EP0747762B1 - Farbphotographische lichtempfindliche Silberhalogenidelemente mit verbesserter Körnigkeit - Google Patents

Farbphotographische lichtempfindliche Silberhalogenidelemente mit verbesserter Körnigkeit Download PDF

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EP0747762B1
EP0747762B1 EP19950108592 EP95108592A EP0747762B1 EP 0747762 B1 EP0747762 B1 EP 0747762B1 EP 19950108592 EP19950108592 EP 19950108592 EP 95108592 A EP95108592 A EP 95108592A EP 0747762 B1 EP0747762 B1 EP 0747762B1
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Prior art keywords
sensitive
green
silver halide
group
layer
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French (fr)
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EP0747762A1 (de
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Enzo Coraluppi
Ferdinando Orengo
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Tulalip Consultoria Comercial SU
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Tulalip Consultoria Comercial SU
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Priority to DE69529977T priority Critical patent/DE69529977T2/de
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Priority to JP14165896A priority patent/JP3549982B2/ja
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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
    • G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function
    • 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
    • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
    • G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
    • G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
    • G03C7/30529—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution having the coupling site in rings of cyclic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32—Colour coupling substances
    • G03C7/36—Couplers containing compounds with active methylene groups
    • G03C7/38—Couplers containing compounds with active methylene groups in rings
    • G03C7/3805—Combination of couplers

Definitions

  • the present invention relates to silver halide color photographic light-sensitive elements containing photographic couplers and, more particularly, 4-equivalent and 2-equivalent 5-pyrazolone magenta dye-forming couplers.
  • color photographic light-sensitive elements using the subtractive process for color reproduction, comprise silver halide emulsion layers selectively sensitive to blue, green and red light and associated with yellow, magenta and cyan dye-forming couplers which form (upon reaction with an oxidized primary amine type color developing agent) the complementary color thereof.
  • an acylacetanilide type coupler is used to form a yellow color image
  • a 5-pyrazolone, pyrazolotriazole, cyanacetophenone or indazolone type coupler is used to form a magenta color image
  • a phenol type such as a phenol or naphthol, coupler is used to form a cyan color image.
  • a color photographic light-sensitive element usually comprises 1) a blue-sensitive silver halide emulsion layer (or layers) which contains a yellow dye-forming coupler and which is mainly sensitive to blue light (substantially to wavelengths less than about 500 nm); 2) a green-sensitive silver halide emulsion layer (or layers) which contains a magenta dye-forming coupler and which is mainly sensitive to green light (substantially to wavelengths of about 500 to 600 nm); and 3) a red-sensitive silver halide emulsion layer (or layers) which contains a cyan dye-forming coupler and which is mainly sensitive to red light (substantially to wavelengths longer than about 590 nm).
  • the silver halide emulsions used in the past for such photographic elements were the so-called mixed emulsions, that is, emulsions comprising a combination of a more sensitive emulsion (containing coarse silver halide grains) and a less sensitive emulsion (containing fine silver halide grains) whereby a straight density-log exposure curve could be obtained for each blue-, green- and red-sensitive layer.
  • the regular layer sequence of having respective red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers is provided by subdividing a part or whole of each of the emulsion layers into higher and lower sensitivity emulsion layers, each subdivided layer containing a color coupler forming substantially the same hue as the other subdivided layer and wherein these layers are coated adjacent to each other.
  • GB 818,687 describes a method for increasing sensitivity in multilayer color photographic elements in which the emulsion layer which is applied closest to the support consists of two partial layers sensitized to the same region of the spectrum, the lower layer consisting of a less sensitive silver halide emulsion layer and the upper layer consisting of a more sensitive silver halide emulsion, both partial layers containing color-forming couplers in the same concentration.
  • An element of this type has, however, the disadvantage that the increase in sensitivity is accompanied by an increase of granularity.
  • GB 923,045 describes a method for increasing the sensitivity of a color photographic element without coarsening the granularity of the dye image by providing an uppermost more sensitive emulsion layer and a lowermost less sensitive emulsion layer, both layers being sensitive to the same region of the visible spectrum and each containing non-diffusing color couplers, with the maximum color density of the more sensitive emulsion layer being adjusted to be lower than that of the less sensitive emulsion layer, in particular being lower in an amount from 0.20 to 0.60.
  • US 3,516,831 describes a process for improving the sharpness of the color image, according to which two layers which are sensitized to the same spectral region of the spectrum contain different couplers, the more sensitive emulsion layer containing 4-equivalent couplers and the less sensitive emulsion layer 2-equivalent couplers.
  • EP 107,112 describes a color photographic element in which at least one of the silver halide emulsion layers is composed of two silver halide emulsion layers sensitive to the same color, the more sensitive layer containing a high reaction rate coupler, and the less sensitive silver halide emulsion layer containing a low reaction rate coupler in a range of 1/1.3 to 1/15 of that of the high reaction rate coupler and a diffusible DIR coupler.
  • DIR couplers The purpose of DIR couplers is to help in reducing graininess and improve sharpness of the image due to intralayer or intraimage effects (that is in the same layers or the same dye image) and improve color reproduction due to interlayer or interimage effects (that is effect between different layers or different dye images).
  • US 3,843,369 describes a method for further increasing the sensitivity of a color photographic element by providing three emulsion layers sensitive to the same spectral region of visible light, the uppermost silver halide emulsion layer having the highest light sensitivity and the lowermost silver halide emulsion layer having the lowest light sensitivity, the uppermost and the intermediate layer each having a maximum density of 0.6 or less.
  • US 4,582,780 describes a method for increasing sensitivity and improving adjacency effects by providing three emulsion layers sensitive to the same spectral region of visible light, the uppermost silver halide emulsion layer having the highest light sensitivity and the lowermost silver halide emulsion layer having the lowest light sensitivity, wherein the maximum color density of the uppermost silver halide emulsion layer, after color development, is lower than 0.60 and the maximum color densities of both the intermediate and the lowermost silver halide emulsion layers, after color development, are each higher than 0.60.
