EP1451284B1 - Method for producing coated bleach activator granules - Google Patents

Method for producing coated bleach activator granules Download PDF

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Publication number
EP1451284B1
EP1451284B1 EP02804191A EP02804191A EP1451284B1 EP 1451284 B1 EP1451284 B1 EP 1451284B1 EP 02804191 A EP02804191 A EP 02804191A EP 02804191 A EP02804191 A EP 02804191A EP 1451284 B1 EP1451284 B1 EP 1451284B1
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Prior art keywords
weight
alkyl
formula
range
acid
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EP02804191A
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German (de)
French (fr)
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EP1451284A1 (en
Inventor
Georg Assmann
Olaf Joachim Blochwitz
Horst-Dieter Speckmann
Jörg Poethkow
Birgit Middelhauve
Gerhard Blasey
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/3925—Nitriles; Isocyanates or quarternary ammonium nitriles
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules

Definitions

  • the invention relates to a process for coating bleach activator-containing granules by treatment with an acidic aqueous solidifier solution which contains polymeric polycarboxylate and / or alkali metal phosphonate as coating and solidification agent, with simultaneous drying in a fluidized bed apparatus.
  • Detergents and cleaners in addition to the indispensable for the washing process ingredients such as surfactants and builders usually other ingredients that can be summarized under the term laundry aids and include as different drug groups such as foam regulators, graying inhibitors, bleaching agents and dye transfer inhibitors.
  • Such auxiliaries also include substances which promote the surfactant performance by the oxidative degradation of soils or those present in the liquor. The same applies mutatis mutandis to cleaners for hard surfaces.
  • inorganic peroxygen compounds particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water releasing hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes.
  • the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for which numerous proposals, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N- acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfuryl amides and cyanurates, as well as carboxylic anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular Sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives such as pentaacetyl-glucose have been reported in the literature.
  • bleach activators for which
  • European Patent Application EP 0 464 880 discloses bleach-enhancing cationic nitriles of the general formula R'R "R"'N + -CR 1 R 2 -CN X - in which R 1 and R 2 are hydrogen or a substituent having at least one C Atom, R 'is a C 1-24 alkyl, alkenyl or alkyl ether group or a group -CR 1 R 2 -CN, and R "and R'" are each a C 1-24 alkyl or hydroxyalkyl group, and the Counteranion X - is an organic sulfonate, an organic sulfate or a carboxylate.
  • WO 99/14296 discloses a process for coating bleach activator grannates containing ammonium nitrile.
  • the object of the invention was to provide a process which makes it possible to use granules which contain a cationic nitrile in particulate detergents and cleaners to incorporate that the cationic nitrile suffers as possible no loss of bleach-activating effect even after storage. It has now been found that the preparation of formulations which meet this requirement is possible by a fluidized bed coating process. In this way, a protective coating can be applied to the granules in a simple manner, without having to accept a decrease in bleach activator effect.
  • the invention relates to a preparation of a coated particulate preparation comprising a compound of formula (I), in the R 1 is -H, -CH 3 , a C 2-24 alkyl or alkenyl radical, a substituted C 2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH 2 , -CN, an alkyl or alkenylaryl radical having a C 1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C 1-24 -alkyl group and at least one further substituent on the aromatic ring
  • R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3, -CH 2 -CH 3, -CH 2 -CH 2 -CH 3, -CH (CH 3) -CH 3, -CH 2 - OH, -CH 2 -CH 2 -OH, -CH (OH) -CH
  • the anions X - include in particular the halides such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, metaphosphate, hexafluorophosphate, carbonate, bicarbonate, sulfate, hydrogen sulfate, C 1-20 alkyl sulfate, C 1-20 -alkyl sulfonate, optionally C 1-18 alkyl-substituted arylsulfonate, chlorate, perchlorate and / or the anions of C 1-24 carboxylic acids such as formate, acetate, laurate, benzoate or citrate, alone or in any mixtures.
  • halides such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, metaphosphat
  • toluenesulfonate or cumene sulfonate is meant the anion of the ortho, meta or para isomer of methylbenzenesulfonic acid or isopropylbenzenesulfonic acid and any mixtures thereof.
  • Para-isopropylbenzenesulfonic acid is particularly preferred.
  • the compound according to general formula I can be formulated in solid form as such or particulate, that is applied to an organic and / or inorganic carrier material, are used as starting material in the coating method according to the invention.
  • the application of the compound of formula (I) can be carried out on the support material such that stirred into a solution of the compound of formula I, as obtained in the preparation thereof, the support material and the optionally aqueous solvent in vacuo, if desired at elevated Temperature, subtracts.
  • the solution of the compound according to formula I can also be sprayed onto the support material and, if appropriate, subsequently subjected to a drying process.
  • Suitable carrier materials are all substances which do not interact in unduly negative ways with the compound according to formula I, for example alkali metal sulfonate, surfactants, organic acids and polymers, alkali metal carbonates, alkali metal sulfates, alkali metal hydrogensulfates, alkali metal bicarbonates, alkali metal phosphates, alkali metal hydrogenphosphates, dialkalihydrogenphosphates and alkali metal silicates and theirs mixtures.
  • such support materials are used whose inner surface is in the range of 10 m 2 / g to 500 m 2 / g, in particular 100 m 2 / g to 450 m 2 / g.
  • silicate carrier materials which are particularly suitable for the purposes of the present invention include, for example, both alkali metal silicates and also silicic acids, silica gels and clays as well as mixtures thereof.
  • the carrier material is preferably free of zeolites.
  • Silicate-containing support material optionally contains, in addition to the silicate component, further particulate inert constituents which do not affect the stability of the compounds according to formula I unreasonably.
  • Silicas prepared by a thermal process flame hydrolysis of SiCl 4
  • fumed silicas are useful as well as silicas prepared by wet processes.
  • Silica gels are colloidal silicas with elastic to solid consistency and a largely loose pore structure, resulting in a high remplissiglceits recommendationdoc. They can be prepared by the action of mineral acids on water glass become.
  • Clays are naturally occurring crystalline or amorphous silicates of aluminum, iron, magnesium, calcium, potassium and sodium, for example kaolin, talc, pyrophyllite, attapulgite, sepiolite, montmorillonite and bauxite.
  • the use of aluminum silicate as a carrier material or as a component of a carrier material mixture is possible.
  • the carrier material preferably has particle sizes in the range from 100 ⁇ m to 1.5 mm.
  • the coated bleach activator granules obtainable by the process according to the invention or the proportion of good grain therefrom preferably has average particle diameters in the range from 0.2 mm to 2.5 mm, in particular in the range from 0.4 mm to 2.0 mm.
  • Its bulk density is preferably in the range of 300 g / l to 1000 g / l, in particular in the range of 400 g / l to 800 g / l.
  • the proportion of compound according to formula (I) is preferably in the range from 10% by weight to 90% by weight, in particular from 15% to 50% by weight. It is preferably used to prepare particulate detergents or cleaners.
  • Wirbel legistrenchtungen which can be used in a process according to the invention are known, for example, from European Patent EP 0 603 207 B1 or German Patent Application DE 197 50 424.
  • the passage openings can be covered by a grid, in particular with mesh sizes smaller than 600 ⁇ m.
  • the grid can be arranged within or above the passage openings.
  • the grid is preferably located immediately below the openings of the inflow base, as is known in principle from German Patent Application DE 197 50 424.
  • a metal gauze with the appropriate mesh size can be sintered or otherwise secured to the underside of a known inflow base.
  • the metal gauze preferably consists of the same material as the distributor plate, in particular of stainless steel.
  • the mesh size of said grid is between 200 and 400 microns. It is also advantageous if the inlet plate used has a pressure drop of at most 10 mbar and in particular at most 6 mbar.
  • the aqueous solidifying and coating solution is applied in a fluidized bed apparatus.
  • Suitable solidifying and coating agents are polymeric polycarboxylates, in particular polymerization products of acrylic acid, methacrylic acid or maleic acid, or copolymers of at least two of these, which can be used in completely or partially neutralized form, in particular in the form of alkali metal salts.
  • phosphonic acid or alkali metal phosphonate can be used.
  • sodium is the particular preferred alkali metal.
  • the setting of the solution is preferably as low as possible Viscosity for good droplet distribution during atomization in the fluidized bed with simultaneous drying.
  • the pH of the solution if it is not from the outset in the acidic range, by addition of system-compatible acids, in particular by addition of sulfuric acid and / or citric acid, to acid values, in particular to values in the pH range of 4 to 4.4 , discontinued. It is preferred that, based on the granules to be coated, so much of the aqueous solution is sprayed on that the coating constitutes 1% by weight to 25% by weight, in particular 2% by weight to 15% by weight.
  • the granules can be discharged in a manner known in principle from the fluidized bed and optionally classified according to the particle size, wherein as stated above undesirably small particles (fine particles) and undesirably large particles (coarse grains) can optionally be returned to a granulation process after a grinding step.
  • the classified good grain can be re-introduced into a fluidized bed apparatus and sprayed onto it solidifying and coating solution in order to further improve the product properties of the granules if necessary.
  • a coated by the process according to the invention granules is storage stable, good free-flowing and of sufficient grain stability to be mixed in a conventional manner with other particulate components of detergents or cleaning agents can.
  • Enveloped granules obtainable by the process according to the invention are preferably used in particular particulate detergents or cleaners in amounts such that these compositions have contents of from 0.1% by weight to 10% by weight, in particular from 0.2% by weight to 7 wt .-% of bleach activator according to formula (I).
  • the stickiness could be eliminated by repeated granulation with a 20% aqueous solution of polymeric polycarboxylate (Sokalan® CP45, manufacturer BASF) under the same conditions with respect to supply air flow, supply air temperature and exhaust air temperature.
  • the polymer content in the granules thus obtained was 5% by weight.
  • the grain size of the granules was in the range of 0.4 mm to 2.0 mm, the bulk density was 700 g / l.
  • the granules were sieved and mixed the proportion with particle sizes of between 0.8 and 1.6 mm with the other detergent components of a detergent formulation.
  • the finished detergent could be used without Verldumpung.
  • a primary granulate was prepared from a 40% strength aqueous solution of the cationic nitrile used in Example 1 while being powdered with sodium cumenesulfonate powder.
  • the supply air volume was 21000 m 3 / h, the supply air temperature was 145 ° C.
  • the exhaust air temperature was adjusted to 65 ° C by the water evaporation of the solution.
  • the batch-operated fluidized bed was so full that the granulation was stopped.
  • the solidification was carried out with the 20% polymer solution used in Example 1 at 110 ° C supply air temperature.
  • the polymer content in the finished granules was 10% by weight.
  • the resulting granules were screened between 0.8 and 1.6 mm.
  • the bulk density was 730 g / l.
  • the finished granules were treated with conventional particulate detergent components to a particulate detergent.
  • a primary granulate was prepared from a 40% strength aqueous solution of the cationic nitrile used in Example 1 by powdering with silica powder (Thixosil® 38A).
  • the supply air volume was 20,000 m 3 / h, the supply air temperature was 140 ° C.
  • the exhaust air temperature was adjusted to 65 ° C by the water evaporation of the solution.
  • the batch-operated fluidized bed was so full that the granulation was stopped.
  • the solidification was carried out with the 20% polymer solution used in Example 1 at 110 ° C supply air temperature.
  • the polymer content in the finished granules was 7 wt .-%.
  • the resulting granules were screened between 0.8 and 1.6 mm.
  • the bulk density was 710 g / l.
  • the granules obtained according to Example 2 was reintroduced into the fluidized bed apparatus and there at the inlet air temperature and 65 ° C exhaust air at 65 ° C exhausted with the previously used 20% polymer solution from the side, so that a 20 wt% coating was formed.
  • the granules obtained according to Example 3 was reintroduced into the fluidized bed apparatus and sprayed there at 130 ° C supply air temperature and 65 ° C exhaust air with the 20% polymer solution from the side, so that a 10 wt% enclosure was formed.
  • a granulate containing trimethylammonium acetonitrile methosulfate was sprayed with the polymer solution used in Example 1 using two-fluid nozzles arranged at the bottom.
  • the supply air volume was 100 m 3 / h, the supply air temperature was 120 ° C and the exhaust air temperature 60 ° C.
  • the two-fluid nozzles were operated with warm air of 75 ° C; the air factor of the nozzles was 1.5 (kg air / kg solution).
  • the proportion of the coating layer on the finished granules was 10 wt .-%. Under the microscope, a complete coating layer was visible.
  • the granules obtained consisted of particles with diameters in the range of 0.8 mm to 2.0 mm and had a bulk density of 750 g / l.

