EP0444267A2 - Liquid foaming detergent - Google Patents
Liquid foaming detergent Download PDFInfo
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- EP0444267A2 EP0444267A2 EP90123936A EP90123936A EP0444267A2 EP 0444267 A2 EP0444267 A2 EP 0444267A2 EP 90123936 A EP90123936 A EP 90123936A EP 90123936 A EP90123936 A EP 90123936A EP 0444267 A2 EP0444267 A2 EP 0444267A2
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- Prior art keywords
- liquid
- cleaning agent
- alkyl
- agent according
- foaming cleaning
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0094—High foaming compositions
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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 compatible, 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. As alkylbenzenesulfonates or sec-alkanesulfonates, both combined with fatty alcohol ether sulfates or fatty alcohol sulfates (EP-A-0 112 047). Small amounts of fatty acid alkanolamides and, more rarely, oxyethylates are added. Other common ingredients are solubilizers, colors and fragrances, preservatives, etc.
- 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.
- Generally recognized methods for determining the cleaning effect are a) the plate test with foaming detergents, the end point of which is determined by the foam disintegration, and b) the fat titration, as a measure of the cleaning power, both of which have very similar results (see G. Jakobi in H. Stache, Tensid Taschenbuch, 2nd edition, Kunststoff 1981, pp. 252 ff.
- Another disadvantage of the known detergents is their 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 very skin-compatible cleaning agent with excellent cleaning action and moderate foaming power, the cleaning surfactant of which is largely biodegradable.
- the invention therefore relates to a liquid foaming cleaning agent consisting 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 ricin oil sulfuric acid ester as a wool detergent.
- U.S. Patent 3,721,633 discloses alkyl polyglycosides in combination with builder substances such as nitrilotriacetic acid or sodium tripolyphosphate, as detergents.
- EP-A-0 105 556 claims the combination of alkyl polyglycosides with fatty alcohol oxyethylates as a liquid detergent.
- detergents which contain only alkyl polyglycosides as cleaning surfactants achieve excellent cleaning effects if these alkyl polyglycosides satisfy the formula I, ie have a sufficiently hydrophobic structure. This is achieved by using fatty alcohols with relatively long hydrocarbon chains in the synthesis, the proportions of fatty alcohol to monosaccharide units being chosen so that the average degree of glycosidation (glycoside units per fatty alkyl radical) is not too high.
- 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 carbohydrates available on an industrial scale are preferred Starch, maltodextrins and especially dextrose.
- alkyl polyglycosides are always mixtures of oligomers, which in turn represent mixtures of different isomeric forms. They are present side by side with ⁇ - and ß-glycosidic bonds in pyranose and furanose form. The junctions between two Saccachrid 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 3 to 40%, preferably 5 to 30%, alkyl polyglycoside in aqueous solution.
- the alkyl polyglycosides are considered to be extremely environmentally compatible.
- the degree of biodegradation for the alkyl polyglycosides according to the invention determined by means of a sewage treatment 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 approx. 50% aqueous amber solution due to the synthesis.
- the solubility in Water is not too high due to the hydrophobic structure setting.
- 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, propylene glycol-1.2, etc.
- the ratio of alkyl polyglycoside / solvent can be 1: 1 to 8: 1.
- solubility can be increased considerably, especially at low temperatures.
- Alkali and alkaline earth metal halides have proven to be suitable electrolytes.
- the ratio of solvent / electrolyte can be 1: 1 to 8: 1.
- constituents of the cleaning agents according to the invention in small amounts are conventional dyes and perfume oils, and also alkanolamines or hydrotropes, such as non-surfactant alkylbenzenesulfonates having 1 to 3 carbon atoms in the alkyl radical - usually as sodium salts - and urea.
- Water-soluble polymers such as carboxymethyl cellulose, hydroxyethyl cellulose, xanthans, polyethylene oxide, polyacrylate, etc., can optionally be added to adjust the viscosity.
- Citric acid, EDTA, NTA and other complexing agents have proven to be further suitable additives.
