EP0563571A2 - Festes Bleichmittel für farbphotographische lichtempfindliche Silberhalogenidmaterialien und Verarbeitungsverfahren dafür - Google Patents

Festes Bleichmittel für farbphotographische lichtempfindliche Silberhalogenidmaterialien und Verarbeitungsverfahren dafür Download PDF

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Publication number
EP0563571A2
EP0563571A2 EP19930102922 EP93102922A EP0563571A2 EP 0563571 A2 EP0563571 A2 EP 0563571A2 EP 19930102922 EP19930102922 EP 19930102922 EP 93102922 A EP93102922 A EP 93102922A EP 0563571 A2 EP0563571 A2 EP 0563571A2
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EP
European Patent Office
Prior art keywords
group
independently represent
hydrogen atom
ammonium
alkali metal
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EP19930102922
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English (en)
French (fr)
Inventor
Yutaka Ueda
Hiroshi Yamashita
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Konica Minolta Inc
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Konica Minolta Inc
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Priority claimed from JP04073394A external-priority patent/JP3084119B2/ja
Priority claimed from JP21344692A external-priority patent/JPH0635151A/ja
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of EP0563571A2 publication Critical patent/EP0563571A2/de
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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
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes

Definitions

  • This invention relates to a processing chemical for silver halide color photographic light sensitive materials and the processing method thereof, particularly, to a solid chemical for bleaching silver halide color photographic light sensitive materials, which is excellent in both solubility and bleaching characteristics, and to a method for processing silver halide color photographic light sensitive materials, which is suitable for protecting global environment and keeping labor safety and hygiene.
  • the processing steps for silver halide color photographic light sensitive materials are basically comprised of a color developing step and a desilvering step.
  • the desilvering step is comprised of a bleaching step and a fixing step or a bleach-fixing step.
  • a rising step, a stabilizing step and so forth may be added as the additional processing steps.
  • Silver halides exposed to light are reduced to be silver in a color developing step and, at the same time, an aromatic primary amine developing agent duly oxidized form a dye upon reacting with a coupler.
  • the reduced silver is oxidized in the color developing step and is then dissolved out in the form of silver ions into a processing solution.
  • the method of regenerating an overflow has such a defect that a space for a stock tank or the like is needed and photofinishers have to carry out complicated operations.
  • this method is difficult to introduce into small-scaled photofinishers such as on-site photofinishers (so-called mini-labs) who are increasing in recent years.
  • the method of replenishing a small amount of a concentrated-solution is satisfactorily suitable to the small-sized photofinishers such as mini-labs, because the space can be saved and any extra apparatus cannot be needed.
  • this method also has some defects.
  • JP OPI Publication discloses a technique for granulating a bleacher.
  • this technique has such a defect that there is a high possibility to deteriorate the solubility of the granulated bleacher when aging it in storage or there is an apprehension that workers' health may be affected by flying up the fine powder of the granulated bleacher when dissolving it.
  • JP OPI Publication No. 51-61837/1976 proposes a tablet-shaped processing chemical.
  • the tablet-shaped chemicals have such an inherent defect that the solubility thereof is inferior to those of granulated chemicals.
  • this patent discloses a technique for containing an expansion-cracking aqueous colloid in a tablet-shaped chemical, for the purpose of enhancing the solubility of a tablet to water.
  • the macromolecular polymerized colloid was proved that the bleaching characteristics are deteriorated in the current rapid-processing conditions. It has, therefore, been difficult that any conventional techniques have been difficult to realize any solid chemicals excellent in solubility and having rapidly bleaching characteristics.
  • Another object of the invention is to provide a solid bleaching chemical excellent in bleaching function.
  • a further object of the invention is to provide a processing technique suitable for maintaining global environment.
  • a still further object of the invention is to provide a processing technique suitable for labor safety and hygiene.
  • A1 to A4 may be the same with or the different from each other and represent each a hydrogen atom, a hydroxy group, -COOM, -PO3(M1)2, -CH2COOM2, -CH2OH or a lower alkyl group, provided that at least one of A1 to A4 represents -COOM, -PO3(M1)2 or -CH2COOM2; and M, M1 and M2 represent each a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group.
  • A11 to A14 may be the same with or the different from each other and represent each -CH2OH, -COOM3 or -PO3(M4)2; M3 and M4 represent each a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group; X represents an alkylene group having 2 to 6 carbon atoms or -(B1O) n -B2- in which n is an integer of 1 to 8 and B1 and B2 may be the same with or the different from each other and represent each an alkylene group having 1 to 5 carbon atoms.
  • A21 to A24 represent may be the same with or the different from each other and represent each -CH2OH, -COOM5 or -PO3(M6)2; M5 and M6 represent each a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group;
  • X1 represents a straight-chained or branched alkylene group having 2 to 6 carbon atoms, a saturated or unsaturated organic group capable of forming a ring or -(B11O) n5 -B12- in which n is an integer of 1 to 8 and B11 and B12 may be the same with or the different from each other and represent each an alkylene group having 1 to 5 carbon atoms; and n1 to n4 is an integer of one or more and may be the same with or the different from each other.
  • R1 and R2 represent each a hydrogen atom, a substituted or unsubstituted alkyl or aryl group
  • L represents either one of the following formulas, wherein Y1 to Y3 represent each an alkylene or arylene group; X2 and X3 represent each an oxygen atom or a sulfur atom; and R3 to R7 represent each a hydrogen atom, an alkyl group or an aryl group.
  • R1 to R3 represent each a hydrogen atom, a substitutable alkyl or aryl group; L is synonymous with the L denoted in the foregoing Formula (A-IV); and W represents a divalent linking group.
