EP1941016B1 - Method for producing granular or powdery detergent compositions - Google Patents

Method for producing granular or powdery detergent compositions Download PDF

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Publication number
EP1941016B1
EP1941016B1 EP06793896A EP06793896A EP1941016B1 EP 1941016 B1 EP1941016 B1 EP 1941016B1 EP 06793896 A EP06793896 A EP 06793896A EP 06793896 A EP06793896 A EP 06793896A EP 1941016 B1 EP1941016 B1 EP 1941016B1
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EP
European Patent Office
Prior art keywords
acid
weight
copolymer
detergent
slurry
Prior art date
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Not-in-force
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EP06793896A
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German (de)
French (fr)
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EP1941016A1 (en
Inventor
Tanja Seebeck
Helmut GÜMBEL
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BASF SE
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BASF SE
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Classifications

    • 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
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents 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
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • liquid or solid components In the preparation of powder detergents or base powders for further processing into solid detergents (for example extrusion with the addition of further components to granules), up to 30 liquid or solid components must be homogenized as intensively and uniformly as possible in partly very different amounts, which is done by slurrying in water.
  • various components e.g. Surfactants and zeolites used as builders, highly viscous mixtures. Since highly concentrated slurries are desired for the subsequent spray drying, it is necessary to use auxiliaries which lower the viscosity of the slurries.
  • WO-A-91/09932 discloses a process for the preparation of granular detergent compositions in which a deflocculant polymer having hydrophilic polymer backbone and hydrophobic side chains is added to the detergent slurry.
  • the backbone is based on unsaturated monocarboxylic acids, dicarboxylic acids and / or alcohols as monomer units.
  • the side chains which may contain polyalkylene oxide blocks, are attached to the backbone via ester, ether or amide functions.
  • a copolymer of acrylic acid and dodecyl maleate is used.
  • the copolymers used according to the invention contain as copolymerized monomer (A) a monoethylenically unsaturated monocarboxylic acid or dicarboxylic acid or a mixture of these acids.
  • the acids can be used in the form of their water-soluble salts, in particular the alkali metal salts, such as potassium and especially sodium salts, or ammonium salts, the dicarboxylic acids can also be wholly or partially in anhydride form. Of course, acid mixtures can also be used.
  • the monomers (A) preferably contain 3 to 10 carbon atoms.
  • Suitable monomers (A) are: acrylic acid, methacrylic acid, crotonic acid, vinylacetic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride and itaconic acid.
  • Particularly preferred monomers (A) are acrylic acid, methacrylic acid and maleic acid (anhydride), with maleic acid (anhydride) being very particularly preferred.
  • the copolymers used according to the invention contain from 20 to 80% by weight, in particular from 30 to 70% by weight, of the monomer (A).
  • suitable monomers (B) are: 1-butene, isobutene, 1-pentene, 1-hexene, diisobutene (2-methyl-4,4-dimethyl-1-pentene), 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, C 18 -C 24 - ⁇ -olefins such as 1-octadecene, 1-eicosene, 1-docoses and 1-tetracoses, C 20 -C 24 - ⁇ -olefin mixtures, 1-hexacoses, polyisobutenes with an average of 12 to 100 carbon atoms and styrene.
  • isobutene, diisobutene and styrene are suitable as monoolefins (B1).
  • Particularly suitable monoolefins (B2) are 1-dodecene, C 18 -C 24 - ⁇ -olefins, C 20 -C 24 - ⁇ -olefin mixtures and polyisobutenes having an average of 12 to 100 carbon atoms.
  • the copolymers used according to the invention contain from 20 to 80% by weight, preferably from 30 to 70% by weight, of the monomer (B).
  • Very particularly preferred copolymers used according to the invention are by free-radical copolymerization of (A) 30 to 70 wt .-% maleic acid (anhydride), (B1) 20 to 40 wt .-% isobutene and (B2) 5 to 20 wt .-% of a C. 18 -C 24 - ⁇ -olefins available.
  • the copolymers used according to the invention have an average molecular weight M w of from 1,000 to 200,000 g / mol, preferably from 2,000 to 50,000 g / mol (determined by gel permeation chromatography at room temperature with aqueous eluent).
  • K values are accordingly from 10 to 150, preferably from 15 to 60 (measured at pH 7 in 1% strength by weight aqueous solution at 25 ° C.) H. Fikentscher, Cellulose Chemistry, Vol. 13, pp. 58-64 and 71-74 (1932 )).
  • copolymers used according to the invention can be prepared by known processes.
  • aqueous polymer solutions or dispersions which have a solids content of from 10 to 70% by weight, preferably from 25 to 60% by weight.
  • the viscosity of aqueous Waschschslurries, in particular of the slurries, which are dried to produce granular or powdered detergent compositions effectively lower, so that even highly concentrated slurries can be handled easily.
  • the slurry concentrations can always be ⁇ 50% by weight, preferably ⁇ 60% by weight, based on the anhydrous detergent components.
  • copolymers used according to the invention additionally bring about stabilization and homogenization of the slurries and prevent separations.
  • the anionic surfactants are preferably added to the detergent in the form of salts.
  • Suitable salts are e.g. Alkali metal salts such as sodium, potassium and lithium salts, and ammonium salts such as hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.
  • Suitable bleaching agents are, for example, adducts of hydrogen peroxide with inorganic salts, such as sodium perborate monohydrate, sodium perborate tetrahydrate and sodium carbonate perhydrate, and percarboxylic acids, such as phthalimidopercaproic acid.
  • Suitable bleach activators are e.g. N, N, N ', N'-tetraacetylethylenediamine (TAED), sodium p-nonanoyloxybenzenesulfonate and N-methylmorpholinium acetonitrile methylsulfate.
  • TAED tetraacetylethylenediamine
  • Enzymes preferably used in detergents are proteases, lipases, amylases, cellulases, oxidases and peroxidases.
  • Suitable color transfer inhibitors are, for example, homo-, co- and graft polymers of 1-vinylpyrrolidone, 1-vinylimidazole or 4-vinylpyridine-N-oxide. Homo- and copolymers of 4-vinylpyridine reacted with chloroacetic acid are also suitable as color transfer inhibitors.
  • the viscosity-lowering effect of the copolymer P was investigated in two detergent slurries.
  • the copolymer P was a copolymer of maleic anhydride, isobutene and 1-octadecene in a weight ratio of 65: 26: 9, which had an average molecular weight M w of 3000 g / mol and a K value of 24 (measured at Value 7 in 1% strength by weight aqueous solution at 25 ° C.).
  • the copolymer was used in the form of a 40 wt .-% aqueous solution.
  • the two detergent slurries were prepared as follows:
  • Two different detergent slurries were prepared with stirring in a 500 ml heatable double-walled stainless steel vessel.
  • the liquid components were first heated to 50 ° C. with stirring for 10 minutes.
  • the stirrer used had a torque absorption.
  • the previously mixed solid components were then uniformly metered in over 4 minutes, with the slurry being further stirred at 150 rpm. After completion of the addition, the slurry was stirred at a constant speed while determining the torque.
  • the torque reflects the force needed to stir the slurry at a constant speed of rotation.
  • Table 1 lists the compositions of the detergent slurries. The amounts mentioned here refer to feedstocks in anhydrous form, i. without water or water of crystallization contained in the total water content.
  • Table 2 summarizes the torques obtained after each 30 minutes. For comparison, the results obtained without polymer addition are included.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

