DE10019142B4 - Esterquats without solvent - Google Patents

Abstract

Esterquatzubereitungen, obtainable by reacting alkanolamines and / or polyamines with a mixture of fatty acids and dicarboxylic acids, the resulting esters are optionally alkoxylated and then quaternized in the absence of solvents.

Description

Field of the invention

The invention relates to esterquats and a special process for their preparation.

State of the art

The term "esterquats" is generally understood to mean quaternized fatty acid triethanolamine ester salts which are widely suitable both for fiber care and for hair care. In recent years, these substances have due to their better ecotoxicological compatibility conventional quaternary ammonium compounds such. B. displaced the known Distearyldimethylammoniumchlorid to a good extent from the market. Surveys on this topic are, for example, by O. Ponsati in C.R. CED Congress, Barcelona, 1992, p. 167, R. Puchta et al. in tens. Surf. Det., 30, 186 (1993), M. Brock in Tens. Surf. Det. 30 394 (1993) and R. Lagerman et al. in J. Am. Oil. Chem. Soc., 71, 97 (1994).

Although esterquats of the prior art have very good performance properties and have a satisfactory biodegradability and a good skin-cosmetic compatibility, the known from the prior art formulations with esterquats are cloudy. In addition, their production is initially possible only with the addition of solvents, such as lower alcohols.

Accordingly, the object of the invention was to provide preparations with esterquats that can be prepared even without the addition of solvents, allow a simple adjustment of a desired esterquat concentration and thus transparent and non-transparent esterquat additions are available. In addition, such preparations should have a good anti-static and anti-static behavior, compared to the prior art, the ironing of textiles much easier and do not exacerbate produced in this way transparent preparations.

Description of the invention

The invention relates to esterquatre formulations which are obtainable by reacting alkanolamines and / or polyamines with a mixture of fatty acids and dicarboxylic acids, optionally alkoxylating the resulting esters and then quaternizing in the absence of solvents.

Another object of the invention is a process for the preparation of Esterquatzubereitungen, in which reacting alkanolamines and / or polyamines with a mixture of fatty acids and dicarboxylic acids, the resulting esters optionally alkoxylated and then quaternized, which are characterized in that the quaternization in Absence of solvents.

Surprisingly, it has been found that esterquatern preparations can be prepared in a simple manner by omitting the usual use of solvents in the quaternization. Such preparations can be further adjusted by the addition of water very easily to any concentration of esterquat and there are both transparent and non-transparent, d. H. cloudy solutions, lotions or creams, available. Furthermore, such preparations show excellent hair and Faseravivageeigenschaften. In addition, fiber treated with these formulations is much easier to iron. Transparent esterquat preparations do not become cloudy even after storage.

esterquats

(1) fatty acids

By fatty acids are meant aliphatic carboxylic acids of the formula (I) R ¹ CO-OH (I) in which R ¹ CO is an aliphatic, linear or branched acyl radical having 8 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds. Typical examples are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitic acid, Stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, the z. As in the pressure splitting of natural fats and oils, in the reduction of aldehydes from the Roelen oxo synthesis or the dimerization of unsaturated fatty acids incurred. Preferred are technical fatty acids having 12 to 18 carbon atoms such as coconut, palm, palm kernel or tallow, preferably in cured or partially cured form.

(2) dicarboxylic acids

Dicarboxylic acids which are suitable as starting materials in the context of the invention follow the formula (II), HOOC- [X] -COOH (II) in which X is an optionally hydroxy-substituted alkylene group having 1 to 10 carbon atoms. Typical examples are succinic acid, maleic acid, glutaric acid, 1,12-dodecanedioic acid and especially adipic acid.

(3) alkanolamines

Alkanolamines, which come into consideration as central nitrogen compounds in the context of the invention, may contain an alkane radical having 1 to 4 carbon atoms. Preferably triethanolamine and their addition products of 1 to 10 and preferably 2 to 5 moles of ethylene oxide are used. Also suitable are mixtures of triethanolamines, such as, for example, methyldiethanolamine with triethanolamine and the like.

(4) polyamines

in der R² für Wasserstoff oder einen gegebenenfalls hydroxysubstituierten Alkylrest mit 1 bis 4 Kohlenstoffatomen, R³ und R⁴ unabhängig voneinander für Wasserstoff, eine (CH₂CH₂O)_mH-Gruppe oder einen gegebenenfalls hydroxysubstituierten Alkylrest mit 1 bis 4 Kohlenstoffatomen, A für eine lineare oder verzweigte Alkylengruppe mit 1 bis 6 Kohlenstoffatomen, n für Zahlen von 1 bis 4 und m für Zahlen von 1 bis 30 steht. Typische Beispiele sind Kondensationsprodukte von Capronsäure, Caprylsäure, 2-Ethylhexansäure, Caprinsäure, Laurinsäure, Isotridecansäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Mischungen mit Ethylendiamin, Propylendiamin, Diethylentriamin, Dipropylentriamin, Triethylentetramin, Tripropylentetramin sowie deren Addukten mit 1 bis 30, vorzugsweise 5 bis 15 und insbesondere 8 bis 12 Mol Ethylenoxid. Der Einsatz von ethoxylierten Polyaminen ist dabei bevorzugt, weil sich auf diese Weise die Hydrophilie der Emulgatoren exakt auf die zu emulgierenden Wirkstoffe einstellen läßt.Polyamines preferably follow the formula (III),

in the R ^{2 is} hydrogen or an optionally hydroxy-substituted alkyl radical having 1 to 4 carbon atoms, R ³ and R ⁴ are each independently hydrogen, a (CH ₂ CH ₂ O) _m H group or an optionally hydroxy-substituted alkyl radical having 1 to 4 carbon atoms, A is a linear or branched alkylene group having 1 to 6 carbon atoms, n is a number from 1 to 4 and m is a number from 1 to 30. Typical examples are condensation products of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and the like technical mixtures with ethylenediamine, propylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine and their adducts with 1 to 30, preferably 5 to 15 and especially 8 to 12 moles of ethylene oxide. The use of ethoxylated polyamines is preferred because in this way the hydrophilicity of the emulsifiers can be set exactly to the active ingredients to be emulsified.

(5) esterification

The fatty acids and the dicarboxylic acids can be used in a molar ratio of 1:10 to 10: 1. However, it has proved to be advantageous to set a molar ratio of 1: 1 to 4: 1 and in particular 1.5: 1 to 3: 1. The trialkanolamines on the one hand and the acids - that is, fatty acids and dicarboxylic acids taken together - can be used in a molar ratio of 1: 1.1 to 1: 2.8 (eg trialkanolamine: fatty acid: dicarboxylic acid (x2) = 1: 1: 0, 5, resulting in a ratio of trialkanolamine: acid of 1: 2). An optimal molar ratio of trialkanolamine: acids has been found to be 1: 1.5 to 1: 1.8.

