Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
  • G03C7/30541—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the released group
  • G03C7/30552—Mercapto
• • 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
  • G03C1/8155—Organic compounds therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/392—Additives
  • G03C7/39208—Organic compounds
  • G03C7/3924—Heterocyclic

Definitions

• n represents an integer of 1 or more.
• FL represents a fluorescent compound; represents a compound with which a chromophore portion of the fluorescent compound is directly substituted; and n represents an integer of 1 or more, wherein R 2 represents a substitutent group with which a benzene ring can be substituted; m represents an integer of 0 to 5; when m is 2 or more, plural R 2 may be the same or different; and R 2 which are adjacent to each other may be condensed mutually to form a ring, wherein R 3 represents a substituent group with which a benzene ring can be substituted; n represents an integer of 0 to 4; when n is 2 or more, plural R 3 's may be the same or different; R3's which are adjacent to each other may be condensed mutually to form a ring; and R 4 represents a hydrogen atom or a substituent group, wherein R6, R e and R 7 each represent a hydrogen atom or a substituent group; X represents a halogen atom; and
• the characteristic feature of the present invention resides in that a fluorescent substance precursor existing in an emulsion layer of a light-sensitive material causes substitution reaction with a mercapto compound released from a divalent coupler represented by the formula (I) during development processing under a basic condition to form a fluorescent substance having high quantum efficiency.
• a preferred reaction example of the above precursor is shown.
• CD represents a color developing agent
• CD ox represents an oxidized product of a color developing agent
• each mother nucleus of a yellow coupler, a magenta coupler and a cyan coupler there can be used each mother nucleus of a yellow coupler, a magenta coupler and a cyan coupler, but preferred mother nuclei are those represented by the following formulae (V) to (XIII).
• -A represents a position bonding to SR 1 .
• the coupler mother nuclei shown above may have a substituent group, and the substituent group may include those mentioned in the description of the above R 1 . Preferred is the case where at least one substituent group is a diffusion-proof group.
• the substituent group represented by R 1 is not particularly limited, and may preferably include an alkyl group or an aryl group which are substituted with a hydroxyl group, a carboxyl group, an amino group, an ureido group, an acylamino group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an aryloxy group, an urethane group, an alkoxy group, a mercapto group, an alkylthio group, an arylthio group or a halogen atom.
• the fluorescent substance precursor may be added in a development processing solution or in an emulsion layer, but preferred is the case where it is added in an emulsion layer, and more preferred is the case where it is added in an emulsion layer containing a divalent coupler represented by the formula (1).
• Synthesis example 1 (synthesis method of 1-4) 71.5 g of an intermediate product (B) was dissolved in 400 ml of dimethylformamide (DMF) at room temperature, and then 51.1 g of bromine was added dropwise to the solution under nitrogen atmosphere. After completion of the dropwise addition, the mixture was stirred for 5 minutes, and then 118.2 g of an intermediate product (A) was added thereto, followed by reaction at room temperature for 6 hours. To the reaction mixture, 600 ml of water and 800 ml of ethyl acetate were added to extract an organic substance, and then ethyl acetate was evaporated under reduced pressure to obtain 186 g of a yellow solid. This solid was recrystallized with 300 ml of acetonitrile to obtain 141 g of white crystals.
• DMF dimethylformamide
• the coupler of the present invention represented by the formula (I) can be used as a material for forming color photographs according to any color-forming method.
• a color-forming method there may be specifically mentioned a coupler-in-developer type color-forming method and a coupler-in-emulsion type color-forming method.
• the coupler of the present invention can be dissolved in an aqueous alkaline solution or an organic solvent (e.g. alcohol) and added in a developing processing solution.
• the coupler of the present invention represented by the formula (I) is used as a material for forming color photographs according to a coupler-in-emulsion type color-forming method
• the coupler of the present invention is used by incorporating in a light-sensitive photographic material.
