EP0872541A2 - Liquid detergent for delicate textiles in the form of a microemulsion - Google Patents

Liquid detergent for delicate textiles in the form of a microemulsion Download PDF

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Publication number
EP0872541A2
EP0872541A2 EP98106391A EP98106391A EP0872541A2 EP 0872541 A2 EP0872541 A2 EP 0872541A2 EP 98106391 A EP98106391 A EP 98106391A EP 98106391 A EP98106391 A EP 98106391A EP 0872541 A2 EP0872541 A2 EP 0872541A2
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EP
European Patent Office
Prior art keywords
alkyl
carbon atoms
radical
formula
alcohol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP98106391A
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German (de)
French (fr)
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EP0872541A3 (en
Inventor
Nuria Dr. Bonastre Gilabret
Rafael Dr. Pi Subirana
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Personal Care and Nutrition GmbH
Original Assignee
Henkel AG and Co KGaA
Cognis Deutschland GmbH and Co KG
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Application filed by Henkel AG and Co KGaA, Cognis Deutschland GmbH and Co KG filed Critical Henkel AG and Co KGaA
Publication of EP0872541A2 publication Critical patent/EP0872541A2/en
Publication of EP0872541A3 publication Critical patent/EP0872541A3/en
Withdrawn legal-status Critical Current

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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017—Multi-phase liquid compositions
    • C11D17/0021—Aqueous microemulsions
    • 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
    • C11D1/86—Mixtures of anionic, cationic, and non-ionic 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
    • C11D1/04—Carboxylic acids or 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
    • C11D1/22—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
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium 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
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the invention relates to liquid mild detergents in the form of microemulsions with a defined Content of ester quats, alkylbenzenesulfonates and alk (en) yl oligoglycosides and the use of ternary mixture for the production of microemulsions.
  • Aqueous detergent mixtures with alkyl oligoglucosides and esterquats and Their use for the production of detergents is known from the international patent application WO 94/06899 (Henkel) Powdery washing powders containing alkyl polyglucosides and alkylbenzenesulfonates are the subject of the two publications EP 0700070 B1 (Procter & Gamble) and EP 0554943 A2 (Unilever).
  • a problem with formulating liquid detergents is to develop preparations that can not only be satisfactorily assessed from an application technology perspective, that is Remove the dirt without attacking sensitive tissue and at the same time one of the tissues to give a pleasant soft feel and the electrostatic charge between the fibers reduce, but also as microemulsions are sufficiently viscous and stable in storage, so that Even when exposed to temperature for several months, neither the viscosity collapses nor segregation entry.
  • the object of the present invention was to microemulsions this to provide complex requirement profiles.
  • the mixtures according to the invention are microemulsions form, have excellent washing and cleaning properties and thus treated Fabrics, especially sensitive textiles such as wool sweaters and the like, not only give it a pleasant soft feel, but also the electrostatic charge lower between the fibers.
  • Another particular advantage is that the microemulsions are sufficiently viscous and can be stored for months, even when exposed to high temperatures, without segregate or decrease in viscosity and it despite the combination of anionic and cationic surfactants do not salt formation.
  • Esterquats (component a) are generally understood to be quaternized fatty acid triethanolamine ester salts . These are known substances which can be obtained by the relevant methods of preparative organic chemistry. In this connection, reference is made to the international patent application WO 91/01295 (Henkel) , after which triethanolamine is partially esterified with fatty acids in the presence of hypophosphorous acid, air is passed through and then quaternized with dimethyl sulfate or ethylene oxide.
  • German Patent DE 4308794 C1 also discloses a process for the preparation of solid ester quats in which the quaternization is carried out of triethanolamine esters in the presence of suitable dispersants, preferably fatty alcohols, and reviews on this topic are given, for example, by R.Puchta et al. in Tens.Surf.Det., 30 , 186 (1993), M.Brock in Tens.Surf.Det 30 , 394 (1993), R. Lagerman et al. In J. Am. Oil. Chem. Soc., 71 , 97 (1994). and I.Shapiro in Cosm.Toil. 109 , 77 (1994) appeared.
  • the quaternized fatty acid triethanolamine ester salts follow the formula (I) in which R 1 CO stands for an acyl radical with 6 to 22 carbon atoms, R 2 and R 3 independently of one another for hydrogen or R 1 CO, R 4 for an alkyl radical with 1 to 4 carbon atoms or a (CH 2 CH 2 O) q H- Group, m, n and p in total stands for 0 or numbers from 1 to 12, q for numbers from 1 to 12 and X for halide, alkyl sulfate or alkyl phosphate.
  • R 1 CO stands for an acyl radical with 6 to 22 carbon atoms
  • R 2 and R 3 independently of one another for hydrogen or R 1 CO
  • R 4 for an alkyl radical with 1 to 4 carbon atoms or a (CH 2 CH 2 O) q H- Group
  • m, n and p in total stands for 0 or numbers from 1 to 12
  • X for halide, alky
  • ester quats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, such as they occur, for example, in the pressure splitting of natural fats and oils.
  • Technical C 12/18 coconut fatty acids and in particular partially hardened C 16/18 tallow or palm fatty acids as well as high elaidic acid C 16/18 fatty acid cuts are preferably used.
  • the fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters.
  • an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous.
  • the preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C 16/18 tallow or palm fatty acid (iodine number 0 to 40).
