EP1263924B1 - Liquid soaps - Google Patents

Abstract

The invention relates to novel liquid soaps, containing (a) 0.1 to 20 wt. % sugar tensides chosen from the following group: (a1) alkyl and/or alkenyl oligoglycosides and/or (a2) fatty acid-N-alkylpoly-hydroxyalkylamides; (b) 0.1 to 20 wt. % fatty acid partial glycerides, (c) 0.5 to 34 wt. % anionic, non-ionic and/or amphoteric co-tensides and (d) 0.5 to 30 wt. % fatty acids, on the condition that these quantities are supplemented with water and optionally, other auxiliary materials and additives up to 100 wt. %.

Description

Field of the Invention

The invention relates to new liquid soap formulations, which are essential components selected sugar surfactants, fatty acid partial glycerides and fatty acids and other co-surfactants contain and their use in liquid soap preparations.

State of the art

The large number of liquid soaps that are offered to the consumer make it clear that there is a constant need among consumers for further improved products especially due to improved stabilities but also good dermatological tolerance, stronger Foaming power, higher creaminess, rinsing power and skin feeling or regreasing distinguished. In contrast, soap manufacturers are looking for soap-containing formulations that in addition to unchanged stability also have constant viscosities and also the allow easy incorporation of hydrolysis-sensitive substances.

US-A-5 296 158 discloses liquid soap preparations which stable in storage even at alkaline pH values and are viscous can produce a creamy foam; these soap preparations contain fatty acid, surfactants and fatty acid partial glycerides.

The complex object of the present invention was therefore to use liquid soaps with to provide the complex requirement profile described.

Description of the invention

(a) 0,1 bis 20 Gew.-% Zuckertenside ausgewählt aus der Gruppe, die gebildet wird von (a1) Alkyl- und/oder Alkenyloligoglykosiden und/oder (a2) Fettsäure-N-alkylpoly-hydroxyalkylamiden,

(b) 0,1 bis 20 Gew.-% Fettsäurepartialglyceride der Formel (III),

in der R⁴CO für einen linearen oder verzweigten, gesättigten und/oder ungesättigten Acylrest mit 12 bis 18 Kohlenstoffatomen, R⁵ und R⁶ unabhängig voneinander für R⁴CO oder OH und die Summe (m+n+p) für 0 oder Zahlen von 1 bis 100 steht, mit der Maßgabe, daß mindestens einer der beiden Reste R⁵ und R⁶ OH bedeutet,

(c) 0,5 bis 34 Gew.-% Co-Tenside, die ausgewählt sind aus der Gruppe, die gebildet wird von alkoxylierten Carbonsäurestern, Monoglycerid(ether)sulfaten, Olefinsulfonaten, Betainen und Fettsäurepolyglycolestersulfaten sowie deren Gemischen,

(d) 0,5 bis 30 Gew.-% Fettsäuren

mit der Maßgabe, daß sich die Mengenangaben mit Wasser und gegebenenfalls weiteren Hilfs- und Zusatzstoffen zu 100 Gew.-% ergänzen.The invention relates to liquid soaps containing

(a) 0.1 to 20% by weight sugar surfactants selected from the group formed by (a1) alkyl and / or alkenyl oligoglycosides and / or (a2) fatty acid N-alkyl polyhydroxyalkylamides,

(b) 0.1 to 20% by weight of fatty acid partial glycerides of the formula (III),

in the R ⁴ CO for a linear or branched, saturated and / or unsaturated acyl radical having 12 to 18 carbon atoms, R ⁵ and R ⁶ independently of one another for R ⁴ CO or OH and the sum (m + n + p) for 0 or numbers is from 1 to 100, with the proviso that at least one of the two radicals R ⁵ and R ^{6 is} OH,

(c) 0.5 to 34% by weight of co-surfactants selected from the group consisting of alkoxylated carboxylic acid esters, monoglyceride (ether) sulfates, olefin sulfonates, betaines and fatty acid polyglycol ester sulfates and mixtures thereof,

(d) 0.5 to 30% by weight of fatty acids

with the proviso that the quantities given add up to 100% by weight with water and possibly other auxiliaries and additives.

Another object of the invention is the use of these agents in liquid soap preparations.

Surprisingly, it was found that liquid soaps made from selected sugar surfactants, Partial glycerides, fatty acids and other co-surfactants can produce partial glycerides via a longer storage periods are stable. It is particularly surprising that it is at the alkaline pH there is no immediate hydrolysis of the partial glyceride, for example glycerol monooleate or the hydrolysis have no influence on the stability and viscosity of the liquid soap formulations Has. Another advantage is the stable and creamy foam and the regreasing or Skin feel.