- the mini-plate test (see R.M. Anstett and E.J. Schuck JAOCS 43, 576 (1966) was carried out to test the detergent effect.
- 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 subject to a defined cooling process to 23 ° C (room temperature). The initial rinse temperature is also 50 ° C.
- Table 1 compares the cleaning effect of individual surfactants, which increases sharply with increasing molecular hydrophobicity in the case of alkyl polyglycosides.
- Table 2 demonstrates that even a strong increase in the surfactant concentration only gives unsatisfactory cleaning effects if the alkyl polyglycoside is too hydrophilic, as in the case of Triton CG 110.
- Table 3a compares the cleaning action of the alkyl polyglycosides according to the invention with those of optimized branded products depending on the detergent concentration for a medium water hardness; Table 3b shows the analogous conditions for soft water.
- Tables 3a and 3b show the excellent cleaning action of the alkyl polyglycosides according to the invention, which, as very environmentally compatible individual surfactants in detergents, achieve an excellent cleaning action.
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Abstract
Description
Die Erfindung betrifft ein umweltverträgliches, flüssiges Reinigungsmittel. Flüssige, schäumende Reinigungsmittel zielen auf die manuelle Reinigung harter Oberflächen insbesondere im Haushalt, wie z. B. Keramik, Porzellan, Glas, Metall und Kunststoff. Das bedeutendste Anwendungsgebiet sind manuelle Spülmittel für die Reinigung von Geschirr.The invention relates to an environmentally compatible, liquid cleaning agent. Liquid, foaming cleaning agents aim at the manual cleaning of hard surfaces, especially in the household, such as. B. ceramics, porcelain, glass, metal and plastic. The most important area of application are manual dishwashing detergents for cleaning dishes.
Moderne Produkte bestehen hier aus neutral eingestellten wäßrigen Formulierungen auf der Basis stark schäumender Tenside. Hauptbestandteile sind Sulfonate, wie z. B. Alkylbenzolsulfonate oder sek.-Alkansulfonate, beide kombiniert mit Fettalkoholethersulfaten oder auch Fettalkoholsulfaten (EP-A- 0 112 047). In geringen Mengen werden zum Teil Fettsäurealkanolamide und seltener Oxethylate zugesetzt. Weitere übliche Bestandteile sind Lösevermittler, Farb- und Duftstoffe, Konservierungsmittel, etc.Modern products here consist of neutral aqueous formulations based on highly foaming surfactants. The main components are sulfonates, such as. As alkylbenzenesulfonates or sec-alkanesulfonates, both combined with fatty alcohol ether sulfates or fatty alcohol sulfates (EP-A-0 112 047). Small amounts of fatty acid alkanolamides and, more rarely, oxyethylates are added. Other common ingredients are solubilizers, colors and fragrances, preservatives, etc.
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.
Allgemein anerkannte Methoden zur Ermittlung der Reinigungswirkung sind a) der Tellertest mit schäumenden Spülmitteln, dessen Endpunkt durch den Schaumzerfall bestimmt wird, und b) die Fett-Titration, als Maß für die Reinigungskraft, die beide zu sehr ähnlichen Ergebnissen (vgl. G. Jakobi in H. Stache, Tensid Taschenbuch, 2. Ausgabe, München 1981, S. 252 ff.) führen.Generally recognized methods for determining the cleaning effect are a) the plate test with foaming detergents, the end point of which is determined by the foam disintegration, and b) the fat titration, as a measure of the cleaning power, both of which have very similar results (see G. Jakobi in H. Stache, Tensid Taschenbuch, 2nd edition, Munich 1981, pp. 252 ff.
