EP0667559B1 - Feste Zusammensetzung zur Behandlung von lichtempfindlichen farbphotographischen Silberhalogenidmaterialien - Google Patents

Feste Zusammensetzung zur Behandlung von lichtempfindlichen farbphotographischen Silberhalogenidmaterialien Download PDF

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Publication number
EP0667559B1
EP0667559B1 EP95101760A EP95101760A EP0667559B1 EP 0667559 B1 EP0667559 B1 EP 0667559B1 EP 95101760 A EP95101760 A EP 95101760A EP 95101760 A EP95101760 A EP 95101760A EP 0667559 B1 EP0667559 B1 EP 0667559B1
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Prior art keywords
composition
solid
granules
weight
samples
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EP95101760A
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French (fr)
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EP0667559A1 (de
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Takashi C/O Konica Corporation Deguchi
Kenji C/O Konica Corporation Kuwae
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Konica Minolta Inc
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Konica Minolta Inc
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Priority claimed from JP1857194A external-priority patent/JPH07225460A/ja
Priority claimed from JP2127894A external-priority patent/JPH07230152A/ja
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Publication of EP0667559A1 publication Critical patent/EP0667559A1/de
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
    • G03C5/265—Supplying of photographic processing chemicals; Preparation or packaging thereof of powders, granulates, tablets

Definitions

  • the invention relates to a solid composition in the form of powder or tablets for a silver halide color photographic light-sensitive material.
  • a silver halide photographic light-sensitive material is usually processed using a color developer, a bleach, a bleach-fixer, a fixer and a stabilizer to obtain an imagewise image.
  • the components of the processing solutions used herein are packaged in plastic bottles for easy use in the form of one or more concentrated solutions and are supplied as a processing solution kit to consumers. The consumers dilute the component solutions of the kit with water to prepare the processing solutions (as starter solutions or replenisher solutions) and use them.
  • mini-labs which process a photographic material using a small automatic processor
  • the processing kit in concentrated solution form still requires much storage space. Further, the cost for transport is not low.
  • the discarded plastic bottles increase year by year and should be recovered, however the recovering is difficult and therefore, development of a processing system in which waste plastics are reduced is demanded.
  • Powder photographic processing agents are considered in order to reduce storage space, transport cost and the amount of the plastic waste.
  • the powder agents produce loose powder when it is dissolved in water, and operators breathe in loose powder particles, resulting in health hazard.
  • the present inventor has found that other photographic solutions may be contaminated with the components of the loose powder and there occurs the possibility of other trouble in developing process.
  • Japanese Patent O.P.I Publication No. 3-39739/1991 discloses a granular agent of an amino polycarboxylic acid ferric complex containing an re-halogenating agent having a specific average particle diameter. This method can prevent the occurrence of loose powder because the agent is not powder, but powder is likely to occur during transport because of its brittleness. Further, the inventors have found that the adherence of the granules to a package or aggregation of the granules is caused during storage such as transport under a high temperature.
  • Japanese Patent O.P.I Publication No. 5-119454/1993 discloses a tablet agent of an amino polycarboxylic acid ferric complex. It has been found, however, that in this method powder is likely to occur during transport because of its brittleness.
  • Japanese Patent O.P.I Publication No. 5-119450/1993 discloses a tablet agent having excellent storage stability and improved strength by controlling a moisture content of a tablet and further discloses a tablet composition having a moisture content of 0.5 to 10.0 wt%.
  • a tablet composition having a moisture content of 0.5 to 10.0 wt% discloses a tablet agent having excellent storage stability and improved strength by controlling a moisture content of a tablet and further discloses a tablet composition having a moisture content of 0.5 to 10.0 wt%.
  • an amino polycarboxylic acid hydrate or a drying weight reduction of the solid composition This method is considered to attain the excellent storage stability and improved strength, but is not satisfactory for the adherence of the tablets to a package or aggregation of the tablets during transport.
  • 5-232656/1993 discloses a tablet agent containing a hydrate salt of an amino polycarboxylic acid ferric complex, but there is no description of the control of a moisture content and the agent is not satisfactory for the prevention of moisture absorption and aggregation of the tablets which is the effects of the invention.
  • a single step comprising bleaching and fixing as a desilvering step is widely employed.
  • the step is unstable since a bleaching agent, an oxidizing agent and a sulfite, a reducing agent are present in the bleach-fixing solution.
  • Japanese Patent O.P.I. Publication No. 4-19655 discloses a method of packaging under vacuum a composition in which a bleaching agent layer and a fixing agent layer are separated and a third layer is provided between them.
  • Japanese Patent O.P.I. Publication No. 5-142708 discloses tablets obtained by compression-molding granules having an average particle diameter of 100 to 800 ⁇ m.
