EP0474915A1 - Detergent - Google Patents

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Publication number
EP0474915A1
EP0474915A1 EP90124033A EP90124033A EP0474915A1 EP 0474915 A1 EP0474915 A1 EP 0474915A1 EP 90124033 A EP90124033 A EP 90124033A EP 90124033 A EP90124033 A EP 90124033A EP 0474915 A1 EP0474915 A1 EP 0474915A1
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EP
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Prior art keywords
liquid
foaming
low
mixtures
carbon atoms
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EP90124033A
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German (de)
French (fr)
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EP0474915B2 (en
EP0474915B1 (en
Inventor
Dieter Dr. Balzer
Rudolf Beck
Willi Gasber
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Sasol Germany GmbH
Wintershall Dea International AG
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Huels AG
Chemische Werke Huels AG
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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
    • C11D3/0026—Low foaming or foam regulating 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
    • 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
    • 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
    • C11D10/045—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
    • 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
    • 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
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to 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 and which, in addition to very good washing results, are outstandingly biodegradable.
  • This object was achieved by a combination of surfactants consisting essentially of alkyl polyglycosides, fatty alcohol oxyethylates and soap.
  • alkyl polyglycoside in combination with fatty alcohol oxyethylates and also with anionic surfactants is known per se.
  • 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, 075 995, 075 996, 094 118 and 317 614 describe the use of alkyl polyglycoside in combination with anionic and / or nonionic surfactants in detergents.
  • the alkyl polyglycoside used is a mixture of at least 2 components which, on the one hand, differ greatly in the chain length of their alkyl groups and, on the other hand, are used in different concentrations.
  • the main components are alkyl polyglycosides, the alkyl groups of which contain 12 to 18 carbon atoms; Secondary components are those whose alkyl group contains 7 to 11 carbon atoms. According to the invention in the above.
  • the surfactant content is a short-chain alkyl polyglycoside content of 1 to 10% and a long-chain content of 2 to 20%.
  • fatty alcohol oxyethylates and other surfactants in small amounts, complexing agents, bleaching agents, optical brighteners, graying inhibitors, corrosion inhibitors, foam regulators, stabilizers, enzymes, enzyme stabilizers, electrolytes, hydrotropic substances, solubilizers, etc.
  • the alkyl polyglycosides used according to the invention can be produced by known processes based on renewable raw materials.
  • 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.
  • 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 or R ' is determined by the choice of the long-chain alcohol.
  • Favorable for economic reasons are the industrially accessible alcohols with 7 to 18 carbon atoms, especially native alcohols from the hydrogenation of carboxylic acids or carboxylic acid derivatives.
  • Ziegler alcohols or oxo alcohols can also be used.
  • the polyglycosyl radicals Z n and Z ' m are determined on the one hand by the selection of the carbohydrate and on the other hand by setting the average degree of polymerization n or m. B. according to DE-OS 19 43 689.
  • polysaccharides e.g. B. starch, maltodextrins, dextrose, galactose, mannose, xylose, etc.
  • the industrially available carbohydrates starch, maltodextrins and especially dextrose are preferred.
  • alkyl polyglycosides are always mixtures of oligomers, which in turn represent mixtures of different isomeric forms. They are present side by side with a- 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 means of 1 H-NMR.
  • the detergents according to the invention contain 1 to 10% short-chain alkyl polyglycoside, preferably 2 to 8%, and 2 to 20% long-chain alkyl polyglycoside, preferably 3 to 15%, the ratio of short-chain to long-chain fraction 1:10 to 2: 1, preferably 2: Is 10 to 1: 1.
  • 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 figure can be seen against the background that with this test method (total degradation) a degree of degradation of 70% 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 / I and EC 50 (daphnia) with 30 mg / I 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 oxyethylates are compounds of the formula III in which R "is a linear or branched, saturated or unsaturated alkyl radical having 8 to 22, preferably 10 to 20 carbon atoms and x 2 to 20, preferably 3 to 15.
  • the compounds are generally formed by the addition of ethylene oxide to longer-chain alcohols prepared in the presence of basic or acidic catalysts.
  • ethylene oxide for economical reasons, commercially available alcohols with 8 to 22 carbon atoms from the hydrogenation of carboxylic acids or carboxylic acid derivatives are favorable.
  • Ziegler alcohols or oxo alcohols can also be used.
  • the alcohol oxyethylates are known to be readily biodegradable; Their data are also favorable with regard to aquatoxicity, skin and mucous membrane compatibility.
  • the detergents according to the invention contain 3 to 30% fatty alcohol oxyethylates, which can also be mixtures. A content of 5 to 20% is preferred.
  • Fatty acid salts or their acids according to the invention correspond to formula IV in which R '"is a saturated or unsaturated alkyl radical having 8 to 22 carbon atoms and P being 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.
  • these are alkane sulfonates, olefin sulfonates, alkylbenzenesulfonates, ⁇ -sulfofatty 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 EDTA, 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 in particular based on stilbene and pyrazoline, foam regulators, graying inhibitors such as, for. B. carboxymethyl cellulose, perfume oils, dyes and other ingredients customary for liquid or powder detergents.
  • 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 in particular based on stil
  • 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 Tab. 1 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 powders listed in Table 2 contain, in addition to the surfactant constituents mentioned according to the invention, each 10% sodium perborate, 4.5% Na, Mg silicate, 14% Na 2 SO 4 , 24% Versalith P, 3% Sokalan CP 5, 8 % Na 3 CO 3 , 3.5% TAED and 0.4% phosphonate.
  • the foaming power was determined in accordance with DIN 53 902, Part 1.
  • the concentration of detergent substance was 1 g / I each, the foam volume was registered after 5 minutes.
  • the Washing capacity was measured both in the Linitest laboratory washing machine (ie with moderate mechanical stress) and in a normal household machine. Here, too, the foam development was checked, which corresponded approximately to the DIN values.
  • Tab. 1 shows the comparison of the properties of the detergents according to the invention as a liquid formulation with those of other known combinations and with a liquid branded detergent, in which one can assume that the formulation has been optimized.
  • the clear point and viscosity correspond approximately to the standard customary for liquid detergents.
  • the foaming power of the formulations according to the invention shows favorable values without further regulating additives. This applies in particular to the washing ability.
  • the detergents according to the invention behave far superior in their washing activity.
  • Tab. 2 shows the comparison of the properties of powdery detergent formulations according to the invention with those of a known combination or with a branded detergent. Bulk density 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 3 g of powder is dissolved in 800 ml of drinking water (13 ° dH).
  • the measured values contain an error of ⁇ 5%.
  • the powders according to the invention behave very similarly and have a much better washing value.
  • washing capacity which is significantly increased when using alkyl polyglycoside, particularly in the case of mixed fabrics, is further improved by the formulation according to the invention.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

