EP0444262A2 - Liquid foaming detergent - Google Patents
Liquid foaming detergent Download PDFInfo
- Publication number
- EP0444262A2 EP0444262A2 EP90123844A EP90123844A EP0444262A2 EP 0444262 A2 EP0444262 A2 EP 0444262A2 EP 90123844 A EP90123844 A EP 90123844A EP 90123844 A EP90123844 A EP 90123844A EP 0444262 A2 EP0444262 A2 EP 0444262A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- percent
- weight
- radical
- alkyl
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0094—High foaming compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
Definitions
- the 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.
- Modern products consist of neutral aqueous formulations based on 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.
- 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.
- 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 accepted test methods are a) the plate test, the end point of which is determined by the foam disintegration, and b) the fat titration, as a measure of the cleaning power, both of which lead to very similar results (see G. Jakobi in H. Stache, Tensid Taschenbuch , 2nd edition, 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.
- liquid cleaning agent which, as cleaning surfactants, contains exclusively a mixture of alkyl polyglycosides of different alkyl chain lengths.
- 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.
- alkyl polyglycosides in combination with builder substances, such as nitrilotriacetic acid or sodium tripolyphosphate are described as detergents.
- EP-A-0 105 556 claims the combination of alkyl polyglycosides with fatty alcohol oxyethylates as a liquid detergent.
- Alkyl polyglycosides used according to the invention satisfy the general formula in which R represents a linear or branched, saturated or unsaturated aliphatic alkyl radical and Z n represents a polyglycosyl radical.
- 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 commercially available surfactant alcohols in particular native fatty alcohols from the hydrogenation of fatty acids or fatty acid derivatives, are favorable for economic reasons. 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 commercially available carbohydrates starch, maltodextrins and especially dextrose are preferred.
- alkyl polyglycosides are always mixtures of oligomers, which in turn represent mixtures of different isomeric forms. They are 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.
- polar solvents such as acetone
- the degree of glycosidation is expediently determined by 1 H NMR certainly.
- the cleaning agents according to the invention usually contain 3 to 50 percent by weight, preferably 5 to 30 percent by weight, of total alkyl polyglycoside in aqueous solution.
- the total polyglycoside consists of at least two components, a hydrophilic component I and a hydrophobic component II.
- I has no or very little cleaning action and serves to increase the solubility in water or to lower the clear point.
- the hydrophobic component II is the actual cleaning agent. What is completely surprising with the mixture is that the cleaning action of component II is largely retained, although I itself has practically no cleaning action.
- the measure for adjusting the hydrophilicity is primarily the hydrophobic remainder of the alkyl polyglycoside.
- hydrophobic alkyl radical is in the range ⁇ C10.
- the adjustment of the hydrophobic component is a little more subtle.
- the alkyl radical should be> C10, at the same time the degree of glycosidation must be reduced to such an extent that the cleaning effect is optimal.
- the quantitative ratio of the two components I / II should be between 1: 1 and 1:10, preferably between 1: 2 and 1: 5.
- 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 SO (gold orfe) and EG 50 (daphnia) and values of> 10,000 mg / kg, 12 or 30 mg / l are 3 to 5 times cheaper than the corresponding values of 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 fall as synthesis-related about 50% aqueous amber solution.
- 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 4: 1.
- the solubility can be increased considerably, especially at low temperatures.
- Alkali and alkaline earth metal halides have proven to be suitable electrolytes.
- the solvent / electrolyte ratio can be 1: 1 to 4: 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 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 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 the analogous conditions for soft water.
- Table 4 summarizes the physical data of some of the preparations according to the invention. Their solubility behavior (clear point) on the one hand and their cleaning values (mini plate test) on the other hand demonstrate the high effectiveness of the new cleaning systems.
Abstract
Description
Die Erfindung betrifft ein umweltverträgliches, flüssiges Reinigungsmittel.The invention relates to an environmentally compatible, 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 aus neutral eingestellten wäßrigen Formulierungen auf der Basis 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 consist of neutral aqueous formulations based on 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.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.
