Patent 1,504,094 and Japanese Patent Application (OPI) Nos. 206834/84, 210440/84 and 92556/85.
  • those dyes formed from pivaloyl acetanilide type couplers are preferred. These dyes have the excellent features that the long wavelength side of their spectral absorptions is sharply cut and that their fastness is excellent. Further, they are easily dispersed in a hydrophilic colloid using a small amount of an organic solvent or using a water-insoluble and organic solvent soluble polymer, in comparison with benzoyl acetanilide type couplers, and thus they enable the provision of a color-forming layer which is thin and has strong physical properties.
  • the yellow dyes which are preferably employed in the present invention are those represented by the following general formula (5-1): wherein R14 and R15, which may be the same or different, each represents a hydrogen atom or a substituent which is ordinarily used for a yellow coupler, provided that both R14 and R15 are not hydrogen atoms at the same time; and represents a coupling residue of an aromatic primary amine developing agent.
  • Suitable examples of the substituents represented by R14 and R15 include an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, an alkoxycarbamoyl group, an aliphatic amido group, an alkylsulfamoyl group, an alkylsulfonamido group, an alkylureido group, an alkyl-substituted succinimido group, an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamido group, an arylureido group, a carboxy group, a sulfo group, a nitro group, a cyano group and a thiocyano group.
  • the coupler used may be, for instance, a polymer coupler including
  • the alkyl group represented by R11 or R12 is preferably an alkyl group having from 1 to 4 carbon atoms.
  • Suitable examples of the substituents for the alkyl group include a hydroxy group, an alkylsulfonamido group and an alkoxy groups.
  • Specific examples of R11 or R12 include an ethyl group, a ⁇ -hydroxyethyl group, a ⁇ -methanesulfonamidoethyl group and a ⁇ -methoxyethyl group.
  • a representative example of the substituent represented by R13 is an alkyl group (for example, a methyl group).
  • magenta dyes used in the present invention those represented by the following general formula (4-1) or (4-2) are preferred.
  • R16 and R17 which may be the same or different, each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, 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
  • R16 or R17 may also be a divalent group to form a bis compound.
  • the magenta dye represented by the general formula (4-1) or (4-2) may be in the form of a polymer dye in which the dye moiety represented by the general formula (4-1) or (4-2) exists at the main chain or the side chain of the polymer and particularly a polymer derived from a vinyl monomer having the moiety represented by the general formula (4-1) or (4-2) is preferred.
  • R16 or R17 represents a linking group connected to a vinyl group.
  • the linking group represented by R16 or R17 in the cases wherein the part represented by the general formula (4-1) or (4-2) is included in a vinyl monomer includes an alkylene group (including a substituted or unsubstituted alkylene group, e.g., a methylene group, an ethylene group, a 1,10-decylene group or -CH2CH2OCH2CH2-), a phenylene group (including a substituted or unsubstituted phenylene group, e.g., a 1,4-phenylene group, a 1,3-phenylene group, or -NHCO-, -CONH-, -O-, -OCO-, and an aralkylene group (e.g., or or a combination thereof.
  • an alkylene group including a substituted or unsubstituted alkylene group, e.g., a methylene group, an ethylene group, a 1,10-decylene group or -
  • linking groups include -NHCO-, -CH2CH2-, -CH2CH2NHCO-, -CONHCH2CH2NHCO-, -CH2CH2OCH2CH2NHCO-, and
  • the vinyl group in the vinyl monomer may further have a substituent in addition to the moiety represented by the general formula (4-1) or (4-2).
  • substituents include a chlorine atom or a lower alkyl group having from 1 to 4 carbon atoms (e.g., a methyl group, an ethyl group or a butyl group).
  • the polymer derived from the vinyl monomer having the dye moiety may be a copolymer with a non-color forming ethylenic monomer.
  • non-color forming ethylenic monomers include an acrylic acid such as acrylic acid, ⁇ -chloroacrylic acid, ⁇ -alacrylic acid (e.g., methacrylic acid), an ester or an amide derived from an acrylic acid (e.g., acrylamide, n-butylacrylamide, tert-butylacrylamide, diacetoneacrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, vinyl propionate, vinyl laurate), acrylonitrile, methacrylonitrile, an aromatic vinyl compound (e.g., styrene and a derivative thereof, vinyltoluene, divinylbenzene, vinylacetophenone,
  • Two or more non-color forming ethylenically unsaturated monomers can be used together.
  • a combination of n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methyl acrylate and diacetoneacrylamide can be used.
  • the non-color forming ethylenically unsaturated monomer which is used to copolymerize with a solid water-insoluble monomer coupler can be selected in such a manner that the copolymer to be formed has good physical properties and/or chemical properties, for example, solubility, compatibility with a binder in a photographic colloid composition such as gelatin, flexibility and heat stability.
  • magenta dyes according to the present invention are characterized by good spectral absorption characteristics wherein the characteristic second absorption on the short wavelength side is not present or, if present, is small and the absorption on the long wavelength side is sharply cut, and by an excellent fastness to high humidity and heat. Further, when polymer magenta dyes are used, they can be dispersed as a latex and thus an organic solvent having a high boiling point is not necessary, or is used only in a reduced amount. As a result, it is possible to decrease the thickness of the color forming layer and to increase the physical strength thereof.
  • the cyan dyes used in the present invention are most typically dyes which are obtained upon an oxidation coupling reaction of phenol type couplers with paraphenylenediamine color developing agents. These phenol type cyan couplers may be used together with naphthol type cyan couplers. Specific examples of naphthol type couplers include those as described, for example, in U.S. Patent 2,474,293 and preferably those as described, for example, in U.S. Patents 4,052,212, 4,146,396, 4,228,233 and 4,296,200. Specific examples of phenol couplers include those as described, for example, in U.S. Patents 2,396,929, 2,801,171, 2,772,162 and 2,895,826.
  • Cyan couplers which are stable against humidity and temperature are advantageously used in the present invention.