Alkyl and / or alkenyl oligoglycosides

Alkyl and alkenyl oligoglycosides which make up the sugar surfactant component (a1) are known nonionic surfactants which follow the formula (I) R ¹ O- [G] _p (I) in which R ^{1 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. Representative of the extensive literature here is the review by Biermann et al. in Starch /force 45, 281 (1993), B.Salka in Cosm.Toil. 108, 89 (1993) and J.Kahre et al. in SÖFW-Journal issue 8, 598 (1995) .

The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (I) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer, and especially here can assume the values p = 1 to 6, the value p for a specific 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 is in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ¹ can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic 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 ¹ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyial alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, as described above, 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.

The preparations according to the invention can contain the alkyl and / or alkenyl oligoglycosides in quantities from 0.1 to 20, preferably 0.5 to 10 and in particular 1 to 5% by weight, based on the total composition - contain.

Fatty acid N-alkyl polyhydroxyalkylamides

Fatty acid N-alkylpolyhydroxyalkylamides which make up sugar surfactant component (a2) are nonionic surfactants which follow the formula (II),

in which R ² CO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ³ for an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 12 carbon atoms and 3 to 10 hydroxyl groups. The fatty acid N-alkyl polyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. With regard to the processes for their production, reference is made to US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798 and international patent application WO 92/06984 . An overview of this topic by H. Kelkenberg can be found in Tens.Surf.Deterg. 25 , 8 (1988).

The fatty acid N-alkylpolyhydroxyalkylamides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (III) :

The fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula ( III ) in which R ^{3 is} an alkyl group and R ² CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, Oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures. Fatty acid N-alkylglucamides of the formula (III) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C _12/14 coconut fatty acid or a corresponding derivative are particularly preferred. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

The use of the fatty acid N-alkylpolyhydroxyalkylamides is also the subject of a large number of publications. Their use as a thickener is known, for example, from European patent application EP 0285768 A1 (Hüls). French published patent application FR 1580491 A (Henkel) describes aqueous detergent mixtures based on sulfates and / or sulfonates, nonionic surfactants and optionally soaps, which contain fatty acid N-alkylglucamides as foam regulators. Mixtures of short- and long-chain glucamides are described in German patent DE 4400632 C1 (Henkel). The German published applications DE 4326959 A1 and DE 4309567 A1 (Henkel) also report on the use of glucamides with longer alkyl residues than pseudoceramides in skin care products and on combinations of glucamides with protein hydrolyzates and cationic surfactants in hair care products. International patent applications WO 92/06153, WO 92/06156, WO 92/06157, WO 92/06158, WO 92/06159 and WO 92/06160 (Procter & Gamble) relate to mixtures of fatty acid N-alkylglucamides with anionic surfactants, Surfactants with a sulfate and / or sulfonate structure, ether carboxylic acids, ether sulfates, methyl ester sulfonates and nonionic surfactants. The use of these substances in a wide variety of washing, rinsing and cleaning agents is described in international patent applications WO 92/06152, WO 92/06154, WO 92/06155, WO 92/06161, WO 92/06162, WO 92/06164, WO 92 / 06170, WO 92/06171 and WO 92/06172 (Procter & Gamble).
The preparations according to the invention can contain the fatty acid N-alkylpolyhydroxyalkylamides in amounts of 0.1 to 20, preferably 0.5 to 10 and in particular 1 to 5% by weight, based on the total composition.

partial glycerides

in der R⁴CO für einen linearen oder verzweigten, gesättigten und/oder ungesättigten Acylrest mit 12 bis 18 Kohlenstoffatomen, R⁵ und R⁶ unabhängig voneinander für R4CO oder OH und die Summe (m+n+p) für 0 oder Zahlen von 1 bis 100, vorzugsweise 5 bis 25 steht, mit der Maßgabe, daß mindestens einer der beiden Reste R⁵ und R⁶ OH bedeutet. Typische Beispiele sind Mono- und/oder Diglyceride auf Basis von Laurinsäure, Isotridecansäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure und Elaeostearinsäure sowie deren technische Mischungen. Vorzugsweise werden technische Laurinsäureglyceride, Palmitinsäureglyceride, Stearinsäureglyceride und/oder Isostearinsäureglyceride und insbesondere Olsäuremonoglyceride eingesetzt, welche einen Monoglyceridanteil im Bereich von 50 bis 95, vorzugsweise 60 bis 90 Gew.-% aufweisen.Partial glycerides which form component (b), that is to say monoglycerides, diglycerides and their technical mixtures, may still contain small amounts of triglycerides due to the production process. The partial glycerides follow the formula ( VI )