The esterification can be carried out in a conventional manner, as described for example in the international patent application WO 91/01295 is described. Advantageously, the esterification takes place at temperatures of 120 to 220 and in particular 130 to 170 ° C and pressures of 0.01 to 1 bar. Suitable catalysts are hypophosphorous acids or their alkali metal salts, preferably Proven sodium hypophosphite, which can be used in amounts of 0.01 to 0.1 and preferably 0.05 to 0.07 wt .-% - based on the starting materials. In view of a particularly high color quality and stability, the concomitant use of alkali and / or alkaline earth boron hydrides, such as potassium, magnesium and especially sodium borohydride has proven to be advantageous. The co-catalysts are usually used in amounts of 50 to 1000 and in particular 100 to 500 ppm - again based on the starting materials - a. Corresponding methods are also the subject of the two German patents DE 4308792 C1 and DE 4409322 C1 , the teachings of which are hereby incorporated by reference. It is possible to use mixtures of fatty acids and dicarboxylic acids or to carry out the esterification with the two components in succession.

(6) Alkoxylation

For the preparation of polyalkylene oxide-containing esterquats one can proceed according to two alternatives. On the one hand, it is possible to use ethoxylated alkanolamines and / or polyamines. This has the advantage that the alkylene oxide distribution in the later resulting ester quat is approximately the same with respect to the three OH groups of the amine. The disadvantage, however, is that the esterification is more difficult for steric reasons. The method of choice is therefore to alkoxylate the ester before quaternization. This can be done in a conventional manner, d. H. in the presence of basic catalysts and at elevated temperatures. Examples of suitable catalysts are alkali metal and alkaline earth metal hydroxides and alkoxides, preferably sodium hydroxide and in particular sodium methoxide; the amount used is usually 0.5 to 5 and preferably 1 to 3 wt .-% - based on the starting materials. When using these catalysts, in the first place, free hydroxyl groups are alkoxylated. However, if the catalysts used are calcined or hydrotalcites hydrophobized with fatty acids, insertion of the alkylene oxides into the ester bonds also occurs. This method is preferred if one desires an alkylene oxide distribution which comes close to when using alkoxylated trialkanolamines. As alkylene oxides, ethylene and propylene oxide and mixtures thereof (random or block distribution) can be used. The reaction is usually carried out at temperatures in the range of 100 to 180 ° C. By incorporating on average 1 to 10 moles of alkylene oxide per mole of ester, the hydrophilicity of the esterquats is increased, the solubility is improved and the reactivity towards anionic surfactants is reduced.

(7) quaternization and alkylating agents

The quaternization of the fatty acid / Dicarbonsäuretrialkanolaminester and / or the Fettsäureamidoamine is carried out without the addition of solvents. The addition of water may be carried out to establish a desired concentration of transparent or non-transparent ester-quat additions after the end of the reaction. Accordingly, all concentrations are conceivable, preferably concentrations of 40 to 100, 60 to 90 and in particular 70 to 80 wt .-% - based on the final composition - selected Esterquatkonzentrationen.

Suitable alkylating agents are alkyl halides such as methyl chloride, dialkyl sulfates such as dimethyl sulfate or diethyl sulfate or dialkyl carbonates such as dimethyl carbonate or diethyl carbonate in question.

Usually, the esters and the alkylating agents are used in a molar ratio of 1: 0.95 to 1: 1.05, ie approximately stoichiometrically. The reaction temperature is usually 40 to 80 and in particular 50 to 60 ° C. Following the reaction, it is advisable to destroy unreacted alkylating agent by adding, for example, ammonia, an (alkanol) amine, an amino acid or an oligopeptide, as described, for example, in the German patent application DE 4026184 A1 is described.

The surface-active preparations according to the invention, preferably cosmetic and / or pharmaceutical preparations, may contain the esterquats in amounts of 5 to 70, preferably 15 to 60 and in particular 30 to 40,% by weight, based on the final concentration.

excipients

Stabilizers prevent the formation of ester quats from becoming unstable. They can be added as further components to the compositions according to the invention and to the surface-active preparations. Suitable stabilizers are fatty acid amidoamines and / or their quaternization products, betaines, nonionic surfactants, polyols and / or derivatives thereof, alcohols and / or hydrotropes, preferably fatty acid amidoamines and / or their quaternization products and betaines.

Stabilizers in amounts of from 0.1 to 30, preferably from 1 to 15, and in particular from 5 to 10,% by weight, based on the final concentration, of the compositions according to the invention may also be present.

Fatty acid amidoamines and / or their quaternization products

in der R⁵CO für einen linearen oder verzweigten, gesättigten oder ungesättigten Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder einen gegebenenfalls hydroxysubstituierten Alkylrest mit 1 bis 4 Kohlenstoffatomen, R³ und R⁴ unabhängig voneinander für Wasserstoff, eine (CH₂CH₂O)_mH-Gruppe oder einen gegebenenfalls hydroxysubstituierten Alkylrest mit 1 bis 4 Kohlenstoffatomen, A für eine lineare oder verzweigte Alkylengruppe mit 1 bis 6 Kohlenstoffatomen, n für Zahlen von 1 bis 4 und m für Zahlen von 1 bis 30 steht. Typische Beispiele sind Kondensationsprodukte von Capronsäure, Caprylsäure, 2-Ethylhexansäure, Caprinsäure, Laurinsäure, Isotridecansäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Mischungen mit Ethylendiamin, Propylendiamin, Diethylentriamin, Dipropylentriamin, Triethylentetramin, Tripropylentetramin sowie deren Addukten mit 1 bis 30, vorzugsweise 5 bis 15 und insbesondere 8 bis 12 Mol Ethylenoxid. Der Einsatz von ethoxylierten Fettsäureamidoaminen ist dabei bevorzugt, weil sich auf diese Weise die Hydrophilie der Emulgatoren exakt auf die zu emulgierenden Wirkstoffe einstellen läßt. Anstelle der Fettsäureamidoamine können auch deren Quaternierungsprodukte eingesetzt werden, die man durch Umsetzung der Amidoamine mit geeigneten Alkylierungsmitteln, wie beispielsweise Methylchlorid oder insbesondere Dimethylsulfat nach an sich bekannten Verfahren erhält. Die Quaternierungsprodukte folgen vorzugsweise der Formel (V),

in der R⁵CO für einen linearen oder verzweigten, gesättigten oder ungesättigten Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder einen gegebenenfalls hydroxysubstituierten Alkylrest mit 1 bis 4 Kohlenstoffatomen, R³ für Wasserstoff, eine (CH₂CH₂O)_mH-Gruppe oder einen gegebenenfalls hydroxysubstituierten Alkylrest mit 1 bis 4 Kohlenstoffatomen, R⁴ für R⁵CO, Wasserstoff, eine (CH₂CH₂O)_mH-Gruppe oder einen gegebenenfalls hydroxysubstituierten Alkylrest mit 1 bis 4 Kohlenstoffatomen, R⁵ für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen, A für eine lineare oder verzweigte Alkylengruppe mit 1 bis 6 Kohlenstoffatomen, n für Zahlen von 1 bis 4, m für Zahlen von 1 bis 30 und X für Halogenid, speziell Chlorid, oder Alkylsulfat, vorzugsweise Methylsulfat steht. Geeignet für diesen Zweck sind beispielsweise die Methylierungsprodukte der bereits oben genannten bevorzugten Fettsäureamidoamine. Es können des weiteren auch Mischungen von Fettsäureamidoaminen und deren Quaternierungsprodukten eingesetzt werden, welche man besonders einfach herstellt, indem man die Quaternierung nicht vollständig, sondern nur bis zu einem gewünschten Grad durchführt.Fatty acid amidoamines are condensation products of fatty acids with optionally ethoxylated di- or oligoamines, which preferably follow the formula (IV),

