EP1941016A1 - Method for producing granular or powdery detergent compositions - Google Patents

Method for producing granular or powdery detergent compositions

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Publication number
EP1941016A1
EP1941016A1 EP06793896A EP06793896A EP1941016A1 EP 1941016 A1 EP1941016 A1 EP 1941016A1 EP 06793896 A EP06793896 A EP 06793896A EP 06793896 A EP06793896 A EP 06793896A EP 1941016 A1 EP1941016 A1 EP 1941016A1
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EP
European Patent Office
Prior art keywords
copolymer
acid
monomer
group
detergent
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Granted
Application number
EP06793896A
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German (de)
French (fr)
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EP1941016B1 (en
Inventor
Tanja Seebeck
Helmut GÜMBEL
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BASF SE
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BASF SE
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Priority to PL06793896T priority Critical patent/PL1941016T3/en
Publication of EP1941016A1 publication Critical patent/EP1941016A1/en
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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 ; 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
    • 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

  • the present invention relates to a process for the preparation of granular or powdered detergent compositions comprising the preparation of a detergent base powder by drying an aqueous detergent slurries, as well as detergent slurries and detergent compositions containing a by radi kaiische Copolymerisation of
  • liquid or solid components In the production of powder detergents or base powders for further processing into solid detergents (eg extrusion with addition of further components to granules), up to 30 liquid or solid components must be homogenized in intensively and uniformly homogeneous amounts, sometimes in very different amounts, which is achieved 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 describes a process for producing granular detergent compositions in which a deflocculant polymer having a hydrophilic polymer main chain 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 maleic acid ester cylester is used.
  • Copolymers of acrylic acid and ethoxylated allyl ethers having an average molecular weight Mw of about 12,000 g / mol are used for this purpose in US Pat. Nos. 5,595,968, 5,618,782 and 5,733,861.
  • WO-A-96/17919 describes copolymers of acrylic acid and maleic acid containing dodecylmercaptan groups as end groups as deflocculants for detergent slurries.
  • 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).
  • the copolymers used according to the invention contain at least one aliphatic or aromatic monoolefin.
  • 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, Ci8-C24- ⁇ -olefins such as 1-octadecene, 1-eicosene, 1-docoses and 1-tetracoses, C2o-C24- ⁇ -olefin mixtures, 1-hexacoses, polyisobutenes with im Average 12 to 100 carbon atoms and styrene.
  • the copolymers used according to the invention as component (B) preferably contain a mixture of (B1) at least one monoolefin having ⁇ 8 carbon atoms and (B2) at least one monoolefin having> 10 carbon atoms.
  • isobutene, diisobutene and styrene are suitable as monoolefins (B1).
  • Particularly suitable monoolefins (B2) are 1-dodecene, Ci8-C24- ⁇ -olefins, C20-C24-0C-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 Ci 8 -C 2 4- ⁇ -olefin obtains lent.
  • the copolymers used according to the invention have an average molecular weight Mw 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).
  • 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., according to H. Fikentscher, Cellulose-Chemie, 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.
  • Solid detergent formulations according to the invention which comprise the copolymers used according to the invention advantageously have e.g. following composition:
  • an organic cobuilder (d) 0 to 10% by weight of an organic cobuilder and (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,
  • 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.
  • Preferred alkylene oxide is ethylene oxide.
  • the alcohols preferably have 10 to 18 carbon atoms.
  • Alkylphenolalkoxylate in particular alkylphenol ethoxylates containing C6-Ci4-alkyl chains and 5 to 30 moles of alkylene oxide / mol.
  • N-alkylglucamides fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates and block copolymers of ethylene oxide, propylene oxide and / or butylene oxide.
  • Suitable anionic surfactants are, for example:
  • Sulfates of (fatty) alcohols having 8 to 22, preferably 10 to 18, carbon atoms in particular CgCn alcohol sulfates, Ci2Ci4-alcohol sulfates, Ci2-Ci8-alcohol sulfate, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmitylsulfate, stearyl sulfate and tallow fatty alcohol sulfate.
  • Sulfated alkoxylated Cs-C22 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 then sulfating the alkoxylation product.
  • a C 8 -C 22 -alcohol preferably a C 10 -C 18 -alcohol, for example a fatty alcohol
  • sulfating the alkoxylation product for the alkoxylation is preferably used ethylene oxide.