Bei der Einschätzung der Reinigungskraft durch den Verbraucher spielt das Schäumvermögen der Lösung eine erhebliche Rolle, etwa in dem Sinne, je länger die Reinigungslösung während des Spülvorganges schäumt desto größer ist auch ihre Reinigungskraft. Allgemein anerkannte Testmethoden sind a) der Tellertest, 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.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. Generally accepted test methods are a) the plate test, the end point of which is determined by the foam disintegration, and b) the fat titration, as a measure of the cleaning power, both of which lead to very similar results (see G. Jakobi in H. Stache, Tensid Taschenbuch , 2nd edition, Munich 1981, pp. 252 ff.).
Wahrscheinlich hat diese Parallelität von qualitativer Schaumexistenz und Reinigungsvermögen die Hersteller konventioneller Spül mittel dazu verführt, höchste Bedeutung dem Schaumvolumen beizumessen. Dies hat zur Folge, daß das Spülgut bei verbraucherüblicher Dosierung des Spülmittels im Schaum verschwindet, was bekanntlich die eigentliche Reinigung herabsetzt und außerdem hinsichtlich des Hautgefühls unangenehm sein kann.This parallelism of qualitative foam existence and cleaning ability probably has the manufacturers of conventional rinsing seduced medium to attach the greatest importance to foam volume. The consequence of this is that the items to be washed disappear into the foam when the detergent is dosed in a customary manner, which is known to reduce 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 unvollständigen biologischen Abbaubarkeit.Another disadvantage with regard to the scarcity of raw material reserves is the predominantly petrochemical basis of the anionic surfactants mentioned, combined with incomplete biodegradability.
Aufgabe der Erfindung war es daher, ein sehr hautverträgliches Reinigungsmittel mit hervorragender Reinigungswirkung bei mäßigem Schaumvermögen zur Verfügung zu stellen, dessen Reinigungstensid biologisch 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 Reinigungstenside ausschließlich ein Gemisch aus Alkylpolyglycosiden verschiedener Alkylkettenlängen enthält.This object was achieved by a liquid cleaning agent which, as cleaning surfactants, contains exclusively a mixture of alkyl polyglycosides of different alkyl chain lengths.
Gegenstand der Erfindung ist daher ein flüssiges Reinigungsmittel, bestehend aus
- 3 bis 40 Gewichtsprozent Alkylpolyglycosid I,
- 3 bis 40 Gewichtsprozent Alkylpolyglycosid II,
- 0 bis 10 Gewichtsprozent Lösungsvermittler,
- 0 bis 10 Gewichtsprozent Elektrolyt,
- 0 bis 3 Gewichtsprozent Additiven und
- Wasser ad 100 Gewichtsprozent.
- 3 to 40 percent by weight alkyl polyglycoside I,
- 3 to 40 percent by weight alkyl polyglycoside II,
- 0 to 10 weight percent solubilizer,
- 0 to 10 percent by weight electrolyte,
- 0 to 3 weight percent additives and
- Water ad 100 weight percent.
Die Verwendung von Alkylpolyglycosiden in Wasch- und Reinigungsmitteln ist in Kombination mit anderen Tensiden bekannt. So beschreibt die AT-PS 135 333 bereits die Wirkung von Laurylglycosid kombiniert mit dem Natriumsalz des 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-0S 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. In US Pat. No. 3,721,633, alkyl polyglycosides in combination with builder substances, such as nitrilotriacetic acid or sodium tripolyphosphate, are described as detergents. EP-A-0 105 556 claims the combination of alkyl polyglycosides with fatty alcohol oxyethylates as a liquid detergent. Manual detergents using alkyl polyglycosides are described in EP-A-0 070 074, EP-A-0 070 075 and EP-A-0 070 076, wherein anionic surfactants are also used as cosurfactants. DE-0S 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 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.It has now been observed, completely surprisingly, that detergents which contain only alkyl polyglycosides as cleaning surfactants achieve excellent cleaning effects if these alkyl polyglycosides 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 allgemeinen Formel
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, 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. The commercially available surfactant alcohols, in particular native fatty alcohols from the hydrogenation of fatty acids or fatty acid derivatives, are favorable for economic reasons. 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 commercially available carbohydrates starch, maltodextrins and especially dextrose are preferred. Since the economically interesting alkyl polyglycoside syntheses are not regio- and stereoselective, the alkyl polyglycosides are always mixtures of oligomers, which in turn represent mixtures of different isomeric forms. They are 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. Der Glycosidierungsgrad wird zweckmäßigerweise mittels
¹H-NMR
bestimmt.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 expediently determined by
1 H NMR
certainly.