  • quaternized fatty acid triethanolamine ester salts of the formula (I) have proven to be particularly advantageous in which R 1 CO for an acyl radical having 16 to 18 carbon atoms, R 2 for R 1 CO, R 3 for hydrogen, R 4 for a methyl group, m , n and p is 0 and X is methyl sulfate.
  • quaternized ester salts of fatty acids with diethanolalkylamines of the formula (II) are also suitable as esterquats, in which R 1 CO for an acyl radical with 6 to 22 carbon atoms, R 2 for hydrogen or R 1 CO, R 4 and R 5 independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.
  • ester quats in which R 1 CO for an acyl radical with 6 to 22 carbon atoms, R 2 for hydrogen or R 1 CO, R 4 , R 6 and R 7 independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.
  • esterquats of the formulas (II) and (III) .
  • the esterquats usually come on the market in the form of 50 to 90% strength by weight alcoholic solutions, which can be diluted with water if required.
  • Alkylbenzenesulfonates which form component (b) are known anionic surfactants which can be obtained on an industrial scale by Friedel-Crafts alkylation of benzene with suitable olefins, core sulfonation of the alkylaromatics formed with gaseous sulfur trioxide and neutralization of the resulting sulfonic acids.
  • alkylbenzenesulfonates of the formula (IV) usually follow, in which R 8 is a linear or branched alkyl radical having 10 to 16 carbon atoms, Ph is a phenyl radical and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • Typical examples are dodecylbenzenesulfonate and tetradecylbenzenesulfonate in the form of their sodium salts.
  • Alkyl and alkenyl oligoglycosides which form component (c) are known nonionic surfactants which follow the formula (V) in which R 9 represents an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry, for example by acid-catalyzed acetalization of glucose with fatty alcohols.
  • 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 oligo glucosides .
  • 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 those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.
  • the alkyl or alkenyl radical R 9 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms.
  • Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, 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 9 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, brassidyl alcohol and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened C 12/14 coconut alcohol with a DP of 1 to 3 are preferred.
  • compositions furthermore contain nonionic surfactants of the fatty alcohol polyglycol ether type, which follow the formula (VI) , in which R 10 represents an alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and q represents numbers from 1 to 10.
  • nonionic surfactants of the fatty alcohol polyglycol ether type which follow the formula (VI) , in which R 10 represents an alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and q represents numbers from 1 to 10.
  • Typical examples are addition products of an average of 1 to 10 and preferably 2 to 7 mol ethylene oxide onto capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, , Elaeostearyl alcohol, arachyl
  • the agents can contain the nonionic surfactants in amounts of 1 to 10, preferably 3 to 5% by weight, based on the agents.
  • the agents can include other typical ingredients, for example Builders, enzymes, enzyme stabilizers, bleaches, optical brighteners, thickeners, soil repellants, Foam inhibitors, solubilizers, inorganic salts and fragrances and dyes.
  • Builders for example Builders, enzymes, enzyme stabilizers, bleaches, optical brighteners, thickeners, soil repellants, Foam inhibitors, solubilizers, inorganic salts and fragrances and dyes.
  • Suitable builders are zeolites, phyllosilicates, phosphates and ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and inorganic phosphonic acids.
  • peroxy bleaching agents sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other bleaching agents are, for example, peroxy carbonate, citrate perhydrates and H 2 O 2 -producing peracid salts of peracids such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 8 to 25% by weight.
  • sodium perborate monohydrate in amounts of 10 to 20% by weight and in particular 10 to 15% by weight is preferred. Due to its ability to bind free water with the formation of the tetrahydrate, it contributes to increasing the stability of the agent.
  • hardened castor oil, salts of long-chain fatty acids preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, aluminum, magnesium, can be used as thickeners - And titanium stearates or the sodium and / or potassium salts of behenic acid, and other polymeric compounds are used.
  • the latter preferably include polyvinylpyrrolidone, urethanes and the salts of polymeric polycarboxylates, for example homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those composed of 50 to 10% maleic acid.
  • the relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably between 50,000 to 120,000, based on the free acid.
  • Water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a relative molecular weight above 1,000,000 are also particularly suitable.
  • the crosslinked polyacrylates are preferably used in amounts of not more than 1% by weight, particularly preferably in amounts of 0.2 to 0.7% by weight.
  • Suitable enzymes are those from the class of proteases, lipase, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus lichenformis and Strptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentes are preferably used. Their proportion can be about 0.2 to 2% by weight.
  • the enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition.
  • the agents can contain further enzyme stabilizers .
  • 0.5 to 1% by weight sodium formate can be used.
  • proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
  • Suitable foam inhibitors contain, for example, known organopolysiloxanes, paraffins or waxes.
  • a particular advantage of the invention is that only within the narrow concentration ranges storage-stable microemulsions can be obtained. Accordingly, another concerns
  • the invention relates to the use of the ternary surfactant mixture for the production of Microemulsions.
  • the examples and comparative examples show that only within the specified narrow concentration ranges stable microemulsions of a sufficiently high viscosity can be obtained simultaneously have a high washability and the fabrics have a pleasant soft feel to lend.