in the R ⁵ CO for a linear or branched, saturated or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or an optionally hydroxy-substituted alkyl radical having 1 to 4 carbon atoms, R ³ and R ^{4 are} independently hydrogen, a (CH ₂ CH ₂ O) _{m is} H or an optionally hydroxy-substituted alkyl radical having 1 to 4 carbon atoms, A is a linear or branched alkylene group having 1 to 6 carbon atoms, n is from 1 to 4 and m is from 1 to 30. Typical examples are condensation products of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and the like technical mixtures with ethylenediamine, propylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine and their adducts with 1 to 30, preferably 5 to 15 and especially 8 to 12 moles of ethylene oxide. The use of ethoxylated fatty acid amidoamines is preferred because in this way the hydrophilicity of the emulsifiers can be set exactly to the active ingredients to be emulsified. Instead of fatty acid amidoamines and their quaternization can be used, which is obtained by reacting the amidoamines with suitable alkylating agents such as methyl chloride or in particular dimethyl sulfate according to known methods. The quaternization products preferably follow the formula (V),

in the R ⁵ CO for a linear or branched, saturated or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or an optionally hydroxy-substituted alkyl radical having 1 to 4 carbon atoms, R ^{3 is} hydrogen, a (CH ₂ CH ₂ O) _m H group or an optionally hydroxy-substituted alkyl radical having 1 to 4 carbon atoms, R ^{4 is} R ⁵ CO, hydrogen, a (CH ₂ CH ₂ O) _m H group or an optionally hydroxy-substituted alkyl radical having 1 to 4 carbon atoms, R ^{5 is} a An alkyl radical having 1 to 4 carbon atoms, A is a linear or branched alkylene group having 1 to 6 carbon atoms, n is from 1 to 4, m is a number from 1 to 30 and X is halide, especially chloride, or alkyl sulfate, preferably methyl sulfate. Suitable for this purpose, for example, the methylation of the above-mentioned preferred Fettsäureamidoamine. Furthermore, it is also possible to use mixtures of fatty acid amidoamines and their quaternization products, which are prepared in a particularly simple manner by carrying out the quaternization not completely but only to a desired degree.

Betaine

Betaines are known surfactants, which are predominantly produced by carboxyalkylation, preferably carboxymethylation of aminic compounds. Preferably, the starting materials are condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, wherein one mole of salt is formed per mole of betaine. Furthermore, the addition of unsaturated carboxylic acids, such as acrylic acid is possible. For nomenclature, and in particular for the distinction between betaines and "real" amphoteric surfactants, reference is made to the article by U. Ploog in Soaps Oils-Fette-Wachse, 108, 373 (1982). Further reviews on this topic can be found, for example, by A. O'Lennick et al. in HAPPI, Nov. 70 (1986), S. Holzman et al. in tens.

in der R⁷ für Alkyl- und/oder Alkenylreste mit 6 bis 22 Kohlenstoffatomen, R⁸ für Wasserstoff oder Alkylreste mit 1 bis 4 Kohlenstoffatomen, R⁹ für Alkylreste mit 1 bis 4 Kohlenstoffatomen, p für Zahlen von 1 bis 6 und A für ein Alkali- und/oder Erdalkalimetall oder Ammonium steht. Typische Beispiele sind die Carboxymethylierungsprodukte von Hexylmethylamin, Hexyldimethylamin, Octyldimethylamin, Decyldimethylamin, Dodecylmethylamin, Dodecyldimethylamin, Dodecylethylmethylamin, C_12/14-Kokosalkyldimethylamin, Myristyldimethylamin, Cetyldimethylamin, Stearyldimethylamin, Stearylethylmethylamin, Oleyldimethylamin, C_16/18-Talgalkyldimethylamin sowie deren technische Gemische. Surf. Det. 23 309 (1986), R. Bibo et al. in Soap Cosm. Chem. Spec., Apr. 46 (1990) and P. Ellis et al. in Euro Cosm. 1, 14 (1994). Examples of suitable betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (VI)

in the R ⁷ for alkyl and / or alkenyl radicals having 6 to 22 carbon atoms, R ^{8 is} hydrogen or alkyl radicals having 1 to 4 carbon atoms, R ^{9 is} alkyl radicals having 1 to 4 carbon atoms, p is from 1 to 6 and A is a Alkali and / or alkaline earth metal or ammonium. Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, dodecylethylmethylamine, C _12/14 cocoalkyldimethylamine, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearylethylmethylamine, oleyldimethylamine, C _16/18 tallowalkyldimethylamine, and technical mixtures thereof.

in der R¹⁰CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen und 0 oder 1 bis 3 Doppelbindungen, m für Zahlen von 1 bis 3 steht und R⁸, R⁹, p und A die oben angegebenen Bedeutungen haben. Typische Beispiele sind Umsetzungsprodukte von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, namentlich Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isosteaitnsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Gemische, mit N,N-Dimethylaminoethylamin, N,N-Dimethylaminopropylamin, N,N-Diethylaminoethylamin und N,N-Diethylaminopropylamin, die mit Natriumchloracetat kondensiert werden. Bevorzugt ist der Einsatz eines Kondensationsproduktes von C_8/18-Kakosfettsäure-N,N-dimethylaminopropylamid mit Natiumchloracetat.Also suitable are carboxyalkylation products of amidoamines which follow the formula (VII),

in which R ¹⁰ CO is an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, m is a number from 1 to 3 and R ⁸ , R ⁹ , p and A have the meanings given above. Typical examples are reaction products of fatty acids having 6 to 22 carbon atoms, namely caproic, caprylic, capric, lauric, myristic, palmitic, palmitic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, linolenic, elaeostearic, arachidic, gadoleic, behenic and erucic acids and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate. The use of a condensation product of C _8/18 -canoic fatty acid-N, N-dimethylaminopropylamide with sodium chloroacetate is preferred.

in der R⁵ für einen Alkylrest mit 5 bis 21 Kohlenstoffatomen, R⁶ für eine Hydroxylgruppe, einen OCOR⁵- oder NHCOR⁶-Rest und m für 2 oder 3 steht. Auch bei diesen Substanzen handelt es sich um bekannte Stoffe, die beispielsweise durch cyclisierende Kondensation von 1 oder 2 Mol Fettsäure mit mehrwertigen Aminen, wie beispielsweise Aminoethylethanolamin (AEEA) oder Diethylentriamin erhalten werden können. Die entsprechenden Carboxyalkylierungsprodukte stellen Gemische unterschiedlicher offenkettiger Betaine dar. Typische Beispiele sind Kondensationsprodukte der oben genannten Fettsäuren mit AEEA, vorzugsweise Imidazoline auf Basis von Laurinsäure oder wiederum C_12/14-Kakosfettsäure, die anschließend mit Natriumchloracetat betainisiert werden.Further suitable suitable starting materials for the betaines to be used in the context of the invention are also imidazolines which follow the formula (VIII),

in which R ^{5 is} an alkyl radical having 5 to 21 carbon atoms, R ^{6 is} a hydroxyl group, an OCOR ⁵ or NHCOR ⁶ radical and m is 2 or 3. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines, such as, for example, aminoethylethanolamine (AEEA) or diethylenetriamine. The corresponding carboxyalkylation products are mixtures of different open-chain betaines. Typical examples are condensation products of the abovementioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C _12/14 coco fatty acid, which are subsequently betainized with sodium chloroacetate.