• the coupler of the present invention represented by the formula (I) can be used generally in an amount of 1 x 10- 3 mole to 1 mole, preferably in the range of 1 x 10- 2 mole to 8 x 10- 1 mole per mole of silver halide.
• the compounds represented by the formula (II) are preferred.
• substituent groups represented by R i , R 2 , R 3 , R 4 , R s , R e , R 7 , R e , R 9 , R 10 and R 11 are not particularly limited, and may typically include each group of alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl and cycloalkyl, and otherwise a halogen atom and each group of cycloalkenyl, alkynyl, hetero ring, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, sulfonyloxy, carbamoyloxy, amino, alkylamino,
• These substituent groups may further have a substituent group.
• the above alkyl group as preferably 1 to 32 carbon atoms, and may be straight or branched.
• the aryl group is preferably a phenyl group.
• the acylamino group may include an alkylcarbonylamino group and an arylcarbonylamino group.
• the sulfonamide group may include an alkylsulfonylamino group and an arylsulfonylamino group.
• the alkyl component and aryl component in the alkylthio group and arylthio group may include the above alkyl group and aryl group.
• the alkenyl group has preferably 2 to 32 carbon atoms, and the cycloalkyl group has preferably 3 to 12, particularly preferably 5 to 7 carbon atoms.
• the alkenyl group may be straight or branched.
• the cycloalkenyl group has preferably 3 to 12, particularly preferably 5 to 7 carbon atoms.
• the sulfonyl group may include an alkylsulfonyl group and an arylsulfonyl group; the sulfinyl group, an alkylsulfinyl group and an arylsulfinyl group; the phosphonyl group, an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group and an arylphosphonyl group; the acyl group, an alkylcarbonyl group and an arylcarbonyl group; the carbamoyl group, an alkylcarbamoyl group and an arylcarbamoyl group; the sulfamoyl group, an alkylsulfamoyl group and an arylsulfamoyl group; the acyloxy group, an alkylcarbonyloxy group and an arylcarbonyloxy group; the sulfonyloxy group, an alkyls
• alkyl group having a substituent group there may be mentioned a halogenated alkyl group, a hydroxyalkyl group, an aminoalkyl group (including a quaternary ammonium salt), a sulfonylalkyl group and an alkoxyalkyl group.
• the above groups may further have a substituent group such as a diffusion-proof group including a long chain hydrocarbon group and a polymer residue.
• substituent groups represented by R 1 to R 11 preferred are each group of amino, hydroxy, acylamino, sulfonamide, alkylamino, anilino, alkoxy, aryloxy, alkylthio, arylthio, sulfonyl and sulfinyl, and more preferred are each group of alkylamino, acylamino and alkoxy.
• * and ** each represents a position consensing to a benzene ring
• R 12 has the same meanings of the above R 1 to R 11 .
• a position which can be substituted in these condensed rings may be substituted with a substituent group represented by R 1 or R 2 .
• the halogen atom represented by X may include fluorine, chlorine, bromine and iodine, preferably chlorine and bromine.
• the method for processing the light-sensitive silver halide photographic material of the present invention can be practiced in the following manner.
• the coupler of the present invention represented by the formula (I) is used in light-sensitive color photographic materials such as color negative and positive films and color printing papers.
• a method in which the coupler of the present invention is incorporated in a silver halide emulsion, and this emulsion is coated on a support to prepare a light-sensitive color material is preferably used.
• the light-sensitive silver halide photographic material of the present invention including color printing papers may be monochromatic or polychromatic.
• Polychromatic light-sensitive materials have constituent units for forming dye images having sensitivities to respective 3 primary color regions of spectra. Each constituent unit can comprise single or multiple emulsion layers having sensitivity to a specific region of spectrum. Constituent layers of the light-sensitive material including constituent unit layers for forming images can be arranged in various orders as known in this field of the art.
• a typical polychromatic light-sensitive material comprises a constituent unit for forming a cyan dye image comprising at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler, a constituent unit for forming a magenta dye image comprising at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler, and a constituent unit forforming a yellow dye image comprising at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, which are carried on a support.
