WO1997031995A1 - Cleaning agent for hard surfaces, with an improved ability to dissolve grease and fat - Google Patents

Cleaning agent for hard surfaces, with an improved ability to dissolve grease and fat Download PDF

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Publication number
WO1997031995A1
WO1997031995A1 PCT/EP1997/000800 EP9700800W WO9731995A1 WO 1997031995 A1 WO1997031995 A1 WO 1997031995A1 EP 9700800 W EP9700800 W EP 9700800W WO 9731995 A1 WO9731995 A1 WO 9731995A1
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WO
WIPO (PCT)
Prior art keywords
cleaning agent
cleaning
fat
alkyl
surfactants
Prior art date
Application number
PCT/EP1997/000800
Other languages
German (de)
French (fr)
Inventor
Norbert Höfel
Klaus HÜLSEWIESCHE
Udo Hees
Dagmar Zaika
Brigitte Giesen
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Publication of WO1997031995A1 publication Critical patent/WO1997031995A1/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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • the present invention relates to liquid cleaning agents with improved fat-emulsifying power and increased cleaning power.
  • Liquid detergents, dishwashing detergents and cleaning agents are usually aqueous solutions of anionic and / or nonionic surfactants and conventional additives.
  • a preferred area of application is the manual washing of dishes.
  • tableware is understood to mean any object that can be used in the preparation or consumption of foodstuffs and which is then generally rinsed in order to free it of residues and food residues adhering to it. These are usually starches, fats and proteins, but also colorants, artificial additives and thermally partially or completely decomposed organic residues.
  • Grease residues in particular are among the problem soils in the food sector. Not only do they form stubborn stains, they also reduce the washing performance of a manual detergent.
  • EP 124367 (Unilever) describes a hand dishwashing detergent which, thanks to polymers, has an increased foam and detergent action.
  • Polymers according to this application are cellulose with hydrophilic groups and guar compounds. The reason for this improved foaming and detergent effect is the increased viscosity of the formulations used there due to the addition of polymer.
  • ternary surfactant combinations are known (ether sulfate, alcohol sulfate, betaine) which, by adding guar derivatives, result in a stable foam which remains stable even with increased grease contamination.
  • JP 6264090 describes a detergent composition which has a high storage stability, good foaming power and thus improved washing properties through a combination of N-acylglutamate and a natural polysaccharide such as xanthan, carrageenan and related substances
  • EP 565950 describes an aqueous cleaning agent in which surfactants are mixed with silicone, glycol and xanthane derivatives in an amount such that the solution obtained remains clear.
  • the cleaning effect of this agent is increased in that the polymer settles on the surface and thus prevents or makes it more difficult for it to be soiled again.
  • JP 2107010 describes how to obtain aqueous emulsions of animal or vegetable fats or oils by adding different types of oil to xanthane derivatives or other natural polymers or their mixtures.
  • the object of the present invention is to improve the cleaning performance of manual dishwashing detergents by adding polymers such as xanthane and its derivatives by improving the fat emulsifiability in the cleaning liquor, the viscosity of the cleaning solutions playing no or a very minor role.
  • the present invention now relates to a liquid cleaning agent, in particular for manual dishwashing, based on an aqueous solution of anionic surfactants, optionally together with nonionic and / or amphoteric surfactants and / or zwitterionic surfactants, solubilizers, solvents, corrosion inhibitors, preservatives, thickeners and Dyes and fragrances, which is characterized in that it additionally contains at least one fat-emulsifying, cleaning-enhancing, water-soluble polymer which is selected from the group of the xanthans and their derivatives.
  • the polymer according to the invention can be present in the cleaning agent in an amount of 0.0001 to 10% by weight, based on the total composition. An amount between 0.005 and 1% by weight is preferred. An amount between 0.05 and 1% by weight is particularly preferred.
  • Another object of the invention is the use of a water-soluble polymer which is selected from the group of xanthans and its derivatives to improve cleaning performance through improved fat emulsifiability of poor dishwashing detergents.
  • Xanthane derivative is the name for chemical reaction products of xanthane, a microbially produced anionic heteropolysaccharide.
  • Xanthan is e.g. B. produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2-15 x 10 6 .
