EP0666898A1 - Process for preparing aqueous solutions of anionic surfactants with improved low-temperature stability. - Google Patents

Process for preparing aqueous solutions of anionic surfactants with improved low-temperature stability.

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Publication number
EP0666898A1
EP0666898A1 EP93923521A EP93923521A EP0666898A1 EP 0666898 A1 EP0666898 A1 EP 0666898A1 EP 93923521 A EP93923521 A EP 93923521A EP 93923521 A EP93923521 A EP 93923521A EP 0666898 A1 EP0666898 A1 EP 0666898A1
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European Patent Office
Prior art keywords
alkyl
carbon atoms
formula
radical
ether
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Application number
EP93923521A
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German (de)
French (fr)
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EP0666898B1 (en
Inventor
Karl-Heinz Schmid
Brigitte Giesen
Andreas Syldath
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C11D1/8305—Mixtures of non-ionic with anionic compounds containing a combination of non-ionic compounds differently alcoxylised or with different alkylated chains
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates 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
    • 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
    • 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
    • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • 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
    • C11D1/126—Acylisethionates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/345—Phosphates or phosphites
    • 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
    • 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
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • the invention relates to a process for improving the low-temperature stability of aqueous anionic surfactant solutions by adding a mixture of selected nonionic surfactants, hand dishwashing detergents which contain these mixtures, and the use of this mixture for producing aqueous anionic surfactant solutions with improved low-temperature stability.
  • Hand dishwashing detergents mainly contain anionic surfactants as active components.
  • Typical primary surfactants are alkylbenzenesulfonates, secondary alkanesulfonates, fatty alcohol ether sulfates and alkyl sulfates. These surfactants are present in the formulations in concentrations of up to a total of about 30% by weight, essentially powerful, synergistic combinations being used.
  • Suitable co-surfactants or secondary surfactants are, for example, betaines, fatty acid alkanolamides, amine oxides and ether carboxylic acids, which are used in much smaller amounts. them the task is to increase the rinsing capacity and foam stability (cf. Seifen- ⁇ le-Fette-Wwachs 115, 149 (1989).
  • EP-B 0 070 074, EP-B 0 070 075, EP-B 0 070 076 and EP-B 0 075 995 and EP-B 0 075 996 foam foaming detergent mixtures of anionic surfactants, alkyl oligoglucosides and optionally amine oxides and their use as dishwashing detergents.
  • EP-B 0 070 074, EP-B 0 070 075, EP-B 0 070 076 and EP-B 0 075 995 and EP-B 0 075 996 (Procter & Gamble) foam foaming detergent mixtures of anionic surfactants, alkyl oligoglucosides and optionally amine oxides and their use as dishwashing detergents.
  • the cold stability of the mixtures is not significantly improved by the addition of the nonionic surfactants mentioned.
  • German patent application DE-Al 40 25 065 also discloses aqueous surfactant mixtures which, in addition to alkyl oligoglucosides and mixtures of long- and short-chain alkyl sulfates, optionally also fatty alcohol polyethylene glycol ethers, preferably addition products of 3 to 10 moles of ethylene oxide with fatty alcohols having 10 to 20 carbon atoms, contain.
  • the surfactant compounds are described as premixes for the production of liquid detergents and cleaning agents.
  • the patent application contains no reference on the cold stability of the mixtures, and on an advantageous use in hand dishwashing detergents.
  • the object of the invention was therefore to provide a process for the preparation of aqueous anionic surfactant solutions which is free from the disadvantages described.
  • the invention relates to a process for the preparation of aqueous solutions of anionic surfactants with improved low-temperature stability, in which mixtures of nonionic surfactants are added to the surfactant solutions, comprising a) alkyl and / or alkenyl oligoglycosides of the formula (I),
  • R 2 represents an alkyl radical having 8 to 11 carbon atoms
  • n represents numbers from 4 to 9
  • m represents 0 or numbers from 1 to 3
  • R 3 is an alkyl radical having 12 to 15 carbon atoms, n is a number from 4 to 9 and m is 0 or a number from 1 to 3.
  • aqueous solutions can contain, for example, anionic surfactants which are selected from the group consisting of alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfofatty acids, alkyl sulfates, Fatty alcohol ether sulfates, glycerin ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, soaps, sulfosuccinates, sulfosuccinamates, sulfotriglycerides, isethionates, taurides, sarcosinates, ether
  • anionic surfactants which are selected from the group consisting of alkylbenzen
  • anionic surfactants contain polyglycol ether chains, they can have both a conventional and a narrow homolog distribution.
  • the surfactants mentioned are exclusively known compounds. With regard to the structure and manufacture of these substances, reference is made to relevant reviews, for example, J.Falbe (ed.), “Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, pp. 54-124 or J.Falbe (ed.), “Catalysts, Tenside und Mineralöladditive ", Thieme Verlag, Stuttgart, 1978, pp. 123-217.
  • Aqueous solutions of the anionic surfactants mentioned are preferably used which contain these in amounts of 1 to 50, preferably 25 to 35% by weight.
  • Alkyl and alkenyl oligoglycosides are known substances that can be obtained by the relevant methods of preparative organic chemistry. Representative of the extensive literature, reference is made here to the documents EP-Al-0 301 298 and WO 90/3977.
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • the alkyl or alkenyl radical R 1 can be derived from primary alcohols having 6 to 11, preferably 8 to 10, carbon atoms. Typical examples are capronic alcohol, caprylic alcohol, capric alcohol and ündecyl alcohol and their technical mixtures, such as those obtained in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the alkyl or alkenyl radical R 1 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, and their technical mixtures, which can be obtained as described above.
  • Alkyl oligoglucosides based on hydrogenated C12 / i4 coconut alcohol with a DP of 1 to 3
  • alkyl oligoglucosides are used which represent mixtures of the short-chain C 8 -C 11 -alkyl oligoglucosides and long-chain C 12 -C 14 -alkyl oligoglucosides mentioned in a weight ratio of 95: 5 to 40:60 and in particular 90: 10 to 50:50 .
  • fatty alcohol polyglycol ethers mentioned as components b) and c) are also fundamentally known substances which are obtained on an industrial scale by the addition of ethylene and / or propylene oxide to primary alcohols and predominantly fatty or oxo alcohols.
