EP0687950A1 - Verarbeitungszusammensetzung in Granulat- oder Tablettenform für die Verarbeitung eines photographischen lichtempfindlichen Silberhalogenidmaterials - Google Patents

Verarbeitungszusammensetzung in Granulat- oder Tablettenform für die Verarbeitung eines photographischen lichtempfindlichen Silberhalogenidmaterials Download PDF

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Publication number
EP0687950A1
EP0687950A1 EP95303582A EP95303582A EP0687950A1 EP 0687950 A1 EP0687950 A1 EP 0687950A1 EP 95303582 A EP95303582 A EP 95303582A EP 95303582 A EP95303582 A EP 95303582A EP 0687950 A1 EP0687950 A1 EP 0687950A1
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Prior art keywords
group
composition
processing
solid composition
solid
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EP95303582A
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English (en)
French (fr)
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Ichiro C/O Konica Corporation Tsuchiya
Wataru C/O Konica Corporation Satake
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Konica Minolta Inc
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Konica Minolta Inc
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Publication of EP0687950A1 publication Critical patent/EP0687950A1/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 present invention relates to a solid photographic processing composition for processing a silver halide photographic light-sensitive material, and more particularly to a granular shape and a tablet shape solid processing composition for processing a silver halide photographic light-sensitive material wherein storage stability has been improved.
  • processing composition kits are made of a concentrated liquid.
  • the processing composition kits have still needed to have a lot of spaces for storing them, and the transportation cost of the kits can also in no way be slighted.
  • the quantity of the waste plastic bottles has increased year by year. It is also needed to retrieve and dispose of the waste plastic bottles.
  • a processing composition capable of reducing the quantity of the waste plastics has been demanded, because the waste plastic bottles can hardly be retrieved and disposed.
  • a pulverized photographic processing agent has not only such a problem that there is an apprehension for the worker's health, because the fine powder thereof is whirled up in the air when dissolving the composition and he may possibly inhale the flying powder, but also such a problem that a whirling processing composition component is mixed in another photographic processing composition and thereby a trouble is produced in the development process.
  • JP OPI Publication Japanese Patent Publication Open to Public Inspection
  • JP OPI Publication Nos. 2-109042/1990 and 2-109043/1990.
  • JP OPI Publication a photographic processing system in which a solid photographic development processing composition is used, and a solid photographic development processing composition applicable to the photographic system are described in JP OPI Publication Nos. 5-119454/1993, 5-113646/1993 and 5-107696/1993.
  • the solid processing composition when transported by sea from Japan to South east Asia, the Middle Near East area and Africa, it takes about 2 to 4 weeks, wherein the difference of temperature between day and night reaches 15 to 20°C and humidity changes by about 20 to 30%RH. In such an occasion, the above-mentioned problem becomes more serious.
  • diethylenetriamine pentaacetic acid ferric complex salt for improving preservability of the above-mentioned processing tank solution.
  • diethylenetriamine pentaacetic acid ferric complex salt since the diffusion property of this diethylenetriamine pentaacetic acid ferric complex salt is small, elution property from a silver halide photographic light-sensitive material is small. Therefore, especially when processing time is short, this diethylenetriamine pentaacetic acid ferric complex salt tends to remain in the light-sensitive material, and yellow stain occures. In order to solve this problem, it is effective to use the above-mentioned organic phosphonic acid compound in a stabilizing processing tank.
  • the solid processing composition containing the organic phosphonic acid compound crumbles when left at high temperature and high humidity for a long time so that fine powder easily tend to occur, resulting in that it is difficult to supply a certain amount of organic phosphonic acid compound accurately to a stabilizing processing tank.
  • yellow stain due to the above-mentioned diethylenetriamine pentaacetic acid ferric complex salt is caused.
  • a first object of the present invention is to provide a solid photographic processing composition wherein form change due to storage for a long time is small and handling convenience is secured.
  • a second object of the present invention is to provide a processing method wherein stable processing performance can be maintained without accompanying the occurrence of yellow stain even when diethylenetriamine pentaacetic acid ferric complex salt is used in the bleaching and fixing step.
  • Fig. 1 is an overall arrangement view of the silver halide photosensitive material processing apparatus.
  • Fig. 2 is a perspective view of the above silver halide photosensitive material processing apparatus.
  • Fig. 3 is a sectional view of the automatic processing apparatus of the present invention.
  • Solid processing composition administrating section 30 Solid processing composition replenishing device 31. Throughout information detecting means 32. Throughout supply control means 33. Accomodating container (cartridge) 34. Accommodating container setting means 35. Supplying means 40. Water replenishing means 41. replenishing water tank 42. Bellows pump 43. Inhallation pipe 44. Water supply pipe 45. Replenishing water supply control means J. Tablet shape solid processing composition W. Replenishing water
  • R1 through R7 independently represent a hydrogen atom, -OH, -COOM, -PO3M2, -SO3M, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms;
  • M represents a hydrogen atom and an alkaline metal atom; and
  • n and m independently represent 0 or 1, provided that they are not 0 at the same time.