Abstract

The present invention relates to methods for coating bleach activator-containing granules by treatment with an acidic aqueous consolidating solution, comprising polymeric polycarboxylate and/or alkali metal phosphonate as coating and consolidation active ingredient, with simultaneous drying in a fluidized-bed apparatus.

Description

Die Erfindung betrifft ein Verfahren zur Umhüllung bleichaktivatorhaltiger Granulate durch Behandeln mit einer sauren wäßrigen Verfestigerlösung, die als Umhüllungs- und Verfestigungswirkstoff polymeres Polycarboxylat und/oder Alkaliphosphonat enthält, bei gleichzeitiger Trocknung in einer Wirbelschichtapparatur.The invention relates to a process for coating bleach activator-containing granules by treatment with an acidic aqueous solidifier solution which contains polymeric polycarboxylate and / or alkali metal phosphonate as coating and solidification agent, with simultaneous drying in a fluidized bed apparatus.

Wasch- und Reinigungsmittel enthalten neben den für den Waschprozess unverzichtbaren Inhaltsstoffen wie Tensiden und Buildermaterialien in der Regel weitere Bestandteile, die man unter dem Begriff Waschhilfsstoffe zusammenfassen kann und die so unterschiedliche Wirkstoffgruppen wie Schaumregulatoren, Vergrauungsinhibitoren, Bleichmittel und Farbübertragungsinhibitoren umfassen. Zu derartigen Hilfsstoffen gehören auch Substanzen, welche die Tensidleistung durch den oxidativen Abbau von auf dem Textil befindlichen Anschmutzungen oder solchen in der Flotte unterstützen. Gleiches gilt sinngemäß auch für Reinigungsmittel für harte Oberflächen. So werden anorganische Persauerstoffverbindungen, insbesondere Wasserstoffperoxid und feste Persauerstoffverbindungen, die sich in Wasser unter Freisetzung von Wasserstoffperoxid lösen, wie Natriumperborat und Natriumcarbonat-Perhydrat, seit langem als Oxidationsmittel zu Desinfektions- und Bleichzwecken verwendet. Die Oxidationswirkung dieser Substanzen hängt in verdünnten Lösungen stark von der Temperatur ab; so erzielt man beispielsweise mit H2O2 oder Natriumperborat in alkalischen Bleichflotten erst bei Temperaturen oberhalb von etwa 60 °C eine ausreichend schnelle Bleiche verschmutzter Textilien. Bei niedrigeren Temperaturen kann die Oxidationswirkung der anorganischen Persauerstoffverbindungen durch Zusatz sogenannter Bleichakrivatoren verbessert werden, für die zahlreiche Vorschläge, vor allem aus den Stoffklassen der N- oder O-Acylverbindungen, beispielsweise mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin, acylierte Glykolurile, insbesondere Tetraacetylglykoluril, N-acylierte Hydantoine, Hydrazide, Triazole, Hydrotriazine, Urazole, Diketopiperazine, Sulfurylamide und Cyanurate, außerdem Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, Carbonsäureester, insbesondere Natrium-nonanoyloxy-benzolsulfonat, Natrium-isononanoyloxy-benzolsulfonat und acylierte Zuckerderivate, wie Pentaacetylglukose, in der Literatur bekannt geworden sind. Durch Zusatz dieser Substanzen kann die Bleichwirkung wäßriger Peroxidflotten so weit gesteigert werden, daß bereits bei Temperaturen unterhalb 60 °C im wesentlichen die gleichen Wirkungen wie mit der Peroxidflotte allein bei 95 °C eintreten.Detergents and cleaners in addition to the indispensable for the washing process ingredients such as surfactants and builders usually other ingredients that can be summarized under the term laundry aids and include as different drug groups such as foam regulators, graying inhibitors, bleaching agents and dye transfer inhibitors. Such auxiliaries also include substances which promote the surfactant performance by the oxidative degradation of soils or those present in the liquor. The same applies mutatis mutandis to cleaners for hard surfaces. Thus, inorganic peroxygen compounds, particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water releasing hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes. The oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H 2 O 2 or sodium perborate in alkaline bleaching liquors only at temperatures above about 60 ° C, a sufficiently fast bleaching of soiled textiles. At lower temperatures, the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for which numerous proposals, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N- acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfuryl amides and cyanurates, as well as carboxylic anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular Sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives such as pentaacetyl-glucose have been reported in the literature. By adding these substances, the bleaching action of aqueous peroxide liquors can be increased so much that even at temperatures below 60 ° C substantially the same effects as with the peroxide solution alone at 95 ° C occur.