  • nonionic surfactants can be produced in this way which have a conventional or narrow homolog distribution, which are equally suitable for being a component of the mixture of nonionic surfactants.
  • the fatty alcohol polyglycol ethers which form component b) are adducts of ethylene and / or propylene oxide with primary alcohols having 8 to 11 carbon atoms.
  • Typical examples are the adducts of an average of 4 to 9, preferably 5 to 7, moles of ethylene oxide or 1 mole of propylene oxide with octanol, decanol or a C 8 -C 10 preliminary fatty alcohol.
  • adducts of ethylene and / or propylene oxide with primary alcohols having 12 to 15 carbon atoms are suitable for the fatty alcohol polyglycol ethers which form optional component c).
  • Typical examples here are adducts of on average 4 to 9, preferably 5 to 7, moles of ethylene oxide or 1 mole Propylene oxide on lauryl alcohol or a C 12 -C 14 coconut fatty alcohol.
  • the fatty alcohol polyglycol ethers which form components b) and c), contain ethylene and propylene glycol units, the ethylene glycol units are preferably at the end of the molecule.
  • the nonionic surfactants mentioned consisting of components a), b) and optionally c
  • this compound can contain components a) and b + c) in a weight ratio of 90:10 to 40:60, preferably 80:20 to 50:50 and contain in particular 70:30 to 50:50, while components b) and c) can be used in a weight ratio of 100: 0 to 70:30.
  • the mixtures of nonionic surfactants can be produced purely mechanically, preferably by stirring, if appropriate at elevated temperatures of 30 to 40 ° C .; a chemical reaction does not take place.
  • the invention further relates to aqueous hand dishwashing detergents with improved low-temperature stability, comprising anionic surfactants and a) alkyl and / or alkenyl oligoglycosides of the formula (I),
  • R 2 represents an alkyl radical having 8 to 11 carbon atoms
  • n represents numbers from 4 to 9
  • m represents 0 or numbers from 1 to 3
  • R 3 is an alkyl radical having 12 to 15 carbon atoms, n is a number from 4 to 9 and m is 0 or a number from 1 to 3.
  • the aqueous hand dishwashing agents according to the invention can have other conventional constituents, for example amphoteric surfactants, foam boosters, fragrances, etc.
  • a typical formulation can contain, for example, 20% by weight of fatty alcohol ether sulfate, 15% by weight of secondary alkane sulfonate, 3% by weight of alkylamidobetaine and 2% by weight of the nonionic surfactant mixture according to the invention (water to 100% by weight).
  • the addition of the mixtures of nonionic surfactants to the aqueous anionic surfactant solutions brings about a lowering of the cold cloud point without this measure having a negative influence on the rinsing performance of the mixtures.
  • Another object of the invention therefore relates to the use of mixtures of nonionic surfactants containing a) alkyl and / or alkenyl oligoglycosides of the formula (I),
  • R 2 represents an alkyl radical having 8 to 11 carbon atoms
  • n represents numbers from 4 to 9
  • m represents 0 or numbers from 1 to 3
  • R 3 stands for an alkyl radical with 12 to 15 carbon atoms, n for numbers from 4 to 9 and m for 0 or numbers from 1 to 3, to improve the low-temperature stability of aqueous solutions of anionic surfactants.
  • test formulations were transferred to a thermostat and cooled there from + 20 ° C to a maximum of -6 ° C (2 ° C / 10 min).
  • the cold cloud point (KTP) indicates the temperature at which the bare solution clouded.
  • the test results are summarized in Tables 1 and 2.
  • the determination of the dishwashing capacity was carried out with the aid of the dish test [Fette, Seifen, Anstrichmitt., 74, 163 (1972)].
  • plates with a diameter of 14 cm were soiled with 1.9 g of beef tallow (melting point 40-42 ° C, acid number 9-10) and stored at a temperature of 0 to 5 ° C for 15 h.
  • the plates were then rinsed at 50 ° C with tap water with a hardness of 16 ° d.
  • the test mixture was used with a dosage of 0.15 water.
  • the rinsing attempt was stopped as soon as the foam blanket tore open and the liquor underneath became visible.
  • Tables 1 and 2 The results of the rinsing tests are summarized in Tables 1 and 2; the number of dishes washed (T) is indicated.

Abstract

Aqueous solutions of anionic surfactants with an improved low-temperature stability are obtained when one adds to them mixtures of nonionic surfactants containing: a) alkyl and/or alkenyl oligoglycosides of the formula (I): R1-O-[G]¿p? in which R?1¿ stands for an alkyl and/or alkenyl group with 6-22 carbon atoms, G for a sugar group with 5 or 6 carbon atoms and p for a number from 1 to 10, b) fatty alcohol polyglycol ethers of formula (II), in which R2 stands for an alkyl group with 8-11 carbon atoms, n for a number from 4 to 9 and m for 0 or a number from 1 to 3, and, as needed, c) fatty alcohol polyglycol ethers of formula (III),in which R3 stands for an alkyl group with 12-15 carbon atoms, n for a number from 4 to 9 and m for 0 or a number from 1 to 3. The products are preferably used in the production of hand dish-washing detergents.

Description

Verfahren zur Herstellung wäßriger Lösungen anionischer Tenside mit verbesserter Kältestabilität  Process for the preparation of aqueous solutions of anionic surfactants with improved low-temperature stability
Gebiet der Erfindung Field of the Invention
Die Erfindung betrifft ein Verfahren zur Verbesserung der Kältestabilität von wäßrigen Aniontensidlösungen durch Zusatz einer Mischung ausgewählter nichtionischer Tenside, Handgeschirrspülmittel, die diese Mischungen enthalten sowie die Verwendung dieser Mischung zur Herstellung von wäßrigen Aniontensidlösungen mit verbesserter Kältestabilität. The invention relates to a process for improving the low-temperature stability of aqueous anionic surfactant solutions by adding a mixture of selected nonionic surfactants, hand dishwashing detergents which contain these mixtures, and the use of this mixture for producing aqueous anionic surfactant solutions with improved low-temperature stability.
