EP0444267B1 - Liquid foaming detergent - Google Patents

Liquid foaming detergent Download PDF

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Publication number
EP0444267B1
EP0444267B1 EP90123936A EP90123936A EP0444267B1 EP 0444267 B1 EP0444267 B1 EP 0444267B1 EP 90123936 A EP90123936 A EP 90123936A EP 90123936 A EP90123936 A EP 90123936A EP 0444267 B1 EP0444267 B1 EP 0444267B1
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EP
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Prior art keywords
cleaning composition
composition according
alkyl
alkyl polyglycoside
weight
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German (de)
French (fr)
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EP0444267A3 (en
EP0444267A2 (en
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Dieter Dr. Balzer
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Sasol Germany GmbH
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Huels AG
Chemische Werke Huels AG
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0094—High foaming compositions
    • 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

  • the polyglycosyl radical Z n is determined, on the one hand, by the selection of the carbohydrate and, on the other hand, by the setting of the average degree of polymerization, e.g. B. according to DE-OS 19 43 689.
  • polysaccharides e.g. B. starch, maltodextrins, dextrose, galactose, mannose, and xylose can be used.
  • the industrially available carbohydrates starch, maltodextrins and especially dextrose are preferred.
  • Alkyl polyglycosides used according to the invention can also be prepared by mixing alkyl polyglycosides with alkyl monoglycosides.
  • the latter can e.g. B. according to EP-A-0 092 355 using polar solvents such as acetone from alkyl polyglycosides.

Description

Die Erfindung betrifft ein umweltverträgliches, neutrales, flüssiges Reinigungsmittel. Flüssige, schäumende Reinigungsmittel zielen auf die manuelle Reinigung harter Oberflächen insbesondere im Haushalt, wie z. B. Keramik, Porzellan, Glas, Metall und Kunststoff. Das bedeutendste Anwendungsgebiet sind manuelle Spülmittel für die Reinigung von Geschirr.The invention relates to an environmentally friendly, neutral, liquid cleaning agent. Liquid, foaming cleaning agents aim at the manual cleaning of hard surfaces, especially in the household, such as. B. ceramics, porcelain, glass, metal and plastic. The most important area of application are manual dishwashing detergents for cleaning dishes.

Moderne Produkte bestehen hier aus neutral eingestellten wäßrigen Formulierungen auf der Basis stark schäumender Tenside. Hauptbestandteile sind Sulfonate, wie z. B. Alkylbenzolsulfonate oder sek.-Alkansulfonate, beide kombiniert mit Fettalkoholethersulfaten oder auch Fettalkoholsulfaten (EP-A-0 112 047). In geringen Mengen werden zum Teil Fettsäurealkanolamide und seltener Oxethylate zugesetzt. Weitere übliche Bestandteile sind Lösevermittler, Farb- und Duftstoffe, Konservierungsmittel, etc.Modern products here consist of neutral aqueous formulations based on highly foaming surfactants. The main components are sulfonates, such as. As alkylbenzenesulfonates or sec-alkanesulfonates, both combined with fatty alcohol ether sulfates or fatty alcohol sulfates (EP-A-0 112 047). Small amounts of fatty acid alkanolamides and, more rarely, oxyethylates are added. Other common ingredients are solubilizers, colors and fragrances, preservatives, etc.

Eine Methode und eine Zusammensetzung zur Reinigung harter Oberflächen wird in WO 86/04349 beschrieben, bei der nichtionische Tenside eingesetzt werden, von denen mindestens 10 % aus dem hautmilden Alkylpolyglycosid bestehen sollen. Diese Rezeptur kann aber nicht auf den Einsatz von (größeren Mengen) eigentlich unerwünschten Buildern verzichten.A method and a composition for cleaning hard surfaces is described in WO 86/04349, in which nonionic surfactants are used, of which at least 10% are said to consist of the skin-mild alkyl polyglycoside. However, this recipe cannot do without the use of (larger amounts) actually undesirable builders.

