EP0542283A1 - A tablet for processing a silver halide photographic light-sensitive material - Google Patents

A tablet for processing a silver halide photographic light-sensitive material Download PDF

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Publication number
EP0542283A1
EP0542283A1 EP92119391A EP92119391A EP0542283A1 EP 0542283 A1 EP0542283 A1 EP 0542283A1 EP 92119391 A EP92119391 A EP 92119391A EP 92119391 A EP92119391 A EP 92119391A EP 0542283 A1 EP0542283 A1 EP 0542283A1
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EP
European Patent Office
Prior art keywords
group
tablet
formula
represent
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP92119391A
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German (de)
French (fr)
Inventor
Ichiro Tsuchiya
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Konica Minolta Inc
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Konica Minolta Inc
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Publication date
Priority claimed from JP29592491A external-priority patent/JPH05134362A/en
Priority claimed from JP2260492A external-priority patent/JPH05216177A/en
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of EP0542283A1 publication Critical patent/EP0542283A1/en
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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

Definitions

  • the present invention relates to a tablet for processing a photographic film, more specifically to a tablet suitable for use in processing a silver halide color photographic material by means of an automatic developing machine.
  • Silver halide photographic light-sensitive materials are, after imagewise exposure, normally subjected to processing with a monochromatic developer, a fixer, a color developer, a bleacher, a bleach-fixer, a stabilizer and the like.
  • these processing liquids are sold in the form of a kit that consists of plastic bottles filled with the concentrates of these liquids. Two or more plastic bottles may be employed for one processing liquid. Users dissolve these concentrates in water to make starting liquids or replenishers.
  • minilaboratories small-sized developing laboratories in which small-sized developing machines are used. With the increase in number of such minilaboratories, more plastic bottles than ever have come to be used to keep processing liquids.
  • plastics Being light-weight and tough, plastics can be utilized in various ways. The world's production of plastics has been on the increase; in 1988, the annual output of plastics exceeded 100 million tons. On the other hand, a large amount of plastics are being discarded as waste. For instance, in Japan, about 40% of the plastics produced each year are discarded. If plastics are thrown away in the ocean, they may affect adversely oceanic lives. In Europe, waste plastics are usually burned up in incinerators which do not have means to treat exhaust gas. The exhaust gas from such incinerators is regarded as the cause of acid rain.
  • granules have such defects that they are likely to settle down at the bottom of a container when dissolved in water (caking), and that they cannot be dissolved well in water since they are covered by wet coating films which are formed during granulation process.
  • a processing liquid can be used in the form of powder or granule.
  • Japanese Patent O.P.I. Publication No. 61837/1976 proposes the use of a processing agent in the form of a tablet.
  • a processing agent in the form of a tablet is poor in storage stability.
  • the color developing agent contained therein tends to be oxidized during storage, forming a tar-like insoluble matter.
  • insoluble matters such as sulfur or sulfides may be formed during storage. The formation of such insoluble matters prevent these tablets from exhibiting their processing performance sufficiently.
  • An object of the present invention is to provide a tablet for processing a silver halide color photographic light-sensitive material with improved storage stability.
  • Another object of the present invention is to enable processing of a photographic film to be performed safely without causing environmental pollution by minimizing the amount of containers including plastic bottles for keeping processing liquids.
  • a tablet for processing a silver halide photographic light-sensitive material characterized in that it is obtained by laying two or more granules differing in composition one on top of another to form a layered structure, followed by pressure molding.
  • the processing tablet of the invention can be prepared according to conventional methods described, for instance, in Japanese Patent O.P.I. Publication Nos. 61837/1976, 155038/1979, 88025/1977 and British Patent No. 1,213,808.
  • two or more granules differing in composition are subjected to pressure molding by means of a multi-layer rotary tablet machine which is prepared by remodeling Clean Press Correct 3151K (manufactured by Kikusui Seisakusho).
  • Pressure molding may be performed with a photographically inactive substance being sandwiched between two layers.
  • the photographically inactive substance may be a water-soluble polymeric material; examples include water-soluble cellulose, water-soluble dextrin, water-soluble polyethylene glycol, water-soluble polyvinyl pyrrolidone and water-soluble polyacrylamide.
  • the tablet according to the invention may be a color developing tablet, a monochromatic developing tablet, a bleaching tablet, a bleach-fixing tablet or a stabilizing tablet.
  • the color developing agent contained in the color developing tablet should preferably be a p-phenylenediamine compound with a water-soluble group for less fogging and the successful manifestation of the effects of the invention.
  • a p-phenylenediamine compound with a water-soluble group is more advantageous, since it will not contaminate a light-sensitive material or irritate users' skin.
  • a p-phenylenediamine compound with a water-soluble group contributes to more successful manifestation of the effects of the invention.
  • the water-soluble group may be one which is present on the amino group or benzene ring of a p-phenylenediamine compound.
  • Preferred examples of the water-soluble group include -(CH2)nCH2OH, -(CH2)mNHSO2(CH2)nCH3, -(CH2)mO(CH2)nCH3, -(CH2CH2O)nCmH2m+1 (wherein m and n each represent an integer of 0 or more), -COOH group and -SO3H group.
  • Preferred examples of a color developing agent to be used in the invention include compound Nos. C-1 to C-16 described in Japanese Patent Application Specification No. 203169/1990, pages 26 to 31, and the following compounds, C'-1, C'-2, and C'-3.
  • color developing agents are normally employed in the form of a salt, such as a hydrochloride, a sulfate and a p-toluenesulfonate.
  • the above color developing agents may be employed either singly or in combination. If need arises, they may be employed together with a monochromatic developing agent, such as phenidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone and metol.
  • a monochromatic developing agent such as phenidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone and metol.
  • the effects of the invention can be produced more satisfactorily and the unexposed portion of a film can be free of fogging when a compound represented by the following formula A or B is incorporated in the color developing tablet.
  • R1 and R2 each represent an alkyl group, an aryl group, R3CO- group or a hydrogen atom, provided that there is no case where R1 and R2 are both hydrogen atoms.
  • R1 and R2 may combine with each other to form a ring.
  • the (un)substituted alkyl group represented by R1 and that represented by R2 may be either identical with or different from each other, and each may preferably be an alkyl group with 1 to 3 carbon atoms.
  • the alkyl group may further contain a carboxyl group, a phosphoric acid group, a sulfo group or a hydroxyl group.
  • R3 represents an (un)substituted alkoxy group, an (un)substituted alkyl group or an (un)substituted aryl group.
  • the ring which may be formed by R1 and R2 may be a heterocyclic ring such as piperidine, pyridine, triazine or morpholine.
  • R11, R12 and R13 each represent ahydrogen atom, an (un)substituted alkyl group, an aryl group or a heterocyclic group.
  • R14 represents a hydroxyl group, a hydroxyamino group, (un)substituted alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group or an amino group.
  • the heterocyclic group is an (un)saturated, 5 to 6-membered ring consisting of C, H, O, N, S and a halogen atom.
  • n represents 0 or 1. When n is 0, R14 represents a group selected from an alkyl group, an aryl group or a heterocyclic group. R13 and R14 may combine with each other to form a heterocyclic ring.
  • hydroxylamine compounds represented by formula A are given in U.S. Patent Nos. 3,287,125, 3,329,034 and 3,287,124.
  • Preferred examples are compound Nos. A-1 to A-39 described in Japanese Patent Application Specification No. 203169/1990, pages 36 to 38, compound Nos. 1 to 53 described in Japanese Patent O.P.I. Publication No. 33845/1991, pages 3 to 6 and compound Nos. 1 to 52 described in Japanese Patent O.P.I. Publication No. 63646/1991.
  • Specific examples of the compound represented by formula B include compound Nos. B-1 to B-33 described in Japanese Patent Application Specification No. 203169/1990, pages 40 to 43 and compound Nos. 1 to 56 described in Japanese Patent O.P.I. publication No. 33846/1991, pages 4 to 6.
  • the compounds represented by formula A or B are normally employed in the form of a free amine, a hydrochloride, a sulfate, a p-toluenesulfonate, an oxalate, a phosphate or an acetate.
  • a hydroxylamine compound represented by formula AL may be employed preferably in the invention as a preservative for a color developer.
  • L represents an (un)substituted alkylene group
  • A represents a carboxyl group, a sulfo group, a phosphono group, a phosphino group, a hydroxyl group, an amino group, an ammonio group, a carbamoyl group or a sulfamoyl group.
  • the amino group, ammonium group, carbamoyl group and sulfamoyl group each may be alkyl-substituted.
  • R represents a hydrogen atom or an (un)substituted alkyl group.
  • the compounds represented by formula A' include compound Nos. 1 to 54 described in Japanese Patent O.P.I. Publication No. 184044/1991, on page 4 at the , lower left column to page 6 at the upper right column. Of them, compound Nos. 1 and 7 are preferable.
  • Compound No. 1 HON(CH2COOH)2
  • Compound No. 7 HON(CH2CH2SO3H)2
  • the compounds represented by formula A' can be prepared by subjecting a commercially-available hydroxylamine to alkylation. Specifically, they can be prepared according to methods described in West German Patent No. 1,159,634 and Inorganica Chimica Acta, 93 (1984), pages 101 to 108.
  • a small amount of a sulfite may be contained as a preservative.
  • Usable sulfites include sodium sulfite, potassium sulfite, sodium bisulfite and potassium bisulfite.
  • the color or monochromatic developing tablet of the invention must contain a buffer, such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, trisodium phosphate, tripotassium phosphate, disodium 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).
  • a buffer such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (boric acid), potassium
  • Examples of a usable development accelerator include thioether compounds described in Japanese Patent Examined Publication Nos. 16088/1962, 5987/1962, 7826/1963, 12380/1969, 9019/1970 and U.S. Patent No. 3,813,247, p-phenylenediamine compounds described in Japanese Patent O.P.I. Publication Nos. 49829/1977 and 15554/1975, quaternary ammonium salts described in Japanese Patent Examined Publication No. 30074/1969, Japanese Patent O.P.I. Publication Nos. 137726/1975, 156826/1981 and 43429/1977, p-aminophenols described in U.S. Patent Nos.
  • chlorine ions and bromine ions may be contained in the color developing tablet of the present invention.
