EP0495176B1 - Detergent powder - Google Patents
Detergent powder Download PDFInfo
- Publication number
- EP0495176B1 EP0495176B1 EP91119602A EP91119602A EP0495176B1 EP 0495176 B1 EP0495176 B1 EP 0495176B1 EP 91119602 A EP91119602 A EP 91119602A EP 91119602 A EP91119602 A EP 91119602A EP 0495176 B1 EP0495176 B1 EP 0495176B1
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- European Patent Office
- Prior art keywords
- alkyl
- fatty alcohol
- mixtures
- powder detergent
- weight
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
- 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
-
- 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
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- 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
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- 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 powdered preparations for washing textiles, the surfactants of which are largely made from renewable raw materials.
- Powder detergents produced either by spray drying or agglomeration processes, today consist of surfactants, builders, bleaches and additives in smaller quantities such as optical brighteners, graying inhibitors, corrosion inhibitors, foam regulators, stabilizers, possibly odorants, dyes etc.
- the focus is usually on the surfactant content, usually a combination of anionic and non-ionic surfactants, the essential basis of which is petroleum today.
- the object of the invention was therefore to find a surfactant combination for powdered detergents which are largely made from renewable raw materials and which are extremely biodegradable, these powders having to achieve very good washing results.
- This object was achieved by a surfactant combination consisting of alkyl polyglycosides with a degree of glycosidation ⁇ 1.4 as well as fatty alcohol oxyethylates, anionic surfactants and soap.
- alkyl polyglycosides in combination with fatty alcohol oxyethylates in the presence of small quantities of anionic surfactants, achieve very good washing results in the powder mixtures according to the invention.
- alkyl polyglycoside in combination with anionic and nonionic surfactants is described in European applications EP-0 075 994, EP-0 075 995 and EP-0 075 996; here the degree of glycosidation is G ⁇ 1.5.
- Alkyl polyglycosides used according to the invention satisfy formula I.
- Alkyl polyglucosides are particularly preferred.
- 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, likewise 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 is determined by the choice of the long-chain alcohol.
- the industrially accessible alcohols with 8 to 18 carbon atoms, in particular 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 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 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 exist side by side with ⁇ - and ⁇ -glycosidic bonds in pyranose and furanose form. The junctions between two Saccachrid residues are also different.
- Alkyl polyglycosides used according to the invention can also be prepared by mixing alkyl polyglycosides with alkyl monoglycosides.
- the latter can e.g. B. according to EP-A 0 092 355 using polar solvents, such as acetone, from alkyl polyglycosides.
- the degree of glycosidation is expediently determined by means of 1 H-NMR.
- the detergents according to the invention contain 2 to 18% alkyl polyglycoside, preferably 3 to 15%.
- 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 plant simulation model / DOC analysis, is 96 ⁇ 3%. This number can be seen against the background that with this test method (total degradation) a degree of degradation ⁇ 70% already indicates the substance to be readily degradable.
- the acute oral toxicity LD 50 (rat) with> 10,000 mg / kg as well as the aquatic toxicity LC 50 (gold orfe) with approx. 12 mg / l and EC 50 (daphnia) with 30 mg / l are by a factor of 3 to 5 cheaper than the corresponding values of today's most important surfactants. The same applies to skin and mucous membrane compatibility.
- the compounds are generally made by addition of ethylene oxide onto longer-chain alcohols in the presence of basic or acidic Catalysts made.
- basic or acidic Catalysts made.
- 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 regarding aquatoxicity, skin and mucous membrane compatibility are also favorable.
- the powder detergents according to the invention contain 2 to 18% fatty alcohol oxyethylates, which can also be mixtures. Contents of 3 to 15% by weight are preferred.
