EP0513138B1 - Aqueous liquid cleaning agent - Google Patents

Aqueous liquid cleaning agent Download PDF

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Publication number
EP0513138B1
EP0513138B1 EP91903675A EP91903675A EP0513138B1 EP 0513138 B1 EP0513138 B1 EP 0513138B1 EP 91903675 A EP91903675 A EP 91903675A EP 91903675 A EP91903675 A EP 91903675A EP 0513138 B1 EP0513138 B1 EP 0513138B1
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Prior art keywords
alkyl
detergents
content
sulfates
fatty
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EP91903675A
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German (de)
French (fr)
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EP0513138A1 (en
EP0513138B2 (en
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Ortburg Guirr
Birgit Dr. Middelhauve
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives

Definitions

  • Liquid cleaning agents usually consist of aqueous solutions of synthetic anionic and / or nonionic surfactants and conventional additives. They are particularly used for cleaning hard surfaces, for example glass, ceramic materials, plastics, painted and polished surfaces.
  • An important area of application for liquid detergents is the manual washing of dinnerware and cookware.
  • the dishes are usually cleaned in slightly diluted liquors at slightly elevated temperatures of around 35 to 45 ° C.
  • the cleaning power of an agent is assessed by the consumer the better and the longer the cleaning liquor foams. Because of the contact of the hands with the cleaning liquor over a longer period of time, the skin-friendliness of the agent is of particular importance when washing dishes.
  • alkyl sulfates and alkyl ether sulfates are not only degraded very well not only in the aerobic activation stage of the sewage treatment plants, but also under anaerobic conditions of sludge digestion (e.g. J. Steber, P. Code, W. Guhl: Fat. Sci. Technol. 90 (1), 32 (1988)).
  • alkyl ether sulfates that is to say salts of sulfated adducts of about 2 to 5 moles of ethylene oxide with fatty alcohols having about 10 to 18, preferably 12 to 16, carbon atoms in the aliphatic radical have good foaming and cleaning power and skin-friendly properties.
  • the commercially available, manual dishwashing detergents are therefore generally aqueous solutions of such alkyl ether sulfates in conjunction with other surfactants, in particular alkylbenzenesulfonates and alkanesulfonates, and also solubilizers, colorants and fragrances.
  • Swiss patent specification 354 195 discloses liquid detergents for manual dishwashing, which are a combination of an alkyl ether sulfate containing alkyl sulfate and a nonionic surfactant of the fatty acid alkanolamide type from mono- or dialkanolamides with no more than 3 carbon atoms in each alkanol residue of saturated fatty acids with 10 Contain up to 14 carbon atoms, together with water, solubilizers, colors and fragrances and, among other things, have a low solidification point.
  • nonionic alkyl monoglucosides not only develop stable foam themselves, but also act as foam stabilizers for other anionic and nonionic surfactants.
  • European patent application 70 074 discloses foaming liquid cleaning agents containing anionic surfactants, in particular alkylbenzenesulfonates, alkylglucosides and amine oxides or fatty acid alkanolamides, the alkylglucosides being alkyloligoglucosides which contain the glucose unit (GE) about 1.5 to 10 times, acts.
  • This value is an average value and also takes into account the presence of alkyl monoglucosides in a corresponding proportion.
  • Alkyl glucosides with a degree of oligomerization higher than 2 are found to be particularly suitable. Mixtures of such alkyl glucosides and alkyl ether sulfates in a ratio of 3: 2 are described as only slightly foaming.
  • German patent specification DE 35 34 082 and the international patent applications WO 86/02943 and WO 89/02912 describe liquid cleaning agents for the manual cleaning of dishes, containing synthetic anionic surfactants of the sulfonate and / or sulfate surfactant type, fatty alkyl glucosides and optionally fatty acid alkanolamides which contain fatty alkyl glucosides with an average of less than 2 GE per fatty alkyl radical, in particular 1 to 1.4 GE.
  • liquid cleaning agents for manual Ge Dishwashing described with an active substance content of 5 to 60 wt .-%, 30 to 60 wt .-% of an alkyl glucoside with preferably 1 to 1.4 GE in the molecule, 12 to 30 wt .-% of a betaine and bis 1.5 times the amount, based on the betaine, can consist of alkyl sulfates and / or alkyl ether sulfates. These surfactant mixtures are said to be characterized by good foam stability and good cleaning performance.
  • the invention thus relates to aqueous liquid cleaning agents, in particular for manual dishwashing, with an active substance content of 10 to 60, preferably 15 to 40 percent by weight, consisting of alkyl sulfates, alkyl ether sulfates, betaines and fatty alkyl glucosides with less than 2, in particular 1 to 1, 4, glucose Units per fatty alkyl radical, which are characterized in that they contain more than 45% of the active substance of alkyl sulfates and alkyl ether sulfates, their content being greater than 1.5 times the betaine content and at least twice the alkyl glucoside content and a maximum of about 50 times the betaine and / or fatty alkyl glucoside.
  • alkyl sulfates or alkyl ether sulfates are preferably used are commercially available, they have a straight-chain, aliphatic C12 - 18 -, preferably C12 - 14 - alkyl residue.
  • the associated cation is preferably an alkali metal or ammonium ion.
  • the degree of ethoxylation is 1 to 5, preferably 2 to 4.
  • alkyl ether sulfate mixture consisting of 50% by weight of a C 12 alkyl ether sulfate and 50% by weight of a C 14 alkyl ether sulfate with 1 is also preferred up to 5, preferably 2 to 4, ethylene oxide groups instead of or together with the alkyl ether sulfate mixture (es) usually used, which contains the same components in a weight ratio of 70:30.
  • alkyl ether sulfate mixture es
  • Small amounts of shorter or longer alkyl chains in alkyl sulfates and / or alkyl ether sulfates change the results only insignificantly.
  • the known proportion of alkyl sulfate in industrially produced alkyl ether sulfates is included here.
  • the claimed alkyl sulfate content is added separately.
  • the quantitative ratio of alkyl sulfate to alkyl ether sulfate is preferably 4: 1 to 1: 5.
  • the alkyl glucosides are of the fatty alcohol glucoside type. Compounds with an average of less than 2 GE per fatty alkyl radical are understood here, in particular those with 1.0 to 1.4 GE.
  • the fatty alkyl radical has 10 to 18, in particular 12 to 14, carbon atoms.
  • “Fatty alkyl” is understood to mean the residues of the fatty alcohols produced by hydrogenation of natural fatty acids that are wholly or predominantly saturated.
  • agents according to the invention can preferably also contain solubilizers, solvents, colorants and fragrances.
  • Alkanolamines polyols, such as ethylene glycol, 1,2-propylene glycol or glycerol, for example, can serve as solubilizers, for example for small amounts of dye and perfume oil.
  • the amounts used are generally between 1 and 15 percent by weight, based on the total agent.
  • solvents such as low molecular weight alkanols with 1 to 4 carbon atoms in the molecule, preferably ethanol and isopropyl alcohol, are used.
  • the amounts used are up to 15 percent by weight, based on the total agent.
  • Viscosity regulators such as urea, sodium chloride, ammonium chloride, magnesium chloride and salts of mono-, di- and tricarboxylic acids and mixtures thereof can also be used individually or in combination in the required amounts.
  • Other common optional additives are corrosion inhibitors and preservatives.
  • a remainder, to be calculated for a total of 100 percent by weight, for the total composition consists of water.
  • liquid cleaning agents according to the invention according to the following examples were obtained by stirring the individual constituents together and allowing the mixture to stand until the bubbles were free.
  • the neutral combinations listed were adjusted with sodium chloride and / or ethanol to viscosities between 300 and 400 mPas (according to Höppler, 20 ° C).
  • the samples were stored at -15 ° C for 24 hours.
  • the temperature at which the products became optically clear was determined as a clear point.
  • the saucers are each covered with 2 g of melted beef tallow (test soil A). Then 8 liters of tap water (16 ° d) at 50 ° C are placed in a bowl. To clean the plates soiled with (A), 4 g, i.e. 0.5 g / l of the detergent was added and the plates washed. The plates listed in Table 3 could be rinsed clean until the foam of the initially foaming solution disappeared.
  • the saucers are each covered with 2 g mixed soiling (test soiling B).
  • This soiling is obtained by mixing water, fat and carbohydrates (Mi No 1 from Henkel) with water. Then 8 liters of tap water (16 ° d) at 45 ° C are placed in a bowl. To clean the plates soiled with (B), 3.2 g, ie 0.4 g / l, of the cleaning agent prepared were added and the plates were washed. The plates that were rinsed clean until the foam disappeared are listed in Table 3.

