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EP0286331B1 - Elément photographique à l'halogénure d'argent sensible à la lumière pour traitement rapide et méthode de traitement à cet effet - Google Patents

Elément photographique à l'halogénure d'argent sensible à la lumière pour traitement rapide et méthode de traitement à cet effet Download PDF

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Publication number
EP0286331B1
EP0286331B1 EP19880302950 EP88302950A EP0286331B1 EP 0286331 B1 EP0286331 B1 EP 0286331B1 EP 19880302950 EP19880302950 EP 19880302950 EP 88302950 A EP88302950 A EP 88302950A EP 0286331 B1 EP0286331 B1 EP 0286331B1
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EP
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Prior art keywords
group
silver halide
independently represent
optionally substituted
layer
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EP19880302950
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German (de)
English (en)
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EP0286331A3 (en
EP0286331A2 (fr
Inventor
Masao Sasaki
Kaoru Onodera
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Konica Minolta Inc
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Konica Minolta Inc
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/83—Organic dyestuffs therefor
    • G03C1/832—Methine or polymethine dyes
    • 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
    • G03C7/396—Macromolecular additives

Definitions

  • the present invention relates to a silver halide photographic light-sensitive element which enables rapid processing and is characterized by sharpness of the dye images produced.
  • the developing speed is greatly influenced by the configuration, size, and composition of the silver halide grains which constitute the emulsion of a photographic light-sensitive element.
  • the halogen composition especially, has a significant influence.
  • the use of a silver halide with a high content of chloride is known to show remarkable increases in developing speed.
  • dyes In order to prevent halation and irradiation, to provide filtering, or to adjust the sensitivity of emulsions, dyes have been included in the hydrophilic colloidal layer which absorb light of a specific wavelength.
  • the dyes used for such purposes must satisfy various requirements, for example: the dye should have satisfactory spectral absorption characteristics depending on the intended purpose; the dye must be completely decolorized in the processing bath, and elute readily out of the photographic element so that no residual staining by the dye occurs after the developing process; the dye should not cause the emulsions to undergo fogging, desensitization, or like adverse influences; the dye is required to have a long shelf life while it is in solution as well as when it is in the photographic element, and should not undergo fading or discoloration.
  • the inventors through their studies on dyes especially in pursuit of their satisfactory decolorization property in rapid processing, discovered that dyes with some specific structures satisfy the requirements when used in combination with a silver halide with a high content of chloride which, as mentioned before, has a high developing speed and suits rapid processing.
  • the object of the present invention is to provide a silver halide photographic light-sensitive element which has improved rapid processing ability and in decolorization property of the dye and produces a picture image with improved sharpness.
  • a silver halide photographic light-sensitive element comprising a support having thereon photographic component layers including at least one silver halide emulsion layer which contains silver halide grains comprising not less than 90 mol% of silver chloride, wherein the proportion of said silver halide grains in said silver halide emulsion layer is not less than 60% by weight of the total silver halide grains contained in said silver halide emulsion layer, and at least one layer among said photographic component layers contains a compound represented by the following formula [I] and a capturing material for fluorescent whitening agent: wherein R1 and R2 independently represent a -CN group, a -CFR5R6 group, a -COR7 group, a -COOR7 group or a -CONHR5 group, in which R5 and R6 independently represent a hydrogen atom, a fluorinated alkyl group having one to four carbon atoms, and R7 represents an alkyl group or an aryl group which may have
  • At least one of the silver halide emulsion layers used in the invention contain silver halide grains comprising not less than 90 mol% of silver chloride grains.
  • These silver halide grains used in the invention comprise not less than 90 mol%, preferably not less than 95 mol% of silver chloride grains.
  • the content of silver bromide grains is preferably 5 mol% or less and that of silver iodide is preferably 0.5 mol% or less.
  • the silver halide grains used in this invention can be used alone or in a mixture with another type of silver halide grains having a different composition.
  • the silver halide grains according to the invention may be used also by mixing with another type of silver halide grains comprising a silver chloride content of less than 10 mol%.
  • the proportion of the silver halide grains comprising not less than 90 mol% of silver chloride grains per total silver halide grains in said emulsion layer is not less than 60 wt%, or, preferably, not less than 80 wt%.
  • composition of the individual silver halide grains used in the present invention may be uniform or be different from the inner portion to the surface. Where the composition differs between the inner and outer portions, the composition may vary in a sequential order or in no sequence.
  • the preferred grain size is within the range from 0.2 to 1.6 »m, or more preferably, within the range from 0.25 to 1.2 »m, with the adaptability to rapid processing, sensitivity, and other photographic properties taken into consideration.
  • the grain size can be measured by normal methods in general use. Methods most generally applicable are described in "Grain Size Analysis” by Labrand (A.S.T.M. Symposium on light Microscopy, 1955, pp. 94-122) and "Theory of Photographic Process” by Meas & James (3rd Ed. McMillan, 1966, Chapter 2).
  • the grain size can be measured by using the projected area of the grain or by using an approximate value of the diameter. When the grains are virtually uniform in shape, the grain size distribution can be determined fairly accurately in terms of diameter or projected area.
  • the grain size distribution of the silver halide grains used in this invention may be multi-dispersed or monodispersed. It is preferably for the distribution to be monodispersed with a variation coefficient of 0.22 or less, or more preferably 0.15 or less.