Die erfindungsgemäßen Reinigungsmittel enthalten gewöhnlich 3 bis 50 Gewichtsprozent, vorzugsweise 5 bis 30 Gewichtsprozent, Gesamt-Alkylpolyglycosid in wäßriger Lösung.The cleaning agents according to the invention usually contain 3 to 50 percent by weight, preferably 5 to 30 percent by weight, of total alkyl polyglycoside in aqueous solution.
Das Gesamtpolyglycosid besteht aus mindestens zwei Komponenten, einer hydrophilen Komponente I und einer hydrophoben Komponente II. I besitzt keine oder eine sehr geringe Reinigungswirkung und dient zur Erhöhung der Löslichkeit in Wasser bzw. zur Absenkung des Klarpunkts. Die hydrophobe Komponente II ist das eigentliche Reinigungsmittel. Völlig überraschend bei der Mischung ist, daß die Reinigungswirkung der Komponente II weitgehend erhalten bleibt, obwohl I selbst praktisch keine Reinigungswirkung besitzt.The total polyglycoside consists of at least two components, a hydrophilic component I and a hydrophobic component II. I has no or very little cleaning action and serves to increase the solubility in water or to lower the clear point. The hydrophobic component II is the actual cleaning agent. What is completely surprising with the mixture is that the cleaning action of component II is largely retained, although I itself has practically no cleaning action.
Maßnahme zur Einstellung der Hydrophilie ist in erster Linie der hydrophobe Rest des Alkylpolyglycosids. So sind übliche Alkylpolyglycoside mit Glycosidierungsgraden zwischen 1,3 bis 2,5 stark löslichkeitsfördernd vorausgesetzt der hydrophobe Alkylrest ist im Bereich < C₁₀. Die Einstellung der hydrophoben Komponente ist etwas subtiler. Der Alkylrest sollte hier > C₁₀ liegen, gleichzeitig ist der Glycosidierungsgrad soweit zu erniedrigen, daß die Reinigungswirkung optimal ist. Das Mengenverhältnis der beiden Komponenten I/II sollte zwischen 1 : 1 und 1 : 10, vorzugsweise zwischen 1 : 2 und 1 : 5 liegen.The measure for adjusting the hydrophilicity is primarily the hydrophobic remainder of the alkyl polyglycoside. Thus, common alkyl polyglycosides with degrees of glycosidation between 1.3 to 2.5 are highly solubility-promoting, provided the hydrophobic alkyl radical is in the range < C₁₀. The adjustment of the hydrophobic component is a little more subtle. The alkyl radical should be> C₁₀, at the same time the degree of glycosidation must be reduced to such an extent that the cleaning effect is optimal. The quantitative ratio of the two components I / II should be between 1: 1 and 1:10, preferably between 1: 2 and 1: 5.
So enthalten erfindungsgemäße Reinigungsmittel 3 bis 40 Gewichtsprozent Alkylpolyglycosid I und 3 bis 40 Gewichtsprozent Alkylpolyglycosid II, wobei I der Formel I
- R₁ =
- gesättiger oder ungesättigte, verzweigter oder unverzweigter Alkylrest mit 7 bis 10 C-Atomen,
- Zn₁ =
- Polyglycosidradikal mit n₁ = 1 bis 3 Hexose- oder Pentoseeinheiten oder Mischungen davon
und II der Formel II
- R₂ =
- gesättigter oder ungesättigter, verzweigter oder unverzweigter Alkylrest mit 11 bis 18 C-Atomen, bevorzugt 12 bis 18 C-Atomen, und
- Zn₂ =
- Polyglycosidradikal mit n₂ = 1 bis 3, bevorzugt 1,1 bis 2 Hexose- oder Pentoseeinheiten oder Mischungen davon
gehorchen.
