EP0486784B2 - Liquid foaming detergent of increased viscosity - Google Patents

Liquid foaming detergent of increased viscosity Download PDF

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EP0486784B2
EP0486784B2 EP91115711A EP91115711A EP0486784B2 EP 0486784 B2 EP0486784 B2 EP 0486784B2 EP 91115711 A EP91115711 A EP 91115711A EP 91115711 A EP91115711 A EP 91115711A EP 0486784 B2 EP0486784 B2 EP 0486784B2
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alkyl
liquid
fatty alcohol
weight
mixtures
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German (de)
French (fr)
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EP0486784A2 (en
EP0486784A3 (en
EP0486784B1 (en
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Dieter Dr. Balzer
Heinz Prof. Dr. Hoffmann
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Huels AG
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • 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
    • C11D1/143—Sulfonic 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
    • C11D1/14—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
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/29—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

Abstract

Conventional liquid dishwashing agents are predominantly produced on a petrochemical basis and have the disadvantage of incomplete biodegradability. A liquid, foaming detergent which has all the beneficial properties of conventional dishwashing agents while, at the same time, being well tolerated by skin and very environmentally compatible is now proposed. The surfactant ingredients are 5 - 40 % alkyl polyglycoside and 0.1 - 2.9 % anionic surfactant and 0 - 3 % other surfactants.

Description

Die Erfindung betrifft ein umweltfreundliches, schäumendes, flüssiges Reinigungsmittel.The invention relates to an environmentally friendly, foaming, liquid cleaning agent.

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.Liquid, foaming cleaning agents are aimed at the manual cleaning of hard surfaces, especially in the Household, such as B. ceramics, porcelain, glass, metal and plastic. The most important application area is manual Dishwashing liquid for cleaning dishes.

Modeme 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. B. alkylbenzenesulfonates or sec-alkanesulfonates, both combined with fatty alcohol ether sulfates or fatty alcohol sulfates (EP-A-0 112 047). In small quantities some fatty acid alkanolamides and more rarely oxethylates added. Other common ingredients are solubilizers, Dyes and fragrances, preservatives etc.

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. 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.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. When the consumer assesses the cleaning power, the foaming power of the solution plays a role considerable role, for example in the sense that the longer the cleaning solution foams during the rinsing process, the more their cleaning power is also greater.

Eine andere wichtige Verbrauchereigenschaft der Reinigungsflüssigkeit ist das Fließverhalten. Zu hohe und auch zu niedrige Viskositäten erschweren die manuelle Dosierung des Reinigungskonzentrats. Sehr niedrige Viskositäten führen ferner zu dem Eindruck geringen Wirkstoffgehaltes. Ideal für Haushaltsprodukte sind mittlere Viskositäten zwischen 150 und 300 mPa·s bei Scherraten von ca. 10 sec-1. Eine weitere bedeutende Eigenschaft ist die Verträglichkeit der Wirkstoffe mit Trinkwasser, wünschenswert sind klare Lösungen.Another important consumer property of the cleaning liquid is the flow behavior. Too high and too low viscosities make manual dosing of the cleaning concentrate difficult. Very low viscosities also lead to the impression of a low active substance content. Medium viscosities between 150 and 300 mPa · s with shear rates of approx. 10 sec -1 are ideal for household products. Another important property is the compatibility of the active ingredients with drinking water, clear solutions are desirable.

Die derzeit üblichen Reinigungsmittel zeigen gewöhnlich ausreichende Reinigungswirkung und ein starkes Schäumvermögen, geeignetes Fließverhalten sowie ausreichende Verträglichkeit mit den Härtebildnern des Wassers. Dagegen weisen diese Mischungen aber eine geringe Hautfreundlichkeit auf, da ihre wesentlichen Bestandteile - nämlich die anionischen Tenside vom Sulfonat- bzw. Sulfat-Typ - in hohem Maße hautreizend sind.The currently common cleaning agents usually show sufficient cleaning power and a strong one Foaming power, suitable flow behavior and sufficient compatibility with the hardness constituents of the water. In contrast, these mixtures are not very skin-friendly because their essential components - namely the anionic surfactants of the sulfonate or sulfate type - are highly irritating to the skin.