  • Linear Cs-CaO alkylbenzenesulfonates (LAS), preferably linear Cg-C 13 -alkylbenzenesulfonates and -alkyltoluenesulfonates.
  • Alkanesulfonates especially C8-C24, preferably Clo-Cis-alkanesulfonates.
  • Soaps such as the Na and K salts of C8-C24 carboxylic acids.
  • 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.
  • Particularly suitable cationic surfactants are:
  • Esterquats especially quaternary esterified mono-, di- and trialkanolamines esterified with Cs-C22 carboxylic acids;
  • R 1 Ci-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
  • R 1 is C 7 -C 22 alkyl
  • Suitable inorganic builders are, in particular: Crystalline and amorphous aluminosilicates with ion-exchanging properties, especially zeolites:
  • 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 phyllosilicates, e.g. ⁇ - and ⁇ -Na2Si2 ⁇
  • 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 can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preferred are Na, Li and
  • Mg carbonates and hydrogencarbonates in particular sodium carbonate and / or sodium bicarbonate.
  • Polyphosphates such as pentasodium triphosphate.
  • organic cobuilders are particularly suitable:
  • Low molecular weight carboxylic acids such as citric acid, hydrophobically modified citric acid, eg. , Agaricic acid, malic acid, tartaric acid, gluconic acid, glutaric acid, succinic acid, imidodisuccinic acid, hydroxydisuccinic acid, oxydibrenic acid, propane tricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, alkyl and alkenyl succinic acids and aminopolycarboxylic acids, e.g.
  • citric acid hydrophobically modified citric acid
  • hydrophobically modified citric acid eg. , Agaricic acid, malic acid, tartaric acid, gluconic acid, glutaric acid, succinic acid, imidodisuccinic acid, hydroxydisuccinic acid, oxydibrenic acid, propane tricarboxylic acid, butanetetracarboxylic acid,
  • Nitrilotriacetic acid ⁇ -alaninediacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, serinediacetic acid, isoserinediacetic acid, glutamic diacetic 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, e.g. Isobutene or long-chain ⁇ -olefins,
  • Vinyl-C 1 -C -alkyl ethers vinyl acetate, vinyl propionate, (meth) acrylic 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.
  • 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.
  • 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 Sei. Ser., Vol. 67, Marcel Decker, New York, 1997, p. 272-304, to find.
  • 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, having an average molecular weight Mw of 3,000 g / mol and a K value of 24 (measured at pH 7 in 1 wt .-% aqueous solution at 25 ° C) had.
  • 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.
  • the slurry was stirred with a constant number of revolutions while determining the torque.
  • 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.
  • 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.
  • nb means that the viscosity of the slurries was very high and the torque was no longer determinable.

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

Verfahren zur Herstellung von granulären oder pulverförmigen WaschmittelzusammensetzungenProcess for the preparation of granular or powdered detergent compositions
Beschreibungdescription
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 radi- kaiische Copolymerisation vonThe present invention relates to a process for the preparation of granular or powdered detergent compositions comprising the preparation of a detergent base powder by drying an aqueous detergent slurries, as well as detergent slurries and detergent compositions containing a by radi kaiische Copolymerisation of
(A) 20 bis 80 Gew.-% mindestens eines Monomeren aus der Gruppe der monoethy- lenisch ungesättigten Monocarbonsäuren, Dicarbonsäuren und Dicarbonsäure- anhydride(A) 20 to 80 wt .-% of at least one monomer from the group of monoethylenically unsaturated monocarboxylic acids, dicarboxylic acids and dicarboxylic acid anhydrides
undand
(B) 20 bis 80 Gew.-% mindestens eines Monomeren aus der Gruppe der aliphati- schen oder aromatischen Monoolefine(B) 20 to 80 wt .-% of at least one monomer from the group of aliphatic or aromatic monoolefins
erhältliches Copolymer.available copolymer.
Bei der Herstellung von Pulverwaschmitteln oder Basispulvern zur Weiterverarbeitung zu festen Waschmitteln (z.B. Extrusion unter Zugabe weiterer Komponenten zu Granu- laten) 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 production of powder detergents or base powders for further processing into solid detergents (eg extrusion with addition of further components to granules), up to 30 liquid or solid components must be homogenized in intensively and uniformly homogeneous amounts, sometimes in very different amounts, which is achieved 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 Entflockungs- polymer 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 Maleinsäuredode- cylester eingesetzt.WO-A-91/09932 describes a process for producing granular detergent compositions in which a deflocculant polymer having a hydrophilic polymer main chain 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 maleic acid ester cylester is used.
