EP0358034B1 - Granulated photographic colour developer and its preparation - Google Patents

Granulated photographic colour developer and its preparation Download PDF

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Publication number
EP0358034B1
EP0358034B1 EP89115441A EP89115441A EP0358034B1 EP 0358034 B1 EP0358034 B1 EP 0358034B1 EP 89115441 A EP89115441 A EP 89115441A EP 89115441 A EP89115441 A EP 89115441A EP 0358034 B1 EP0358034 B1 EP 0358034B1
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EP
European Patent Office
Prior art keywords
granulated
developer
granules
granulated materials
mixture
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EP89115441A
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German (de)
French (fr)
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EP0358034A3 (en
EP0358034A2 (en
Inventor
Peter Dr. Kühnert
Peter Dr. Feyen
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Agfa Gevaert AG
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Agfa Gevaert AG
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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 granulated, color photographic developer and a manufacturing method of such a developer who quickly resolved can be.
  • Color photographic developers usually include a number of solid components, e.g. the real one Developer substance, antioxidant, complexing agent, Sodium sulfite, alkali donors and alkali halides. Because these compounds react chemically with each other can, they are assembled separately and first mixed immediately before use.
  • Such color developers are processed in the publication "Agglacolor Selst, Der Negativ / Positiv-Prozess ", pages 10, 11, 36, 37 (1972)”. Suitable assemblies are powders and liquid concentrates, the latter changing more and more over the years have prevailed, especially since some developers liquid Contain ingredients that understandably do not can be made up in powder form, for example Benzyl alcohol.
  • the three or four concentrates in certain mixing ratios and optionally with the addition of Water mixed with stirring.
  • the invention thus relates to a method for Production of a granular preparation of the solid Components of a color photographic developer, thereby characterized in that the antioxidant, the developer substance and the alkali donor of a color photographic developer separated on one Particle size ⁇ 10 microns, then optionally with the addition of a granulating liquid and a binder subject to powder agglomeration and in vacuo dries, mixes the individual granules and is water vapor-tight packed up.
  • the granules of the solid components thus produced of a color photographic developer are mechanical stable, of uniform grain size, show a large Solution speed and unlimited durability are dust-free and free-flowing.
  • the crushing of the solid components to particle sizes ⁇ 10 ⁇ m is usually done by jet milling.
  • the powder agglomeration is preferably carried out in a fluidized bed performed, taking the one to be agglomerated Particles optionally granulating liquid, for example Add 200 ml water per kg powder and if necessary some binder, such as corn starch.
  • the average particle diameter of the granules is ⁇ 150 ⁇ m and is in particular 150 to 3,000 ⁇ m.
  • a protective gas for example nitrogen.
  • the other components of the developer like anti-limescale, Complexing agent for heavy metal ions, sodium sulfite and alkali halide can also form granules processed and mixed into the mixture.
  • each of these additives with one of the three essential ones Granulate components (developer substance, antioxidant or alkali dispenser) and to granulate.
  • Suitable color developer compounds are aromatic compounds of the p-phenylenediamine type containing at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methanesulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.
  • Other useful color developers are described, for example, in J. Amer. Chem. Soc. 73 , 3106 (1951) and G. Haist
  • Another object of the invention is a granulate mixture containing at least 3 different granules of integral parts of a color photographic Developer, a granulate containing the antioxidant, a granulate the developer substance and a Granules containing the alkali dispenser, and the middle one Particle diameter of the individual granules at least Is 150 ⁇ m.
  • 1 kg of crystallized hydroxylammonium sulfate is in an Alexander sieve with a mesh size of 0.6 mm and then in an air jet mill on one average particle diameter ⁇ 10 ⁇ m milled.
  • the granules are 90 min. at 40 ° C in a vacuum post-dried.
  • Mixture C Mixture D a) Disodium salt of 1-hydroxyethane-1,1-diphosphonic acid 34 g --- b) Sodium sulfite 39 g 39 g c) Ethylenediaminetetraacetic acid --- 24 g d) Potassium carbonate 336 g 336 g e) Sodium bicarbonate 15 g 15 g f) Potassium bromide 15 g 15 g 439 g 429 g
  • the individual granules A, B, C and D are mixed in the following weight ratio in a laboratory mixer, whereby work must be carried out with the exclusion of moisture: Granules A 2.4 g Granules B 4.52 g Granules C 21.95 g Granules D 21.45 g total weight 50.32 g
  • the mixed granulate is excluded from moisture (Transfer of very dry air) with plastic and aluminum foil laminated paper bags that be welded shut immediately.