The invention relates to a method for producing granular or powdery detergent compositions, involving the production of a detergent base powder by drying an aqueous detergent slurry. The invention is characterized in that a copolymer is added to the slurry. This copolymer can be obtained by radically copolymerizing: (A) 20 to 80 % by weight of at least one monomer from the group of monoethylenically unsaturated monocarboxylic acids, dicarboxylic acids and dicarboxylic acid anhydrides, and; (B) 20 to 80 % by weight at least one monomer from the group of aliphatic or aromatic monoolefins.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von granulären oder pulverförmigen Waschmittelzusammensetzungen, umfassend die Herstellung eines Waschmittelbasispulvers durch Trocknung eines wäßrigen Waschmittelslurries, sowie Waschmittelslurries und Waschmittelzusammensetzungen, enthaltend ein durch radikalische Copolymerisation von

  1. (A) 20 bis 80 Gew.-% mindestens eines Monomeren aus der Gruppe der monoethylenisch ungesättigten Monocarbonsäuren, Dicarbonsäuren und Dicarbonsäureanhydride
    und
  2. (B) 20 bis 80 Gew.-% mindestens eines Monomeren aus der Gruppe der aliphatischen oder aromatischen Monoolefine
erhältliches Copolymer.The present invention relates to a process for the preparation of granular or powdered detergent compositions, which comprises the preparation of a detergent base powder by drying an aqueous detergent slurries, and detergent slurries and detergent compositions containing a by free radical copolymerization of
  1. (A) 20 to 80 wt .-% of at least one monomer from the group of monoethylenically unsaturated monocarboxylic acids, dicarboxylic acids and dicarboxylic anhydrides
    and
  2. (B) 20 to 80 wt .-% of at least one monomer from the group of aliphatic or aromatic monoolefins
available copolymer.

Bei der Herstellung von Pulverwaschmitteln oder Basispulvern zur Weiterverarbeitung zu festen Waschmitteln (z.B. Extrusion unter Zugabe weiterer Komponenten zu Granulaten) müssen bis zu 30 flüssige oder feste Komponenten in teilweise sehr unterschiedlichen Mengen möglichst intensiv und gleichmäßig homogenisiert werden, was durch Aufschlämmen in Wasser geschieht. Hierbei ergeben verschiedene Komponenten, z.B. Tenside und die als Builder eingesetzten Zeolithe, hochviskose Mischungen. Da für die anschließende Sprühtrocknung möglichst hochkonzentrierte Slurries gewünscht sind, ist der Einsatz von Hilfsmitteln erforderlich, die die Viskosität der Slurries erniedrigen.In the preparation of powder detergents or base powders for further processing into solid detergents (for example extrusion with the addition of further components to granules), up to 30 liquid or solid components must be homogenized as intensively and uniformly as possible in partly very different amounts, which is done by slurrying in water. Here, various components, e.g. Surfactants and zeolites used as builders, highly viscous mixtures. Since highly concentrated slurries are desired for the subsequent spray drying, it is necessary to use auxiliaries which lower the viscosity of the slurries.

In der WO-A-91/09932 wird ein Verfahren zur Herstellung von granulären Waschmittelzusammensetzungen beschrieben, bei dem dem Waschmittelslurry ein Entflockungspolymer mit hydrophiler Polymerhauptkette und hydrophoben Seitenketten zugesetzt wird. Die Hauptkette basiert auf ungesättigten Monocarbonsäuren, Dicarbonsäuren und/oder Alkoholen als Monomereinheiten. Die Seitenketten, die Polyalkylenoxidblöcke enthalten können, sind über Ester-, Ether- oder Amidfunktionen an die Hauptkette gebunden. In den Beispielen wird ein Copolymer aus Acrylsäure und Maleinsäuredodecylester eingesetzt.In the WO-A-91/09932 discloses a process for the preparation of granular detergent compositions in which a deflocculant polymer having hydrophilic polymer backbone and hydrophobic side chains is added to the detergent slurry. The backbone is based on unsaturated monocarboxylic acids, dicarboxylic acids and / or alcohols as monomer units. The side chains, which may contain polyalkylene oxide blocks, are attached to the backbone via ester, ether or amide functions. In the examples, a copolymer of acrylic acid and dodecyl maleate is used.

In den US-A-5 595 968 , 5 618 782 und 5 733 861 werden für diesen Zweck Copolymere von Acrylsäure und ethoxylierten Allylethern mit einem mittleren Molekulargewicht Mw von etwa 12 000 g/mol eingesetzt.In the US-A-5 595 968 . 5,618,782 and 5,733,861 For this purpose, copolymers of acrylic acid and ethoxylated allyl ethers having an average molecular weight M w of about 12,000 g / mol are used.

Schließlich beschreibt die WO-A-96/17919 Copolymere von Acrylsäure und Maleinsäure, die Dodecylmercaptanreste als Endgruppen enthalten, als Entflockungsmittel für Waschmittelslurries.Finally, that describes WO-A-96/17919 Copolymers of acrylic acid and maleic acid containing dodecylmercaptan groups as end groups as deflocculants for detergent slurries.

Der Erfindung lag die Aufgabe zugrunde, die Herstellung von festen Waschmittelzusammensetzungen durch Einsatz von viskositätsemiedrigenden Polymeren auf vorteilhafte Weise zu ermöglichen.It is an object of the invention to advantageously enable the preparation of solid detergent compositions by the use of viscosity-reducing polymers.