Abstract

Aqueous liquid cleaning agent, especially for dishwashing by hand, with an active substance content of 10 to 60, preferably 15 to 40 % wt., consisting of alkyl sulphates, alkyl ether sulphates, betains and alkyl glucosides containing more than 45 % alkyl sulphates and alkyl ether sulphates in the active substance, whereby their content is more than 1.5 times the betain content and at least double the alkyl glucoside content.

Description

Flüssige Reinigungsmittel bestehen meist aus wäßrigen Lösungen von synthetischen anionischen und/oder nichtionischen Tensiden und üblichen Zusatzstoffen. Sie werden besonders zum Reinigen harter Oberflächen, zum Beispiel von Glas, keramischen Materialien, Kunststoffen, lackierten und polierten Oberflächen verwendet. Ein wichtiges Anwendungsgebiet für flüssige Reinigungsmittel ist das manuelle Spülen von Eß- und Kochgeschirr. Die Geschirreinigung wird üblicherweise bei leicht erhöhten Temperaturen von etwa 35 bis 45 °C in stark verdünnten Flotten durchgeführt. Dabei wird vom Verbraucher die Reinigungskraft eines Mittels im allgemeinen umso besser beurteiltje stärker und je länger die Reinigungsflotte schäumt. Wegen des Kontakts der Hände mit der Reinigungsflotte über einen längeren Zeitraum ist bei manuellem Spülen von Geschirr auch die Hautfreundlichkeit des Mittels von besonderer Bedeutung. Schon aus diesen Gründen stellt der Fachmann bei der Auswahl der Komponenten und der Zusammensetzung eines Mittels für das manuelle Reinigen von Geschirr andere Überlegungen an, als bei flüssigen Reinigungsmitteln für sonstige harte Oberflächen. Zunehmend sind aber auch ökologische Gesichtspunkte in das Blickfeld des Interesses gerückt. Sowerden Mittel bevorzugt, die frei sind von für solche Mittel im allgemeinen üblichen Anteilen an Aniontensiden auf petrochemischer Basis wie z. B. Alkylbenzolsulfonaten und Alkansulfonaten .Liquid cleaning agents usually consist of aqueous solutions of synthetic anionic and / or nonionic surfactants and conventional additives. They are particularly used for cleaning hard surfaces, for example glass, ceramic materials, plastics, painted and polished surfaces. An important area of application for liquid detergents is the manual washing of dinnerware and cookware. The dishes are usually cleaned in slightly diluted liquors at slightly elevated temperatures of around 35 to 45 ° C. In general, the cleaning power of an agent is assessed by the consumer the better and the longer the cleaning liquor foams. Because of the contact of the hands with the cleaning liquor over a longer period of time, the skin-friendliness of the agent is of particular importance when washing dishes. For these reasons alone, the expert makes different considerations when selecting the components and the composition of an agent for the manual cleaning of dishes than with liquid detergents for other hard surfaces. However, ecological aspects are also increasingly becoming the focus of interest. Preference is given to agents which are free from the proportions of anionic surfactants based on petrochemicals, such as, for example, which are generally customary for such agents. B. alkylbenzenesulfonates and alkanesulfonates.

