EP0457965A1 - Low foaming washing-machine detergents - Google Patents
Low foaming washing-machine detergents Download PDFInfo
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- EP0457965A1 EP0457965A1 EP90124032A EP90124032A EP0457965A1 EP 0457965 A1 EP0457965 A1 EP 0457965A1 EP 90124032 A EP90124032 A EP 90124032A EP 90124032 A EP90124032 A EP 90124032A EP 0457965 A1 EP0457965 A1 EP 0457965A1
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- Prior art keywords
- liquid
- foaming
- low
- machine detergent
- detergent according
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Classifications
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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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/06—Ether- or thioether carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
Definitions
- the present invention relates to low-foaming liquid or powdery preparations for washing textiles, the surfactants of which are largely made from renewable raw materials.
- Liquid detergents today mainly consist of anionic surfactants, especially alkylbenzenesulfonate, fatty alcohol oxyethylate and soap, whereas washing powders contain not only the surfactants alkylbenzenesulfonate and fatty alcohol oxyethylate, but also builder substances, bleaching agents and other electrolytes as essential active ingredients.
- surfactants in particular those based on petrochemicals, are used.
- the object of the invention was therefore to find a surfactant combination for low-foaming detergents, which are largely made from renewable raw materials, which are extremely biodegradable and achieve very good washing results.
- surfactants which essentially consists of alkyl polyglycosides, ether carboxylates and soap.
- the invention therefore relates to a low-foaming, liquid or powdered machine detergent, which is characterized in that the surfactant component consists of 5 to 30% alkyl polyglycoside, 5 to 30% alkanol ether carboxylate, 5 to 30% soap and 0 to 3% other surfactants consists.
- alkyl polyglycoside in combination with anionic surfactants is known.
- DE-OS 593 422 already mentions the washing effect-enhancing effect of alkyl glycoside in soaps.
- Later documents such as EP-A 0 075 994, 0 105 556, 0 199 765 or DE-OS 37 02 286 describe the use of alkyl polyglycosides in combination with a number of known anionic surfactants in detergents. The most important in terms of quantity is the most important surfactant, alkylbenzenesulfonate.
- components depending on the state of aggregation are other surfactants in small quantities, complexing agents, bleaching agents, optical brighteners, graying inhibitors, corrosion inhibitors, foam regulators, stabilizers, enzymes, enzyme stabilizers, electrolytes, hydrotropic substances, solubilizers, etc.
- Alkyl polyglycosides used according to the invention satisfy formula I.
- the alkyl polyglycosides used according to the invention can be produced by known processes based on renewable raw materials. For example, dextrose is reacted with n-butanol to give butylpolyglycoside mixtures in the presence of an acidic catalyst, which are transglycosidated with long-chain alcohols in the presence of an acidic catalyst to give the desired alkylpolyglycoside mixtures. Or dextrose is immediately reacted with the desired long-chain alcohol.
- 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 z. B. according to DE-OS 19 43 689.
- polysaccharides e.g. B. starch, maltodextrins, dextrose, galactose, mannose, xylose, etc. are used will.
- the industrially 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 exist side by side with ⁇ - and ⁇ -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 detergents according to the invention contain 5 to 30% alkyl polyglycoside, preferably 7 to 20%.
- 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) with> 10,000 mg / kg as well as the aquatic toxicity LC 50 (gold orfe) with approx. 12 mg / l and EC 50 (daphnia) with 30 mg / l are by a factor of 3 to 5 cheaper than the corresponding values of today's most important surfactants. The same applies to skin and mucous membrane compatibility.
- Fatty alcohol ether carboxylates are compounds of either formula II or III, (R'-O (CH2-CH2-O) x CH2COO) m M m + II, in which R 'is a linear or branched, saturated or unsaturated alkyl radical having 8 to 22 preferably 10 to 18 carbon atoms, x 1 to 40, preferably 3 to 30, m 1 or 2 and M is hydrogen, alkali, alkaline earth metal, ammonium or alkanolammonium or ([R '' - O (CH2-CH2-O) y ] 2CHCOO) z N z + III in which R '' is a linear or branched, saturated or unsaturated alkyl radical having 8 to 22, preferably 10 to 18 carbon atoms, y 1 to 4, preferably 3 to 30, z 1 or 2 and NH, alkali, alkaline earth metal, ammonium, alkanolammonium.
- the carboxymethylated oxethylates can be according to DE-OS 24 18 444 or EP-A 0 106 018 by reacting oxethylates of the formula R'-O (CH2-CH2-O) n H with chloroacetic acid or a salt of chloroacetic acid in the presence of alkali metal hydroxide or other bases. But other manufacturing processes such. B. by means of catalytic oxidation according to EP-A 0 018 681 or 0 039 111 are suitable.
- Bisalkanol ethoxylate acetates can be e.g. B. according to DE-OS 39 02 663 from oxyethylates and dichloroacetic acid.
- Corresponding alcohols for the production of the fatty alcohol ether carboxylates are preferably fatty alcohols or Ziegler alcohols, in exceptional cases also oxo alcohols.
- the carboxymethylation following the oxethylation can be carried out with the appropriate driving style be complete so that the fatty alcohol ether carboxylates are purely anionic surfactants.
- the products contain certain amounts of unreacted oxyethylate.
- the formulas II and III therefore usually mean a mixture with different amounts of unreacted oxethylates. Accordingly, a degree of implementation can be defined. A degree of conversion between 70 and 100% is preferred.
- the fatty alcohol ether carboxylates are also very environmentally friendly surfactants. Biodegradation rates above 90% were determined using a sewage plant simulation model / DOC analysis.
- the acute oral toxicity LD 50 (rat) and the aquatic toxicity LC 50 (gold orfe) are about as favorable as that of the alkyl polyglucosides. The same applies to skin and mucous membrane compatibility.
- the detergents according to the invention contain 5 to 30% fatty alcohol ether carboxylates, which can also be mixtures. A content of 7 to 20% fatty alcohol ether carboxylate is preferred.
- Fatty acid salts or their acids according to the invention correspond to formula IV R '''COOP IV, in which R '''is a saturated or unsaturated alkyl radical having 8 to 22 carbon atoms and P is hydrogen, alkali, ammonium or alkanolammonium.
- the detergents according to the invention contain 5 to 30%, preferably 7 to 20% soap, which will usually be a mixture of different components.