Demgemäß wurde ein Verfahren zur Herstellung von granulären oder pulverförmigen Waschmittelzusammensetzungen, umfassend die Herstellung eines Waschmittelbasispulvers durch Trocknung eines wäßrigen Waschmittelslurries, gefunden, welches dadurch gekennzeichnet ist, daß man dem Slurry ein Copolymer zusetzt, das durch radikalische Copolymerisation von

  1. (A) 20 bis 80 Gew.-% mindestens eines Monomeren aus der Gruppe der monoethylenisch ungesättigten Monocarbonsäuren, Dicarbonsäuren und Dicarbonsäureanhydride
    und
  2. (B) 20 bis 80 Gew.-% Monomere aus der Gruppe der aliphatischen oder aromatischen Monoolefine
erhältlich ist,
wobei die erfindungsgemäß eingesetzten Copolymere als Komponente (B) eine Mischung aus (B1) mindestens einem Monoolefin mit ≤ 8 Kohlenstoffatomen und (B2) mindestens einem Monoolefin mit ≥ 10 Kohlenstoffatomen enthalten.Accordingly, there has been found a process for the preparation of granular or powdered detergent compositions comprising the preparation of a detergent base powder by drying an aqueous detergent slurry, which comprises adding to the slurry a copolymer obtained by radical copolymerization of
  1. (A) 20 to 80 wt .-% of at least one monomer from the group of monoethylenically unsaturated monocarboxylic acids, dicarboxylic acids and dicarboxylic anhydrides
    and
  2. (B) 20 to 80 wt .-% of monomers from the group of aliphatic or aromatic monoolefins
available,
wherein the copolymers used according to the invention as component (B) comprise a mixture of (B1) at least one monoolefin having ≦ 8 carbon atoms and (B2) at least one monoolefin having ≥ 10 carbon atoms.

Außerdem wurde ein Verfahren zur Erniedrigung der Viskosität von Waschmittelslurries gefunden, welches dadurch gekennzeichnet ist, daß man dem Slurry diese Copolymere zusetzt.In addition, a process for reducing the viscosity of Waschmittellurries was found, which is characterized in that the slurry is added to these copolymers.

Weiterhin wurden Waschmittelslurries und Waschmittelzusammensetzungen gefunden, welche diese Copolymere enthalten.Furthermore, detergent slurries and detergent compositions containing these copolymers have been found.

Die erfindungsgemäß eingesetzten Copolymere enthalten als einpolymerisiertes Monomer (A) eine monoethylenisch ungesättigte Monocarbonsäure oder Dicarbonsäure oder eine Mischung dieser Säuren. Die Säuren können in Form ihrer wasserlöslichen Salze, insbesondere der Alkalimetallsalze, wie Kalium- und vor allem Natriumsalze, oder Ammoniumsalze, zum Einsatz kommen, die Dicarbonsäuren können auch ganz oder teilweise in Anhydridform vorliegen. Selbstverständlich können auch Säuremischungen eingesetzt werden.The copolymers used according to the invention contain as copolymerized monomer (A) a monoethylenically unsaturated monocarboxylic acid or dicarboxylic acid or a mixture of these acids. The acids can be used in the form of their water-soluble salts, in particular the alkali metal salts, such as potassium and especially sodium salts, or ammonium salts, the dicarboxylic acids can also be wholly or partially in anhydride form. Of course, acid mixtures can also be used.

Die Monomere (A) enthalten vorzugsweise 3 bis 10 Kohlenstoffatome.The monomers (A) preferably contain 3 to 10 carbon atoms.

Als Beispiele für geeignete Monomere (A) seien im einzelnen genannt: Acrylsäure, Methacrylsäure, Crotonsäure, Vinylessigsäure, Maleinsäure, Maleinsäureanhydrid, Fumarsäure, Citraconsäure, Citraconsäureanhydrid und Itaconsäure.Specific examples of suitable monomers (A) are: acrylic acid, methacrylic acid, crotonic acid, vinylacetic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride and itaconic acid.

Besonders bevorzugte Monomere (A) sind Acrylsäure, Methacrylsäure und Maleinsäure(anhydrid), wobei Maleinsäure(anhydrid) ganz besonders bevorzugt ist.Particularly preferred monomers (A) are acrylic acid, methacrylic acid and maleic acid (anhydride), with maleic acid (anhydride) being very particularly preferred.

Die erfindungsgemäß eingesetzten Copolymere enthalten 20 bis 80 Gew.-%, insbesondere 30 bis 70 Gew.-%, des Monomers (A).The copolymers used according to the invention contain from 20 to 80% by weight, in particular from 30 to 70% by weight, of the monomer (A).

Beispiele für geeignete Monomere (B) sind im einzelnen: 1-Buten, Isobuten, 1-Penten, 1-Hexen, Diisobuten (2-Methyl-4,4-dimethyl-1-penten), 1-Decen, 1-Dodecen, 1-Tetradecen, 1-Hexadecen, C18-C24-α-Olefine, wie 1-Octadecen, 1-Eicosen, 1-Docosen und 1-Tetracosen, C20-C24-α-Olefingemische, 1-Hexacosen, Polyisobutene mit im Mittel 12 bis 100 Kohlenstoffatomen und Styrol.Specific examples of suitable monomers (B) are: 1-butene, isobutene, 1-pentene, 1-hexene, diisobutene (2-methyl-4,4-dimethyl-1-pentene), 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, C 18 -C 24 -α-olefins such as 1-octadecene, 1-eicosene, 1-docoses and 1-tetracoses, C 20 -C 24 -α-olefin mixtures, 1-hexacoses, polyisobutenes with an average of 12 to 100 carbon atoms and styrene.

Als Monoolefine (B1) eignen sich dabei insbesondere Isobuten, Diisobuten und Styrol. Besonders geeignete Monoolefine (B2) sind 1-Dodecen, C18-C24-α-Olefine, C20-C24-α-Olefingemische und Polyisobutene mit im Mittel 12 bis 100 Kohlenstoffatomen.In particular, isobutene, diisobutene and styrene are suitable as monoolefins (B1). Particularly suitable monoolefins (B2) are 1-dodecene, C 18 -C 24 -α-olefins, C 20 -C 24 -α-olefin mixtures and polyisobutenes having an average of 12 to 100 carbon atoms.

Die erfindungsgemäß eingesetzten Copolymere enthalten 20 bis 80 Gew.-%, vorzugsweise 30 bis 70 Gew.-%, des Monomers (B).The copolymers used according to the invention contain from 20 to 80% by weight, preferably from 30 to 70% by weight, of the monomer (B).