  • the xanthan is formed from a chain of ⁇ -1,4-linked glucose (cellulose) with side chains.
  • the structure of the subgroups (“repeated units”) consists of glucose, mannose, glucuronic acid, acetate and pyruvate. The number of pyruvate units determines the viscosity of the xanthane.
  • Xanthan is obtained in two-day batch cultures with a yield of 70-90%, based on the carbohydrate used, yields of 25-30 g / l are achieved, and the culture is worked up after the culture has been killed by precipitation with, for example, 2-propanol, and xanthan is then dried and ground.
  • the manual rinsing agents according to the invention can contain anionic and non-ionic and / or amphoteric and / or zwitterionic surfactants or a mixture thereof. These agents are preferably present in 0.5-50% by weight, particularly preferably in 3-35% by weight, based on the total agent.
  • Anionic surfactants according to the present invention can be aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkane sulfonates, olefin sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates, and lingin sulfonates.
  • aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkane sulfonates, olefin sulfonates, ether sulfonates, n-alkyl ether sulf
  • Fatty acid cyanamides, sulfosuccinic acid esters, fatty acid isethionates, acylaminoalkane sulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates can also be used in the context of the present invention.
  • Nonionic surfactants in the context of the present invention can be alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters.
  • alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters.
  • Ethylene oxide, propylene oxide, block polymers and fatty acid alkanolamides and can also be used
  • Fatty acid polyglycol ether Fatty acid polyglycol ether.
  • nonionic surfactants that can be used according to the invention are the polyol surfactants and here in particular the glucose surfactants, such as alkyl polyglucoside and fatty acid glucamides. Glycerol fatty acid esters and sorbitan esters as well as amine oxides and fluorosurfactants can also be used.
  • the amphoteric surfactants which can be used according to the invention include the alkyl betaines, the alkyl amido betaines, the imidazolinium betaines and the aminopropionates, as well as the sulfobetaines and biosurfactants.
  • Particularly preferred surfactants are the alkyl sulfates, the alkyl ether sulfates, the alkyl fatty acid alkanolamides, the alkyl glycosides and the fatty acid amide alkyl betaines.
  • the solvents to be added if necessary are low molecular weight alkanols with 1 to 4 carbon atoms in the molecule, preferably ethanol and isopropanol.
  • Solubilizers for example for dyes and perfume oils, can be used, for example, as alkanolamines, polyols such as ethylene glycol, propylene glycol, 1, 2 glycerol and other mono- and polyhydric alcohols, and also alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical.
  • the preferred thickeners which can also be used if necessary include urea, sodium chloride, sodium sulfate, magnesium sulfate, ammonium chloride and magnesium chloride and the combination of these thickeners.
  • corrosion inhibitors and preservatives are sodium benzoate, formaldehyde and sodium sulfite.
  • the liquid cleaning agents according to the invention can be obtained by stirring the individual components together in any order.
  • the polymer is preferably mixed with water beforehand, causing it to swell.
  • test solutions (10 g washing-up liquid / 40 g water) with city water of 16 ° d were prepared in a 400 ml beaker, covered with 50 g olive oil (Olio Dante ®) at room temperature (20 to 30 ° C) and covered with a Propeller stirrer (blade length 50 mm made of V2A steel) with a speed of 1200 revolutions per minute stirred exactly 2 minutes.
  • the impeller was roughly at the border of the two phases.
  • the emulsion was then poured into a 250 ml measuring cylinder with a diameter of 3.6 cm (2 ml graduation, industrial standard) and the aqueous phase which separated out was determined after 1 hour and after 4 hours. The less water was separated in the unit of time, the more stable the emulsion and thus the oil / fat-carrying capacity of the cleaning agent solution, which means a significant cleaning boost.
  • Viscosity (mPas) ⁇ 5 ⁇ 5 according to Brookfield, spindle 18, 30 rpm

Abstract

The invention concerns a liquid cleaning agent, in particular for hand washing-up, based on an aqueous solution of anionic surfactants, optionally together with non-ionic and/or amphoteric and/or zwitterionic surfactants, solubilizers, solvents, corrosion inhibitors, preservatives, thickening agents as well as colorants and fragrances. The main aim of the invention is to increase the cleaning performance by improving the ability of the agent to emulsify grease and fat in the cleaning water. This is achieved by adding at least one water-soluble polymer which emulsifies grease and fat and increases the cleaning power, the polymer being selected from the group comprising xanthane and its derivatives.

