EP0611986A1 - Feststoffzusammensetzung zur photographischen Verarbeitung eines farbphotographischen lichtempfindlichen Silberhalogenidmaterials - Google Patents

Feststoffzusammensetzung zur photographischen Verarbeitung eines farbphotographischen lichtempfindlichen Silberhalogenidmaterials Download PDF

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Publication number
EP0611986A1
EP0611986A1 EP94102254A EP94102254A EP0611986A1 EP 0611986 A1 EP0611986 A1 EP 0611986A1 EP 94102254 A EP94102254 A EP 94102254A EP 94102254 A EP94102254 A EP 94102254A EP 0611986 A1 EP0611986 A1 EP 0611986A1
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European Patent Office
Prior art keywords
group
tablet
photographic processing
processing
tablets
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EP94102254A
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English (en)
French (fr)
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Ichiro C/O Konica Corporation Tsuchiya
Shigeharu C/O Konica Corporation Koboshi
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Konica Minolta Inc
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Konica Minolta Inc
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Publication of EP0611986A1 publication Critical patent/EP0611986A1/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
    • 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
    • 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

Definitions

  • the present invention relates to a solid photographic processing composition for silver halide photographic light-sensitive material, more specifically a solid photographic processing composition for silver halide photographic light-sensitive material having excellent solubility, practically sufficient strength and remarkably improved chemical stability.
  • Silver halide color photographic light-sensitive materials (hereinafter also referred to as light-sensitive materials or photographic materials) are processed in developing, desilvering, washing, stabilizing and other processes after exposure.
  • Silver halide black-and-white photographic light-sensitive materials are developed and fixed after exposure.
  • a black-and-white developer or a color developer, a bleacher or a bleach-fixer, a fixer, tap water or deionized water, a stabilizing solution and a dye stabilizer are used for development, desilvering, fixing, washing, waterless washing and dye stabilization, respectively.
  • processing solutions The liquids capable of performing these processes are called processing solutions.
  • Each processing solution is usually kept at a temperature of 30 to 40°C, in which the light-sensitive material is immersed and processed.
  • the automatic processing machine mentioned herein is generally a processing machine having a developing portion, a fixing portion, a desilvering portion, a washing or stabilizing portion and a drying portion, and a means for automatically sequentially transporting the photographic light-sensitive material to the processing tanks.
  • the processing solution in each processing tank is supplemented with a processing agent to keep the activity of the processing solution in the processing tank constant.
  • processing is carried out while supplying the previously prepared replenisher from the replenisher tank to the processing tank as appropriate.
  • the replenisher to be stored in the replenisher tank is usually prepared in a separate place, but in mini-labs etc., the replenisher is usually prepared in a given amount in a replenisher tank equipped near the processing tank in the processing machine at a time by manual dissolution or mixing dissolution using a mechanical mixer.
  • the silver halide photographic light-sensitive material processing agent (hereinafter also referred to as photographic processing agent) is supplied in the form of powder or liquid; it is prepared as a solution by manually dissolving the powder in a given amount of water. In the case of a liquid processing agent, it is prepared as a dilution by adding a given amount of water and stirring the mixture, since it is supplied in a concentrated state.
  • Replenisher tanks may be set by the automatic processing machine, requiring considerable space. Also, in recently-increasing mini-labs, replenisher tanks are housed in the automatic processing machine; in this case as well, sufficient space must be available for the replenisher tanks, each of which should contain at least 5 to 10 liters of replenisher.
  • any processing agent for replenishment is divided in some parts to ensure constantly good performance in photographic processing.
  • the color developer replenisher is divided in three or four parts, and the bleach-fixer replenisher for color photography is supplied in two parts: a part of the oxidant ferric salt of organic acid and a part of the reducing agent thiosulfate.
  • said dense part of ferric salt of organic acid and said dense part of thiosulfate are mixed together and diluted with a given amount of water before using.
  • Said dense parts are placed in containers such as plastic containers, which containers are packed in outer packages, such as corrugated cardboard boxes, for 1 unit of commercial distribution.
  • the processing agent for replenishment in a kit of part agents is dissolved, diluted, mixed and then diluted to a given volume before using.
  • Said processing agent for replenishment has the following drawbacks:
  • First, almost all conventional kits comprise dense aqueous solutions concentrated for improved operability, most of which are very dangerous because of extreme pH values of not higher than 2.0 or not lower than 12.0 in that they are harmful to the human body by skin contact etc. Also, many of them are strong oxidants or reducing agents, possessing very dangerous corrosivity in transport by ships or aircraft.
  • the aqueous solution is subject to limitation as to solubility, being heavier and bulkier than in the case of solid. Since the concentrated solution is a dangerous article as stated above, its containers must be sufficiently tough to prevent destruction and spillage even if it is fallen; plastic container disposal poses a problem.
