EP0405238B1 - Granulated photographic fixing composition and its preparation - Google Patents
Granulated photographic fixing composition and its preparation Download PDFInfo
- Publication number
- EP0405238B1 EP0405238B1 EP90111254A EP90111254A EP0405238B1 EP 0405238 B1 EP0405238 B1 EP 0405238B1 EP 90111254 A EP90111254 A EP 90111254A EP 90111254 A EP90111254 A EP 90111254A EP 0405238 B1 EP0405238 B1 EP 0405238B1
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- EP
- European Patent Office
- Prior art keywords
- fixative
- bleach
- granulated
- granulate
- photographic
- 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.)
- Expired - Lifetime
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
- G03C5/265—Supplying of photographic processing chemicals; Preparation or packaging thereof of powders, granulates, tablets
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/38—Fixing; Developing-fixing; Hardening-fixing
Definitions
- the present invention relates to a granular, photographic fixing agent and a method for producing such a fixing agent which can be quickly dissolved.
- Photographic fixing agents and bleach-fixing agents usually contain a thiosulfate as the fixing substance, which is intended to dissolve undeveloped silver halide and silver halide which has newly formed by bleaching the metallic silver from the photographic material.
- thiosulfate ammonium thiosulfate [(NH4) 2S2O3] is largely used due to its fast fixing reaction, but this has a serious disadvantage. Powders of this substance bake when standing, even in the absence of atmospheric moisture, to form solid lumps that have to be crushed with difficulty and are difficult to dose then when the ammonium thiosulfate powder is mixed with the other components of the fixing or bleach-fixing bath.
- the sodium thiosulfate used as an alternative is also disadvantageous because it dissolves poorly in water and forms crusts on the bottom of the fixing or bleach-fixing bath.
- the fixing or bleach-fixing agent is largely offered and used in a liquid formulation.
- this has the disadvantage of increased costs due to water ballast.
- the object of the invention is to provide a form of assembly for ammonium thiosulfate which is firm and yet easy to dose and which dissolves quickly in the bath.
- granulated fixing agents can be prepared by grinding a thiosulfate together with a disulfite and optionally other solid substances such that the maximum of the particle diameter distribution curve is less than 10 ⁇ m, the ground particles are subjected to powder agglomeration and the granules are dried in vacuo , if necessary mixed with the granules of the bleaching agent and packed in a water vapor-tight manner.
- the granules of the solid components of a photographic fixing or bleach-fixing agent produced in this way are mechanically stable, of uniform grain size, show a high dissolution rate and unlimited durability, are dust-free and free-flowing.
- Preferred thiosulfates are alkali, in particular sodium, and ammonium thiosulfate.
- Alkali and ammonium disulfite are suitable as disulfites.
- the solid constituents are usually comminuted to particle sizes of ⁇ 10 ⁇ m by jet milling.
- the powder agglomeration is preferably carried out in a fluidized bed, granulation liquid, for example 200 ml of water per kg of powder and, if appropriate, some binder, for example corn starch, being added to the particles to be agglomerated.
- the average particle diameter of the granules should preferably be ⁇ 150 ⁇ m and is in particular 150 to 3000 ⁇ m.
- thiosulfate granules are complexing agents such as ethylenediaminetetraacetic acid (EDTA) and agents for adjusting the desired pH such as sodium carbonate.
- EDTA ethylenediaminetetraacetic acid
- granules are preferably produced separately from the fixing agent and bleaching agent and mixed with one another.
- the granules of the bleaching agent contain an iron (III) complex or an iron (III) complex salt, for example an ammonium iron complex salt from EDTA, the propylenediamine tetraacetic acid (PDTA), diethylenetriaminepentaacetic acid (DTPA) or nitrilotriacetic acid (NTA) and optionally free complexing agents, for example EDTA, PDTA, DTPA or NTA.
- an iron (III) complex or an iron (III) complex salt for example an ammonium iron complex salt from EDTA, the propylenediamine tetraacetic acid (PDTA), diethylenetriaminepentaacetic acid (DTPA) or nitrilotriacetic acid (NTA) and optionally free complexing agents, for example EDTA, PDTA, DTPA or NTA.
