EP0403948A1 - Liquid detergent - Google Patents

Liquid detergent Download PDF

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Publication number
EP0403948A1
EP0403948A1 EP90111177A EP90111177A EP0403948A1 EP 0403948 A1 EP0403948 A1 EP 0403948A1 EP 90111177 A EP90111177 A EP 90111177A EP 90111177 A EP90111177 A EP 90111177A EP 0403948 A1 EP0403948 A1 EP 0403948A1
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EP
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Prior art keywords
weight
fatty
alkyl
composition according
salts
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EP90111177A
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German (de)
French (fr)
Inventor
Karl Schwadtke
Eric Dr. Sung
Eduard Dr. Smulders
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP0403948A1 publication Critical patent/EP0403948A1/en
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap

Definitions

  • the invention relates to a liquid detergent which contains surface-active alkyl glucosides and which, owing to its textile-protecting properties, is outstandingly suitable for the manual washing of highly sensitive textiles. It is largely made up of surfactants obtained from native raw materials.
  • a detergent is known from European patent application 70 074, which contains alkyl glucosides and anionic surfactants in a ratio of 1:10 to 10: 1.
  • Preferred is the use of anionic surfactant mixtures in which one component is alkylbenzenesulfonate, and the use of alkyl sulfates and / or soaps in conjunction with amides and / or amine oxides.
  • European patent applications 75 994 and 75 995 describe detergents which contain alkyl glucosides and nonionic surfactants in a ratio of 1:10 to 10: 1 and, as further possible constituents, builder substances and up to 15% other surfactants, including soaps.
  • the agents can contain up to 10% unsaturated soap (oleate).
  • the detergents disclosed in European patent application 92 877 which also include liquid detergents, contain alkyl glucosides and anionic surfactants in a weight ratio of greater than 1, preferably from 2: 1 to 6: 1; but it will also be there Weight ratio of anionic surfactant to alkyl glucoside from 1: 1 to 6: 1 disclosed.
  • liquid cleaning agents can contain mixtures of 5-50% by weight anionic surfactants, 1/4-20% by weight nonionic surfactants, 1/2-30% by weight alkyl glucosides, 20-80% by weight water and optionally contain surfactants of the amide type, amine oxides and builder substances.
  • European patent application 106 692 discloses builder-free liquid detergents which, in addition to alkyl glucosides, contain nonionic and cationic surfactants as well as polyethylene glycol and optionally fatty acid amide.
  • Canadian patent application 1 216 488 describes mild, aqueous liquid detergents which contain 1/2-75% by weight alkyl glucoside, 1-60% by weight of an alkaline builder and as further possible constituents up to 50% by weight of others contain usual surfactants.
  • builder-containing liquid detergents which contain 5 to 50% by weight of surfactants, at least half of which consist of alkyl glucosides.
  • liquid detergents which contain 3 to 45% by weight of anionic surfactants and 0.3 to 20% by weight of alkyl glucosides and which are used in the temperature range between 37 and 60 ° C.
  • Anionic surfactants used with preference are ⁇ -olefin sulfonates and alkyl ether sulfates.
  • the object of the invention was to provide a liquid detergent which can be used universally at temperatures of 15 to 90 ° C, manually and mechanically and is also particularly suitable for washing highly sensitive textiles in the temperature range between 15 and 40 ° C.
  • the invention relates to a liquid detergent containing anionic surfactants and alkyl glucosides, which is characterized in that it (A) 3-20% by weight fatty alkyl sulfates in the form of the sodium salts, (B) 10-25% by weight soaps, consisting of salts (B1) unsaturated C12 to C18 fatty acids and (B2) saturated C12 to C18 fatty acids in the weight ratio (B1) to (B2) of 3: 1 to 1: 3, and (C) 1 - 10 wt .-% alkyl glucosides of the general formula RO (G) x , where R is a fatty alkyl radical, G is a glucose unit and x is a number between 1 and 10.
  • fatty alkyl sulfates (A) are the sulfuric acid monoesters of C12 to C18 fatty alcohols, such as lauryl, myristyl or cetyl alcohol, and the fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil as well as tallow, which additionally contain portions of unge saturated alcohols, e.g. B. oleyl alcohol. Mixtures in which the proportions of the alkyl radicals are 50-70% by weight on C12, 18-30% by weight on C14, 5-15% by weight on C16, below 3% are preferred. -% on C10 and less than 10 wt .-% are distributed on C18.
  • the proportion of fatty alkyl sulfates (A) in the compositions is preferably 3-16% by weight.
  • Suitable as soaps (B) are the salts of saturated and unsaturated fatty acids with C12 to C18 chain lengths in the form of their mixtures.
  • a preferably used soap mixture is formed from sodium oleate (B1) and the sodium salts of the saturated C12 - C16 fatty acid mixtures (B2).
  • the proportion of C12 - C14 fatty acids in component (B2) is advantageously at least 60% by weight, preferably at least 75% by weight (calculated as fatty acid).
  • Suitable for this are, for. B. coconut fatty acids, from which the portions with 10 and 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 (B1) and the sodium salt of lauric acid (B2) is also preferred.
  • the weight ratio of (B1) to (B2) is preferably 2: 1 to 1: 2.
  • fatty alkyl glucosides are particularly suitable glucosides with a C8 to C22 alkyl radical, preferably with an alkyl radical consisting essentially of C12 to C18, which is derived from lauryl, myristyl, cetyl and stearyl alcohol and from technical fractions, which are preferably contain saturated alcohols.
  • alkyl glucosides the alkyl radical to 50-70 wt .-% C12 and 18-30 wt .-% C1 ent holds.
  • the index number x is any number between 1 and 10; it indicates the degree of oligomerization, ie the distribution of monoglucosides and oligoglucosides.
  • the average degree of oligomerization x preferably has a value of 1.1-3.0 and in particular of significantly less than 1.5. A degree of oligomerization between 1.1 and 1.4 is particularly preferred.
  • the pH of the agents according to the invention is 7 to 10.5, preferably 7 to 9.5.
  • the preferably builder-free agents advantageously contain as solvent a mixture of ethanol and 1,2-propanediol and water.
  • the proportion of organic solvents is 8-20% by weight, preferably 10-17% by weight.
  • the weight ratio of ethanol to 1,2-propanediol is 3: 1 to 1: 2, preferably 2: 1 to 1: 1.5.
  • the proportion of water is chosen so that non-gelling solutions are formed which are stable against segregation, for which 45-55% by weight water is generally sufficient. A greater dilution of the agents with water has no advantages because of the greater packaging requirements.
  • the clear liquid agents can contain further nonionic surfactants of the type of the adducts of 1-10 moles of ethylene oxide with primary C12 to C18 fatty alcohols and their mixtures such as coconut oil, tallow oil or oleyl alcohols.
  • Oxo alcohols alcohols produced by the method of oxosynthesis or hydroformylation
  • the proportion of fatty alcohol ethoxylates in the compositions can be 0-17% by weight, preferably up to 14% by weight.
  • triethanolamine to the detergent in amounts of up to 8% by weight.
  • the agents can contain small amounts of free sodium hydroxide solution, which are required to set higher pH values between 8.5 and 10.5.
  • the detergents can contain known additives commonly used in detergents, for example salts of citric acid in amounts of 0.1-2, preferably 0.3-1% by weight (calculated as free acid), salts of polyphosphonic acids, optical Brighteners, enzymes, enzyme stabilizers, filler salts as well as colors and fragrances.
  • the neutral-reacting sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate and diethylenetriamine pentamethylene phosphonate are preferably used as salts of polyphosphonic acids in amounts of 0.1 1.5% by weight.
  • the total phosphorus content in the compositions is preferably less than 0.5%.
  • Suitable enzymes are those from the class of proteases, lipases, amylases or mixtures thereof. Their proportion can be 0.2-1% by weight. 0.5-1.5% by weight sodium formate can be used as the enzyme stabilizer. It is also possible to use proteases with soluble calcium salts and a calcium content of preferably 1.2% by weight, based on the enzyme, are stabilized.
  • Suitable non-surfactant-like foam inhibitors are, 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. B. from silicone, paraffins or waxes.
  • agents (A) contain 5-15% by weight of fatty alkyl sulfate, (B) 10-20% by weight of soaps, consisting of the salt of (B1) oleic acid and (B2) saturated C12- to C16- Fatty acids or their mixtures in the weight ratio (B1) to (B2) such as 2: 1 to 1: 2, (C) 1-8, preferably 1-5% by weight fatty alkyl glucoside, 10-15% by weight 1,2- Propanediol and ethanol, 3-5% by weight triethanolamine and 0.5-1% by weight salt of citric acid (calculated as free acid).
  • soaps consisting of the salt of (B1) oleic acid and (B2) saturated C12- to C16- Fatty acids or their mixtures in the weight ratio (B1) to (B2) such as 2: 1 to 1: 2, (C) 1-8, preferably 1-5% by weight fatty alkyl glucoside, 10-15% by weight 1,2- Propanediol and ethanol, 3-5% by weight tri
  • agents (A) and (B) contain, as above, (C) 1-5% by weight of fatty alkyl glucoside, 12-17% by weight of 1,2-propanediol and ethanol, 0.5-1 % By weight salt of citric acid (based on free acid) and 0.5-1% by weight sodium polyphosphonate.
  • agents containing (A) 5-12% by weight fatty alkyl sulfate, (B) 10-18% by weight soaps consisting of (B1) sodium oleate and (B2) the sodium salt of saturated C12- bis C16 fatty acids or mixtures thereof in a weight ratio (B1) to (B2) as 2: 1 to 1: 1, (C) 1-4% by weight of fatty alkyl glucoside, 2-5% by weight of fatty alcohols with 1-10 moles of ethylene oxide per mole of fatty alcohol, 10-17% by weight % 1,2-propanediol and ethanol, 0.3-1% by weight salt of citric acid (calculated as free acid) and 0-1% by weight sodium polyphosphonate.
  • soaps consisting of (B1) sodium oleate and (B2) the sodium salt of saturated C12- bis C16 fatty acids or mixtures thereof in a weight ratio (B1) to (B2) as 2: 1 to 1: 1, (C) 1-4% by weight of fatty alkyl glucoside,
  • Nitrogen-free universal liquid detergents are particularly advantageous, the (A) 3-8% by weight fatty alkyl sulfate, (B) 12-20% by weight soaps, consisting of (B1) sodium oleate and (B2) the sodium salt of saturated C12- to C16 -Fatty acids or their mixtures in the weight ratio (B1) to (B2) such as 2: 1 to 1: 2, (C) 1-3% by weight of fatty alkyl glucoside, 8-14% by weight of fatty alcohol with 1-10 moles of ethylene oxide per Mol of fatty alcohol, 10-17 wt .-% 1,2-propanediol and ethanol, 0-1 wt .-% salt of citric acid (based on free acid) and 0-1 wt .-% sodium polyphosphonate.
  • soaps consisting of (B1) sodium oleate and (B2) the sodium salt of saturated C12- to C16 -Fatty acids or their mixtures in the weight ratio (B1) to (B2) such as 2:
  • all of these agents can contain enzymes and enzyme stabilizers.
  • the agents are notable for easy assembly, storage stability and easy mixing with water. When used in machine washing processes, they also show good washing-in behavior.
  • the invention further relates to a method for producing the liquid detergents described above.
  • the liquid detergents can be produced in a manner known per se.
  • the oleic acid and the C12- to C16 fatty acid or the C12-C16 fatty acid mixture and optionally citric acid are first preheated to 50 - 80 ° C, the water, sodium contains hydroxide and 1,2-propanediol and possibly triethanolamine, dissolved with stirring and converted into their salts.
  • the remaining components of the liquid detergent can be added in any order.
  • the alkyl sulfate is advantageously added before the addition of alkyl glucoside and, if appropriate, fatty alcohol ethoxylate. If the detergents contain enzymes, the last component is stirred into the liquid detergent at room temperature.
  • the agents were prepared in such a way that a mixture of water, sodium hydroxide (D), 1,2-propanediol (F2) and optionally triethanolamine (G) was first heated to 70.degree.
  • the fatty acids (B1) and (B2) and possibly citric acid were added to the warm solution (H) stirred in.
  • Phosphonate (I) fatty alkyl sulfate (A), alkyl glucoside (C) and fatty alcohol ethoxylate (E) were added in the order given with constant stirring.
  • ethanol (F1) was added to the clear solution.
  • the enzyme, formate and colorants and fragrances, which belong to the remaining constituents, were added, if desired.
  • fatty alkyl sulfate in the above composition is partially or completely replaced by lauryl, myristyl or cetyl sulfate, by the sulfation product of oleyl alcohol or by the sulfation products of fatty alcohol mixtures obtained from palm and palm kernel oil and tallow and by mixtures of these becomes.
  • soap-forming saturated fatty acids (B2) specified in the above composition are partially or completely replaced by lauric, myristic or palmitic acid or by natural fatty acid mixtures such as hydrogenated tallow and by mixtures of these.
  • fatty alcohol ethoxylate used in the above agents in whole or in part, by pure C12-, C14-, C16-, saturated and unsaturated C18-fatty alcohol with 1-10 ethylene oxide groups (EO) or other native fatty alcohol mixtures
  • EO ethylene oxide groups
  • from palm, palm kernel oil or tallow fat can be obtained by C12-C14 fatty alcohol with 3 EO, C12-C14 fatty alcohol with 4 EO, C12-C18 fatty alcohol with 3 EO, C12-C18 fatty alcohol with 5 EO, by a Mixture of C12-C18 fatty alcohol with 5 EO and C12-C14 fatty alcohol with 3 EO, by cetyloleyl alcohol (iodine number 50 - 55) with 2 EO, cetyloleyl alcohol (iodine number 50 - 55) with 7 EO, cetyloleyl alcohol (iodine number 50 - 55) with 50% EO, by a mixture of cetyloleyl alcohol (i
  • the agents according to the invention are distinguished by a skin-friendly surfactant combination that is very readily biodegradable.