  • R1 to R3 and R6 to R9 represent each a hydrogen atom or a substitutable alkyl or aryl group
  • R4 and R5 represent each a hydrogen atom, a halogen atom, a cyano group, a nitro group, an acyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, a sulfonyl group, a sulfinyl group or a substitutable alkyl or aryl group, provided, R4 and R5 may be associated so as to form a 5-membered or 6-membered ring;
  • A represents a carboxy group, a phosphono group, a sulfo group, a hydroxy group or an alkyl metal salt or ammonium salt thereof;
  • Y represents an alkylene group or an arylene group, provided, Y may have a substituent; and t and
  • X2-A2-COOM2 wherein X2 represents a halogen atom, an amino group, a hydroxy group, a methoxy group, -COOM2 or -SO3M2; A2 represents an alkylene, alkenylene or arylene group which may form a saturated or unsaturated ring, provided, A2 may have a substituent; and M2 represents a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group.
  • A3 represents an alkylene, alkenylene or arylene group which may form a saturated or unsaturated ring, provided, A3 may have a substituent; and M3 represents a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group.
  • the above-mentioned solid bleaching chemical is desirable to be a tablet consisting of one part.
  • the ratio of the ammonium ions thereof to the whole cation thereof is to be preferably not more than 50 mol% and more preferably not more than 20 mol%.
  • the above-mentioned solid bleaching chemical preferably contains a carbonate or a bicarbonate.
  • the method of processing the silver halide color photographic light sensitive material relating to the invention is characterized in that the above-mentioned solid bleaching chemicals are used when color development of the silver halide color photographic light sensitive materials is carried out, followed by bleaching or bleach-fixing treatment.
  • the compounds represented by the above-given Formula (A-I) can be synthesized in any ordinary synthesizing methods detailed in, for example, JP OPI Publication Nos. 63-267750/1988, 63-267751/1988, 2-115172/1990 and 2-295954/1990.
  • those desirably applicable to the invention include the exemplified compounds (A-I-1), (A-I-2), (A-I-13) and (A-I-15).
  • the alkylene groups represented by X include, for example, the groups of ethylene, propylene or butylene.
  • the alkylene groups represented by B1 and B2 include, for example, methylene, ethylene and trimethylene. These alkylene groups may also have a substituent including, for example, a lower alkyl group such as a methyl group, an ethyl group, or a hydroxy group.
  • the particularly desirable compounds include, for example, (A-II-1), (A-II-3) and (A-II-14).
  • the alkylene groups represented by B11 and B12 include, for example, those of methylene, ethylene and trimethylene. These alkylene groups may have a substituent including, for example, a lower alkyl group such as a methyl group and an ethyl group, and a hydroxy group.
  • the particularly desirable compounds include, for example, (A-III-1), (A-III-2), (A-III-6), (A-III-35), (A-III-36), (A-III-37) and (A-III-38).
  • the alkyl groups represented by R1 and R2 include, for example, those of the straight-chained, the branched and the cyclic, each having 1 to 10 carbon atoms and, among them, a methyl group and an ethyl group are particularly desirable.
  • the aryl groups represented by R1 and R2 include, preferably, a phenyl group. When R1 and R2 represent each an alkyl or aryl group, each of these groups may have a substituent.
  • R1 and R2 include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkinyl group, an alkoxy group, an aryl group, a substituted amino group, an acylamino group, a sulfonylamino group, a ureido group, a urethane group, an aryloxy group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfo group, a carboxy group, a phosphono group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acyloxy group, a carbonamido group, a sul
  • the alkylene groups represented by U1 through Y3 include, for example, a methylene group, an ethylene group or a propylene group.
  • the arylene groups represented thereby include, for example, a phenylene group.
  • Each of the alkylene groups and arylene groups represented by Y1 through Y3 may have each a substituent.
  • the substituents applicable thereto include, for example, those given for the substituents to R1 and R2 and, among these substituents, the following substituents are desirable.
  • the desirable ones include, for example, the compounds represented by the following Formula (B-I) or (B-II).
  • R1 and R2 represent each a hydrogen atom, an alkyl group or an aryl group
  • L1 and L2 represent each an alkylene group or an arylene group
  • M represents a hydrogen atom, an alkali metal, an ammonium group or an organic ammonium group.
  • R1 through R4 are each synonymous with R1 and R2 denoted in Formula (B-I); and L1 through L3 and M are each also synonymous with those denoted in Formula (B-I).
  • the particularly desirable ones include, for example, (A-IV-1), (A-IV-8), (A-IV-13), (A-IV-19), (A-IV-20), (A-IV-21) and (A-IV-22).
  • the alkyl and aryl groups each represented by R1 through R3 include the same groups represented by R1 and R2 denoted in Formula (A-IV), and the substituents thereto are the same as mentioned above.
  • the alkylene and arylene groups represented by Y1 through Y3 include the same groups as those represented by Y1 through Y3 denoted in Formula (A-IV), and the substituents thereto are the same as mentioned above.
  • the divalent linking groups represented by W include, desirably, an alkylene group having 2 to 8 carbon atoms (including a cyclohexylene group), an arylene group having 6 to 10 carbon atoms, wherein B1 and B2 represent each an alkylene or arylene group and n is an integer of 1 to 3.
  • Z represents a hydrogen atom, an unsubstituted alkyl or aryl group, or an alkyl or aryl group substituted with -COOM, -SO3M or -OH; and M represents a hydrogen atom, an alkali metal or an ammonium group.
  • the desirable ones include the compounds represented by the following Formula (B-III) or (B-IV).
  • R1 and R2 represent each a hydrogen atom, an alkyl group or an aryl group
  • L1 through L4 represent each an alkylene group or an arylene group
  • M1 and M2 represent each a hydrogen atom, an alkali metal, an ammonium group or an organic ammonium group.
  • R1 through R4 are each synonymous with R1 and R2 each denoted in Formula (B-III)
  • L1 through L4 and M1 and M2 are each synonymous with those denoted in Formula (B-III).
  • the particularly desirable compounds include those represented by (A-V-1), (A-V-4), (A-V-6), (A-V-13), (A-V-16), (A-V-20), (A-V-23), (A-V-26), (A-V-27), (A-V-29), (A-V-30) and (A-V-33).
  • the particularly desirable compounds include (A-VI-1), (A-VI-3), (A-VI-4) and (A-VI-16).