Description

„Reinigungsmittel für harte Oberflächen mit verbesserter Fettlösekraft" "Cleaning agents for hard surfaces with improved grease-dissolving power"
Die vorliegende Erfindung betrifft flüssige Reinigungsmittel mit verbessertem Fett- emulgiervermögen und verstärkter Reinigungskraft.The present invention relates to liquid cleaning agents with improved fat-emulsifying power and increased cleaning power.
Flüssige Wasch-, Spül- und Reinigungsmittel stellen meist wäßrige Lösungen von anionischen und/oder nichtionischen Tensiden und üblichen Zusatzstoffen dar. Ein bevorzugtes Anwendungsgebiet ist das manuelle Spülen von Geschirr. Unter Geschirr wird im folgenden jeder Gegenstand verstanden, der in der Zubereitung oder im Verzehr von Lebensmittel eingesetzt werden kann, und der danach in der Regel gespült wird, um ihn von darauf anhaftenden Rückständen und Lebens¬ mittelresten zu befreien. Dies sind in der Regel Stärken, Fette und Eiweiße aber auch Farbstoffe, künstliche Zusatzstoffe und thermisch teilweise oder vollständig zersetzte organische Rückstände.Liquid detergents, dishwashing detergents and cleaning agents are usually aqueous solutions of anionic and / or nonionic surfactants and conventional additives. A preferred area of application is the manual washing of dishes. In the following, tableware is understood to mean any object that can be used in the preparation or consumption of foodstuffs and which is then generally rinsed in order to free it of residues and food residues adhering to it. These are usually starches, fats and proteins, but also colorants, artificial additives and thermally partially or completely decomposed organic residues.
Besonders Fettrückstände gehören zu den Problemanschmutzungen im Lebens¬ mittelbereich. Sie bilden nicht nur hartnäckige Flecken sondern führen auch zu einer Verringerung der Waschleistung eines manuellen Spülmittels.Grease residues in particular are among the problem soils in the food sector. Not only do they form stubborn stains, they also reduce the washing performance of a manual detergent.
Der Zusatz von natürlichen und synthetischen Polymeren zu Reinigungsmittel¬ zusammensetzungen zwecks Verbesserung der Waschleistung ist bekannt. So beschreibt die EP 124367 (Unilever) ein Handgeschirrspülmittel, das durch Poly¬ mere eine erhöhte Schaum- und Detergenzwirkung zeigt. Polymere gemäß dieser Anmeldung sind Zellulose mit hydrophilen Gruppen und Guar-Verbindungen. Ursache dieser verbesserten Schaum- und Detergenzwirkung ist die durch die Polymerzugabe erhöhte Viskosität der dort verwendeten Formulierungen.The addition of natural and synthetic polymers to cleaning agent compositions for the purpose of improving the washing performance is known. For example, EP 124367 (Unilever) describes a hand dishwashing detergent which, thanks to polymers, has an increased foam and detergent action. Polymers according to this application are cellulose with hydrophilic groups and guar compounds. The reason for this improved foaming and detergent effect is the increased viscosity of the formulations used there due to the addition of polymer.