- the granules of the bleaching agent are preferably produced in the same way as the granules of the fixing agent and in particular have an average particle diameter in the same range.
- the agent according to the invention preferably contains 35 to 85% by weight of thiosulfate, 5 to 15% by weight of disulfite and, in the case of a bleach-fixing agent, 30 to 50% by weight of iron (III) complex or iron (III) complex salt.
- the bleach-fix bath granules are produced by mixing two individual granules A and B. The following quantities of substance are used per liter of ready-to-use solution:
- the chemicals listed under A are - in the specified mixing ratio - crushed in a so-called Alexander mill to about 1 mm grain size and then in an air jet mill to a particle size of 5 ⁇ m, ground.
- the ground material is then granulated in portions of approximately 500 grams on a commercially available fluidized bed granulator (Strea-1 laboratory device from Aeromatic, Bubendorf / Switzerland).
- the colorless product obtained does not clump and is non-dusting and free-flowing.
- the chemicals listed under B are mixed and granulated in the same granulator (as in A) by spraying on 50% by weight ammonium iron EDTA solution, which contains excess ammonia, in about 7 minutes. 200 ml of this solution are sprayed onto 600 g of mixture B at room temperature.
- Granules A and B are mixed to produce the ready-to-use mixed granulate.
- the mixture of 91.1 g of granules A and 57.8 g of granules B gives the amount of mixed granules required for 1 liter of bleach-fixing bath.
- the mixed granulate is free-flowing, free-flowing and non-dusting. With stirring, it dissolves in water at room temperature in 45 seconds to a dark red solution. This is no different from a second sample made from the same amount of the corresponding powdered chemicals.
- the mixed granulate, packed airtight and moisture-proof, has an unlimited shelf life.
- the photographic effectiveness corresponds entirely to a bleach-fix bath which was produced from non-granulated chemicals according to the same recipe.
- the mixture After comminution in the so-called Alexander mill, the mixture is ground in an air jet mill to an average particle size of approximately 5 ⁇ m.
- the colorless granules are dust-free, free-flowing and non-clumping. Sealed in aluminum-coated bags, it has an unlimited shelf life. It dissolves in water with stirring within about 10 seconds to a colorless and clear solution with a pH of 7.3.
- this solution corresponds entirely to a second one, which was produced from the same chemicals without granulation using the same recipe.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Detergent Compositions (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
Die vorliegende Erfindung betrifft ein granuliertes, fotografisches Fixiermittel und ein Verfahren zur Herstellung eines solchen Fixiermittels, das rasch aufgelöst werden kann.The present invention relates to a granular, photographic fixing agent and a method for producing such a fixing agent which can be quickly dissolved.
Fotografische Fixiermittel und Bleichfixiermittel enthalten üblicherweise ein Thiosulfat als Fixiersubstanz, die nicht entwickeltes Silberhalogenid und durch Bleichen des metallischen Silbers neuentstandenes Silberhalogenid aus dem fotografischen Material lösen soll. Als Thiosulfat wird auf Grund seiner schnellen Fixierreaktion weitgehend Ammoniumthiosulfat [(NH₄)₂S₂O₃] eingesetzt, das aber einen gravierenden Nachteil hat. Pulver dieser Substanz backen beim Stehen selbst unter Ausschluß von Luftfeuchtigkeit zu festen Klumpen zusammen, die mühsam zerkleinert werden müssen und schlecht zu dosieren sind Dieser Effekt tritt auch dann auf, wenn das Ammoniumthiosulfat-Pulver mit den anderen Bestandteilen des Fixier- oder Bleichfixierbades gemischt wird. Auch das ersatzweise verwendete Natriumthiosulfat ist nachteilig, da es sich in Wasser schlecht löst und auf dem Boden des Fixier- oder Bleichfixierbades Krusten bildet. Um diese Schwierigkeit zu umgehen, wird das Fixier- oder Bleichfixiermittel weitgehend in einer flüssigen Konfektionierung angeboten und eingesetzte. Das hat aber den Nachteil erhöhter Kosten durch den Wasserballast.Photographic fixing agents and bleach-fixing agents usually contain a thiosulfate as the fixing substance, which is intended to dissolve undeveloped silver halide and silver halide which has newly formed by bleaching the metallic silver from the photographic material. As thiosulfate, ammonium thiosulfate [(NH₄) ₂S₂O₃] is largely used due to its fast fixing reaction, but this has a serious disadvantage. Powders of this substance bake when standing, even in the absence of atmospheric moisture, to form solid lumps that have to be crushed with difficulty and are difficult to dose then when the ammonium thiosulfate powder is mixed with the other components of the fixing or bleach-fixing bath. The sodium thiosulfate used as an alternative is also disadvantageous because it dissolves poorly in water and forms crusts on the bottom of the fixing or bleach-fixing bath. In order to avoid this difficulty, the fixing or bleach-fixing agent is largely offered and used in a liquid formulation. However, this has the disadvantage of increased costs due to water ballast.