  • the part agents are separately contained in respective containers; some processing agents for replenishment comprise several bottles of part agents so that each unit of commercial distribution thereof involves a considerable number of containers, which requires much space for storage and transportation.
  • the color developer replenishing agent for CPK-2-20QA a processing solution for color printing paper
  • part A a kit including a preservative
  • part B a kit including a color developing agent
  • part C alkaline agent
  • the bleach-fixer replenisher is available in 8-liter units, wherein three part agents are contained in respective bottles.
  • the stabilizer replenisher is available in 10-liter units, wherein two part agents are contained in respective bottles.
  • replenishing agents are stored and transported in respective outer packages of various sizes.
  • the outer package size ranges from about 17 x 14 x 16.5 cm for the stabilizer replenisher to about 18.5 x 30.5 x 22.5 cm for the bleach-fixer replenisher; it is not possible to pile packages of replenishers in storing or transporting them or in stocking them at dealer shops unless they are of the same kind, so that much space is required.
  • plastic container disposal has been of major concern.
  • plastic containers for photographic use are cheap, conveniently storable and transportable and excellent in chemical resistance, they pose problems of accumulation in the environment because they are hardly biodegradable, and emission of large amounts of carbon dioxide upon burning, which contribute to global warming and acid rain.
  • problems posed on the user side they include decrease in the available working area due to occupation of the narrow working space by crowding plastic containers, which are too tough to compress.
  • the fourth drawback is poor chemical stability.
  • the life time of a replenisher is at most 2 weeks even in the presence of a floating lid.
  • a given volume of water is placed in the replenisher tank, after which dense kit A, which contains a preservative, is added, followed by stirring, and dense kit B, which contains a color developing agent, is then added, followed by stirring, and dense kit C, which contains an alkaline agent, is then added, followed by stirring, and finally water is added to make a given volume.
  • dense kit A which contains a preservative
  • dense kit B which contains a color developing agent
  • dense kit C which contains an alkaline agent
  • the color developer replenisher prepared from dense kits or powder is also known to pose some problems in the replenisher tank. For example, if the replenisher remains unused for a long time, crystals can deposit on the inside wall of the replenisher tank, the replenisher becomes susceptible to oxidation, and tar forms. Under some storage conditions, other problems arise, including separation of easily-crystallizing components of the replenisher, such as the color developing agent, at low temperatures; some makers specify replenisher storage conditions and instruct the users to keep their replenishers under those conditions.
  • a replenisher e.g., a color developer replenisher for color printing paper
  • a replenisher e.g., a color developer replenisher for color printing paper
  • the bleach-fixer is characterized by considerably poor storage stability. This is because the bleach-fixer is usually of high acidity and considerably low pH for neutralizing the alkalinity of the dye fixer carried over by the printing paper being processed because the bleach-fixing process immediately follows the process with a color developer of high pH. It is said that at low pH values, any bleach-fixer comprising a thiosulfate and an oxidant is considerably poor in storage stability and cannot be replenished at low replenishing rates. The same applies to the fixer and stabilizer.
  • supplying means such as a bellows pump are used to supply the dense kit as such directly to the processing tank and a given volume of replenishing water is added independently, to improve the low efficiency in dissolving operation.
  • This method really obviates solution preparing operation and is free of the problem of poor storage stability because no replenisher solution is prepared, in comparison with the above method, wherein the replenisher is prepared from a dense kit or powder.
  • the major problem is the increased size of the automatic processing machine because of the necessity for a dense kit tank for supplying the dense kit and a pump for supplying the dense kit.
  • the dense kit of color developer replenisher is divided in three parts; the dense kit of bleach-fixer replenisher, three parts; and the dense kit of stabilizer replenisher, two parts.
  • eight tanks and eight pumps are required.
  • three tanks and three pumps are sufficient, since each replenisher requires one tank and one pump.
  • more tanks and more pumps than in the conventional method are required for supplying the dense kits, and a pump for water used to prepare the replenisher is also required.
  • bellows pump precision is not so high, it is difficult to accurately discharge a plurality of solutions simultaneously, which can result in an imbalanced composition.
  • Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) Nos. 133332/1979 and 155038/1979 disclose powdered photographic processing agents
  • the methods described in these publications serve to improve replenisher stability without using plastic containers because they use no liquid photographic processing agent, they have drawbacks such as blocking during storage cause dissolution failure or dust formation at the time of processing solution preparation deteriorates the working environment when the processing agent is a powder.
  • this method requires a foaming agent to cause foaming action, resulting in a drawback that processing agent components in a more amount than the essentially desired is required due to reduction in processing performance per tablet when non-essential components are added to the photographic processing agent, while the desired foaming effect can be maintained by containment of a large amount of a foaming agent in cases of agents of low active ingredient content per tablet like pharmaceuticals.