Ganz besonders bevorzugte erfindungsgemäß eingesetzte Copolymere sind durch radikalische Copolymerisation von (A) 30 bis 70 Gew.-% Maleinsäure(anhydrid), (B1) 20 bis 40 Gew.-% Isobuten und (B2) 5 bis 20 Gew.-% eines C18-C24-α-Olefins erhältlich.Very particularly preferred copolymers used according to the invention are by free-radical copolymerization of (A) 30 to 70 wt .-% maleic acid (anhydride), (B1) 20 to 40 wt .-% isobutene and (B2) 5 to 20 wt .-% of a C. 18 -C 24 -α-olefins available.

Die erfindungsgemäß eingesetzten Copolymere haben ein mittleres Molekulargewicht Mw von 1 000 bis 200 000 g/mol, bevorzugt von 2 000 bis 50 000 g/mol (bestimmt durch Gelpermeationschromatographie bei Raumtemperatur mit wäßrigem Elutionsmittel).The copolymers used according to the invention have an average molecular weight M w of from 1,000 to 200,000 g / mol, preferably from 2,000 to 50,000 g / mol (determined by gel permeation chromatography at room temperature with aqueous eluent).

Ihre K-Werte liegen dementsprechend bei 10 bis 150, vorzugsweise bei 15 bis 60 (gemessen beim pH-Wert 7 in 1 gew.-%iger wäßriger Lösung bei 25°C; nach H. Fikentscher, Cellulose-Chemie, Bd. 13, S. 58-64 und 71-74 (1932 )).Their K values are accordingly from 10 to 150, preferably from 15 to 60 (measured at pH 7 in 1% strength by weight aqueous solution at 25 ° C.) H. Fikentscher, Cellulose Chemistry, Vol. 13, pp. 58-64 and 71-74 (1932 )).

Die erfindungsgemäß eingesetzten Copolymere können nach bekannten Verfahren hergestellt werden.The copolymers used according to the invention can be prepared by known processes.

Üblicherweise werden sie in Form von insbesondere wäßrigen Polymerlösungen oder Dispersionen erhalten, die einen Feststoffgehalt von 10 bis 70 Gew.-%, bevorzugt 25 bis 60 Gew.-%, aufweisen.Usually, they are obtained in the form of, in particular, aqueous polymer solutions or dispersions which have a solids content of from 10 to 70% by weight, preferably from 25 to 60% by weight.

Mit den erfindungsgemäß eingesetzten Copolymeren läßt sich die Viskosität von wäßrigen Waschmittelslurries, insbesondere von den Slurries, die zur Herstellung von granulären oder pulverförmigen Waschmittelzusammensetzungen getrocknet werden, wirkungsvoll erniedrigen, so daß auch hochkonzentrierte Slurries problemlos gehandhabt werden können. So können die Slurrykonzentrationen stets ≥ 50 Gew.-%, bevorzugt ≥ 60 Gew.-%, bezogen auf die wasserfreien Waschmittelkomponenten, betragen.With the copolymers used in the invention, the viscosity of aqueous Waschmittelslurries, in particular of the slurries, which are dried to produce granular or powdered detergent compositions, effectively lower, so that even highly concentrated slurries can be handled easily. Thus, the slurry concentrations can always be ≥ 50% by weight, preferably ≥ 60% by weight, based on the anhydrous detergent components.

Die erfindungsgemäß eingesetzten Copolymere bewirken zudem eine Stabilisierung und Homogenisierung der Slurries und verhindern Separationen.The copolymers used according to the invention additionally bring about stabilization and homogenization of the slurries and prevent separations.

Sie werden den Slurries in der Regel in Mengen von 0,01 bis 10 Gew.-%, bevorzugt 0,05 bis 5 Gew.-% und besonders bevorzugt 0,1 bis 5 Gew.-%, bezogen auf den Gesamtansatz, zugesetzt.They are added to the slurries usually in amounts of from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight and more preferably from 0.1 to 5% by weight, based on the total batch.

Sie können dabei entweder der Gesamtmischung zugesetzt oder in beliebigen Teilmengen einzelnen Waschmittelkomponenten, z.B. den Tensiden oder den Builder-Premixes, deren Feststoffgehalte auf diese Weise auch bereits angehoben werden können, beigemengt werden.They may either be added to the total mixture or in any subsets of individual detergent components, e.g. the surfactants or builder premixes whose solids contents can be raised in this way, are added.

Erfindungsgemäße feste Waschmittelformulierungen, welche die erfindungsgemäß eingesetzten Copolymere enthalten, weisen vorteilhaft z.B. folgende Zusammensetzung auf:

  1. (a) 0,01 bis 10 Gew.-% mindestens eines erfindungsgemäßen Copolymers,
  2. (b) 0,5 bis 40 Gew.-% mindestens eines nichtionischen, anionischen und/oder kationischen Tensids,
  3. (c) 0,5 bis 80 Gew.-% eines anorganischen Builders,
  4. (d) 0 bis 10 Gew.-% eines organischen Cobuilders und
  5. (e) 0 bis 60 Gew.-% anderer üblicher Inhaltsstoffe, wie Stellmittel, Enzyme, Parfum, Komplexbildner, Korrosionsinhibitoren, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, Farbübertragungsinhibitoren, Vergrauungsinhibitoren, Soil-Release-Polyester, Faser- und Farbschutzadditve, Silicone, Farbstoffe, Bakterizide, Auflösungsverbesserer und/oder Sprengmittel,
wobei die Summe der Komponenten (a) bis (e) 100 Gew.-% ergibt.Solid detergent formulations according to the invention which contain the copolymers used according to the invention advantageously have, for example, the following composition:
  1. (a) from 0.01 to 10% by weight of at least one copolymer according to the invention,
  2. (b) 0.5 to 40% by weight of at least one nonionic, anionic and / or cationic surfactant,
  3. (c) 0.5 to 80% by weight of an inorganic builder,
  4. (d) 0 to 10% by weight of an organic cobuilder and
  5. (e) from 0% to 60% by weight of other conventional ingredients such as sizing agents, enzymes, perfume, chelating agents, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, dye transfer inhibitors, grayness inhibitors, soil release polyesters, fiber and color protective additives, silicones, dyes, Bactericides, dissolution enhancers and / or disintegrants,
wherein the sum of components (a) to (e) gives 100 wt .-%.