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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)
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Abstract

Liquid detergents containing 3 to 20 wt.% of fatty alkyl sulphates, 10 to 25 wt.% of a soap mixture of salts of unsaturated and saturated C12 to C18 fatty acids in a weight ratio of 3:1 to 1:3 and 1 to 10 wt.% of alkylglucosides are general purpose detergents which can be used at temperatures of 15 to 90 DEG C and are particularly suitable for washing delicate textiles. They are composed essentially of tensides obtained from natural raw materials.

Description

Die Erfindung betrifft ein Flüssigwaschmittel, das oberflächen­aktive Alkylglucoside enthält und das sich aufgrund seiner tex­tilschonenden Eigenschaften hervorragend zum manuellen Waschen hochempfindlicher Textilien eignet. Es ist größtenteils aus Ten­siden, die aus nativen Rohstoffen gewonnen werden, aufgebaut.The invention relates to a liquid detergent which contains surface-active alkyl glucosides and which, owing to its textile-protecting properties, is outstandingly suitable for the manual washing of highly sensitive textiles. It is largely made up of surfactants obtained from native raw materials.

Aus der europäischen Patentanmeldung 70 074 ist ein Waschmittel bekannt, das Alkylglucoside und Aniontenside im Verhältnis 1 : 10 bis 10 : 1 enthält. Bevorzugt ist die Verwendung von Aniontensid­gemischen, in denen eine Komponente Alkylbenzolsulfonat ist, sowie der Einsatz von Alkylsulfaten und/oder Seifen in Verbindung mit Amiden und/oder Aminoxiden.A detergent is known from European patent application 70 074, which contains alkyl glucosides and anionic surfactants in a ratio of 1:10 to 10: 1. Preferred is the use of anionic surfactant mixtures in which one component is alkylbenzenesulfonate, and the use of alkyl sulfates and / or soaps in conjunction with amides and / or amine oxides.