Description

Die vorliegende Erfindung betrifft einen granulierten, farbfotografischen Entwickler und ein Verfahren zur Herstellung eines solchen Entwicklers, der rasch aufgelöst werden kann.The present invention relates to a granulated, color photographic developer and a manufacturing method of such a developer who quickly resolved can be.

Farbfotografische Entwickler enthalten üblicherweise eine Reihe von festen Bestandteilen, z.B. die eigentliche Entwicklersubstanz, Oxidationsschutzmittel, Komplexbildner, Natriumsulfit, Alkalispender und Alkalihalogenide. Da diese Verbindungen miteinander chemisch reagieren können, werden sie getrennt konfektioniert und erst unmittelbar vor der Benutzung gemischt. Solche Farbentwickler werden in der Druckschrift "Agglacolor Selst Verarbeitet, Der Negativ/Positiv-Prozeß", Seiten 10, 11, 36, 37 (1972)" beschrieben. Geeignete Konfektionierungen sind Pulver und Flüssigkonzentrate, wobei sich letztere im Laufe der Jahre mehr und mehr durchgesetzt haben, zumal manche Entwickler flüssige Bestandteile enthalten, die verständlicherweise nicht in Pulverform konfektionierbar sind, beispielsweise Benzylalkohol. Color photographic developers usually include a number of solid components, e.g. the real one Developer substance, antioxidant, complexing agent, Sodium sulfite, alkali donors and alkali halides. Because these compounds react chemically with each other can, they are assembled separately and first mixed immediately before use. Such color developers are processed in the publication "Agglacolor Selst, Der Negativ / Positiv-Prozess ", pages 10, 11, 36, 37 (1972)". Suitable assemblies are powders and liquid concentrates, the latter changing more and more over the years have prevailed, especially since some developers liquid Contain ingredients that understandably do not can be made up in powder form, for example Benzyl alcohol.

Zur Herstellung des gebrauchsfertigen Entwicklers werden dann die drei oder vier Konzentrate in bestimmten Mischungsverhältnissen und gegebenenfalls unter Zusatz von Wasser unter Rühren gemischt.To produce the ready-to-use developer then the three or four concentrates in certain mixing ratios and optionally with the addition of Water mixed with stirring.

Da solche Konzentrate nur eine begrenzte Lagerzeit haben und aufgrund des darin enthaltenen Wassers hohe Transportkosten verursachen, besteht ein Bedarf an festen farbfotografischen Entwicklerzubereitungen, die wenigstens die folgenden Bedingungen erfüllen müssen:

  • 1. Die Zubereitung enthält alle festen Bestandteile des gebrauchsfertigen farbfotografischen Entwicklers.
  • 2. Die feste Zubereitungsform löst sich in kürzester Zeit auf.
  • 3. Die feste Zubereitung ist nicht-staubend.
    • Since such concentrates only have a limited storage time and, because of the water contained therein, cause high transport costs, there is a need for solid color photographic developer preparations which must at least meet the following conditions:
  • 1. The preparation contains all solid components of the ready-to-use color photographic developer.
  • 2. The solid preparation form dissolves in a very short time.
  • 3. The solid preparation is non-dusting.

    • Aus der DE-A-37 33 861 ist zwar bekannt, Schwarzweiß-Entwickler als schnell sich auflösendes trockenes Pulver bereit zu stellen, wobei dieses durch das Herstellen einer flüssigen fotografischen Entwicklerlösung, das Entfernen des Lösungsmittels zur Gewinnung eines Pulvers und das Verpacken des Pulvers zum Ausschluß der Berührung desselben mit der Atmosphäre erhalten wird, und wobei man sich zur Entfernung des Lösungsmittels der Gefriertrocknung oder Sprühtrocknung bedient, jedoch läßt sich dieses Verfahren nicht auf farbfotografische Entwickler übertragen, die eine völlig andere Zusammensetzung aufweisen. Außerdem sind die dort erreichten Lösezeiten von mindestens 2 bis 4 Minuten je nach Art des verwendeten Entwicklers noch zu lang. From DE-A-37 33 861 black and white developers are known as a rapidly dissolving dry powder to provide, this by manufacturing a liquid photographic developer solution that Remove the solvent to obtain a powder and packaging the powder to exclude contact it is preserved with the atmosphere, and taking one to remove the solvent Freeze drying or spray drying are used, however this process cannot be based on color photography Developers transferred that have a completely different composition exhibit. In addition, those are reached there Release times of at least 2 to 4 minutes depending on the type of the developer used is still too long.