Als nichtionische Tenside (b) eignen sich dabei vor allem:

  • Alkoxylierte C8-C22-Alkohole, wie Fettalkoholalkoxylate, Oxoalkoholalkoxylate und Guerbet-Alkoholalkoxylate: Die Alkoxylierung kann mit C2-C20-Alkylenoxiden, vorzugsweise Ethylenoxid, Propylenoxid und/oder Butylenoxid erfolgen. Es können Blockcopolymerisate oder statistische Copolymere vorliegen. Pro mol Alkohol enthalten sie üblicherweise 2 bis 50 mol, vorzugsweise 3 bis 20 mol, mindestens eines Alkylenoxids. Bevorzugtes Alkylenoxid ist Ethylenoxid. Die Alkohole haben vorzugsweise 10 bis 18 Kohlenstoffatome.
  • Alkylphenolalkoxylate, insbesondere Alkylphenolethoxylate, die C6-C14-Alkylketten und 5 bis 30 mol Alkylenoxid/mol enthalten.
  • Alkylpolyglucoside, die C8-C22-, vorzugsweise C10-C18-Alkylketten und in der Regel 1 bis 20, vorzugsweise 1,1 bis 5, Glucosideinheiten enthalten.
  • N-Alkylglucamide, Fettsäureamidalkoxylate, Fettsäurealkanolamidalkoxylate sowie Blockcopolymere aus Ethylenoxid, Propylenoxid und/oder Butylenoxid.
Suitable nonionic surfactants (b) are, in particular:
  • Alkoxylated C 8 -C 22 -alcohols, such as fatty alcohol alkoxylates, oxo alcohol alkoxylates and Guerbet alcohol alkoxylates: The alkoxylation can be carried out using C 2 -C 20 -alkylene oxides, preferably ethylene oxide, propylene oxide and / or butylene oxide. There may be block copolymers or random copolymers. They usually contain from 2 to 50 mol, preferably from 3 to 20 mol, of at least one alkylene oxide per mole of alcohol. Preferred alkylene oxide is ethylene oxide. The alcohols preferably have 10 to 18 carbon atoms.
  • Alkylphenolalkoxylate, especially alkylphenol ethoxylates containing C 6 -C 14 alkyl chains and 5 to 30 moles of alkylene oxide / mol.
  • Alkylpolyglucosides containing C 8 -C 22 -, preferably C 10 -C 18 -alkyl chains and usually 1 to 20, preferably 1.1 to 5, glucoside units.
  • N-alkylglucamides, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates and block copolymers of ethylene oxide, propylene oxide and / or butylene oxide.

Geeignete anionische Tenside sind beispielsweise:

  • Sulfate von (Fett)Alkoholen mit 8 bis 22, vorzugsweise 10 bis 18, Kohlenstoffatomen, insbesondere C9C11-Alkoholsulfate, C12C14-Alkoholsulfate, C12-C18-Alkoholsulfate, Laurylsulfat, Cetylsulfat, Myristylsulfat, Palmitylsulfat, Stearylsulfat und Talgfettalkoholsulfat.
  • Sulfatierte alkoxylierte C8-C22-Alkohole (Alkylethersulfate): Verbindungen dieser Art werden beispielsweise dadurch hergestellt, daß man zunächst einen C8-C22-, vorzugsweise einen C10-C18-Alkohol, z.B. einen Fettalkohol, alkoxyliert und das Alkoxylierungsprodukt anschließend sulfatiert. Für die Alkoxylierung verwendet man vorzugsweise Ethylenoxid.
  • Lineare C8-C20-Alkylbenzolsulfonate (LAS), vorzugsweise lineare C9-C13-Alkylbenzolsulfonate und -Alkyltoluolsulfonate.
  • Alkansulfonate, insbesondere C8-C24-, vorzugsweise C10-C18-Alkansulfonate.
  • Seifen, wie die Na- und K-Salze von C8-C24-Carbonsäuren.
Suitable anionic surfactants are, for example:
  • Sulfates of (fatty) alcohols having 8 to 22, preferably 10 to 18, carbon atoms, in particular C 9 C 11 -alcohol sulfates, C 12 C 14 -alcohol sulfates, C 12 -C 18 -alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmitylsulfate, stearyl sulfate and tallow fatty alcohol sulfate.
  • Sulfated alkoxylated C 8 -C 22 -alcohols (alkyl ether sulfates): compounds of this type are prepared, for example, by first alkoxylating a C 8 -C 22 -alcohol, preferably a C 10 -C 18 -alcohol, for example a fatty alcohol, and the alkoxylation product subsequently sulfated. For the alkoxylation is preferably used ethylene oxide.
  • Linear C 8 -C 20 -alkylbenzenesulfonates (LAS), preferably linear C 9 -C 13 -alkylbenzenesulfonates and -alkyltoluenesulfonates.
  • Alkanesulfonates, in particular C 8 -C 24 -, preferably C 10 -C 18 -alkanesulfonates.
  • Soaps, such as the Na and K salts of C 8 -C 24 carboxylic acids.

Die anionischen Tenside werden dem Waschmittel vorzugsweise in Form von Salzen zugegeben. Geeignete Salze sind dabei z.B. Alkalimetallsalze, wie Natrium-, Kalium- und Lithiumsalze, und Ammoniumsalze, wie Hydroxyethylammonium-, Di(hydroxyethyl)ammonium- und Tri(hydroxyethyl)ammoniumsalze.The anionic surfactants are preferably added to the detergent in the form of salts. Suitable salts are e.g. Alkali metal salts such as sodium, potassium and lithium salts, and ammonium salts such as hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.

Als besonders geeignete kationische Tenside seien genannt:

  • C7-C25-Alkylamine;
  • N,N-Dimethyl-N-(C7-C25-hydroxyalkyl)ammoniumsalze;
  • mit Alkylierungsmitteln quaternisierte Mono- und Di-(C7-C25-alkyl)dimethylammoniumverbindungen;
  • Esterquats, insbesondere quaternäre veresterte Mono-, Di- und Trialkanolamine, die mit C8-C22-Carbonsäuren verestert sind;
  • Imidazolinquats, insbesondere 1-Alkylimidazoliniumsalze der Formeln I oder II
    Figure imgb0001
     in denen die Variablen folgende Bedeutung haben:
    • R1 C1-C25-Alkyl oder C2-C25-Alkenyl;
    • R2 C1-C4-Alkyl oder C1-C4-Hydroxyalkyl;
    • R3 C1-C4-Alkyl, C1-C4-Hydroxyalkyl oder ein Rest R1-(CO)-X-(CH2)p- (X: -O- oder -NH-; p: 2 oder 3),
wobei mindestens ein Rest R1 C7-C22-Alkyl ist.Particularly suitable cationic surfactants are:
  • C 7 -C 25 -alkylamines;
  • N, N-dimethyl-N- (C 7 -C 25 -hydroxyalkyl) ammonium salts;
  • mono- and di (C 7 -C 25 -alkyl) dimethylammonium compounds quaternized with alkylating agents;
  • Esterquats, in particular quaternary esterified mono-, di- and trialkanolamines esterified with C 8 -C 22 -carboxylic acids;
  • Imidazolinquats, in particular 1-Alkylimidazoliniumsalze of the formulas I or II
    Figure imgb0001
     in which the variables have the following meaning:
    • R 1 is C 1 -C 25 alkyl or C 2 -C 25 alkenyl;
    • R 2 is C 1 -C 4 alkyl or C 1 -C 4 hydroxyalkyl;
    • R 3 is C 1 -C 4 -alkyl, C 1 -C 4 -hydroxyalkyl or a radical R 1 - (CO) -X- (CH 2 ) p - (X: -O- or -NH-; p: 2 or 3)
wherein at least one radical R 1 is C 7 -C 22 alkyl.