  • the amount of chlorine ions should preferably be 1.0 ⁇ 10 ⁇ 2 to 1.5 ⁇ 10 ⁇ 1 mol, still preferably 3.5 ⁇ 10 ⁇ 2 to 1.0 ⁇ 10 ⁇ 1 mol, per liter of a color developer. If it exceeds 1.5 ⁇ 10 ⁇ 1 mol/l, development will be retarded, and it will be impossible to obtain a higher maximum density rapidly.
  • the amount of chlorine ions is smaller than 3.5 ⁇ 10 ⁇ 2 mol/l, stains will be formed, and photographic properties (in particular, minimum density) will vary considerably during continuous processing.
  • the amount of bromine ions should preferably be 3.0 ⁇ 10 ⁇ 5 to 1.0 ⁇ 10 ⁇ 3 mol, still preferably 5.0 ⁇ 10 ⁇ 5 to 5.0 ⁇ 10 ⁇ 4 mol, per liter of a color developer. If it exceeds 1.0 ⁇ 10 ⁇ 3 mol/l, development will be retarded, and maximum density and sensitivity will be lowered. When the amount of bromine ions is lower than 3.0 ⁇ 10 ⁇ 5/l, stains will be formed, and photographic properties (in particular, minimum density) will vary considerably during continuous processing.
  • sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride and cadmium chloride may be employed as a chlorine ion-supplying material.
  • sodium chloride and potassium chloride are preferable.
  • Chlorine ions may be supplied in the form of a counter ion of a fluorescent brightener to be added to the color developing tablet.
  • Bromine ion-supplying materials include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide and thallium bromide. Of them, preferable are potassium bromide and sodium bromide.
  • the color developing tablet of the invention may contain an antifoggant in addition to chloride and bramide ions, if need arises.
  • an alkali metal halide such as potassium iodide and an organic antifoggant may be employed.
  • an organic antifoggant use can be made of a nitrogen-containing heterocyclic compound such as benzotriazole, 6-nitrobenzimidazole, 5-nitroindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine and adenine.
  • a triazinyl stilbene fluorescent brightener to the color developing tablet of the invention.
  • a compound represented by formula E is preferable as such brightener.
  • X1, X2, Y1 and Y2 each represent a hydroxyl group, a halogen atom (e.g; chlorine, bromine), an alkyl group, an aryl group or -N(R21)(R22) group, or OR25 (where R21 and R22 each represent a hydrogen atom, an (un)substituted alkyl group, an (un)substituted aryl group, R23 and R24 each represent an (un)substituted alkylene group, R25 represents a hydrogen atom, an (un)substituted alkyl group or an (un)substituted aryl group), and M represents a cation.
  • a halogen atom e.g; chlorine, bromine
  • R21 and R22 each represent a hydrogen atom, an (un)substituted alkyl group, an (un)substituted aryl group
  • R23 and R24 each represent an (un)substitute
  • the compounds represented by formula E can be prepared by conventional methods. Representative examples of these compounds are given below. Of them, compound Nos. E-4, E-24, E-34, E-35, E-36, E-37 and E-41 are preferable. These compounds should preferably be employed in an amount of 0.2 to 10 g, still preferably 0.4 to 5 g, per 1000 ml of a color developer.
  • the color or monochromatic developing tablet of the invention may further contain, if necessary, an organic solvent such as methyl cellosolve, methonol, acetone, dimethylformamide, ⁇ -cyclodextrin and compounds described in Japanese Patent Examined Publication Nos. 33378/1972 and 9509/1968. These organic solvents serve to increase the solubility of a color developing agent.
  • an organic solvent such as methyl cellosolve, methonol, acetone, dimethylformamide, ⁇ -cyclodextrin and compounds described in Japanese Patent Examined Publication Nos. 33378/1972 and 9509/1968.
  • an auxiliary developing agent may be employed.
  • the auxiliary developing agent may be metol, phenidone, N,N-diethyl-p-aminophenol hydrochloride or N,N,N',N'-tetramethyl-p-phenylenediamine hydrochloride.
  • the amount should preferably be 0.01 to 1.0 g/l.
  • An anti-stain agent, an anti-sludge agent and other additives may be contained in the color or monochromatic developing tablet of the invention.
  • a chelating agent represented by the following formula K (described in Japanese Patent Application Specification No. 240400/1990, from the 9th line from the bottom of page 69 to page 75 and example compound Nos. K-1 to 22) to the color or monochromatic developing tablet of the invention.
  • compound Nos. K-2, K-9, K-12, K-13, K-17 and K-19 are preferable.
  • the effects of the invention can be realized effectively when compound No. K-2 or compound No. K-9 is added to a color developer.
  • the amounts of these chelating agents should preferably be 0.1 to 20 g, still preferably 0.2 to 8 g, per 1000 ml of a color or monochromatic developer.
  • the color or monochromatic developing tablet of the invention may further contain an anionic surfactant, a cationic surfactant, an amphoteric surfactant or a nonionic surfactant. If need arises, various surfactants including an alkylsulfonic acid, an arylsulfonic acid, an aliphatic carboxylic acid and an aromatic carboxylic acid may be added.
  • the bleaching or bleach-fixing tablet of the invention should preferably contain, as a bleaching agent, a ferric complex salt of an organic acid represented by formula I, II, III or IV.
  • A1 to A4 whether identical or not, represent -CH2OH, -COOM or -PO3M1M2.
  • M, M1 and M2 each represent a hydrogen atom, an alkali metal or ammonium X represents an (un)substituted alkylene group with 3 to 6 carbon atoms.
  • compound Nos. I-1, I-3, I-4, I-5 and I-9 are preferable.
  • the use of compound No. I-1 is most desirable.
  • A1 to A4 have the same meanings as A1 to A4 in formula I.
  • n represents an integer of 1 to 8.
  • B1 and B2 Whether identical or not, each represent an (un)substituted alkylene group with 2 to 5 carbon atoms (e.g. ethylene, propylene, butylene, pentamethylene).
  • substituent use can be made of a hydroxyl group and a lower alkyl group with 1 to 3 carbon atoms (e.g. methyl, ethyl, propyl).
  • ferric complex salts of these compounds II-1 to II-7
  • use can be made of sodium salts, potassium salts or ammonium salts of these ferric complex salts.
  • ammonium salts are most desirable.
  • compound Nos. II-1, II-2 and II-3 are preferable.
  • the use of compound No. II-1 is most desirable.
  • R1 represents a hydrogen atom or a hydroxyl group.
  • n represents 1 or 2.
  • x represents 2 or 3 and y represents 0 or 1, provided that the total of x and y is always 3.
  • III-1 nitrilomonopropionodiacetic acid
  • III-1 HOOCH22-N-CH2CH2COOH
  • A1 to A4 have the same meanings as A1 to A4 in formula I.
  • M represents a hydrogen atom, an alkali metal atom (e.g. sodium, potassium) or other cations (e.g. ammonium, methyl ammonium, trimethyl ammonium).
  • X represents an (un)substituted alkylene group with 2 to 6 carbon atoms or -(B1O)n-B2- (where B1 and B2, whether identical or not, each represent an (un)substituted alkylene group with 1 to 5 carbon atoms).
  • the alkylene group represented by X may be ethylene, trimethylene or tetramethylene.
  • the alkylene group represented by B1 or B2 may be methylene, ethylene or trimethylene.
  • the substituent for the alkylene group represented by X, B1 or B2 may be a hydroxyl group or an alkyl group with 1 to 3 carbon atoms (e.g. methyl, ethyl).
  • n represents an integer of 1 to 8, preferably 1 to 4.
  • Preferred examples of the compounds represented by formula IV are given below.
  • As the ferric complex salts of these compounds, IV-1 to IV-17 use can be made of sodium salts, potassium salts or ammonium salts of these ferric complex salts.
  • ferric complex salts of the compounds represented by any one of formulae I to IV may also be employed as the bleaching agent.
  • Rapid processing can be attained by incorporating at least one member selected from imidazole, its derivatives, and compound Nos. I to IX (including example compounds) described in Japanese Patent O.P.I. Publication No. 295258/1989 into the bleach-fixing or fixing tablet.
  • the bleaching or bleach-fixing tablet may also contain a halide such as ammonium bromide, potassium bromide and sodium bromide, a fluorescent brightener, an antifoamer or a surfactant.
  • a halide such as ammonium bromide, potassium bromide and sodium bromide
  • a fluorescent brightener such as an infoamer or a surfactant.
  • the fixing agent to be employed for the bleach-fixing or fixing tablet of the invention it is preferable to employ a thiocyanate or a thiosulfate.
  • the amount of a thiocyanate should be 0.1 mol/l or more. In the processing of a color negative, it should preferably be 0.5 mol/l or more, still preferably 1.0 mol/l or more.
  • the amount of a thiosulfate should be 0.2 mol/l or more. In the processing of a color negative, it should preferably be 0.5 mol/l or more.
  • the objects of the invention can be attained more successfully by the combined use of a thiocyanate and a thiosulfate.
  • the fixing or bleach-fixing tablet of the invention may further contain two or more pH buffers each consisting of a salt. It is desirable to add a large amount of a rehalogenating agent such as an alkali halide or an ammonium halide (e.g. potassium bromide, sodium bromide, sodium chloride, ammonium bromide). An alkylamine or a polyethylene oxide, which is normally added to a fixer or bleach-fixer may also be contained in a suitable amount.
  • a rehalogenating agent such as an alkali halide or an ammonium halide (e.g. potassium bromide, sodium bromide, sodium chloride, ammonium bromide).
  • An alkylamine or a polyethylene oxide which is normally added to a fixer or bleach-fixer may also be contained in a suitable amount.
  • the fixing or bleach-fixing tablet of the invention should preferably contain a compound represented by formula FA described in Japanese Patent Application Specification No. 295258/1989 (including its example compounds).
  • the compounds represented by formula FA can be synthesized by conventional methods, such as those described in U.S. Patent Nos. 3,335,161 and 3,260,718.
  • the compounds represented by formula FA can be employed either singly or in combination. Good results can be obtained when these compounds are employed in amounts of 0.1 to 200 g per 1000 ml of fixer or bleach-fixer.
  • the stabilizing tablet of the invention should preferably contain a chelating agent of which the stability constant of ferric ions is 8 or more.
  • the stability constant as referred to herein is that described in L.G. Sillen, A.E. Martell; "Stability Constants of Metal-ion Complexes", The Chemical Society, London (1964), S.Chaberek, A.E. Martell; "Organic Sequestering Agents", Wiley (1959), and other publications.
  • Examples of the chelating agent of which the stability constant of ferric ions is 8 or more include those described in Japanese Patent Application Specification Nos. 234776/1990 and 324507/1989.
  • the amounts of these chelating agents should preferably be 0.01 to 50 g, still preferably 0.05 to 20 g, per 1000 ml of a stabilizer.
  • an ammonium compound can be supplied by ammonium salts of various inorganic compounds, and the amount should preferably be 0.001 to 2.0 mol, still preferably, 0.002 to 1.0 mol, per 1000 ml of a stabilizer. It is preferable to add a sulfite to the stabilizing tablet.
  • the stabilizing tablet should preferably contain a metal salt in combination with the above chelating agent.
  • a metal salt examples include those of Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb, Sn, Zn, Ti, Zr, Mg, Al or Sr.
  • These metal salts are supplied in the form of an inorganic salt such as a halide, a hydroxide, a sulfate, a carbonate, a phosphate and an acetate or in the form of a water-soluble chelating agent.
  • the amounts of these metal salts should preferably be 1 ⁇ 10 ⁇ 4 to 1 ⁇ 10 ⁇ 1 mol, still preferably 4 ⁇ 10 ⁇ 4 to 2 ⁇ 10 ⁇ 2 mol, per 1000 ml of a stabilizer.
  • a salt of an organic acid e.g. citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid
  • a pH adjustor e.g. phosphate, borate, hydrochloric acid, sulfate.
  • a fungicide or two or more fungicides in combination may be employed in an amount that will not affect adversely the effects of the invention.
  • Color developing tablets for a color negative were prepared according to the following procedures.
  • hyroxylamine sulfate 60 g was milled to an average particle diameter of 10 ⁇ m by means of an air-jet mill.
  • the powder was placed in a commercially-available fluidized bed spray granulator, where the powder was sprayed with 3.0 ml of water for about 7 minutes at room temperature, whereby the powder was granulated.
  • the granule obtained was dried for 8 minutes at an air temperature of 63°C, and then subjected to vacuum drying at 40°C for 90 minutes to remove most of the water contained therein.
  • the granules obtained by the above procedures were shaped into tablets by means of a multi-layer rotary tablet machine (prepared by remodeling Clean Press Correct, manufactured by Kikusui Seisakusho) in such a manner that granule C (2.65 g), granule A (0.6 g) and granule B (1.1 g) would constitutute the 1st (the lowermost) layer, the 2nd layer and the 3rd layer (the uppermost) layer, respectively.
  • Color developing tablets (sample Nos. 1-2 to 1-6, 10 tablets for each sample) were prepared in substantially the same manner as in procedures A to D, except that, in procedure D, 0.1 g of a water-soluble cellulose (shown in Table 1) was put between the 1st layer and the 2nd layer, and between the 2nd layer and the 3rd layer.
  • a water-soluble cellulose shown in Table 1
  • the granules obtained by procedures A to C were mixed uniformly at 25°C by a mixer placed in a room that had been subjected to moisture conditioning to a relative humidity of 50% or less. Then, 4.35 g of the mixture obtained was placed in a multi-layer rotary tablet machine (prepared by remodeling Tough Press Correct 1527 HU, manufactured by Kikusui Seisakusho), and shaped into a tablet at a compression pressure of 1000 kg/cm2. This procedure was repeated to obtain 10 comparative color developing tablets (sample No. 1-7).
  • the color developing tablets of the invention hardly formed a tar-like insoluble matter when dissolved in water after the storage at a higher temperature.
  • Color developing tablets for color paper were prepared according to the following procedures.
  • Color developing tablets were prepared in substantially the same manner as in Example 1, except that, in procedure E, a water-soluble cellulose was replaced by an equal amount of polyvinyl pyrrolidone (PVPK-17, 30) or polyethylene glycol (PEG 1000, 2000). The tablets were examined for tar-like insoluble matter in the same way as in Example 1. The results obtained were similar to those obtained in Example 1.
  • Color developer replenishing tablets for color paper were prepared according to the following procedures.
  • CD-3 [1-(N-ethyl-N-methanesulfoneamidoethyl)-3-methyl-p-phenylenediamine sesquisulfate monohydrate], a developing agent, was milled and granulated in substantially the same manner as in procedure B in Example 1, except that the amount of water used for spraying, the drying temperature and the drying time were 4.8 ml, 63°C and 8 minutes, respectively.
  • the granules obtained by procedures G to I were shaped into a tablet in substantially the same manner as in procedure D in Example 1.
  • the amounts of granule G, granule H and granule I were 0.4 g, 0.54 g and 2.39 g, respectively.
  • 50 color developing tablets for color paper (sample No. 3-1) were obtained.
  • Color developing tablets for color paper (sample Nos. 3-2 to 3-5, 50 tablets for each sample) were prepared in substantially the same manner as in procedures G to J, except that, in procedure J, 0.05 g of a compound shown in Table 2 was put between the 1st layer and the 2nd layer, and between the 2nd layer and the 3rd layer.
  • Granules G to I were mixed uniformly and shaped into a tablet in substantially the same manner as in procedure F in Example 1, except that the amount of the mixture placed in the tablet machine was 3.33 g, whereby 50 comparative color developing tablets (sample No. 3-6) were obtained.
  • Color developing tablets were prepared in substantially the same manner as in Example 3, except that CD-3 employed in procedure H was replaced by an equimolar amount of compound No. CL-2.
  • the tablets were examined for possible tar-like insoluble matter in the same way as in Example 3. The results revealed that the tablets of the invention hardly formed a tar-like insoluble matter when dissolved in water after the long-term storage.
  • Color developing tablets were prepared in substantially the same manner as in Example 3, except that the diethylhydroxylamine oxalate employed in procedure G was replaced by an equimolar amount of compound No. 1 or 7 described in Japanese Patent O.P.I. Publication No. 184044/1991, pages 4 to 6.
  • the tablets were examined for the possible tar-like insoluble matter in the same way as in Example 3. The results obtained were similar to those obtained in Example 3.
  • Bleach-fixing tablets for color paper were prepared according to the following procedures.
  • Granules M and N were shaped into a tablet in substantially the same manner as in procedure D in Example 1, except that the shaping was performed such that the granule M (4.05 g) and granule N (7.05 g) would constitute the 1st layer and the 2nd layer, respectively.
  • Bleach-fixing tablets (sample Nos. 6-2 to 6-5) were prepared in substantially the same manner as in procedures M to O, except that, in procedure O, 0.05 g of a compound shown in Table 3 was put between the 1st layer and the 2nd layer.
  • Granules M and N were mixed uniformly and shaped into a tablet in substantially the same manner as in procedure F in Example 1, except that the amount of the mixture placed in the tablet machine was 11.1 g, whereby a comparative bleach-fixing tablet (sample No. 6-6) was obtained.
  • the bleach-fixing tablets of the invention hardly formed an insoluble matter when dissolved in water after the storage at a higher temperature.
  • Bleach-fixing tablets were prepared in substantially the same manner as in Example 6, except that the ferric sodium ethylenediamine tetraacetate employed in procedure M was replaced by an equal amount of compound IV-1. The tablets were examined for possible insoluble matter in the same way as in Example 6. The results obtained were similar to those obtained in Example 6.
  • Color developing tablets for a color negative were prepared according to the following procedures.
  • hydroxylamine sulfate 50 g was milled to an average particle diameter of 10 ⁇ m by means of an air-jet mill.
  • the powder obtained was placed in a commercially-available fluidized bed spray granulator, where the powder was sprayed with 3.0 ml of water for about 7 minutes at room temperature, whereby the powder was granulated.
  • the granule obtained was dried for 8 minutes at an air temperature of 63°C, and then subjected to vacuum drying at 40°C for 90 minutes to remove most of the water contained therein.
  • Color developing tablets (sample Nos. 8-2 to 8-5, 200 tablets for each sample) were prepared in substantially the same manner as in procedures A to D, except that the outer surface of granule B (constituting the innermost layer) and that of granule A (constituting the 2nd layer) were each coated with a water-soluble cellulose shown in Table 4.
  • the granules obtained by procedures A to C were mixed uniformly at 25°C by a mixer placed in a room that had been subjected to moisture conditioning to a relative humidity of 50% or less. Then, 4.25 g of the mixture obtained was placed in each mortar of a multi-layer rotary tablet compressing machine (prepared by remodeling Tough Press Correct 1527 HU, manufactured by Kikusui Seisakusho), and shaped into a tablet at a compression pressure of 1000 kg/cm2. As a result, 200 comparative color developing tablets (sample No. 8-6) were obtained.
  • the color developing tablets of the invention hardly formed a tar-like insoluble matter when dissolved in water after the storage at a higher temperature.
  • Color developing tablets for color paper were prepared according to the following procedures.
  • Color developing tablets were prepared in substantially the same manner as in Example 8, except that a water-soluble cellulose employed in procedure E was replace by an equal amount of polyvinyl pyrrolidone (PVPK-17, 30) or polyethylene glycol (PEG 1000, 2000).
  • PVPK-17, 30 polyvinyl pyrrolidone
  • PEG 1000, 2000 polyethylene glycol
  • Color developer replenishing tablets for color paper were prepared according to the following procedures.
  • CD-3 [1-(N-ethyl-N-methanesulfoneamidoethyl)-3-methyl-p-phenylenediamine sesquisulfate monohydrate], a developing agent, was milled and granulated in substantially the same manner as in procedure B in Example 8, except that the amount of water employed for spraying, the drying temperature and the drying time were 4.8 ml, 63°C and 8 minutes, respectively.
  • the granules obtained by procedures G to I were shaped into a tablet in substantially the same manner as in procedure D in Example 8.
  • the amounts of granule H, granule G and granule I were 0.5 g, 0.4 g and 2.39 g, respectively.
  • 50 color developing tablets (sample 10-1) were obtained.
  • Color developing tablets (sample Nos. 10-2 to 10-5, 50 tablets for each sample) were prepared in substantially the same manner as in Example 10, except that, in procedure J, the outer surface of the innermost layer and that of the 2nd layer were each coated with a compound shown in Table 5.
  • Color developing tablets were prepared in substantially the same manner as in Example 10, except that CD-3 employed in procedure H was replaced by an equimolar amount of compound CL-2.
  • the tablets were examined for possible tar-like insoluble matter in the same way as in Example 10. The results revealed that the tablets of the invention hardly formed a tar-like insoluble matter when dissolved in water after the long-term storage.
  • Color developing tablets were prepared in substantially the same manner as in Example 10, except that diethylhydroxylamine oxalate employed in procedure G was replaced by an equimolar amount of compound No. 1 or 7 described in Japanese Patent O.P.I. Publication No. 184044/1991, pages 4 to 6.
  • the tablets were examined for the formation of a tar-like insoluble matter in the same way as in Example 10. The results obtained were similar to those obtained in Example 10.
  • Bleach-fixing tablets for color paper were prepared according to the following procedures.
  • the granules obtained by procedures M and N were shaped into a tablet in substantially the same manner as in procedure D in Example 8.
  • the shaping was performed such that granule M (4.05 g) and granule N (7.05 g) would constitute the outer layer and the inner layer, respectively.
  • a bleach-fixing tablet for color paper (sample No. 13-1) was obtained.
  • Sample Nos. 13-1 to 13-5 were prepared in substantially the same manner as in procedure O, except that the outer surface of the inside core was coated with a compound shown in Table 6.
  • Granules M and N were mixed and shaped into a tablet in substantially the same manner as in procedure F in Example 8, except that the amount of the mixture placed in the tablet machine was 11.1 g, whereby a comparative bleach-fixing tablet (sample No. 13-6) was obtained.
  • the bleach-fixing tablets of the invention hardly formed an insoluble matter when dissolved in water after the storage at a higher temperature.
  • Bleach-fixing tablets for color paper were prepared in substantially the same manner as in Example 13, except that ferric sodium ethylenediamine tetraacetate employed in procedure M was replaced by an equal amount of compound D-1.
  • the tablets obtained were examined for possible insoluble matter in the same way as in Example 13. The results obtained were similar to those obtained in Example 13.