  • grain size herein used means the diameter when the silver halide grains are spherical. When the grains are cubic or of a shape other than spherical, it refers to the diameter obtained by converting the projected image into a corresponding circular area.
  • the silver halide grains may be formed in any desired configurations.
  • One preferable configuration is a cube having the ⁇ 100 ⁇ face as a crystalline face. It is also possible to produce grains having octahedral, tetradecahedral or dodecahedral configuration by a method described, for example, in U.S. Patent Nos. 4,183,756 and 4,225,666, and Japanese Patent O.P.I. Publication No. 26589/1980 and Japanese Patent Examined Publication No. 42737/1980 and in literature such as The Journal of Photographic Science 21 , 39(1973).
  • a metal ion is optionally added and incorporated into the interior and/or the surface of the grains.
  • a cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or iridium complex salt, rhodium salt or rhodium complex salt, and iron salt or iron complex salt may be used.
  • the silver halide grains used for the emulsion according to this invention are preferably grains wherein a latent image is primarily formed on the grains' surface.
  • the emulsion used in the invention is preferably chemically sensitized by a conventional method.
  • a sulfur-sensitizing method using a sulfur compound which is reactive with silver ions or by using active gelatin is a sulfur-sensitizing method using a sulfur compound which is reactive with silver ions or by using active gelatin; a selenium-sensitizing method using a selenium compound; a reduction-sensitizing method using a reducing substance; and a noble metal-sensitizing method using a noble metal compound such as gold.
  • Such methods can be used individually or in combination.
  • Chalcogen sensitizers are useful for chemical sensitization.
  • sulfur sensitizers and selenium sensitizers are advantageous.
  • the sulfur sensitizers useful for this purpose are, for example, thiosulfate, alkyl thiocarbazide, thiourea, aryl isothiocyanate, cystine, p-toluene thiosulfonate, and rhodanine.
  • Sulfur sensitizers useful for this purpose are also found in the specifications of U.S. Patent Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668 3,501,131, and 3,656,955, West German OLS Patent No.
  • the selenium sensitizers useful for the purpose are selenides such as aliphatic isoselenocyanates such as alkyl isoselenocyanate; selenoureas, selenoketones, selenoamides, selenocarboxylates and esters; selenophosphates; selenides such as diethylselenide, and diethyldiselenide. Examples of such sensitizers are described in U.S. Patent Nos. 1,574,944, 1,602,592, and 1,623,499.
  • Reduction sensitization can be used in combination with other sensitizing processes.
  • the reducing agents useful for this purpose are stannous chloride, thiourea dioxide, hydrazine, and polyamide.
  • Noble metal compounds other than gold such as a palladium compound, can also be used in combination.
  • the silver halide grains used in this invention may contain a gold compound.
  • a gold compound suitable for use in the present invention may have a oxidation number of +1 or +3, whereby a wide variety of gold compounds are applicable.
  • Some examples of such gold compounds are chloraurate, potassium chloraurate, auric trichloride, potassium auric thiocyanate, potassium iodine aurate, tetracyanoauric azide, ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide, and gold selenide.
  • a gold compound can be used either to sensitize the silver halide grains or in such a way not to contribute to sensitization totally.
  • a gold compound used in a quantity of a range of 10 ⁇ 8 mol to 10 ⁇ 1 mol, or, more preferably, 10 ⁇ 7 mol to 10 ⁇ 2 mol per mol silver halide.
  • a gold compound can be added at any of the stages of formation of the silver halide grains, for example at physical ripening, chemical ripening, or after the chemical ripening.
  • the emulsion produced is preferably spectrally sensitized at a desired wavelength range by using a sensitizing dye.
  • the sensitizing dyes can be used singly or in combination of two or more kinds.
  • a supersensitizing dye is more preferably used.
  • This is a dye or compound not having the spectral sensitization function or not actually absorbing visible light, but such a dye or compound is capable of enhancing the sensitizing action of the sensitizing dyes.
  • silver halide grains used for the other emulsion layers No specific restriction applies to the silver halide grains used for the other emulsion layers. But, it is preferable for such silver halide grains to comprise not less than 90 mol% of silver chloride grains.
  • the photographic light-sensitive element according to the present invention contains a compound expressed by formula [I] and a capturing material for fluorescent whitening agent in at least one layer selected from among the photographic component layers, that is, the silver halide emulsion layers, or from among the non-light-sensitive layers, for example, the intermediate layer, protective layer, filter layer, or anti-halation layer.
  • R1 and R2 independently represent -CN, -CFR5R6, -COR7, -COOR7, or -CONHR5, wherein R5 and R6 independently represent a hydrogen atom, a fluorinated alkyl group with 1 to 4 carbon atoms, for example, difluoromethyl group, trifluoromethyl group, 1,1,2,2-tetrafluoroethyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, and 1,1,2,2,3,3-hexafluoropropyl group.
  • R7 in -COR7 or -COOR7 represented by R1 or R2 represents an optionally substituted alkyl group or aryl group.
  • R3 and R4 independently represent a hydrogen atom, or an optionally substituted aliphatic group, alicyclic group, aromatic group, or heterocyclic group, of which the aliphatic group is, for example, an alkyl group or alkenyl group; the alicyclic group is, for example, a cycloalkyl group; the aromatic group is, for example, an aryl group such as phenyl or naphthyl; the heterocyclic group is, for example, benzothiazolyl group or benzoxazolyl group.