Aus der europäischen Patentanmeldung EP 0 464 880 sind bleichverstärkende kationische Nitrile der allgemeinen Formel R'R"R"'N+-CR1R2-CN X- bekannt, in der R1 und R2 Wasserstoff oder ein Substituent mit mindestens einem C-Atom, R' eine C1-24-Alkyl-, Alkenyl- oder Alkylethergruppe oder eine Gruppe -CR1R2-CN, und R" sowie R'" jeweils eine C1-24-Alkyl- oder Hydroxyalkylgruppe ist und das Gegenanion X- ein organisches Sulfonat, ein organisches Sulfat oder ein Carboxylat ist.European Patent Application EP 0 464 880 discloses bleach-enhancing cationic nitriles of the general formula R'R "R"'N + -CR 1 R 2 -CN X - in which R 1 and R 2 are hydrogen or a substituent having at least one C Atom, R 'is a C 1-24 alkyl, alkenyl or alkyl ether group or a group -CR 1 R 2 -CN, and R "and R'" are each a C 1-24 alkyl or hydroxyalkyl group, and the Counteranion X - is an organic sulfonate, an organic sulfate or a carboxylate.

Aus der internationalen Patentanmeldung WO 98/23719 ist bekannt, daß Verbindungen der allgemeinen Formel R1R2R3N+CH2CN X- , in denen R1, R2 und R3 unabhängig voneinander eine Alkyl-, Alkenyl- oder Arylgruppe mit 1 bis 18 C-Atomen ist, wobei die Gruppen R2 und R3 auch Teil eines das N-Atom und gegebenenfalls weitere Heteroratome einschließenden Heterocyclusses sein können, und X ein ladungsausgleichendes Anion ist, als Aktivatoren für insbesondere anorganische Persauerstoffverbindungen in wäßrigen Reinigungslösungen für Geschirr verwendet werden können. Dadurch erhält man eine Verbesserung der Oxidations- und Bleichwirkung insbesondere anorganischer Persauerstoffverbindungen bei niedrigen Temperaturen unterhalb von 80 °C, insbesondere im Temperaturbereich von ca. 15 °C bis 55 °C. Die kationischen Nitrile sind jedoch insbesondere in Kombination mit weiteren Inhaltsstoffen von Wasch-und Reinigungsmitteln normalerweise wenig lagerstabil und insbesondere empfindlich gegenüber Feuchtigkeit.It is known from international patent application WO 98/23719 that compounds of the general formula R 1 R 2 R 3 N + CH 2 CN X - , in which R 1 , R 2 and R 3 independently of one another are an alkyl, alkenyl or aryl group with 1 to 18 carbon atoms, wherein the groups R 2 and R 3 may also be part of a heterocycle comprising the N-atom and optionally further heteroatoms, and X is a charge-balancing anion, as activators for in particular inorganic peroxygen compounds in aqueous cleaning solutions for Dishes can be used. This results in an improvement of the oxidation and bleaching action of inorganic peroxygen compounds in particular at low temperatures below 80 ° C, in particular in the temperature range of about 15 ° C to 55 ° C. However, the cationic nitriles, especially in combination with other ingredients of detergents and cleaners are usually less stable on storage and especially sensitive to moisture.

Aus der internationalen Patentanmeldung WO 00/50556 ist die Herstellung fester Zubereitungen, die kationisches Nitril und festes Trägermaterial enthalten, durch ein Vakuum-Dampftrocknungsverfahren in einem Mischer bekannt.International Patent Application WO 00/50556 discloses the preparation of solid formulations containing cationic nitrile and solid support by a vacuum steam-drying process in a mixer.

Die WO 99/14296 offenbart ein verfahren zur Umhüllung von Bleichaktivatorgrannlaten enthaltend Ammoniumnitril.WO 99/14296 discloses a process for coating bleach activator grannates containing ammonium nitrile.

Aufgabe der Erfindung war, em Verfahren zur Verfügung zu stellen, das es erlaubt, Granulate, die ein kationisches Nitril enthalten, so in teilchenförmige Wasch- und Reinigungsmittel einzuarbeiten, daß das kationische Nitril auch nach Lagerung möglichst keinen Verlust an bleichaktivierender Wirkung erleidet. Es wurde nun gefunden, daß die Herstellung von Zubereitungen, welche diese Forderung erfüllen, durch ein Wirbelschicht-Umhüllungsverfahren möglich ist. Auf diese Weise lässt sich in einfacher Weise eine schützende Umhüllung auf die Granulate aufbringen, ohne daß man eine Abnahme an Bleichaktivatorwirkung in Kauf nehmen muß.The object of the invention was to provide a process which makes it possible to use granules which contain a cationic nitrile in particulate detergents and cleaners to incorporate that the cationic nitrile suffers as possible no loss of bleach-activating effect even after storage. It has now been found that the preparation of formulations which meet this requirement is possible by a fluidized bed coating process. In this way, a protective coating can be applied to the granules in a simple manner, without having to accept a decrease in bleach activator effect.

Gegenstand der Erfindung ist ein Herstellung einer umhüllten teilchenförmigen Zubereitung, enthaltend eine Verbindung nach Formel(I),

Figure imgb0001
in der R1 für -H, -CH3, einen C2-24-Alkyl- oder -Alkenylrest, einen substituierten C2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH2, -CN, einen Alkyl- oder Alkenylarylrest mit einer C1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C1-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R2 und R3 unabhängig voneinander ausgewählt sind aus -CH2-CN, -CH3, -CH2-CH3, -CH2-CH2-CH3, -CH(CH3)-CH3, -CH2-OH, -CH2-CH2-OH, -CH(OH)-CH3, -CH2-CH2-CH2-OH, -CH2-CH(OH)-CH3, -CH(OH)-CH2-CH3, -(CH2CH2-O)nH mit n = 1, 2, 3, 4, 5 oder 6, R4 und R5 unabhängig voneinander eine voranstehend für R1, R2 oder R3 angegebene Bedeutung haben und X ein ladungsausgleichendes Anion ist, dadurch gekennzeichnet, daß man den in fester, insbesondere pulverförmiger Form vorliegenden Bleichaktivator gemäß Formel (I), gewünschtenfalls in Abmischung mit Bindemittel und/oder festem Füllstoff oder als vorgefertigtes Granulat, bei gleichzeitiger Trocknung in einer Wirbelschichtapparatur mit einer sauren wäßrigen Verfestigerlösung, die als Umhüllungs-und Verfestigungswirkstoff polymeres Polycarboxylat und/oder Phosphonsäure beziehungsweise Alkaliphosphonat enthält, besprüht.The invention relates to a preparation of a coated particulate preparation comprising a compound of formula (I),
Figure imgb0001
 in the R 1 is -H, -CH 3 , a C 2-24 alkyl or alkenyl radical, a substituted C 2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH 2 , -CN, an alkyl or alkenylaryl radical having a C 1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C 1-24 -alkyl group and at least one further substituent on the aromatic ring, R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3, -CH 2 -CH 3, -CH 2 -CH 2 -CH 3, -CH (CH 3) -CH 3, -CH 2 - OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH) - CH 2 -CH 3 , - (CH 2 CH 2 -O) n H with n = 1, 2, 3, 4, 5 or 6, R 4 and R 5 independently of one another above for R 1 , R 2 or R 3 have the meaning given and X is a charge-balancing anion, characterized in that the present in solid, in particular powder form bleach activator according to formula (I), gewünsch if appropriate in admixture with binder and / or solid filler or as prefabricated granules, with simultaneous drying in a fluidized bed apparatus with an acidic aqueous Verfestigerlösung containing as wrapping and solidification agent polymeric polycarboxylate and / or phosphonic acid or alkali metal phosphonate sprayed.