Wahrscheinlich hat diese Parallelität von qualitativer Schaumexistenz und Reinigungsvermögen die Hersteller konventioneller Spülmittel dazu verführt, höchste Bedeutung dem Schaumvolumen beizumessen. Dies hat zur Folge, daß das Spülgut bei verbraucherüblicher Dosierung des Spülmittels im Schaum verschwindet, was bekanntlich außerdem die eigentliche Reinigung herabsetzt und auch hinsichtlich des Hautgefühls unangenehm sein kann.This parallelism of qualitative foam existence and cleaning ability probably has the manufacturers of conventional detergents seduced to attach the greatest importance to the foam volume. The result of this is that the items to be washed disappear into the foam when the detergent is dosed in a customary manner, which, as is known, also reduces the actual cleaning and can also be uncomfortable with regard to the feeling on the skin.
Ein weiterer Nachteil der bekannten Spülmittel ist ihre geringe Hautfreundlichkeit, da ihre wesentlichen Bestandteile - nämlich die anionischen Tenside vom Sulfonat- bzw. Sulfat-Typ - in hohem Maße hautreizend sind.Another disadvantage of the known detergents is their low skin-friendliness, since their essential components - namely the anionic surfactants of the sulfonate or sulfate type - are highly irritating to the skin.
Und ebenfalls von Nachteil im Hinblick auf die Verknappung der Rohstoffreserven ist die überwiegend petrochemische Basis der genannten anionischen Tenside, verbunden mit einer unvollsständigen biologischen Abbaubarkeit.Another disadvantage with regard to the scarcity of raw material reserves is the predominantly petrochemical basis of the anionic surfactants mentioned, combined with incomplete biodegradability.
Aufgabe der Erfindung war es daher, ein sehr hautverträgliches Reinigungsmittel mit hervorragender Reinigungswirkung bei mäßigem Schaumvermögen zur Verfügung zu stellen, dessen Reinigungstensid biologisch weitgehendst abbaubar sind.The object of the invention was therefore to provide a very skin-compatible cleaning agent with excellent cleaning action and moderate foaming power, the cleaning surfactant of which is largely biodegradable.
Diese Aufgabe wurde gelöst durch ein flüssiges Reinigungsmittel, das als Reinigungstensid ausschließlich Alkylpolyglycosid enthält.This object has been achieved by a liquid cleaning agent which contains only alkyl polyglycoside as the cleaning surfactant.
Gegenstand der Erfindung ist daher ein flüssiges schäumendes Reinigungsmittel, 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 Ricinölschwefelsäueesters 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 Fettalkyl-Rest 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. Die Verwendung eines kommerziellen Alkylpolyglycosids (Triton CG 110) in manuellen Spülmitteln in Kombination mit anderen Tensiden wird auch in Rohm & Haas, Techn. Bulletin, Triton CG 110, Mai 1975, erwähnt.The use of alkyl polyglycosides in detergents and cleaning agents is known in combination with other surfactants. AT-PS 135 333 already describes the effect of lauryl glycoside combined with the sodium salt of ricin oil sulfuric acid ester as a wool detergent. U.S. Patent 3,721,633 discloses alkyl polyglycosides in combination with builder substances such as nitrilotriacetic acid or sodium tripolyphosphate, as detergents. EP-A-0 105 556 claims the combination of alkyl polyglycosides with fatty alcohol oxyethylates as a liquid detergent. Manual detergents using alkyl polyglycosides are described in EP-A-0 070 074, EP-A-0 070 075 and EP-A-0 070 076, wherein anionic surfactants are also 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-A-0 199 765 describes a liquid detergent or dishwashing detergent with a similar claim. The use of a commercial alkyl polyglycoside (Triton CG 110) in manual detergents in combination with other surfactants is also mentioned in Rohm & Haas, Technical Bulletin, Triton CG 110, May 1975.
Allen diesen Schriften ist die Kombination von Alkylpolyglycosiden mit anderen, meist anionischen Tensiden gemeinsam. Es war daher anzunehmen, daß die Wechselwirkung der Alkylpolyglycoside mit anderen Tensiden für die Reinigungswirkung entscheidend ist.All of these documents have in common the combination of alkyl polyglycosides with other, usually anionic, surfactants. It was therefore to be assumed that the interaction of the alkyl polyglycosides with other surfactants is crucial for the cleaning action.