  • the compounds represented by the above-given Formulas (A-I) through (A-VI) may be added in an amount within the range of, preferably 0.01 to 1 mol per liter of a processing solution used and, more preferably 0.05 to 0.6 mols per liter of a processing solution used.
  • the preferable compounds include, Exemplified Compounds (II-3), (II-5), (II-6), (II-10), (II-11), (II-12), (II-16), (II-17), (II-18), (II-19) and (III-4) and, more preferable compounds include (II-5), (II-6) and (II-16). It is one of the desirable embodiments to make combination use of two or more kinds of the compounds represented by these Formulas (II) and (III) for keeping the desired pH of a bleacher.
  • the above-given compounds are used in a form of a sodium salt or a potassium salt and, desirably in the form of a potassium salt.
  • the compounds represented by the foregoing Formulas (II) and (III) may be added in an amount within the range of, desirably 0.05 to 1 mol per liter of a processing solution used and, more desirably 0.1 to 0.6 mols per liter of a processing solution used.
  • the bleachers of the invention are desired not to contain any acetic acid and any acetate substantially.
  • the bleachers of the invention are allowed to contain an excessive amount of chelating agents to the iron ion contained in the bleachers, besides the ferric complex salts of the compounds represented by the foregoing Formulas (A-I), (A-II), (A-III), (A-IV), (A-V) and (A-VI).
  • the free chelating agents are preferably the compounds represented by the foregoing Formulas (A-I), (A-II), (A-III), (A-IV), (A-V) and (A-VI).
  • they may also be the other generally known chelating agents than the above-mentioned chelating agents.
  • the bleachers of the invention may further contain a halide such as ammonium bromide, potassium bromide or sodium bromide, a nitrate such as ammonium nitrate or potassium nitrate, and various kinds of fluorescent whitening agents, defoaming agents or surfactants.
  • a halide such as ammonium bromide, potassium bromide or sodium bromide
  • a nitrate such as ammonium nitrate or potassium nitrate
  • various kinds of fluorescent whitening agents, defoaming agents or surfactants are examples of fluorescent whitening agents, defoaming agents or surfactants.
  • the solid bleaching chemical of the invention is to be comprised of one and single part that is a single kind of a tablet containing the whole component necessary to bleach silver halide color photographic light sensitive materials.
  • the solid bleaching chemical of the invention is also allowed to embody a layered form in which some compounds of the tablet components easily reactable with each other are partitioned off with an inert compound, a film or the like.
  • the ammonium ion proportion of a solid bleaching chemical to the whole cation thereof is preferably not more than 50 mol% and, more preferably, not more than 20 mol%, from the viewpoints of the aging preservation of the solid bleaching chemical and the odor prevention when the bleachers are dissolved to be a processing solution.
  • the solubility thereof can further be improved.
  • the solid bleaching chemical relating to the invention are granulated in advance of preparing them, it is preferable to granulate the compounds represented by Formulas (II) and (III) and a carbonate separately.
  • the color developers applicable to the processing methods relating to the invention are desired to contain a paraphenylene diamine type color developing agent.
  • the typical exemplified compounds thereof include (C-1) through (C-16) given in JP O.P.I. Publication No. 4-86741/1992, pp.26 to 31; (1) through (8) given in JP OPI Publication No. 61-289350/1986, pp.29 to 31; and (1) through (26) given in JP OPI Publication No. 3-246543/1991, pp.5 to 9; and, more desirably, (C-1) and (C-3) given in JP O.P.I. Publication No. 2-203169/1990; Exemplified Compound (2) given in JP O.P.I. Publication No. 61-289350/1986; and Exemplified Compound (1) given in JP OPI Publication No. 3-246543/1991.
  • the color developers relating to the invention are also allowed to contain a hydroxylamine derivative, a hydrazine derivative or a reducing sugar as a preservative. It is more desirable to make combination use of a sulfite such as sodium sulfite, potassium sulfite or sodium bisulfite. Besides the above, any well-known chelating agents, fluorescent whitening agents, surfactants and halides may also be contained therein.
  • a thiosulfate and a thiocyanate may desirably be used as a principal fixing agent and the both of them can also be used in combination.
  • the fixers are also allowed to contain any well-known pH buffers, chelating agents, sulfites and sulfite-releasable compounds.
  • the proportion of ammonium ions to the whole cation content of a bleacher is to be desirably not more than 50% and, more desirably not more than 20%.
  • the stabilizers relating to the invention can contain formaldehyde. It is, however, desirable to contain formaldehyde by an aldehyde amine condensate such as hexamethylene tetramine, an N-methylol compound, hydroxybenzaldehyde and the derivatives thereof, and a formaldehyde-releasable compound, each in place of formaldehyde.
  • an aldehyde amine condensate such as hexamethylene tetramine, an N-methylol compound, hydroxybenzaldehyde and the derivatives thereof, and a formaldehyde-releasable compound, each in place of formaldehyde.
  • the stabilizers relating to the invention can also contain any well-known chelating agents, surfactant, fluorescent whitening agents and antimolds.
  • the method therefor preferably comprises the steps of adding a solid chemical to a dissolving section provided at a position coming contact with a tank solution, dissolving it in water to be a solution and then replenishing the solution.
  • the automatic processors desirably applicable to the invention are each comprised of a processing tank (so-called a main-tank) for processing a silver halide color photographic light sensitive material and a dissolving section (so-called a sub-tank) for dissolving a solid chemical and each have a structural form in which the processing tank and the dissolving section are connected through and each of the solutions is circulated between the processing tank and the dissolving section by providing with a circulation means.
  • a dissolving device for positively dissolving a solid chemical duly supplied.
  • an automatic processor with a means for detecting the processed quantities of silver halide color photographic light sensitive materials, a device for automatically supplying solid chemicals to the foregoing dissolving section so as to meet the processed quantities of the light sensitive materials and a water replenishing device for carrying out the above-mentioned water replenishments.
  • the conventional hand-working dissolution can substantially be eliminated, so that any operators do not inhale any flying chemical parts in their working time, and their hands, clothes and any equipments around there cannot be contaminated. It is also possible to supply the processing chemicals having an environmental aptitude without using any plastic bottles.