  • the present inventors have found that it is difficult obtain a solid processing composition having a stable property and less powder occurrence as above described using the above methods, since the influence of vibration during transport, heat during storage or atmospheric moisture during production or usage is great.
  • a first object of the invention is provide a solid processing composition for a silver halide color photographic light-sensitive material in which fine powder occurrence is reduced during vibration.
  • a second object is to provide a solid processing composition for a silver halide color photographic light-sensitive material preventing an adherence under a high temperature.
  • a third object of the invention is to provide a solid processing composition for bleach-fixing in the form of granules or tablets for a silver halide color photographic light-sensitive material giving high storage stability during storage under high temperature.
  • a fourth object is to provide a solid processing composition for bleach-fixing in the form of granules or tablets for a silver halide color photographic light-sensitive material which does not cause fine powder occurrence due to vibration during transport or atmospheric moisture during production or usage.
  • the solid processing composition for bleaching is distinguished from the solid processing composition for bleach-fixing.
  • the solid processing composition for bleaching of the invention refers to a solid processing composition containing an amino polycarboxylic acid ferric complex and not containing a fixing agent.
  • the solid processing composition for bleach-fixing of the invention refers to a solid processing composition containing an amino polycarboxylic acid ferric complex and a fixing agent such as a thiosulfate or a thiocyanate.
  • the solid processing composition for bleaching is preferable in view of prevention of adherence under a high temperature.
  • the solid processing composition for bleach-fixing is preferable in view of high storage stability under a high temperature.
  • the inventors have studied a solid composition for a silver halide color photographic light-sensitive material and found the following:
  • the solid composition comprising an amino polycarboxylic acid ferric complex
  • the amino polycarboxylic acid ferric complex in the composition is anhydrous
  • the solidified amino polycarboxylic acid ferric complex is broken to fine powder due to vibration during transport and a problem of the resulting powder scatter occurs. Further, the appearance also varies under a high temperature or humidity.
  • the drying weight reduction at 50°C of the composition exceeds 10.0 % by weight, the solid processing composition adheres to a package and the aggregation of the composition due to adherence of water drops to the surface thereof, so-called blocking phenomenon causes.
  • the composition containing a fixing agent produces insoluble matter during storage under high temperature.
  • solid components other than an amino polycarboxylic acid ferric complex are broken to fine powder due to vibration. Further, the appearance also varies due to moisture absorption.
  • the solid composition is sometimes exposed to a high humidity, at a temporary time other than time packaged and isolated from atmospheric air, for example, at dissolution before its usage or its packaging on production. It has been found that in such cases the composition containing a fixing agent absorbs atmospheric moisture to damage and causes powder occurrence, resulting in a serious problem on handling it.
  • the reason that the temperature condition of the drying weight reduction in the invention is 50°C is that the temperature corresponds to upper limit occurred during distribution.
  • the different temperature may give a different weight reduction but the reduction is within the scope of the invention in view of the object of the invention.
  • the drying weight reduction at 50°C of the composition may be 0.1 to 10.0 % by weight, however, in view of the effects of the invention, in the case of the composition not containing thiosulfate or thiocyanate the reduction is preferably 0.5 to 8.0 % by weight, and more preferably 1.0 to 6.0 % by weight.
  • the drying weight reduction at 50°C of the composition containing a fixing agent is preferably 0.3 to 5 % by weight, and more preferably 0.5 to 3 % by weight.
  • the solid processing composition of the invention it is essential to contain at least an amino polycarboxylic acid ferric complex hydrate, and different two or more kinds of complexes may be used in combination. In such a case one half or more of the complex hydrate is preferably used in view of the effects of the invention.
  • the amino polycarboxylic acid ferric complex ⁇ hydrate used in the invention is in a crystal form or in other solid forms (e.g., amorphous or gel), and contains water as crystal water, coordinate water or others. The water may be contained in any ratio in the complex hydrate.
  • the amino polycarboxylic acid ferric complex hydrate used in the invention includes one having no uniform composition in which an optional amount of water is removed by applying heat.
  • the water of the complex hydrate used in the invention is contained in the above described forms, and the water content of the complex hydrate is represented by the mol ratio of water in the complex hydrate to the complex.
  • the mol ratio is especially preferably 0.3 to 3.5 in the solid composition not containing thiosulfates or thiocyanate and 0.3 to 3.5 in the solid composition containing thiosulfates or thiocyanates, in view of the effects of the invention.
  • the mol ratio of the amino polycarboxylic acid ferric complex hydrate used in the invention is obtained by a conventional method such as heat weight analysis, differential thermal analysis, Karl Fischer method or elemental analysis.
  • the content of the amino polycarboxylic acid ferric complex ⁇ hydrate in the solid processing composition of the invention is preferably 10 to 70 weight %.
  • the shape of the amino polycarboxylic acid ferric complex hydrate of the invention is in the form of granules or tablets, and the granules herein referred to include first order particles as powder or secondary order particles obtained by granulating.
