EP0486784A2 - Liquid foaming detergent of increased viscosity - Google Patents
Liquid foaming detergent of increased viscosity Download PDFInfo
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- EP0486784A2 EP0486784A2 EP91115711A EP91115711A EP0486784A2 EP 0486784 A2 EP0486784 A2 EP 0486784A2 EP 91115711 A EP91115711 A EP 91115711A EP 91115711 A EP91115711 A EP 91115711A EP 0486784 A2 EP0486784 A2 EP 0486784A2
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- liquid
- cleaning agent
- fatty alcohol
- foaming cleaning
- agent according
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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
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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
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/06—Ether- or thioether carboxylic acids
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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
- C11D1/02—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
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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
- C11D1/02—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
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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
- C11D1/02—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
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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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
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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
- C11D1/662—Carbohydrates or derivatives
Definitions
- the invention relates to an environmentally friendly, foaming, 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.
- 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). Small amounts of fatty acid alkanolamides and, more rarely, oxyethylates are added. Other common ingredients are solubilizers, colors and fragrances, preservatives etc.
- the rinsing process usually takes place at a slightly elevated temperature (30 to 50 ° C) in dilute solutions.
- a slightly elevated temperature (30 to 50 ° C)
- the skin compatibility of the detergent because of the long skin contact of the user, the skin compatibility of the detergent.
- the foaming power of the solution plays a significant role, for example in the sense that the longer the cleaning solution foams during the rinsing process, the greater its cleaning power.
- 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. Average viscosities between 150 and 300 mPa ⁇ s at 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.
- the currently customary cleaning agents usually show sufficient cleaning action and a high foaming power, suitable flow behavior and sufficient compatibility with the hardness constituents of the water.
- these mixtures have a low skin-friendliness, since their essential components - namely the anionic surfactants of the sulfonate or sulfate type - are highly irritating to the skin.
- the object of the invention was therefore to provide a cleaning agent which implies all the desired properties, with high skin tolerance and excellent environmental compatibility.
- the object was achieved by a liquid cleaning agent which largely contains only alkyl polyglycoside as the surfactant.
- 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 .-%.
- alkyl polyglycosides in detergents and cleaning agents is known in combination with other surfactants.
- 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.
- alkyl polyglycosides in combination with builder substances, such as nitrilotriacetic acid or sodium tripolyphosphate are described as detergents.
- 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 sulfate or alkyl ether sulfates in each case in combination with fatty acid alkanolamides serve as cosurfactants.
- EP-AO 199 765 describes a liquid detergent or dishwashing detergent with a similar claim.
- EP-O 199 765 describes cleaning liquids with a minimum anionic cosurfactant content of 3%.
- alkyl polyglycoside as the only surfactant component in the cleaning liquid.
- Defacto pure alkyl polyglycoside solutions also have excellent cleaning effects, provided they are sufficiently hydrophobic. The latter is achieved through a longer-chain hydrophobic alkyl radical or through a less pronounced hydrophilic part of the molecule.
- Alkyl polyglycosides used according to the invention satisfy formula I.
- 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 in the presence of an acidic catalyst to give the desired alkylpolyglycoside mixtures.
- 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.
- the industrially accessible surfactant alcohols with 10 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.
- the polyglycosyl radical Z n is determined, on the one hand, by the selection of the carbohydrate and, on the other hand, by setting the average degree of polymerization n. B. according to DE-OS 19 43 689.
- polysaccharides e.g. B. starch, maltodextrins, dextrose, galactose, mannose, xylose etc.
- the industrially available carbohydrates starch, maltodextrins and especially dextrose are preferred.
- alkyl polygylcosides are always mixtures of oligomers, which in turn represent mixtures of different isomeric forms. They exist side by side with ⁇ - and ⁇ -glycosidic bonds in pyranose and furanose form. The links between two saccharide residues are also different.
- 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.
- the degree of glycosidation is advantageously determined by means of 1 H-NMR.
- the cleaning agents according to the invention contain 5 to 40%, preferably 10 to 30%, of alkyl polyglycoside in aqueous solution.
- the alkyl polyglycosides are considered to be extremely environmentally compatible.
- the degree of biodegradation for the alkyl polygylcosides 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.