  • the solid chemical called in the invention includes not only a tablet, a granule and powder, but also those packed or coated with a soluble film such as an alkali-soluble or water-soluble film.
  • the powder called in the invention herein is the aggregate of fine crystals.
  • the granule called in the invention is one granulating the powder, which is a granule having a particle size within the range of 50 to 5000 ⁇ m.
  • the tablet in the invention is one obtained by molding powder into a certain shape through compression molding, or one obtained by molding a granule formed in advance into a certain shape through compression molding.
  • the tableted chemicals are desirably used from the viewpoint of remarkably displaying the effects of the invention.
  • a photographic processing chemical can be solidified in any desired means such as that a conc. liquid, fine powdered or granulated photographic processing chemical and a water-soluble binder are kneaded together and are then molded, and that a coated layer is formed on the surface of a temporarily molded photographic processing chemical by spraying a water-soluble binder thereon.
  • a conc. liquid, fine powdered or granulated photographic processing chemical and a water-soluble binder are kneaded together and are then molded, and that a coated layer is formed on the surface of a temporarily molded photographic processing chemical by spraying a water-soluble binder thereon.
  • the desirable tablet preparation processes include, for example, the process in which a powdered solid processing chemical is granulated and is then tableted.
  • This tablet preparation process is improved in solubility and preservability more than in a solid processing chemicals simply prepared by mixing up the solid processing chemical components and then by forming them in a tableting step. Resultingly, this process has the advantage that the photographic characteristics can also be stabilized.
  • the granulation processes for forming tablets it is possible to use any well-known processes such as the processes of a rolling granulation, an extrusion granulation, a compression granulation, a cracking granulation, a stirring granulation, a fluidized-layer granulation and a spray-dry granulation.
  • the average particle size of the resulting granules applicable to the invention is to be within the range of, desirably 100 to 800 ⁇ m and, more desirably 200 to 750 ⁇ m.
  • an average particle size is smaller than 100 ⁇ m or larger than 800 ⁇ m, the chemical components cannot be uniformed or the so-called segregation is produced, when the above-mentioned granules are mixed up and compressed. This is an undesirable phenomenon.
  • the granularity distribution is desirable when not less than 60% of granule particles are within the deviation range of ⁇ 100 to 150 ⁇ m.
  • any one of the known compressors such as a hydraulic press, a single shot tablet machine, a rotary tablet machine and a briquetting machine may be used.
  • the resulting compressed solid processing chemicals can take any forms. It is however desirable that they are cylinder-formed, that is, they are tableted, from the viewpoints of productivity and handling convenience.
  • the tableted processing chemicals can be prepared in any ordinary processes including, for example, those detailed in JP OPI Publication Nos. 51-61837/1976, 54-155038/1979 and 52-88025/1977; and British Patent No. 1,213,808.
  • the granulated processing chemicals can be prepared in any ordinary processes including, for example, those detailed in JP OPI Publication Nos. 2-109042/1990, 2-109043/1990, 3-39735/1991 and 3-39739/1991.
  • the powdered processing chemicals can be prepared in any ordinary processes including, for example, those detailed in JP OPI Publication No. 54-133332/1979; British Patent Nos. 725,892 and 729,862; and German Patent No. 3,733,861.
  • the bulk density of the above-mentioned solid chemical is to be within the range of, preferably 1.0 g/cm3 to 2.5 g/cm3, from the viewpoints of the solubility thereof and the effects of the objects of the invention.
  • the bulk density thereof is higher than 1.0 g/cm3, it is desirable from the viewpoint of the strength of the resulting solidified matters.
  • the bulk density thereof is lower than 2.5 g/cm3, it is desirable from the viewpoint of the solubility of the resulting solidified matters.
  • a solidified processing chemical is of the granulated or the powdered, the bulk density thereof is to be within the range of, preferably, 0.40 to 0.95 g/cm3.
  • a tableted replenishment chemical for bleaching color negatives was prepared in the following manner.
  • Ferric potassium salts of the compounds represented by Formulas (A-I) through (A-VI) shown in Table 1 in an amount of 0.30 mols and 60 g of organic acid represented by Formula (II) or (III) shown in Table 1 were pulverized through an air-jet fine-pulverizer so as to have an average particle size of 10 ⁇ m.
  • the resulting fine powder was granulated through a commercially available fluidized-bed spray granulator at room temperature for about 6 minutes by spraying 2.5 ml of water over the powder and the resulting granules were dried at 65°C for 7 minutes, followed by drying in vacuum at 40°C for 2 hours so as to almost completely remove the moisture of the granules.
  • Potassium bromide in an amount of 40 g and about 30 g of potassium carbonate were pulverized in the same manner as in Procedure (1). Water was sprayed in an amount of 0.5 ml so as to granulate them and the resulting granules were dried at 65°C for 5 minutes, followed by drying in vacuum at 40°C for 2 hours so as to almost completely remove the moisture of the granules.
  • the amount of potassium carbonate was so controlled as to meet the amount of organic acid added in Procedure (1) so that the pH of the resulting tableted chemicals could be controlled to be about 4 when the tablet chemicals were dissolved in water.
  • the granules prepared in the above-mentioned Procedures (1) and (2) were uniformly mixed up together by a mixer for 10 minutes in a room controlled to be 25°C and not higher than 40%RH.
  • the resulting mixture was compression-tableted to make a tablet having a diameter of 3cm by making use of a solidifying tablet machine modified of Tough-Press Collect 1527HU manufactured by Kikusui Mfg. Works, Inc., so that 50 pieces of tablet-shaped replenishment chemicals for color negatives could be prepared by uniformly arranging the mixture.
  • the granules have a bulk density of 0.65 g/cm2, and the tablet chemicals have a bulk density of 1.7 g/cm2.
  • the effects can remarkably be displayed particularly when the tablet-shaped chemicals contain the iron salts of the compounds represented by Formulas (A-I), (A-II) and (A-III).