- Anionic surfactants :
- Anionic surfactants used are alkylbenzene sulfonate, alkane sulfonates, olefin sulfonates, fatty alcohol sulfates and fatty alcohol ether sulfates or their mixtures with 9 to 20 carbon atoms in the alkyl or alkylene group. Na, K, NH4, Mg and their mixtures are the counterions. These anionic surfactants, which can be present in the mixtures according to the invention in amounts of 0 to 12% by weight, are not to be understood as soap. Amounts of 1 to 10% by weight are preferred.
- Fatty acid salts or their acids according to the invention correspond to formula III R '''COOP III, 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 0.5 to 30% soap, which will usually be a mixture of different components. Contents of 1 to 25% are preferred.
- 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 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, S. (1988).
- concentration of the bleaching agents is 0 to 40%, preferably 0-30%.
- Adjusting agents such as low molecular weight monohydric or dihydric alcohols, alkyl ethers of polyhydric alcohols, hydrotropics 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 are optionally used according to the invention
- the total use concentration of the powder detergents according to the invention is 0.1-10 g / l for the surfactant fraction according to the invention. 0.2-7 g / l are preferred.
- the washing powders listed in Table 1 contain, in addition to the surfactant components mentioned according to the invention, 11% sodium perborate, 1.7% sodium metasilicate, 2.5% magnesium silicate, 14% Na2SO4, 3% Sokalan R CP 5, 9% soda, 23% wessalith R P, 4% TAED R and 0.5% Sequion R 10 NA 2.
- the washing powders listed in Table 2 contain, in addition to the surfactant components mentioned, 11% sodium perborate, 1.7% sodium metasilicate, 2.5% magnesium silicate, 14% Na2SO4, 14.5% Na5P3O10, 4% soda, 14% Wessalith R P, 3% TAED R , 0.5% Sequion R 10 NA 2 and 1% Na3PO4.
- the liquid components were added to the mixture of solid components in small portions with intensive stirring. Stirring ensures sample homogeneity.
- the known methods were used to characterize the powders in terms of bulk density and angle of repose.
- the washability was determined in a normal household washing machine, and the foam development was also checked.
Abstract
Description
Die vorliegende Erfindung betrifft pulverförmige Zubereitungen zum Waschen von Textilien, deren Tenside weitestgehend aus nachwachsenden Rohstoffen hergestellt werden.The present invention relates to powdered preparations for washing textiles, the surfactants of which are largely made from renewable raw materials.
Pulverwaschmittel, hergestellt entweder durch Sprühtrocknungs- oder Agglomerationsverfahren bestehen heute aus Tensiden, Buildern, Bleichmitteln sowie Zusätzen in kleineren Mengen wie optischen Aufhellern, Vergrauungsinhibitoren, Korrosionsinhibitoren, Schaumregulatoren, Stabilisatoren, evtl. Geruchsstoffen, Farbstoffen etc. Im Vordergrund steht gewöhnlich der tensidische Anteil, meist eine Kombination aus anionischen und nichtionischen Tensiden, dessen wesentliche Basis heute das Erdöl ist.Powder detergents, produced either by spray drying or agglomeration processes, today consist of surfactants, builders, bleaches and additives in smaller quantities such as optical brighteners, graying inhibitors, corrosion inhibitors, foam regulators, stabilizers, possibly odorants, dyes etc. The focus is usually on the surfactant content, usually a combination of anionic and non-ionic surfactants, the essential basis of which is petroleum today.
Im Hinblick auf die zukünftige Rohstoffsituation (Erdölverknappung) ist eine petrochemische Basis ein erheblicher Nachteil. Ein weiterer Nachteil besteht darin, daß die biologische Abbaubarkeit dieser Tenside nicht das entsprechende Niveau auf nativer Basis erreicht.With regard to the future raw material situation (oil shortage), a petrochemical basis is a considerable disadvantage. Another disadvantage is that the biodegradability of these surfactants does not reach the corresponding level on a native basis.