  • the particle diameter of a granular solid processing composition granules having a particle diameter of less than 149 ⁇ m is preferably 30 % by weight or less, more preferably 15 % by weight or less and still more preferably 10 % by weight or less.
  • the above described granulating procedures may be used.
  • a bleaching agent and fixing agent crystallized to suitable size from the solution may be used and granules sieved by screening or classifying the crystals may be used.
  • the granules and crystals may be used in combination.
  • the particle diameter of the invention refers to the diameter measured by a sieve according to JIS, and the above "granules having a particle diameter of less than 149 ⁇ m is 30 % or less " means that the weight of the granules minus sieve screened by a sieve having a 149 ⁇ m mesh according to JIS is 30 % or less based on the total weight of the granules.
  • the solid processing composition of the invention contains an amino polycarboxylic acid ferric complex hydrate and a fixing agent
  • an amino polycarboxylic acid ferric complex hydrate as a bleaching agent and a sulfite as a fixing agent
  • at least one of them is preferably granules, since the effects of the invention are markedly displayed. It is more preferable that both agents are granules. This is because of another effect in which fine loose powder is reduced during storage as well as the above mentioned effects.
  • the drying weight reduction at 50°C of the composition herein referred to is obtained from the weight reduced after the composition is heated at 50°C to the constant weight which is measured with an electronic moisture meter available on the market.
  • the solid processing composition of the invention is a solid bleaching composition comprising at least one hydrate salt of an amino polycarboxylic acid ferric complex, and it may be a simple mixture of solid materials or a mixture of granules obtained by granulating several powdered solid materials in admixture.
  • any of the well-known methods such as a rolling granulation, an extrusion granulation, a compression granulation, a cracking granulation, a stirring granulation, a fluidized-layer granulation and water spray-drying granulation.
  • the above described solid bleaching composition is compression-molded into tablets, whereby the tablets exhibit the effect of the invention markedly and the effective prevention of fine powder increase during storage.
  • the solid processing tablet is produced by well known compressors.
  • the compressors for producing the tablets include a hydraulic press machine, a single tableting machine, a rotary tableting machine and a bricketing machine can be used.
  • the solid processing tablet may be in any form, but is preferably in the cylindrical form in view of producibility or processability.
  • the solid processing agent of the invention comprises at least one ferric complex of an amino polycarboxylic acid hydrate, and two or more kinds ferric complexes of the amino polycarboxylic acid hydrates may be used therein.
  • the ferric complex of an amino polycarboxylic acid is preferably used in the form of an ferric complex of an amino polycarboxylic acid (free acid) represented by the following Formula (I) and the ferric complex is more preferably used in combination with an amino polycarboxylic acid (free acid). It is especially preferable that the ferric complex is used in combination with the same acid as the amino polycarboxylic acid (free acid) constituting the complex.
  • the salt of the ferric complex of an amino polycarboxylic acid such as potassium salt, sodium salt or ammonium salt can be also used.
  • the salt of the amino polycarboxylic acid such as potassium salt or sodium salt can be also used.
  • T 1 represents a hydrogen atom, a hydroxy group, a carboxy group, a sulfo group, a carbamoyl group, a phosphono group, a phosphon group, a sulfamoyl group, a substituted or unsubstituted alkyl group, an alkoxy group, an alkylsulfonamido group, an alkylthio group, an acylamino group or a hydroxamic acid group, a hydroxyalkyl group or wherein W 1 represents a substituted or unsubstituted alkylene, arylene, alkenylene, cycloalkylene or aralkylene group or wherein X represents -O-, -S-, a divalent heterocyclic group or
  • R 1 through R 5 independently represent a hydrogen atom, a hydroxy group, a carboxy group, a sulfo group, a carbamoyl group, a phosphono group, a phosphon group, a sulfamoyl group, a sulfonamido group, an acylamino group or a hydroxamic acid group, provided that at least one of R 1 through R 5 is a carboxy group.
  • L 1 through L 7 independently represent a substituted or unsubstituted alkylene, arylene, alkenylene, cycloalkylene or aralkylene group; and l 1 through l 7 independently represent an integer of 0 to 6, provided that l 5 through l 6 are not simultaneously 0.
  • the compounds of the invention include any isomers and may be constituted in any content thereof.
  • Fe (III) complex in which the ratio of the acid to Fe (III) is 1:2 is preferable.
  • ferric complex of an amino polycarboxylic acid in the invention (exemplified compounds II) and the preferable crystal water content will be shown below, but the invention is not limited thereto.
  • Amino polycarboxylic acid Fe (III) complex (Exemplified compound II) Preferable amount of crystal water of amino polycarboxylic acid Fe(III) complex No.