Ein weiterer gravierender Nachteil im Hinblick auf die Verknappung der Rohstoffreserven ist die überwiegend petrochemische Basis der genannten anionischen Tenside, verbunden mit einer unvollständigen biologischen Abbaubarkeit.Another major disadvantage with regard to the scarcity of raw material reserves is the predominant one petrochemical base of the anionic surfactants mentioned, combined with incomplete biodegradability.

Aufgabe der Erfindung war es daher, ein Reinigungsmittel zur Verfügung zu stellen, das alle gewünschten Eigenschaften impliziert, bei gleichzeitiger hoher Hautverträglichkeit und hervorragender Umweltverträglichkeit.The object of the invention was therefore to provide a cleaning agent which has all the desired properties implies, at the same time high skin tolerance and excellent environmental compatibility.

Die Aufgabe wurde gelöst durch ein flüssiges Reinigungsmittel, das als Tensid weitgehend nur Alkylpolyglycosid enthält.The object was achieved by a liquid cleaning agent which, as a surfactant, was largely only alkyl polyglycoside contains.

Gegenstand der Erfindung ist daher ein flüssiges, schäumendes Reinigungsmittel mit erhöhter Viskosität bestehend aus

  • 5 bis 40 Gew.-% Alkylpolyglycosid,
  • 0,1 bis 2,9 Gew.-% anionischem Tensid,
  • 0 bis 3 Gew.-% anderen Tensiden,
    •    sowie üblichen nichttensidischen Additiven und Wasser ad 100 Gew.-%.The invention therefore relates to a liquid, foaming cleaning agent with increased viscosity consisting of
  • 5 to 40% by weight alkyl polyglycoside,
  • 0.1 to 2.9% by weight of anionic surfactant,
  • 0 to 3% by weight of other surfactants,
    • and conventional non-surfactant additives and water ad 100 wt .-%.

    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 Cotensid miteingesetzt werden. Analogen Inhalt hat auch die DE-OS 35 34 082, wobei Fettalkylglycoside mit 1 bis 1,4 Glycosideinheiten pro Fettalkylrest genannt werden. Als Cotenside dienen hierbei Alkylsulfat oder Alkylethersulfate jeweils in Kombination mit Fettsäurealkanolamiden. Schließlich beschreibt EP-A-0 199 765 ein Flüssigwaschmittel oder Spülmittel mit ähnlichem Anspruch.The use of alkyl polyglycosides in detergents and cleaning agents is in combination with other surfactants known. 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 U.S. Patent 3,721,633, alkyl polyglycosides are used in combination with builder substances, such as nitrilotriacetic acid or sodium tripolyphosphate, as a detergent. The EP-A-0 claims a combination of alkyl polyglycosides with fatty alcohol oxyethylates as a liquid detergent 105 556. Manual detergents using alkyl polyglycosides are described in EP-A-0 070 074, EP-A-0 070 075 and EP-A-0 070 076, where u. a. anionic surfactants used as cosurfactant will. DE-OS 35 34 082 also has analogous content, fatty alkyl glycosides having 1 to 1.4 glycoside units per Fatty alkyl radical can be called. Alkyl sulfate or alkyl ether sulfates are used in combination in each case as cosurfactants with fatty acid alkanolamides. Finally, EP-A-0 199 765 describes a liquid detergent or detergent with the like Claim.

    Alle diese Kombinationen implizieren bei vergleichsweiser mehr oder minder guter Reinigungswirkung den Nachteil relativ hohen Gehalts an nicht rein nativen bzw. auf petrochemischer Basis beruhenden Cotensiden und damit meist auch den der eingeschränkten Umweltverträglichkeit und Hautfreundlichkeit.
    So fordert z. B. die EP-A-0 070 074 einen Mindest-Cotensidgehalt an Alkylbenzolsulfonat von 50 % oder bei Sulfaten von 60 % bezogen auf Gesamttensid.    All of these combinations imply the disadvantage of relatively high levels of non-purely native or petrochemical-based cosurfactants, and thus usually also of limited environmental compatibility and skin friendliness, with a comparatively more or less good cleaning action.
    So calls for. B. EP-A-0 070 074 a minimum cosurfactant content of alkylbenzenesulfonate of 50% or for sulfates of 60% based on total surfactant.

    Und die EP-0 199 765 beschreibt Reinigungsflüssigkeiten mit einem Mindestgehalt an anionischem Cotensid von 3%. And EP-0 199 765 describes cleaning liquids with a minimum content of anionic cosurfactant 3%.