Als anorganische Builder eignen sich insbesondere:

  • Kristalline und amorphe Alumosilikate mit ionenaustauschenden Eigenschaften, wie vor allem Zeolithe: Verschiedene Typen von Zeolithen sind geeignet, insbesondere die Zeolithe A, X, B, P, MAP und HS in ihrer Na-Form oder in Formen, in denen Na teilweise gegen andere Kationen wie Li, K, Ca, Mg oder Ammonium ausgetauscht ist.
  • Kristalline Silikate, wie insbesondere Disilikate und Schichtsilikate, z.B. δ- und β-Na2Si2O5. Die Silikate können in Form ihrer Alkalimetall-, Erdalkalimetall- oder Ammoniumsalze eingesetzt werden, bevorzugt sind die Na-, Li- und Mg-Silicate.
  • Amorphe Silikate, wie Natriummetasilikat und amorphes Disilikat.
  • Carbonate und Hydrogencarbonate: Diese können in Form ihrer Alkalimetall-, Erdalkalimetall- oder Ammoniumsalze eingesetzt werden. Bevorzugt sind Na-, Li- und Mg-Carbonate und -Hydrogencarbonate, insbesondere Natriumcarbonat und/oder Natriumhydrogencarbonat.
  • Polyphosphate, wie Pentanatriumtriphosphat.
Suitable inorganic builders are, in particular:
  • Crystalline and amorphous aluminosilicates with ion-exchanging properties, especially zeolites: Various types of zeolites are suitable, in particular the zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na is partially reactive with other cations as Li, K, Ca, Mg or ammonium is exchanged.
  • Crystalline silicates, in particular disilicates and sheet silicates, for example δ- and β-Na 2 Si 2 O 5 . The silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preference being given to the Na, Li and Mg silicates.
  • Amorphous silicates such as sodium metasilicate and amorphous disilicate.
  • Carbonates and bicarbonates: These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preference is given to Na, Li and Mg carbonates and hydrogen carbonates, in particular sodium carbonate and / or sodium bicarbonate.
  • Polyphosphates, such as pentasodium triphosphate.

Als organische Cobuilder eignen sich vor allem:

  • Niedermolekulare Carbonsäuren, wie Citronensäure, hydrophob modifizierte Citronensäure, z. B. Agaricinsäure, Äpfelsäure, Weinsäure; Gluconsäure, Glutarsäure, Bernsteinsäure, Imidodibernsteinsäure, Hydroxydibernsteinsäure, Oxydibernsteinsäure, Propantricarbonsäure, Butantetracarbonsäure, Cyclopentantetracarbonsäure, Alkyl- und Alkenylbernsteinsäuren und Aminopolycarbonsäuren, z.B. Nitrilotriessigsäure, β-Alanindiessigsäure, Ethylendiamintetraessigsäure, Diethylentriaminpentaessigsäure, Serindiessigsäure, Isoserindiessigsäure, Glutamindiessigsäure, N-(2-Hydroxyethyl)iminodiessigsäure, Ethylendiamindibernsteinsäure und Methyl- und Ethylglycindiessigsäure.
  • Oligomere und polymere Carbonsäuren, wie Homopolymere von Acrylsäure und Asparaginsäure, Oligomaleinsäuren, Copolymere der Maleinsäure mit Acrylsäure, Methacrylsäure oder C2-C22-Olefinen, z.B. Isobuten oder langkettigen α-Olefinen, Vinyl-C1-C8-alkylether, Vinylacetat, Vinylpropionat, (Meth)Acrylsäureester von C1-C8-Alkoholen und Styrol. Bevorzugt sind die Homopolymere der Acrylsäure und Copolymere von Acrylsäure mit Maleinsäure. Die oligomeren und polymeren Carbonsäuren werden in Säureform oder als Natriumsalz eingesetzt.
As organic cobuilders are particularly suitable:
  • Low molecular weight carboxylic acids such as citric acid, hydrophobically modified citric acid, e.g. B. agaricic acid, malic acid, tartaric acid; Gluconic acid, glutaric acid, succinic acid, imidodisuccinic acid, hydroxydisuccinic acid, oxydisuccinic acid, propanetricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, alkyl- and alkenylsuccinic acids and aminopolycarboxylic acids, eg nitrilotriacetic acid, β-alaninediacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, serinediacetic acid, isoserinediacetic acid, glutaminediacetic acid, N- (2-hydroxyethyl) iminodiacetic acid , Ethylenediamine disuccinic acid and methyl and ethylglycinediacetic acid.
  • Oligomeric and polymeric carboxylic acids, such as homopolymers of acrylic acid and aspartic acid, oligomaleic acids, copolymers of maleic acid with acrylic acid, methacrylic acid or C 2 -C 22 -olefins, for example isobutene or long-chain α-olefins, vinyl-C 1 -C 8 -alkyl ethers, vinyl acetate, Vinyl propionate, (meth) acrylic acid esters of C 1 -C 8 -alcohols and styrene. Preferred are the homopolymers of acrylic acid and copolymers of acrylic acid with maleic acid. The oligomeric and polymeric carboxylic acids are used in acid form or as the sodium salt.

Geeignete Bleichmittel sind beispielsweise Addukte von Wasserstoffperoxid an anorganische Salze, wie Natriumperborat-Monohydrat, Natriumperborat-Tetrahydrat und Natriumcarbonat-Perhydrat, und Percarbonsäuren, wie Phthalimidopercapronsäure.Suitable bleaching agents are, for example, adducts of hydrogen peroxide with inorganic salts, such as sodium perborate monohydrate, sodium perborate tetrahydrate and sodium carbonate perhydrate, and percarboxylic acids, such as phthalimidopercaproic acid.

