EP0384487B1 - Matériau photographique couleur à l'halogénure d'argent - Google Patents

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

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Publication number
EP0384487B1
EP0384487B1 EP90103586A EP90103586A EP0384487B1 EP 0384487 B1 EP0384487 B1 EP 0384487B1 EP 90103586 A EP90103586 A EP 90103586A EP 90103586 A EP90103586 A EP 90103586A EP 0384487 B1 EP0384487 B1 EP 0384487B1
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EP
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Prior art keywords
group
silver halide
photographic material
mol
silver
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German (de)
English (en)
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EP0384487A3 (fr
EP0384487A2 (fr
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Nobuo C/O Fuji Photo Film Co. Ltd. Sakai
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32—Colour coupling substances
    • G03C7/36—Couplers containing compounds with active methylene groups
    • G03C7/38—Couplers containing compounds with active methylene groups in rings
    • G03C7/381—Heterocyclic compounds
    • G03C7/382—Heterocyclic compounds with two heterocyclic rings
    • G03C7/3825—Heterocyclic compounds with two heterocyclic rings the nuclei containing only nitrogen as hetero atoms
    • 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
    • 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
    • G03C7/39212—Carbocyclic
    • G03C7/39216—Carbocyclic with OH groups

Definitions

  • the present invention relates to a silver halide color photographic material, and more particularly, a silver halide color photographic material high in sensitivity and contrast and excellent in color reproduction and dye image stability.
  • the size of silver halide grains is made large to increase the amount of absorption of light per grain, or that when the emulsion has spectrally been sensitized, for example, the amount of the spectral sensitizing dye is increased to augment the amount of light absorption.
  • the size of silver halide grains is made large, it is known that the developing speed often lowers. It is also known that an increase in a spectral sensitizing dye brings about development obstruction or desilvering obstruction. Consequently, when these methods are used in practice, in many cases problems often arise.
  • JP-B means examined Japanese patent publication
  • JP-B No. 18939/1981 describes that an emulsion produced by covering cores of silver bromide with silver chloride, or by depositing a layer of silver bromide on cores of silver chloride, has both the advantages of silver chloride and silver bromide.
  • the technique disclosed therein covers generally a wide range of layered-type emulsions consisting of cores of a silver halide covered with different silver halide layers, and according to the test results obtained by the present inventors, the disclosed technique did not necessarily provide emulsions having preferable performance.
  • JP-A means unexamined published Japanese patent application
  • No. 9137/1983 describes a technique wherein a layered-type silver bromochloroiodide emulsion with the outermost layer composed of 50 mol% or over of silver bromide is chemically sensitized with an unstable sulfur compound in the presence of particulate silver chloride.
  • JP-A means unexamined published Japanese patent application
  • No. 9137/1983 describes a technique wherein a layered-type silver bromochloroiodide emulsion with the outermost layer composed of 50 mol% or over of silver bromide is chemically sensitized with an unstable sulfur compound in the presence of particulate silver chloride.
  • the preparation of a layered-type emulsion was attempted according to this technique, it was also found that the gradation of the foot of the characteristic curve was liable to become soft gradation, and when pressure was applied, desensitization was apt to occur.
  • JP-A Nos. 95736/1983 and 108533/1983 disclose techniques concerning high silver chloride emulsions having a layered-type structure. According to the former disclosure, it is stated that by allowing a layer mainly consisting of silver bromide to be present inside the grain, rapid processing becomes possible and an emulsion high in sensitivity can be obtained, but when the technique was tested, it was found that if pressure was applied to the emulsion grains, desensitization was liable to occur, and therefore it was difficult to use the technique in practice.
  • JP-A Nos. 222844/1985 and 222845/1985 disclose techniques concerning high silver chloride emulsions rendered to have a layered structure. However, even according to these techniques, the defects as described above were not overcome.
  • the formation is effected generally in such a manner that an aromatic primary amine color-developing agent is oxidized when silver halide grains in the silver halide color photographic material that has been exposed to light are reduced, and the oxidized product couples with couplers previously included in the silver halide color photographic material.
  • couplers three kind of couplers are used, which will form three dyes: yellow, magenta, and cyan respectively in order, to effect color reproduction by the subtractive process.
  • the factors include, to begin with, the spectral sensitivity and the interlayer effect of photographic materials for photographing, and, in the case of photographic materials for prints, for example, the matching of its spectral sensitivity with the color-developed dyes of the photographic material for photographing, the overlapping of the spectral sensitivities of the photographic layers different in color sensitivity, the spectral absorption characteristics of the color-developed dyes, and color contamination of the processed photographic layers different in the color-developed dyes, which influence the level of the color reproduction.
  • couplers include, for example, solubility in high-boiling organic solvents, dispersibility and dispersion stability in silver halide emulsions, photographic characteristics, spectral absorption characteristics of the color-developed dyes, and fastness of dye images to light, heat, and humidity.
  • spectral absorption characteristics of the color-developed dyes are important so as to make the color reproduction, quality of color photographics good, and even if couplers capable of forming color-developed dyes having preferable spectral absorption characteristics are used, the significance will lower considerably if mixing of colors as mentioned above occurs.
  • dye image fastness has increasingly become an important matter, in particular dye image fastness to light is important, and in current color papers, one big problem is fading of magenta dyes or the occurrence of brown stain attributable to a reaction between color-undeveloped magenta couplers and light.
  • magenta couplers As means of improving magenta couplers to solve such a problem, a technique is known using, instead of conventionally used 5-pyrazolone four-equivalent couplers, 5-pyrazolone two-equivalent couplers.
  • magenta couplers for example, magenta couplers having a nitrogen-linked coupling releasable group described, for example, in US-A-4,310,619, and magenta couplers having a sulfur-linked coupling releasable group described in US-A-4,351,897 are known.
  • magenta couplers having a coupling releasable arylthio group described in the latter U.S. Patent have many practically excellent points, including the stability of the couplers themselves, their levels are still not satisfactory.
  • magenta couplers other than 5-pyrazolone couplers As magenta couplers other than 5-pyrazolone couplers, pyrazoloazole magenta couplers are known. In contrast to 5-pyrazolone couplers, for pyrazoloazole magenta couplers it is known that the spectral absorption characteristics of the color-developed dyes are good, the fastness to light is good, and stain due to the color-undeveloped coupler is less, and pyrazoloazole magenta couplers are the most excellent magenta couplers practically.
  • Couplers of this type are described, for example, in US-A-3,369,879 and 3,725,067, Research Disclosure 24220 (June 1984), Research Disclosure 24230 (June 1983), US-A-4,500,630 and 4,540,654, JP-A Nos. 65245/1986, 65246/1986, and 147254/1986, and EP-B-0,226,849.
  • pyrazolo[5,1-c][1,2,4]triazoles and pyrazolo[1,5-b][1,2,4]triazoles are preferable in view of the combined performance of color-forming properties, the spectral absorption characteristics of the color-developed dye, and dye image fastness, and in particular pyrazolo[1,5,-b][1,2,4]triazoles described in US-A-4,540,654 can preferably be used.
  • couplers as mentioned above are combined with, as a substituent, a branched alkyl group, as described in JP-A No. 65245/1986, those wherein a sulfonamido group is introduced in the molecule, as described in JP-A No. 65246/1986, those wherein an alkoxyphenylsulfonamido group is introduced, as described in JP-A No. 147254/1986, or those wherein an alkoxy group or an aryloxy group is introduced to the 6-position, as described in EP-B-0,226,849 and 0,294,785, are more preferable.
  • EP-A-0 295 439 discloses a silver halide photographic material comprising a support having thereon at least one emulsion layer containing surface latent image type mono-disperse silver chlorobromide emulsions consisting of silver chlorobromide which is essentially free of silver iodide which are obtained by subjecting the surface of silver halide grains, which have a plurality of layers which have different halogen compositions within the grains, to halogen conversion.
  • the object of the present invention is to provide a silver halide color photographic material high in sensitivity and contrast and excellent in color reproduction and dye image stability.
  • the object of the present invention is to prevent processing color contamination that is apt to occur in silver halide color photographic materials excellent in color reproduction and dye image stability, thereby providing a silver halide color photographic material whose quality is made markedly high and is stabilized.