  • EP 583,020 discloses a technique for improving granularity by providing a multilayer color photographic elements comprising a plurality of blue, green and three red sensitive silver halide emulsion layers, the layers being arranged on the support in the sequence: a red least sensitive layer, a green least sensitive layer, a red mid-sensitive layer, a red most sensitive layer, a green most sensitive layer, a blue most sensitive layer, and a blue least sensitive layer.
  • EP 608,464 discloses a technique for enhancing the speed-granularity relationship of dye images by providing multicolor photographic elements containing blue, green and red sensitive layer units wherein at least one layer unit contains three superimposed silver halide emulsion layers of different sensitivity comprising silver bromoiodide tabular grains of different iodide content.
  • 2-equivalent 5-pyrazolone magenta couplers having an arylthio group attached to the 4-position of the pyrazolone ring have a number of advantages compared to 4-equivalent 5-pyrazolone magenta couplers in which the 4-position of the pyrazolone ring is free (that is having only hydrogen atoms).
  • 2-equivalent 5-pyrazolone couplers require only two equivalent of silver to produce each molecule of dye, are less sensitive to certain chemical vapors, for example formaldehyde, and have high dye light and dye dark stability.
  • 2-equivalent 5-pyrazolone magenta couplers have the disadvantage that they may cause worsening of granularity.
  • the present invention relates to a multilayer color photographic element comprising a support having coated thereon red-, green- and blue-sensitive silver halide emulsion layers comprising, respectively, cyan, magenta and yellow dye-forming couplers, wherein the green-sensitive layer comprises three green-sensitive layers having different sensitivity, an uppermost green-sensitive layer being more sensitive than an intermediate green-sensitive layer which is more sensitive than a lowermost green-sensitive layer, the layers arranged with the lowermost green-sensitive layer being closer to the support, the intermediate green-sensitive layer being adjacent said lowermost green-sensitive layer and the uppermost green-sensitive layer being above the intermediate green-sensitive layer, characterized in that the uppermost green-sensitive emulsion layer comprises 4-equivalent 5-pyrazolone magenta dye-forming couplers, and the intermediate and the lowermost green-sensitive emulsion layers comprise 2-equivalent 4-arylthio-5-pyrazolone magenta dye-forming couplers.
  • the color photographic elements containing the aforesaid layer arrangement provide good speed-granularity relationship.
  • said 2-equivalent 4-arylthio-5-pyrazolone magenta coupler for use in this invention may be represented by 1-phenyl-3-anilino-4-phenylthio-5-pyrazolone magenta couplers of the following formula (I): wherein a represents an integer from 0 to 3, b represents an integer from 0 to 2, R 1 and R 2 are each individually hydrogen, alkyl, alkoxy, halogen, aryl, aryloxy, acylamino, sulfonamido, sulfamoyl, carbamoyl, arylsulfonyl, aryloxycarbonyl, alkoxycarbonyl, alkoxysulfonyl, aryloxysulfonyl, alkylureido, arylureido, nitro, cyano, hydroxyl or carboxy group, R 3 is halogen atom, alkyl group or aryl group, X is a direct atom
  • examples of R 1 and R 2 include hydrogen; alkyl group, including straight or branched chain alkyl group, such as alkyl group containing 1 to 8 carbon atoms, for example methyl, trifluoromethyl, ethyl, butyl, and octyl; alkoxy group, such as an alkoxy group having 1 to 8 carbon atoms, for example methoxy, ethoxy, propoxy, 2-methoxyethoxy, and 2-ethylhexyloxy; halogen, such as chlorine, bromine, and fluorine; aryl group, such as phenyl, naphthyl, and 4-tolyl; aryloxy group, such as phenoxy, p-methoxyphenoxy, p-methylphenoxy, naphthyloxy, and tolyloxy; acylamino group, such as acetamido, benzamido, butyramido, and t-butylcarbonamido;
  • R 3 examples include halogen, such as chlorine, bromine, and fluorine; alkyl group, including straight or branched chain alkyl group, such as alkyl group containing 1 to 8 carbon atoms, for example methyl, trifluoromethyl, ethyl, butyl, and octyl; aryl group, such as phenyl, naphthyl, and 4-tolyl.
  • halogen such as chlorine, bromine, and fluorine
  • alkyl group including straight or branched chain alkyl group, such as alkyl group containing 1 to 8 carbon atoms, for example methyl, trifluoromethyl, ethyl, butyl, and octyl
  • aryl group such as phenyl, naphthyl, and 4-tolyl.
  • ballasting group is a ballasting group, i.e., an organic group of such size and configuration as to render a group to which it is attached non-diffusible from the layer in which is coated in a photographic element.
  • Said ballasting group may include an organic hydrophobic residue having 8 to 32 carbon atoms bonded to the coupler either directly or through a divalent linking group X, such as an alkylene, imino, ether, thioether, carbonamido, sulfonamido, ureido, ester, imido, carbamoyl, and sulfamoyl group.
  • ballasting groups include alkyl groups (linear, branched, or cyclic), alkenyl groups, alkoxy groups, alkylaryl groups, alkylaryloxy groups, acylamidoalkyl groups, alkoxyalkyl groups, alkoxyaryl groups, alkyl groups substituted with an aryl group ar a heterocyclic group, aryl groups substituted with an aryloxyalkoxycarbonyl group, and residues containing both an alkenyl or alkenyl long-chain aliphatic group and a carboxy or sulfo water-soluble group, as described, for example, in US 3,337,344, 3,418,129, 3,892,572, 4,138,258, and 4,451,559, and in GB 1,494,777.
  • alkyl group includes not only such alkyl moiety as methyl, ethyl, butyl, octyl, stearyl, etc., but also moieties bearing substituent groups such as halogen, cyano, hydroxyl, nitro, amino, carboxylate, etc.
  • alkyl moiety includes only methyl, ethyl, stearyl, cyclohexyl, etc.
  • the sum of sigma values of substituents on the 1-phenyl and 3-anilino groups, such as R 1 , R 3 and -X-Ball is less than 1.3.