  • the methine group represented by each of L1, L2, L3, L4, and L5 may be substituted by an alkyl or aryl group with 1 to 4 carbon atoms.
  • R1 and R2 prefferably be -CN, -CF3 , -CONH2, or -COR7, and for R7 to be alkyl . It is preferable for R3 and R4 to be an aromatic group, especially preferably to be 4-sulfophenyl group, 2,5-di-sulfophenyl group, or their salts.
  • such a dye it is preferable for such a dye to contain at least one water soluble group (such as sulfo group, carboxyl group, or their salts) in its molecular structure.
  • dyes applicable effectively to the practice of the present invention are shown in the specification of Japanese Application No. 8796/1986, pp. 179-199, which are Examples (2), (3), (7), (9), (15), (16), (18), (19), (21), (22), (24), (25), (27) , (33), (34), (35), (40) , (42) , (43), (44), (45), (46), (47), (48), (49), (50), (51), (52) , (53) , (54) , (55) , (58), (59) , (60), and (62).
  • dyes which may be used in the present invention can be synthesized by the method described in the above-mentioned specification of Japanese Patent Application No. 8796/1986.
  • the dyes according to the invention expressed by formula [I] can be used as anti-irradiation dyes by introducing them into a silver halide emulsion layer or as filter dyes or anti-halation dyes by introducing them into non-light-sensitive hydrophilic colloidal layers.
  • a dye used in the invention is incorporated into a silver halide emulsion layer
  • a dye used in the invention can be used in combination with another different dye not of formula (I) or in combination with a dye of formula [I], depending on the purpose of the use.
  • a dye embodying the invention can be incorporated into a silver halide light-sensitive emulsion or other hydrophilic colloidal layer, usually by dissolving the dye or an organic/inorganic alkali salt of the dye in an aqueous solution or an organic solvent, such as alcohol, glycol, cellosolve, dimethylformaldehyde, dibutyl phthalate, and tricresylphosphate. Then dispersing it, if necessary, by emulsifying, adding it to a coating solution, and then by applying to and drying over the support.
  • the dye can be added to a coating solution for a different layer rather than that of the capturing material so that the dye, once the solution is applied, is allowed to diffuse and eventually be incorporated, before the solution completely dries, into a layer which contains the capturing material for fluorescent whitening agent.
  • the dye used in the invention is present in the layer containing a capturing material for fluorescent whitening agent.
  • the quantities of the dyes used vary depending on the purpose of application and are not restricted to any specific amounts. But, generally, it is preferable for the dye to be applied at a rate of 0.01 - 1.0 mg/dm2, or, more preferably, 0.03 - 0.4 mg/dm2.
  • One of the effective means of improving the whiteness of a silver halide photographic light-sensitive element including particularly a photographic print paper is the method of adding a water-soluble fluorescent whitening agent into the hydrophilic colloidal layer of a light-sensitive element.
  • the fluorescent whitening agents include, for example, the compounds of a diaminostilbene, a benzidine, an imidazole, a triazole or an imidazolone, each having a hydrophilic group, as described in Japanese Patent O.P.I. No. 71049-1984.
  • a fluorescent whitening agent added into the hydrophilic colloidal layer of a light-sensitive element will be eluted from the hydrophilic colloidal layer into the processing solution during the course of processing the light-sensitive element.
  • Any compound capable of capturing a fluorescent whitening agent may be used in the invention. It is, however, preferred that it is a non-color-developable hydrophilic synthetic macro-molecular polymer.
  • hydrophilic polymers include polyvinyl pyrrolidone or copolymers having vinyl pyrrolidone as repeating units, wherein the examples of monomers capable of forming repeating units together with vinyl pyrrolidone include acrylic acid, methacrylate acid, amide compounds of acrylic acid and methacrylic acid, such as acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-methyloylacrylamide, N-hydroxyethylacrylamide, N-tert-butylacrylamide, N-cyclohexylacrylamide, diacetoneacrylamide, N-(1,1-dimethyl-3-hydroxybutyl)acrylamide, N-( ⁇ -morpholino)ethylacrylamide, N-benzylacrylamide, N-acryloylmorpholine, N-methacryloylmorpholine, N-methyl-N-acryloylpiperazine, N-acryloylpiperazine, N-N-
  • polymer of N-vinylamide compound expressed by a formula CH2 CHNR1COR2, in which R1 represents an alkyl group and R2 represents a hydrogen atom or an alkyl group; hydrophilic polymer including a cationic nitrogen-containing active group described in Japanese Patent O.P.I. Publication No. 42732/1973; polymers of morpholino alkylalkenoylamide described in Japanese Patent Examined Publication No. 2522/1969; copolymers of vinyl alcohol and vinyl-pyrrolidone described in Japanese Patent Examined Publication No. 20738/1972; polymers described in Japanese Patent Examined Publication No.
  • hydrophilic polymers it is preferable for said hydrophilic polymers to have a molecular weight of not less than 1,000, in particular, a molecular weight of not less than 10,000, in terms of weight-average molecular weight. Still more advantageous is a molecular weight in the range of 50,000-1,000,000.
