EP0582608B1 - Liquid washing agent - Google Patents

Liquid washing agent Download PDF

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Publication number
EP0582608B1
EP0582608B1 EP92909170A EP92909170A EP0582608B1 EP 0582608 B1 EP0582608 B1 EP 0582608B1 EP 92909170 A EP92909170 A EP 92909170A EP 92909170 A EP92909170 A EP 92909170A EP 0582608 B1 EP0582608 B1 EP 0582608B1
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EP
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Prior art keywords
weight
citric acid
detergent
alkyl
polyhydric alcohol
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EP92909170A
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German (de)
French (fr)
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EP0582608A1 (en
Inventor
Karl Schwadtke
Eric Sung
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric 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
    • C11D1/14—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
    • C11D1/66—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

  • Liquid detergents are an alternative to powder detergents, whereby liquid detergents are to be understood below as pourable products as well as products with pasty or ointment-like consistency. Compared to powder detergents, the liquid detergents have some handling advantages and other performance focuses. In particular, larger amounts of nonionic surfactants can be incorporated into liquid detergents than into powder detergents, which has the advantage of greater effectiveness against oily and greasy soiling.
  • Liquid detergents have been known for a long time. Nevertheless, it is desirable to look for further improvements in washing performance and in terms of the possibility of producing the liquid detergents using largely renewable raw materials.
  • a liquid detergent which can be used universally at washing temperatures of 15-90 ° C. and is particularly suitable for washing highly sensitive textiles is known from German patent application DE-A-39 20 480. It contains anionic surfactants, nonionic surfactants, alkyl glucosides, soaps of unsaturated and saturated fatty acids, polyhydric alcohol and citric acid in certain weight ratios. The object of the present invention is to further improve this detergent.
  • the present invention therefore relates to a liquid detergent containing anionic surfactants of the sulfonate and sulfate type, nonionic surfactants, alkyl glucosides, a mixture of soaps of unsaturated and saturated fatty acids, polyhydric alcohols and citric acid or sodium citrate, the agent of the present invention being characterized in that that it contains 10 to 20% by weight of citric acid or sodium citrate, calculated as citric acid, 3 to 10% by weight of anionic surfactants of the sulfonate and sulfate type and that the degree of oligomerization of the alkyl glucosides used is between 1.10 and 1.45.
  • the liquid detergent of DE-A-39 20 480 also contains citric acid; Indeed the citric acid content in the agents of DE-A-39 20 480 is very much lower; it is below 2% by weight.
  • GB-A-2232420 relates to extremely mild, strictly anionic surfactant-free liquid detergents with a translucent appearance. These can preferably contain citric acid in amounts of 2 to 5% by weight. Due to the citric acid content according to the invention, a significant improvement in washing performance compared to the known agents of the prior art is achieved, so that better washing results are achieved either with the same or a lower dosage than with liquid detergents of the prior art, or, on the other hand, by a substantial lower dosage of the detergent according to the invention can achieve an equally good washing performance.
  • Suitable anionic surfactants for the detergents according to the invention are surfactants of the sulfonate and in particular sulfate type.
  • Suitable sulfates are sulfuric acid monoesters of C 12 -C 18 fatty alcohols, such as, for example, lauryl, myristyl or cetyl alcohol and the fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil and tallow, which may additionally contain proportions of unsaturated alcohols, for example oleyl alcohol.
  • Mixtures in which the proportions of the alkyl radicals are 50 to 70% by weight on C 12 , 18 to 30% by weight on C 14 , 5 to 15% by weight on C 16 , are preferred 3% by weight on C 10 and less than 10% by weight on C 18 are distributed.
  • the proportion of these anionic surfactants in the agents according to the invention is 3 to 10% by weight.
  • Nonionic surfactants in the sense of the present patent application are addition products of 1 to 10 mol ethylene oxide and / or propylene oxide with primary C 12 to C 18 fatty alcohol and their mixtures such as coconut oil, tallow fat or oleyl alcohol. Oxoalcohol ethoxylates are also suitable, but less preferred due to their production from fossil raw materials.
  • the nonionic surfactants mentioned can be present in the agents according to the invention in an amount of 15 to 30% by weight. This proportion does not include the alkyl glucosides, which are also nonionic surfactants.