Aufgabe der Erfindung war es daher, eine Tensidkombination für pulverförmige Waschmittel aufzufinden, die weitestgehend aus nachwachsenden Rohstoffen hergestellt werden und die hervorragend biologisch abbaubar sind, wobei diese Pulver sehr gute Waschergebnisse erzielen müssen.The object of the invention was therefore to find a surfactant combination for powdered detergents which are largely made from renewable raw materials and which are extremely biodegradable, these powders having to achieve very good washing results.
Diese Aufgabe wurde gelöst durch eine Tensidkombination bestehend aus Alkylpolyglycosiden mit einem Glycosidierungsgrad ≦ 1,4 sowie Fettalkoholoxethylaten, Aniontensiden und Seife.This object was achieved by a surfactant combination consisting of alkyl polyglycosides with a degree of glycosidation ≦ 1.4 as well as fatty alcohol oxyethylates, anionic surfactants and soap.
Gegenstand der Erfindung ist daher ein Waschmittelpulver, dessen tensidischer Anteil
2 bis 18 Gew.-% Alkylpolyglycosid,
≦ 12 Gew.-% Aniontensid,
2 bis 18 Gew.-% Fettalkoholoxethylat und
0,5 bis 30 Gew.-% Seife
enthält, welches dadurch gekennzeichnet ist, daß das Alkylpolyglycosid der Formel I
R-O-Zn I,
in der R für einen linearen oder verzweigten, gesättigten oder ungesättigten aliphatischen Alkylrest mit 8 bis 18 Kohlenstoffatomen oder Gemische davon und Zn für einen Polyglycosylrest mit n = 1,0 bis 1,4 Hexose- oder Pentoseeinheiten oder Gemische stehen, entspricht.The invention therefore relates to a detergent powder, the surfactant component
2 to 18% by weight alkyl polyglycoside,
≦ 12% by weight anionic surfactant,
2 to 18 wt .-% fatty alcohol oxyethylate and
0.5 to 30 wt% soap
contains, which is characterized in that the alkyl polyglycoside of formula I
RON n I,
in which R represents a linear or branched, saturated or unsaturated aliphatic alkyl radical having 8 to 18 carbon atoms or mixtures thereof and Z n represents a polyglycosyl radical with n = 1.0 to 1.4 hexose or pentose units or mixtures.
Überraschenderweise wurde gefunden, daß Alkylpolyglycoside in Kombination mit Fettalkoholoxethylaten bei gleichzeitiger Anwesenheit von anionischen Tensiden in kleinen Mengen in den erfindungsgemäßen Pulvermischungen sehr gute Waschergebnisse erzielen.Surprisingly, it was found that alkyl polyglycosides in combination with fatty alcohol oxyethylates, in the presence of small quantities of anionic surfactants, achieve very good washing results in the powder mixtures according to the invention.
Die Verwendung von Alkylpolyglycosid in Kombination mit anionischen und nichtionischen Tensiden wird in den europäischen Anmeldungen EP-0 075 994, EP-0 075 995 und EP-0 075 996 beschrieben; hierbei liegt der Glycosidierungsgrad aber bei G ≧ 1,5.The use of alkyl polyglycoside in combination with anionic and nonionic surfactants is described in European applications EP-0 075 994, EP-0 075 995 and EP-0 075 996; here the degree of glycosidation is G ≧ 1.5.
Eine spezielle Abmischung von Alkylpolyglycosid mit Alkylsulfat wird in EP-0 370 312 beansprucht; hier liegt der Glycosidierungsgrad bei 1 bis 10.A special mixture of alkyl polyglycoside with alkyl sulfate is claimed in EP-0 370 312; here the degree of glycosidation is 1 to 10.
Ähnlich spezielle Abmischungen von Alkylpolyglycosiden, bei denen als weiterer tensidischer Anteil Alkylbenzolsulfonat oder Niotensid empfohlen wird, sind in der Broschüre "Henkel APG" (April 1990) aufgeführt.Similarly, special mixtures of alkyl polyglycosides, in which alkylbenzenesulfonate or nonionic surfactant is recommended as a further surfactant component, are listed in the brochure "Henkel APG" (April 1990).