  • Typical examples of those couplers include phenol cyan couplers having an alkyl group more than a methyl group at the meta-position of the phenol nucleus as described in, for example, U.S. Patent 3,772,002, cyan couplers as described in U.S. Patents 2,772,162, 3,758,308, 4,126,396, 4,334,011 and 4,327,173, West German Patent Application (OLS) No. 3,329,729 and European Patent 121,365 and cyan couplers as described in, for example, U.S. Patents 3,446,622, 4,333,999, 4,451,559 and 4,427,767.
  • the cyan dyes according to the present invention can cover a wavelength range of 600 ⁇ m to 700 ⁇ m by using two or more dyes represented by the general formula (1) or (2) in combination.
  • the cyan dyes can provide cyan color images having a small absorption on the short wavelength side and they are excellent in fastness to high humidity and heat.
  • the dyes which form images according to the present invention are preferably used in combination with one or more kinds of organic solvents having a high boiling point of at least 160°C represented by the general formula (7), (8), (9), (10) or (11) as shown below. Details of these organic solvents are described in Japanese Patent Application (OPI) No. 215272/87, pages 138 to 144. Further, it is particularly preferred that the dyes are used in combination with water-insoluble, organic solvent-soluble polymers as described in, for example, Japanese Patent Publication No. 30474/73, U.S. Patent 3,619,195 and International Application No. PCT/JP 87/00492 filed July 9, 1987.
  • the dyes may be used in combination with loaded polymeric latexes as described in U.S. Patent 4,203,716.
  • W1 - COO - W2 (8) W1 - O - W2 (11) wherein W1, W2 and W3 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group;
  • W4 represents W1, -O-W1 or -S-W1;
  • n represents an integer from 1 to 5, when n is two or more, two or more W4's may be the same or different; and W1 and W2 in the general formula (11) may be connected with each other to form a condensed ring.
  • water-insoluble, organic solvent-soluble polymers include polyvinyl acetate, polyvinyl propionate, and polymethyl methacrylate.
  • These polymers may be employed together with the above described organic solvent having a high boiling point of at least 160°C.
  • the dyes according to the present invention are used in combination with color fading preventing agents or antioxidizing agents represented by the general formula (12) or (13) shown below.
  • R20 represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or a hydrolyzable protective group
  • R21, R22, R23, R24 and R25 which may be the same or different, each represents a hydrogen atom or a substituent
  • R30 represents a hydrogen atom, an aliphatic group, an acyl group, a sulfonyl group, a sulfinyl group, an oxy radical group or a hydroxy group
  • A represents a non-metallic atomic group necessary to form a 5-membered, 6-membered or 7-membered ring
  • R26, R27, R28 and R29 which may be the same or different, each represents a hydrogen atom or an alky
  • substituents represented by R21 or R25 include a hydrogen atom and an alkyl group, and preferred examples of the alkyl group include a straight chain or branched chain alkyl group having from 1 to 8 carbon atoms, particularly a methyl group, an n-butyl group, a t-butyl group, a t-pentyl group and an n-octyl group.
  • substituents represented by R22, R23 or R24 include a hydrogen atom, an alkyl group, -NHR31, an alkoxy group and -COO-R32, R31 represents a nitrogen-containing heterocyclic group and R32 represents an alkyl group or an aryl group.
  • the above-mentioned alkyl, alkoxy or aryl group means a substituted or unsubstituted alkyl, alkoxy or aryl group.
  • R20 and R21 or two of R21, R22, R23, R24 and R25 which are present in ortho-positions of each other may be connected with each other to form a 5-membered, 6-membered or 7-membered ring.
  • R26 and R27, R28 and R29 or R30 and R26 may be connected with each other to form a 5-membered, 6-membered or 7-membered ring.
  • the color print according to a preferred embodiment of the present invention can be obtained by subjecting to color development processing, after imagewise exposure, a color printing paper which comprises a thin reflective support having thereon a yellow color forming layer containing a blue-sensitive silver halide emulsion and a yellow color forming coupler, a magenta color forming layer containing a green-sensitive silver halide emulsion and a magenta color forming coupler, and a cyan color forming layer containing a red-sensitive silver halide emulsion and a cyan color forming coupler, and optionally further, e.g., an antihalation layer, an intermediate layer, a yellow filter layer and a protective layer, if appropriate for the desired photographic material.
  • a color printing paper which comprises a thin reflective support having thereon a yellow color forming layer containing a blue-sensitive silver halide emulsion and a yellow color forming coupler, a magenta color forming layer containing a green-sensitive silver
  • the silver halide emulsion which is used in the present invention is usually prepared by mixing an aqueous solution of a water-soluble silver salt (for example, silver nitrate) with an aqueous solution of a water-soluble halide (for example, potassium bromide, sodium chloride, potassium iodide or a mixture thereof) in the presence of an aqueous solution of a water-soluble polymer (for example, gelatin).
  • a mixed silver halide for example, silver chlorobromide, silver chloroiodobromide and silver iodobromide are representative examples.
  • the silver halide which is preferably employed in the present invention is silver chloroiodobromide, silver iodochloride or silver iodobromide, each containing 3 mol% or less silver iodide.
  • the silver halide grains may have different layers in the inner portion and the surface portion, multi-phase structures containing junctions, or may be uniform throughout the grains. Further, a mixture of these silver halide grains having different structures may be employed. For instance, with respect to silver chlorobromide grains having different phases, those having nuclei or a single layer or plural layers which are rich in silver bromide as compared with the mean halogen composition in their inner portion, or those having nuclei or a single layer or plural layers which are rich in silver chloride as compared with the mean halogen composition in their inner portion may be employed. Therefore, surface layers of the grains are rich in silver bromide as compared with the mean halogen composition or contrary to this, surface layers are rich in silver chloride.
  • the average grain size of the silver halide grains is preferably from 0.1 ⁇ m to 2 ⁇ m, and particularly from 0.15 ⁇ m to 1 ⁇ m.
  • the grain size distribution may be either narrow or broad.
  • a so-called monodispersed silver halide emulsion having a narrow grain size distribution which comprises at least 90%, particularly at least 95% by number or by weight of the total silver halide grains having a size within the range of the average grain size ⁇ 40% is preferably employed in the present invention.