Aus der GB 2103236 (Colgate) sind ternäre Tensidkombinationen bekannt (Ethersulfat, Alkoholsulfat, Betain), die durch Zusatz von Guarderivaten einen stabilen Schaum ergeben, der auch bei erhöhter Fettanschmutzung stabil bleibt. Die JP 6264090 beschreibt eine Reinigungsmittelzusammensetzung, die eine hohe Lagerstabilität, ein gutes Schaumvermögen und damit verbesserte Wascheigen¬ schaften durch eine Kombination von N-Acylglutamat und einem natürlichen Poly- saccharid wie Xanthan, Carrageenan und verwandten Stoffen erhältFrom GB 2103236 (Colgate) ternary surfactant combinations are known (ether sulfate, alcohol sulfate, betaine) which, by adding guar derivatives, result in a stable foam which remains stable even with increased grease contamination. JP 6264090 describes a detergent composition which has a high storage stability, good foaming power and thus improved washing properties through a combination of N-acylglutamate and a natural polysaccharide such as xanthan, carrageenan and related substances
Die EP 565950 beschreibt ein wäßriges Reinigungsmittel, in dem Tenside mit Sili¬ kon, Glykol und Xanthanderivaten in einer Menge gemischt werden, daß die erhal¬ tene Lösung noch klar bleibt. Die Reinigungswirkung dieses Mittels wird dadurch erhöht, daß sich das Polymer auf der Oberfläche absetzt und so eine Wieder- anschmutzung verhindert oder erschwert wird.EP 565950 describes an aqueous cleaning agent in which surfactants are mixed with silicone, glycol and xanthane derivatives in an amount such that the solution obtained remains clear. The cleaning effect of this agent is increased in that the polymer settles on the surface and thus prevents or makes it more difficult for it to be soiled again.
Die verbesserte Reinigungsleistung dieser Reinigungsmittelzusammensetzungen beruhen auf der wohlbekannten verdickenden Wirkung solcher natürlicher Polymere und der Schaumstabilisierung, die für das manuelle Geschirrspülen äußerst erwünscht ist.The improved cleaning performance of these detergent compositions is due to the well known thickening effect of such natural polymers and the foam stabilization which is extremely desirable for manual dishwashing.
Die JP 2107010 beschreibt schließlich, wie man wäßrige Emulsionen von tierischen oder pflanzlichen Fetten oder Ölen erhält, indem man Xanthanderivate oder andere natürliche Polymere oder deren Mischungen mit verschiedenen ölsorten versetzt.Finally, JP 2107010 describes how to obtain aqueous emulsions of animal or vegetable fats or oils by adding different types of oil to xanthane derivatives or other natural polymers or their mixtures.
Keine dieser Schriften beschreibt den Einsatz von natürlichen Polymeren wie Xanthanderivaten zur verbesserten Fettemulgierung in manuellen Geschirrspül¬ mitteln.None of these documents describes the use of natural polymers such as xanthane derivatives for improved fat emulsification in manual dishwashing detergents.
Aufgabe der vorliegenden Erfindung ist die Verbesserung der Reinigungsleistung von manuellen Geschirrspülmitteln durch Zusatz von Polymeren wie des Xanthans und seiner Derivate durch die Verbesserung der Fettemulgierbarkeit in der Reini¬ gungsflotte, wobei die Viskosität der Reinigungslösungen keine oder eine sehr untergeordnete Rolle spielt. Gegenstand der vorliegenden Erfindung ist nun ein flüssiges Reinigungsmittel, insbesondere für das manuelle Geschirrspülen, auf Basis einer wäßrigen Lösung von anionischen Tensiden, gegebenenfalls zusammen mit nichtionischen und/oder amphoteren Tensiden und/oder zwitterionischen Tensiden, Lösungsvermittlern, Lösungsmitteln, Korrosionsinhibitoren, Konservierungsmitteln, Verdickungsmitteln sowie Färb- und Duftstoffen, das dadurch gekennzeichnet ist, daß es zusätzlich mindestens ein fettemulgierendes, reinigungsverstärkendes, wasserlösliches Poly¬ mer enthält, welches ausgewählt ist aus der Gruppe des Xanthans und seiner Deri¬ vate. Dabei kann das erfindungsgemäße Polymer in dem Reinigungsmittel in einer Menge von 0,0001 bis 10 Gew.-% bezogen auf die gesamt Zusammensetzung vor¬ handen sein. Bevorzugt ist eine Menge zwischen 0,005 und 1 Gew.-%. Besonders bevorzugt ist eine Menge zwischen 0.05 und 1 Gew.-%.The object of the present invention is to improve the cleaning performance of manual dishwashing detergents by adding polymers such as xanthane and its derivatives by improving the fat emulsifiability in the cleaning liquor, the viscosity of the cleaning solutions playing no or a very minor role. The present invention now relates to a liquid cleaning agent, in particular for manual dishwashing, based on an aqueous solution of anionic surfactants, optionally together with nonionic and / or amphoteric surfactants and / or zwitterionic surfactants, solubilizers, solvents, corrosion inhibitors, preservatives, thickeners and Dyes and fragrances, which is characterized in that it additionally contains at least one fat-emulsifying, cleaning-enhancing, water-soluble polymer which is selected from the group of the xanthans and their derivatives. The polymer according to the invention can be present in the cleaning agent in an amount of 0.0001 to 10% by weight, based on the total composition. An amount between 0.005 and 1% by weight is preferred. An amount between 0.05 and 1% by weight is particularly preferred.