  • the number of carbon in aforesaid alkyl group is preferably 1 to 4.
  • the alkyl group may be either straight-chained or branched and may have a substituent.
  • the preferable substituent is -OH, -COOM, -PO3M2, -SO3M and -NR8R9.
  • R8 and R9 independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • M represents a hydrogen atom and an alkaline metal.
  • the preferable is an alkaline metal.
  • n and m independently represent 0 or 1, provided that they are not 0 at the same time.
  • R1 through R9 may be the same or different.
  • T1 represents a hydrogen atom, a hydroxy group, a carboxy group, a sulfo group, a carbamoyl group, a phosphono group, a phosphone group, a sulfamoyl group, a substituted or unsubstituted alkyl group, an alkoxy group, an alkylsulfonamido group, an alkylthio group, an acylamino group, a hydroxamic acid group, a hydroxyalkyl group or W1 represents a substituted or unsubstituted alkylene group, an arylene group, an alkenylene group, a cycloalkylene group, an aralkylene group or ( ⁇ L5-X L6 ; X represents -O-, -S-, a divalent heterocyclic group or R1 through R5 independently represent a hydrogen atom, a hydroxy group, a
  • Compound represented by Formula [II] is used as a free acid.
  • they can be used as a salt of alkaline metal and alkaline earth metal.
  • the alkaline metal salt sodium salt and potassium salt
  • the solid processing composition of the present invention means a processing composition in the solid form such as in the granular shape or tablet shape.
  • a solid processing composition of the invention is granular shape
  • its average particle size is preferably 100 to 3000 ⁇ m, more preferably 150 to 1500 ⁇ m and most preferably 300 to 1000 ⁇ m.
  • the average particle size referred here is a weight average value obtained by means of a sieving method using a standard sieve of JIS standards.
  • the above-mentioned granular shape processing composition is preferable to be subjected to a granulating step, from the viewpoint of the present invention.
  • the solid processing composition of the present invention is tablet-shape, it can take an arbitrary form depending upon the state of application.
  • the tablet-shape processing composition of the present invention can be manufactured by the use of a conventional compressor such as an hydraulic press, a single-shot type tableting machine, a rotary type tableting machine and a briquetting machine.
  • a conventional compressor such as an hydraulic press, a single-shot type tableting machine, a rotary type tableting machine and a briquetting machine.
  • a decreasing ratio of decreasing weight of a granular shape solid composition after drying at 50 °C to weight of a granular shape solid composition before drying is defined as follows.
  • a granular shape solid composition is stored in a sealed container under the conditions of a temperature of 25 °C and a Relative humidity of 40 %RH for two days.
  • a decreasing weight is measured under the conditions, and then, a decreasing ratio of the present invention is calculated from the following equation by using the decreasing weight.
  • a decreasing ratio (wt%) ((W b - W a )/W b ) ⁇ 100:
  • W a is a weight of a granular shape solid composition after drying at 50 °C
  • W b is a weight of a granular shape solid composition before drying.
  • a decreasing ratio in weight of the solid processing composition is in the range of 0.5 to 10 wt%, preferably 0.8 to 8 wt% and more preferably 1.2 to 6 wt%.
  • the granular shape processing composition of the present invention can be granulated by the use of a conventional granulation process such as a fluidized-bedding granulation process, a stirring granulation process, a rolling granulation process, an extruding granulation process and a compressing granulation process.
  • a conventional granulation process such as a fluidized-bedding granulation process, a stirring granulation process, a rolling granulation process, an extruding granulation process and a compressing granulation process.
  • so-called wet-type granulation process wherein a solvent is used for granulating is preferable.
  • polar solvents such as alcohol, acetone, acetonitrile and water are cited.
  • their mixtures may be used. From a viewpoint of the present invention, the preferable is water.
  • the preferable added amount of the above-mentioned solvent is 1 to 20 wt/V and more preferably 3 to 10 wt/V to a raw material powder. When it is less than 1 wt/V, sufficient granulating is not conducted. When exceeding 20 wt/V, drying time becomes longer and the raw material may be deteriorated during granulation process.
  • the saccharides of the invention refer to monosaccharides or polysaccharides in which monosaccharides bind through a glycoside bondage.
  • Monosaccharides refer to as a generic term of derivatives in a wide range such as 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 of the invention include derivatives derived from saccharide skeleton represented by the above formula.
  • the preferable are sugar alcohols having a primary or secondary alcohol group to which an aldehyde or ketone group of saccharides is reduced.
  • the especially preferable is a hexitol having 6 carbon atoms.
  • 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, and starches include maltose or dextrins that starches are hydrolyzed to various decomposition compounds.
  • Celluloses may be in an alkali salt form in view of solubility.