Stand der Technik State of the art
Handgeschirrspülmittel enthalten als Wirkkomponenten überwiegend anionische Tenside. Typische Primärtenside sind dabei Alkylbenzolsulfonate, sekundäre Alkansulfonate, Fettalkohol- ethersulfate und Alkylsulfate. Diese Tenside sind in Konzentrationen bis zu insgesamt etwa 30 Gew.-% in den Formulierungen enthalten, wobei im wesentlichen leistungsstarke synergistisch wirkende Kombinationen eingesetzt werden. Als Co-oder Sekundärtenside kommen beispielsweise Betaine, Fettsäurealkanolamide, Aminoxide und Ethercarbonsäuren in Betracht, die in wesentlich geringeren Mengen eingesetzt werden. Ihnen fällt die Aufgabe zu, das Spülvermögen und die Schaumstabilität zu steigern (vgl. Seifen-Öle-Fette-Wachse 115, 149 (1989). Hand dishwashing detergents mainly contain anionic surfactants as active components. Typical primary surfactants are alkylbenzenesulfonates, secondary alkanesulfonates, fatty alcohol ether sulfates and alkyl sulfates. These surfactants are present in the formulations in concentrations of up to a total of about 30% by weight, essentially powerful, synergistic combinations being used. Suitable co-surfactants or secondary surfactants are, for example, betaines, fatty acid alkanolamides, amine oxides and ether carboxylic acids, which are used in much smaller amounts. them the task is to increase the rinsing capacity and foam stability (cf. Seifen-Öle-Fette-Wwachs 115, 149 (1989).
Ein Problem bei der Formulierung solcher Mittel, besteht in der vergleichsweise geringen Kältestabilität wäßriger Aniontensidlösungen. Insbesondere dann, wenn Formulierungen oder Teilformulierungen vor dem Verbrauch eine gewisse Zeit bevorratet werden müssen, kann es daher zu unerwünschten Austrübungen oder bei Außenlagerung sogar zum Erstarren des Produktes kommen. One problem with the formulation of such agents is the comparatively low cold stability of aqueous anionic surfactant solutions. In particular, if formulations or partial formulations have to be stored for a certain time before consumption, undesirable clouding or even solidification of the product can occur if stored outdoors.
In diesem Zusammenhang werden in den Europäischen Patenten EP-B 0 070 074, EP-B 0 070 075, EP-B 0 070 076 sowie EP-B 0 075 995 und EP-B 0 075 996 (Procter & Gamble) schäumende Detergensgemische von anionischen Tensiden, Alkyloligoglucosiden und gegebenenfalls Aminoxiden und deren Verwendung als Geschirrspülmittel vorgeschlagen. Durch den Zusatz der genannten nichtionischen Tensiden wird die Kältestabilität der Gemische jedoch nicht nennenswert verbessert. In this context, the European patents EP-B 0 070 074, EP-B 0 070 075, EP-B 0 070 076 and EP-B 0 075 995 and EP-B 0 075 996 (Procter & Gamble) foam foaming detergent mixtures of anionic surfactants, alkyl oligoglucosides and optionally amine oxides and their use as dishwashing detergents. However, the cold stability of the mixtures is not significantly improved by the addition of the nonionic surfactants mentioned.
Aus der Deutschen Patentanmeldung DE-Al 40 25 065 (Henkel) sind ferner wäßrige Tensidmischungen bekannt, die neben Alkyloligoglucosiden sowie Gemischen von lang- und kurzkettigen Alkylsulfaten gegebenenfalls auch Fettalkoholpolyethylenglycolether, vorzugsweise Anlagerungsprodukte von 3 bis 10 Mol Ethylenoxid an Fettalkohole mit 10 bis 20 Kohlenstoffatomen, enthalten. Die Tensidcompounds werden als Vorgemische zur Herstellung flüssiger Wasch- und Reinigungsmittel beschrieben. Die Patentanmeldung enthält jedoch weder einen Hinweis auf die Kältestabilität der Gemische, noch auf eine vorteilhafte Verwendung in Handgeschirrspülmitteln. German patent application DE-Al 40 25 065 (Henkel) also discloses aqueous surfactant mixtures which, in addition to alkyl oligoglucosides and mixtures of long- and short-chain alkyl sulfates, optionally also fatty alcohol polyethylene glycol ethers, preferably addition products of 3 to 10 moles of ethylene oxide with fatty alcohols having 10 to 20 carbon atoms, contain. The surfactant compounds are described as premixes for the production of liquid detergents and cleaning agents. However, the patent application contains no reference on the cold stability of the mixtures, and on an advantageous use in hand dishwashing detergents.
Die Aufgabe der Erfindung bestand somit darin, ein Verfahren zur Herstellung von wäßrigen Aniontensidlösungen zur Verfügung zu stellen, das frei von den geschilderten Nachteilen ist. The object of the invention was therefore to provide a process for the preparation of aqueous anionic surfactant solutions which is free from the disadvantages described.
Beschreibung der Erfindung Description of the invention
Gegenstand der Erfindung ist ein Verfahren zur Herstellung wäßriger Lösungen anionischer Tenside mit verbesserter Kältestabilität, bei dem man den Tensidlösungen Mischungen nichtionischer Tenside zusetzt, enthaltend a) Alkyl- und/oder Alkenyloligoglykoside der Formel (I), The invention relates to a process for the preparation of aqueous solutions of anionic surfactants with improved low-temperature stability, in which mixtures of nonionic surfactants are added to the surfactant solutions, comprising a) alkyl and / or alkenyl oligoglycosides of the formula (I),
R1-O-[G]p (I) in der R1 für einen Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht, b) Fettalkoholpolyglycolether der Formel (II), R 1 -O- [G] p (I) in which R 1 is an alkyl and / or alkenyl radical having 6 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10, b ) Fatty alcohol polyglycol ether of the formula (II),
in der R2 für einen Alkylrest mit 8 bis 11 Kohlenstoffatomen, n für Zahlen von 4 bis 9 und m für 0 oder Zahlen von 1 bis 3 steht, und gegebenenfalls c) Fettalkoholpolyglycolether der Formel (III), in which R 2 represents an alkyl radical having 8 to 11 carbon atoms, n represents numbers from 4 to 9 and m represents 0 or numbers from 1 to 3, and optionally c) fatty alcohol polyglycol ether of the formula (III),
in der R3 für einen Alkylrest mit 12 bis 15 Kohlenstoffatomen, n für Zahlen von 4 bis 9 und m für 0 oder Zahlen von 1 bis 3 steht. in which R 3 is an alkyl radical having 12 to 15 carbon atoms, n is a number from 4 to 9 and m is 0 or a number from 1 to 3.