  • the capturing material used in the invention can be incorporated into any of the photographic structural layers, that is, in a light-sensitive layer or in a non-light-sensitive layer. It is preferable for the capturing material of the invention to be contained in a non-light-sensitive layer.
  • the capturing material of the invention prefferably be used at a rate of 0.05 to 3.0 mg/dm2, more preferably 0.1 to 20 mg/dm2. It is also preferable for the capturing material of the invention to be used at a rate of 0.1 to 50 wt%, or, more preferably, at a rate of 1 to 30 wt% per amount of gelatin which is used as a binder in the photographic structural layer where the capturing material is contained.
  • a sensitizing dye used in the invention preferably in the green-sensitive silver halide emulsion layer is one expressed by the following formula [B]: wherein Z11 and Z12 individually represent an optionally substituted group of atoms required to form a benzene ring or naphthalene ring condensed on the oxazole ring.
  • the preferable substituents are halogen atoms, aryl group, alkyl group, or alkoxy group. Halogen atoms, phenyl group, and methoxy group are more preferable as substituents, and phenyl group is most preferable as a substituent.
  • both Z11 and Z12 represent a benzene ring condensed on the oxazole ring, wherein at least one of these benzene rings has a substituent phenyl group in the 5-position, or one of these benzene ring has a substituent phenyl group in the 5-position, and the other benzene ring has in the 5-position a halogen atom as a substituent group.
  • R21 and R22 individually represent an alkyl group, alkenyl group, or aryl group, preferably an alkyl group. It is more preferable for R21 and R22 individually to be alkyl groups having a carboxyl or sulfo group as a substituent group. The more preferable example of R21 and R22 is a sulfoalkyl group having 1 to 4 carbon atoms, where the most preferable is a sulfoethyl group.
  • R23 represents a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms, or, preferably, a hydrogen atom or ethyl group.
  • X1 ⁇ represents an anion, such as a halogen ion of chloride, bromine, or iodine, or an anion such as CH3SO - 4 , or C2H5SO - 4 .
  • n represents 1 or 0. When a compound forms an inner salt, however, n represents 0.
  • sensitizing dyes preferable in the practice of the present invention expressed by the formula [B], will now be shown hereunder.
  • the sensitizing dye preferably used in the invention to be incorporated into the red-sensitive silver halide emulsion layer to be one expressed by the following formula [C] or another expressed by the following formula [D], wherein R represents a hydrogen atom, or an optionally substituted alkyl group; R11 through R14 individually represent an optionally substituted alkyl group or aryl group; Z1, Z2, Z4, and Z5 individually represent a group of atoms required to form a benzene or naphthalene ring condensed into a thiazole or selenazole ring; Z3 represents a group of hydrocarbon atoms required to form a six-membered ring; l represents 1 or 2; Z represents a sulfur atom or selenium atom; X ⁇ represents an anion.
  • R in the formulas above represents preferably an hydrogen atom, methyl group or ethyl group. It is especially preferable for R to be a hydrogen atom or ethyl group.
  • R11, R12, R13, and R14 individually represent an optionally substituted straight-chained or branched alkyl or aryl group.
  • the rings formed by Z1, Z2, Z4, and Z5 are optionally substituted.
  • Preferred substituents are halogen atoms, aryl group, alkyl group, and alkoxy group. Particularly preferred substituents are halogen atoms such as chlorine atom, phenyl group, or methoxy group.
  • the ring formed by Z3 is optionally substituted, for example, by an alkyl group.
  • X represents an anion (such as Cl ⁇ , Br ⁇ , I ⁇ , CH3SO - 4 , and C2H5SO - 4 ); and l represents 1 or 2.
  • the sensitizing dye is dissolved in a water soluble solvent such as a pyridine, methyl alcohol ethyl alcohol, methyl Cellosolve and acetone (or the mixture of any of these solvents).
  • a water soluble solvent such as pyridine, methyl alcohol ethyl alcohol, methyl Cellosolve and acetone (or the mixture of any of these solvents).
  • the solution is then diluted with water to form a solution which may be added into a coating solution.
  • any of the sensitizing dyes may be dissolved in water to prepare a solution to be added into a coating solution.
  • the amount of sensitizing dye being added is not specifically limited.
  • a preferred range of addition is 2 x 10 ⁇ 6 to 1 x 10 ⁇ 3 mol, in particular, 5 x 10 ⁇ 6 to 5 x 10 ⁇ 4 mol per mol silver halide.
  • the silver halide photographic light-sensitive element of the invention having the constitution described above may be, for example, a color negative film, color positive film, or color photographic paper.
  • the effect of the invention is best demonstrated when the material takes the form of a color photographic paper, which will be directly appreciated by human vision.
  • the silver halide photographic light-sensitive elements of the invention may be monochromatic or multi-color.
  • the multi-color silver halide photographic light-sensitive element usually comprises a support having thereon, in an appropriate order and number, silver halide emulsion layers containing as photographic couplers each of magenta, yellow and cyan couplers, as well as non-light-sensitive layers. The order and number of these layers may be deliberately changed in accordance with the target performance and intended application.
  • the silver halide photographic light-sensitive element used in embodying the invention is the preferred multi-color light-sensitive element
  • the preferred layer configuration comprises a support provided sequentially thereon in the order of a yellow dye-image forming layer, intermediate layer, magenta dye-image forming layer, intermediate layer, cyan dye-image forming layer, intermediate layer, and protective layer.