  • Amino polycarboxylic acid (Exemplified Compound I) Cation Mol of crystal water per mol of the complex II-1 I-1 Na + 3 II-2 I-1 K + 2 II-3 I-1 NH 4 + 2 II-4 I-2 Na + 3 II-5 I-2 K + 1 II-6 I-2 NH 4 + 1 II-7 I-8 NH 4 + 2 II-8 I-3 K + , H + 1 II-9 I-3 NH 4 + , H + 1 II-10 I-5 Na + 1 II-11 I-5 K + 1 II-12 I-5 NH 4 + 1 II-13 I-14 - 2 II-14 I-28 K + 1 II-15 I-26 K + 1 II-16 I-10 - 1.5
  • Exemplified compound II-1 represents sodium iron (III) ethylenediaminetetraacetate ferric complex trihydrate.
  • the saccharides in the invention refer to monosaccharides or polysaccharides in which monosaccharides bind through a glycoside bondage.
  • Monosaccharides refer to a single polyhydroxy aldehyde, polyhydroxy ketone or their derivatives such as reduced derivatives, oxidized derivatives, deoxy derivatives, amino derivatives or thio derivatives. Most of them are represented by the general formula C n H 2n O n .
  • the monosaccharides in the invention include derivatives derived from saccharide skeleton represented by the above formula.
  • the preferable are sugar alcohols having a primary or secondary alcohol group to which an aldehyde or ketone group is reduced.
  • Polysaccharides include celluloses, starches or glycogens.
  • the celluloses include derivatives such as cellulose ethers in which all or a part of hydroxy group are etherified, starches include dextrins that starches are hydrolyzed to various decomposition compounds or maltose.
  • Celluloses may be in an alkali salt form in view of solubility.
  • celluloses or dextrins are preferably used, and dextrins are more preferably used.
  • A-9 through A-19 are preferably used.
  • B-1 through B-28 are preferably used, Saccharides exist widely in the nature, and are available on the market.
  • the derivatives can be readily prepared by reduction, oxidation or dehydration reactions.
  • the water-soluble polymer includes a polyethylene glycol, a polypropylene glycol, a block polymer of a polyethylene glycol and a polypropylene glycol (Pluronic type), polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl acetal, polyvinyl acetate, an aminoalkylmethacrylate copolymer, methacrylic acid-methacrylate copolymer, methacrylic acid-acrylate copolymer, and methacrylic acid betaine type polymer.
  • the polyethylene glycol, polypropylene glycol or Pluronic type polymer has a weight average molecular weight of preferably 500 to 10000 and more preferably 2,000 to 8,000.
  • These saccharides or water-soluble polymers may be used singly or in combination.
  • the amount used thereof is preferably 0.5 to 30 % by weight, based on the weight of the solid composition of the invention.
  • the amount of the saccharides or water-soluble polymers is more preferably 0.5 to 20 % by weight and still more preferably 1.0 to 20 % by weight based on the weight of the solid composition of the invention.
  • the amount thereof is more preferably 3 to 20 % by weight and still more preferably 5 to 15 % by weight based on the weight of the solid composition of the invention.
  • the addition of the above described saccharide or water-soluble polymer may be carried out on mixing components in the form of granules, powder or crystal particle before tableting.
  • the solid processing composition in the invention preferably contains a compound represented by the following Formula [A] A(-COOM) n wherein A represents an n valent organic group, n represents an integer of 1 to 6, and M represents an ammonium, an alkali metal (sodium, potassium or lithium) or a hydrogen atom.
  • the n valent organic group represented by A includes an alkylene group (such as methylene, ethylene, trimethylene or tetramethylene), an alkenylene group (such as ethenylene), an alkinylene group (such as ethynylene), a cycloalkylene group (such as 1,4-cyclohexanediyl), an arylene group (such as o-phenylene group or p-phenylene), an alkanetriyl group (such as 1,2,3-propanetriyl) or an arylenetriyl group (such as 1,2,4-benzenetriyl).
  • an alkylene group such as methylene, ethylene, trimethylene or tetramethylene
  • an alkenylene group such as ethenylene
  • an alkinylene group such as ethynylene
  • a cycloalkylene group such as 1,4-cyclohexanediyl
  • an arylene group
  • the above n valent organic group includes a group having a substituent (such as a hydroxy group, an alkyl group or a halogen atom).
  • a substituent such as a hydroxy group, an alkyl group or a halogen atom.
  • the examples include 1,2-dihydroxyethylene, hydroxyethylene, 2-hydroxy-1,2,3-propanetriyl, methyl-p-phenylene, 1-hydroxy-2-chloroethylene, chloromethylene or chloroethenylene.
  • the preferable compound represented by Formula [A] will be shown below.
  • the salt of the above acid includes an ammonium salt, a lithium salt, a sodium salt or a potassium salt, and the sodium salt or potassium salt is preferable in view of storage stability.
  • These organic acids or salts thereof may be used singly or in combination.