A low-foam, liquid or powdered machine detergent containing 3 to 30% of alkyl polyglycoside 3 to 30% of fatty alcohol ethoxylate 5 to 30% of soap and 0 to 5% of other surfactants characterised in that the alkyl polyglycoside is a mixture of at least 2 components of the formulae I and II <IMAGE> in which R is a linear or branched, saturated or unsaturated alkyl radical with 8 to 11 carbon atoms or mixtures thereof, Zn is a polyglycosyl radical with n = 1 to 3 hexose or pentose units or mixtures thereof, R' is a linear or branched, saturated or unsaturated alkyl radical with 12 to 18 carbon atoms or mixtures thereof, Z'm is a polyglycosyl radical with m = 1 to 3 hexose or pentose units or mixtures thereof.

Description

Die vorliegende Erfindung betrifft flüssige oder pulverförmige Zubereitungen zum Waschen von Textilien, deren Tenside weitestgehend aus nachwachsenden Rohstoffen hergestellt werden.The present invention relates to 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 biologische Abbaubarkeit und Ökotoxizität dieser Tenside häufig 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 and ecotoxicity of these surfactants often do 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 und die neben sehr guten Waschergebnissen hervorragend biologisch abbaubar sind.The object of the invention was therefore to find a surfactant combination for low-foaming detergents which are largely made from renewable raw materials and which, in addition to very good washing results, are outstandingly biodegradable.

Diese Aufgabe wurde gelöst durch eine Tensidkombination, die im wesentlichen aus Alkylpolyglycosiden, Fettalkoholoxethylaten und Seife besteht.This object was achieved by a combination of surfactants consisting essentially of alkyl polyglycosides, fatty alcohol oxyethylates and soap.

Gegenstand der Erfindung ist daher ein schwachschäumendes, flüssiges oder pulverförmiges Maschinen-Waschmittel enthaltend

  • 3 bis 30 % Alkylpolyglykosid
  • 3 bis 30 % Fettalkoholoxethylat
  • 5 bis 30 % Seife und
  • 0 bis 5 % andere Tenside

welches dadurch gekennzeichnet ist, daß das Alkylpolyglycosid eine Mischung aus 2 Komponenten der Formeln 1 bzw. 11
Figure imgb0001
Figure imgb0002
enthält, in denen R ein linearer oder verzweigter, gesättigter oder ungesättigter Alkylrest mit 8 bis 11 Kohlenstoffatomen oder Gemische davon, Zn ein Polyglycosyl radikal mit n = 1 bis 3 Hexose- oder Pentoseeinheiten oder Mischungen davon, R' ein linearer oder verzweigter, gesättigter oder ungesättigter Alkylrest mit 12 bis 18 Kohlenstoffatomen oder Gemische davon, Z'm ein Polyglycosylradikal mit m = 1 bis 3 Hexose- oder Pentoseeinheiten oder Gemische davon bedeuten.The invention therefore relates to a low-foaming, liquid or powdered machine detergent
  • 3 to 30% alkyl polyglycoside
  • 3 to 30% fatty alcohol oxyethylate
  • 5 to 30% soap and
  • 0 to 5% other surfactants

which is characterized in that the alkyl polyglycoside is a mixture of 2 components of the formulas 1 and 11
Figure imgb0001
Figure imgb0002
 contains in which R is a linear or branched, saturated or unsaturated alkyl radical having 8 to 11 carbon atoms or mixtures thereof, Z n is a polyglycosyl radical with n = 1 to 3 hexose or pentose units or mixtures thereof, R 'is a linear or branched, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms or mixtures thereof, Z ' m is a polyglycosyl radical with m = 1 to 3 hexose or pentose units or mixtures thereof.

Die Verwendung von einem Alkylpolyglycosid in Kombination mit Fettalkoholoxethylaten und auch mit anionischen Tensiden ist an sich bekannt. So erwähnt bereits die DE-OS 593 422 die wascheffektverstärkende Wirkung von Alkylglycosid bei Seifen. Spätere Schriften wie EP-A 0 075 994, 075 995, 075 996, 094 118 und 317 614 beschreiben den Einsatz von Alkylpolyglycosid in Kombination mit anionischen und/oder nichtionischen Tensiden in Waschmitteln.The use of an alkyl polyglycoside in combination with fatty alcohol oxyethylates and also with anionic surfactants is known per se. 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, 075 995, 075 996, 094 118 and 317 614 describe the use of alkyl polyglycoside in combination with anionic and / or nonionic surfactants in detergents.

Überraschend wurde nun aber festgestellt, daß die erfindungsgemäße Formulierung mit 2 unterschiedlichen Alkylpolyglycosiden hervorragende Waschergebenisse liefert.Surprisingly, it has now been found that the formulation according to the invention with 2 different alkyl polyglycosides delivers excellent washing results.