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  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Abstract

Disclosed is a tablet for supplying to a solution for processing a sliver halide photographic light-sensitive material so as to keep the property of the solution comprising a processing agent, wherein the tablet is prepared by stacking two or more granules or powders differing in composition in a layered construction and thereafter applied pressure on said granules or powder in the layered construction.
The tablet used in a solution for processing a sliver halide photographic light-sensitive material is improvement in a storage stability.

Description

    FIELD OF THE INVENTION
  • The present invention relates to a tablet for processing a photographic film, more specifically to a tablet suitable for use in processing a silver halide color photographic material by means of an automatic developing machine.
    • BACKGROUND OF THE INVENTION
  • Silver halide photographic light-sensitive materials are, after imagewise exposure, normally subjected to processing with a monochromatic developer, a fixer, a color developer, a bleacher, a bleach-fixer, a stabilizer and the like. For users' convenience, these processing liquids are sold in the form of a kit that consists of plastic bottles filled with the concentrates of these liquids. Two or more plastic bottles may be employed for one processing liquid. Users dissolve these concentrates in water to make starting liquids or replenishers.
  • In recent years, small-sized developing laboratories in which small-sized developing machines are used (minilaboratories) have been increasing rapidly in number. With the increase in number of such minilaboratories, more plastic bottles than ever have come to be used to keep processing liquids.
  • Being light-weight and tough, plastics can be utilized in various ways. The world's production of plastics has been on the increase; in 1988, the annual output of plastics exceeded 100 million tons. On the other hand, a large amount of plastics are being discarded as waste. For instance, in Japan, about 40% of the plastics produced each year are discarded. If plastics are thrown away in the ocean, they may affect adversely oceanic lives. In Europe, waste plastics are usually burned up in incinerators which do not have means to treat exhaust gas. The exhaust gas from such incinerators is regarded as the cause of acid rain.
  • With a view to solve this problem, there is a strong movement in Europe to impose legal restrictions on the use of plastics; specifically, to make a new law totally prohibiting the use of plastics, obliging the recycling and plastics, obliging the use of biodegradable plastics, or the like.
  • In view of the harmful influence of waste plastics on environment, the use of a large amount of plastic bottles for keeping processing liquids is unfavorable.
  • To eliminate the need to use plastic bottles, preparation of a processing agent concentrate in the form of powder was proposed. However, since powdery concentrate tends to fly, it may be inhaled by users during dissolution work, injuring their health, or it may enter the containers of other processing liquids while it is flying, causing contamination of these liquids. Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) Nos. 109042/1990, 109043/1990, 39735/1991 and U.S. Patent No. 2,843,484 each proposed the granulation of a powdery concentrate. The use of a granular concentrate is, however, accompanied by the same problems as mentioned above. Moreover, granules have such defects that they are likely to settle down at the bottom of a container when dissolved in water (caking), and that they cannot be dissolved well in water since they are covered by wet coating films which are formed during granulation process. At present, only a limited kind of a processing liquid can be used in the form of powder or granule.
  • Japanese Patent O.P.I. Publication No. 61837/1976 proposes the use of a processing agent in the form of a tablet.
  • Though being free from the troubles accompanying the above-mentioned powdery or granular processing agent, a processing agent in the form of a tablet is poor in storage stability. In the case of a tablet for color developing, the color developing agent contained therein tends to be oxidized during storage, forming a tar-like insoluble matter. In the case of a tablet for fixing or bleach-fixing, insoluble matters such as sulfur or sulfides may be formed during storage. The formation of such insoluble matters prevent these tablets from exhibiting their processing performance sufficiently.
    • SUMMARY OF THE INVENTION
  • An object of the present invention is to provide a tablet for processing a silver halide color photographic light-sensitive material with improved storage stability.
  • Another object of the present invention is to enable processing of a photographic film to be performed safely without causing environmental pollution by minimizing the amount of containers including plastic bottles for keeping processing liquids.
    • CONSTITUTION OF THE INVENTION
  • The above objects can be attained by a tablet for processing a silver halide photographic light-sensitive material characterized in that it is obtained by laying two or more granules differing in composition one on top of another to form a layered structure, followed by pressure molding.
  • The processing tablet of the invention can be prepared according to conventional methods described, for instance, in Japanese Patent O.P.I. Publication Nos. 61837/1976, 155038/1979, 88025/1977 and British Patent No. 1,213,808.
  • To allow a tablet to have a layered structure, two or more granules differing in composition are subjected to pressure molding by means of a multi-layer rotary tablet machine which is prepared by remodeling Clean Press Correct 3151K (manufactured by Kikusui Seisakusho).
  • Pressure molding may be performed with a photographically inactive substance being sandwiched between two layers.
  • The photographically inactive substance may be a water-soluble polymeric material; examples include water-soluble cellulose, water-soluble dextrin, water-soluble polyethylene glycol, water-soluble polyvinyl pyrrolidone and water-soluble polyacrylamide.
  • The tablet according to the invention may be a color developing tablet, a monochromatic developing tablet, a bleaching tablet, a bleach-fixing tablet or a stabilizing tablet.
  • The color developing agent contained in the color developing tablet should preferably be a p-phenylenediamine compound with a water-soluble group for less fogging and the successful manifestation of the effects of the invention.
  • As compared with a p-phenylenediamine compound without a water-soluble group (e.g. N,N-diethyl-p-phenylenediamine), a p-phenylenediamine compound with a water-soluble group is more advantageous, since it will not contaminate a light-sensitive material or irritate users' skin. When employed in the tablet of the present invention, a p-phenylenediamine compound with a water-soluble group contributes to more successful manifestation of the effects of the invention.
  • The water-soluble group may be one which is present on the amino group or benzene ring of a p-phenylenediamine compound. Preferred examples of the water-soluble group include -(CH₂)nCH₂OH, -(CH₂)mNHSO₂(CH₂)nCH₃, -(CH₂)mO(CH₂)nCH₃, -(CH₂CH₂O)nCmH₂m₊₁ (wherein m and n each represent an integer of 0 or more), -COOH group and -SO₃H group.
  • Preferred examples of a color developing agent to be used in the invention include compound Nos. C-1 to C-16 described in Japanese Patent Application Specification No. 203169/1990, pages 26 to 31, and the following compounds, C'-1, C'-2, and C'-3.
  • The present invention will be described in detail with reference to example. However, it should be understood that the present invention is by no means restricted to such examples.
    Figure imgb0001
    Figure imgb0002
    Figure imgb0003
    Figure imgb0004
       These color developing agents are normally employed in the form of a salt, such as a hydrochloride, a sulfate and a p-toluenesulfonate.
  • The above color developing agents may be employed either singly or in combination. If need arises, they may be employed together with a monochromatic developing agent, such as phenidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone and metol.
  • The effects of the invention can be produced more satisfactorily and the unexposed portion of a film can be free of fogging when a compound represented by the following formula A or B is incorporated in the color developing tablet.
    • Formula A
  • Figure imgb0005
  • In the formula, R₁ and R₂ each represent an alkyl group, an aryl group, R₃CO- group or a hydrogen atom, provided that there is no case where R₁ and R₂ are both hydrogen atoms. R₁ and R₂ may combine with each other to form a ring.
  • In formula A, the (un)substituted alkyl group represented by R₁ and that represented by R₂ may be either identical with or different from each other, and each may preferably be an alkyl group with 1 to 3 carbon atoms. The alkyl group may further contain a carboxyl group, a phosphoric acid group, a sulfo group or a hydroxyl group. R₃ represents an (un)substituted alkoxy group, an (un)substituted alkyl group or an (un)substituted aryl group. The ring which may be formed by R₁ and R₂ may be a heterocyclic ring such as piperidine, pyridine, triazine or morpholine.
    • Formula B
  • Figure imgb0006
  • In the formula, R₁₁, R₁₂ and R₁₃ each represent ahydrogen atom, an (un)substituted alkyl group, an aryl group or a heterocyclic group. R₁₄ represents a hydroxyl group, a hydroxyamino group, (un)substituted alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group or an amino group. The heterocyclic group is an (un)saturated, 5 to 6-membered ring consisting of C, H, O, N, S and a halogen atom. R₁₅ represents a divalent group selected from -CO-, -SO₂- and -C(=NH)-. n represents 0 or 1. When n is 0, R₁₄ represents a group selected from an alkyl group, an aryl group or a heterocyclic group. R₁₃ and R₁₄ may combine with each other to form a heterocyclic ring.
  • Specific examples of the hydroxylamine compounds represented by formula A are given in U.S. Patent Nos. 3,287,125, 3,329,034 and 3,287,124. Preferred examples are compound Nos. A-1 to A-39 described in Japanese Patent Application Specification No. 203169/1990, pages 36 to 38, compound Nos. 1 to 53 described in Japanese Patent O.P.I. Publication No. 33845/1991, pages 3 to 6 and compound Nos. 1 to 52 described in Japanese Patent O.P.I. Publication No. 63646/1991.
  • The present invention will be described in detail with reference to example. However, it should be understood that the present invention is by no means restricted to such examples.
    • (JPI No. 203169/1990)
  • Figure imgb0007
    Figure imgb0008
    Figure imgb0009
    Figure imgb0010
    • (JPI No. 33845/1991)
  • Figure imgb0011
    Figure imgb0012
    Figure imgb0013
    Figure imgb0014
    Figure imgb0015
    Figure imgb0016
    Figure imgb0017
    Figure imgb0018
    Figure imgb0019
    • (JPI No. 63646/1991)
  • Figure imgb0020
    Figure imgb0021
    Figure imgb0022
    Figure imgb0023
    Figure imgb0024
    Figure imgb0025
    Figure imgb0026
    Figure imgb0027
    Figure imgb0028
  • Specific examples of the compound represented by formula B include compound Nos. B-1 to B-33 described in Japanese Patent Application Specification No. 203169/1990, pages 40 to 43 and compound Nos. 1 to 56 described in Japanese Patent O.P.I. publication No. 33846/1991, pages 4 to 6.
    • (JPI No. 203169/1990)
  • Figure imgb0029
    Figure imgb0030
    Figure imgb0031
    • (JPI No. 33846/1991)
  • Figure imgb0032
    Figure imgb0033
    Figure imgb0034
    Figure imgb0035
    Figure imgb0036
    Figure imgb0037
    Figure imgb0038
    Figure imgb0039
    Figure imgb0040
  • The compounds represented by formula A or B are normally employed in the form of a free amine, a hydrochloride, a sulfate, a p-toluenesulfonate, an oxalate, a phosphate or an acetate.