  • a silver halide color photographic material that has photographic layers that include at least one silver halide emulsion layer containing a yellow coupler, at least one silver halide emulsion layer containing a magenta coupler, and at least one silver halide emulsion layer containing a cyan coupler, on a support in the stated order, with said yellow coupler-containing silver halide emulsion layer nearest the support, characterized in that (a) said magenta coupler is a compound represented by the below-given formula (I), (b) the coating amount of the hydrophilic colloid in the nonphotosensitive layer positioned between said yellow coupler-containing silver halide emulsion layer and said magenta coupler-containing silver halide emulsion layer is 1.1 g/m 2 or over, (c) said nonphotographic layer contains a compound represented by the below-given formula (II) in an amount between 7.75 x 10 -5 mol/m 2 and
  • methine represented by Za, Zb, or Zc in formula (I) include substituted and unsubstituted methine.
  • substituents of methine can be mentioned 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 aryloxycarbonylamino group, a
  • the silver halide emulsion used in the present silver halide color photographic material is silver chlorobromide substantially free from silver iodide.
  • substantially free from silver iodide means that the silver iodide content is 1 mol% or below, preferably 0.5 mol% or below, and most preferably silver iodide is not contained at all.
  • the content ratio of silver chloride to silver bromide may take any value ranging from a value indicating nearly pure silver chloride to a value indicating nearly pure silver bromide, it is desirable that the silver bromide content is between 0.3 mol% and 97 mol%.
  • the silver bromide content of the emulsion is made high, and a silver bromide content of 45 % or over is good, with 60 % or over preferred.
  • the crystalline grains contained therein have at least two partial structures, wherein the difference of the silver bromide content preferably is 10 mol% or over.
  • partial structures refers to a structure wherein the inside and the surface of the crystal grain are different in halogen composition, and which may be a so-called core-shell structure or a layered structure having plural layers.
  • the layered structure may not necessarily be continuous, and it may be a structure wherein discontinuous layers have been grown, for example, on the corners or planes of the crystal grain epitaxially.
  • the core section of crystalline grains having a core-shell structure may have a high silver bromide content, and the shell section may have a low silver bromide content, or conversely the core section may have a low silver bromide content and the shell section may have a high silver bromide content.
  • the boundary between the partial structures of such a crystalline grain that are different in halogen composition may be a distinct boundary with respect to the composition, or a boundary where the composition continuously changes due to the formation of a mixed crystal due to the difference of the composition.
  • the constitutional silver halide molar ratio of the core to the shell is preferably in the range of 2 : 98 to 98 : 2, more preferably 10 : 90 to 95 : 10, further more preferably 40 : 60 to 90 : 10, and most preferably 67 : 33 to 90 : 10.
  • the difference of the silver bromide content between the core section and the shell section may vary depending on the constitutional silver halide molar ratio between the core section and the shell section, it is preferred that the difference is at least 10 mol% or over, but less than 100 mol%, more preferably between 10 mol% and 50 mol%, and most preferably between 15 mol% and 35 mol%. If the difference of the silver bromide content between two or more partial structures is not large, the effect of the grain is not so different from a grain having a uniform structure, whereas if the composition difference is too large, it is not preferable because a problem concerning the performance, such as pressure desensitization, is liable to occur.
  • the suitable composition difference is dependent on the constitutional ratio of the partial structures, and the nearer the constitutional ratio is to 0 : 100 or 100 : 0, the more preferable it is to make greater the composition difference, and the nearer the constitutional ratio is to 1 : 1, the more preferable it is to make the composition difference reduce to a certain range of 10 mol% or over.
  • halogen conversion used in the present invention is defined as "conversion of the composition of already formed silver halide crystals by the addition of a material containing a halide ion capable of forming a more sparingly soluble silver salt.”
  • a material containing a halide ion capable of forming a more sparingly soluble silver salt As a typical example thereof, the reaction wherein silver chloride is converted to silver bromide, when potassium bromide is added to pure silver chloride grains, can be mentioned.
  • halogen conversion includes such a reaction as will occur when a silver halide crystal that will undergo halogen conversion which is a mixed crystal of silver chlorobromide, is treated in the solution containing bromide ions in an amount exceeding the equilibrium concentration of bromide ions, thereby allowing the composition of the surface silver halide to be converted to be rich in silver bromide.
  • a donor that can control the supply or the supply speed of bromide ions can also be used.
  • a donor for example, an organic bromide, an inorganic bromide having a suitable solubility for water, and a bromide wherein the capsule membrane is coated with a semipermeable film can be used.
  • a fine grain silver halide having a silver bromide content higher than the silver bromide content of the grain surface before the halogen conversion can also be used.
  • the amount of halogen conversion is between 0.5 mol% and to 15 mol% for the total silver halide. If the amount of halogen conversion is 0.5 mol% or below, the effect of the present invention is barely exhibited, whereas if the amount exceeds 20 mol%, it is not preferable because desensitization due to pressure, as mentioned above, becomes great.
  • the step of preparing the silver halide emulsion is made up of a step of forming silver halide grains by the reaction of a water soluble silver salt and a water-soluble halide, a step of desalting, and a step of chemically ripening.
  • the time when halogen conversion is effected in the present invention is preferably before the chemical ripening step, more preferably before the desalting step, of the above steps, and particularly preferably halogen conversion is effected after the grain formation step.
  • the silver halide emulsions in the silver halide emulsion layers are chemically sensitized.
  • sulfur sensitization is preferable, but sulfur sensitization may be carried out together with reduction sensitization or gold sensitization.
  • the chemical sensitization with sulfur used in the present invention is carried out by using active gelatin or a compound containing sulfur capable of reacting with silver (e.g., thiosulfates, thioureas, mercapto compounds, and rhodanines), and specific examples thereof are described, for example, in US-A-1,574,944, 2,278,947, 2,410,689, 2,728,668, and 3,656,955.
  • active gelatin or a compound containing sulfur capable of reacting with silver e.g., thiosulfates, thioureas, mercapto compounds, and rhodanines
  • the silver halide emulsions in the silver halide emulsion layers may be subjected to a chemical sensitization process in the presence of a nucleic acid or its dispersion before the completion of the chemical sensitization.
  • the nucleic acid used includes deoxyribonucleic acids (DNA) and ribonucleic acids (RNA), and, as nucleic acid degradation products, degradation intermediates, and adenine, guanine, uracil, cytosine, and thymine, which may be used alone or in combination.
  • DNA deoxyribonucleic acids
  • RNA ribonucleic acids
  • the chemical sensitization process in the present invention can be carried out in any pH range, if it is carried out at a pH in the range of 7.0 to 9.0, more preferable results will be obtained.
  • the silver chlorobromide emulsion grains used in the present invention are ones that have a regular crystal shape, such as a cubic shape and an octahedral shape, or an irregular crystal shape, such as a spherical shape and a tabular shape, or a composite of these.
  • a mixture of grains having various crystal shapes can be used, with grains having a regular shape preferably used.
  • the silver halide emulsion used in the present invention is a tabular grain emulsion wherein grains having a thickness of 0.5 microns or below, preferably 0.3 microns or below, a diameter of 0.6 microns or over, and an average aspect ratio of 5 or over, account for 50 % or over of the total projective area, or a monodisperse emulsion having a statistical deviation coefficient (the value S/ d ⁇ obtained by dividing the standard deviation S by the diameter d ⁇ with the projective area approximated to a circle) of 20 % or below.
  • a mixture of two or more tabular grain emulsions and monodisperse emulsions may be used.
  • the photographic emulsion used in the present invention can be put in due condition by processes described, for example, by P. Glafkides in Chimie et Physique Photographeque (published by Paul Montel in 1967), by G.F. Duffin in Photographic Emulsion Chemistry (published by Focal Press in 1966), and by V.L. Zelikman et at. in Making and Coating Photographic Emulsion (published by Focal Press in 1964).
  • a silver halide solvent for example, ammonia, potassium thiocyanate, ammonium thiocyanate, a thioether compound (e.g., those described in US-A-3,271,157, 3,574,628, 3,704,130, 4,297,439, and 4,276,374), a thion compound (e.g., those described in JP-A Nos. 144319/1978, 82408/1978, and 77737/1980), and an amine compound (e.g., those described in JP-A No. 100717/1979).