Nonionic surfactants

• – Anlagerungsprodukte von 2 bis 50 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 8 bis 22 C-Atomen, an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe sowie Alkylamine mit 8 bis 22 Kohlenstoffatomen im Alkylrest;
• – Alkyl- und/oder Alkenyloligoglykoside mit 8 bis 22 Kohlenstoffatomen im Alk(en)ylrest und deren ethoxylierte Analoga;
• – Anlagerungsprodukte von 1 bis 15 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;
• – Anlagerungsprodukte von 15 bis 60 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;
• – Partialester von Glycerin und/oder Sorbitan mit ungesättigten, linearen oder gesättigten, verzweigten Fettsäuren mit 12 bis 22 Kohlenstoffatomen und/oder Hydroxycarbonsäuren mit 3 bis 18 Kohlenstoffatomen sowie deren Addukte mit 1 bis 30 Mol Ethylenoxid;
• – Partialester von Polyglycerin (durchschnittlicher Eigenkondensationsgrad 2 bis 8), Polyethylenglycol (Molekulargewicht 200 bis 5000), Trimethylolpropan, Pentaerythrit, Zuckeralkoholen (z. B. Sorbit), Alkylglucosiden (z. B. Methylglucosid, Butylglucosid, Laurylglucosid) sowie Polyglucosiden (z. B. Cellulose) mit gesättigten und/oder ungesättigten, linearen oder verzweigten Fettsäuren mit 12 bis 22 Kohlenstoffatomen und/oder Hydroxycarbonsäuren mit 3 bis 18 Kohlenstoffatomen sowie deren Addukte mit 1 bis 30 Mol Ethylenoxid;
• – Mischester aus Pentaerythrit, Fettsäuren, Citronensäure und Fettalkohol gemäß DE 1165574 PS und/oder Mischester von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, Methylglucose und Polyolen, vorzugsweise Glycerin oder Polyglycerin.
• – Mono-, Di- und Trialkylphosphate sowie Mono-, Di- und/oder Tri-PEG-alkylphosphate und deren Salze;
• – Wollwachsalkohole;
• – Polysiloxan-Polyalkyl-Polyether-Copolymere bzw. entsprechende Derivate sowie
• – Polyalkylenglycole.

Nonionic surfactants come from at least one of the following groups in question:

• - Addition products of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 8 to 22 carbon atoms, to alkylphenols having 8 to 15 carbon atoms in the alkyl group and Alkylamines having 8 to 22 carbon atoms in the alkyl radical;
• - alkyl and / or Alkenyloligoglykoside having 8 to 22 carbon atoms in the alk (en) ylrest and their ethoxylated analogs;
• - addition products of 1 to 15 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;
• - Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;
• - partial esters of glycerol and / or sorbitan with unsaturated, linear or saturated, branched fatty acids having 12 to 22 carbon atoms and / or hydroxycarboxylic acids having 3 to 18 carbon atoms and their adducts with 1 to 30 moles of ethylene oxide;
• Partial esters of polyglycerol (average intrinsic condensation degree 2 to 8), polyethylene glycol (molecular weight 200 to 5000), trimethylolpropane, pentaerythritol, sugar alcohols (eg sorbitol), alkylglucosides (eg methylglucoside, butylglucoside, laurylglucoside) and polyglucosides (e.g. Cellulose) with saturated and / or unsaturated, linear or branched fatty acids containing 12 to 22 carbon atoms and / or hydroxycarboxylic acids containing 3 to 18 carbon atoms and adducts thereof with 1 to 30 moles of ethylene oxide;
• Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE 1165574 PS and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol.
• - Mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts;
• - wool wax alcohols;
• - Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives and
• - Polyalkylene glycols.

The addition products of ethylene oxide and / or of propylene oxide to fatty alcohols, fatty acids, alkylphenols or castor oil are known, commercially available products. These are mixtures of homologues whose mean degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate, with which the addition reaction is carried out corresponds. C _12/18 fatty acid _mono- and diesters of addition products of ethylene oxide with glycerol are made DE 2024051 PS known as a refatting agent for cosmetic preparations.

Alkyl and / or alkenyl oligoglycosides, their preparation and their use are known from the prior art. They are prepared in particular by reacting glucose or oligosaccharides with primary alcohols having 8 to 18 carbon atoms. With regard to the glycoside radical, both monoglycosides in which a cyclic sugar residue is glycosidically linked to the fatty alcohol and oligomeric glycosides having a degree of oligomerization of preferably approximately 8 are suitable. The degree of oligomerization is a statistical mean, which is based on a homolog distribution typical for such technical products.

Typical examples of suitable partial glycerides are hydroxystearic hydroxystearic acid diglyceride, isostearic acid, Isostearinsäurediglycerid, Ölsäuremonogrycerid, oleic acid diglyceride, Ricinolsäuremoglycerid, Ricinolsäurediglycerid, Linolsäuremonoglycerid, Linolsäurediglycerid, Linolensäuremonoglycerid, Linolensäurediglycerid, Erucasäuremonoglycerid, Erucasäurediglycerid, Weinsäuremonoglycerid, Weinsäurediglycerid, Citronensäuremonoglycerid, Citronendiglycerid, Apfelsäuremonoglycerid, malic acid diglyceride and technical mixtures thereof, which may contain minor amounts of triglyceride from the manufacturing process. Also suitable are addition products of 1 to 30, preferably 5 to 10 moles of ethylene oxide to said Partialglyceride.

As sorbitan sorbitan, sorbitan sesquiisostearate, Sorbitan, sorbitan triisostearate, sorbitan monooleate, sorbitan, sorbitan, Sorbitanmonoerucat, Sorbitansesquierucat, Sorbitandierucat, Sorbitantrierucat, Sorbitanmonoricinoleat, Sorbitansesquiricinoleat, Sorbitandiricinoleat, Sorbitantriricinoleat, Sorbitanmonohydroxystearat, Sorbitansesquihydroxystearat, Sorbitandihydroxystearat, Sorbitantrihydroxystearat, Sorbitanmonotartrat, Sorbitansesquitartrat, Sorbitanditartrat, Sorbitantritartrat come , Sorbitan monocitrate, sorbitan siccitrate, sorbitan citrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan adipate, sorbitan trimaleate, and technical mixtures thereof. Also suitable are addition products of 1 to 30, preferably 5 to 10 moles of ethylene oxide to said sorbitan esters.

Typical examples of suitable polyglycerol esters are Polyglyceryl-2 Dipolyhydroxystearate (Dehymuls ^® PGPH), Polyglycerin-3-Diisostearate (Lameform ^® TGI), Polyglyceryl-4 isostearate (Isolan ^® GI 34), Polyglyceryl-3 Oleate, Diisostearoyl Polygluceryl-3 Diisostearate (Isolan ^® PDI), Polyglyceryl-3 methylglucose Distearate (Tego Care ^® 450), Polyglyceryl-3 Beeswax (Cera Bellina ^®), Polyglyceryl-4 Caprate (polyglycerol Caprate T2010 / 90), Polyglyceryl-3 Cetyl ether (Chimexane ^® NL), Polyglyceryl -3 Distearate (Cremophor ^® GS 32) and Polyglyceryl polyricinoleates (Admul ^® WOL 1403) polyglyceryl dimerates Isostearate and mixtures thereof.