    Eine ideale Problemlösung würde in Verwendung von Alkylpolyglycosid als einzigem tensidischem Bestandteil der Reinigungsflüssigkeit bestehen. Defacto besitzen auch reine Alkylpolyglycosidlösungen hervorragende Reinigungswirkungen, vorausgesetzt sie sind ausreichend hydrophob eingestellt. Letzteres gelingt durch einen längerkettigen hydrophoben Alkylrest bzw. durch einen weniger ausgeprägten hydrophilen Molekülteil.An ideal solution would be to use alkyl polyglycoside as the only surfactant component of the cleaning liquid. Defacto pure alkyl polyglycoside solutions also have excellent cleaning effects, provided they are sufficiently hydrophobic. The latter succeeds through a longer chain hydrophobic alkyl radical or by a less pronounced hydrophilic part of the molecule.

    Es wurde nun überraschend gefunden, daß bei Zusatz von äußerst geringen Mengen von Aniontensid zu Alkylpolyglycosiden gutes Schäumvermögen und hohe Spülwirkung bei guter Hautverträglichkeit bei den erfindungsgemäßen flüssigen Reinigungsmitteln zu beobachten ist, wobei eine Viskositätssteigerung im Vergleich zu dem reinen Alkylpolyglycosidkonzentrat um den Faktor 15 bis 20 zu beobachten ist.It has now surprisingly been found that when extremely small amounts of anionic surfactant are added to alkyl polyglycosides good foaming power and high rinsing effect with good skin tolerance in the inventive Liquid cleaning agents can be observed, with an increase in viscosity compared to the pure alkyl polyglycoside concentrate is observed by a factor of 15 to 20.

    AlkylpolyglycosideAlkyl polyglycosides

    Erfindungsgemäß eingesetzte Alkylpolyglycoside genügen der Formel I R-O-Zn , in der R für einen linearen oder verzweigten, gesättigten oder ungesättigten aliphatischen Alkylrest mit 10 bis 18 Kohlenstoffatomen oder Gemische davon und Zn für einen Polyglycosylrest mit n = 1,0 bis 3 Hexose- oder Pentoseeinheiten oder Gemische davon stehen.Alkyl polyglycosides used according to the invention satisfy formula I. RON n , in which R represents a linear or branched, saturated or unsaturated aliphatic alkyl radical having 10 to 18 carbon atoms or mixtures thereof and Z n represents a polyglycosyl radical with n = 1.0 to 3 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 Alkylpolyglycoside mit n = 1,1 bis 1,5.Alkyl polyglycosides with fatty alkyl radicals having 12 to 16 carbon atoms and a polyglycosyl radical are preferred from n = 1.1 to 2. Particularly preferred are alkyl polyglycosides with n = 1.1 to 1.5.

    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 based on renewable methods using known methods Raw materials are manufactured. For example, dextrose in the presence of an acid catalyst with n-butanol converted to butyl polyglycoside mixtures, which also with long-chain alcohols in the presence of a acid catalyst to the desired alkyl polyglycoside mixtures umglycosidiert.

    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 10 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 selected by the choice of the long chain Alcohol. The commercially available surfactant alcohols are favorable for economic reasons with 10 to 18 carbon atoms, especially 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 n z. B. nach DE-OS 19 43 689 festgelegt. Im Prinzip können bekanntlich Polysaccharide, z. B. Stärke, Maltodextrine, Dextrose, Galaktose, Mannose, Xylose etc. 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 Saccharidresten sind unterschledlich.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 n. B. according to DE-OS 19 43 689. In principle, it is known that polysaccharides, e.g. B. starch, maltodextrins, dextrose, galactose, mannose, xylose etc. 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 saccharide residues are also negligible.

    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. anreichem.Alkyl polyglycosides used according to the invention can also be mixed with alkyl polyglycosides Prepare alkyl monoglycosides. The latter can e.g. B. according to EP-A-0 092 355 using polar solvents such as acetone, gain from alkyl polyglycosides or rich.

    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 5 bis 40 %, vorzugsweise 10 bis 30 %, Alkylpolyglycosid in wäßriger Lösung.The cleaning agents according to the invention contain 5 to 40%, preferably 10 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 friendly. The degree of biodegradation determined by means of a sewage plant simulation model / DOC analysis for the alkyl polyglycosides according to the invention at 96 ± 3%. This number can be seen against the background that with this test method (total degradation) a degree of degradation> 70% 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) und 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.Acute oral toxicity LD 50 (rat) and aquatic toxicity LC 50 (gold orfe) and EC 50 (daphnia) and values of> 10,000 mg / kg, 12 or 30 mg / l are 3 to 5 times cheaper than the corresponding values of the most important surfactants today. The same applies to the skin and mucous membrane compatibility, which is particularly important for detergents.