Dadurch gelingt es, den Bleichaktivator gemäß Formel (I) beziehungsweise ein diesen enthaltendes Teilchen mit einem Umhüllungsmaterial vollständig zu umhüllen. Außerdem wird bei Verwendung der polymeres Polycarboxylat und/oder Phosphonsäure beziehungsweise Allcaliphosphonat enthaltenden Lösung eine Zunahme der Kornfestigkeit des Bleichaktivatorteilchens beobachtet.This makes it possible to completely envelop the bleach activator according to formula (I) or a particle containing it with a wrapping material. Furthermore When using the polymeric polycarboxylate and / or phosphonic acid or allcaliphosphonate-containing solution, an increase in the grain strength of the bleach activator particle is observed.

Die Herstellung von Verbindungen gemäß Formel I kann nach bekannten Verfahren oder in Anlehnung an diese erfolgen, wie sie zum Beispiel in der genannten Patentliteratur oder von Abraham in Progr. Phys. Org. Chem. 11 (1974), S. lff, oder von Arnett in J. Am. Chem. Soc. 102 (1980), S. 5892ff. veröffentlicht worden sind.The preparation of compounds of the formula I can be carried out by known processes or by analogy thereto, as described, for example, in the abovementioned patent literature or by Abraham in Progr. Phys. Org. Chem. 11 (1974), p. Lff, or Arnett in J. Am. Chem. Soc. 102 (1980), p. 5892ff. have been published.

Bevorzugt ist die Verwendung von Verbindungen gemäß Formel I, in denen R1, R2 und R3 gleich sind. Unter diesen sind solche Verbindungen bevorzugt, in denen die genannten Reste Methylgruppen bedeuten. Andererseits sind auch solche Verbindungen bevorzugt, bei denen mindestens 1 oder 2 der genannten Reste Methylgruppen sind und die anderen mehrere C-Atome aufweisen.Preference is given to the use of compounds of the formula I in which R 1 , R 2 and R 3 are identical. Among these, preference is given to those compounds in which the radicals mentioned are methyl groups. On the other hand, those compounds are preferred in which at least 1 or 2 of the radicals mentioned are methyl groups and the others have a plurality of carbon atoms.

Zu den Anionen X- gehören insbesondere die Halogenide wie Chlorid, Fluorid, Iodid und Bromid, Nitrat, Hydroxid, Phosphat, Hydrogenphosphat, Dihydrogenphosphat, Pyrophosphat, Metaphosphat, Hexafluorophosphat, Carbonat, Hydrogencarbonat, Sulfat, Hydrogensulfat, C1-20-Alkylsulfat, C1-20-Alkylsulfonat, gegebenenfalls C1-18-alkylsubstituiertes Arylsulfonat, Chlorat, Perchlorat und/oder die Anionen von C1-24-Carbonsäuren wie Formiat, Acetat, Laurat, Benzoat oder Citrat, allein oder in beliebigen Mischungen.The anions X - include in particular the halides such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, metaphosphate, hexafluorophosphate, carbonate, bicarbonate, sulfate, hydrogen sulfate, C 1-20 alkyl sulfate, C 1-20 -alkyl sulfonate, optionally C 1-18 alkyl-substituted arylsulfonate, chlorate, perchlorate and / or the anions of C 1-24 carboxylic acids such as formate, acetate, laurate, benzoate or citrate, alone or in any mixtures.

Bevorzugt sind Verbindungen gemäß Formel I, in denen X- Chlorid, Sulfat, Hydrogensulfat, Ethosulfat, C12/18-, C12/16- oder C13/15-Alkylsulfat, Laurylsulfat, Dodecylbenzolsulfonat, Toluolsulfonat, Cumolsulfonat, Xylolsulfonat oder Methosulfat oder Mischungen aus diesen ist. Unter Toluolsulfonat beziehungsweise Cumolsulfonat werden dabei das Anion des ortho-, meta- oder para-Isomeren der Methylbenzolsulfonsäure beziehungsweise Isopropylbenzolsulfonsäure und beliebige Mischungen aus diesen verstanden. Para-Isopropylbenzolsulfonsäure ist besonders bevorzugt.Preference is given to compounds of the formula I in which X - chloride, sulfate, hydrogensulfate, ethosulfate, C 12/18 , C 12/16 or C 13/15 -alkyl sulfate, lauryl sulfate, dodecylbenzenesulfonate, toluenesulfonate, cumene sulfonate, xylenesulfonate or methosulfate or Mixtures of these is. By toluenesulfonate or cumene sulfonate is meant the anion of the ortho, meta or para isomer of methylbenzenesulfonic acid or isopropylbenzenesulfonic acid and any mixtures thereof. Para-isopropylbenzenesulfonic acid is particularly preferred.

Die Verbindung gemäß allgemeiner Formel I kann in fester Form als solche oder teilchenförmig konfektioniert, das heißt aufgebracht auf ein organisches und/oder anorganisches Trägermaterial, als Ausgangsmaterial im erfindungsgemäßen Umhüllungsverfahren eingesetzt werden. Dabei kann das Aufbringen der Verbindung gemäß Formel (I) auf das Trägermaterial derart geschehen, daß man in eine Lösung der Verbindung gemäß Formel I, wie sie im Rahmen deren Herstellung anfällt, das Trägermaterial einrührt und das gegebenenfalls wäßrige Lösungsmittel im Vakuum, gewünschtenfalls bei erhöhter Temperatur, abzieht. Man kann die Lösung der Verbindung gemäß Formel I aber auch auf das Trägermaterial aufsprühen und dabei oder gegebenenfalls anschließend einem Trocknungsprozeß unterwerfen. Auch das Umhüllen der gemäß den in den deutschen Patentanmeldungen DE 197 40 668 oder DE 197 40 671 offenbarten Verfahren hergestellten Bleichaktivatorgranulate ist durch das erfindungsgemäße Verfahren möglich und stellt eine bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens dar. Es ist bevorzugt, wenn die durch den Konfektionierungsprozeß entstehenden Teilchen einen Durchmesser im Bereich von 0,4 mm bis 3 mm aufweisen. Als Trägermaterialien kommen alle Substanzen in Betracht, die nicht in unzumutbar negativer Weise mit der Verbindung gemäß Formel I wechselwirken, zum Beispiel Alkalicumolsulfonat, Tenside, organische Säuren und Polymere, Alkalicarbonate, Alkalisulfate, Alkalihydrogensulfate, Alkalihydrogencarbonate, Alkaliphosphate, Alkalidihydrogenphosphate, Dialkalihydrogenphosphate und Alkalisilikate und deren Mischungen. Es werden vorzugsweise solche Trägermaterialien verwendet, deren innere Oberfläche im Bereich von 10 m2/g bis 500 m2/g, insbesondere 100 m2/g bis 450 m2/g liegt. Zu den im Rahmen der vorliegenden Erfindung besonders geeigneten silikatischen Trägermaterialien gehören beispielsweise sowohl Alkalisilikate wie auch Kieselsäuren, Kieselgele und Tone sowie deren Gemische. Das Trägermaterial ist jedoch vorzugsweise frei von Zeolithen. Silikatenthaltendes Trägermaterial enthält neben der Silikat-Komponente gegebenenfalls weitere teilchenförmige inerte Bestandteile, welche die Stabilität der Verbindungen gemäß Formel I nicht unzumutbar beeinträchtigen. Kieselsäuren, die nach einem Thermalprozeß (Flammenhydrolyse von SiCl4) hergestellt worden sind (sogenannte pyrogene Kieselsäuren), sind ebenso brauchbar wie durch Naßverfahren hergestellte Kieselsäuren. Kieselgele sind colloidale Kieselsäuren mit elastischer bis fester Konsistenz und einer weitgehend losen Porenstruktur, wodurch sich ein hohes Flüssiglceitsaufnahmevermögen ergibt. Sie können durch Einwirken von Mineralsäuren auf Wasserglas hergestellt werden. Tone sind natürlich vorkommende kristalline oder amorphe Silikate des Aluminiums, Eisens, Magnesiums, Calciums, Kaliums und Natriums, zum Beispiel Kaolin, Talkum, Pyrophyllit, Attapulgit, Sepiolit, Montmorillionit und Bauxit. Auch der Einsatz von Aluminiumsilikat als Trägermaterial oder als Komponente einer Trägermaterialmischung ist möglich. Vorzugsweise weist das Trägermaterial Teilchengrößen im Bereich von 100 µm bis 1,5 mm auf.The compound according to general formula I can be formulated in solid form as such or particulate, that is applied to an organic and / or inorganic carrier material, are used as starting material in the coating method according to the invention. In this case, the application of the compound of formula (I) can be carried out on the support material such that stirred into a solution of the compound of formula I, as obtained in the preparation thereof, the support material and the optionally aqueous solvent in vacuo, if desired at elevated Temperature, subtracts. However, the solution of the compound according to formula I can also be sprayed onto the support material and, if appropriate, subsequently subjected to a drying process. The wrapping of the bleach activator granules prepared according to the processes disclosed in German patent applications DE 197 40 668 or DE 197 40 671 is also possible by the process according to the invention and represents a preferred embodiment of the process according to the invention. It is preferred if the particles formed by the fabrication process have a diameter in the range of 0.4 mm to 3 mm. Suitable carrier materials are all substances which do not interact in unduly negative ways with the compound according to formula I, for example alkali metal sulfonate, surfactants, organic acids and polymers, alkali metal carbonates, alkali metal sulfates, alkali metal hydrogensulfates, alkali metal bicarbonates, alkali metal phosphates, alkali metal hydrogenphosphates, dialkalihydrogenphosphates and alkali metal silicates and theirs mixtures. Preferably, such support materials are used whose inner surface is in the range of 10 m 2 / g to 500 m 2 / g, in particular 100 m 2 / g to 450 m 2 / g. The silicate carrier materials which are particularly suitable for the purposes of the present invention include, for example, both alkali metal silicates and also silicic acids, silica gels and clays as well as mixtures thereof. However, the carrier material is preferably free of zeolites. Silicate-containing support material optionally contains, in addition to the silicate component, further particulate inert constituents which do not affect the stability of the compounds according to formula I unreasonably. Silicas prepared by a thermal process (flame hydrolysis of SiCl 4 ) (so-called fumed silicas) are useful as well as silicas prepared by wet processes. Silica gels are colloidal silicas with elastic to solid consistency and a largely loose pore structure, resulting in a high Flüssiglceitsaufnahmevermögen. They can be prepared by the action of mineral acids on water glass become. Clays are naturally occurring crystalline or amorphous silicates of aluminum, iron, magnesium, calcium, potassium and sodium, for example kaolin, talc, pyrophyllite, attapulgite, sepiolite, montmorillonite and bauxite. The use of aluminum silicate as a carrier material or as a component of a carrier material mixture is possible. The carrier material preferably has particle sizes in the range from 100 μm to 1.5 mm.