- the acute oral toxicity LD 50 (rat) as well as the aquatic toxicity LC 50 (gold orfe) and EC 50 (daphnia) and values of> 10,000 mg / kg, 12 or 30 mg / l are three to five times cheaper than the corresponding values of today's most important surfactants. The same applies to the skin and mucous membrane compatibility, which is particularly important for detergents.
- 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.
- 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, NH4 and Mg or mixtures thereof.
- 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.
- solvents such as low-molecular, mono- and polyhydric alcohols and glycol ethers
- the solubility can be increased significantly, especially at low temperatures.
- Particularly suitable solvents are ethanol, isopropanol, 1,2-propylene glycol, etc. Typical concentrations in the cleaning agent and 3 to 12% in the aqueous solution.
- the solubility can be achieved especially at low temperatures, e.g. T. increase significantly.
- Alkali and alkaline earth metal halides have proven to be suitable electrolytes.
- the ratio of solvent / electrolyte can be 1: 1 to 8: 1.
- additives are nonionic, ampholytic and / or zwitterionic surfactants with total concentrations between 0 and 3% in the aqueous solution.
- the cleaning liquid according to the invention can contain small amounts (0.1 to 3 percent by weight) of customary dyes and perfume oils, and also alkanolamines or hydrotropes, such as non-surfactant alkylbenzenesulfoants having 1 to 3 carbon atoms in the alkyl radical - usually as sodium salts - and urea.
- water-soluble polymers such as carboxmethyl cellulose, hydroxyethyl cellulose, xanthans, polyethylene oxide, polyacrylate, etc. can optionally be added.
- Citric acid, EDTA, NTA and other complexing agents have proven to be further suitable additives.
- the mini dish test (cf. RM Anstett and EJ Schuck JAOCS 43, 576 (1966) was carried out to test the detergent action.
- 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 reproducible results.
- Disappearing foam shows the number of cleaned plates (watch glasses). Pork lard served as soiling, which was applied to the glasses at 50.0 ° C, which are then subjected to a defined cooling process to 23 ° C (room temperature).
- the initial rinse temperature is also 50 ° C.
- the foaming power of the cleaning agent was determined in accordance with DIN 53 902, Part 1.
- the concentration of detergent substance was 1 g / l in each case.
- the foam volume was registered after 5 minutes.
- the viscosity of the cleaning liquid was measured in a rotary viscometer (Haake RV 20) under defined shear rates (D approx. 10 sec ⁇ 1).
- 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 brings about a clarification of the liquid.
- foaming power and viscosity increase sharply and very soon reach the level of commercially available cleaning agents (Example 7 (V).
- the cleaning effect is not affected by the addition of anionic surfactants as part of the measurement error and corresponds completely to the standard on the market.
Abstract
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 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. B. 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.
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, the skin compatibility of the detergent. When the consumer assesses the cleaning power, the foaming power of the solution plays a significant role, for example in the sense that the longer the cleaning solution foams during the rinsing process, the greater its cleaning power.
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. Average viscosities between 150 and 300 mPa · s at 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 customary cleaning agents usually show sufficient cleaning action and a high foaming power, suitable flow behavior and sufficient compatibility with the hardness constituents of the water. In contrast, these mixtures have a low skin-friendliness, since 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 serious 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 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 implies all the desired properties, with 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 largely contains only alkyl polyglycoside as the surfactant.
Gegenstand der Erfindung ist daher ein flüssiges, schäumendes Reinigungsmittel mit erhöhter Viskosität bestehend aus
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-O 199 765 ein Flüssigwaschmittel oder Spülmittel mit ähnlichem Anspruch.The use of alkyl polyglycosides in detergents and cleaning agents is known in combination with other surfactants. 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. The combination of alkyl polyglycosides EP-A-0 105 556 claims fatty alcohol oxyethylates as the 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, Anionic surfactants are 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 sulfate or alkyl ether sulfates in each case in combination with fatty acid alkanolamides serve as cosurfactants. Finally, EP-AO 199 765 describes a liquid detergent or dishwashing detergent with a similar 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-O 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 a relatively high content of non-purely native or petrochemical-based cosurfactants, and therefore usually also of limited environmental compatibility and skin friendliness, with a comparatively more or less good cleaning effect.
So calls for. B. EP-AO 070 074 a minimum cosurfactant content of alkylbenzenesulfonate of 50% or for sulfates of 60% based on total surfactant.