  • Suitable alkyl glucosides which are also contained in the liquid detergent according to the invention are, in particular, glucosides having a C 8 to C 22 alkyl radical, preferably having an alkyl radical consisting essentially of C 12 to C 18 , which is derived from lauryl, myristyl, Cetyl and stearyl alcohol and technical fractions, which preferably contain saturated alcohols.
  • the use of is particularly preferred Alkyl glucosides, the alkyl radical of which contains 50 to 70% by weight of C 12 and 18 to 30% by weight of C 14 .
  • the degree of oligomerization (DP) of the alkyl glucosides used in the detergents according to the invention is between 1.10 and 1.45.
  • An essential component of the liquid detergent according to the invention is a mixture of soaps of unsaturated and saturated fatty acids.
  • the fatty acids have 12 to 18 carbon atoms.
  • a preferably used soap mixture is formed from sodium oleate and the sodium salts of the saturated C 12 to C 16 fatty acid mixtures.
  • the proportion of C 12 to C 14 fatty acids is expediently at least 60% by weight, preferably at least 75% by weight (calculated as fatty acid). Suitable for this purpose are, for example, coconut fatty acids, from which the portions with 10 or fewer carbon atoms are largely separated.
  • oleic acid and coconut fatty acid can still contain certain proportions of stearic acid, but their proportion, based on soap-forming fatty acids, should be at most 25% by weight, preferably less than 20% by weight.
  • a soap mixture of sodium oleate and the sodium salt of lauric acid is also preferred.
  • the weight ratio of saturated to unsaturated fatty acid is preferably about 2: 1 to 1: 2.
  • the liquid detergents according to the invention contain at least one polyhydric alcohol as solvent.
  • 1,2-Propanediol or preferably glycerol can be used as the polyhydric alcohol.
  • the liquid detergent according to the present invention can also contain monohydric alcohol, preferably ethanol.
  • An essential component of the present invention of the present liquid detergent is the high content of citric acid or sodium citrate, which makes up 10 to 20% by weight, calculated as citric acid.
  • Preferred liquid detergents contain 12 to 18% by weight of citric acid or sodium citrate, calculated as citric acid. It is unpredictable for the person skilled in the art that the citric acid content, which is many times higher than that of the prior art, can result in a drastic increase in the washing result. You can therefore with the detergent according to the invention at the same or even at a lower dosage than with the agent of the prior art technology to achieve better washing results or achieve a comparable washing result by significantly lower dosage.
  • Typical detergent ingredients are, for example, optical brighteners, enzymes, enzyme stabilizers, dyes, fragrances and complexing agents.
  • Foam inhibitors may also be present, for example organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Mixtures of different foam inhibitors can also advantageously be used, e.g. those made of silicone, paraffins or waxes.
  • the detergents according to the invention have liquid to pasty consistencies at room temperatures.
  • Pasty detergents can be produced in a liquid state at elevated temperature, for example at 70 ° C., using units for the production of liquid products. After cooling, such products assume a pasty consistency that is stable in storage.
  • the constituents of the detergents according to the invention can be largely or completely produced from renewable raw materials and are readily biodegradable.
  • the detergents had the following composition: Table 1 Detergent composition% by weight A B Coconut alkyl sulfate Na 4.5 5.0 Coconut alcohol + 7 moles of ethylene oxide 12.0 25.0 C 12/14 alkyl glucoside 1,4 1.5 1.5 Lauric acid Na 8.0 8.0 Palm kernel acid Na 6.0 6.0 Glycerin 5.0 7.0 citric acid 0.5 15.0 Caustic soda 2.6 1.5 Ethanol 6.0 - Protease 0.5 0.5 Amylase 0.05 0.05 Rest: water, dye, fragrance, optical brightener, viscosity regulator
  • the liquid detergent A was compared with the paste-like detergent B in a 1-stage washing program at 60 ° C in an automatic drum washing machine (type AEG-LAVA 670) at a water hardness of 16 ° C.
  • Detergent A with 120 grams and detergent B with 92.5 grams were dosed into 18 liters of washing water.
  • the washing result was evaluated by determining the color difference dE (w) in the Minolta CR-200 tester.
  • detergent B according to the invention gave better results. Even if only 60 g of the detergent according to the invention were dosed compared to 120 g of the detergent of the prior art, the tendency towards better washing results was obtained with the detergent according to the invention, namely for all types of soiling tested (skin fat / pigment, enzyme-specific soils, bleachable soils and cosmetics). Soiling).

Abstract

PCT No. PCT/EP92/00913 Sec. 371 Date Nov. 3, 1993 Sec. 102(e) Date Nov. 3, 1993 PCT Filed Apr. 25, 1992 PCT Pub. No. WO92/19711 PCT Pub. Date Nov. 12, 1992.An aqueous liquid detergent comprising an anionic surfactant, a nonionic surfactant, an alkyl glucoside, a soap of an unsaturated or saturated fatty acid, a polyhydric alcohol and from abut 10 to abut 20% by weight of citric acid or an alkali metal salt thereof.