- anionic, nonionic, zwitterionic and ampholytic surfactants are to be used according to the invention.
- these are alkanesulfonates, olefinsulfonates, alkylbenzenesulfonates, ⁇ -sulfo fatty acid esters, fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic acid esters, alkanoloxethylates, fatty acid alkanolamides, amine oxides, betaines, sulfobetaines, etc.
- builders should be mentioned as non-surfactant components.
- water-soluble builders such as different polyphosphates, phosphonates, carbonates, polycarboxylates, citronates, polyacetates such as NTA and DETA, etc. or mixtures thereof are used. These compounds are usually used as alkali salts, preferably as sodium salts. Although not complexing, sodium sulfate should also be mentioned here.
- water-insoluble builders such as aluminosilicates of suitable particle size, is also according to the invention (cf. EP-A 0 075 994).
- the concentration of the builders in the detergent is 0 to 70%, preferably 0 to 50%.
- Bleaching agents such as sodium perborate, optionally combined with bleach activators such as tetraacetylethylene diamine etc. or percarbonate, are also used according to the invention; Other bleaching agents are of course also possible (cf. K. Engel, Tenside Surfactants 25, p. 21 (1988).
- concentration of the bleaching agents is 0 to 40%, preferably 0 to 30%.
- Adjusting agents such as low molecular weight mono- or dihydric alcohols, alkyl ethers of polyhydric alcohols, hydrotropics such as alkylbenzenesulfonates with 1 to 3C atoms in the alkyl radical, alkanolamines or urea, enzymes such as in particular proteases and enzyme stabilizers, corrosion inhibitors such as alkali silicates, optical brighteners may be used according to the invention especially based on and stilbene and pyrazoline, foam regulators, graying inhibitors such.
- the total use concentration in the machine detergents according to the invention is 0.3-20 g / l for the surfactant fraction. 0.5-10 g / l are preferred.
- the invention is illustrated by the following examples.
- the liquid detergent formulations listed in Tables 1 and 2 each contain 6% triethanolamine, 12% ethanol, 6% 1,2-propylene glycol and water ad 100% in addition to the surfactant components mentioned according to the invention.
- the foaming power was determined in accordance with DIN 53 902, Part 1.
- the concentration of detergent substance was 1 g / l, the foam volume was registered after 5 minutes.
- the washability was measured both in the Linitest laboratory washing machine (i.e. with moderate mechanical stress) and in a normal household machine.
- 11 x 18 cm rags made of WFK test fabric with skin fat pigment soiling served as model fabric: polyester (PE), mixed fabric (MG) and cotton (BW), and drinking water (13 ° dH) as water.
- Polyester was washed at 30 ° C, blended fabrics and cotton at 60 ° C.
- the active ingredient concentration was 1 g / l, in the household washing machine 5 g / l, the pH in each case about 7, the liquor ratio in about 1: 60 and 1: 4, the washing times in both cases were about 30 minutes .
- Tables 1 and 2 show the comparison of the properties of the detergents according to the invention as a liquid formulation with those of other known combinations and of a liquid branded detergent, in which one can assume that the formulation has been optimized.
- the clear point and viscosity fully correspond to the standard customary for liquid detergents.
- the foaming power of the formulations according to the invention shows - without further regulating additives - very favorable values. This applies in particular to the washing ability.
- the formulations according to the invention behave far more effectively here than other known combinations, the surfactant content of which also consists of anionic surfactant, alkyl polyglucoside and soap (comparative examples 1 and 2).
- Tab. 3 shows the comparison of the properties of powdery detergent formulations according to the invention with those of a known combination or a branded detergent. Bulk density, angle of repose and foaming power were determined according to DIN methods. The solubility can be estimated by plotting the electrical conductivity over time, 80% of an average final conductivity being taken as the measured value when 1 g of powder is dissolved in 800 ml of drinking water (13 ° dH). The measured values contain an error of ⁇ 5%.
- Example 20 Apart from a much higher bulk density, typical of agglomerated washing powders compared to the spray-dried brand product (example 20), the powders according to the invention behave very similarly and better in their washing values. Again, the washing effects, which are greatly improved in contrast to known formulations of Example 15 with anionic surfactants, are clear.
Abstract
Description
Die vorliegende Erfindung betrifft schwachschäumende flüssige oder pulverförmige Zubereitungen zum Waschen von Textilien, deren Tenside weitestgehend aus nachwachsenden Rohstoffen hergestellt werden.The present invention relates to low-foaming liquid or powdery preparations for washing textiles, the surfactants of which are largely made from renewable raw materials.
Flüssige Waschmittel bestehen heute vor allem aus anionischen Tensiden, insbesondere Alkylbenzolsulfonat, Fettalkoholoxethylat und Seife, wohingegen Waschpulver neben den Tensiden Alkylbenzolsulfonat und Fettalkoholoxethylat als wesentliche Wirkstoffe noch Buildersubstanzen, Bleichmittel und andere Elektrolyte enthalten. Gemeinsam ist flüssigen und pulverförmigen Waschmittelformulierungen, daß als Tenside insbesondere solche auf petrochemischer Basis eingesetzt werden.Liquid detergents today mainly consist of anionic surfactants, especially alkylbenzenesulfonate, fatty alcohol oxyethylate and soap, whereas washing powders contain not only the surfactants alkylbenzenesulfonate and fatty alcohol oxyethylate, but also builder substances, bleaching agents and other electrolytes as essential active ingredients. Common to liquid and powder detergent formulations is that surfactants, in particular those based on petrochemicals, are used.
Im Hinblick auf die zukünftige Rohstoffsituation (Erdölverknappung) ist diese petrochemische Basis ein erheblicher Nachteil. Ein weiterer Nachteil besteht darin, daß die biologische Abbaubarkeit dieser Tenside nicht das entsprechende Niveau von Tensiden auf nativer Basis erreichen.In view of the future raw material situation (oil shortage), this petrochemical basis is a considerable disadvantage. Another disadvantage is that the biodegradability of these surfactants does not reach the corresponding level of surfactants on a native basis.