  • Ferric potassium salt bleacher of the compounds represented by Formula (A-III) shown in Table 1 in an amount of 0.3 mols 30 g of succinic acid (Exemplified Compound II-6) and 35 g of maleic acid (Exemplified Compound II-5) were pulverized through an air-jet fine-pulverizer so as to have an average particle size of 10 ⁇ m.
  • the resulting fine powder was granulated through a commercially available fluidized-bed spray granulator at room temperature for about 6 minutes by spraying 2.5 ml of water over the powder and the resulting granules were dried at 65°C for 7 minutes, followed by drying in vacuum at 40°C for 2 hours so as to almost completely remove the moisture of the granules.
  • Potassium bromide in an amount of 40 g and 50 g of potassium hydrogen carbonate were pulverized in the same manner as in Procedure (1). Water was sprayed in an amount of 0.5 ml so as to granulate them and the resulting granules were dried at 65°C for 5 minutes, followed by drying in vacuum at 40°C for 2 hours so as to almost completely remove the moisture of the granules.
  • the granules prepared in the above-mentioned Procedures (1) and (2) were uniformly mixed up together by a mixer for 10 minutes in a room controlled to be 25°C and not higher than 40%RH.
  • the resulting mixture was compression-tableted to make a tablet having a diameter of 3cm by making use of a solidifying tablet machine modified of Tough-Press Collect 1527HU manufactured by Kikusui Mfg. Works, Inc., so that 50 pieces of tablet-shaped replenishment chemicals for color negatives could be prepared by uniformly arranging the mixture.
  • the tableted chemicals were each prepared in the same manner as before, except that the proportion of ammonium ions to the whole cation of the tableted chemical was adjusted as shown in Table 2 and that the ferric potassium ethylenediamine tetraacetate monohydrate (A-III-35) or ferric potassium 3-propanediamine tetraacetate monohydrate (A-III-36), potassium hydrogen carbonate and potassium bromide were replaced in order by the same mols of ferric ammonium ethylenediamine tetraacetate dihydrate or ferric ammonium 3-propanediamine tetraacetate monohydrate, ammonium hydrogen carbonate and ammonium bromide.
  • Example 1 One thousand mili litre of water was put in a beaker and was then controlled to be 25°C. While water was kept stirred with a magnetic stirrer, 5 pieces of the above-obtained chemicals were put therein and the solubilities thereof were evaluated. On the other hand, 2 pieces of the above-obtained chemicals were aged in a free state at 30°C and 50%RH for 2 weeks and the appearance of the aged chemicals were observed with the eye. The evaluation criteria were the same as in Example 1.
  • Ferric potassium 1,3-propanediamine tetraacetate monohydrate (A-III-36) of 120 g, potassium maleate (II-11) of 66 g and potassium bromide of 40 g were pulverized in the same manner as in Procedure (1) of Example 1, so as to granulate them. Water was sprayed in an amount of 3.0 ml. After granulating them, the resulting granules were dried at 65°C for 7 minutes.
  • Ferric potassium 1,3-propanediamine tetraacetate monohydrate (A-III-36) of 120 g, maleic acid (II-5) of 40 g, potassium bromide of 40 g and potassium carbonate of 60 g were mixed up together and the resulting mixture thereof was then pulverized in the same manner as in Procedure (1) of Example 1, so as to granulate them. Water was sprayed in an amount of 3.0 ml. After granulating them, the resulting granules were dried at 65°C for 7 minutes.
  • Ferric potassium 1,3-propanediamine tetraacetate monohydrate (A-III-36) of 120 g and maleic acid (II-5) of 40 g were pulverized in the same manner as in Procedure (1) of Example 1, so as to granulate them. Water was sprayed in an amount of 2.5 ml. After granulating them, the resulting granules were dried at 65°C for 7 minutes. Besides the above, 40 g of potassium bromide and 50 g of potassium carbonate were pulverized in the same manner so as to granulate them. Water was sprayed in an amount of 0.5 ml. After granulating them, the resulting granules were dried at 65°C for 5 minutes.
  • the tableted chemicals for processing color negative films were each prepared in the following procedures.
  • Developing agent CD-4 (4-amino-3-methyl-N-ethyl- ⁇ -(hydroxy) ethyl aniline sulfate) of 60 g was pulverized through an air-jet fine pulverizer so as to have an average particle size of 10 ⁇ m.
  • the resulting fine powder was granulated by spraying 5.0 ml of water through a commercially available fluidized-bed spray granulator at room temperature for about 7 minutes.
  • the resulting granules were dried at 63°C for 8 minutes.
  • the dried granules were dried again in the vacuum condition at 40°C for 2 hours, so that the moisture therein was almost completely removed.
  • Hydroxylamine sulfate of 60 g was pulverized in the same manner as in Procedure (1) and was then granulated by spraying 2.6 ml of water over them. After completing the granulation, the resulting granules were dried at 65°C for 7 minutes. Next, the resulting dried granules were dried again in the vacuum conditions at 40°C for 2 hours, so that the moisture therein could be almost completely removed.
  • Disodium 1-hydroxyethane-1,1-diphosphonate of 58 g, sodium sulfite of 70 g, potassium carbonate of 618 g, sodium hydrogen carbonate of 30 g, sodium bromide of 6 g and diethylenetriamine pentaacetate of 40 g were each pulverized in the same manner as in Procedure (1).
  • the resulting pulverized matters were uniformly mixed up by a commercially available mixer.
  • the resulting mixture was granulated in the same manner as in Procedure (1) by spraying 200 ml of water over them. After completing the granulation, they were dried at 65°C for 15 minutes. Then, the resulting dried granules were dried again in the vacuum conditions at 40°C for 2 hours, so that the moisture therein could be almost completely removed.
  • the granules prepared each in the above-described Procedures (1) through (3) were uniformly mixed up for 10 minuted by making use of a mixer in a room so controlled as to be 25°C and 40%RH.
  • the resulting mixture was compression-tableted so that the filling amount per tablet could be 5.0 g by a tablet machine, a modified Tough Pressed Collect 1527HU manufactured by Kikusui Mfg. Works, Inc. Thereby 160 pieces of the tableted replenishing chemicals for color developing color negatives were prepared.