  • A hydroxylamine compound represented by formula AL may be employed preferably in the invention as a preservative for a color developer.
    • Formula A'
  • Figure imgb0041
  • In the formula, L represents an (un)substituted alkylene group, A represents a carboxyl group, a sulfo group, a phosphono group, a phosphino group, a hydroxyl group, an amino group, an ammonio group, a carbamoyl group or a sulfamoyl group. The amino group, ammonium group, carbamoyl group and sulfamoyl group each may be alkyl-substituted. R represents a hydrogen atom or an (un)substituted alkyl group.
  • Specific examples of the compounds represented by formula A' include compound Nos. 1 to 54 described in Japanese Patent O.P.I. Publication No. 184044/1991, on page 4 at the , lower left column to page 6 at the upper right column. Of them, compound Nos. 1 and 7 are preferable.
       Compound No. 1: HON(CH₂COOH)₂
       Compound No. 7: HON(CH₂CH₂SO₃H)₂
       The compounds represented by formula A' can be prepared by subjecting a commercially-available hydroxylamine to alkylation. Specifically, they can be prepared according to methods described in West German Patent No. 1,159,634 and Inorganica Chimica Acta, 93 (1984), pages 101 to 108.
  • In the color or monochormatic developing tablet of the invention, a small amount of a sulfite may be contained as a preservative. Usable sulfites include sodium sulfite, potassium sulfite, sodium bisulfite and potassium bisulfite.
  • The color or monochromatic developing tablet of the invention must contain a buffer, such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, trisodium phosphate, tripotassium phosphate, disodium 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 a usable development accelerator include thioether compounds described in Japanese Patent Examined Publication Nos. 16088/1962, 5987/1962, 7826/1963, 12380/1969, 9019/1970 and U.S. Patent No. 3,813,247, p-phenylenediamine compounds described in Japanese Patent O.P.I. Publication Nos. 49829/1977 and 15554/1975, quaternary ammonium salts described in Japanese Patent Examined Publication No. 30074/1969, Japanese Patent O.P.I. Publication Nos. 137726/1975, 156826/1981 and 43429/1977, p-aminophenols described in U.S. Patent Nos. 2,610,122 and 4,119,462, amine compounds described in U.S. Patent Nos. 2,494,903, 3,128,182, 4,230,796, 3,253,919, 2,482,546, 2,596,926, 3,582,346, and Japanese Patent Examined Publication No. 11431/1964, polyalkylene oxides described in Japanese Patent Examined Publication Nos. 16088/1962, 25201/1967, 11431/1966, 23883/1967 and U.S. Patent Nos. 3,128,183 and 3,532,501, 1-phenyl-3-pyrazolidones, hydrazines, mesoion-type compounds, ion-type compounds and imidazoles.
  • To prevent fogging and other troubles, chlorine ions and bromine ions may be contained in the color developing tablet of the present invention. The amount of chlorine ions should preferably be 1.0 × 10⁻² to 1.5 × 10⁻¹ mol, still preferably 3.5 × 10⁻² to 1.0 × 10⁻¹ mol, per liter of a color developer. If it exceeds 1.5 × 10⁻¹ mol/l, development will be retarded, and it will be impossible to obtain a higher maximum density rapidly. When the amount of chlorine ions is smaller than 3.5 × 10⁻² mol/l, stains will be formed, and photographic properties (in particular, minimum density) will vary considerably during continuous processing.
  • The amount of bromine ions should preferably be 3.0 × 10⁻ ⁵ to 1.0 × 10⁻³ mol, still preferably 5.0 × 10⁻⁵ to 5.0 × 10⁻⁴ mol, per liter of a color developer. If it exceeds 1.0 × 10⁻³ mol/l, development will be retarded, and maximum density and sensitivity will be lowered. When the amount of bromine ions is lower than 3.0 × 10⁻⁵/l, stains will be formed, and photographic properties (in particular, minimum density) will vary considerably during continuous processing.
  • When chloride ions are added directly to the color developing tablet of the invention, sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride and cadmium chloride may be employed as a chlorine ion-supplying material. Of them, sodium chloride and potassium chloride are preferable.
  • Chlorine ions may be supplied in the form of a counter ion of a fluorescent brightener to be added to the color developing tablet.
  • Bromine ion-supplying materials include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide and thallium bromide. Of them, preferable are potassium bromide and sodium bromide.
  • The color developing tablet of the invention may contain an antifoggant in addition to chloride and bramide ions, if need arises. As the antifoggant, an alkali metal halide such as potassium iodide and an organic antifoggant may be employed. As the organic antifoggant, use can be made of a nitrogen-containing heterocyclic compound such as benzotriazole, 6-nitrobenzimidazole, 5-nitroindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine and adenine.
  • To attain the objects of the invention more successfully, it is preferable to add a triazinyl stilbene fluorescent brightener to the color developing tablet of the invention. A compound represented by formula E is preferable as such brightener.
    • Formula E
  • Figure imgb0042
  • In the formula, X₁, X₂, Y₁ and Y₂ each represent a hydroxyl group, a halogen atom (e.g; chlorine, bromine), an alkyl group, an aryl group or -N(R₂₁)(R₂₂) group,
    Figure imgb0043
    or OR₂₅ (where R₂₁ and R₂₂ each represent a hydrogen atom, an (un)substituted alkyl group, an (un)substituted aryl group, R₂₃ and R₂₄ each represent an (un)substituted alkylene group, R₂₅ represents a hydrogen atom, an (un)substituted alkyl group or an (un)substituted aryl group), and M represents a cation.
  • Examples of the groups and their substituents in formula E are given in Japanese Patent Application Specification No. 240400/1990, from the 8th line from the bottom of page 62 to the 3rd line from the bottom of page 64. Specific examples of the compounds represented by formula E are compound Nos. E-1 to 45 described on pages 65 to 67 of the same specification.
  • The compounds represented by formula E can be prepared by conventional methods. Representative examples of these compounds are given below. Of them, compound Nos. E-4, E-24, E-34, E-35, E-36, E-37 and E-41 are preferable. These compounds should preferably be employed in an amount of 0.2 to 10 g, still preferably 0.4 to 5 g, per 1000 ml of a color developer.
    Figure imgb0044
    Figure imgb0045
  • The color or monochromatic developing tablet of the invention may further contain, if necessary, an organic solvent such as methyl cellosolve, methonol, acetone, dimethylformamide, β-cyclodextrin and compounds described in Japanese Patent Examined Publication Nos. 33378/1972 and 9509/1968. These organic solvents serve to increase the solubility of a color developing agent.
  • In combination with a color developing agent, an auxiliary developing agent may be employed. The auxiliary developing agent may be metol, phenidone, N,N-diethyl-p-aminophenol hydrochloride or N,N,N',N'-tetramethyl-p-phenylenediamine hydrochloride. The amount should preferably be 0.01 to 1.0 g/l.
  • An anti-stain agent, an anti-sludge agent and other additives may be contained in the color or monochromatic developing tablet of the invention.
  • To attain the objects of the invention successfully, it is preferable to add a chelating agent represented by the following formula K (described in Japanese Patent Application Specification No. 240400/1990, from the 9th line from the bottom of page 69 to page 75 and example compound Nos. K-1 to 22) to the color or monochromatic developing tablet of the invention.
    • Formula K
  • Figure imgb0046
  • The present invention will be described in detail with reference to example. However, it should be understood that the present invention is by no means restricted to such examples.
    Figure imgb0047
    Figure imgb0048
    Figure imgb0049
    Figure imgb0050
    Figure imgb0051
  • Of these chelating agents, compound Nos. K-2, K-9, K-12, K-13, K-17 and K-19 are preferable. The effects of the invention can be realized effectively when compound No. K-2 or compound No. K-9 is added to a color developer.
  • The amounts of these chelating agents should preferably be 0.1 to 20 g, still preferably 0.2 to 8 g, per 1000 ml of a color or monochromatic developer.
  • The color or monochromatic developing tablet of the invention may further contain an anionic surfactant, a cationic surfactant, an amphoteric surfactant or a nonionic surfactant. If need arises, various surfactants including an alkylsulfonic acid, an arylsulfonic acid, an aliphatic carboxylic acid and an aromatic carboxylic acid may be added.
  • The bleaching or bleach-fixing tablet of the invention should preferably contain, as a bleaching agent, a ferric complex salt of an organic acid represented by formula I, II, III or IV.
    • Formula I
  • Figure imgb0052
  • In the formula, A₁ to A₄, whether identical or not, represent -CH₂OH, -COOM or -PO₃M₁M₂. M, M₁ and M₂ each represent a hydrogen atom, an alkali metal or ammonium X represents an (un)substituted alkylene group with 3 to 6 carbon atoms.
  • The compounds represented by formula I will be explained in detail.
  • Explanation of A₁ to A₄ will be omitted since they have the same meaning as A₁ to A₄ described in Japanese Patent Application Specification No. 260628/1990, 15 lines from the top to of page 12 to 3 lines from the top of page 15, from the top.
  • Preferred examples of the compounds represented by formula I are given below.
    • I-1:
    1,3-propanediaminetetraacetic acid
    I-2:
    2-hydroxy-1,3-propanediaminetetraacetic acid
    I-3:
    2,3-propanediaminetetraacetic acid
    I-4:
    1,4-butanediaminetetraacetic acid
    I-5:
    2-methyl-1,3-propanediaminetetraacetic acid
    I-6:
    N-(2-hydroxyethyl)-1,3-propanediaminetriacetic acid
    I-7:
    1,3-propanediaminetetrakismethylene phosphonic acid
    I-8:
    2-hydroxy-1, 3-propanediaminetetrakismethylene phosphonic acid.
    I-9:
    2,2-dimethyl-1,3-propanediaminetetraacetic acid
    I-10:
    2,4-butanediaminetetraacetic acid
    I-11:
    2,4-pentanediaminetetraacetic acid
    I-12:
    2-methyl-2,4-pentanediaminetetraacetic acid
       As the ferric complex salts of these compounds, use can be made of sodium salts, potassium salts or ammonium salts of these ferric complex salts. In regard of the successful attainment of the objects of the invention and improved solubility, ammonium salts are most desirable.
  • In the present invention, compound Nos. I-1, I-3, I-4, I-5 and I-9 are preferable. The use of compound No. I-1 is most desirable.
  • The compounds represented by formula II will be explained in detail.
    • Formula II
  • Figure imgb0053
  • In the formula, A₁ to A₄ have the same meanings as A₁ to A₄ in formula I. n represents an integer of 1 to 8. B₁ and B₂, Whether identical or not, each represent an (un)substituted alkylene group with 2 to 5 carbon atoms (e.g. ethylene, propylene, butylene, pentamethylene). As the substituent, use can be made of a hydroxyl group and a lower alkyl group with 1 to 3 carbon atoms (e.g. methyl, ethyl, propyl).
  • Preferred examples of the compounds represented by formula II are given below.
    Figure imgb0054
    Figure imgb0055
       As the ferric complex salts of these compounds, II-1 to II-7, use can be made of sodium salts, potassium salts or ammonium salts of these ferric complex salts. In regard of the successful attainment of the objects of the invention and improved solubility, ammonium salts are most desirable.
  • In the present invention, compound Nos. II-1, II-2 and II-3 are preferable. The use of compound No. II-1 is most desirable.
  • The compounds represented by formula III will be explained in detail.
    • Formula III
  • Figure imgb0056
  • In the formula, R₁ represents a hydrogen atom or a hydroxyl group. n represents 1 or 2. x represents 2 or 3 and y represents 0 or 1, provided that the total of x and y is always 3.
  • Of the compounds represented by formula III, preferred are nitrilomonopropionodiacetic acid (III-1) and nitrilotriacetic acid.
    III-1