In den US-A-5 595 968, 5 618 782 und 5 733 861 werden für diesen Zweck Copolyme- re von Acrylsäure und ethoxylierten Allylethern mit einem mittleren Molekulargewicht Mw von etwa 12 000 g/mol eingesetzt. Schließlich beschreibt die WO-A-96/17919 Copolymere von Acrylsäure und Maleinsäure, die Dodecylmercaptanreste als Endgruppen enthalten, als Entflockungsmittel für Waschmittelslurries.Copolymers of acrylic acid and ethoxylated allyl ethers having an average molecular weight Mw of about 12,000 g / mol are used for this purpose in US Pat. Nos. 5,595,968, 5,618,782 and 5,733,861. Finally, WO-A-96/17919 describes 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 Viskositätserniedrigenden 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-lowering 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 vonAccordingly, 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
(A) 20 bis 80 Gew.-% mindestens eines Monomeren aus der Gruppe der monoethy- lenisch ungesättigten Monocarbonsäuren, Dicarbonsäuren und Dicarbonsäure- anhydride(A) 20 to 80 wt .-% of at least one monomer from the group of monoethylenically unsaturated monocarboxylic acids, dicarboxylic acids and dicarboxylic acid anhydrides
undand
(B) 20 bis 80 Gew.-% mindestens eines Monomeren aus der Gruppe der aliphati- schen oder aromatischen Monoolefine(B) 20 to 80 wt .-% of at least one monomer from the group of aliphatic or aromatic monoolefins
erhältlich ist.is available.
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 Mo- nomer (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 Säuremi- schungen 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. Als Beispiele für geeignete Monomere (A) seien im einzelnen genannt: Acrylsäure, Methacrylsäure, Crotonsäure, Vinylessigsäure, Maleinsäure, Maleinsäureanhydrid, Fumarsäure, Citraconsäure, Citraconsäureanhydrid und Itaconsäure.The monomers (A) preferably contain 3 to 10 carbon atoms. 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 Maleinsäu- re(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.-%, insbe- sondere 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).
Als einpolymerisiertes Monomer (B) enthalten die erfindungsgemäß eingesetzten Copolymere mindestens ein aliphatisches oder aromatisches Monoolefin.As copolymerized monomer (B), the copolymers used according to the invention contain at least one aliphatic or aromatic monoolefin.
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-Tetra- decen, 1-Hexadecen, Ci8-C24-α-Olefine, wie 1-Octadecen, 1-Eicosen, 1-Docosen und 1-Tetracosen, C2o-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, Ci8-C24-α-olefins such as 1-octadecene, 1-eicosene, 1-docoses and 1-tetracoses, C2o-C24-α-olefin mixtures, 1-hexacoses, polyisobutenes with im Average 12 to 100 carbon atoms and styrene.
Bevorzugt enthalten 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.The copolymers used according to the invention as component (B) preferably contain a mixture of (B1) at least one monoolefin having <8 carbon atoms and (B2) at least one monoolefin having> 10 carbon atoms.
Als Monoolefine (B1) eignen sich dabei insbesondere Isobuten, Diisobuten und Styrol. Besonders geeignete Monoolefine (B2) sind 1-Dodecen, Ci8-C24-α-Olefine, C20-C24-0C- 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, Ci8-C24-α-olefins, C20-C24-0C-olefin mixtures and polyisobutenes having an average of 12 to 100 carbon atoms.
Die erfindungsgemäß eingesetzten Copolymere enthalten 20 bis 80 Gew.-%, vorzugs- weise 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 Ci8-C24-α-Olefins erhält- lieh.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 Ci 8 -C 2 4-α-olefin obtains lent.