- R₁ =
- saturated or unsaturated, branched or unbranched alkyl radical with 7 to 10 carbon atoms,
- Z n ₁ =
- Polyglycoside radical with n₁ = 1 to 3 hexose or pentose units or mixtures thereof
and II of formula II - R₂ =
- saturated or unsaturated, branched or unbranched alkyl radical having 11 to 18 carbon atoms, preferably 12 to 18 carbon atoms, and
- Z n ₂ =
- Polyglycoside radical with n₂ = 1 to 3, preferably 1.1 to 2 hexose or pentose units or mixtures thereof
to obey.
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 SO (Goldorfe) und EG 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 SO (gold orfe) and EG 50 (daphnia) and values of> 10,000 mg / kg, 12 or 30 mg / l are 3 to 5 times cheaper than the corresponding values of 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.The alkyl polyglycosides according to the invention fall as synthesis-related about 50% aqueous amber solution.
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 4 : 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 4: 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 4 : 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 solvent / electrolyte ratio can be 1: 1 to 4: 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 Komplexbildner erwiesen.Citric acid, EDTA, NTA and other complexing agents have proven to be further suitable additives.
Die nachfolgenden Beispiele sollen die Erfindung verdeutlichen. Zur Testung der Spülmittelwirkung wurde der Minitellertest (vgl. R.M. Anstett u. E.J. Schuck JAOCS 43, 576 (1966) durchgeführt.The following examples are intended to illustrate the invention. The mini dish test (cf. RM Anstett and EJ Schuck JAOCS 43, 576 (1966) was carried out to test the detergent action.
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 die analogen Verhältnisse bei weichem Wasser.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 the analogous conditions for soft water.
Minitellertest, Konzentration Waschaktive Substanz: 0,075 g/l,
Trinkwasser: 13° dH
Drinking water: 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
In Tabelle 4 sind die physikalischen Daten einiger erfindungsgemäßer Zubereitungen zusammengestellt. Ihr Löslichkeitsverhalten (Klarpunkt) einerseits und ihre Reinigungswerte (Minitellertest) andererseits demonstrieren die hohe Wirksamkeit der neuen Reinigungssysteme.Table 4 summarizes the physical data of some of the preparations according to the invention. Their solubility behavior (clear point) on the one hand and their cleaning values (mini plate test) on the other hand demonstrate the high effectiveness of the new cleaning systems.
Trotz des hohen Anteils an nichtreinigender Substanz (siehe auch Tabelle 2) ist eine überraschende Reinigungswirkung zu beobachten.Despite the high proportion of non-cleaning substance (see also Table 2), a surprising cleaning effect can be observed.
Claims (7)
daß das Alkylpolyglycosid I der Formel I
that the alkyl polyglycoside I of formula I
dadurch gekennzeichnet,
daß R₂ ein Fettalkylrest mit 12 bis 18 Kohlenstoffatomen, Zn₂ ein Polyglucosylradikal mit n₂ = 1,1 bis 2 Glycosideinheiten bedeutet.Liquid, foaming cleaning agent according to claims 1 and 2,
characterized,
that R₂ is a fatty alkyl radical having 12 to 18 carbon atoms, Z n ₂ is a polyglucosyl radical with n₂ = 1.1 to 2 glycoside units.
dadurch gekennzeichnet,
daß die Mengenverhältnisse von
R₁-O-Zn₁ zu R₂-O-Zn₂
sich wie 1 : 1 bis 1 : 10 verhalten.Liquid, foaming cleaning agent according to claims 1 to 3,
characterized,
that the proportions of
R₁-OZ n ₁ to R₂-OZ n ₂
behave like 1: 1 to 1:10.