  • celluloses or dextrins are preferably used, and dextrins are more preferably used.
  • B-(66) through (83) are preferably used, and B-(74) through (84) are more preferably used.
  • C-(21) through (64) are preferably used, and compounds, C-(21) through (48) are more preferably used.
  • the content of the saccharide in the solid processing composition of the invention is preferably 0.5 to 30, and more preferably 1.0 to 20 by weight of the solid processing composition.
  • the derivatives can be easily prepared by reduction, oxidation or dehydration reactions.
  • conventional water-soluble polymers can be used.
  • Aforesaid polymers include polyalkylene glycols, polyvinyl pyrrolidones, polyvinyl alcohols and polyacrylic acids.
  • the preferable are polyethylene glycols, polyvinyl pyrrolidones and polyvinyl alcohol. The more preferable is polyethylene glycols.
  • the average molecular weight of polyethylene glycols of the present invention is preferably 600 to 20,000, more preferably 1,000 to 20,000 and most preferably 3,000 to 20,000.
  • the number average molecular weight of polyvinyl alcohols of the present invention is preferably 2,000 to 200,000 and more preferably 3,000 to 100,000.
  • the number average molecular weight of polyvinyl pyrrolidone of the invention is preferably 10,000 to 700,000.
  • a triazinylstilbene fluorescent brightening agent from the viewpoint of the effects of the objects of the present invention.
  • a compound represented by Formula [E] is preferable: wherein X2, X3, Y1 and Y2 independently represent a hydroxyl group, a halogen atom such as chlorine or bromine, an alkyl group, an aryl group, or -OR25.
  • R21 and R22 independently represent a hydrogen atom, an alkyl group (including its substituted group) or an aryl group (including its substituted group)
  • R23 and R24 represent an alkylene group (including its substituted group)
  • R25 represents a hydrogen atom, an alkyl group (including its substituted group) or an aryl group (including its substituted group)
  • M represents a cation, incidentally, details of each group represented by Formula [E] or its substituents are the same as a description in Japanese Patent OPI Publication No. 118649/1992, pp. 16 and 17.
  • Practical examples of compounds represented by Formula [E] are those described in Japanese Patent Application No. 301432/1992, paragraph No. 0159 through 0164. These compounds can be synthesized by a conventional method.
  • E-4, E-24, E-34, E-35, E-36, E-37 and E-41 are preferably employed.
  • the solid processing composition when the solid processing composition is a tablet, as a means for supplying the solid processing composition to a processing tank, conventional methods as described in Japanese Utility Publication Open to Public Inspection Nos. 1377783/1988, 97522/1988 and 85732/1989 are cited. Basically, any method is allowed provided that a function to supply the tablet agent to the processing tank is provided.
  • the solid processing composition when the solid processing composition is granule or powder, methods of dropping caused by gravity described in Japanese Utility Model Publication Open to Public Inspection Nos. 81964/1987 and 84151/1988 and Japanese Patent OPI Publication No. 292375/1989 and methods using a screw described in Japanese Utility Publication Nos. 105159/1988 and 195345/1988 are conventional.
  • the present invention is not limited thereto.
  • any place is allowed for supplying the solid processing composition of the present invention, provided that it is in the processing tank.
  • the preferable is a place which is communicated with a processing solution which processes the light-sensitive material and where a processing solution is circulating with aforesaid processing section.
  • a processing solution is circulating with aforesaid processing section.
  • the solid processing composition is supplied into a processing solution whose temperature has been regulated.
  • An amount of the solid processing composition for one supply is preferably 0.1 g or more from the viewpoint of the effects of the present invention, durability of supplying device and accuracy of the amount supplied. In addition, it is preferred to be 50 g or less from the viewpoint of the effects of the present invention and time for dissolution.
  • Replenishing water of the present invention means replenishing water supplied to the processing tank in accordance with the volume of light-sensitive material to be processed.
  • the so-called evaporation-replenishing water for replenishing evaporation of moisture from the processing tank is not substantially included thereto. Accordingly, the amount of adding replenishing water in the present invention is the amount of total added amount of moisture supplied to the processing tank minuses the amount of moisture evaporated.
  • the added amount of replenishing water supplied to a stabilizing processing tank is 50 to 400 ml per 1 m2 of light-sensitive material.
  • it is preferably 100 to 200 ml.
  • Illustrated compound I-1 300 g of 3Na salt and 600 g of sodium carbonate monohydrate was crushed by the use of a hammer mill available on the market until the average particle size becomes 50 ⁇ m. The resulting fine powder was mixed for 10 minutes in a commercially available stirring granulating machine and following this, 85 ml of water was added, granulated for about 10 minutes. Next, the resulting granulated composition was dried by the use of a commercially available fluidized-bed drier. By regulating drying conditions, the decreasing ratio in weight of said composition after drying was regulated as described in Table 1, Thus, granular shape samples 1-1 through 1-9 were prepared.