  • a silver halide solvent for example, ammonia, potassium thiocyanate, ammonium thiocyanate, a thioether compound (e.g., those described in US-A-3,271,157, 3,574,628, 3,704,130, 4,297,439, and 4,276,374), a thion compound (e.g., those described in JP-A Nos. 144319/1978
  • a cadmium salt for example, a zinc salt, a thallium salt, an iridium salt or its complex salt, a rhodium salt or its complex salt, or an iron salt or its complex salt may also be present.
  • the silver halide emulsion is generally sensitized spectrally.
  • spectral sensitization use can be made of a common methine dye, and details thereof are described in JP-A No. 215272/1987, page 22, lines 3 to 38 in the right upper column, and in the Attached Paper B of Amendment thereof dated March 16, 1987.
  • the silver halide photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fogging in the process of the production of photographic materials, or fogging during the storage or photographic processing of photographic materials, or for the purpose of stabilizing the photographic performance. That is, various compounds known as antifoggants or stabilizers can be added, such as azoles, for example benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, and benzimidazoles (particularly nitro- or halogen-substituted benzimidazoles); heterocyclic mercapto compounds, for example mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole and phenyl-substituted 1-phenyl-5-mercaptotetrazole), and mercaptopyrimidines; hetero
  • magenta couplers represented by formula (I) in the present invention are described in detail.
  • the term "polymer” means one having two or more groups represented by formula (I) in the molecule, which includes bis-forms and polymer couplers.
  • the polymer coupler may be a homopolymer consisting only of a monomer (preferably one having a vinyl group, which is referred hereinafter to as vinyl monomer) having a moiety represented by formula (I), or it may be a copolymer of such a monomer with a non-color-forming ethylenically-unsaturated monomer that will not couple with the oxidized product of an aromatic primary amine developing agent.
  • magenta dye-forming couplers represented by formula (I) preferable ones are those represented by the following formulae (Ia), (Ib), (Ic), (Id), (Ie), (If), and (Ig):
  • couplers represented by formulae (Ia) to (Ig) preferable ones for the objects of the present invention are those represented by formulae (Ia), (Id), and (Ie), and more preferably those represented by formula (Ie).
  • R 11 , R 12 , and R 13 which may be the same or different, each represent 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 aryloxycarbonylamino group, a sulfonamido group, a carbamo
  • R 11 , R 12 , and R 13 each represent a hydrogen atom, a halogen atom (e.g., a chlorine atom or a bromine atom), an alkyl group (e.g., methyl, propyl, t-butyl, trifluoromethyl, tridecyl, 3-(2,4-di-t-amylphenoxy)propyl, allyl, 2-dodecyloxyethyl, 3-phenoxypropyl, 2-hexylsulfonyl-ethyl, cyclopentyl, and benzyl), an aryl group (e.g., phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl and 4-tetradecaneamidophenyl), a heterocyclic group (e.g., 2-furyl, 2-thienyl, 2-pyrimidyl, and 2-benzothiazolyl), a heterocyclic
  • phenylureido, methylureido, and N,N-dibutylureido an imido group (e.g., N-succinimido, 3-benzylhydantoinyl, and 4-(2-ethylhexanoylamino)phthalamido), a sulfamoylamino group (e.g., N,N-dipropylsulfamoylamino and N-methyldecylsulfamoylamino), an alkylthio group (e.g., methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, and 3-(4-t-butylphenoxy)propylthio), an arylthio group (e.g., phenylthio, 2-butoxy-5-t-octylphenylthio, 3-p
  • R 12 and R 13 may bond together to form a 5- to 6-membered ring.
  • R 11 , R 12 , R 13 , or X becomes a bivalent group to form a bis-form
  • R 11 , R 12 , and R 13 each represent a substituted or unsubstituted alkylene group (e.g., methylene, ethylene, 1,10-decylene, or -CH 2 CH 2 -O-CH 2 CH 2 -), a substituted or unsubstituted phenylene group (e.g., 1,4-phenylene, 1,3-phenylene, a group -NHCO-R 14 -CONH- (wherein R 14 represents a substituted or unsubstituted alkylene group or phenylene group, such as -NHCOCH 2 CH 2 CONH-, or or a group S-R 14 -S- (wherein R 14 represents a substituted or unsubstituted alkylene group, such as -S-CH 2 CH 2 -S or and X represents a bivalent group that is formed suitably
  • the linking group represented by R 11 , R 12 , R 13 or X, when the coupler represented by one of formulae (Ia), (Ib), (Ic), (Id), (Ie), (If), and (Ig) is contained in a vinyl monomer includes groups formed by combining groups selected from substituted or unsubstituted alkylene groups (e.g., methylene, ethylene, 1,10-decylene, and -CH 2 CH 2 OCH 2 CH 2 -), substituted or unsubstituted phenylene groups (e.g., 1,4-phenylene, 1,3-phenylene, or -NHCO-, -CONH-, -O-, -OCO-, and aralkylene groups (e.g., or
  • Preferable linking groups are -NHCO-, -CH 2 CH 2 -, -CH 2 CH 2 NHCO-, -CONH-CH 2 CH 2 NHCO- , -CH 2 CH 2 O-CH 2 CH 2 -NHCO-, and
  • the vinyl group may have substituents other than one represented by formulae (Ia), (Ib), (Ic), (Id), (Ie), (If), or (Ig), and a preferable substituent is a chlorine atom or a lower alkyl group having 1 to 4 carbon atoms (e.g., methyl and ethyl).
  • the monomer that contains coupler represented by one of formulae (Ia), (Ib), (Ic), (Id), (Ie), (If), and (Ig) may form a copolymer with a non-color-forming ethylenically-unsaturated monomer that will not couple with the oxidized product of aromatic primary amine developing agents.
  • non-color-forming ethylenically-unsaturated monomer that will not couple with the oxidized product of aromatic primary amine developing agents can be mentioned, for example, acrylic acid, ⁇ -chloroacrylic acid, ⁇ -alkylacrylic acids (e.g., methacrylic acid) and esters and amides derived from these acrylic acids (e.g., acrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and ⁇ -hydroxy methacrylate
  • Two or more of such non-color-forming ethylenically-unsaturated monomers can be used together.
  • n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, or methyl acrylate and diacetoneacrylamide may be used together.
  • the non-color-forming ethylenically-unsaturated monomer to be copolymerized with a water-insoluble solid monomer coupler can be selected in such a manner that the physical properties and/or chemical properties of the copolymer, such as the solubility of the copolymer, the compatibility with the binder (such as gelatin) of the photographic colloid composition, and the flexibility and heat stability of the photographic colloid composition, are influenced favorably.
  • the polymer couplers used in the present invention may be water-soluble ones or water-insoluble ones, and of these, polymer coupler latices are particularly preferable.
  • pyrazoloazole magenta couplers represented by formula (I) used in the present invention and methods for synthesizing them are described for example in JP-A Nos. 162548/1984, 43659/1985, 171956/1984, 172982/1985, and 33552/1985, and US-A-3,061,432.
  • pyrazoloazole couplers are preferable, and particularly preferable pyrazolotriazole couplers are those wherein the 2-, 3-, or 6-position has a branched alkyl group (which may be substituted) and the split-off group is a halogen atom, or the 2- or 3-position has an alkoxy group or an aryl group, the 6-position has an alkoxy group or an aryloxy group, and the split-off group is a split-off group through a sulfur atom.
  • the magenta coupler represented by formula (I) used in the present invention is contained generally in an amount of 0.005 to 4 mol, preferably 0.05 to 2 mol, in the silver halide emulsion layer.
  • magenta couplers and their vinyl monomers related to the present invention are given below, although the present invention is not intended to be limited to them only.
  • R 15 and R 16 each represent a hydrogen atom, a substituted or unsubstituted alkyl group (preferably having 1 to 24 carbon atoms, e.g., methyl, ethyl, n-butyl, n-amyl, t-amyl, n-octyl, t-octyl, n-dodecyl, n-octadecyl, 2-methoxyethyl, 2-ethoxyethyl, 2-phenylethyl, benzyl, and 3-cyanopropyl), a substituted or unsubstituted alkenyl group (preferably having 2 to 24 carbon atoms, e.g., ally, octenyl, and oleyl), a substituted or unsubstituted aryl group (preferably having 6 to 24 carbon atoms, e.g., phenyl, tolyl, 4-t-butylphenyl,
  • R 17 , R 18 , R 19 , and R 20 each represent a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, or bromine), a substituted or unsubstituted alkyl group (preferably having 1 to 24 carbon atoms, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-amyl, i-amyl, n-octyl, t-octyl, n-dodecyl, n-octadecyl, 2-methoxyethyl, 2-ethoxyethyl, 2-phenylethyl, benzyl, and 3-cyanopropyl), a substituted or unsubstituted alkenyl group (preferably having 2 to 24 carbon atoms, e.g., ally and octenyl), a substitute
  • the number of carbon atom is preferably 1 to 24 when the substituent contains carbon atom.