Außerdem haben Vergleichsuntersuchungen (siehe Tab. 2) gezeigt, daß z. B. Triton CG 110 allein keine Spülwirkung besitzt.In addition, comparative studies (see Tab. 2) have shown that, for. B. Triton CG 110 alone has no rinsing effect.
Völlig überraschend wurde nun beobachtet, daß Spülmittel, die als Reinigungstensid ausschließlich Alkylpolyglycoside enthalten, hervorragende Reinigungswirkungen erzielen, wenn diese Alkylpolyglycoside der Formel I genügen, d. h. eine ausreichend hydrophobe Struktur aufweisen. Dies gelingt durch Verwendung von Fettalkoholen mit relativ langen Kohlenwasserstoffketten bei der Synthese, wobei die Mengenverhältnisse von Fettalkohol zu Monosaccharideinheiten so zu wählen sind, daß der mittlere Glycosidierungsgrad (Glycosideinheiten pro Fettalkylrest) nicht zu hoch ist.Completely surprisingly, it has now been observed that detergents which contain only alkyl polyglycosides as cleaning surfactants achieve excellent cleaning effects if these alkyl polyglycosides satisfy the formula I, ie have a sufficiently hydrophobic structure. This is achieved by using fatty alcohols with relatively long hydrocarbon chains in the synthesis, the proportions of fatty alcohol to monosaccharide units being chosen so that the average degree of glycosidation (glycoside units per fatty alkyl radical) is not too high.
Erfindungsgemäß eingesetzte Alkylpolyglycoside genügen der Formel I
Bevorzugt werden Alkylpolyglycoside mit Fettalkylresten mit 12 bis 16 Kohlenstoffatomen sowie einem Polyglycosylrest von n = 1,1 bis 2. Besonders bevorzugt werden Alkylpolyglucoside.Alkyl polyglycosides with fatty alkyl radicals having 12 to 16 carbon atoms and a polyglycosyl radical of n = 1.1 to 2 are preferred. Alkyl polyglucosides are particularly preferred.
Die erfindungsgemäß eingesetzten Alkylpolyglycoside können nach bekannten Verfahren auf Basis nachwachsender Rohstoffe hergestellt werden. Beispielsweise wird Dextrose in Gegenwart eines sauren Katalysators mit n-Butanol zu Butylpolyglycosidgemischen umgesetzt, welche mit langkettigen Alkoholen ebenfalls in Gegenwart eines sauren Katalysators zu den gewünschten Alkylpolyglycosidgemischen umglycosidiert werden.The alkyl polyglycosides used according to the invention can be produced by known processes based on renewable raw materials. For example, dextrose is reacted with n-butanol to give butylpolyglycoside mixtures in the presence of an acidic catalyst, which are transglycosidated with long-chain alcohols in the presence of an acidic catalyst to give the desired alkylpolyglycoside mixtures.
Die Struktur der Produkte ist in bestimmten Grenzen varriierbar. 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 Polymerisationsgrade 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 Kohlehydrate 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 ß-glycosidischen Bindungen in Pyranose- und Furanoseform vor. Auch die Verknüpfungsstellen zwischen zwei Saccachridresten sind unterschiedlich.The polyglycosyl radical Z n is determined, on the one hand, by the selection of the carbohydrate and, on the other hand, by 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 carbohydrates available on an industrial scale are preferred Starch, maltodextrins and especially dextrose. 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 are present side by side with α- and ß-glycosidic bonds in pyranose and furanose form. The junctions between two Saccachrid residues are also different.
Erfindungsgemäß eingesetzte Alkylpolyglycoside lassen sich auch durch Abmischen von Alkylpolyglycosiden mit Alkylmonoglycosiden herstellen. Letztere kann man z. B. nach EP-A 0 092 355 mittels polarer Lösemittel, wie Aceton, aus Alkylpolyglycosiden gewinnen bzw. anreichern.Alkyl polyglycosides used according to the invention can also be prepared by mixing alkyl polyglycosides with alkyl monoglycosides. The latter can e.g. B. according to EP-A 0 092 355 using polar solvents, such as acetone, from alkyl polyglycosides.