    Es wurde nun gefunden, daß sich granulierte Zusammensetzungen herstellen lassen, die alle festen Bestandteile eines farbfotografischen Entwicklers enthalten, indem man die Bestandteile so mahlt, daß das Maximum der Teilchendurchmesserverteilungskurve unter 10 µm liegt, die gemahlenen Teilchen einer Pulveragglomeration unterwirft, die Granulate im Vakuum trocknet, miteinander mischt und wasserdampfdicht verpackt.It has now been found that granular compositions All solid components by a color photographic developer by the components are ground so that the maximum of the particle diameter distribution curve is less than 10 µm subjecting ground particles to powder agglomeration, the granules dry in a vacuum with each other mixes and packaged waterproof.

    Gegenstand der Erfindung ist somit ein Verfahren zur Herstellung einer granulierten Zubereitung der festen Bestandteile eines farbfotografischen Entwicklers, dadurch gekennzeichnet, daß man das Oxidationsschutzmittel, die Entwicklersubstanz und den Alkalispender eines farbfotografischen Entwicklers getrennt auf eine Teilchengröße <10 µm mahlt, anschließend gegebenenfalls unter Zusatz einer Granulierflüssigkeit und eines Bindemittels einer Pulveragglomeration unterwirft und im Vakuum trocknet, die einzelnen Granulate mischt und wasserdampfdicht verpackt.The invention thus relates to a method for Production of a granular preparation of the solid Components of a color photographic developer, thereby characterized in that the antioxidant, the developer substance and the alkali donor of a color photographic developer separated on one Particle size <10 microns, then optionally with the addition of a granulating liquid and a binder subject to powder agglomeration and in vacuo dries, mixes the individual granules and is water vapor-tight packed up.

    Die so hergestellten Granulate der festen Bestandteile eines farbfotografischen Entwicklers sind mechanisch stabil, von einheitlicher Korngröße, zeigen eine große Lösungsgeschwindigkeit und unbegrenzte Haltbarkeit, sind staubfrei und rieselfähig.The granules of the solid components thus produced of a color photographic developer are mechanical stable, of uniform grain size, show a large Solution speed and unlimited durability are dust-free and free-flowing.

    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 crushing of the solid components to particle sizes <10 µm is usually done by jet milling. The powder agglomeration is preferably carried out in a fluidized bed performed, taking the one to be agglomerated Particles optionally granulating liquid, for example Add 200 ml water per kg powder and if necessary some binder, such as corn starch.

    Der mittlere Teilchendurchmesser der Granulate ist ≥150 µm und beträgt insbesondere 150 bis 3.000 µm. Bei besonders sauerstoffempfindlichen Bestandteilen ist es vorzuziehen, das Mahlen, Granulieren, Trocknen, Mischen und Verpacken unter einem Schutzgas, beispielsweise Stickstoff, vorzunehmen.The average particle diameter of the granules is ≥150 µm and is in particular 150 to 3,000 µm. For components that are particularly sensitive to oxygen it is preferable to grind, granulate, Drying, mixing and packaging under a protective gas, for example nitrogen.

    Die übrigen Bestandteile des Entwicklers wie Kalkschutzmittel, Komplexbildner für Schwermetallionen, Natriumsulfit und Alkalihalogenid können ebenfalls zu Granulaten verarbeitet und der Mischung zugemischt werden. Es ist jedoch aus ökonomischen Gründen vorzuziehen, jeden dieser Zusätze mit einem der drei essentiellen Granulatbestandteile (Entwicklersubstanz, Oxidationsschutzmittel oder Alkalispender) zusammen zu mahlen und zu granulieren.The other components of the developer like anti-limescale, Complexing agent for heavy metal ions, sodium sulfite and alkali halide can also form granules processed and mixed into the mixture. However, for economic reasons, it is preferable each of these additives with one of the three essential ones Granulate components (developer substance, antioxidant or alkali dispenser) and to granulate.