Und die EP-O 199 765 beschreibt Reinigungsflüssigkeiten mit einem Mindestgehalt an anionischem Cotensid von 3 %.And EP-O 199 765 describes cleaning liquids with a minimum anionic cosurfactant content of 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 to the problem would be to use alkyl polyglycoside as the only surfactant component in the cleaning liquid. Defacto pure alkyl polyglycoside solutions also have excellent cleaning effects, provided they are sufficiently hydrophobic. The latter is achieved through a longer-chain hydrophobic alkyl radical or through 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 action with good skin tolerance can be observed in the liquid cleaning agents according to the invention, with a viscosity increase by a factor of 15 to 20 compared to the pure alkyl polyglycoside concentrate watch is.
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 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 I,
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 Alkylpolygylcoside 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 polygylcosides with fatty alkyl radicals with 12 to 16 carbon atoms and a polyglycosyl radical with n = 1.1 to 2 are preferred. Alkyl polyglycosides with n = 1.1 to 1.5 are particularly preferred.
Die erfindungsgemäß eingesetzten Alklypolyglycoside 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 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 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 determined by the choice of the long-chain alcohol. Favorable for economic reasons are the industrially accessible surfactant alcohols with 10 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 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 Alkylpolygylcosidsynthesen nicht regio- und stereoselektiv verlaufen, sind die Alkylpolygylcoside 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 unterschiedlich.The polyglycosyl radical Z n is determined, on the one hand, by the selection of the carbohydrate and, on the other hand, by setting 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. Because the economically interesting alkyl polygylcoside syntheses not being regio- and stereoselective, the alkyl polygylcosides 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 links between two saccharide 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-O 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 advantageously 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 erfindunsgemäßen Alkylpolygylcoside 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 polygylcosides 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) 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.The acute oral toxicity LD 50 (rat) as well as the aquatic toxicity LC 50 (gold orfe) and EC 50 (daphnia) and values of> 10,000 mg / kg, 12 or 30 mg / l are three to five times cheaper than the corresponding values of today's most important surfactants. 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.
Geeigente 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, NH₄ 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.
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 und 3 bis 12 % in der wäßrigen Lösung.By adding solvents such as low-molecular, mono- and polyhydric alcohols and glycol ethers, the solubility can be increased significantly, especially at low temperatures. Particularly suitable solvents are ethanol, isopropanol, 1,2-propylene glycol, etc. Typical concentrations in the cleaning agent and 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 Lösemittel/Elektrolyt kann 1 : 1 bis 8 : 1 betragen.In combination of the solvent with electrolytes, the solubility can be achieved especially at low temperatures, e.g. T. increase significantly. Alkali and alkaline earth metal halides have proven to be suitable electrolytes. The ratio of solvent / electrolyte 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 Alkylbenzolsulfoante mit 1 bis 3 Kohlenstoffatomen im Alkylrest - gewöhnlich als Natriumsalze - sowie Harnstoff enthalten.Finally, the cleaning liquid according to the invention can contain small amounts (0.1 to 3 percent by weight) of customary dyes and perfume oils, and also alkanolamines or hydrotropes, such as non-surfactant alkylbenzenesulfoants 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 Carboxmethylcellulose, Hydroxyethylcellulose, Xanthane, Polyethylenoxid, Polyacrylat etc. zugesetzt werden.To set a suitable viscosity, water-soluble polymers such as carboxmethyl cellulose, hydroxyethyl cellulose, xanthans, polyethylene oxide, polyacrylate, etc. can optionally 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.
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.
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-Anfangstemepratur beträgt ebenfalls 50 °C.The mini dish test (cf. RM Anstett and EJ Schuck JAOCS 43, 576 (1966) was carried out to test the detergent action.
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 reproducible results. Disappearing foam shows the number of cleaned plates (watch glasses). Pork lard served as soiling, which was applied to the glasses at 50.0 ° C, which are then subjected to a defined cooling process to 23 ° C (room temperature). The initial rinse temperature is also 50 ° C.
Das Schaumvermögen 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,
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 to -20 ° C. in a Shukoff flask and then heated. 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 anionsichen 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 (cf. Example 1 (V) brings about a clarification of the liquid. At the same time, foaming power and viscosity increase sharply and very soon reach the level of commercially available cleaning agents (Example 7 (V). The cleaning effect is not affected by the addition of anionic surfactants as part of the measurement error and corresponds completely to the standard on the market.