  • the values of sigma constants can be easily found in the published literature (see, for example, "The Chemists' Companion", A.J. Gordon and R.A. Ford, John Wiley & Sons, New York, 1972, "Progress in Physical Organic Chemistry", V. 13, R.W. Taft, John Wiley & Sons, New York, "Substituents Constants for Correlation Analysis in Chemistry and Biology", C. Hansch and A.J.
  • alkyl group -017
  • chlorine atom 0.23
  • alkoxycarbonyl group 0.45
  • acylamino group 0.21
  • sulfamoyl group 0.57
  • alkylsulfonyl group 0.78
  • carbamoyl 0.36.
  • a preferred embodiment is represented by the above formula wherein the groups R 1 are chlorine atoms, a is 3, and the chlorine atoms are attached to the carbon atoms in position 2, 4 and 6 with respect to the carbon atom attached to the nitrogen atom.
  • a particularly preferred embodiment is represented by the above formula wherein the group R 3 is a chlorine atom.
  • Couplers include: wherein Q represents a coupling-off group according to the invention.
  • the 4-equivalent 5-pyrazolone magenta coupler for use in this invention may be represented by the following formula (II): wherein R 1 , R 3 and a have the same meaning as in formula (I), and n represents 0 or 1.
  • a preferred embodiment is represented by the above formula (II) wherein the groups R 1 are chlorine atoms, a is 3, and the chlorine atoms are attached to the carbon atoms in position 2, 4 and 6 with respect to the carbon atom attached to the nitrogen atom.
  • the green-sensitive layer is composed of three silver halide emulsion layers sensitized to the same spectral region of the visible spectrum, the uppermost silver halide emulsion layer of which having the highest sensitivity and the lowermost silver halide emulsion layer having the lowest sensitivity, as described for example in US 3,843,369 and US 4,582,780.
  • the three silver halide emulsions are arranged so that light travels through the uppermost highest sensitivity green-sensitive layer before striking the lowermost lowest sensitivity green-sensitive layer.
  • the difference in sensitivity between the highest and the lowest green-sensitive layers is preferably such that extended latitude in the photographic element is achieved without an appreciable distortion of the shape of the sensitometric curve.
  • this difference in sensitivity should be within the range of from about 0.2 to about 1 logE (E being dosage of exposure), and preferably will be about 0.3 to 0.6 logE.
  • the intermediate medium sensitivity emulsion layer having an intermediate sensitivity between the sensitivity of the uppermost highest sensitivity emulsion layer and the lowermost lowest sensitivity emulsion layer, generally has a sensitivity difference from the highest sensitivity emulsion layer of 0.1 to 0.55 logE and a sensitivity difference with the lowest sensitivity emulsion layer of 0.1 to 0.55 logE. Also, the uppermost highest sensitivity green-sensitive emulsion layer produces upon development a colored image of lower color density than the intermediate and the lowermost green-sensitive emulsion layers.
  • the uppermost highest sensitivity green-sensitive emulsion layer is relatively "starved" with respect to its color coupler content in order to improve granularity of this layer (as disclosed by US 3,843,369 and US 4,582,780). That is, relatively smaller amounts of coupler are used in the highest sensitivity layer, such that, upon exposure and development, this layer produces a colored image which is less dense than that produced in the lowest sensitivity layer.
  • the uppermost highest sensitivity green-sensitive silver halide emulsion layer comprises the 4-equivalent 5-pyrazolone magenta coupler
  • the intermediate medium sensitivity and the lowermost lowest sensitivity green-sensitive silver halide emulsion layers comprise the 2-equivalent 5-pyrazolone magenta coupler as described above.
  • the 4-equivalent 5-pyrazolone magenta dye-forming coupler is preferably used in an amount ranging from 0.01 to 0.5 mol per mol of silver halide, more preferably 0.02 to 0.1 mol
  • the 2-equivalent 5-pyrazolone magenta dye-forming coupler is preferably used in an amount ranging from 0.01 to 0.5 mol per mol of silver halide, more preferably 0.02 to 0.1 mol
  • the 2-equivalent 5-pyrazolone magenta dye-forming coupler is preferably used in an amount ranging from 0.02 to 1.0 mol per mol of silver halide, more preferably 0.04 to 0.2 mol.
  • the color photographic elements of the present invention can be conventional photographic elements containing a silver halide as a light-sensitive substance.
  • the silver halides used in the multilayer color photographic elements of this invention may be a fine dispersion (emulsion) of silver chloride, silver bromide, silver chloro-bromide, silver iodo-bromide and silver chloro-iodo-bromide grains in a hydrophilic binder.
  • Preferred silver halides are silver iodo-bromide or silver iodo-chloro-bromide containing 1 to 20% mole silver iodide.
  • the iodide can be uniformly distributed among the emulsion grains, or iodide level can varied among the grains.
  • the silver halides can have a uniform grain size or a broad grain size distribution.
  • the silver halide grains may be regular grains having a regular crystal structure such as cubic, octahedral, and tetradecahedral, or the spherical or irregular crystal structure, or those having crystal defects such as twin plane, or those having a tabular form, or the combination thereof.
  • cubic grains is intended to include substantially cubic grains, that is grains which are regular cubic grains bounded by crystallographic faces (100), or which may have rounded edges and/or vertices or small faces (111), or may even be nearly spherical when prepared in the presence of soluble iodides or strong ripening agents, such as ammonia. Particularly good results are obtained with silver halide grains having average grain sizes in the range from 0.2 to 3 ⁇ m, more preferably from 0.4 to 1.5 ⁇ m. Preparation of silver halide emulsions comprising cubic silver iodobromide grains is described, for example, in Research Disclosure, Vol. 184, Item 18431, Vol. 176, Item 17644 and Vol. 308, Item 308119.
  • the tabular silver halide grains contained in the emulsion of this invention have an average diameter:thickness ratio (often referred to in the art as aspect ratio) of at least 2:1, preferably 2:1 to 20:1, more preferably 3:1 to 14:1, and most preferably 3:1 to 8:1.
  • Average diameters of the tabular silver halide grains suitable for use in this invention range from about 0.3 ⁇ m to about 5 ⁇ m, preferably 0.5 ⁇ m to 3 ⁇ m, more preferably 0.8 ⁇ m to 1.5 ⁇ m.