  • R 15 and R 16 each are preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably R 15 and R 16 are both hydrogen atoms
  • R 17 , R 18 , R 19 , and R 20 each are preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, more preferably sum of carbon atom numbers of R 17 , R 18 , R 19 , and R 20 is 24 or below.
  • the number of carbon atom above-mentioned means a total number of carbon atoms.
  • These compounds are added together with a hydrophilic colloid to the nonphotosensitive layer situated between the yellow coupler-containing silver halide emulsion layer and the magenta coupler-containing silver halide emulsion layer, in an amount between 7.75 x 10 -5 mol/m 2 and 9.00 x 10 -4 mol/m 2 , with the coating amount of the hydrophilic colloid being 1.1 g/m 2 or over.
  • the coating amount of the hydrophilic colloid is meant the solid content of the hydrophilic colloid used in the particular nonphotosensitive layer.
  • the amount of the hydrophilic colloid in the nonphotosensitive layer is less than 1.1 g/m 2 , the effect of the present invention will not be sufficiently exhibited, and although the greater the amount thereof is, the more highly the effect thereof is exhibited, a highly greater amount will result in such an adverse effect that the development of the silver halide emulsion layer situated nearer the support is made slow.
  • the coating amounts of the hydrophilic colloid to be contained in the particular nonphotosensitive layer and the compound represented by formula (II) are about 1.0 g/m 2 or below and about 1.0 x 10 -4 mol/m 2 or below respectively, even, for example, in commercially available color papers or in known literature, including JP-A No. 267050/1986, whereas in the present invention their coating amounts are greater than those, which is one of features of the present invention.
  • the coating amount of the hydrophilic colloid is 1.1 g/m 2 or over, preferably the coating amount is in the range of 1.1 to 3.0 g/m 2 , and more preferably in the range of 1.1 to 2.2 g/m 2 .
  • the coating amount of the compound represented by formula (II) is between 7.75 x 10 -5 mol/m 2 and 9.00 x 10 -4 mol/m 2 , preferably between 1.00 x 10 -4 mol/m 2 and 8.00 x 10 -4 mol/m 2 , and more preferably between 1.00 x 10 -4 mol/m 2 and 4.0 x 10 -4 mol/m 2 .
  • gelatin is preferably used, although other hydrophilic colloids can be used.
  • proteins such as gelatin derivatives, graft polymers of gelatin and other polymer, albumin, and case in; cellulose derivatives, such as hydroxyethyl cellulose, carboxymethylcellulose, and cellulose sulfate; saccharide derivatives, such as starch derivatives and sodium alginate; and various synthetic hydrophilic polymers, such as homopolymers and copolymers, for example polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole, can be used.
  • gelatin general-purpose lime-treated gelatin as well as acid-processed gelatins and enzyme-processed gelatins, as described in Bull. Soc. Sci. Phot. Japan, No. 16, page 30 (1966), can be used, and hydrolyzates of gelatin can also be used.
  • Cyan couplers and yellow couplers preferably used in the present invention are those represented by the following formulae (III), (IV) and (V): wherein R 1 , R 2 , and R 4 each represent a substituted or unsubstituted aliphatic, aromatic, or heterocyclic group, R 3 , R 5 , and R 6 each represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, or an acylamino group, R 3 may represent, together with R 4 , a non-metal atom group forming a nitrogen-containing 5-membered ring or 6-membered ring, and Y 1 and Y 2 each represent a hydrogen atom or a group that can split off when the compound couples with the oxidized product of developing agents.
  • R 1 , R 2 , and R 4 each represent a substituted or unsubstituted aliphatic, aromatic, or heterocyclic group
  • R 3 , R 5 , and R 6 each represent
  • R 5 in formula (IV) is preferably an aliphatic group, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentadecyl group, a t-butyl group, a cyclohexyl group, a cyclohexylmethyl group, a phenylthiomethyl group, a dodecyloxyphenylthiomethyl group, a butaneamidomethyl group, and a methoxymethyl group.
  • cyan couplers represented by formula (III) or (IV) are as follows:
  • R 1 in formula (III) is preferably an aryl group or a heterocyclic group, and more preferably an aryl group that is substituted by a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamido group, a sulfamoyl group, a sulfonyl group, a sulfamido group, an oxycarbonyl group, or a cyano group.
  • R 3 and R 2 in formula (III) do not together from a ring, preferably R 2 represents a substituted or unsubstituted alkyl group or aryl group, and particularly preferably an alkyl group substituted by a substituted aryloxy group, and R 3 represents preferably a hydrogen atom.
  • R 4 in formula (IV) represents a substituted or unsubstituted alkyl group or aryl group, and particularly preferably an alkyl group that is substituted by a substituted aryloxy group.
  • R 5 in formula (IV) represents an alkyl group having 2 to 15 carbon atoms or a methyl group having a substituent with 1 or more carbon atoms, the substituent preferably being an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.
  • R 5 in formula (IV) represents an alkyl group having 2 to 15 carbon atoms, and particularly preferably an alkyl group having 2 to 4 carbon atoms.
  • R 6 in formula (IV) represents a hydrogen atom or a halogen atom, with a chlorine atom or a fluorine atom being particularly preferable.
  • Y 1 and Y 2 in formula (III) and (IV) each represent a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, or a sulfonamido group.
  • R 11 represents a halogen atom or an alkoxy group
  • R 12 represents a hydrogen atom, a halogen atom, or an alkoxy group
  • A represents -NHCOR 13 , -NHSO 2 -R 13 , -SO 2 NHR 13 , -COOR 13 , or in which R 13 and R 14 each represent an alkyl group
  • Y 5 represents a split-off group.
  • the substituents of R 12 , R 13 , and R 4 are the same as those allowed for R 1 , and preferably the split-off group Y 5 is of a type wherein the split-off will occur at the oxygen atom or the nitrogen atom, with particular preference given to the latter.
  • couplers represented by formulae (III) to (V) are:
  • the addition can be carried out by the oil-in-water dispersion method, known as the oil protect method, wherein the coupler is dissolved in a solvent and the solution is emulsified and dispersed into an aqueous gelatin solution containing a surface-active agent.
  • water or an aqueous gelatin solution may be added to a coupler solution containing a surface-active agent, to obtain an oil-in-water dispersion with phase inversion of emulsion being accompanied.
  • Couplers soluble in alkalis can be dispersed by the so-called Fischer dispersion method.
  • the low-boiling organic solvent may be removed from the coupler dispersion, for example, by distillation, noodle washing, or ultrafiltration, and the resulting mixture may be mixed with a photographic emulsion.
  • water-insoluble polymer compounds and/or high-boiling organic solvents having a dielectric constant of 2 to 20 (25°C) and a refractive index of 1.3 to 1.7 (25°C) are preferably used.
  • high-boiling organic solvents preferably high-boiling organic solvents represented by the following formulae (A) to (E) are used.
  • high-boiling organic solvents represented by formula (A) to (E) can be used in the present invention if they are compounds which have a melting point of 100°C or below and a boiling point of 140°C, are incompatible with water, and are good solvents for the coupler.
  • the melting point of the high-boiling organic solvents is 80°C or below.
  • the boiling point of the high-boiling organic solvents is 160°C or over, and more preferably 170°C or over.
  • the couplers can also be emulsified and dispersed into a hydrophilic colloid aqueous solution by impregnating them into a loadable latex polymer (e.g., see US-A-4,203,716) in the presence or absence of the above-mentioned high-boiling point organic solvent, or by dissolving it in a water-insoluble and organic-solvent-soluble polymer.
  • a loadable latex polymer e.g., see US-A-4,203,716
  • monopolymers or copolymers described on pages 12 to 30 of International Publication No. WO 88/00723 are used, and more preferably acrylamide polymers are used because, for example, the dye image is stabilized.
  • the photographic material that is prepared according to the present invention may contain, as a color antifoggant, for example, a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, or an ascorbic acid derivative.