Es wird als Alkylpolyglycosid eine Mischung aus mindestens 2 Komponenten einsetzt, die sich einerseits hinsichtlich der Kettenlänge ihrer Alkylgruppen stark unterscheiden und andererseits in unterschiedlicher Konzentration verwendet werden. Hauptkomponenten sind hierbei Alkylpolyglycoside, deren Alkylgruppen 12 bis 18 Kohlenstoffatome enthalten; Nebenkomponenten sind solche, deren Alkylgruppe 7 bis 11 Kohlenstoffatome enthalten. Erfindungsgemäß in dem o. a. tensidischen Anteil ist ein Gehalt an kurzkettigem Alkylpolyglycosid von 1 bis 10 % und an langkettigem von 2 bis 20 %.The alkyl polyglycoside used is a mixture of at least 2 components which, on the one hand, differ greatly in the chain length of their alkyl groups and, on the other hand, are used in different concentrations. The main components are alkyl polyglycosides, the alkyl groups of which contain 12 to 18 carbon atoms; Secondary components are those whose alkyl group contains 7 to 11 carbon atoms. According to the invention in the above. The surfactant content is a short-chain alkyl polyglycoside content of 1 to 10% and a long-chain content of 2 to 20%.

Weitere Bestandteile des erfindungsgemäßen Waschmittels in Abhängigkeit vom Aggregationszustand sind Fettalkoholoxethylate, sowie weitere Tenside in kleinen Mengen, Komplexbildner, Bleichmittel, optische Aufheller, Vergrauungsinhibitoren, Korrosionsinhibitoren, Schaumregulatoren, Stabilisatoren, Enzyme, Enzymstabilisatoren, Elektrolyte, hydrotrope Substanzen, Löslichkeitsvermittler, etc.Other constituents of the detergent according to the invention, depending on the state of aggregation, are fatty alcohol oxyethylates and other surfactants in small amounts, complexing agents, bleaching agents, optical brighteners, graying inhibitors, corrosion inhibitors, foam regulators, stabilizers, enzymes, enzyme stabilizers, electrolytes, hydrotropic substances, solubilizers, etc.

AlkylpolyglycosideAlkyl polyglycosides

Erfindungsgemäß eingesetzte kürzerkettige Alkylpolyglycoside genügen der Formel I,

Figure imgb0003
in der R für einen linearen oder verzweigten, gesättigten oder ungesättigten aliphatischen Alkylrest mit 7 bis 11 Kohlenstoffatomen oder Gemische davon und Zn für einen Polyglycosylrest mit n = 1,0 bis 3 Hexose-oder Pentoseeinheiten oder Gemische davon stehen.Shorter-chain alkyl polyglycosides used according to the invention satisfy the formula I
Figure imgb0003
 in the R for a linear or branched, saturated or unsaturated aliphatic alkyl radical with 7 to 11 carbon atoms or mixtures thereof and Z n stand for a polyglycosyl radical with n = 1.0 to 3 hexose or pentose units or mixtures thereof.

Bevorzugt werden Alkylpolyglycoside mit Alkylresten mit 8 bis 11 Kohlenstoffatomen sowie einem Polyglycosylrest von n = 1,1 bis 2. Besonders bevorzugt werden Alkylpolyglucoside.Alkyl polyglycosides with alkyl radicals having 8 to 11 carbon atoms and a polyglycosyl radical from n = 1.1 to 2 are preferred. Alkyl polyglucosides are particularly preferred.

Erfindungsgemäß eingesetzte längerkettige Alkylpolyglycoside genügen der Formel 11,

Figure imgb0004
in der R' für einen linearen oder verzweigten, gesättigten oder ungesättigten aliphatischen Alkylrest mit 12 bis 18 Kohlenstoffatomen oder Gemische davon und Z'm für einen Polyglycosylrest mit n = 1,0 bis 3 Hexose- oder Pentoseeinheiten oder Gemische davon stehen.Longer-chain alkyl polyglycosides used according to the invention satisfy formula 11,
Figure imgb0004
 in which R 'is a linear or branched, saturated or unsaturated aliphatic alkyl radical having 12 to 18 carbon atoms or mixtures thereof and Z' m is a polyglycosyl radical with n = 1.0 to 3 hexose or pentose units or mixtures thereof.

Bevorzugt werden Alkylpolyglycoside mit Fettalkylresten mit 12 bis 16 Kohlenstoffatomen sowie einem Polyglycosylrest von n = 1,1 bis 2. Besonders bevorzugt werden Alkylpolyglucoside.Alkyl polyglycosides with fatty alkyl radicals having 12 to 16 carbon atoms and a polyglycosyl radical of n = 1.1 to 2 are preferred. Alkyl polyglucosides are particularly preferred.

Die erfindungsgemäß eingesetzten Alkylpolyglycoside können nach bekannten Verfahren auf Basis nachwachsender Rohstoffe hergestellt werden.The alkyl polyglycosides used according to the invention can be produced by known processes based on renewable raw materials.

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.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 bzw. R' wird durch die Auswahl des langkettigen Alkohols festgelegt. Günstig aus wirtschaftlichen Gründen sind die großtechnisch zugänglichen Alkohole mit 7 bis 18 C-Atomen insbesondere native Alkohole aus der Hydrierung von Carbonsäuren bzw. Carbonsäurederivaten. Verwendbar sind auch Ziegleralkohole oder Oxoalkohole.The structure of the products can be varied within certain limits. The alkyl radical R or R 'is determined by the choice of the long-chain alcohol. Favorable for economic reasons are the industrially accessible alcohols with 7 to 18 carbon atoms, especially native alcohols from the hydrogenation of carboxylic acids or carboxylic acid derivatives. Ziegler alcohols or oxo alcohols can also be used.

Die Polyglycosylreste Zn bzw. Z'm werden einerseits durch die Auswahl des Kohlenhydrats und andererseits durch die Einstellung des mittleren Polymerisationsgrads n bzw. m 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 a- und ß-glycosidischen Bindungen in Pyranose- und Furanoseform vor. Auch die Verknüpfungsstellen zwischen zwei Saccachridresten sind unterschiedlich.The polyglycosyl radicals Z n and Z ' m are determined on the one hand by the selection of the carbohydrate and on the other hand by setting the average degree of polymerization n or m. B. according to DE-OS 19 43 689. In principle, it is known that polysaccharides, e.g. B. starch, maltodextrins, dextrose, galactose, mannose, xylose, etc. can be used. The industrially available carbohydrates starch, maltodextrins and especially dextrose are preferred. Since the economically interesting alkyl polyglycoside syntheses are not regio- and stereoselective, the alkyl polyglycosides are always mixtures of oligomers, which in turn represent mixtures of different isomeric forms. They are present side by side with a- 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 means of 1 H-NMR.

