EP0358035A2 - Granulated colour-photographic developer, and its manufacture - Google Patents

Granulated colour-photographic developer, and its manufacture Download PDF

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Publication number
EP0358035A2
EP0358035A2 EP89115442A EP89115442A EP0358035A2 EP 0358035 A2 EP0358035 A2 EP 0358035A2 EP 89115442 A EP89115442 A EP 89115442A EP 89115442 A EP89115442 A EP 89115442A EP 0358035 A2 EP0358035 A2 EP 0358035A2
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EP
European Patent Office
Prior art keywords
granulated
developer
fluidized bed
granulate
granules
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP89115442A
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German (de)
French (fr)
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EP0358035A3 (en
Inventor
Peter Dr. Kühnert
Hans Dr. Uhlemann
Axel Dr. Vogel
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Agfa Gevaert AG
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Agfa Gevaert AG
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Publication of EP0358035A2 publication Critical patent/EP0358035A2/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
    • G03C5/265—Supplying of photographic processing chemicals; Preparation or packaging thereof of powders, granulates, tablets
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers

Definitions

  • the present invention relates to a granular color photographic developer and a method for producing such a developer which can be quickly dissolved.
  • Color photographic developers usually contain a number of solid components, for example the actual developer substance, antioxidants, complexing agents, sodium sulfite, alkali donors and alkali halides. Since these compounds can react chemically with one another, they are packaged separately and only mixed immediately before use. Suitable formulations are powders and liquid concentrates, the latter having become more and more established over the years, especially since some developers contain liquid constituents which, understandably, cannot be formulated in powder form, for example benzyl alcohol.
  • the three or four concentrates are then mixed in certain mixing ratios and, if appropriate, with the addition of water with stirring.
  • compositions can be produced which contain all the solid constituents of a color photographic developer by spraying the developer substance in dissolved form into a fluidized bed which separates the fine material components escaping from the fluidized bed with the exhaust gas and as nuclei for the formation of granules returns the fluidized bed, influences the granulation process in the fluidized bed by setting the classifying gas flow in such a way that a granulate of the size specified by the classifying gas flow is produced, removes the finished granulate via one or more counterflow gravity classifiers used in the inflow floor of the fluidized bed apparatus, dries in vacuo , mixed with the other components of the developer, granulated by any process, and packed in a water vapor-tight manner.
  • the invention thus relates to a process for producing a granulated preparation of the solid constituents of a color photographic developer, characterized in that the developer substance of a color photographic developer is sprayed in dissolved form into a fluidized bed, which separates the fine material portions escaping from the fluidized bed with the exhaust gas and as germs leads back to the fluidized bed for the formation of granules, influences the granulation process in the fluidized bed by adjusting the classifying gas flow in such a way that a granulate in the range given by the classifying gas flow Size arises, the finished granules are removed via one or more countercurrent gravity classifiers used in the inflow base of the fluidized bed apparatus, dried in vacuo, mixed with the other components of the developer, granulated by any process, and packed in a water-vapor-tight manner.
  • the granulate of the developer substance of a color photographic developer produced in this way is mechanically stable, of uniform grain size, shows a high dissolution speed and unlimited durability, is dust-free and free-flowing.
  • the grains are particularly spherical.
  • An aqueous solution of the developer substance is preferably used, the concentration of which is in particular 10 to 70% by weight.
  • the average particle diameter of the developer substance granules should preferably be ⁇ 150 ⁇ m and is in particular 150 to 3,000 ⁇ m.
  • the method according to the invention allows a very narrow particle diameter distribution.
  • ⁇ 80% of the grains are within a range that does not deviate from the desired grain diameter by more than ⁇ 100 ⁇ m.
  • a protective gas for example nitrogen.
  • the other solid constituents of the developer such as antioxidants, alkali donors, limescale inhibitors, complexing agents for heavy metal ions, sodium sulfite and alkali halide can be granulated by any process.
  • a suitable method is, for example, that the substance to be granulated is ground to a particle size of ⁇ 10 ⁇ m, then optionally subjected to powder agglomeration with the addition of a granulating liquid and a binder, and dried in vacuo.
  • Antioxidants and alkali dispensers should preferably be granulated separately.
  • the remaining constituents can also be granulated separately or partly with the antioxidant and partly with the alkali dispenser.
  • the auxiliaries are granulated in particular to the same mean grain diameter as that of the developer substance; the deviation of the individual granules from the average grain diameter can be greater than with the developer substance.
  • the granulate mixture produced in this way is mechanically stable, of uniform grain size, shows a high rate of dissolution and unlimited shelf life, is dust-free and free-flowing.
  • 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.
  • Another object of the invention is a granule mixture containing a granulated developer substance, a granulated antioxidant and a granulated alkali dispenser, characterized in that the granulated developer substance is spherical and has an average particle diameter ⁇ 150 microns, 80% of the grains being within a range that deviates from the desired grain diameter by no more than ⁇ 100 ⁇ m.
  • the compound is used as a 50% by weight aqueous solution.
  • the granulation takes place in a glass shot with a diameter of 225 mm by repeatedly spraying the aqueous solution onto solid germs located in the fluidized bed.
  • a quantity of about 1 kg of solid CD 3 as starting granules is placed on the perforated bottom of a glass shot with a diameter of 225 mm according to DE-A-35 07 376, example 1, via a filling funnel. Then the fluidizing gas flow is switched on: flow cross-section 225 mm diameter, throughput 127 kg / h nitrogen at 100 ° C. Exhaust gas temperature 62 ° C.
  • a 50% by weight aqueous CD 3 solution kept at room temperature is sprayed into the fluidized bed of inert gas via a two-component nozzle.
  • the product is fed to the nozzle via a peristaltic pump.
  • the solid nuclei (or the starting granulate) initially formed from the evaporating droplets in the fluidized bed grow onion-like to the desired size through repeated spraying.
  • the diameter of the individual grains can be set within narrow limits via the speed of the classifying gas flow.
  • An extended attachment with a diameter of around 500 mm above the glass shot serves as a pre-cutter for the medium grain and to solidify the spray droplets that have not hit the bed.
  • the fine material to be separated from the exhaust gas flow is returned by a top filter.
  • the filter is cleaned, the fine material falls back into the fluidized bed in an avalanche-like form so that the germs are again exposed to the spray jet.
  • the finished granulate is discharged by the classifier after 20 minutes.
  • the bed content remains at around 1 kg CD 3.
  • the finished granulate is collected in a sealed bottle that is operated as a change template.
  • the gas throughput through the classifier is 9.5 kg / h at 62 ° C.
  • Granule color very light, almost colorless, no pink color cast.
  • Granulate form beads Bulk density: 730 g / l; the product is free-flowing and dust-free
  • the granules are 90 minutes. post-dried at 40 ° C in a vacuum.
  • Mixture C Mix 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 hydrogen carbonate 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 4.52 g Granules B 2.4 g Granules C 21.95 g Granules D 21.45 g total weight 50.32 g
  • the mixed granulate is packed in paper bags lined with plastic and aluminum foil, with the exclusion of moisture (conduction of very dry air), which are sealed immediately.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Glanulating (AREA)