Der Spülvorgang findet gewöhnlich bei etwas erhöhter Temperatur (30 bis 50 °C) in verdünnten Lösungen statt. Von besonderer Bedeutung, wegen des langen Hautkontaktes des Anwenders ist die Hautverträglichkeit des Spülmittels. So ist zum Beispiel der in US-H 468 beschriebene Reiniger für harte Oberflächen auf alleiniger Basis des als hautmild bekannten Alkylpolyglycosids durch die Anwesenheit von 0.1 bis zu 50 Gewichtsprozent die Haut stark angreifenden Alkali- oder Ammoniumhydroxids trotz offensichtlich guter Reinigungswirkung als manuelles Spülmittel ungeeignet. Bei der Einschätzung der Reinigungskraft durch den Verbraucher spielt das Schäumvermögen der Lösung eine erhebliche Rolle, etwa in dem Sinne, je länger die Reinigungslösung während des Spülvorganges schäumt desto größer ist auch ihre Reinigungskraft. Allgemein anerkannte Methoden zur Ermittlung der Reinigungswirkung sind a) der Tellertest mit schäumenden Spülmitteln, dessen Endpunkt durch den Schaumzerfall bestimmt wird, und b) die Fett-Titration, als Maß für die Reinigungskraft, die beide zu sehr ähnlichen Ergebnissen (vgl. G. Jakobi in H. Stache, Tensid Taschenbuch, 2. Ausgabe, München 1981, S. 252 ff.) führen.The rinsing process usually takes place at a slightly elevated temperature (30 to 50 ° C) in dilute solutions. Of particular importance because of the long skin contact of the user is the skin compatibility of the detergent. For example, the cleaner for hard surfaces described in US Pat. No. H 468, based solely on the alkyl polyglycoside known as mild to the skin, is unsuitable as a manual dishwashing detergent due to the presence of 0.1 to 50 percent by weight of alkali metal or ammonium hydroxide, which is very aggressive to the skin, despite the obviously good cleaning action. When the cleaning power is assessed by the consumer, the foaming power of the solution plays a significant role, for example in the sense that the longer it is Cleaning solution foams during the rinsing process, the greater its cleaning power. Generally recognized methods for determining the cleaning effect are a) the plate test with foaming detergents, the end point of which is determined by the foam disintegration, and b) the fat titration, as a measure of the cleaning power, both of which lead to very similar results (see G. Jakobi in H. Stache, Tensid Taschenbuch, 2nd edition, Munich 1981, pp. 252 ff.).

Wahrscheinlich hat diese Parallelität von qualitativer Schaumexistenz und Reinigungsvermögen die Hersteller konventioneller Spülmittel dazu verführt, höchste Bedeutung dem Schaumvolumen beizumessen. Dies hat zur Folge, daß das Spülgut bei verbraucherüblicher Dosierung des Spülmittels im Schaum verschwindet, was bekanntlich außerdem die eigentliche Reinigung herabsetzt und auch hinsichtlich des Hautgefühls unangenehm sein kann.This parallelism of qualitative foam existence and cleaning ability probably led the manufacturers of conventional detergents to attach the greatest importance to the foam volume. The result of this is that the items to be washed disappear into the foam when the detergent is used in a customary dosage, which, as is known, also reduces the actual cleaning and can also be uncomfortable with regard to the feeling on the skin.

Ein weiterer Nachteil der bekannten Spülmittel ist ihre geringe Hautfreundlichkeit, da ihre wesentlichen Bestandteile - nämlich die anionischen Tenside vom Sulfonat- bzw. Sulfat-Typ - in hohem Maße hautreizend sind.Another disadvantage of the known detergents is their poor skin-friendliness, since their essential components - namely the anionic surfactants of the sulfonate or sulfate type - are highly irritating to the skin.

Und ebenfalls von Nachteil im Hinblick auf die Verknappung der Rohstoffreserven ist die überwiegend petrochemische Basis der genannten anionischen Tenside, verbunden mit einer unvollständigen biologischen Abbaubarkeit.Another disadvantage with regard to the scarcity of raw material reserves is the predominantly petrochemical basis of the anionic surfactants mentioned, combined with incomplete biodegradability.

Aufgabe der Erfindung war es daher, ein sehr hautverträgliches Reinigungsmittel mit hervorragender Reinigungswirkung bei mäßigem Schaumvermögen zur Verfügung zu stellen, dessen Reinigungstensid biologisch weitestgehend abbaubar ist.The object of the invention was therefore to provide a very skin-compatible cleaning agent with excellent cleaning action and moderate foaming power, the cleaning surfactant of which is largely biodegradable.

Diese Aufgabe wurde gelöst durch ein flüssiges Reinigungsmittel, das als Reinigungstensid ausschließlich Alkylpolyglycosid enthält.This object has been achieved by a liquid cleaning agent which contains only alkyl polyglycoside as the cleaning surfactant.

Gegenstand der Erfindung ist daher ein neutrales, flüssiges schäumendes Reinigungsmittel, bestehend aus

  • 3 bis 40 Gewichtsprozent Alkylpolyglycosid,
  • 0 bis 30 Gewichtsprozent Lösungsvermittler,
  • 0 bis 10 Gewichtsprozent Elektrolyt,
  • 0 bis 3 Gewichtsprozent Additiven und
  • Wasser ad 100 Gewichtsprozent.
The invention therefore relates to a neutral, liquid foaming cleaning agent consisting of
  • 3 to 40 percent by weight alkyl polyglycoside,
  • 0 to 30 weight percent solubilizer,
  • 0 to 10 percent by weight electrolyte,
  • 0 to 3 percent by weight of additives and
  • Water ad 100 weight percent.