Erfindungsgemäß eingesetzte Alkylpolyglycoside genügen der Formel I
R-O-Zn I,
in der R für einen linearen oder verzweigten, gesättigten oder ungesättigten aliphatischen Alkylrest mit 8 bis 18 Kohlenstoffatomen oder Gemische davon und Zn für einen Polyglycosylrest mit n = 1,0 bis 1,4 Hexose- oder Pentoseeinheiten oder Gemische davon stehen. Bevorzugt werden Alkylpolyglycoside mit Alkylresten mit 9 bis 16 Kohlenstoffatomen sowie einem Polyglycosylrest von n = 1,1 bis 1,4. Besonders bevorzugt werden Alkylpolyglucoside.Alkyl polyglycosides used according to the invention satisfy formula I.
RON n I,
in the R for a linear or branched, saturated or unsaturated aliphatic alkyl radical having 8 to 18 carbon atoms or Mixtures thereof and Z n stand for a polyglycosyl radical with n = 1.0 to 1.4 hexose or pentose units or mixtures thereof. Alkyl polyglycosides with alkyl radicals with 9 to 16 carbon atoms and a polyglycosyl radical with n = 1.1 to 1.4 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, likewise in the presence of an acidic catalyst, to give the desired alkylpolyglycoside mixtures. Or dextrose is immediately reacted with the desired long-chain alcohol.
Die Struktur der Produkte ist in bestimmten Grenzen variierbar. Der Alkylrest R wird durch die Auswahl des langkettigen Alkohols festgelegt. Günstig aus wirtschaftlichen Gründen sind die großtechnisch zugänglichen Alkohole mit 8 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 is determined by the choice of the long-chain alcohol. Favorable for economic reasons are the industrially accessible alcohols with 8 to 18 carbon atoms, in particular native alcohols from the hydrogenation of carboxylic acids or carboxylic acid derivatives. Ziegler alcohols or oxo alcohols can also be used.
Die Polyglycosylreste Zn werden 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 radicals Z n 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 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 exist side by side with α- and β-glycosidic bonds in pyranose and furanose form. The junctions between two Saccachrid residues are also different.
Erfindungsgemäß eingesetzte Alkylpolyglycoside lassen sich auch durch Abmischen von Alkylpolyglycosiden mit Alkylmonoglycosiden herstellen. Letztere kann man z. B. nach EP-A 0 092 355 mittels polarer Lösemittel, wie Aceton, aus Alkylpolyglycosiden gewinnen bzw. anreichern.Alkyl polyglycosides used according to the invention can also be prepared by mixing alkyl polyglycosides with alkyl monoglycosides. The latter can e.g. B. according to EP-A 0 092 355 using polar solvents, such as acetone, from alkyl polyglycosides.
Der Glycosidierungsgrad wird zweckmäßigerweise mittels ¹H-NMR bestimmt.The degree of glycosidation is expediently determined by means of 1 H-NMR.
Die erfindungsgemäßen Waschmittel enthalten 2 bis 18 % Alkylpolyglycosid, vorzugsweise 3 bis 15 %.The detergents according to the invention contain 2 to 18% alkyl polyglycoside, preferably 3 to 15%.
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 plant simulation model / DOC analysis, is 96 ± 3%. This number can be seen against the background that with this test method (total degradation) a degree of degradation ≧ 70% already indicates the substance to be readily degradable.
Auch die akute orale Toxizität LD 50 (Ratte) mit > 10 000 mg/kg sowie die aquatische Toxizität LC 50 (Goldorfe) mit ca. 12 mg/l und EC 50 (Daphnien) mit 30 mg/l liegen um den Faktor 3 bis 5 günstiger als die entsprechenden Werte der heute wichtigsten Tenside. Ähnliches gilt für die Haut- und Schleimhautverträglichkeit.The acute oral toxicity LD 50 (rat) with> 10,000 mg / kg as well as the aquatic toxicity LC 50 (gold orfe) with approx. 12 mg / l and EC 50 (daphnia) with 30 mg / l are by a factor of 3 to 5 cheaper than the corresponding values of today's most important surfactants. The same applies to skin and mucous membrane compatibility.