Abstract

A granular mixture containing a granulated developer substance, a granulated anti-oxidising agent and a granulated alkali donor, the granulated developer substance being spherical and having a mean particle diameter of >/= 150 mu m, and 80 % of the grains being within a range which does not deviate by more than +/- 100 mu m from the desired grain diameter, does not form dust, is free-flowing, infinitely stable in water vapour-tight packaging and dissolves within a very short time.

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 granular color photographic developer and a method for producing such a developer which can be quickly dissolved.

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. 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 contain a number of solid components, for example the actual developer substance, antioxidants, complexing agents, sodium sulfite, alkali donors and alkali halides. Since these compounds can react chemically with one another, they are packaged separately and only mixed immediately before use. Suitable formulations are powders and liquid concentrates, the latter having become more and more established over the years, especially since some developers contain liquid constituents which, understandably, cannot be formulated 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, the three or four concentrates are then mixed in certain mixing ratios and, if appropriate, with the addition of water 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 Zubereitung ist nicht-staubend.
Since such concentrates only have a limited storage time and, because of the water contained therein, cause high transportation 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 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 Entwicklers noch zu lang.From DE-A-37 33 861 it is known to provide black and white developers as a rapidly dissolving dry powder, this being done by preparing a liquid photographic developer solution, removing the solvent to obtain a powder and packaging the powder for Exclusion of the contact with the atmosphere is obtained, and using freeze drying or spray drying to remove the solvent, however, this method can not be applied to color photographic developers which have a completely different composition. In addition, the dissolution times of at least 2 to 4 minutes achieved there are still too long, depending on the type of developer.