Die Verwendung von Alkylpolyglycosiden in Wasch- und Reinigungsmitteln ist in Kombination mit anderen Tensiden bekannt. So beschreibt die AT-PS 135 333 bereits die Wirkung von Laurylglycosid kombiniert mit dem Natriumsalz des Ricinolschwefelsäureesters als Wollwaschmittel. In der US-PS 3 721 633 werden Alkylpolyglycoside in Kombination mit Buildersubstanzen, wie Nitrilotriessigsäure oder Natriumtripolyphosphat, als Waschmittel beschrieben. Die Kombination von Alkylpolyglycosiden mit Fettalkoholoxethylaten als flüssiges Waschmittel beansprucht die EP-A-0 105 556. Manuelle Spülmittel unter Verwendung von Alkylpolyglycosiden werden in den Druckschriften EP-A-0 070 074, EP-A-0 070 075 und EP-A-0 070 076 beschrieben, wobei u.a. anionische Tenside als Cotenside miteingesetzt werden. Analogen Inhalt hat auch die DE-OS 35 34 082, wobei Fettalkylglycoside mit 1 bis 1,4 Glycosideinheiten pro Fettalkyl-Rest genannt werden. Als Cotenside dienen hierbei Alkylsulfate oder Alkylethersulfate jeweils in Kombination mit Fettsäurealkanolamiden. Schließlich beschreibt EP-A-0 199 765 ein Flüssigwaschmittel oder Spülmittel mit ähnlichem Anspruch. Die Verwendung eines kommerziellen Alkylpolyglycosids (Triton CG 110) in manuellen Spülmitteln in Kombination mit anderen Tensiden wird auch in Rohm & Haas, Techn. Bulletin, Triton CG 110, Mai 1975, erwähnt.The use of alkyl polyglycosides in detergents and cleaning agents is known in combination with other surfactants. For example, AT-PS 135 333 already describes the effect of lauryl glycoside combined with the sodium salt of ricinol sulfuric acid ester as a wool detergent. In US Pat. No. 3,721,633, alkyl polyglycosides in combination with builder substances, such as nitrilotriacetic acid or sodium tripolyphosphate, are described as detergents. EP-A-0 105 556 claims the combination of alkyl polyglycosides with fatty alcohol oxyethylates as a liquid detergent. Manual detergents using alkyl polyglycosides are described in EP-A-0 070 074, EP-A-0 070 075 and EP-A-0 070 076, among others anionic surfactants can be used as cosurfactants. DE-OS 35 34 082 also has analogous content, fatty alkyl glycosides having 1 to 1.4 glycoside units per fatty alkyl radical being mentioned. Alkyl sulfates or alkyl ether sulfates in each case in combination with fatty acid alkanolamides serve as cosurfactants. Finally, EP-A-0 199 765 describes a liquid detergent or dishwashing detergent with a similar claim. The use of a commercial alkyl polyglycoside (Triton CG 110) in manual detergents in combination with other surfactants is also mentioned in Rohm & Haas, Technical Bulletin, Triton CG 110, May 1975.

Alle diese Schriften betreffen die Kombination von Alkylpolyglycosiden mit anderen, meist anionischen Tensiden. Es war daher anzunehmen, daß die Wechselwirkung der Alkylpolyglycoside mit anderen Tensiden für die Reinigungswirkung entscheidend ist.All of these publications relate to the combination of alkyl polyglycosides with other, usually anionic, surfactants. It was therefore to be assumed that the interaction of the alkyl polyglycosides with other surfactants is crucial for the cleaning action.

Außerdem haben Vergleichsuntersuchungen (siehe Tab. 2) gezeigt, daß z. B. Triton CG 110 allein keine Spülwirkung besitzt.In addition, comparative studies (see Tab. 2) have shown that, for. B. Triton CG 110 alone has no flushing effect.

Völlig überraschend wurde nun beobachtet, daß Spülmittel, die als Reinigungstensid ausschließlich Alkylpolyglycoside enthalten, hervorragende Reinigungswirkungen erzielen, wenn diese Alkylpolyglycoside der Formel I genügen, d. h. eine ausreichend hydrophobe Struktur aufiveisen. Dies gelingt durch Verwendung von Fettalkoholen mit relativ langen Kohlenwasserstoffketten bei der Synthese, wobei die Mengenverhältnisse von Fettalkohol zu Monosaccharideinheiten so zu wählen sind, daß der mittlere Glycosidierungsgrad (Glycosideinheiten pro Fettalkylrest) nicht zu hoch ist.Completely surprisingly, it has now been observed that detergents which contain only alkyl polyglycosides as cleaning surfactants achieve excellent cleaning effects if these alkyl polyglycosides satisfy the formula I, ie they have a sufficiently hydrophobic structure. This can be achieved by using fatty alcohols relatively long hydrocarbon chains in the synthesis, the proportions of fatty alcohol to monosaccharide units to be chosen so that the average degree of glycosidation (glycoside units per fatty alkyl radical) is not too high.

Alkylpolyglycoside:Alkyl polyglycosides:

Erfindungsgemäß eingesetzte Alkylpolyglycoside genügen der Formel I

        R-O-Zn     I,

in der R für einen linearen oder verzweigten, gesättigten oder ungesättigten aliphatischen Alkylrest mit 12 bis 18 Kohlenstoffatomen oder Gemische davon und Zn für einen Polyglycosylrest mit n = 1,0 bis 2 Hexose- oder Pentoseeinheiten oder Gemische davon stehen.Alkyl polyglycosides used according to the invention satisfy formula I.