In einer weiteren bevorzugten Ausführungsform der Erfindung geht man so vor, daß man zunächst die Schritte

  • a) Ansatz einer wäßrigen Lösung, enthaltend kationisches Nitril, vorzugsweise in Mengen von 10 Gew.-% bis 90 Gew.-%, insbesondere von 15 Gew.-% bis 50 Gew.-%, und gegebenenfalls Alkalicumolsulfonat, insbesondere Natriumcumolsulfonat,
  • b) gegebenenfalls Einstellen der Lösung auf einen sauren pH-Wert, insbesondere durch Zugabe von Schwefelsäure und/oder Zitronensäure
  • c) Verdüsung und Trocknung der Lösung in einer Wirbelschichtapparatur,
  • d) gegebenenfalls Abpuderung des so erhaltenen Primärgranulats unter Einsatz von Kieselsäure, Zeolith und/oder Alkalicumolsulfonat, insbesondere Na-Cumolsulfonat, in der Wirbelschicht,
durchführt und das so erhaltene gegebenenfalls abgepuderte Granulat mit der wäßrigen Verfestiger- und Umhüllungslösung bei gleichzeitiger Trocknung in der gleichen oder gegebenenfalls einer nachgeschalteten zweiten Wirbelschichtapparatur besprüht. Danach kann das Granulat aus der Wirbelschichtapparatur ausgetragen und gegebenenfalls in Gutkorn und Grob-/Feinkorn, insbesondere durch Sieben, getrennt werden. Gegebenenfalls kann sich die Rückführung von Feinkorn und/oder aufgemahlenem Grobkorn in die Wirbelschicht in Schritt c) und/oder die Rückführung von Feinkorn und/oder aufgemahlenem Grobkorn in den Abpuderungsschritt d) anschließen.In a further preferred embodiment of the invention, the procedure is that of initially carrying out the steps
  • a) preparation of an aqueous solution containing cationic nitrile, preferably in amounts of from 10% by weight to 90% by weight, in particular from 15% by weight to 50% by weight, and optionally alkali metal sulfonate, in particular sodium cumene sulfonate,
  • b) optionally adjusting the solution to an acidic pH, in particular by adding sulfuric acid and / or citric acid
  • c) atomization and drying of the solution in a fluidized bed apparatus,
  • d) optionally powdering of the resulting primary granules using silica, zeolite and / or Alkalicumolsulfonat, in particular Na-cumene sulfonate, in the fluidized bed,
and spraying the optionally powdered granules thus obtained with the aqueous solidifying and coating solution with simultaneous drying in the same or optionally a downstream second fluidized bed apparatus. Thereafter, the granules can be discharged from the fluidized bed apparatus and optionally in good grain and coarse / fine grain, in particular by sieving, separated. Optionally, the recirculation of fine grain and / or ground coarse grain in the fluidized bed in step c) and / or the return of fine grain and / or ground coarse grain in the Abpuderungsschritt d) follow.

Das durch das erfindungsgemäße Verfahren erhältliche umhüllte Bleichaktivatorgranulat beziehungsweise der Gutkornanteil daran weist vorzugsweise mittlere Teilchendurchmesser im Bereich von 0,2 mm bis 2,5 mm, insbesondere im Bereich von 0,4 mm bis 2,0 mm auf. Sein Schüttgewicht liegt vorzugsweise im Bereich von 300 g/l bis 1000 g/l, insbesondere im Bereich von 400 g/l bis 800 g/l. Der Anteil an Verbindung gemäß Formel (I) liegt vorzugsweise im Bereich von 10 Gew.-% bis 90 Gew.%, insbesondere von 15 Gew.-% bis 50 Gew.-%. Es wird vorzugsweise zur Herstellung teilchenförmiger Wasch- oder Reinigungsmittel verwendet.The coated bleach activator granules obtainable by the process according to the invention or the proportion of good grain therefrom preferably has average particle diameters in the range from 0.2 mm to 2.5 mm, in particular in the range from 0.4 mm to 2.0 mm. Its bulk density is preferably in the range of 300 g / l to 1000 g / l, in particular in the range of 400 g / l to 800 g / l. The proportion of compound according to formula (I) is preferably in the range from 10% by weight to 90% by weight, in particular from 15% to 50% by weight. It is preferably used to prepare particulate detergents or cleaners.