Die wäßrigen Lösungen, deren Kälteverhalten im Sinne des erfindungsgemäßen Verfahrens es zu verbessern gilt, können beispielsweise Aniontenside enthalten, die ausgewählt sind aus der Gruppe, die gebildet wird von Alkylbenzolsulfonaten, Alkansulfonaten, Olefinsulfonaten, Alkylethersulfonaten, Glycerinethersulfonaten, α-Methylestersulfonaten, Sulfofettsäuren, Alkylsulfaten, Fettalkoholethersulfaten, Glycerinethersulfaten, Hydroxymischethersulfaten, Monoglycerid(ether)Sulfaten, Fettsäureamid(ether)Sulfaten, Seifen, Sulfosuccinaten, Sulfosuccinamaten, Sulfotriglyceriden, Isethionaten, Tauriden, Sarcosinaten, Ethercarbonsäuren, Alkyloligoglucosidsulfaten und Alkyl(ether)phosphaten sowie Betaintensiden. Sofern die anionischen Tenside Polyglycoletherketten enthalten, können sie sowohl eine konventionelle, als auch eine eingeengte Homologenverteilung aufweisen. Bei den genannten Tensiden handelt es sich ausschließlich um bekannte Verbindungen. Hinsichtlich Struktur und Herstellung dieser Stoffe sei auf einschlägige Übersichtsarbeiten beispielsweise J.Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, S.54-124 oder J.Falbe (ed.), "Katalysatoren, Tenside und Mineralöladditive", Thieme Verlag, Stuttgart, 1978, S.123-217 verwiesen. The aqueous solutions, the cold behavior of which is to be improved in the sense of the process according to the invention, can contain, for example, anionic surfactants which are selected from the group consisting of alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfofatty acids, alkyl sulfates, Fatty alcohol ether sulfates, glycerin ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, soaps, sulfosuccinates, sulfosuccinamates, sulfotriglycerides, isethionates, taurides, sarcosinates, ether carboxylic acids, alkyl oligoglainosulfonates and phosphates. If the anionic surfactants contain polyglycol ether chains, they can have both a conventional and a narrow homolog distribution. The surfactants mentioned are exclusively known compounds. With regard to the structure and manufacture of these substances, reference is made to relevant reviews, for example, J.Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, pp. 54-124 or J.Falbe (ed.), "Catalysts, Tenside und Mineralöladditive ", Thieme Verlag, Stuttgart, 1978, pp. 123-217.
Vorzugsweise werden wäßrige Lösungen der genannten anionischen Tenside eingesetzt, die diese in Mengen von 1 bis 50, vorzugsweise 25 bis 35 Gew.-% enthalten. Aqueous solutions of the anionic surfactants mentioned are preferably used which contain these in amounts of 1 to 50, preferably 25 to 35% by weight.
Alkyl- und Alkenyloligoglykoside stellen bekannte Stoffe dar, die nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden können. Stellvertretend für das umfangreiche Schrifttum sei hier auf die Schriften EP-Al-0 301 298 und WO 90/3977 verwiesen. Alkyl and alkenyl oligoglycosides are known substances that can be obtained by the relevant methods of preparative organic chemistry. Representative of the extensive literature, reference is made here to the documents EP-Al-0 301 298 and WO 90/3977.
Die Alkyl- und/oder Alkenyloligoglykoside können sich von Aldosen bzw. Ketosen mit 5 oder 6 Kohlenstoffatomen, vorzugsweise der Glucose ableiten. Die bevorzugten Alkylund/oder Alkenyloligoglykoside sind somit Alkyl- und/oder Alkenyloligoglucoside. The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
Die Indexzahl p in der allgemeinen Formel (I) gibt den Oli- gomerisierungsgrad (DP-Grad), d. h. die Verteilung von Mono- und Oligoglykosiden an und steht für eine Zahl zwischen 1 und 10. Während p in einer gegebenen Verbindung stets ganzzahlig sein muß und hier vor allem die Werte p = 1 bis 6 annehmen kann, ist der Wert p für ein bestimmtes Alkyloligoglykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkyl- und/oder Alkenyloligoglykoside mit einem mittleren Oligomerisierungsgrad p von 1,1 bis 3,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche Alkyl- und/oder Alkenyl- oligoglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1,7 ist und insbesondere zwischen 1,2 und 1,4 liegt. The index number p in the general formula (I) indicates the degree of oligomerization (DP degree), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer and here can assume the values p = 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, most of the time represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.
Der Alkyl- bzw. Alkenylrest R1 kann sich von primären Alkoholen mit 6 bis 11, vorzugsweise 8 bis 10 Kohlenstoffatomen ableiten. Typische Beispiele sind Capronalkohol, Caprylalko- hol, Caprinalkohol und ündecylalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hydrierung von technischen Fettsäuremethylestern oder im Verlauf der Hydrierung von Aldehyden aus der Roelen' sehen Oxosynthese anfallen. Bevorzugt sind Alkyloligoglucoside der Kettenlänge C8-C10 (Dp = 1 bis 3), die als Vorlauf bei der destillativen Auftrennung von technischem C8-C18-Kokosfettalkohol anfallen und mit einem Anteil von weniger als 15, vorzugsweise weniger 6 Gew.-% C12-Alkohol verunreinigt sein können sowie Alkyloligoglucoside auf Basis technischer C9/11-Oxoalkohole (DP = 1 bis 3). The alkyl or alkenyl radical R 1 can be derived from primary alcohols having 6 to 11, preferably 8 to 10, carbon atoms. Typical examples are capronic alcohol, caprylic alcohol, capric alcohol and ündecyl alcohol and their technical mixtures, such as those obtained in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length C 8 -C 10 (Dp = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C 8 -C 18 coconut fatty alcohol by distillation and in a proportion of less than 15, preferably less than 6,% by weight. % C 12 alcohol as an impurity, and also alkyl oligoglucosides based on technical-C 9/11 oxo alcohols (DP = 1 to 3).