Die europäischen Patentanmeldungen 75 994 und 75 995 beschreiben Waschmittel, die Alkylglucoside und nichtionische Tenside im Ver­hältnis 1 : 10 bis 10 : 1 und als weitere mögliche Bestandteile Buildersubstanzen und bis zu 15 % andere Tenside, darunter auch Seifen, enthalten. Dabei können in den Mitteln bis zu 10 % unge­sättigte Seife (Oleat) enthalten sein.European patent applications 75 994 and 75 995 describe detergents which contain alkyl glucosides and nonionic surfactants in a ratio of 1:10 to 10: 1 and, as further possible constituents, builder substances and up to 15% other surfactants, including soaps. The agents can contain up to 10% unsaturated soap (oleate).

Die in der europäischen Patentanmeldung 92 877 offenbarten Wasch­mittel, die auch Flüssigwaschmittel umfassen, enthalten Alkylglu­coside und Aniontenside in einem Gewichtsverhältnis von größer als 1, vorzugsweise von 2 : 1 bis 6 : 1; aber es wird dort auch ein Gewichtsverhältnis des Aniontensides zum Alkylglucosid von 1 : 1 bis 6 : 1 offenbart.The detergents disclosed in European patent application 92 877, which also include liquid detergents, contain alkyl glucosides and anionic surfactants in a weight ratio of greater than 1, preferably from 2: 1 to 6: 1; but it will also be there Weight ratio of anionic surfactant to alkyl glucoside from 1: 1 to 6: 1 disclosed.

Flüssige Reinigungsmittel können nach der europäischen Patentan­meldung 105 556 Mischungen von 5 - 50 Gew.-% Aniontensiden, 1/4 - 20 Gew.-% Niotensiden, 1/2 - 30 Gew.-% Alkylglucosiden, 20 - 80 Gew.-% Wasser und gegebenenfalls Tenside vom Typ der Amide, Amin­oxide und Buildersubstanzen enthalten.According to European patent application 105 556, liquid cleaning agents can contain mixtures of 5-50% by weight anionic surfactants, 1/4-20% by weight nonionic surfactants, 1/2-30% by weight alkyl glucosides, 20-80% by weight water and optionally contain surfactants of the amide type, amine oxides and builder substances.

Aus der europäischen Patentanmeldung 106 692 sind builderfreie Flüssigwaschmittel bekannt, die außer Alkylglucosiden nichtio­nische und kationische Tenside sowie Polyethylenglykol und gege­benenfalls Fettsäureamid enthalten.European patent application 106 692 discloses builder-free liquid detergents which, in addition to alkyl glucosides, contain nonionic and cationic surfactants as well as polyethylene glycol and optionally fatty acid amide.

Aus der europäischen Patentanmeldung EP 216 301 sind manuelle flüssige Geschirrspülmittel bekannt, die eine Kombination aus an­ionischen Tensiden vom Typ der Sulfate und/oder Sulfonate sowie tensidische Fettsäurealkanolamide und Alkylglucoside enthalten.Manual liquid dishwashing detergents are known from European patent application EP 216 301, which contain a combination of anionic surfactants of the sulfate and / or sulfonate type as well as surfactant fatty acid alkanolamides and alkyl glucosides.

In der kanadischen Patentanmeldung 1 216 488 werden milde, wäßrige Flüssigwaschmittel beschrieben, die 1/2 - 75 Gew.-% Alkylglucosid, 1 - 60 Gew.-% einer alkalischen Buildersubstanz und als weitere mögliche Bestandteile bis zu 50 Gew.-% an anderen üblichen Ten­siden enthalten.Canadian patent application 1 216 488 describes mild, aqueous liquid detergents which contain 1/2-75% by weight alkyl glucoside, 1-60% by weight of an alkaline builder and as further possible constituents up to 50% by weight of others contain usual surfactants.

In der internationalen Patentanmeldung WO 86/05187 wird eine Kom­bination von 1 bis 70 Gew.-% Alkylglucosiden und 0,005 bis 5 Gew.-% Enzym in flüssigen Waschmitteln beansprucht. Vorzugsweise enthalten diese Mittel anionische und weitere nichtionische Ten­side.The international patent application WO 86/05187 claims a combination of 1 to 70% by weight of alkyl glucosides and 0.005 to 5% by weight of enzyme in liquid detergents. These agents preferably contain anionic and other nonionic surfactants.

Aus der internationalen Patentanmeldung WO 87/06949 sind builder­haltige Flüssigwaschmittel bekannt, die 5 bis 50 Gew.-% Tenside enthalten, wovon mindestens die Hälfte aus Alkylglucosiden be­steht.From the international patent application WO 87/06949 builder-containing liquid detergents are known which contain 5 to 50% by weight of surfactants, at least half of which consist of alkyl glucosides.

Die internationale Patentanmeldung WO 86/02943 beschreibt Flüssig­waschmittel, die 3 bis 45 Gew.-% Aniontenside und 0,3 bis 20 Gew.-% Alkylglucoside enthalten und die im Temperaturbereich zwi­schen 37 und 60 °C eingesetzt werden. Bevorzugt verwendete Anion­tenside sind α-Olefinsulfonate und Alkylethersulfate.International patent application WO 86/02943 describes liquid detergents which contain 3 to 45% by weight of anionic surfactants and 0.3 to 20% by weight of alkyl glucosides and which are used in the temperature range between 37 and 60 ° C. Anionic surfactants used with preference are α-olefin sulfonates and alkyl ether sulfates.

Aufgabe der Erfindung war es, ein Flüssigwaschmittel, das univer­sell bei Temperaturen von 15 bis 90 °C, manuell und maschinell an­wendbar ist und sich insbesondere auch zum Waschen hochempfind­licher Textilien im Temperaturbereich zwischen 15 und 40 °C eig­net, zu schaffen.The object of the invention was to provide a liquid detergent which can be used universally at temperatures of 15 to 90 ° C, manually and mechanically and is also particularly suitable for washing highly sensitive textiles in the temperature range between 15 and 40 ° C.

Gegenstand der Erfindung ist ein Flüssigwaschmittel, enthaltend Aniontenside und Alkylglucoside, das dadurch gekennzeichnet ist, daß es (A) 3 - 20 Gew.-% Fettalkylsulfate in Form der Natrium­salze, (B) 10 - 25 Gew.-% Seifen, bestehend aus Salzen (B1) un­gesättigter C₁₂ bis C₁₈-Fettsäuren und (B2) gesättigter C₁₂- bis C₁₈-Fettsäuren im Gewichtsverhältnis (B1) zu (B2) von 3 : 1 bis 1 : 3, und (C) 1 - 10 Gew.-% Alkylglucoside der allgemeinen Formel RO(G)x, wobei R einen Fettalkylrest, G eine Glucoseeinheit und x eine Zahl zwischen 1 und 10 darstellt, enthält.The invention relates to a liquid detergent containing anionic surfactants and alkyl glucosides, which is characterized in that it (A) 3-20% by weight fatty alkyl sulfates in the form of the sodium salts, (B) 10-25% by weight soaps, consisting of salts (B1) unsaturated C₁₂ to C₁₈ fatty acids and (B2) saturated C₁₂ to C₁₈ fatty acids in the weight ratio (B1) to (B2) of 3: 1 to 1: 3, and (C) 1 - 10 wt .-% alkyl glucosides of the general formula RO (G) x , where R is a fatty alkyl radical, G is a glucose unit and x is a number between 1 and 10.