  • a color antifoggant for example, a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, or an ascorbic acid derivative.
  • various discoloration inhibitors can be used.
  • organic discoloration inhibitors for cyan, magenta, and/or yellow images typical examples are hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols, including bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, and hindered amines, and ether or ester derivatives thereof, obtained by silylating or alkylating the phenolic hydroxyl group of these compounds.
  • Metal complexes such as (bissalicylaldoxymato)nickel complexes and (bis-N,N-dialkyldithiocarbamato)nickel complexes can also be used.
  • organic discoloration inhibitors are described in the following patent specifications.
  • Hydroquinones are described, for example, in US-A-2,360,290, 2,418,613, 2,700,453, 2,701,197, 2,728,659, 2,732,300, 2,735,765, 3,982,944, and 4,430,425, GB-B-1,363,921, and US-A-2,710,801 and 2,816,028; 6-hydroxychromans, 5-hydroxycoumarans, and spirochromans are described, for example, in US-A-3,432,300, 3,573,050, 3,574,627, 3,698,909, and 3,764,337, and JP-A No.
  • gallic acid derivatives, methylenedioxybenzenes, and aminophenols are described, for example, in US-A-3,457,079 and 4,332,886 and JP-B No. 21144/1981, respectively; hindered amines are described, for example, in US-A-3,336,135 and 4,268,563, GB-B-1,32889, 1,354,313, and 1,410,846, JP-B No. 1420/1976, and JP-A Nos.
  • These compounds are coemulsified with respective couplers generally in amounts of 5 to 100 wt.% for respective couplers, and are added to photosensitive layers to attain the purpose.
  • couplers generally in amounts of 5 to 100 wt.% for respective couplers, and are added to photosensitive layers to attain the purpose.
  • it is more effective to introduce an ultraviolet-absorbing agent into the cyan color-forming layer and the layers opposite the cyan color-forming layer.
  • benzotriazoles substituted by a aryl group e.g., those described in US-A-3,533,794
  • 4-thiazolidone compounds e.g., those described in US-A-3,314,794 and 3,352,681
  • benzophenone compounds e.g., those described in JP-A No. 2784/1971
  • cinnamate compounds e.g., those described in US-A-3,705,805 and 3,707,375
  • butadiene compounds e.g., those described in US-A-4,045,229
  • benzooxidol compounds e.g., those described in US-A-3,700,455
  • Ultraviolet-absorbing couplers e.g., ⁇ -naphthol-type cyan dye-forming couplers
  • ultraviolet-absorbing polymers etc.
  • These ultraviolet-absorbing agents may be mordanted to a particular layer.
  • benzotriazoles substituted by an aryl group are particularly preferable.
  • a compound (F), which will chemically bond to the aromatic amine developing agent remaining after the color-developing process, to form a chemically inactive and substantially colorless compound, and/or a compound (G), which will chemically bond to the oxidized product of the aromatic amine color developing agent remaining after the color-developing process, to form a chemically inactive and substantially colorless compound are used simultaneously or separately, for example, to prevent the occurrence of stain due to the formation of a color-developed dye by the reaction of the couplers with the color-developing agent remaining in the layer during storage after the processing or with the oxidized product of the color-developing agent, and to prevent other side effects.
  • Preferable as compound (F) are those that can react with p-anisidine at the second-order reaction-specific rate k 2 (in trioctyl phosphate at 80°C) in the range of 1.0 l/mol ⁇ sec to 1 x 10 -5 l/mol ⁇ sec.
  • the second-order reaction-specific rate can be determined by the method described in JP-A No. 158545/1983.
  • compound (F) More preferable as compound (F) are those that can be represented by the following formula (FI) or (FII): Formula (FI) R 21 - (A) n - X 3 wherein R 21 and R 22 each represent an aliphatic group, an aromatic group, or a heterocyclic group, n is 1 or 0, A represents a group that will react with an aromatic amine developing agent to form a chemical bond therewith, X 3 represents a group that will react with the aromatic amine developing agent and split off, B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, Y 3 represents a group that will facilitate the addition of the aromatic amine developing agent to the compound represented by formula (FII), and R 21 and X 3 , or Y 3 and R 22 or B, may bond together to form a ring structure.
  • R 21 and X 3 , or Y 3 and R 22 or B may bond together to
  • Preferable examples of the compounds represented by formulae (FI) and (FII) include those described, for example, in JP-A Nos. 158545/1988, 283338/1987, and 2042/1989, and EP-B-277589.
  • compound (G) which will chemically bond to the oxidized product of the aromatic amine developing agent remaining after color development processing, to form a chemically inactive and colorless compound
  • formula (GI) R - Z wherein R represents an aliphatic group, an aromatic group, or a heterocyclic group, Z represents a nucleophilic group or a group that will decompose in the photographic material to release a nucleophilic group.
  • the compounds represented by formula (GI) are ones wherein Z represents a group whose Pearson's nucleophilic n CH 3 I value (R.G. Pearson, et al., J. Am. Chem. Soc. , 90 , 319 (1968)) is 5 or over, or a group derived therefrom.
  • the photographic material prepared in accordance with the present invention may contain, in the hydrophilic colloid layer, water-soluble dyes as filter dyes or to prevent irradiation and for other various purposes.
  • dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes.
  • oxonol dyes, hemioxonol dyes, and merocyanine dyes are useful.
  • gelatin is advantageously used, but other hydrophilic colloids can be used alone or in combination with gelatin.
  • gelatin may be lime-treated gelatin or acid-processed gelatin. Details of the manufacture of gelatin is described by Arthur Veis in The Macromolecular Chemistry of Gelatin (published by Academic Press, 1964).
  • a base to be used in the present invention a transparent film, such as cellulose nitrate film, and polyethylene terephthalate film or a reflection-type base that is generally used in photographic materials can be used.
  • a reflection-type base is more preferable.
  • the “reflection base” to be used in the present invention is one that enhances reflectivity, thereby making sharper the dye image formed in the silver halide emulsion layer, and it includes one having a base coated with a hydrophobic resin containing a dispersed light-reflective substance, such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and also a base made of a hydrophobic resin containing a dispersed light-reflective substance.
  • baryta paper polyethylene-coated paper, polypropylene-type synthetic paper, a transparent base having a reflective layer, or additionally using a reflective substance, such as glass plate, polyester films of polyethylene terephthalate, cellulose triacetate, or cellulose nitrate, polyamide film, polycarbonate film, polystyrene film, and vinyl chloride resin, which may be suitably selected in accordance with the purpose of the application.
  • a reflective substance such as glass plate
  • polyester films of polyethylene terephthalate, cellulose triacetate, or cellulose nitrate, polyamide film, polycarbonate film, polystyrene film, and vinyl chloride resin which may be suitably selected in accordance with the purpose of the application.
  • a white pigment is kneaded well in the presence of a surface-active agent, and it is preferable that the surface of the pigment particles has been treated with a divalent to tetravalent alcohol.
  • the occupied area ratio (%) per unit area prescribed for the white pigments finely divided particles can be obtained most typically by dividing the observed area into contiguous unit areas of 6 ⁇ m x 6 ⁇ m, and measuring the occupied area ratio (%) (Ri) of the finely divided particles projected onto the unit areas.
  • the deviation coefficient of the occupied area ratio (%) can be obtained based on the ratio s/R, wherein s stands for the standard deviation of Ri, and R stands for the average value of Ri.
  • the number (n) of the unit areas to be subjected is 6 or over. Therefore, the deviation coefficient s/R can be obtained by
  • the deviation coefficient of the occupied area ratio (%) of the finely divided particles of a pigment is 0.15 or below, and particularly 0.12 or below. If the deviation coefficient is 0.08 or below, it can be considered that the substantial dispersibility of the particles is substantially "uniform.”
  • the color developer to be used in the developing process for the photographic material of the present invention is preferably an aqueous alkali solution whose major component is an aromatic primary amine color-developing agent.
  • this color-developing agent aminophenol compounds are useful, but preferably p-phenylenediamine compounds are used.
  • Typical examples thereof include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesufonamidoethylaniline, and 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyaniline, and their sulfates, hydrochlorides, and p-toluenesulfonates. Two or more of them may be combined to achieve the purpose.