RO-Zn I,

in which R represents a linear or branched, saturated or unsaturated aliphatic alkyl radical having 12 to 18 carbon atoms or mixtures thereof and Z n represents a polyglycosyl radical with n = 1.0 to 2 hexose or pentose units or mixtures thereof.

Bevorzugt werden Alkylpolyglycoside mit Fettalkylresten mit 12 bis 16 Kohlenstoffatomen sowie einem Polyglycosylrest von n = 1,1 bis 2. Besonders bevorzugt werden Alkylpolyglucoside.Alkyl polyglycosides with fatty alkyl radicals having 12 to 16 carbon atoms and a polyglycosyl radical from n = 1.1 to 2 are preferred. Alkyl polyglucosides are particularly preferred.

Die erfindungsgemäß eingesetzten Alkylpolyglycoside können nach bekannten Verfahren auf Basis nachwachsender Rohstoffe hergestellt werden. Beispielsweise wird Dextrose in Gegenwart eines sauren Katalysators mit n-Butanol zu Butylpolyglycosidgemischen umgesetzt, welche mit langkettigen Alkoholen ebenfalls in Gegenwart eines sauren Katalysators zu den gewünschten Alkylpolyglycosidgemischen umglycosidiert werden.The alkyl polyglycosides used according to the invention can be produced by known processes based on renewable raw materials. For example, dextrose is reacted with n-butanol to give butylpolyglycoside mixtures in the presence of an acidic catalyst, which are transglycosidated with long-chain alcohols, likewise in the presence of an acidic catalyst, to give the desired alkylpolyglycoside mixtures.

Die Struktur der Produkte ist in bestimmten Grenzen variierbar. Der Alkylrest R wird durch die Auswahl des langkettigen Alkohols festgelegt. Günstig aus wirtschaftlichen Gründen sind die großtechnisch zugänglichen Tensidalkohole mit 12 bis 18 C-Atomen, insbesondere native Fettalkohole aus der Hydrierung von Fettsäuren bzw. Fettsäurederivaten. Verwendbar sind auch Ziegleralkohole oder Oxoalkohole.The structure of the products can be varied within certain limits. The alkyl radical R is determined by the choice of the long-chain alcohol. Favorable for economic reasons are the industrially accessible surfactant alcohols with 12 to 18 carbon atoms, in particular native fatty alcohols from the hydrogenation of fatty acids or fatty acid derivatives. Ziegler alcohols or oxo alcohols can also be used.

Der Polyglycosylrest Zn wird einerseits durch die Auswahl des Kohlenhydrats und andererseits durch die Einstellung des mittleren Polymerisationsgrades z. B. nach DE-OS 19 43 689 festgelegt. Im Prinzip können bekanntlich Polysaccharide, z. B. Stärke, Maltodextrine, Dextrose, Galaktose, Mannose, und Xylose, eingesetzt werden. Bevorzugt sind die großtechnisch verfügbaren Kohlenhydrate Stärke, Maltodextrine und besonders Dextrose. Da die wirtschaftlich interessanten Alkylpolyglycosidsynthesen nicht regio- und stereoselektiv verlaufen, sind die Alkylpolyglycoside stets Gemische von Oligomeren, die ihrerseits Gemische verschiedener isomerer Formen darstellen. Sie liegen nebeneinander mit α- und β-glycosidischen Bindungen in Pyranose- und Furanoseform vor. Auch die Verknüpfungsstellen zwischen zwei Saccachridresten sind unterschiedlich.The polyglycosyl radical Z n is determined, on the one hand, by the selection of the carbohydrate and, on the other hand, by the setting of the average degree of polymerization, e.g. B. according to DE-OS 19 43 689. In principle, it is known that polysaccharides, e.g. B. starch, maltodextrins, dextrose, galactose, mannose, and xylose can be used. The industrially available carbohydrates starch, maltodextrins and especially dextrose are preferred. Since the economically interesting alkyl polyglycoside syntheses are not regio- and stereoselective, the alkyl polyglycosides are always mixtures of oligomers, which in turn represent mixtures of different isomeric forms. They exist side by side with α- and β-glycosidic bonds in pyranose and furanose form. The junctions between two Saccachrid residues are also different.

Erfindungsgemäß eingesetzte Alkylpolyglycoside lassen sich auch durch Abmischen von Alkylpolyglycosiden mit Alkylmonoglycosiden herstellen. Letztere kann man z. B. nach EP-A-0 092 355 mittels polarer Lösemittel wie Aceton aus Alkylpolyglycosiden gewinnen bzw. anreichern.Alkyl polyglycosides used according to the invention can also be prepared by mixing alkyl polyglycosides with alkyl monoglycosides. The latter can e.g. B. according to EP-A-0 092 355 using polar solvents such as acetone from alkyl polyglycosides.

Der Glycosidierungsgrad wird zweckmäßigerweise mittels 1H-NMR bestimmt.The degree of glycosidation is expediently determined by means of 1 H-NMR.