Der Glycosidierungsgrad wird zweckmäßigerweise mittels ¹H-NMR bestimmt.The degree of glycosidation is advantageously determined by means of 1 H-NMR.
Die erfindungsgemäßen Reinigungsmittel enthalten 3 bis 40 % vorzugsweise 5 bis 30 % Alkylpolyglycosid in wäßriger Lösung.The cleaning agents according to the invention contain 3 to 40%, preferably 5 to 30%, alkyl polyglycoside in aqueous solution.
Im Vergleich zu allen anderen in Reinigungsmitteln eingesetzten Tensiden gelten die Alkylpolyglycoside als überaus umweltverträglich. So liegt der mittels Kläranlagen-Simulationsmodell/DOC-Analyse bestimmte biologische Abbaugrad für die erfindungsgemäßen Alkylpolyglycoside bei 96 ± 3 %. Diese Zahl ist vor dem Hintergrund zu sehen, daß bei diesem Testverfahren (Totalabbau) bereits ein Abbaugrad > 70 % die Substanz als gut abbaubar indiziert.Compared to all other surfactants used in cleaning agents, the alkyl polyglycosides are considered to be extremely environmentally compatible. The degree of biodegradation for the alkyl polyglycosides according to the invention, determined by means of a sewage treatment 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 bernsteinfarbene Lösung an. Die Löslichkeit in Wasser ist aufgrund der hydrophoben Struktureinstellung nicht allzu hoch.The alkyl polyglycosides according to the invention are obtained as an approx. 50% aqueous amber solution due to the synthesis. The solubility in Water is not too high due to the hydrophobic structure setting.
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, Propylenglykol-1.2, etc. Das Verhältnis von Alkylpolyglycosid/Lösemittel kann 1 : 1 bis 8 : 1 betragen.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, propylene glycol-1.2, etc. The ratio of alkyl polyglycoside / solvent can be 1: 1 to 8: 1.
In Kombination der Lösungsvermittler mit Elektrolyten läßt sich die Löslichkeit besonders auch bei niedrigen Temperaturen erheblich erhöhen. Als geeignete Elektrolyte haben sich Alkali- und Erdalkalihalogenide erwiesen. Das Verhältnis von Lösemittel/Elektrolyt kann 1 : 1 bis 8 : 1 betragen.In combination with the solubilizers with electrolytes, the solubility can be increased considerably, especially at low temperatures. Alkali and alkaline earth metal halides have proven to be suitable electrolytes. The ratio of solvent / electrolyte can be 1: 1 to 8: 1.
Weitere Bestandteile der erfindungsgemäßen Reinigungsmittel in geringen Mengen (0,1 bis 3 Gewichtsprozent) sind übliche Farbstoffe und Parfümöle sowie Alkanolamine oder auch Hydrotropica, wie nichttensidische Alkylbenzolsulfonate mit 1 bis 3 Kohlenstoffatomen im Alkylrest - gewöhnlich als Natriumsalze - sowie Harnstoff.Other constituents of the cleaning agents according to the invention in small amounts (0.1 to 3 percent by weight) are conventional dyes and perfume oils, and also alkanolamines or hydrotropes, such as non-surfactant alkylbenzenesulfonates having 1 to 3 carbon atoms in the alkyl radical - usually as sodium salts - and urea.
Zur Einstellung geeigneter Viskosität können gegebenenfalls wasserlösliche Polymere, wie Carboxymethylcellulose, Hydroxyethylcellulose, Xanthane, Polyethylenoxid, Polyacrylat, etc., zugesetzt werden.Water-soluble polymers, such as carboxymethyl cellulose, hydroxyethyl cellulose, xanthans, polyethylene oxide, polyacrylate, etc., can optionally be added to adjust the viscosity.
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.The mini-plate test (see R.M. Anstett and E.J. Schuck JAOCS 43, 576 (1966) was carried out to test the detergent effect.