Die erfindungsgemäßen Waschmittel enthalten 1 bis 10 % kurzkettiges Alkylpolyglycosid, vorzugsweise 2 - 8 %, sowie 2 - 20 % langkettiges Alkylpolyglycosid, vorzugsweise 3 - 15 %, wobei das Verhältnis von kurzkettigem zu langkettigem Anteil 1 : 10 bis 2 : 1, vorzugsweise 2 : 10 bis 1 : 1 beträgt.The detergents according to the invention contain 1 to 10% short-chain alkyl polyglycoside, preferably 2 to 8%, and 2 to 20% long-chain alkyl polyglycoside, preferably 3 to 15%, the ratio of short-chain to long-chain fraction 1:10 to 2: 1, preferably 2: Is 10 to 1: 1.

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 figure can be seen against the background that with this test method (total degradation) a degree of degradation of 70% 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/I und EC 50 (Daphnien) mit 30 mg/I 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 / I and EC 50 (daphnia) with 30 mg / I 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.

FettalkoholoxethylateFatty alcohol oxyethylates

Fettalkoholoxethylate sind Verbindungen der Formel 111

Figure imgb0005
in der R" ein linearer oder verzweigter, gesättigter oder ungesättigter Alkylrest mit 8 bis 22, vorzugsweise 10 - 20 Kohlenstoffatomen und x 2 bis 20, vorzugsweise 3 bis 15 bedeuten.Fatty alcohol oxyethylates are compounds of the formula III
Figure imgb0005
 in which R "is a linear or branched, saturated or unsaturated alkyl radical having 8 to 22, preferably 10 to 20 carbon atoms and x 2 to 20, preferably 3 to 15.

Die Verbindungen werden im allgemeinen durch Anlagerung von Ethylenoxid an längerkettige Alkohole in Gegenwart von basischen oder sauren Katalysatoren hergestellt. Günstig aus wirtschaftlichen Gründen sind großtechnisch zugängliche Alkohole mit 8 bis 22 C-Atomen aus der Hydrierung von Carbonsäuren bzw. Carbonsäurederivaten. Verwendbar sind aber auch Ziegleralkohole oder Oxoalkohole.The compounds are generally formed by the addition of ethylene oxide to longer-chain alcohols prepared in the presence of basic or acidic catalysts. For economical reasons, commercially available alcohols with 8 to 22 carbon atoms from the hydrogenation of carboxylic acids or carboxylic acid derivatives are favorable. Ziegler alcohols or oxo alcohols can also be used.

Die Alkoholoxethylate sind bekanntlich biologisch sehr gut abbaubar; günstig ebenfalls sind ihre Daten hinsichtlich Aquatoxizität, Haut- und Schleimhautverträglichkeit.The alcohol oxyethylates are known to be readily biodegradable; Their data are also favorable with regard to aquatoxicity, skin and mucous membrane compatibility.

Die erfindungsgemäßen Waschmittel enthalten 3 bis 30 % Fettalkoholoxethylate, die auch Gemische sein können. Bevorzugt wird ein Gehalt von 5 bis 20 %.The detergents according to the invention contain 3 to 30% fatty alcohol oxyethylates, which can also be mixtures. A content of 5 to 20% is preferred.

SeifeSoap

Erfindungsgemäße fettsaure Salze bzw. ihre Säuren entsprechen der Formel IV

Figure imgb0006
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
Figure imgb0006
 in which R '"is a saturated or unsaturated alkyl radical having 8 to 22 carbon atoms and P being 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.

Weitere tensidische BestandteileOther surfactant components

Erfindungsgemäß einzusetzen sind bis zu 5 % weitere anionische, nichtionische, zwitterionische und ampholytische Tenside. Insbesondere sind dies Alkansulfonate, Olefinsulfonate, Alkylbenzolsulfonate, a-Sulfofettsäureester, Fettalkoholsulfate, Fettalkoholethersulfate, Sulfobernsteinsäureester, Alkanoloxethylate, Fettsäurealkanolamide, Amminoxide, Betaine, Sulfobetaine, etc.According to the invention, up to 5% of other anionic, nonionic, zwitterionic and ampholytic surfactants are to be used. In particular, these are alkane sulfonates, olefin sulfonates, alkylbenzenesulfonates, α-sulfofatty acid esters, fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic acid esters, alkanoloxethylates, fatty acid alkanolamides, amine oxides, betaines, sulfobetaines, etc.

Weitere nicht-tensidische BestandteileOther non-surfactant components

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 EDTA, 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 EDTA, 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 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 in particular based on stilbene and pyrazoline, foam regulators, graying inhibitors such as, for. B. carboxymethyl cellulose, perfume oils, dyes and other ingredients customary for liquid or powder detergents.

Die Gesamteinsatzkonzentration in den erfindungsgemäßen Maschinenwaschmitteln beträgt für den tensidischen Anteil 0,3 - 20 g/I. Bevorzugt werden 0,5 - 10 g/I.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.

BeispieleExamples

Durch die nachfolgenden Beispiele wird die Erfindung erläutert. Die in Tab. 1 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 Tab. 1 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.

Die in Tab. 2 aufgeführten Pulver enthalten außer den genannten, erfindungsgemäß verwendeten tensidischen Bestandteilen jeweils 10 % Natriumperborat, 4,5 % Na,Mg-Silikat, 14 % Na2S04, 24 % Versalith P, 3 % Sokalan CP 5, 8 % Na3C03, 3,5 % TAED und 0,4 % Phosponat.The powders listed in Table 2 contain, in addition to the surfactant constituents mentioned according to the invention, each 10% sodium perborate, 4.5% Na, Mg silicate, 14% Na 2 SO 4 , 24% Versalith P, 3% Sokalan CP 5, 8 % Na 3 CO 3 , 3.5% TAED and 0.4% phosphonate.