  • the tabular silver halide grains suitable for use in this invention have a thickness of less than 0.4 ⁇ m, preferably less than 0.3 ⁇ m and more preferably less than 0.2 ⁇ m.
  • the tabular grain characteristics described above can be readily ascertained by procedures well known to those skilled in the art.
  • the term “diameter” is defined as the diameter of a circle having an area equal to the projected area of the grain.
  • the term “thickness” means the distance between two substantially parallel main planes constituting the tabular silver halide grains. From the measure of diameter and thickness of each grain the diameter:thickness ratio of each grain can be calculated, and the diameter:thickness ratios of all tabular grains can be averaged to obtain their average diameter:thickness ratio.
  • the average diameter:thickness ratio is the average of individual tabular grain diameter:thickness ratios. In practice, it is simpler to obtain an average diameter and an average thickness of the tabular grains and to calculate the average diameter:thickness ratio as the ratio of these two averages. Whatever the used method may be, the average diameter:thickness ratios obtained do not greatly differ.
  • the silver halide emulsion layer containing tabular silver halide grains at least 15%, preferably at least 25%, and, more preferably, at least 50% of the silver halide grains are tabular grains having an average diameterthickness ratio of not less than 2:1.
  • Each of the above proportions, "15%”, “25%” and “50%” means the proportion of the total projected area of the tabular grains having a diameter:thickness ratio of at least 2:1 and a thickness lower than 0.4 ⁇ m, as compared to the projected area of all of the silver halide grains in the layer.
  • photosensitive silver halide emulsions can be formed by precipitating silver halide grains in an aqueous dispersing medium comprising a binder, gelatin preferably being used as a binder.
  • the silver halide grains may be precipitated by a variety of conventional techniques.
  • the silver halide emulsion can be prepared using a single-jet method, a double-jet method, or a combination of these methods or can be matured using, for instance, an ammonia method, a neutralization method, an acid method, or can be performed an accelerated or constant flow rate precipitation, interrupted precipitation, ultrafiltration during precipitation, etc.
  • References can be found in Trivelli and Smith, The Photographic Journal, Vol. LXXIX, May 1939, pp. 330-338, T.H. James, The Theory of The Photographic Process, 4th Edition, Chapter 3, US Patent Nos.
  • One common technique is a batch process commonly referred to as the double-jet precipitation process by which a silver salt solution in water and a halide salt solution in water are concurrently added into a reaction vessel containing the dispersing medium.
  • the shape and size of the formed silver halide grains can be controlled by the kind and concentration of the solvent existing in the gelatin solution and by the addition speed.
  • Double-jet precipitation processes are described, for example, in GB 1,027,146, GB 1,302,405, US 3,801,326, US 4,046,376, US 3,790,386, US 3,897,935, US 4,147,551, and US 4,171,224.
  • the single jet method in which a silver nitrate solution is added in a halide and gelatin solution has been long used for manufacturing photographic emulsion.
  • the formed silver halide grains are a mixture of different kinds of shapes and sizes.
  • Precipitation of silver halide grains usually occurs in two distinct stages. In a first stage, nucleation, formation of fine silver halide grain occurs. This is followed by a second stage, the growth stage, in which additional silver halide formed as a reaction product precipitates onto the initially formed silver halide grains, resulting in a growth of these silver halide grains. Batch double-jet precipitation processes are typically undertaken under conditions of rapid stirring of reactants in which the volume within the reaction vessel continuously increases during silver halide precipitation and soluble salts are formed in addition to the silver halide grains.
  • hydrophilic dispersing agents for the silver halides can be employed.
  • hydrophilic dispersing agent any hydrophilic polymer conventionally used in photography can be advantageously employed including gelatin, a gelatin derivative such as acylated gelatin, graft gelatin, etc., albumin, gum arabic, agar agar, a cellulose derivative, such as hydroxyethylcellulose, carboxymethylcellulose, etc., a synthetic resin, such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, etc.
  • Other hydrophilic materials useful known in the art are described, for example, in Research Disclosure, Vol. 308, Item 308119, Section IX.
  • the silver halide grain emulsion for use in the present invention can be chemically sensitized using sensitizing agents known in the art. Sulfur containing compounds, gold and noble metal compounds, and polyoxylakylene compounds are particularly suitable.
  • the silver halide emulsions may be chemically sensitized with a sulfur sensitizer, such as sodium thiosulfate, allylthiocyanate, allylthiourea, thiosulfinic acid and its sodium salt, sulfonic acid and its sodium salt, allylthiocarbamide, thiourea, cystine, etc.; an active or inert selenium sensitizer; a reducing sensitizer such as stannous salt, a polyamine, etc.; a noble metal sensitizer, such as gold sensitizer, more specifically potassium aurithiocyanate, potassium chloroaurate, etc.; or a sensitizer of a water soluble salt such as for instance of ruthenium, rhodium
  • the silver halide emulsion for use in the present invention can be spectrally sensitized with dyes from a variety of classes, including the polymethyne dye class, which includes the cyanines, merocyanines, complex cyanines and merocyanines, oxonols, hemioxonols, styryls, merostyryls, and streptocyanine.
  • the polymethyne dye class which includes the cyanines, merocyanines, complex cyanines and merocyanines, oxonols, hemioxonols, styryls, merostyryls, and streptocyanine.
  • the cyanine spectral sensitizing dyes include, joined by a methine linkage, two basic heterocyclic nuclei, such as those derived from quinoline, pyrimidine, isoquinoline, indole, benzindole, oxazole, thiazole, selenazole, imidazole, benzoxazole, benzothiazole, benzoselenazole, benzoimidazole, naphthoxazole, naphthothiazole, naphthoselenazole, tellurazole, oxatellurazole.