Aus der Literatur (z. B. Landesgewerbeanstalt, Bayern, Heft 5 (1987), K. Goßler und R. Miess: Verhalten von linearen Alkylbenzolsulfonaten aus Haushaltswaschmitteln bei derAbwasserbehandlung - Literaturstudie) ist bekannt, daß die oben genannten Aniontenside unter aeroben Bedingungen - wie sie in der Belebtstufe von Kläranlagen vorliegen - biologisch abbaubar sind, aber unter anaeroben Bedingungen der Schlammfaulung keinen oder nur partiellen Abbau aufweisen. Wählt man jedoch die hier bevorzugten Alkylsulfate und Alkylethersulfate als Tenside, so werden diese nicht nur in der aeroben Belebtstufe der Kläranlagen, sondern auch unter anaeroben Bedingungen der Schlammfaulung sehr gut endabgebaut (z.B. J. Steber, P. Code, W. Guhl: Fat. Sci. Technol. 90 (1), 32 (1988)).From the literature (e.g. Landesgewerbeanstalt, Bayern, Issue 5 (1987), K. Goßler and R. Miess: Behavior of linear alkylbenzenesulfonates from household detergents in wastewater treatment - literature study) it is known that the above-mentioned anionic surfactants under aerobic conditions - such as they are present in the activated stage of sewage treatment plants - are biodegradable, but show no or only partial degradation under anaerobic conditions of sludge digestion. However, if one chooses the preferred alkyl sulfates and alkyl ether sulfates as surfactants, these are not only degraded very well not only in the aerobic activation stage of the sewage treatment plants, but also under anaerobic conditions of sludge digestion (e.g. J. Steber, P. Code, W. Guhl: Fat. Sci. Technol. 90 (1), 32 (1988)).

Es ist auch allgemein bekannt, daß sogenannte Alkylethersulfate, das heißt Salze von sulfatierten Anlagerungsprodukten von etwa 2 bis 5 Mol Ethylenoxid an Fettalkohole mit etwa 10 bis 18, vorzugsweise 12 bis 16 Kohlenstoffatomen im aliphatischen Rest eine gute Schaum- und Reinigungskraft sowie hautfreundliche Eigenschaften besitzen. Die marktüblichen, manuell anwendbaren Geschirreinigungsmittel (alias Geschirrspülmittel) stellen daher im allgemeinen wäßrige Lösungen solcher Alkylethersulfate in Verbindung mit anderen Tensiden, insbesondere Alkylbenzolsulfonaten und Alkansulfonaten, sowie Lösungsvermittlern, Farb- und Duftstoffen dar.It is also generally known that so-called alkyl ether sulfates, that is to say salts of sulfated adducts of about 2 to 5 moles of ethylene oxide with fatty alcohols having about 10 to 18, preferably 12 to 16, carbon atoms in the aliphatic radical have good foaming and cleaning power and skin-friendly properties. The commercially available, manual dishwashing detergents (also known as dishwashing detergents) are therefore generally aqueous solutions of such alkyl ether sulfates in conjunction with other surfactants, in particular alkylbenzenesulfonates and alkanesulfonates, and also solubilizers, colorants and fragrances.

Aus der schweizerischen Patentschrift 354 195 sind flüssige Reinigungsmittel für das manuelle Geschirrspülen bekannt, die eine Kombination aus einem Alkylsulfat enthaltenden Alkylethersulfat und einem nichtionischen Tensid vom Typ des Fettsäurealkanolamids aus Mono- oder Dialkanolamiden mit nicht mehr als 3 Kohlenstoffatomen in jedem Alkanolrest von gesättigten Fettsäuren mit 10 bis 14 Kohlenstoffatomen, zusammen mit Wasser, Lösungsvermittlern, Farb- und Duftstoffen enthalten und unter anderem einen niedrigen Erstarrungspunkt aufweisen.Swiss patent specification 354 195 discloses liquid detergents for manual dishwashing, which are a combination of an alkyl ether sulfate containing alkyl sulfate and a nonionic surfactant of the fatty acid alkanolamide type from mono- or dialkanolamides with no more than 3 carbon atoms in each alkanol residue of saturated fatty acids with 10 Contain up to 14 carbon atoms, together with water, solubilizers, colors and fragrances and, among other things, have a low solidification point.

Aus der US-Patentschrift 3 219 656 ist bereits bekannt, daß nichtionische Alkylmonoglucoside nicht nur selbst stabilen Schaum entwickeln, sondern als Schaumstabilisatoren für andere anionische und nichtionische Tenside wirken.It is already known from US Pat. No. 3,219,656 that nonionic alkyl monoglucosides not only develop stable foam themselves, but also act as foam stabilizers for other anionic and nonionic surfactants.