dadurch gekennzeichnet,
daß als Lösungsvermittler niedemolekulare, ein- und mehrwertige Alkohole, Ether von mehrwertigen Alkoholen, Alkanolamine und/- oder hydrophope Substanzen verwendet werden.Liquid, foaming cleaning agent according to claims 1 to 4,
characterized,
that low molecular weight, mono- and polyhydric alcohols, ethers of polyhydric alcohols, alkanolamines and / or hydrophobic substances are used as solubilizers.
dadurch gekennzeichnet,
daß als Elektrolyte Alkalihalogenide, Erdalkalihalogenide bzw. deren Gemische eingesetzt werden.Liquid, foaming cleaning agent according to claims 1 to 5,
characterized,
that alkali metal halides, alkaline earth metal halides or mixtures thereof are used as electrolytes.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19904005958 DE4005958A1 (en) | 1990-02-26 | 1990-02-26 | Foaming liq. detergent based on alkyl poly-glycoside mixt. |
| DE4005958 | 1990-02-26 |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| EP0444262A2 true EP0444262A2 (en) | 1991-09-04 |
| EP0444262A3 EP0444262A3 (en) | 1992-01-22 |
| EP0444262B1 EP0444262B1 (en) | 1996-02-28 |
| EP0444262B2 EP0444262B2 (en) | 2004-10-06 |
Family
ID=6400955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90123844A Expired - Lifetime EP0444262B2 (en) | 1990-02-26 | 1990-12-11 | Liquid foaming detergent |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0444262B2 (en) |
| DE (2) | DE4005958A1 (en) |
| DK (1) | DK0444262T3 (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 |
| WO1993007249A1 (en) * | 1991-10-10 | 1993-04-15 | Henkel Corporation | Preparation of improved alkylpolyglycoside surfactant mixtures |
| WO1994003569A1 (en) * | 1992-07-30 | 1994-02-17 | Henkel Kommanditgesellschaft Auf Aktien | Process for producing storable non-ionic tensides |
| WO1994029416A1 (en) * | 1993-06-16 | 1994-12-22 | Henkel Kommanditgesellschaft Auf Aktien | Ultramild surfactant mixtures |
| WO1994029417A1 (en) * | 1993-06-16 | 1994-12-22 | Henkel Kommanditgesellschaft Auf Aktien | Ultramild surfactant mixtures |
| 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 |
| WO2012011892A1 (en) * | 2010-07-19 | 2012-01-26 | Colgate-Palmolive Company | Cleansing composition with decyl and coco glucosides |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5449763A (en) * | 1991-10-10 | 1995-09-12 | Henkel Corporation | Preparation of alkylpolyglycosides |
| DE19944543C2 (en) * | 1999-09-17 | 2002-04-18 | Cognis Deutschland Gmbh | surfactant mixtures |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3547828A (en) * | 1968-09-03 | 1970-12-15 | Rohm & Haas | Alkyl oligosaccharides and their mixtures with alkyl glucosides and alkanols |
| EP0136844A2 (en) * | 1983-09-06 | 1985-04-10 | Henkel Kommanditgesellschaft auf Aktien | Glycoside-containing detergents |
| USH171H (en) * | 1985-06-24 | 1986-12-02 | A. E. Staley Manufacturing Company | Branched chain glycosides |
| US4725489A (en) † | 1986-12-04 | 1988-02-16 | Airwick Industries, Inc. | Disposable semi-moist wipes |
| EP0280143A1 (en) † | 1987-02-25 | 1988-08-31 | Henkel Kommanditgesellschaft auf Aktien | Liquid cleaning agent |
| US5449763A (en) † | 1991-10-10 | 1995-09-12 | Henkel Corporation | Preparation of alkylpolyglycosides |
-
1990
- 1990-02-26 DE DE19904005958 patent/DE4005958A1/en not_active Withdrawn
- 1990-12-11 DK DK90123844T patent/DK0444262T3/en active
- 1990-12-11 EP EP90123844A patent/EP0444262B2/en not_active Expired - Lifetime
- 1990-12-11 DE DE59010166T patent/DE59010166D1/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3547828A (en) * | 1968-09-03 | 1970-12-15 | Rohm & Haas | Alkyl oligosaccharides and their mixtures with alkyl glucosides and alkanols |
| EP0136844A2 (en) * | 1983-09-06 | 1985-04-10 | Henkel Kommanditgesellschaft auf Aktien | Glycoside-containing detergents |
| USH171H (en) * | 1985-06-24 | 1986-12-02 | A. E. Staley Manufacturing Company | Branched chain glycosides |