  • Ferric potassium 1,3-propanediamine tetraacetate monohydrate (A-III-36) of 237 g, organic acid shown in Table 4 and represented by Formulas (II) and (III), and 1,3-propanediamine tetraacetate of 10 g were each pulverized and then granulated. After completing the granulation upon spraying 5.0 ml of water over them, the resulting granules were dried at 60°C for 7 minutes. Next, the dried granules were dried again in the vacuum conditions at 40°C for 2 hours so that the moisture therein could be almost completely removed.
  • Potassium bromide of 60 g and potassium carbonate of 60 g were each pulverized and granulated in the same manner as in Procedure (1). After completing the granulation upon spraying 1.0 ml of water, the resulting granules were dried at 70°C for 3 minutes. Next, the dried granules were dried again in the vacuum conditions at 40°C for 120 minutes so that the moisture therein was almost completely removed. The amount of the potassium carbonate was adjusted so as to meet the amount of organic acid added in Procedure (5) so that the pH could be constant when the resulting tablets were dissolved in water.
  • the granules prepared each in the above-described Procedures (5) and (6) were uniformly mixed up for 10 minuted by making use of a mixer in a room so controlled as to be 25°C and 40%RH.
  • the resulting mixture was compression-tableted so that the filling amount per tablet could be 6.0 g by a tablet machine, a modified Tough Pressed Collect 1527HU manufactured by Kikusui Mfg. Works, Inc. Thereby 80 pieces of the tableted replenishing chemicals for bleaching color negatives were prepared.
  • Potassium thiosulfate of 950 g, sodium thiocyanate of 2020 g, sodium sulfite of 120 g, potassium carbonate of 150 g and disodium ethylenediamine tetraacetate of 10 g were each pulverized and granulated in the same manner as in Procedure (1). After completing the granulation upon spraying 30.0 ml of water over them, the resulting granules were dried at 65°C for 60 minutes. Next, the resulting dried granules were dried again in the vacuum conditions at 40°C for 480 minutes so that the moisture therein could be almost completely removed.
  • the granules prepared each in the above-described Procedure (8) were uniformly mixed up for 10 minuted by making use of a mixer in a room so controlled as to be 25°C and 40%RH. Next, the resulting mixture was compression-tableted so that the filling amount per tablet could be 13.0 g by a tablet machine, a modified Tough Pressed Collect 1527HU manufactured by Kikusui Mfg. Works, Inc. Thereby 200 pieces of the tableted replenishing chemicals for fixing color negatives were prepared.
  • the granules prepared each in the above-described Procedure (10) were uniformly mixed up for 10 minuted by making use of a mixer in a room so controlled as to be 25°C and 40%RH.
  • the resulting mixture was compression-tableted so that the filling amount per tablet could be 0.2 g by a tablet machine, a modified Tough Pressed Collect 1527HU manufactured by Kikusui Mfg. Works, Inc. Thereby 1060 pieces of the tableted replenishing chemicals for fixing color negatives were prepared.
  • a Konica Color Negative Film Processor CL-KP-50QA was so modified as to be equipped with the following tablet chemical supplying function, a liquid level detecting function and a water supplying function.
  • Fig.1 is a schematic plan view showing one example of the automatic processors relating to the invention, wherein the control mechanism for the color negative film processing unit is schematically illustrated.
  • solidified photographic processing chemical replenishing device 8 When a color negative film is introduced into light sensitive material inlet 13, passing through light sensitive material area detecting sensor 7 and then detecting a certain area thereof, solidified photographic processing chemical replenishing device 8, water replenishing tank 10 and replenishment water supplying means 12 are each operated upon receipt of a signal given from control section 11, so that the solidified photographic processing chemicals and replenishment water for preparing solutions are supplied to each of processing tanks 1, 2, 3 and 5 in a necessary amount, respectively.
  • Fig.2 is a schematic illustration showing one example of solidified photographic processing chemical supplying devices 8 for which the solidified photographic processing chemicals are used in the form of solidified tablets.
  • solidified photographic processing chemical pushing claw 23 Upon receipt of a signal given from light sensitive material area detecting sensor 7 and when control section 11 is operated and solidified photographic processing chemical supplying cam 22 is then operated, solidified photographic processing chemical pushing claw 23 supplies one or some tablets of solidified photographic processing chemicals 24 stored in cartridge 25 into filtering device 21 provided in sub-tank 20 that is a solidified photographic chemical dissolving section of each of processing tanks 1, 2, 3 and 5.
  • Solidified photographic processing chemical 24 duly supplied is gradually dissolved and then supplied into main processing tank 16 by circulation pump 18.
  • the solubility of solidified photographic processing chemical 24 can more be improved when the whole or major parts of the circulating current of processing solution 17, which is being circulated by circulation pump 18 between main processing tank 16 and sub-tank 20, is so constituted as to pass directly through filtering device 21 provided in sub-tank 20.
  • 19 is a thermostat heater; 26 is a pushing spring for compression-keeping solidified photographic processing chemical 24 stored in cartridge 25; 27 is a communicating pipe communicating between main processing tank 16 and sub-tank 20 of each processing tank 1, 2, 3 and 5; and 28 is an overflow outlet.
  • solution level detecting sensor 9 detects the lowered level and sends a signal to control section 11 so as to operate replenishment water supplying means 12, so that replenishment water for compensating the evaporation is supplied up to the regular solution level.
  • solution level detecting sensor 9 detects the regular level and sends a signal to control section 11 so as to stop the operation of replenishment water supplying means 12.
  • the following table shows the standard processing conditions for an automatic processor. Processing step Processing temperature Processing time Color developing 38.0 ⁇ 0.3°C 3min.15sec. Bleaching 38.0 ⁇ 1.0°C 45sec. Fixing - 1 38.0 ⁇ 1.0°C 45sec. Fixing - 2 38.0 ⁇ 1.0°C 45sec. Stabilizing -1 38.0 ⁇ 3.0°C 20sec. Stabilizing -2 38.0 ⁇ 3.0°C 20sec. Stabilizing -3 38.0 ⁇ 3.0°C 20sec. Drying 60°C 60sec.
