EP0691571B1 - Entwicklungsgranulat oder -tablette für photographische lichtempfindliche Silberhalogenidmaterialien und Verfahren zu dessen Herstellung - Google Patents

Entwicklungsgranulat oder -tablette für photographische lichtempfindliche Silberhalogenidmaterialien und Verfahren zu dessen Herstellung Download PDF

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Publication number
EP0691571B1
EP0691571B1 EP19950304013 EP95304013A EP0691571B1 EP 0691571 B1 EP0691571 B1 EP 0691571B1 EP 19950304013 EP19950304013 EP 19950304013 EP 95304013 A EP95304013 A EP 95304013A EP 0691571 B1 EP0691571 B1 EP 0691571B1
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EP
European Patent Office
Prior art keywords
group
granules
carbon atoms
tablet
particle size
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EP19950304013
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English (en)
French (fr)
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EP0691571A1 (de
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Ichiro C/O Konica Corporation Tsuchiya
Takashi C/O Konica Corporation Deguchi
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Konica Minolta Inc
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Konica Minolta Inc
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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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
    • G03C5/265—Supplying of photographic processing chemicals; Preparation or packaging thereof of powders, granulates, tablets
    • 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
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers

Definitions

  • the invention relates to a solid developing composition for a silver halide photographic light-sensitive material and a manufacturing method thereof, and particularly a solid developing composition having improved storage stability for a silver halide photographic light-sensitive material and a manufacturing method thereof.
  • a developing composition for a silver halide photographic light-sensitive material is usually supplied in the form of plural concentrated solutions (kit) to consumers.
  • kit plural concentrated solutions
  • a processing kit in which plural concentrated solutions are packaged in plastic bottles of 100 milliliter to 5 liter, is supplied to customers, but the processing kit still requires much storage space. Further, the cost for transport is not low. The discarded plastic bottles increase year by year, causing an environmental problem.
  • the processing kit for developer is usually supplied in plural separate parts. The consumers mix the parts in a specific proportion to prepare developer replenisher, but errors frequently occur during the mixing operations.
  • Powder photographic processing compositions are considered in order to overcome the above problems.
  • the powder compositions produce loose powder when dissolved in water, and operators breathe in loose powder particles, resulting in health hazard.
  • other photographic solutions may be contaminated with the components of the loose powder and there occurs the possibility of other troubles in developing process.
  • Patent O.P.I Publication Nos. 2-109042/1990 and 2-109043/1990 disclose a technique of using a granular mixture of photographic processing agents.
  • Patent O.P.I Publication Nos. 5-119454/1993 and 5-113646/1993 disclose a photographic processing system using a granular or tablet processing agent.
  • the above described techniques can prevent fine powder occurrence of the solid processing agent, but there is a problem particularly in a tablet developing composition that it is difficult to discharge tablets in a cartridge or to quantitatively supply tablets in a supplying device on account of expansion of the tablets during storage.
  • the problem is noticeably displayed particularly when the tablets are transported by ship from Japan to Southeast Asia, the Middle and Near East or Africa in 2 to 4 weeks, during which the temperature difference between day and night is 15-20°C and the humidity difference between day and night is 20-30%.
  • Japanese Patent O.P.I. Publication No. 5-119454/1993 discloses a method of obtaining a solid processing composition having a desired component content by using granular compositions having an average particle size within a specific range.
  • this reference does not disclose a tablet developing composition and the method disclosed therein could not sufficiently solve the above problems.
  • 5-142708/1993 discloses a method of mixing granular compositions having an average particle size within a specific range and then tableting the mixture to obtain a solid processing composition. This method prevents an inner reaction of a tablet color developing composition during a long term storage, but is not sufficient to prevent expansion of the tablet.
  • an object of the invention is to provide a method of manufacturing a granular developing composition and a method of manufacturing a tablet from said granular developing composition, wherein the resulting tablet-form developing composition has a desired component content ratio and shows less expansion during storage.
  • the present inventors have made an intensive study, and have solved the above problems by controlling the size of granules containing a photographic component to a specific particle size.
  • the solid processing composition of the invention refers to a processing composition in the form of granules or tablets.
  • the content of granules having a particle size of 1000 ⁇ m or more is not more than 10 weight % based on the total weight of the granules.