Der Alkyl- bzw. Alkenylrest R1 kann sich ferner auch von primären Alkoholen mit 12 bis 22, vorzugsweise 12 bis 14 Kohlenstoffatomen ableiten. Typische Beispiele sind Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol, sowie deren technische Gemische, die wie oben beschrieben erhalten werden können. Bevorzugt sind Alkyloligoglucoside auf Basis von gehärtetem C12/i4-Kokosalkohol mit einem DP von 1 bis 3. In einer besonderen Ausführungsform der Erfindung werden Alkyloligoglucoside eingesetzt, die Mischungen der genannten kurzkettigen C8-C11-Alkyloligoglucoside und langkettigen C12- C14-Alkyloligoglucoside im Gewichtsverhältnis 95 : 5 bis 40 : 60 und insbesondere 90 : 10 bis 50 : 50 darstellen. The alkyl or alkenyl radical R 1 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hydrogenated C12 / i4 coconut alcohol with a DP of 1 to 3 In a particular embodiment of the invention, alkyl oligoglucosides are used which represent mixtures of the short-chain C 8 -C 11 -alkyl oligoglucosides and long-chain C 12 -C 14 -alkyl oligoglucosides mentioned in a weight ratio of 95: 5 to 40:60 and in particular 90: 10 to 50:50 .
Auch bei den als Komponenten b) und c) genannten Fettalkoholpolyglycolethern handelt es sich um grundsätzlich bekannte Stoffe, die großtechnisch durch Anlagerung von Ethylen- und/oder Propylenoxid an primäre Alkohole und dabei vorwiegend Fett- bzw. Oxoalkohole erhalten werden. In Abhängigkeit des für die Oxalkylierung verwendeten Katalysatorsystems können auf diese Weise nichtionische Tenside hergestellt werden, die eine konventionelle oder aber eine eingeengte Homologenverteilung aufweisen, welche in gleicher Weise für als Bestandteil der Mischung nichtioniεcher Tenside geeignet sind. The fatty alcohol polyglycol ethers mentioned as components b) and c) are also fundamentally known substances which are obtained on an industrial scale by the addition of ethylene and / or propylene oxide to primary alcohols and predominantly fatty or oxo alcohols. Depending on the catalyst system used for the oxyalkylation, nonionic surfactants can be produced in this way which have a conventional or narrow homolog distribution, which are equally suitable for being a component of the mixture of nonionic surfactants.
Bei den Fettalkoholpolyglycolethern, die die Komponente b) bilden, handelt es sich gemäß Formel (II) um Addukte von Ethylen- und/oder Propylenoxid an primäre Alkohole mit 8 bis 11 Kohlenstoffatomen. Typische Beispiele sind die Addukte von durchschnittlich 4 bis 9, vorzugsweise 5 bis 7 Mol Ethylenoxid oder 1 Mol Propylenoxid an Octanol, Decanol oder einen C8-C10-Vorlauf-Fettalkohol. According to formula (II), the fatty alcohol polyglycol ethers which form component b) are adducts of ethylene and / or propylene oxide with primary alcohols having 8 to 11 carbon atoms. Typical examples are the adducts of an average of 4 to 9, preferably 5 to 7, moles of ethylene oxide or 1 mole of propylene oxide with octanol, decanol or a C 8 -C 10 preliminary fatty alcohol.
Für die Fettalkoholpolyglycolether, die die fakultative Komponente c) bilden, kommen gemäß Formel (III) entsprechend Anlagerungsprodukte von Ethylen- und/oder Propylenoxid an primäre Alkohole mit 12 bis 15 Kohlenstoffatomen in Betracht. Typische Beispiele sind hier Addukte von durchschnittlich 4 bis 9, vorzugsweise 5 bis 7 Mol Ethylenoxid oder 1 Mol Propylenoxid an Laurylalkohol oder einen C12-C14-Kokosfettalkohol. According to formula (III), adducts of ethylene and / or propylene oxide with primary alcohols having 12 to 15 carbon atoms are suitable for the fatty alcohol polyglycol ethers which form optional component c). Typical examples here are adducts of on average 4 to 9, preferably 5 to 7, moles of ethylene oxide or 1 mole Propylene oxide on lauryl alcohol or a C 12 -C 14 coconut fatty alcohol.
Enthalten die Fettalkoholpolyglycolether, die die Komponenten b) und c) bilden Ethylen- und Propylenglycoleinheiten, so befinden sich die Ethylenglycoleinheiten vorzugsweise am Ende des Moleküls. If the fatty alcohol polyglycol ethers, which form components b) and c), contain ethylene and propylene glycol units, the ethylene glycol units are preferably at the end of the molecule.
Im Sinne des erfindungsgemäßen Verfahrens können die genannten Niotenside, bestehend aus den Komponenten a), b) und gegebenenfalls c) den wäßrigen Lösungen anionischer Tenside in solchen Mengen zugesetzt, daß das Gewichtsverhältnis Aniontensid : Niotensid in den Lösungen 98 : 2 bis 20 : 80 und vorzugsweise 95 : 5 bis 50 : 50 beträgt. For the purposes of the process according to the invention, the nonionic surfactants mentioned, consisting of components a), b) and optionally c), can be added to the aqueous solutions of anionic surfactants in amounts such that the weight ratio of anionic surfactant: nonionic surfactant in solutions 98: 2 to 20:80 and is preferably 95: 5 to 50:50.
Betrachtet man die Mischung der nichtionischen Tensiden als ein Compound, welches man den anionischen Tensidlösungen zusetzt, so kann dieses Compound die Komponenten a) und b+c) im Gewichtsverhältnis 90 : 10 bis 40 : 60, vorzugsweise 80 : 20 bis 50 : 50 und insbesondere 70 : 30 bis 50 : 50 enthalten, während die Komponenten b) und c) untereinander im Gewichtsverhältnis 100 : 0 bis 70 : 30 eingesetzt werden können. If the mixture of nonionic surfactants is regarded as a compound which is added to the anionic surfactant solutions, this compound can contain components a) and b + c) in a weight ratio of 90:10 to 40:60, preferably 80:20 to 50:50 and contain in particular 70:30 to 50:50, while components b) and c) can be used in a weight ratio of 100: 0 to 70:30.
