EP0457965B2 - Low foaming washing-machine detergents - Google Patents

Low foaming washing-machine detergents Download PDF

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Publication number
EP0457965B2
EP0457965B2 EP90124032A EP90124032A EP0457965B2 EP 0457965 B2 EP0457965 B2 EP 0457965B2 EP 90124032 A EP90124032 A EP 90124032A EP 90124032 A EP90124032 A EP 90124032A EP 0457965 B2 EP0457965 B2 EP 0457965B2
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EP
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Prior art keywords
foaming
low
fatty alcohol
liquid detergent
alkyl
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German (de)
French (fr)
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EP0457965B1 (en
EP0457965A1 (en
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Dieter Dr. Balzer
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Sasol Germany GmbH
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Sasol Germany GmbH
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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
    • 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
    • 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
    • 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 preparations for Washing of textiles, the tensides 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 powder in addition to the surfactants alkyl benzene sulfonate and fatty alcohol oxyethylate as essential active ingredients, builder substances, bleaching agents and other electrolytes contain.
  • anionic surfactants especially alkylbenzenesulfonate, Fatty alcohol oxyethylate and soap
  • washing powder in addition to the surfactants alkyl benzene sulfonate and fatty alcohol oxyethylate as essential active ingredients, builder substances, bleaching agents and other electrolytes contain.
  • surfactants in particular those based on petrochemicals are used.
  • the object of the invention was therefore to provide a surfactant combination for low-foaming detergents find that are largely made from renewable raw materials that are exceptionally organic are degradable and achieve very good washing results.
  • the invention therefore relates to a low-foaming, liquid machine washing detergent, which is characterized in that the surfactant component consists of 5 to 30% alkyl polyglycoside, 5 to 30% fatty alcohol ether carboxylate, 5 to 30% soap and 0 to 3% other surfactants consists.
  • alkyl polyglycoside in combination with anionic surfactants is known. So 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.
  • Other components 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.
  • RON n 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.
  • Alkyl polyglycosides with fatty alkyl radicals having 10 to 16 carbon atoms and one are preferred Polyglycosyl radical from n 1.1 to 2. Alkylpolyglucosides are particularly preferred.
  • the alkyl polyglycosides used according to the invention can be based on known processes renewable raw materials are produced. For example, dextrose is in the presence of an acid Catalyst with n-butanol converted to butyl polyglycoside mixtures, which with long-chain alcohols also glycosidated in the presence of an acid catalyst to give the desired alkyl polyglycoside mixtures become. 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 selected of long chain alcohol.
  • the industrially accessible ones are favorable for economic reasons
  • Ziegler alcohols or oxo alcohols can also be used.
  • the polyglycosyl radical Z n is determined, on the one hand, by the selection of the carbohydrate and, on the other hand, by setting the average degree of polymerization n z. 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 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 mixed by mixing alkyl polyglycosides with alkyl monoglycosides.
  • the latter can e.g. B. according to EP-A 0 092 355 by means of polar Obtain or enrich solvents, such as acetone, from alkyl polyglycosides.
  • the degree of glycosidation is expediently 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 Compared to almost all other surfactants used in detergents, the alkyl polyglycosides apply as extremely environmentally friendly. So lies the one determined by means of a sewage treatment plant simulation model / DOC analysis degree of biodegradation for the alkyl polyglycosides according to the invention at 96 ⁇ 3%. That number is before Background to see that with this test method (total degradation) already a degree of degradation> 70% Substance indicated as readily degradable.
  • the acute oral toxicity LD 50 (rat) with> 10,000 mg / kg and the aquatic toxicity LC 50 (Gold orfe) with approx. 12 mg / l and EC 50 (daphnia) with 30 mg / l are cheaper by a factor of 3 to 5 than that corresponding values of the most important surfactants today. The same applies to skin and mucous membrane compatibility.
  • Fatty alcohol ether carboxylates are compounds of either formula II (R'-O (CH 2 -CH 2 -O) x CH 2 COO) m M m + 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 hydrogen, alkali, alkaline earth metal, ammonium or alkanolammonium is, or III ([R "-O (CH 2 -CH 2 -O) y ] 2 CHCOO) z N z + 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 40, preferably 3 to 30, z 1 or 2 and MH, alkali, alkaline earth metal, ammonium or 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 (CH 2 -CH 2 -O) n H with chloroacetic acid or a salt of chloroacetic acid in the presence of alkali 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.
  • Corresponding alcohols for the production of the fatty alcohol ether carboxylates are preferably fatty alcohols or Ziegleral alcohols, in exceptional cases also oxo alcohols.
  • the one following the oxethylation Carboxymethylation can be complete if the procedure is appropriate, so that the fatty alcohol ether carboxylates are purely anionic surfactants.
  • the carboxymethylation is incomplete, they contain Products certain amounts of unreacted oxyethylate. With formulas II and III is therefore usually a Mixture with different amounts of unreacted oxethylates meant. Accordingly, define a degree of implementation. A degree of conversion between 70 and 100% is preferred.
  • the fatty alcohol ether carboxylates are also very environmentally friendly surfactants. So using a sewage treatment plant simulation model / DOC analysis biodegradation rates found above 90%.
  • the acute oral Toxicity LD 50 (rat) and aquatic toxicity LC 50 (gold orfe) are about as favorable as that the alkyl polyglucoside. The same applies to skin and mucous membrane compatibility.
  • the detergents according to the invention contain 5 to 30% fatty alcohol ether carboxylates, which also include mixtures could be. 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 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%, most of the soap will be a mixture of different components.
  • alkanesulfonates are alkanesulfonates, olefinsulfonates, 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, Citrates, polyacetates such as NTA and EDTA etc. or their mixtures. These connections will be usually used as alkali salts, preferably as sodium salts. Although not complex, too To mention sodium sulfate here.
  • Builders such as aluminosilicates of suitable particle size (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 are also optionally combined with bleach activators such as tetraacetylethylene diamine etc. or percarbonate; of course also come into question other bleaching agents (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 1- or 2-valent alcohols may be used according to the invention, Alkyl ethers of polyhydric alcohols, hydrotropes such as alkylbenzenesulfonates with 1 to 3 carbon 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, in particular based on stilbene and pyrazoline, Foam regulators, graying inhibitors such as B. carboxymethyl cellulose, perfume oils, dyes and further ingredients customary for liquid or powder detergents.
  • hydrotropes such as alkylbenzenesulfonates with 1 to 3 carbon 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 in particular based
  • Liquid detergent formulations contain, in addition to the surfactants mentioned, used according to the invention Each contains 6% triethanolamine, 12% ethanol, 6% 1,2-propylene glycol and water ad 100 %.
  • the foaming power was determined in accordance with DIN 53 902, Part 1.
  • the concentration on detergent substance was 1 g / l, the foam volume was registered after 5 minutes.
  • the Washing ability was both in the Linitest laboratory washing machine (i.e. with moderate mechanical stress) as well as measured in a normal household machine.
  • 11 x 18 cm served as the model fabric large rags made of WFK test fabric with skin fat pigment soiling: polyester (PE), mixed fabric (MG) and cotton (BW), as water drinking water (13 ° dH).
  • Polyester was mixed at 30 ° C and cotton washed at 60 ° C.
  • the active substance concentration was in the Linitest laboratory washing machine at 1 g / l, in the household washing machine at 5 g / l, the pH at about 7, the liquor ratio at 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 brand detergent, in which one can presuppose a formulation optimization.
  • the clear point and viscosity fully correspond to the standard customary for liquid detergents.
  • the formulations according to the invention behave far more effectively here than other known combinations, their surfactant content also consists of anionic surfactant, alkyl polyglucoside and soap (Comparative Examples 1 and 2).