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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)
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  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

Liquid fine laundry agent in micro-emulsion form contains: (a) 5-7 wt.% ester-quaternary; (b) 7-10 wt.% alkyl-benzene-sulphonates; and (c) 4-8 wt.% alk(en)yl-oligo-glycosides, balance being water and optionally other usual additives.

Description

Gebiet der ErfindungField of the Invention

Die Erfindung betrifft flüssige Feinwaschmittel in Form von Mikroemulsionen mit einem definierten Gehalt an Esterquats, Alkylbenzolsulfonaten und Alk(en)yloligoglykosiden sowie die Verwendung der ternären Mischung zur Herstellung von Mikroemulsionen.The invention relates to liquid mild detergents in the form of microemulsions with a defined Content of ester quats, alkylbenzenesulfonates and alk (en) yl oligoglycosides and the use of ternary mixture for the production of microemulsions.

Stand der TechnikState of the art

Beim Einsatz von Waschmitteln wird üblicherweise zwischen flüssigen und pulverförmigen oder granulierten Produkten sowie solchen für den universellen Einsatz oder die Behandlung von empfindlichen Textilien (

Figure 00010001
Feinwaschmittel") unterschieden. Demzufolge werden für diesen Zweck in der Regel milde" Tenside eingesetzt, also oberflächenaktive Substanzen, die auch gegenüber der menschlichen Haut wenig aggressiv sind. So werden beispielsweise in der internationalen Patentanmeldung WO 87/02050 (Henkel Corp.) Feinwaschmittel mit einem Gehalt an Alkylpolyglucosiden vorgeschlagen. Wäßrige Detergensgemische mit Alkyloligoglucosiden und Esterquats und deren Verwendung zur Herstellung von Waschmitteln sind aus der internationalen Patentanmeldung WO 94/06899 (Henkel) bekannt. Pulverförmige Waschpulver mit einen Gehalt an Alkylpolyglucosiden und Alkylbenzolsulfonaten sind Gegenstand der beiden Druckschriften EP 0700070 B1 (Procter & Gamble) und EP 0554943 A2 (Unilever).When using detergents, a distinction is usually made between liquid and powdery or granulated products and those for universal use or the treatment of sensitive textiles (
Figure 00010001
Delicates "). As a result, are usually used for this purpose mild "surfactants are used, that is to say surface-active substances which are also not very aggressive to human skin. For example, in the international patent application WO 87/02050 (Henkel Corp.), mild detergents containing alkyl polyglucosides are proposed. Aqueous detergent mixtures with alkyl oligoglucosides and esterquats and Their use for the production of detergents is known from the international patent application WO 94/06899 (Henkel) Powdery washing powders containing alkyl polyglucosides and alkylbenzenesulfonates are the subject of the two publications EP 0700070 B1 (Procter & Gamble) and EP 0554943 A2 (Unilever).

Ein Problem bei der Formulierung flüssiger Feinwaschmittel besteht darin, Zubereitungen zu entwickeln, die nicht nur aus anwendungstechnischer Sicht zufriedenstellend beurteilt werden können, also den Schmutz entfernen ohne empfindliches Gewebe anzugreifen und gleichzeitig den Geweben einen angenehmen Weichgriff zu verleihen sowie die elektrostatische Aufladung zwischen den Fasern herabzusetzen, sondern auch als Mikroemulsionen ausreichend viskos und lagerstabil sind, so daß auch bei Temperaturbelastung über mehrere Monate weder die Viskosität zusammenbricht noch Entmischung eintritt. Die Aufgabe der vorliegenden Erfindung hat darin bestanden, Mikroemulsionen dieses komplexen Anforderungsprofils zur Verfügung zu stellen. A problem with formulating liquid detergents is to develop preparations that can not only be satisfactorily assessed from an application technology perspective, that is Remove the dirt without attacking sensitive tissue and at the same time one of the tissues to give a pleasant soft feel and the electrostatic charge between the fibers reduce, but also as microemulsions are sufficiently viscous and stable in storage, so that Even when exposed to temperature for several months, neither the viscosity collapses nor segregation entry. The object of the present invention was to microemulsions this to provide complex requirement profiles.

Beschreibung der ErfindungDescription of the invention

Gegenstand der Erfindung sind Flüssige Feinwaschmittel in Mikroemulsionsform, enthaltend

  • (a) 5 bis 7, vorzugsweise 5 bis 6 Gew.-% Esterquats,
  • (b) 7 bis 10, vorzugsweise 7 bis 8 Gew.-% Alkylbenzolsulfonate und
  • (c) 4 bis 8, vorzugsweise 5 bis 6 Gew.-% Alkyl- und/oder Alkenyloligoglykoside,
    • mit der Maßgabe, daß sich die Mengenangaben mit Wasser und gegebenenfalls weiteren üblichen Hilfs- und Zusatzstoffen zu 100 Gew.-% ergänzen.The invention relates to liquid mild detergents in microemulsion form containing
  • (a) 5 to 7, preferably 5 to 6% by weight of ester quats,
  • (b) 7 to 10, preferably 7 to 8 wt .-% alkylbenzenesulfonates and
  • (c) 4 to 8, preferably 5 to 6% by weight of alkyl and / or alkenyl oligoglycosides,
    • with the proviso that the amounts given with water and, if appropriate, other conventional auxiliaries and additives are 100% by weight.

    Übenaschenderweise wurde gefunden, daß die erfindungsgemäßen Mischungen Mikroemulsionen bilden, über ausgezeichnete Wasch- und Reinigungseigenschaften verfügen und damit behandelten Geweben, insbesondere empfindlichen Textilien wie beispielsweise Wollpullovern und dergleichen, nicht nur einen angenehmen Weichgriff verleihen, sondern auch die elektrostatische Aufladung zwischen den Fasern herabsetzen. Ein besonderer Vorteil liegt ferner darin, daß die Mikroemulsionen ausreichend viskos und auch bei Temperaturbelastung über Monate lagerstabil sind, ohne sich zu entmischen oder in der Viskosität abnehmen und es trotz der Kombination von anionischen und kationischen Tensiden nicht zur Salzbildung kommt.It has surprisingly been found that the mixtures according to the invention are microemulsions form, have excellent washing and cleaning properties and thus treated Fabrics, especially sensitive textiles such as wool sweaters and the like, not only give it a pleasant soft feel, but also the electrostatic charge lower between the fibers. Another particular advantage is that the microemulsions are sufficiently viscous and can be stored for months, even when exposed to high temperatures, without segregate or decrease in viscosity and it despite the combination of anionic and cationic surfactants do not salt formation.