  • each granular shape sample was poured into a laboratory dish. Under 25°C and 80%RH, the samples were stored for one week. The samples before and after storing were sieved with a sieve shaker for 5 minutes. The weight of fine particle which passed 100 mesh (in accordance with the JIS) was measured.
  • the granular shape processing compositions of the present invention are excellent in terms of strength without crumbling after the lapse of time in storage under high humidity so that they are extremely excellent in terms of handling convenience.
  • the tablet shape processing compositions of the present invention show less deterioration of hardness so that they are excellent in terms of storage stability.
  • Example 2 In the same procedure as in Example 1 except that the proportion of 3 sodium salt of the illustrated compound I-2 and sodium carbonate monohydrate was changed as shown in Table 2, granular shape samples 2-1 through 2-7 and tablet shape samples 2-8 through 2-14 were prepared. They were subjected to the same experiment as in Example 1.
  • Table 2 shows the results thereof.
  • Table 2 Sample No. wt% of 3 sodium salt of Illustrated compound I-2 Decreasing ratio (wt%) after drying Strength before storage Strength after storage Fluidity before storage Fluidity after storage 2-1 15 2.4 7.9 wt% 9.1 wt% B B 2-2 22 3.1 8.2 wt% 9.2 wt% B B 2-3 42 2.6 8.1 wt% 9.7 wt% A B 2-4 46 2.8 7.8 wt% 9.6 wt% A A 2-5 51 3.3 7.9 wt% 9.9 wt% A A 2-6 60 2.9 8.4 wt% 9.8 wt% A A 2-7 78 3.0 8.3 wt% 10.1 wt% A A 2-8 15 2.4 9.2 kg 7.4 kg - - 2-9 22 3.1 9.4 kg 7.3 kg - - 2-10 42 2.6 8.8 kg 7.3 kg - - 2-11 46 2.8 8.7 kg 7.2 kg - - 2-12 51 3.3 8.4 kg
  • illustrated compound I-1 provides the effects of the present invention more preferably.
  • granular shape processing composition samples were prepared.
  • a commercially available hammer mil 3,200 g of illustrated compound I-1 ⁇ 3sodium salt, 150 g of sodium carbonate monohydrate and 1400 g of illustrated compound of Formula [II] (described in Table 4) were crushed until the average particle size becomes 50 ⁇ m.
  • This fine powder was mixed for 10 minutes in a commercially available stirring granulating machine.
  • the resulting mixture was granulated for about 10 minutes by adding water.
  • the resulting granule was dried by the use of a commercially available fluidized-bed drier.
  • the decreasing ratio (wt%) after drying was regulated as described in Table 4 so that granular shape samples 4-1 through 4-9 were prepared.
  • Table 4 shows the results thereof.
  • Table 4 Sample No. Illustrated compound of Formula [II] Decreasing ratio (wt%) after drying Strength before storage Strength after storage 4-1 II-1 3.6 6.4 wt% 9.5 wt% 4-2 II-1 ⁇ 2 sodium salt 3.2 6.3 wt% 7.2 wt% 4-3 II-2 ⁇ 2 sodium salt 2.4 6.5 wt% 7.5 wt% 4-4 II-3 3.5 7.1 wt% 9.8 wt% 4-5 II-3 ⁇ 5 sodium salt 2.8 6.2 wt% 7.4 wt% 4-6 II-5 ⁇ 2 sodium salt 3.1 6.8 wt% 7.3 wt% 4-7 II-8 2.9 7.4 wt% 9.2 wt% 4-8 II-14 3.3 7.6 wt% 9.4 wt% 4-9 II-17 ⁇ 1 sodium salt 3.4 6.7 wt% 7.7 wt% 4-10 II-1 3.6 15.4 kg 13.3 kg 4-11
  • Swelling degree of tablet (%) ⁇ [Thickness of tablet composition after storage (mm) - Thickness of tablet composition before storage (mm)] ⁇ /[Thickness of tablet composition before storage (mm)] ⁇ x 100 o: Swelling degree: less than 1% ⁇ : Swelling degree: 1 to 3 % ⁇ : Swelling degree: 5 % or more ⁇ : Incapable of measuring. Table 5 shows the results thereof.
  • Granular shape samples were prepared in accordance with the following procedure.
  • the loss on drying was regulated to as described in Table 6 for preparing granule sample.
  • sodium N-lauroyl sarcosinate was added by 0.5 wt% for mixing for 3 minutes.
  • the resulting mixture was compression-molded by the use of an hydraulic press to prepare a tablet samples 7-1 through 7-9 each having a diameter of 30 mm, thickness of 10 mm and weight of 8.7 g.
  • the automatic processing apparatus of this example is a modified NPS818 type automatic processing apparatus manufactured by Konica Co., Ltd.
  • Fig. 1 is a schematic illustration showing the construction of a silver halide photosensitive material processing apparatus (printer processor) in which the automatic processing apparatus A and photographic printer B are integrated.