  • the particle size of the invention refers to that according to JIS (JAPAN INDUSTRIAL STANDARD), and is measured by using a JIS standard screen.
  • granules having a particle size of 1000 ⁇ m or more refer to granules remained on a 1000 ⁇ m (16 mesh) screen after sieving by using the screen.
  • the content of granules having a particle size of 1000 ⁇ m or more is preferably not more than 8 weight %, and more preferably not more than 5 weight %.
  • the content of granules having a particle size of 350 to 1000 ⁇ m is preferably not less than 40 weight %, and more preferably not less than 40 to 74 weight % in view of the effects of the invention and discoloration during storage. It is also preferable in view of discoloration during storage that the content of granules having a particle size of 500 to 1000 ⁇ m is not less than 40 weight %.
  • the method of adjusting granules to the particle size within the invention includes a well known method such as a method of crushing larger particles using a commercial dresser or a method of sieving using a screen.
  • a commercial dresser There are hammer mill type, roll mill type or screen mill type commercial dressers.
  • a screen of not more than 1.2 mm is preferably used, and a screen of 0.8 to 1.2 mm is more preferably used.
  • the granular processing composition of the invention can be obtained by using any of the well-known processes such as the processes of a fluidized-layer granulation, a stirring granulation, a rolling granulation, an extrusion granulation and a compression granulation.
  • the drying weight reduction of the solid composition in the invention is preferably 0.5-5 weight %, and more preferably 0.8-2 weight % in view of the effects of the invention.
  • the drying weight reduction referred to herein is a weight variation amount calculated from the weight reduced, which is measured under circumstances of 25°C and 40%RH after the composition is heated at 50°C to a constant weight which is measured with a commercial electronic moisture meter.
  • a wet granulating method is preferable which is carried out in the presence of a solvent.
  • the solvent used in the wet granulating method is preferably a polar solvent such as alcohol, acetone, acetonitrile or water or a mixture thereof, and more preferably water.
  • the addition amount of the solvent is preferably 1 to 20 weight %, and more preferably 3 to 10 weight % based on the total weight of material used. When the amount of the solvent is less than 1 weight %, the granulation is not completed, and when the amount of the solvent exceeds 20 weight %, the granulation requires a longer time and granule properties are deteriorated during the granulation.
  • the solid processing tablet whose manufacture is facilitated by the invention may be in any form according to the intended use, but is preferably in disk form in view of ease of producibility or processability.
  • the solid processing tablet is produced by well known compressors.
  • the compressors for producing the tablets include a hydraulic press machine, a single tableting machine, a rotary tableting machine and a briqueting machine can be used.
  • the developing agent used in the invention includes a color developing agent and a black-and-white developing agent.
  • the invention is noticeably effected using a p-phenylenediamine color developing agent.
  • R 1 and R 2 may be the same or different, and independently represent a substituted or unsubstituted alkyl group.
  • R 3 represents a hydrogen atom, a halogen atom, an unsubstituted amino group, a hydroxyl group, an alkylamino group, an alkyl group, an alkoxy group, an amido group, a sulfonamide group, an alkoxycarbonylamino group, a ureido group or a sulfamoylamino group.
  • R 4 through R 11 may be the same or different, and independently represent a hydrogen atom, a halogen atom, an unsubstituted amine group, a nitro group, a hydroxyl group, a cyano group, an alkyl group, an alkylamino group, an alkoxy group, an amido group, a sulfonamide group, a carbamoyl group, an alkoxycarbonylamino group, a ureido group, a sulfamoylamino group, a sulfonyl group, a carboxyl group or a sulfo group.
  • R 12 represents a hydrogen atom, a halogen atom, an unsubstituted amine group, a hydroxyl group, an alkylamino group, an alkyl group, an alkoxy group, an amido group, a sulfonamide group, an alkoxycarbonylamino group, a ureido group or a sulfamoylamino group.
  • the alkyl group represented by R 1 , R 2 and R 3 includes a straight-chained or branched alkyl group having preferably 1 to 6 carbon atoms, which may have a substituent.
  • the preferable substituent includes an alkenyl group, an alkinyl group, an aryl group, a nitro group, a halogen atom, an unsubstituted amine group, a hydroxyl group, a cyano group, an alkylamino group, an alkoxy group, an amido group, a sulfonamide group, a carbamoyl group, an alkoxycarbonylamino group, a ureido group, a sulfamoylamino group, a sulfonyl group, a carboxyl group and a sulfo group.