    Die erfindungsgemäßen Alkylpolyglycoside fallen synthesebedingt als etwa 50%ige wäßrige Lösung an. Die Löslichkeit in Wasser ist aufgrund der hydrophoben Struktureinstelleung nicht allzu hoch.The alkyl polyglycosides according to the invention are obtained as an approximately 50% aqueous solution due to the synthesis. The solubility in water is not too high due to the hydrophobic structure setting.

    Anionische TensideAnionic surfactants

    Geeignete anionische Tenside sind Fettalkoholethersulfate, Fettalkoholsulfate, Fettalkoholetherphosphate, carboxymethylierte Fettalkoholoxethylate, Paraffinsulfonate, Olefinsulfonate, Alkylbenzolsulfonate sowie deren Gemische. Besonders geeignet sind anionische Tenside mit Alkyl- bzw. Alkylenresten von 10 bis 20 Kohlenstoffatomen im hydrophoben Molekülteil. Bevorzugt sind Fettalkoholethersulfate mit 1 bis 4 mol Ethylenoxid/mol, carboxymethylierte Fettalkoholoxethylate mit 2 bis 10 mol Ethylenoxid/mol und Fettalkoholsulfate. Bevorzugte Kationen sind Na, K, NH4 und Mg bzw. deren Mischungen.Suitable anionic surfactants are fatty alcohol ether sulfates, fatty alcohol sulfates, fatty alcohol ether phosphates, carboxymethylated fatty alcohol oxethylates, paraffin sulfonates, olefin sulfonates, alkylbenzenesulfonates and mixtures thereof. Anionic surfactants with alkyl or alkylene radicals of 10 to 20 carbon atoms in the hydrophobic part of the molecule are particularly suitable. Fatty alcohol ether sulfates with 1 to 4 mol ethylene oxide / mol, carboxymethylated fatty alcohol oxethylates with 2 to 10 mol ethylene oxide / mol and fatty alcohol sulfates are preferred. Preferred cations are Na, K, NH 4 and Mg or mixtures thereof.

    Die erfindungsgemäßen Reinigungskonzentrate enthalten 0,1 bis 2,9 % anionisches Tensid in wäßriger Lösung. Bevorzugt sind 0,15 bis 2,5 %.The cleaning concentrates according to the invention contain 0.1 to 2.9% anionic surfactant in aqueous solution. 0.15 to 2.5% are preferred.

    Weitere BestandteileOther components

    Durch Zusatz von Lösemitteln wie niedermolekulare, ein- und mehrwertige Alkohole sowie Glykolether läßt sich die Löslichkeit besonders auch bei niedrigen Temperaturen erheblich erhöhen. Besonders geeignete Lösemittel sind Ethanol, Isopropanol, Propylenglycol-1,2 etc. Typische Konzentrationen im Reinigungsmittel sind 3 bis 12 % in der wäßrigen Lösung.By adding solvents such as low molecular weight, mono- and polyhydric alcohols and glycol ethers significantly increase solubility, especially at low temperatures. Particularly suitable solvents are Ethanol, isopropanol, propylene glycol-1,2 etc. Typical concentrations in the detergent are 3 to 12% in the aqueous solution.

    In Kombination des Lösungsmittels mit Elektrolyten läßt sich die Löslichkeit besonders auch bei niedrigen Temperaturen z. T. erheblich erhöhen. Als geeignete Elektrolyte haben sich Alkali- und Erdalkalihalogenide erwiesen. Das Verhältnis von Lösemitlel/Elektrolyt kann 1:1 bis 8:1 betragen.In combination with the solvent and electrolytes, the solubility can be achieved especially at low temperatures e.g. T. increase significantly. Alkali and alkaline earth halides have proven to be suitable electrolytes. The Solvent / electrolyte ratio can be 1: 1 to 8: 1.

    Weitere Additive sind nichtionische, ampholytische und/oder zwitterionische Tenside mit Gesamtkonzentrationen zwischen 0 und 3 % in der wäßrigen Lösung.Other additives are nonionic, ampholytic and / or zwitterionic surfactants with total concentrations between 0 and 3% in the aqueous solution.