Das Schaumvermögen wurde entsprechend DIN 53 902, Teil 1, bestimmt. Die Konzentration an waschaktiver Substanz betrug jeweils 1 g/I, 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, hierbei wurde ebenfalls die Schaumentwicklung überprüft, die in etwa den DIN-Werten entsprach.The foaming power was determined in accordance with DIN 53 902, Part 1. The concentration of detergent substance was 1 g / I each, the foam volume was registered after 5 minutes. The Washing capacity was measured both in the Linitest laboratory washing machine (ie with moderate mechanical stress) and in a normal household machine. Here, too, the foam development was checked, which corresponded approximately to the DIN values.

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/I, bei der Haushaltswaschmaschine bei 5 g/I, der pH jeweils bei etwa 7, das Flottenverhältnis bei etwa 1 : 60 bzw. 1 : 4, die Waschzeiten in beiden Fällen betrugen etwa 30 Minuten.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 / I, in the household washing machine 5 g / I, 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).

Flüssige FormulierungenLiquid formulations

Tab. 1 zeigt den Vergleich der Eigenschaften der erfindungsgemäßen Waschmittel als Flüssigformulierung mit denen anderer bekannten Kombinationen sowie mit einem flüssigen Markenwaschmittel, bei dem man eine Rezepturoptimierung voraussetzen kann. Klarpunkt und Viskosität entsprechen in etwa dem für flüssige Waschmittel marktüblichen Standard. Das Schäumvermögen der erfindungsgemäßen Formulierungen zeigt - ohne weitere regulierende Additive - günstige Werte. Insbesondere gilt dies für das Waschvermögen.Tab. 1 shows the comparison of the properties of the detergents according to the invention as a liquid formulation with those of other known combinations and with a liquid branded detergent, in which one can assume that the formulation has been optimized. The clear point and viscosity correspond approximately to the standard customary for liquid detergents. The foaming power of the formulations according to the invention shows favorable values without further regulating additives. This applies in particular to the washing ability.

Im Vergleich mit dem Markenwaschmittel (Beispiel 13(V) und selbst auch mit den Alkylpolyglycosidhaltigen Formulierungen (Beispiele 1 (V) bis 5 (V) verhalten sich die erfindungsgemäßen Waschmittel in ihrer Waschaktivität weit überlegen.In comparison with the branded detergent (Example 13 (V) and even with the alkyl polyglycoside-containing formulations (Examples 1 (V) to 5 (V)), the detergents according to the invention behave far superior in their washing activity.

Pulverformulierungen:Powder formulations:

Tab. 2 zeigt den Vergleich der Eigenschaften von erfindungsgemäßen pulverigen Waschmittelformulierungen mit denen einer bekannten Kombination bzw. mit einem Markenwaschmittel. Schüttdichte und Schäumvermögen wurden nach DIN-Methoden bestimmt.Tab. 2 shows the comparison of the properties of powdery detergent formulations according to the invention with those of a known combination or with a branded detergent. Bulk density and foaming power were determined according to DIN methods.

Eine Abschätzung der Löslichkeit gelingt mittels zeitlicher Auftragung der elektrischen Leitfähigkeit, wobei als Meßwert 80 % einer mittleren Endleitfähigkeit beim Auflösen von 3 g Pulver in 800 ml Trinkwasser (13 °dH) genommen wurde. Die Meßwerte beinhalten einen Fehler von ± 5 %.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 3 g of powder is dissolved in 800 ml of drinking water (13 ° dH). The measured values contain an error of ± 5%.

Abgesehen von einer etwas höheren Schüttdichte, typisch für agglomerierte Waschpulver im Vergleich zu dem sprühgetrockneten Markenprodukt (Beispiel 23) verhalten sich die erfindungsgemäßen Pulver sehr ähnlich und in ihren Waschwerten weit besser.Apart from a somewhat higher bulk density, typical of agglomerated washing powders compared to the spray-dried brand product (example 23), the powders according to the invention behave very similarly and have a much better washing value.

Überraschend ist, daß das bei Verwendung von Alkylpolyglycosid besonders bei Mischgeweben deutlich erhöhte Waschvermögen durch die erfindungsgemäße Formulierung nochmals verbessert wird.It is surprising that the washing capacity, which is significantly increased when using alkyl polyglycoside, particularly in the case of mixed fabrics, is further improved by the formulation according to the invention.

Folgende Abkürzungen wurden in den Tabellen verwendet:

  • TritonR BG 10 - Alkylpolyglycosid von Rohm und Haas
  • TritonR CG 110 - Alkylpolyglycosid von Rohm und Haas
  • C12C14 [G 1.2] - C12/14-Alkylpolyglycosid mit einem Glycosidierungsgrad von 1.2
  • C12C13 [G 1.1] - C12/13-Alkylpolyglycosid mit einem Glycosidierungsgrad von 1.1
  • C12C13 [G 1.7] - C12/13-Alkylpolyglycosid mit einem Glycosidierungsgrad von 1.7
  • MARLIPALR 24/60 - C12/14-Alkenoloxethylat mit 6 mol EO/mol
  • MARLIPALR 24/80 - C12/14-Alkenoloxethylat mit 8 mol EO/mol
  • Seife 1 - Kokosfettsärue neutralisiert mit Triethanolamin
  • Seife 2 - 90 Teile Rindertalg, 10 Teile Kokos mit NaOH verseift
  • PE - Polyester
  • MG - Mischgewebe
  • BW - Baumwolle
    Figure imgb0007
    Figure imgb0008
    Figure imgb0009
    Figure imgb0010
The following abbreviations were used in the tables:
  • Triton R BG 10 - alkyl polyglycoside from Rohm and Haas
  • Triton R CG 110 - alkyl polyglycoside from Rohm and Haas
  • C 12 C 14 [G 1.2] - C 12/14 alkyl polyglycoside with a degree of glycosidation of 1.2
  • C 12 C 13 [G 1.1] - C 12/13 alkyl polyglycoside with a degree of glycosidation of 1.1
  • C 12 C 13 [G 1.7] - C 12/13 alkyl polyglycoside with a degree of glycosidation of 1.7
  • MARLIPAL R 24/60 - C 12/14 alkenol oxyethylate with 6 mol EO / mol
  • MARLIPAL R 24/80 - C 12/14 alkenol oxyethylate with 8 mol EO / mol
  • Soap 1 - coconut fatty acid neutralized with triethanolamine
  • Soap 2 - 90 parts beef tallow, 10 parts coconut saponified with NaOH
  • PE - polyester
  • MG - blended fabric
  • BW - cotton
    Figure imgb0007
    Figure imgb0008
    Figure imgb0009
    Figure imgb0010