in which R ⁴ CO is a linear or branched, saturated and / or unsaturated acyl radical having 12 to 18 carbon atoms, R ⁵ and R ⁶ independently of one another for R4CO or OH and the sum (m + n + p) for 0 or numbers of 1 to 100, preferably 5 to 25, with the proviso that at least one of the two radicals R ⁵ and R ^{6 is} OH. Typical examples are mono- and / or diglycerides based on lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid and elaeostearic acid and their technical mixtures. Technical lauric acid glycerides, palmitic acid glycerides, stearic acid glycerides and / or isostearic acid glycerides and in particular oleic acid monoglycerides are used which have a monoglyceride content in the range from 50 to 95, preferably 60 to 90% by weight.

The preparations according to the invention can contain the fatty acid partial glycerides in amounts of 0.1 to 20 preferably 0.5 to 10 and in particular 1 to 5 wt .-% - based on the total composition - contain.

Anionic, nonionic and / or amphoteric co-surfactants

Anionic, nonionic and / or amphoteric surfactants are suitable as co-surfactants, which may additionally be present as component (c). Typical examples of anionic surfactants are soaps, alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxymischogether sulfate sulfate, hydroxymischogether sulfate sulfate, hydroxymischogether sulfate sulfates, , Mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids, such as, for example, acyl lactylates, acyl tartrates, acyl glutamates and acyl asucate fats (alkyl oligoglucate), vegetable olate proteinate, alkyl oligoglucate glyphate, phosphates. If the anionic surfactants contain polyglycol ether chains, these can have a conventional, but preferably a narrow, homolog distribution. Typical examples of non-ionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, optionally partially oxidized alk (en) yl oligoglycosides or especially glucoramide acid-based vegetable derivatives, , Polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are exclusively known compounds. With regard to the structure and manufacture of these substances, reference is made to relevant reviews, for example, J.Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, pp. 54-124 or J.Falbe (ed.), " Tenside und Mineralöladditive ", Thieme Verlag, Stuttgart, 1978, pp. 123-217 . Typical examples of particularly suitable mild, ie particularly skin-compatible, surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid taurides, fatty acid glutamates, α-olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines, amphoacetals and / or protein fatty acid condensates, preferably based on wheat proteins.

In a particular embodiment of the invention, selected cationic surfactants such as Dehyquart® E [N- (2-hydroxyhexadecyl-1) -N, N-dimethyl-N-2-hydroxyethylammonium chloride] and Gluadin® WQ (cationic protein derivative) from Cognis in question.

Monoglyceride (ether) sulfates

in der R⁷CO für einen linearen oder verzweigten Acylrest mit 6 bis 22 Kohlenstoffatomen, x, y und z in Summe für 0 oder für Zahlen von 1 bis 30, vorzugsweise 2 bis 10, und X für ein Alkali- oder Erdalkalimetall steht. Typische Beispiele für im Sinne der Erfindung geeignete Monoglycerid(ether)sulfate sind die Umsetzungsprodukte von Laurinsäuremonoglycerid, Kokosfettsäuremonoglycerid, Palmitinsäuremonoglycerid, Stearinsäuremonoglycerid, Ölsäuremonoglycerid und Talgfettsäuremonoglycerid sowie deren Ethylenoxidaddukte mit Schwefeltrioxid oder Chlorsulfonsäure in Form ihrer Natriumsalze. Vorzugsweise werden Monoglyceridsulfate der Formel (V) eingesetzt, in der R⁷CO für einen linearen Acylrest mit 8 bis 18 Kohlenstoffatomen steht. Vorzugsweise werden die Monoglycerid(ether)sulfate als trockente Granulate oder Pulver eingesetzt, die man beispielsweise durch Trocknung wäßriger Pasten in einem Flashdryer erhalten kann.Monoglyceride sulfates and monoglyceride ether sulfates are known substances which can be obtained by the relevant methods of preparative organic chemistry. The usual starting point for their production is triglycerides, which, if appropriate, are transesterified to the monoglycerides after ethoxylation and subsequently sulfated and neutralized. It is also possible to react the partial glycerides with suitable sulfating agents, preferably gaseous sulfur trioxide or chlorosulfonic acid [cf. EP 0561825 B1, EP 0561999 B1 (Henkel)]. If desired, the neutralized substances can be subjected to ultrafiltration in order to reduce the electrolyte content to a desired level [ DE 4204700 A1 (Henkel)]. Overviews of the chemistry of the monoglyceride sulfates are, for example, by AK Biswas et al. in J.Am.Oil.Chem.Soc. 37 , 171 (1960) and FU Ahmed J.Am.Oil.Chem. Soc. 67 , 8 (1990) . The monoglyceride (ether) sulfates to be used in accordance with the invention follow the formula ( V ),