    EsterquatsEsterquats

    Unter der Bezeichnung Esterquats" (Komponente a) werden im allgemeinen quaternierte Fettsäuretriethanolaminestersalze verstanden. Es handelt sich dabei um bekannte Stoffe, die man nach den einschlägigen Methoden der präparativen organischen Chemie erhalten kann. In diesem Zusammenhang sei auf die Internationale Patentanmeldung WO 91/01295 (Henkel) verwiesen, nach der man Triethanolamin in Gegenwart von unterphosphoriger Säure mit Fettsäuren partiell verestert, Luft durchleitet und anschließend mit Dimethylsulfat oder Ethylenoxid quaterniert. Aus der Deutschen Patentschrift DE 4308794 C1 (Henkel) ist überdies ein Verfahren zur Herstellung fester Esterquats bekannt, bei dem man die Quaternierung von Triethanolaminestern in Gegenwart von geeigneten Dispergatoren, vorzugsweise Fettalkoholen, durchführt. Übersichten zu diesem Thema sind beispielsweise von R.Puchta et al. in Tens.Surf.Det., 30, 186 (1993), M.Brock in Tens.Surf.Det. 30, 394 (1993), R.Lagerman et al. in J.Am.Oil.Chem.Soc., 71, 97 (1994) sowie I.Shapiro in Cosm.Toil. 109, 77 (1994) erschienen.Under the label Esterquats "(component a) are generally understood to be quaternized fatty acid triethanolamine ester salts . These are known substances which can be obtained by the relevant methods of preparative organic chemistry. In this connection, reference is made to the international patent application WO 91/01295 (Henkel) , after which triethanolamine is partially esterified with fatty acids in the presence of hypophosphorous acid, air is passed through and then quaternized with dimethyl sulfate or ethylene oxide. German Patent DE 4308794 C1 (Henkel) also discloses a process for the preparation of solid ester quats in which the quaternization is carried out of triethanolamine esters in the presence of suitable dispersants, preferably fatty alcohols, and reviews on this topic are given, for example, by R.Puchta et al. in Tens.Surf.Det., 30 , 186 (1993), M.Brock in Tens.Surf.Det 30 , 394 (1993), R. Lagerman et al. In J. Am. Oil. Chem. Soc., 71 , 97 (1994). and I.Shapiro in Cosm.Toil. 109 , 77 (1994) appeared.

    Die quaternierten Fettsäuretriethanolaminestersalze folgen der Formel (I),

    Figure 00030001
    in der R1CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R2 und R3 unabhängig voneinander für Wasserstoff oder R1CO, R4 für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder eine (CH2CH2O)qH-Gruppe, m, n und p in Summe für 0 oder Zahlen von 1 bis 12, q für Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht. Typische Beispiele für Esterquats, die im Sinne der Erfindung Verwendung finden können, sind Produkte auf Basis von Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Isostearinsäure, Stearinsäure, Ölsäure, Elaidinsäure, Arachinsäure, Behensäure und Erucasäure sowie deren technische Mischungen, wie sie beispielsweise bei der Druckspaltung natürlicher Fette und Öle anfallen. Vorzugsweise werden technische C12/18-Kokosfettsäuren und insbesondere teilgehärtete C16/18-Talg- bzw. Palmfettsäuren sowie elaidinsäurereiche C16/18-Fettsäureschnitte eingesetzt. Zur Herstellung der quaternierten Ester können die Fettsäuren und das Triethanolamin im molaren Verhältnis von 1,1 : 1 bis 3 : 1 eingesetzt werden. Im Hinblick auf die anwendungstechnischen Eigenschaften der Esterquats hat sich ein Einsatzverhältnis von 1,2 : 1 bis 2,2 : 1, vorzugsweise 1,5 : 1 bis 1,9 : 1 als besonders vorteilhaft erwiesen. Die bevorzugten Esterquats stellen technische Mischungen von Mono-, Di- und Triestern mit einem durchschnittlichen Veresterungsgrad von 1,5 bis 1,9 dar und leiten sich von technischer C16/18-Talg- bzw. Palmfettsäure (Iodzahl 0 bis 40) ab. Aus anwendungstechnischer Sicht haben sich quaternierte Fettsäuretriethanolaminestersalze der Formel (I) als besonders vorteilhaft erwiesen, in der R1CO für einen Acylrest mit 16 bis 18 Kohlenstoffatomen, R2 für R1CO, R3 für Wasserstoff, R4 für eine Methylgruppe, m, n und p für 0 und X für Methylsulfat steht.The quaternized fatty acid triethanolamine ester salts follow the formula (I)
    Figure 00030001
    in which R 1 CO stands for an acyl radical with 6 to 22 carbon atoms, R 2 and R 3 independently of one another for hydrogen or R 1 CO, R 4 for an alkyl radical with 1 to 4 carbon atoms or a (CH 2 CH 2 O) q H- Group, m, n and p in total stands for 0 or numbers from 1 to 12, q for numbers from 1 to 12 and X for halide, alkyl sulfate or alkyl phosphate. Typical examples of ester quats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, such as they occur, for example, in the pressure splitting of natural fats and oils. Technical C 12/18 coconut fatty acids and in particular partially hardened C 16/18 tallow or palm fatty acids as well as high elaidic acid C 16/18 fatty acid cuts are preferably used. The fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters. With regard to the application properties of the ester quats, an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1, has proven to be particularly advantageous. The preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C 16/18 tallow or palm fatty acid (iodine number 0 to 40). From an application point of view, quaternized fatty acid triethanolamine ester salts of the formula (I) have proven to be particularly advantageous in which R 1 CO for an acyl radical having 16 to 18 carbon atoms, R 2 for R 1 CO, R 3 for hydrogen, R 4 for a methyl group, m , n and p is 0 and X is methyl sulfate.

    Neben den quaternierten Fettsäuretriethanolaminestersalzen kommen als Esterquats ferner auch quaternierte Estersalze von Fettsäuren mit Diethanolalkylaminen der Formel (II) in Betracht,

    Figure 00030002
    in der R1CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R2 für Wasserstoff oder R1CO, R4 und R5 unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht.In addition to the quaternized fatty acid triethanolamine ester salts, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (II) are also suitable as esterquats,
    Figure 00030002
    in which R 1 CO for an acyl radical with 6 to 22 carbon atoms, R 2 for hydrogen or R 1 CO, R 4 and R 5 independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.

    Als weitere Gruppe geeigneter Esterquats sind schließlich die quaternierten Estersalze von Fettsäuren mit 1,2-Dihydroxypropyldialkylaminen der Formel (III) zu nennen,

    Figure 00040001
    in der R1CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R2 für Wasserstoff oder R1CO, R4, R6 und R7 unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht.Finally, the quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula (III) should be mentioned as a further group of suitable ester quats,
    Figure 00040001
    in which R 1 CO for an acyl radical with 6 to 22 carbon atoms, R 2 for hydrogen or R 1 CO, R 4 , R 6 and R 7 independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.