  • two or more monodispersed silver halide emulsions which have different grain sizes from each other can be mixed in one emulsion layer or can be coated in the form of superimposed layers which have substantially the same spectral sensitivity.
  • two or more polydispersed silver halide emulsions or combinations of a monodispersed emulsion and a polydispersed emulsion may be employed in a mixture or in the form of superimposed layers.
  • the silver halide grains which can be used in the present invention may have a regular crystal structure, for example, a cubic, octahedral, dodecahedral or tetradecahedral structure, an irregular crystal structure, for example, a spherical structure, or a composite structure thereof.
  • tabular silver halide grains can be used.
  • a silver halide emulsion wherein tabular silver halide grains having a ratio of diameter/thickness of not less than 5, preferably not less than 8 account for at least 50% of the total silver halide grains present, calculated based on the projected area of the silver halide grains can be employed.
  • mixtures of silver halide grains having different crystal structures may be used.
  • These silver halide emulsions may be those of the surface latent image type in which the latent images are formed mainly on the surface thereof, or those of the internal latent image type in which the latent images are formed mainly in the interior thereof.
  • Dyes are employed in the present invention for various purposes, for example, as filter dyes, for irradiation prevention or for antihalation.
  • examples of such dyes which are preferably used are oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes and azo dyes.
  • cyanine dyes, azomethine dyes, triarylmethane dyes and phthalocyanine dyes are also useful.
  • Oil-soluble dyes may be added to the hydrophilic colloid layer by emulsification using an oil droplet-in-water dispersing method.
  • inorganic or organic hardening agents may be employed in order to harden the hydrophilic colloid layers applied on the support.
  • active halogen compounds for example, 2,4-dichloro-6-hydroxy-1,3,5-triazine
  • active vinyl compounds for example, 1,3-bisvinylsulfonyl-2-propanol, 1,2-bisvinylsulfonylacetamidoethane or a vinyl type polymer having a vinylsulfonyl group in its side chain
  • N-carbamoylpyridinium salts and haloamidinium salts are excellent in view of their high hardening speed.
  • the color developing solution used for development processing of the color photographic light-sensitive material of the present invention to obtain a color print is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as the main component.
  • an aromatic primary amine color developing agent As a color developing agent, while an aminophenol type compound is useful, a p-phenylenediamine type compound is preferably used.
  • Typical examples of the p-phenylenediamine type compounds include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline, or a sulfate, hydrochloride or p-toluenesulfonate thereof.
  • These diamines are preferably employed in the form of salts since the salts are generally more stable than their free forms.
  • the color developing solution generally contains pH buffering agents such as carbonates, borates or phosphates of alkali metals, and development inhibitors or antifogging agents such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds.
  • pH buffering agents such as carbonates, borates or phosphates of alkali metals
  • development inhibitors or antifogging agents such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds.
  • the color developing solution may also contain, for example, preservatives such as, for example, hydroxylamines, derivatives thereof (for example, N,N-dialkyl substituted derivatives) or sulfites; organic solvents such as, for example, triethanolamine, derivatives thereof or diethylene glycol; development accelerators such as, for example, benzylalcohol, polyethyleneglycol, quaternary ammonium salts or amines; competing couplers; nucleating agents such as, for example, sodium borohydride; auxiliary developing agents such as, for example, 1-phenyl-3-pyrazolidone; viscosity imparting agents; various chelating agents as represented, for example, by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids and phosphonocarboxylic acids; and antioxidants as described in West German Patent Application (OLS) No. 2,622,950.
  • preservatives such as, for example, hydroxylamines, derivatives thereof (for example, N,
  • the color development is usually conducted after the black-and-white development.
  • the photographic emulsion layer is usually subjected to bleach processing.
  • the bleach processing can be carried out simultaneously with or separately from fix processing. Further, in order to perform rapid processing, a processing method in which bleach-fix processing is conducted after bleach processing can be employed.
  • bleaching agents iron (III) salts of ethylenediaminetetraacetic acid, iron (III) salts of diethylenetriaminepentaacetic acid and persulfates are preferred in view of rapid processing and less environmental pollution.
  • ethylenediaminetetraacetic acid iron (III) complex salts are particularly useful both in an independent bleaching solution and in a mono-bath bleach-fixing solution.
  • thiosulfates are ordinarily employed as fixing agents.
  • sulfites, bisulfites, carbonylbisulfite adducts, for instance are preferably employed as preservatives.
  • water wash processing and/or stabilization processing are usually conducted.
  • various known compounds may be employed, for instance, for the purpose of preventing precipitation or saving water.
  • a water softener such as, for example, an inorganic phosphoric acid, an aminopolycarboxylic acid, an organic aminopolyphosphonic acid, or an organic phosphoric acid for the purpose of preventing the formation of precipitation
  • a sterilizer or antimold for the purpose of preventing the propagation of various bacteria, algae and molds
  • a metal salt such as, for example, a magnesium salt, an aluminum salt or bismuth salt
  • a surface active agent for the purpose of reducing the drying load or preventing drying marks
  • various hardening agents may be added, if desired.
  • the compounds as described in L.E. West, Photo. Sci. Eng. , Vol. 6, pages 344 to 359 (1965) may be added.
  • the addition of chelating agents and antimolds may be added.
  • the color photographic light-sensitive material according to the present invention may contain, if appropriate, various 1-phenyl-3-pyrazolidones for the purpose of accelerating the color development.
  • Typical examples of the compounds include those as described in Japanese Patent Application (OPI) Nos. 64339/81, 144547/82, 211147/82, 50532/83, 50536/83, 50533/83, 50534/83, 50535/83 and 115438/83.
  • the various kinds of processings described above can be conducted in a temperature range of from 10°C to 50°C.
  • the standard temperature is from 33°C to 38°C, it is possible to carry out the processing at higher temperatures in order to accelerate the processing whereby the processing time is shortened, or on the other hand, at lower temperatures in order to achieve an improvement in image quality and to maintain the stability of the processing solutions.
  • the photographic processing may be conducted utilizing color intensification using cobalt or hydrogen peroxide as described in West German Patent Application (OLS) No. 2,226,770 or U.S. Patent 3,674,499.