Examples of other suitable polyol esters are the mono-, di- and triesters of trimethylolpropane or pentaerythritol with lauric acid, coconut fatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like, which are optionally reacted with from 1 to 30 mol of ethylene oxide.

• • Glycerin;
• • Alkylenglycole, wie beispielsweise Ethylenglycol, Diethylenglycol, Propylenglycol, Butylenglycol, Hexylenglycol sowie Polyethylenglycole mit einem durchschnittlichen Molekulargewicht von 100 bis 1.000 Dalton;
• • technische Oligoglyceringemische mit einem Eigenkondensationsgrad von 1,5 bis 10 wie etwa technische Diglyceringemische mit einem Diglyceringehalt von 40 bis 50 Gew.-%;
• • Methyolverbindungen, wie insbesondere Trimethylolethan, Trimethylolpropan, Trimethylolbutan, Pentaerythrit und Dipentaerythrit;
• • Niedrigalkylglucoside, insbesondere solche, mit 1 bis 8 Kohlenstoffen im Alkylrest, wie beispielsweise Methyl- und Butylglucosid;
• • Zuckeralkohole mit 5 bis 12 Kohlenstoffatomen, wie beispielsweise Sorbit oder Mannit,
• • Zucker mit 5 bis 12 Kohlenstoffatomen, wie beispielsweise Glucose oder Saccharose;
• • Aminozucker, wie beispielsweise Glucamin;
• • Dialkoholamine, wie Diethanolamin oder 2-Amino-1,3-propandiol und/oder deren Derivate, wie C1 bis C4 Ether, z. B. Butyldiglycolmethylether und/oder C1 bis C4 Carbonate, z. B. Propylenglycolcarbonat, Glycerincarbonat etc.. Vorzugsweise werden Glycerin, Propylenglycol, Butylenglycol, Hexylenglycol sowie Polyethylenglycole mit einem durchschnittlichen Molekulargewicht im Bereich von 100 bis 1.000 Dalton eingesetzt. Die erfindungsgemäßen Mittel können die Polyole in Mengen von 0 bis 30, vorzugsweise 0,1 bis 15 und insbesondere 0,5 bis 5 Gew.-% – bezogen auf die Endkonzentration – enthalten.

Polyols and / or Derivatives Polyols preferably have 2 to 15 carbon atoms and at least two hydroxyl groups. The polyols may contain other functional groups, in particular amino groups, or be modified with nitrogen. Typical examples are

• • glycerin;
• Alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and polyethylene glycols having an average molecular weight of 100 to 1,000 daltons;
• Technical Oligoglyceringemische with an intrinsic degree of condensation of 1.5 to 10 such as technical Diglyceringemische with a diglycerol content of 40 to 50 wt .-%;
• Methyolverbindungen, in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
• Lower alkyl glucosides, especially those having from 1 to 8 carbons in the alkyl radical, such as, for example, methyl and butyl glucoside;
• Sugar alcohols having 5 to 12 carbon atoms, such as sorbitol or mannitol,
• • sugars having 5 to 12 carbon atoms, such as glucose or sucrose;
• • amino sugars, such as glucamine;
• • Dialcoholamines, such as diethanolamine or 2-amino-1,3-propanediol and / or derivatives thereof, such as C1 to C4 ethers, for. Butyl diglycol methyl ether and / or C1 to C4 carbonates, e.g. Preferably, glycerol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols having an average molecular weight in the range of 100 to 1,000 daltons are used. The compositions of the invention may contain the polyols in amounts of 0 to 30, preferably 0.1 to 15 and in particular 0.5 to 5 wt .-% - based on the final concentration.

alcohols

Suitable alcohols in the context of the invention are methanol, ethanol, propanol, butanol and / or derivatives thereof.

hydrotropes

Suitable hydrotropes in the context of the invention are aromatic alkylsulfonates, such as, preferably, tolulsulonates, cumene sulfonates, xylene sulfonates and the like. a. in question.

Industrial Applicability

• (a) 5 bis 90, vorzugsweise 15 bis 80 und insbesondere 30 bis 40 Gew.-% Esterquats und gegebenenfalls
• (b) 0 bis 50, vorzugsweise 0,5 bis 30 und insbesondere 1 bis 10 Gew.-% Stabilisatoren

mit der Maßgabe, dass sich die Mengenangaben mit Wasser und gegebenenfalls weiteren Hilfs- und Zusatzstoffen zu 100 Gew.-% ergänzen.In a preferred embodiment of the invention, the esterquatern preparations contain, based on the final concentration,

• (A) 5 to 90, preferably 15 to 80 and in particular 30 to 40 wt .-% esterquats and optionally
• (B) 0 to 50, preferably 0.5 to 30 and especially 1 to 10 wt .-% stabilizers

with the proviso that the amounts are supplemented with water and optionally other auxiliaries and additives to 100 wt .-%.

The compositions according to the invention can be used in surface-active preparations, for example cosmetic and / or pharmaceutical preparations, including hair shampoos, hair lotions, bubble baths, shower baths, oral and dental care products, creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, emulsions, wax / fat formulations. Be used masses, stick preparations, powders or ointments, cleaning agents, preferably washing, rinsing, cleaning and finishing agents and preparations for the treatment of textiles, preferably ironing aids and the like. They may also be used as further additives mild surfactants, oil components, emulsifiers, superfatting agents, pearlescent waxes, bodying agents, Thickening agents, polymers, silicone compounds, fats, waxes, stabilizers, biogenic agents, Deowirkstoffe, anti-dandruff agents, film formers, swelling agents, other UV protection factors, antioxidants, hydrotropes, preservatives, insect repellents, self-tanning, solubilizers, perfume oils, dyes, anti-microbial agents and the like.

Typical examples of suitable milds, d. H. particularly skin-compatible surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, α-olefinsulfonates, ether carboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines and / or protein fatty acid condensates, the latter preferably based on wheat proteins.

As oil components of the required polarity are in particular Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of branched C ₆ -C ₁₃ carboxylic acids with linear C ₆ -C ₂₂ fatty alcohols, esters of linear C ₆ -C _22- fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C ₆ -C ₂₂ fatty alcohols, in particular dioctyl malates, esters of linear and / or branched fatty acids with polyhydric alcohols (such as, for example, propylene glycol , Dimerdiol or trimer triol) and / or Guerbet alcohols, liquid mono- / di- / Triglyceridmisungen based on C ₆ -C ₁₈ fatty acids, esters of C ₆ -C ₂₂ fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, especially benzoic acid, esters of C ₆ -C ₁₂ dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydro xyl groups, branched primary alcohols, substituted cyclohexanes, linear and branched C ₆ -C ₂₂ fatty alcohol, Guerbetcarbonate, esters of benzoic acid with linear and / or branched C ₆ -C ₂₂ alcohols (eg. B. Finsolv ^® TN), linear or branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, ring-opening products of epoxidized fatty acid esters with polyols into consideration.

As superfatting agents, substances such as lanolin and lecithin as well as polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used, the latter also serving as foam stabilizers.

Suitable pearlescing waxes are, for example: alkylene glycol esters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polyhydric, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances, such as fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides having 12 to 22 carbon atoms with fatty alcohols having 12 to 22 carbon atoms and / or polyols having 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.