• the light-sensitive material can possess additional layers, for example, a filter layer, an intermediate layer, a protective layer and a subbing layer.
• the coupler of the present invention represented by the formula (I) may be incorporated in an emulsion according to a known method in the art.
• the coupler of the present invention or a combination thereof is dissolved in a high boiling point organic solvent having a boiling point of 175 °C or higher such as tricresyl phosphate and dibutyl phthalate or a low boiling point solvent such as butyl acetate and butyl propionate, or a mixture thereof, if necessary, and the solution was mixed with an aqueous gelatin solution containing a surfactant.
• the mixture was emulsified by a high speed rotary mixer or a colloid mill, and then added in silver halide.
• the silver halide emulsion to be used in the present invention can be prepared.
• the silver halide composition preferably used in the light-sensitive material of the present invention is silver chloride, silver chlorobromide or silver chloroiodobromide. Further, it may be a mixture of a combination such as a mixture of silver chloride and silver bromide.
• a chlorine atom is preferably contained as a halogen composition of silver halide, and silverchloride, silver chlorobromide or silver chloroiodobromide containing at least 1 % of silver chloride is particularly preferred.
• the silver halide emulsion can be chemically sensitized according to a conventional method. Further, it can be optically sensitized to a desired wavelength region.
• compounds known as an antifoggant or a stabilizer in the photographic field can be added for the purpose of preventing fog during preparation of the light-sensitive material, storage or photographic processing and/or maintaining photographic performances stably.
• a color antifoggant a dye image stabilizer, an UV prevention agent, an antistatic agent, a matte agent and a surfactant which are generally used in a light-sensitive material can be used.
• Color development can be effected by using a color developing solution in which a color developing agent and other additives known in this field of the art are added.
• color development can be also effected by incorporating a color developing agent in a hydrophilic colloid layer of the light-sensitive silver halide photographic material as such or as its precursor, and processing by using an alkaline activated bath.
• the light-sensitive silver halide photographic material of the present invention is subjected to bleaching processing and fixing processing after color development. Bleaching processing may be carried out simultaneously with fixing processing.
• washing processing is generally carried out. Also, stabilizing processing may be carried out in place of washing processing, or both processings may be used in combination.
• the coupler of the present invention represented by the formula (1) and a coupler known in this field of the art can be used in combination.
• Said coupler may be tetravalent or divalent.
• a coupler having effect of color correction a competitive coupler and a compound which releases a photographically useful fragment such as a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a hardener, a fogging agent, an antifoggant, a chemical sensitizer, a spectral sensitizer and a desenditizer by coupling with an oxidized product of a developing agent.
• a colorless coupler which undergoes a couling reaction with an oxidized product of an aromatic primary amine developer, but does not form a dye can be also used in combination.
• a yellow coupler which can be used preferably in combination of the coupler of the present invention represented by the formula (I)
• benzoylacetanilide type and pivaloylacetanilide type couplers there may be included benzoylacetanilide type and pivaloylacetanilide type couplers.
• a magenta coupler there may be mentioned 5-pyrazolone type, pyrazolotriazole type and indazolone type couplers.
• a cyan dye-forming coupler there may be mentioned phenol type, naphthol type, pyrazoloquinazolone type, pyrazolopyrimidine type, pyrazolotriazole type and imidazole type couplers.
• a yellow coupler which can be used in combination, there may be mentioned, for example, compounds disclosed in OLS 2,163.812, Japanese Unexamined Patent Publications No. 26133/1972, No. 29432/1973, No. 65321/1975, No. 3631/1976, No. 50734/1976, No. 102636/1976, No. 6683511973, No. 94432/1973, No. 1229/1974 and No. 10736/1974, and Japanese Patent Publications No. 33410/1976 and No. 25733/1977, and these compounds can be synthesized according to methods disclosed in these publications.
• magenta couplers which can be used in combination are shown below.