  • two basic heterocyclic nuclei such as those derived from quinoline, pyrimidine, isoquinoline, indole, benzindole, oxazole, thiazole, selenazole, imidazole, benzoxazole, benzothiazole, benzoselenazole, benzoimidazole, naphthoxazole, naph
  • the merocyanine spectral sensitizing dyes include, joined by a methine linkage, a basic heterocyclic nucleus of the cyanine-dye type and an acidic nucleus, which can be derived from barbituric acid, 2-thiobarbituric acid, rhodanine, hydantoin, 2-thiohydantoin, 2-pyrazolin-5-one, 2-isoxazolin-5-one, indan-1,3-dione, cyclohexane-1,3-dione, 1,3-dioxane-4,6-dione, pyrazolin-3,5-dione, pentane-2,4-dione, alkylsulfonylacetonitrile, malononitrile, isoquinolin-4-one, chromane-2,4-dione, and the like.
  • One or more spectral sensitizing dyes may be used. Dyes with sensitizing maxima at wavelengths throughout the visible and infrared spectrum and with a great variety of spectral sensitivity curve shapes are known. The choice and relative proportion of dyes depends on the region of the spectrum to which sensitivity is desired and on the shape of the spectral sensitivity desired.
  • sensitizing dyes can be found in Venkataraman, The chemistry of Synthetic Dyes , Academic Press, New York, 1971, Chapter V, James, The Theory of the Photographic Process, 4th Ed., Macmillan, 1977, Chapter 8, F.M.Hamer, Cyanine Dyes and Related Compounds, John Wiley and Sons, 1964, and in Research Disclosure 308119, Section III, 1989.
  • the silver halide emulsions for use in this invention can contain optical brighteners, antifogging agents and stabilizers, filtering and antihalo dyes, hardeners, coating aids, plasticizers and lubricants and other auxiliary substances, as for instance described in Research Disclosure 17643, Sections V, VI, VIII, X, XI and XII, 1978, and in Research Disclosure 308119, Sections V, VI, VIII, X, XI, and XII, 1989.
  • the silver halide emulsion for use in the present invention can be used for the manufacture of multilayer light-sensitive silver halide color photographic elements, such as color negative photographic elements, color reversal photographic elements, color positive photographic elements, false color address photographic elements (such as those disclosed in US 4,619,892) and the like, the preferred ones being color negative photographic elements.
  • color negative photographic elements such as color negative photographic elements, color reversal photographic elements, color positive photographic elements, false color address photographic elements (such as those disclosed in US 4,619,892) and the like, the preferred ones being color negative photographic elements.
  • Silver halide multilayer color photographic elements for use in the present invention usually comprise, coated on a support, at least two red sensitized silver halide emulsion layers associated with cyan dye-forming color couplers, three green sensitized silver halide emulsion layers associated with magenta dye-forming color couplers and at least two blue sensitized silver halide emulsion layers associated with yellow dye-forming color couplers.
  • These elements additionally comprise other non-light sensitive layers, such as intermediate layers, filter layers, antihalation layers and protective layers, thus forming a multilayer structure.
  • These color photographic elements, after imagewise exposure to actinic radiation, are processed in a chromogenic developer to yield a visible color image.
  • the layer units can be coated in any conventional order, but in a preferred layer arrangement the red-sensitive layers are coated nearest the support and are overcoated by the green-sensitive layers, a yellow filter layer and the blue-sensitive layers.
  • Suitable color couplers are preferably selected from the couplers having diffusion preventing groups, such as groups having a hydrophobic organic residue of about 8 to 32 carbon atoms, introduced into the coupler molecule in a non-splitting-off position. Such a residue is called a "ballast group".
  • the ballast group is bonded to the coupler nucleus directly or through an imino, ether, carbonamido, sulfonamido, ureido, ester, imido, carbamoyl, sulfamoyl bond, etc. Examples of suitable ballasting groups are described in US patent 3,892,572.
  • Said non-diffusible couplers are introduced into the light-sensitive silver halide emulsion layers. On exposure and color development, said couplers give a color which is complementary to the light color to which the silver halide emulsion layers are sensitive.
  • At least one non-diffusible cyan image-forming color coupler is associated with red-sensitive silver halide emulsion layers
  • 4-equivalent and 2-equivalent 5-pyrazolone non-diffusible magenta image-forming color couplers are associated with green-sensitive silver halide emulsion layers
  • at least one non-diffusible yellow image-forming color coupler is associated with blue-sensitive silver halide emulsion layers.
  • color couplers may be 4-equivalent and/or 2-equivalent couplers, the latter requiring a smaller amount of silver halide for color production.
  • 2-equivalent couplers derive from 4-equivalent couplers since, in the coupling position, they contain a substituent which is released during coupling reaction.
  • 2-equivalent couplers which may be used in silver halide color photographic elements include both those substantially colorless and those which are colored ("masking couplers").
  • the 2-equivalent couplers also include white couplers which do not form any dye on reaction with the color developer oxidation products.
  • the 2-equivalent color couplers include also DIR couplers which are capable of releasing a diffusing development inhibiting compound on reaction with the color developer oxidation products.
  • cyan-forming couplers are conventional phenol compounds and ⁇ -naphthol compounds.
  • Examples of cyan couplers can be selected from those described in US patents 2,369,929; 2,474,293; 3,591,383; 2,895,826; 3,458,315; 3,311,476; 3,419,390; 3,476,563 and 3,253,924; in British patent 1,201,110, and in Research Disclosure 308119, Section VII, 1989.
  • magenta-forming couplers which can be used in combination with the 4-equivalent and 2-equivalent magenta image-forming couplers described hereinbefore, are conventional pyrazolone type compounds, indazolone type compounds, cyanoacetyl compounds, pyrazolotriazole type compounds, etc., and particularly preferred are pyrazolone type compounds.
  • Magenta-forming couplers are described for example in US patents 2,600,788, 2,983,608, 3,062,653, 3,127,269, 3,311,476, 3,419,391, 3,519,429, 3,558,319, 3,582,322, 3,615,506, 3,834,908 and 3,891,445,in DE patent 1,810,464, in DE patent applications 2,408,665, 2,417,945, 2,418,959 and 2,424,467; in JP patent applications 20,826/76, 58,922/77, 129,538/74, 74,027/74, 159,336/75, 42,121/77, 74,028/74, 60,233/75, 26,541/76 and 55,122/78, and in Research Disclosure 308119, Section VII, 1989.
