EP0358034B1 - Granulated photographic colour developer and its preparation - Google Patents
Granulated photographic colour developer and its preparation Download PDFInfo
- 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
- Authority
- EP
- European Patent Office
- Prior art keywords
- granulated
- developer
- granules
- granulated materials
- mixture
- 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
Links
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000008187 granular material Substances 0.000 claims description 41
- 239000002245 particle Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
- 238000005054 agglomeration Methods 0.000 claims description 4
- 230000002776 aggregation Effects 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims 8
- 239000000470 constituent Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 235000008504 concentrate Nutrition 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000010902 jet-milling Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- QNGVNLMMEQUVQK-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C=C1 QNGVNLMMEQUVQK-UHFFFAOYSA-N 0.000 description 1
- 241001136792 Alle Species 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- VGYYSIDKAKXZEE-UHFFFAOYSA-L hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 239000001013 indophenol dye Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Cosmetics (AREA)
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:
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.
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.
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.
Mischung C und D werden getrennt in der folgenden Art
granuliert:
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:
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.
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.
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.
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)
- 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.
- A mixture of granulated materials according to claim 1, wherein the average particle diameter of the individual granulated materials is 150 to 3000 µm.
- A mixture of granulated materials according to claim 1 which is packed in a water vapour-tight manner.
- 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.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3830023 | 1988-09-03 | ||
DE3830023A DE3830023A1 (en) | 1988-09-03 | 1988-09-03 | GRANULATED, COLOR PHOTOGRAPHIC DEVELOPER AND ITS MANUFACTURE |
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 |
Family
ID=6362256
Family Applications (1)
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 |
Country Status (4)
Country | Link |
---|---|
US (1) | US4923786A (en) |
EP (1) | EP0358034B1 (en) |
JP (1) | JP2793853B2 (en) |
DE (2) | DE3830023A1 (en) |
Families Citing this family (38)
Publication number | Priority date | Publication date | Assignee | Title |
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DE3830023A1 (en) | 1988-09-03 | 1990-03-15 | Agfa Gevaert Ag | GRANULATED, COLOR PHOTOGRAPHIC DEVELOPER AND ITS MANUFACTURE |
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 |
CA2035049C (en) * | 1990-01-31 | 1996-09-17 | Audenried W. Knapp | 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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US5780211A (en) * | 1991-05-01 | 1998-07-14 | Konica Corporation | Processing composition in the tablet form for silver halide photographic light-sensitive material |
EP0540990B1 (en) * | 1991-11-06 | 1998-07-15 | Konica Corporation | Tablet-shaped processing agent and method for processing silver halide photographic light sensitive materials |
EP0542283A1 (en) * | 1991-11-12 | 1993-05-19 | Konica Corporation | A tablet for processing a silver halide photographic light-sensitive material |
JP2700841B2 (en) * | 1991-11-20 | 1998-01-21 | コニカ株式会社 | Tablet for processing silver halide color light-sensitive material and method for producing the same |
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 |
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 |
JP2929339B2 (en) * | 1992-07-16 | 1999-08-03 | コニカ株式会社 | Black-and-white processing agent |
JP2916970B2 (en) * | 1992-10-13 | 1999-07-05 | 富士写真フイルム株式会社 | Color developing composition for color photography |