Ein weiterer Gegenstand der Erfindung ist die Verwendung eines wasserlöslichen Polymers, das ausgewählt ist aus der Gruppe des Xanthans und seiner Derivate zur Verbesserung der Reinigungsleistung durch verbesserte Fettemulgierbarkeit von mangeilen Geschirrspülmitteln.Another object of the invention is the use of a water-soluble polymer which is selected from the group of xanthans and its derivatives to improve cleaning performance through improved fat emulsifiability of poor dishwashing detergents.
Dabei ist Xanthanderivat die Bezeichnung für chemische Umsetzungsprodukte des Xanthans, eines mikrobiell hergestellten anionischen Heteropolysaccharids. Xanthan wird z. B. von Xanthomonas campestris und einigen anderen Spezies unter aeroben Bedingungen mit einem Molekulargewicht von 2-15 x 106 produziert. Das Xanthan wird aus einer Kette von ß-1 ,4-gebundene Glucose (Zellulose) mit Seitenketten gebildet. Die Struktur der Untergruppen („repeated units") besteht aus Glucose, Mannose, Glucuronsäure, Acetat und Pyruvat. Die Anzahl der Pyruvat- Einheiten bestimmt die Viskosität des Xanthans. Xanthan wird in zweitägigen Batch-Kulturen mit einer Ausbeute von 70-90 %, bezogen auf eingesetztes Kohlenhydrat, produziert. Dabei werden Ausbeuten von 25-30 g/l erreicht. Die Aufarbeitung erfolgt nach Abtöten der Kultur durch Fällung mit z. B. 2-Propanol. Xanthan wird anschließend getrocknet und gemahlen. In den erfindungsgemäßen manuellen Spülmittetn können anionische und nicht¬ ionische und/oder amphotere und/oder zwitterionische Tenside oder deren Mischung enthalten sein. Bevorzugt sind diese Mittel in 0,5-50 Gew.-% enthalten, besonders bevorzugt in 3-35 Gew.-% bezogen auf das gesamte Mittel.Xanthane derivative is the name for chemical reaction products of xanthane, a microbially produced anionic heteropolysaccharide. Xanthan is e.g. B. produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2-15 x 10 6 . The xanthan is formed from a chain of β-1,4-linked glucose (cellulose) with side chains. The structure of the subgroups (“repeated units”) consists of glucose, mannose, glucuronic acid, acetate and pyruvate. The number of pyruvate units determines the viscosity of the xanthane. Xanthan is obtained in two-day batch cultures with a yield of 70-90%, based on the carbohydrate used, yields of 25-30 g / l are achieved, and the culture is worked up after the culture has been killed by precipitation with, for example, 2-propanol, and xanthan is then dried and ground. The manual rinsing agents according to the invention can contain anionic and non-ionic and / or amphoteric and / or zwitterionic surfactants or a mixture thereof. These agents are preferably present in 0.5-50% by weight, particularly preferably in 3-35% by weight, based on the total agent.
Anionische Tenside gemäß der vorliegenden Erfindung können aliphatische Sulfate wie Fettalkoholsulfate, Fettalkoholethersulfate, Dialkylethersulfate, Monoglycerid- sulfate und aliphatische Sulfonate wie Alkansulfonate, Olefinsulfonate, Ether- sulfonate, n-Alkylethersulfonate, Estersulfonate, und Lingninsulfonate sein. Ebenfalls im Rahmen der vorliegenden Erfindung verwendbar sind Fettsäure- cyanamide, Sulfobemsteinsäureester, Fettsäureisethionate, Acylaminoalkan- sulfonate (Fettsäuretauride), Fettsäuresarcosinate, Ethercarbonsäuren und Alkyl(ether)phosphate.Anionic surfactants according to the present invention can be aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkane sulfonates, olefin sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates, and lingin sulfonates. Fatty acid cyanamides, sulfosuccinic acid esters, fatty acid isethionates, acylaminoalkane sulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates can also be used in the context of the present invention.