Es wurde nun gefunden, daß sich granulierte Zusammenset­zungen herstellen lassen, die alle festen Bestandteile eines farbfotografischen Entwicklers enthalten, indem man die Entwicklersubstanz in gelöster Form in ein Wir­belbett einsprüht, die mit dem Abgas aus dem Wirbel­bett entweichenden Feingutanteile abscheidet und als Keime für die Granulatbildung in das Wirbelbett zurück­führt, durch Einstellung des Sichtgasstromes den Granu­lationsprozeß im Wirbelbett so beeinflußt, daß ein Gra­nulat in der durch den Sichtgasstrom vorgegebenen Größe entsteht, das fertige Granulat über einen oder mehrere in den Anströmboden der Wirbelbettapparatur eingesetzte Gegenstrom-Schwerkraft-Sichter entnimmt, im Vakuum trocknet, mit den übrigen, nach einem beliebigen Prozeß granulierten Bestandteilen des Entwicklers mischt und wasserdampfdicht verpackt.It has now been found that granulated compositions can be produced which contain all the solid constituents of a color photographic developer by spraying the developer substance in dissolved form into a fluidized bed which separates the fine material components escaping from the fluidized bed with the exhaust gas and as nuclei for the formation of granules returns the fluidized bed, influences the granulation process in the fluidized bed by setting the classifying gas flow in such a way that a granulate of the size specified by the classifying gas flow is produced, removes the finished granulate via one or more counterflow gravity classifiers used in the inflow floor of the fluidized bed apparatus, dries in vacuo , mixed with the other components of the developer, granulated by any process, and packed in a water vapor-tight manner.

Gegenstand der Erfindung ist somit ein Verfahren zur Herstellung einer granulierten Zubereitung der festen Bestandteile eines farbfotografischen Entwicklers, da­durch gekennzeichnet, daß man die Entwicklersubstanz eines farbfotografischen Entwicklers in gelöster Form in ein Wirbelbett einsprüht, die mit dem Abgas aus dem Wirbelbett entweichenden Feingutanteile abscheidet und als Keime für die Granulatbildung in das Wirbelbett zurückführt, durch Einstellung des Sichtgasstromes den Granulationsprozeß im Wirbelbett so beeinflußt, daß ein Granulat in der durch den Sichtgasstrom vorgegebenen Größe entsteht, das fertige Granulat über einen oder mehrere in den Anströmboden der Wirbelbettapparatur ein­gesetzte Gegenstrom-Schwerkraft-Sichter entnimmt, im Vakuum trocknet, mit den übrigen, nach einem beliebigen Prozeß granulierten Bestandteilen des Entwicklers mischt und wasserdampfdicht verpackt.The invention thus relates to a process for producing a granulated preparation of the solid constituents of a color photographic developer, characterized in that the developer substance of a color photographic developer is sprayed in dissolved form into a fluidized bed, which separates the fine material portions escaping from the fluidized bed with the exhaust gas and as germs leads back to the fluidized bed for the formation of granules, influences the granulation process in the fluidized bed by adjusting the classifying gas flow in such a way that a granulate in the range given by the classifying gas flow Size arises, the finished granules are removed via one or more countercurrent gravity classifiers used in the inflow base of the fluidized bed apparatus, dried in vacuo, mixed with the other components of the developer, granulated by any process, and packed in a water-vapor-tight manner.

Das so hergestellte Granulat der Entwicklersubstanz eines farbfotografischen Entwicklers ist mechanisch stabil, von einheitlicher Korngroße, zeigt eine große Lösungsgeschwindigkeit und unbegrenzte Haltbarkeit, ist staubfrei und rieselfähig. Die Körner sind insbesondere kugelförmig.The granulate of the developer substance of a color photographic developer produced in this way is mechanically stable, of uniform grain size, shows a high dissolution speed and unlimited durability, is dust-free and free-flowing. The grains are particularly spherical.