  • a magazine M in which a roll of photographic paper, which is an unexposed silver halide photographic material, is accommodated.
  • the photographic paper is pulled out from the magazine M and conveyed by the feed rollers R1 and cut into a predetermined size by the cutter C.
  • a sheet of photographic paper can be provided.
  • This sheet of photographic paper is conveyed by the belt conveyance means Be.
  • an image of the original O is exposed onto the sheet of photographic paper by a light source and lens L in the exposure section E.
  • the exposed sheet of photographic paper is further conveyed by a plurality of pairs of feed rollers R2, R3 and R4, so that the sheet of photographic paper is introduced into the automatic processing apparatus A.
  • the sheet of photographic paper is successively conveyed by a roller conveyance means (the reference numeral is not attached to the means) into the color development tank 1A, bleaching and fixing tank 1B and stabilizing tanks (the first stabilizing tank 1C, the second stabilizing tank 1D, and the third stabilizing tank 1E), wherein these 3 tanks substantially compose a processing tank 1. Due to the foregoing, the sheet of exposed photographic paper is subjected to color development, bleaching and fixing processing and stabilizing processing. After the processing has been completed, the sheet of photographic paper is dried by the drying section 5, and then discharged outside of the apparatus.
  • the one-dotted chain line in the drawing shows a conveyance passage of the silver halide photosensitive material.
  • the photosensitive material is cut into a sheet and introduced into the automatic processing apparatus A, however, a strip-shaped photosensitive material may be introduced into the automatic processing apparatus A in the present invention.
  • the processing efficiency can be enhanced when an accumulator for temporarily stocking the photosensitive material is provided between the automatic processing apparatus A and photographic printer B.
  • the automatic processing apparatus A of the present invention may be constructed integrally with the photographic printer B, or alternatively the automatic processing apparatus A of the present invention may be constructed separately from the photographic printer B.
  • the silver halide photosensitive material processed by the automatic processing apparatus A of the present invention is not limited to the exposed photographic paper, but an exposed negative film may be applied to the automatic processing apparatus A of the present invention. It should be noted that the present invention is not limited to the specific embodiment described above. It is possible to apply the present invention to an automatic processing apparatus substantially composed of 4 tanks of a color developing tank, bleaching tank, fixing tank and stabilizing tank.
  • the color development tank 1A, the bleaching and fixing tank 1B and the third stabilizing tanks 1E are respectively provided with the solid processing composition supply devices 3A, 3B and 3E for supplying the solid processing composition.
  • Fig. 2 is a perspective view showing the entire photosensitive material processing apparatus in which the automatic processing apparatus A of the present invention, photographic printer B and sorter C are integrally combined.
  • the cover Al of the automatic processing apparatus A is opened upward, and the accommodating container D having solid processing composition is inserted into the attaching section A2 from the left upper to the right lower position in the drawing. After that, they are fixed.
  • Fig. 3 is a sectional view of the auxiliary tank and processing composition supply means of the color development tank A taken on line I - I in Fig. 1.
  • the construction of the bleaching and fixing tank 1B and that of the stabilizing tanks are the same as the construction of the color development tank 1A. Therefore, the explanation of the processing tank 1 can be applied to all tanks of the color development tank 1A, the bleaching and fixing tank lb, and the stabilizing tanks (the first stabilizing tank 1C, the second stabilizing tank 1D, and the third stabilizing 1E).
  • the conveyance means for conveying the photosensitive material is omitted in the drawing.
  • the processing tank 1 for processing the photosensitive material is provided with an auxiliary tank 2 and a solid processing composition charging section 20 integrally attached to the outside of the partition wall forming the processing tank 1.
  • the processing tank 1 and the auxiliary tank 2 are separate from each other by the partition wall 21A on which a communication window 21 is formed, so that the processing solution can be communicated through the communication window 21.
  • the auxiliary tank 2 is provided with an enclosure 25 in which the tablets J are received.
  • the enclosure 25 is made of material such as a net so that the processing solution can pass through the enclosure 25, however, the tablets J in the form of a solid body can not pass through the enclosure 25 until they are dissolved in the solution.
  • a cylindrical filter 22 is disposed below the auxiliary tank 2 in such a manner that the cylindrical filter 22 can be replaced.
  • the cylindrical filter 22 removes an undissolved object such as precipitations in the processing solution.
  • a circulation pipe 23 connected with the suction side of a circulation pump 24 (circulation means) is inserted into the filter 22 penetrating through the lower wall of the auxiliary tank 2.
  • the circulation system includes the circulation pipe 23 forming a circulation passage of the processing solution, and also includes the circulation pump 24, the processing tank 1 and the auxiliary tank 2.