Description

Flüssige Waschmittel stellen gegenüber pulverförmigen Waschmitteln eine alternative Anbietungsform dar, wobei unter flüssigen Waschmitteln im folgenden gießbare Produkte ebenso wie Produkte mit pastenförmiger oder salbenartiger Konsistenz verstanden werden sollen. Die flüssigen Waschmittel haben im Vergleich zu pulverförmigen Waschmitteln einige Handhabungsvorteile und andere Leistungsschwerpunkte. Insbesondere lassen sich in flüssige Waschmittel größere Mengen an nichtionischen Tensiden als in pulverförmige Waschmittel einarbeiten, was den Vorteil einer größeren Wirksamkeit gegenüber öligen und fettigen Verschmutzungen hat.Liquid detergents are an alternative to powder detergents, whereby liquid detergents are to be understood below as pourable products as well as products with pasty or ointment-like consistency. Compared to powder detergents, the liquid detergents have some handling advantages and other performance focuses. In particular, larger amounts of nonionic surfactants can be incorporated into liquid detergents than into powder detergents, which has the advantage of greater effectiveness against oily and greasy soiling.

Flüssige Waschmittel sind seit langem bekannt. Trotzdem ist es wünschenswert, nach weiteren Verbesserungen hinsichtlich der Waschleistung und hinsichtlich der Möglichkeit, die flüssigen Waschmittel unter weitgehender Verwendung von nachwachsenden Rohstoffen herzustellen, zu suchen. Ein flüssiges Waschmittel, das universell bei Waschtemperaturen von 15 - 90 °C anwendbar und insbesondere zum Waschen hochempfindlicher Textilien geeignet ist, ist aus der Deutschen Patentanmeldung DE-A-39 20 480 bekannt. Es enthält anionische Tenside, nichtionische Tenside, Alkylglucoside, Seifen ungesättigter und gesättigter Fettsäuren, mehrwertigen Alkohol und Citronensäure in bestimmten Gewichtsverhältnissen. Dieses Waschmittel weiter zu verbessern, ist Aufgabe der vorliegenden Erfindung.Liquid detergents have been known for a long time. Nevertheless, it is desirable to look for further improvements in washing performance and in terms of the possibility of producing the liquid detergents using largely renewable raw materials. A liquid detergent which can be used universally at washing temperatures of 15-90 ° C. and is particularly suitable for washing highly sensitive textiles is known from German patent application DE-A-39 20 480. It contains anionic surfactants, nonionic surfactants, alkyl glucosides, soaps of unsaturated and saturated fatty acids, polyhydric alcohol and citric acid in certain weight ratios. The object of the present invention is to further improve this detergent.

Gegenstand der vorliegenden Erfindung ist daher ein Flüssigwaschmittel, enthaltend anionische Tenside vom Typ der Sulfonate und Sulfate, nichtionische Tenside, Alkylglucoside, ein Gemisch aus Seifen ungesättigter und gesättigter Fettsäuren, mehrwertigen Alkoholen und Citronensäure bzw. Natriumcitrat, wobei das Mittel der vorliegenden Erfindung dadurch gekennzeichnet ist, daß es 10 bis 20 Gew.-% Citronensäure bzw. Natriumcitrat, berechnet als Citronensäure, 3 bis 10 Gew.-% Aniontenside vom Typ der Sulfonate und Sulfate enthält und der Oligomerisierungsgrad der verwendeten Alkylglucoside zwischen 1,10 und 1,45 liegt. Das Flüssigwaschmittel der DE-A-39 20 480 enthält zwar auch Citronensäure; allerdings ist der Citronensäuregehalt in den Mitteln der DE-A-39 20 480 sehr viel geringer; er liegt unter 2 Gew.-%. GB-A-2232420 betrifft extrem milde, streng aniontensidfreie Flüssigwaschmittel mit transluzentem Erscheinungsbild. Diese können Citronensäure vorzugsweise in Mengen von 2 bis 5 Gew.-% enthalten. Durch den erfindungsgemäßen Gehalt an Citronensäure wird eine deutliche Verbesserung der Waschleistung gegenüber den bekannten Mitteln des Standes der Technik erreicht, so daß man entweder bei gleicher oder auch niedrigerer Dosierung bessere Waschergebnisse als mit Flüssigwaschmitteln des Standes der Technik erzielt, oder wobei man andererseits durch eine wesentlich geringere Dosierung des erfindungsgemäßen Waschmittels eine gleichgute Waschleistung erzielen kann.The present invention therefore relates to a liquid detergent containing anionic surfactants of the sulfonate and sulfate type, nonionic surfactants, alkyl glucosides, a mixture of soaps of unsaturated and saturated fatty acids, polyhydric alcohols and citric acid or sodium citrate, the agent of the present invention being characterized in that that it contains 10 to 20% by weight of citric acid or sodium citrate, calculated as citric acid, 3 to 10% by weight of anionic surfactants of the sulfonate and sulfate type and that the degree of oligomerization of the alkyl glucosides used is between 1.10 and 1.45. The liquid detergent of DE-A-39 20 480 also contains citric acid; Indeed the citric acid content in the agents of DE-A-39 20 480 is very much lower; it is below 2% by weight. GB-A-2232420 relates to extremely mild, strictly anionic surfactant-free liquid detergents with a translucent appearance. These can preferably contain citric acid in amounts of 2 to 5% by weight. Due to the citric acid content according to the invention, a significant improvement in washing performance compared to the known agents of the prior art is achieved, so that better washing results are achieved either with the same or a lower dosage than with liquid detergents of the prior art, or, on the other hand, by a substantial lower dosage of the detergent according to the invention can achieve an equally good washing performance.