Als Bleichaktivatoren eignen sich z.B. N,N,N',N'-Tetraacetylethylendiamin (TAED), Natrium-p-nonanoyloxybenzolsulfonat und N-Methylmorpholiniumacetonitrilmethylsulfat.Suitable bleach activators are e.g. N, N, N ', N'-tetraacetylethylenediamine (TAED), sodium p-nonanoyloxybenzenesulfonate and N-methylmorpholinium acetonitrile methylsulfate.

Vorzugsweise in Waschmitteln eingesetzte Enzyme sind Proteasen, Lipasen, Amylasen, Cellulasen, Oxidasen und Peroxidasen.Enzymes preferably used in detergents are proteases, lipases, amylases, cellulases, oxidases and peroxidases.

Geeignete Farbübertragungsinhibitoren sind beispielsweise Homo-, Co- und Pfropfpolymere von 1-Vinylpyrrolidon, 1-Vinylimidazol oder 4-Vinylpyridin-N-oxid. Auch mit Chloressigsäure umgesetzte Homo- und Copolymere des 4-Vinylpyridins eignen sich als Farbübertragungsinhibitoren.Suitable color transfer inhibitors are, for example, homo-, co- and graft polymers of 1-vinylpyrrolidone, 1-vinylimidazole or 4-vinylpyridine-N-oxide. Homo- and copolymers of 4-vinylpyridine reacted with chloroacetic acid are also suitable as color transfer inhibitors.

Waschmittelinhaltsstoffe sind im übrigen allgemein bekannt. Detaillierte Beschreibungen sind z.B. in den WO-A-99/06524 und 99/04313 sowie in Liquid Detergents, Editor: Kuo-Yann Lai, Surfactant Sci. Ser., Vol. 67, Marcel Decker, New York, 1997, p. 272-304, zu finden.Detergent ingredients are otherwise well known. Detailed descriptions are e.g. in WO-A-99/06524 and 99/04313 as well as in Liquid Detergents, Editor: Kuo-Yann Lai, Surfactant Sci. Ser., Vol. 67, Marcel Decker, New York, 1997, p. 272-304, to find.

BeispieleExamples

Die viskositätserniedrigende Wirkung des Copolymers P wurde in zwei Waschmittelslurries untersucht.The viscosity-lowering effect of the copolymer P was investigated in two detergent slurries.

Bei dem Copolymer P handelte es sich um ein Copolymer aus Maleinsäureanhydrid, Isobuten und 1-Octadecen im Gewichtsverhältnis 65:26:9, das ein mittleres Molekulargewicht Mw von 3 000 g/mol und einen K-Wert von 24 (gemessen beim pH-Wert 7 in 1 gew.-%iger wäßriger Lösung bei 25°C) aufwies. Das Copolymer wurde in Form einer 40 gew.-%igen wäßrigen Lösung eingesetzt.The copolymer P was a copolymer of maleic anhydride, isobutene and 1-octadecene in a weight ratio of 65: 26: 9, which had an average molecular weight M w of 3000 g / mol and a K value of 24 (measured at Value 7 in 1% strength by weight aqueous solution at 25 ° C.). The copolymer was used in the form of a 40 wt .-% aqueous solution.

Die beiden Waschmittelslurries wurden wie folgt hergestellt:The two detergent slurries were prepared as follows:

In einem 500 ml beheizbaren doppelwandigen Edelstahlgefäß wurden unter Rühren zwei verschiedene Waschmittelslurries hergestellt. Dazu wurden zunächst die flüssigen Komponenten unter Rühren 10 min auf 50°C temperiert. Der verwendete Rührer verfügte über eine Drehmomentsaufnahme. In 4 min wurden dann die zuvor gemischten festen Komponenten gleichmäßig zudosiert, wobei der Slurry bei 150 U/min weitergerührt wurde. Nach beendeter Zugabe wurde der Slurry mit gleichbleibender Umdrehungszahl unter Bestimmung des Drehmoments weitergerührt.Two different detergent slurries were prepared with stirring in a 500 ml heatable double-walled stainless steel vessel. For this purpose, the liquid components were first heated to 50 ° C. with stirring for 10 minutes. The stirrer used had a torque absorption. The previously mixed solid components were then uniformly metered in over 4 minutes, with the slurry being further stirred at 150 rpm. After completion of the addition, the slurry was stirred at a constant speed while determining the torque.

Das Drehmoment gibt die Kraft wieder, die benötigt wird, um den Slurry bei konstanter Umdrehungsgeschwindigkeit zu rühren. Je niedriger das Drehmoment ist, desto niedriger ist die Viskosität des Waschmittelslurries.The torque reflects the force needed to stir the slurry at a constant speed of rotation. The lower the torque, the lower the viscosity of the detergent slurry.

In Tabelle 1 sind die Zusammensetzungen der Waschmittelslurries aufgeführt. Die genannten Mengen beziehen sich dabei auf Einsatzstoffe in wasserfreier Form, d.h. ohne Wasseranteile oder Kristallwasser, die im Gesamtwassergehalt enthalten sind.Table 1 lists the compositions of the detergent slurries. The amounts mentioned here refer to feedstocks in anhydrous form, i. without water or water of crystallization contained in the total water content.

In Tabelle 2 sind die jeweils nach 30 min erhaltenen Drehmomente zusammengestellt. Zum Vergleich sind dabei die ohne Polymerzusatz erhaltenen Ergebnisse mitaufgeführt.Table 2 summarizes the torques obtained after each 30 minutes. For comparison, the results obtained without polymer addition are included.

Das Ergebnis nb bedeutet dabei, daß die Viskosität des Slurries sehr hoch war und das Drehmoment nicht mehr bestimmbar war. Tabelle 1: Zusammensetzung der Waschmnittelslurries Einsatzstoff Slurry 1 Slurry 2 [Gew.-%] [Gew.-%] Dodecylbenzolsulfonat, Na-Salz 14,1 17,2 C13/15-Oxoalkohol x 7 EO 7,6 6,2 Zeolith A 21,7 - Soda 16,3 7,8 Natriummetasilikat 10,9 - Natriumtripolyphosphat - 15,6 Natriumsulfat - 27,3 Copolymer P 1,1 1,8 Gesamtwassergehalt 28,3 24,1 Gesamtfeststoffgehalt 71,7 75,9 Tabelle 2: Bestimmung des Drehmoments Drehmoment [Ncm] nach 30 min Slurry 1 Slurry 2 mit Copolymer P 12 28 ohne Copolymer P nb nb The result nb means that the viscosity of the slurries was very high and the torque was no longer determinable. Table 1: Composition of the washing agent slurries feedstock Slurry 1 Slurry 2 [Wt .-%] [Wt .-%] Dodecylbenzenesulfonate, Na salt 14.1 17.2 C 13/15 -oxo alcohol x 7 EO 7.6 6.2 Zeolite A 21.7 - soda 16.3 7.8 metasilicate 10.9 - sodium tripolyphosphate - 15.6 sodium sulphate - 27.3 Copolymer P 1.1 1.8 Total water content 28.3 24.1 Total solids content 71.7 75.9 Torque [Ncm] after 30 min Slurry 1 Slurry 2 with copolymer P 12 28 without copolymer P nb nb