Aufgabe der Erfindung war es daher, eine Tensidkombination für schwachschäumende Waschmittel zu finden, die weitestgehend aus nachwachsenden Rohstoffen hergestellt werden, die hervorragend biologisch abbaubar sind und sehr gute Waschergebnisse erzielen.The object of the invention was therefore to find a surfactant combination for low-foaming detergents, which are largely made from renewable raw materials, which are extremely biodegradable and achieve very good washing results.
Diese Aufgabe wurde gelöst durch eine Tensidkombination, die im wesentlichen aus Alkylpolyglycosiden, Ethercarboxylaten und Seife besteht.This object was achieved by a combination of surfactants, which essentially consists of alkyl polyglycosides, ether carboxylates and soap.
Gegenstand der Erfindung ist daher ein schwachschäumendes, flüssiges oder pulverförmiges Maschinen-Waschmittel, welches dadurch gekennzeichnet ist, daß der tensidische Anteil aus
5 bis 30 % Alkylpolyglycosid,
5 bis 30 % Alkanolethercarboxylat,
5 bis 30 % Seife und
0 bis 3 % andere Tenside
besteht.The invention therefore relates to a low-foaming, liquid or powdered machine detergent, which is characterized in that the surfactant component consists of
5 to 30% alkyl polyglycoside,
5 to 30% alkanol ether carboxylate,
5 to 30% soap and
0 to 3% other surfactants
consists.
Überraschenderweise wurde gefunden, daß mit den erfindungsgemäßen Kombinationen sehr gute Waschergebnisse erzielt werden.Surprisingly, it was found that very good washing results are achieved with the combinations according to the invention.
Die Verwendung von Alkylpolyglycosid in Kombination mit anionischen Tensiden ist bekannt. So erwähnt bereits die DE-OS 593 422 die wascheffektverstärkende Wirkung von Alkylglykosid bei Seifen. Spätere Schriften wie EP-A 0 075 994, 0 105 556, 0 199 765 oder DE-OS 37 02 286 beschreiben den Einsatz von Alkylpolyglycosiden in Kombination mit einer Reihe bekannter anionischer Tenside in Waschmitteln. Im Vordergrund steht dabei jeweils das mengenmäßig bedeutendste Tensid Alkylbenzolsulfonat.The use of alkyl polyglycoside in combination with anionic surfactants is known. DE-OS 593 422 already mentions the washing effect-enhancing effect of alkyl glycoside in soaps. Later documents such as EP-A 0 075 994, 0 105 556, 0 199 765 or DE-OS 37 02 286 describe the use of alkyl polyglycosides in combination with a number of known anionic surfactants in detergents. The most important in terms of quantity is the most important surfactant, alkylbenzenesulfonate.
Die Verwendung in Waschmitteln von carboxymethylierten Fettalkoholoxethylaten, die eine Untergruppe der Ethercarboxylate darstellen, ist aus DE-OSS 23 27 234 und 33 20 340 bekannt; neu hingegen ist der Einsatz von Bisalkanolalkoxylatacetaten, die ebenfalls eine Untergruppe der Ethercarboxylate sind. Ebenso unbekannt ist die Verwendung der Ethercarboxylate im Zusammenhang mit Alkylpolyglycosiden in Waschmitteln.The use in detergents of carboxymethylated fatty alcohol oxyethylates, which are a subset of the ether carboxylates, is known from DE-OSS 23 27 234 and 33 20 340; however, the use of bisalkanol alkoxylate acetates, which are also a subset of ether carboxylates, is new. The use of the ether carboxylates in connection with alkyl polyglycosides in detergents is also unknown.
Weitere Bestandteile in Abhängigkeit vom Aggregationszustand (flüssige oder pulverförmige Formulierungen) sind weitere Tenside in kleinen Mengen, Komplexbildner, Bleichmittel, optische Aufheller, Vergrauungsinhibitoren, Korrosionsinhibitoren, Schaumregulatoren, Stabilisatoren, Enzyme, Enzymstabilisatoren, Elektrolyte, hydrotrope Substanzen, Löslichkeitsvermittler, etc.Other components depending on the state of aggregation (liquid or powder formulations) are other surfactants in small quantities, complexing agents, bleaching agents, optical brighteners, graying inhibitors, corrosion inhibitors, foam regulators, stabilizers, enzymes, enzyme stabilizers, electrolytes, hydrotropic substances, solubilizers, etc.
Erfindungsgemäß eingesetzte Alkylpolyglycoside genügen der Formel I
R-O-Zn I,
in der R für einen linearen oder verzweigten, gesättigten oder ungesättigten aliphatischen Alkylrest mit 10 bis 18 Kohlenstoffatomen oder Gemische davon und Zn für eine Polyglycosylrest mit n = 1,0 bis 3 Hexose- oder Pentoseeinheiten oder Gemische davon stehen.Alkyl polyglycosides used according to the invention satisfy formula I.
RO-Zn I,
in which R represents a linear or branched, saturated or unsaturated aliphatic alkyl radical having 10 to 18 carbon atoms or mixtures thereof and Z n represents a polyglycosyl radical with n = 1.0 to 3 hexose or pentose units or mixtures thereof.
Bevorzugt werden Alkylpolyglycoside mit Fettalkylresten mit 10 bis 16 Kohlenstoffatomen sowie einem Polyglycosylrest von n = 1,1 bis 2. Besonders bevorzugt werden Alkylpolyglucoside.Alkyl polyglycosides with fatty alkyl radicals having 10 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. Oder Dextrose wird unmittelbar mit dem gewünschten langkettigen Alkohol umgesetzt.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. Or dextrose is immediately reacted with the desired long-chain alcohol.
Die Struktur der Produkte ist in bestimmten Grenzen variierbar. Der Alkylrest R wird durch die Auswahl des langkettigen Alkohols festgelegt. Günstig aus wirtschaftlichen Gründen sind die großtechnisch zugänglichen Tensidalkohole mit 10 bis 18 C-Atomen, insbesondere native Fettalkohole aus der Hydrierung von Fettsäuren bzw. Fettsäurederivaten. Verwendbar sind auch Ziegleralkohole oder Oxoalkohole.The structure of the products can be varied within certain limits. The alkyl radical R is determined by the choice of the long-chain alcohol. Favorable for economic reasons are the industrially accessible surfactant alcohols with 10 to 18 carbon atoms, in particular native fatty alcohols from the hydrogenation of fatty acids or fatty acid derivatives. Ziegler alcohols or oxo alcohols can also be used.