    Hinsichtlich der Auswahl der bevorzugten Fettsäuren und des optimalen Veresterungsgrades gelten die für (I) genannten Beispiele auch für die Esterquats der Formeln (II) und (III). Üblicherweise gelangen die Esterquats in Form 50 bis 90 Gew.-%iger alkoholischer Lösungen in den Handel, die bei Bedarf problemlos mit Wasser verdünnt werden können.With regard to the selection of the preferred fatty acids and the optimal degree of esterification, the examples given for (I) also apply to the esterquats of the formulas (II) and (III) . The esterquats usually come on the market in the form of 50 to 90% strength by weight alcoholic solutions, which can be diluted with water if required.

    AlkylbenzolsulfonateAlkylbenzenesulfonates

    Alkylbenzolsulfonate, die die Komponente (b) bilden, stellen bekannte anionische Tenside dar, die man großtechnisch durch Friedel-Crafts Alkylierung von Benzol mit geeigneten Olefinen, Kernsulfonierung der gebildeten Alkylaromaten mit gasförmigem Schwefeltrioxid und Neutralisation der resultieren Sulfonsäuren erhält. Üblicherweise folgen die Alkylbenzolsulfonate der Formel (IV),

    Figure 00040002
    in der R8 für einen linearen oder verzweigten Alkylrest mit 10 bis 16 Kohlenstoffatomen, Ph für einen Phenylrest und X für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht. Typische Beispiele sind Dodecylbenzolsulfonat und Tetradecylbenzolsulfonat in Form ihrer Natriumsalze.Alkylbenzenesulfonates which form component (b) are known anionic surfactants which can be obtained on an industrial scale by Friedel-Crafts alkylation of benzene with suitable olefins, core sulfonation of the alkylaromatics formed with gaseous sulfur trioxide and neutralization of the resulting sulfonic acids. The alkylbenzenesulfonates of the formula (IV) usually follow,
    Figure 00040002
    in which R 8 is a linear or branched alkyl radical having 10 to 16 carbon atoms, Ph is a phenyl radical and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples are dodecylbenzenesulfonate and tetradecylbenzenesulfonate in the form of their sodium salts.

    Alkyl- und/oder AlkenyloligoglykosideAlkyl and / or alkenyl oligoglycosides

    Alkyl- und Alkenyloligoglykoside, die die Komponente (c) bilden, stellen bekannte nichtionische Tenside dar, die der Formel (V) folgen,

    Figure 00040003
    in der R9 für einen Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht. Sie können nach den einschlägigen Verfahren der präparativen organischen Chemie, beispielsweise durch sauer katalysierte Acetalisierung von Glucose mit Fettalkoholen erhalten werden. Die Alkyl- und/oder Alkenyloligoglykoside können sich von Aldosen bzw. Ketosen mit 5 oder 6 Kohlenstoffatomen, vorzugsweise der Glucose ableiten. Die bevorzugten Alkyl- und/oder Alkenyloligoglykoside sind somit Alkyl- und/oder Alkenyloligoglucoside. Die Indexzahl p in der allgemeinen Formel (V) gibt den Oligomerisierungsgrad (DP), 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 Alkenyloligoglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1,7 ist und insbesondere zwischen 1,2 und 1,4 liegt. Der Alkyl- bzw. Alkenylrest R9 kann sich von primären Alkoholen mit 4 bis 11, vorzugsweise 8 bis 10 Kohlenstoffatomen ableiten. Typische Beispiele sind Butanol, Capronalkohol, Caprylalkohol, Caprinalkohol und Undecylalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hydrierung von technischen Fettsäuremethylestern oder im Verlauf der Hydrierung von Aldehyden aus der Roelen'schen Oxosynthese erhalten werden. 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 6 Gew.-% C12-Alkohol verunreinigt sein können sowie Alkyloligoglucoside auf Basis technischer C9/11-Oxoalkohole (DP = 1 bis 3). Der Alkyl- bzw. Alkenylrest R9 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, Brassidylalkohol sowie deren technische Gemische, die wie oben beschrieben erhalten werden können. Bevorzugt sind Alkyloligoglucoside auf Basis von gehärtetem C12/14-Kokosalkohol mit einem DP von 1 bis 3.Alkyl and alkenyl oligoglycosides which form component (c) are known nonionic surfactants which follow the formula (V)
    Figure 00040003
    in which R 9 represents an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry, for example by acid-catalyzed acetalization of glucose with fatty alcohols. 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 oligo glucosides . The index number p in the general formula (V) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p must always be an integer in a given compound and especially here can assume the values p = 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, which usually 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 those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4. The alkyl or alkenyl radical R 9 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, 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 with a proportion of less than 6% by weight of C 12 - Alcohol can be contaminated and alkyl oligoglucosides based on technical C 9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R 9 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, brassidyl alcohol and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened C 12/14 coconut alcohol with a DP of 1 to 3 are preferred.

    FettalkoholpolyglycoletherFatty alcohol polyglycol ether

    In einer besonderen Ausführungsform der vorliegenden Erfindung enthalten die Mittel weiterhin nichtionische Tenside vom Typ der Fettalkoholpolyglycolether, die der Formel (VI) folgen,