  • yellow-forming couplers are conventional open-chain ketomethylene type couplers. Particular examples of such couplers are benzoylacetanilide type and pivaloyl acetanilide type compounds. Yellow-forming couplers that can be used are specifically described in US patents 2,875,057, 3,235,924, 3,265,506, 3,278,658, 3,369,859, 3,408,194, 3,415,652 3,528,322, 3,551,151, 3,682,322, 3,725,072 and 3,891,445, in DE patents 2,219,917, 2,261,361 and 2,414,006, in GB patent 1,425,020, in JP patent 10,783/76 and in JP patent applications 26,133/72, 73,147/73, 102,636/76, 6,341/75, 123,342/75, 130,442/75, 1,827/76, 87,650/75, 82,424/77 and 115,219/77, and in Research Disclosure 3081
  • Colored couplers can be used which include those described for example in US patents 3,476,560, 2,521,908 and 3,034,892, in JP patent publications 2,016/69, 22,335/63, 11,304/67 and 32,461/69, in JP patent applications 26,034/76 and 42,121/77 and in DE patent application 2,418,959.
  • the light-sensitive silver halide color photographic element may contain high molecular weight color couplers as described for example in US Pat. No. 4,080,211, in EP Pat. Appl. No. 27,284 and in DE Pat Appl. Nos. 1,297,417, 2,407,569, 3,148,125, 3,217,200, 3,320,079, 3,324,932, 3,331,743, and 3,340,376, and in Research Disclosure 308119, Section VII, 1989.
  • Colored cyan couplers can be selected from those described in US patents 3,934,802; 3,386,301 and 2,434,272, colored magenta couplers can be selected from the colored magenta couplers described in US patents 2,434,272; 3,476,564 and 3,476,560 and in British patent 1,464,361.
  • Colorless couplers can be selected from those described in British patents 861,138; 914,145 and 1,109,963 and in US patent 3,580,722 and in Research Disclosure 308119, Section VII, 1989.
  • couplers providing diffusible colored dyes can be used together with the above mentioned couplers for improving graininess and specific examples of these couplers are magenta couplers described in US Pat. No. 4,366,237 and GB Pat. No. 2,125,570 and yellow, magenta and cyan couplers described in EP Pat. No. 96,873, in DE Pat. Appl. No. 3,324,533 and in Research Disclosure 308119, Section VII, 1989.
  • 2-equivalent couplers are those couplers which carry in the coupling position a group which is released in the color development reaction to give a certain photographic activity, e.g. as development inhibitor or accelerator or bleaching accelerator, either directly or after removal of one or further groups from the group originally released.
  • 2-equivalent couplers include the known DIR couplers as well as DAR, FAR and BAR couplers. Typical examples of said couplers are described in DE Pat. Appl. Nos. 2,703,145, 2,855,697, 3,105,026, 3,319,428, 1,800,420, 2,015,867, 2,414,006, 2,842,063, 3,427,235, 3,209,110, and 1,547,640, in GB Pat. Nos. 953,454 and 1,591,641, in EP Pat. Appl. Nos. 89,843, 117,511, 118,087, 193,389, and 301,477 and in Research Disclosure 308119, Section VII, 1989.
  • non-color forming DIR coupling compounds which can be used in silver halide color elements include those described in US patents 3,938,996; 3,632,345; 3,639,417; 3,297,445 and 3,928,041; in German patent applications S.N. 2,405,442; 2,523,705; 2,460,202; 2,529,350 and 2,448,063; in Japanese patent applications S.N. 143,538/75 and 147,716/75, in British patents 1,423,588 and 1,542,705 and 301,477 and in Research Disclosure 308119, Section VII, 1989.
  • the couplers can be incorporated into the silver halide emulsion layer by the dispersion technique, which consists of dissolving the coupler in a water-immiscible high-boiling organic solvent and then dispersing such a solution in a hydrophilic colloidal binder under the form of very small droplets.
  • the preferred colloidal binder is gelatin, even if some other kinds of binders can be used.
  • Another type of introduction of the couplers into the silver halide emulsion layer consists of the so-called "loaded-latex technique".
  • a detailed description of such technique can be found in BE patents 853,512 and 869,816, in US patents 4,214,047 and 4,199,363 and in EP patent 14,921. It consists of mixing a solution of the couplers in a water-miscible organic solvent with a polymeric latex consisting of water as a continuous phase and of polymeric particles having a mean diameter ranging from 0.02 to 0.2 micrometers as a dispersed phase.
  • couplers having a water-soluble group such as a carboxyl group, a hydroxy group, a sulfonic group or a sulfonamido group, can be added to the photographic layer for example by dissolving them in an alkaline water solution.
  • the layers of the photographic elements can be coated on a variety of supports, such as cellulose esters supports (e.g., cellulose triacetate supports), paper supports, polyesters film supports (e.g., polyethylene terephthalate film supports or polyethylene naphthalate film supports), and the like, as described in Research Disclosure 308119, Section XVII, 1989.
  • supports such as cellulose esters supports (e.g., cellulose triacetate supports), paper supports, polyesters film supports (e.g., polyethylene terephthalate film supports or polyethylene naphthalate film supports), and the like, as described in Research Disclosure 308119, Section XVII, 1989.
  • the photographic elements according to this invention may be processed after exposure to form a visible image upon association of the silver halides with an alkaline aqueous medium in the presence of a developing agent contained in the medium or in the material, as known in the art
  • the aromatic primary amine color developing agent used in the photographic color developing composition can be any of known compounds of the class of p-phenylendiamine derivatives, widely employed in various color photographic process.
  • Particularly useful color developing agents are the p-phenylendiamine derivatives, especially the N,N-dialkyl-p-phenylene diamine derivatives wherein the alkyl groups or the aromatic nucleus can be substituted or not substituted.