Die erfindungsgemäßen Reinigungsmittel enthalten 3 bis 40 %, vorzugsweise 5 bis 30 %, Alkylpolyglycosid in wäßriger Lösung.The cleaning agents according to the invention contain 3 to 40%, preferably 5 to 30%, of alkyl polyglycoside in aqueous solution.

Im Vergleich zu allen anderen in Reinigungsmitteln eingesetzten Tensiden gelten die Alkylpolyglycoside als überaus umweltverträglich. So liegt der mittels Kläranlagen-Simulationsmodell/DOC-Analyse bestimmte biologische Abbaugrad für die erfindungsgemäßen Alkylpolyglycoside bei 96 ± 3 %. Diese Zahl ist vor dem Hintergrund zu sehen, daß bei diesem Testverfahren (Totalabbau) bereits ein Abbaugrad > 70 % die Substanz als gut abbaubar indiziert.Compared to all other surfactants used in cleaning agents, the alkyl polyglycosides are considered to be extremely environmentally compatible. The degree of biodegradation for the alkyl polyglycosides according to the invention, determined by means of a sewage plant simulation model / DOC analysis, is 96 ± 3%. This number can be seen against the background that with this test method (total degradation) a degree of degradation> 70% already indicates that the substance is readily degradable.

Auch die akute orale Toxizität LD 50 (Ratte) sowie die aquatische Toxizität LC 50 (Goldorfe) und EC 50 (Daphnien) mit Werten von > 10 000 mg/kg, 12 bzw. 30 mg/l liegen um den Faktor 3 bis 5 günstiger als die entsprechenden Werte der heute wichtigsten Tenside. Ähnliches gilt für die bei Spülmitteln besonders wichtige Haut - und Schleimhautverträglichkeit.The acute oral toxicity LD 50 (rat) as well as the aquatic toxicity LC 50 (gold orfe) and EC 50 (daphnia) with values of> 10,000 mg / kg, 12 and 30 mg / l are three to five times cheaper than the corresponding values of the most important surfactants today. The same applies to the skin that is particularly important for detergents - and mucosal tolerance.

Die erfindungsgemäßen Alkylpolyglycoside fallen synthesebedingt als etwa 50 %ige wäßrige bernsteinfarbene Lösungen an. Die Löslichkeit in Wasser ist aufgrund der hydrophoben Struktureinstellung nicht allzu hoch.The alkyl polyglycosides according to the invention are obtained as a result of the synthesis as approximately 50% aqueous amber-colored solutions. The solubility in water is not too high due to the hydrophobic structure.

Lösevermittler:Solvency mediator:

Durch Zusatz von Lösemitteln wie Ethanol, Isopropanol, und Propylenglykol-1.2 läßt sich die Löslichkeit besonders auch bei niedrigen Temperaturen erheblich erhöhen. Das Verhältnis von Alkylpolyglycosid/Lösemittel kann 1 : 1 bis 8 : 1 betragen.By adding solvents such as ethanol, isopropanol and propylene glycol-1.2, the solubility can be increased significantly, especially at low temperatures. The ratio of alkyl polyglycoside / solvent can be 1: 1 to 8: 1.

Elektrolyte:Electrolytes:

In Kombination der Lösevermittler mit Elektrolyten läßt sich die Löslichkeit besonders auch bei niedrigen Temperaturen erheblich erhöhen. Als geeignete Elektrolyte haben sich Alkali- und Erdalkalihalogenide erwiesen. Das Verhältnis von Lösemittel/Elektrolyt kann 1 : 1 bis 8 : 1 betragen.In combination with the solubilizers with electrolytes, the solubility can be increased considerably, especially at low temperatures. Alkali and alkaline earth halides have proven to be suitable electrolytes. The solvent / electrolyte ratio can be 1: 1 to 8: 1.

Additive:Additives:

Weitere Bestandteile der erfindungsgemäßen Reinigungsmittel in geringen Mengen (0,1 bis 3 Gewichtsprozent) sind übliche Farbstoffe und Parfümöle sowie Alkanolamine oder auch Hydrotropica, wie nichttensidische Alkylbenzolsulfonate mit 1 bis 3 Kohlenstoffatomen im Alkylrest - gewöhnlich als Natriumsalze - sowie Harnstoff.Other constituents of the cleaning agents according to the invention in small amounts (0.1 to 3 percent by weight) are conventional dyes and perfume oils, and also alkanolamines or hydrotropes, such as non-surfactant alkylbenzenesulfonates having 1 to 3 carbon atoms in the alkyl radical - usually as sodium salts - and urea.

Zur Einstellung geeigneter Viskosität können gegebenenfalls wasserlösliche Polymere wie Carboxymethylcellulose, Hydroxyethylcellulose, Xanthane, Polyethylenoxid, und Polyacrylat, zugesetzt werden.Water-soluble polymers such as carboxymethyl cellulose, hydroxyethyl cellulose, xanthans, polyethylene oxide and polyacrylate can optionally be added to adjust the viscosity.

BeispieleExamples

Die nachfolgenden Beispiele sollen die Erfindung verdeutlichen.The following examples are intended to illustrate the invention.