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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

In a low foam, liq. or powder machine washing compsn., the surfactant component contains 5-30% of alkylpolyglycoside, 5-30% of alkanol ether carboxylate, 5-30% of soap, and 0-3% of other surfactants. The alkylpolyglycoside is R-O-Zn and is esp. a fatty alcohol polyglucoside. The alkanol ether carboxylate is (R'-O(CH2CH2-O)xCH2COO)mMm+ or ((R''-O(CH2CH2-O)y)2CHCOO)zNz+, and the soap is R'''COOP. R = 10-18C (un)branched, (un)satd. alkyl; Zn = polyglycosyl radical with n = 1-3 hexose or pentose units; n esp. = 1.1-2; R'' = 8-22C (un)branched alkyl; x, y = 1-40; esp. x = 3-20; z = 1 or 2; m = 1 or 2 (1); M, N = H, alkali(ne earth), NH4 or alkanolammonium, pref. Na, K, NH4 or alkanolammonium; R' = 8-22C (10-18C) (un)satd., (un)branched alkyl; R''' = 8-22C satd. and/or unsatd. alkyl; P = H, alkali, NH4 or alkanolammonium. The concn. of the tenside component is 0.3-20 g/l. The compsn. may contain builders, bleaches, suspension agents, enzymes, stabilisers, greying inhibitors, corrosion inhibitors, optical brighteners, dyes, perfume oils and opt. other non-surfactant components.