Claims (8)

1. Schwachschäumendes, flüssiges oder pulverförmiges Maschinen-Waschmittel enthaltend 3 bis 30 % Alkylpolyglycosid 3 bis 30 % Fettalkoholoxethylat 5 bis 30 % Seife und 0 bis 5 % andere Tenside
dadurch gekennzeichnet,
daß das Alkylpolyglycosid eine Mischung aus mindestens 2 Komponenten der Formeln 1 bzw. 11
Figure imgb0011
Figure imgb0012
enthält, in denen R ein linearer oder verzweigter, gesättigter oder ungesättigter Alkylrest mit 8 bis 11 Kohlenstoffatomen oder Gemische davon, Zn ein Polyglycosyl radikal mit n = 1 bis 3 Hexose- oder Pentoseeinheiten oder Mischungen davon, R' ein linearer oder verzweigter, gesättigter oder ungesättigter Alkylrest mit 12 bis 18 Kohlenstoffatomen oder Gemische davon, Z'm ein Polyglycosylradikal mit m = 1 bis 3 Hexose- oder Pentoseeinheiten oder Gemische davon bedeuten.1. Low-foaming, liquid or powdered machine detergent containing 3 to 30% alkyl polyglycoside 3 to 30% fatty alcohol oxyethylate 5 to 30% soap and 0 to 5% other surfactants
characterized,
that the alkyl polyglycoside is a mixture of at least 2 components of the formulas 1 and 11
Figure imgb0011
Figure imgb0012
 contains in which R is a linear or branched, saturated or unsaturated alkyl radical having 8 to 11 carbon atoms or mixtures thereof, Z n is a polyglycosyl radical with n = 1 to 3 hexose or pentose units or mixtures thereof, R 'is a linear or branched, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms or mixtures thereof, Z ' m is a polyglycosyl radical with m = 1 to 3 hexose or pentose units or mixtures thereof. 2. Schwachschäumendes, flüssiges oder pulverförmiges Waschmittel nach Anspruch 1,
dadurch gekennzeichnet,
daß die Alkylpolyglycosidkomponenten nach Formel 1 bzw. II im Verhältnis 1 : 10 bis 2 : 1 eingesetzt werden.2. Low-foaming, liquid or powder detergent according to claim 1,
characterized,
that the alkyl polyglycoside components according to formula 1 or II are used in a ratio of 1:10 to 2: 1. 3. Schwachschäumendes, flüssiges oder pulverförmiges Waschmittel nach den Ansprüchen 1 und 2, dadurch gekennzeichnet,
daß die Alkylpolyglycoside Fettalkoholglucoside mit n = 1.1 bis 2 und m = 1.1 bis 2 sind.3. Low-foaming, liquid or powder detergent according to claims 1 and 2, characterized in that
that the alkyl polyglycosides are fatty alcohol glucosides with n = 1.1 to 2 and m = 1.1 to 2. 4. Schwachschäumendes, flüssiges oder pulverförmiges Waschmittel nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet,
daß das Fettalkoholoxethylat der Formel III
Figure imgb0013
entspricht, in der R" ein linearer oder verzweigter, gesättigter oder ungesättigter Alkylrest mit 8 bis 22 Kohlenstoffatomen und x = 2 bis 20 bedeuten.4. Low-foaming, liquid or powder detergent according to claims 1 to 3, characterized in that
that the fatty alcohol oxyethylate of the formula III
Figure imgb0013
 in which R "is a linear or branched, saturated or unsaturated alkyl radical having 8 to 22 carbon atoms and x = 2 to 20. 5. Schwachschäumendes, flüssiges oder pulverförmiges Waschmittel nach Anspruch 4, dadurch gekennzeichnet,
daß R" in Formel III 10 - 20 Kohlenstoffatome und x = 3 bis 15 bedeuten.5. Low-foaming, liquid or powder detergent according to claim 4, characterized in that
that R "in formula III means 10-20 carbon atoms and x = 3 to 15. 6. Schwachschäumendes, flüssiges oder pulverförmiges Waschmittel nach Ansprüchen 1 bis 5,
dadurch gekennzeichnet,
daß die Seife der Formel IV
Figure imgb0014
entspricht, in der R"' ein gesättigter und/oder ungesättigter Alkylrest mit 8 bis 22 Kohlenstoffatomen und P Wasserstoff, Alkali, Ammonium oder Alkanolammonium bedeuten.6. Low-foaming, liquid or powder detergent according to claims 1 to 5,
characterized,
that the soap of formula IV
Figure imgb0014
 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. 7. Schwachschäumendes, flüssiges oder pulverförmiges 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.7. Low-foaming, liquid or powder detergent according to claims 1 to 6, characterized in that
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. 8. Schwachschäumendes, flüssiges oder pulverförmiges Waschmittel nach den Ansprüchen 1 bis 7, dadurch gekennzeichnet,
daß die Konzentration des tensidischen Anteils 0,3 bis 20 g/I beträgt.8. Low-foaming, liquid or powder detergent according to claims 1 to 7, characterized in that
that the concentration of the surfactant portion is 0.3 to 20 g / l.
EP90124033A 1990-09-13 1990-12-13 Detergent Expired - Lifetime EP0474915B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4029035 1990-09-13
DE4029035A DE4029035A1 (en) 1990-09-13 1990-09-13 LAUNDRY DETERGENT