    Als Farbentwicklerverbindung lassen sich sämtliche Entwicklerverbindungen verwenden, die die Fähigkeit besitzen, in Form ihres Oxidationsproduktes mit Farbkupplern zu Azomethin- bzw. Indophenolfarbstoffen zu reagieren. Geeignete Farbentwicklerverbindungen sind aromatische, mindestens eine primäre Aminogruppe enthaltende Verbindungen vom p-Phenylendiamintyp, beispielsweise N,N-Dialkyl-p-phenylendiamine wie N,N-Diethyl-p-phenylendiamin, 1-(N-Ethyl-N-methansulfonamidoethyl)-3-methyl-p-phenylendiamin, 1-(N-Ethyl-N-hydroxy-ethyl)-3-methyl-p-phenylendiamin und 1-(N-Ethyl-N-methoxyethyl)-3-methyl-p-phenylendiamin. Weitere brauchbare Farbentwickler sind beispielsweise in J. Amer. Chem. Soc. 73, 3106 (1951) und G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, Seite 545 ff. beschrieben.All developer compounds which have the ability to react in the form of their oxidation product with color couplers to form azomethine or indophenol dyes can be used as the color developer compound. Suitable color developer compounds are aromatic compounds of the p-phenylenediamine type containing at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methanesulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine. Other useful color developers are described, for example, in J. Amer. Chem. Soc. 73 , 3106 (1951) and G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, page 545 ff.

    Ein weiterer Gegenstand der Erfindung ist eine Granulatmischung enthaltend wenigstens 3 unterschiedliche Granulate von festen Bestandteilen eines farbfotografischen Entwicklers, wobei ein Granulat das Oxidationsschutzmittel, ein Granulat die Entwicklersubstanz und ein Granulat den Alkalispender enthält, und der mittlere Teilchendurchmesser der einzelnen Granulate mindestens 150 µm beträgt. Another object of the invention is a granulate mixture containing at least 3 different granules of integral parts of a color photographic Developer, a granulate containing the antioxidant, a granulate the developer substance and a Granules containing the alkali dispenser, and the middle one Particle diameter of the individual granules at least Is 150 µm.

    Beispielexample Herstellung des Granulats aus dem Oxidationsschutzmittel (Granulat A)Production of the granules from the antioxidant (Granulate A)

    1 kg kristallisiertes Hydroxylammoniumsulfat wird in einem Alexandersieb der Maschengröße 0,6 mm zerkleinert und anschließend in einer Luftstrahlmühle auf einen mittleren Teilchendurchmesser < 10 µm gemahlen.1 kg of crystallized hydroxylammonium sulfate is in an Alexander sieve with a mesh size of 0.6 mm and then in an air jet mill on one average particle diameter <10 µm milled.

    500 g von diesem Mahlgut werden in einem handelsüblichen Wirbelschicht-Sprühgranulator (Strea 1-Laborgerät der Firma Aeromatic, Bubendorf/Schweiz) durch Aufsprühen von insgesamt 38 ml Wasser innerhalb von 7 min. bei Raumtemperatur granuliert und danach bei einer Lufttemperatur von 63°C 8 min. lang getrocknet. Alle Granulatkörner > 2000 µm werden durch Sieben entfernt.500 g of this regrind are in a commercial Fluid bed spray granulator (Strea 1 laboratory device from Aeromatic, Bubendorf / Switzerland) by spraying on a total of 38 ml of water within 7 min. at room temperature granulated and then at an air temperature from 63 ° C 8 min. dried long. All granules > 2000 µm are removed by sieving.

    Danach wird das Granulat noch 90 min. bei 40°C im Vakuum nachgetrocknet.Then the granules are 90 min. at 40 ° C in a vacuum post-dried.