In einem erfindungsgemäßen Verfahren einsetzbare Wirbelschichtvornchtungen sind beispielsweise aus der europäischen Patentschrift EP 0 603 207 B1 oder der deutschen Patentanmeldung DE 197 50 424 bekannt. Zur verbesserten Vermeidung des Durchfallens der Granulate durch die im Anströmboden befindlichen Durchtrittsöffnungen, wodurch sie in Kontakt mit Oberflächen relativ hoher Temperatur kämen, können die Durchtrittsöffnungen von einem Gitternetz, insbesondere mit Maschenweiten kleiner als 600 µm, bedeckt sein. Dabei kann das Gitternetz innerhalb oder oberhalb der Durchtrittsöffnungen angeordnet sein. Vorzugsweise liegt das Gitternetz jedoch unmittelbar unterhalb der Durchtrittsöffnungen des Anströmbodens, wie das im Prinzip aus der deutschen Patentanmeldung DE 197 50 424 bekannt ist. In einer praktischen Ausführungsform kann auf die Unterseite eines an sich bekannten Anströmbodens eine Metall-Gaze mit der entsprechenden Maschenweite aufgesintert oder auf andere Weise befestigt sein. Die Metall-Gaze besteht vorzugsweise aus dem gleichen Material wie der Anströmboden, insbesondere aus Edelstahl. Mit dem feinmaschigen Gitternetz wird ein Durchfallen von Partikeln insbesondere bei einem unplanmäßigen Stillstand der Anlage, aber auch insbesondere im Falle besonders schwerer Partikel mit Schüttgewichten um 1000 g/l auch während des Betriebes, verhindert. Vorzugsweise liegt die Maschenweite des genannten Gitternetzes zwischen 200 und 400 µm. Von Vorteil ist es außerdem, wenn der eingesetzte Anströmboden einen Druckverlust von höchstens 10 mbar und insbesondere höchstens 6 mbar hat.Wirbelschichtvornchtungen which can be used in a process according to the invention are known, for example, from European Patent EP 0 603 207 B1 or German Patent Application DE 197 50 424. For improved prevention of the granules from falling through the passage openings in the distributor plate, whereby they would come into contact with surfaces of relatively high temperature, the passage openings can be covered by a grid, in particular with mesh sizes smaller than 600 μm. In this case, the grid can be arranged within or above the passage openings. However, the grid is preferably located immediately below the openings of the inflow base, as is known in principle from German Patent Application DE 197 50 424. In a practical embodiment, a metal gauze with the appropriate mesh size can be sintered or otherwise secured to the underside of a known inflow base. The metal gauze preferably consists of the same material as the distributor plate, in particular of stainless steel. With the fine-meshed grid is falling through of particles especially at an unscheduled shutdown of the system, but also in particular in the case of very heavy particles with bulk densities of 1000 g / l, even during operation, prevented. Preferably, the mesh size of said grid is between 200 and 400 microns. It is also advantageous if the inlet plate used has a pressure drop of at most 10 mbar and in particular at most 6 mbar.

Erfindungsgemäß wird die wäßrige Verfestiger- und Umhüllungslösung in einem Wirbelschichtapparat aufgebracht. Als Verfestiger- und Umhüllungswirkstoff kommen polymere Polycarboxylate, insbesondere Polymerisationsprodukte von Acrylsäure, Methacrylsäure oder Maleinsäure, oder Copolymerisate aus mindestens zweien von diesen, in Frage, die in vollständig oder teilweise neutralisierter Form, insbesondere in Form der Alkalisalze, eingesetzt werden können. Alternativ oder zusätzlich zu polymerem Polycarboxylat kann Phosphonsäure beziehungsweise Alkaliphosphonat zum Einsatz kommen. In dem genannten Alkalisalzen ist Natrium das jeweils bevorzugte Alkalimetall. Bevorzugt ist die Einstellung der Lösung auf eine möglichst niedrige Viskosität zur guten Tropfenverteilung bei der Verdüsung in die Wirbelschicht bei gleichzeitiger Trocknung. Der pH-Wert der Lösung wird, falls er nicht von vorneherein im sauren Bereich liegt, durch Zugabe systemverträglicher Säuren, insbesondere durch Zugabe von Schwefelsäure und/oder Zitronensäure, auf saure Werte, insbesondere auf Werte im pH-Bereich von 4 bis 4,4, eingestellt. Es ist bevorzugt, daß man - bezogen auf zu umhüllendes Granulat - so viel der wäßrigen Lösung aufsprüht, daß die Umhüllung 1 Gew.-% bis 25 Gew.-%, insbesondere 2 Gew.-% bis 15 Gew.-% ausmacht.According to the invention, the aqueous solidifying and coating solution is applied in a fluidized bed apparatus. Suitable solidifying and coating agents are polymeric polycarboxylates, in particular polymerization products of acrylic acid, methacrylic acid or maleic acid, or copolymers of at least two of these, which can be used in completely or partially neutralized form, in particular in the form of alkali metal salts. Alternatively or in addition to polymeric polycarboxylate, phosphonic acid or alkali metal phosphonate can be used. In the alkali metal salt mentioned, sodium is the particular preferred alkali metal. The setting of the solution is preferably as low as possible Viscosity for good droplet distribution during atomization in the fluidized bed with simultaneous drying. The pH of the solution, if it is not from the outset in the acidic range, by addition of system-compatible acids, in particular by addition of sulfuric acid and / or citric acid, to acid values, in particular to values in the pH range of 4 to 4.4 , discontinued. It is preferred that, based on the granules to be coated, so much of the aqueous solution is sprayed on that the coating constitutes 1% by weight to 25% by weight, in particular 2% by weight to 15% by weight.

Anschließend kann das Granulat in im Prinzip bekannter Weise aus der Wirbelschicht ausgetragen und gegebenenfalls nach der Teilchengröße klassiert werden, wobei wie oben ausgeführt unerwünscht kleine Teilchen (Feinkorn) und unerwünscht große Teilchen (Grobkorn) nach einem Mahlschritt gegebenenfalls in einen Granulationsprozeß zurückgeführt werden können. In einer besonderen Ausführungsform des erfindungsgemäßen Verfahrens kann das klassierte Gutkorn erneut in eine Wirbelschichtapparatur eingebracht und auf es Verfestiger- und Umhüllungslösung aufgesprüht werden, um die Produkteigenschaften des Granulats falls nötig noch weiter zu verbessern.Subsequently, the granules can be discharged in a manner known in principle from the fluidized bed and optionally classified according to the particle size, wherein as stated above undesirably small particles (fine particles) and undesirably large particles (coarse grains) can optionally be returned to a granulation process after a grinding step. In a particular embodiment of the process according to the invention, the classified good grain can be re-introduced into a fluidized bed apparatus and sprayed onto it solidifying and coating solution in order to further improve the product properties of the granules if necessary.

Ein nach dem erfindungsgemäßen Verfahren umhülltes Granulat ist lagerstabil, gut rieselfähig und von ausreichender Kornstabilität, um in gebräuchlicher Weise mit anderen teilchenförmigen Bestandteilen von Wasch- oder Reinigungsmitteln vermischt werden zu können. Nach dem erfindungsgemäßen Verfahren erhältliche umhüllte Granulate werden in insbesondere teilchenförmigen Wasch- oder Reinigungsmitteln vorzugsweise in solchen Mengen eingesetzt, daß diese Mittel Gehalte von 0,1 Gew.-% bis 10 Gew.-%, insbesondere von 0,2 Gew.-% bis 7 Gew.-% an Bleichaktivator gemäß Formel (I) aufweisen.A coated by the process according to the invention granules is storage stable, good free-flowing and of sufficient grain stability to be mixed in a conventional manner with other particulate components of detergents or cleaning agents can. Enveloped granules obtainable by the process according to the invention are preferably used in particular particulate detergents or cleaners in amounts such that these compositions have contents of from 0.1% by weight to 10% by weight, in particular from 0.2% by weight to 7 wt .-% of bleach activator according to formula (I).