  • the variation of the composition in each processing solution can be prevented by using a replenisher for each processing solution, whereby a constant finish can be achieved.
  • the amount of replenisher can be reduced to one half or less of the standard amount of replenishment for the purpose of reducing the costs.
  • Direct positive color prints can be obtained with respect to the color photographic light-sensitive materials by using an internal latent image type emulsion which was not previously fogged as a silver halide emulsion, and performing a fogging treatment after the imagewise exposure but before or during the color development step.
  • a method conducting fogging exposure or a method using a nucleating agent are effective. More specifically, a light fogging method and a chemical fogging method (a method using a nucleating agent together with a nucleating accelerator) as described, for example, in U.S. Application Serial No. 60,790 filed June 12, 1987, pages 55 to 88, or European Patent Application No. 87 108489.3 filed June 12, 1987, pages 55 to 88 (corresponding to Japanese Patent Application No. 136949/86) can be utilized.
  • the color photographic print obtained by development processing of the color photographic light-sensitive material according to the present invention advantageously not only has a good fastness to light, humidity and heat but also has an excellent sharpness of color images.
  • the support composed of a vinyl chloride resin used in the present invention is excellent in flexibility and strength and its variation in the degree of elasticity on change in humidity is small and can be ignored in comparison with other photographic supports.
  • the color photographic light-sensitive material and the color photographic print according to the present invention can be suitably employed as, for instance, ID cards, cashing cards and telephone cards.
  • a support composed of a hard vinyl chloride resin (a copolymer containing at least 50 mol% of vinyl chloride monomer component, with the remainder thereof being vinylidene chloride and methyl methacrylate, and further containing 12 parts by weight of TiO2 per 100 parts of total weight of the copolymer) and having a thickness of 150 ⁇ m and an average reflectance in the visible range of 85% or more, provided with subbing treatment, the first layer to the seventh layer described below were coated to prepare a color photographic light-sensitive material which was designated Sample 101.
  • the support used was in conformity with a standard of JIS-K-6734-Class C, No. 1, as described in JIS published by Japanese Standards Association.
  • coated amounts shown below are in g/m2, and the coated amounts of silver halide shown below are measured as silver.
  • the following dyes were used as spectral sensitizing dyes in the emulsion layers, respectively.
  • Samples 102 and A' were prepared in the same manner as described for sample 101 except for changing couplers as shown in Table 1 below.
  • composition of each processing solution used in the above-described processing steps is as follows: Developing Solution Trisodium nitrilotriacetate 2.0 g Benzyl alcohol 15 ml Diethylene glycol 10 ml Sodium sulfite 2.0 g Potassium bromide 0.5 g Hydroxylamine sulfate 3.0 g 4-Amino-3-methyl-N-ethyl-N-[ ⁇ -(methanesulfonamido)ethyl]-p-phenylenediamine sulfate 5.0 g Sodium carbonate (monohydrate) 30 g Water to make 1 l (pH: 10.1) Bleach-Fixing Solution Ammonium thiosulfate (54 wt%) 150 ml Sodium sulfite 15 g Ammonium iron (III) ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 4 g Water to make 1 l (pH: 6.9)
  • the sharpness of Samples 101, 102 and A' thus-processed was determined.
  • the sharpness is a value indicating clearness of the outlines of images and the ability to duplicate fine images.
  • the value known as CTF was used herein.
  • CTF means the degree of decrease in amplitude against a spatial frequency as a rectangular wave.
  • the sharpness at 15 lines/mm of spatial frequency thus-measured is shown in Table 2 below. The larger value indicates the better sharpness.
  • Silver Halide Emulsion (7) for a blue-sensitive silver halide emulsion layer was prepared in the following manner.
  • Solution 9 Sulfuric acid (1N) 20 ml Solution 11 KBr 0.18 g NaCl 8.51 g H2O to make 130 ml Solution 12 AgNO3 25 g H2O to make 130 ml Solution 13 Pb(CH3COO)2 ⁇ 3H2O (0.1%) 28 ml Solution 14 KBr 0.70 g NaCl 34.05 g H2O to make 285 ml Solution 15 AgNO3 100 g H2O to make 285 ml
  • Solution 8 was heated at 60°C, Solution 9 and Solution 10 were added thereto and then Solution 11 and Solution 12 were added thereto simultaneously over a period of 60 min.
  • Solution 11 and Solution 12 were added thereto simultaneously over a period of 60 min.
  • Solution 13 was added and then after 9 min Solution 14 and Solution 15 were added simultaneously over a period of 25 min.
  • the temperature was dropped and the mixture was desalted.
  • Water and gelatin were added thereto for dispersion and the pH was adjusted to 6.0 whereby a mono-dispersed cubic silver chlorobromide emulsion (having an average grain size of 1.00 ⁇ m, a coefficient of variation of 0.11 and a silver bromide content of 1 mol%) was obtained.
  • the emulsion was subjected to optimum chemical sensitization using triethyl thiourea and chloroauric acid. Thereafter, the Spectral Sensitizer (S-1) shown below was added in an amount of 5 x 10 ⁇ 4 mol per mol of silver halide.
  • Silver Halide Emulsion (8) for a green-sensitive silver halide emulsion layer and Silver Halide Emulsion (9) for a red-sensitive silver halide emulsion layer were prepared in the same manner as described above except for changing the amounts of chemicals used in Solution 8 and Solution 10, the kinds and amounts of spectral sensitizers, and the temperatures and times for addition.
  • Spectral Sensitizer (S-2) shown below was used for Silver Halide Emulsion (8) and Spectral Sensitizer (S-3) shown below was used for Silver Halide Emulsion (9).