Aus der europäischen Patentanmeldung 70 074 sind schäumende flüssige Reinigungsmittel mit einem Gehalt an Aniontensiden, insbesondere Alkylbenzolsulfonaten, Alkylglucosiden und Aminoxiden beziehungsweise Fettsäurealkanolamiden bekannt, wobei es sich bei den Alkylglucosiden um Alkyloligoglucoside, welche die Glucoseeinheit (GE) etwa 1,5 bis 10 mal enthalten, handelt. Dieser Wert ist ein Mittelwert und berücksichtigt auch das Vorliegen von Alkylmonoglucosiden in einem entsprechenden Anteil. Als besonders geeignet werden Alkylglucoside mit einem Oligomerisierungsgrad von höher als 2 herausgestellt. Mischungen aus solchen Alkylglucosiden und Alkylethersulfaten im Verhältnis 3 : 2 werden als nur schwach schaumverbessernd beschrieben.European patent application 70 074 discloses foaming liquid cleaning agents containing anionic surfactants, in particular alkylbenzenesulfonates, alkylglucosides and amine oxides or fatty acid alkanolamides, the alkylglucosides being alkyloligoglucosides which contain the glucose unit (GE) about 1.5 to 10 times, acts. This value is an average value and also takes into account the presence of alkyl monoglucosides in a corresponding proportion. Alkyl glucosides with a degree of oligomerization higher than 2 are found to be particularly suitable. Mixtures of such alkyl glucosides and alkyl ether sulfates in a ratio of 3: 2 are described as only slightly foaming.

In der deutschen Patentschrift DE 35 34 082 sowie in den internationalen Patentanmeldungen WO 86/02943 und WO 89/02912 werden flüssige Reinigungsmittel für das manuelle Reinigen von Geschirr, enthaltend synthetische Aniontenside vom Typ der Sulfonat- und/oder Sulfattenside, Fettalkylglucoside und gegebenenfalls Fettsäurealkanolamide beschrieben, die Fettalkylglucoside mit durchschnittlich weniger als 2 GE pro Fettalkyl-Rest, insbesondere 1 bis 1,4 GE, enthalten.The German patent specification DE 35 34 082 and the international patent applications WO 86/02943 and WO 89/02912 describe liquid cleaning agents for the manual cleaning of dishes, containing synthetic anionic surfactants of the sulfonate and / or sulfate surfactant type, fatty alkyl glucosides and optionally fatty acid alkanolamides which contain fatty alkyl glucosides with an average of less than 2 GE per fatty alkyl radical, in particular 1 to 1.4 GE.

Aus der deutschen Offenlegungsschrift 37 06 015 ist bekannt, daß man durch Zusatz von Aniontensiden, vorzugsweise Alkylethersulfaten oder Alkylsulfaten und Betainen zu flüssigen Reinigungsmitteln aus Sulfosuccinaten und Alkylglucosiden Leistungssteigerungen im Spülvermögen und Verbesserungen der Lagerstabilität erzielen kann.It is known from German Offenlegungsschrift 37 06 015 that by adding anionic surfactants, preferably alkyl ether sulfates or alkyl sulfates and betaines, to liquid cleaning agents made from sulfosuccinates and alkyl glucosides, performance improvements in rinsing capacity and improvements in storage stability can be achieved.

In der europäischen Patentanmeldung 341 071 werden flüssige Reinigungsmittel für das manuelle Geschirrspülen mit einem Aktivsubstanzgehalt von 5 bis 60 Gew.-% beschrieben, der zu 30 bis 60 Gew.-% aus einem Alkylglucosid mit vorzugsweise 1 bis 1,4 GE im Molekül, zu 12 bis 30 Gew.-% aus einem Betain und bis zur 1,5fachen Menge, bezogen auf das Betain, aus Alkylsulfaten und/oder Alkylethersulfaten bestehen kann. Diese Tensidmischungen sollen sich durch gute Schaumstabilität und gute Reinigungsleistung auszeichnen.In European patent application 341 071 liquid cleaning agents for manual Ge Dishwashing described with an active substance content of 5 to 60 wt .-%, 30 to 60 wt .-% of an alkyl glucoside with preferably 1 to 1.4 GE in the molecule, 12 to 30 wt .-% of a betaine and bis 1.5 times the amount, based on the betaine, can consist of alkyl sulfates and / or alkyl ether sulfates. These surfactant mixtures are said to be characterized by good foam stability and good cleaning performance.

Von wäßrigen Reinigungsmitteln, die speziell für das manuelle Reinigen von Geschirr konzipiert sind, erwartet der Verbraucher aber nicht nur eine hohe Reinigungskraft und eine gute Schaumbildung und Schaumstabilität bei Fettbelastung sowie ökologische Verträglichkeit, sondern auch ein optisch ansprechendes Erscheinungsbild. Viele Produkte zur manuellen Reinigung von Geschirr werden häufig in transparenten und/oder transluzenten Flaschen angeboten. Im Handel sollen die Produkte, auch wenn sie über längere Zeit in üblicherweise nicht temperierten Lagern gestanden haben, daher optisch einwandfrei, d. h. transparent vorliegen. Als besonders günstig werden solche Produkte betrachtet, die einen Klarpunktvon unterca. 15 °C aufweisen.From aqueous cleaning agents that are specially designed for the manual cleaning of dishes, the consumer not only expects a high cleaning power and good foaming and foam stability when exposed to fat as well as ecological compatibility, but also a visually appealing appearance. Many products for manual cleaning of dishes are often offered in transparent and / or translucent bottles. In the trade, the products, even if they have been in warehouses that are usually not at a constant temperature, should be optically flawless. H. are transparent. Products that have a clear point of less than approx. 15 ° C.