Der Polyglycosylrest Zn wird einerseits durch die Auswahl des Kohlenhydrats und andererseits durch die Einstellung des mittleren Polymerisationsgrads n z. B. nach DE-OS 19 43 689 festgelegt. Im Prinzip können bekanntlich Polysaccharide, z. B. Stärke, Maltodextrine, Dextrose, Galaktose, Mannose, Xylose, etc. eingesetzt werden. Bevorzugt sind die großtechnisch verfügbaren Kohlenhydrate Stärke, Maltodextrine und besonders Dextrose. Da die wirtschaftlich interessanten Alkylpolyglycosidsynthesen nicht regio- und stereoselektiv verlaufen, sind die Alkylpolyglycoside stets Gemische von Oligomeren, die ihrerseits Gemische verschiedener isomerer Formen darstellen. Sie liegen nebeneinander mit α- und β-glycosidischen Bindungen in Pyranose- und Furanoseform vor. Auch die Verknüpfungsstellen zwischen zwei 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 z. 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. are used will. The industrially available carbohydrates starch, maltodextrins and especially dextrose are preferred. Since the economically interesting alkyl polyglycoside syntheses are not regio- and stereoselective, the alkyl polyglycosides are always mixtures of oligomers, which in turn represent mixtures of different isomeric forms. They exist side by side with α- and β-glycosidic bonds in pyranose and furanose form. The junctions between two Saccachrid residues are also different.
Erfindungsgemäß eingesetzte Alkylpolyglycoside lassen sich auch durch Abmischen von Alkylpolyglycosiden mit Alkylmonoglycosiden herstellen. Letztere kann man z. B. nach EP-A 0 092 355 mittels polarer Lösemittel, wie Aceton, aus Alkylpolyglycosiden gewinnen bzw. anreichern.Alkyl polyglycosides used according to the invention can also be prepared by mixing alkyl polyglycosides with alkyl monoglycosides. The latter can e.g. B. according to EP-A 0 092 355 using polar solvents, such as acetone, from alkyl polyglycosides.
Der Glycosidierungsgrad wird zweckmäßigerweise mittels ¹H-NMR bestimmt.The degree of glycosidation is advantageously determined by means of 1 H-NMR.
Die erfindungsgemäßen Waschmittel enthalten 5 bis 30 % Alkylpolyglykosid, vorzugsweise 7 bis 20 %.The detergents according to the invention contain 5 to 30% alkyl polyglycoside, preferably 7 to 20%.
Im Vergleich zu fast allen anderen in Waschmitteln 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 almost all other surfactants used in detergents, 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) mit > 10 000 mg/kg sowie die aquatische Toxizität LC 50 (Goldorfe) mit ca. 12 mg/l und EC 50 (Daphnien) mit 30 mg/l liegen um den Faktor 3 bis 5 günstiger als die entsprechenden Werte der heute wichtigsten Tenside. Ähnliches gilt für die Haut- und Schleimhautverträglichkeit.The acute oral toxicity LD 50 (rat) with> 10,000 mg / kg as well as the aquatic toxicity LC 50 (gold orfe) with approx. 12 mg / l and EC 50 (daphnia) with 30 mg / l are by a factor of 3 to 5 cheaper than the corresponding values of today's most important surfactants. The same applies to skin and mucous membrane compatibility.
Fettalkoholethercarboxylate sind Verbindungen entweder der Formel II oder III,
(R'-O(CH₂-CH₂-O)xCH₂COO)mMm+ II,
in der R' ein linearer oder verzweigter, gesättigter oder ungesättigter Alkylrest mit 8 bis 22 vorzugsweise 10 bis 18 Kohlenstoffatomen, x 1 bis 40, vorzugsweise 3 bis 30, m 1 oder 2 und M Wasserstoff, Alkali, Erdalkali, Ammonium oder Alkanolammonium ist oder
([R''-O(CH₂-CH₂-O)y]₂CHCOO)zNz+ III
in der R'' ein linearer oder verzweigter, gesättigter oder ungesättigter Alkylrest mit 8 bis 22 vorzugsweise 10 bis 18 Kohlenstoffatomen, y 1 bis 4 vorzugsweise 3 bis 30, z 1 oder 2 und N H, Alkali, Erdalkali, Ammonium, Alkanolammonium bedeuten.Fatty alcohol ether carboxylates are compounds of either formula II or III,
(R'-O (CH₂-CH₂-O) x CH₂COO) m M m + II,
in which R 'is a linear or branched, saturated or unsaturated alkyl radical having 8 to 22 preferably 10 to 18 carbon atoms, x 1 to 40, preferably 3 to 30, m 1 or 2 and M is hydrogen, alkali, alkaline earth metal, ammonium or alkanolammonium or
([R '' - O (CH₂-CH₂-O) y ] ₂CHCOO) z N z + III
in which R '' is a linear or branched, saturated or unsaturated alkyl radical having 8 to 22, preferably 10 to 18 carbon atoms, y 1 to 4, preferably 3 to 30, z 1 or 2 and NH, alkali, alkaline earth metal, ammonium, alkanolammonium.
Verbindungen entsprechend Formel II nennt man carboxymethylierte Oxethylate, die entsprechend Formel III Bisalkanolethoxylatacetate.Compounds corresponding to formula II are called carboxymethylated oxethylates, those corresponding to formula III are bisalkanol ethoxylate acetates.
Die carboxymethylierten Oxethylate kann man nach DE-OS 24 18 444 bzw. EP-A 0 106 018 durch Umsetzung von Oxethylaten der Formel R'-O(CH₂-CH₂-O)nH mit Chloressigsäure oder einem Salz der Chloressigsäure in Gegenwart von Alkalihydroxid oder anderen Basen herstellen. Aber auch andere Herstellungsverfahren z. B. mittels katalytischer Oxydation entsprechend EP-A 0 018 681 bzw. 0 039 111 sind geeignet.The carboxymethylated oxethylates can be according to DE-OS 24 18 444 or EP-A 0 106 018 by reacting oxethylates of the formula R'-O (CH₂-CH₂-O) n H with chloroacetic acid or a salt of chloroacetic acid in the presence of alkali metal hydroxide or other bases. But other manufacturing processes such. B. by means of catalytic oxidation according to EP-A 0 018 681 or 0 039 111 are suitable.