Aufgabe der Erfindung ist, eine Konfektionierungsform für Ammoniumthiosulfat zu schaffen, die fest und doch gut dosierbar ist und sich im Bad schnell löst.The object of the invention is to provide a form of assembly for ammonium thiosulfate which is firm and yet easy to dose and which dissolves quickly in the bath.
Es wurde nun gefunden, daß sich granulierte Fixiermittel herstellen lassen, indem man ein Thiosulfat gemeinsam mit einem Disulfit und gegebenenfalls weiteren festen Substanzen so mahlt, daß das Maximum der Teilchendurchmesserverteilungskurve unter 10 µm liegt, die gemahlenen Teilchen einer Pulveragglomeration unterwirft, das Granulat im Vakuum trocknet, gegebenenfalls mit dem Granulat des Bleichmittels mischt und wasserdampfdicht verpackt.It has now been found that granulated fixing agents can be prepared by grinding a thiosulfate together with a disulfite and optionally other solid substances such that the maximum of the particle diameter distribution curve is less than 10 μm, the ground particles are subjected to powder agglomeration and the granules are dried in vacuo , if necessary mixed with the granules of the bleaching agent and packed in a water vapor-tight manner.
Die so hergestellten Granulate der festen Bestandteile eines fotografischen Fixier- oder Bleichfixiermitels sind mechanisch stabil, von einheitlicher Korngröße, zeigen eine große Lösungsgeschwindigkeit und unbegrenzte Haltbarkeit, sind staubfrei und rieselfähig.The granules of the solid components of a photographic fixing or bleach-fixing agent produced in this way are mechanically stable, of uniform grain size, show a high dissolution rate and unlimited durability, are dust-free and free-flowing.
Als Thiosulfate kommen vorzugsweise Alkali-, insbesondere Natrium-, und Ammoniumthiosulfat in Frage.Preferred thiosulfates are alkali, in particular sodium, and ammonium thiosulfate.
Als Disulfite kommen Alkali- und Ammoniumdisulfit, insbesondere Natriumdisulfit, in Betracht.Alkali and ammonium disulfite, in particular sodium disulfite, are suitable as disulfites.
Die Zerkleinerung der festen Bestandteile auf Partikelgrößen < 10 µm erfolgt üblicherweise durch Strahlmahlen. Die Pulveragglomeration wird vorzugsweise in einem Wirbelbett durchgeführt, wobei man den zu agglomerierenden Partikeln gegebenenfalls Granulierflüssigkeit, beispielsweise 200 ml Wasser pro kg Pulver zusetzt und gegebenenfalls etwas Bindemittel, beispielsweise Maisstärke.The solid constituents are usually comminuted to particle sizes of <10 μm by jet milling. The powder agglomeration is preferably carried out in a fluidized bed, granulation liquid, for example 200 ml of water per kg of powder and, if appropriate, some binder, for example corn starch, being added to the particles to be agglomerated.
Der mittlere Teilchendurchmesser der Granulate soll vorzugsweise ≧ 150 µm sein und beträgt insbesondere 150 bis 3000 µm.The average particle diameter of the granules should preferably be ≧ 150 μm and is in particular 150 to 3000 μm.