Zur Testung der Spülmittelwirkung wurde der Minitellertest (vgl. R.M. Anstett u. E.J. Schuck JAOCS 43, 576 (1966) durchgeführt.To test the detergent effect, the mini-plate test (see R.M. Anstett and E.J. Schuck JAOCS 43, 576 (1966) was carried out.

Hierbei werden mit Fett beladene Uhrgläser bei erhöhter Temperatur mit einem Pinsel in der Tensidlösung manuell gereinigt. Die Versuchsbedingungen (Präparationen, Geometrien, Stoffmengen und -konzentrationen, Temperaturen, Temperaturgradienten, Zeiten) sind genau definiert. Der Test wird von mehreren Personen durchgeführt und liefert gut reproduzierbare Ergebnisse. Verschwindender Schaum zeigt die Anzahl der gereinigten Teller (Uhrgläser) an. Als Anschmutzung diente Schweineschmalz, das bei 50 °C auf die Gläser aufgebracht wurde, die so dann einem definierten Abkühlungsprozeß auf 23 °C (Raumtemperatur) unterliegen. Die Spül-Anfangstemperatur beträgt ebenfalls 50 °C.Watch glasses loaded with grease are manually cleaned at elevated temperature with a brush in the surfactant solution. The test conditions (preparations, geometries, amounts and concentrations of substances, temperatures, temperature gradients, times) are precisely defined. The test is carried out by several people and provides well reproducible results. Disappearing foam shows the number of cleaned plates (watch glasses). Pork lard served as soiling, which was applied to the glasses at 50 ° C, which are then subject to a defined cooling process to 23 ° C (room temperature). The initial rinse temperature is also 50 ° C.

Tabelle 1 vergleicht die Reinigungswirkung von Einzeltensiden, die bei Alkylpolyglycosiden stark mit steigender Molekülhydrophobie zunimmt.Table 1 compares the cleaning effect of individual surfactants, which increases sharply with increasing molecular hydrophobicity in the case of alkyl polyglycosides.

Tabelle 2 demonstriert, daß auch eine starke Erhöhung der Tensidkonzentration nur unbefriedigende Reinigungswirkungen ergibt, wenn das Alkylpolyglycosid zu hydrophil ist, wie im Falle von Triton CG 110.Table 2 demonstrates that even a strong increase in the surfactant concentration only gives unsatisfactory cleaning effects if the alkyl polyglycoside is too hydrophilic, as in the case of Triton CG 110.

Tabelle 3a vergleicht die Reinigungswirkung der erfindungsgemäßen Alkylpolyglykoside mit denen optimierter Markenprodukte in Abhängigkeit der Spülmittelkonzentration für einen mittleren Wasserhärtegrad; Tabelle 3b gibt die analogen Verhältnisse bei weichem Wasser an. Tabelle 1 Minitellertest, Konzentration Waschaktive Substanz: 0,075 g/l, Trinkwasser: 13° dH Tensid Anzahl gereinigter Teller a) C10-C13-Alkylbenzolsulfonat-Na 10 b) C12-C14-O (EO)2 SO4 Na 14 c) C12C14 O (EO)8 H 8 d) C8C10 G1.8 (Triton CG 110)* 0 e) C10C12 G1.5 1 f) C10C12 G1.2 5 g) C12C13 G1.7 14 h) C12C14 G1.4 18 i) C12C14 G1.2 22 * C8C10-Alkylglucosid mit 1,8 Glucosylteilen pro Alkylrest Table 3a compares the cleaning action of the alkyl polyglycosides according to the invention with those of optimized branded products depending on the detergent concentration for a medium water hardness; Table 3b shows the analogous conditions for soft water. Table 1 Mini plate test, concentration of detergent: 0.075 g / l, drinking water: 13 ° dH Surfactant Number of cleaned plates a) C 10 -C 13 alkylbenzenesulfonate Na 10th b) C 12 -C 14 -O (EO) 2 SO 4 Na 14 c) C 12 C 14 O (EO) 8 H 8th d) C 8 C 10 G 1.8 (Triton CG 110) * 0 e) C 10 C 12 G 1.5 1 f) C 10 C 12 G 1.2 5 g) C 12 C 13 G 1.7 14 h) C 12 C 14 G 1.4 18th i) C 12 C 14 G 1.2 22 * C 8 C 10 alkyl glucoside with 1.8 glucosyl parts per alkyl radical