  • One end of the circulation pipe 23 is communicated with the delivery side of the circulation pump 24, and the other end penetrates a lower wall of the processing tank 1, so that the circulation pipe 23 is communicated with the processing tank 1. Due to the foregoing construction, when the circulation pump 24 is operated, the processing solution is sucked from the auxiliary tank 2 and discharged into the processing tank 1, so that the discharged processing solution is mixed with the processing solution in the processing tank 1, and then sent to the auxiliary tank 2. In this way, the processing solution is circulated.
  • the circulating direction of the processing composition is not limited to the direction shown in Fig. 3, but the direction may be reverse to that shown in Fig. 3.
  • a waste solution pipe 11 is provided for permitting the processing solution in the processing tank 1 to overflow, so the solution level can be maintained constant and an increase in the components conveyed from other tanks into the processing tank 1 can be prevented. Further, an increase in the components oozing out from the photosensitive material can be prevented.
  • a rod-shaped heater 26T penetrates an upper wall of the auxiliary tank 2, and is dipped in the processing solution in the auxiliary tank 2.
  • the processing solution in the auxiliary tank 2 and processing tank 1 is heated by this heater 26 in accordance with a temperature detected by a thermometer not shown in the drawing arranged in the auxiliary tank 2.
  • the heater 26T is a temperature regulating means for regulating the temperature of the processing solution in the processing tank 1, so that the temperature can be controlled in an appropriate range, for example, in a range from 20 to 55°C.
  • a photoelectric sensor to be used as a throughput information detecting means 31 is disposed at an entrance of the automatic processing apparatus A, and detects the throughput of the photosensitive material to be processed.
  • This throughput information detecting means 31 is comprised of a plurality of detecting members that are disposed in a transverse direction.
  • This throughput information detecting means 31 detects the width of photosensitive material, and the result of detection is used for counting the detection time. Since the conveyance speed of photosensitive material is previously set in a mechanical manner, the throughput of photosensitive material, that is, the area of processed photosensitive material can be calculated form the width and time information.
  • An infrared ray sensor, micro switch and ultrasonic sensor capable of detecting the width and conveyance time of photosensitive material can be used for this throughput information detecting means 31.
  • a means for indirectly detecting the area of processed photosensitive material may be used for this throughput information detecting means 31.
  • a means for detecting an amount of printed photosensitive material may be adopted, or alternatively, a means for detecting an amount of processed photosensitive material, the area of which is predetermined, may be adopted.
  • Concerning the detecting time in this example, detection is carried out before processing, however, detection may be carried out after processing or while the photosensitive material is being dipped in the processing solution.
  • the throughput information detecting means 31 may be disposed at an appropriate position so that detection can be conducted after processing or while the photosensitive material is being processed. It is not necessary to provide the throughput information detecting means 31 for each processing tank 1A, 1B, 1C, 1D, 1E, and it is preferable that one throughput information detecting means 31 is provided for one automatic processing apparatus A.
  • the solid processing composition supply control means 32 receives a signal from the throughput information detecting means 31 so that the supply of the processing composition conducted by the solid processing composition supply means 30T is controlled and further the supply of replenishment water conducted by the replenishment water supply means 40T is controlled.
  • the solid processing composition replenishing device 30T used for the photosensitive material processing apparatus of the present invention is disposed above the processing tank 1 of the photosensitive material processing apparatus, and comprises an accommodating container 33, accommodating container charging means 34, supply means 35 and drive means 36T, wherein the solid processing composition replenishing device 30T is tightly closed by an upper cover 301.
  • the upper cover 301 is rotatably connected with a main body 101 accommodating the processing tank 1 and auxiliary tank 2, through a support shaft 302 attached to the back of the main body.
  • the upper cover 301 is lifted upward as shown by a one-dotted chain line in the drawing, so that the front and upper portions of the apparatus can be widely opened. In this way, inspection of the solid processing composition replenishing device 30T, and replacement of the filter 22 can be easily conducted.
  • a skylight 303 is rotatably connected with a portion of the upper surface of the upper cover 301.
  • the accommodating container 33 is attached or replaced.
  • the replenishment water supply means 40T includes: a replenishment water tank 41, bellows pump 43, suction pipe 43, and water feed pump 44.
  • Replenishment water W accommodated in the replenishment water tank 41 is sucked by the action of the bellows pump 42 and flows in the suction pipe 43. After that, replenishment water W is extruded by the bellows pump 42 and flows in the water supply pipe 44. In this way, replenishment water W is supplied to an upper portion of the processing solution accommodated in the auxiliary tank 2.
  • a drive motor of the bellows pump 42 is rotated being controlled by the replenishment water supply control means 45, so that replenishment water W is intermittently replenished by the bellows pump 42.
  • a solid processing composition for processing photographic color paper was made in the following manner.
  • Solid processing composition (1) for developing photographic color paper was prepared as follows.
  • the developing agent of CD-3 is used, that is, 1350.0 g of 4-amino-3-methyl-N-ethyl-[b-(methanesulfonamido)ethyl]aniline sulfate is crushed by a Bandam Mill available on the market so that the average particle size can be 10 mm.