Als anionische Tenside kommen für die erfindungsgemäßen Waschmittel Tenside vom Typ der Sulfonate und insbesondere der Sulfate in Frage. Geeignete Sulfate sind Schwefelsäuremonoester der C12-C18-Fettalkohole, wie beispielsweise Lauryl-, Myristyl- oder Cetylalkohol und der aus Kokosöl, Palm- und Palmkernöl sowie Talg gewonnenen Fettalkoholgemische, die zusätzlich noch Anteile an ungesättigten Alkoholen, z.B. Oleylalkohol, enthalten können. Eine bevorzugte Verwendung finden dabei Gemische, in denen die Anteile der Alkylreste zu 50 bis 70 Gew.-% auf C12, zu 18 bis 30 Gew.-% auf C14, zu 5 bis 15 Gew.-% auf C16, unter 3 Gew.-% auf C10 und unter 10 Gew.-% auf C18 verteilt sind. Der Anteil an diesen anionischen Tensiden in den erfindungsgemäßen Mitteln liegt bei 3 bis 10 Gew.-%.Suitable anionic surfactants for the detergents according to the invention are surfactants of the sulfonate and in particular sulfate type. Suitable sulfates are sulfuric acid monoesters of C 12 -C 18 fatty alcohols, such as, for example, lauryl, myristyl or cetyl alcohol and the fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil and tallow, which may additionally contain proportions of unsaturated alcohols, for example oleyl alcohol. Mixtures in which the proportions of the alkyl radicals are 50 to 70% by weight on C 12 , 18 to 30% by weight on C 14 , 5 to 15% by weight on C 16 , are preferred 3% by weight on C 10 and less than 10% by weight on C 18 are distributed. The proportion of these anionic surfactants in the agents according to the invention is 3 to 10% by weight.

Nichtionische Tenside im Sinne der vorliegenden Patentanmeldung sind Anlagerungsprodukte von 1 bis 10 Mol Ethylenoxid und/oder Propylenoxid an primären C12-bis C18-Fettalkohol und deren Gemische wie Kokos-, Talgfett- oder Oleylalkohol. Oxoalkohol-Ethoxylate sind gleichfalls geeignet, jedoch aufgrund ihrer Herstellung aus fossilen Rohstoffen weniger bevorzugt. Die genannten nichtionischen Tenside können in den erfindungsgemäßen Mitteln zu 15 bis 30 Gew.-% enthalten sein. In diesem Anteil sind die ebenfalls zu den nichtionischen Tensiden zählenden Alkylglucoside nicht enthalten.Nonionic surfactants in the sense of the present patent application are addition products of 1 to 10 mol ethylene oxide and / or propylene oxide with primary C 12 to C 18 fatty alcohol and their mixtures such as coconut oil, tallow fat or oleyl alcohol. Oxoalcohol ethoxylates are also suitable, but less preferred due to their production from fossil raw materials. The nonionic surfactants mentioned can be present in the agents according to the invention in an amount of 15 to 30% by weight. This proportion does not include the alkyl glucosides, which are also nonionic surfactants.