Es wird vorzugsweise eine wäßrige Lösung der Entwickler­substanz eingesetzt, deren Konzentration insbesondere 10 bis 70 Gew.-% beträgt.An aqueous solution of the developer substance is preferably used, the concentration of which is in particular 10 to 70% by weight.

Der mittlere Teilchendurchmesser des Entwicklersub­stanzgranulates soll vorzugsweise ≧ 150 µm sein und be­trägt insbesondere 150 bis 3.000 µm. Das erfindungsge­mäße Verfahren gestattet eine sehr enge Teilchendurch­messerverteilung. Vorzugsweise liegen ≧ 80 % der Körner innerhalb eines Bereiches, der vom gewünschten Korn­durchmesser um nicht mehr als ± 100 µm abweicht. Bei be­sonders sauerstoffempfindlichen Entwicklersubstanzen ist es vorzuziehen, das Granulieren, Trocknen, Mischen und Verpacken unter einem Schutzgas, beispielsweise Stick­stoff, vorzunehmen.The average particle diameter of the developer substance granules should preferably be ≧ 150 μm and is in particular 150 to 3,000 μm. The method according to the invention allows a very narrow particle diameter distribution. Preferably, ≧ 80% of the grains are within a range that does not deviate from the desired grain diameter by more than ± 100 µm. In the case of developer substances which are particularly sensitive to oxygen, it is preferable to carry out the granulation, drying, mixing and packaging under a protective gas, for example nitrogen.

Die übrigen festen Bestandteile des Entwicklers wie Oxidationsschutzmittel, Alkalispender, Kalkschutzmittel, Komplexbildner für Schwermetallionen, Natriumsulfit und Alkalihalogenid können nach einem beliebigen Verfahren granuliert werden.The other solid constituents of the developer such as antioxidants, alkali donors, limescale inhibitors, complexing agents for heavy metal ions, sodium sulfite and alkali halide can be granulated by any process.

Ein geeignetes Verfahren besteht beispielsweise darin, daß man die zu granulierende Substanz auf eine Teilchen­größe < 10 µm mahlt, anschließend gegebenenfalls unter Zusatz einer Granulierflüssigkeit und eines Bindemittels einer Pulveragglomeration unterwirft und im Vakuum trocknet.A suitable method is, for example, that the substance to be granulated is ground to a particle size of <10 μm, then optionally subjected to powder agglomeration with the addition of a granulating liquid and a binder, and dried in vacuo.

Oxidationsschutzmittel und Alkalispender sind dabei vor­zugsweise getrennt zu granulieren. Die übrigen Bestand­teile können ebenfalls separat oder teils mit dem Oxida­tionsschutzmittel, teils mit dem Alkalispender zusammen granuliert werden.Antioxidants and alkali dispensers should preferably be granulated separately. The remaining constituents can also be granulated separately or partly with the antioxidant and partly with the alkali dispenser.

Die Hilfsmittel werden insbesondere auf den gleichen mittleren Korndurchmesser wie den der Entwicklersubstanz granuliert; die Abweichung der einzelnen Granulate vom mittleren Korndurchmesser kann größer sein als bei der Entwicklersubstanz.The auxiliaries are granulated in particular to the same mean grain diameter as that of the developer substance; the deviation of the individual granules from the average grain diameter can be greater than with the developer substance.

Die so hergestellte Granulatmischung ist mechanisch sta­bil, von einheitlicher Korngröße, zeigt eine große Lö­sungsgeschwindigkeigt und unbegrenzte Haltbarkeit, ist staubfrei und rieselfähig.The granulate mixture produced in this way is mechanically stable, of uniform grain size, shows a high rate of dissolution and unlimited shelf life, is dust-free and free-flowing.

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-hydroxy­ethyl)-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. 1-(N-Ethyl-N-methansulfon­amido-ethyl)-3-methyl-p-phenylendiamin-Sesquisulfat, Mo­nohydrat (CD 3) ist bevorzugt.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. Further 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. 1- (N-Ethyl-N-methanesulfonamido-ethyl) -3-methyl-p-phenylenediamine sesquisulfate, monohydrate (CD 3) is preferred.