BeispieleExamples Beispiel 1example 1

In einer Wirbelschichtapparatur (Glatt® AGT 400 mit 40 cm Durchmesser) wurden bei 400 m3/h Zuluftstrom, einer Zulufttemperatur von 95 °C und einer Ablufttemperatur von 55 °C aus einer homogenen wäßrigen Lösung von Trimethylammoniumacetonitril-methosulfat und Na-Cumolsulfonat (Massenverhältnis 1:1, Trockensubstanzanteil 30 %) bei einem Durchsatz der Lösung von 3 kg/h innerhalb von 5 h ein Granulat hergestellt, das noch sehr klebrig war. Die Klebrigkeit konnte durch eine nochmalige Granulation mit einer 20 %-igen wäßrigen Lösung von polymerem Polycarboxylat (Sokalan® CP45, Hersteller BASF) bei gleichen Bedingungen bezüglich Zuluftstrom, Zulufttemperatur und Ablufttemperatur beseitigt werden. Der Polymeranteil im dem so erhaltenen Granulat betrug 5 Gew.%. Die Korngröße der Granulate lag im Bereich von 0,4 mm bis 2,0 mm, das Schüttgewicht betrug 700 g/l. Anschließend wurde das Granulat gesiebt und der Anteil mit Korngrößen von zwischen 0,8 und 1,6 mm mit den anderen Waschmittelkomponenten einer Waschmittelrezeptur vermischt. Das fertige Waschmittel konnte ohne Verldumpung eingesetzt werden.In a fluidized bed apparatus (Glatt® AGT 400 with 40 cm diameter) were at 400 m 3 / h supply air, a supply air temperature of 95 ° C and an exhaust air temperature of 55 ° C from a homogeneous aqueous solution of trimethylammoniumacetonitrile methosulfate and sodium cumenesulfonate (mass ratio 1: 1, dry matter content 30%) produced at a throughput of the solution of 3 kg / h within 5 h granules, which was still very sticky. The stickiness could be eliminated by repeated granulation with a 20% aqueous solution of polymeric polycarboxylate (Sokalan® CP45, manufacturer BASF) under the same conditions with respect to supply air flow, supply air temperature and exhaust air temperature. The polymer content in the granules thus obtained was 5% by weight. The grain size of the granules was in the range of 0.4 mm to 2.0 mm, the bulk density was 700 g / l. Subsequently, the granules were sieved and mixed the proportion with particle sizes of between 0.8 and 1.6 mm with the other detergent components of a detergent formulation. The finished detergent could be used without Verldumpung.

Beispiel 2Example 2

In einer Wirbelschichtapparatur mit 1,8 m Durchmesser (Glatt® AGT 1800) wurde ein Primärgranulat aus einer 40 %-igen wäßrigen Lösung des in Beispiel 1 eingesetzten kationischen Nitrils unter Abpuderung mit Na-Cumolsulfonat - Pulver hergestellt. Die Zuluftmenge lag bei 21000 m3/h, die Zulufttemperatur betrug 145 °C. Die Ablufttemperatur wurde auf 65°C durch die Wasserverdampfung der Lösung eingestellt. Nach 1 h war die im Batch betriebene Wirbelschicht so voll, daß die Granulation beendet wurde. Die Verfestigung wurde mit der in Beispiel 1 eingesetzten 20 %-igen Polymerlösung bei 110 °C Zulufttemperatur durchgeführt. Der Polymergehalt im fertigen Granulat lag bei 10 Gew.%. Das erhaltene Granulat wurde zwischen 0,8 und 1,6 mm abgesiebt. Das Schüttgewicht lag bei 730 g/l.In a fluidized-bed apparatus with a diameter of 1.8 m (Glatt® AGT 1800), a primary granulate was prepared from a 40% strength aqueous solution of the cationic nitrile used in Example 1 while being powdered with sodium cumenesulfonate powder. The supply air volume was 21000 m 3 / h, the supply air temperature was 145 ° C. The exhaust air temperature was adjusted to 65 ° C by the water evaporation of the solution. After 1 h, the batch-operated fluidized bed was so full that the granulation was stopped. The solidification was carried out with the 20% polymer solution used in Example 1 at 110 ° C supply air temperature. The polymer content in the finished granules was 10% by weight. The resulting granules were screened between 0.8 and 1.6 mm. The bulk density was 730 g / l.

Das fertige Granulat wurde mit üblichen teilchenförmigen Waschmittelkomponenten zu einem teilchenförmigen Waschmittel aufbereitet.The finished granules were treated with conventional particulate detergent components to a particulate detergent.

Beispiel 3Example 3

In einer Wirbelschichtapparatur mit 1,8 m Durchmesser (Glatt® AGT 1800) wurde ein Primärgranulat aus einer 40 %-igen wäßrigen Lösung des in Beispiel 1 eingesetzten kationischen Nitrils unter Abpuderung mit Kieselsäure-Pulver (Thixosil® 38A) hergestellt. Die Zuluftmenge lag bei 20000 m3/h, die Zulufttemperatur betrug 140 °C. Die Ablufttemperatur wurde auf 65°C durch die Wasserverdampfung der Lösung eingestellt. Nach 1 h war die im Batch betriebene Wirbelschicht so voll, daß die Granulation beendet wurde. Die Verfestigung wurde mit der in Beispiel 1 eingesetzten 20 %-igen Polymerlösung bei 110 °C Zulufttemperatur durchgeführt. Der Polymergehalt im fertigen Granulat lag bei 7 Gew.-%. Das erhaltene Granulat wurde zwischen 0,8 und 1,6 mm abgesiebt. Das Schüttgewicht lag bei 710 g/l.In a fluidized bed apparatus with a diameter of 1.8 m (Glatt® AGT 1800), a primary granulate was prepared from a 40% strength aqueous solution of the cationic nitrile used in Example 1 by powdering with silica powder (Thixosil® 38A). The supply air volume was 20,000 m 3 / h, the supply air temperature was 140 ° C. The exhaust air temperature was adjusted to 65 ° C by the water evaporation of the solution. After 1 h, the batch-operated fluidized bed was so full that the granulation was stopped. The solidification was carried out with the 20% polymer solution used in Example 1 at 110 ° C supply air temperature. The polymer content in the finished granules was 7 wt .-%. The resulting granules were screened between 0.8 and 1.6 mm. The bulk density was 710 g / l.

Beispiel 4Example 4

Das gemäß Beispiel 2 erhaltene Granulat wurde erneut in die Wirbelschichtapparatur eingeführt und dort bei 130 °C Zulufttemperatur und 65 °C Abluft mit der zuvor bereits eingesetzten 20 %-igen Polymerlösung von der Seite bedüst, so daß eine 20 gewichtsprozentige Umhüllung entstand. Ebenso wurde das gemäß Beispiel 3 erhaltene Granulat erneut in die Wirbelschichtapparatur eingeführt und dort bei 130 °C Zulufttemperatur und 65 °C Abluft mit der 20 %-igen Polymerlösung von der Seite bedüst, so daß eine 10 gewichtsprozentige Umhüllung entstand.The granules obtained according to Example 2 was reintroduced into the fluidized bed apparatus and there at the inlet air temperature and 65 ° C exhaust air at 65 ° C exhausted with the previously used 20% polymer solution from the side, so that a 20 wt% coating was formed. Likewise, the granules obtained according to Example 3 was reintroduced into the fluidized bed apparatus and sprayed there at 130 ° C supply air temperature and 65 ° C exhaust air with the 20% polymer solution from the side, so that a 10 wt% enclosure was formed.

Beispiel 5Example 5

In einer Wirbelschichtapparatur mit 15 cm Durchmesser (Glatt® AGT 1800) wurde ein Trimethylammoniumacetonitril-methosulfat enthaltendes Granulat mit der in Beispiel 1 eingesetzten Polymerlösung unter Einsatz unten angeordneter Zweistoffdüsen besprüht. Die Zuluftmenge lag bei 100 m3/h, die Zulufttemperatur betrug 120 °C und die Ablufttemperatur 60 °C. Die Zweistoffdüsen wurden mit Warmluft von 75 °C betrieben; der Luftfaktor der Düsen betrug 1,5 (kg Luft/kg Lösung). Der Anteil der Umhüllungsschicht am fertigen Granulat lag bei 10 Gew.-%. Unter dem Mikroskop war eine vollständige Coatingschicht zu erkennen. Das erhaltene Granulat bestand aus Teilchen mit Durchmessern im Bereich von 0,8 mm bis 2,0 mm und besaß ein Schüttgewicht von 750 g/l.In a fluidized bed apparatus with 15 cm diameter (Glatt® AGT 1800), a granulate containing trimethylammonium acetonitrile methosulfate was sprayed with the polymer solution used in Example 1 using two-fluid nozzles arranged at the bottom. The supply air volume was 100 m 3 / h, the supply air temperature was 120 ° C and the exhaust air temperature 60 ° C. The two-fluid nozzles were operated with warm air of 75 ° C; the air factor of the nozzles was 1.5 (kg air / kg solution). The proportion of the coating layer on the finished granules was 10 wt .-%. Under the microscope, a complete coating layer was visible. The granules obtained consisted of particles with diameters in the range of 0.8 mm to 2.0 mm and had a bulk density of 750 g / l.