Nichtionische Tenside im Rahmen der vorliegenden Erfindung können Alkoxylate sein wie Polyglycolether, Fettalkoholpolygycolether, Alkylphenolpolyglycolether, endruppenverschlossene Polyglycolether, Mischether und Hydroxymischether und Fettsäurepolyglycolester sein. Ebenfalls verwendbar sind Ethylenoxid, Propylenoxid, Blockpolymere und Fettsäurealkanolamide undNonionic surfactants in the context of the present invention can be alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Ethylene oxide, propylene oxide, block polymers and fatty acid alkanolamides and can also be used
Fettsäurepolyglycolether. Eine wichtige Klasse nichtionischer Tenside die erfindungsgemäß verwendet werden kann, sind die Polyol-Tenside und hier besonders die Glucotenside, wie Alkylpolyglucosid und Fettsäureglucamide. Aber auch Glycerin-Fettsäureester und Sorbitanester sowie Aminoxide und Fluortenside können verwendet werden. Zu den Amphotensiden die erfindungsgemäß eingesetzt werden können, zählen die Alkylbetaine, die Alkylamidobetaine, die Imidazoliniumbetaine und die Aminopropionate, genauso wie die Sulfobetaine und Biotenside.Fatty acid polyglycol ether. An important class of nonionic surfactants that can be used according to the invention are the polyol surfactants and here in particular the glucose surfactants, such as alkyl polyglucoside and fatty acid glucamides. Glycerol fatty acid esters and sorbitan esters as well as amine oxides and fluorosurfactants can also be used. The amphoteric surfactants which can be used according to the invention include the alkyl betaines, the alkyl amido betaines, the imidazolinium betaines and the aminopropionates, as well as the sulfobetaines and biosurfactants.
Besonders bevorzugte Tenside sind die Alkylsulfate, die Alkylethersulfate, die Alkyl-Fettsäurealkanolamide, die Alkylglycoside und die Fettsäureamidalkylbetaine. Bei den bei Bedarf zuzusetzenden Lösungsmitteln handelt es sich um niedermole¬ kulare Alkanole mit 1 bis 4 Kohlenstoffatomen im Molekül vorzugsweise um Ethanol und Isopropanol.Particularly preferred surfactants are the alkyl sulfates, the alkyl ether sulfates, the alkyl fatty acid alkanolamides, the alkyl glycosides and the fatty acid amide alkyl betaines. The solvents to be added if necessary are low molecular weight alkanols with 1 to 4 carbon atoms in the molecule, preferably ethanol and isopropanol.
Als Lösungsvermittler, etwa für Farbstoffe und Parfümöle können beispielsweise Alkanolamine, Polyole wie Ethylenglycol, Propylenglycol, 1 ,2 Glycerin und andere ein- und mehrwertige Alkohole, sowie Alkylbenzolsulfonate mit 1 bis 3 Kohlenstoff¬ atomen im Alkylrest dienen.Solubilizers, for example for dyes and perfume oils, can be used, for example, as alkanolamines, polyols such as ethylene glycol, propylene glycol, 1, 2 glycerol and other mono- and polyhydric alcohols, and also alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical.
Zu den bevorzugten Verdickungsmitteln, die bei Bedarf ebenfalls einzusetzen sind, zählen Harnstoff, Natriumchlorid, Natriumsulfat, Magnesiumsulfat, Ammoniumchlorid und Magnesiumchlorid sowie die Kombination dieser Verdickungsmittel.The preferred thickeners which can also be used if necessary include urea, sodium chloride, sodium sulfate, magnesium sulfate, ammonium chloride and magnesium chloride and the combination of these thickeners.
Als Korrosionsinhibitoren und Konservierungsmittel sind beispielsweise Natrium- benzoat, Formaldehyd und Natriumsulfit zu nennen.Examples of corrosion inhibitors and preservatives are sodium benzoate, formaldehyde and sodium sulfite.