  • the alkenyl group as the substituent includes a vinyl group and an allyl group
  • the alkinyl group includes an ethenyl group
  • the aryl group includes a phenyl group, a tolyl group and a naphthyl group
  • the halogen atom includes a fluorine atom, a chlorine atom and a bromine atom.
  • the alkylamino group includes an alkylamino group having 1 to 16 carbon atoms, and preferably 1 to 6 carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a N,N-dimethylamino, N,N-diethylamino or N-butylamino group.
  • a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a N,N-dimethylamino, N,N-diethylamino or N-butylamino group.
  • the alkoxy group includes an alkoxy group having 1 to 16 carbon atoms, and preferably 1 to 6 carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a methoxy, ethoxy, 2-methoxyethoxy, 2-hydoxyethoxy, 2-hydoxybutoxy and 2-methanesulfonylethoxy group.
  • a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a methoxy, ethoxy, 2-methoxyethoxy, 2-hydoxyeth
  • the amido group includes an amido group having 1 to 16 carbon atoms, and preferably 1 to 6 carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including an acetoamido, 2-methoxypropionamido and pentanoylamido group.
  • a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including an acetoamido, 2-methoxypropionamido and pentanoylamido group.
  • the sulfonamido group includes a sulfonamido group having 1 to 16 carbon atoms, and preferably 1 to 6 carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a methanesulfonamido and benzenesulfonamido group.
  • a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a methanesulfonamido and benzenesulfonamido group.
  • the carbamoyl group includes a carbamoyl group having 1 to 16 carbon atoms, and preferably 1 to 6 carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a carbamoyl, N,N-dimethylcarbamoyl, N-ethylcarbamoyl and N-butylcarbamoyl group.
  • a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a carbamoyl, N,N-dimethylcarbamoyl, N
  • the ureido group includes a ureido group having 1 to 16 carbon atoms, and preferably 1 to 6 carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a ureido, methylureido and N,N-diethylureido group.
  • a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a ureido, methylureido and N,N-diethylureido group.
  • the sulfamoylamino group includes a sulfamoylamino group having 0 to 16 carbon atoms, and preferably 0 to 6 carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a sulfamoylamino, dimethylsulfamoylamino and dipropylsulfamoylamino group.
  • a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a sulfamoylamino, dimethylsulfam
  • the sulfonyl group includes a sulfonyl group having 1 to 16 carbon atoms, and preferably 1 to 6 carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a methanesulfonyl and methanesulfonyl group.
  • a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a methanesulfonyl and methanesulfonyl group.
  • R 4 through R 11 may be the same or different, and independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkyl group, a cycloalkyl group, an amino group, an alkylamino group, an alkoxy group, an amido group, a sulfonamide group, a carbamoyl group, an alkoxycarbonylamino group, a ureido group, a sulfamoylamino group, a sulfonyl group, a carboxyl group or a sulfo group.
  • the halogen atom includes a fluorine atom, a chlorine atom and a bromine atom.
  • the alkyl group includes a straight-chained or branched alkyl group having 1 to 16 carbon atoms, and preferably 1 to 6 carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a methyl, ethyl, propyl, isopropyl, t-butyl, hydroxymethyl, methanesulfonamidomethyl, 2-hydroxyethyl, 3-hydroxypropyl, benzyl, 2-methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-me
  • the cycloalkyl group may have 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and may have the same substituents as specified above for the alkyl group.
  • the alkylamino group includes an alkylamino group having 1 to 16 carbon atoms, and preferably 1 to 6 carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a N,N-dimethylamino, N,N-diethylamino or N-butylamino group.
  • a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a N,N-dimethylamino, N,N-diethylamino or N-butylamino group.
  • the alkoxy group includes an alkoxy group having 1 to 16 carbon atoms, and preferably 1 to 6 carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a methoxy, ethoxy, 2-methoxyethoxy, 2-hydoxyethoxy, 2-hydoxybutoxy and 2-methanesulfonylethoxy group.
  • a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a methoxy, ethoxy, 2-methoxyethoxy, 2-hydoxyeth
  • the amido group includes an amido group having 1 to 16 carbon atoms, and preferably 1 to 6 carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including an acetoamido, 2-methoxypropionamido and pentanoylamido group.