  • the color developer generally contains, for example, pH buffers, such as carbonates, borates, or phosphates of alkali metals, development restrainers, such as bromides, iodides, benzimidazoles, benzothiazoles, or mercapto compounds, or antifoggants.
  • pH buffers such as carbonates, borates, or phosphates of alkali metals
  • development restrainers such as bromides, iodides, benzimidazoles, benzothiazoles, or mercapto compounds, or antifoggants.
  • the color developer contains various preservatives, such as hydroxyamine, diethylhydroxylamine, sulfites, hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonates, and triethylenediamine(1,4-diazabicyclo[2,2,2]octane), organic solvents, such as ethylene glycol and diethylene glycol, development accelerators, such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, dye forming couplers, competing couplers, fogging agents, such as sodium boron hydride, auxiliary developers, such as 1-phenyl-3-pyrazolidone, viscosity increasers, and various chelate agents, such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, for example ethylenediaminetetraacetic acid, nitrilotriacetic acid, di
  • black-and-white development is first carried out, and then color development is carried out.
  • a known black-and-white developing agent such as hydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, and aminophenols such as N-methyl-p-aminophenol, which may be used alone or in combination.
  • the pH of this color developer and black-and-white developing solution is 9 to 12.
  • the replenishing amount of these developing solutions is generally 3 or below per square meter of the color photographic material to be processed, though the replenishing amount changes depending on the type of color photographic material, and if the concentration of bromide ions in the replenishing solution is lowered previously, the replenishing amount can be lowered to 500 m or below per square meter of the color photographic material. If it is intended to lower the replenishing amount, it is preferable to prevent the evaporation of the solution and oxidation of the solution with air by reducing the area of the processing tank that is in contact with the air.
  • the photographic emulsion layer are generally subjected to a bleaching process after color development.
  • the bleaching process can be carried out together with the fixing process (bleach-fixing process), or it can be carried out separately from the fixing process. Further, to quicken the process bleach-fixing may be carried out after the bleaching process. In accordance with the purpose, the process may be arbitrarily carried out using a bleach-fixing bath having two successive tanks, or a fixing process may be carried out before the bleach-fixing process, or a bleaching process.
  • bleaching agent use can be made of, for example, compounds of polyvalent metals, such as iron (III), cobalt (III), chromium (VI), and copper (II), peracids, quinones, and nitro compounds.
  • polyvalent metals such as iron (III), cobalt (III), chromium (VI), and copper (II), peracids, quinones, and nitro compounds.
  • typical bleaching agents use can be made of ferricyanides; dichromates; organic complex salts of iron (II) or cobalt (III), such as complex salts of aminopolycarboxylic acids, for example ethylenediaminetetraacetic acid, diethylenetriaminetetraacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycoletherdiaminetetraacetic acid, citric acid, tartaric acid, and malic acid; persulf
  • aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts are particularly useful in a bleaching solution as well as a bleach-fix solution.
  • the pH of the bleaching solution or the bleach-fix solution using these aminopolycarboxylic acid iron (III) complex salts is generally 5.5 to 8, but if it is required to quicken the process, the process can be effected at a lower pH.
  • bleach-accelerating solution In the bleaching solution, the bleach-fix solution, and the baths preceding them a bleach-accelerating solution may be used if necessary.
  • useful bleach-accelerating agents are compounds having a mercapto group or a disulfide linkage, described in US-A-3,893,858, DE-B-1,290,812, JP-A No. 95630/1978, and Research Disclosure No. 17129 (July, 1978); thiazolidine derivatives, described in JP-A No. 140129/1975 thiourea derivatives, described in US-A-3,706,561; iodide salts, described in JP-A No.
  • thiosulfates As a fixing agent can be mentioned thiosulfates, thiocyanates, thioether-type compounds, thioureas, and large amounts of iodide salts, although thiosulfate is used usually, and in particular ammonium thiosulfate is widely used.
  • thiosulfate is used usually, and in particular ammonium thiosulfate is widely used.
  • sulfite salt As the preservative for bleach-fix solution sulfite salt, bisulfite salt, or carbonyl-bisulfite adduct is preferable.
  • the silver halide color photographic material of the present invention undergoes, after a desilvering process such as fixing or bleach-fix, a washing step and/or a stabilizing step.
  • the amount of washing water may be set within a wide range depending on the characteristics (e.g., due to the materials used, such as couplers), the application of the photographic material, the washing temperature, the number of washing tanks (the number of steps), the type of replenishing system, including, for example, the counter-current system and the direct flow system, and other various conditions.
  • the relationship between the number of water-washing tanks and the amount of washing water in the multi-stage counter-current system can be found according to the method described in Journal of Society of Motion Picture and Television Engineers , Vol. 64, pages 248 to 253 (May, 1955).
  • Bokin Bobaizai no Kagaku in " Biseibutsu no Mekkin, Sakkin, Bobaigijutsu” edited by Eiseigijutsu-kai, and in " Bokin Bobaizai Jiten ", edited by Nihon Bokin Bobai-Gakkai, can be used.
  • the pH of the washing water used in processing the present photographic material is 4 to 9, preferably 5 to 8.
  • the washing water temperature and the washing time to be set may vary depending, for example, on the characteristics and the application of the photographic material, and they are generally selected in the range of 15 to 45°C for 20 sec. to 10 min., and preferably in the range of 25 to 40°C for 30 sec. to 5 min.
  • the photographic material of the present invention can be processed directly with a stabilizing solution instead of the above washing.
  • a stabilizing process any of known processes, for example, a multi-step counter-current stabilizing process or its low-replenishing-amount process, described in JP-A Nos. 8543/1982, 14834/1983, and 220345/1985.
  • the above washing process is further followed by a stabilizing process, and as an example thereof can be mentioned a stabilizing bath that is used as a final bath for color photographic materials for photography, which contains formalin and a surface-active agent.
  • a stabilizing bath that is used as a final bath for color photographic materials for photography, which contains formalin and a surface-active agent.
  • each kind of the chelating agents and bactericides may be added.
  • the over-flowed solution due to the replenishing of washing solution and/or stabilizing solution may be reused in other steps, such as a desilvering step.
  • the silver halide color photographic material of the present invention may contain therein a color-developing agent for the purpose of simplifying and quickening the process.
  • a color-developing agent for the purpose of simplifying and quickening the process.
  • a precursor for a color-developing agent for example, indoaniline-type compounds described in US-A-3,342,597, Schiff base-type compounds described in US-A-3,342,599 and Research Disclosure Nos. 14850 and 15159, aldol compounds described in Research Disclosure No. 13924, metal salt complexes described in US-A-3,719,492, and urethane-type compounds described in JP-A No. 135628/1978 can be mentioned.
  • the present silver halide color photographic material may contain, if necessary, various 1-phenyl-3-pyrazolidones. Typical compounds are described in JP-A No. 64339/1981, 144547/1982, and 115438/1983.
  • the various processing solutions used for the present invention are used at 10 to 50°C. Although generally a temperature of 33 to 38°C is standard, a higher temperature can be used to accelerate the process to reduce the processing time, or a lower temperature can be used to improve the image quality or the stability of the processing solutions. Also, to save the silver of the photographic material, a process using hydrogen peroxide intensification or cobalt intensification described in DE-B-2,226,770 and US-A-3,674,499 may be carried out.
  • the silver halide color photographic material of the present invention is high in sensitivity and contrast, and excellent in color reproduction and dye image stability. According to the present invention, processing color contamination, which is liable to occur in silver halide color photographic materials excellent in color reproduction and dye image stability, can be prevented, thereby permitting a silver halide color photographic material to be provided wherein the quality is made fairly high, and which is stabilized.
  • a photographic material was prepared by multi-coatings composed of the following layer composition on a two-side polyethylene laminated paper support.
  • each layer is shown below. Each ingredient is indicated in a coating amount (g/m 2 ), but the coating amount of the silver halide emulsion is indicated in terms of silver.
  • Second layer Gelatin 0.89 Color-mix inhibitor (H-1) 0.024 Solvent (mixture of Solv-3 and Solv-4 in a volume ratio of 1 : 1) 0.20
  • Fourth Layer (Ultraviolet ray absorbing layer): Gelatin 1.43 Ultraviolet adsorbent (mixture of UV-1, -2, and -3 in a molar ratio of 1 : 4 : 4) 0.47 Color-mix inhibitor (Cpd-4) 0.05 Solvent (Solv-6) 0.24
  • Sixth Layer Ultraviolet ray absorbing layer
  • Gelatin 0.38 Ultraviolet absorbent mixture of UV-1, -2, and -3 in a molar ratio of 1 : 4 : 4) 0.13 Solvent (Solv-6) 0.06 Seventh layer (Protective layer)
  • Fourth Layer (Ultraviolet
  • the sodium salt of 1-oxy-3,5-dichloro-s-triazine was used as a hardener of gelatin for each layer.