  • the present inventors investigated the solubility of photographic processing tablets, and found that the solubility can be controlled without addition of special additives such as a disintegrating agent and foaming agent by adjusting tablet strength.
  • a solid photographic processing composition for silver halide photographic light-sensitive material in the form of tablets prepared by compressing a powder or granules comprising at least one processing agent component, wherein mechanical strength Z falls within the range: 0.3 ⁇ Z ⁇ 3.5 where Z is the ratio of the crushing strength (kg) of the tablet to the major axis length (mm) of the tablet.
  • the present invention is hereinafter described in more detail.
  • Figure 1 is a cross-sectional view of a processing agent receiving portion and processing agent supplying means in an automatic processing machine equipped with a means of replenishing water supplier.
  • Figure 2 is a plane view and oblique view of a tablet supplying apparatus and a plane view of a package.
  • Figure 3 shows the correlation between the compressing surface of hardness meter and the direction of the major axis of a tablet.
  • Figure 4 shows the correlation between compressing direction for crushing in measurement and compressing direction in compression molding of a tablet.
  • known granulating methods can be used, including tumbling granulation, extrusion granulation, compressive granulation, disintegration granulation, stirring granulation, fluidized bed granulation and spray drying granulation.
  • a granulation product having an average grain size of 100 to 800 ⁇ m, more preferably 200 to 750 ⁇ m, since unevenness in the composition, or so-called segregation, is not likely upon granulation product mixing and compression.
  • the grain size distribution is preferably such that not less than 60% of the grains fall within the range of ⁇ 100 to 150 ⁇ m apart from the average grain size.
  • a known compressing machine such as a hydraulic press, a single tabletting machine, a rotary tabletting machine or a briquetting machine, can be used.
  • the solid processing agent obtained by compression can take any shape, cylindrical agents, i.e., so-called tablets, are preferred from the viewpoint of productivity and handling quality.
  • components such as an alkali agent, a reducing agent, a bleaching agent and a preservative, are separately granulated, whereby the above effect is enhanced.
  • the mechanical strength Z of the solid photographic processing composition of the present invention is more than 0.3 and not more than 3.5, preferably between 0.5 and 3.0. Mechanical strength values of under 0.3 result in a very brittle solid photographic processing composition not suitable for practical use. Mechanical strength values exceeding 3.0 result in loss of solid photographic processing composition elasticity, which in turn lead to cracking tendency and significant deterioration of its solubility.
  • a tablet is defined to be a solid agent pressed into a fixed shape through compression molding.
  • the crushing strength of a tablet is represented by a value of pressure applied to the tablet to destroy it in the direction perpendicular to that of compression molding for the tablet (namely, in parallel with a compressed plane of the tablet in compression molding).
  • the measurement conditions were a room temperature of 25 °C and a humidity of 50 % RH, and a measurement was taken by the use of a SPEED CHECKER TS-50N (produced by Okada Seiko Co., Ltd.), the value was measured under the compressing speed of 5 to 78 mm/min. With regard to the compressing speed, the optimum one is selected depending upon the size and the form of a tablet agent.
  • the longitudinal length of the tablet agent is defined to be a diameter of the disk, while when it is polygonal, the longitudinal length is defined to be a distance between a plane of the tablet which is in parallel to the compressing surface of a hardness tester (which is different from a compressing surface of a tablet in compression molding) and a point or a surface of the tablet which is farthest from the plane in the crushing direction of the hardness tester.
  • the longitudinal length is defined to be the maximum length of the tablet whose both ends are respectively in contact with compressing surfaces of the hardness tester.
  • Mechanical strength Z is concretely measured as Figures 3A through 3F and Figure 4.
  • the tablets of the present invention may take any form, disk-like tablets are preferred from the viewpoint of productivity and handling.
  • the major axis length of the tablet is the diameter of the tablet, which may be set at any level according to purpose of use, preferably 5 to 50 mm, more preferably 7 to 30 mm from the viewpoint of productivity.
  • the ratio x/h of the major axis length x and thickness h of the tablet is preferably within the range 1.0-6.0, more preferably 2.5-5.0. If the ratio decreases below 1.0, tablet thickness increases, resulting in deteriorated solubility and productivity. If the ratio exceeds 6.0, the desired strength cannot be obtained.
  • solid photographic processing composition relating to the present invention may be used in any mode of use according to purpose, it is preferable, from the viewpoint of automatic processing agent size reduction, waste liquid volume reduction, etc., to add it as a replenisher directly to a processing chamber of the automatic processing agent.
  • the tablets of the present invention preferably have a weight of 0.1 to 30 g per tablet.
  • a p-phenylenediamine compound having a water-solubilizing group is preferably used as a color developing agent in the color developer for the present invention, since it enhances the desired effect of the invention and causes little fogging.