Folgende Abkürzungen wurden in den Tabellen verwendet:
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 according to the invention of
Folgende Abkürzungen/Maßgaben wurden in Abbildung I verwendet:
- S =
- Schaum [ml] bei 25 °C nach 300 sec.
- =
- Viskosität [mPa·s] bei 25 °C
- T =
- Reinigungswirkung [Teller]
- K =
- Klarpunkt [°C]
- S =
- Foam [ml] at 25 ° C after 300 sec.
- =
- Viscosity [mPa · s] at 25 ° C
- T =
- Cleaning effect [plate]
- K =
- Clear point [° C]
Claims (10)
dadurch gekennzeichnet,
daß das Alkylpolygylcosid der Formel I
R-O-Zn I
entspricht, wobei R ein gesättigter oder ungesättigter, verzweigter oder unverzweigter Alkylrest mit 10 bis 18 Kohlenstoffatomen, Zn ein Polyglycosylradikal mit n = 1 bis 3 Hexose- oder Pentoseeinheiten oder Mischungen davon bedeuten.Liquid, foaming cleaning agent according to claim 1,
characterized,
that the alkyl polygylcoside of formula I
RON n I
corresponds, where R is a saturated or unsaturated, branched or unbranched alkyl radical having 10 to 18 carbon atoms, Z n is a polyglycosyl radical with n = 1 to 3 hexose or pentose units or mixtures thereof.
dadurch gekennzeichnet,
daß das Alkylpolyglycosid der Formel I
R-O-Zn I
entspricht, wobei R ein gesättigter oder ungesättigter, Fettalkohol mit 10 bis 18 Kohlenstoffatomen und Zn ein Polyglycosylradikal mit n = 1,1 bis 2 Glycosideinheiten bedeuten.Liquid, foaming cleaning agent according to claim 1,
characterized,
that the alkyl polyglycoside of formula I
RON n I
corresponds, where R is a saturated or unsaturated, fatty alcohol having 10 to 18 carbon atoms and Z n is a polyglycosyl radical with n = 1.1 to 2 glycoside units.
dadurch gekennzeichnet,
daß das anionische Tensid aus Fettalkoholethersulfat, Fettalkoholsulfat, carboxymethyliertem Fettalkoholoxethylat, Olefinsulfonat, Alkansulfonat, Alkylbenzolsulfonat oder Gemischen davon besteht.Liquid, foaming cleaning agent according to claims 1 to 3,
characterized,
that the anionic surfactant consists of fatty alcohol ether sulfate, fatty alcohol sulfate, carboxymethylated fatty alcohol oxyethylate, olefin sulfonate, Alkanesulfonate, alkylbenzenesulfonate or mixtures thereof.
dadurch gekennzeichnet,
daß das anionische Tensid Fettalkoholethersulfat ist.Liquid, foaming cleaning agent according to claims 1 to 4,
characterized,
that the anionic surfactant is fatty alcohol ether sulfate.
dadurch gekennzeichnet,
daß das anionische Tensid Fettalkoholsulfat ist.Liquid, foaming cleaning agent according to claims 1 to 4,
characterized,
that the anionic surfactant is fatty alcohol sulfate.
dadurch gekennzeichnet,
daß das anionische Tensid carboxymethyliertes Fettalkoholoxethylat ist.Liquid, foaming cleaning agent according to claims 1 to 4,
characterized,
that the anionic surfactant is carboxymethylated fatty alcohol oxyethylate.
dadurch gekennzeichnet,
daß das anionische Tensid Alkansulfonat ist.Liquid, foaming cleaning agent according to claims 1 to 4,
characterized,
that the anionic surfactant is alkanesulfonate.
dadurch gekennzeichnet,
daß als weitere Zusätze Lösemittel wie ein- und mehrwertige Alkohole, Elektrolyte, Komplexbildner, Hydrotropica, Polymere, Farbstoffe, Duftstoffe etc. verwendet werden.Liquid, foaming cleaning agent according to claims 1 to 8,
characterized,
that solvents such as mono- and polyhydric alcohols, electrolytes, complexing agents, hydrotropics, polymers, dyes, fragrances etc. are used as further additives.