| US4725489A (en) † | 1986-12-04 | 1988-02-16 | Airwick Industries, Inc. | Disposable semi-moist wipes |
| EP0280143A1 (en) † | 1987-02-25 | 1988-08-31 | Henkel Kommanditgesellschaft auf Aktien | Liquid cleaning agent |
| US5449763A (en) † | 1991-10-10 | 1995-09-12 | Henkel Corporation | Preparation of alkylpolyglycosides |
Non-Patent Citations (2)
| Title |
|---|
| C.F. Putnik et al, Soap Cosmet. Chem. Spec., 1986, 62, n°6, S. 34-37, 74 † |
| J. Falbe, Surfactants in consumer products Springer-Verlag, Heidelberg, 1987, S. 104-106 † |
Cited By (15)
| 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 |
| 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 |
| 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 |
| WO1993007249A1 (en) * | 1991-10-10 | 1993-04-15 | Henkel Corporation | Preparation of improved alkylpolyglycoside surfactant mixtures |
| US5734029A (en) * | 1991-10-10 | 1998-03-31 | Henkel Corporation | Preparation of improved alkypolygloycoside surfactant mixtures |
| US5556573A (en) * | 1992-07-30 | 1996-09-17 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of storable nonionic surfactants |
| WO1994003569A1 (en) * | 1992-07-30 | 1994-02-17 | Henkel Kommanditgesellschaft Auf Aktien | Process for producing storable non-ionic tensides |
| WO1994029417A1 (en) * | 1993-06-16 | 1994-12-22 | Henkel Kommanditgesellschaft Auf Aktien | Ultramild surfactant mixtures |
| WO1994029416A1 (en) * | 1993-06-16 | 1994-12-22 | Henkel Kommanditgesellschaft Auf Aktien | Ultramild surfactant mixtures |
| US5658875A (en) * | 1993-06-16 | 1997-08-19 | Henkel Kommanditgesellschaft Auf Aktien | Ultramild surfactant mixtures |
| US5663137A (en) * | 1993-06-16 | 1997-09-02 | Henkel Kommanditgesellschaft Auf Aktien | Ultramild surfactant mixtures II |
| 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 |
| WO2012011892A1 (en) * | 2010-07-19 | 2012-01-26 | Colgate-Palmolive Company | Cleansing composition with decyl and coco glucosides |
| RU2555356C2 (en) * | 2010-07-19 | 2015-07-10 | Колгейт-Палмолив Компани | Detergent composition with decyl and coco glucosides |
Also Published As
| Publication number | Publication date |
|---|---|
| DE59010166D1 (en) | 1996-04-04 |
| DE4005958A1 (en) | 1991-08-29 |
| EP0444262B2 (en) | 2004-10-06 |
| EP0444262B1 (en) | 1996-02-28 |
| EP0444262A3 (en) | 1992-01-22 |
| DK0444262T3 (en) | 1996-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0216301B1 (en) | Liquid cleaning agent | |
| EP0280143B1 (en) | Liquid cleaning agent | |
| EP0474915B2 (en) | Detergent | |
| AT394572B (en) | STRONG FOAMING, LIQUID FINE CLEANING AGENT BASED ON NON-ionic surfactants, AND METHOD FOR THE PRODUCTION THEREOF | |
| AT396110B (en) | CLEAR, AQUEOUS DETERGENT | |
| EP0570619B1 (en) | Process for cleaning bathroom fittings | |
| EP0743975B1 (en) | Hard surface cleaning agent | |
| DE3905939A1 (en) | TENSIDE COMBINATION | |
| EP0444262B1 (en) | Liquid foaming detergent | |
| EP0513138B2 (en) | Aqueous liquid cleaning agent | |
| EP0444267B1 (en) | Liquid foaming detergent | |
| EP0486784B2 (en) | Liquid foaming detergent of increased viscosity | |
| EP0486786A1 (en) | Liquid, foaming detergent | |
| EP0490040B1 (en) | Liquid detergent | |
| WO1999057235A1 (en) | Dishwashing detergent with an antibacterial effect | |
| DE4016819A1 (en) | Low foam liq. or powder machine washing compsn. with surfactant - comprising alkyl-poly:glycoside, alkanol ether carboxylate and soap | |
| EP0918085B1 (en) | C8-C22-Carboxylic acid amide ether sulphate tenside combinations being mild to the skin | |
| EP0729499A1 (en) | Method of cleaning bathroom fittings (ii) | |
| WO1990008813A1 (en) | Liquid detergents | |
| DE19607799A1 (en) | Hard surface cleaner with improved grease-dissolving power | |