Als Fettalkylsulfate (A) eignen sich die Schwefelsäuremonoester der C₁₂- bis C₁₈-Fettalkohole, wie Lauryl-, Myristyl- oder Cetyl­alkohol, und der aus Kokosöl, Palm- und Palmkernöl sowie Talg ge­wonnen Fettalkoholgemische, die zusätzlich noch Anteile an unge­ sättigten Alkoholen, z. B. Oleylalkohol, enthalten können. Eine bevorzugte Verwendung finden dabei Gemische, in denen die Anteile der Alkylreste zu 50 - 70 Gew.-% auf C₁₂, zu 18 - 30 Gew.-% auf C₁₄, zu 5 - 15 Gew.-% auf C₁₆, unter 3 Gew.-% auf C₁₀ und unter 10 Gew.-% auf C₁₈ verteilt sind. Der Anteil an Fettalkylsulfaten (A) in den Mitteln beträgt vorzugsweise 3 - 16 Gew.-%.As fatty alkyl sulfates (A) are the sulfuric acid monoesters of C₁₂ to C₁₈ fatty alcohols, such as lauryl, myristyl or cetyl alcohol, and the fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil as well as tallow, which additionally contain portions of unge saturated alcohols, e.g. B. oleyl alcohol. Mixtures in which the proportions of the alkyl radicals are 50-70% by weight on C₁₂, 18-30% by weight on C₁₄, 5-15% by weight on C₁₆, below 3% are preferred. -% on C₁₀ and less than 10 wt .-% are distributed on C₁₈. The proportion of fatty alkyl sulfates (A) in the compositions is preferably 3-16% by weight.

Als Seifen (B) sind die Salze von gesättigten und ungesättigten Fettsäuren mit C₁₂- bis C₁₈-Kettenlängen in Form ihrer Gemische geeignet. Ein bevorzugt verwendetes Seifengemisch wird aus Na­triumoleat (B1) und den Natriumsalzen der gesättigten C₁₂ - C₁₆-­Fettsäuregemische (B2) gebildet. Der Anteil an C₁₂ - C₁₄-Fett­säuren in der Komponente (B2) 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 (B1) und dem Natriumsalz der Laurinsäure (B2). Das Gewichtsver­hältnis von (B1) zu (B2) beträgt vorzugsweise 2 : 1 bis 1 : 2.Suitable as soaps (B) are the salts of saturated and unsaturated fatty acids with C₁₂ to C₁₈ chain lengths in the form of their mixtures. A preferably used soap mixture is formed from sodium oleate (B1) and the sodium salts of the saturated C₁₂ - C₁₆ fatty acid mixtures (B2). The proportion of C₁₂ - C₁₄ fatty acids in component (B2) is advantageously at least 60% by weight, preferably at least 75% by weight (calculated as fatty acid). Suitable for this are, for. B. coconut fatty acids, from which the portions with 10 and 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 (B1) and the sodium salt of lauric acid (B2) is also preferred. The weight ratio of (B1) to (B2) is preferably 2: 1 to 1: 2.

Als Fettalkylglucoside (C) 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 - 70 Gew.-% C₁₂ und 18 - 30 Gew.-% C₁₄ ent­ hält. Die Indexzahl x ist eine beliebige Zahl zwischen 1 und 10; sie gibt den Oligomerisierungsgrad, d. h. die Verteilung von Mono­glucosiden und Oligoglucosiden an. Während x in einer gegebenen Verbindung immer eine ganze Zahl sein muß und hier vor allem die Werte x = 1 - 6 annehmen kann, ist der Wert x für ein spezielles Produkt eine analytisch ermittelte rechnerische Größe, die mei­stens eine gebrochene Zahl darstellt. Vorzugsweise hat der mitt­lere Oligomerisierungsgrad x einen Wert von 1,1 - 3,0 und insbe­sondere von deutlich kleiner als 1,5. Besonders bevorzugt ist ein Oligomerisierungsgrad zwischen 1,1 und 1,4.As fatty alkyl glucosides (C) are particularly suitable glucosides with a C₈ to C₂₂ alkyl radical, preferably with an alkyl radical consisting essentially of C₁₂ to C₁₈, which is derived from lauryl, myristyl, cetyl and stearyl alcohol and from technical fractions, which are preferably contain saturated alcohols. Particularly preferred is the use of alkyl glucosides, the alkyl radical to 50-70 wt .-% C₁₂ and 18-30 wt .-% C₁ ent holds. The index number x is any number between 1 and 10; it indicates the degree of oligomerization, ie the distribution of monoglucosides and oligoglucosides. While x must always be an integer in a given connection and can take on the values x = 1 - 6, the value x is an analytically determined mathematical quantity for a special product, which usually represents a fractional number. The average degree of oligomerization x preferably has a value of 1.1-3.0 and in particular of significantly less than 1.5. A degree of oligomerization between 1.1 and 1.4 is particularly preferred.

Der pH-Wert der erfindungsgemäßen Mittel beträgt 7 bis 10,5, vor­zugsweise 7 bis 9,5.The pH of the agents according to the invention is 7 to 10.5, preferably 7 to 9.5.

Die vorzugsweise buildersubstanzfreien Mittel enthalten als Lö­sungsmittel vorteilhafterweise ein Gemisch aus Ethanol und 1,2-­Propandiol sowie Wasser. Der Anteil der organischen Lösungsmittel beträgt 8 - 20 Gew.-%, vorzugsweise 10 - 17 Gew.-%. Das Gewichts­verhältnis von Ethanol zu 1,2-Propandiol beträgt 3 : 1 bis 1 : 2, vorzugsweise 2 : 1 bis 1 : 1,5. Der Anteil des Wassers wird so gewahlt, daß nicht gelierende Lösungen entstehen, die stabil gegen Entmischung sind, wozu im allgemeinen 45 - 55 Gew.-% Wasser aus­reichen. Ein stärkeres Verdünnen der Mittel mit Wasser bringt we­gen des größeren Verpackungsbedarfs keine Vorteile.The preferably builder-free agents advantageously contain as solvent a mixture of ethanol and 1,2-propanediol and water. The proportion of organic solvents is 8-20% by weight, preferably 10-17% by weight. The weight ratio of ethanol to 1,2-propanediol is 3: 1 to 1: 2, preferably 2: 1 to 1: 1.5. The proportion of water is chosen so that non-gelling solutions are formed which are stable against segregation, for which 45-55% by weight water is generally sufficient. A greater dilution of the agents with water has no advantages because of the greater packaging requirements.

Die klarflüssigen Mittel können zusätzlich zu Alkylglucosid wei­tere nichtionische Tenside vom Typ der Anlagerungsprodukte von 1 - 10 Mol Ethylenoxid an primäre C₁₂- bis C₁₈-Fettalkohole und deren Gemische wie Kokos-, Talgfett- oder Oleylalkohole enthalten. Oxo­alkohole (nach der Methode der Oxosynthese bzw. Hydroformylierung hergestellte Alkohole) sind gleichfalls geeignet, jedoch aufgrund ihrer Herkunft aus fossilen Rohstoffen weniger bevorzugt. Der An­teil der Fettalkoholethoxylate in den Mitteln kann 0 - 17 Gew.-%, vorzugsweise bis zu 14 Gew.-%, betragen.In addition to alkyl glucoside, the clear liquid agents can contain further nonionic surfactants of the type of the adducts of 1-10 moles of ethylene oxide with primary C₁₂ to C₁₈ fatty alcohols and their mixtures such as coconut oil, tallow oil or oleyl alcohols. Oxo alcohols (alcohols produced by the method of oxosynthesis or hydroformylation) are also suitable, but because of less preferred because of their origin from fossil raw materials. The proportion of fatty alcohol ethoxylates in the compositions can be 0-17% by weight, preferably up to 14% by weight.

In einigen Fällen, insbesondere beim Waschen hochempfindlicher Textilien aus Seide oder Wolle, kann es von Vorteil sein, den Mit­teln zusätzlich Triethanolamin in Mengen von maximal 8 Gew.-% zu­zusetzen.In some cases, especially when washing highly sensitive textiles made of silk or wool, it may be advantageous to add triethanolamine to the detergent in amounts of up to 8% by weight.

Außerdem können die Mittel geringe Mengen an freier Natronlauge enthalten, die zur Einstellung höherer pH-Werte zwischen 8,5 und 10,5 erforderlich sind.In addition, the agents can contain small amounts of free sodium hydroxide solution, which are required to set higher pH values between 8.5 and 10.5.