  • the fixer is replenished into the second tank and the overflow therefrom flows into the first tank.
  • the stabilizer is replenished into the third tank and the overflow therefrom flows into the second and first tanks in order.
  • This system is called a cascade system.
  • the processing solutions used in the automatic processor were prepared in the following procedures.
  • the system was so provided as to put 1 liter of a solution having the same compositions as those of the color developing solution therein and then to introduce the overflow from the reservoir tank into a waste solution collecting tank when 1 liter or more of an overflow is reserved in the tank.
  • Each of 20 pieces of the tableted replenishing chemicals prepared in the above-described procedures were set to the tableted replenishing chemical supplying device provided to the automatic processor in the course of controlling the temperature of the automatic processor.
  • the setting was so arranged as to put one each of the tableted replenishing chemicals into the overflow reservoir tank and, at the same time, to supply 40 ml of warmed replenishing water into the color developing tank, 10 ml thereof into the fixing tank and 80 ml thereof into the stabilizing tank respectively from a warmed water supplying tank, when every 2 rolls of 135 size, 24 exposure film were processed.
  • the light sensitive material samples were exposed wedgewise to light in an ordinary method and were then running-processed. The running processes were continuously carried out until replenishing the amount twice as much as the capacity of the bleaching tank (in 2R).
  • the processed photographic light sensitive materials Of the processed photographic light sensitive materials, the residual silver contents in the maximum color developed area thereof were each measured. Also, the densities of the processed samples were each measured and the Dmin values of the blue and green rays of light (Blue and Green) were each measured. Further, the processed samples were each cut in half and each one of them was processed again in the formula of the following reprocessing solution. The samples were dipped in the processing solution at 35°C for 6 min. 30 sec.
  • Ferric ammonium ethylenediamine tetraacetate monohydrate was added by water to make 1.0 liter and the pH was adjusted with aqueous ammonia to be 6.0.
  • Example 4 The running experiments were tried in the same manner as in Example 4 by making use of the same light sensitive materials as used in Example 4, except that the processing conditions were changed as follows. Processing step Processing temperature Processing time Color developing 38.0 ⁇ 0.3°C 3min.15sec. Bleaching 38.0 ⁇ 1.0°C 45sec. Bleach-fixing 38.0 ⁇ 1.0°C 45sec. Fixing 38.0 ⁇ 1.0°C 45sec. Stabilizing - 1 38.0 ⁇ 3.0°C 20sec. Stabilizing - 2 38.0 ⁇ 3.0°C 20sec. Stabilizing - 3 38.0 ⁇ 3.0°C 20sec. Drying 60°C 60sec.
  • the bleacher and fixer were replenished into a bleaching tank and a fixing tank respectively, and the overflows from the both tanks were flowed into a bleach-fixing tank.
  • the cascade system was also applied in which the stabilizer was replenished into the third tank and the overflow therefrom was flowed into the second tank and then into the first tank in order.
  • the tableted chemicals for processing color paper were prepared in the following procedures.
  • Developing agent CD-3 (4-amino-3-methyl-N-ethyl-N-( ⁇ -methanesulfonamido) ethyl) aniline sulfate) of 100 g was pulverized through an air-jet fine pulverizer so as to have an average particle size of 10 ⁇ m.
  • the resulting fine powder was granulated by spraying 4.5 ml of water through a commercially available fluidized-bed spray granulator at room temperature for about 5 minutes.
  • the resulting granules were dried at 65°C for 8 minutes.
  • the dried granules were dried again in the vacuum condition at 40°C for 2 hours, so that the moisture therein was almost completely removed.
  • Diethylhydroxylamine oxalate of 185 g was pulverized in the same manner as in Procedure (A) and was then granulated by spraying 3.0 ml of water over them. After completing the granulation, the resulting granules were dried at 50°C for 10 minutes. Next, the resulting dried granules were dried again in the vacuum conditions at 40°C for 2 hours, so that the moisture therein could be almost completely removed.
  • Cinopal SFP manufactured by Ciba-Geigy AG
  • 30.0 g sodium sulfite of 3.7 g
  • potassium carbonate 500 g
  • potassium bromide 500 g
  • diethylenetriamine pentaacetate 25 g
  • sodium p-toluenesulfonate 100 g
  • potassium hydroxide of 200 g were each pulverized in the same manner as in Procedure (A).
  • the resulting pulverized matters were uniformly mixed up by a commercially available mixer.
  • the resulting mixture was granulated in the same manner as in Procedure (A) by spraying 200 ml of water over them. After completing the granulation, they were dried at 65°C for 15 minutes. Then, the resulting dried granules were dried again in the vacuum conditions at 40°C for 2 hours, so that the moisture therein could be almost completely removed.
  • the granules prepared each in the above-described Procedures (A) through (C) were uniformly mixed up for 10 minutes by making use of a mixer in a room so controlled as to be 25°C and 40%RH or lower.
  • the resulting mixture was compression-tableted so that the filling amount per tablet could be 5.86 g by a tablet machine, a modified Tough Pressed Collect 1527HU manufactured by Kikusui Mfg. Works, Inc. Thereby 150 pieces of the tableted replenishing chemicals for color paper were prepared.
  • Potassium carbonate of 10 g and sodium 1-hydroxyethane-1,1--diphosphonate of 200 g were pulverized and granulated in the same manners as in Procedure (A). After they were granulated by spraying 1.0 ml of water over them, they were dried at 70°C for 3 minutes. Next, the dried granules were dried again in the vacuum condition at 40°C for 2 hours, so that the moisture therein were almost completely removed.
  • Cinopal SFP manufactured by Ciba-Geigy AG
  • 150 g sodium sulfite of 300 g
  • zinc sulfite septihydrate of 20 g zinc sulfite septihydrate of 20 g
  • ethylenediamine tetraacetate of 150 g were each pulverized and granulated in the same manner as in Procedure (A). After they were granulated by spraying 10.0 ml of water over them, they were dried at 65°C for 5 minutes. Then, the resulting dried granules were dried again in the vacuum conditions at 40°C for 8 hours, so that the moisture therein could be almost completely removed.