  • Examples of p-phenylene diamine developers include the salts of: N,N-diethyl-p-phenylendiamine, 2-amino-5-diethylamino-toluene, 4-amino-N-ethyl-N-( ⁇ -methanesulphonamidoethyl)-m-toluidine, 4-amino-3-methyl-N-ethyl-N-( ⁇ -hydroxyethyl)-aniline, 4-amino-3-( ⁇ -methylsulfonamidoethyl)-N,N-diethylaniline, 4-amino-N,N-diethyl-3-(N'-methyl- ⁇ -methylsulfonamido)-aniline, N-ethyl-N-methoxy-ethyl-3-methyl-p-phenylenediamine and the like, as described, for instance, in US patents No. 2,552,241; 2,556,271; 3,656,950
  • Examples of commonly used developing agents of the p-phenylene diamine salt type are: 2-amino-5-diethylaminotoluene hydrochloride (generally known as CD2 and used in the developing solutions for color positive photographic material), 4-amino-N-ethyl-N-( ⁇ -methanesulfonamidoethyl)-m-toluidine sesquisulfate monohydrate (generally known as CD3 and used in the developing solution for photographic papers and color reversal materials) and 4-amino-3-methyl-N-ethyl-N-( ⁇ -hydroxy-ethyl)-aniline sulfate (generally known as CD4 and used in the developing solutions for color negative photographic materials).
  • CD2 2-amino-5-diethylaminotoluene hydrochloride
  • CD3 4-amino-N-ethyl-N-( ⁇ -methanesulfonamidoethyl)-m-toluidine
  • Said color developing agents are generally used in a quantity from about 0.001 to about 0.1 moles per liter, preferably from about 0.0045 to about 0.04 moles per liter of photographic color developing compositions.
  • the processing comprises at least a color developing bath and, optionally, a prehardening bath, a neutralizing bath, a first (black and white) developing bath, etc.
  • a color developing bath and, optionally, a prehardening bath, a neutralizing bath, a first (black and white) developing bath, etc.
  • These baths are well known in the art and are described for instance in Research Disclosure 17643, 1978, and in Research Disclosure 308119, Sections XIX and XX, 1989.
  • the bleaching bath is a water solution having a pH equal to 5.60 and containing an oxidizing agent, normally a complex salt of an alkali metal or of ammonium and of trivalent iron with an organic acid, e.g., EDTA.Fe.NH 4 , wherein EDTA is the ethylenediaminotetracetic acid, or PDTA.Fe.NH 4 , wherein PDTA is the propylenediaminotetraacetic acid.
  • an oxidizing agent normally a complex salt of an alkali metal or of ammonium and of trivalent iron with an organic acid, e.g., EDTA.Fe.NH 4 , wherein EDTA is the ethylenediaminotetracetic acid, or PDTA.Fe.NH 4 , wherein PDTA is the propylenediaminotetraacetic acid.
  • this bath is continuously aired to oxidize the divalent iron which forms while bleaching the silver image and regenerated, as known in the art, to maintain the bleach effectiveness.
  • the bad working of these operations may cause the drawback of the loss of cyan density of the dyes.
  • the blix bath can contain known fixing agents, such as for example ammonium or alkali metal thiosulfates.
  • Both bleaching and fixing baths can contain other additives, e.g., polyalkyleneoxide compounds, as described for example in GB patent 933,008 in order to increase the effectiveness of the bath, or thioether compounds known as bleach accelerators.
  • a multilayer silver halide color photographic film A1 was prepared by coating a cellulose triacetate support base, subbed with gelatin, with the following layers in the following order:
  • Film A2 was prepared in a similar manner as film A1, but containing in the 8th uppermost highest sensitivity green-sensitive layer 0.175 g/m 2 of the magenta dye-forming coupler M1 and 0.006 g/m 2 of the magenta dye-forming DIR coupler M2.
  • Film A3 was prepared in a similar manner as film A1, but replacing in the 8th uppermost highest sensitivity green-sensitive layer the magenta dye-forming coupler M1 with 0.246 g/m 2 of the magenta dye-forming coupler M6.
  • Film A4 was prepared in a similar manner as film A1, but replacing in the 8th uppermost highest sensitivity green-sensitive layer the magenta dye-forming coupler M1 with 0.266 g/m 2 of the magenta dye-forming coupler M5.
  • the characteristic curve for the green light absorption was obtained conventionally.
  • Table 1 reports values of fog (Dmin), maximum optical density (Dmax), sensitivity in Log E at density of 0.2 above Dmin (Speed1), toe contrast (Gamma), values of interimage effects (IIE) and granularity (RMS) for the green-sensitive layer.
  • the interimage effects were calculated as follows. Samples of each film were exposed to a light source having a color temperature of 5,500 K through a Kodak WrattenTM W99 filter and an optical step wedge (selective exposure). Other samples of each film were exposed as above but without any filter (white light exposure). All the exposed samples were developed as described above.
  • a multilayer color photographic film B1 was prepared similar to film A1 of Example 1, but having the following composition for the 6th, 7th and 8th green-sensitive layers:
  • a multilayer color photographic element B2 was prepared similar to film B1, but containing in the 7th green-sensitive layer 0.218 g/m 2 of the magenta dye-forming coupler M1 and 0.0213 g/m 2 of the magenta dye-forming DIR coupler M2, and in the 8th green-sensitive layer 0.273 g/m 2 of the magenta dye-forming coupler M6 instead of coupler M1.
  • a multilayer color photographic element B3 was prepared similar to film B1, but containing in the 7th green-sensitive layer 0.303 g/m 2 of the magenta dye-forming coupler M6 instead of coupler M1 and magenta dye-forming DIR coupler M2 was omitted, and in the 8th green-sensitive layer 0.116 g/m 2 of the magenta dye-forming coupler M1.
  • film B2 having the 4-equivalent 5-pyrazolone magenta coupler in the uppermost highest sensitivity green-sensitive emulsion layer, gives better interimage effects and granularity.