  • dye-forming couplers preferably contain within the molecular structure a group known as a "ballast group" which has not less than 8 carbon atoms and is capable of making the coupler non-diffusible.
  • the preferred yellow dye-forming couplers are acylacetanilide couplers.
  • benzoylacetanilide compounds and pyvaloylacetanilide compounds are particularly advantageous.
  • the preferred compounds are those represented by the following formula [Y].
  • R y1 represents a halogen atom, or an optionally substituted alkoxy group.
  • R y2 represents a hydrogen atom, halogen atom, or an optionally substituted alkoxy group.
  • R y3 represents an optionally substituted acylamino group, alkoxycarbonyl group, alkylsulfamoyl group, arylsulfamoyl group, alkylureide group, arylureide group, succinimide group, alkoxy group or aryloxy group.
  • Z y1 represents a group being capable of split off by the reaction with an oxidation product of the color developing agent.
  • useful yellow coupler are those described, for example, in British Patent No. 1,077,874, Japanese Patent Examined Publication No. 40757/1970, Japanese Patent O.P.I. Publication Nos. 1031/1972, 26133/1972, 94432/1973, 87650/1975, 3631/1976, 115219/1977, 99433/1979, 133329/1979, and 30127/1981, U.S. Patent Nos.
  • the preferred magenta dye-forming couplers are 5-pyrazolone couplers and pyrazoloazole couplers.
  • the particularly preferred couplers are those represented by the following formula [P] or [a].
  • Ar represents an aryl group.
  • R p1 represents a hydrogen atom or a substituent group.
  • R p2 represents a substituent group.
  • Y represents a group capable of being split off by the reaction with an oxidation product of the color developing agent.
  • W represents -NH-, -NHCO- (N atom being bonded to a carbon atom on the pyrazolone nuclei), or -NHCONH-.
  • m represents an integer, 1 or 2.
  • Z a represents a group of non-metal atoms required for forming a nitrogen-heterocycle.
  • the heterocycle formed by this Z a may have a substituent.
  • X represents a hydrogen atom, or a group capable of being split off by the reaction with an oxidation product of the color developing agent.
  • R a represents a hydrogen atom, or a substituent group.
  • the examples of a substituent group represented by R a include a halogen atom, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkinyl group, aryl group, heterocyclic group, acyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue group, bridged hydrocarbon compound residue group, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group, ureide group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, and heterocyclic thio group.
  • magenta coupler examples are described, for example, in U.S. Patent Nos. 2,600,788, 3,061,432, 3,062,653, 3,127,269, 3,311,476, 3,152,896, 3,419,391, 3,519,429, 3,555,318, 3,684,514, 3,888,680, 3,907,571, 3,928,044 3,930,861, 3,930,866, and 3,933,500, Japanese Patent O.P.I. Publication Nos. 29639/1974, 111631/1974, 129538/1974, 58922/1977, 62454/1980, 118034/1980, 38043/1981, 35858/1982, and 23855/1985, British Patent No.
  • the cyan dye-forming couplers preferably used are phenol and naphthol cyan dye forming couplers.
  • the particularly preferred couplers are those represented by the following formula [E] or [F].
  • R e1 represents an alkyl group, cycloalkyl group or heterocyclic group.
  • R e2 represents an alkyl group or phenyl group.
  • R e3 represents a hydrogen atom, halogen atom, alkyl group or alkoxy group.
  • Z e1 represents a hydrogen atom, or a group being capable of split off by the reaction with an oxidation product of the color developing agent.
  • R e1 through R e3 are optionally substituted.
  • R f1 represents an alkyl group such as a methyl group, ethyl group, propyl group, butyl group, and nonyl group.
  • R f2 represents an alkyl group such as a methyl group and ethyl group.
  • R f3 represents a hydrogen atom, halogen atom such as fluorine, chlorine and bromide, or alkyl group.
  • Z f1 represents a hydrogen atom, or a group capable of being split off by the reaction with an oxidation product of the color developing agent.
  • R f1 through R f3 may have a substituent group.
  • the dye forming coupler preferably used in the invention is incorporated into each silver halide emulsion layer, preferably, at a rate of 1 x 10 ⁇ 3 to 1 mol, or, more preferably, 1 x 10 ⁇ 2 to 8 x 10 ⁇ 1 mol per mol silver halide.
  • the preferable binder, or protective colloid, incorporated into the silver halide photographic light-sensitive element according to the invention is gelatin.
  • Other useful binders include a gelatin derivative, graft polymer of gelatin and another high-molecular compound, protein, sugar derivative, cellulose derivative, and hydrophilic colloid of synthesized high-molecular compound such as monomer or polymer.
  • the photographic emulsion layers and other hydrophilic colloid layers of the silver halide photographic light-sensitive element of the invention are preferably hardened by using hardeners individually or in combination which enhance layer strength by bridging between binder, or protective colloidal, molecules.
  • the hardeners are preferably incorporated at a rate enough to eliminate hardeners added to processing solutions. However, the hardeners may be added to processing solutions.
  • a chlorotriazine hardener represented by the following formula [HDA] or [HDB], is preferably used to harden the silver halide emulsion layers.