Als weitere Bestandteile der Thiosulfatgranulate kommen Komplexbildner wie Ethylendiamintetraessigsäure (EDTA) und Mittel zur Einstellung des gewünschten pH-Wertes wie Natriumcarbonat in Frage.Other constituents of the thiosulfate granules are complexing agents such as ethylenediaminetetraacetic acid (EDTA) and agents for adjusting the desired pH such as sodium carbonate.
Im Falle von Bleichfixiermitteln werden vorzugsweise von Fixiermittel und Bleichmittel getrennt Granulate hergestellt und miteinander vermischt.In the case of bleach-fixing agents, granules are preferably produced separately from the fixing agent and bleaching agent and mixed with one another.
Das Granulat des Bleichmittels enthält einen Eisen(III)-komplex oder ein Eisen(III)-komplexsalz, z.B. ein Ammoniumeisenkomplexsalz der EDTA, der Propylendiamin tetraessigsäure (PDTA), der Diethylentriaminpentaessigsäure (DTPA) oder der Nitrilotriessigsäure (NTA) sowie gegebenenfalls freien Komplexbildner, z.B. EDTA, PDTA, DTPA oder NTA.The granules of the bleaching agent contain an iron (III) complex or an iron (III) complex salt, for example an ammonium iron complex salt from EDTA, the propylenediamine tetraacetic acid (PDTA), diethylenetriaminepentaacetic acid (DTPA) or nitrilotriacetic acid (NTA) and optionally free complexing agents, for example EDTA, PDTA, DTPA or NTA.
Das Granulat des Bleichmittels wird vorzugsweise genauso hergestellt wie das Granulat des Fixiermittels und hat insbesondere einen mittleren Teilchendurchmesser im gleichen Bereich.The granules of the bleaching agent are preferably produced in the same way as the granules of the fixing agent and in particular have an average particle diameter in the same range.
Vorzugsweise enthält das erfindungsgemäße Mittel 35 bis 85 Gew.-% Thiosulfat, 5 bis 15 Gew.-% Disulfit und, im Falle eines Bleichfixiermittels, 30 bis 50 Gew.-% Eisen(III)-komplex oder Eisen(III)-komplexsalz.The agent according to the invention preferably contains 35 to 85% by weight of thiosulfate, 5 to 15% by weight of disulfite and, in the case of a bleach-fixing agent, 30 to 50% by weight of iron (III) complex or iron (III) complex salt.
Das Bleichfixierbad-Granulat wird durch Mischen von zwei Einzelgranulaten A und B hergestellt. Pro Liter gebrauchsfertige Lösung werden die folgenden Stoffmengen eingesetzt:
Die unter A aufgeführten Chemikalien werden - im angegebenen Mischungsverhältnis - in einer sog. Alexandermühle auf etwa 1 mm Korngröße zerkleinert und danach in einer Luftstrahlmühle auf eine Teilchengröße von 5 µm, gemahlen. Danach wird das Mahlgut in Portionen von etwa 500 Gramm auf einem handelsüblichen Wirbelschicht-Granulator (Strea-1-Laborgerät der Firma Aeromatic, Bubendorf/Schweiz) granuliert.The chemicals listed under A are - in the specified mixing ratio - crushed in a so-called Alexander mill to about 1 mm grain size and then in an air jet mill to a particle size of 5 µm, ground. The ground material is then granulated in portions of approximately 500 grams on a commercially available fluidized bed granulator (Strea-1 laboratory device from Aeromatic, Bubendorf / Switzerland).
Dazu werden 50 ml Wasser als Granulierflüssigkeit innerhalb von etwa 2 min in das Wirbelbett eingesprüht. Danach wird durch Erwärmen der Fluidisierungsluft auf 70°C etwa 6 min lang getrocknet, bis die Produkttemperatur 60°C erreicht hat. Das Gutkorn wird von etwa 5 % Unterkorn (< 0,15 mm) durch Absieben abgetrennt. Anschließend wird im Vakuum bei Raumtemperatur nachgetrocknet.For this purpose, 50 ml of water as granulating liquid are sprayed into the fluidized bed within about 2 minutes. Thereafter, drying is carried out by heating the fluidizing air to 70 ° C. for about 6 minutes until the product temperature has reached 60 ° C. The good grain is separated from about 5% undersize (<0.15 mm) by sieving. It is then dried in vacuo at room temperature.