Es wurde nun überraschenderweise gefunden, daß quaternäre Kombinationen aus Alkylsulfat, Alkylethersulfat, Betain und Alkylglucosid mit einer bestimmten quantitativen Zusammensetzung zu einem besseren Kälteverhalten, charakterisiert durch den Klarpunkt, führen als bekannte binäre, ternäre oder quaternäre Kombinationen aus diesen Tensiden. Je niedriger der Klarpunkt liegt, desto besser sind die Reinigungsmittel zu bewerten.It has now surprisingly been found that quaternary combinations of alkyl sulfate, alkyl ether sulfate, betaine and alkyl glucoside with a certain quantitative composition lead to better cold behavior, characterized by the clear point, than known binary, ternary or quaternary combinations of these surfactants. The lower the clear point, the better the cleaning agents are to be rated.

Die Erfindung betrifft somit wäßrige flüssige Reinigungsmittel, insbesondere für die manuelle Geschirreinigung, mit einem Aktivsubstanzgehalt von 10 bis 60, vorzugsweise 15 bis 40 Gewichtsprozent, bestehend aus Alkylsulfaten, Alkylethersulfaten, Betainen und Fettalkylglucosiden mit weniger als 2, insbesondere 1 bis 1, 4, Glucose einheiten pro Fettalkylrest, die dadurch gekennzeichnet sind, daß sie mehr als 45 % der Aktivsubstanz an Alkylsulfaten und Alkylethersulfaten enthalten, wobei deren Gehalt größer als das 1,5fache des Betaingehalts ist und das wenigstens Doppelte des Alkylglucosidgehalts sowie maximal etwa das 50fache des Betain- und/oder Fettalkylglucosid gehaltes ausmacht.The invention thus relates to aqueous liquid cleaning agents, in particular for manual dishwashing, with an active substance content of 10 to 60, preferably 15 to 40 percent by weight, consisting of alkyl sulfates, alkyl ether sulfates, betaines and fatty alkyl glucosides with less than 2, in particular 1 to 1, 4, glucose Units per fatty alkyl radical, which are characterized in that they contain more than 45% of the active substance of alkyl sulfates and alkyl ether sulfates, their content being greater than 1.5 times the betaine content and at least twice the alkyl glucoside content and a maximum of about 50 times the betaine and / or fatty alkyl glucoside.

Die bevorzugt eingesetzten Alkylsulfate beziehungsweise Alkyl ethersulfate sind handelsüblich, sie weisen einen geradkettigen, aliphatischen C12 - 18-, vorzugsweise C12 - 14 - Alkylrest auf. Das zugehörige Kation ist vorzugsweise ein Alkalimetall- oder Ammoniumion. Bei Alkylethersulfaten liegt der Ethoxylierungsgrad bei 1 bis 5, vorzugsweise bei 2 bis 4. Weiterhin bevorzugt ist der Einsatz eines Alkylethersulfatgemisches, bestehend aus 50 Gew.-% eines C12-Alkylethersulfates und 50 Gew. -% eines C14-Alkylether sulfates mit 1 bis 5, vorzugsweise 2 bis 4 Ethylenoxidgruppen anstelle des oder zusammen mit dem üblicherweise eingesetzten Alkylethersulfatgemisch(es), das die gleichen Komponenten im Gewichtsvethältnis 70 : 30 enthält. Geringe Mengen an kürzeren oder längeren Alkylketten in Alkylsulfaten und/oder Alkylethersulfaten verändern die Ergebnisse nur unwesentlich. Der bekannte Alkylsulfatanteil in technisch hergestellten Alkylethersulfaten wird hier diesen zugerechnet. Der beanspruchte Alkylsulfatgehalt wird gesondert zugesetzt. Das Mengenverhältnis von Alkylsulfat zu Alkylethersulfat beträgt dabei vorzugsweise 4 : 1 bis 1 : 5.The alkyl sulfates or alkyl ether sulfates are preferably used are commercially available, they have a straight-chain, aliphatic C12 - 18 -, preferably C12 - 14 - alkyl residue. The associated cation is preferably an alkali metal or ammonium ion. In the case of alkyl ether sulfates, the degree of ethoxylation is 1 to 5, preferably 2 to 4. The use of an alkyl ether sulfate mixture consisting of 50% by weight of a C 12 alkyl ether sulfate and 50% by weight of a C 14 alkyl ether sulfate with 1 is also preferred up to 5, preferably 2 to 4, ethylene oxide groups instead of or together with the alkyl ether sulfate mixture (es) usually used, which contains the same components in a weight ratio of 70:30. Small amounts of shorter or longer alkyl chains in alkyl sulfates and / or alkyl ether sulfates change the results only insignificantly. The known proportion of alkyl sulfate in industrially produced alkyl ether sulfates is included here. The claimed alkyl sulfate content is added separately. The quantitative ratio of alkyl sulfate to alkyl ether sulfate is preferably 4: 1 to 1: 5.

Als Betaine können "einfache Betaine" des Types:

Figure imgb0001
und/oder "Amidobetaine" des Types:
Figure imgb0002

  • eingesetzt werden; dabei gilt für:
  • R1 bzw. R4 = C8 - 18 linear oder verzweigt,
  • R2 bzw. R3 = CH3, C2H5, C3H7.
As betaines "simple betaines" of the type can:
Figure imgb0001
 and / or "amidobetaines" of the type:
Figure imgb0002
  • be used; the following applies to:
  • R 1 and R 4 = C 8-18 linear or branched,
  • R 2 or R 3 = CH 3 , C 2 H 5 , C 3 H 7 .