  • granules of the complex may be mixed with granules of the organic acid and/or the salt.
  • granules of a mixture of the complex with the organic acid and/or the salt displays the effects of the invention more markedly. Further, the mixture, compression-molded into tablets, gives tablets excellent in the strength.
  • a thiosulfate or a thiocyanate is preferably used, and a thiosulfate is more preferably used. Both agent may be used in combination.
  • the fixing agent is preferably used in the form of sodium, potassium or ammonium salt, and two or more kinds of the salts may be used in combination.
  • the thiosulfate content of the solid processing composition of the invention is preferably 20 to 70 weight %.
  • a preservative is preferably used, and a sulfite, a bisulfite or metabisulfite is preferable as the preservative.
  • the preservative is preferably used in the form of sodium, potassium or ammonium salt, and two or more kinds of the preservatives may be used in combination.
  • the preservative content of the solid processing composition of the invention is preferably 5 to 30 weight %.
  • the buffering agent may be optionally used in the solid processing composition of the invention.
  • the buffering agent includes an amino acid (for example, glycine, alanine, aspartic acid, or glutamic acid or salts thereof) or an acetate (for example, sodium acetate, potassium acetate, ammonium acetate, or lithium acetate), and two or more kinds of the compounds may be used in combination.
  • the solid composition of the invention may contain an alkali halide or an ammonium halide (for example, sodium bromide, potassium bromide, ammonium bromide, sodium chloride, potassium chloride or ammonium chloride).
  • an alkali halide or an ammonium halide for example, sodium bromide, potassium bromide, ammonium bromide, sodium chloride, potassium chloride or ammonium chloride.
  • Procedure (1-6) was carried out in the same way as in Procedure (1-5) to obtain granules, except that 100 ml of water was added instead of 50 ml of polyethylene glycol #600. The resulting granules were dried at 60°C for 4 hours using a fluid-bed type dryer. Thus, samples (1-16) through (1-20) were obtained.
  • the evaluation criteria are as follows:
  • the evaluation criteria are as follows:
  • a solid bleaching composition for a silver halide color light-sensitive material less in powder occurrence and in adherence to packages is obtained by using the amino polycarboxylic acid ferric complex hydrate and controlling a weight reduction at 50°C to be 0.1 to 10.0 % by weight.
  • Exemplified ferric complex (shown in table 2) 1900 g Free acid of the above complex 100 g Succinic acid 700 g Disodium maleate monohydrate 300 g Adipic acid 200 g D-Mannitol 500 g Potassium bromide 900 g
  • Samples (2-6) through (2-21) were prepared in the same manner as in Procedure (2-1), except that the added amount of water, drying temperature or drying time is suitably changed.
  • Sample (2-22) was prepared in the same manner as in Procedure (2-1), except that 1200 g of sodium hydrogen sulfate was added instead of succinic acid, disodium maleate monohydrate and adipic acid. The drying weight reduction at 50°C of the sample was measured. The results are shown in Table 2.
  • a solid bleaching composition for a silver halide color light-sensitive material less in powder occurrence and in adherence to packages is obtained by using the amino polycarboxylic acid ferric complex hydrate and controlling a weight reduction at 50°C to be 0.1 to 10.0 % by weight.
  • the weight reduction at 50°C is preferably 0.5 to 8.0 % by weight, and more preferably 1.0 to 6.0 % by weight.
  • the solid composition of the invention displays more improved effects by adding a compound represented by Formula [A].
  • Example 2 Samples were prepared, granulated, dried and evaluated in the same manner as in Example 2, except that ferric complexes (II-5), (II-9), (II-11) or (II-12) was used instead of ferric complex used in sample (2-1). The same results as Example 2 were obtained.
  • Samples (3-1) through (3-11) were prepared in the same manner as in Example 2, except that ferric complexes shown in Table 3 was used and the crystal water was adjusted to be a mol number shown in Table 3. The evaluation was carried out in the same manner as in Example 1. The appearance of the samples was evaluated before and after 10 g of the samples in petri glass were stored at 30°C and 70%Rh for 4 hours.
  • the evaluation criteria are as follows:
  • Samples (4-1) through (4-14) were prepared in the same manner as in sample (2-1) of Example 2, except that the amount of mannitol shown in Table 4 was used or compounds shown in Table 4 were used instead of D-mannitol.
  • the evaluation was carried out in the same manner as in Example 4. The results are shown in Table 4.
  • the tablets for a solid bleaching composition (5-23) through (5-27) were prepared in the same manner as in Procedure (6-1) to have a weight per tablet of 11g and a diameter of 30 mm.
  • Samples were stored for 4 hours under the same condition as Experiment (4-1) of Example 4 and placed on a polyethylene plate at 25°C and 45%RH.
  • the polyethylene plate was fixed using Static Friction Tester HEIDON-10 (produced by HEIDON Co.) and the angle ⁇ at which the samples move on the polyethylene plate was measured.