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 true EP0486784A2 (en) | 1992-05-27 |
EP0486784A3 EP0486784A3 (en) | 1992-10-07 |
EP0486784B1 EP0486784B1 (en) | 1996-08-14 |
EP0486784B2 EP0486784B2 (en) | 1999-08-18 |
Family
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 |
Country Status (7)
Country | Link |
---|---|
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) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0570619A1 (en) * | 1992-05-18 | 1993-11-24 | Henkel KGaA | Process for cleaning bathroom fittings |
WO1994012601A1 (en) * | 1992-11-26 | 1994-06-09 | Henkel Kommanditgesellschaft Auf Aktien | Viscous aqueous surfactant preparations |
US5837065A (en) * | 1994-03-23 | 1998-11-17 | Amway Corporation | Concentrated all-purpose light duty liquid cleaning composition and method of use |
WO2001007547A1 (en) * | 1999-07-21 | 2001-02-01 | Henkel Kommanditgesellschaft Auf Aktien | Cleansing agent for hard surfaces |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Citations (6)
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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 |
EP0282863A2 (en) * | 1987-03-14 | 1988-09-21 | Henkel Kommanditgesellschaft auf Aktien | Liquid alkaline cleaning concentrates |
EP0370312A2 (en) * | 1988-11-17 | 1990-05-30 | Henkel Kommanditgesellschaft auf Aktien | Washing and cleaning agent containing a surfactant mixture of alkyl glycosides and anionic surfactants |
WO1991013959A1 (en) * | 1990-03-05 | 1991-09-19 | The Procter & Gamble Company | Light-duty liquid dishwashing detergent compositions |
EP0384983B1 (en) * | 1989-02-25 | 1993-06-09 | Hüls Aktiengesellschaft | Detergent composition |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MY106599A (en) * | 1988-12-19 | 1995-06-30 | Kao Corp | Detergent composition |
-
1990
- 1990-11-17 DE DE4036663A patent/DE4036663A1/en not_active Withdrawn
-
1991
- 1991-09-17 DE DE59108078T patent/DE59108078D1/en not_active Expired - Fee Related
- 1991-09-17 EP EP91115711A patent/EP0486784B2/en not_active Expired - Lifetime
- 1991-09-17 AT AT91115711T patent/ATE141321T1/en not_active IP Right Cessation
- 1991-11-13 JP JP3296992A patent/JPH04292696A/en active Pending
- 1991-11-14 NO NO914470A patent/NO179289C/en unknown
- 1991-11-15 CA CA002055650A patent/CA2055650A1/en not_active Abandoned
-
1996
- 1996-09-12 GR GR960402378T patent/GR3021025T3/en unknown
Patent Citations (6)
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 |
EP0282863A2 (en) * | 1987-03-14 | 1988-09-21 | Henkel Kommanditgesellschaft auf Aktien | Liquid alkaline cleaning concentrates |
EP0370312A2 (en) * | 1988-11-17 | 1990-05-30 | Henkel Kommanditgesellschaft auf Aktien | Washing and cleaning agent containing a surfactant mixture of alkyl glycosides and anionic surfactants |
EP0384983B1 (en) * | 1989-02-25 | 1993-06-09 | Hüls Aktiengesellschaft | Detergent composition |
WO1991013959A1 (en) * | 1990-03-05 | 1991-09-19 | The Procter & Gamble Company | Light-duty liquid dishwashing detergent compositions |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0570619A1 (en) * | 1992-05-18 | 1993-11-24 | Henkel KGaA | Process for cleaning bathroom fittings |
WO1993023511A1 (en) * | 1992-05-18 | 1993-11-25 | Henkel Kommanditgesellschaft Auf Aktien | Process for cleaning bathroom fittings |
WO1994012601A1 (en) * | 1992-11-26 | 1994-06-09 | Henkel Kommanditgesellschaft Auf Aktien | Viscous aqueous surfactant preparations |
US5837065A (en) * | 1994-03-23 | 1998-11-17 | Amway Corporation | Concentrated all-purpose light duty liquid cleaning composition and method of use |
WO2001007547A1 (en) * | 1999-07-21 | 2001-02-01 | Henkel Kommanditgesellschaft Auf Aktien | Cleansing agent for hard surfaces |
Also Published As
Publication number | Publication date |
---|---|
NO179289B (en) | 1996-06-03 |
EP0486784B2 (en) | 1999-08-18 |
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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