Die Beispiele g) bis i) sind erfindungsgemäß. Tabelle 2 (Vergleichsversuche) Minitellertest mit Triton CG 110* (Rohm & Haas) in Abhängigkeit von der Wässerhärte und der Tensidkonzentration Wasserhärte Waschaktive Substanz g/l Anzahl gereinigter Teller a) 2 0,075 0 b) 2 0,15 1 c) 13 0,15 0 d) 13 0,3 1 * C8C10-Alkylglucosid mit 1,8 Glucosylteilen pro Alkylrest Tabelle 3a Minitellertest mit hydrophob eingestellten Alkylpolyglycosiden im Vergleich zu Markenspülmitteln, Wasser: 13° dH, pH 6-7 Produkt Waschaktive Substanz g/l Anzahl gereinigter Teller a) C12C14 G1.2 0,075 22 b) C12C13 G1.1 0,075 20 c) "Pril" 0,075 20 d) "Palmolive" 0,075 20 e) "Frosch" 0,075 18 f) C12C14 G1.1 0,05 16 g) C12C14 G1.2 0,05 15 h) "Pril" 0,05 14 i) C12C14 G1.2 0,025 3 j) "Pril" 0,025 2 Tabelle 3b Minitellertest mit hydrophob eingestellten Alylpolyglycosiden im Vergleich zu Markenspülmitteln, Wasser: 2° dH, pH 6-7 Produkt Waschaktive Substanz g/l Anzahl gereinigter Teller a) C12C14 G1.1 0,075 27 b) C12C14 G1.2 0,075 26 c) C12C13 G1.1 0,075 25 d) "Pril" 0,075 25 e) "Palmolive" 0,075 25 f) "Frosch" 0,075 25 Examples g) to i) are according to the invention. Table 2 (Comparative tests) Mini plate test with Triton CG 110 * (Rohm & Haas) depending on the water hardness and the surfactant concentration Water hardness Wash-active substance g / l Number of cleaned plates a) 2nd 0.075 0 b) 2nd 0.15 1 c) 13 0.15 0 d) 13 0.3 1 * C 8 C 10 alkyl glucoside with 1.8 glucosyl parts per alkyl radical Mini plate test with hydrophobic alkyl polyglycosides compared to branded detergents, water: 13 ° dH, pH 6-7 product Wash-active substance g / l Number of cleaned plates a) C 12 C 14 G 1.2 0.075 22 b) C 12 C 13 G 1.1 0.075 20th c) "Pril" 0.075 20th d) "Palmolive" 0.075 20th e) "frog" 0.075 18th f) C 12 C 14 G 1.1 0.05 16 g) C 12 C 14 G 1.2 0.05 15 h) "Pril" 0.05 14 i) C 12 C 14 G 1.2 0.025 3rd j) "Pril" 0.025 2nd Mini-plate test with hydrophobic alyl polyglycosides compared to branded detergents, water: 2 ° dH, pH 6-7 product Wash-active substance g / l Number of cleaned plates a) C 12 C 14 G 1.1 0.075 27 b) C 12 C 14 G 1.2 0.075 26 c) C 12 C 13 G 1.1 0.075 25th d) "Pril" 0.075 25th e) "Palm Olive" 0.075 25th f) "frog" 0.075 25th

Aus den Tabellen 3a und 3b ergibt sich die hervorragende Reinigungswirkung der erfindungsgemäßen Alkylpolyglycoside, die als sehr umweltverträgliche Einzeltenside in Spülmitteln eine hervorragende Reinigungswirkung erzielen. Tabelle 4 Daten und Reinigungswirkung erfindungsgemäßer Zubereitungen Zusammensetzung (Gew.-%) a b c d e f g h C12C14 G1.2 20 20 20 20 - - - "Pril" C12C13 G1.1 - - - - 20 20 20 Ethanol 10 10 10 - - - - i-Propanol - - - 10 10 - - NaCl - 5 7 5 5 - - KCl - - - - - - - CaCl2 - - - - - - 5 Klarpt. (°C) 14 11 9 10 -3 2 1 11 Viskosität (25 °C) 80 50 40 20 30 180 160 200 (mPa s) pH 6,7 6,5 6,5 6,3 7,5 7,5 7,8 6,8 Anzahl der gereinigten Teller 13° dH, 50 °C 21 X 22 21 23 21 20 20 X = nicht gemessen Tables 3a and 3b show the excellent cleaning action of the alkyl polyglycosides according to the invention, which, as very environmentally compatible individual surfactants in detergents, achieve an excellent cleaning action. Table 4 Data and cleaning effect of preparations according to the invention Composition (% by weight) a b c d e f G H C 12 C 14 G 1.2 20th 20th 20th 20th - - - "Pril" C 12 C 13 G 1.1 - - - - 20th 20th 20th Ethanol 10th 10th 10th - - - - i-propanol - - - 10th 10th - - NaCl - 5 7 5 5 - - KCl - - - - - - - CaCl 2 - - - - - - 5 Of course. (° C) 14 11 9 10th -3 2nd 1 11 Viscosity (25 ° C) 80 50 40 20th 30th 180 160 200 (mPa s) pH 6.7 6.5 6.5 6.3 7.5 7.5 7.8 6.8 Number of cleaned plates 13 ° dH, 50 ° C 21 X 22 21 23 21 20th 20th X = not measured

In Tabelle 4 sind die physikalischen Daten einiger erfindungsgemäßen Zubereitungen zusammengestellt. Die ebenfalls aufgeführten Reinigungswerte (Minitellertest) demonstrieren die hohe Wirksamkeit der neuen Reinigungssysteme.The physical data of some preparations according to the invention are summarized in Table 4. The cleaning values also listed (mini plate test) demonstrate the high effectiveness of the new cleaning systems.