Die Alkylglucoside sind vom Typ der Fettalkoholglucoside. Man versteht hier darunter Verbindungen mit durchschnittlich weniger als 2 GE pro Fettalkyl-Rest, insbesondere solche mit 1,0 bis 1,4 GE. Der Fettalkylrest weist 10 bis 18, insbesondere 12 bis 14 Kohlenstoffatome auf. Unter "Fettalkyl" werden die Reste der durch Hydrierung von natürlichen Fettsäuren hergestellten Fettalkohole, die ganz oder überwiegend gesättigt sind, verstanden.The alkyl glucosides are of the fatty alcohol glucoside type. Compounds with an average of less than 2 GE per fatty alkyl radical are understood here, in particular those with 1.0 to 1.4 GE. The fatty alkyl radical has 10 to 18, in particular 12 to 14, carbon atoms. “Fatty alkyl” is understood to mean the residues of the fatty alcohols produced by hydrogenation of natural fatty acids that are wholly or predominantly saturated.

Weiterhin können die erfindungsgemäßen Mittel bevorzugt auch noch Lösungsvermittler, Lösungsmittel, Farb- und Duftstoffe enthalten .Furthermore, the agents according to the invention can preferably also contain solubilizers, solvents, colorants and fragrances.

Als Lösungsvermittler, etwa für geringe Farbstoff- und Parfumölzusätze, können beispielsweise Alkanolamine, Polyole, wie Ethylenglykol, Propylenglykol-1,2 oder Glycerin dienen. Ihre Einsatzmengen liegen im allgemeinen zwischen 1 und 15 Gewichtsprozent, bezogen auf das gesamte Mittel.Alkanolamines, polyols, such as ethylene glycol, 1,2-propylene glycol or glycerol, for example, can serve as solubilizers, for example for small amounts of dye and perfume oil. The amounts used are generally between 1 and 15 percent by weight, based on the total agent.

Zusätzlich werden meist Lösungsmittel, wie niedermolekulare Alkanole mit 1 bis 4 Kohlenstoffatomen im Molekül, vorzugsweise Ethanol und Isopropylalkohol eingesetzt. Ihre Einsatzmengen betragen bis zu 15 Gewichtsprozent, bezogen auf das gesamte Mittel. Auch Viskositätsregulatoren wie Harnstoff, Natriumchlorid, Ammoniumchlorid, Magnesiumchlorid und Salze von Mono-, Di- und Tricarbonsäuren und Gemischen daraus können einzeln oder kombiniert in erforderlichen Mengen eingesetzt werden. Weitere übliche fakultative Zusätze sind Korrosionsinhibitoren und Konservierungsmittel.In addition, mostly solvents such as low molecular weight alkanols with 1 to 4 carbon atoms in the molecule, preferably ethanol and isopropyl alcohol, are used. The amounts used are up to 15 percent by weight, based on the total agent. Viscosity regulators such as urea, sodium chloride, ammonium chloride, magnesium chloride and salts of mono-, di- and tricarboxylic acids and mixtures thereof can also be used individually or in combination in the required amounts. Other common optional additives are corrosion inhibitors and preservatives.

Ein etwa noch auf insgesamt 100 Gewichtsprozent zu berechnender Rest für das Gesamtmittel besteht jeweils aus Wasser.A remainder, to be calculated for a total of 100 percent by weight, for the total composition consists of water.

Die erfindungsgemäßen flüssigen Reinigungsmittel nach den folgenden Beispielen wurden durch Zusammenrühren der einzelnen Bestandteile und Stehenlassen des Gemisches bis zur Blasenfreiheit erhalten.The liquid cleaning agents according to the invention according to the following examples were obtained by stirring the individual constituents together and allowing the mixture to stand until the bubbles were free.

BeispieleExamples Beispiel 1:Example 1:

Folgende Substanzen wurden eingesetzt:

  • FAS : C12-14-Alkylsulfat, Na-Salz
  • FES-1 : C12-14-Alkylethersulfat, 2 EO, Na-Salz
  • Betain-1 : C8-18-Dimethylacylamidobetain
  • APG : C12-14-Alkylglucosid 1,4 GE
  • EtOH : Ethanol
The following substances were used:
  • FAS: C 12-14 alkyl sulfate, Na salt
  • FES-1: C 12-14 alkyl ether sulfate, 2 EO, Na salt
  • Betaine-1: C 8-18 dimethylacylamidobetaine
  • APG: C 12-14 alkyl glucoside 1.4 GE
  • EtOH: ethanol

Die aufgeführten, neutralen Kombinationen wurden mit Kochsalz und/oder Ethanol auf Viskositäten zwischen 300 und 400 mPas (nach Höppler, 20 °C) eingestellt. Die Proben wurden 24 Stunden bei -15 °C gelagert. Als Klarpunkt wurde die Temperatur bestimmt, bei welcher die Produkte wieder optisch klar wurden.The neutral combinations listed were adjusted with sodium chloride and / or ethanol to viscosities between 300 and 400 mPas (according to Höppler, 20 ° C). The samples were stored at -15 ° C for 24 hours. The temperature at which the products became optically clear was determined as a clear point.

Die folgenden Ergebnisse (Tabelle 1) zeigen, daß die quaternären Kombinationen aus Alkylsulfat, Alkylethersulfat, Betain und Alkylpolyglucosid über einen weiten Mischungsbereich ein hervorragendes Kälteverhalten aufweisen.