            (HOOCH₂)₂-N-CH₂CH₂COOH



       The compounds represented by formula IV will be explained in detail.
    • Formula IV
  • Figure imgb0057
  • In the formula, A₁ to A₄ have the same meanings as A₁ to A₄ in formula I. M represents a hydrogen atom, an alkali metal atom (e.g. sodium, potassium) or other cations (e.g. ammonium, methyl ammonium, trimethyl ammonium). X represents an (un)substituted alkylene group with 2 to 6 carbon atoms or -(B₁O)n-B₂- (where B₁ and B₂, whether identical or not, each represent an (un)substituted alkylene group with 1 to 5 carbon atoms).
  • The alkylene group represented by X may be ethylene, trimethylene or tetramethylene. The alkylene group represented by B₁ or B₂ may be methylene, ethylene or trimethylene. The substituent for the alkylene group represented by X, B₁ or B₂ may be a hydroxyl group or an alkyl group with 1 to 3 carbon atoms (e.g. methyl, ethyl). n represents an integer of 1 to 8, preferably 1 to 4. Preferred examples of the compounds represented by formula IV are given below.
    Figure imgb0058
    Figure imgb0059
    Figure imgb0060
       As the ferric complex salts of these compounds, IV-1 to IV-17, use can be made of sodium salts, potassium salts or ammonium salts of these ferric complex salts.
  • Besides the ferric complex salts of the compounds represented by any one of formulae I to IV, the ferric complex salts of the following compounds may also be employed as the bleaching agent.
    • (I'-1) Ethylenediaminetetraacetic acid
    • (I'-2) Trans-1,2-cyclohexanediaminetetraacetic acid
    • (I'-3) Hydroxyethylglycinic acid
    • (I'-4) Ethylenediaminetetrakismethylene phosphonic acid
    • (I'-5) Nitrilotrismethylene phosphonic acid
    • (I'-6) Diethylenetriaminepentakismethylene phosphonic acid
    • (I'-7) Diethylenetriaminepentaacetic acid
    • (I'-8) Ethylenediamineorthohydroxyphenyl acetic acid
    • (I'-9) Hydroxyethyl ethylenediamine tetraacetic acid
    • (I'-10) Ethylenediaminedipropionic acid
    • (I'-11) Ethylenediaminediacetic acid
    • (I'-12) Hydroxyethyl iminodiacetic acid
    • (I'-13) Nitrilotripropionic acid
    • (I'-14) Triethylenetetraminehexaacetic acid
    • (I'-15) Ethylenediaminetetrapropionic acid
       The ferric complex salts of these organic acids should preferably be employed in amounts of 0.1 to 2.0 mol, still preferably 0.15 to 1.5 mol, per 1,000 ml of a bleacher or bleach-fixer.
  • Rapid processing can be attained by incorporating at least one member selected from imidazole, its derivatives, and compound Nos. I to IX (including example compounds) described in Japanese Patent O.P.I. Publication No. 295258/1989 into the bleach-fixing or fixing tablet.
  • Besides the above accelerators, example compounds described in Japanese Patent O.P.I. Publication No. 123459/1987, pages 51 to 115, Japanese Patent O.P.I. Publication No. 17445/1988, pages 22 to 25, compounds described in Japanese Patent O.P.I. Publication Nos. 95630/1978 and 28426/1978 can also be employed for the same purpose.
  • The bleaching or bleach-fixing tablet may also contain a halide such as ammonium bromide, potassium bromide and sodium bromide, a fluorescent brightener, an antifoamer or a surfactant.
  • As the fixing agent to be employed for the bleach-fixing or fixing tablet of the invention, it is preferable to employ a thiocyanate or a thiosulfate. The amount of a thiocyanate should be 0.1 mol/l or more. In the processing of a color negative, it should preferably be 0.5 mol/l or more, still preferably 1.0 mol/l or more. The amount of a thiosulfate should be 0.2 mol/l or more. In the processing of a color negative, it should preferably be 0.5 mol/l or more.
  • The objects of the invention can be attained more successfully by the combined use of a thiocyanate and a thiosulfate.
  • The fixing or bleach-fixing tablet of the invention may further contain two or more pH buffers each consisting of a salt. It is desirable to add a large amount of a rehalogenating agent such as an alkali halide or an ammonium halide (e.g. potassium bromide, sodium bromide, sodium chloride, ammonium bromide). An alkylamine or a polyethylene oxide, which is normally added to a fixer or bleach-fixer may also be contained in a suitable amount.
  • The fixing or bleach-fixing tablet of the invention should preferably contain a compound represented by formula FA described in Japanese Patent Application Specification No. 295258/1989 (including its example compounds). By the addition of this compound, not only are the effects of the invention manifested sufficiently, but also an unexpected effect where a very small amount of sludge is formed during the long-time processing of few light-sensitive materials can be realized.
  • The compounds represented by formula FA can be synthesized by conventional methods, such as those described in U.S. Patent Nos. 3,335,161 and 3,260,718. The compounds represented by formula FA can be employed either singly or in combination. Good results can be obtained when these compounds are employed in amounts of 0.1 to 200 g per 1000 ml of fixer or bleach-fixer.
  • The stabilizing tablet of the invention should preferably contain a chelating agent of which the stability constant of ferric ions is 8 or more. The stability constant as referred to herein is that described in L.G. Sillen, A.E. Martell; "Stability Constants of Metal-ion Complexes", The Chemical Society, London (1964), S.Chaberek, A.E. Martell; "Organic Sequestering Agents", Wiley (1959), and other publications.
  • Examples of the chelating agent of which the stability constant of ferric ions is 8 or more include those described in Japanese Patent Application Specification Nos. 234776/1990 and 324507/1989. The amounts of these chelating agents should preferably be 0.01 to 50 g, still preferably 0.05 to 20 g, per 1000 ml of a stabilizer.
  • It is preferable to add an ammonium compound to the stabilizing tablet. An ammonium compound can be supplied by ammonium salts of various inorganic compounds, and the amount should preferably be 0.001 to 2.0 mol, still preferably, 0.002 to 1.0 mol, per 1000 ml of a stabilizer. It is preferable to add a sulfite to the stabilizing tablet.
  • Further, the stabilizing tablet should preferably contain a metal salt in combination with the above chelating agent. Examples of usable metal salts include those of Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb, Sn, Zn, Ti, Zr, Mg, Al or Sr. These metal salts are supplied in the form of an inorganic salt such as a halide, a hydroxide, a sulfate, a carbonate, a phosphate and an acetate or in the form of a water-soluble chelating agent. The amounts of these metal salts should preferably be 1 × 10⁻⁴ to 1 × 10⁻¹ mol, still preferably 4 × 10⁻⁴ to 2 × 10⁻² mol, per 1000 ml of a stabilizer.
  • It is possible to add to the stabilizing tablet a salt of an organic acid (e.g. citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid) and a pH adjustor (e.g. phosphate, borate, hydrochloric acid, sulfate). In the invention, a fungicide (or two or more fungicides in combination) may be employed in an amount that will not affect adversely the effects of the invention.
    • EXAMPLES Example 1
  • Color developing tablets for a color negative were prepared according to the following procedures.
    • Procedure A... Granule A
  • 60 g of hyroxylamine sulfate was milled to an average particle diameter of 10 µm by means of an air-jet mill. The powder was placed in a commercially-available fluidized bed spray granulator, where the powder was sprayed with 3.0 ml of water for about 7 minutes at room temperature, whereby the powder was granulated. The granule obtained was dried for 8 minutes at an air temperature of 63°C, and then subjected to vacuum drying at 40°C for 90 minutes to remove most of the water contained therein.
    • Procedure B....Granule B
  • 110 g of CD-4 [4-amino-3-methyl-N-ethyl-N-β-hydroxylethyl aniline sulfate], a developing agent, was milled and granulated in substantially the same manner as in procedure A, except that the amount of water employed for spraying was 2.6 ml. After the granulation, the granule was dried at 60°C for 7 minutes, and then subjected to vacuum drying at 40°C for 90 minutes to remove most of the water contained therein.
    • Procedure C....Granule C
  • 50 g of sodium 1-hydroxyethane-1,1-diphosphonate, 70 g of sodium sulfite, 616 g of potassium carbonate, 30 g of sodium hydrogen carbonate and 14 g of sodium bromide were uniformly mixed by means of a commercially-available mixer. The mixture was milled and granulated in substantially the same manner as in procedure A, except that the amount of water employed for spraying was 190 ml. After the granulation, the granules were dried at 70°C for 10 minutes, and then subjected to vacuum drying at 40°C for 90 minutes to remove most of the water contained therein.
    • Procedure D
  • The granules obtained by the above procedures were shaped into tablets by means of a multi-layer rotary tablet machine (prepared by remodeling Clean Press Correct, manufactured by Kikusui Seisakusho) in such a manner that granule C (2.65 g), granule A (0.6 g) and granule B (1.1 g) would constitutute the 1st (the lowermost) layer, the 2nd layer and the 3rd layer (the uppermost) layer, respectively.
  • The above procedure was repeated to obtain 10 color developer replenishing tablets (sample No. 1-1).
    • Procedure E
  • Color developing tablets (sample Nos. 1-2 to 1-6, 10 tablets for each sample) were prepared in substantially the same manner as in procedures A to D, except that, in procedure D, 0.1 g of a water-soluble cellulose (shown in Table 1) was put between the 1st layer and the 2nd layer, and between the 2nd layer and the 3rd layer.
    • Procedure F
  • The granules obtained by procedures A to C were mixed uniformly at 25°C by a mixer placed in a room that had been subjected to moisture conditioning to a relative humidity of 50% or less. Then, 4.35 g of the mixture obtained was placed in a multi-layer rotary tablet machine (prepared by remodeling Tough Press Correct 1527 HU, manufactured by Kikusui Seisakusho), and shaped into a tablet at a compression pressure of 1000 kg/cm2. This procedure was repeated to obtain 10 comparative color developing tablets (sample No. 1-7).
    • Experiment
  • Five tablets of each sample were put into a polyethylene bag. The bag was sealed up and stored at 65°C for 1 month. Then, these tablets were dissolved in 500 ml of water to examine the formation of a tar-like insoluble matter. The results are shown in Table 1. Table 1
    Sample No. Water-soluble cellulose Formation of a tar-like insoluble matter
    1-1 - B Present invention
    1-2 Sodium carboxymethyl cellulose A Present invention
    1-3 Hydroxyethyl cellulose A Present invention
    1-4 Hyroxymethyl cellulose A Present invention
    1-5 Hydroxypropyl cellulose A Present invention
    1-6 Gum arabic A Present invention
    1-7 - C Comparative
  • From the results, it can be understood that the color developing tablets of the invention hardly formed a tar-like insoluble matter when dissolved in water after the storage at a higher temperature.
  • Color developing tablets for color paper were prepared according to the following procedures.
    • Example 2
  • Color developing tablets were prepared in substantially the same manner as in Example 1, except that, in procedure E, a water-soluble cellulose was replaced by an equal amount of polyvinyl pyrrolidone (PVPK-17, 30) or polyethylene glycol (PEG 1000, 2000). The tablets were examined for tar-like insoluble matter in the same way as in Example 1. The results obtained were similar to those obtained in Example 1.
    • Example 3
  • Color developer replenishing tablets for color paper were prepared according to the following procedures.
    • Procedure G...Granule G
  • 200 g of diethylhydroxylamine oxalate was milled and granulated in substantially the same manner as in procedure A in Example 1, except that the amount of water used for spraying, the drying temperature and the drying time were 10 ml, 70°C and 70 minutes, respectively.
    • Procedure H...Granule H
  • 270 g of CD-3 [1-(N-ethyl-N-methanesulfoneamidoethyl)-3-methyl-p-phenylenediamine sesquisulfate monohydrate], a developing agent, was milled and granulated in substantially the same manner as in procedure B in Example 1, except that the amount of water used for spraying, the drying temperature and the drying time were 4.8 ml, 63°C and 8 minutes, respectively.
    • Procedure I
  • 6 g of sodium sulfite, 900 g of potassium carbonate, 45 g of sodium hydrogen carbonate, 75 g of tinopal SFP and 100 g of sodium diethylenetriamine pentaacetate were uniformly mixed, milled and granulated in substantially the same manner as in procedure C in Example 1, except that the amount of water employed for spraying, the drying temperature and the drying time were 140 ml, 73°C and 10 minutes, respectively.
    • Procedure J
  • The granules obtained by procedures G to I were shaped into a tablet in substantially the same manner as in procedure D in Example 1. The amounts of granule G, granule H and granule I were 0.4 g, 0.54 g and 2.39 g, respectively. As a result, 50 color developing tablets for color paper (sample No. 3-1) were obtained.
    • Procedure K
  • Color developing tablets for color paper (sample Nos. 3-2 to 3-5, 50 tablets for each sample) were prepared in substantially the same manner as in procedures G to J, except that, in procedure J, 0.05 g of a compound shown in Table 2 was put between the 1st layer and the 2nd layer, and between the 2nd layer and the 3rd layer.
    • Procedure L
  • Granules G to I were mixed uniformly and shaped into a tablet in substantially the same manner as in procedure F in Example 1, except that the amount of the mixture placed in the tablet machine was 3.33 g, whereby 50 comparative color developing tablets (sample No. 3-6) were obtained.
    • Experiment
  • Three tablets of each sample were put into a polyethylene bag. The bag was sealed up and stored at 60°C for 1 month. These tablets were dissolved in 500 ml of water for examining possible tar-like insoluble matter. The results obtained are shown in Table 2. Table 2
    Sample No. Compound between layers Formation of a tar-like insoluble matter
    3-1 - B Present invention
    3-2 Hydroxypropyl cellulose A Present invention
    3-3 PVP K-17 A Present invention
    3-4 PEG 1000 A Present invention
    3-5 PEG 2000 A Present invention
    3-6 - C Comparative
  • It can be understood from the results that the color developing tablets of the invention hardly generated a tar-like insoluble matter when dissolved in water after the long-term storage.
    • Example 4
  • Color developing tablets were prepared in substantially the same manner as in Example 3, except that CD-3 employed in procedure H was replaced by an equimolar amount of compound No. CL-2. The tablets were examined for possible tar-like insoluble matter in the same way as in Example 3. The results revealed that the tablets of the invention hardly formed a tar-like insoluble matter when dissolved in water after the long-term storage.
    • Example 5