Bisalkanolethoxylatacetate lassen sich z. B. nach DE-OS 39 02 663 aus Oxethylaten und Dichloressigsäure herstellen.Bisalkanol ethoxylate acetates can be e.g. B. according to DE-OS 39 02 663 from oxyethylates and dichloroacetic acid.
Entsprechende Alkohole zur Herstellung der Fettalkoholethercarboxylate sind vorzugsweise Fettalkohole oder Ziegleralkohole, in Ausnahmefällen auch Oxoalkohole. Die sich an die Oxethylierung anschließende Carboxymethylierung kann bei entsprechender Fahrweise vollständig sein, so daß die Fettalkoholethercarboxylate rein anionische Tenside sind. Alternativ bei nicht vollständiger Carboxymethylierung enthalten die Produkte gewisse Mengen nicht-umgesetztes Oxethylat. Mit den Formeln II und III ist daher meist ein Gemisch mit unterschiedlichen Mengen an nicht umgesetzten Oxethylaten gemeint. Demgemäß läßt sich ein Umsetzungsgrad definieren. Bevorzugt wird ein Umsetzungsgrad zwischen 70 und 100 %.Corresponding alcohols for the production of the fatty alcohol ether carboxylates are preferably fatty alcohols or Ziegler alcohols, in exceptional cases also oxo alcohols. The carboxymethylation following the oxethylation can be carried out with the appropriate driving style be complete so that the fatty alcohol ether carboxylates are purely anionic surfactants. Alternatively, if the carboxymethylation is incomplete, the products contain certain amounts of unreacted oxyethylate. The formulas II and III therefore usually mean a mixture with different amounts of unreacted oxethylates. Accordingly, a degree of implementation can be defined. A degree of conversion between 70 and 100% is preferred.
Auch die Fettalkoholethercarboxylate sind sehr umweltverträgliche Tenside. So wurden mittels Kläranlagen-Simulationsmodell/DOC-Analyse biologische Abbauraten oberhalb 90 % festgestellt. Die akute orale Toxizität LD 50 (Ratte) sowie die aquatische Toxizität LC 50 (Goldorfe) sind etwa ebenso günstig wie die der Alkylpolyglucoside. Ähnliches gilt auch für die Haut- und Schleimhautverträglichkeit.The fatty alcohol ether carboxylates are also very environmentally friendly surfactants. Biodegradation rates above 90% were determined using a sewage plant simulation model / DOC analysis. The acute oral toxicity LD 50 (rat) and the aquatic toxicity LC 50 (gold orfe) are about as favorable as that of the alkyl polyglucosides. The same applies to skin and mucous membrane compatibility.
Die erfindungsgemäßen Waschmittel enthalten 5 bis 30 % Fettalkoholethercarboxylate, die auch Gemische sein können. Bevorzugt wird ein Gehalt von 7 bis 20 % Fettalkoholethercarboxylat.The detergents according to the invention contain 5 to 30% fatty alcohol ether carboxylates, which can also be mixtures. A content of 7 to 20% fatty alcohol ether carboxylate is preferred.
Erfindungsgemäße fettsaure Salze bzw. ihre Säuren entsprechen der Formel IV
R'''COOP IV,
in der R''' ein gesättigter oder ungesättigter Alkylrest mit 8 bis 22 C-Atomen und P Wasserstoff, Alkali, Ammonium oder Alkanolammonium bedeuten.Fatty acid salts or their acids according to the invention correspond to formula IV
R '''COOP IV,
in which R '''is a saturated or unsaturated alkyl radical having 8 to 22 carbon atoms and P is hydrogen, alkali, ammonium or alkanolammonium.
Die erfindungsgemäßen Waschmittel enthalten 5 bis 30 %, vorzugsweise 7 bis 20 % Seife, die meist ein Gemisch von verschiedenen Komponenten sein wird.The detergents according to the invention contain 5 to 30%, preferably 7 to 20% soap, which will usually be a mixture of different components.
Erfindungsgemäß einzusetzen sind bis zu 3 % weitere anionische, nichtionische, zwitterionische und ampholytische Tenside. Insbesondere sind dies Alkansulfonate, Olefinsulfonate, Alkylbenzolsulfonate, α-Sulfofettsäureester, Fettalkoholsulfate, Fettalkoholethersulfate, Sulfobernsteinsäureester, Alkanoloxethylate, Fettsäurealkanolamide, Amminoxide, Betaine, Sulfobetaine ,etc.Up to 3% of further anionic, nonionic, zwitterionic and ampholytic surfactants are to be used according to the invention. In particular, these are alkanesulfonates, olefinsulfonates, alkylbenzenesulfonates, α-sulfo fatty acid esters, fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic acid esters, alkanoloxethylates, fatty acid alkanolamides, amine oxides, betaines, sulfobetaines, etc.
Als nichttensidische Bestandteile sind in erster Linie Builder zu nennen. Erfindungsgemäß verwendet werden wasserlösliche Builder wie unterschiedliche Polyphosphate, Phosphonate, Carbonate, Polycarboxylate, Citronate, Polyacetate wie NTA und DETA, etc. bzw. deren Gemische. Diese Verbindungen werden gewöhnlich als Alkalisalze, vorzugsweise als Natriumsalze eingesetzt. Obwohl nicht komplexierend ist auch Natriumsulfat hier zu nennen. Ebenfalls erfindungsgemäß ist die Verwendung von wasserunlöslichen Buildern, wie Alumosilikaten geeigneter Teilchengröße (vgl. EP-A 0 075 994). Die Konzentration der Builder im Waschmittel beträgt 0 bis 70 %, vorzugsweise 0 bis 50 %.First of all, builders should be mentioned as non-surfactant components. According to the invention, water-soluble builders such as different polyphosphates, phosphonates, carbonates, polycarboxylates, citronates, polyacetates such as NTA and DETA, etc. or mixtures thereof are used. These compounds are usually used as alkali salts, preferably as sodium salts. Although not complexing, sodium sulfate should also be mentioned here. The use of water-insoluble builders, such as aluminosilicates of suitable particle size, is also according to the invention (cf. EP-A 0 075 994). The concentration of the builders in the detergent is 0 to 70%, preferably 0 to 50%.