As consistency factors are primarily fatty alcohols or hydroxy fatty alcohols having 12 to 22 and preferably 16 to 18 carbon atoms and in addition partial glycerides, fatty acids or hydroxy fatty acids into consideration. Preference is given to a combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates. Suitable thickening agents are, for example, Aerosil types (hydrophilic silicic acids), polysaccharides, especially xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, (eg. B. Carbopole ^® from Goodrich or Synthalene ^® from Sigma), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with narrow homolog distribution or Alkyloligoglucoside and electrolytes such as sodium chloride and ammonium chloride.

Suitable cationic polymers are, for example, cationic cellulose derivatives, such as. Example, a quaternized hydroxyethylcellulose obtainable under the name Polymer JR 400 ^® from Amerchol, cationic starch, copolymers of diallyl ammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers, such. As Luviquat ^® (BASF), condensation products of polyglycols and amines, quaternized collagen polypeptides, for example lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat® ^® L / Grunau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers such. B. amidomethicones, copolymers of adipic acid and dimethylaminohydroxypropyl diethylenetriamine (Cartaretine ^® / Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat ^® 550 / Chemviron), Polyaminopolyamide, such as. B. described in the FR 2252840 A and their crosslinked water-soluble polymers, cationic chitin derivatives such as quaternized chitosan, optionally microcrystalline distributed, condensation products of dihaloalkylene, such as. B. dibromobutane with bis-dialkylamines, such as. B. bis-dimethylamino-1,3-propane, cationic guar gum, such as. ^Jaguar® CBS, ^Jaguar® C-17, ^Jaguar® C-16 from Celanese, quaternized ammonium salt polymers, e.g. B. Mirapol ^® A-15, Mirapol ^® AD-1, Mirapol ^® AZ-1 from Miranol.

Examples of anionic, zwitterionic, amphoteric and nonionic polymers are vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinylaerylate copolymers, vinyl acetate / butytmaleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and their esters, uncrosslinked polyols crosslinked with polyols, acrylamidopropyltrimethylammonium chloride / acrylate Copolymers, octylacrylamide / methyl methacrylate / tert.butylaminaethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, vinylpyrolidone / dimethylaminoethyl methacrylate / vinylcaprolactam terpolymers and optionally derivatized cellulose ethers and silicones in question.

Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl-modified silicone compounds which may be both liquid and resin-form at room temperature. Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units and hydrogenated silicates. A detailed overview of suitable volatile silicones can also be found in Todd et al. in Cosm. Toil. 91, 27 (1976).

Typical examples of fats are glycerides, as waxes come u. a. Beeswax, carnauba wax, candelilla wax, montan wax, paraffin wax, hydrogenated castor oils, solid fatty acid esters or microwaxes, optionally in combination with hydrophilic waxes, e.g. As cetylstearyl alcohol or partial glycerides in question. As stabilizers metal salts of fatty acids, such as. B. magnesium, aluminum and / or zinc stearate or -ricinoleat used.

Biogenic active ingredients are, for example, tocopherol, tocopherol acetate, tocopherol patmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes.

As Deowirkstoffe come z. As antiperspirants such as aluminum chlorohydrates in question. These are colorless, hygroscopic crystals which easily deliquesce in the air and are formed on evaporation of aqueous aluminum chloride solutions. Aluminum chlorohydrate is used for the production of antiperspirant and deodorizing preparations and is likely to act via the partial occlusion of the sweat glands by protein and / or polysaccharide precipitation [cf. J. Soc. Cosm. Chem. 24, 281 (1973)]. Under the brand Locron® ^® of Hoechst AG, Frankfurt / FRG, for example, is, an aluminum trading, _[2 (OH) ₅ Cl Al] corresponds to the formula 2.5 · H ₂ O and its use is particularly preferred [see. J. Pharm. Pharmacol. 26, 531 (1975)]. In addition to the chlorohydrates, it is also possible to use aluminum hydroxylactates and acidic aluminum / zirconium salts. As further Deowirkstoffe esterase inhibitors can be added. These are preferably trialkyl such as trimethyl citrate, tripropyl, triisopropyl, tributyl citrate and especially triethyl citrate (Hydagen® ^® CAT, Henkel KGaA, Dusseldorf / FRG). The substances inhibit the enzyme activity and thereby reduce odors. The cleavage of the citric acid ester is likely to release the free acid, which lowers the pH level on the skin, thereby inhibiting the enzymes. Further substances which are suitable as esterase inhibitors are sterol sulfates or phosphates, such as, for example, lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and their esters, for example glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, Adipic acid monoethyl ester, diethyl adipate, malonic acid and diethyl malonate, hydroxycarboxylic acids and their esters such as citric acid, malic acid, tartaric acid or diethyl tartrate. Antibacterial agents that affect the bacterial flora and kill sweat-degrading bacteria or inhibit their growth may also be included in the stick formulations. Examples of these are chitosan, phenoxyethanol and chlorhexidine gluconate. Particularly effective are also 5-chloro-2- (2,4-dichlorophenoxy) phenol has proven that is marketed under the brand name Irgasan ^® by Ciba-Geigy, Basle / CH.

Climbazole, octopirox and zinc pyrethion can be used as anti-dandruff agents. Common film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, Polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or salts thereof and similar compounds.

Suitable swelling agents for aqueous phases are montmorillonites, clay minerals, pemulen and alkyl-modified carbopol types (Goodrich). Further suitable polymers or swelling agents can be reviewed by R. Lochhead in Cosm. Toil. 108, 95 (1993).

• • 4-Aminobenzoesäurederivate, vorzugsweise 4-(Dimethylamino)benzoesäure-2-ethylhexylester, 4-(Dimethylamino)benzoesäure-2-octylester und 4-(Dimethylamino)benzoesäuremylester,
• • Ester der Salicylsäure, vorzugsweise Salicylsäure-2-ethylhexylester, Salicylsäure-4-isopropylbenzylester, Salicylsäurehomomenthylester;
• • Derivate des Benzophenons, vorzugsweise 2-Hydroxy-4-methoxybenzophenon, 2-Hydroxy-4-methoxy-4'-methylbenzophenon, 2,2'-Dihydroxy-4-methoxybenzophenon;
• • Ester der Benzalmalonsäure, vorzugsweise 4-Methoxybenzmalonsäuredi-2-ethylhexylester,
• • Triazinderivate, wie z. B. 2,4,6-Trianilino-(p-carbo-2'-ethyl-1'-hexyloxy)-1,3,5-triazin und Octyl Triazon, wie in der EP 0818450 A1 beschrieben;
• • Propan-1,3-dione, wie z. B. 1-(4-tert.Butylphenyl)-3-(4'methoxyphenyl)propan-1,3-dion;
• • Ketotricyclo(5.2.1.0)decan-Derivate, wie in der EP 0694521 B1 beschrieben.

Under UV sun protection factors are, for example, at room temperature, liquid or crystalline organic substances present (sunscreen) to understand that are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, eg. B. to give off heat again. UV-B filters can be oil-soluble or water-soluble. As oil-soluble substances z. To name, for example:

• 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and methyl 4- (dimethylamino) benzoate,
• Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate;
• Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;
• Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate,
• Triazine derivatives, such as. 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and octyl triazone, as described in U.S.P. EP 0818450 A1 described;
• • Propane-1,3-dione, such as B. 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione;
• • Ketotricyclo (5.2.1.0) decane derivatives as described in U.S. Pat EP 0694521 B1 described.