    Schließlich kann die erfindungsgemäße Reinigungsflüssigkeit in geringen Mengen (0,1 bis 3 Gewichtsprozent) übliche Farbstoffe und Parfümöle sowie Alkanolamine oder auch Hydrotropica, wie nichttensidische Alkylbenzolsulfonate mit 1 bis 3 Kohlenstoffatomen im Alkylrest - gewöhnlich als Natriumsalze - sowie Hamstoff enthalten.Finally, the cleaning liquid according to the invention can be used in small amounts (0.1 to 3 percent by weight) Usual dyes and perfume oils as well as alkanolamines or hydrotropics, such as non-surfactant alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical - usually as sodium salts - and urea.

    Zur Einstellung geeigneter Viskosität können gegebenfalls wasserlösliche Polymere, wie Carboxmethylcellulose, Hydroxyethylcellulose, Xanthane, Polyethylenoxid, Polyacrylat etc. zugesetzt werden.To set a suitable viscosity, water-soluble polymers, such as carboxymethyl cellulose, Hydroxyethyl cellulose, xanthans, polyethylene oxide, polyacrylate etc. can be added.

    Als weitere geeignete Additive haben sich Zitronensäure, EDTA, NTA und andere Komplexierungsmittel erwiesen.Citric acid, EDTA, NTA and other complexing agents have proven to be further suitable additives.

    BeispieleExamples

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

    Zur Testung der Spulmittelwirkung wurde der Minitellertest (vgl. R.M. Anstett u. E.J. Schuck JAOCS 43, 576 (1966) durchgeführt.
    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 50,0 °C auf die Gläser aufgebracht wurde, die sodann einem definierten Abkühlungsprozeß auf 23 °C (Raumtemperatur) unterliegen. Die Spül-Anfangstemperatur beträgt ebenfalls 50 °C.    The mini dish test (cf. RM Anstett and EJ Schuck JAOCS 43, 576 (1966) was carried out to test the effect of the detergent.
    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). Lard served as soiling, which was applied to the glasses at 50.0 ° C, which are then subjected to a defined cooling process to 23 ° C (room temperature). The initial rinse temperature is also 50 ° C.

    Das Schäumvermögen des Reinigungsmittels wurde entsprechend DIN 53 902, Teil 1, bestimmt. Die Konzentration an waschaktiver Substanz betrug jeweils 1 g/l. Registriert wurde das Schaumvolumen nach 5 Minuten.The foaming power of the cleaning agent was determined in accordance with DIN 53 902, Part 1. The concentration of wash-active substance was 1 g / l each. The foam volume was registered after 5 minutes.

    Die Viskosität der Reinigungsflüssigkeit wurde in einem Rotationsviskosimeter (Haake RV 20) unter definierten Scherraten (D ca. 10 sec-1) gemessen.The viscosity of the cleaning liquid was measured in a rotary viscometer (Haake RV 20) under defined shear rates (D approx. 10 sec -1 ).

    Zur Klarpunktbestimmung wurden 10 g Reinigungsmittel in einem Shukoffkolben auf -20 °C abgekühlt und sodann erwärmt. Gemessen wird die Temperatur des Produktes bei völliger Klärung.To determine the clear point, 10 g of cleaning agent were cooled in a Shukoff flask to -20 ° C. and then warmed up. The temperature of the product is measured with complete clarification.

    Die Tabellen 1 a und 1 b zeigen die Eigenschaften der erfindungsgemäßen Zubereitungen. Der Zusatz von kleinen Mengen anionischen Tensids zu Lösungen von hydrophob eingestellten Alkylpolyglycosid (vgl. Beispiel 1 (V) führt eine Klärung der Flüssigkeit herbei. Gleichzeitig nehmen Schäumvermögen und Viskosität stark zu und erreichen sehr bald das Niveau marktüblicher Reinigungsmittel (Beispiel 7 (V). Die Reinigungswirkung wird durch den Zuatz an anionischen Tensiden im Rahmen des Meßfehlers nicht beeinflußt und entspricht völlig dem marktüblichen Standard.Tables 1 a and 1 b show the properties of the preparations according to the invention. The addition of small Amounts of anionic surfactant to solutions of hydrophobically adjusted alkyl polyglycoside (see Example 1 (V) leads one Clarify the liquid. At the same time, foaming and viscosity increase significantly and reach very soon the level of commercially available cleaning agents (Example 7 (V). The cleaning effect is due to the addition of anionic Surfactants are not affected by the measurement error and are fully in line with the market standard.