  • the evaluation criteria are as follows:
  • Granules having different water content were prepared in the same manner as in Procedure (7-2), except that the added amount of water, drying temperature and drying time were suitably varied.
  • the resulting granules were mixed with granules (A7) in a cross rotary mixer available on the market at room temperature to obtain samples (7-1), (7-2) and (7-4) through (7-8).
  • Granules A' were prepared in the same manner as in Procedure (7-1), except that Fe(III) complex having no crystal water was used instead of exemplified Fe(III) complex used in Procedure (7-1). The same procedures as in Procedure (7-4) was carried out, except that granules A' were used instead of granules (A1) to obtain samples (7-9) through (7-11).
  • Procedure (7-4) The same procedures as in Procedure (7-4) was carried out, except that exemplified compounds (II-9), (II-11), (II-6) and (II-13) were used instead of exemplified compounds (II-1) to obtain samples (7-12) through (7-22), (7-23) through (7-33), (7-34) through (7-37) and (7-38) through (7-40), respectively.
  • the drying weight reduction at 50°C of samples (7-1) through (7-40) was measured.
  • the drying weight reduction is obtained by weight reduced after the samples are heated at 50°C in a shelf-type dryer to the constant weight.
  • the evaluation criteria are as follows:
  • the evaluation criteria are as follows:
  • Example 7 The experiments and evaluations were carried out in the same manner as in Example 1, except that Exemplified compounds (II-2), (II-3), (II-9), and (II-10) were used instead of Fe(III) complex used in Example 7. The same results as Example 7 were obtained.
  • Granules of A part were prepared in the same manner as in Procedure (7-1), except that the mole ratio of the crystal water in the Fe(III) complexes was dried to be as shown in Table 8. Thereafter, procedures were carried out in the same manner as in Example 1 to obtain samples (9-1) through (9-4) and (9-17). Further, Iron (III) complexes (II-9), (II-12) and (II-13) were subjected to the same procedures as above to obtain samples (9-5) through (9-8), (9-9) through (9-12) and (9-13) through (9-16), respectively.
  • the inventive samples give excellent vibration test results, excellent storage stability and less powder occurrence under open condition.
  • Sample (7-4) in Example 1 was subjected to screening, and screened with a sieve having a 149 ⁇ m mesh (JIS). Thereafter, granules having a particle diameter of not less than 149 ⁇ m and granules having a particle diameter of less than 149 ⁇ m were mixed so that the weight ratio of the granules having a particle diameter of less than 149 ⁇ m was shown in Table 9. Thus, samples (10-1) through (10-6) were obtained. Sample (7-8) was subjected to the same procedures as above to obtain samples (10-7) and (10-8).
  • Samples (10-1) through (10-8) were evaluated in the same manner as in Experiments (7-1). The results are shown in Table 9.
  • Sample No. APC ⁇ Fe Weight Ratio wt% Vibration Test Storage Stability Exemplified Compound Crystal Water Mol ratio 10-1 II-1 3 0 1.02 o ⁇ o ⁇ Invention 10-2 II-1 3 5 1.02 o ⁇ o ⁇ Invention 10-3 II-1 3 10 1.02 o ⁇ o ⁇ -o ⁇ Invention 10-4 II-1 3 15 1.02 o ⁇ Invention 10-5 II-1 3 30 1.02 o ⁇ - ⁇ Invention 10-6 II-1 3 40 1.02 ⁇ Invention 10-7 II-1 3 0 14.7 X Comparison 10-8 II-1 3 30 14.7 X Comparison
  • the ratio is preferably 30 % or less.
  • the compounds of A part independently were pulverized to have an average particle size of not more than 50 ⁇ m.
  • the resulting powders were mixed in a cross rotary mixer available on the market at room temperature and the mixture was granulated for 8 minutes in a stirring granulator available on the market by adding 50 ml of deionized water.
  • the resulting granules were dried at 40°C for 3 hours using a fluid-bed type dryer available on the market. Thus, granules (A11) were obtained.
  • Procedures were carried out in the same manner as in Procedures (11-1) to (11-3), except that saccharides or water-soluble polymers were varied as shown Tables 10 and 11. Thus, samples (11-2) through (11-20) were obtained.
  • Exemplified compound (EDTA-Na ⁇ 3H 2 O) 700 g Maleic acid 150 g Potassium thiosulfate 1000 g Potassium sulfite 300 g Potassium metabisulfite 50 g Ethylenediaminetetraacetic acid 50 g Saccharide or Water-Soluble Polymer See Tables 10 and 11
  • the evaluation criteria are as follows:
  • inventive samples using saccharides or water-soluble polymers in an amount of 1 to 30 wt% shows further improved results.
  • Polyethylene glycol of #2000, #4000 or #6000 is preferable in less powder adherence as compared with polyethylene glycol of #600.