Außer den genannten Inhaltsstoffen können die Mittel bekannte, in Waschmitteln üblicherweise eingesetzte Zusatzstoffe, beispiels­weise Salze der Citronensäure in Mengen von 0,1 - 2, vorzugsweise 0,3 - 1 Gew.-% (berechnet als freie Säure), Salze von Polyphos­phonsäuren, optische Aufheller, Enzyme, Enzymstabilisatoren, Füll­salze sowie Farb- und Duftstoffe enthalten.In addition to the ingredients mentioned, the detergents can contain known additives commonly used in detergents, for example salts of citric acid in amounts of 0.1-2, preferably 0.3-1% by weight (calculated as free acid), salts of polyphosphonic acids, optical Brighteners, enzymes, enzyme stabilizers, filler salts as well as colors and fragrances.

Als Salze von Polyphosphonsäuren werden vorzugsweise die neutral reagierenden Natriumsalze von beispielsweise 1-Hydroxyethan-1,1-­diphosphonat und Diethylentriamin-pentamethylenphosphonat in Men­gen von 0,1 1,5 Gew.-% verwendet. Vorzugsweise beträgt der Phosphor-Gesamtanteil in den Mitteln weniger als 0,5 %.The neutral-reacting sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate and diethylenetriamine pentamethylene phosphonate are preferably used as salts of polyphosphonic acids in amounts of 0.1 1.5% by weight. The total phosphorus content in the compositions is preferably less than 0.5%.

Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Amylasen bzw. deren Gemische in Frage. Ihr Anteil kann 0,2 - 1 Gew.-% betragen. Als Enzymstabilisator kann 0,5 - 1,5 Gew.-% Na­triumformiat eingesetzt werden. Möglich ist auch der Einsatz von Proteasen, die mit löslichen Calciumsalzen und einem Calciumgehalt von vorzugsweise 1,2 Gew.-%, bezogen auf das Enzym, stabilisiert sind.Suitable enzymes are those from the class of proteases, lipases, amylases or mixtures thereof. Their proportion can be 0.2-1% by weight. 0.5-1.5% by weight sodium formate can be used as the enzyme stabilizer. It is also possible to use proteases with soluble calcium salts and a calcium content of preferably 1.2% by weight, based on the enzyme, are stabilized.

Beim Einsatz in maschinellen Waschverfahren kann es von Vorteil sein, den Mitteln übliche Schauminhibitoren zuzusetzen. Geeignete nichttensidartige Schauminhibitoren sind beispielsweise Organo­polysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallin­wachse und deren Gemische mit silanierter Kieselsäure. Mit Vorteil können auch Gemische verschiedener Schauminhibitoren verwendet werden, z. B. solche aus Silikonen, Paraffinen oder Wachsen.When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable non-surfactant-like foam inhibitors are, 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. B. from silicone, paraffins or waxes.

In einer bevorzugten Ausführungsform enthalten die Mittel (A) 5 - 15 Gew.-% Fettalkylsulfat, (B) 10 - 20 Gew.-% Seifen, bestehend aus dem Salz der (B1) Ölsäure und (B2) gesattigten C₁₂- bis C₁₆-­Fettsäuren oder deren Gemischen im Gewichtsverhältnis (B1) zu (B2) wie 2 : 1 bis 1 : 2, (C) 1 - 8, vorzugsweise 1 - 5 Gew.-% Fettal­kylglucosid, 10 - 15 Gew.-% 1,2-Propandiol und Ethanol, 3 - 5 Gew.-% Triethanolamin und 0,5 - 1 Gew.-% Salz der Citronensäure (berechnet als freie Säure).In a preferred embodiment, agents (A) contain 5-15% by weight of fatty alkyl sulfate, (B) 10-20% by weight of soaps, consisting of the salt of (B1) oleic acid and (B2) saturated C₁₂- to C₁₆- Fatty acids or their mixtures in the weight ratio (B1) to (B2) such as 2: 1 to 1: 2, (C) 1-8, preferably 1-5% by weight fatty alkyl glucoside, 10-15% by weight 1,2- Propanediol and ethanol, 3-5% by weight triethanolamine and 0.5-1% by weight salt of citric acid (calculated as free acid).

In einer weiteren bevorzugten Ausführungsform enthalten die Mittel (A) und (B) wie oben, (C) 1 - 5 Gew.-% Fettalkylglucosid, 12 - 17 Gew.-% 1,2-Propandiol und Ethanol, 0,5 - 1 Gew.-% Salz der Citro­nensäure (bezogen auf freie Säure) und 0,5 - 1 Gew.-% Natriumpoly­phosphonat.In a further preferred embodiment, agents (A) and (B) contain, as above, (C) 1-5% by weight of fatty alkyl glucoside, 12-17% by weight of 1,2-propanediol and ethanol, 0.5-1 % By weight salt of citric acid (based on free acid) and 0.5-1% by weight sodium polyphosphonate.

Ebenso bevorzugt ist die Verwendung von Mitteln, enthaltend (A) 5 - 12 Gew.-% Fettalkylsulfat, (B) 10 - 18 Gew.-% Seifen, bestehend aus (B1) Natriumoleat und (B2) dem Natriumsalz von gesättigten C₁₂- bis C₁₆-Fettsäuren oder deren Gemischen im Gewichtsverhältnis (B1) zu (B2) wie 2 : 1 bis 1 : 1, (C) 1 - 4 Gew.-% Fettalkylglu­cosid, 2 - 5 Gew.-% Fettalkohole mit 1 - 10 Mol Ethylenoxid pro Mol Fettalkohol, 10 - 17 Gew.-% 1,2-Propandiol und Ethanol, 0,3 - 1 Gew.-% Salz der Citronensäure (berechnet als freie Säure) und 0 - 1 Gew.-% an Natriumpolyphosphonat.Also preferred is the use of agents containing (A) 5-12% by weight fatty alkyl sulfate, (B) 10-18% by weight soaps consisting of (B1) sodium oleate and (B2) the sodium salt of saturated C₁₂- bis C₁₆ fatty acids or mixtures thereof in a weight ratio (B1) to (B2) as 2: 1 to 1: 1, (C) 1-4% by weight of fatty alkyl glucoside, 2-5% by weight of fatty alcohols with 1-10 moles of ethylene oxide per mole of fatty alcohol, 10-17% by weight % 1,2-propanediol and ethanol, 0.3-1% by weight salt of citric acid (calculated as free acid) and 0-1% by weight sodium polyphosphonate.

Besonders vorteilhaft sind stickstofffreie universelle Flüssig­waschmittel, die (A) 3 - 8 Gew.-% Fettalkylsulfat, (B) 12 - 20 Gew.-% Seifen, bestehend aus (B1) Natriumoleat und (B2) dem Na­triumsalz von gesättigten C₁₂- bis C₁₆-Fettsäuren oder deren Ge­mischen im Gewichtsverhältnis (B1) zu (B2) wie 2 : 1 bis 1 : 2, (C) 1 - 3 Gew.-% Fettalkylglucosid, 8 - 14 Gew.-% Fettalkohol mit 1 - 10 Mol Ethylenoxid pro Mol Fettalkohol, 10 - 17 Gew.-% 1,2-­Propandiol und Ethanol, 0 - 1 Gew.-% Salz der Citronensäure (be­zogen auf freie Säure) und 0 - 1 Gew.-% Natriumpolyphosphonat ent­halten.Nitrogen-free universal liquid detergents are particularly advantageous, the (A) 3-8% by weight fatty alkyl sulfate, (B) 12-20% by weight soaps, consisting of (B1) sodium oleate and (B2) the sodium salt of saturated C₁₂- to C₁₆ -Fatty acids or their mixtures in the weight ratio (B1) to (B2) such as 2: 1 to 1: 2, (C) 1-3% by weight of fatty alkyl glucoside, 8-14% by weight of fatty alcohol with 1-10 moles of ethylene oxide per Mol of fatty alcohol, 10-17 wt .-% 1,2-propanediol and ethanol, 0-1 wt .-% salt of citric acid (based on free acid) and 0-1 wt .-% sodium polyphosphonate.