    Figure 00050001
    in der R10 für einen Alkyl- und/oder Alkenylrest mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen und q für Zahlen von 1 bis 10 steht. Typische Beispiele sind Anlagerungsprodukte von durchschnittlich 1 bis 10 und vorzugsweise 2 bis 7 Mol Ethylenoxid an Capronalkohol, Caprylalkohol, 2-Ethylhexylalkohol, Caprinalkohol, Laurylalkohol, Isotridecylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Linolylalkohol, Linolenylalkohol, Elaeostearylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol und Brassidylalkohol sowie deren technische Mischungen, die z.B. bei der Hochdruckhydrierung von technischen Methylestern auf Basis von Fetten und Ölen oder Aldehyden aus der Roelen'schen Oxosynthese sowie als Monomerfraktion bei der Dimerisierung von ungesättigten Fettalkoholen anfallen. Bevorzugt sind Anlagerungsprodukte von 3 bis 5 Mol Ethylenoxid an technische Fettalkohole mit 12 bis 18 Kohlenstoffatomen wie beispielsweise Kokos-, Palm-, Palmkern- oder Talgfettalkohol. Die Mittel können die Niotenside in Mengen von 1 bis 10, vorzugsweise 3 bis 5 Gew.-% - bezogen auf die Mittel - enthalten.In a particular embodiment of the present invention, the compositions furthermore contain nonionic surfactants of the fatty alcohol polyglycol ether type, which follow the formula (VI) ,
    Figure 00050001
    in which R 10 represents an alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and q represents numbers from 1 to 10. Typical examples are addition products of an average of 1 to 10 and preferably 2 to 7 mol ethylene oxide onto capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, , Elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, which are used, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohol. Addition products of 3 to 5 moles of ethylene oxide with technical fatty alcohols with 12 to 18 carbon atoms such as, for example, coconut, palm, palm kernel or tallow fatty alcohol are preferred. The agents can contain the nonionic surfactants in amounts of 1 to 10, preferably 3 to 5% by weight, based on the agents.

    Weitere Hilfs- und ZusatzstoffeOther auxiliaries and additives

    Die Mittel können neben den genannten Tensiden weitere typische Inhaltsstoffe wie beispielsweise Builder, Enzyme, Enzymstabilisatoren, Bleichmittel, optische Aufheller, Verdickungsmittel, Soil repellants, Schauminhibitoren, Lösungsvermittler, anorganische Salze sowie Duft- und Farbstoffe aufweisen.In addition to the surfactants mentioned, the agents can include other typical ingredients, for example Builders, enzymes, enzyme stabilizers, bleaches, optical brighteners, thickeners, soil repellants, Foam inhibitors, solubilizers, inorganic salts and fragrances and dyes.

    Geeignete Builder sind Zeolithe, Schichtsilicate, Phosphate sowie Ethylendiamintetraessigsäure, Nitrilotriessigsäure, Citronensäure sowie anorganische Phosphonsäuren. Unter den als Peroxy-Bleichmittel dienenden Verbindungen haben das Natriumperborat-Tetrahydrat und das Natriumperborat-Monohydrat eine besondere Bedeutung. Weitere Bleichmittel sind beispielsweise Peroxycarbonat, Citratperhydrate sowie H2O2-liefernde persaure Salze der Persäuren wie Perbenzoate, Peroxyphthalate oder Diperoxydodecandisäure. Sie werden üblicherweise in Mengen von 8 bis 25 Gew.-% eingesetzt. Bevorzugt ist der Einsatz von Natriumperborat-Monohydrat in Mengen von 10 bis 20 Gew.-% und insbesondere von 10 bis 15 Gew.-%. Durch seine Fähigkeit, unter Ausbildung des Tetrahydrats freies Wasser binden zu können, trägt es zur Erhöhung der Stabilität des Mittels bei. Als Verdickungsmittel können beispielsweise gehärtetes Rizinusöl, Salze von langkettigen Fettsäuren, die vorzugsweise in Mengen von 0 bis 5 Gew.-% und insbesondere in Mengen von 0,5 bis 2 Gew.-%, beispielsweise Natrium-, Kalium-, Aluminium-, Magnesium- und Titan-Stearate oder die Natrium und/oder Kaliumsalze der Behensäure, sowie weitere polymere Verbindungen eingesetzt werden. Zu den letzten gehören bevorzugt Polyvinylpyrrolidon, Urethane und die Salze polymerer Polycarboxylate, beispielsweise homopolymerer oder copolymerer Polyacrylate, Polymethacrylate und insbesondere Copolymere der Acrylsäure mit Maleinsäure, vorzugsweise solche aus 50 bis 10% Maleinsäure. Die relative Molekülmasse der Homopolymeren liegt im allgemeinen zwischen 1000 und 100000, die der Copolymeren zwischen 2000 und 200000, vorzugsweise zwischen 50000 bis 120000, bezogen auf die freie Säure. Insbesondere sind auch wasserlösliche Polyacrylate geeignet, die beispielsweise mit etwa 1% eines Polyallylethers der Sucrose quervernetzt sind und die eine relative Molekülmasse oberhalb 1000000 besitzen Beispiele hierfür sind unter dem Namen Carbopol® 940 und 941 erhältliche Polymere. Die quervernetzten Polyacrylate werden vorzugsweise in Mengen nicht über 1 Gew.-% besonders bevorzugt in Mengen von 0,2 bis 0,7 Gew.-% eingesetzt. Als Enzyme kommen solche aus der Klasse der Proteasen, Lipase, Amylasen, Cellulasen bzw. deren Gemische in Frage. Besonders gut geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus subtilis, Bacillus lichenformis und Strptomyces griseus gewonnene enzymatische Wirkstoffe. Vorzugsweise werden Proteasen vom Subtilisin-Typ und insbesondere Proteasen, die aus Bacillus lentes gewonnen werden, eingesetzt. Ihr Anteil kann etwa 0,2 bis 2 Gew.-% betragen. Die Enzyme können an Trägerstoffen adsorbiert oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen. Zusätzlich zu mono- und polyfunktionellen Alkoholen und Phosphonaten können die Mittel weitere Enzymstabilisatoren enthalten. Beispielsweise können 0,5 bis 1 Gew.-% Natriumformiat eingesetzt werden. Möglich ist auch der Einsatz von Proteasen, die mit löslichen Calciumsalzen und einem Calciumgehalt von vorzugsweise etwa 1,2 Gew.-%, bezogen auf das Enzym, stabilisiert sind. Besonders vorteilhaft ist jedoch der Einsatz von Borverbindungen, beispielsweise von Borsäure, Boroxid, Borax und anderen Alkalimetallboraten wie den Salzen der Orthoborsäure (H3BO3), der Metaborsäure (HBO2) und der Pyroborsäure (Tetraborsäure H2B4O7). Beim Einsatz im maschinellen Waschverfahren kann es von Vorteil sein, den Mitteln übliche Schauminhibitoren zuzusetzen. Geeignete Schauminhibitoren enthalten beispielsweise bekannte Organopolysiloxane, Paraffine oder Wachse.Suitable builders are zeolites, phyllosilicates, phosphates and ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and inorganic phosphonic acids. Among the compounds used as peroxy bleaching agents , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other bleaching agents are, for example, peroxy carbonate, citrate perhydrates and H 2 O 2 -producing peracid salts of peracids such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 8 to 25% by weight. The use of sodium perborate monohydrate in amounts of 10 to 20% by weight and in particular 10 to 15% by weight is preferred. Due to its ability to bind free water with the formation of the tetrahydrate, it contributes to increasing the stability of the agent. For example, hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, aluminum, magnesium, can be used as thickeners - And titanium stearates or the sodium and / or potassium salts of behenic acid, and other polymeric compounds are used. The latter preferably include polyvinylpyrrolidone, urethanes and the salts of polymeric polycarboxylates, for example homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those composed of 50 to 10% maleic acid. The relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably between 50,000 to 120,000, based on the free acid. Water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a relative molecular weight above 1,000,000 are also particularly suitable. Examples of these are polymers obtainable under the name Carbopol® 940 and 941. The crosslinked polyacrylates are preferably used in amounts of not more than 1% by weight, particularly preferably in amounts of 0.2 to 0.7% by weight. Suitable enzymes are those from the class of proteases, lipase, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus lichenformis and Strptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentes are preferably used. Their proportion can be about 0.2 to 2% by weight. The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition. In addition to mono- and polyfunctional alcohols and phosphonates, the agents can contain further enzyme stabilizers . For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous. When used in the machine washing process, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors contain, for example, known organopolysiloxanes, paraffins or waxes.