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 Elutionsmit- tel). 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. Fikent- scher, Cellulose-Chemie, Bd. 13, S. 58-64 und 71-74 (1932)).The copolymers used according to the invention have an average molecular weight Mw 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). 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., according to H. Fikentscher, Cellulose-Chemie, 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:Solid detergent formulations according to the invention which comprise the copolymers used according to the invention advantageously have e.g. following composition:
(a) 0,01 bis 10 Gew. -% mindestens eines erfindungsgemäßen Copolymers,(a) 0.01 to 10% by weight of at least one copolymer according to the invention,
(b) 0,5 bis 40 Gew.-% mindestens eines nichtionischen, anionischen und/oder kationischen Tensids,(b) 0.5 to 40% by weight of at least one nonionic, anionic and / or cationic surfactant,
(c) 0,5 bis 80 Gew.-% eines anorganischen Builders,(c) 0.5 to 80% by weight of an inorganic builder,
(d) 0 bis 10 Gew.-% eines organischen Cobuilders und (e) 0 bis 60 Gew.-% anderer üblicher Inhaltsstoffe, wie Stellmittel, Enzyme, Parfüm, Komplexbildner, Korrosionsinhibitoren, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, Farbübertragungsinhibitoren, Vergrauungsinhibitoren, Soil-Release- Polyester, Faser- und Farbschutzadditve, Silicone, Farbstoffe, Bakterizide, Auflösungsverbesserer und/oder Sprengmittel,(d) 0 to 10% by weight of an organic cobuilder and (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,
wobei die Summe der Komponenten (a) bis (e) 100 Gew.-% ergibt.wherein the sum of components (a) to (e) gives 100 wt .-%.
Als nichtionische Tenside (b) eignen sich dabei vor allem:Suitable nonionic surfactants (b) are, in particular:
Alkoxylierte C8-C22-Alkohole, wie Fettalkoholalkoxylate, Oxoalkoholalkoxylate und Guerbet-Alkoholalkoxylate: Die Alkoxylierung kann mit C2-C2o-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.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, insbesondere Alkylphenolethoxylate, die C6-Ci4-Alkylketten und 5 bis 30 mol Alkylenoxid/mol enthalten.- Alkylphenolalkoxylate, in particular alkylphenol ethoxylates containing C6-Ci4-alkyl chains and 5 to 30 moles of alkylene oxide / mol.
Alkylpolyglucoside, die C8-C22-, vorzugsweise Cio-Cis-Alkylketten und in der Regel 1 bis 20, vorzugsweise 1 ,1 bis 5, Glucosideinheiten enthalten.Alkylpolyglucosides containing C8-C22, preferably Cio-Cis-alkyl chains and usually 1 to 20, preferably 1, 1 to 5, glucoside units.
N-Alkylglucamide, Fettsäureamidalkoxylate, Fettsäurealkanolamidalkoxylate sowie Blockcopolymere aus Ethylenoxid, Propylenoxid und/oder Butylenoxid.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:Suitable anionic surfactants are, for example:
Sulfate von (Fett)Alkoholen mit 8 bis 22, vorzugsweise 10 bis 18, Kohlenstoffatomen, insbesondere CgCn-Alkoholsulfate, Ci2Ci4-Alkoholsulfate, Ci2-Ci8-Alkohol- sulfate, Laurylsulfat, Cetylsulfat, Myristylsulfat, Palmitylsulfat, Stearylsulfat und Talgfettalkoholsulfat.Sulfates of (fatty) alcohols having 8 to 22, preferably 10 to 18, carbon atoms, in particular CgCn alcohol sulfates, Ci2Ci4-alcohol sulfates, Ci2-Ci8-alcohol sulfate, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmitylsulfate, stearyl sulfate and tallow fatty alcohol sulfate.
Sulfatierte alkoxylierte Cs-C22-Alkohole (Alkylethersulfate): Verbindungen dieser Art werden beispielsweise dadurch hergestellt, daß man zunächst einen C8-C22-, vorzugsweise einen Cio-Cis-Alkohol, z.B. einen Fettalkohol, alkoxyliert und das AIk- oxylierungsprodukt anschließend sulfatiert. Für die Alkoxylierung verwendet man vorzugsweise Ethylenoxid. Lineare Cs-Cao-Alkylbenzolsulfonate (LAS), vorzugsweise lineare Cg-Ci3-Alkylben- zolsulfonate und -Alkyltoluolsulfonate.Sulfated alkoxylated Cs-C22 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 then sulfating the alkoxylation product. For the alkoxylation is preferably used ethylene oxide. Linear Cs-CaO alkylbenzenesulfonates (LAS), preferably linear Cg-C 13 -alkylbenzenesulfonates and -alkyltoluenesulfonates.