  • Example 7 In samples (7-1) through (7-11) in Example 7 compounds of A part were mixed for 10 minutes without granulating, and granules of B part (the same as Example 7) and sodium N-lauroylsarcosine was added and mixed for 3 minutes. The resulting mixture was compression-tableted in the same manner as in Procedure (12-1) to have a weight per tablet of 12 g and a diameter of 30 mm. Thus, tablets for a solid bleach-fixing composition (12-12) through (12-22) were obtained.
  • the compounds of B part in Example 7 were mixed and exposed to moisture under high humidity to increase the weight and dried.
  • the resulting mixture was mixed with granules of A part in Example 7 and sodium N-lauroylsarcosine was added and mixed for 3 minutes.
  • the resulting mixture was compression-tableted in the same manner as in Procedure (12-1) to have a weight per tablet of 12 g and a diameter of 30 mm.
  • Tablet for a solid bleach-fixing composition (12-23) through (12-28) were obtained.
  • the drying weight reduction at 50°C of Table 11 was obtained by measuring samples after tableting pulverized with a mortar, but samples before tableting was substantially the same value.
  • the bleach-fixing composition gives more preferable results.
  • the composition shows far more preferable results as compared with one in which a bleaching agent or a fixing agent is granulated separately. Further, the tablets show especially preferable results as compared with Example 7.
  • a part Fe(III) complex (Exemplified compound) 1200 g Saccharide or Water-Soluble Polymer See Tables 13 to 15 Sodium carbonate monohydrate 500 g B part Ammonium thiosulfate 720 g Sodium thiosulfate 80 g Sodium metabisulfite 300 g Ethylenediaminetetraacetic acid 50 g Saccharide or Water-Soluble Polymer See Tables 13 to 15 C part Water-Soluble Polymer See Tables 13 to 15
  • Procedures were carried out in the same manner as in procedures (13-1) through (13-3), except that exemplified compounds as shown in Tables 13 and 14 were used. Thus, tablets for a solid bleach-fixing composition (13-1) through (13-48) were obtained. The adding amount of water, drying temperature and drying time were adjusted to give the weight reduction shown in Tables 13 through 15. The weight reduction at 50°C were measured in the same manner as in Example 12.
  • One tablet of the samples was placed in an aluminium package and tightly sealed and were stored at 50°C for 2 weeks.
  • the resulting tablets were placed on a polyethylene plate at 25°C and 45%RH.
  • the polyethylene plate was fixed using Static Friction Tester HEIDON-10 (produced by HEIDON Co.) and the angle ⁇ at which the samples move on the polyethylene plate was measured. Three tablets of each sample were measured.
  • the evaluation criteria are as follows:
  • the tablet sliding at a less angle is more preferable in view of handling.
  • two kinds of signs show a different evaluation result in three time measurement.
  • the samples of the invention give improved results in view of the effects of the invention, when saccharides or water-soluble polymers are added to each of granules containing a Fe(III) complex and granules containing a sulfite.
  • saccharides or water-soluble polymers are added to the solid composition as well as to the above granules, further improved results are obtained.
  • water soluble polymers having an average molecular weight of 2000 to 8000 gives preferable sliding property.

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

Claims (20)

  1. Eine feste Behandlungszusammensetzung in Form von Granalien oder Tabletten für lichtempfindliches farbphotographisches Silberhalogenidmaterial, wobei die Zusammensetzung ein Aminopolycarbonsäure-Ferri-Komplex-Hydrat umfasst, worin die Trockengewichtsverminderung der Zusammensetzung bei 50 °C 0,1 bis 10,0 Gew.-% beträgt, wobei das Trockengewicht aus dem reduzierten Gewicht erhalten wird, nachdem die Zusammensetzung bis zur Gewichtskonstanz auf 50 °C erhitzt wurde.
  2. Die feste Zusammensetzung aus Anspruch 1, worin die Zusammensetzung eine feste Behandlungszusammensetzung zum Bleichen ist.
  3. Die feste Zusammensetzung aus Anspruch 2, worin das Molverhältnis von Kristallwasser des Fern-Komplexes im Ferri-Komplex-Hydrat dem folgenden Ausdruck genügt: 0,3 ≤ Kristallwasser / Ferri-Komplex ≤ 3,0
  4. Die feste Zusammensetzung aus Anspruch 2, worin die Zusammensetzung des weiteren eine Verbindung umfasst, die durch die folgende Formel (A) verkörpert wird: A(-COOM)n worin A eine n-valente organische Gruppe verkörpert, n eine ganze Zahl von 1 bis 6 verkörpert und M ein Ammonium, ein Alkalimetall (Natrium, Kalium oder Lithium) oder ein Wasserstoffatom verkörpert.