Die Herstellung der Mischungen nichtionischer Tenside kann ebenso wie die Bereitstellung der kältestabilisierten Aniontensidmischungen auf rein mechanischem Wege, vorzugsweise durch Verrühren gegebenenfalls bei erhöhten Temperaturen von 30 bis 40°C erfolgen; eine chemische Reaktion findet nicht statt. Ein weiterer Gegenstand der Erfindung betrifft ferner wäßrige Handgeschirrspülmittel mit verbesserter Kältestabilität, enthaltend anionische Tenside sowie a) Alkyl- und/oder Alkenyloligoglykoside der Formel (I), The mixtures of nonionic surfactants, like the provision of the cold-stabilized anionic surfactant mixtures, can be produced purely mechanically, preferably by stirring, if appropriate at elevated temperatures of 30 to 40 ° C .; a chemical reaction does not take place. The invention further relates to aqueous hand dishwashing detergents with improved low-temperature stability, comprising anionic surfactants and a) alkyl and / or alkenyl oligoglycosides of the formula (I),
R1-O-[G]p (I) in der R1 für einen Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht, b) Fettalkoholpolyglycolether der Formel (II), R 1 -O- [G] p (I) in which R 1 is an alkyl and / or alkenyl radical having 6 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10, b ) Fatty alcohol polyglycol ether of the formula (II),
in der R2 für einen Alkylrest mit 8 bis 11 Kohlenstoffatomen, n für Zahlen von 4 bis 9 und m für 0 oder Zahlen von 1 bis 3 steht, und gegebenenfalls c) Fettalkoholpolyglycolether der Formel (III), in which R 2 represents an alkyl radical having 8 to 11 carbon atoms, n represents numbers from 4 to 9 and m represents 0 or numbers from 1 to 3, and optionally c) fatty alcohol polyglycol ether of the formula (III),
in der R3 für einen Alkylrest mit 12 bis 15 Kohlenstoffatomen, n für Zahlen von 4 bis 9 und m für 0 oder Zahlen von 1 bis 3 steht. in which R 3 is an alkyl radical having 12 to 15 carbon atoms, n is a number from 4 to 9 and m is 0 or a number from 1 to 3.
Neben den anionischen Tensiden, die bereits zuvor exemplarisch genannt worden sind, können die erfindungsgemäßen wäßrigen Handgeschirrmittel weitere übliche Bestandteile, beispielsweise amphotere Tenside, Schaumbooster, Duftstoffe etc. aufweisen. Eine typische Rezeptur kann beispielsweise 20 Gew.-% Fettalkoholethersulfat, 15 Gew.-% sekundäres Alkansulfonat, 3 Gew.-% Alkylamidobetain und 2 Gew.-% der erfindungsgemäßen nichtionischen Tensidmischung (Wasser ad 100 Gew. -% ) enthalten. In addition to the anionic surfactants, which have already been mentioned by way of example, the aqueous hand dishwashing agents according to the invention can have other conventional constituents, for example amphoteric surfactants, foam boosters, fragrances, etc. A typical formulation can contain, for example, 20% by weight of fatty alcohol ether sulfate, 15% by weight of secondary alkane sulfonate, 3% by weight of alkylamidobetaine and 2% by weight of the nonionic surfactant mixture according to the invention (water to 100% by weight).
Gewerbliche Anwendbarkeit Industrial applicability
Im Sinne des Erfindung bewirkt die Zugabe der Mischungen nichtionischer Tenside zu den wäßrigen Aniontensidlösungen eine Absenkung des Kältetrübungspunktes ohne daß durch diese Maßnahme die Spülleistung der Gemische negativ beinflußt wird. For the purposes of the invention, the addition of the mixtures of nonionic surfactants to the aqueous anionic surfactant solutions brings about a lowering of the cold cloud point without this measure having a negative influence on the rinsing performance of the mixtures.
Ein weiterer Gegenstand der Erfindung betrifft daher die Verwendung von Mischungen nichtionischer Tenside, enthaltend a) Alkyl- und/oder Alkenyloligoglykoside der Formel (I), Another object of the invention therefore relates to the use of mixtures of nonionic surfactants containing a) alkyl and / or alkenyl oligoglycosides of the formula (I),
R1-O-[G]p (I) in der R1 für einen Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen vonl bis 10 steht, b) Fettalkoholpolyglycolether der Formel (II), R 1 -O- [G] p (I) in which R 1 is an alkyl and / or alkenyl radical having 6 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10, b) fatty alcohol polyglycol ether of the formula (II),
in der R2 für einen Alkylrest mit 8 bis 11 Kohlenstoffatomen, n für Zahlen von 4 bis 9 und m für 0 oder Zahlen von 1 bis 3 steht, und gegebenenfalls c) Fettalkoholpolyglycolether der Formel (III), in which R 2 represents an alkyl radical having 8 to 11 carbon atoms, n represents numbers from 4 to 9 and m represents 0 or numbers from 1 to 3, and optionally c) fatty alcohol polyglycol ether of the formula (III),
in der R3 für einen Alkylrest mit 12 bis 15 Kohlenstoffatomen, n für Zahlen von 4 bis 9 und m für 0 oder Zahlen von 1 bis 3 steht, zur Verbesserung der Kältestabilität wäßriger Lösungen anionischer Tenside. in which R 3 stands for an alkyl radical with 12 to 15 carbon atoms, n for numbers from 4 to 9 and m for 0 or numbers from 1 to 3, to improve the low-temperature stability of aqueous solutions of anionic surfactants.