Erfindungsgemäß eingesetzt werden ferner Bleichmittel wie Natriumperborat gegebenenfalls kombiniert mit Bleichaktivatoren wie Tetraacetylethylendiamin etc. oder Percarbonat; in Frage kommen natürlich auch andere Bleichmittel (vgl. K. Engel, Tenside Surfactants 25, S. 21 (1988). Die Konzentration der Bleichmittel beträgt 0 bis 40 %, vorzugsweise 0- 30 %.Bleaching agents such as sodium perborate, optionally combined with bleach activators such as tetraacetylethylene diamine etc. or percarbonate, are also used according to the invention; Other bleaching agents are of course also possible (cf. K. Engel, Tenside Surfactants 25, p. 21 (1988). The concentration of the bleaching agents is 0 to 40%, preferably 0 to 30%.
Erfindungsgemäß einzusetzen sind ggf. Stellmittel wie niedermolekulare 1- oder 2-wertige Alkohole, Alkylether von mehrwertigen Alkoholen, Hydrotropica wie Alkylbenzolsulfonate mit 1 bis 3C-Atomen im Alkylrest, Alkanolamine oder Harnstoff, Enzyme wie insbesondere Proteasen sowie Enzymstabilisatoren, Korrosionsinhibitoren wie Alkalisilikate, optische Aufheller insbesondere auf und Stilben- und Pyrazolinbasis, Schaumregulatoren, Vergrauungsinhibitoren wie z. B. Carboxymethylcellulose, Parfümöle, Farbstoffe und weitere für flüssige bzw. pulverförmige Waschmittel übliche Inhaltsstoffe.Adjusting agents such as low molecular weight mono- or dihydric alcohols, alkyl ethers of polyhydric alcohols, hydrotropics such as alkylbenzenesulfonates with 1 to 3C atoms in the alkyl radical, alkanolamines or urea, enzymes such as in particular proteases and enzyme stabilizers, corrosion inhibitors such as alkali silicates, optical brighteners may be used according to the invention especially based on and stilbene and pyrazoline, foam regulators, graying inhibitors such. B. carboxymethyl cellulose, perfume oils, dyes and other ingredients customary for liquid or powder detergents.
Die Gesamteinsatzkonzentration in den erfindungsgemäßen Maschinen-Waschmitteln beträgt für den tensidischen Anteil 0,3 - 20 g/l. Bevorzugt werden 0,5 - 10 g/l.The total use concentration in the machine detergents according to the invention is 0.3-20 g / l for the surfactant fraction. 0.5-10 g / l are preferred.
Durch die nachfolgenden Beispiele wird die Erfindung erläutert. Die in Tab. 1 und 2 aufgeführten Flüssigwaschmittelformulierungen enthalten außer den genannten, erfindungsgemäß verwendeten tensidischen Bestandteilen jeweils 6 % Triethanolamin, 12 % Ethanol, 6 % 1,2-Propylenglykol und Wasser ad 100 %.The invention is illustrated by the following examples. The liquid detergent formulations listed in Tables 1 and 2 each contain 6% triethanolamine, 12% ethanol, 6% 1,2-propylene glycol and water ad 100% in addition to the surfactant components mentioned according to the invention.
Das Schaumvermögen wurde entsprechend DIN 53 902, Teil 1, bestimmt. Die Konzentration an waschaktiver Substanz betrug jeweils 1 g/l, registriert wurde das Schaumvolumen nach 5 Minuten. Das Waschvermögen wurde sowohl in der Linitestlaborwaschmaschine (d. h. bei mäßiger mechanischer Belastung) als auch in einer normalen Haushaltsmaschine gemessen. Als Modellgewebe dienten 11 x 18 cm große Lappen aus WFK-Testgewebe mit Hautfett-Pigmentanschmutzung: Polyester (PE), Mischgewebe (MG) und Baumwolle (BW), als Wasser Trinkwasser (13 °dH). Polyester wurde bei 30 °C, Mischgewebe und Baumwolle bei 60 °C gewaschen. Bei der Linitestlaborwaschmaschine lag die Wirkstoffkonzentration bei 1 g/l, bei der Haushaltswaschmaschine bei 5 g/l, der pH jeweils bei etwa 7, das Flottenverhältnis bei etwa 1 : 60 bzw. 1 : 4, die Waschzeiten in beiden Fällen betrugen etwa 30 Minuten.The foaming power was determined in accordance with DIN 53 902, Part 1. The concentration of detergent substance was 1 g / l, the foam volume was registered after 5 minutes. The washability was measured both in the Linitest laboratory washing machine (i.e. with moderate mechanical stress) and in a normal household machine. 11 x 18 cm rags made of WFK test fabric with skin fat pigment soiling served as model fabric: polyester (PE), mixed fabric (MG) and cotton (BW), and drinking water (13 ° dH) as water. Polyester was washed at 30 ° C, blended fabrics and cotton at 60 ° C. In the Linitest laboratory washing machine, the active ingredient concentration was 1 g / l, in the household washing machine 5 g / l, the pH in each case about 7, the liquor ratio in about 1: 60 and 1: 4, the washing times in both cases were about 30 minutes .
Bei der Linitestmaschine wurde der Waschvorgang nach jeweiligem Spülen 2 mal wiederholt. Die Waschwerte nach dem Trocknen der Gewebe wurden - wie üblich - spektralphotometrisch relativ zu einem Weißstandard (Datacolor, 560 nm) gemessen.In the Linitest machine, the washing process was repeated twice after each rinse. The washing values after drying the fabrics were - as usual - measured spectrophotometrically relative to a white standard (Datacolor, 560 nm).
Tab. 1 und 2 zeigen den Vergleich der Eigenschaften der erfindungsgemäßen Waschmittel als Flüssigformulierung mit denen anderer bekannter Kombinationen sowie eines flüssigen Markenwaschmittels, bei dem man eine Rezepturoptimierung voraussetzen kann.