Gegebenenfalls können in allen diesen Mitteln Enzyme sowie Enzym­stabilisatoren enthalten sein.If necessary, all of these agents can contain enzymes and enzyme stabilizers.

Die Mittel zeichnen sich durch eine gute Konfektionierbarkeit, Lagerstabilität und leichte Vermischbarkeit mit Wasser aus. Bei der Verwendung in maschinellen Waschverfahren zeigen sie zudem ein gutes Einspülverhalten.The agents are notable for easy assembly, storage stability and easy mixing with water. When used in machine washing processes, they also show good washing-in behavior.

Die Erfindung betrifft ferner ein Verfahren zur Herstellung der oben beschriebenen Flüssigwaschmittel. Dabei können die Flüssig­waschmittel in an sich bekannter Weise hergestellt werden. Vor­zugsweise werden die Ölsäure und die C₁₂- bis C₁₆-Fettsäure bzw. das C₁₂-C₁₆-Fettsäuregemisch und ggf. Citronensäure zunächst in einer auf 50 - 80 °C vorgewärmten Mischung, die Wasser, Natrium­ hydroxid und 1,2-Propandiol und ggf. Triethanolamin enthält, unter Rühren gelöst und in ihre Salze überführt. Die übrigen Bestand­teile des Flüssigwaschmittels können in beliebiger Reihenfolge zugegeben werden. Vorteilhafterweise erfolgt die Zugabe von Al­kylsulfat vor der Zugabe von Alkylglucosid und ggf. Fettalkohol­ethoxylat. Falls die Mittel Enzyme enthalten, werden diese als letzte Komponente bei Raumtemperatur in das Flüssigwaschmittel eingerührt.The invention further relates to a method for producing the liquid detergents described above. The liquid detergents can be produced in a manner known per se. Preferably, the oleic acid and the C₁₂- to C₁₆ fatty acid or the C₁₂-C₁₆ fatty acid mixture and optionally citric acid are first preheated to 50 - 80 ° C, the water, sodium contains hydroxide and 1,2-propanediol and possibly triethanolamine, dissolved with stirring and converted into their salts. The remaining components of the liquid detergent can be added in any order. The alkyl sulfate is advantageously added before the addition of alkyl glucoside and, if appropriate, fatty alcohol ethoxylate. If the detergents contain enzymes, the last component is stirred into the liquid detergent at room temperature.

BeispieleExamples

Erfindungsgemäße Flüssigwaschmittel können aus den in Tabelle 1 aufgeführten Komponenten zusammengesetzt sein, wobei im einzelnen bedeutet:

  • (A) Natriumfettalkylsulfat mit einer C-Kettenverteilung von 1 Gew.-% C₁₀, 62 Gew.-% C₁₂, 23 Gew.-% C₁₄, 11 Gew.-% C₁₆, 3 Gew.-% C₁₈; der Gehalt an freiem Fettalkohol im Fettalkohol­sulfat betrug weniger als 1 Gew.-%.
  • (B1) Ölsäure, technisch
  • (B2) Kokosfettsäure (C₁₂-C₁₈)
    Das Fettsäuregemisch (B1 + B2) enthielt insgesamt 10 Gew.-% Stea­rinsäure, bezogen auf das Fettsäuregemisch; technische Ölsäure bestand zu 12 Gew.-% aus Palmitinsäure.
  • (C) C₁₂-C₁₄-Alkylglucosid (native Basis); Oligomerisierungsgrad x = 1,4
  • (D) Natriumhydroxid
  • (E) C₁₂-C₁₈-Fettalkohol mit 7 Ethylenoxidgruppen (EO)
  • (F1) Ethanol
  • (F2) 1,2-Propandiol
  • (G) Triethanolamin
  • (H) Citronensäure (berechnet als freie Saure)
  • (I) Natriumphosphonat: 1-Hydroxyethan 1,1-diphosphonat oder Di­ethylentriamin-pentamethylenphosphonat.
Liquid detergents according to the invention can be composed of the components listed in Table 1, where in particular means:
  • (A) sodium fatty alkyl sulfate with a C chain distribution of 1% by weight C₁₀, 62% by weight C₁₂, 23% by weight C₁₄, 11% by weight C₁₆, 3% by weight C₁₈; the content of free fatty alcohol in the fatty alcohol sulfate was less than 1% by weight.
  • (B1) oleic acid, technical
  • (B2) coconut fatty acid (C₁₂-C₁₈)
    The fatty acid mixture (B1 + B2) contained a total of 10% by weight of stearic acid, based on the fatty acid mixture; Industrial oleic acid consisted of 12% by weight of palmitic acid.
  • (C) C₁₂-C₁₄ alkyl glucoside (native base); Degree of oligomerization x = 1.4
  • (D) sodium hydroxide
  • (E) C₁₂-C₁₈ fatty alcohol with 7 ethylene oxide groups (EO)
  • (F1) ethanol
  • (F2) 1,2-propanediol
  • (G) triethanolamine
  • (H) citric acid (calculated as free acid)
  • (I) Sodium phosphonate: 1-hydroxyethane, 1,1-diphosphonate or diethylene triamine pentamethylene phosphonate.

Die Mittel wurden in der Weise hergestellt, daß zunächst eine Mi­schung aus Wasser, Natriumhydroxid (D), 1,2-Propandiol (F2) und ggf. Triethanolamin (G) auf 70 °C erwärmt wurde. In die warme Lö­sung wurden die Fettsäuren (B1) und (B2) und ggf. Citronensäure (H) eingerührt. Die Zugabe von Phosphonat (I), Fettalkylsulfat (A), Alkylglucosid (C) und Fettalkoholethoxylat (E) erfolgte in der angegebenenen Reihenfolge unter ständigem Rühren. Nach Abküh­lung auf 35 °C wurde der klaren Lösung Ethanol (F1) zugefügt. Nach dem Abkühlen auf Raumtemperatur erfolgte - falls gewünscht - die Zugabe von Enzym, Formiat sowie Farb- und Duftstoffen, die zu den restlichen Bestandteilen gehören.

Figure imgb0001
Figure imgb0002
 The agents were prepared in such a way that a mixture of water, sodium hydroxide (D), 1,2-propanediol (F2) and optionally triethanolamine (G) was first heated to 70.degree. The fatty acids (B1) and (B2) and possibly citric acid were added to the warm solution (H) stirred in. Phosphonate (I), fatty alkyl sulfate (A), alkyl glucoside (C) and fatty alcohol ethoxylate (E) were added in the order given with constant stirring. After cooling to 35 ° C., ethanol (F1) was added to the clear solution. After cooling to room temperature, the enzyme, formate and colorants and fragrances, which belong to the remaining constituents, were added, if desired.
Figure imgb0001
Figure imgb0002

Weitere erfindungsgemäße Mittel werden erhalten, wenn das Fettal­kylsulfat in der obigen Zusammensetzung teilweise oder ganz durch Lauryl-, Myristyl- oder Cetylsulfat, durch das Sulfatierungspro­dukt von Oleylalkohol oder durch die Sulfatierungsprodukte von aus Palm- und Palmkernöl und Talg gewonnenen Fettalkoholgemischen so­wie durch Mischungen von diesen ersetzt wird.Further agents according to the invention are obtained if the fatty alkyl sulfate in the above composition is partially or completely replaced by lauryl, myristyl or cetyl sulfate, by the sulfation product of oleyl alcohol or by the sulfation products of fatty alcohol mixtures obtained from palm and palm kernel oil and tallow and by mixtures of these becomes.

Weitere erfindungsgemäße Mittel werden auch erhalten, wenn die in der obigen Zusammensetzung angegebenen seifenbildenden gesättigten Fettsäuren (B2) teilweise oder ganz durch Laurin-, Myristin- oder Palmitinsäure oder durch natürliche Fettsäuregemische wie hydrier­tem Talg sowie durch Mischungen von diesen ersetzt werden.Further agents according to the invention are also obtained if the soap-forming saturated fatty acids (B2) specified in the above composition are partially or completely replaced by lauric, myristic or palmitic acid or by natural fatty acid mixtures such as hydrogenated tallow and by mixtures of these.