  • the granules prepared each in the above-described Procedures (H) and (I) were uniformly mixed up for 10 minutes by making use of a mixer in a room so controlled as to be 25°C and 40%RH or lower.
  • the resulting mixture was compression-tableted so that the filling amount per tablet could be 0.66 g by a tablet machine, a modified Tough Pressed Collect 1527HU manufactured by Kikusui Mfg. Works, Inc. Thereby 1000 pieces of the tableted replenishing chemicals for color paper were prepared.
  • a Konica Color Paper Type QA Processor CL-PP-718 was so modified as to be equipped with a tableted chemical supplying function, a liquid level detecting function and a warm water supplying function. And, the following processing experiments were tried with the above-modified processor.
  • the standard processing conditions for the automatic processor will be given in the table below. Processing step Processing temperature Processing time Color developing 35 ⁇ 0.3°C 45sec. Bleaching 35 ⁇ 1.0°C 20sec. Fixing 33 ⁇ 1.0°C 30sec. Stabilizing - 1 33 ⁇ 3.0°C 30sec. Stabilizing - 2 33 ⁇ 3.0°C 30sec. Drying 72 ⁇ 5.0°C 40sec.
  • Warmed water kept at 35°C of 18 liters was put in the color developing tank of an automatic processor and 314 pieces of tableted replenishing chemicals for color developing color paper were then put therein and dissolved.
  • Color paper prepared in the procedures described in the example given in JP Application No. 3-47516/1991 was exposed wedgewise to light in an ordinary method and was then running-processed in the foregoing processing steps. However, the running processes were carried out continuously until the amount replenished was added as twice as much as the capacity of the bleaching tank (2R).

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP19930102922 1992-02-25 1993-02-25 Festes Bleichmittel für farbphotographische lichtempfindliche Silberhalogenidmaterialien und Verarbeitungsverfahren dafür Withdrawn EP0563571A2 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP04073394A JP3084119B2 (ja) 1992-02-25 1992-02-25 ハロゲン化銀写真感光材料の処理方法
JP73394/92 1992-02-25
JP21344692A JPH0635151A (ja) 1992-07-17 1992-07-17 ハロゲン化銀カラー写真感光材料用固形漂白処理剤およびその処理方法
JP213446/92 1992-07-17

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0591934A1 (de) * 1992-10-05 1994-04-13 Fuji Photo Film Co., Ltd. Photographische Verarbeitungszusammensetzung und photographisches Verarbeitungsverfahren
EP0649057A2 (de) * 1993-10-15 1995-04-19 Fuji Photo Film Co., Ltd. Photograpische Verarbeitungszusammensetzung zugehöriges Verarbeitungsverfahren
EP0664481A2 (de) * 1994-01-19 1995-07-26 Eastman Kodak Company Bleichstarter für farbphotographische Verfahren
EP0667559A1 (de) * 1994-02-15 1995-08-16 Konica Corporation Feste Zusammensetzung zur Behandlung von lichtempfindlichen farbphotographischen Silberhalogenidmaterialien
EP0681217A1 (de) * 1994-04-28 1995-11-08 Konica Corporation Feste photographische Behandlungszusammensetzung zur Entwicklung eines lichtempfindlichen photographischen Silberhalogenidmaterials
GB2293020B (en) * 1993-05-20 1997-08-27 Dow Chemical Co Succinic acid derivative degradable chelants, uses and compositions thereof
US5733342A (en) * 1993-04-22 1998-03-31 Basf Aktiengesellschaft Hydroxamic acids and hydroxamic acid ethers, and the use thereof as complexing agents
EP1455226A1 (de) * 2003-03-03 2004-09-08 Fuji Photo Film Co., Ltd. Festes granuliertes photographisches Verarbeitungsagens und dessen Herstellungsverfahren

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0591934A1 (de) * 1992-10-05 1994-04-13 Fuji Photo Film Co., Ltd. Photographische Verarbeitungszusammensetzung und photographisches Verarbeitungsverfahren
US5733342A (en) * 1993-04-22 1998-03-31 Basf Aktiengesellschaft Hydroxamic acids and hydroxamic acid ethers, and the use thereof as complexing agents
GB2293020B (en) * 1993-05-20 1997-08-27 Dow Chemical Co Succinic acid derivative degradable chelants, uses and compositions thereof
EP0649057A2 (de) * 1993-10-15 1995-04-19 Fuji Photo Film Co., Ltd. Photograpische Verarbeitungszusammensetzung zugehöriges Verarbeitungsverfahren
EP0649057A3 (de) * 1993-10-15 1995-09-20 Fuji Photo Film Co Ltd Photograpische Verarbeitungszusammensetzung zugehöriges Verarbeitungsverfahren.
EP0664481A2 (de) * 1994-01-19 1995-07-26 Eastman Kodak Company Bleichstarter für farbphotographische Verfahren
EP0664481A3 (de) * 1994-01-19 1995-11-22 Eastman Kodak Co Bleichstarter für farbphotographische Verfahren.
EP0667559A1 (de) * 1994-02-15 1995-08-16 Konica Corporation Feste Zusammensetzung zur Behandlung von lichtempfindlichen farbphotographischen Silberhalogenidmaterialien
EP0681217A1 (de) * 1994-04-28 1995-11-08 Konica Corporation Feste photographische Behandlungszusammensetzung zur Entwicklung eines lichtempfindlichen photographischen Silberhalogenidmaterials
US5866310A (en) * 1994-04-28 1999-02-02 Konica Corporation Solid photographic processing composition for developing a silver halide photographic light-sensitive material
EP1455226A1 (de) * 2003-03-03 2004-09-08 Fuji Photo Film Co., Ltd. Festes granuliertes photographisches Verarbeitungsagens und dessen Herstellungsverfahren

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