• magenta coupler which can be used in combination, there may be mentioned, for example, compounds disclosed in U.S. Patent No. 3,684,514, U.K. Patent No. 1,183,515, Japanese Patent Publications No. 6031/1965, No. 6035/1965, No. 15754/1969, No. 40757/1970 and No. 19032/1971, Japanese Unexamined Patent Publications No. 13041/1975, No. 129035/1978, No. 37646/1976 and No. 62454/1980, U.S. Patent No. 3,725,067, U.K. Patents No. 1,252,418 and No. 1,334,515, Japanese Unexamined Patent Publications No. 171956/1984, No.
• a cyan coupler which can be used in combination, there may be mentioned, for example, compounds disclosed in U.S. Patents No. 2,423,730 and No. 2,801,171, and Japanese Unexamined Patent Publications No. 112038/1975, No. 134644/1975, No. 109630/1978, No. 55380/1979, No. 65134/1981, No. 80045/1981, No. 155538/1982, No. 204545/1982, No. 98731/1983 and No. 31953/1984, and these compounds can be synthesized according to methods disclosed in these publications.
• a red-sensitive emulsion layer comprising 1.2 g of gelatin, 0.30 g of a red-sensitive silver chlorobromide emulsion (containing 96 mole % of silver chloride) and 19.1 x 10- 4 mole of Cyan coupler C-1 dissolved in 1.35 g of dioctyl phosphate.
• a protective layer containing 0.50 g of gelatin As a hardener, 2,4-dichloro-6-hydroxy-s-triazine sodium salt was added in an amount of 0.017 per gram of gelatin.
• Samples 101 and 102 obtained as described above were subjected to wedge exposure according to a conventional method, respectively, and development processing was carried out according to the following steps.
• the processing solutions used in the respective processing steps had compositions shown below. (Color developing solution) made up to 1 liter in total with addition of water, and adjusted pH to 10.20.
• Layer constitution Pro layer, BH layer, BL layer, YF layer, GH layer, GL layer, IL layer, RH layer, RL layer and support.
• RL layer, RH layer, GL layer, GH layer, BL layer, BH layer, IL layer, YF layer and Pro layer are explained. Their amounts added are amouts per 1 m 2 . Amounts of silver halide and colloidal silver are those calculated on silver.
• Emulsion II A layer containing 1.0 g of an emulsion having an average grain size (r) of 0.47 ⁇ m and a variation coefficient (S/
• RH layer high sensitivity red-sensitive silver halide emulsion layer
• Emulsion III AgBrl containing 6 mole % of Agl on average
• M-19 magenta coupler
• D-1 DIR compound
• GH layer high sensitivity green-sensitive silver halide emulsion layer
• M-19 magenta coupler
• Y-12 yellow coupler
• D-1 DIR compound
• DBP dibutyl phthalate
• a layer comprising 2.3 g of gelatin.
• the processing solutions used in the respective processing steps had compositions shown below. (Color developing solution) made up to 1 liter with addition of water, and adjusted pH to 10.6 with sodium hydroxide.
• the layer was so coated that 6.8 mg/100 cm 2 of a yellow coupler (Y-9), 3.2 mg/100 cm 2 calculated on silver of a blue-sensitive silver chlorobromide emulsion (containing 99.5 mole % of silver chloride), 3.5 mg/100 cm 2 of dibutyl phthalate and 13.5 mg/100 cm2 of gelatin were attached.
• Y-9 yellow coupler
• 3.2 mg/100 cm 2 calculated on silver of a blue-sensitive silver chlorobromide emulsion containing 99.5 mole % of silver chloride
• 3.5 mg/100 cm 2 of dibutyl phthalate and 13.5 mg/100 cm2 of gelatin were attached.
• the layer was so coated that 0.75 mg/100 cm 2 of 2,5-di-t-octylhydroquinone (HQ-1), 0.5 mg/100 cm 2 of dibutyl phthalate and 9.0 mg/100 cm 2 of gelatin were attached.