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 so dann einem definierten Abkühlungsprozeß auf 23 °C (Raumtemperatur) unterliegen. Die Spül-Anfangstemperatur beträgt ebenfalls 50 °C.Watch glasses loaded with grease are manually cleaned at elevated temperature with a brush in the surfactant solution. The test conditions (preparations, geometries, amounts and concentrations of substances, temperatures, temperature gradients, times) are precisely defined. The test is carried out by several people and provides 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 subject to a defined cooling process to 23 ° C (room temperature). The initial rinse temperature is also 50 ° C.
Tabelle 1 vergleicht, die Reinigungswirkung von Einzeltensiden, die bei Alkylpolyglycosiden stark mit steigender Molekülhydrophobie zunimmt.Table 1 compares the cleaning effect of individual surfactants, which increases sharply with increasing molecular hydrophobicity in the case of alkyl polyglycosides.
Tabelle 2 demonstriert, daß auch eine starke Erhöhung der Tensidkonzentration nur unbefriedigende Reinigungswirkungen ergibt, wenn das Alkylpolyglycosid zu hydrophil ist, wie im Falle von Triton CG 110.Table 2 demonstrates that even a strong increase in the surfactant concentration only gives unsatisfactory cleaning effects if the alkyl polyglycoside is too hydrophilic, as in the case of Triton CG 110.
Tabelle 3a vergleicht die Reinigungswirkung der erfindungsgemäßen Alkylpolyglykoside mit denen optimierter Markenprodukte in Abhängigkeit der Spülmittelkonzentration für einen mittleren Wasserhärtegrad; Tabelle 3b gibt die analogen Verhältnisse bei weichem Wasser an.Table 3a compares the cleaning action of the alkyl polyglycosides according to the invention with those of optimized branded products depending on the detergent concentration for a medium water hardness; Table 3b shows the analogous conditions for soft water.
Minitellertest, Konzentration Waschaktive Substanz: 0,075 g/l, Trinkwasser: 13° dH
Die Beispiele e) bis i) sind erfindungsgemäß.Examples e) to i) are according to the invention.
Minitellertest mit Triton CG 110* (Rohm & Haas) in Abhängigkeit von der Wässerhärte und der Tensidkonzentration
Minitellertest mit hydrophob eingestellten Alkylpolyglycosiden im Vergleich zu Markenspülmitteln, Wasser: 13° dH, pH 6-7
Minitellertest mit hydrophob eingestellten Alylpolyglycosiden im Vergleich zu Markenspülmitteln, Wasser: 2° dH, pH 6-7
Aus den Tabellen 3a und 3b ergibt sich die hervorragende Reinigungswirkung der erfindungsgemäßen Alkylpolyglycoside, die als sehr umweltverträgliche Einzeltenside in Spülmitteln eine hervorragende Reinigungswirkung erzielen.Tables 3a and 3b show the excellent cleaning action of the alkyl polyglycosides according to the invention, which, as very environmentally compatible individual surfactants in detergents, achieve an excellent cleaning action.
Daten und Reinigungswirkung erfindungsgemäßer Zubereitungen
In Tabelle 4 sind die physikalischen Daten einiger erfindungsgemäßen Zubereitungen zusammengestellt. Die ebenfalls aufgeführten Reinigungswerte (Minitellertest) demonstrieren die hohe Wirksamkeit der neuen Reinigungssysteme.The physical data of some preparations according to the invention are summarized in Table 4. The cleaning values also listed (mini plate test) demonstrate the high effectiveness of the new cleaning systems.