DE69406817T2 (en) * | 1993-01-19 | 1998-05-28 | Konishiroku Photo Ind | Solid composition for processing photographic light-sensitive silver halide color materials and their processing methods |
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 |
JPH07114151A (en) * | 1993-08-23 | 1995-05-02 | Konica Corp | Solid processing agent for silver halide photographic sensitive material |
JPH07248585A (en) * | 1994-01-21 | 1995-09-26 | Konica Corp | Solid processing agent for development of silver halide photographic sensitive material |
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 |
DE69520079T2 (en) | 1994-04-19 | 2001-06-21 | Konica Corp., Tokio/Tokyo | Manufacturing process for solid processing compositions for photographic light-sensitive silver halide materials |
JPH0829924A (en) * | 1994-05-09 | 1996-02-02 | Konica Corp | Color developer granulated material for silver halide color photographic material, granulation method therefor, and solid processing agent and tablet type solid processing agent using the granulated 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 |
DE69518592T2 (en) * | 1994-06-14 | 2001-04-26 | Konica Corp., Tokio/Tokyo | Development granules or tablets for silver halide photographic light-sensitive materials and process for producing 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 |
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 |
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 |
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 |
US5900355A (en) * | 1998-03-26 | 1999-05-04 | Eastman Kodak Company | Method of making uniformly mixed dry photographic processing composition using hot melt binder |
US6077653A (en) * | 1998-07-29 | 2000-06-20 | Eastman Kodak Company | Photographic developing compositions and methods of using 1,4-cyclohexanediones as antioxidants |
US6130029A (en) * | 1999-06-14 | 2000-10-10 | Eastman Chemical Company | Stabilized phenylenediamine color developer compositions |
US7135275B2 (en) | 2003-08-28 | 2006-11-14 | Fuji Photo Film Co., Ltd. | Solid bleach-fixing composition for silver halide color photographic light-sensitive material, and method for processing silver halide color 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 |
EP2009977A3 (en) | 2007-05-09 | 2011-04-27 | FUJIFILM Corporation | Electromagnetic shielding film and optical filter |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB190906652A (en) * | 1909-03-19 | 1910-01-27 | Oppenheimer Son And Company Lt | Improvements relating to Preparation and Packeting of Chemical Substances used in Photography. |
US3981732A (en) * | 1971-08-19 | 1976-09-21 | Fuji Photo Film Co., Ltd. | Granular p-phenylenediamine color developing agent |
NL7402981A (en) * | 1973-03-16 | 1974-09-18 | ||
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 |
DK166954B1 (en) * | 1985-03-28 | 1993-08-09 | Deltagraph As | PROCEDURE FOR PACKAGING TWO REACTIVE, PARTICULATED SUBSTANCES |
US5314069A (en) | 1985-03-28 | 1994-05-24 | Deltagraph A/S | Process for obtaining a package containing mutually reactive particulate materials and a package containing such materials |
JPS62110739A (en) * | 1985-11-06 | 1987-05-21 | Dai Ichi Kogyo Seiyaku Co Ltd | Method for granulating water-soluble cellulose derivative |
US4816384A (en) * | 1986-10-09 | 1989-03-28 | E. I. Du Pont De Nemours And Company | Powdered packaged developer |
DE3830023A1 (en) | 1988-09-03 | 1990-03-15 | Agfa Gevaert Ag | GRANULATED, COLOR PHOTOGRAPHIC DEVELOPER AND ITS MANUFACTURE |
-
1988
- 1988-09-03 DE DE3830023A patent/DE3830023A1/en not_active Withdrawn
-
1989
- 1989-08-18 US US07/395,598 patent/US4923786A/en not_active Expired - Lifetime
- 1989-08-22 DE DE58909852T patent/DE58909852D1/en not_active Expired - Fee Related
- 1989-08-22 EP EP89115441A patent/EP0358034B1/en not_active Expired - Lifetime
- 1989-09-02 JP JP1226400A patent/JP2793853B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
"Agfacolor Selbst Verarbeitet, Der Negativ/Positiv-Prozess", 1972, Seiten 10,11,36 und 37 * |
Also Published As
Publication number | Publication date |
---|---|
JPH02109042A (en) | 1990-04-20 |
DE58909852D1 (en) | 1999-09-02 |
US4923786A (en) | 1990-05-08 |
EP0358034A2 (en) | 1990-03-14 |
JP2793853B2 (en) | 1998-09-03 |
DE3830023A1 (en) | 1990-03-15 |
EP0358034A3 (en) | 1990-06-06 |
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