  • Color developing tablets were prepared in substantially the same manner as in Example 3, except that the diethylhydroxylamine oxalate employed in procedure G was replaced by an equimolar amount of compound No. 1 or 7 described in Japanese Patent O.P.I. Publication No. 184044/1991, pages 4 to 6. The tablets were examined for the possible tar-like insoluble matter in the same way as in Example 3. The results obtained were similar to those obtained in Example 3.
    • Example 6
  • Bleach-fixing tablets for color paper were prepared according to the following procedures.
    • Procedure M....Granule M
  • 80 g of ferric sodium ethylenediamine tetraacetate and 1.0 g of ethylenediaminetetraacetic acid were uniformly mixed, milled and granulated in substantially the same manner as in procedure C in Example 1, except that the amount of water used for spraying, the drying temperature and the drying time were 7.9 ml, 80°C and 10 minutes, respectively.
    • Procedure N....Granule N
  • 70 g of sodium thiosulfate, 35 g of potassium thiocyanate, 26 g of sodium sulfite, 3.5 g of sulfinic acid and 6.5 g of potassium bromide were uniformly mixed, milled and granulated in substantially the same manner as in procedure C in Example 1, except that the amount of water employed for spraying, the drying temperature and the drying time were 8.75 ml, 77°C and 10 minutes, respectively.
    • Procedure O
  • Granules M and N were shaped into a tablet in substantially the same manner as in procedure D in Example 1, except that the shaping was performed such that the granule M (4.05 g) and granule N (7.05 g) would constitute the 1st layer and the 2nd layer, respectively.
    • Procedure P
  • Bleach-fixing tablets (sample Nos. 6-2 to 6-5) were prepared in substantially the same manner as in procedures M to O, except that, in procedure O, 0.05 g of a compound shown in Table 3 was put between the 1st layer and the 2nd layer.
  • Granules M and N were mixed uniformly and shaped into a tablet in substantially the same manner as in procedure F in Example 1, except that the amount of the mixture placed in the tablet machine was 11.1 g, whereby a comparative bleach-fixing tablet (sample No. 6-6) was obtained.
    • Experiment
  • Each sample tablet was put into a polyethylene bag. The bag was sealed up and stored at 70°C for 2 months. These tablets were then dissolved in 250 ml of water to find out whether insoluble matter formed. The results obtained are shown in Table 3. Table 3
    Sample No. Compound between layers Formation of an insoluble matter
    6-1 - B Present invention
    6-2 Hydroxymethyl cellulose A Present invention
    6-3 PVP K-25 A Present invention
    6-4 PEG 1000 A Present invention
    6-5 PEG 4000 A Present invention
    6-6 - C Comparative
  • As is understood from the results, the bleach-fixing tablets of the invention hardly formed an insoluble matter when dissolved in water after the storage at a higher temperature.
    • Example 7
  • Bleach-fixing tablets were prepared in substantially the same manner as in Example 6, except that the ferric sodium ethylenediamine tetraacetate employed in procedure M was replaced by an equal amount of compound IV-1. The tablets were examined for possible insoluble matter in the same way as in Example 6. The results obtained were similar to those obtained in Example 6.
    • Example 8
  • Color developing tablets for a color negative were prepared according to the following procedures.
    • Procedure A...Granule A
  • 50 g of hydroxylamine sulfate was milled to an average particle diameter of 10 µm by means of an air-jet mill. The powder obtained was placed in a commercially-available fluidized bed spray granulator, where the powder was sprayed with 3.0 ml of water for about 7 minutes at room temperature, whereby the powder was granulated. The granule obtained was dried for 8 minutes at an air temperature of 63°C, and then subjected to vacuum drying at 40°C for 90 minutes to remove most of the water contained therein.
    • Procedure B...Granule B
  • 110 g of CD-4 [4-amino-3-methyl-N-ethyl-N-hydroxylethyl aniline sulfate], a developing agent, was milled and granulated in substantially the same manner as in procedure A in Example 1, except that the amount of water employed for spraying was 2.6 ml. After the granulation, the granule was dried at 60°C for 7 minutes, and then subjected to vacuum drying at 40°C for 90 minutes to remove most of the water contained therein.
    • Procedure C...Granule C
  • 50 g of sodium 1-hydroxyethane-1,1-diphosphonate, 70 g of sudium sulfite, 600 g of potassium carbonate, 46 g of sodium hydrogen carbonate, 14 g of sodium bromide and 40 g of sodium diethylenetriamine pentaacetate were uniformly mixed by means of a commercially-available mixer. The mixture was milled and granulated in substantially the same manner as in procedure A, except that the amount of water employed for spraying was 190 ml. After the granulation, the granules were dried at 70°C for 10 minutes, and then subjected to vacuum drying at 40°C for 90 minutes to remove most of the water contained therein.
    • Procedure D
  • 1.1 g of granule B was shaped into a tablet to obtain tablet B. Then, 0.5 g of granule A was also shaped into a tablet to obtain tablet A. In preparing tablet A, compression was performed with tablet B being contained in granule A. Finally, tablet A was put in 2.65 g of granule C, followed by compression to prepare 200 color developing tablets (sample No. 8-1).
    • Procedure E
  • Color developing tablets (sample Nos. 8-2 to 8-5, 200 tablets for each sample) were prepared in substantially the same manner as in procedures A to D, except that the outer surface of granule B (constituting the innermost layer) and that of granule A (constituting the 2nd layer) were each coated with a water-soluble cellulose shown in Table 4.
    • Procedure F
  • The granules obtained by procedures A to C were mixed uniformly at 25°C by a mixer placed in a room that had been subjected to moisture conditioning to a relative humidity of 50% or less. Then, 4.25 g of the mixture obtained was placed in each mortar of a multi-layer rotary tablet compressing machine (prepared by remodeling Tough Press Correct 1527 HU, manufactured by Kikusui Seisakusho), and shaped into a tablet at a compression pressure of 1000 kg/cm². As a result, 200 comparative color developing tablets (sample No. 8-6) were obtained.
    • Experiment
  • Ten tablets of each sample were put into a polyethylene bag. The bag was sealed up and stored at 70°C and 40% RH for 1 month. Then, these tablets were dissolved in 500 ml of water to examine for possible tar-like insoluble matter. The amount of CD-4 in each tablet was measured, and compared with the amount before storage, which was taken as 100. The results obtained are shown in Table 4. Table 4
    Sample No. Water-soluble cellulose Formation of a tar-like insoluble matter CD-4 remaining ratio
    8-1 - A 92 Present invention
    8-2 Sodium carboxymethyl cellulose A 98 Present invention
    8-3 Hyroxymethyl cellulose A 98 Present invention
    8-4 Hydroxyethyl cellulose A 97 Present invention
    8-5 Hydroxypropyl cellulose A 96 Present invention
    8-6 - C 79 Comparative
  • As is understood from the results, the color developing tablets of the invention hardly formed a tar-like insoluble matter when dissolved in water after the storage at a higher temperature.
  • Color developing tablets for color paper were prepared according to the following procedures.
    • Example 9
  • Color developing tablets were prepared in substantially the same manner as in Example 8, except that a water-soluble cellulose employed in procedure E was replace by an equal amount of polyvinyl pyrrolidone (PVPK-17, 30) or polyethylene glycol (PEG 1000, 2000). The tablets obtained were examined for tar-like insoluble matter in the same way as in Example 8. The results obtained were similar to those obtained in Example 8.
  • Color developer replenishing tablets for color paper were prepared according to the following procedures.
    • Procedure G...Granule G
  • 180 g of diethylhydroxylamine oxalate was milled and granulated in substantially the same manner as in procedure A in Example 8, except that the amount of water employed for spraying, the drying temperature and the drying time were changed to 10 ml, 70°C and 70 minutes, respectively.
    • Procedure H...Granule H
  • 270 g of CD-3 [1-(N-ethyl-N-methanesulfoneamidoethyl)-3-methyl-p-phenylenediamine sesquisulfate monohydrate], a developing agent, was milled and granulated in substantially the same manner as in procedure B in Example 8, except that the amount of water employed for spraying, the drying temperature and the drying time were 4.8 ml, 63°C and 8 minutes, respectively.
    • Procedure I...Granule I
  • 6 g of sodium sulfite, 850 g of potassium carbonate, 65 g of sodium hydrogen carbonate, 85 g of tinopal SFG and 120 g of sodium diethylenetriamine pentaacetate were mixed, milled and granulated in substantially the same manner as in procedure C in Example 8, except that the amount of water employed for spraying, the drying temperature and the drying time were 140 ml, 73°C and 10 minutes, respectively.
    • Procedure J
  • The granules obtained by procedures G to I were shaped into a tablet in substantially the same manner as in procedure D in Example 8. The amounts of granule H, granule G and granule I were 0.5 g, 0.4 g and 2.39 g, respectively. As a result, 50 color developing tablets (sample 10-1) were obtained.
    • Procedure K
  • Color developing tablets (sample Nos. 10-2 to 10-5, 50 tablets for each sample) were prepared in substantially the same manner as in Example 10, except that, in procedure J, the outer surface of the innermost layer and that of the 2nd layer were each coated with a compound shown in Table 5.
    • Procedure L
  • The granules obtained by procedures G to I were mixed and shaped into a tablet in substantially the same manner as in procedure F in Example 8, except that the amount of the mixture placed in the tablet machine was 3.33 g. As a result, 50 comparative color developing tablets for color paper (sample No. 10-6) were obtained.
    • Experiment
  • Five tablets of each sample were put into a polyethylene bag. The bag was sealed up and stored at 60°C and 30% RH for 2 months. These tablets were then dissolved in 500 ml of water to examine for possible tar-like insoluble matter and the remaining ratio of CD-3. The results obtained are shown in Table 5. Table 5
    Sample No. Coating compound Formation of a tar-like insoluble matter CD-3 remaining ratio
    10-1 - A 89 Present invention
    10-2 Hydroxypropyl cellulose A 98 Present invention
    10-3 PVP K-17 A 94 Present invention
    10-4 PEG 2000 A 95 Present invention
    10-5 PEG 4000 A 96 Present invention
    10-6 C 72 Comparative
  • It is understood from the results that the color developing tablets of the invention hardly formed a tar-like insoluble matter when dissolved in water after the long-term storage.
    • Example 11
  • Color developing tablets were prepared in substantially the same manner as in Example 10, except that CD-3 employed in procedure H was replaced by an equimolar amount of compound CL-2. The tablets were examined for possible tar-like insoluble matter in the same way as in Example 10. The results revealed that the tablets of the invention hardly formed a tar-like insoluble matter when dissolved in water after the long-term storage.
    • Example 12
  • Color developing tablets were prepared in substantially the same manner as in Example 10, except that diethylhydroxylamine oxalate employed in procedure G was replaced by an equimolar amount of compound No. 1 or 7 described in Japanese Patent O.P.I. Publication No. 184044/1991, pages 4 to 6. The tablets were examined for the formation of a tar-like insoluble matter in the same way as in Example 10. The results obtained were similar to those obtained in Example 10.
    • Example 13
  • Bleach-fixing tablets for color paper were prepared according to the following procedures.
    • Procedure M....Granule M
  • 80 g of ferric sodium ethylenediamine tetraacetate and 1.0 g of ethylenediaminetetraacetic acid were uniformly mixed, milled and granulated in substantially the same manner as in procedure C in Example 8, except that the amount of water employed for spraying, the drying temperature and the drying time were 7.9 ml, 80°C and 10 minutes, respectively.
    • Procedure N....Granule N
  • 70 g of sodium thiosulfate, 35 g of potassium thiocyanate, 26 g of sodium sulfite, 3.5 g of sulfinic acid and 6.5 g of potassium bromide were mixed, milled and granulated in substantially the same manner as in procedure C in Example 8, except that the amount of water employed for spraying, the drying temperature and the drying time were 8.75 ml, 77°C and 10 minutes, respectively.
    • Procedure O
  • The granules obtained by procedures M and N were shaped into a tablet in substantially the same manner as in procedure D in Example 8. The shaping was performed such that granule M (4.05 g) and granule N (7.05 g) would constitute the outer layer and the inner layer, respectively. As a result, a bleach-fixing tablet for color paper (sample No. 13-1) was obtained.
    • Procedure P
  • Sample Nos. 13-1 to 13-5 were prepared in substantially the same manner as in procedure O, except that the outer surface of the inside core was coated with a compound shown in Table 6.
    • Procedure Q
  • Granules M and N were mixed and shaped into a tablet in substantially the same manner as in procedure F in Example 8, except that the amount of the mixture placed in the tablet machine was 11.1 g, whereby a comparative bleach-fixing tablet (sample No. 13-6) was obtained.
    • Experiment
  • Two tablets of each sample were put into a polyethylene bag. The bag was sealed up and stored at 65°C and 40% RH for 3 months. These tablets were then dissolved in 250 ml of water to examine for possible insoluble matter. The results obtained are shown in Table 6. Table 6
    Sample No. Compound between layers Formation of an insoluble matter
    13-1 - B Present invention
    13-2 Hydroxypropyl cellulose A Present invention
    13-3 PVP K-25 A Present invention
    13-4 PEG 1000 A Present invention
    13-5 PEG 4000 A Present invention
    13-6 - C Comparative
  • As is understood from the results, the bleach-fixing tablets of the invention hardly formed an insoluble matter when dissolved in water after the storage at a higher temperature.
    • Example 14
  • Bleach-fixing tablets for color paper were prepared in substantially the same manner as in Example 13, except that ferric sodium ethylenediamine tetraacetate employed in procedure M was replaced by an equal amount of compound D-1. The tablets obtained were examined for possible insoluble matter in the same way as in Example 13. The results obtained were similar to those obtained in Example 13.
  • In Tables 1 to 6, the symbols employed are defined as follows:
    • C:
    A large amount of insoluble matters varying in size was observed.
    B:
    A small amount of insoluble matter was observed.
    A:
    No insoluble matter was observed.