in which R ⁷ CO stands for a linear or branched acyl radical with 6 to 22 carbon atoms, x, y and z in total for 0 or for numbers from 1 to 30, preferably 2 to 10, and X stands for an alkali or alkaline earth metal. Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride as well as their ethylene oxide adducts or their formulated with sulfuric acid trioxide. Monoglyceride sulfates of the formula ( V ) are preferably used, in which R ⁷ CO represents a linear acyl radical having 8 to 18 carbon atoms. The monoglyceride (ether) sulfates are preferably used as dry granules or powders, which can be obtained, for example, by drying aqueous pastes in a flash dryer.

Betaine

in der R¹⁰ 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, q für Zahlen von 1 bis 6 und X 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. Weiterhin kommen auch Carboxyalkylierungsprodukte von Amidoaminen in Betracht, die der Formel (VII) folgen,

in der R¹¹CO 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, q und X 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, Isostearinsäure, 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-KokosfettsäureN,N-dimethylaminopropylamid mit Natriumchloracetat.Betaines are known substances which are predominantly produced by carboxyalkylation, preferably carboxymethylation, of aminic compounds. The starting materials are preferably condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, one mol of salt being formed per mole of betaine. The addition of unsaturated carboxylic acids, such as acrylic acid, is also possible. Regarding the nomenclature and in particular the distinction between betaines and "real" amphoteric surfactants, reference is made to U. Ploog's contribution in Seifen-Öle-Fette-Wwachs, 198 , 373 (1982) . Further overviews 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.Surf. Det. 23: 309 (1986), R. Bilbo 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 which R ¹⁰ for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R ⁸ for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ⁹ for alkyl radicals with 1 to 4 carbon atoms, q for numbers from 1 to 6 and X for a Alkali and / or alkaline earth metal or ammonium. Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C _12/14 -Kokosalkyldimethylamin, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearyl, oleyl, C _16/18 tallow alkyl dimethyl amine and technical mixtures thereof. Carboxyalkylation products of amidoamines which follow the formula (VII) are also suitable,

in which R ¹¹ CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, m represents numbers from 1 to 3 and R ⁸ , R ⁹ , q and X have the meanings given above. Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gadoleic acid and arachic acid, arachic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of C _8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate.

fatty acid polyglycol ester

Fatty acid polyglycolsulfates preferably follow the formula (VIII) , R ¹² COO (AO) _w SO ₃ X (VIII) in the R ¹² CO for a linear or branched, saturated or unsaturated acyl radical having 6 to 22 carbon atoms, w for numbers of 1 to 3 on average and AO for a CH ₂ CH ₂ O-, CH ₂ CH (CH ₃ ) O- and / or CH (CH ₃ ) CH ₂ O radical and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium, are known anionic surfactants and are prepared by sulfating the corresponding fatty acid polyglycol esters. These in turn can be obtained using the relevant preparative processes in organic chemistry. For this purpose, ethylene oxide, propylene oxide or their mixture is added to the corresponding fatty acids in a random or block distribution, this reaction being acid-catalyzed, but preferably in the presence of bases, such as sodium methylate or calcined hydrotalcite. If a degree of alkoxylation of 1 is desired, the intermediates can also be prepared by esterifying the fatty acids with an appropriate alkylene glycol. The sulfation of the fatty acid polyglycol esters can be carried out in a manner known per se using chlorosulfonic acid or preferably gaseous sulfur trioxide, the molar ratio between fatty acid polyglycol ester and sulfating agent being in the range from 1: 0.95 to 1: 1.2, preferably 1: 1 to 1: 1 , 1 and the reaction temperature can be 30 to 80 and preferably 50 to 60 ° C. It is also possible to undersulfate the fatty acid polyglycol esters, ie to use significantly fewer sulfating agents than would be stoichiometrically required for complete conversion. If, for example, one chooses molar amounts of fatty acid polyglycol ester to sulfating agent from 1: 0.5 to 1: 0.95, mixtures of fatty acid polyglycol ester sulfates and fatty acid polyglycol esters are obtained, which are also advantageous for a whole range of applications. In order to avoid hydrolysis, it is very important to carry out the neutralization at a pH in the range from 5 to 9, preferably 7 to 8. Typical examples of suitable starting materials are the addition products of 1 to 3 mol of ethylene oxide and / or propylene oxide, but preferably the adducts with 1 mol of ethylene oxide or 1 mol of propylene oxide with caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, Palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, which are then sulfated and neutralized as described above. Fatty acid polyglycol ester sulfates of the formula ( VIII ) are preferably used in which R ¹² CO stands for an acyl radical having 12 to 18 carbon atoms, x for an average of 1 or 2, AO for a CH ₂ CH ₂ O group and X for sodium or ammonium, such as for example lauric acid + 1EO sulfate sodium salt, lauric acid + 1EO sulfate ammonium salt, coconut fatty acid + 1E0 sulfate sodium salt, coconut fatty acid + 1EO sulfate ammonium salt, tallow fatty acid + 1EO sulfate sodium salt, tallow fatty acid + 1EO sulfate and their ammonium salt mixtures.