Claims (8)
dadurch gekennzeichnet,
daß das Alkylpolyglycosid der Formel I
characterized,
that the alkyl polyglycoside of formula I
dadurch gekennzeichnet,
daß das Alkylpolyglycosid der Formel I
characterized,
that the alkyl polyglycoside of formula I
dadurch gekennzeichnet,
daß als Lösemittel Ethanol, i-Propanol oder Propylenglykol-1.2 oder Gemische davon verwendet werden.Liquid, foaming cleaning agent according to claims 1 to 3,
characterized,
that ethanol, i-propanol or propylene glycol-1.2 or mixtures thereof are used as solvents.
dadurch gekennzeichnet,
daß das Verhältnis Alkypolyglycosid/Lösemittel 1 : 1 bis 8 : 1 beträgt.Liquid, foaming cleaning agent according to claims 1 to 4,
characterized,
that the ratio of alkypolyglycoside / solvent is 1: 1 to 8: 1.
dadurch gekennzeichnet,
daß das Verhältnis Lösemittel/Elektroyt 1 : 1 bis 8 : 1 beträgt.Liquid, foaming cleaning agent according to claims 1 to 5,
characterized,
that the ratio solvent / electroyt is 1: 1 to 8: 1.
dadurch gekennzeichnet,
daß als Elektrolyt-, Alkali- und/oder Erdalkalichlorid verwendet wird.Liquid, foaming cleaning agent according to claims 1 to 6,
characterized,
that is used as electrolyte, alkali and / or alkaline earth chloride.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4005959A DE4005959A1 (en) | 1990-02-26 | 1990-02-26 | LIQUID, FOAMING DETERGENT |
DE4005959 | 1990-02-26 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0444267A2 true EP0444267A2 (en) | 1991-09-04 |
EP0444267A3 EP0444267A3 (en) | 1991-12-18 |
EP0444267B1 EP0444267B1 (en) | 1997-05-14 |
Family
ID=6400956
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90123936A Revoked EP0444267B1 (en) | 1990-02-26 | 1990-12-12 | Liquid foaming detergent |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0444267B1 (en) |
DE (2) | DE4005959A1 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0507047A2 (en) * | 1991-03-30 | 1992-10-07 | Hüls Aktiengesellschaft | Emulsifiers for preparing oil-in-water emulsions of etheric oils useful for cosmetic on medical purposes |
EP0570619A1 (en) * | 1992-05-18 | 1993-11-24 | Henkel KGaA | Process for cleaning bathroom fittings |
EP0750034A2 (en) * | 1995-06-20 | 1996-12-27 | Th. Goldschmidt AG | Storage stable, concentrated surfactant composition based on alkylglycosides |
WO1997032957A1 (en) * | 1996-03-04 | 1997-09-12 | S.C. Johnson & Son, Inc. | Stable aqueous silane solutions for cleaning hard surfaces |
US5807816A (en) * | 1995-05-10 | 1998-09-15 | Lever Brothers Company, Division Of Conopco, Inc. | Light duty cleaning composition |
US5837065A (en) * | 1994-03-23 | 1998-11-17 | Amway Corporation | Concentrated all-purpose light duty liquid cleaning composition and method of use |
US6087319A (en) * | 1996-03-04 | 2000-07-11 | S. C. Johnson & Son, Inc. | Stable aqueous silane solutions for cleaning hard surfaces |
DE10221335A1 (en) * | 2002-05-10 | 2003-11-27 | Braun Gmbh | Alcohol-containing fluid for use in device for cleansing electric razors contains a nonionic surfactant and optionally also fat replacement agent |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5449763A (en) * | 1991-10-10 | 1995-09-12 | Henkel Corporation | Preparation of alkylpolyglycosides |
Citations (5)
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---|---|---|---|---|
US3721633A (en) * | 1969-10-06 | 1973-03-20 | Atlas Chem Ind | Aqueous built liquid detergents containing alkyl glycosides |
WO1986004349A1 (en) * | 1985-01-29 | 1986-07-31 | A.E. Staley Manufacturing Company | Method and compositions for hard surface cleaning |