  • R d1 represents a chlorine atom, hydroxy group, an optionally substituted alkyl group, alkoxy group, alkylthio group, or an -OM group (M represents a monovalent metal atom), -NR′R ⁇ group (R′ and R ⁇ independently represent a hydrogen atom, alkyl group or aryl group), or -NHCOR′′′ group (R′′′ represents an alkyl group or aryl group).
  • R d2 is the same as R d1 above, except that it may not represent a chlorine atom.
  • R d3 and R d4 independently represent a chlorine atom, hydroxy group, or an optionally substituted alkyl group, alkoxy group, or an -OM group in which M represents a monovalent metal atom.
  • Q and Q′ independently represent a connecting group such as -O-, -S- or -NH-.
  • L represents an alkylene group or an arylene group.
  • the hardener represented by formula either [HDA] or [HDB] is preferably incorporated into silver halide emulsion layers and other structural layers by dissolving the hardener in water, or a solvent compatible with water such as methanol and ethanol, thereby adding the resultant solution to a coating solution for these structural layers.
  • the method of addition can be either a batch process or an in-line process.
  • the timing of addition is not specifically limited. However, the preferred timing of addition is immediately before the application of coating solutions.
  • hardeners are added at a rate of 0.5 to 100 mg, or, preferably, at a rate of 2.0 to 50 mg per 1 gram gelatin being applied.
  • additives such as an anti-stain agent, image-stabilizing agent, ultraviolet absorbent, plasticizer, latex, surface active agent, matting agent, lubricant, and anti-static agent, may optionally be added.
  • the silver halide photographic light-sensitive element according to the invention may generally form an image by color developing known in the art.
  • the color developing agents incorporated into the color developers, according to the invention include aminophenol derivatives and p-phenylenediamine derivatives widely used in various color photographic processes.
  • the pH value of a color developer solution is normally higher than 7, or, most usually, approx. 10 to 13.
  • the color developing temperature is usually higher than 15°C, or, generally, within a range of 20 to 50°C.
  • the preferred temperature is higher than 30°C.
  • a conventional color developing requires 3 to 4 minutes, while the preferred color developing time intended for rapid processing is usually within a range of 20 to 60 seconds, more preferably, 30 to 50 seconds.
  • the silver halide photographic light-sensitive element of the invention is subjected to bleaching and fixing.
  • the bleaching and the fixing may be performed simultaneously.
  • the element After the fixing, the element is usually subjected to rinsing with water. Stabilizing may substitute the rinsing, or these two steps may be used in combination.
  • the silver halide photographic light-sensitive element of the invention excels in rapid processability, as well as in decolorization of the dyes, wherein the resultant photographic image has improved sharpness.
  • Em-A through Em-E above were, using a conventional method, subjected to sulfur sensitization by adding sodium thiosulfate, and further subjected to optical sensitization using exemplified sensitizing dye No. C-9.
  • red-sensitive silver halide emulsions Em-R Nos. A through E were prepared.
  • mono-color light-sensitive element sample No. 1 was prepared.
  • the amounts added for each coating solution are indicated by amounts applied per each independent coat formed.
  • Light-sensitive element sample Nos. 2 through 44 were prepared in manner identical with that of sample No. 1 above, except that the combination of Em, type of compound represented by formula [I], layer containing material for capturing fluorescent whitening agent, and coating solution dissolving them, were modified as listed in Table-1, each substance was used in the same proportion.
  • sample No. 45 was prepared in a manner identical with that of sample No. 10, except that the following sensitizing dye A was used instead of exemplified sensitizing dye No. C-9 in Em-E.
  • Sample Nos. 46 and 47 were prepared in a manner identical with sample No. 10, except that polyvinyl pyrrolidone in the second layer of sample No. 10 was replaced for No. 46 with a like weight of polyvinyl alcohol, with a polymerization degree of approx. 500 and a saponification degree of 88%; and for No. 47 with a copolymer (1 : 1, by molecular ratio) of vinyl pyrrolidone and methacrylic acid.
  • Sample Nos. 48, 49 and 50 were prepared in a manner identical with sample No.
  • Sample No. 51 was prepared in a manner identical with that of sample No. 10, except that a hardener, examplified compound No. HD-2, in the first and second layers was replaced with the same weight of the following hardener H-1.
  • the pH level was adjusted to 7.1 using potassium carbonate or glacial acetic acid, thereby water was added to prepare a one liter solution.
  • sample Nos. 1 and 2 which used an emulsion, not prescribed for use in the invention, having a lower silver chloride content and containing comparative dye and a capturing material used in the invention for fluorescent whitening agent, respectively showed insufficient sensitivity and maximum density, and, especially, greater stain, and also failed to attain satisfactory level of sharpness.
  • Sample Nos. 3 through 5 having an emulsion of the invention of a higher silver chloride content unlike sample Nos. 1 and 2, showed still insufficient improvement in stain and sharpness, in spite of improved sensitivity and maximum density.
  • Sample No. 6 and sample Nos. 8 through 51 respectively incorporating a dye represented by formula [I] according to the invention respectively showed improvement to nearly satisfactory level in terms of stain.
  • HD-5, HD-13, or HD-15 instead of HD-2, achieved the same effects above.