Die erfindungsgemäß eingesetzten Fettalkoholoxethylate entsprechen Verbindungen der Formel II
R''-O-(CH₂-CH₂-O)xH II,
in der R'' ein linearer oder verzweigter, gesättigter oder ungesättigter Alkylrest mit 8 bis 22, vorzugsweise 10 bis 20 Kohlenstoffatomen und x = 2 bis 20, vorzugsweise 3 bis 15 bedeuten.The fatty alcohol oxyethylates used according to the invention correspond to compounds of the formula II
R '' - O- (CH₂-CH₂-O) x H II,
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 made by addition of ethylene oxide onto longer-chain alcohols in the presence of basic or acidic Catalysts made. For economic 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 regarding aquatoxicity, skin and mucous membrane compatibility are also favorable.
Die erfindungsgemäßen pulverförmigen Waschmittel enthalten 2 bis 18 % Fettalkoholoxethylate, die auch Gemische sein können. Bevorzugt sind Gehalte von 3 bis 15 Gew.-%.The powder detergents according to the invention contain 2 to 18% fatty alcohol oxyethylates, which can also be mixtures. Contents of 3 to 15% by weight are preferred.
Als Aniontenside finden Alkylbenzolsulfonat, Alkansulfonate, Olefinsulfonate, Fettalkoholsulfate und Fettalkoholethersulfate bzw. ihre Mischungen mit 9 bis 20 C-Atomen in der Alkyl- bzw. Alkylengruppe Verwendung. Na, K, NH₄, Mg sowie deren Gemische sind die Gegenionen. Unter diesen Aniontensiden, die in Mengen von 0 bis 12 Gew.-% in den erfindungsgemäßen Mischungen anwesend sein können, wird keine Seife verstanden. Bevorzugt sind Mengen von 1 bis 10 Gew.-%.Anionic surfactants used are alkylbenzene sulfonate, alkane sulfonates, olefin sulfonates, fatty alcohol sulfates and fatty alcohol ether sulfates or their mixtures with 9 to 20 carbon atoms in the alkyl or alkylene group. Na, K, NH₄, Mg and their mixtures are the counterions. These anionic surfactants, which can be present in the mixtures according to the invention in amounts of 0 to 12% by weight, are not to be understood as soap. Amounts of 1 to 10% by weight are preferred.
Erfindungsgemäße fettsaure Salze bzw. ihre Säuren entsprechen der Formel III
R'''COOP III,
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 III
R '''COOP III,
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 0,5 bis 30 % Seife, die meist ein Gemisch von verschiedenen Komponenten sein wird. Bevorzugt werden Gehalte von 1 bis 25 %.The detergents according to the invention contain 0.5 to 30% soap, which will usually be a mixture of different components. Contents of 1 to 25% are preferred.
Als nicht-tensidische 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 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, citrates, 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. (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, S. (1988). The concentration of the bleaching agents is 0 to 40%, preferably 0-30%.
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 pulverförmige Waschmittel übliche Inhaltsstoffe.Adjusting agents such as low molecular weight monohydric or dihydric alcohols, alkyl ethers of polyhydric alcohols, hydrotropics 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 are optionally used according to the invention Brighteners based in particular on stilbene and pyrazoline, foam regulators, graying inhibitors such as, for. B. carboxymethyl cellulose, perfume oils, dyes and other ingredients common to powder detergents.