| DD290441A5 (en) | METHOD FOR PRODUCING A POWDER-SOUND CLEANING AGENT FOR GLASS AND PORCELAIN SURFACES |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 19901211 |
|
| AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): DE DK FR GB IT NL SE |
|
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): DE DK FR GB IT NL SE |
|
| 17Q | First examination report despatched |
Effective date: 19950216 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE DK FR GB IT NL SE |
|
| REF | Corresponds to: |
Ref document number: 59010166 Country of ref document: DE Date of ref document: 19960404 |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19960409 |
|
| ET | Fr: translation filed | ||
| ITF | It: translation for a ep patent filed |
Owner name: SOCIETA' ITALIANA BREVETTI S.P.A. |
|
| REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 |
|
| PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Effective date: 19961211 |
|
| REG | Reference to a national code |
Ref country code: DK Ref legal event code: EBP |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19961212 |
|
| PLBF | Reply of patent proprietor to notice(s) of opposition |
Free format text: ORIGINAL CODE: EPIDOS OBSO |
|
| 26 | Opposition filed |
Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN Effective date: 19961118 |
|
| NLR1 | Nl: opposition has been filed with the epo |
Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN |
|
| PLBF | Reply of patent proprietor to notice(s) of opposition |
Free format text: ORIGINAL CODE: EPIDOS OBSO |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19970701 |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 19970701 |
|
| EUG | Se: european patent has lapsed |
Ref document number: 90123844.4 |
|
| RAP2 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: DEGUSSA-HUELS AKTIENGESELLSCHAFT |
|
| PLAW | Interlocutory decision in opposition |
Free format text: ORIGINAL CODE: EPIDOS IDOP |
|
| APAC | Appeal dossier modified |
Free format text: ORIGINAL CODE: EPIDOS NOAPO |
|
| APAE | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOS REFNO |
|
| APAC | Appeal dossier modified |
Free format text: ORIGINAL CODE: EPIDOS NOAPO |
|
| RAP2 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: RWE-DEA AKTIENGESELLSCHAFT FUER MINERALOEL UND CHE |
|
| RAP2 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: SASOL GERMANY GMBH |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: TP Ref country code: FR Ref legal event code: CD |
|
| APBU | Appeal procedure closed |
Free format text: ORIGINAL CODE: EPIDOSNNOA9O |
|
| PUAH | Patent maintained in amended form |
Free format text: ORIGINAL CODE: 0009272 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT MAINTAINED AS AMENDED |
|
| 27A | Patent maintained in amended form |
Effective date: 20041006 |
|
| AK | Designated contracting states |
Kind code of ref document: B2 Designated state(s): DE DK FR GB IT NL SE |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20041221 Year of fee payment: 15 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20041229 Year of fee payment: 15 |
|
| GBTA | Gb: translation of amended ep patent filed (gb section 77(6)(b)/1977) |
Effective date: 20050112 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20050223 Year of fee payment: 15 |
|
| ET3 | Fr: translation filed ** decision concerning opposition | ||
| APAH | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOSCREFNO |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20051211 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20051211 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060701 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20051211 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060831 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20060831 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: TP Ref country code: FR Ref legal event code: CD Ref country code: FR Ref legal event code: CA |