Alkansulfonate, insbesondere C8-C24-, vorzugsweise Clo-Cis-Alkansulfonate.Alkanesulfonates, especially C8-C24, preferably Clo-Cis-alkanesulfonates.
Seifen, wie die Na- und K-Salze von C8-C24-Carbonsäuren.Soaps, such as the Na and K salts of C8-C24 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(hydroxy- ethyl)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:Particularly suitable cationic surfactants are:
- C7-C25-Alkylamine;- C7-C25-alkylamines;
N,N-Dimethyl-N-(C7-C25-hydroxyalkyl)ammoniumsalze;N, N-dimethyl-N- (C7-C25-hydroxyalkyl) ammonium salts;
mit Alkylierungsmitteln quaternisierte Mono- und Di-(C7-C25-alkyl)dimethylammo- niumverbindungen;mono- and di- (C 7 -C 25 -alkyl) dimethylammonium compounds quaternized with alkylating agents;
Esterquats, insbesondere quaternäre veresterte Mono-, Di- und Trialkanolamine, die mit Cs-C22-Carbonsäuren verestert sind;Esterquats, especially quaternary esterified mono-, di- and trialkanolamines esterified with Cs-C22 carboxylic acids;
- Imidazolinquats, insbesondere 1-Alkylimidazoliniumsalze der Formeln I oder Il- Imidazolinquats, in particular 1-Alkylimidazoliniumsalze of the formulas I or II
in denen die Variablen folgende Bedeutung haben:in which the variables have the following meaning:
R1 Ci-C25-Alkyl oder C2-C25-Alkenyl;R 1 Ci-C 25 alkyl or C 2 -C 25 alkenyl;
R2 Ci-C4-Alkyl oder Ci-C4-Hydroxyalkyl;R 2 is C 1 -C 4 -alkyl or C 1 -C 4 -hydroxyalkyl;
R3 Ci-C4-Alkyl, Ci-C4-Hydroxyalkyl oder ein Rest R1-(CO)-X-(CH2)P- (X: -O- oderR 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 oder 3), wobei mindestens ein Rest R1 C7-C22-Alkyl ist.-NH-; p: 2 or 3), wherein at least one 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.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.
Kristalline Silikate, wie insbesondere Disilikate und Schichtsilikate, z.B. δ- und ß- Na2Si2θδ Die Silikate können in Form ihrer Alkalimetall-, Erdalkalimetall- oder Ammoniumsalze eingesetzt werden, bevorzugt sind die Na-, Li- und Mg-Silicate.Crystalline silicates, in particular disilicates and phyllosilicates, e.g. δ- and β-Na2Si2θδ 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.
Amorphe Silikate, wie Natriummetasilikat und amorphes Disilikat.Amorphous silicates such as sodium metasilicate and amorphous disilicate.
Carbonate und Hydrogencarbonate: Diese können in Form ihrer Alkalimetall-, Erd- alkalimetall- oder Ammoniumsalze eingesetzt werden. Bevorzugt sind Na-, Li- undCarbonates and bicarbonates: These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preferred are Na, Li and
Mg-Carbonate und -Hydrogencarbonate, insbesondere Natriumcarbonat und/oder Natriumhydrogencarbonat.Mg carbonates and hydrogencarbonates, in particular sodium carbonate and / or sodium bicarbonate.
Polyphosphate, wie Pentanatriumtriphosphat.Polyphosphates, such as pentasodium triphosphate.