Ein weiter Gegenstand der Erfindung ist eine Granulat­mischung enthalten eine granulierte Entwicklersubstanz, ein granuliertes Oxidationsschutzmittel und einen gra­nulierten Alkalispender, dadurch gekennzeichnet, daß die granulierte Entwicklersubstanz kugelförmig ist und einen mittleren Teilchendurchmesser ≧ 150 µm aufweist, wobei 80 % der Körner innerhalb eines Bereiches liegen, der vom gewünschten Korndurchmesser um nicht mehr als ± 100 µm abweicht.Another object of the invention is a granule mixture containing a granulated developer substance, a granulated antioxidant and a granulated alkali dispenser, characterized in that the granulated developer substance is spherical and has an average particle diameter ≧ 150 microns, 80% of the grains being within a range that deviates from the desired grain diameter by no more than ± 100 µm.

Beispiel:Example: Granulation der Farbenentwicklersubstanz CD 3 (MG = 436,5) (Granulat A)Granulation of the color developer substance CD 3 (MG = 436.5) (granulate A)

Die Verbindung wird als 50 gew.-%ige wässrige Lösung eingesetzt. Die Granulation erfolgt in einem Glasschuß mit 225 mm Durchmesser durch wiederholtes Aufsprühen der wässrigen Lösung auf feste, in der Wirbelschicht be­findliche Keime.The compound is used as a 50% by weight aqueous solution. The granulation takes place in a glass shot with a diameter of 225 mm by repeatedly spraying the aqueous solution onto solid germs located in the fluidized bed.

Zunächst wird eine Menge von etwa 1 kg festem CD 3 als Startgranulat über einen Einfülltrichter auf den Loch­boden eines Glasschusses mit 225 mm Durchmesser gemäß DE-A-35 07 376, Beispiel 1 gebracht. Dann wird der Fluidisierungsgasstrom eingeschaltet: Anströmquerschnitt 225 mm Durchmesser, Durchsatz 127 kg/h Stickstoff von 100°C.
Abgastemperatur 62°C.First, a quantity of about 1 kg of solid CD 3 as starting granules is placed on the perforated bottom of a glass shot with a diameter of 225 mm according to DE-A-35 07 376, example 1, via a filling funnel. Then the fluidizing gas flow is switched on: flow cross-section 225 mm diameter, throughput 127 kg / h nitrogen at 100 ° C.
Exhaust gas temperature 62 ° C.

Nun wird eine auf Raumtemperatur gehaltene 50 gew.-%ige wäßrige CD 3-Lösung über eine Zweistoffdüse in das Fließbett aus Inertgas gesprüht. Die Zufuhr des Produkts zur Düse erfolgt über eine Schlauchpumpe. Die aus den verdampfenden Tröpfchen im Wirbelbett zunächst gebil­deten Feststoffkeime (bzw. das Startgranulat) wachsen durch das mehrfache Besprühen zwiebelartig bis auf die gewünschte Größe an. Der Durchmesser der einzelnen Kör­ner kann dabei in engen Grenzen über de Geschwindigkeit des Sichtergasstroms eingestellt werden.Now a 50% by weight aqueous CD 3 solution kept at room temperature is sprayed into the fluidized bed of inert gas via a two-component nozzle. The product is fed to the nozzle via a peristaltic pump. The solid nuclei (or the starting granulate) initially formed from the evaporating droplets in the fluidized bed grow onion-like to the desired size through repeated spraying. The diameter of the individual grains can be set within narrow limits via the speed of the classifying gas flow.

Ein erweiterter Aufsatz von rund 500 mm Durchmesser über dem Glasschuß dient als Vorabschneider für das Mittel­korn und zur Verfestigung der Sprühtröpchen, die im Bett nicht getroffen haben.An extended attachment with a diameter of around 500 mm above the glass shot serves as a pre-cutter for the medium grain and to solidify the spray droplets that have not hit the bed.

Die Rückführung des aus dem Abgasstrom abzuscheidenden Feingutes erfolgt durch ein Aufsatzfilter. Beim Ab­reinigen des Filters fällt das Feingut in agglomerier­ter Form lawinenartig in das Fließbett zurück, so daß die Keime erneut dem Sprühstrahl ausgesetzt werden.The fine material to be separated from the exhaust gas flow is returned by a top filter. When the filter is cleaned, the fine material falls back into the fluidized bed in an avalanche-like form so that the germs are again exposed to the spray jet.