Das erhaltene, farblose Produkt klumpt nicht und ist nichtstaubend und rieselfähig.The colorless product obtained does not clump and is non-dusting and free-flowing.
Die unter B aufgeführten Chemikalien werden gemischt und im selben Granulator (wie bei A) durch Aufsprühen von 50 gew.-%iger Ammoniumeisen-EDTA-Lösung, die überschüssiges Ammoniak enthält, in etwa 7 min granuliert. Auf 600 g der Mischung B werden 200 ml dieser Lösung bei Raumtemperatur aufgesprüht.The chemicals listed under B are mixed and granulated in the same granulator (as in A) by spraying on 50% by weight ammonium iron EDTA solution, which contains excess ammonia, in about 7 minutes. 200 ml of this solution are sprayed onto 600 g of mixture B at room temperature.
Anschließend wird im selben Gerät durch Erwärmen der Fluidisierungsluft auf 70°C 10 min lang getrocknet, bis die Produkttemperatur 55°C erreicht hat. Nach Absieben von wenig Überkorn wird 3 bis 4 Stunden im Vakuum bei Raumtemperatur getrocknet. Das erhaltene rotbraune und rieselfähige Produkt ist staubfrei und nichtklumpend.It is then dried in the same device by heating the fluidizing air to 70 ° C for 10 minutes until the product temperature has reached 55 ° C. After sieving a little oversize, it is dried for 3 to 4 hours in vacuo at room temperature. The red-brown and free-flowing product obtained is dust-free and non-clumping.
Zur Herstellung des gebrauchsfertigen Mischgranulats werden die Granulate A und B gemischt. Dabei ergibt die Mischung aus 91,1 g Granulat A und 57,8 g Granulat B die für 1 Liter Bleichfixierbad erforderliche Menge Mischgranulat.Granules A and B are mixed to produce the ready-to-use mixed granulate. The mixture of 91.1 g of granules A and 57.8 g of granules B gives the amount of mixed granules required for 1 liter of bleach-fixing bath.
Wie die Einzelgranulate ist das Mischgranulat rieselfähig, frei fließend und nichtstaubend. Unter Rühren löst es sich in Wasser bei Raumtemperatur in 45 Sekunden zu einer dunkelroten Lösung auf. Diese unterscheidet sich nicht von einer zweiten Probe, die aus der gleichen Menge der entsprechenden pulverförmigen Chemikalien hergstellt wurde.Like the individual granules, the mixed granulate is free-flowing, free-flowing and non-dusting. With stirring, it dissolves in water at room temperature in 45 seconds to a dark red solution. This is no different from a second sample made from the same amount of the corresponding powdered chemicals.
Das Mischgranulat ist, luft- und feuchtigkeitsdicht verpackt, unbegrenzt haltbar. Die photographische Wirksamkeit entspricht völlig einem Bleichfixierbad, das aus nichtgranuliertem Chemikalien nach demselben Ansatzrezept hergestellt wurde.The mixed granulate, packed airtight and moisture-proof, has an unlimited shelf life. The photographic effectiveness corresponds entirely to a bleach-fix bath which was produced from non-granulated chemicals according to the same recipe.
Herstellung eines Fixierbad-Granulats zur Verarbeitung von Colornegativ- oder Schwarzweißfilm.Production of a fixing bath granulate for processing color negative or black and white film.
Zur Herstellung eines Granulats für 1 Liter gebrauchsfertige Lösung werden folgende festen Chemikalien im angegebenen Verhältnis gemischt:
Die Mischung wird nach Vorzerkleinerung in der sog. Alexandermühle in einer Luftstrahlmühle auf eine mittlere Teilchengröße von etwa 5 µm gemahlen.After comminution in the so-called Alexander mill, the mixture is ground in an air jet mill to an average particle size of approximately 5 μm.