  • the p-phenylenediamine compounds having a water-solubilizing group are advantageous over the p-phenylenediamine compounds having no water-solubilizing group, such as N,N-diethyl-p-phenylenediamine, that they do not contaminate the light-sensitive material and are not irritative to skin upon skin contact.
  • their use in combination with the color developer for the present invention allows more efficient accomplishment of the desired object of the invention.
  • the p-phenylenediamine compound for the present invention has at least one water-solubilizing group as described above on the amino group or benzene nucleus thereof.
  • Preferred water-solubilizing groups include: -(CH2) n -CH2OH, -(CH2) m -NHSO2-(CH2) n -CH3, -(CH2) m -O-(CH2) n -CH3, -(CH2CH2O) n C m H 2m+1 (m and n independently represent an integer of not less than 0), a -COOH group and a -SO3H group.
  • color developing agents preferably used for the present invention are C-1 through C-16 described on pages 26 through 31 of Japanese Patent Application No. 203169/1990.
  • the color developing agent described above is used normally in the form of a salt such as hydrochloride, sulfate or p-toluenesulfonate.
  • color developing agents may be used singly or in combination, and may be used in combination with black-and-white developing agents such as phenidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone and Metol as desired.
  • R1 and R2 independently represent an alkyl group, an aryl group, or a hydrogen atom, provided that they do not represent a hydrogen atom concurrently.
  • the alkyl groups represented by R1 and R2 may be identical or not, each of which preferably has 1 to 3 carbon atoms. These alkyl groups may have a carboxylate group, a phosphate group, a sulfonate group or a hydroxyl group.
  • R' represents an alkoxy group, an alkyl group or an aryl group.
  • the alkyl groups and aryl groups for R1, R2 and R' include those having a substituent.
  • R1 and R2 may bind together to form a ring, such as a heterocyclic ring like piperidine, pyridine, triazine or morpholine.
  • R11, R12 and R13 independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group or heterocyclic group
  • R14 represents a hydroxyl group, a hydroxyamino group, a substituted or unsubstituted alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group or amino group.
  • the heterocyclic group is a 5- or 6-membered ring comprising C, H, O, N, S and halogen atoms, whether saturated or unsaturated.
  • R15 represents a divalent group selected from the group consisting of -CO-, -SO2- and n represents 0 or 1. Provided that n is 0, R14 represents a group selected from an alkyl group, an aryl group and a heterocyclic group; R13 and R14 may cooperate to form a heterocyclic group.
  • hydroxylamine compound represented by formula A examples are given in US Patent Nos. 3287125, 33293034 and 3287124 and other publications. Particularly preferable compounds are compound Nos. A-1 through A-39 described on pages 36 through 38 of Japanese Patent Application No. 203169/1990, compound Nos. 1 through 53 described on pages 3 through 6 of Japanese Patent O.P.I. Publication No. 33845/1991 and compound Nos. 1 through 52 described on pages 5 through 7 of Japanese Patent O.P.I. Publication No. 63646/1991.
  • Examples of the compound represented by formula B are compound Nos. B-1 through B-33 described on pages 40 through 43 of Japanese Patent Application No. 203169/1990 and compound Nos. 1 through 56 described on pages 4 through 6 of Japanese Patent O.P.I. Publication No. 33846/1991.
  • the color developer and black-and-white developer used for the present invention may incorporate a trace amount of sulfite as a preservative.
  • sulfites include sodium sulfite, potassium sulfite, sodium bisulfite and potassium bisulfite.
  • the color developer and black-and-white developer used for the present invention must contain a buffer.
  • buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (boric acid), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).
  • Examples of developing accelerators which can be added as necessary include the thioether compounds disclosed in Japanese Patent Examined Publication Nos. 16088/1962, 5987/1962, 7826/1963, 12380/1969 and 9019/1970 and US Patent No. 3813247, the p-phenylenediamine compounds disclosed in Japanese Patent O.P.I. Publication Nos. 49829/1977 and 15554/1975, the quaternary ammonium salts disclosed in Japanese Patent O.P.I. Publication Nos. 137726/1975, 156826/1981 and 43429/1977 and Japanese Patent Examined Publication No. 30074/1969, the p-aminophenols disclosed in US Patent Nos.
  • the color developer contains substantially no benzyl alcohol, specifically not more than 2.0 ml per liter of color developer, more preferably absolutely no benzyl alcohol.
  • the color developer contains substantially no benzyl alcohol, better results are obtained with less fluctuation in photographic properties in continuous processing, particularly less increase in the degree of staining.
  • chlorine and bromine ions must be present in the color developer.