Claims (9)

  1. A neutral, liquid, foaming cleaning composition, comprising
    3 to 40 per cent by weight of alkyl polyglycoside,
    zero to 30 per cent by weight of solvent,
    zero to 10 per cent by weight of water-soluble electrolyte,
    zero to 3 per cent by weight of additives
    and water to 100 per cent by weight,
    where the alkyl polyglycoside corresponds to the formula I

            R-O-Zn     I

    in which R is a saturated or unsaturated, branched or unbranched alkyl radical having 12 to 18 carbon atoms and Zn is a polyglycosyl radical with n = 1 to 2 hexose or pentose units or mixtures, and
    where ethanol, i-propanol or 1,2-propylene glycol is used as solvent, and conventional dyes, perfume oils, alkanolamines, hydrotropes, urea are used as additives, and water-soluble polymers are used to adjust the viscosity.
  2. A cleaning composition according to claim 1, characterized in that the alkyl polyglycoside corresponds to the formula I

            R-O-Zn     I

    where R is a saturated or unsaturated fatty alcohol having 12 to 18 carbon atoms and Zn is a polyglycosyl radical with n = 1.1 to 1.7 glucoside units.
  3. A cleaning composition according to claim 1, characterized in that the alkyl polyglycoside corresponds to the formula I

            R-O-Zn     I

    where R is a saturated or unsaturated fatty alcohol having 12 to 18 carbon atoms and Zn is a polyglycosyl radical with n = 1.1 to 1.4 glucoside units.
  4. A cleaning composition according to claim 1, characterized in that the alkyl polyglycoside corresponds to the formula I

            R-O-Zn     I

    where R is a saturated or unsaturated fatty alcohol having 12 to 14 carbon atoms and Zn is a polyglycosyl radical with n = 1.1 to 1.4 glucoside units.
  5. A cleaning composition according to any one of the preceding claims, characterized in that the alkyl polyglycoside/solvent ratio is 1:1 to 8:1.
  6. A cleaning composition according to any one of the preceding claims, characterized in that alkali metal and/or alkaline earth metal chlorides are used as electrolyte.
  7. A cleaning composition according to any one of the preceding claims, characterized in that the solvent/electrolyte ratio is 1:1 to 8:1.
  8. A cleaning composition according to any one of the preceding claims, characterized in that the alkyl polyglycoside is an alkyl polyglucoside.
  9. The use of the cleaning composition according to any one of claims 1 to 8 as manual dishwashing composition.
EP90123936A 1990-02-26 1990-12-12 Liquid foaming detergent Revoked EP0444267B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4005959 1990-02-26
DE4005959A DE4005959A1 (en) 1990-02-26 1990-02-26 LIQUID, FOAMING DETERGENT

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EP0444267A2 EP0444267A2 (en) 1991-09-04
EP0444267A3 EP0444267A3 (en) 1991-12-18
EP0444267B1 true EP0444267B1 (en) 1997-05-14

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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4110506A1 (en) * 1991-03-30 1992-10-01 Huels Chemische Werke Ag EMULSIFIERS FOR THE PRODUCTION OF OIL-IN-WATER EMULSIONS OF ETHERIC OILS USED IN COSMETICS OR MEDICINE
US5449763A (en) * 1991-10-10 1995-09-12 Henkel Corporation Preparation of alkylpolyglycosides
DE4216380A1 (en) * 1992-05-18 1993-11-25 Henkel Kgaa Procedure for cleaning bathroom fittings
AU675833B2 (en) * 1994-03-23 1997-02-20 Amway Corporation Concentrated all-purpose light duty liquid cleaning composition and method of use
GB9509452D0 (en) * 1995-05-10 1995-07-05 Unilever Plc Light duty cleaning composititon
JPH093498A (en) * 1995-06-20 1997-01-07 Th Goldschmidt Ag Stably storable concentrated water-based surfactant composition
GB9604623D0 (en) * 1996-03-04 1996-05-01 Johnson & Son Inc S C Stable aqueous silane solutions
US6087319A (en) * 1996-03-04 2000-07-11 S. C. Johnson & Son, Inc. Stable aqueous silane solutions for cleaning hard surfaces
DE10221335B4 (en) * 2002-05-10 2006-05-24 Braun Gmbh Use of a cleaning liquid for electric razors

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3721633A (en) * 1969-10-06 1973-03-20 Atlas Chem Ind Aqueous built liquid detergents containing alkyl glycosides
US4627931A (en) * 1985-01-29 1986-12-09 A. E. Staley Manufacturing Company Method and compositions for hard surface cleaning
USH468H (en) * 1985-11-22 1988-05-03 A. E. Staley Manufacturing Company Alkaline hard-surface cleaners containing alkyl glycosides
DE3706015A1 (en) * 1987-02-25 1988-11-17 Henkel Kgaa LIQUID DETERGENT
JPH0699708B2 (en) * 1989-03-20 1994-12-07 花王株式会社 Neutral liquid detergent composition

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DE4005959A1 (en) 1991-08-29
DE59010718D1 (en) 1997-06-19
EP0444267A2 (en) 1991-09-04

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