    Gewerbliche AnwendbarkeitIndustrial applicability

    Ein besonderer Vorteil der Erfindung besteht darin, daß nur innerhalb der engen Konzentrationsbereiche lagerstabile Mikroemulsionen erhalten werden. Dementsprechend betrifft ein weiterer Gegenstand der Erfindung die Verwendung der ternären Tensidmischung zur Herstellung von Mikroemulsionen. A particular advantage of the invention is that only within the narrow concentration ranges storage-stable microemulsions can be obtained. Accordingly, another concerns The invention relates to the use of the ternary surfactant mixture for the production of Microemulsions.

    BeispieleExamples

    Die Beschaffenheit verschiedener Testprodukte wurde unmittelbar nach der Herstellung sowie nach Lagerung beurteilt. Dabei bedeutet in der Zeile Mikroemulsion" (+), daß die Mischung als Mikroemulsion vorlag, (-), daß keine Mikroemulsion gebildet wurde. In der folgenden Zeile ist die Stabilität nach Lagerung angegeben; (+) steht für stabil, (-) für getrennt. Die Viskosität der Zubereitungen wurde unmittelbar nach der Herstellung nach der Brookfield-Methode in einem RVT-Viskosimeter (20°C, Spindel 1, 10 Upm) gemessen. Anschließend wurde Baumwollgewebe (Testanschmutzung: Sebum) in einer Haushaltswaschmaschine mit einem Fassungsvermögen von 50 l mit den Zubereitungen bei 40°C gewaschen (Einsatzmenge 1 g/l) und der Weißgrad photometrisch gegen einen Standard bestimmt. Der Weichgriff wurde von einem Panel erfahrener Personen subjektiv auf einer Skala von (1) = weich bis (4) = hart bewertet. Die Zusammensetzungen und Ergebnisse sind in Tabelle 1 zusammengefaßt. Die Beispiele 1 bis 4 sind erfindungsgemäß, die Versuche V1 bis V4 dienen zum Vergleich. Zusammensetzung und Performance von flüssigen Feinwaschmtteln Zusammensetzung / Performance 1 2 3 4 V1 V2 V3 V4 Methylquaternierter Dipalmettsäuretriethanolaminester, Methylsulfatsalz 5,0 5,0 6,0 6,0 8,0 2,0 2,5 5,0 Dodecylbenzolsulfonat-Natriumsalz 8,5 10,0 8,0 10,0 7,0 12,0 7,0 7,0 Kokosalkylpolyglucosid 7,0 4,0 6,0 4,0 4,0 6,0 7,5 10,0 Kokosfettalkohol+3EO 3,0 3,0 3,0 3,0 3,0 3,0 3,0 3,0 Ölsäure-Triethanolaminsalz 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 Wasser ad 100 Mikroemulsion + + + + - - + + Lagerstabilität (3 w, 40°C) + + + + - - - - Viskosität [mPas] 6085 5900 4625 4890 335 930 4170 4670 Remission [%-rel] 65,0 62,0 63,3 64,1 - - 55,1 60,0 Weichgriff 1,5 2,0 1,5 2,0 - - 3,0 2,5 The nature of various test products was assessed immediately after manufacture and after storage. Here means in the line Microemulsion "(+) that the mixture was in the form of a microemulsion, (-) that no microemulsion was formed. The following line shows the stability after storage; (+) stands for stable, (-) for separated. The viscosity of the Preparations were measured immediately after production using the Brookfield method in an RVT viscometer (20 ° C., spindle 1, 10 rpm) and then cotton fabric (test soiling: sebum) was added to the preparations in a household washing machine with a capacity of 50 l Washed at 40 ° C. (quantity used 1 g / l) and the degree of whiteness determined photometrically against a standard The softness was assessed subjectively by a panel of experienced persons on a scale from (1) = soft to (4) = hard. The compositions and results are summarized in Table 1. Examples 1 to 4 are according to the invention, experiments V1 to V4 are used for comparison. Composition and performance of liquid delicates Composition / performance 1 2nd 3rd 4th V1 V2 V3 V4 Methyl quaternized dipalmetic acid triethanolamine ester, methyl sulfate salt 5.0 5.0 6.0 6.0 8.0 2.0 2.5 5.0 Dodecylbenzenesulfonate sodium salt 8.5 10.0 8.0 10.0 7.0 12.0 7.0 7.0 Coconut alkyl polyglucoside 7.0 4.0 6.0 4.0 4.0 6.0 7.5 10.0 Coconut fatty alcohol + 3EO 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Oleic acid triethanolamine salt 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 water ad 100 Microemulsion + + + + - - + + Storage stability (3 w, 40 ° C) + + + + - - - - Viscosity [mPas] 6085 5900 4625 4890 335 930 4170 4670 Remission [% -rel] 65.0 62.0 63.3 64.1 - - 55.1 60.0 Soft grip 1.5 2.0 1.5 2.0 - - 3.0 2.5