Claims (10)

  1. A tablet for supplying to a solution for processing a sliver halide photographic light-sensitive material so as to keep the property of the solution comprising a processing agent, wherein the tablet is prepared by stacking two or more granules or powders differing in composition in a layered construction and thereafter applied pressure on said granules or powder in the layered construction.
  2. The tablet of claim 1, wherein the layered construction comprises a core and a shell covered the core.
  3. The tablet of claim 1, wherein said tablet further comprises a photographically inactive layer.
  4. The tablet of claim 3, wherein the photographically inactive layer comprises a substance selected from the group consisting of water-soluble cellulose, water-soluble dextrin, water-soluble polyethylene glycol, water-soluble polyvinyl pyrrolidone and water-soluble polyacrylamide.
  5. The tablet of claim 1, wherein the processing agent is a color developing agent.
  6. The tablet of claim 5, wherein the tablet said color developing agent is a p-phenylene diamine having a water-soluble group selected from the group consisting of -(CH₂)nCH₂OH, -(CH₂)mNHSO₂(CH₂)nCH₃, -(CH₂)mO(CH₂)nCH₃, -(CH₂CH₂O)nCmH2m+1 wherein m and n each represent an integer of not less than 0, -COOH and -SO₃H.
  7. The tablet of claim 6, wherein the tablet further comprises a compound selected from the group consisting of Formula A, Formula B and Formula C:
    Formula A
    Figure imgb0061
     Formula B
    Figure imgb0062
     Formula C
    Figure imgb0063
     wherein R₁ and R₂ each represent a hydrogen atom, an alkyl group, an aryl group, or R₃CO- wherein R₃ represents an alkyl group, an alkoxyl group or an aryl group, R₁ and R₂ may combine with each other to form a ring; R₁₁, R₁₂ and R₁₃ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; R₁₄ represents a hydroxyl group, a hydroxyamino group, an alkyl group, an aryl group, a heterocyclic group, an alkoxyl group, an aryloxy group, a carbamoyl group or an amino group, R₁₅ represents -CO-, -SO₂-or -C(=NH)-, n is an integer of 0 to 1, provided that when n is 0, R₁₃ and R₁₄ may form a heterocyclic ring together, L represents an alkylene group, A represents a carboxyl group, a sulfo group, a phosphono group, a phosphino group, a hydroxyl group, an amino group, an ammonium group, a carbamoyl group or a sulfamoyl group, R represents a hydrogen atom or an alkyl group.
  8. The tablet of claim 5, wherein the tablet further comprises a fluorescent whitening agent represented by Formula E:
    Formula E
    Figure imgb0064
     wherein X₁, X₂, Y₁ and Y₂ each represent a hydroxyl group, a halogen atom, an alkyl group, an aryl group, -N(R₂₁) (R₂₂),
    Figure imgb0065
     or OR₂₅; R₂₁ and R₂₂ each represent a hydrogen atom, an alkyl group or an aryl group, R₂₃ and R₂₄ each represent an alkylene group, R₂₅ represents a hydrogen atom, an alkyl group or an aryl group, M represents a cation.
  9. The tablet of claim 1, wherein said processing agent is a bleaching agent.
  10. The tablet of claim 9, wherein said bleaching agent is selected by ferric complex of the organic acids consisting of Formula I, Formula II, Formula III and Formula IV:
    Formula I
    Figure imgb0066
     wherein A₁, A₂, A₃ and A₄ each represent a -CH2OH group, a -COOH group or a -PO₃M₁M₂ group, M, M₁ and M₂ each represent a hydrogen atom, an alkaline metal or an ammonium group, X represents an alkylene group having a carbon number of 3 to 6;
    Formula II
    Figure imgb0067
     wherein A₁, A₂, A₃ and A₄ each represent a -CH2OH group, a -COOH group or a -PO₃M₁M₂ group, n is an integer of 1 to 8, B₁ and B₂ each represent an alkylene group having a carbon number of 2 to 5,
    Formula III
    Figure imgb0068
     wherein R₁ represents a hydrogen atom or a hydroxyl group, n is an integer of 1 to 2, x is an integer of 2 or 3, y is an integer of 0 or 1, the sum of x and y is 3,
    Formula IV
    Figure imgb0069
     wherein A₁, A₂, A₃ and A₄ each represent a -CH2OH- group, a -COOH group or a -PO₃M₁M₂ group, M, M₁ and M₂ each represent a hydrogen atom, an alkaline metal or an ammonium group, X represents an alkylene group having a carbon number of 2 to 6 or a -(B₁O)n-B₂- group, B₁ and B₂ each represent an alkylene group having a carbon number of 1 to 5.
EP92119391A 1991-11-12 1992-11-12 A tablet for processing a silver halide photographic light-sensitive material Withdrawn EP0542283A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP29592491A JPH05134362A (en) 1991-11-12 1991-11-12 Treating tablet for silver halide photographic sensitive material
JP295924/91 1991-11-12
JP2260492A JPH05216177A (en) 1992-02-07 1992-02-07 Tablet for treating silver halide photographic material
JP22604/92 1992-02-07

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0624821A1 (en) * 1993-05-10 1994-11-17 Konica Corporation Tablet for processing silver halide color photographic light-sensitive materials
EP0657778A1 (en) * 1993-11-11 1995-06-14 Konica Corporation A method for processing a silver halide color photographic light-sensitive material and producing a color image
EP0678781A1 (en) * 1994-02-03 1995-10-25 Konica Corporation Solid processing agent for silver halide photographic light-sensitive materials
EP1113320A2 (en) * 1999-12-27 2001-07-04 Fuji Photo Film Co., Ltd. Granulated solid processing agent for silver halide photographic material and producing method of the same
EP1328845A1 (en) * 2000-09-12 2003-07-23 Fuji Hunt Photographic Chemicals, Inc. Compact color photographic developer concentrate and solid component therefor

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US2196901A (en) * 1939-11-06 1940-04-09 American Cyanamid Co Photographic developer
FR2286415A1 (en) * 1974-09-26 1976-04-23 Veronesi Fiorenzo Chemical cpd. tablets for photographic prooessing - contg. inert binder and expanding-disintegrating agent, giving ease of dosing
US3981732A (en) * 1971-08-19 1976-09-21 Fuji Photo Film Co., Ltd. Granular p-phenylenediamine color developing agent
EP0196551A2 (en) * 1985-03-28 1986-10-08 Deltagraph A/S A process for obtaining a package containing mutually reactive particulate materials and a package containing such materials
EP0358034A2 (en) * 1988-09-03 1990-03-14 Agfa-Gevaert AG Granulated photographic colour developer and its preparation
EP0407752A1 (en) * 1989-06-27 1991-01-16 Agfa-Gevaert AG Granulated colour photographic bleaching agent and its preparation
EP0447655A1 (en) * 1990-03-23 1991-09-25 Agfa-Gevaert AG Granulated photochemicals

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US2196901A (en) * 1939-11-06 1940-04-09 American Cyanamid Co Photographic developer
US3981732A (en) * 1971-08-19 1976-09-21 Fuji Photo Film Co., Ltd. Granular p-phenylenediamine color developing agent
FR2286415A1 (en) * 1974-09-26 1976-04-23 Veronesi Fiorenzo Chemical cpd. tablets for photographic prooessing - contg. inert binder and expanding-disintegrating agent, giving ease of dosing
EP0196551A2 (en) * 1985-03-28 1986-10-08 Deltagraph A/S A process for obtaining a package containing mutually reactive particulate materials and a package containing such materials
EP0358034A2 (en) * 1988-09-03 1990-03-14 Agfa-Gevaert AG Granulated photographic colour developer and its preparation
EP0407752A1 (en) * 1989-06-27 1991-01-16 Agfa-Gevaert AG Granulated colour photographic bleaching agent and its preparation
EP0447655A1 (en) * 1990-03-23 1991-09-25 Agfa-Gevaert AG Granulated photochemicals

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0624821A1 (en) * 1993-05-10 1994-11-17 Konica Corporation Tablet for processing silver halide color photographic light-sensitive materials
EP0657778A1 (en) * 1993-11-11 1995-06-14 Konica Corporation A method for processing a silver halide color photographic light-sensitive material and producing a color image
US5556736A (en) * 1993-11-11 1996-09-17 Konica Corporation Method for processing a silver halide color photographic light-sensitive material and producing a color image
EP0678781A1 (en) * 1994-02-03 1995-10-25 Konica Corporation Solid processing agent for silver halide photographic light-sensitive materials
US5663039A (en) * 1994-02-03 1997-09-02 Konica Corporation Solid processing agent for silver halide photographic light-sensitive materials
EP1113320A2 (en) * 1999-12-27 2001-07-04 Fuji Photo Film Co., Ltd. Granulated solid processing agent for silver halide photographic material and producing method of the same
EP1113320A3 (en) * 1999-12-27 2002-07-03 Fuji Photo Film Co., Ltd. Granulated solid processing agent for silver halide photographic material and producing method of the same
US6524780B2 (en) 1999-12-27 2003-02-25 Fuji Photo Film Co., Ltd. Granulated solid processing agent for silver halide photographic material and producing method of the same
EP1457817A1 (en) * 1999-12-27 2004-09-15 Fuji Photo Film Co., Ltd. Granulated solid processing agent for silver halide photographic material and producing method of the same
EP1328845A1 (en) * 2000-09-12 2003-07-23 Fuji Hunt Photographic Chemicals, Inc. Compact color photographic developer concentrate and solid component therefor
EP1328845A4 (en) * 2000-09-12 2004-05-26 Fuji Hunt Photo Chem Compact color photographic developer concentrate and solid component therefor

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