Als Alkylglucoside, die in dem erfindungsgemäßen Flüssigwaschmittel ebenfalls enthalten sind, eignen sich insbesondere Glucoside mit einem C8- bis C22-Alkylrest, vorzugsweise mit einem im wesentlichen aus C12 bis C18 bestehenden Alkylrest, der sich von Lauryl-, Myristyl-, Cetyl- und Stearylalkohol sowie von technischen Fraktionen, die vorzugsweise gesättigte Alkohole enthalten, ableitet. Besonders bevorzugt ist der Einsatz von Alkylglucosiden, deren Alkylrest zu 50 bis 70 Gew.-% C12 und-18 bis 30 Gew.-% C14 enthält. Der Oligomerisierungsgrad (D.P.) der in den erfindungsgemäßen Waschmitteln verwendeten Alkylglucosiden liegt zwischen 1,10 und 1,45.Suitable alkyl glucosides which are also contained in the liquid detergent according to the invention are, in particular, glucosides having a C 8 to C 22 alkyl radical, preferably having an alkyl radical consisting essentially of C 12 to C 18 , which is derived from lauryl, myristyl, Cetyl and stearyl alcohol and technical fractions, which preferably contain saturated alcohols. The use of is particularly preferred Alkyl glucosides, the alkyl radical of which contains 50 to 70% by weight of C 12 and 18 to 30% by weight of C 14 . The degree of oligomerization (DP) of the alkyl glucosides used in the detergents according to the invention is between 1.10 and 1.45.

Ein wesentlicher Bestandteil des erfindungsgemäßen Flüssigwaschmittels ist ein Gemisch aus Seifen ungesättigter und gesättigter Fettsäuren. Die Fettsäuren haben 12 bis 18 Kohlenstoffatome. Ein bevorzugt verwendetes Seifengemisch wird aus Natriumoleat und den Natriumsalzen der gesättigten C12-bis C16-Fettsäuregemische gebildet. Der Anteil an C12- bis C14-Fettsäuren beträgt zweckmäßigerweise mindestens 60 Gew.-%, vorzugsweise mindestens 75 Gew.-% (gerechnet als Fettsäure). Geeignet hierfür sind z.B. Kokosfettsäuren, von denen die Anteile mit 10 und weniger C-Atomen weitgehend abgetrennt sind. Wie bei technischen Fettsäureschnitten üblich, können die Ölsäure sowie die Kokosfettsäure noch gewisse Anteile an Stearinsäure enthalten, jedoch soll deren Anteil, bezogen auf seifenbildende Fettsäuren, höchstens 25 Gew.-%, vorzugsweise weniger als 20 Gew.-% betragen. Ebenso bevorzugt ist ein Seifengemisch aus Natriumoleat und dem Natriumsalz der Laurinsäure. Das Gewichtsverhältnis von gesättigter zu ungesättigter Fettsäure beträgt vorzugsweise etwa 2:1 bis 1:2.An essential component of the liquid detergent according to the invention is a mixture of soaps of unsaturated and saturated fatty acids. The fatty acids have 12 to 18 carbon atoms. A preferably used soap mixture is formed from sodium oleate and the sodium salts of the saturated C 12 to C 16 fatty acid mixtures. The proportion of C 12 to C 14 fatty acids is expediently at least 60% by weight, preferably at least 75% by weight (calculated as fatty acid). Suitable for this purpose are, for example, coconut fatty acids, from which the portions with 10 or fewer carbon atoms are largely separated. As is customary in technical fatty acid cuts, oleic acid and coconut fatty acid can still contain certain proportions of stearic acid, but their proportion, based on soap-forming fatty acids, should be at most 25% by weight, preferably less than 20% by weight. A soap mixture of sodium oleate and the sodium salt of lauric acid is also preferred. The weight ratio of saturated to unsaturated fatty acid is preferably about 2: 1 to 1: 2.

Als Lösungsmittel enthalten die erfindungsgemäßen Flüssigwaschmittel neben Wasser wenigstens einen mehrwertigen Alkohol. Als mehrwertiger Alkohol kann 1,2-Propandiol oder vorzugsweise Glycerin verwendet werden. Daneben kann das Flüssigwaschmittel gemäß der vorliegenden Erfindung auch noch einwertigen Alkohol, vorzugsweise Ethanol enthalten.In addition to water, the liquid detergents according to the invention contain at least one polyhydric alcohol as solvent. 1,2-Propanediol or preferably glycerol can be used as the polyhydric alcohol. In addition, the liquid detergent according to the present invention can also contain monohydric alcohol, preferably ethanol.