  • a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including an acetoamido, 2-methoxypropionamido and pentanoylamido group.
  • the sulfonamido group includes a sulfonamido group having 1 to 16 carbon atoms, and preferably 1 to 6 carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a methanesulfonamido and benzenesulfonamido group.
  • a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a methanesulfonamido and benzenesulfonamido group.
  • the carbamoyl group includes a carbamoyl group having 1 to 16 carbon atoms, and preferably 1 to 6 carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a carbamoyl, N,N-dimethylcarbamoyl, N-ethylcarbamoyl and N-butylcarbamoyl group.
  • a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a carbamoyl, N,N-dimethylcarbamoyl, N
  • the alkoxycarbonylamino group includes an alkoxycarbonylamino group having 1 to 16 carbon atoms, and preferably 1 to 6 carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a methoxycarbonylamino, ethoxycarbonylamino and butoxycarbonylamino group.
  • a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a methoxycarbonylamino, ethoxycarbonylamino and butoxycarbonylamino group.
  • the ureido group includes a ureido group having 1 to 16 carbon atoms, and preferably 1 to 6 carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a ureido, methylureido and N,N-diethylureido group.
  • a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a ureido, methylureido and N,N-diethylureido group.
  • the sulfamoylmino group includes a sulfamoylmino group having 0 to 16 carbon atoms, and preferably 0 to 6 carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a sulfamoylmino, dimethylsulfamoylmino and dipropypsulfamoylmino group.
  • a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a sulfamoylmino, dimethylsulfam
  • the sulfonyl group includes a sulfonyl group having 1 to 16 carbon atoms, and preferably 1 to 6 carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a methanesulfonyl and ethanesulfonyl group.
  • a substituent such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a methanesulfonyl and ethanesulfonyl group.
  • the above color developing agents are usually used in the form of hydrochloride, sulfate or p-toluenesulfonic acid salt.
  • the example of the black-and-white developing agent includes phenidone, hydroquinone, metol, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone and hydroquinone monosulfonic acid.
  • the alkali agent used in the invention is a compound giving pH 8 or more in its aqueous solution.
  • the preferable example includes sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfo-salicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfo-salicylate).
  • Sodium carbonate and sodium bicarbonate are especially preferable.
  • the solid processing composition whose manufacture is facilitated by the invention may optionally contain a chelating agent, a development accelerating agent, a development inhibitor (halides), a fluorescent brightening agent or a preservative as usually used in a developer.
  • the preservative includes a sulfite (sodium sulfite or potassium sulfite), a bisulfite (sodium bisulfite or potassium bisulfite), a metabisulfite (sodium metabisulfite orpotassium metabisulfite) and a hydroxylamine derivative.
  • the solid developing composition preferably contains a compound represented by Formula (H) or (B).
  • the invention is more effected by the above compound.
  • the solid developing composition containing the above compound shows improved storage stability, strength, stable photographic properties and prevention of fog.
  • the solid processing composition contain a hydroxyamine compound represented by Formula (H).
  • the granular processing composition containing a developing agent is obtained by mixing the developing agent with the hydroxyamine compound and then granulating the mixture.
  • the content in the granules containing the compound of granules having a particle size of not less than 1000 ⁇ m is preferably not more than 10 weight %, and the content in the granules containing the compound of granules having a particle size of 350 to 1000 ⁇ m is also preferably 40 to 74 weight %.
  • R 21 and R 22 independently represent a hydrogen atom or a substituted or unsubstituted alkyl group.
  • the compound represented by Formula (H) is preferably a compound represented by Formula (H') in view of the invention.
  • L represents a straight chained or branched, alkylene group having 1 to 10 carbon atoms, which may have a substituent, and preferably 1 to 5 carbon atoms.
  • the example includes a methylene, ethylene, trimethylene and propylene group, and the substituent includes a carboxyl group, a sulfone group, a phosphone group, a phosphinic acid residue, a hydroxy group and an ammonio group which may have an alkyl group having 1 to about 5 carbon atoms.