  • 1000.0 g of polyethylene glycol having a number average molecular weight of 6000 is added and mixed uniformly by a mixer available on the market.
  • the mixture is subjected to a granulating machine available on the market for 7 minutes at room temperature while 50 ml of water is added to the mixture. In this way, the granulation is effected.
  • the thus obtained granules are dried by a fluidized-bed dryer for 2 hours at a temperature of 40°C, so that the moisture in the granules is substantially completely removed.
  • All the granules made in Operations (1) to (3) are mixed for 10 minutes using a cross rotary type mixer available on the market at room temperature.
  • 50.0 g of N-myristoyl-alanine sodium salt is added and mixed uniformly by a mixer available on the market for 3 minutes.
  • This is defined to be a sample embodiment 1.
  • the mixture is subjected to a rotary type tableting machine (Clean Press Correct H18 manufactured by Kikusui Seisakusho Co.), and tablets are made under the condition that the diameter is 30 mm, the thickness is 10 mm, and the amount of charging per one tablet is 10.5 g.
  • the tablet making force is set at 7 t, and tablets are continuously made.
  • tablets of the solid processing composition for color development of photographic color paper are made.
  • obtained tablets of the solid processing composition are defined to be sample embodiment 2.
  • Granulated products obtained by Operations (5) and (6) are mixed in the same manner as in Operation (4).
  • 800.0 g of polyethylene glycol having a number average molecular weight of 4000, 600 g of potassium carbonate and 97.0 g of sodium N-lauroyl sarcosinate are added to the resulting mixture.
  • the resulting mixture is mixed for 3 minutes by the use of a mixer. This is defined to be Sample embodiment 1.
  • Example 7 The same tablet shape processing composition as prepared in Example 7 is used.
  • Example embodiment 2 By the use of a tablet shape composition (Sample embodiment 2) prepared in Example 7 and by means of an automatic processor shown in the above-mentioned Figs. 1 through 3, a sample described in Japanese patent Publication Open to Public Inspection No. 264550/1992, Example 1 containing silver chloride content of 99.5 mol% is exposed by a conventional method, and then, processed in accordance with the following processing step.
  • Processing step Processing temperature Processing time Amount of replenishing a tablet Added amount of replenishing water Color developing 40.0 ⁇ 0.5°C Described in table 1 6.5 g/m2 62 ml/m2 Bleach-fixing 35.0 ⁇ 1.0°C 22 sec. 13.6 g/m2 60 ml/m2 Stabilizing 1 33.0 ⁇ 3.0°C 22 sec.
  • Stabilizing is a counter flow type from 3 to 1.
  • 60 ml/m2 is flowed into a bleach fixing tank as a replenishing water.
  • a tablet is set to a tablet supplying device provided on the automatic processor. Supplying interval is adjusted so that the supplying amount becomes the above-mentioned value.
  • the supplying amount for one time is 2 tablets (21.0 g) for color developing, 2 tablets (22.0 g) for bleach-fixing and 2 tablets (8.7 g) for stabilizing.
  • amount of replenishing water is adjusted and processing is conducted.
  • the starting solution of each processing tank in the automatic processor the following formula is used.
  • Tetrasodium 1-hydroxyethylidene-1,1-diphosphoric acid 4.0 g
  • Diethylenetriamine pentaacetic acid 2.0 g
  • Sodium sulfite 0.8 g
  • Sodium carbonate 0.5 g
  • o-phenylphenol 0.08 g pH is adjusted to 8.0 ⁇ 0.5 by the use of potassium carbonate or sulfuric acid.
  • a tablet type processing composition for stabilizing use is stored for one week in accordance with Experiment 2 described in Example 1.
  • running processing is conducted. The running processing is conducted for 2 weeks in terms of color paper 7.5 m2 per day.
  • a color paper sample is subjected to wedge light exposure in accordance with a conventional method. Its minimum reflection blue density (Dmin(Y)) is measured by means of an X-rite (produced by Nippon Heihan Kizai Co., Ltd.).
  • Table 7 shows the results thereof.