Erfindungswesentlicher Bestandteil der vorliegenden Flüssigwaschmittel ist der hohe Gehalt an Citronensäure, bzw. an Natriumcitrat, der 10 bis 20 Gew.-%, berechnet als Citronensäure ausmacht. Bevorzugte Flüssigwaschmittel enthalten 12 bis 18 Gew.-% Citronensäure oder Natriumcitrat, berechnet als Citronensäure. Daß durch den um ein vielfaches höhere Citronensäuregehalt gegenüber den Mitteln des Standes der Technik eine drastische Steigerung des Waschergebnisses zu bewirken ist, ist für den Fachmann nicht vorhersehbar. Man kann daher mit dem erfindungsgemäßen Waschmittel bei gleicher oder auch bei niedrigerer Dosierung als mit dem Mitteln des Standes der Technik bessere Waschergebnisse erzielen oder durch deutlich geringere Dosierung ein vergleichbares Waschergebnis erzielen.An essential component of the present invention of the present liquid detergent is the high content of citric acid or sodium citrate, which makes up 10 to 20% by weight, calculated as citric acid. Preferred liquid detergents contain 12 to 18% by weight of citric acid or sodium citrate, calculated as citric acid. It is unpredictable for the person skilled in the art that the citric acid content, which is many times higher than that of the prior art, can result in a drastic increase in the washing result. You can therefore with the detergent according to the invention at the same or even at a lower dosage than with the agent of the prior art technology to achieve better washing results or achieve a comparable washing result by significantly lower dosage.

Erfindungsgemäße Waschmittel haben insbesondere die folgende Zusammensetzung:

4 bis 6 Gew.-%
anionisches Tensid, vorzugsweise Fettalkylsulfate in Form der Natriumsalze,
18 bis 28 Gew.-%
nichtionisches Tensid, vorzugsweise Fettalkoholethoxylate,
1 bis 4 Gew.-%
Alkylglucosid der Formel RO(G)x, in der R einen Fettalkylrest, G eine Glukoseeinheit und x einen Wert von 1,10 bis 1,45 bedeutet,
5 bis 10 Gew.-%
mehrwertigen Alkohol,
12 bis 18 Gew.-%
Citronensäure bzw. Na-citrat, berechnet als Citronensäure
Detergents according to the invention have in particular the following composition:
4 to 6% by weight
anionic surfactant, preferably fatty alkyl sulfates in the form of the sodium salts,
18 to 28% by weight
nonionic surfactant, preferably fatty alcohol ethoxylates,
1 to 4% by weight
Alkyl glucoside of the formula RO (G) x , in which R is a fatty alkyl radical, G is a glucose unit and x is a value from 1.10 to 1.45,
5 to 10% by weight
polyhydric alcohol,
12 to 18% by weight
Citric acid or Na citrate, calculated as citric acid

Rest Wasser und übliche Waschmittelinhaltsstoffe in geringen Mengen.Rest of water and usual detergent ingredients in small quantities.

Übliche Waschmittelinhaltsstoffe sind beispielsweise optische Aufheller, Enzyme, Enzymstabilisatoren, Farbstoffe, Duftstoffe und Komplexbildner. Ferner können Schauminihibitoren zugegen sein, beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure sowie Paraffine, Wachse, mikrokristalline Wachse und deren Gemische mit silanierter Kieselsäure. Mit Vorteil können auch Gemische verschiedener Schauminhibitoren verwendet werden, z.B. solche aus Silikonen, Paraffinen oder Wachsen.Typical detergent ingredients are, for example, optical brighteners, enzymes, enzyme stabilizers, dyes, fragrances and complexing agents. Foam inhibitors may also be present, for example organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Mixtures of different foam inhibitors can also advantageously be used, e.g. those made of silicone, paraffins or waxes.

Die erfindungsgemäßen Waschmittel haben bei Raumtemperaturen flüssige bis pastöse Konsistens. Pastöse Waschmittel lassen sich bei erhöhter Temperatur beispielsweise bei 70 °C in flüssigem Zustand unter Verwendung von Aggregaten für die Herstellung von Flüssigprodukten herstellen. Nach Abkühlung nehmen derartige Produkte eine lagerstabile pastöse Konsistenz an.The detergents according to the invention have liquid to pasty consistencies at room temperatures. Pasty detergents can be produced in a liquid state at elevated temperature, for example at 70 ° C., using units for the production of liquid products. After cooling, such products assume a pasty consistency that is stable in storage.

Sie lassen sich beispielsweise aus Tuben leicht ausdrücken und haben eine sehr gute Löslichkeit. Die Bestandteile der erfindungsgemäßen Waschmittel sind weitgehend oder vollständig aus nachwachsenden Rohstoffen herstellbar und biologisch leicht abbaubar.For example, they can be easily expressed from tubes and have very good solubility. The constituents of the detergents according to the invention can be largely or completely produced from renewable raw materials and are readily biodegradable.