  • A represents a carboxyl group, a sulfone group, a phosphone group, a phosphinic acid residue, a hydroxy group, an amino group which may have an alkyl group having 1 to 5 carbon atoms, an ammonio group which may have an alkyl group having 1 to 5 carbon atoms, a carbamoyl group which may have an alkyl group having 1 to 5 carbon atoms, a sulfamoyl group which may have an alkyl group having 1 to about 5 carbon atoms and a substituted or unsubstituted alkylsulfonyl group.
  • A-L- represents a carboxymethyl, carboxyethyl, carboxypropyl, sulfoethyl, sulfopropyl, sulfobutyl, phosphonomethyl, phosphonoethyl and hydroxyethyl group.
  • R 23 represents a straight chained or branched, alkyl group having 1 to 10 carbon atoms, which may have a substituent.
  • the substituent includes a carboxyl group, a sulfone group, a phosphone group, a phosphinic acid residue, a hydroxy group and an ammonio group which may have an alkyl group having 1 to 5 carbon atoms, provided that R 23 and L may combine to form a ring.
  • the compounds are usually used in free amine or in the form of hydrochloric acid, sulfate, p-toluenesulfonic acid, oxalic acid, phosphoric acid or acetic acid salt.
  • the compounds represented by Fomula (H) or (H') are preferably solids in view of the objects of the invention. Of these, H-1, H-6, H-17, H-18 and H-25 are especially preferable, and the examples will be given below.
  • Formula (B) R 11 -N(-R 12 )-N(-R 13 )-(R 15 ) n -R 14
  • R 11 , R 12 and R 13 independently represent a substituted or unsubstituted alkyl, aryl or heterocyclic group;
  • R 14 represents a hydroxy group, a hydroxyamino group or a substituted or unsubstituted alkyl, aryl, heterocyclic, alkoxy, aryloxy, carbamoyl or amino group.
  • the heterocyclic group includes a saturated or unsaturated 5- or 6-membered cyclic group;
  • the preferable example of compounds represented by Formula (B) includes (B-1) through (B-33) on pages 40 to 43 of Japanese Patent O.P.I. Publication No. 4-86741/1992 and (1) through (56) on pages 4 to 6 of Japanese Patent O.P.I. Publication No. 3-33846/1991.
  • the developing composition of the invention may contain an alkali halide such as potassiun iodide or an organic antifoggant, a nitrogen-containing heterocyclic compound such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolidine or adenine.
  • an alkali halide such as potassiun iodide or an organic antifoggant
  • a nitrogen-containing heterocyclic compound such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole,
  • the developing composition of the invention preferably contain a triadinylstylbene fluorescent brightening agent.
  • the fluorescent brightening agent is preferably a compound represented by the following Formula (E), wherein X 2 , X 3 , Y 1 and Y 2 independently represent a hydroxy group, a halogen atom such as chlorine or bromine, an alkyl group, an aryl group, or -OR 25 in which R 21 and R 22 independently represent a hydrogen atom, an alkyl group (which may have a substituent), or an aryl group (which may have a substituent), R 23 and R 24 independently represent an alkylene group (which may have a substituent), and R 25 represents a hydrogen atom, an alkyl group (which may have a substituent) or an aryl group (which may have a substituent); and M represents a cation.
  • E Triadinylstylbene fluorescent brightening agent
  • the groups or substituents thereof in Formula (E) is the same as those described on pages 16 and 17 of Japanese Patent O.P.I. Publication No. 4-118649/1992.
  • the examples of the compounds are preferably compounds represented by [Chemical 8] through [Chemical 16] of Japanese Patent O.P.I. Publication No. 5-119454/1993. These compounds can be synthesized by the conventional method. Of these compounds the compounds especially preferably used are E-4, E-24, E-34, E-35, E-36, E-37 and E-41.
  • the developing composition of the invention may contain an auxiliary developing agent such as metol, phenidone, N,N-diethyl-p-aminophenol hydrochloride or N,N,N',N''-tetramethyl-p-phenylenediamine hydrochloride, or additives such as an anti-staining agent, an anti-sludging agent and an interlayer accelerating agent.
  • an auxiliary developing agent such as metol, phenidone, N,N-diethyl-p-aminophenol hydrochloride or N,N,N',N''-tetramethyl-p-phenylenediamine hydrochloride
  • additives such as an anti-staining agent, an anti-sludging agent and an interlayer accelerating agent.