Klarpunkt und Viskosität entsprechen völlig dem für flüssige Waschmittel marktüblichen Standard. Das Schäumvermögen der erfindungsgemäßen Formulierungen Zeigt - ohne weitere regulierende Additive - sehr günstige Werte. Insbesondere gilt dies für das Waschvermögen. Die erfindungsgemäßen Formulierungen verhalten sich hier weit effektiver als andere bekannte Kombinationen, deren tensidischer Anteil ebenfalls aus anionischem Tensid, Alkylpolyglucosid und Seife besteht (Vergleichsbeispiele 1 und 2).The clear point and viscosity fully correspond to the standard customary for liquid detergents. The foaming power of the formulations according to the invention shows - without further regulating additives - very favorable values. This applies in particular to the washing ability. The formulations according to the invention behave far more effectively here than other known combinations, the surfactant content of which also consists of anionic surfactant, alkyl polyglucoside and soap (comparative examples 1 and 2).
Tab. 3 zeigt den Vergleich der Eigenschaften von erfindungsgemäßen pulverigen Waschmittelformulierungen mit denen einer bekannten Kombination bzw. eines Markenwaschmittels. Schüttdichte, Schüttwinkel und Schäumvermögen wurden nach DIN-Methoden bestimmt. Eine Abschätzung der Löslichkeit gelingt mittels zeitlicher Auftragung der elektrischen Leitfähigkeit, wobei als Meßwert 80 % einer mittleren Endleitfähigkeit beim Auflösen von 1 g Pulver in 800 ml Trinkwasser (13 °dH) genommen wurde. Die Meßwerte beinhalten einen Fehler von ± 5 %.
Abgesehen von einer wesentlich höheren Schüttdichte, typisch für agglomerierte Waschpulver im Vergleich zu dem sprühgetrockneten Markenprodukt (Beispiel 20) verhalten sich die erfindungsgemäßen Pulver sehr ähnlich und in ihren Waschwerten besser. Deutlich sind auch hier wieder die im Gegensatz zu bekannten Formulierungen Beispiel 15 mit anionischen Tensiden stark verbesserten Wascheffekte.Apart from a much higher bulk density, typical of agglomerated washing powders compared to the spray-dried brand product (example 20), the powders according to the invention behave very similarly and better in their washing values. Again, the washing effects, which are greatly improved in contrast to known formulations of Example 15 with anionic surfactants, are clear.
Claims (8)
daß der tensidische Anteil aus
5 bis 30 % Alkylpolyglycosid,
5 bis 30 % Alkanolethercarboxylat,
5 bis 30 % Seife und
0 bis 3 % andere Tenside
besteht.Low-foaming, liquid or powdered machine detergent characterized in that
that the surfactant portion
5 to 30% alkyl polyglycoside,
5 to 30% alkanol ether carboxylate,
5 to 30% soap and
0 to 3% other surfactants
consists.
dadurch gekennzeichnet,
daß das Alkylpolyglycosid der Formel I
R-O-Zn I
entspricht, wobei R ein linearer oder verzweigter, gesättigter oder ungesättigter Alkylrest mit 10 bis 18 Kohlenstoffatomen oder Gemische davon und Zn ein Polyglycosylradikal mit n = 1 bis 3 Hexose- oder Pentoseeinheiten oder Mischungen davon bedeutet.Low-foaming, liquid or powdered machine detergent according to claim 1,
characterized,
that the alkyl polyglycoside of formula I
RON n I
corresponds, where R is a linear or branched, saturated or unsaturated alkyl radical having 10 to 18 carbon atoms or mixtures thereof and Z n is a polyglycosyl radical with n = 1 to 3 hexose or pentose units or mixtures thereof.
dadurch gekennzeichnet,
daß das Alkylpolyglycosid ein Fettalkoholpolyglucosid mit n = 1.1 bis 2 ist.Low-foaming, liquid or powdered machine detergent according to claims 1 and 2,
characterized,
that the alkyl polyglycoside is a fatty alcohol polyglucoside with n = 1.1 to 2.
dadurch gekennzeichnet,
daß das Alkanolethercarboxylat der Formel II oder III
[R'-O(CH₂-CH₂-O)xCH₂COO]mMm+ II
([R''-O(CH₂-CH₂-O)y]₂CHCOO)zNz+ III
entspricht, in der R'und R'' gesättigte oder ungesättigte, linear oder verzweigte Alkylreste mit 8 bis 22 Kohlenstoffatomen, x und y 1 bis 40, m und z 1 oder 2 sowie M und N Wasserstoff, Alkali, Erdalkali, Ammonium oder Alkanolammonium bedeuten.Low-foaming, liquid or powdered machine detergent according to claims 1 to 3,
characterized,
that the alkanol ether carboxylate of the formula II or III
[R'-O (CH₂-CH₂-O) x CH₂COO] m M m + II
([R '' - O (CH₂-CH₂-O) y ] ₂CHCOO) z N z + III
corresponds in which R 'and R''are saturated or unsaturated, linear or branched alkyl radicals having 8 to 22 carbon atoms, x and y 1 to 40, m and z 1 or 2 and M and N being hydrogen, alkali, alkaline earth metal, ammonium or alkanolammonium mean.
Maschinen-Waschmittel nach Anspruch 4,
dadurch gekennzeichnet,
daß das Alkanolethercarboxylat ein carboxymethyliertes Fettalkoholoxethylat entsprechend Formel II ist, in der R'10 bis 18 Kohlenstoffatome, x = 3 - 20, m = 1 und M Natrium, Kalium, Ammonium oder Alkanolammonium bedeuten.Low-foaming, liquid or powdery
Machine detergent according to claim 4,
characterized,
that the alkanol ether carboxylate is a carboxymethylated fatty alcohol oxyethylate corresponding to formula II, in which R'10 to 18 carbon atoms, x = 3 - 20, m = 1 and M mean sodium, potassium, ammonium or alkanolammonium.
dadurch gekennzeichnet,
daß die Seife der Formel IV
R'''COOP IV
entspricht, in der R''' ein gesättigter und/oder ungesättigter Alkylrest mit 8 bis 22 Kohlenstoffatomen und P Wasserstoff, Alkali, Ammonium oder Alkanolammonium bedeuten.Low-foaming, liquid or powdered machine detergent according to claims 1 to 5,
characterized,
that the soap of formula IV
R '''COOP IV
in which R '''is a saturated and / or unsaturated alkyl radical having 8 to 22 carbon atoms and P is hydrogen, alkali, ammonium or alkanolammonium.