Figure imgb0003
The following results (Table 1) show that the quaternary combinations of alkyl sulfate, alkyl ether sulfate, betaine and alkyl polyglucoside have excellent cold behavior over a wide range of mixtures.
Figure imgb0003

Beispiel 2:Example 2:

Die folgenden Ergebnisse (Tabelle 2) zeigen, daß die quaternären Kombinationen aus Alkylsulfat, Alkylethersulfat, Betain und Alkylpolyglucosid über einen weiten Mischungsbereich - auch in Gegenwart größerer Mengen an Alkohol - ein hervorragendes Kälteverhalten aufweisen. Die Viskositäten wurden wie in Beispiel 1 beschrieben eingestellt und der Klarpunkt entsprechend bestimmt.

Figure imgb0004
The following results (Table 2) show that the quaternary combinations of alkyl sulfate, alkyl ether sulfate, betaine and alkyl polyglucoside have an excellent low-temperature behavior over a wide mixing range - even in the presence of large amounts of alcohol. The viscosities were set as described in Example 1 and the clear point was determined accordingly.
Figure imgb0004

Beispiel 3Example 3

Die folgenden Ergebnisse zeigen, daß die quaternären Kombinationen aus Alkylsulfat, Alkylethersulfat, Betain und Alkylpolyglucosid nicht nur Vorteile bezüglich ihres Kälteverhaltens aufweisen, sondern auch zu ausgezeichneten spültechnischen Ergebnissen führen. Die Reinigungsleistung wurde mit Hilfe des Tellertestes bestimmt, der im folgenden beschrieben wird:The following results show that the quaternary combinations of alkyl sulfate, alkyl ether sulfate, betaine and alkyl polyglucoside not only have advantages in terms of their low-temperature behavior, but also lead to excellent washing results. The cleaning performance was determined using the plate test, which is described below:

(A): Rindertalganschmutzung(A): Beef tallow soiling

Die Untertassen werden mit jeweils 2 g geschmolzenem Rindertalg (Testanschmutzung A) überzogen. Dann werden 8 I Leitungswasser (16 °d) von 50 °C in eine Schüssel gegeben. Zum Reinigen der mit (A) angeschmutzten Teller wurden 4 g, d.h. 0,5 g/l, des Reinigungsmittels zugegeben und die Teller gewaschen. Bis zum Verschwinden des Schaumes der anfangs stark schäumenden Lösung konnten die in Tabelle 3 aufgeführten Teller sauber gespült werden.The saucers are each covered with 2 g of melted beef tallow (test soil A). Then 8 liters of tap water (16 ° d) at 50 ° C are placed in a bowl. To clean the plates soiled with (A), 4 g, i.e. 0.5 g / l of the detergent was added and the plates washed. The plates listed in Table 3 could be rinsed clean until the foam of the initially foaming solution disappeared.

(B): Mischanschmutzung(B): mixed soiling

Die Untertassen werden mit jeweils 2 g Mischanschmutzung (Testanschmutzung B) überzogen. Diese Anschmutzung erhält man durch eine in Wasser verrührte Mischung aus Eiweiß, Fett und Kohlenhydraten (Mi No 1 von Henkel). Dann werden 8 I Leitungswasser (16°d) von 45 °C in eine Schüssel gegeben. Zum Reinigen der mit (B) angeschmutzten Teller wurden 3,2 g, d.h. 0,4 g/l, des hergestellten Reinigungsmittels zugegeben und die Teller gewaschen. Die bis zum Verschwinden des Schaumes sauber gespülten Teller sind in Tabelle 3 aufgeführt.

Figure imgb0005
The saucers are each covered with 2 g mixed soiling (test soiling B). This soiling is obtained by mixing water, fat and carbohydrates (Mi No 1 from Henkel) with water. Then 8 liters of tap water (16 ° d) at 45 ° C are placed in a bowl. To clean the plates soiled with (B), 3.2 g, ie 0.4 g / l, of the cleaning agent prepared were added and the plates were washed. The plates that were rinsed clean until the foam disappeared are listed in Table 3.
Figure imgb0005

Beispiel 4:Example 4:

Die folgenden Ergebnisse (Tabelle 4) zeigen, daß nicht nur Amidobetaine (Betain-1), sondern auch einfache Betaine (Betain-2) eingesetzt werden können. Als Alkylethersulfate können nicht nur Produkte mit einem mittleren EO-Grad von ca. 2 und normaler Kokos-Kettenverteilung (C12: C14=70 :30) eingesetzt werden, sondern auch Produkte mit einem mittleren EO-Grad von ca. 3,6 und einer Kettenverteilung C12:C14=50:50. Folgende Substanzen wurden eingesetzt:

  • FES-2 : C12-14-Alkylethetsulfat, 3,6 EO, Na-Salz
  • Betain-2 : C12-18-Dimethylalkylacetobetain
Figure imgb0006
 The following results (Table 4) show that not only amido betaines (betaine-1) but also simple betaines (betaine-2) can be used. Not only products with an average EO degree of approx. 2 and normal coconut chain distribution (C12: C 14 = 70: 30) can be used as alkyl ether sulfates, but also products with an average EO degree of approx. 3.6 and a chain distribution C 12 : C 14 = 50:50. The following substances were used:
  • FES-2: C 12-14 -Alkylethetsulfat, 3.6 EO, sodium salt
  • Betaine-2: C 12-18 dimethylalkylacetobetaine
Figure imgb0006

Beispiel 5:Example 5:

Die folgenden Ergebnisse zeigen, daß nicht nur die binären Tensidkombinationen aus Alkylsulfat und Alkylethersulfat zu Produkten mit gutem Kälteverhalten führen, sondern daß auch die ternären Tensidkombinationen aus Alkylsulfat und verschiedenen Alkylethersulfaten diesen Anforderungen genügen.