  • the color or black-and-white developing composition of the invention preferably contains a chelating agent (especially, exemplified compounds K-1 through K-22) represented by the following Formula (K) which is described on described on pages 16 and 17 of Japanese Patent O.P.I. Publication No. 4-118649/1992.
  • a chelating agent especially, exemplified compounds K-1 through K-22
  • Formula (K) A 1 -R 1 -N(-R 2 -A 2 )-E-N(-R 3 -A 3 )-R 4 -A 4
  • K-2, K-9, K-12, K-13, K-17 and K-19 are preferable, and K-2 and K-9 are especially preferable.
  • the solid developing composition of the invention contains at least one selected from compound represented by the following Formula (D).
  • Formula (D) R 1 -CON(-R 2 )-L 1 -COOM wherein R 1 represents an alkyl group; R 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; L 1 represents an alkylene group having 1 to 5 carbon atoms; and M represents a hydrogen atom, an alkali metal atom or NH 4 .
  • R 1 represents a straight-chained or branched, substituted or unsubstituted, saturated or unsaturated aliphatic group having preferably 3 to 30 carbon atoms
  • R 2 represents a hydrogen atom or a straight-chained or branched, substituted or unsubstituted, saturated or unsaturated aliphatic group having 1 to 5 carbon atoms, preferably a hydrogen atom or a methyl, ethyl, propyl, butyl or amyl group and more preferably a methyl group
  • L 1 represents a straight-chained or branched, substituted or unsubstituted, alkylene or alkenylene group having 1 to 5 carbon atoms, preferably a methylene, ethylene, propylene, butylene, carboxymethylmethylene, carboxymethylethylene or carboxyethylethylene group and more preferably an ethylene group
  • the substituent includes a carboxymethyl, carboxyethyl, carboxypropyl,
  • the content of the above compounds in the tablet composition is 0.1 to 5.0 wt%, and preferably 0.3 to 3.0 wt% based on the total weight of the tablet composition.
  • the solid processing composition of the invention containing saccharides shows more markedly the effects of the invention.
  • the saccharides in the invention refer to monosaccharides, polysaccharides in which monosaccharides bind through a glycoside bondage or derivatives thereof.
  • Monosaccharides refer to as a polyhydroxy aldehyde, polyhydroxy ketone or their derivatives such as reduced derivatives, oxidized derivatives, deoxy derivatives, amino derivatives or thio derivatives. Most of them are represented by the general formula C n H 2n O n .
  • the monosaccharides in the invention include derivatives derived from saccharide skeleton represented by the above formula.
  • the preferable are sugar alcohols having a primary or secondary alcohol group to which an aldehyde or ketone group of saccharides is reduced, and hexitol having six carbon atoms is especially preferable.
  • Polysaccharides include celluloses, starches or glycogens.
  • the celluloses include derivatives such as cellulose ethers in which all or a part of hydroxy group are etherified, starches include maltose or dextrins that starches are hydrolyzed to various decomposition compounds.
  • Celluloses may be in an alkali salt form in view of solubility.
  • celluloses or dextrins are preferably used, and dextrins are more preferably used.
  • B-(66) through (85) are preferably used, and B-(74) through (85) are more preferably used.
  • D-(21) through (64) are preferably used, and compounds, D-(21) through (49) are more preferably used.
  • the content of the saccharide in the solid color developing composition of the invention is preferably 0.5 to 30 wt%, and more preferably 1.0 to 20 wt%.
  • a granule color developing composition and a tablet color developing composition were prepared according to the following procedures.
  • Expansion Degree of Tablets (%) (thickness after storage (mm)- thickness (mm) before storage) ⁇ 100 / thickness (mm) before storage
  • the solid processing composition containing granules having a particle size exceeding 1000 ⁇ m in an amount of not less than 10 wt% shows greater deviation in the content of a developing agent and greater expansion during storage of tablet samples.
  • the solid processing composition of the invention containing granules having a particle size within the range of the invention shows less deviation in the content of the developing agent and less expansion during storage of tablet samples, giving excellent handling properties.
  • a tablet color developing composition were prepared according to the following procedures.
  • Example 2 The procedures were carried out in the same manner as in Example 2, except that Exemplified Compound C-1, C-15, C-17, C-18 or C-19 was used instead of the color developing agent used in Example 2. The evaluation was out in the same manner as in Example 2. The results were the same as Example 2.