Die erfindungsgemäßen flüssigen Reinigungsmittel können durch Zusammenrühren der einzelnen Bestandteile in beliebiger Reihenfolge erhalten werden. Bevorzugt wird dabei das Polymer vorher mit Wasser versetzt, wodurch es vorquillt. The liquid cleaning agents according to the invention can be obtained by stirring the individual components together in any order. The polymer is preferably mixed with water beforehand, causing it to swell.
Beispiele:Examples:
An einer Spülmittelrezeptur gemäß EP 513 138, vergleichbar Beispiel 1 (mit 10 % Fettalkoholsulfat, 6 % Fettalkoholethersulfat, 1,5 % Betain und 2 % Alkylpoiy- glycosid, 5 % Ethanol und 1 ,3 % Kochsalz) wurde bei Zusatz von Xanthan (Keltrol® T) der Einfluß auf das sogenannte Fett-Emulgiervermögen nach der Rührmethode geprüft. Hierzu wurde die Emulsionsstabilität von Olivenöl in den Reinigungsmittel-Lösungen ermittelt. Hierzu wurden 50 g Prüflösungen (10 g Spülmittel / 40 g Wasser) mit Stadtwasser von 16 °d in einem 400 ml-Becherglas hergestellt, bei Raumtemperatur (20 bis 30 °C) mit 50 g Olivenöl (Olio Dante ®) überschichtet und mit einem Propellerrührer (Flügellänge 50 mm aus V2A-Stahl) mit einer Drehzahl von 1200 Umdrehungen pro Minute genau 2 Minuten gerührt. Der Rührflügel befand sich dabei etwa an der Grenze der beiden Phasen. Anschließend wurde die Emulsion in einem 250 ml-Meßzylinder mit einem Durch¬ messer von 3,6 cm (2 ml-Graduierung, Industrienorm) gegossen und die sich abscheidende wäßrige Phase nach 1 Stunde und nach 4 Stunden ermittelt. Je weniger Wasser in der Zeiteinheit abgeschieden wurde, desto stabiler war die Emulsion und somit das Öl-/Fetttragevermögen der Reinigungsmittellösung, was eine wesentliche Reinigungsverstärkung bedeutet.A detergent formulation according to EP 513 138, comparable to Example 1 (with 10% fatty alcohol sulfate, 6% fatty alcohol ether sulfate, 1.5% betaine and 2% alkyl polyglycoside, 5% ethanol and 1.3% sodium chloride) was added with the addition of xanthan (Keltrol ® T) the influence on the so-called fat emulsifying ability tested by the stirring method. For this purpose, the emulsion stability of olive oil in the detergent solutions was determined. For this purpose, 50 g test solutions (10 g washing-up liquid / 40 g water) with city water of 16 ° d were prepared in a 400 ml beaker, covered with 50 g olive oil (Olio Dante ®) at room temperature (20 to 30 ° C) and covered with a Propeller stirrer (blade length 50 mm made of V2A steel) with a speed of 1200 revolutions per minute stirred exactly 2 minutes. The impeller was roughly at the border of the two phases. The emulsion was then poured into a 250 ml measuring cylinder with a diameter of 3.6 cm (2 ml graduation, industrial standard) and the aqueous phase which separated out was determined after 1 hour and after 4 hours. The less water was separated in the unit of time, the more stable the emulsion and thus the oil / fat-carrying capacity of the cleaning agent solution, which means a significant cleaning boost.
Mischung 1 2Mixture 1 2
Anteil Keltrol® (Gew.%) 0 0,1Portion of Keltrol® (% by weight) 0 0.1
Emulgieren 1h (»ml Wasser) 7 3Emulsify 1h (»ml water) 7 3
Emulgieren 4h (»ml Wasser) 25 8Emulsify 4h (»ml water) 25 8
Viskosität (mPas) < 5 <5 nach Brookfield, Spindel 18, 30 Upm,Viscosity (mPas) <5 <5 according to Brookfield, spindle 18, 30 rpm,
20 °C, 20%ige Lösung20 ° C, 20% solution
Die Beispiele zeigen, daß das Emulgiervermögen der Formulierungen bei Einsatz der erfindungsgemäßen Verbindungen zunimmt. The examples show that the emulsifying power of the formulations increases when the compounds according to the invention are used.