Die folgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf einzuschränken. Beispiele The following examples are intended to explain the subject matter of the invention in more detail without restricting it. Examples
I. Eingesetzte Tenside I. Surfactants used
A1) C12/14-Kokosalkyloligoglucosid, DP-Grad : 1,35 A1) C 12/14 cocoalkyl oligoglucoside, DP grade: 1.35
Plantaren(R) APG 600 CS UP Plantaren (R) APG 600 CS UP
B1) Octanol-4EO, desodoriert B1) Octanol-4EO, deodorized
Dehydol(R) O4 "DEO" Dehydol (R) O4 "DEO"
B2) 0ctanol-7E0, desodoriert B2) 0ctanol-7E0, deodorized
B3) Decanol-7E0, desodoriert B3) Decanol-7E0, deodorized
B4) C10/14-Fettalkohol-7EO (eingeengte Homologenverteilung) B4) C 10/14 fatty alcohol-7EO (narrow homolog distribution)
C1) C12/14-Kokosalkohol-3,5 EO-sulfat-Natriumsalz C1) C 12/14 coconut alcohol 3.5 EO sulfate sodium salt
Texapon(R) LS35 Texapon (R) LS35
C2) C12/14-Kokosalkohol-2,8 EO-sulfat-Natriumsalz C2) C 12/14 coconut alcohol 2.8 EO sulfate sodium salt
Texapon(R) K14S28 Texapon (R) K14S28
D1) Betain auf Basis C12/14-Kokosfettsäure D1) Betaine based on C 12/14 coconut fatty acid
Dehyton(R) GDehyton (R) G
D2) Betain auf Basis C12/14-Kokosfettsäure D2) Betaine based on C 12/14 coconut fatty acid
Dehyton(R) K Dehyton (R) K
Alle eingesetzten Tenside sind Verkaufsprodukte der Fa . Henkel KGaA, Düsseldorf/FRG. II. Testmethoden a) Kälteverhalten All surfactants used are sales products from Henkel KGaA, Düsseldorf / FRG. II. Test methods a) Cold behavior
Die Testrezepturen wurden in einen Thermostaten überführt und dort von + 20°C bis auf maximal -6°C abgekühlt (2°C/10 min). Mit dem Kältetrübungspunkt (KTP) ist in die Temperatur angegeben, bei der die blanke Lösung eintrübte. Die Versuchsergebnisse sind in Tab.1 und 2 zusammengefaßt. The test formulations were transferred to a thermostat and cooled there from + 20 ° C to a maximum of -6 ° C (2 ° C / 10 min). The cold cloud point (KTP) indicates the temperature at which the bare solution clouded. The test results are summarized in Tables 1 and 2.
b) Tellerspülvermöσen (TSV) b) Dishwashing capacity (TSV)
Die Ermittlung des Tellerspülvermögens wurde mit Hilfe des Teller-Testes [Fette, Seifen, Anstrichmitt., 74, 163 (1972)] durchgeführt. Hierzu wurden Teller mit einem Durchmesser von 14 cm mit je 1,9 g Rindertalg (Schmelzpunkt 40-42°C, Säurezahl 9-10) angeschmutzt und 15 h bei einer Temperatur von 0 bis 5°C gelagert. Anschließend wurden die Teller bei 50°C mit Leitungswasser der Härte 16°d gespült. Die Prüfmischung wurde mit einer Dosierung von 0,15 Wasser eingesetzt. Der Spülversuch wurde abgebrochen, sobald die Schaumdecke an der Oberfläche aufriß und die darunter befindliche Flotte sichtbar wurde. Die Ergebnisse der Spülversuche sind in Tab.1 und 2 zusammengefaßt; angegeben ist die Anzahl gespülter Teller (T). The determination of the dishwashing capacity was carried out with the aid of the dish test [Fette, Seifen, Anstrichmitt., 74, 163 (1972)]. For this purpose, plates with a diameter of 14 cm were soiled with 1.9 g of beef tallow (melting point 40-42 ° C, acid number 9-10) and stored at a temperature of 0 to 5 ° C for 15 h. The plates were then rinsed at 50 ° C with tap water with a hardness of 16 ° d. The test mixture was used with a dosage of 0.15 water. The rinsing attempt was stopped as soon as the foam blanket tore open and the liquor underneath became visible. The results of the rinsing tests are summarized in Tables 1 and 2; the number of dishes washed (T) is indicated.

Claims

Patentansprüche Claims
1. Verfahren zur Herstellung wäßriger Lösungen anionischer Tenside mit verbesserter Kältestabilität, bei dem man den Tensidlösungen Mischungen nichtionischer Tenside zusetzt, enthaltend a) Alkyl- und/oder Alkenyloligoglykoside der Formel (I), 1. A process for the preparation of aqueous solutions of anionic surfactants with improved low-temperature stability, in which mixtures of nonionic surfactants are added to the surfactant solutions, comprising a) alkyl and / or alkenyl oligoglycosides of the formula (I),
R1-O-[G]p (I) in der R1 für einen Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht, b) Fettalkoholpolyglycolether der Formel (II), R 1 -O- [G] p (I) in which R 1 is an alkyl and / or alkenyl radical having 6 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10, b ) Fatty alcohol polyglycol ether of the formula (II),
in der R2 für einen Alkylrest mit 8 bis 11 Kohlenstoffatomen, n für Zahlen von 4 bis 9 und m für 0 oder Zahlen von 1 bis 3 steht, und gegebenenfalls c ) Fettalkoholpolyglycolether der Formel ( III ) , in which R 2 stands for an alkyl radical with 8 to 11 carbon atoms, n for numbers from 4 to 9 and m for 0 or numbers from 1 to 3, and optionally c) fatty alcohol polyglycol ethers of the formula (III),
in der R3 für einen Alkylrest mit 12 bis 15 Kohlenstoffatomen, n für Zahlen von 4 bis 9 und m für 0 oder Zahlen von 1 bis 3 steht. in which R 3 is an alkyl radical having 12 to 15 carbon atoms, n is a number from 4 to 9 and m is 0 or a number from 1 to 3.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man wäßrige Lösungen anionischer Tenside einsetzt, die ausgewählt aus der Gruppe, die gebildet wird von Alkylbenzolsulfonaten, Alkansulfonaten, Olefinsulfonaten, Alkylethersulfonaten, Glycerinethersulfonaten, O-Methylestersulfonaten, Sulfofettsäuren, Alkylsulfaten, Fettalkoholethersulfaten, Glycerinethersulfaten, Hydroxymischethersulfaten, Monoglycerid(ether)Sulfaten, Fettsäureamid(ether)Sulfaten, Seifen, Sulfosuccinaten, Sulfosuccinamaten, Sulfotriglyceriden, Isethionaten, Tauriden, Sarcosinaten, Ethercarbonsäuren, Alkyloligoglucosidsulfaten und Alkyl(ether)phosphaten sowie Betaintensiden. 2. The method according to claim 1, characterized in that aqueous solutions of anionic surfactants are used which are selected from the group consisting of alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, O-methyl ester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerols Hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, soaps, sulfosuccinates, sulfosuccinamates, sulfotriglycerides, isethionates, taurides, sarcosinates, ether carboxylic acids, alkyl oligoglucoside sulfates and alkyl (ether) phosphates and betaine surfactants.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man Alkylglucoside der Formel (I) einsetzt, in der R1 für einen Alkylrest mit 6 bis 11 Kohlenstoffatomen, G für einen Glucoserest und p für Zahlen von 1 bis 3 steht. 3. The method according to claim 1, characterized in that alkyl glucosides of the formula (I) are used in which R 1 is an alkyl radical having 6 to 11 carbon atoms, G is a glucose radical and p is a number from 1 to 3.