Als organische Cobuilder eignen sich vor allem:As organic cobuilders are particularly suitable:
Niedermolekulare Carbonsäuren, wie Citronensäure, hydrophob modifizierte Citro- nensäure, z. B. Agaricinsäure, Äpfelsäure, Weinsäure, Gluconsäure, Glutarsäure, Bernsteinsäure, Imidodibernsteinsäure, Hydroxydibernsteinsäure, Oxydibernstein- säure, Propantricarbonsäure, Butantetracarbonsäure, Cyclopentantetracarbonsäu- re, Alkyl- und Alkenylbernsteinsäuren und Aminopolycarbonsäuren, z.B. Nitrilotri- essigsäure, ß-Alanindiessigsäure, Ethylendiamintetraessigsäure, Diethylentriamin- pentaessigsäure, Serindiessigsäure, Isoserindiessigsäure, Glutamindiessigsäure, N-(2-Hydroxyethyl)iminodiessigsäure, Ethylendiamindibernsteinsäure und Methyl- und Ethylglycindiessigsäure.Low molecular weight carboxylic acids, such as citric acid, hydrophobically modified citric acid, eg. , Agaricic acid, malic acid, tartaric acid, gluconic acid, glutaric acid, succinic acid, imidodisuccinic acid, hydroxydisuccinic acid, oxydibrenic acid, propane tricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, alkyl and alkenyl succinic acids and aminopolycarboxylic acids, e.g. Nitrilotriacetic acid, β-alaninediacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, serinediacetic acid, isoserinediacetic acid, glutamic diacetic acid, N- (2-hydroxyethyl) iminodiacetic acid, ethylenediamine disuccinic acid and methyl- and ethylglycinediacetic acid.
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,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, e.g. Isobutene or long-chain α-olefins,
Vinyl-Ci-Cs-alkylether, Vinylacetat, Vinylpropionat, (Meth)Acrylsäureester von d- Cs-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. Geeignete Bleichmittel sind beispielsweise Addukte von Wasserstoffperoxid an anorganische Salze, wie Natriumperborat-Monohydrat, Natriumperborat-Tetrahydrat und Natriumcarbonat-Perhydrat, und Percarbonsäuren, wie Phthalimidopercapronsäure.Vinyl-C 1 -C -alkyl ethers, vinyl acetate, vinyl propionate, (meth) acrylic 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. 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), Na- trium-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, Amyla- sen, 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 Sei. 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 Sei. Ser., Vol. 67, Marcel Decker, New York, 1997, p. 272-304, to find.
BeispieleExamples
Die viskositätserniedrigende Wirkung des Copolymers P wurde in zwei Waschmittel- slurries 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, having an average molecular weight Mw of 3,000 g / mol and a K value of 24 (measured at pH 7 in 1 wt .-% aqueous solution at 25 ° C) had. 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 Umdre- hungszahl unter Bestimmung des Drehmoments weitergerührt. 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.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 with a constant number of revolutions while determining the torque. 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.The result nb means that the viscosity of the slurries was very high and the torque was no longer determinable.
Tabelle 1 : Zusammensetzung der WaschmnittelslurriesTable 1: Composition of the washing agent slurries
Tabelle 2: Bestimmung des DrehmomentsTable 2: Determination of torque

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von granulären oder pulverförmigen Waschmittelzusammensetzungen, umfassend die Herstellung eines Waschmittelbasispulvers durch Trocknung eines wäßrigen Waschmittelslurries, dadurch gekennzeichnet, daß man dem Slurry ein Copolymer zusetzt, das durch radikalische Copolymeri- sation von1. A process for the preparation of granular or powdered detergent compositions, comprising the preparation of a detergent base powder by drying an aqueous Waschmittellurries, characterized in that the slurry is added to a copolymer by free radical copolymerization of
(A) 20 bis 80 Gew.-% mindestens eines Monomeren aus der Gruppe der mo- noethylenisch ungesättigten Monocarbonsäuren, Dicarbonsäuren und Di- carbonsäureanhydride(A) 20 to 80 wt .-% of at least one monomer from the group of monoethylenically unsaturated monocarboxylic acids, dicarboxylic acids and dicarboxylic anhydrides
undand
(B) 20 bis 80 Gew.-% mindestens eines Monomeren aus der Gruppe der aliphatischen oder aromatischen Monoolefine(B) 20 to 80 wt .-% of at least one monomer from the group of aliphatic or aromatic monoolefins
erhältlich ist.is available.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß man ein Copolymer auf Basis mindestens eines Monomers (A) aus der Gruppe Maleinsäure, Maleinsäureanhydrid und Acrylsäure einsetzt.2. The method according to claim 1, characterized in that one uses a copolymer based on at least one monomer (A) from the group of maleic acid, maleic anhydride and acrylic acid.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man ein Copo- lymer auf Basis mindestens eines Monomers (B) aus der Gruppe Isobuten, Diiso- buten, 1-Dodecen, Ci8-C24-α-Olefine, C2o-C24-α-Olefingemische, Polyisobutene mit im Mittel 12 bis 100 Kohlenstoff atomen und Styrol einsetzt.3. The method according to claim 1 or 2, characterized in that a copolymer based on at least one monomer (B) from the group isobutene, diisobutene, 1-dodecene, Ci8-C24-α-olefins, C2o-C24 α-olefin mixtures, polyisobutenes with an average of 12 to 100 carbon atoms and styrene used.