  • Table 7 Sample No. Decreasing ratio (wt%) Minimum reflection blue-density 8-1 0.4 0.12 8-2 0.5 0.08 8-3 0.8 0.06 8-4 1.3 0.04 8-5 2.4 0.05 8-6 5.8 0.04 8-7 7.3 0.06 8-8 9.6 0.08 8-9 11.1 0.14
  • aforesaid solid processing composition can provide stable processing performance, even using after storage for a long time under high humidity environment.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • General Physics & Mathematics (AREA)
  • Medicinal Preparation (AREA)
EP95303582A 1994-05-27 1995-05-26 Verarbeitungszusammensetzung in Granulat- oder Tablettenform für die Verarbeitung eines photographischen lichtempfindlichen Silberhalogenidmaterials Withdrawn EP0687950A1 (de)

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JP11544994 1994-05-27
JP115449/94 1994-05-27

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5731468A (en) * 1997-04-03 1998-03-24 The Dow Chemical Company Preparation of disodium ethylenediamine-N,N'-disuccinate

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JPS6281964U (de) 1985-11-08 1987-05-25
JPS6384151U (de) 1986-11-20 1988-06-02
JPS6397522U (de) 1986-12-12 1988-06-24
JPS63105159U (de) 1986-12-26 1988-07-07
JPS63137783U (de) 1987-02-27 1988-09-12
JPS63195345U (de) 1987-05-30 1988-12-15
JPH0185732U (de) 1987-11-27 1989-06-07
JPH01292375A (ja) 1988-05-20 1989-11-24 Ricoh Co Ltd トナーカートリッジ
JPH02109043A (ja) 1988-09-03 1990-04-20 Agfa Gevaert Ag 粒状カラー写真現像剤及びその製造法
JPH02109042A (ja) 1988-09-03 1990-04-20 Agfa Gevaert Ag 粒状カラー写真現像剤及びその製造方法
JPH04118649A (ja) 1990-06-29 1992-04-20 Konica Corp ハロゲン化銀カラー写真感光材料の処理方法
JPH04264550A (ja) 1991-02-20 1992-09-21 Konica Corp ハロゲン化銀カラー写真感光材料の処理方法
JPH04301432A (ja) 1991-03-29 1992-10-26 Sekisui Chem Co Ltd 耐食性強化プラスチック管の製造方法
JPH05100370A (ja) * 1991-10-07 1993-04-23 Konica Corp 写真用処理剤
JPH05107696A (ja) 1991-04-03 1993-04-30 Eastman Kodak Co 検知可能なフイルム速度標識を備えたフイルムカセツト
JPH05113646A (ja) 1991-10-21 1993-05-07 Konica Corp ハロゲン化銀カラー写真感光材料用発色現像処理錠剤
JPH05119450A (ja) 1991-10-30 1993-05-18 Konica Corp 錠剤型処理剤
JPH05119454A (ja) 1991-05-01 1993-05-18 Konica Corp ハロゲン化銀写真感光材料用自動現像機
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JPS6281964U (de) 1985-11-08 1987-05-25
JPS6384151U (de) 1986-11-20 1988-06-02
JPS6397522U (de) 1986-12-12 1988-06-24
JPS63105159U (de) 1986-12-26 1988-07-07
JPS63137783U (de) 1987-02-27 1988-09-12
JPS63195345U (de) 1987-05-30 1988-12-15
JPH0185732U (de) 1987-11-27 1989-06-07
JPH01292375A (ja) 1988-05-20 1989-11-24 Ricoh Co Ltd トナーカートリッジ
JPH02109043A (ja) 1988-09-03 1990-04-20 Agfa Gevaert Ag 粒状カラー写真現像剤及びその製造法
JPH02109042A (ja) 1988-09-03 1990-04-20 Agfa Gevaert Ag 粒状カラー写真現像剤及びその製造方法
JPH04118649A (ja) 1990-06-29 1992-04-20 Konica Corp ハロゲン化銀カラー写真感光材料の処理方法
JPH04264550A (ja) 1991-02-20 1992-09-21 Konica Corp ハロゲン化銀カラー写真感光材料の処理方法
JPH04301432A (ja) 1991-03-29 1992-10-26 Sekisui Chem Co Ltd 耐食性強化プラスチック管の製造方法
JPH05107696A (ja) 1991-04-03 1993-04-30 Eastman Kodak Co 検知可能なフイルム速度標識を備えたフイルムカセツト
JPH05119454A (ja) 1991-05-01 1993-05-18 Konica Corp ハロゲン化銀写真感光材料用自動現像機
JPH05100370A (ja) * 1991-10-07 1993-04-23 Konica Corp 写真用処理剤
JPH05113646A (ja) 1991-10-21 1993-05-07 Konica Corp ハロゲン化銀カラー写真感光材料用発色現像処理錠剤
JPH05119450A (ja) 1991-10-30 1993-05-18 Konica Corp 錠剤型処理剤
EP0611989A1 (de) * 1993-01-19 1994-08-24 Konica Corporation Feste Zusammensetzung zur Verarbeitung von photographischen lichtempfindlichen Silberhalogenidfarbmaterialien und deren Verarbeitungsverfahren
EP0636930A1 (de) * 1993-07-28 1995-02-01 Konica Corporation Stabilisatorzusammensetzung zur Behandlung von photographischen lichtempfindlichen Silberhalogenidmaterial und Verfahren zur Behandlung von lichtempfindlichem Silberhalogenidmaterial unter Verwendung dieser Zusammensetzung
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5731468A (en) * 1997-04-03 1998-03-24 The Dow Chemical Company Preparation of disodium ethylenediamine-N,N'-disuccinate

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