  • a tablet color developing composition were prepared according to the following procedures.
  • the composition containing not less than 40wt% of granules having a particle size of 350 to 1000 ⁇ m shows improved results in deviation of developing agent content and in expansion of tablets.
  • the composition containing not less than 40wt% of granules having a particle size of 500 to 1000 ⁇ m further prevents coloration during storage in addition to the above effects.
  • a tablet black-and-white developing composition were prepared according to the following procedures.
  • Example 1 The above obtained granule and tablet samples were evaluated in the same manner as in Example 1. The results showed 10 % greater expansion than that of tablet samples in Example 4, but the same deviation as that of Example 4 in the developing agent content.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (8)

  1. Verfahren zur Herstellung einer Entwicklungszusammensetzung für ein lichtempfindliches photographisches Silberhalogenid-Aufzeichnungsmaterial in folgenden Stufen:
    Granulieren einer Entwicklerverbindung zur Zubereitung eines ersten die Entwicklerverbindung enthaltenden Granulats, Granulieren eines alkalischen Mittels zur Zubereitung eines zweiten das alkalische Mittel enthaltende Granulats und Vermischen des ersten Granulats mit dem zweiten Granulat, wobei der Gehalt an Körnchen einer Teilchengröße von 1000 µm oder mehr (JIS) in dem ersten Granulat nicht mehr als 10 Gew.-% auf der Basis des Gesamtgewichts des ersten Granulats und der Gehalt an Körnchen einer Teilchengröße von 1000 um oder mehr (JIS) in dem zweiten Granulat nicht mehr als 10 Gew.-% auf der Basis des Gesamtgewichts des zweiten Granulats betragen.
  2. Verfahren nach Anspruch 1, wobei der Gehalt an Körnchen einer Teilchengröße von 350 - 1000 µm in den ersten und zweiten Granulaten nicht weniger als 40 Gew.-% beträgt.
  3. Verfahren nach Anspruch 1, wobei der Gehalt an Körnchen einer Teilchengröße von 350 - 1000 µm in den ersten und zweiten Granulaten 40 bis 74 Gew.-% beträgt.
  4. Verfahren nach Anspruch 1, wobei der Gehalt an Körnchen einer Teilchengröße von 500 - 1000 um in den ersten und zweiten Granulaten nicht weniger als 40 Gew.-% beträgt.
  5. Verfahren nach Anspruch 1, wobei das Mischungsverhältnis erstes Granulat/zweites Granulat 1/1 bis 1/20 beträgt.
  6. Verfahren nach Anspruch 1, wobei die Entwicklerverbindung aus einer p-Phenylendiaminfarbentwicklerverbindung besteht.
  7. Verfahren nach Anspruch 1, wobei das alkalische Mittel aus einem Alkalimetallcarbonat besteht.
  8. Verfahren nach Anspruch 1, bei welchem das erste Granulat und das zweite Granulat nach dem Vermischen zu einer Tablette formgepreßt werden.
EP19950304013 1994-06-14 1995-06-09 Entwicklungsgranulat oder -tablette für photographische lichtempfindliche Silberhalogenidmaterialien und Verfahren zu dessen Herstellung Expired - Lifetime EP0691571B1 (de)

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JP132135/94 1994-06-14

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JP3743164B2 (ja) * 1998-06-12 2006-02-08 コニカミノルタホールディングス株式会社 ハロゲン化銀写真感光材料用固体処理剤の製造方法

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DE3830023A1 (de) 1988-09-03 1990-03-15 Agfa Gevaert Ag Granulierter, farbfotografischer entwickler und seine herstellung
DE3830022A1 (de) 1988-09-03 1990-03-15 Agfa Gevaert Ag Granulierter, farbfotografischer entwickler und seine herstellung
JP2663223B2 (ja) 1991-05-01 1997-10-15 コニカ株式会社 ハロゲン化銀写真感光材料用自動現像機
JP3038415B2 (ja) 1991-10-21 2000-05-08 コニカ株式会社 ハロゲン化銀カラー写真感光材料用発色現像処理錠剤
JP2700841B2 (ja) 1991-11-20 1998-01-21 コニカ株式会社 ハロゲン化銀カラー感光材料処理用錠剤及びその製造方法

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