  • Samples 101 to 117 having layers based on the above-described composition in which the silver halide emulsion and magenta coupler of the third layer and the coating amounts of gelatin and the color-mix inhibitor and the coating amount thereof of the second layer were changed as shown in Table 2 were prepared.
  • Silver halide emulsions used in the third layer were prepared as follows: First, a chemically unsensitized silver chlorobromide emulsion (I) was prepared as follows: First solution: H 2 O 900 ml NaCl 6.9 g KBr 0.4 g Gelatin 32.0 g Fourth solution: AgNO 3 140.0 g NH 4 NO 3 (50%) 1.5 ml H 2 O to make 60.0 ml Fifth solution: KBr 11.8 g NaCl 2.5 g H 2 O to make 240.0 ml Sixth solution: AgNO 3 20.0 g NH 4 NO 3 (50%) 0.5 ml H 2 O to make 200.0 ml
  • the first solution was heated to 65°C and the second solution was added thereto. Thereafter the third solution and fourth solution were added simultaneously over 50 minutes. After 10 minutes, the fifth solution and the sixth solution were added simultaneously over 12 minutes and 10 minutes, respectively. Five minutes after the completion of the addition, the temperature was lowered, and desalting was effected. Then water and dispersed gelatin were added thereto, and the pH was adjusted to 6.5, thereby was obtained a monodisperse cubic silver chlorobromide emulsion (I) having an average grain size of 0.46 ⁇ m, a deviation coefficient (the value obtained by dividing the standard deviation by the average grain size: s/ d ⁇ ) of 0.09, and a silver bromide content of 90 mol%.
  • I monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.46 ⁇ m, a deviation coefficient (the value obtained by dividing the standard deviation by the average grain size: s/ d ⁇ ) of 0.09, and a silver bro
  • Chemically unsensitized emulsion (II) was prepared by the same procedure as above for emulsion (I) except that the addition period of the fifth solution was changed to 10 minutes.
  • Chemically unsensitized emulsion (III) was prepared by the same procedure as above for emulsion (I) except that in the third solution, 87.5 g of KBr and 6.3 g of NaCl were used, and in the fifth solution, 12.5 g of KBr and 1.2 g of NaCl were used.
  • Chemically unsensitized emulsion (IV) was prepared by the same procedure as above for emulsion (I) except that in the third solution, 55.5 g of KBr and 0.5 g of NaCl were used, in the fourth solution, 80 g of AgNO 3 was used, in the fifth solution, 45.0 g of KBr and 6.8 g of NaCl were used, and in the sixth solution, 80 g of AgNO 3 was used.
  • Emulsions (II) to (IV) had the same average grain size, the same deviation coefficient, and the same bromide content as those of emulsion (I).
  • a ribonucleic acid (available under the trade name RNA-F, manufactured by Sanyo-kokusaku Pulp Co., Ltd.) in the amount of 300 mg/mol of silver halide was added to each of the chemically unsensitized emulsions (I) to (IV), the pH was adjusted to 7.7, and each of them was chemically sensitized with triethyl thiourea. The temperature was 50°C, and the time was selected so that the maximum sensitivity might be obtained under the conditions. For the adjustment of the pH, sodium hydroxide was used.
  • Emulsions A to D The obtained silver halide emulsions were designated Emulsions A to D.
  • each sample was processed by the processing process shown below. Processing step Temperature Time Color Development 33°C 3 min. 30 sec. Bleach-fixing 33°C 1 min. 30 sec. Water Washing 1 30 - 34°C 60 sec. Water Washing 2 30 - 34°C 60 sec. Water Washing 3 30 - 34°C 60 sec. Drying 70 - 80°C 50 sec. (Three tanks counter-current flow system from tank of water washing 3 toward tank of water washing 1 was employed.)
  • compositions of each processing solution were as follows: Bleach-fixing solution Water 400 ml Ammonium thiosulfate (700 g/e) 150 ml Sodium sulfite 18 g Iron (III) ammonium ethylenediaminetetraacetate dihydrate 55 g Disodium ethylenediaminetetraacetate 5 g Water to make 1000 ml pH (25°C) 6.70
  • the results of the magenta density measured by using a green filter are shown in Table 3.
  • the sensitivity is expressed by the reciprocal of the exposure amount that gave an optical density higher than the fog density by 0.5, and is given by the relative value with the sensitivity of Sample 101 assumed to be 100.
  • the gradation is given by the difference of logarithms of exposure amounts that gave optical densities higher than the fog densities by 1.0 and 0.2 respectively.
  • the spectral density and the light fastness were evaluated.
  • Table 4 Sample No.
  • Samples 101 to 117 were stored for 2 weeks under conditions of 35°C and 60 % RH, they were exposed to light and processed in the same manner as described above, and the changes in sensitivity and gradation between before and after the storage were evaluated.
  • Samples 101 to 117 which were prepared in Example 1 were subjected to the processing according to the following processing process. Processing step Temperature Time Color development 38°C 1 min. 40 sec. Bleach-fixing 35°C 60 sec. Rinsing 1 33 - 35°C 20 sec. Rinsing 2 33 - 35°C 20 sec. Rinsing 3 33 - 35°C 20 sec. Drying 70 - 80°C 50 sec.
  • composition of the respective processing solution were as follows: Bleach-fixing solution Water 400 ml Ammonium thiosulfate (700 g/l) 80 ml Sodium sulfite 24 g Iron (III) ammonium ethylenediaminetetraacetate dihydrate 30 g Disodium ethylenediaminetetraacetate 5 g Water to make 1000 ml pH (25°C) 6.50
  • Ion-exchanged water (each of calcium and magnesium was 3 ppm or below)
  • Example 1 The above shown process was used for evaluation of Samples 101 to 117 in the same manner as in Example 1, and the exactly same results as in Example 1 were obtained.

Claims (17)

  1. Matière photographique couleur à base d'halogénure d'argent qui comprend des couches photographiques qui englobent, sur un support et dans l'ordre indiqué, au moins une couche d'émulsion d'halogénure d'argent contenant un coupleur jaune, au moins une couche d'émulsion d'halogénure d'argent contenant un coupleur magenta et au moins une couche d'émulsion d'halogénure d'argent contenant un coupleur cyan, ladite couche d'émulsion d'halogénure d'argent contenant le coupleur jaune étant la plus proche du support, matière dans laquelle
    (a) ledit coupleur magenta est un composé représenté par la formule (I) ci-après,
    (b) la quantité de revêtement du colloïde hydrophile dans la couche non photosensible placée entre ladite couche d'émulsion d'halogénure d'argent contenant le coupleur jaune et ladite couche d'émulsion d'halogénure d'argent contenant le coupleur magenta est de 1,1 g/m2 ou plus,
    (c) ladite couche non photographique contient un composé représenté par la formule (II) donnée ci-après, suivant une quantité variant entre 7,75 x 10-5 mol/m2 et 9,00 x 10-4 mol/m2, et
    (d) au moins une couche d'émulsion d'halogénure d'argent, sur le support, contient une émulsion de bromure de chlore argenté monodispersé, du type à image latente en surface, qui comprend du bromure de chlore argenté à peu près sans iodure d'argent, et qui est obtenue en soumettant à une conversion d'halogène la surface des grains d'halogénure d'argent ayant plusieurs structures partielles différentes dans leur composition d'halogène :
    Figure imgb0176
       dans laquelle R1 représente un atome d'hydrogène ou un substituant, X représente un groupe pouvant être libéré lors de la réaction d'accouplement avec le produit oxydé d'un agent développateur amine primaire aromatique, Za, Zb et Zc représentent chacun un méthine, =N- ou -NH- et une des liaisons Za-Zb et Zb-Zc est une liaison double, l'autre étant une liaison simple ; si la liaison Zb-Zc est une liaison double carbone-carbone, elle peut faire partie du noyau aromatique ; un polymère dimère ou supérieur peut être formé par R1 ou X ; ou, si Za, Zb ou Zc est un méthine substitué, un polymère dimère ou supérieur peut être formé par le méthine substitué ;
    Figure imgb0177
        dans laquelle R15 et R16 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe alkényle, un groupe aryle, un groupe acyle, un groupe cyclo-alkyle ou un groupe hétérocyclique contenant de l'azote, R17, R18, R19 et R20 représentent chacun un atome d'hydrogène, un atome d'halogène, un groupe alkyle, un groupe alkényle, un groupe aryle, un groupe cyclo-alkyle, un groupe alkoxy, un groupe alkylthio, un groupe arylthio, un groupe thio hétérocyclique contenant de l'azote, un groupe aryloxy, un groupe acyle, un groupe acylamino, un groupe alkylamino, un groupe alkoxycarbonyle, un groupe carbamyle, un groupe sulfamyle ou un groupe acide sulfonique, à condition que, lorsque R17, R18, R19 et R20 sont, en même temps, des atomes d'hydrogène, R15 et R16 ne soient pas, en même temps, des atomes d'hydrogène, R18 et R20 pouvant former ensemble une liaison pour constituer un noyau à 5 éléments ou un noyau à 6 éléments.