Der Austrag des fertigen Granulats durch den Sichter be­ginnt nach 20 min. Dabei bleibt der Bettinhalt weiterhin bei etwa 1 kg CD 3. Aufgefangen wird das fertige Granu­lat in einer dichtend aufgesetzten Flasche, die als Wechselvorlage betrieben wird.The finished granulate is discharged by the classifier after 20 minutes. The bed content remains at around 1 kg CD 3. The finished granulate is collected in a sealed bottle that is operated as a change template.

Der Gasdurchsatz durch den Sichter ist 9.5 kg/h bei 62°C.The gas throughput through the classifier is 9.5 kg / h at 62 ° C.

Eigenschaften des erhaltenen Granulats: (Granulat A) Properties of the granules obtained: (Granules A)

Granulatfarbe: Sehr hell, nahezu farblos, kein rosa Farbstich.
Granulatform: Kügelchen
Schüttdichte: 730 g/l; das Produkt ist freifließend und staubfrei
Granulatfeuchte: 4.2 % nach Karl Fischer
Mittlere Korngröße: 400 µm (rund 90 % der Körner liegen im Bereich 300 bis 500 µm)
Lagerfähigkeit: UnbegrenztGranule color: very light, almost colorless, no pink color cast.
Granulate form: beads
Bulk density: 730 g / l; the product is free-flowing and dust-free
Granulate moisture: 4.2% according to Karl Fischer
Average grain size: 400 µm (around 90% of the grains are in the range 300 to 500 µm)
Shelf life: unlimited

Herstellung des Granulats aus dem Oxidationsschutzmittel (Granulat B)Production of the granulate from the antioxidant (granulate B)

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 crushed in an Alexander sieve with a mesh size of 0.6 mm and then ground in an air jet mill to an average particle diameter of <10 μm.

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 und danach bei einer Lufttempera­tur von 63°C 8 min. lang getrocknet. Alle Granulatkörner > 2000 µm werden durch Sieben entfernt.500 g of this ground material are in a commercially available fluidized bed spray granulator (Strea 1 laboratory device from Aeromatic, Bubendorf / Switzerland) by spraying a total of 38 ml of water and then at an air temperature of 63 ° C for 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 minutes. post-dried at 40 ° C in a vacuum.

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)

Folgende Chemikalien werden zusammengemischt: Mischung C Mischung D a) Dinatriumsalz der 1-Hydroxyethan-1,1-diphosphonsäure 34 g --- b) Natriumsulfit 39 g 39 g c) Ethylendiamintetraessigsäure --- 24 g d) Kaliumcarbonat 336 g 336 g e) Natriumhydrogencarbonat 15 g 15 g f) Kaliumbromid 15 g 15 g 439 g 429 g The following chemicals are mixed together: Mixture C Mix 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 hydrogen carbonate 15 g 15 g f) potassium bromide 15 g 15 g 439 g 429 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 Granulat 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 granulate 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.

Herstelung 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 4,52 g Granulat B 2,4 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 4.52 g Granules B 2.4 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 packed in paper bags lined with plastic and aluminum foil, with the exclusion of moisture (conduction of very dry air), which are sealed immediately.

Eigenschaftenproperties

  • 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 can be kept indefinitely with the exclusion of moisture during manufacture and packaging.

Claims (4)