• • 2-Phenylbenzimidazol-5-sulfonsäure und deren Alkali-, Erdalkali-, Ammonium-, Alkylammonium-, Alkanolammonium- und Glueammoniumsalze;
• • Sulfonsäurederivate von Benzophenonen, vorzugsweise 2-Hydroxy-4-methoxybenzophenon-5-sulfonsäure und ihre Salze;
• • Sulfonsäurederivate des 3-Benzylidencamphers, wie z. B. 4-(2-Oxo-3-bornylidenmethyl)benzolsulfonsäure und 2-Methyl-5-(2-oxo-3-bomyliden)sulfonsäure und deren Salze.

Suitable water-soluble substances are:

• 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glueammonium salts;
• Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts;
• Sulfonic acid derivatives of 3-Benzylidencamphers, such as. B. 4- (2-oxo-3-bionylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.

In addition to the two groups of primary light stabilizers mentioned above, it is also possible to use secondary light stabilizers of the antioxidant type which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates the skin. Typical examples of these are amino acids (eg glycine, histidine, Tyrosine, tryptophan) and their derivatives, imidazoles (eg urocanic acid) and their derivatives, peptides such as D, L-camosine, D-camosine, L-camosine and their derivatives (eg anserine), carotenoids, carotenes ( eg α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives (eg dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (eg thioredoxin, glutathione, Cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) as well as their salts, dilauryl thiodipropionate, D isearylthiodipropionate, thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (e.g. B. Buthioninsulfoximine, Homocysteinsulfoximin, Butioninsulfone, penta-, hexa-, Heptathioninsulfoximin) in very low tolerated dosages (eg., Pmol to mol / kg), further (metal) chelators (eg., Α-hydroxy fatty acids, palmitic acid, Phytic acid, lactoferrin), α-hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (eg γ-linolenic acid , Linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (eg ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (eg vitamin E acetate) , Vitamin A and derivatives (vitamin A palmitate) and benzylic resin, benzylic acid, rutinic acid and derivatives thereof, α-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordihydroguaiacetic acid, North ihydroguajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, superoxide dismutase, zinc and its derivatives (e.g. ZnO, ZnSO ₄ ) selenium and its derivatives (eg selenium methionine), stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, Nucleotides, nucleosides, peptides and lipids) of said active substances.

• • Glycerin;
• • Alkylenglycole, wie beispielsweise Ethylenglycol, Diethylenglycol, Propylenglycol, Butylenglycol, Hexylenglycol sowie Polyethylenglycole mit einem durchschnittlichen Molekulargewicht von 100 bis 1.000 Dalton;
• • technische Oligoglyceringemische mit einem Eigenkondensationsgrad von 1,5 bis 10 wie etwa technische Diglyceringemische mit einem Diglyceringehalt von 40 bis 50 Gew.-%;
• • Methyolverbindungen, wie insbesondere Trimethylolethan, Trimethylolpropan, Trimethylolbutan, Pentaerythrit und Dipentaerythrit;
• • Niedrigalkylglucoside, insbesondere solche mit 1 bis 8 Kohlenstoffen im Alkylrest, wie beispielsweise Methyl- und Butylglucosid;
• • Zuckeralkohole mit 5 bis 12 Kohlenstoffatomen, wie beispielsweise Sorbit oder Mannit,
• • Zucker mit 5 bis 12 Kohlenstoffatomen, wie beispielsweise Glucose oder Saccharose;
• • Aminozucker, wie beispielsweise Glutamin;
• • Dialkoholamine, wie Diethanolamin oder 2-Amino-1,3-propandiol.

Hydrotropes such as, for example, ethanol, isopropyl alcohol, or polyols can also be used to improve the flow behavior. Polyols contemplated herein preferably have from 2 to 15 carbon atoms and at least two hydroxyl groups. The polyols may contain other functional groups, in particular amino groups, or be modified with nitrogen. Typical examples are

• • glycerin;
• Alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and polyethylene glycols having an average molecular weight of 100 to 1,000 daltons;
• Technical Oligoglyceringemische with an intrinsic degree of condensation of 1.5 to 10 such as technical Diglyceringemische with a diglycerol content of 40 to 50 wt .-%;
• Methyolverbindungen, in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
• Lower alkyl glucosides, especially those having 1 to 8 carbons in the alkyl radical, such as, for example, methyl and butyl glucoside;
• Sugar alcohols having 5 to 12 carbon atoms, such as sorbitol or mannitol,
• • sugars having 5 to 12 carbon atoms, such as glucose or sucrose;
• • amino sugars, such as glutamine;
• Dialcohols, such as diethanolamine or 2-amino-1,3-propanediol.

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and the other classes of substances listed in Appendix 6, Part A and B of the Cosmetics Regulation. Suitable insect repellents are N, N-diethyl-m-toluamide, 1,2-pentanediol or insect repellent 3535, suitable as a self-tanner is dihydroxyacetone.

As perfume oils are called mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers (lily, lavender, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (aniseed, coriander, caraway, juniper), fruit peel (bergamot, lemon, Oranges), roots (macis, angelica, celery, cardamom, costus, iris, calmus), wood (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), Needles and twigs (spruce, fir, pine, pines), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Furthermore, animal raw materials come into question, such as civet and Castoreum. Typical synthetic fragrance compounds are ester type products, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. The ethers include, for example, benzyl ethyl ether to the aldehydes z. B. the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones z. The alcohols include anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol, and terpineol; the hydrocarbons include mainly the terpenes and balsams. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Also essential oils of lower volatility, which are mostly used as aroma components, are suitable as perfume oils, eg. B. sage oil, camomile oil, clove oil, lemon balm oil, mint oil, cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil. Preferably, bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzylacetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, idol, hedione, Sandelice, citron oil, tangerine oil, orange oil, Allylamylglycolat, Cyclovertal, lavandin oil, Muscat Sage oil, β-damascone, geranium oil Bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, fixolide NP, evemyl, iraldeine gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilllat, irotyl and floramate alone or in mixtures.

Dyes which may be used for cosmetic purposes suitable and approved substances, such as those in the publication "Cosmetic Dyes" of the Dye Commission of Deutsche Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pp. 81-196 are compiled. These dyes are usually used in concentrations of 0.001 to 0.1 wt .-%, based on the total mixture.

Typical examples of antimicrobial agents are preservatives having specific activity against gram-positive bacteria such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether, chlorhexidine (1,6-di- (4-chlorophenyl-biguanido) -hexane) or TCC (3,4,4'-trichlorocarbanilide). Also, numerous fragrances and essential oils have antimicrobial properties. Typical examples are the active ingredients eugenol, menthol and thymol in clove, mint and thyme oil. An interesting natural deodorant is the terpene alcohol farnesol (3,7,11-trimethyl-2,6,10-dodecatrien-1-ol), which is present in lime blossom oil and has a lily-of-the-valley odor. Glycerol monolaurate has also proven itself as a bacteriostat. The proportion of additional germ-inhibiting agents is usually about 0.1 to 2% by weight, based on the solids content of the preparations.

The total amount of auxiliaries and additives may be 1 to 50, preferably 5 to 40 wt .-% - based on the means - amount. The preparation of the agent can be carried out by conventional cold or hot processes; It is preferable to work according to the phase inversion temperature method.