  • the effects of the invention were achieved by a sample prepared by simultaneously applying and drying not only a coating solution for the first layer, which was unlike the original coating solution, prepared by incorporating the dye used in the invention No. 2, 4, 6 or 7 into the coating solution for the first layer on Example-3, but a coating solution for the second layer, protective layer, containing polyvinyl pyrrolidone, weight average molecular weight, 360,000, in an amount of 0.55 mg/dm2, gelatin in an amount of 20 mg/dm2, and a hardener in an amount of 0.05 mg/dm2.
  • Em-A through Em-E To Em-A through Em-E was added sodium thiosulfate by a conventional method, whereby each emulsion was subjected to sulfur sensitization, and then, to spectral sensitization using sensitizing dye, exemplified compound No. B-11.
  • Green-sensitive silver halide emulsions Em-G Nos. A through E were prepared.
  • mono-color light-sensitive element sample No. 2-1 was prepared.
  • the amounts added for each coating solution are indicated by amounts applied per each independent coat formed.
  • Light-sensitive element sample Nos. 2-2 through 2-17 were prepared in a manner identical with that of sample No. 2 above, except that the combination of type of compound represented by formula [I], and coating solution dissolving it, was modified as listed in Table-2, each substance was used in the same proportion.
  • Em-D sensitized by gold and sulfur as mentioned above was subjected to spectral sensitization using a sensitizing dye, exemplified compound No. D-3, so as to prepare red-sensitive silver halide emulsion Em-R No. D2.
  • Em-E was spectrally sensitized using sensitizing dye, exemplified compound No.
  • Em-F was spectrally sensitized using the following sensitizing dye SD-A, so as to prepare blue-sensitive silver halide emulsion Em-B No. F.
  • the amounts added for each coating solution are indicated by amounts applied per each independent coat formed.
  • Sample Nos. 3-1 through 3-26 were prepared by variously changing type and amount added of a compound represented by formula [I] into the third and fifth layers, and also by changing type and amount added by a compound as a capturing material used in the invention into the sixth layer. Additionally, sample Nos. 3-27 through 3-32 were prepared by incorporating a dye used in the invention into a coating solution for the second, fourth, sixth or seventh layer.
  • Those dyes added into the third and fifth layers as listed in Table-3 were as follows: comparative dye No. 1 was the same as that in example-1, comparative dye No. 2 was the same as that in example-2.
  • the structural formulas of high boiling organic solvents S-1 and S-2, ultraviolet absorbents UV-1 and UV-2, and sensitizing dye SD-A are as follows.
  • Table-3 lists the test results.
  • Sample Nos. 4-1 through 4-16 were prepared in a manner identical with sample No. 3-25 in Example-3, except that the combination of a yellow coupler in the first layer, a magenta coupler in the third layer, and a cyan coupler in the fifth layer was changed, while maintaining same mol ratios, as listed in Table-4 below.

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Claims (11)

  1. Elément photographique photosensible à base d'halogénure d'argent, comprenant un support portant des couches de composant photographique, englobant au moins une couche d'émulsion d'halogénure d'argent, qui contient des grains d'halogénure d'argent contenant pas moins de 90 % en moles de chlorure d'argent, dans lequel la proportion desdits grains d'halogénure d'argent dans ladite couche d'émulsion d'halogénure d'argent n'est pas inférieure à 60 % en poids du poids total des grains d'halogénure d'argent contenus dans ladite couche d'émulsion d'halogénure d'argent, et au moins une couche parmi lesdites couches de composant photographique contient un composé représenté par la formule [I] ci-après, et un matériau piège pour un agent de blanchiment fluorescent:
    Figure imgb0168
     dans laquelle R₁ et R₂ représentent indépendamment un groupe -CN, un groupe -CFR₅R₆, un groupe -COR₇, un groupe -COOR₇, un groupe -CONHR₅ ou un groupe -CF₃, dans lesquels R₅ et R₆ représentent indépendamment un atome d'hydrogène, un groupe alkyle fluoré ayant un à quatre atomes de carbone, et R₇ représente un groupe alkyle ou un groupe aryle qui peut porter un susbtituant; R₃ et R₄ représentent indépendamment un atome d'hydrogène ou un groupe aliphatique, un groupe alicyclique, un groupe aromatique ou un groupe hétérocyclique, dont chacun peut être éventuellement susbtitué ; L₁, L₂, L₃, L₄ et L₅ représentent indépendamment un groupe méthine éventuellement substitué ; et m et n représentent indépendamment un nombre entier valant 0 ou 1.
  2. Elément selon la revendication 1, dans lequel ledit matériau piège est un homo- ou copolymère de vinylpyrrolidone.
  3. Elémént selon la revendication 1 ou 2, dans lequel les substituants R₃ et R₄ du composé de formule [I] représentent chacun indépendamment un groupe 4-sulfophényle ou 2,5-disulfophényle.
  4. Elément selon la revendication 1, 2 ou 3, dans lequel le poids de revêtement dudit matériau piège est compris dans la gamme allant de 0,05 mg/dm² à 3,0 mg/dm².
  5. Elément selon la revendication 4, dans lequel le poids de revêtement dudit matériau piège est compris dans la gamme allant de 0,1 mg/dm² à 2,0 mg/dm².
  6. Elément selon l'une quelconque des revendications précédentes, dans lequel la quantité dudit matériau piège est comprise dans la gamme allant de 0,1 % à 50 % en poids par rapport à l'autre liant contenu dans la couche de composant photographique qui contient ledit matériau piège.