  2. Matière photographique couleur à base d'halogénure d'argent selon la revendication 1, dans laquelle l'émulsion d'halogénure d'argent, dans la matière photographique à base d'halogénure d'argent, a une teneur en iodure d'argent de 1 % mol ou moins.
  3. Matière photographique couleur à base d'halogénure d'argent selon la revendication 1, dans laquelle l'émulsion d'halogénure d'argent, dans la matière photographique à base d'halogénure d'argent, a une teneur en bromure d'argent comprise entre 0,3 % mol et 97 % mol.
  4. Matière photographique couleur à base d'halogénure d'argent selon la revendication 3, dans laquelle la teneur en bromure d'argent est de 45 % mol ou plus.
  5. Matière photographique couleur à base d'halogénure d'argent selon la revendication 1, dans laquelle la différence de teneur en bromure d'argent d'au moins deux structures partielles du grain d'halogénure d'argent est de 10 % mol ou plus.
  6. Matière photographique couleur à base d'halogénure d'argent selon la revendication 1, dans laquelle le grain d'halogénure d'argent a une structure en couches ayant plusieurs couches servant de structure partielle.
  7. Matière photographique couleur à base d'halogénure d'argent selon la revendication 1, dans laquelle le grain d'halogénure d'argent a une structure coeur-enveloppe dont l'intérieur et la surface sont différents concernant la composition d'halogènes.
  8. Matière photographique couleur à base d'halogénure d'argent selon la revendication 7, dans laquelle le rapport molaire d'halogénure d'argent constitutif coeur sur enveloppe est dans la plage comprise entre 2 : 98 et 98 : 2.
  9. Matière photographique couleur à base d'halogénure d'argent selon la revendication 7, dans laquelle la différence de teneur en bromure d'argent entre la section coeur et la section enveloppe de la structure coeur-enveloppe est dans une plage comprise entre 10 % mol et 50 % mol.
  10. Matière photographique couleur à base d'halogénure d'argent selon la revendication 1, dans laquelle la conversion d'halogène de la surface du grain est effectuée en ajoutant des ions de bromure sous la forme d'un composé soluble de bromure ou d'un donneur de bromure.
  11. Matière photographique couleur à base d'halogénure d'argent selon la revendication 1, dans laquelle la quantité de conversion d'halogène est comprise entre 0,5 % mol et 15 % mol pour la totalité d'halogénure d'argent.
  12. Matière photographique couleur à base d'halogénure d'argent selon la revendication 1, dans laquelle la conversion d'halogène de la surface du grain est effectuée avant une phase de maturation chimique.
  13. Matière photographique couleur à base d'halogénure d'argent selon la revendication 1, dans laquelle le composé représenté par la formule (I) est sélectionné parmi le groupe constitué de composés représentés par les formules (Ia), (Ib), (Ic), (Id), (Ie), (If) et (Ig) :
    Figure imgb0178
    Figure imgb0179
    Figure imgb0180
    Figure imgb0181
        dans lesquelles les composés R11, R12 et R13, pouvant être les mêmes ou différents, représentent chacun un atome d'hydrogène, un atome d'halogène, un groupe alkyle, un groupe aryle, un groupe hétérocyclique, un groupe cyano, un groupe alkoxy, un groupe aryloxy, un groupe oxy hétérocyclique, un groupe acyloxy, un groupe carbamyloxy, un groupe silyloxy, un groupe sulfonyloxy, un groupe acylamino, un groupe aniline, un groupe uréide, un groupe imide, un groupe sulfamylamino, un groupe carbamylamino, un groupe alkylthio, un groupe arylthio, un groupe thio hétérocyclique, un groupe alkoxycarbonylamino, un groupe aryloxycarbonylamino, un groupe sulfonamido, un groupe carbamyle, un groupe acyle, un groupe sulfamyle, un groupe sulfonyle, un groupe sulfinyle, un groupe alkoxy-carbonyle ou un groupe aryloxycarbonyle, X représente un atome d'halogène, un groupe carboxyle ou un groupe qui se lie à l'atome de carbone dans la position d'accouplement via un atome d'oxygène, un atome d'azote ou un atome de soufre, et qui peut être libéré lors de la réaction d'accouplement, R11, R12, R13 ou X pouvant devenir un groupe bivalent pour constituer une forme bis.
  14. Matière photographique couleur à base d'halogénure d'argent selon la revendication 1, dans laquelle le coupleur magenta représenté par la formule (I) est contenu suivant une quantité allant de 0,005 à 4 mol dans la couche d'émulsion d'halogénure d'argent.
  15. Matière photographique couleur à base d'halogénure d'argent selon la revendication 1, dans laquelle la quantité de revêtement du colloïde hydrophile dans la couche non photosensible située entre la couche d'halogénure d'argent contenant le coupleur jaune et la couche d'halogénure d'argent contenant le coupleur magenta est dans la plage comprise entre 1,1 et 3,0 g/m2.
  16. Matière photographique couleur à base d'halogénure d'argent selon la revendication 1, dans laquelle la quantité de revêtement du composé représenté par la formule (II) est dans la plage comprise entre 1,00 x 10-4 mol/m2 et 8,00 x 10-4 mol/m2.
  17. Matière photographique couleur à base d'halogénure d'argent selon la revendication 1, dans laquelle chacun des R15 et R16 dans la formule (II) est un atome d'hydrogène ou un groupe alkyle ayant entre 1 et 8 atomes de carbone, chacun des R17, R18, R19 et R20 dans la formule (II) étant un atome d'hydrogène ou un groupe alkyle ayant entre 1 et 18 atomes de carbone.
EP90103586A 1989-02-23 1990-02-23 Matériau photographique couleur à l'halogénure d'argent Expired - Lifetime EP0384487B1 (fr)

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EP0628866A1 (fr) * 1993-06-04 1994-12-14 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière
US5387500A (en) * 1993-06-24 1995-02-07 Eastman Kodak Company Color photographic elements containing a combination of pyrazoloazole couplers

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EP0350046A2 (fr) * 1988-07-06 1990-01-10 Fuji Photo Film Co., Ltd. Procédé de formation d'image colorée

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JPS58215643A (ja) * 1982-06-09 1983-12-15 Konishiroku Photo Ind Co Ltd 明室用ハロゲン化銀写真感光材料
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US4633092A (en) * 1984-11-13 1986-12-30 Eastman Kodak Company Light sensing device
JPS61165756A (ja) * 1985-01-17 1986-07-26 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料
AU6892687A (en) * 1986-01-23 1987-08-14 Fuji Photo Film Co., Ltd. Process for forming colored image
JPS62215272A (ja) * 1986-02-17 1987-09-21 Fuji Photo Film Co Ltd カラ−画像形成方法
JPH0713728B2 (ja) * 1987-05-15 1995-02-15 富士写真フイルム株式会社 ハロゲン化銀写真感光材料

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EP0350046A2 (fr) * 1988-07-06 1990-01-10 Fuji Photo Film Co., Ltd. Procédé de formation d'image colorée

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DE69031544D1 (de) 1997-11-13
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DE69031544T2 (de) 1998-02-12
JPH02221959A (ja) 1990-09-04

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