  • the color developer in the processing tank contain bromine ions at a concentration of 3.0 x 10 ⁇ 3 to 1.0 x 10 ⁇ 3 mol/l, more preferably 5.0 x 10 ⁇ 3 to 5 x 10 ⁇ 4 mol/l, and still more preferably 1 x 10 ⁇ 4 to 3 x 10 ⁇ 4 mol/l.
  • it is preferable to prepare the solid processing agent to make the color developer in the processing tank have a bromine concentration within the above range.
  • chlorine ions are added directly to the color developer
  • examples of chlorine ion sources include sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride and cadmium chloride, with preference given to sodium chloride and potassium chloride.
  • Chlorine ions may also be supplied in the form of a counterpart salt of the color developer or the brightening agent added thereto.
  • bromine ion sources include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide and thallium bromide, with preference given to potassium bromide and sodium bromide.
  • the color developer and black-and-white developer used for the present invention may incorporate antifogging agents which are optionally selected as necessary.
  • Antifogging agents which can be used include alkali metal halides such as potassium iodide and organic antifogging agents.
  • organic antifogging agents include nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolidine and adenine.
  • a triazinylstilbene brightening agent is added to the color developer and black-and-white developer used for the present invention.
  • Said brightening agent is preferably represented by the following formula E: wherein X2, X3, Y1 and Y2 independently represent a hydroxyl group, a chlorine atom, a bromine atom or another halogen atom, an alkyl group, an aryl group, or -OR25.
  • R21 and R22 independently represent a hydrogen atom, an alkyl group (may be substituted) or an aryl group (may be substituted);
  • R23 and R24 each represent an alkylene group (may be substituted);
  • R25 represents a hydrogen atom, an alkyl group (may be substituted) or an aryl group (may be substituted);
  • M represents a cation.
  • E-4, E-24, E-34, E-35, E-36, E-37 and E-41 are preferably used. It is preferable to prepare the solid processing agent so that the amount of these compounds added falls within the range from 0.2 to 10 g, preferably from 0.4 to 5 g per liter of color developer.
  • the color developer and black-and-white developer used for the present invention may also incorporate organic solvents such as methyl cellosolve, methanol, acetone, dimethylformamide, ⁇ -cyclodextrin and the compounds described in Japanese Patent Examined Publication Nos. 33378/1972 and 9509/1969 for increasing the solubility of the developing agent as necessary.
  • organic solvents such as methyl cellosolve, methanol, acetone, dimethylformamide, ⁇ -cyclodextrin and the compounds described in Japanese Patent Examined Publication Nos. 33378/1972 and 9509/1969 for increasing the solubility of the developing agent as necessary.
  • auxiliary developing agents may be used in combination with the principal developing agent.
  • auxiliary developing agents include Metol, phenidone, N,N-diethyl-p-aminophenol hydrochloride and N,N,N',N'-tetramethyl-p-phenylenediamine hydrochloride.
  • the color developer and the black-and-white developer incorporate one of the chelating agent represented by the following formula K and example compound Nos. K-1 through K-22, described in line 8 from bottom, page 63, through line 3 from bottom, page 64, of Japanese Patent Application No. 240400/1990.
  • A1 through A4 independently represent a hydrogen atom, a hydroxyl group, -COOM or -PO3(M)2; M represents a hydrogen atom or an atom of alkali metal.
  • E represents a substituted or unsubstituted alkylene group; a cycloalkylene group, a phenylene group, -R5OR5-, -R5OR5OR5- or -R5ZR5-, Z represents >N-R5-A5 or >N-A5.
  • R1 through R5 independently represent a substituted or unsubstituted alkylene group.
  • K-2, K-9, K-12, K-13, K-17 and K-19 are preferably used, with more preference given to K-2 and K-9, since their addition to the color developer enhances the effect of the invention.
  • these chelating agents it is preferable to add these chelating agents to the solid processing agent so that their amount falls within the range from 0.1 to 20 g, preferably from 0.2 to 8 g per liter of color developer or black-and-white developer.
  • the color developer and black-and-white developer may also contain anionic, cationic, amphoteric and nonionic surfactants.
  • Various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids and aromatic carboxylic acids may be added as necessary.
  • the bleaching agents which are preferably used in the bleacher or bleach-fixer relating to the present invention are ferric complex salts of the organic acid represented by the following formula C: wherein A1 through A4, whether identical or not, independently represent -CH2OH, -COOM or -PO3M1M2 (M, M1 and M2 independently represent a hydrogen atom, an atom of alkali metal or ammonium); X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms.
  • A1 through A4 in the formula are not described in detail here, since they are identical with A1 through A4 described in line 15, page 12, through line 3, page 15, of Japanese Patent Application No. 260628/1989.