Claims (6)

  1. A process for producing granular or pulverulent detergent compositions, comprising the production of a detergent base powder by drying an aqueous detergent slurry, which comprises adding to the slurry a copolymer which is obtainable by free-radical copolymerization of
    (A) from 20 to 80% by weight of at least one monomer from the group of the monoethylenically unsaturated monocarboxylic acids, dicarboxylic acids and dicarboxylic anhydrides
    and
    (B) from 20 to 80% by weight of monomers from the group of the aliphatic or aromatic monoolefins, the copolymers used in accordance with the invention comprising a mixture of (B1) at least one monoolefin having ≤ 8 carbon atoms and (B2) at least one monoolefin having ≥ 10 carbon atoms as component (B).
  2. The process according to claim 1, wherein a copolymer based on at least one monomer (A) from the group of maleic acid, maleic anhydride and acrylic acid is used.
  3. The process according to claims 1 to 2, wherein a copolymer is used which is obtainable by free-radical copolymerization of (A) from 30 to 70% by weight of maleic acid or maleic anhydride, (B1) from 20 to 40% by weight of isobutene and (B2) from 5 to 20% by weight of a C18-C24-α-olefin.
  4. A process for lowering the viscosity of aqueous detergent slurries, which comprises adding a copolymer as defined in claims 1 to 3 to the slurry.
  5. A detergent slurry comprising a copolymer as defined in claims 1 to 3.
  6. A detergent composition comprising a copolymer as defined in claims 1 to 3.
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Publication number Priority date Publication date Assignee Title
DE102005041349A1 (en) * 2005-08-31 2007-03-01 Basf Ag Phosphate-free cleaning formulation, useful for dishwasher, comprises: copolymers from monoethylenic unsaturated monocarboxylic acids; complexing agent; nonionic surfactant, bleaching agent; builder; enzyme; and additives
JP5208906B2 (en) * 2009-11-13 2013-06-12 本田技研工業株式会社 Inverted pendulum type vehicle
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Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE757034A (en) 1969-10-08 1971-04-05 Knapsack Ag SUPPORTING SUBSTANCES FOR DETERIVES AND CLEANING AGENTS
US3676373A (en) * 1970-07-20 1972-07-11 Gulf Research Development Co Detergent compositions
GB1551239A (en) 1975-09-21 1979-08-30 Procter & Gamble Built detergent compositions
JPS5919598B2 (en) * 1977-09-12 1984-05-07 ライオン株式会社 Granular detergent composition with excellent rinsability and powder properties
GB2040990B (en) * 1977-11-17 1982-10-06 Procter & Gamble Granular detergent compositions for improved greasy soil removal
JPS57192499A (en) * 1981-05-20 1982-11-26 Lion Corp Manufacture of granular detergent
DE3380356D1 (en) * 1982-09-01 1989-09-14 Unilever Nv Abrasive agglomerates for use in scouring cleaning compositions
US4762637A (en) * 1986-11-14 1988-08-09 Lever Brothers Company Encapsulated bleach particles for machine dishwashing compositions
US5205960A (en) * 1987-12-09 1993-04-27 S. C. Johnson & Son, Inc. Method of making clear, stable prespotter laundry detergent
US5376288A (en) * 1989-06-21 1994-12-27 Noro Nordisk A/S Detergent additive granulate and detergent
GB8928023D0 (en) 1989-12-12 1990-02-14 Unilever Plc Detergent compositions
US5232622A (en) * 1990-06-20 1993-08-03 Rohm And Haas Company Chlorine-free machine dishwashing
US5281352A (en) * 1992-08-27 1994-01-25 Church & Dwight Co., Inc. Low-phosphate machine dishwashing detergents
DE4300239A1 (en) 1993-01-07 1994-07-14 Basf Ag Use of partially esterified copolymers containing carboxyl groups as dispersants
US5998360A (en) * 1994-09-22 1999-12-07 Crosfield Limited Granules based on silicate antiredeposition agent mixtures and method for manufacturing same
MX9704132A (en) 1994-12-05 1998-02-28 Colgate Palmolive Co Granular detergent compositions containing deflocculating polymers.
US5733861A (en) 1995-05-23 1998-03-31 Basf Corporation Hydrophilic copolymers for reducing the viscosity of detergent slurries
US5595968A (en) 1995-05-23 1997-01-21 Basf Corporation Polymeric dispersants for soda ash based detergent slurries
US5618782A (en) 1995-05-23 1997-04-08 Basf Corporation Hydrophilic copolymers for reducing the viscosity of detergent slurries
FR2739866A1 (en) * 1995-10-13 1997-04-18 Rohm & Haas France CLEANING COMPOSITIONS CONTAINING A LIME SOAP DISPERSER AND PROCESS FOR PREPARING THE SAME
EP0906394B1 (en) * 1996-03-26 2003-06-11 Basf Aktiengesellschaft Improved detergent and tableware cleaner
DE19621983A1 (en) 1996-06-03 1997-12-04 Basf Ag Use of copolymers of hydrophilic and hydrophobic monomers to increase the rate of dissolution of particulate detergent formulations in water
JP3680453B2 (en) * 1996-10-16 2005-08-10 チッソ株式会社 Thermoplastic resin composition for cleaning
US6716808B1 (en) * 1999-01-21 2004-04-06 The Procter & Gamble Company Detergent compositions comprising hybrid zeolite builders containing an occluded nonsilicate
DE10104469A1 (en) * 2001-02-01 2002-08-08 Basf Ag Copolymers to prevent glass corrosion
DE10104470A1 (en) * 2001-02-01 2002-08-08 Basf Ag Detergent formulations to prevent discoloration of plastic objects
FR2862235B1 (en) * 2003-11-13 2007-12-28 Rhodia Chimie Sa EMULSION FOR VEHICULATING HYDROPHOBIC ACTIVE MATERIAL TO AQUEOUS SUBSTRATE

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