  • Samples 103 and 104 were prepared in the same manner as described for Samples 101 and 102, respectively, except that the silver halide emulsions used in the first layer, the third layer and the fifth layer were changed to Silver Halide Emulsions (7), (8) and (9), respectively. These samples were stepwise exposed in the same manner as described in Example 1 and then subjected to development processing consisting or color development, bleach-fixing and rinse steps as shown below. Processing Step Temperature Time Color Development 35°C 45 s Bleach-Fixing 35°C 45 s Rinse 28 to 35°C 1 min 30 s
  • compositions of each processing solution used in the above-described processing steps are as follows: Color Developing Solution: Water 800 ml Pentasodium diethylenetriaminepentaacetate 1.0 g Sodium sulfite 0.2 g N,N-Diethylhydroxylamine 4.2 g Potassium bromide 0.01 g Sodium chloride 1.5 g Triethanolamine 8.0 g N-Ethyl-N-( ⁇ -methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 4.5 g Potassium carbonate 30.0 g 4,4'-Diaminostilbene type brightening agent (Whitex 4 manufactured by Sumitomo Chemical Co., Ltd.) 2.0 g Water to make 1,000 ml pH 10.1 Bleach-Fixing Solution: Water 700 ml Ammonium thiosulfate (54% by weight aq.
  • Emulsions A to H were prepared as follows.
  • Emulsion A Emulsion A
  • An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to a gelatin aqueous solution under vigorous stirring at 75°C over a period of 40 min to obtain a monodispersed silver bromide emulsion containing octahedral grains of 0.4 ⁇ m in average grain size.
  • Four mg of sodium thiosulfate and 4 mg of chloroauric acid (4 hydrate) were added to the emulsion per mol of silver, followed by heating at 75°C for 80 min to effect chemical sensitization.
  • the thus obtained silver bromide grains were used as cores, and were allowed to further grow in the same precipitating environment as the first step for 40 min to finally obtain an octahedral monodispersed core/shell silver bromide emulsion of 0.6 ⁇ m in average grain size (coefficient of variation : 14%). After washing with water and desalting of the emulsion, 0.9 mg of sodium thiosulfate were added thereto per mol of silver, followed by heating at 65°C for 60 min to effect chemical sensitization. Thus, internal latent image type silver halide emulsion A was obtained.
  • aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to a gelatin aqueous solution under vigorous stirring at 75°C over a period of 40 min to obtain a monodispersed silver bromide emulsion containing octahedral grains of 0.4 ⁇ m in average grain size.
  • Four mg of sodium thiosulfate and 4 mg of chloroauric acid (4 hydrate) were added to this emulsion per mol of silver, followed by heating at 75°C for 80 min to effect chemical sensitization.
  • the thus obtained silver bromide grains were used as cores, and were allowed to further grow by adding a 2 mol/l sodium chloride aqueous solution and a 1 mol/l silver nitrate aqueous solution at 75°C for 40 min to obtain a cubic core/shell silver chlorobromide emulsion of 0.6 ⁇ m in average grain size (coefficient of variation: 15%). After washing with water and desalting of the emulsion, 0.5 mg of sodium thiosulfate were added thereto per mol of silver, then heated at 55°C for 60 min to effect chemical sensitization, whereby silver halide emulsion D was obtained.
  • aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to a gelatin aqueous solution under vigorous stirring at 75°C over a period of 60 min to obtain a silver bromide emulsion.
  • 100 mg of 3,4-dimethyl-1,3-thiazoline-2-thione and 15 g of benzimidazole per mol of silver were added to a precipitation tank. After the completion of precipitation, crystals of 1.1 ⁇ m in average grain size were obtained. Then, 5.4 mg of sodium thiosulfate and 3.9 mg of potassium chloroaurate were added to the emulsion per mol of silver, followed by heating at 75°C for 80 min to effect chemical sensitization.
  • aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to a gelatin aqueous solution containing potassium bromide under vigorous stirring at 75°C over a period of about 60 min to obtain a silver bromide emulsion.
  • 150 mg of 3,4-dimethyl-1,3-thiazoline-2-thione as a silver halide solvent and 15 g of benzimidazole per mol of silver were added to the aqueous gelatin solution. After the completion of precipitation, uniform grain size octahedral silver bromide crystals of 0.8 ⁇ m in average grain size were obtained.
  • An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to a gelatin aqueous solution containing 0.3 g of 3,4-dimethyl-1,3-thiazoline-2-thione per mol of silver under vigorous stirring at 75°C over a period of 20 min to obtain a monodispersed silver bromide emulsion containing octahedral grains of 0.4 ⁇ m in average grain size.
  • 6 mg of sodium thiosulfate and 6 mg of chloroauric acid (4 hydrate) were added to the emulsion per mol of silver, followed by heating at 75°C for 80 min to effect chemical sensitization.
  • the thus obtained silver bromide grains were used as cores, and were allowed to further grow in the same precipitating environment as the first step for 40 min to finally obtain an octahedral monodispersed core/shell silver bromide emulsion of 0.7 ⁇ m in average grain size. After washing with water and desalting of the emulsion, 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (4 hydrate) were added thereto per mol of silver, followed by heating at 60°C for 60 min to effect chemical sensitization. Thus, internal latent image type silver halide emulsion H was obtained.
  • Coating solutions for the second layer to the seventh layer were also prepared in the same manner as the coating solution for the first layer.
  • Sodium salt of 1-hydroxy-3,5-dichloro-s-triazine was used as a gelatin hardener for each layer.
  • Spectral sensitizers used for individual emulsions are shown below.
  • the following dyes were employed as irradiation preventing dyes in the emulsion layers, respectively.
  • the coating solutions for the first layer to the seventh layer were coated on the support to prepare the multilayer silver halide direct positive color photographic printing papers A to H.
  • the direct positive color photographic printing papers A to H thus prepared were imagewise exposed at color temperature of 4,800°K in an amount of 100 CMS at 1/10 second and then subjected to Processing Step A (pH of the color developing solution: 10.2) shown below and Processing Step B (same a Processing Step A except adjusting the pH of the color developing solution to 11.0), respectively.
  • Processing Step A pH of the color developing solution: 10.2
  • Processing Step B standarde a Processing Step A except adjusting the pH of the color developing solution to 11.0
  • the stabilizing baths were replenished according to a so-called countercurrent replenishing system of adding the replenisher to the stabilizing bath (3), introducing the overflow from the stabilizing bath (3) into the stabilizing bath (2), and the overflow from the stabilizing bath (2) into the stabilizing bath (1).