• HQ-1 2,5-di-t-octylhydroquinone
• Green-sensitive silver halide emulsion layer Green-sensitive silver halide emulsion layer
• the layer was so coated that 5.5 mg/100 cm 2 of a magenta coupler (M-2), 2.5 mg/100 cm 2 calculated on silver of a green-sensitive silver chlorobromide emulsion (containing 99.5 mole % of silver chloride), 3.0 mg/100 cm 2 of dibutyl phthalate and 12.0 mg/100 cm 2 of gelatin were attached.
• M-2 magenta coupler
• M-2 green-sensitive silver chlorobromide emulsion
• the layer was so coated that 0.7 mg/100 cm 2 of a UV absorber (UV-1), 6.0 mg/100 cm 2 of dibutyl phthalate, 0.5 mg/100 cm 2 of HQ-1 and 12.0 mg/100 cm 2 of gelatin were attached.
• UV-1 a UV absorber
• 6.0 mg/100 cm 2 of dibutyl phthalate a UV absorber
• 0.5 mg/100 cm 2 of HQ-1 a UV absorber
• 12.0 mg/100 cm 2 of gelatin were attached.
• Red-sensitive silver halide emulsion layer Fifth layer. Red-sensitive silver halide emulsion layer
• the layer was so coated that 4.2 mg/100 cm 2 of a cyan coupler (C-3), 3.0 mg/100 cm 2 calculated on silver of a red-sensitive silver chlorobromide emulsion (containing 99.5 mole % of silver chloride), 3.5 mg/100 cm 2 of tricresyl phosphate and 11.5 mg/100 cm 2 of gelatin were attached.
• C-3 cyan coupler
• C-3 red-sensitive silver chlorobromide emulsion
• 3.5 mg/100 cm 2 of tricresyl phosphate 11.5 mg/100 cm 2 of gelatin were attached.
• the layer was so coated that 8.0 mg/100 cm 2 of gelatin was attached.
• Stabilizing solution made up to I liter in total with addition of water, and adjusted pH to 7.0 with sulfuric acid or potassium hydroxide.
• Example 4 The respective samples used in Example 4 were left to stand for 3 days in a dark place under high temperature and high humidity conditions of a temperature of 60 "C and a relative humidity of 80 %, and then the samples were subjected to exposure and processed according to the same method as in Example 4.
• fog, sensitivity, y and Dm were measured according to a conventional method, it was found that the measured values of Samples 302 and 303 of the present invention were substantially the same as those of Comparative sample 301.
• Example 9 The respective samples used in Example 9 were left to stand for 3 days in a dark place under high temperature and high humidity conditions of a temperature of 60 °C and a relative humidity of 80 %, and then the samples were subjected to exposure and processed according to the same method as in Example 9.
• fog, sensitivity, y and Dm were measured according to a conventional method, it was found that the measured values of Samples 602 and 603 of the present invention were substantially the same as those of Comparative sample 301.
• Sample 702 obtained as described above was subjected to wedge exposure and development processing was carried out in the same manner as in Sample 101 of Example 1, and then evaluated.
• Example 14 The respective samples used in Example 14 were left to stand for 3 days in a dark place under high temperature and high humidity conditions of a temperature of 60 °C and a relative humidity of 80 %, and then the samples were subjected to exposure and processed according to the same method as in Example 14.
• fog, sensitivity, y and Dm were measured according to a conventional method, it was found that the measured values of Samples 902 and 903 of the present invention were substantially the same as those of Comparative sample 301.
• Samples 101 and 1002 obtained as described above were processed in the same manner as in Sample 101 of Example 1, and evaluated.
• Example 19 The respective samples used in Example 19 were left to stand for 3 days in a dark place under high temperature and high humidity conditions of a temperature of 60 °C and a relative humidity of 80 %, and then the samples were subjected to exposure and processed according to the same method as in Example 19.
• fog, sensitivity, y and Dm were measured according to a conventional method, it was found that the measured values of Samples 1202 and 1203 of the present invention were substantially the same as those of Comparative sample 301.

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• 1991
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