    Die Beispiele und Vergleichsbeispiele zeigen, daß nur innerhalb der angegebenen engen Konzentrationsbereiche stabile Mikroemulsionen einer ausreichend hohen Viskosität erhalten werden, die gleichzeitig über ein hohes Waschvermögen verfügen und den Geweben einen angenehmen Weichgriff verleihen.The examples and comparative examples show that only within the specified narrow concentration ranges stable microemulsions of a sufficiently high viscosity can be obtained simultaneously have a high washability and the fabrics have a pleasant soft feel to lend.

    Claims (8)

    Flüssige Feinwaschmittel in Mikroemulsionsform, enthaltend (a) 5 bis 7 Gew.-% Esterquats, (b) 7 bis 10 Gew.-% Alkylbenzolsulfonate und (c) 4 bis 8 Gew.-% Alkyl- und/oder Alkenyloligoglykoside, mit der Maßgabe, daß sich die Mengenangaben mit Wasser und gegebenenfalls weiteren üblichen Hilfs- und Zusatzstoffen zu 100 Gew.-% ergänzen.Containing liquid mild detergent in microemulsion form (a) 5 to 7% by weight of ester quats, (b) 7 to 10% by weight alkylbenzenesulfonates and (c) 4 to 8% by weight of alkyl and / or alkenyl oligoglycosides, with the proviso that the amounts given with water and, if appropriate, other conventional auxiliaries and additives are 100% by weight. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß sie Esterquats der Formel (I) enthalten,
    Figure 00090001
    in der R1CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R2 und R3 unabhängig voneinander für Wasserstoff oder R1CO, R4 für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder eine (CH2CH2O)qH-Gruppe, m, n und p in Summe für 0 oder Zahlen von 1 bis 12, q für Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht.    Agents according to claim 1, characterized in that they contain ester quats of the formula (I) ,
    Figure 00090001
    in which R 1 CO stands for an acyl radical with 6 to 22 carbon atoms, R 2 and R 3 independently of one another for hydrogen or R 1 CO, R 4 for an alkyl radical with 1 to 4 carbon atoms or a (CH 2 CH 2 O) q H- Group, m, n and p in total stands for 0 or numbers from 1 to 12, q for numbers from 1 to 12 and X for halide, alkyl sulfate or alkyl phosphate.         Mittel nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß sie Esterquats der Formel (II) enthalten,
    Figure 00090002
    in der R1CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R2 für Wasserstoff oder R1CO, R4 und R5 unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht.    Agents according to Claims 1 and 2, characterized in that they contain ester quats of the formula (II) ,
    Figure 00090002
    in which R 1 CO for an acyl radical with 6 to 22 carbon atoms, R 2 for hydrogen or R 1 CO, R 4 and R 5 independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.         Mittel nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß sie Esterquats der Formel (III) enthalten,
    Figure 00100001
    in der R1CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R2 für Wasserstoff oder R1CO, R4, R6 und R7 unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht.    Agents according to Claims 1 to 3, characterized in that they contain ester quats of the formula (III) ,
    Figure 00100001
    in which R 1 CO for an acyl radical with 6 to 22 carbon atoms, R 2 for hydrogen or R 1 CO, R 4 , R 6 and R 7 independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.         Mittel nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß sie Alkylbenzolsulfonate der Formel (IV) enthalten,
    Figure 00100002
    in der R8 für einen linearen oder verzweigten Alkylrest mit 10 bis 16 Kohlenstoffatomen, Ph für einen Phenylrest und X für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht.    Agents according to Claims 1 to 4, characterized in that they contain alkylbenzenesulfonates of the formula (IV) ,
    Figure 00100002
    in which R 8 is a linear or branched alkyl radical having 10 to 16 carbon atoms, Ph is a phenyl radical and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.         Mittel nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß sie Alkyl- und Alkenyloligoglyside der Formel (V) enthalten,
    Figure 00100003
    in der R9 für einen Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht.    Agents according to Claims 1 to 5, characterized in that they contain alkyl and alkenyl oligoglysides of the formula (V) ,
    Figure 00100003
    in which R 9 represents an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10.         Mittel nach den Ansprüchen 1 bis 6, dadurch gekennzeichnet, daß sie weiterhin Fettalkoholpolyglycolether der Formel (VI) enthalten,
    Figure 00100004
    in der R10 für einen Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen und q für Zahlen von 1 bis 10 steht.    Agents according to Claims 1 to 6, characterized in that they further contain fatty alcohol polyglycol ethers of the formula (VI) ,
    Figure 00100004
    in which R 10 represents an alkyl and / or alkenyl radical having 6 to 22 carbon atoms and q represents numbers from 1 to 10.         Verwendung von Mischungen nach Anspruch 1 zur Herstellung von Mikroemulsionen.Use of mixtures according to claim 1 for the production of microemulsions.
    EP98106391A 1997-04-16 1998-04-08 Liquid detergent for delicate textiles in the form of a microemulsion Withdrawn EP0872541A3 (en)

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