Claims

Patentansprüche: Claims:
1. Flüssiges Reinigungsmittel auf Basis einer wässrigen Lösung von anionischen Tensiden, gegebenenfalls zusammen mit nichtionischen und/oder amphoteren und/ oder zwitterionischen Tensiden, Lösungsvermittlern, Lösungsmitteln, Korro¬ sionsinhibitoren, Konservierungsmitteln, Verdickungsmitteln sowie Färb- und Duftstoffen, dadurch gekennzeichnet, daß es zusätzlich mindestens ein fett- emulgierendes, reinigungsverstärkendes, wasserlösliches Polymer enthält, welches ausgewählt ist aus der Gruppe des Xanthans und seiner Derivate.1. Liquid cleaning agent based on an aqueous solution of anionic surfactants, optionally together with nonionic and / or amphoteric and / or zwitterionic surfactants, solubilizers, solvents, corrosion inhibitors, preservatives, thickeners and colorants and fragrances, characterized in that it additionally contains at least one fat-emulsifying, cleaning-enhancing, water-soluble polymer which is selected from the group of xanthans and its derivatives.
2. Reinigungsmittel nach Anspruch 1 , dadurch gekennzeichnet daß es das Polymer in einer Menge von 0,0001 bis 10 Gew.-% bezogen auf die gesamte Zusammensetzung enthält.2. Cleaning agent according to claim 1, characterized in that it contains the polymer in an amount of 0.0001 to 10 wt .-% based on the entire composition.
3. Reinigungsmittel nach den Ansprüchen 1 und 2, dadurch gekennzeichnet daß es das Polymer in einer Menge von 0,005 bis 1 Gew.-% bezogen auf die gesamte Zusammensetzung enthält.3. Cleaning agent according to claims 1 and 2, characterized in that it contains the polymer in an amount of 0.005 to 1 wt .-% based on the entire composition.
4. Reinigungsmittel nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet daß es anionische und gegebenenfalls nichtionische und/oder amphotere und/oder zwitterionische Tenside in zusammen 0,5 - 50 Gew.-% bezogen auf das gesamte Mittel enthalten.4. Cleaning agent according to claims 1 to 3, characterized in that it contains anionic and optionally nonionic and / or amphoteric and / or zwitterionic surfactants in a total of 0.5-50% by weight, based on the total agent.
5. Reinigungsmittel nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet daß es anionische und gegebenenfalls nichtionische und/oder amphotere und/oder zwitterionische Tenside in zusammen 3 - 35 Gew.-% bezogen auf das gesamte Mittel enthalten.5. Cleaning agent according to claims 1 to 4, characterized in that it contains anionic and optionally nonionic and / or amphoteric and / or zwitterionic surfactants in a total of 3 - 35 wt .-% based on the total agent.
6. Reinigungsmittel nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet daß die Tenside ausgewählt sind aus der Gruppe der Alkylsulfate, der Alkylethersulfate, der Alkyl-Fettsäurealkanolamide, der Alkylglycoside und der Fettsäureamidalkyl- betaine sowie deren Mischungen. 6. Cleaning agent according to claims 1 to 5, characterized in that the surfactants are selected from the group of alkyl sulfates, alkyl ether sulfates, alkyl fatty acid alkanolamides, alkyl glycosides and fatty acid amide alkyl betaine and mixtures thereof.
7. Verwendung eines wasserlöslichen Polymers, das ausgewählt ist aus der Gruppe des Xanthans und seiner Derivate, zur Verbesserung der Reinigungsleistung durch verbesserte Fettemulgierbarkeit von manuellen Geschirrspülmitteln. 7. Use of a water-soluble polymer, which is selected from the group of xanthans and its derivatives, to improve cleaning performance through improved fat emulsifiability of manual dishwashing detergents.
PCT/EP1997/000800 1996-03-01 1997-02-20 Cleaning agent for hard surfaces, with an improved ability to dissolve grease and fat WO1997031995A1 (en)

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Publication number Priority date Publication date Assignee Title
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