USH468H (en) * | 1985-11-22 | 1988-05-03 | A. E. Staley Manufacturing Company | Alkaline hard-surface cleaners containing alkyl glycosides |
EP0280143A1 (en) * | 1987-02-25 | 1988-08-31 | Henkel Kommanditgesellschaft auf Aktien | Liquid cleaning agent |
EP0388810B1 (en) * | 1989-03-20 | 1996-06-19 | Kao Corporation | Neutral liquid detergent composition |
-
1990
- 1990-02-26 DE DE4005959A patent/DE4005959A1/en not_active Withdrawn
- 1990-12-12 EP EP90123936A patent/EP0444267B1/en not_active Revoked
- 1990-12-12 DE DE59010718T patent/DE59010718D1/en not_active Revoked
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3721633A (en) * | 1969-10-06 | 1973-03-20 | Atlas Chem Ind | Aqueous built liquid detergents containing alkyl glycosides |
WO1986004349A1 (en) * | 1985-01-29 | 1986-07-31 | A.E. Staley Manufacturing Company | Method and compositions for hard surface cleaning |
USH468H (en) * | 1985-11-22 | 1988-05-03 | A. E. Staley Manufacturing Company | Alkaline hard-surface cleaners containing alkyl glycosides |
EP0280143A1 (en) * | 1987-02-25 | 1988-08-31 | Henkel Kommanditgesellschaft auf Aktien | Liquid cleaning agent |
EP0388810B1 (en) * | 1989-03-20 | 1996-06-19 | Kao Corporation | Neutral liquid detergent composition |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5605651A (en) * | 1991-03-30 | 1997-02-25 | Huels Aktiengesellschaft | Emulsifiers for the preparation of oil-in-water emulsions of essential oils usable in cosmetics or medicine |
EP0507047A3 (en) * | 1991-03-30 | 1993-02-03 | Huels Aktiengesellschaft | Emulsifiers for preparing oil-in-water emulsions of etheric oils useful for cosmetic on medical purposes |
EP0507047A2 (en) * | 1991-03-30 | 1992-10-07 | Hüls Aktiengesellschaft | Emulsifiers for preparing oil-in-water emulsions of etheric oils useful for cosmetic on medical purposes |
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 |
US5837065A (en) * | 1994-03-23 | 1998-11-17 | Amway Corporation | Concentrated all-purpose light duty liquid cleaning composition and method of use |
US5807816A (en) * | 1995-05-10 | 1998-09-15 | Lever Brothers Company, Division Of Conopco, Inc. | Light duty cleaning composition |
EP0750034A3 (en) * | 1995-06-20 | 1997-03-05 | Goldschmidt Ag Th | Storage stable, concentrated surfactant composition based on alkylglycosides |
EP0750034A2 (en) * | 1995-06-20 | 1996-12-27 | Th. Goldschmidt AG | Storage stable, concentrated surfactant composition based on alkylglycosides |
WO1997032957A1 (en) * | 1996-03-04 | 1997-09-12 | S.C. Johnson & Son, Inc. | Stable aqueous silane solutions for cleaning hard surfaces |
AU718739B2 (en) * | 1996-03-04 | 2000-04-20 | S.C. Johnson & Son, Inc. | Stable aqueous silane solutions for cleaning hard surfaces |
US6087319A (en) * | 1996-03-04 | 2000-07-11 | S. C. Johnson & Son, Inc. | Stable aqueous silane solutions for cleaning hard surfaces |
US6451755B1 (en) | 1996-03-04 | 2002-09-17 | S. C. Johnson & Son, Inc. | Stable aqueous silane solutions for cleaning hard surfaces |
DE10221335A1 (en) * | 2002-05-10 | 2003-11-27 | Braun Gmbh | Alcohol-containing fluid for use in device for cleansing electric razors contains a nonionic surfactant and optionally also fat replacement agent |
DE10221335B4 (en) * | 2002-05-10 | 2006-05-24 | Braun Gmbh | Use of a cleaning liquid for electric razors |
Also Published As
Publication number | Publication date |
---|---|
EP0444267B1 (en) | 1997-05-14 |
DE59010718D1 (en) | 1997-06-19 |
EP0444267A3 (en) | 1991-12-18 |
DE4005959A1 (en) | 1991-08-29 |
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