  • a ferric complex salt of the organic acid represented by formula C is preferably used for the present invention, since a small amount is sufficient to solidify itself because of the high bleaching capability so that weight and size reduction is possible, and since it offers an additional effect of improving the storage stability of solid processing agent.
  • the ferric complex salts of these compounds C-1 through C-12 may be sodium salts, potassium salts or ammonium salts thereof, which can be selected optionally. From the viewpoint of the desired effect of the present invention and solubility, ammonium salts of these ferric complex salts are preferably used.
  • C-1, C-3, C-4, C-5 and C-9 are preferred, with more preference given to C-1.
  • ferric complex salts of the following compounds and others can be used as bleaching agents for the bleacher or bleach-fixer in addition to the iron complex salts of the compound represented by the above formula C.
  • the bleacher may incorporate at least one of the imidazole described in Japanese Patent O.P.I. Publication No. 295258/1989, derivatives thereof and the compounds represented by formulas I through IX given in the same publication, whereby rapid processing is facilitated.
  • the bleacher or bleach-fixer may incorporate halides such as ammonium bromide, potassium bromide and sodium bromide, various brightening agents, defoaming agents and surfactants.
  • the fixing agents which are preferably used in the fixer or bleach-fixer for the present invention are thiocyanates and thiosulfates.
  • the amount of thiocyanate added is preferably not less than 0.1 mol/l, more preferably not less than 0.5 mol/l, and still more preferably not less than 1.0 mol/l for processing a color negative film.
  • the amount of thiosulfate added is preferably not less than 0.2 mol/l, more preferably not less than 0.5 mol/l for processing a color negative film.
  • the object of the present invention can be more efficiently accomplished by using a thiocyanate and a thiosulfate in combination.
  • the fixer or bleach-fixer for the present invention may contain two or more pH regulators comprising various salts. It is also desirable to add a large amount of a re-halogenating agent such as an alkali halide or an ammonium halide, e.g., potassium bromide, sodium bromide, sodium chloride or ammonium bromide.
  • a re-halogenating agent such as an alkali halide or an ammonium halide, e.g., potassium bromide, sodium bromide, sodium chloride or ammonium bromide.
  • Compounds which are known to be added to fixer or bleach-fixer such as alkylamines and polyethylene oxides, may be added as appropriate.
  • a compound represented by the following formula FA described on page 56 of Japanese Patent O.P.I. Publication No. 295258/1989, to the fixer or bleach-fixer, whereby not only the effect of the invention is enhanced but also an additional effect is obtained in that sludge formation in the processing solution capable of fixing is significantly suppressed during prolonged processing of a small amount of light-sensitive material.
  • Compounds represented by formula FA can be synthesized by ordinary methods such as those described in US Patent Nos. 3335161 and 3260718. These compounds represented by formula FA may be used singly or in combination.
  • the chelate stability constant is the constant which is well known in L.G. Sillen and A.E. Martell, "Stability Constants of Metal-Ion Complexes", The Chemical Society, London (1964), S. Chaberek and A.E. Martell, "Organic Sequestering Agents", Wiley (1959), and other publications.
  • chelating agents having a ferric ion chelate stability constant of over 8 include those described in Japanese Patent Application Nos. 234776/1990 and 324507/1989.
  • the amount of the above chelating agent used is preferably 0.01 to 50 g, more preferably 0.05 to 20 g per liter of stabilizer, within which content range good results are obtained.
  • Ammonium compounds are preferably added to the stabilizer, which are supplied as ammonium salts of various inorganic compounds.
  • the amount of ammonium compound added preferably falls within the range from 0.001 to 1.0 mol, more preferably from 0.002 to 2.0 mol per liter of stabilizer.
  • the stabilizer preferably contains a sulfite.
  • the stabilizer preferably contains a metal salt in combination with the chelating agent described above.
  • metal salts include salts of Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb, Sn, Zn, Ti, Zr, Mg, Al and Sr, and it can be supplied as an inorganic salt such as halide, hydroxide, sulfate, carbonate, phosphate or acetate, or a water-soluble chelating agent.
  • the amount of metal salt added preferably falls within the range from 1 x 10 ⁇ 4 to 1 x 10 ⁇ 1 mol, more preferably from 4 x 10 ⁇ 4 to 2 x 10 ⁇ 2 mol per liter of stabilizer.
  • Color developer tablets for color printing paper were prepared as follows:
  • Example 1 Samples were prepared and tested in the same manner as in Example 1, except that CD-3 was replaced with CD-4 [4-amino-3-methyl-N-ethyl- ⁇ -hydroxyethylaniline sulfate]. Almost the same results as in Example 1 were obtained.