olefin

The liquid soaps according to the invention can contain olefin sulfonates which are usually obtained by addition of SO ₃ onto olefins of the formula (IX) R ¹⁴ -CH = CH-R ¹³ (IX) where R ¹⁴ and R ¹³ independently represent H or alkyl radicals having 1 to 20 carbon atoms, with the proviso that R ¹⁴ and R ¹³ together have at least 6 and preferably 10 to 16 carbon atoms. Regarding production and use, see the review article J.Am.Oil. Soc. 55 , 70 (1978) .

Internal olefin sulfonates, but preferably α-olefin sulfonates, can be used which result when R ¹⁴ or R ^{13 are} hydrogen. Typical examples of olefin sulfonates used are the sulfonation products which are obtained by treating SO ₃ with 1-, 2-butene, 1-, 2-, 3-hexene, 1-, 2-, 3-, 4-octene, 1- , 2-, 3-, 4-, 5-decene, 1-, 2-, 3-, 4-, 5-, 6- dodecene, 1-, 2-, 3-, 4-, 5-, 6- , 7-tetradecene, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-hexadecene, 1-, 2-, 3-, 4-, 5-, 6-, 7- , 8-, 9-octadecene, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-eicosen and 1-, 2-, 3-, 4- , 5-, 6-, 7-, 8-, 9-, 10- and 11-docosen. After sulfonation has taken place, neutralization is carried out, after which the olefin sulfonate is present in the mixture as an alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium, glucammonium, preferably sodium salt. Both olefin sulfonates in aqueous paste, preferably at a pH of 7 to 10, and also as anhydrous products, preferably as granules, can be used, as can be obtained by conventional spray drying, drying in a thin layer ("flash dryer") DE 19710152 C1 (Henkel) or in a fluidized bed dryer ("sket system").

Alkoxylated carboxylic acid esters

Alkoxylated carboxylic acid esters are known from the prior art. For example, such alkoxylated carboxylic acid esters can be obtained by reacting alkoxylated carboxylic acids with alcohols. For the purposes of the present invention, however, the compounds are preferably prepared by reacting carboxylic acid esters with alkylene oxides using catalysts, in particular using calcined hydrotalcite according to German Offenlegungsschrift DE 3914131 A, which provide compounds with a restricted homolog distribution. Both carboxylic acid esters of monohydric alcohols and polyhydric alcohols can be alkoxylated by this process. Alkoxylated carboxylic acid esters of the formula (X) are preferably used in accordance with the present invention, R ¹⁵ CO (AlkO) _n OR ¹⁶ (X) in which R ¹⁵ CO stands for an aliphatic acyl radical having 6 to 30 C atoms, AlkO for alkylene oxide, n for numbers from 1 to 30 and R ¹⁶ for an aliphatic alkyl radical with 1 to 8 carbon atoms. AlkO stands for the alkylene oxides which are reacted with the carboxylic acid esters and include ethylene oxide, propylene oxide and / or butylene oxide, preferably ethylene oxide and / or propylene oxide, in particular ethylene oxide alone.