Claims (12)

  1. Method for producing a coated particulate preparation, comprising a compound according to formula (I),
    Figure imgb0003
     in which R1 is -H, -CH3, a C2-24-alkyl or -alkenyl radical, a substituted C2-24-alkyl or -alkenyl radical with at least one substituent from the group -Cl, -Br, -OH, -NH2, -CN, an alkyl or alkenylaryl radical with a C1-24-alkyl group, or is a substituted alkyl or alkenylaryl radical with a C1-24-alkyl group and at least one further substituent on the aromatic ring, R2 and R3, independently of one another, are chosen from -CH2-CN, -CH3, -CH2-CH3, -CH2-CH2-CH3, -CH(CH3)-CH3, -CH2-OH, -CH2-CH2-OH, -CH(OH)-CH3, -CH2-CH2-CH2-OH, -CH2-CH(OH)-CH3, -CH(OH)-CH2-CH3, -(CH2CH2-O)nH where n = 1, 2, 3, 4, 5 or 6, R4 and R5, independently of one another, have a meaning given above for R1, R2 or R3, and X is a charge-balancing anion, characterized in that the bleach activator according to formula (I) present in solid, in particular pulverulent, form is sprayed, if desired in a mixture with binders and/or a solid filler or in the form of preprepared granules, with simultaneous drying in a fluidized-bed apparatus with an acidic aqueous solution which comprises, as coating and consolidation active ingredient, polymeric polycarboxylate and/or phosphonic acid or alkali metal phosphonate.
  2. Method according to Claim 1, characterized in that the pH of the aqueous solution is adjusted to acidic values by adding sulphuric acid and/or citric acid.
  3. Method according to Claim 1 or 2, characterized in that the aqueous solution has a pH in the range from 4 to 4.4.
  4. Method according to any of Claims 1 to 3, characterized in that - based on the granules to be coated, the amount of aqueous solution sprayed is such that the coating constitutes 1% by weight to 25% by weight, in particular 2% by weight to 15% by weight.
  5. Method according to any of Claims 1 to 4, characterized in that the coating and consolidation active ingredient used is a polymerization product of acrylic acid, methacrylic acid or maleic acid, or a copolymer of at least two of these and/or phosphonic acid or alkali metal phosphonate.
  6. Method according to any of Claims 1 to 5, characterized in that a compound according to formula I is used in which R1, R2 and R3 are identical and, in particular, are methyl groups.
  7. Method according to any of Claims 1 to 6, characterized in that a compound according to formula I is used in which the anion X- is halide, such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate, hydrogenphosphate, dihydrogenphosphate, pyrophosphate, metaphosphate, hexafluorophosphate, carbonate, hydrogencarbonate, sulphate, hydrogensulphate, C1-20-alkyl sulphate, C1-20-alkylsulphonate, optionally C1-18-alkylsubstituted arylsulphonate, chlorate, perchlorate and/or an anion of C1-24-carboxylic acid, such as formate, acetate, laurate, benzoate or citrate, alone or in any mixtures.
  8. Method according to Claim 7, characterized in that a compound according to formula I is used in which the anion X- is chloride, sulphate, hydrogensulphate, methosulphate, ethosulphate, C12/18-, C12/16- or C13/15-alkyl sulphate, lauryl sulphate, dodecylbenzenesulphonate, toluenesulphonate, cumenesulphonate, xylenesulphonate or mixtures thereof.
  9. Method according to any of Claims 1 to 8, characterized in that the coated particulate preparation has an average particle diameter in the range from 0.2 mm to 2.5 mm, in particular in the range from 0.4 mm to 2.0 mm.
  10. Method according to any of Claims 1 to 9, characterized in that the bulk density of the coated particulate preparation is in the range from 300 g/l to 1000 g/l, in particular in the range from 400 g/l to 800 g/l.
  11. Method according to any of Claims 1 to 10, characterized in that the proportion of compound according to formula (I) in the coated particulate preparation is in the range from 10% by weight to 90% by weight, in particular from 15% by weight to 50% by weight.
  12. Use of the coated particulate preparation obtainable by the method according to any of Claims 1 to 11 for producing particulate detergents or cleaners.
EP02804191A 2001-12-04 2002-11-22 Method for producing coated bleach activator granules Expired - Lifetime EP1451284B1 (en)

Applications Claiming Priority (3)

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DE10159388 2001-12-04
DE10159388A DE10159388A1 (en) 2001-12-04 2001-12-04 Process for the production of coated bleach activator granules
PCT/EP2002/013127 WO2003048290A1 (en) 2001-12-04 2002-11-22 Method for producing coated bleach activator granules

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EP1451284B1 true EP1451284B1 (en) 2006-05-03

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JP (1) JP2005514467A (en)
AT (1) ATE325182T1 (en)
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DE10314441A1 (en) * 2003-03-31 2004-10-21 Henkel Kgaa Bleach activator compounds
DE102004012568A1 (en) * 2004-03-12 2005-12-08 Henkel Kgaa Bleach activators and process for their preparation
DE102016015660A1 (en) * 2016-12-31 2018-07-05 Weylchem Wiesbaden Gmbh Granules, their use and detergents and cleaning agents containing them

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DE4127323A1 (en) * 1991-08-20 1993-02-25 Henkel Kgaa METHOD FOR PRODUCING TENSIDE GRANULES
WO1994003395A1 (en) * 1992-08-01 1994-02-17 The Procter & Gamble Company Peroxyacid bleach precursor compositions
US6183665B1 (en) * 1995-06-07 2001-02-06 The Clorox Company Granular N-alkyl ammonium acetonitrile compositions
US5814242A (en) * 1995-06-07 1998-09-29 The Clorox Company Mixed peroxygen activator compositions
US5888419A (en) * 1995-06-07 1999-03-30 The Clorox Company Granular N-alkyl ammonium acetontrile compositions
US6235218B1 (en) * 1995-06-07 2001-05-22 The Clorox Company Process for preparing N-alkyl ammonium acetonitrile compounds
DE19649375A1 (en) * 1996-11-29 1998-06-04 Henkel Kgaa Acetonitrile derivatives as bleach activators in detergents
DE19740668A1 (en) * 1997-09-16 1999-03-18 Clariant Gmbh Storage-stable bleach activator granulate obtained using acid-modified layered silicate as binder
DE19740671A1 (en) * 1997-09-16 1999-03-18 Clariant Gmbh Bleach activator granulate containing ammonium nitrile and layered silicate
DE19740669A1 (en) * 1997-09-16 1999-03-18 Clariant Gmbh Coated ammonium nitrile bleach activator granules used in e.g. detergents
DE19750424A1 (en) * 1997-11-14 1999-05-20 Henkel Kgaa Production of detergent granules with high bulk density
DE19841184A1 (en) * 1998-09-09 2000-03-16 Clariant Gmbh bleach activator
JP2002532615A (en) * 1998-12-15 2002-10-02 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン Acetonitrile derivatives as bleach activators
DE19908051A1 (en) * 1999-02-25 2000-08-31 Henkel Kgaa Process for the preparation of compounded acetonitrile derivatives
DE10038086A1 (en) * 2000-08-04 2002-02-14 Clariant Gmbh Process for the preparation of hydrolysis-stable ammonium nitriles
DE10038832A1 (en) * 2000-08-04 2002-03-28 Henkel Kgaa Coated bleach activators
DE10049237A1 (en) * 2000-09-28 2002-04-11 Basf Ag Coated, granular N-alkylammonium acetonitrile salts and their use as a bleach activator
US20030166484A1 (en) * 2000-09-28 2003-09-04 Kingma Arend Jouke Coated, granular n-alkylammonium acetonitrile salts and use thereof as bleach activators
DE10057045A1 (en) * 2000-11-17 2002-05-23 Clariant Gmbh Particulate bleach activators based on acetonitriles
DE10159386A1 (en) * 2001-12-04 2003-06-12 Henkel Kgaa Process for the production of bleach activator granules

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DE10159388A1 (en) 2003-06-12
WO2003048290A1 (en) 2003-06-12
JP2005514467A (en) 2005-05-19
ATE325182T1 (en) 2006-06-15
EP1451284A1 (en) 2004-09-01
ES2260519T3 (en) 2006-11-01
AU2002365628A1 (en) 2003-06-17
US20040248754A1 (en) 2004-12-09

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