  • composition of each processing solution used in the above described processing steps is as follows: Color Developing Solution: Mother Solution Diethylenetriaminepentaacetic acid 2.0 g Benzyl alcohol 12.8 g Diethylene glycol 3.4 g Sodium sulfite 2.0 g Sodium bromide 0.26 g Hydroxylamine sulfate 2.60 g Sodium chloride 3.20 g 3-Methyl-4-amino-N-ethyl-N-( ⁇ -methanesulfonamidoethyl)aniline 4.25 g Potassium carbonate 30.0 g Brightening agent (stilbene type) 1.0 g Water to make 1,000 ml pH 10.20
  • Stabilizing solution Mother Solution 1-Hydroxyethylidene-1,1'-di phosphonic acid (60%) 1.6 ml Bismuth chloride 0.35 g Polyvinylpyrrolidone 0.25 g Aqueous ammonia 2.5 ml Trisodium nitrilotriacetate 1.0 g 5-Chloro-2-methyl-4-isothiazolin3-one 50 mg 2-Octyl-4-isothiazolin-3-one 50 mg Brightening agent (4,4'-diamino-stilbene type) 1.0 g Water to make 1,000 ml pH 7.5
  • the pH was adjusted with potassium hydroxide or hydrochloric acid.
  • the first layer to the eleventh layer as described in Example 1 of Japanese Patent Application (OPI) No. 174760/87, pages 18, upper half portion in the right-hand column to page 21, lower half portion in the right-hand column were coated on a reflective support composed of a vinyl chloride resin containing white pigments provided with subbing treatment in place of the first layer to the seventh layer to prepare a reversal color photographic light-sensitive material.
  • the color photographic material was processed according to the prescribed development processing steps. A reversal color photographic print having excellent sharpness and no irregularity of image density was obtained.

Claims (25)

  1. Matériau photographique couleur à l'halogénure d'argent comprenant un support réfléchissant constitué d'une résine de chlorure de vinyle contenant un pigment blanc et sur lequel sont disposées dans un ordre approprié au moins une couche d'émulsion d'halogénure d'argent sensible au rouge contenant un coupleur chromogène cyan représenté par la formule générale (1) ou (2) représentées ci-dessous, au moins une couche d'émulsion d'halogénure d'argent sensible au vert contenant un coupleur chromogène magenta représenté par la formule générale (3) ou (4) représentées ci-dessous, et au moins une couche d'émulsion d'halogénure d'argent sensible au bleu contenant un coupleur chromogène jaune représenté par la formule générale (5) représentée ci-dessous :
    Figure imgb0124
    Figure imgb0125
     dans lesquelles R₁, R₄ et R₅ représentent chacun un groupement aliphatique, un groupement aromatique, un groupement hétérocyclique, un groupement amino aromatique ou un groupement amino hétérocyclique ; R₂ représente un groupement aliphatique ; R₃ et R₆ représentent chacun un atome d'hydrogène, un atome d'halogène, un groupement aliphatique, un groupement oxy aliphatique ou un groupement acylamino ; R₇ et R₈ représentent chacun un groupement phényle substitué ou non substitué ; R₉ représente un atome d'hydrogène ou un substituant; R₂ et R₃ ou R₅ et R₆ peuvent être reliés les uns aux autres de façon à former un cycle comportant 5 à 7 chaînons ; Q représente un groupement N-phénylcarbamoyle substitué ou non substitué ; Za et Zb, qui peuvent être identiques ou différents représentent chacun un groupement -CH=, un groupement
    Figure imgb0126
     ou un groupement -N= ; R₁₀ représente le même substituant que R₉ ; et X₁, X₂, X₃, X₄ et X₅ représentent chacun un atome d'hydrogène ou un groupement capable d'être libéré par réaction avec un produit d'oxydation d'un développateur de type amine aromatique primaire.
  2. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel X₁ et X₂ représentent chacun un atome de chlore, X₃ et X₄ représentent chacun un atome d'hydrogène ou un groupement capable d'être libéré contenant un atome de soufre en tant qu'atome partant; et X₅ représente un groupement capable d'être libéré contenant un atome d'oxygène ou un atome d'azote en tant qu'atome partant.
  3. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel la résine de chlorure de vinyle est un copolymère contenant un monomère chlorure de vinyle.
  4. Matériau photographique couleur à l'halogénure d'argent selon la revendication 3, dans lequel le monomère chlorure de vinyle représente au moins 50 % en poids du composant monomérique total.
  5. Matériau photographique couleur à l'halogénure d'argent selon la revendication 3, dans lequel le composant comonomère est choisi parmi les suivants : méthacrylate de méthyle, oléfine fluorée, éther vinylique, bromure de vinyle, acétate de vinyle, acide maléique, dichlorobutadiène, fluorure de vinyle, fluorure de vinylidène, trifluorochloroéthylène, tétrafluoroéthylène, chlorure de vinylidène, acrylonitrile, styrène, butadiène et chloroprène.
  6. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel le pigment blanc est choisi parmi les suivants : blanc de titane, blanc de zinc, carbonate de calcium, sulfate de baryum, blanc de plomb, pigments et colorants organiques blancs et agents de luminosité.
  7. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel la quantité totale du pigment blanc ajouté est comprise entre 1 partie en poids et 30 parties en poids pour 100 parties en poids du produit constitué de résine de chlorure de vinyle.
  8. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel le pouvoir réfléchissant moyen du support réfléchissant dans une gamme visible est compris entre 80 et 98 %.
  9. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel l'épaisseur du support réfléchissant est comprise entre 50 µm et 500 µm.
  10. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel la surface du support réfléchissant sur laquelle est déposée une couche de colloïde hydrophile est soumise à un traitement substratant.
  11. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel le matériau photographique couleur comprend de plus un composé libérant un inhibiteur de développement.
  12. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel l'émulsion d'halogénure d'argent utilisée dans les couches d'émulsion d'halogénure d'argent est une émulsion d'halogénure d'argent monodispersée.