Alkoxylated carboxylic acid esters of the formula (X) are particularly suitable, in which R ¹⁵ CO is a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and in particular 10 to 18 carbon atoms, AlkO for ethylene oxide and / or propylene oxide, n on average for numbers 5 to 20 and R ^{16 is} an aliphatic alkyl radical having 1 to 8, preferably 1 to 4 carbon atoms and in particular methyl. Preferred acyl radicals are derived from carboxylic acids having 6 to 22 carbon atoms of natural or synthetic origin, in particular from linear, saturated and / or unsaturated fatty acids, including technical mixtures thereof, as are obtainable by fat cleavage from animal and / or vegetable fats and oils, for example from coconut oil, palm kernel oil, palm oil, soybean oil, sunflower oil, rape oil, cottonseed oil, fish oil, beef tallow and lard. Examples of such carboxylic acids are 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 / or erucic acid ,

Particularly suitable are alkoxylated carboxylic acid esters of the formula ( X ) in which R ¹⁵ CO is a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 10 to 18 carbon atoms, AlkO for ethylene oxide and / or propylene oxide, preferably ethylene oxide, n for numbers from 5 to 20 and R ^{16 represents} a methyl radical. Examples of such compounds are methyl lauric acid, methyl coconut fatty acid and methyl tallow fatty acid alkoxylated with an average of 5, 7, 9 or 11 mol ethylene oxide.

The liquid soaps according to the invention can contain the surfactants in amounts of 0.5 to 34, preferably 1 to 30 and in particular 5 to 25 wt .-% - based on the total composition - contain.

fatty acids

Fatty acids which form component (d) are to be understood as aliphatic carboxylic acids of the formula ( XI ) R ¹⁷ CO-OH (XI) R ¹⁷ CO-OH (XI) in which R ¹⁷ CO represents an aliphatic, linear or branched acyl radical having 6 to 22, preferably 12 to 18 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, 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 technical mixtures thereof , which occur, for example, in the pressure splitting of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or in the dimerization of unsaturated fatty acids. Technical fatty acids with 12 to 18 carbon atoms such as coconut, palm, palm kernel or tallow fatty acid are preferred.

The preparations according to the invention can preferably contain the fatty acids in amounts of 0.5 to 30 1 to 20 and in particular 5 to 15 wt .-% - based on the total composition - contain.

liquid soaps

(a) 0,1 bis 20, vorzugsweise 0,5 bis 10 und insbesondere 1 bis 5 Gew.-% Zuckertenside ausgewählt aus der Gruppe, die gebildet wird von (a1) Alkyl- und/oder Alkenyloligoglykosiden und/oder (a2) Fettsäure-N-alkylpoly-hydroxyalkylamiden,

(b) 0,1 bis 20, vorzugsweise 0,5 bis 10 und insbesondere 1 bis 5 Gew.-% Fettsäurepartialglyceride,

(c) 0,5 bis 34, vorzugsweise 1 bis 30 und insbesondere 5 bis 25 Gew.-% anionische, nichtionische und/oder amphotere Co-Tenside,

(d) 0,5 bis 30, vorzugsweise 1 bis 20 und insbesondere 5 bis 15 Gew.-% Fettsäuren

mit der Maßgabe, daß sich die Mengenangaben mit Wasser, vorzugsweise 40 bis 65 und insbesondere 50 bis 60 Gew.-% Wasser, gegebenenfalls mit weiteren üblichen Hilfs- und Zusatzstoffen zu 100 Gew.-% ergänzen.Liquid soaps with constant viscosity, high stability and particularly advantageous skin feel contain the ingredients in the following amounts - based on the total composition -:

(a) 0.1 to 20, preferably 0.5 to 10 and in particular 1 to 5% by weight of sugar surfactants selected from the group formed by (a1) alkyl and / or alkenyl oligoglycosides and / or (a2) fatty acid N-alkyl poly-hydroxyalkylamides,

(b) 0.1 to 20, preferably 0.5 to 10 and in particular 1 to 5% by weight of fatty acid partial glycerides,

(c) 0.5 to 34, preferably 1 to 30 and in particular 5 to 25% by weight of anionic, nonionic and / or amphoteric co-surfactants,

(d) 0.5 to 30, preferably 1 to 20 and in particular 5 to 15% by weight of fatty acids

with the proviso that the amounts given with water, preferably 40 to 65 and in particular 50 to 60% by weight of water, are optionally supplemented with other customary auxiliaries and additives to 100% by weight.

The liquid soaps according to the invention have a pH of 7 to 11, preferably 8 to 10 and in particular 8.5 to 9.5.