Description

Die vorliegende Erfindung betrifft schwachschäumende flüssige Zubereitungen zum Waschen von Textilien, deren Tenside weitestgehend aus nachwachsenden Rohstoffen hergestellt werden.The present invention relates to low-foaming liquid preparations for Washing of textiles, the tensides 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 powder in addition to the surfactants alkyl benzene sulfonate and fatty alcohol oxyethylate as essential active ingredients, builder substances, bleaching agents and other electrolytes contain. Common to liquid and powder detergent formulations is that they are 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 erreicht.With regard to the future raw material situation (oil shortage), this petrochemical basis is one considerable disadvantage. Another disadvantage is that the biodegradability of these surfactants did 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 provide a surfactant combination for low-foaming detergents find that are largely made from renewable raw materials that are exceptionally organic are degradable 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 surfactant combination consisting essentially of alkyl polyglycosides, There are ether carboxylates and soap.

Gegenstand der Erfindung ist daher ein schwachschäumendes, flüssiges Maschinen-Waschmittel, welches dadurch gekennzeichnet ist, daß der tensidische Anteil aus
   5 bis 30 % Alkylpolyglycosid,
   5 bis 30 % Fettalkoholethercarboxylat,
   5 bis 30 % Seife und
   0 bis 3 % anderen Tensiden
besteht.The invention therefore relates to a low-foaming, liquid machine washing detergent, which is characterized in that the surfactant component consists of
5 to 30% alkyl polyglycoside,
5 to 30% fatty alcohol 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 the combinations according to the invention are very good Washing results can be achieved.

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. So 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.Use in detergents of carboxymethylated fatty alcohol oxyethylates, which is a subgroup which represent ether carboxylates is known from DE-OSS 23 27 234 and 33 20 340; however, it is new Use of bisalkanol alkoxylate acetates, which are also a subset of the ether carboxylates. As well the use of ether carboxylates in connection with alkyl polyglycosides in detergents is unknown.

Weitere Bestandteile sind weitere Tenside in kleinen Mengen, Komplexbildner, Bleichmittel, optische Aufheller, Vergrauungsinhibitoren, Korrosionsinhibitoren, Schaumregulatoren, Stabilisatoren, Enzyme, Enzymstabilisatoren, Elektrolyte, hydrotrope Substanzen, Löslichkeitsvermittler, etc.Other components 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.

AlkylpolyglykosideAlkylpolyglykoside

Erfindungsgemäß eingesetzte Alkylpolyglycoside genügen der Formel I R-O-Zn in der R für einen linearen oder verzweigten, gesättigten oder ungesättigten aliphatischen Alkylrest mit 10 bis 18 Kohlenstoffatomen oder Gemische davon und Zn für einen Polyglycosylrest mit n = 1,0 bis 3 Hexose- oder Pentoseeinheiten oder Gemische davon stehen.Alkyl polyglycosides used according to the invention satisfy formula I. RON n 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 one are preferred Polyglycosyl radical from n = 1.1 to 2. Alkylpolyglucosides 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 based on known processes renewable raw materials are produced. For example, dextrose is in the presence of an acid Catalyst with n-butanol converted to butyl polyglycoside mixtures, which with long-chain alcohols also glycosidated in the presence of an acid catalyst to give the desired alkyl polyglycoside mixtures become. 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 selected of long chain alcohol. The industrially accessible ones are favorable for economic reasons 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. 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 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 mixed by mixing alkyl polyglycosides with alkyl monoglycosides. The latter can e.g. B. according to EP-A 0 092 355 by means of polar Obtain or enrich solvents, such as acetone, from alkyl polyglycosides.

Der Glycosidierungsgrad wird zweckmäßigerweise mittels 1H-NMR bestimmt.The degree of glycosidation is expediently 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 apply as extremely environmentally friendly. So lies the one determined by means of a sewage treatment plant simulation model / DOC analysis degree of biodegradation for the alkyl polyglycosides according to the invention at 96 ± 3%. That number is before Background to see that with this test method (total degradation) already a degree of degradation> 70% Substance indicated as 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 and the aquatic toxicity LC 50 (Gold orfe) with approx. 12 mg / l and EC 50 (daphnia) with 30 mg / l are cheaper by a factor of 3 to 5 than that corresponding values of the most important surfactants today. The same applies to skin and mucous membrane compatibility.