  13. Epreuve photographique en couleur comprenant un support réfléchissant constitué d'une résine de chlorure de vinyle contenant un pigment blanc et comportant, disposées sur celui-ci dans un ordre approprié au moins une couche d'émulsion contenant un colorant cyan obtenu par réaction d'un coupleur chromogène cyan représenté par la formule générale (1) ou (2) représentées ci-dessous, avec un produit d'oxydation d'un développateur de type amine aromatique primaire, au moins une couche d'émulsion contenant un colorant magenta obtenu par réaction d'un coupleur chromogène magenta représenté par la formule générale (3) ou (4) représentées ci-dessous, avec un produit d'oxydation d'un développateur de type amine aromatique primaire, et au moins une couche d'émulsion contenant un colorant jaune obtenu par réaction d'un coupleur chromogène jaune représenté par la formule générale (5) représentée ci-dessus, avec un produit d'oxydation d'un développateur de type amine aromatique primaire
    Figure imgb0127
     dans lesquelles R₁, R₄ et R₅ représentent chacun un groupement aliphatique, un groupement aromatique, un groupement hétérocyclique, un groupement amino aromatique ou un groupement amino hétérocyclique ; R₂ représente un groupement aliphatique, R₃ et R₆ représentent chacun un atome d'hydrogène, un atome d'halogène, un groupement aliphatique, un groupement oxy aliphatique ou un groupement acylamino ; R₇ et R₈ représentent chacun un groupement phényle substitué ou non substitué ; R₉ représente un atome d'hydrogène ou un substituant ; R₂ et R₃ ou R₅ et R₆ peuvent être liés les uns avec les autres pour former un cycle comportant 5 à 7 chaînons ; Q représente un groupement N-phénylcarbamoyle substitué ou non substitué ; Za et Zb, qui peuvent être identiques ou différents, représentent chacun un groupement -CH=, un groupement
    Figure imgb0128
     ou un groupement -N= ; R₁₀ représente le même substituant que R₉ ; et X₁, X₂, X₃, X₄ et X₅ représentent chacun un atome d'hydrogène ou un groupement capable d'être libéré par réaction avec un produit d'oxydation d'un développateur de type amine aromatique primaire.
  14. Epreuve photographique couleur selon la revendication 13, dans laquelle le colorant jaune est un colorant représenté par la formule générale suivante (5-1):
    Figure imgb0129
     dans laquelle R₁₄ et R₁₅, qui peuvent être identiques ou différents, représentent chacun un atome d'hydrogène ou un substituant qui est utilisé de façon usuelle pour un coupleur jaune, à condition que R₁₄ et R₁₅ ne représentent pas en même temps des atomes d'hydrogène ; et
    Figure imgb0130
     représente un résidu d'une réaction de couplage d'un développateur de type amine aromatique primaire.
  15. Epreuve photographique couleur selon la revendication 14, dans laquelle le substituant représenté par R₁₄ ou R₁₅ est choisi parmi les suivants : groupements alkyle, alcényle, alcoxy, alcoxycarbonyle, atome d'halogène, groupements alcoxycarbamoyle, amido aliphatique, alkylsulfamoyle, alkylsulfonamido, alkyluréido, succinimido alkyle-substitué, aryloxy, aryloxycarbonyle, arylcarbamoyle, arylamido, arylsulfamoyle, arylsulfonamide, aryluréido, carboxyle, sulfo, nitro, cyano et thiocyano.
  16. Epreuve photographique couleur selon la revendication 14, dans laquelle
    Figure imgb0131
     représente un résidu d'une réaction de couplage d'un dérivé de phénylènediamine représenté par la formule générale (6) :
    Figure imgb0132
     dans laquelle R₁₁ et R₁₂ représentent chacun un groupement alkyle substitué ou non substitué ; et R₁₃ représente 1 à 4 atomes d'hydrogène ou 1 à 4 substituants.
  17. Epreuve photographique couleur selon la revendication 16, dans laquelle un substituant du groupement alkyle substitué représenté par R₁₁ ou R₁₂ est choisi parmi les suivants : groupements hydroxyle, alkylsulfonamido et alcoxy et le substituant représenté par R₁₃ est un groupement alkyle.
  18. Epreuve photographique couleur selon la revendication 13, dans laquelle le colorant magenta est un colorant représenté par les formules générales suivantes (4-1) ou (4-2) :
    Figure imgb0133
     dans lesquelles R₁₆ et R₁₇, qui peuvent être identiques ou différents, représentent chacun un atome d'hydrogène, un atome d'halogène, un groupement alkyle, aryle, hétérocyclique, cyano, alcoxy, aryloxy, oxy hétérocyclique, acyloxy, carbamoyloxy, silyloxy, sulfonyloxy, acylamino, anilino, uréido, imido, sulfamoylamino, carbamoylamino, alkylthio, arylthio, thio hétérocyclique, alcoxycarbonylamino, aryloxycarbonylamino, sulfonamido, carbamoyle, acyle, sulfamoyle, sulfonyle, sulfinyle, alcoxycarbonyle ou aryloxycarbonyle, ou R₁₆ et R₁₇ peuvent être un groupement divalent pour former un composé dimère ou un groupement de liaison destiné à former un colorant polymérique, et
    Figure imgb0134
     représente un résidu d'une réaction de couplage d'un développateur de type amine aromatique primaire.
  19. Epreuve photographique couleur selon la revendication 18, dans laquelle le groupement de liaison est lié à un groupement vinylique à partir duquel le polymère est constitué.
  20. Epreuve photographique couleur selon la revendication 13, dans laquelle le colorant cyan est constitué de deux colorants ou plus formés à partir de deux coupleurs chromogènes cyan ou plus représentés par la formule générale (1) ou (2).