4. Verfahren nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß man ein Copolymer einsetzt, das auf einer Mischung aus (B1 ) mindestens einem Mono- olefin mit < 8 Kohlenstoffatomen und (B2) mindestens einem Monoolefin mit > 10 Kohlenstoff atomen als Komponente (B) basiert.4. Process according to claims 1 to 3, characterized in that one uses a copolymer which on a mixture of (B1) at least one monoolefin having <8 carbon atoms and (B2) at least one monoolefin having> 10 carbon atoms as a component (B) based.
5. Verfahren nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß man ein Copolymer einsetzt, das durch radikalische Copolymerisation von (A) 30 bis 705. Process according to claims 1 to 4, characterized in that one uses a copolymer obtained by free-radical copolymerization of (A) 30 to 70
Gew.-% Maleinsäure oder Maleinsäureanhydrid, (B1 ) 20 bis 40 Gew.-% Isobuten und (B2) 5 bis 20 Gew.-% eines Cis-C24-a-Olefins erhältlich ist.Wt .-% maleic acid or maleic anhydride, (B1) 20 to 40 wt .-% isobutene and (B2) 5 to 20 wt .-% of a cis-C24-α-olefin is available.
6. Verfahren zur Erniedrigung der Viskosität von wäßrigen Waschmittelslurries, da- durch gekennzeichnet, daß man dem Slurry ein Copolymer gemäß den Ansprüchen 1 bis 5 zusetzt. 6. A process for lowering the viscosity of aqueous Waschmittelslurries, characterized in that the slurry is added to a copolymer according to claims 1 to 5.
7. Waschmittelsluπϊes, enthaltend ein Copolymer gemäß den Ansprüchen 1 bis 5.7. Waschmittelsluπϊes containing a copolymer according to claims 1 to 5.
8. Waschmittelzusammensetzungen, enthaltend ein Copolymer gemäß den Ansprüchen 1 bis 5. 8. Detergent compositions containing a copolymer according to claims 1 to 5.
EP06793896A 2005-10-05 2006-09-29 Method for producing granular or powdery detergent compositions Not-in-force EP1941016B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL06793896T PL1941016T3 (en) 2005-10-05 2006-09-29 Method for producing granular or powdery detergent compositions

Applications Claiming Priority (2)

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DE102005047833A DE102005047833A1 (en) 2005-10-05 2005-10-05 Process for the preparation of granular or powdered detergent compositions
PCT/EP2006/066868 WO2007039554A1 (en) 2005-10-05 2006-09-29 Method for producing granular or powdery detergent compositions

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EP1941016A1 true EP1941016A1 (en) 2008-07-09
EP1941016B1 EP1941016B1 (en) 2012-07-04

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EP (1) EP1941016B1 (en)
JP (1) JP5080480B2 (en)
CN (1) CN101278038B (en)
CA (1) CA2624919C (en)
DE (1) DE102005047833A1 (en)
ES (1) ES2388701T3 (en)
PL (1) PL1941016T3 (en)
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WO2019211170A1 (en) * 2018-05-04 2019-11-07 Basf Se Granules or powders and methods for their manufacture
CN109234070B (en) * 2018-09-18 2020-12-15 祥瑞博特生物科技（北京）有限责任公司 Washing product containing styrene-acrylic acid-maleic anhydride copolymer and application thereof

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CN101278038A (en) 2008-10-01
JP2009511651A (en) 2009-03-19
CN101278038B (en) 2012-11-28
ES2388701T3 (en) 2012-10-17
EP1941016B1 (en) 2012-07-04
CA2624919C (en) 2015-01-27
PL1941016T3 (en) 2012-10-31
US20080255022A1 (en) 2008-10-16
CA2624919A1 (en) 2007-04-12
JP5080480B2 (en) 2012-11-21
WO2007039554A1 (en) 2007-04-12
DE102005047833A1 (en) 2007-04-19
US8486884B2 (en) 2013-07-16

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