Waschmittel nach den Ansprüchen 1 bis 6,
dadurch gekennzeichnet,
daß als nichttensidische Bestandteile Builder, Bleichmittel, Stellmittel, Enzyme, Stabilisatoren, Vergrauungsinhibitoren, Korrosionsinhibitoren, optische Aufheller, Farbstoffe, Parfümöle und ggf. weitere Additive enthalten sind.Low-foaming, liquid or powdered machine
Detergent according to claims 1 to 6,
characterized,
that builders, bleaching agents, adjusting agents, enzymes, stabilizers, graying inhibitors, corrosion inhibitors, optical brighteners, dyes, perfume oils and possibly other additives are contained as non-surfactant constituents.
mittel nach den Ansprüchen 1 bis 7,
dadurch gekennzeichnet,
daß die Konzentration des tensidischen Anteils 0,3 - 2O g/l beträgt.Low-foaming, liquid or powdered machine wash
agent according to claims 1 to 7,
characterized,
that the concentration of the surfactant portion is 0.3-2O g / l.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4016819 | 1990-05-25 | ||
| DE4016819A DE4016819A1 (en) | 1990-05-25 | 1990-05-25 | Low foam liq. or powder machine washing compsn. with surfactant - comprising alkyl-poly:glycoside, alkanol ether carboxylate and soap |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0457965A1 true EP0457965A1 (en) | 1991-11-27 |
| EP0457965B1 EP0457965B1 (en) | 1995-06-21 |
| EP0457965B2 EP0457965B2 (en) | 2002-04-24 |
Family
ID=6407153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90124032A Expired - Lifetime EP0457965B2 (en) | 1990-05-25 | 1990-12-13 | Low foaming washing-machine detergents |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0457965B2 (en) |
| JP (1) | JPH04227998A (en) |
| AT (1) | ATE124083T1 (en) |
| CA (1) | CA2043147A1 (en) |
| DE (2) | DE4016819A1 (en) |
| DK (1) | DK0457965T3 (en) |
| ES (1) | ES2075873T3 (en) |
| NO (1) | NO178233C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997042299A1 (en) * | 1996-05-08 | 1997-11-13 | Henkel Corporation | Alkyl polyglycoside ether carboxylates |
| WO1999024538A1 (en) * | 1997-11-10 | 1999-05-20 | Henkel Corporation | Alkyl polyglycoside ether carboxylates |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4331297A1 (en) * | 1993-09-15 | 1995-03-16 | Henkel Kgaa | Bar soaps |
| US6350727B1 (en) * | 2000-01-28 | 2002-02-26 | Amway Corporation | Non-streaking no-wipe cleaning compositions with improved cleaning capability |
| JP2004035808A (en) * | 2002-07-05 | 2004-02-05 | Nissan Soap Co Ltd | Liquid detergent composition |
| JP4247086B2 (en) * | 2003-10-06 | 2009-04-02 | 花王株式会社 | Cleaning composition |
| EP3266859A1 (en) * | 2016-07-05 | 2018-01-10 | Basf Se | Composition suitable as degreasing agent for removing greasy and/or oil type deposits |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0070075A2 (en) * | 1981-07-13 | 1983-01-19 | THE PROCTER & GAMBLE COMPANY | Foaming dishwashing liquid compositions |
| US4483787A (en) * | 1983-12-28 | 1984-11-20 | The Procter & Gamble Company | Concentrated aqueous detergent compositions |
| DE3702286A1 (en) * | 1986-01-30 | 1987-08-06 | Colgate Palmolive Co | LIQUID DETERGENT COMPOSITION FOR CLEANING AND SOFTENING OF TEXTILES AT THE SAME TIME |
| GB2206602A (en) * | 1987-07-09 | 1989-01-11 | Sandoz Ltd | Liquid laundry detergent compositions |
-
1990
- 1990-05-25 DE DE4016819A patent/DE4016819A1/en not_active Withdrawn
- 1990-12-13 ES ES90124032T patent/ES2075873T3/en not_active Expired - Lifetime
- 1990-12-13 EP EP90124032A patent/EP0457965B2/en not_active Expired - Lifetime
- 1990-12-13 AT AT90124032T patent/ATE124083T1/en not_active IP Right Cessation
- 1990-12-13 DE DE59009297T patent/DE59009297D1/en not_active Expired - Fee Related
- 1990-12-13 DK DK90124032.5T patent/DK0457965T3/en active
-
1991
- 1991-05-23 NO NO911993A patent/NO178233C/en unknown
- 1991-05-23 CA CA002043147A patent/CA2043147A1/en not_active Abandoned
- 1991-05-24 JP JP3119854A patent/JPH04227998A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0070075A2 (en) * | 1981-07-13 | 1983-01-19 | THE PROCTER & GAMBLE COMPANY | Foaming dishwashing liquid compositions |
| US4483787A (en) * | 1983-12-28 | 1984-11-20 | The Procter & Gamble Company | Concentrated aqueous detergent compositions |
| DE3702286A1 (en) * | 1986-01-30 | 1987-08-06 | Colgate Palmolive Co | LIQUID DETERGENT COMPOSITION FOR CLEANING AND SOFTENING OF TEXTILES AT THE SAME TIME |
| GB2206602A (en) * | 1987-07-09 | 1989-01-11 | Sandoz Ltd | Liquid laundry detergent compositions |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997042299A1 (en) * | 1996-05-08 | 1997-11-13 | Henkel Corporation | Alkyl polyglycoside ether carboxylates |
| US5908928A (en) * | 1996-05-08 | 1999-06-01 | Henkel Corporation | Alkyl polyglycoside ether carboxylates |
| WO1999024538A1 (en) * | 1997-11-10 | 1999-05-20 | Henkel Corporation | Alkyl polyglycoside ether carboxylates |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE124083T1 (en) | 1995-07-15 |
| EP0457965B2 (en) | 2002-04-24 |
| DE59009297D1 (en) | 1995-07-27 |
| EP0457965B1 (en) | 1995-06-21 |
| NO178233B (en) | 1995-11-06 |
| NO911993L (en) | 1991-11-26 |
| JPH04227998A (en) | 1992-08-18 |
| CA2043147A1 (en) | 1991-11-26 |
| NO178233C (en) | 1996-02-14 |
| DE4016819A1 (en) | 1991-12-19 |
| DK0457965T3 (en) | 1995-11-06 |
| NO911993D0 (en) | 1991-05-23 |
| ES2075873T3 (en) | 1995-10-16 |
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