    Folgende Abkürzungen wurden in den Tabellen verwendet:

    APG 1 ≙
    Alkylpolyglycosid mit Alkylkettenlänge C12/14 und G = 1,2
    APG 2 ≙
    Alkylpolyglycosid mit Alkylkettenlänge C12/13 und G = 1,1
    Alkylethersulfat ≙
    Alkylkette = C12/14, 2 mol E0/mol, Na-Salz
    Alkyletheracetat ≙
    Alkylkette = C12/14, 4 mol E0/mol, Na-Salz
    Alkylsulfat ≙
    Alkylkette = C12/14, Na-Salz
    PS ≙
    n-Paraffinsulfonat mit Alkylkette = C13/17
    ABS ≙
    Alkylbenzolsulfonat mit Alkylkette = C10/13
    Eigenschaften der erfindungsgemäßen Zubereitungen Zusammensetzung (Gew.-%) 1 (V) 2 3 4 5 6 7 (V) APG 1 15 15 15 15 15 15 marktübliches Spülmittel Alkylethersulfat - - - 0,5 1 2,5 Alkylsulfat - 0,5 1,5 - - - Eigenschaften Klarpkt. [°C] trüb 16 13 15 13 11 11 Viskosität [mPa·s], 25°C 18 220 200 320 200 280 200 Schaumvermögen [ml], 1 g/l, 25 °C 80 150 300 170 300 420 410 Anzahl der gereinigten Teller 13°dH, 50 °C 21 21 22 21 21 22 20 1 (V) und 7 (V) stellen Vergleichsbeispiele dar Eigenschaften der erfindungsgemäßen Zubereitungen Zusammensetzung (Gew.-%) 8 9 10 11 12 13 (V) 14 APG 1 15 15 15 17,5 17,5 - - APG 2 - - - - - 15 15 Alkylethersulfat 0,75 - - 2,5 - - - Alkyletheracetat - - - - - - 1 PS 0,75 1,5 - - 2,5 - - ABS - - 2 - - - - Ethanol - 5 - 5 5 5 5 Eigenschaften Klarpkt. [°C] 13 14 10 12 12 5 Viskosität [mPa·s], 25°C 230 200 350 160 160 205 Schäumvermögen [ml], 1 g/l, 25 °C 330 270 380 260 110 200 Anzahl der gereinigten Teller 13 °dH, 50 °C 22 22 22 21 20 18 19 13 (V) stellt Vergleichsbeispiel dar The following abbreviations were used in the tables:
    APG 1 ≙
    Alkyl polyglycoside with alkyl chain length C 12/14 and G = 1.2
    APG 2 ≙
    Alkyl polyglycoside with alkyl chain length C 12/13 and G = 1.1
    Alkyl ether sulfate ≙
    Alkyl chain = C 12/14 , 2 mol E0 / mol, Na salt
    Alkyl ether acetate ≙
    Alkyl chain = C 12/14 , 4 mol E0 / mol, Na salt
    Alkyl sulfate ≙
    Alkyl chain = C 12/14 , Na salt
    PS ≙
    n-paraffin sulfonate with alkyl chain = C 13/17
    ABS ≙
    Alkylbenzenesulfonate with alkyl chain = C 10/13
    Properties of the preparations according to the invention Composition (% by weight) 1 (V) 2nd 3rd 4th 5 6 7 (V) APG 1 15 15 15 15 15 15 commercially available detergent Alkyl ether sulfate - - - 0.5 1 2.5 Alkyl sulfate - 0.5 1.5 - - - characteristics Clear point [° C] cloudy 16 13 15 13 11 11 Viscosity [mPa · s], 25 ° C 18th 220 200 320 200 280 200 Foaming power [ml], 1 g / l, 25 ° C 80 150 300 170 300 420 410 Number of cleaned plates 13 ° dH, 50 ° C 21 21 22 21 21 22 20th 1 (V) and 7 (V) represent comparative examples Properties of the preparations according to the invention Composition (% by weight) 8th 9 10th 11 12th 13 (V) 14 APG 1 15 15 15 17.5 17.5 - - APG 2 - - - - - 15 15 Alkyl ether sulfate 0.75 - - 2.5 - - - Alkyl ether acetate - - - - - - 1 PS 0.75 1.5 - - 2.5 - - SECTION - - 2nd - - - - Ethanol - 5 - 5 5 5 5 characteristics Clear point [° C] 13 14 10th 12th 12th 5 Viscosity [mPa · s], 25 ° C 230 200 350 160 160 205 Foaming power [ml], 1 g / l, 25 ° C 330 270 380 260 110 200 Number of cleaned plates 13 ° dH, 50 ° C 22 22 22 21 20th 18th 19th 13 (V) represents comparative example