Die Gesamteinsatzkonzentration der erfindungsgemäßen Pulverwaschmittel beträgt für den erfindungsgemäßen tensidischen Anteil 0,1 - 10 g/l. Bevorzugt werden 0,2 - 7 g/l.The total use concentration of the powder detergents according to the invention is 0.1-10 g / l for the surfactant fraction according to the invention. 0.2-7 g / l are preferred.
Durch die nachfolgenden Beispiele wird die Erfindung erläutert.The invention is illustrated by the following examples.
Die in Tabelle 1 aufgeführten Waschpulver enthalten außer den genannten, erfindungsgemäß verwendeten tensidischen Bestandteilen jeweils 11 % Natriumperborat, 1,7 % Natriummetasilikat, 2,5 % Magnesiumsilikat, 14 % Na₂SO₄, 3 % SokalanR CP 5, 9 % Soda, 23 % WessalithR P, 4 % TAEDR und 0,5 % SequionR 10 NA 2.The washing powders listed in Table 1 contain, in addition to the surfactant components mentioned according to the invention, 11% sodium perborate, 1.7% sodium metasilicate, 2.5% magnesium silicate, 14% Na₂SO₄, 3% Sokalan R CP 5, 9% soda, 23% wessalith R P, 4% TAED R and 0.5% Sequion R 10 NA 2.
Die in Tabelle 2 aufgeführten Waschpulver enthalten außer den genannten tensidischen Bestandteilen 11 % Natriumperborat, 1,7 % Natriummetasilikat, 2,5 % Magnesiumsilikat, 14 % Na₂SO₄, 14,5 % Na₅P₃O₁₀, 4 % Soda, 14 % WessalithR P, 3 % TAEDR, 0,5 % SequionR 10 NA 2 und 1 % Na₃PO₄.The washing powders listed in Table 2 contain, in addition to the surfactant components mentioned, 11% sodium perborate, 1.7% sodium metasilicate, 2.5% magnesium silicate, 14% Na₂SO₄, 14.5% Na₅P₃O₁₀, 4% soda, 14% Wessalith R P, 3% TAED R , 0.5% Sequion R 10 NA 2 and 1% Na₃PO₄.
Zur Herstellung der Pulver wurden die Flüssigkomponenten in einer Mischmaschine dem vorgelegten Gemisch der festen Komponenten unter intensiven Rühren in kleinen Portionen zugefügt. Nachrühren gewährleistet Probenhomogenität.To produce the powders, the liquid components were added to the mixture of solid components in small portions with intensive stirring. Stirring ensures sample homogeneity.
Zur Charakterisierung der Pulver hinsichtlich Schüttdichte und Schüttwinkel wurden die bekannten Methoden verwendet. Das Waschvermögen wurde in einer normalen Haushaltswaschmaschine bestimmt, hierbei wurde ebenfalls die Schaumentwicklung geprüft.The known methods were used to characterize the powders in terms of bulk density and angle of repose. The washability was determined in a normal household washing machine, and the foam development was also checked.
Als Modellgewebe dienten 11 x 18 cm große Lappen aus WFK-Testgewebe mit Hautfett-Pigmentanschmutzung: Polyester (PE), Mischgewebe (MG) und Baumwolle (BW), die auf Baumwollhandtüchern aufgenäht sind. Gleichzeitig wird die Waschmaschine mit 4 kg Ballastgewebe beschickt. Als Wasser dient Trinkwasser (13° dH), die Wirkstoffkonzentration beträgt 5 g/l, der pH jeweils 8, das Flottenverhältnis 1 : 4 und die Waschzeit etwa 60 Minuten. Die Waschwerte nach dem Trocknen der Gewebe wurden - wie üblich - spektralphotometrisch relativ zu einem Weißstandard (Datacolor, 560 nm) gemessen.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), which are sewn onto cotton towels. At the same time, the washing machine is loaded with 4 kg of ballast fabric. Drinking water (13 ° dH) serves as water, the active ingredient concentration is 5 g / l, the pH is 8 in each case, the liquor ratio is 1: 4 and the washing time is about 60 minutes. The washing values after drying the fabrics were - as usual - measured spectrophotometrically relative to a white standard (Datacolor, 560 nm).