FettalkoholethercarboxylateFettalkoholethercarboxylate

Fettalkoholethercarboxylate sind Verbindungen entweder der Formel II (R'-O(CH2-CH2-O)xCH2COO)mMm+ 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 III ([R"-O(CH2-CH2-O)y]2CHCOO)z Nz+ in der R" einen linearen oder verzweigten, gesättigten oder ungesättigten Alkylrest mit 8 bis 22, vorzugsweise 10 bis 18, Kohlenstoffatomen, y 1 bis 40, vorzugsweise 3 bis 30, z 1 oder 2 und M H, Alkali, Erdalkali, Ammonium oder Alkanolammonium bedeuten.Fatty alcohol ether carboxylates are compounds of either formula II (R'-O (CH 2 -CH 2 -O) x CH 2 COO) m M m + 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 hydrogen, alkali, alkaline earth metal, ammonium or alkanolammonium is, or III ([R "-O (CH 2 -CH 2 -O) y ] 2 CHCOO) z N z + 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 40, preferably 3 to 30, z 1 or 2 and MH, alkali, alkaline earth metal, ammonium or alkanolammonium ,

Verbindungen entsprechend Formel II nennt man carboxymethylierte Oxethylate, die entsprechend Formel III Bisfettalkoholethoxylatacetate.Compounds corresponding to formula II are called carboxymethylated oxethylates, which correspond Formula III bis fatty alcohol 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 (CH 2 -CH 2 -O) n H with chloroacetic acid or a salt of chloroacetic acid in the presence of alkali 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.

Bisfettalkoholethoxylatacetate lassen sich z. B. nach DE-OS 39 02 663 aus Oxethylaten und Dichloressigsäure herstellen.Bisfettalkoholethoxylatacetate z. B. according to DE-OS 39 02 663 from oxyethylates and dichloroacetic acid produce.

Entsprechende Alkohole zur Herstellung der Fettalkoholethercarboxylate sind vorzusweise 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 Ziegleral alcohols, in exceptional cases also oxo alcohols. The one following the oxethylation Carboxymethylation can be complete if the procedure is appropriate, so that the fatty alcohol ether carboxylates are purely anionic surfactants. Alternatively, if the carboxymethylation is incomplete, they contain Products certain amounts of unreacted oxyethylate. With formulas II and III is therefore usually a Mixture with different amounts of unreacted oxethylates meant. Accordingly, define a degree of implementation. 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. So using a sewage treatment plant simulation model / DOC analysis biodegradation rates found above 90%. The acute oral Toxicity LD 50 (rat) and aquatic toxicity LC 50 (gold orfe) are about as favorable as that the alkyl polyglucoside. 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 also include mixtures could be. A content of 7 to 20% fatty alcohol ether carboxylate is preferred.

SeifeSoap

Erfindungsgemäße fettsaure Salze bzw. ihre Säuren entsprechen der Formel IV R '''COOP in der R''' einen gesättigten oder ungesättigten 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 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%, most of the soap will be a mixture of different components.

Weitere tensidische BestandteileOther surfactant 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, Aminoxide, Betaine, Sulfobetaine usw.According to the invention, up to 3% of further anionic, nonionic, zwitterionic and ampholytic surfactants. In particular, these are alkanesulfonates, olefinsulfonates, 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, Citrate, Polyacetate wie NTA und EDTA usw. 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. Used according to the invention water-soluble builders such as different polyphosphates, phosphonates, carbonates, polycarboxylates, Citrates, polyacetates such as NTA and EDTA etc. or their mixtures. These connections will be usually used as alkali salts, preferably as sodium salts. Although not complex, too To mention sodium sulfate here. The use of water-insoluble is also according to the invention Builders, such as aluminosilicates of suitable particle size (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 %.According to the invention, bleaching agents such as sodium perborate are also optionally combined with bleach activators such as tetraacetylethylene diamine etc. or percarbonate; of course also come into question other bleaching agents (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 3 C-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 1- or 2-valent alcohols may be used according to the invention, Alkyl ethers of polyhydric alcohols, hydrotropes such as alkylbenzenesulfonates with 1 to 3 carbon 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, in particular based on stilbene and pyrazoline, Foam regulators, graying inhibitors such as B. carboxymethyl cellulose, perfume oils, dyes and further ingredients customary for liquid or powder detergents.

BeispieleExamples

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 listed in Tab. 1 and 2 Liquid detergent formulations contain, in addition to the surfactants mentioned, used according to the invention Each contains 6% triethanolamine, 12% ethanol, 6% 1,2-propylene glycol and water ad 100 %.

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 on detergent substance was 1 g / l, the foam volume was registered after 5 minutes. The Washing ability was both in the Linitest laboratory washing machine (i.e. with moderate mechanical stress) as well as measured in a normal household machine. 11 x 18 cm served as the model fabric large rags made of WFK test fabric with skin fat pigment soiling: polyester (PE), mixed fabric (MG) and cotton (BW), as water drinking water (13 ° dH). Polyester was mixed at 30 ° C and cotton washed at 60 ° C. The active substance concentration was in the Linitest laboratory washing machine at 1 g / l, in the household washing machine at 5 g / l, the pH at about 7, the liquor ratio at 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 Wash values after drying the fabrics were - as usual - spectrophotometrically relative to one White standard (Datacolor, 560 nm) measured.