  • the granulation products obtained in the above procedures (2) through (4) were uniformly mixed in a mixer for about 10 minutes in a room conditioned at 25°C temperature and under 40% RH. To this mixture, 6 g of N-lauloylsalcosine sodium salt was added, followed by mixing for 3 minutes. The resulting mixture was subjected to compressive tabletting at the packing rates per tablet and diameters shown in Table 2, using a tabletting machine, a modification of Tough Press Correct 1527HU, produced by Kikusui Seisakusho, to yield 80 tablets of each of bleacher replenisher tablet samples 2-1 through 2-10 for color negative films.
  • Fixing tablets for color negative films were prepared as follows:
  • the granulation product prepared in the above procedure (6) and 13 g of N-lauloylsalcosine sodium salt were mixed in a mixer for about 3 minutes in a room conditioned at 25°C temperature and under 40% RH.
  • the mixture was subjected to compressive tabletting at the packing rates per tablet and diameters shown in Table 3, using a tabletting machine, a modification of Tough Press Correct 1527HU, produced by Kikusui Seisakusho, to yield 100 tablets of each of fixer replenisher tablet samples 3-1 through 3-12 for color negative films.
  • the granulation product prepared in the above procedure (8) was subjected to compressive tabletting at the packing rates per tablet and diameters shown in Table 4, using a tabletting machine, a modification of Tough Press Correct 1527HU, produced by Kikusui Seisakusho, in a room conditioned at 25°C temperature and under 40% RH. to yield 200 tablets of each of stabilizer replenisher tablet samples 4-1 thorough 4-12 for color negative films.
  • the Konica QA paper type 5 (produced by konica Corporation) was processed according to the following processing steps, using the NPS-808 (produced by Konica Corporation), modified to have the configuration illustrated in Figure 1.
  • the replenishing water in the replenishing tank was deionized water. Processing step Processing time Processing temperature Tank capacity Color development 22 seconds 38.0°C 12 l Bleach-fixation 22 seconds 37.5°C 12 l Stabilization 1 22 seconds 35°C 12 l Stabilization 2 22 seconds 35°C 12 l Stabilization 3 22 seconds 35°C 12 l Drying 50 seconds 55°C
  • Stabilization was achieved by the counterflow method from 3 to 1. The entire overflow from stabilization 1 was allowed to enter the bleach-fixing bath. Carry-over per m2 of light-sensitive material was 45 ml from the color developing tank to the bleach-fixing tank, 50 ml from the bleach-fixing tank to the stabilizing tank and 40 ml from stabilization 1 to 2, from stabilization 2 to 3 and from stabilization 3 to drying.
  • the opening area of each of the color developing, bleach-fixing and stabilizing tanks was 4.5 cm2 per liter of processing solution.
  • the ambient conditions for the automatic processing machine were 27°C temperature and 60% RH, and replenishing water was supplied upon the water loss due to evaporation reached 100 ml.
  • the amount of replenishing water was calculated using the equation (1) shown in Japanese Patent O.P.I. Publication No. 280042/1991.
  • the light-sensitive material was continuously processed at 2.0 m2 per day for 2 months.
  • compositions of the processing solutions used are as follows: Color developer Potassium bromide 0.02 g Potassium chloride 3.2 g Potassium carbonate 30 g Potassium sulfite 0.2 g Sodium diethylenetriaminepentaacetate 2 g Sodium nitrilotrimethylenephosphonate Tinopal SFP 2 g 2 g Disodium N,N-bis(sulfonatoethyl)hydroxylamine 4-amino-3-methyl-N-ethyl-N-( ⁇ - 5 g methanesulfonamidoethyl)aniline sulfate CD-3 7 g Water was added to make a total quantity of 1 l, and pH was adjusted to 10.10.
  • Processing tablets for color printing paper were prepared in accordance with the following procedures:
  • the resulting mixture was subjected to compressive tabletting using a tabletting machine, a modification of Tough Press Correct 1527HU, produced by Kikusui Seisakusho, at the packing rates per tablet shown in Table 1, to yield 110 tablets of color developer replenisher tablet agent D for color printing paper.
  • the resulting mixture was subjected to compressive tabletting using a tabletting machine, a modification of Tough Press Correct 1527HU, produced by Kikusui Seisakusho, at a packing rate of 5.8 g per tablet, to yield 170 tablets of bleach-fixer replenisher tablet agent A for color printing paper.
  • the resulting mixture was subjected to compressive tabletting using a tabletting machine, a modification of Tough Press Correct 1527HU, produced by Kikusui Seisakusho, at a packing rate of 9.2 g per tablet, to yield 180 tablets of bleach-fixer replenisher tablet agent B for color printing paper.
  • each tablet agent was sealed in a laminated polymer resin film of PET/polyvinyl alcohol-ethylene copolymer/polyethylene at 1 tablet for each of color developer replenisher tablet agents A through D, 1 tablet for each of bleach-fixer replenisher tablet agents A and B and 1 tablet for the stabilizer replenisher tablet agent, and consecutive 20 packages were prepared as a cartridge.