    Herstellung des Granulats der Entwicklersubstanz CD 4* (Granulat B)Production of the granules of the developer substance CD 4 * (Granulate B)

    1 kg CD 4 wird wie vorstehend beschrieben strahlgemahlen. 326 g des Produkts werden im selben Gerät wie oben granuliert. Dabei werden innerhalb von 4 min. 7 ml Wasser von Raumtemperatur eingesprüht. Dann wird 8 min. mit max. 60°C warmer Luft getrocknet. Durch Sieben wird das Überkorn (> 2000 µm) entfernt. Das Produkt wird wie Granulat A nachgetrocknet.1 kg of CD 4 is jet milled as described above. 326 g of the product are in the same device as above granulated. Thereby within 4 min. 7 ml Water sprayed from room temperature. Then 8 min. with max. 60 ° C warm air dried. Through seven will the oversize (> 2000 µm) removed. The product will be like Granules A dried.

    Herstellung der Granulate für den alkalischen Entwicklerteil (Granulat C und Granulat D)Production of the granules for the alkaline developer part (Granulate C and Granulate D)

    Mischung CMixture C Mischung DMix D a)a) Dinatriumsalz der 1-Hydroxyethan-1,1-diphosphonsäureDisodium salt of 1-hydroxyethane-1,1-diphosphonic acid 34 g34 g ------ b)b) NatriumsulfitSodium sulfite 39 g39 g 39 g39 g c)c) EthylendiamintetraessigsäureEthylenediaminetetraacetic acid ------ 24 g24 g d)d) KaliumcarbonatPotassium carbonate 336 g336 g 336 g336 g e)e) NatriumhydrogencarbonatSodium bicarbonate 15 g15 g 15 g15 g f)f) KaliumbromidPotassium bromide 15 g15 g 15 g15 g 439 g439 g 429 g429 g

    Mischung C und D werden getrennt in der folgenden Art granuliert:

  • 1. Homogenisierung im Lödige-Mischer
  • 2. Luftstrahlmahlung auf mittleren Teilchendurchmesser < 10 µm
  • 3. Wirbelschicht-Sprühgranulation- wie bei den Granulaten A und B - durch Aufsprühen von 110 (bzw. 115) ml Wasser innerhalb von 6 min. (bzw. 7 min.) Trocknung jeweils 10 min. bei 70 bis 80°C Lufttemperatur.
  • 4. Absieben von Unter- und Überkorn (< 200 µm; > 2000 µm)
  • 5. Nachtrocknung im Vakuum wie oben beschrieben.
    • Mixture C and D are granulated separately in the following manner:
  • 1. Homogenization in the Lödige mixer
  • 2. Air jet grinding on average particle diameter <10 µm
  • 3. Fluidized bed spray granulation - as with granules A and B - by spraying 110 (or 115) ml of water within 6 minutes. (or 7 min.) Drying 10 min each. at 70 to 80 ° C air temperature.
  • 4. Screening undersize and oversize particles (<200 µm;> 2000 µm)
  • 5. Post-drying in a vacuum as described above.

    • Herstellung des gebrauchsfertigen Mischgranulats:Production of the ready-to-use mixed granulate:

    Zur Herstellung des gebrauchsfertigen Mischgranulats werden die einzelnen Granulate A, B, C und D im folgenden Gewichtsverhältnis in einem Labormischer gemischt, wobei unter Feuchtigkeitsausschluß gearbeitet werden muß: Granulat A 2,4 g Granulat B 4,52 g Granulat C 21,95 g Granulat D 21,45 g Gesamtgewicht 50,32 g To produce the ready-to-use mixed granulate, the individual granules A, B, C and D are mixed in the following weight ratio in a laboratory mixer, whereby work must be carried out with the exclusion of moisture: Granules A 2.4 g Granules B 4.52 g Granules C 21.95 g Granules D 21.45 g total weight 50.32 g

    Verpackungpackaging

    Das Mischgranulat wird unter Feuchtigkeitsausschluß (Überleiten von sehr trockener Luft) in mit Kunststoff und Aluminiumfolie kaschierte Papiertüten verpackt, die sofort zugeschweißt werden.The mixed granulate is excluded from moisture (Transfer of very dry air) with plastic and aluminum foil laminated paper bags that be welded shut immediately.