1. Granulatmischung enthaltend eine granulierte Ent­wicklersubstanz, ein granuliertes Oxidationsschutz­mittel und einen granulierten Alkalispender, da­durch gekennzeichnet, daß die granulierte Entwick­lersubstanz kugelförmig ist und einen mittleren Teilchendurchmesser ≧ 150 µm aufweist, wobei 80 % der Körner innerhalb eines Bereiches liegen, der vom gewünschten Korndurchmesser um nicht mehr als ± 100 µm abweicht.1. Granulate mixture containing a granulated developer substance, a granulated antioxidant and a granulated alkali dispenser, characterized in that the granulated developer substance is spherical and has an average particle diameter ≧ 150 µm, 80% of the grains being within a range which does not exceed the desired grain diameter deviates more than ± 100 µm. 2. Granulatmischung nach Anspruch 1, wobei der mitt­lere Teilchendurchmesser des Entwicklersubstanz-­Granulates 150 bis 3000 µm beträgt.2. Granulate mixture according to claim 1, wherein the average particle diameter of the developer substance granules is 150 to 3000 microns. 3. Granulatmischung nach Anspruch 1, die wasserdampf­dicht verpackt ist.3. Granulate mixture according to claim 1, which is packed in a water vapor-tight manner. 4. Verfahren zur Herstellung einer granulierten Zubereitung der festen Bestandteile eines farb­fotografischen Entwicklers, dadurch gekennzeichnet, daß man die Entwicklersubstanz eines farbfoto­grafischen Entwicklers in gelöster Form in ein Wirbelbett einsprüht, die mit dem Abgas aus dem Wirbelbett entweichenden Feingutanteile abscheidet und als Keime für die Granulatbildung in das Wir­belbett zurückführt, durch Einstellung des Sicht­gasstromes den Granulationsprozeß im Wirbelbett so beeinflußt, daß ein Granulat in der durch den Sichtgasstrom vorgegebenen Größe entsteht, das fertige Granulat über einen oder mehrere in den Anströmboden der Wirbelbettapparatur eingesetzte Gegenstrom-Schwerkraft-Sichter entnimmt, im Vakuum trocknet, mit den übrigen, nach einem beliebigen Prozeß granulierten Bestandteilen des Entwicklers mischt und wasserdampfdicht verpackt.4. A process for the preparation of a granulated preparation of the solid constituents of a color photographic developer, characterized in that the developer substance of a color photographic developer is sprayed into a fluidized bed in a dissolved form, which separates fine particles escaping from the fluidized bed with the exhaust gas and as germs for the formation of granules the fluidized bed returns the granulation process in the fluidized bed by adjusting the sight gas flow Influences that a granulate in the size specified by the classifying gas flow is produced, the finished granulate is removed via one or more countercurrent gravity classifiers used in the inflow floor of the fluidized bed apparatus, dried in a vacuum, with the other components of the developer, granulated by any process mixes and packaged waterproof.
EP19890115442 1988-09-03 1989-08-22 Granulated colour-photographic developer, and its manufacture Withdrawn EP0358035A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19883830022 DE3830022A1 (en) 1988-09-03 1988-09-03 GRANULATED, COLOR PHOTOGRAPHIC DEVELOPER AND ITS MANUFACTURE
DE3830022 1988-09-03

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EP0358035A2 true EP0358035A2 (en) 1990-03-14
EP0358035A3 EP0358035A3 (en) 1991-02-27

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EP (1) EP0358035A3 (en)
JP (1) JPH02109043A (en)
DE (1) DE3830022A1 (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0547796A1 (en) * 1991-12-17 1993-06-23 Konica Corporation Solid chemicals for processing silver halide photographic light-sensitive material
US5366853A (en) * 1991-11-06 1994-11-22 Konica Corporation Tablet-shaped processing agent and method for processing silver halide photographic light sensitive materials
US5384233A (en) * 1992-06-15 1995-01-24 Konica Corporation Chemicals kit including a container formed of multilayer film, for processing photographic light-sensitive materials
EP0711592A3 (en) * 1994-11-11 1997-03-05 Konishiroku Photo Ind Method of manufacturing solid processing composition for silver halide photographic light-sensitive materials
US5900355A (en) * 1998-03-26 1999-05-04 Eastman Kodak Company Method of making uniformly mixed dry photographic processing composition using hot melt binder
US5922521A (en) * 1998-03-26 1999-07-13 Eastman Kodak Company Uniformly mixed dry photographic processing composition and method of preparation
US5945265A (en) * 1998-03-26 1999-08-31 Eastman Kodak Company Uniformly mixed dry photographic developing composition containing antioxidant and method of preparation
EP1434102A1 (en) * 2002-12-24 2004-06-30 Konica Minolta Holdings, Inc. Developer composition for lithographic printing plate