Wie die Tabelle 1 (phosphatfreie Waschpulver) und Tabelle 2 (phosphathaltige Waschpulver) zeigen, unterscheiden sich die Pulvereigenschaften nur unwesentlich jeweils von den marktüblichen Produkten.As Table 1 (phosphate-free washing powder) and Table 2 (phosphate-containing washing powder) show, the powder properties differ only slightly from the products on the market.
Überraschend dagegen ist das bei den erfindungsgemäßen Formulierungen deutlich verbesserte Waschvermögen sowohl gegenüber den Marktprodukten 9 (V) bis 7 (V) als auch gegenüber bekannten alkylpolyglycosidhaltigen Formulierungen [1 (V) bis 3 (V)]. Folgende Abkürzungen wurden in den Tabellen verwendet:
- C₁₂C₁₃ [G 1.1]
- - C12/13-Alkylpolyglycosid mit einem Glycosidierungsgrad von 1.1
- C₁₂C₁₄ [G 1.2]
- - C12/14-Alkylpolyglycosid mit einem Glycosidierungsgrad von 1.2
- C₁₂C₁₄ [G 1.4]
- - C12/14-Alkylpolyglycosid mit einem Glycosidierungsgrad von 1.4
- C₁₂C₁₄O(EO)₆H
- - Fettalkoholoxethylat mit Alkylkette = C12/14 und 6 Mol EO/mol
- C₁₀C₁₃-ABS-Na
- - Alkylbenzolsulfonat mit Alkylkette = C₁₀ - C₁₃, Na-Salz
- C₁₆C₁₈-SO₄Na
- - Alkylsulfat mit Alkylkette = C16/18, Na-Salz
- PE
- - Polyester
- MG
- - Mischgewebe
- BW
- - Baumwolle
- C₁₂C₁₃ [G 1.1]
- - C 12/13 alkyl polyglycoside with a degree of glycosidation of 1.1
- C₁₂C₁₄ [G 1.2]
- - C 12/14 alkyl polyglycoside with a degree of glycosidation of 1.2
- C₁₂C₁₄ [G 1.4]
- - C 12/14 alkyl polyglycoside with a degree of glycosidation of 1.4
- C₁₂C₁₄O (EO) ₆H
- - Fatty alcohol oxyethylate with alkyl chain = C 12/14 and 6 mol EO / mol
- C₁₀C₁₃-ABS-Na
- - Alkylbenzenesulfonate with an alkyl chain = C₁₀ - C₁₃, Na salt
- C₁₆C₁₈-SO₄Na
- - Alkyl sulfate with alkyl chain = C 16/18 , Na salt
- PE
- - polyester
- MG
- - blended fabrics
- BW
- - cotton
Claims (5)
- A powder detergent whose surfactant portion contains
2 to 18% by weight of alkyl polyglycoside,
≦ 12% by weight of anionic surfactant,
2 to 18% by weight of fatty alcohol oxyethylate and
0.5 to 30% by weight of soap,
characterized in that the alkyl polyglycoside corresponds to the formula I
R-O-Zn I,
in which R is a linear or branched, saturated or unsaturated aliphatic alkyl radical having 8 to 18 carbon atoms or mixtures thereof, and Zn is a polyglycosyl radical with n = 1.0 to 1.4 hexose or pentose units or mixtures. - A powder detergent according to claim 1, characterized in that the fatty alcohol oxyethylate corresponds to the formula II
R''-O-(CH₂-CH₂-O)xH II
in which R'' is a linear or branched, saturated or unsaturated alkyl radical having 8 to 22 carbon atoms and x is 2 to 20. - A powder detergent according to either of claims 1 and 2, characterized in that the anionic surfactant is alkylbenzenesulphonate, alkanesulphonate, olefin-sulphonate, fatty alcohol sulphate and/or fatty alcohol ether sulphate, where in each case the alkyl or alkylene group contains 9 to 18 C atoms, and Na, K, NH₄, Mg and mixtures thereof are the counter-ions.