BeispieleExamples

Die folgenden Waschversuche wurden mit einem bekannten Flüssigwaschmittel des Standes der Technik A und einem erfindungsgemäßen Waschmittel B durchgeführt. Die Waschmittel hatten die folgende Zusammensetzung: Tabelle 1 Zusammensetzung Waschmittel Gew.-% A B Kokosalkylsulfat-Na 4,5 5,0 Kokosalkohol + 7 Mol Ethylenoxid 12,0 25,0 C12/14-Alkylglucosid-1,4 1,5 1,5 Laurinsäure-Na 8,0 8,0 Palmkernsäure-Na 6,0 6,0 Glycerin 5,0 7,0 Zitronensäure 0,5 15,0 Natronlauge 2,6 1,5 Ethanol 6,0 - Protease 0,5 0,5 Amylase 0,05 0,05 Rest: Wasser, Farbstoff, Duftstoff, optischer Aufheller, Viskositätsregulator The following washing tests were carried out using a known liquid detergent from prior art A and a detergent B according to the invention. The detergents had the following composition: Table 1 Detergent composition% by weight A B Coconut alkyl sulfate Na 4.5 5.0 Coconut alcohol + 7 moles of ethylene oxide 12.0 25.0 C 12/14 alkyl glucoside 1,4 1.5 1.5 Lauric acid Na 8.0 8.0 Palm kernel acid Na 6.0 6.0 Glycerin 5.0 7.0 citric acid 0.5 15.0 Caustic soda 2.6 1.5 Ethanol 6.0 - Protease 0.5 0.5 Amylase 0.05 0.05 Rest: water, dye, fragrance, optical brightener, viscosity regulator

Das flüssige Waschmittel A wurde in einem 1-Gang-Waschprogramm bei 60 °C in einer automatischen Trommelwaschmaschine (Typ AEG-LAVA 670) bei einer Wasserhärte von 16 °C mit dem pastenförmigen Waschmittel B verglichen. Auf 18 Liter Waschwasser wurde Waschmittel A mit 120 Gramm und Waschmittel B mit 92,5 Gramm dosiert. Gewaschen wurden, zusammen mit 3,5 kg normal verschmutzter Haushaltswäsche, Prüftextilien aus Baumwolle, veredelt, und aus Polyester/Baumwolle, veredelt, jeweils mit künstlichen und natürlichen Anschmutzungen versehen. Die Auswertung des Waschergebnisses erfolgte durch Ermittlung des Farbabstandes dE (w) im Prüfgerät Minolta CR-200. Man erhielt dabei die in den Tabellen 2 und 3 aufgeführten Waschergebnisse, wobei für den Farbabstand die Komplementärwerte zum Ausgangswert (AW) angegeben werden, so daß der höhere Wert die bessere Waschleistung bedeutet. Tabelle 2, Baumwolle, veredelt zu AW Lippenstift Make up Wimperntusche Rotwein Tee Waldbeere Waschmittel A 27,7 38,6 21,7 13,8 4,4 31,7 Waschmittel B 34,3 39,7 41,3 19,9 6,8 38,9 Tabelle 3, Polyester/Baumwolle, veredelt zu AW Lippenstift Make up Wimperntusche Rotwein Tee Waldbeere Waschmittel A 8,5 33,4 26,0 15,9 4,4 36,4 Waschmittel B 13,7 36,5 32,1 18,5 5,7 39,6 The liquid detergent A was compared with the paste-like detergent B in a 1-stage washing program at 60 ° C in an automatic drum washing machine (type AEG-LAVA 670) at a water hardness of 16 ° C. Detergent A with 120 grams and detergent B with 92.5 grams were dosed into 18 liters of washing water. Was washed, together with 3.5 kg of normally soiled household laundry, test textiles made of cotton, refined, and made of polyester / cotton, refined, each with artificial and natural Soiling provided. The washing result was evaluated by determining the color difference dE (w) in the Minolta CR-200 tester. The washing results listed in Tables 2 and 3 were obtained, the complementary values to the starting value (AW) being given for the color difference, so that the higher value means the better washing performance. Table 2, Cotton, refined to AW lipstick make up Mascara red wine tea Forest berry Detergent A 27.7 38.6 21.7 13.8 4.4 31.7 Detergent B 34.3 39.7 41.3 19.9 6.8 38.9 Polyester / cotton, refined to AW lipstick make up Mascara red wine tea Forest berry Detergent A 8.5 33.4 26.0 15.9 4.4 36.4 Detergent B 13.7 36.5 32.1 18.5 5.7 39.6