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EP0474915A1 true EP0474915A1 (en) 1992-03-18
EP0474915B1 EP0474915B1 (en) 1995-06-21
EP0474915B2 EP0474915B2 (en) 1998-06-10

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EP90124033A Expired - Lifetime EP0474915B2 (en) 1990-09-13 1990-12-13 Detergent

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JP (1) JP3132731B2 (en)
AT (1) ATE124084T1 (en)
CA (1) CA2051189A1 (en)
DE (2) DE4029035A1 (en)
DK (1) DK0474915T3 (en)
ES (1) ES2076285T5 (en)
GR (2) GR3017036T3 (en)
NO (1) NO178232C (en)

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DE4101070A1 (en) * 1991-01-16 1992-07-23 Huels Chemische Werke Ag WASHING POWDER
WO1993020179A1 (en) * 1992-03-30 1993-10-14 Henkel Kommanditgesellschaft Auf Aktien Detergents for hard surfaces
WO1994010279A1 (en) * 1992-10-29 1994-05-11 Henkel Kommanditgesellschaft Auf Aktien Process for preparing aqueous solutions of anionic surfactants with improved low-temperature stability
US5370816A (en) * 1990-09-13 1994-12-06 Huels Aktiengesellschaft Detergent composition containing a mixture of alkyl polyglycosides
FR2712595A1 (en) * 1993-11-19 1995-05-24 Seppic Sa A concentrate comprising alkyl glycosides and uses thereof.
WO1996037285A1 (en) * 1995-05-24 1996-11-28 Societe D'exploitation De Produits Pour Les Industries Chimiques - Seppic Alkylpolyglycoside-based emulsifying composition and uses thereof
US5670474A (en) * 1994-12-02 1997-09-23 Lever Brothers Company, Division Of Conopco, Inc. High performance detergent powders
WO1997049789A1 (en) * 1996-06-21 1997-12-31 Henkel Kommanditgesellschaft Auf Aktien Improved-care washing process for textiles
EP0976817A1 (en) * 1998-07-30 2000-02-02 Henkel Kommanditgesellschaft auf Aktien Alkylpolyglycosides as co-builders
WO2001021743A1 (en) * 1999-09-22 2001-03-29 Cognis Deutschland Gmbh & Co. Kg Surfactant mixtures
WO2001072149A1 (en) * 2000-03-28 2001-10-04 Henkel Kommanditgesellschaft Auf Aktien Washing of fruit and vegetables

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US5759979A (en) * 1993-04-05 1998-06-02 Henkel Kommanditgesellschaft Auf Aktien Detergent mixtures comprising APG and fatty alcohol polyglycol ether
DE4313908A1 (en) * 1993-04-28 1994-11-03 Huels Chemische Werke Ag Water-softening formulations
DE4319699A1 (en) * 1993-06-16 1994-12-22 Henkel Kgaa Ultra mild surfactant blends
DE4319700A1 (en) * 1993-06-16 1994-12-22 Henkel Kgaa Ultra mild surfactant blends
US5532224A (en) * 1993-12-22 1996-07-02 Alcon Laboratories, Inc. Contact lens cleaning composition containing polyalklene oxide modified siloxanes
WO1995033036A1 (en) * 1994-06-01 1995-12-07 Henkel Corporation Enhanced performance of amphoteric surfactants
ES2213164T3 (en) * 1994-10-26 2004-08-16 Novozymes A/S PRODUCTION METHOD OF A MILK PROTEIN HYDROLYZE.
US5525256A (en) * 1995-02-16 1996-06-11 Henkel Corporation Industrial and institutional liquid cleaning compositions containing alkyl polyglycoside surfactants
MX9708785A (en) * 1995-06-01 1998-02-28 Henkel Corp The use of c16-c18alkylpolyglycosides as defoamers in cleaning compositions.
AU6257496A (en) * 1995-06-21 1997-01-22 Henkel Corporation Method for increasing the efficacy of an odor masking agent
MX9800441A (en) * 1995-07-17 1998-04-30 Henkel Corp The use of alkoxylated alcohols to control foaming of alkyl polyglycosides in cleaning compositions.
US5895605A (en) * 1997-01-14 1999-04-20 Henkel Corporation Defoaming compositions
US6110977A (en) * 1997-01-14 2000-08-29 Henkel Corporation Alkyl polyglycoside compositions having reduced viscosity and inhibited crystallization
US6117934A (en) * 1997-02-03 2000-09-12 Henkel Corporation Alkylpolyglycoside containing surfactant blends for emulsion polymerization
US6350787B1 (en) 1997-06-10 2002-02-26 Cognis Corporation Defoamers for aqueous systems
US6387962B1 (en) * 1997-06-10 2002-05-14 Cognis Corporation Defoamers for aqueous systems
US6245401B1 (en) 1999-03-12 2001-06-12 Kimberly-Clark Worldwide, Inc. Segmented conformable breathable films
US6107268A (en) * 1999-04-16 2000-08-22 Kimberly-Clark Worldwide, Inc. Sorbent material
US6355583B1 (en) 1998-05-30 2002-03-12 Kimberly-Clark Worldwide, Inc. Multi-functional sorbent material
PE20000627A1 (en) 1998-05-30 2000-07-26 Kimberly Clark Co ABSORBENT MATERIAL
WO2000050560A1 (en) * 1999-02-22 2000-08-31 Cognis Corporation Low viscosity high active blends of alkyl polyglycosides and alcohol ethoxylates
DE19928922A1 (en) * 1999-06-24 2000-12-28 Cognis Deutschland Gmbh Foam-controlled solid laundry detergent containing anionic surfactant, useful in domestic laundry, contains (poly)ethylene glycol monoether with mixture of long-chain alk(en)yl groups and alk(en)yloligoglycoside as nonionic surfactants
US6384010B1 (en) 2000-06-15 2002-05-07 S.C. Johnson & Son, Inc. All purpose cleaner with low organic solvent content
JP2004035808A (en) * 2002-07-05 2004-02-05 Nissan Soap Co Ltd Liquid detergent composition
US6730650B1 (en) 2002-07-09 2004-05-04 The Dial Corporation Heavy-duty liquid detergent composition comprising anionic surfactants
US8993502B2 (en) 2008-02-21 2015-03-31 S. C. Johnson & Son, Inc. Cleaning composition having high self-adhesion to a vertical hard surface and providing residual benefits
US9481854B2 (en) 2008-02-21 2016-11-01 S. C. Johnson & Son, Inc. Cleaning composition that provides residual benefits
US8980813B2 (en) 2008-02-21 2015-03-17 S. C. Johnson & Son, Inc. Cleaning composition having high self-adhesion on a vertical hard surface and providing residual benefits
US9410111B2 (en) 2008-02-21 2016-08-09 S.C. Johnson & Son, Inc. Cleaning composition that provides residual benefits
US8287658B2 (en) * 2009-06-02 2012-10-16 Ecolab Usa Inc. Biodegradable surfactant blend
BR112013001310B1 (en) 2010-07-19 2018-03-20 Colgate-Palmolive Company Coconut and decyl glycoside cleaning composition and method of manufacture
KR200471048Y1 (en) * 2011-04-15 2014-02-04 류동주 patio chair for work
US8455426B1 (en) * 2012-05-04 2013-06-04 AGAIA International, Inc. Cleaning compositions
JP2019151566A (en) * 2018-03-01 2019-09-12 ロレアル Sprayable composition