Examples

example 1

In a stirred reactor, 601 g (2.9 mol) of coconut fatty acid, 303 g (2.08 mol), adipic acid and 1.6 g of hypophosphoric acid were introduced and heated to 70 ° C under reduced pressure of 20 mbar. Subsequently, 618 g (4.15 mol) of triethanolamine were added dropwise in portions and the temperature was increased simultaneously to 120 ° C. After completion of the addition, the batch was heated to 170 ° C, the pressure lowered to 3 mbar and the mixture was stirred for a period of 2.5 h at these conditions until the acid number had dropped to a value below 5 mg KQH / g , Subsequently, the mixture was cooled to 60 ° C and the vacuum was broken by introducing nitrogen.

For the quaternization 483 g of the reaction mixture over a period of 1 h at such a rate with 171 g (1.357 mol) of dimethyl sulfate were added that the temperature did not rise above 60 to 70 ° C. After completion of the addition, the mixture was allowed to stir for a further 3 hours and then added to 164 g of water. A transparent yellow esterquat solution having a concentration of 80% by weight and an acid number of 6.05 was obtained.

Example 2

In a stirred reactor, 550 g (2.0 mol) of partially hydrogenated palm oil fatty acid, 212 g (1.5 mol) of adipic acid and 1 g of sodium phosphite were placed and heated to 70 ° C under reduced pressure of 20 mbar. Subsequently, 434 g (2.9) of triethanolamine were added dropwise in portions and the temperature was increased simultaneously to 120 ° C. After completion of the addition, the batch was heated to 170 ° C, the pressure lowered to 3 mbar and the mixture was stirred for a period of 2.5 h at these conditions until the acid number had dropped to a value below 5 mg KOH / g , Subsequently, the mixture was cooled to 60 ° C and the vacuum was broken by introducing nitrogen.

For the quaternization, 593 g (1.54 mol) of the reaction mixture were admixed with 184 g (1.46 mol) of dimethyl sulfate over a period of 1 h at a rate such that the temperature did not rise above 70 to 80 ° C. After completion of the addition, the mixture was allowed to stir for a further 3 hours and then added 777 g of water. There was obtained a yellow ester quatpaste having a concentration of 50% by weight.

Example 3

In a stirred reactor, 550 g (2.0 mol) of partially hydrogenated palm oil fatty acid, 212 g (1.5 mol) of adipic acid and 1 g of sodium phosphite were placed and heated to 70 ° C under reduced pressure of 20 mbar. Subsequently, 434 g (2.9) of triethanolamine were added dropwise in portions and the temperature was increased simultaneously to 120 ° C. After completion of the addition, the batch was heated to 170 ° C, the pressure lowered to 3 mbar and the mixture was stirred for a period of 2.5 h at these conditions until the acid number had dropped to a value below 5 mg KOH / g , Then the mixture was cooled to 60 ° C and the vacuum was broken by passing in nitrogen.

For the quaternization, 473 g of the reaction _{mixture were} admixed over a period of 2 h with 150 g (0.45 mol) of a condensation product of C _12/18 coconut _fatty acid with dimethylaminopropylamine (amidoamine). Subsequently, the mixture was added at such a rate with 203 g (1.61 mol) of dimethyl sulfate, that the temperature did not rise above 70 to 80 ° C. After completion of the addition, the mixture was allowed to stir for a further 3 hours and then added to 1,240 g of water. A liquid ester quatemulsion having a concentration of 40% by weight was obtained. Table 1: Lubricant - Quantities in% by weight - Zusammensetzun9 1 2 3 4 5 6 7 Esterquat according to Example 1 52 39 - 40 19 5 Esterquat according to Example 3 - - 59 - - - - Esterquat according to Example 2 - - - - - 30 - Dehyton ^® PK cocoamidopropyl - 31 - - - - 42 A - - - 9 - Glucopon ^® 215 CSUP fatty alcohol C8-10 polyglycoside - - - 40 - - Castor oil + 18 EO - - 29 - 7 7 2 glycerin - - - 10 - 4 2 A) Condensation product of C _12/18 coconut _fatty acid with dimethylaminopropylamine quaternized with dimethyl sulfate in 85% isopropaniol

Claims (10)

Esterquatzubereitungen, obtainable by reacting alkanolamines and / or polyamines with a mixture of fatty acids and dicarboxylic acids, the resulting esters are optionally alkoxylated and then quaternized in the absence of solvents. Composition according to Claim 1, characterized in that fatty acids of the formula (1) R ¹ CO-OH (I) in which R ¹ CO is an aliphatic, linear or branched acyl radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds and dicarboxylic acids of the formula (II) HOOC- [X] -COOH (II) in which X is an optionally hydroxy-substituted alkylene group having 1 to 10 carbon atoms, is used. Composition according to Claims 1 and / or 2, characterized in that the fatty acids and the dicarboxylic acids are used in a molar ratio of 1:10 to 10: 1. Composition according to at least one of claims 1 to 3, characterized in that one uses the alkanolamines and / or polyamines on the one hand and the sum of fatty acids and dicarboxylic acids on the other hand in a molar ratio of 1: 1.1 to 1: 2.8. Composition according to at least one of claims 1 to 4, characterized in that they further contain fatty acid amidoamines of the formula (IV),

in the R ⁵ CO for a linear or branched, saturated or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or an optionally hydroxy-substituted alkyl radical having 1 to 4 carbon atoms, R ³ and R ^{4 are} independently hydrogen, a (CH ₂ CH ₂ O) _{m is} H or an optionally hydroxy-substituted alkyl radical having 1 to 4 carbon atoms, A is a linear or branched alkylene group having 1 to 6 carbon atoms, n is from 1 to 4 and m is from 1 to 30. Composition according to at least one of claims 1 to 5, characterized in that they further contain quaternized fatty acid amidoamines of the formula (V),

in the R ⁵ CO for a linear or branched, saturated or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or an optionally hydroxy-substituted alkyl radical having 1 to 4 carbon atoms, R ^{3 is} hydrogen, a (CH ₂ CH ₂ O) _m H group or an optionally hydroxy-substituted alkyl radical having 1 to 4 carbon atoms, R ^{4 is} R ⁵ CO, hydrogen, a (CH ₂ CH ₂ O) _m H group or an optionally hydroxy-substituted alkyl radical having 1 to 4 carbon atoms, R ^{6 is} a An alkyl group having 1 to 4 carbon atoms, A is a linear or branched alkylene group having 1 to 6 carbon atoms, n is a number from 1 to 4, m is a number from 1 to 30 and X is halide or alkyl sulfate. Agent according to at least one of Claims 1 to 6, characterized in that it furthermore comprises betaines of the formula (VI)

in the R ⁷ for alkyl and / or alkenyl radicals having 6 to 22 carbon atoms, R ^{8 is} hydrogen or alkyl radicals having 1 to 4 carbon atoms, R ^{9 is} alkyl radicals having 1 to 4 carbon atoms, p is from 1 to 6 and A is a Alkali and / or alkaline earth metal or ammonium. Composition according to at least one of Claims 1 to 7, characterized in that it further comprises betaines of the formula (VII)

in which R ¹⁰ CO is an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, m is a number from 1 to 3 and R ⁸ , R ⁹ , p and A have the meanings given above. Process for the preparation of esterquatern preparations in which alkanolamines and / or polyamines are reacted with a mixture of fatty acids and dicarboxylic acids, the resulting esters are optionally alkoxylated and then quaternized, characterized in that the quaternization is carried out in the absence of solvents. Use of agents according to claim 1 in surface-active preparations.