Other auxiliaries and additives

These agents can also be used as further auxiliaries and additives, oil bodies, emulsifiers, pearlescent waxes, Consistency agents, thickeners, superfatting agents, stabilizers, polymers, silicone compounds, Fats, waxes, lecithins, phospholipids, biogenic agents, swelling agents, film formers, tyrosine inhibitors (Depigmenting agents), hydrotropes, solubilizers, preservatives, perfume oils, dyes and the like included.

oil body

Guerbet alcohols based on fatty alcohols with 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C ₆ -C ₂₂ fatty acids with linear or branched C ₆ -C ₂₂ fatty alcohols or esters of branched C ₆ -C ₄ come as oil bodies, for example ₁₃ -carboxylic acids with linear or branched C ₆ -C ₂₂ -fatty alcohols, such as myristyl myristate, myristyl palmitate, myristyl stearate, Myristylisostearat, myristyl, Myristylbehenat, Myristylerucat, cetyl myristate, cetyl palmitate, cetyl stearate, Cetylisostearat, cetyl oleate, cetyl behenate, Cetylerucat, Stearylmyristat, stearyl palmitate, stearyl stearate , Stearylisostearat, stearyl oleate, stearyl behenate, Stearylerucat, isostearyl, isostearyl palmitate, Isostearylstearat, isostearyl isostearate, Isostearyloleat, isostearyl behenate, Isostearyloleat, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, Oleylbehenat, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl, Behenylisostearat, behenyl oleate, Behenyl behenate, behenylerucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. In addition, esters of linear C ₆ -C ₂₂ fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of C ₁₈ -C ₃₈ alkylhydroxycarboxylic acids with linear or branched C ₆ -C ₂₂ fatty alcohols (cf. DE 19756377 A1 ), in particular dioctyl malates, esters of linear and / or branched fatty acids with polyhydric alcohols (such as propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides based on C ₆ -C ₁₀ fatty acids, liquid mono- / di / triglyceride mixtures based on C ₆ -C ₁₈ fatty acids (cf. EP 97/00434 ), esters of C ₆ -C ₂₂ fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C ₂ -C ₁₂ dicarboxylic acids with linear or branched alcohols with 1 to 22 carbon atoms or polyols with 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C ₆ -C ₂₂ fatty alcohol carbonates such as dicaprylyl carbonates (Cetiol® CC), Guerbet carbonates based on fatty alcohols with 6 to 18, preferably 8 to 10 C atoms, esters of benzoic acid with linear and / or branched C ₆ -C ₂₂ alcohols (e.g. Finsolv® TN ), linear or branched, symmetrical or asymmetrical dialkyl ethers with 6 to 22 carbon atoms per alkyl group, such as dicaprylyl ether (Cetiol® OE), ring opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicones, silicon methicone types etc.) and / or aliphatic or naphthenic hydrocarbons , such as squalane, squalene or dialkylcyclohexanes.

emulsifiers

Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/ oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 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 400 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;

Block-Copolymere z.B. Polyethylenglycol-30 Dipolyhydroxystearate;

Polymeremulgatoren, z.B. Pemulen-Typen (TR-1,TR-2) von Goodrich;

Polyalkylenglycole sowie

Glycerincarbonat.

Suitable emulsifiers are, for example, nonionic surfactants from at least one of the following groups:

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms, with alkylphenols with 8 to 15 carbon atoms in the alkyl group and alkylamines with 8 to 22 carbon atoms in the alkyl radical;

Alkyl and / or alkenyl oligoglycosides with 8 to 22 carbon atoms in the alk (en) yl radical and their ethoxylated analogs;

Addition products of 1 to 15 moles of ethylene oxide with castor oil and / or hardened castor oil;

Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil;

Partial esters of glycerol and / or sorbitan with unsaturated, linear or saturated, branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 mol ethylene oxide;

Partial esters of polyglycerol (average degree of self-condensation 2 to 8), polyethylene glycol (molecular weight 400 to 5000), trimethylolpropane, pentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosaturated (e.g. cellulose) or unsaturated (e.g. cellulose) , linear or branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts 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 with 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;

Lanolin alcohol;

Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;

Block copolymers, for example polyethylene glycol 30 dipolyhydroxystearate;

Polymer emulsifiers, for example Pemulen types (TR-1, TR-2) from Goodrich;

Polyalkylene glycols as well

Glycerol carbonate.

The adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols or with castor oil are known, commercially available products. These are mixtures of homologs, the average degree of alkoxylation of which is the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate, with which the addition reaction is carried out. C _12/18 fatty acid _monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE 2024051 PS as refatting agents for cosmetic preparations.

Sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, Sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, Sorbitan sesquierucate, sorbitan dierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitan sesquicinoleate, Sorbitan diricinoleate, sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, Sorbitan dihydroxystearate, sorbitan trihydroxystearate, sorbitan monotartrate, sorbitan sesquitartrate, Sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate, Sorbitan Tricitrate, Sorbitan Monomaleate, Sorbitan Sesquimaleate, Sorbitan Dimaleate, Sorbitan Trimaleate as well as their technical mixtures. Addition products from 1 to 30 are also suitable, preferably 5 to 10 moles of ethylene oxide to the sorbitan esters mentioned.