    Eigenschaftencharacteristics

  • 1. Das Mischgranulat ist rieselfähig und nicht staubend1. The mixed granulate is free-flowing and not dusty
  • 2. Farbe: farblos2. Color: colorless
  • 3. Auflösungsgeschwindigkeit:
    50,32 g des Mischgranulats werden unter leichtem Rühren in 950 ml Wasser von ca. 25°C gegeben. Nach 22 Sekunden sind sämtliche festen Teilchen gelöst. Die Lösung ist gelblich gefärbt und klar.     3. Dissolution rate:
    50.32 g of the mixed granules are added to 950 ml of water at approx. 25 ° C with gentle stirring. After 22 seconds, all solid particles are dissolved. The solution is colored yellow and clear.
  • 4. Photographische Eigenschaften
    In dem durch Auflösen des Mischgranulats hergestellten Colornegativ-Filmentwickler wurden Testfilme entwickelt. Hierbei gab es im Vergleich mit einem herkömmlichen Entwickler des gleichen Typs keine sensitometrischen Unterschiede.    4. Photographic properties
    Test films were developed in the color negative film developer produced by dissolving the mixed granules. There were no sensitometric differences compared to a conventional developer of the same type.
  • 5. Lagerstabilität des Entwicklergranulats
    Unter Feuchtigkeitsausschluß bei Herstellung und Verpackung ist das Mischgranulat unbegrenzt haltbar.    5. Storage stability of the developer granules
    The mixed granulate has an unlimited shelf life with the exclusion of moisture during manufacture and packaging.

    • Claims (4)

    1. A mixture of granulated materials containing at least three different granulated materials of solid constituents of a colour photographic developer, wherein one granulated material contains the antioxidant, one granulated material contains the developer substance and one granulated material contains the source of alkali, and the average particle diameter of the individual granulated materials is at least 150 µm.
    2. A mixture of granulated materials according to claim 1, wherein the average particle diameter of the individual granulated materials is 150 to 3000 µm.
    3. A mixture of granulated materials according to claim 1 which is packed in a water vapour-tight manner.
    4. A process for the preparation of a mixture of granulated materials according to claim 1,
      characterised in that the antioxidant, the developer substance and the source of alkali of a colour photographic developer are ground separately to a particle size of < 10 µm, then undergo a powder agglomeration optionally with the addition of a granulating liquid and a binder and are dried under vacuum, the individual granulated materials are mixed and packed in a water vapour-tight manner.
    EP89115441A 1988-09-03 1989-08-22 Granulated photographic colour developer and its preparation Expired - Lifetime EP0358034B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE3830023A DE3830023A1 (en) 1988-09-03 1988-09-03 GRANULATED, COLOR PHOTOGRAPHIC DEVELOPER AND ITS MANUFACTURE
    DE3830023 1988-09-03

    Publications (3)

    Publication Number Publication Date
    EP0358034A2 EP0358034A2 (en) 1990-03-14
    EP0358034A3 EP0358034A3 (en) 1990-06-06
    EP0358034B1 true EP0358034B1 (en) 1999-07-28

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    Application Number Title Priority Date Filing Date
    EP89115441A Expired - Lifetime EP0358034B1 (en) 1988-09-03 1989-08-22 Granulated photographic colour developer and its preparation

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    US (1) US4923786A (en)
    EP (1) EP0358034B1 (en)
    JP (1) JP2793853B2 (en)
    DE (2) DE3830023A1 (en)

    Families Citing this family (38)

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    US5055384A (en) * 1989-05-10 1991-10-08 Agfa Gevaert Aktiengesellschaft Granulated photographic fixative and its preparation
    DE3920921A1 (en) * 1989-06-27 1991-01-03 Agfa Gevaert Ag GRANULAR, COLOR PHOTOGRAPHIC BLEACHING AGENT AND ITS MANUFACTURE
    US5098819A (en) * 1990-01-31 1992-03-24 Knapp Audenried W Non-toxic photographic developer composition
    DE4009310A1 (en) * 1990-03-23 1991-09-26 Agfa Gevaert Ag GRANULATED PHOTOCHEMICALS
    JPH0485536A (en) * 1990-07-30 1992-03-18 Konica Corp Packaged photographic solid processing agent
    DE4025560A1 (en) * 1990-08-11 1992-02-13 Agfa Gevaert Ag PHOTO CHEMICALS WITH REDUCED STAUBANT
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    JPH02109042A (en) 1990-04-20
    DE58909852D1 (en) 1999-09-02
    JP2793853B2 (en) 1998-09-03
    DE3830023A1 (en) 1990-03-15
    EP0358034A3 (en) 1990-06-06
    EP0358034A2 (en) 1990-03-14
    US4923786A (en) 1990-05-08

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