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JP2843877B2 (en) * 1992-01-18 1999-01-06 コニカ株式会社 Photographic processing agents
JPH07248597A (en) * 1994-03-09 1995-09-26 Konica Corp Automatic developing machine for silver halide photographic sensitive material as well as supplying method and supplying device for solid processing agent for silver halide photographic sensitive material
EP0687950A1 (en) 1994-05-27 1995-12-20 Konica Corporation Granular and tablet-shape processing composition for processing a silver halide photographic light-sensitive material
EP0691571B1 (en) 1994-06-14 2000-08-30 Konica Corporation Developing granule or tablet for silver halide photographic light-sensitive materials and method of manufacturing the same
US5557362A (en) 1994-06-16 1996-09-17 Konica Corporation Silver halide photosensitive material automatic developing apparatus
JPH0869098A (en) 1994-08-31 1996-03-12 Konica Corp Automatic developing machine for silver halide photographic sensitive material
JPH08160588A (en) 1994-12-06 1996-06-21 Konica Corp Automatic developing machine for silver halide photographic sensitive material
JP3574986B2 (en) 1996-01-16 2004-10-06 コニカミノルタホールディングス株式会社 Solid processing agent for silver halide photographic light-sensitive material and method of processing silver halide photographic light-sensitive material
JP5588597B2 (en) 2007-03-23 2014-09-10 富士フイルム株式会社 Manufacturing method and manufacturing apparatus of conductive material
US8426749B2 (en) 2007-05-09 2013-04-23 Fujifilm Corporation Electromagnetic shielding film and optical filter

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FR1548123A (en) * 1966-12-28 1968-11-29
US3981732A (en) * 1971-08-19 1976-09-21 Fuji Photo Film Co., Ltd. Granular p-phenylenediamine color developing agent
GB2195783A (en) * 1986-10-09 1988-04-13 Du Pont A powdered packaged developer and a process of preparation

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FR1548123A (en) * 1966-12-28 1968-11-29
US3981732A (en) * 1971-08-19 1976-09-21 Fuji Photo Film Co., Ltd. Granular p-phenylenediamine color developing agent
GB2195783A (en) * 1986-10-09 1988-04-13 Du Pont A powdered packaged developer and a process of preparation

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CHEMICAL ABSTRACTS, vol. 83, no. 16, 20 Oktober 1975 Columbus, Ohio, USA V.K.KISLITSYN ET AL.: "ATOMIZATION OF LIQUID SORBENTS,USED IN PHOTOGRAPHY,BY CENTRIFUGAL SPRAYER" Seite 563; ref. no. 139809C *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5366853A (en) * 1991-11-06 1994-11-22 Konica Corporation Tablet-shaped processing agent and method for processing silver halide photographic light sensitive materials
EP0547796A1 (en) * 1991-12-17 1993-06-23 Konica Corporation Solid chemicals for processing silver halide photographic light-sensitive material
US5384233A (en) * 1992-06-15 1995-01-24 Konica Corporation Chemicals kit including a container formed of multilayer film, for processing photographic light-sensitive materials
EP0711592A3 (en) * 1994-11-11 1997-03-05 Konishiroku Photo Ind Method of manufacturing solid processing composition for silver halide photographic light-sensitive materials
US5900355A (en) * 1998-03-26 1999-05-04 Eastman Kodak Company Method of making uniformly mixed dry photographic processing composition using hot melt binder
US5922521A (en) * 1998-03-26 1999-07-13 Eastman Kodak Company Uniformly mixed dry photographic processing composition and method of preparation
US5945265A (en) * 1998-03-26 1999-08-31 Eastman Kodak Company Uniformly mixed dry photographic developing composition containing antioxidant and method of preparation
US6093523A (en) * 1998-03-26 2000-07-25 Eastman Kodak Company Uniformly mixed dry photographic developing composition containing antioxidant
US6110654A (en) * 1998-03-26 2000-08-29 Eastman Kodak Company Uniformly mixed dry photographic processing composition
EP1434102A1 (en) * 2002-12-24 2004-06-30 Konica Minolta Holdings, Inc. Developer composition for lithographic printing plate

Also Published As

Publication number Publication date
EP0358035A3 (en) 1991-02-27
DE3830022A1 (en) 1990-03-15
JPH02109043A (en) 1990-04-20

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