Figure imgb0007
The following results show that not only the binary surfactant combinations of alkyl sulfate and alkyl ether sulfate lead to products with good cold behavior, but also that the ternary surfactant combinations of alkyl sulfate and various alkyl ether sulfates meet these requirements.
Figure imgb0007

Beispiel 6:Example 6:

Die folgenden Ergebnisse zeigen, daß der Aktivsubstanzgehalt der erfindungsgemäßen Formulierungen über einen weiten Bereich variieren kann und jedenfalls Vorteile gegenüber den entsprechenden Kombinationen nach der EP-Anmeldung 341 071 (Formeln A und B) erhalten werden.

Figure imgb0008
The following results show that the active substance content of the formulations according to the invention can vary over a wide range and in any case advantages over the corresponding combinations according to EP application 341 071 (formulas A and B) are obtained.
Figure imgb0008

Claims (6)

1. Water-based liquid detergents, more particularly manual dishwashing detergents, with an active substance content of 10 to 60% by weight and preferably 15 to 40% by weight, consisting of a quaternary combination of alkyl sulfates, alkyl ether sulfates, betaines and fatty alkyl glucosides containing less than 2 and, more particularly, 1 to 1.4 glucose units per fatty alkyl radical, characterized in that more than 45% of the active substance consists of alkyl sulfates and alkyl ether sulfates, their content being greater than 1.5 times the betaine content and making up at least twice the fatty alkyl glucoside content and at most about 50 times the betaine and/orfatty alkyl glucoside content.
2. Detergents as claimed in claim 1, characterized in that the fatty alkyl component of the fatty alkyl glucosides contains 10 to 18 and more particularly 12 to 14 carbon atoms.
3. Detergents as claimed in claims 1 and 2, characterized in that the alkyl sulfates contain linear aliphatic C12-18 and preferably C12-14 alkyl radicals.
4. Detergents as claimed in claims 1 to 3, characterized in that the alkyl ether sulfates contain linear aliphatic C12-18 and preferably C12-14 alkyl radicals and 1 to 5 and preferably 2 to 4 ethylene oxide groups.
5. Detergents as claimed in claims 1 to 4, characterized in that the ratio by weight of alkyl sulfate to alkyl ether sulfate is 4:1 to 1:5.
6. Detergents as claimed in claims 1 to 5, characterized in that they additionally contain compounds from the group of solubilizers, solvents, dyes, fragrances and preservatives.
EP91903675A 1990-02-02 1991-01-24 Aqueous liquid cleaning agent Expired - Lifetime EP0513138B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4003098A DE4003098A1 (en) 1990-02-02 1990-02-02 WAESSFUL LIQUID CLEANING AGENT
DE4003098 1990-02-02
PCT/EP1991/000134 WO1991011506A1 (en) 1990-02-02 1991-01-24 Aqueous liquid cleaning agent

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EP0513138A1 EP0513138A1 (en) 1992-11-19
EP0513138B1 true EP0513138B1 (en) 1994-08-17
EP0513138B2 EP0513138B2 (en) 1997-06-18

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DE4234487A1 (en) * 1992-10-14 1994-04-21 Henkel Kgaa Aqueous mixtures of detergents
FR2709679B1 (en) * 1993-08-06 1995-10-06 Seppic Sa Concentrated aqueous compositions of alkylpolyglycosides and their uses.
DE4435495C2 (en) * 1994-10-04 1997-08-14 Henkel Kgaa Pumpable aqueous surfactant concentrates
DE19506207A1 (en) * 1995-02-23 1996-08-29 Goldschmidt Ag Th A storage stable, concentrated surfactant composition based on alkylglucosides
GB9509452D0 (en) * 1995-05-10 1995-07-05 Unilever Plc Light duty cleaning composititon
DE19534369C2 (en) * 1995-09-15 2000-06-15 Cognis Deutschland Gmbh Aqueous hand dishwashing liquid
DE19542569A1 (en) * 1995-11-15 1997-05-22 Henkel Kgaa Fatty alcohol (ether) sulfates with improved cold behavior
DE19548068C1 (en) 1995-12-21 1997-06-19 Henkel Kgaa Process for the production of light colored, low viscosity surfactant concentrates
US5932535A (en) * 1995-12-21 1999-08-03 Henkel Kommanditgesellschaft Auf Aktien Process for the production of light-colored, low-viscosity surfactant concentrates
DE19620703A1 (en) * 1996-05-23 1997-11-27 Henkel Kgaa Skin-friendly dishwashing liquid
DE19714369A1 (en) * 1997-04-08 1998-10-15 Henkel Kgaa Means for cleaning hard surfaces
DE19929511C2 (en) * 1999-06-29 2003-04-10 Cognis Deutschland Gmbh Highly concentrated flowable anionic surfactant mixtures
US6673760B1 (en) * 2000-06-29 2004-01-06 Ecolab Inc. Rinse agent composition and method for rinsing a substrate surface
FR2826017B1 (en) * 2001-06-15 2004-06-11 Cognis France Sa SURFACTANT MIXTURES

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GR76189B (en) * 1981-07-13 1984-08-03 Procter & Gamble
US4554098A (en) * 1982-02-19 1985-11-19 Colgate-Palmolive Company Mild liquid detergent compositions
DE3534082A1 (en) * 1985-09-25 1987-04-02 Henkel Kgaa LIQUID DETERGENT
GB8810820D0 (en) * 1988-05-06 1988-06-08 Unilever Plc Detergent compositions

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EP0513138B2 (en) 1997-06-18

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