  • each of the above-described replenisher tablet cartridge was shaken for 6 hours using a commercially available vibrator, tablets were added using the supplying apparatus illustrated in Figure 1.
  • the setting was such that one tablet was added upon processing of 1 m2 of color printing paper, and 76 ml of replenishing water for the color developing bath, 42 ml of replenishing water for the bleach-fixing bath and 247 ml of replenishing water for the stabilizing bath would be supplied from the replenishing water tank simultaneously.
  • the undissolved tablets clog the processing solution circulatory pump, also resulting in an important trouble of automatic processing machine shutdown.
  • the tablets of the present invention are sufficiently strong to endure vibration, allowing continuous processing without any trouble with only 1 or 2 tablets remaining undissolved in the dissolution chamber. Also, the photographic performance obtained in processing with the tablets of the present invention was satisfactory in every aspect.
  • the present invention makes it possible to provide an automatic processing machine allowing the use of solid chemicals without no troublesome operation by the user as a result of obviation of liquid chemicals involving the risk in transportation or handling.
  • Processing tablet for a color negative film were prepared under the following procedure.

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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)
EP94102254A 1993-02-15 1994-02-14 Feststoffzusammensetzung zur photographischen Verarbeitung eines farbphotographischen lichtempfindlichen Silberhalogenidmaterials Withdrawn EP0611986A1 (de)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5827635A (en) * 1996-01-23 1998-10-27 Eastman Kodak Company High temperature color development of photographic silver bromoiodide color negative films using stabilized color developer solution
US5866310A (en) * 1994-04-28 1999-02-02 Konica Corporation Solid photographic processing composition for developing a silver halide photographic light-sensitive material
EP1003077A2 (de) * 1998-11-18 2000-05-24 Tetenal Photowerk GmbH & Co Verfahren zur Herstellung von als Tablette formulierten fotografischen Prozesschemikalien
EP0679940B1 (de) * 1994-04-28 2001-01-24 Konica Corporation Feste Verarbeitungszusammensetzung für photographische lichtempfindliche Silberhalogenidmaterialien
US6520694B1 (en) 2002-01-18 2003-02-18 Eastman Kodak Company System and method for processing photographic film images

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH614865A5 (en) * 1976-10-20 1979-12-28 Ciba Geigy Ag Method for agglomerating a substance from a liquid system
EP0220103A1 (de) * 1985-10-02 1987-04-29 Roquette Frˬres Unmittelbar pressbares Maltitolpulver und Verfahren zu dessen Herstellung
EP0466372A1 (de) * 1990-06-29 1992-01-15 Konica Corporation Verfahren zur Verarbeitung farbphotographischer lichtempfindlicher Silberhalogenidmaterialien
EP0540990A1 (de) * 1991-11-06 1993-05-12 Konica Corporation Tablettenförmiges Behandlungsmittel und Methode zur Verarbeitung photographischer lichtempfindlicher Silberhalogenidmaterialien

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH614865A5 (en) * 1976-10-20 1979-12-28 Ciba Geigy Ag Method for agglomerating a substance from a liquid system
EP0220103A1 (de) * 1985-10-02 1987-04-29 Roquette Frˬres Unmittelbar pressbares Maltitolpulver und Verfahren zu dessen Herstellung
EP0466372A1 (de) * 1990-06-29 1992-01-15 Konica Corporation Verfahren zur Verarbeitung farbphotographischer lichtempfindlicher Silberhalogenidmaterialien
EP0540990A1 (de) * 1991-11-06 1993-05-12 Konica Corporation Tablettenförmiges Behandlungsmittel und Methode zur Verarbeitung photographischer lichtempfindlicher Silberhalogenidmaterialien

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5866310A (en) * 1994-04-28 1999-02-02 Konica Corporation Solid photographic processing composition for developing a silver halide photographic light-sensitive material
EP0679940B1 (de) * 1994-04-28 2001-01-24 Konica Corporation Feste Verarbeitungszusammensetzung für photographische lichtempfindliche Silberhalogenidmaterialien
US5827635A (en) * 1996-01-23 1998-10-27 Eastman Kodak Company High temperature color development of photographic silver bromoiodide color negative films using stabilized color developer solution
EP1003077A2 (de) * 1998-11-18 2000-05-24 Tetenal Photowerk GmbH & Co Verfahren zur Herstellung von als Tablette formulierten fotografischen Prozesschemikalien
EP1003077A3 (de) * 1998-11-18 2000-09-20 Tetenal Photowerk GmbH & Co Verfahren zur Herstellung von als Tablette formulierten fotografischen Prozesschemikalien
US6520694B1 (en) 2002-01-18 2003-02-18 Eastman Kodak Company System and method for processing photographic film images

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