Etwa 700 g einer solchen Mischung werden in dem oben beschriebenen Stea 1-Granulator durch Aufsprühen von 110 ml Wasser innerhalb von 5 min granuliert. Das Aufsprühen wird mehrmals unterbrochen, damit eine gleichmäßige Korngrößenverteilung erzielt wird. Das erhaltene Granulat wird anschließend durch Erwärmen der Fluidisierungsluft auf 55°C 10 min lang getrocknet. Geringe Mengen Über- und Unterkorn werden abgesiebt. Es schließt sich eine 2-stündige Trocknung im Vakuum bei Raumtemperatur an.About 700 g of such a mixture are granulated in the Stea 1 granulator described above by spraying 110 ml of water within 5 minutes. The spraying is interrupted several times so that an even grain size distribution is achieved. The granules obtained are then dried by heating the fluidizing air to 55 ° C. for 10 minutes. Small amounts of oversize and undersize are screened off. This is followed by drying in vacuo at room temperature for 2 hours.
Das farblose Granulat ist staubfrei, rieselfähig und nichtklumpend. Eingeschweißt in alukaschierte Beutel, ist es unbegrenzt haltbar. In Wasser löst es sich unter Rühren innerhalb von etwa 10 sec zu einer farblosen und klaren Lösung vom pH-Wert 7,3 auf.The colorless granules are dust-free, free-flowing and non-clumping. Sealed in aluminum-coated bags, it has an unlimited shelf life. It dissolves in water with stirring within about 10 seconds to a colorless and clear solution with a pH of 7.3.
In der photografischen Wirkung entspricht diese Lösung völlig einer zweiten, die aus den gleichen Chemikalien ohne Granulation nach demselben Ansatzrezept hergestellt wurde.In terms of its photographic effect, this solution corresponds entirely to a second one, which was produced from the same chemicals without granulation using the same recipe.
Claims (7)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3933226 | 1989-05-10 | ||
| DE3920920 | 1989-06-27 | ||
| DE19893920920 DE3920920A1 (en) | 1989-06-27 | 1989-06-27 | Granular photographic fixative or bleach fixative |
| DE19893933226 DE3933226A1 (en) | 1989-10-05 | 1989-10-05 | Granular photographic fixative or bleach fixative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0405238A1 EP0405238A1 (en) | 1991-01-02 |
| EP0405238B1 true EP0405238B1 (en) | 1992-08-19 |
Family
ID=25882361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90111254A Expired - Lifetime EP0405238B1 (en) | 1989-06-27 | 1990-06-14 | Granulated photographic fixing composition and its preparation |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5055384A (en) |
| EP (1) | EP0405238B1 (en) |
| JP (1) | JPH0339735A (en) |
| DE (1) | DE59000265D1 (en) |
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|---|---|---|---|---|
| EP0479262B1 (en) * | 1990-10-02 | 1997-08-13 | Fuji Photo Film Co., Ltd. | Method of processing silver halide color photographic material |
| US5780211A (en) * | 1991-05-01 | 1998-07-14 | Konica Corporation | Processing composition in the tablet form for silver halide photographic light-sensitive material |
| DE69231432T2 (en) * | 1991-05-31 | 2001-02-22 | Konishiroku Photo Ind | Processing method for black-and-white silver halide photographic light-sensitive materials |
| JPH0593989A (en) * | 1991-10-03 | 1993-04-16 | Konica Corp | Packaging material for photographic processing agent |
| JP3088155B2 (en) * | 1991-10-21 | 2000-09-18 | 富士写真フイルム株式会社 | Photographic processing agents |
| DE69226238T2 (en) * | 1991-11-06 | 1998-11-19 | Konishiroku Photo Ind | Tablet treating agent and method for processing photographic light-sensitive silver halide materials |