  21. Epreuve photographique couleur selon la revendication 13, dans laquelle les colorants sont utilisés en combinaison avec un ou plusieurs types de solvants organiques ayant un point de fusion élevé d'au moins 160°C, qui sont représentés par la formule générale suivante (7), (8), (9), (10) ou (11) :
    Figure imgb0135

            W₁ - COO - W₂   (8)

    Figure imgb0136
    Figure imgb0137

            W₁ - O - W₂   (11)



    dans lesquelles W₁, W₂ et W₃ représentent chacun un groupement alkyle substitué ou non substitué, un groupement cycloalkyle substitué ou non substitué, un groupement alcényle substitué ou non substitué, un groupement aryle substitué ou non substitué ou un groupement hétérocyclique substitué ou non substitué ; W₄ représente W₁, -O-W₁ ou -S-W₁ ; n représente un nombre entier compris entre 1 et 5, quand n vaut deux ou plus, deux W₄ ou plus peuvent être identiques ou différents ; et dans la formule générale (11) W₁ et W₂ peuvent être liés l'un avec l'autre de façon à former un cycle condensé.
  22. Epreuve photographique couleur selon la revendication 13, dans laquelle les colorants sont utilisés en combinaison avec un ou plusieurs polymères solubles dans des solvants organiques, insolubles dans l'eau.
  23. Epreuve photographique couleur selon la revendication 13, dans laquelle les colorants sont utilisés en combinaison avec un ou plusieurs types d'agents de prévention de l'affaiblissement des couleurs ou d'agents anti-oxydants représentés par la formule générale (12) ou (13) :
    Figure imgb0138
     dans lesquelles R₂₀ représente un atome d'hydrogène, un groupement aliphatique, un groupement aromatique, un groupement hétérocyclique ou un groupement protecteur hydrolysable ; R₂₁, R₂₂, R₂₃, R₂₄ et R₂₅, qui peuvent être identiques ou différents, représentent chacun un atome d'hydrogène ou un substituant ; R₃₀ représente un atome d'hydrogène, un groupement aliphatique, acyle, sulfonyle, sulfinyle, radical oxy ou un groupement hydroxyle ; A représente un groupement atomique non métallique nécessaire pour constituer un cycle à 5, 6 ou 7 chaînons ; et R₂₆, R₂₇, R₂₈ et R₂₉, qui peuvent être identiques ou différents, représentent chacun un atome d'hydrogène ou un groupement alkyle, ou R₂₀ et R₂₁ ou deux parmi R₂₁, R₂₂, R₂₃, R₂₄ et R₂₅ qui sont présents en position ortho l'un par rapport à l'autre peuvent être liés l'un avec l'autre de façon à former un cycle à 5, 6 ou 7 chaînons, ou R₂₆ et R₂₇, R₂₈ et R₂₉ ou R₃₀ et R₂₆ peuvent être liés l'un avec l'autre pour former un noyau à 5, 6 ou 7 chaînons.
  24. Epreuve photographique couleur préparée en mettant en oeuvre au moins une étape de traitement du matériau photographique couleur à l'halogénure d'argent selon la revendication 1, après exposition selon une image, avec un révélateur chromogène contenant un développateur chromogène de type amine aromatique primaire.
  25. Epreuve photographique couleur préparée en collant une épreuve photographique couleur obtenue en mettant en oeuvre au moins une étape de traitement du matériau photographique couleur à l'halogénure d'argent selon la revendication 1 mais en utilisant un support transparent à la place du support réfléchissant, après exposition selon une image, avec un révélateur chromogène contenant un développateur chromogène de type amine aromatique primaire, sur un support réfléchissant constitué d'une résine de chlorure de vinyle contenant un pigment blanc.
EP19870117764 1986-12-02 1987-12-01 Matériau photographique couleur à l'halogénure d'argent et épreuve photographique couleur Expired - Lifetime EP0270078B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP28745686 1986-12-02
JP287456/86 1986-12-02
JP95440/87 1987-04-20
JP62095440A JPH07119964B2 (ja) 1986-12-02 1987-04-20 ハロゲン化銀カラ−写真感光材料及びカラ−写真プリント

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EP0270078A2 EP0270078A2 (fr) 1988-06-08
EP0270078A3 EP0270078A3 (en) 1990-08-16
EP0270078B1 true EP0270078B1 (fr) 1994-05-11

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Publication number Priority date Publication date Assignee Title
JPH0693105B2 (ja) * 1987-06-10 1994-11-16 富士写真フイルム株式会社 マゼンタ色素形成カプラ−
JP2767422B2 (ja) * 1988-01-30 1998-06-18 コニカ株式会社 ハロゲン化銀写真感光材料
US6818390B2 (en) 2002-11-15 2004-11-16 Agfa-Gevaert Deformable color photographic silver halide material
EP1567914A1 (fr) * 2002-11-15 2005-08-31 AgfaPhoto GmbH Materiau photographique couleur deformable d'halogenure d'argent
US6821719B2 (en) 2002-11-15 2004-11-23 Agfa-Gevaert Process for producing a deformed image without significant image degradation

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Publication number Priority date Publication date Assignee Title
FR2245616B1 (fr) * 1973-07-28 1977-10-14 Basf Ag
JPS52102722A (en) * 1976-02-24 1977-08-29 Fuji Photo Film Co Ltd Photosensitive material for color photography
EP0065329B1 (fr) * 1981-05-18 1985-05-02 Agfa-Gevaert N.V. Matériau polymère à base de chlorure de vinyle traité en surface et comprenant une couche adhérente hydrophile
JPS59111848A (ja) * 1982-12-17 1984-06-28 帝人株式会社 易滑性ポリエステルフイルム
JPS59200234A (ja) * 1983-04-28 1984-11-13 Fuji Photo Film Co Ltd 写真用支持体
JPS60229029A (ja) * 1984-04-26 1985-11-14 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料
US4540657A (en) * 1984-06-06 1985-09-10 Eastman Kodak Company Photographic coupler solvents and photographic elements employing same
JPS61120140A (ja) * 1984-11-15 1986-06-07 Konishiroku Photo Ind Co Ltd 反射写真材料およびその製造方法
JPS61248736A (ja) * 1985-04-26 1986-11-06 富士写真フイルム株式会社 セルロ−スエステルフイルム

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DE3789800D1 (de) 1994-06-16
EP0270078A3 (en) 1990-08-16
EP0270078A2 (fr) 1988-06-08
JPS63264746A (ja) 1988-11-01
JPH07119964B2 (ja) 1995-12-20

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