  7. Elément selon la revendication 6, dans lequel la quantité dudit matériau piège est comprise dans la gamme allant de 1 % à 30 % en poids par rapport au liant contenu dans la couche de composant photographique qui contient ledit matériau piège.
  8. Elément selon l'une quelconque des revendications précédentes, dans lequel le poids de revêtement dudit composé représenté par la formule [I] est compris dans la gamme allant de 0,01 mg/dm² à 1,0 mg/dm².
  9. Elément selon la revendication 8, dans lequel le poids de revêtement dudit composé représenté par la formule [I] est compris dans la gamme allant de 0,03 mg/dm² à 0,4 mg/dm².
  10. Elément selon l'une quelconque des revendications précédentes, dans lequel au moins une dite couche d'émulsion d'halogénure d'argent contenant des grains d'halogénure d'argent comprenant pas moins de 90 % en moles de chlorure d'argent est soumise à une sensibilisation spectrale avec au moins un colorant sensibilisant choisi parmi les composés représentés par la formule suivante [C] ou [D] :
    Figure imgb0169
    Figure imgb0170
     dans laquelle R représente un atome d'hydrogène ou un groupe alkyle éventuellement substitué ; R₁₁ à R₁₄ représentent indépendamment un groupe alkyle éventuellement substitué ou un groupe aryle éventuellement substitué ; Z₁, Z₂, Z₄ et Z₅ représentent indépendamment un groupe d'atomes nécessaires pour compléter un noyau benzénique ou un cycle naphtalénique condensé en un cycle thiazole ou sélénazole ; Z₃ représente un groupe hydrocarboné nécessaire pour compléter un cycle à six maillons; I représente un nombre entier qui vaut 1 ou 2; Z représente un atome de soufre ou un atome de sélénium ; et X⁻ représente un anion.
  11. Elément selon l'une quelconque des revendications précédentes, dans lequel lesdites couches de composant photographique sont durcies à l'aide d'un durcisseur choisi parmi les composés représentés par la formule suivante [HDA] OU [HDB] :
    Figure imgb0171
     dans laquelle Rd1 représente un atome de chlore, un groupe hydroxy ou un groupe alkyle, alcoxy ou alkylthio éventuellement substitué, un groupe -OM, un groupe -NR′R˝ ou un groupe -NHCOR, dans lequel M représente un atome de métal monovalent; R′ et R˝ représentent indépendamment un atome d'hydrogène, un groupe alkyle ou aryle éventuellement substitué ; et R représente un groupe alkyle ou aryle éventuellement substitué ; et Rd2 représente un groupe identique à celui défini pour Rd1, excepté le chlore ;
    Figure imgb0172
     dans laquelle Rd3 et Rd4 représentent indépendamment un atome de chlore, un groupe hydroxy ou un groupe alkyle ou alcoxy éventuellement substitué, ou un groupe -OM, dans lequel M représente un atome de métal monovalent ;Q et Q′ représentent indépendamment un atome de liaison ou un groupe -O-, -S- ou -NH-; L représente un groupe alkylène ou un groupe arylène ; et p et q représentent indépendamment un nombre entier qui vaut 0 ou 1.
EP19880302950 1987-04-04 1988-03-31 Elément photographique à l'halogénure d'argent sensible à la lumière pour traitement rapide et méthode de traitement à cet effet Expired - Lifetime EP0286331B1 (fr)

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JP8352187 1987-04-04
JP83521/87 1987-04-04
JP327694/87 1987-12-24
JP32769487A JPS6426850A (en) 1987-04-04 1987-12-24 Silver halide photographic sensitive material having superior rapid processability and superior sharpness of obtained dye image

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EP0316013A3 (fr) * 1987-11-11 1990-08-16 Fuji Photo Film Co., Ltd. Matériau photographique à l'halogénure d'argent avec au moins une couche hydrophile colorée
JPH0297940A (ja) * 1988-10-04 1990-04-10 Konica Corp ハロゲン化銀写真感光材料
JPH087421B2 (ja) * 1988-10-07 1996-01-29 富士写真フイルム株式会社 カラー画像形成方法
JPH03265847A (ja) * 1990-03-15 1991-11-26 Konica Corp ハロゲン化銀写真感光材料
JP2676115B2 (ja) * 1990-06-01 1997-11-12 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
US5922525A (en) * 1996-04-08 1999-07-13 Eastman Kodak Company Photographic material having a red sensitized silver halide emulsion layer with improved heat sensitivity
US5925509A (en) * 1995-09-29 1999-07-20 Eastman Kodak Company Photographic material having a red sensitized silver halide emulsion layer with improved heat sensitivity
US6120982A (en) * 1995-09-29 2000-09-19 Eastman Kodak Company Red sensitizing dye combinations for high chloride emulsions

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NL251799A (fr) * 1959-05-19
DE1547833A1 (de) * 1965-02-12 1969-11-13 Fuji Photo Film Co Ltd Photographische lichtempfindliche Materialien
GB1311884A (en) * 1969-05-30 1973-03-28 Agfa Gevaert Light-sensitive silver halide photographic materials incorporating
JPS52117123A (en) * 1976-03-26 1977-10-01 Fuji Photo Film Co Ltd Silver halide light sensitive material containing dye
JPS60221747A (ja) * 1984-04-18 1985-11-06 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料

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