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Claims (9)

  1. Photographisches Silberhalogenid-Element, umfassend einen Träger der mit rot-, grünund blau-empfindlichen Silberhalogenid-Emulsionsschichten beschichtet ist, umfassend jeweils cyanfarbenen, magentafarbenen und gelben Farbstoff bildende Kuppler, wobei die grün-empfindliche Schicht drei grün-empfindliche Schichten mit unterschiedlicher Empfindlichkeit umfasst, eine oberste grün-empfindliche Schicht, die empfindlicher ist, als eine dazwischenliegende grün-empfindliche Schicht, die empfindlicher ist, als eine unterste grün-empfindliche Schicht, wobei die Schichten so angeordnet sind, dass die unterste grün-empfindliche Schicht näher am Träger, die dazwischenliegende grün-empfindliche Schicht benachbart zu der untersten grün-empfindlichen Schicht und die oberste grün-empfindliche Schicht über der dazwischenliegenden grün-empfindlichen Schicht ist, dadurch gekennzeichnet, dass die oberste grün-empfindliche Emulsionsschicht 4-äquivalente 5-Pyrazolon magentafarbenen Farbstoff bildende Kuppler und die dazwischenliegende und die unterste grün-empfindliche Emulsionsschichten 2-äquivalente 4-Arylthio-5-pyrazolon magentafarbenen Farbstoff bildende Kuppler enthalten.
  2. Photographisches Element gemäß Anspruch 1, wobei der 2-äquivalente 4-Arylthio-5-pyrazolon magentafarbenen Farbstoff bildende Kuppler durch die Formel
    Figure 00420001
    wiedergegeben ist, wobei
    a eine ganze Zahl von 0 bis 3 ist,
    b eine ganze Zahl von 0 bis 2 ist,
    R1 und R2 jeweils unabhängig voneinander ein Wasserstoffatom oder Alkyl, Alkoxy, Halogen, Aryl, Aryloxy, Acylamino, Sulfonamido, Sulfamoyl, Carbamoyl, Arylsulfonyl, Aryloxycarbonyl, Alkoxycarbonyl, Alkoxysulfonyl, Aryloxysulfonyl, Alkylureido, Arylureido, Nitro, Cyano, Hydroxyl oder Carboxy sind,
    R3 ein Halogenatom, ein Alkylrest oder ein Arylrest ist,
    X eine direkte Bindung oder eine Linkergruppe ist,
    Ball ein Ballastrest ist, der einen damit verbundenen Rest in photographischen Beschichtungen nicht-diffusionsfähig macht, und
    die Summe der sigma-Werte von R1, R3 und X-Ball weniger als 1,3 ist.
  3. Photographisches Element gemäß Anspruch 2, wobei Ball einen hydrophoben Rest von mindestens 8 Kohlenstoffatomen umfasst.
  4. Photographisches Element gemäß Anspruch 2, wobei R1 ein Chloratom ist, a für 3 steht und Chloratome in den Positionen 2, 4 und 6, in Bezug auf das Kohlenstoffatom, das mit dem Stickstoffatom verbunden ist, stehen.
  5. Photographisches Element gemäß Anspruch 2, wobei R3 ein Chloratom ist.
  6. Photographisches Element gemäß Anspruch 1, wobei der 4-äquivalente 5-Pyrazolon magentafarbenen Farbstoff bildende Kuppler durch die Formel
    Figure 00430001
    wiedergegeben ist, wobei
    a eine ganze Zahl von 0 bis 3 ist,
    R1 ein Wasserstoffatom oder Alkyl, Alkoxy, Halogen, Aryl, Aryloxy, Acylamino, Sulfonamido, Sulfamoyl, Carbamoyl, Arylsulfonyl, Aryloxycarbonyl, Alkoxycarbonyl, Alkoxysulfonyl, Aryloxysulfonyl, Alkylureido, Arylureido, Nitro, Cyano, Hydroxyl oder Carboxy ist,
    R3 ein Halogenatom, ein Alkylrest oder ein Arylrest ist,
    X eine direkte Bindung oder eine Linkergruppe ist,
    Ball ein Ballastrest ist, der einen damit verbundenen Rest in photographischen Beschichtungen nicht-diffusionsfähig macht, und
    n für 0 oder 1 steht.
  7. Photographisches Element gemäß Anspruch 6, wobei R1 ein Chloratom ist, a für 3 steht und Chloratome in den Positionen 2, 4 und 6, in Bezug auf das Kohlenstoffatom, das mit dem Stickstoffatom verbunden ist, stehen.
  8. Photographisches Element gemäß Anspruch 1, wobei der 4-äquivalente 5-Pyrazolon magentafarbenen Farbstoff bildende Kuppler in der obersten, grün-empfindlichen Emulsionsschicht mit der höchsten Empfindlichkeit in einer Menge von 0,01 bis 0,5 Mol pro Mol Silberhalogenid verwendet wird.
  9. Photographisches Element gemäß Anspruch 1, das aus einem Träger besteht, umfassend in der Reihenfolge eine Antihalationsschicht, drei Schichten von Silberhalogenidemulsionen, die empfindlich gemacht wurden für das rote Licht, mit vom Träger aus ansteigender Empfindlichkeit und die cyanfarbenen Farbstoff bildende Kuppler enthalten, drei Schichten von Silberhalogenidemulsionen, die empfindlich gemacht wurden für das grüne Licht, mit vom Träger aus ansteigender Empfindlichkeit und die magentafarbenen Farbstoff bildende Kuppler enthalten, eine gelben Farbstoff Filterschicht und zwei Schichten von Silberhalogenidemulsionen, die empfindlich gemacht wurden für das blaue Licht, mit vom Träger aus ansteigender Empfindlichkeit und die gelben Farbstoff bildende Kuppler enthalten.
EP19950108592 1995-06-06 1995-06-06 Farbphotographische lichtempfindliche Silberhalogenidelemente mit verbesserter Körnigkeit Expired - Lifetime EP0747762B1 (de)

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EP19950108592 EP0747762B1 (de) 1995-06-06 1995-06-06 Farbphotographische lichtempfindliche Silberhalogenidelemente mit verbesserter Körnigkeit
JP14165896A JP3549982B2 (ja) 1995-06-06 1996-06-04 粒状度を向上したハロゲン化銀カラー写真用感光性要素

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