In allen Fällen führte das erfindungsgemäße Waschmittel B zu den besseren Ergebnissen. Auch wenn von dem erfindungsgemäßen Waschmittel nur 60 g gegenüber 120 g des Waschmittels des Standes der Technik dosiert wurden, erhielt man mit dem erfindungsgemäßen Waschmittel die tendenziell besseren Waschergebnisse und zwar für alle geprüften Anschmutzungsarten (Hautfett/Pigment, enzymspezifische Anschmutzungen, bleichbare Anschmutzungen und Kosmetik-Anschmutzungen).In all cases, detergent B according to the invention gave better results. Even if only 60 g of the detergent according to the invention were dosed compared to 120 g of the detergent of the prior art, the tendency towards better washing results was obtained with the detergent according to the invention, namely for all types of soiling tested (skin fat / pigment, enzyme-specific soils, bleachable soils and cosmetics). Soiling).

Claims (4)

  1. A liquid detergent containing anionic surfactants of the sulfonate and sulfate types, nonionic surfactants, alkyl glucosides, a mixture of soaps of unsaturated and saturated fatty acids, polyhydric alcohol and citric acid or sodium, characterized in that it contains 10 to 20% by weight of citric acid or sodium citrate, expressed as citric acid, and 3 to 10% by weight of anionic surfactants of the sulfonate and sulfate types and in that the degree of oligomerization of the alkyl glucosides used is between 1.10 and 1.45.
  2. A detergent as claimed in claim 1, characterized in that it contains 12 to 18% by weight of citric acid or sodium citrate, expressed as citric acid.
  3. A detergent as claimed in claim 1 or 2, characterized in that it contains glycerol as the polyhydric alcohol.
  4. A detergent as claimed in any of claims 1 to 3, characterized in that it contains
    4 to 6% by weight   of anionic surfactant, preferably fatty alkyl sulfates in the form of the sodium salts,
    18 to 28% by weight   of nonionic surfactant, preferably fatty alcohol ethoxylates,
    1 to 4% by weight   of alkyl glucoside corresponding to the formula RO(G)x, in which R is an alkyl radical, G is a glucose unit and x has a value of 1.10 to 1.45,
    5 to 10% by weight   of polyhydric alcohol,
    12 to 18% by weight   of citric acid or Na citrate, expressed as citric acid,
    remainder water and typical detergent ingredients in small quantities.
EP92909170A 1991-05-03 1992-04-25 Liquid washing agent Expired - Lifetime EP0582608B1 (en)

Applications Claiming Priority (3)

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DE4114491 1991-05-03
DE4114491A DE4114491A1 (en) 1991-05-03 1991-05-03 LIQUID DETERGENT
PCT/EP1992/000913 WO1992019711A1 (en) 1991-05-03 1992-04-25 Liquid washing agent

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EP0582608B1 true EP0582608B1 (en) 1997-07-09

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MX9800441A (en) * 1995-07-17 1998-04-30 Henkel Corp The use of alkoxylated alcohols to control foaming of alkyl polyglycosides in cleaning compositions.
WO1998020097A1 (en) * 1996-11-07 1998-05-14 Henkel Corporation Glycerine personal cleansing bar with alkyl polyglucoside
US5952287A (en) * 1997-06-03 1999-09-14 Henkel Corporation Microemulsion composition for cleaning hard surfaces
US6224685B1 (en) * 1997-06-03 2001-05-01 Henkel Corporation Microemulsion composition for cleaning hard surfaces
DE19952831A1 (en) * 1999-11-02 2001-05-03 Henkel Ecolab Gmbh & Co Ohg Paste detergent
US20070207939A1 (en) 2006-02-10 2007-09-06 Gyorgyi Fenyvesi Compositions comprising mono and di esters of biologically-based 1,3-propanediol
WO2011000107A1 (en) * 2009-07-01 2011-01-06 Protiva Biotherapeutics, Inc. Novel lipid formulations for delivery of therapeutic agents to solid tumors
DE102015201702A1 (en) * 2015-01-30 2016-08-04 Henkel Ag & Co. Kgaa Acid liquid compact detergent containing hydroxycarboxylic acid, nonionic surfactant and enzyme
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US5520836A (en) 1996-05-28
US5441662A (en) 1995-08-15
DE4114491A1 (en) 1992-11-05
DE59208692D1 (en) 1997-08-14
WO1992019711A1 (en) 1992-11-12
ATE155166T1 (en) 1997-07-15

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