Ebenso werden weitere erfindungsgemäße Mittel dadurch erhalten, daß das in den obigen Mitteln eingesetzte Fettalkoholethoxylat ganz oder teilweise durch reinen C₁₂-, C₁₄-, C₁₆-, gesättigten und ungesättigten C₁₈-Fettalkohol mit 1 - 10 Ethylenoxidgruppen (EO) oder anderen nativen Fettalkoholmischungen, die beispielsweise aus Palm-, Palmkernöl oder Talgfett gewonnen werden, durch C₁₂-C₁₄-­Fettalkohol mit 3 EO, C₁₂-C₁₄-Fettalkohol mit 4 EO, C₁₂-C₁₈-Fett­alkohol mit 3 EO, C₁₂-C₁₈-Fettalkohol mit 5 EO, durch ein Gemisch von C₁₂-C₁₈-Fettalkohol mit 5 EO und C₁₂-C₁₄-Fettalkohol mit 3 EO, durch Cetyloleylalkohol (Jodzahl 50 - 55) mit 2 EO, Cetyloleylal­kohol (Jodzahl 50 - 55) mit 7 EO, Cetyloleylalkohol (Jodzahl 50 - 55) mit 50 % EO, durch ein Gemisch von Cetyloleylalkohol mit 5 EO und Cetyloleylalkohol mit 10 EO oder durch Mischungen von diesen ersetzt wird.Likewise, further agents according to the invention are obtained in that the fatty alcohol ethoxylate used in the above agents, in whole or in part, by pure C₁₂-, C₁₄-, C₁₆-, saturated and unsaturated C₁₈-fatty alcohol with 1-10 ethylene oxide groups (EO) or other native fatty alcohol mixtures For example, from palm, palm kernel oil or tallow fat can be obtained by C₁₂-C₁₄ fatty alcohol with 3 EO, C₁₂-C₁₄ fatty alcohol with 4 EO, C₁₂-C₁₈ fatty alcohol with 3 EO, C₁₂-C₁₈ fatty alcohol with 5 EO, by a Mixture of C₁₂-C₁₈ fatty alcohol with 5 EO and C₁₂-C₁₄ fatty alcohol with 3 EO, by cetyloleyl alcohol (iodine number 50 - 55) with 2 EO, cetyloleyl alcohol (iodine number 50 - 55) with 7 EO, cetyloleyl alcohol (iodine number 50 - 55) with 50% EO, by a mixture of cetyloleyl alcohol with 5 EO and cetyloleyl alcohol with 10 EO or by mixtures of these.

Ebenfalls erfindungsgemäße Produkte werden erhalten, wenn das in der obigen Zusammensetzung angegebene Alkylglucosid ganz oder teil­weise durch C₁₂-Alkylglucosid mit x = 1,1 - 3, C₁₄-Alkylglucosid mit x = 1,1 - 3, C₁₆-Alkylglucosid mit x = 1.1 - 3, C₁₈-Alkyl­glucosid mit x = 1,1 - 3 sowie Alkylglucosiden mit x = 1,1 - 3, deren Fettalkylrest sich von anderen technischen Fraktionen, die im wesentlichen gesättigte Fettalkohole enthalten, ableitet, er­setzt wird.Products according to the invention are also obtained when the alkyl glucoside specified in the above composition is wholly or partly by C₁₂-alkyl glucoside with x = 1.1 - 3, C₁₄-alkyl glucoside with x = 1.1 - 3, C₁₆-alkyl glucoside with x = 1.1 - 3, C₁₈-alkyl glucoside with x = 1.1 - 3 and alkyl glucosides with x = 1.1 - 3, whose fatty alkyl radical differs from other technical fractions essentially contain saturated fatty alcohols, is derived, is replaced.

Die erfindungsgemäßen Mittel zeichnen sich durch eine hautfreund­liche Tensidkombination, die sehr gut biologisch abbaubar ist, aus.The agents according to the invention are distinguished by a skin-friendly surfactant combination that is very readily biodegradable.

Das Waschvermögen der Mittel 1 bis 16 bei 30 °C (Waschmittelkon­zentration 3 g/l, Gewichtsverhältnis von Textilgut zu Waschlösung 1 : 40, Wasserhärte 16 °d = 160 mg CaO/Liter) erwies sich bei ei­ner von Hand durchgeführten Waschbehandlung von Wolltextilien als befriedigend und mit bekannten Mitteln des Handels vergleichbar.The washing power of detergents 1 to 16 at 30 ° C (detergent concentration 3 g / l, weight ratio of textile to washing solution 1:40, water hardness 16 ° d = 160 mg CaO / liter) proved to be satisfactory when washing wool textiles by hand and comparable with known means of trade.

Die Prüfung der Waschleistung in einer Haushaltswaschmaschine mit horizontal angeordneter Wäschetrommel (Typ Miele W 760) erfolgte unter folgenden Bedingungen:
Einlaugenverfahren
Waschtemperatur: 60 °C
Wasserhärte: 16 °d (160 mg CaO/Liter)
Waschmitteldosierung: 180 g
Menge Füllwäsche: 3 kg
Dreifachbestimmung
Anschmutzungen:

  • I Staub/Hautfett auf Baumwolle
  • II Staub/Hautfett auf veredelter Baumwolle
  • III Staub/Hautfett auf Mischgewebe aus Polyester und veredelter Baumwolle
  • IV Staub/Wollfett auf Wolle
  • V Lippenstift auf Mischgewebe gemäß III
  • VI Make-up auf Mischgewebe gemäß III
  • VII Tee auf Baumwolle
  • VIII Rotwein auf Baumwolle
The washing performance was checked in a household washing machine with a horizontally arranged washing drum (type Miele W 760) under the following conditions:
Soaking process
Washing temperature: 60 ° C
Water hardness: 16 ° d (160 mg CaO / liter)
Detergent dosage: 180 g
Amount of filling laundry: 3 kg
Triple determination
Soiling :
  • I dust / skin fat on cotton
  • II Dust / skin oil on refined cotton
  • III Dust / skin fat on mixed fabrics made of polyester and finished cotton
  • IV dust / wool grease on wool
  • V Lipstick on blended fabrics according to III
  • VI Make-up on mixed fabrics according to III
  • VII Tea on cotton
  • VIII red wine on cotton

Die optische Auswertung der Waschergebnisse (Tabelle 2) erfolgte mit einem Zeiss-Reflektometer bei 460 nm. Tabelle 2 Mittel % Remission bei Anschmutzugen I II III IV V VI VII VIII 2 - - - 55,8 45,6 46,3 44,0 45,2 6 - - - 58,4 47,5 44,7 46,1 42,7 8 59,6 60,3 60,1 59,9 47,5 46,2 45,3 44,0 11 63,9 64,2 62,7 63,5 48,6 48,3 47,5 46,2 14 62,4 62,5 61,3 - 48,5 48,1 48,3 47,0 15 61,9 61,8 63,0 - 49,2 49,1 48,0 46,7 16 62,9 62,9 61,7 62,4 48,4 47,2 47,9 44,5 The optical evaluation of the washing results (Table 2) was carried out using a Zeiss reflectometer at 460 nm. Table 2 medium % Remission on soiling I. II III IV V VI VII VIII 2nd - - - 55.8 45.6 46.3 44.0 45.2 6 - - - 58.4 47.5 44.7 46.1 42.7 8th 59.6 60.3 60.1 59.9 47.5 46.2 45.3 44.0 11 63.9 64.2 62.7 63.5 48.6 48.3 47.5 46.2 14 62.4 62.5 61.3 - 48.5 48.1 48.3 47.0 15 61.9 61.8 63.0 - 49.2 49.1 48.0 46.7 16 62.9 62.9 61.7 62.4 48.4 47.2 47.9 44.5

Claims (8)