- A powder detergent according to any of claims 1 to 3, characterized in that the soap corresponds to the formula III
R'''COOP III
in which R''' is a saturated and/or unsaturated alkyl radical having 8 to 22 carbon atoms and P is hydrogen, alkali metal, ammonium or alkanolammonium. - A powder detergent according to any of claims 1 to 4, characterized in that the surfactant portion concentration used is 0.1 to 10 g/l.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4101070A DE4101070A1 (en) | 1991-01-16 | 1991-01-16 | WASHING POWDER |
| DE4101070 | 1991-01-16 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0495176A2 EP0495176A2 (en) | 1992-07-22 |
| EP0495176A3 EP0495176A3 (en) | 1992-10-14 |
| EP0495176B1 true EP0495176B1 (en) | 1995-06-21 |
Family
ID=6423098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91119602A Revoked EP0495176B1 (en) | 1991-01-16 | 1991-11-16 | Detergent powder |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0495176B1 (en) |
| AT (1) | ATE124080T1 (en) |
| DE (2) | DE4101070A1 (en) |
| DK (1) | DK0495176T3 (en) |
| ES (1) | ES2074204T3 (en) |
| NO (1) | NO920186L (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7297672B2 (en) | 2002-12-03 | 2007-11-20 | Unilever Home & Personal Care Usa Division Of Conopco, Inc. | Laundry treatment compositions comprising a β1-4 linked substituted polysaccharide |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19807807A1 (en) * | 1998-02-26 | 1999-09-02 | Henkel Kgaa | Powdery to granular detergent and cleaning agent |
| WO2011047498A1 (en) | 2009-10-20 | 2011-04-28 | Unilever Plc | Improvements to laundry compositions |
| WO2011047951A1 (en) | 2009-10-20 | 2011-04-28 | Unilever Plc | Laundry compositions |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GR76286B (en) * | 1981-09-28 | 1984-08-04 | Procter & Gamble | |
| US4536319A (en) * | 1983-10-04 | 1985-08-20 | The Procter & Gamble Company | Compositions comprising alkylpolysaccharide detergent surfactant |
| DE4029035A1 (en) * | 1990-09-13 | 1992-03-19 | Huels Chemische Werke Ag | LAUNDRY DETERGENT |
-
1991
- 1991-01-16 DE DE4101070A patent/DE4101070A1/en not_active Withdrawn
- 1991-11-16 EP EP91119602A patent/EP0495176B1/en not_active Revoked
- 1991-11-16 DK DK91119602.0T patent/DK0495176T3/en active
- 1991-11-16 AT AT91119602T patent/ATE124080T1/en not_active IP Right Cessation
- 1991-11-16 ES ES91119602T patent/ES2074204T3/en not_active Expired - Lifetime
- 1991-11-16 DE DE59105791T patent/DE59105791D1/en not_active Revoked
-
1992
- 1992-01-15 NO NO92920186A patent/NO920186L/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7297672B2 (en) | 2002-12-03 | 2007-11-20 | Unilever Home & Personal Care Usa Division Of Conopco, Inc. | Laundry treatment compositions comprising a β1-4 linked substituted polysaccharide |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0495176A2 (en) | 1992-07-22 |
| NO920186L (en) | 1992-07-17 |
| DK0495176T3 (en) | 1995-10-02 |
| NO920186D0 (en) | 1992-01-15 |
| DE4101070A1 (en) | 1992-07-23 |
| EP0495176A3 (en) | 1992-10-14 |
| DE59105791D1 (en) | 1995-07-27 |
| ATE124080T1 (en) | 1995-07-15 |
| ES2074204T3 (en) | 1995-09-01 |
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