  5. Die feste Zusammensetzung aus Anspruch 2, worin die Zusammensetzung des weiteren wenigstens eines, gewählt aus einem Wasserlöslichen Polymer und einem Saccharid, enthält.
  6. Die feste Zusammensetzung aus Anspruch 2, worin die Zusammensetzung des weiteren wenigstens eines, gewählt aus einem wasserlöslichen Polymer und einem Saccharid in einer Menge von 0,5 bis 20,0 Gew.-%, enthält.
  7. Die feste Zusammensetzung aus Anspruch 2, worin die Zusammensetzung in Tabletten formgepresst ist.
  8. Die feste Zusammensetzung aus Anspruch 1, des weiteren ein Fixiermittel enthaltend.
  9. Die feste Zusammensetzung aus Anspruch 8, worin die Zusammensetzung eine feste Behandlungszusammensetzung für die Bleichfixierung ist.
  10. Die feste Zusammensetzung aus Anspruch 9, worin die Zusammensetzung in Form von Granalien vorliegt und der Gehalt an Granalien, die einen Teilchendurchmesser von weniger als 149 µm besitzen, nicht mehr als 30 Gew.-% beträgt.
  11. Die feste Bleichzusammensetzung aus Anspruch 9, worin das Aminopolycarbonsäure-Ferri-Komplex-Hydrat in Form von Granalien vorliegt.
  12. Die feste Zusammensetzung aus Anspruch 9, worin das Fixiermittel ein Thiosulfat.
  13. Die feste Zusammensetzung aus Anspruch 9, worin das gesamte oder ein Teil des Fixiermittels in Form von Granalien vorliegt.
  14. Die feste Zusammensetzung aus Anspruch 9, worin die Zusammensetzung des weiteren wenigstens eines, gewählt aus einem wasserlöslichen Polymer und einem Saccharid in einer Menge von 1,0 bis 30,0 Gew.-%, enthält.
  15. Die feste Zusammensetzung aus Anspruch 9, worin eine Zusammensetzung, enthaltend ein Aminopolycarbonsäure-Ferri-Komplex-Hydrat und ein Fixiermittel in Tabletten formgepresst ist.
  16. Die feste Zusammensetzung aus Anspruch 15, worin das Fixiermittel ein Thiosulfat ist.
  17. Die feste Zusammensetzung aus Anspruch 15, worin das Aminopolycarbonsäure-Ferri-Komplex-Hydrat in Form von Granalien vorliegt.
  18. Die feste Zusammensetzung aus Anspruch 15, worin das Fixiermittel in Form von Granalien vorliegt.
  19. Die feste Zusammensetzung aus Anspruch 15, worin das Aminocarbonsäure-Ferri-Komplex-Hydrat in den einen Granalien ist und das Fixiermittel in den anderen Granalien ist.
  20. Die feste Zusammensetzungen aus Anspruch 15, worin die Zusammensetzung wenigstens eines, gewählt aus einem wasserlöslichen Polymer und einem Saccharid in einer Menge von 1,0 bis 30,0 Gew.-%, enthält.
EP95101760A 1994-02-15 1995-02-10 Feste Zusammensetzung zur Behandlung von lichtempfindlichen farbphotographischen Silberhalogenidmaterialien Expired - Lifetime EP0667559B1 (de)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP18571/94 1994-02-15
JP1857194A JPH07225460A (ja) 1994-02-15 1994-02-15 ハロゲン化銀カラー写真感光材料漂白用固体処理剤
JP1857194 1994-02-15
JP2127894 1994-02-18
JP21278/94 1994-02-18
JP2127894A JPH07230152A (ja) 1994-02-18 1994-02-18 ハロゲン化銀カラー写真感光材料の漂白定着用固体処理剤

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EP0667559B1 true EP0667559B1 (de) 2000-06-07

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JPH1124213A (ja) * 1997-07-01 1999-01-29 Konica Corp ハロゲン化銀写真感光材料用固体処理剤及びその造粒方法

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Publication number Priority date Publication date Assignee Title
DE3920921A1 (de) * 1989-06-27 1991-01-03 Agfa Gevaert Ag Granuliertes, farbfotografisches bleichmittel und seine herstellung
DE69214248T2 (de) * 1991-05-01 1997-04-30 Konishiroku Photo Ind Automatisches entwicklungsgerät für lichtempfindlichen träger auf silberhalogenidbasis
EP0563571A2 (de) * 1992-02-25 1993-10-06 Konica Corporation Festes Bleichmittel für farbphotographische lichtempfindliche Silberhalogenidmaterialien und Verarbeitungsverfahren dafür
JPH0627619A (ja) * 1992-05-13 1994-02-04 Fuji Photo Film Co Ltd カラー写真用漂白定着組成物

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Hackh's Chemical Dictionary, 4th Ed., 1972, page 329 *
W.A.Ritschel, Die Tablette, 1966, p. 231 to 234 *

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