Flüssige Formulierungen:Liquid formulations:

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.

Figure 00050001
Figure 00060001
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 brand detergent, in which one can presuppose a formulation optimization.
Figure 00050001
Figure 00060001

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 - 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, their surfactant content also consists of anionic surfactant, alkyl polyglucoside and soap (Comparative Examples 1 and 2).

Claims (7)

  1. A low-foaming, liquid detergent for machines, characterized in that
    the surfactant content consists of
    5 to 30% of alkyl polyglycoside,
    5 to 30% of fatty alcohol ether-carboxylate,
    5 to 30% of soap and
    0 to 3% of other surfactants.
  2. A low-foaming, liquid detergent for machines according to claim 1,
    characterized in that
    the alkyl polyglycoside corresponds to the formula I R-O-Zn wherein R denotes a linear or branched, saturated or unsaturated alkyl radical having 10 to 18 carbon atoms or mixtures thereof and Zn denotes a poly-glycosyl radical, where n = 1 to 3 hexose or pentose units or mixtures thereof.
  3. A low-foaming, liquid detergent for machines according to either of claims 1 and 2,
    characterized in that
    the alkyl polyglycoside is a fatty alcohol polyglucoside where n = 1.1 to 2.
  4. A low-foaming, liquid detergent for
    machines according to any of claims 1 to 3,
    characterized in that
    the fatty alcohol ether-carboxylate corresponds to the formula II or III [R'-O(CH2-CH2-O)xCH2COO]mMm+ ([R''-O(CH2-CH2-O)y]2CHCOO)zNz+ in which R' and R'' denote saturated or unsaturated, linear or branched alkyl radicals having 8 to 22 carbon atoms, x and y denote 1 to 40, m and z denote 1 or 2 and M and N denote hydrogen, an alkali metal, an alkaline earth metal, ammonium or alkanolammonium.
  5. A low-foaming, liquid detergent for machines according to claim 4,
    characterized in that
    the fatty alcohol ether-carboxylate is a carboxymethylated fatty alcohol oxyethylate corresponding to formula II, in which R' denotes 10 to 18 carbon atoms, x = 3 - 20, m = 1 and M denotes sodium, potassium, ammonium or alkanolammonium.
  6. A low-foaming, liquid detergent for machines according to any of claims 1 to 5,
    characterized in that
    the soap corresponds to the formula IV R'''COOP in which R''' denotes a saturated or unsaturated alkyl radical having 8 to 22 carbon atoms and P denotes hydrogen, an alkali metal, ammonium or alkanolammonium.
  7. A low-foaming, liquid detergent for machines according to any of claims 1 to 6,
    characterized in that
    it contains builders, bleaching agents, standardizing agents, enzymes, stabilizers, greying inhibitors, corrosion inhibitors, optical brighteners, dyestuffs, perfume oils and if desired further additives as non-surfactant constituents.
EP90124032A 1990-05-25 1990-12-13 Low foaming washing-machine detergents Expired - Lifetime EP0457965B2 (en)

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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

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DE4331297A1 (en) * 1993-09-15 1995-03-16 Henkel Kgaa Bar soaps
AU2668297A (en) * 1996-05-08 1997-11-26 Henkel Corporation Alkyl polyglycoside ether carboxylates
WO1999024538A1 (en) * 1997-11-10 1999-05-20 Henkel Corporation Alkyl polyglycoside ether carboxylates
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

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EP0070075B2 (en) * 1981-07-13 1992-11-04 THE PROCTER & GAMBLE COMPANY Foaming dishwashing liquid compositions
US4483787A (en) * 1983-12-28 1984-11-20 The Procter & Gamble Company Concentrated aqueous detergent compositions
IL81354A (en) * 1986-01-30 1990-11-05 Colgate Palmolive Co Liquid detergent having improved softening properties
FR2617862B1 (en) * 1987-07-09 1994-01-07 Sandoz Sa BUILDER FREE DETERGENT COMPOSITIONS

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ES2075873T3 (en) 1995-10-16
DK0457965T3 (en) 1995-11-06
NO178233B (en) 1995-11-06
ATE124083T1 (en) 1995-07-15
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JPH04227998A (en) 1992-08-18
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NO178233C (en) 1996-02-14
NO911993L (en) 1991-11-26

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