    Das Diagramm (Abb. I) zeigt die Eigenschaften der erfindungsgemäßen Zubereitungen von APG 1/Alkylethersulfat in Abhängigkeit des Ethersulfatzusatzes im Detail, wobei der Gehalt an APG 1 = 15 Gew.-% beträgt. Während das Schäumvermögen mit Ethersulfatzusatz sehr stark zunimmt, ändert sich der Klarpunkt nur relativ gering. Völlig unerwartet ist das ausgeprägte Viskositätsmaximum im Bereich niedriger Aniontensidkonzentrationen. Diese - die vorliegende Erfindung mitbegründende Eigenschaft wurde auch beim Zusatz anderer Aniontenside beobachtet. Mit Hilfe eines solchen Diagramms lassen sich Reinigungsmittel auch hinsichtlich optimaler Umweltverträglichkeit maßschneidern.The diagram (Fig. I) shows the properties of the preparations of APG 1 / alkyl ether sulfate according to the invention depending on the ether sulfate addition in detail, the APG content being 1 = 15% by weight. During that Foaming power increases very strongly with the addition of ether sulfate, the clear point changes only relatively little. Completely unexpected is the pronounced viscosity maximum in the range of low anionic surfactant concentrations. This - the present Property co-founding the invention was also observed when other anionic surfactants were added. With help Such a diagram can also be used to tailor cleaning agents with regard to optimal environmental compatibility.

    Folgende Abkürzungen/Maßgaben wurden in Abbildung I verwendet:

    S =
    Schaum [ml] bei 25 °C nach 300 sec.
    η =
    Viskosität [mPa·s] bei 25 °C
    T =
    Reinigungswirkung [Teller]
    K =
    Klarpunkt [°C]
    APG 1 ≙
    Alkylpolyglycosid mit Alkylkettenlänge = C12/14 und Glycosidierungsgrad = 1,2
    Alkylethersulfat ≙
    Alkylkette = C12/14, 2 mol E0/mol, Na-Salz
    The following abbreviations / measures were used in Figure I:
    S =
    Foam [ml] at 25 ° C after 300 sec.
    η =
    Viscosity [mPa · s] at 25 ° C
    T =
    Cleaning effect [plate]
    K =
    Clear point [° C]
    APG 1 ≙
    Alkyl polyglycoside with alkyl chain length = C 12/14 and degree of glycosidation = 1.2
    Alkyl ether sulfate ≙
    Alkyl chain = C 12/14 , 2 mol E0 / mol, Na salt

    Claims (4)

    1. A liquid, foaming detergent composition of increased viscosity, characterised in that it comprises
      >5 to 40% by weight of alkylpolyglycoside,
      0.1 to 2.9% by weight of anionic surfactant,
      0 to 3% by weight of other surfactants,
      and customary non-surfactant additives and water to 100% by weight, the anionic surfactant having been selected from the group of the fatty alcohol ether sulphates, the fatty alcohol sulphates, the fatty alcohol ether phosphates, the carboxymethylated fatty alcohol ethoxylates, the paraffinsulphonates, the olefinsulphonates, the alkylbenzenesulphonates or mixtures thereof and the alkylpolyglycoside conforming to the formula I R-O-Zn where R is a saturated or unsaturated, branched or unbranched alkyl radical of from 10 to 18 carbon atoms and Zn is a polyglycosyl radical with n = 1.0 to 1.5 hexose or pentose units or mixtures thereof.
    2. A liquid, foaming detergent composition according to claim 1, characterised in that the alkylpolyglycoside has the formula I R-O-Zn where R is a saturated or unsaturated, branched or unbranched alkyl radical of from 10 to 18 carbon atoms and Zn is a polyglycosyl radical with n = 1.1 to 1.5 hexose or pentose units or mixtures thereof.
    3. A liquid, foaming detergent composition according to either of the preceding claims, characterised in that solvents such as monohydric and polyhydric alcohols, electrolytes, complexing agents, hydrotropes, polymers, dyes and fragrances are used as further additives.
    4. The use of the liquid detergent composition according to any one of the preceding claims as a dishwashing detergent.
    EP91115711A 1990-11-17 1991-09-17 Liquid foaming detergent of increased viscosity Expired - Lifetime EP0486784B2 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE4036663 1990-11-17
    DE4036663A DE4036663A1 (en) 1990-11-17 1990-11-17 LIQUID, LUBRICANT CLEANING AGENT WITH INCREASED VISCOSITY