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man Alkylglucoside der Formel (I) einsetzt, in der R1 für einen Alkylrest mit 12 bis 22 Kohlenstoffatomen, G für einen Glucoserest und p für Zahlen von 1 bis 3 steht. 4. The method according to claim 1, characterized in that alkyl glucosides of the formula (I) are used in which R 1 is an alkyl radical having 12 to 22 carbon atoms, G is a glucose radical and p is a number from 1 to 3.
5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man wäßrige Lösungen anionischer Tenside einsetzt, die diese in Mengen von 1 bis 50 Gew.-% enthalten. 5. The method according to claim 1, characterized in that aqueous solutions of anionic surfactants are used which contain these in amounts of 1 to 50 wt .-%.
6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die nichtionischen Tenside den wäßrigen Lösungen anionischer Tenside in solchen Mengen zusetzt, daß das Gewichtsverhältnis Aniontensid : Niotensid in den Lösungen 98 : 2 bis 20 : 80 beträgt. 6. The method according to claim 1, characterized in that the nonionic surfactants are added to the aqueous solutions of anionic surfactants in such quantities that the weight ratio of anionic surfactant: nonionic surfactant in the solutions is 98: 2 to 20:80.
7. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Komponenten a) und b+c) im Gewichtsverhältnis 90 : 10 bis 40 : 60 einsetzt. 7. The method according to claim 1, characterized in that components a) and b + c) are used in a weight ratio of 90:10 to 40:60.
8. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Komponenten b) und c) im Gewichtsverhältnis 100 : 0 bis 70 : 30 einsetzt. 8. The method according to claim 1, characterized in that components b) and c) are used in a weight ratio of 100: 0 to 70:30.
9. Wäßrige Handgeschirrspülmittel mit verbesserter Kältestabilität, enthaltend anionische Tenside sowie a) Alkyl- und/oder Alkenyloligoglykoside der Formel (I), 9. Aqueous hand dishwashing detergent with improved low-temperature stability, containing anionic surfactants and a) alkyl and / or alkenyl oligoglycosides of the formula (I),
Rl-O-[G]p (I) in der R1 für einen Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht, b) Fettalkoholpolyglycolether der Formel (II), R l -O- [G] p (I) in which R 1 is an alkyl and / or alkenyl radical having 6 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10, b) fatty alcohol polyglycol ether of the formula (II),
in der R2 für einen Alkylrest mit 8 bis 11 Kohlenstoffatomen, n für Zahlen von 4 bis 9 und m für 0 oder Zahlen von 1 bis 3 steht, und gegebenenfalls c) Fettalkoholpolyglycolether der Formel (III), in which R 2 represents an alkyl radical having 8 to 11 carbon atoms, n represents numbers from 4 to 9 and m represents 0 or numbers from 1 to 3, and optionally c) fatty alcohol polyglycol ether of the formula (III),
in der R3 für einen Alkylrest mit 12 bis 15 Kohlenstoffatomen, n für Zahlen von 4 bis 9 und m für 0 oder Zahlen von 1 bis 3 steht. in which R 3 is an alkyl radical having 12 to 15 carbon atoms, n is a number from 4 to 9 and m is 0 or a number from 1 to 3.
10. Verwendung von Mischungen nichtionischer Tenside, enthaltend a) Alkyl- und/oder Alkenyloligoglykoside der Formel (I), 10. Use of mixtures of nonionic surfactants containing a) alkyl and / or alkenyl oligoglycosides of the formula (I),
R1-O-[G]p (I) in der R1 für einen Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht, b) Fettalkoholpolyglycolether der Formel (II), R 1 -O- [G] p (I) in which R 1 is an alkyl and / or alkenyl radical having 6 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10, b) fatty alcohol polyglycol ether of the formula (II),
in der R2 für einen Alkylrest mit 8 bis 11 Kohlenstoffatomen, n für Zahlen von 4 bis 9 und m für 0 oder Zahlen von 1 bis 3 steht, und gegebenenfalls c) Fettalkoholpolyglycolether der Formel (III), in which R 2 represents an alkyl radical having 8 to 11 carbon atoms, n represents numbers from 4 to 9 and m represents 0 or numbers from 1 to 3, and optionally c) fatty alcohol polyglycol ether of the formula (III),
in der R3 für einen Alkylrest mit 12 bis 15 Kohlenstoffatomen, n für Zahlen von 4 bis 9 und m für 0 oder Zahlen von 1 bis 3 steht, zur Verbesserung der Kältestabilität wäßriger Lösungen anionischer Tenside. in which R 3 stands for an alkyl radical with 12 to 15 carbon atoms, n for numbers from 4 to 9 and m for 0 or numbers from 1 to 3, to improve the low-temperature stability of aqueous solutions of anionic surfactants.
EP93923521A 1992-10-29 1993-10-21 Use of mixtures of nonionic surfactants Expired - Lifetime EP0666898B1 (en)

Applications Claiming Priority (3)

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DE4236506 1992-10-29
DE4236506A DE4236506A1 (en) 1992-10-29 1992-10-29 Process for the preparation of aqueous solutions of anionic surfactants with improved low-temperature stability
PCT/EP1993/002914 WO1994010279A1 (en) 1992-10-29 1993-10-21 Process for preparing aqueous solutions of anionic surfactants with improved low-temperature stability

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EP0666898B1 EP0666898B1 (en) 1997-04-09

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WO1994010279A1 (en) 1994-05-11
US5599787A (en) 1997-02-04
ES2100574T3 (en) 1997-06-16
DE4236506A1 (en) 1994-05-05
JPH08502540A (en) 1996-03-19
DE59306137D1 (en) 1997-05-15

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