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EP0075994A2 (en) * 1981-09-28 1983-04-06 THE PROCTER &amp; GAMBLE COMPANY Detergent compositions containing mixture of alkylpolysaccharide and amine oxide surfactants and fatty acid soap
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JPH0692600B2 (en) * 1988-11-25 1994-11-16 日本コーンスターチ株式会社 Higher alkyl glycoside composition
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EP0075994A2 (en) * 1981-09-28 1983-04-06 THE PROCTER &amp; GAMBLE COMPANY Detergent compositions containing mixture of alkylpolysaccharide and amine oxide surfactants and fatty acid soap
USH171H (en) * 1985-06-24 1986-12-02 A. E. Staley Manufacturing Company Branched chain glycosides

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5370816A (en) * 1990-09-13 1994-12-06 Huels Aktiengesellschaft Detergent composition containing a mixture of alkyl polyglycosides
DE4101070A1 (en) * 1991-01-16 1992-07-23 Huels Chemische Werke Ag WASHING POWDER
US5591376A (en) * 1992-03-30 1997-01-07 Henkel Kommanditgesellschaft Auf Aktien Cleaning compositions for hard surfaces
WO1993020179A1 (en) * 1992-03-30 1993-10-14 Henkel Kommanditgesellschaft Auf Aktien Detergents for hard surfaces
WO1994010279A1 (en) * 1992-10-29 1994-05-11 Henkel Kommanditgesellschaft Auf Aktien Process for preparing aqueous solutions of anionic surfactants with improved low-temperature stability
US5599787A (en) * 1992-10-29 1997-02-04 Henkel Kommanditgesellschaft Auf Aktien Aqueous anionic surfactant solutions stable at low temperature comprising glycoside and alkoxylated nonionic surfactant mixtures and processes of making same
FR2712595A1 (en) * 1993-11-19 1995-05-24 Seppic Sa A concentrate comprising alkyl glycosides and uses thereof.
WO1995013863A1 (en) * 1993-11-19 1995-05-26 Societe D'exploitation De Produits Pour Les Industries Chimiques, S.E.P.P.I.C. Alkylglycoside-containing concentrate and uses thereof
US5670471A (en) * 1993-11-19 1997-09-23 Societe D'exploitation De Produits Pour Les Industries Chimiques, S.E.P.P.I.C. Concentrate comprising alkylglycoside mixture and fatty alcohol and corresponding methods of use
US5670474A (en) * 1994-12-02 1997-09-23 Lever Brothers Company, Division Of Conopco, Inc. High performance detergent powders
FR2734496A1 (en) * 1995-05-24 1996-11-29 Seppic Sa EMULSIFIER COMPOSITION BASED ON ALKYLPOLYGLYCOSIDES AND USES THEREOF
WO1996037285A1 (en) * 1995-05-24 1996-11-28 Societe D'exploitation De Produits Pour Les Industries Chimiques - Seppic Alkylpolyglycoside-based emulsifying composition and uses thereof
WO1997049789A1 (en) * 1996-06-21 1997-12-31 Henkel Kommanditgesellschaft Auf Aktien Improved-care washing process for textiles
EP0976817A1 (en) * 1998-07-30 2000-02-02 Henkel Kommanditgesellschaft auf Aktien Alkylpolyglycosides as co-builders
WO2001021743A1 (en) * 1999-09-22 2001-03-29 Cognis Deutschland Gmbh & Co. Kg Surfactant mixtures
WO2001072149A1 (en) * 2000-03-28 2001-10-04 Henkel Kommanditgesellschaft Auf Aktien Washing of fruit and vegetables

Also Published As

Publication number Publication date
DK0474915T3 (en) 1995-11-20
NO178232C (en) 1996-02-14
JP3132731B2 (en) 2001-02-05
GR3017036T3 (en) 1995-11-30
NO913615L (en) 1992-03-16
GR3027759T3 (en) 1998-11-30
JPH04234499A (en) 1992-08-24
CA2051189A1 (en) 1992-03-14
ATE124084T1 (en) 1995-07-15
DE4029035A1 (en) 1992-03-19
ES2076285T3 (en) 1995-11-01
NO913615D0 (en) 1991-09-12
DE59009299D1 (en) 1995-07-27
NO178232B (en) 1995-11-06
ES2076285T5 (en) 1998-11-01
EP0474915B2 (en) 1998-06-10
US5370816A (en) 1994-12-06
EP0474915B1 (en) 1995-06-21

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