    Publications (4)

    Publication Number Publication Date
    EP0486784A2 EP0486784A2 (en) 1992-05-27
    EP0486784A3 EP0486784A3 (en) 1992-10-07
    EP0486784B1 EP0486784B1 (en) 1996-08-14
    EP0486784B2 true EP0486784B2 (en) 1999-08-18

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    ID=6418450

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP91115711A Expired - Lifetime EP0486784B2 (en) 1990-11-17 1991-09-17 Liquid foaming detergent of increased viscosity

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    EP (1) EP0486784B2 (en)
    JP (1) JPH04292696A (en)
    AT (1) ATE141321T1 (en)
    CA (1) CA2055650A1 (en)
    DE (2) DE4036663A1 (en)
    GR (1) GR3021025T3 (en)
    NO (1) NO179289C (en)

    Families Citing this family (6)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE4216380A1 (en) * 1992-05-18 1993-11-25 Henkel Kgaa Procedure for cleaning bathroom fittings
    DE4239679A1 (en) * 1992-11-26 1994-06-01 Henkel Kgaa Viscous aqueous surfactant preparations
    US5501813A (en) * 1993-11-02 1996-03-26 Henkel Corporation Thickener for aqueous compositions
    US5597406A (en) * 1993-11-02 1997-01-28 Henkel Corporation Method of thickening aqueous formulations
    AU675833B2 (en) * 1994-03-23 1997-02-20 Amway Corporation Concentrated all-purpose light duty liquid cleaning composition and method of use
    DE19933404A1 (en) * 1999-07-21 2001-01-25 Henkel Kgaa Use of sugar surfactant(s) to adjust the viscosity of an aqueous surfactant-containing medium to give a thickened medium for disinfecting and/or cleaning sanitary surfaces

    Family Cites Families (7)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US4396520A (en) * 1982-04-26 1983-08-02 The Procter & Gamble Company Detergent compositions
    WO1986002943A1 (en) * 1984-11-06 1986-05-22 A.E. Staley Manufacturing Company Monoglycosides as viscosity modifiers in detergents
    DE3708330A1 (en) * 1987-03-14 1988-09-22 Henkel Kgaa LIQUID, ALKALINE CLEANER CONCENTRATES
    DE3838808A1 (en) * 1988-11-17 1990-05-23 Henkel Kgaa DETERGENT AND CLEANING AGENT, CONTAINING A TENSIDE MIXTURE OF ALKYL GLYCOSIDES AND ANIONSIDE
    MY106599A (en) * 1988-12-19 1995-06-30 Kao Corp Detergent composition
    DE3905939A1 (en) * 1989-02-25 1990-08-30 Huels Chemische Werke Ag TENSIDE COMBINATION
    US5118440A (en) * 1990-03-05 1992-06-02 The Procter & Gamble Company Light-duty liquid dishwashing detergent composition containing alkyl polysaccharide and alpha-sulfonated fatty acid alkyl ester surfactants

    Also Published As

    Publication number Publication date
    NO179289B (en) 1996-06-03
    EP0486784A2 (en) 1992-05-27
    NO179289C (en) 1996-09-11
    EP0486784A3 (en) 1992-10-07
    JPH04292696A (en) 1992-10-16
    DE59108078D1 (en) 1996-09-19
    CA2055650A1 (en) 1992-05-18
    GR3021025T3 (en) 1996-12-31
    NO914470D0 (en) 1991-11-14
    NO914470L (en) 1992-05-18
    ATE141321T1 (en) 1996-08-15
    EP0486784B1 (en) 1996-08-14
    DE4036663A1 (en) 1992-05-21

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