1. Flüssigwaschmittel, enthaltend Aniontenside und Alkylgluco­side, dadurch gekennzeichnet. daß es (A) 3 - 20 Gew.-% Fett­alkylsulfate in Form der Natriumsalze, (B) 10 - 25 Gew.-% Seifen, bestehend aus Salzen (B1) ungesättigter C₁₂- bis C₁₈-­Fettsäuren und (B2) gesattigter C₁₂- bis C₁₈-Fettsäuren im Ge­wichtsverhältnis (B1) zu (B2) von 3 : 1 bis 1 : 3, und (C) 1 - 10 Gew.-% Alkylglucoside der allgemeinen Formel RO(G)x, wobei R einen Fettalkylrest, G eine Glucoseeinheit und x eine Zahl zwischen 1 und 10 darstellt, enthält.1. Liquid detergent containing anionic surfactants and alkyl glucosides, characterized. that it is (A) 3 - 20% by weight fatty alkyl sulfates in the form of the sodium salts, (B) 10 - 25% by weight soaps consisting of salts (B1) unsaturated C₁₂- to C₁₈ fatty acids and (B2) saturated C₁₂- to C₁₈ fatty acids in the weight ratio (B1) to (B2) from 3: 1 to 1: 3, and (C) 1-10 wt .-% alkylglucosides of the general formula RO (G) x , where R is a fatty alkyl radical, G is a Glucose unit and x represents a number between 1 and 10 contains. 2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß es ein Fettalkylsulfat (A) enthält, in dem die Anteile der Alkylreste wie folgt verteilt sind:
50 - 70 Gew.-% C₁₂, 18 - 30 Gew.-% C₁₄, 5 - 15 Gew.-% C₁₆, unter 3 Gew.-% an C₁₀ und unter 10 Gew.-% C₁₈.2. Composition according to claim 1, characterized in that it contains a fatty alkyl sulfate (A) in which the proportions of the alkyl radicals are distributed as follows:
50-70% by weight of C₁₂, 18-30% by weight of C₁₄, 5-15% by weight of C₁₆, less than 3% by weight of C₁₀ and less than 10% by weight of C₁₈. 3. Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß (B) aus einem Seifengemisch aus (B1) Natriumoleat und (B2) dem Natriumsalz der Laurinsäure oder eines C₁₂-C₁₆-Fettsäurege­misches besteht, wobei das Gewichtsverhältnis (B1) zu (B2) 2 : 1 bis 1 : 2 beträgt.3. Composition according to claim 1 or 2, characterized in that (B) consists of a soap mixture of (B1) sodium oleate and (B2) the sodium salt of lauric acid or a C₁₂-C₁₆ fatty acid mixture, the weight ratio (B1) to (B2 ) Is 2: 1 to 1: 2. 4. Mittel nach einem oder mehreren der Ansprüche 1 - 3, dadurch gekennzeichnet, daß es Alkylglucoside mit einem Oligomerisie­rungsgrad x zwischen 1,1 bis 3, vorzugsweise 1,1 bis 1,4 ent­hält.4. Composition according to one or more of claims 1-3, characterized in that it contains alkyl glucosides with a degree of oligomerization x between 1.1 to 3, preferably 1.1 to 1.4. 5. Mittel nach einem oder mehreren der Ansprüche 1 - 4, dadurch gekennzeichnet, daß es Anlagerungsprodukte von 1 - 10 Mol Ethylenoxid an primäre C₁₂- bis C₁₈-Fettalkohole und deren Gemische enthält.5. Composition according to one or more of claims 1-4, characterized in that it contains addition products of 1-10 moles of ethylene oxide with primary C₁₂ to C₁₈ fatty alcohols and mixtures thereof. 6. Mittel nach Anspruch 5, dadurch gekennzeichnet, daß der Anteil der Fettalkoholethoxylate bis zu 17 Gew.-%, vorzugsweise bis zu 14 Gew.-% betragt.6. Composition according to claim 5, characterized in that the proportion of fatty alcohol ethoxylates is up to 17 wt .-%, preferably up to 14 wt .-%. 7. Mittel nach einem oder mehreren der Ansprüche 1 - 6, dadurch gekennzeichnet, daß es bis zu 8 Gew.-% Triethanolamin enthält.7. Composition according to one or more of claims 1-6, characterized in that it contains up to 8 wt .-% triethanolamine. 8. Verfahren zur Herstellung eines Flüssigwaschmittels, enthal­tend (A) 3 - 20 Gew.-% Fettalkylsulfate in Form der Natrium­salze, (B) 10 -25 Gew.-% Seifen, bestehend aus Salzen (B1) der Ölsäure und (B2) einer oder mehrerer gesättigter C₁₂- bis C₁₆-Fettsäuren im Gewichtsverhältnis (B1) zu (B2) von 3 : 1 bis 1 : 3, dadurch gekennzeichnet, daß das Flüssigwaschmittel in an sich bekannter Weise hergestellt wird.8. A process for the preparation of a liquid detergent containing (A) 3-20% by weight of fatty alkyl sulfates in the form of the sodium salts, (B) 10-25% by weight of soaps, consisting of salts (B1) of oleic acid and (B2) one or more saturated C₁₂ to C₁₆ fatty acids in a weight ratio (B1) to (B2) of 3: 1 to 1: 3, characterized in that the liquid detergent is produced in a manner known per se.
EP90111177A 1989-06-22 1990-06-13 Liquid detergent Withdrawn EP0403948A1 (en)

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DE3920480 1989-06-22

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992013055A1 (en) * 1991-01-29 1992-08-06 Henkel Kommanditgesellschaft Auf Aktien Liquid washing agents
WO1992019711A1 (en) * 1991-05-03 1992-11-12 Henkel Kommanditgesellschaft Auf Aktien Liquid washing agent

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4029035A1 (en) * 1990-09-13 1992-03-19 Huels Chemische Werke Ag LAUNDRY DETERGENT
DE4034840A1 (en) * 1990-11-02 1992-05-07 Henkel Kgaa ENZYMATIC LIQUID DETERGENT
DE4039223A1 (en) * 1990-12-08 1992-06-11 Huels Chemische Werke Ag LIQUID DETERGENT
DE4127946C2 (en) * 1991-08-25 2002-02-14 Kreussler Chem Fab Use of a cleaning booster

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0075994A2 (en) * 1981-09-28 1983-04-06 THE PROCTER & GAMBLE COMPANY Detergent compositions containing mixture of alkylpolysaccharide and amine oxide surfactants and fatty acid soap
EP0092877A2 (en) * 1982-04-26 1983-11-02 THE PROCTER & GAMBLE COMPANY Detergent compositions
EP0216301A2 (en) * 1985-09-25 1987-04-01 Henkel Kommanditgesellschaft auf Aktien Liquid cleaning agent

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0075994A2 (en) * 1981-09-28 1983-04-06 THE PROCTER & GAMBLE COMPANY Detergent compositions containing mixture of alkylpolysaccharide and amine oxide surfactants and fatty acid soap
EP0092877A2 (en) * 1982-04-26 1983-11-02 THE PROCTER & GAMBLE COMPANY Detergent compositions
EP0216301A2 (en) * 1985-09-25 1987-04-01 Henkel Kommanditgesellschaft auf Aktien Liquid cleaning agent

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992013055A1 (en) * 1991-01-29 1992-08-06 Henkel Kommanditgesellschaft Auf Aktien Liquid washing agents
US6121227A (en) * 1991-01-29 2000-09-19 Henkel Kommanditgesellschaft Auf Aktien Liquid detergent
WO1992019711A1 (en) * 1991-05-03 1992-11-12 Henkel Kommanditgesellschaft Auf Aktien Liquid washing agent
US5441662A (en) * 1991-05-03 1995-08-15 Henkel Kommanditgesellschaft Auf Aktien Liquid detergent
US5520836A (en) * 1991-05-03 1996-05-28 Henkel Kommanditgesellschaft Auf Aktien Liquid detergent

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WO1990015855A1 (en) 1990-12-27
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