| US5270154A (en) * | 1992-01-31 | 1993-12-14 | Fuji Hunt Photographic Chemicals Inc. | Method of making flowable alkaline thiosulfate/alkaline sulfite and the product thereof |
| JPH05289248A (en) * | 1992-04-08 | 1993-11-05 | Konica Corp | Photographic processing agent |
| JPH0627619A (en) * | 1992-05-13 | 1994-02-04 | Fuji Photo Film Co Ltd | Color photographic bleach-fixing composition |
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| JP2934997B2 (en) * | 1993-01-21 | 1999-08-16 | コニカ株式会社 | Processing method of black and white silver halide photographic material |
| US5480768A (en) * | 1993-02-17 | 1996-01-02 | Konica Corporation | Method for processing exposed silver halide photographic light-sensitive material using a solid processing composition replenisher |
| DE69400979T2 (en) * | 1993-05-10 | 1997-06-12 | Konishiroku Photo Ind | Tablet for processing a color photographic light-sensitive material |
| US5409805A (en) * | 1993-07-29 | 1995-04-25 | Konica Corporation | Solid processing agent for silver halide photographic light-sensitive materials |
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| JPH0869098A (en) | 1994-08-31 | 1996-03-12 | Konica Corp | Automatic developing machine for silver halide photographic sensitive material |
| US5624793A (en) * | 1994-11-11 | 1997-04-29 | Konica Corporation | Method of manufacturing solid processing composition for silver halide photographic light-sensitive materials |
| JPH08160588A (en) | 1994-12-06 | 1996-06-21 | Konica Corp | Automatic developing machine for silver halide photographic sensitive material |
| US5618658A (en) * | 1995-02-22 | 1997-04-08 | Fuji Hunt Photographic Chemicals, Inc. | Process for producing an ammonium thiosulfate product |
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Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2543086A (en) * | 1947-11-22 | 1951-02-27 | Eastman Kodak Co | Method of preparing dustless photographic fixing powders |
| GB1099790A (en) * | 1966-02-01 | 1968-01-17 | Goldschmidt Ag Th | Flowable ammonium thiosulfate and method for its manufacture |
| DE1911609C3 (en) * | 1969-03-07 | 1975-10-16 | Hoechst Ag, 6000 Frankfurt | Photographic Fixing Salt Mixture |
| BE758333A (en) * | 1969-11-03 | 1971-04-01 | Eastman Kodak Co | NEW PHOTOGRAPHIC COMPOSITION OF |
| JPS511425A (en) * | 1974-06-18 | 1976-01-08 | Matsushita Electric Ind Co Ltd | Azobenzenjudotaino seizohoho |
| JPS51151135A (en) * | 1975-06-09 | 1976-12-25 | Fuaburika Kimufuoto | Method of producing black and white movie and photographic film treating special composition developing reagent |
| JPS54133332A (en) * | 1978-04-07 | 1979-10-17 | Oriental Photo Ind Co Ltd | Preparation of powdered bleaching agent for photograph |
| JPS6132848A (en) * | 1984-07-26 | 1986-02-15 | Konishiroku Photo Ind Co Ltd | Enclosing bag of photographic treating agent |
| JP2556339B2 (en) * | 1987-09-29 | 1996-11-20 | コニカ株式会社 | Photographic processing agent having long-term processing stability and processing method of photographic light-sensitive material |
| DE3830023A1 (en) * | 1988-09-03 | 1990-03-15 | Agfa Gevaert Ag | GRANULATED, COLOR PHOTOGRAPHIC DEVELOPER AND ITS MANUFACTURE |
-
1990
- 1990-06-13 US US07/537,893 patent/US5055384A/en not_active Expired - Fee Related
- 1990-06-14 EP EP90111254A patent/EP0405238B1/en not_active Expired - Lifetime
- 1990-06-14 DE DE9090111254T patent/DE59000265D1/en not_active Expired - Fee Related
- 1990-06-26 JP JP2165822A patent/JPH0339735A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE59000265D1 (en) | 1992-09-24 |
| JPH0339735A (en) | 1991-02-20 |
| EP0405238A1 (en) | 1991-01-02 |
| US5055384A (en) | 1991-10-08 |
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