Typical examples of suitable polyglycerol esters are polyglyceryl-2 dipolyhydroxystearate (Dehymuls® PGPH), polyglycerol-3-diisostearals (Lameform® TGI), polyglyceryl-4 isostearates (Isolan® GI 34), Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3 Diisostearate (Isolan® PDI), Polyglyceryl-3 Methyl glucose 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 Polyricinoleate (Admul® WOL 1403) Polyglyceryl Dimerate isostearates and their mixtures. Examples of other suitable polyol esters are mono-, di- and triesters of trimethylolpropane, optionally reacted with 1 to 30 mol of ethylene oxide or pentaerythritol with lauric acid, coconut fatty acid, tallow fatty acid, palmitic acid, stearic acid, Oleic acid, behenic acid and the like.

Ampholytic surfactants can also be used as emulsifiers. Ampholytic surfactants are surface-active compounds which, in addition to a C _8/18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or - SO ₃ H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 C. Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12/18 acylsarcosine. Finally, cationic surfactants are also suitable as emulsifiers, those of the esterquat type, preferably methylquaternized difatty acid triethanolamine ester salts, being particularly preferred.

Fats and waxes

wobei R typischerweise für lineare aliphatische Kohlenwasserstoffreste mit 15 bis 17 Kohlenstoffatomen und bis zu 4 cis-Doppelbindungen steht. Als Beispiele für natürliche Lecithine seien die Kephaline genannt, die auch als Phosphatidsäuren bezeichnet werden und Derivate der 1,2-Diacyl-sn-glycerin-3-phosphorsäuren darstellen. Dem gegenüber versteht man unter Phospholipiden gewöhnlich Mono- und vorzugsweise Diester der Phosphorsäure mit Glycerin (Glycerinphosphate), die allgemein zu den Fetten gerechnet werden. Daneben kommen auch Sphingosine bzw. Sphingolipide in Frage.Typical examples of fats are glycerides, ie solid or liquid vegetable or animal products, which essentially consist of mixed glycerol esters of higher fatty acids. Natural waxes, such as candelilla wax, camauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, come among others , Ouricury wax, montan wax, beeswax, shellac wax, walrus, lanolin (wool wax), pretzel fat, ceresin, ozokerite (earth wax), petrolatum, paraffin waxes, micro waxes; chemically modified waxes (hard waxes), such as montan ester waxes, Sasol waxes, hydrogenated jojoba waxes and synthetic waxes, such as polyalkylene waxes and polyethylene glycol waxes. In addition to fats, fat-like substances such as lecithins and phospholipids can also be used as additives. The person skilled in the art understands the term lecithins as those glycerophospholipids which are formed from fatty acids, glycerol, phosphoric acid and choline by esterification. Lecithins are therefore often referred to in the specialist world as phosphatidylcholines (PC) and follow the general formula

where R typically stands for linear aliphatic hydrocarbon radicals with 15 to 17 carbon atoms and up to 4 cis double bonds. Examples of natural lecithins are the cephalins, which are also referred to as phosphatidic acids and are derivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids. In contrast, phospholipids are usually understood to be mono- and preferably diesters of phosphoric acid with glycerol (glycerol phosphates), which are generally classed as fats. In addition, sphingosines or sphingolipids are also suitable.

pearlescent

Pearlescent waxes that can be used 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 polyvalent, optionally hydroxy-substituted carboxylic acids with fatty alcohols with 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances like for example fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total at least Have 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 with 12 to 22 Carbon atoms with fatty alcohols with 12 to 22 carbon atoms and / or polyols with 2 to 15 Carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.

Consistency agents and thickeners

The main consistency agents are fatty alcohols or hydroxy fatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms and also hydroxy fatty acids. Is preferred a combination of these substances with fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates. Suitable thickeners are, for example, Aerosil types (hydrophilic silicas), polysaccharides, especially xanthan gum, guar guar, agar agar, alginates and tylosen, carboxymethyl cellulose and hydroxyethyl cellulose, as well as higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, (e.g. Carbopole® and Pemulen types by Goodrich; Synthalene® from Sigma; Keltrol types from Kelco; Seppic Sepigel types; Salcare types from Allied Colloids), polyacrylamides, polymers, polyvinyl alcohol and polyvinyl pyrrolidone, surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as Pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with a narrow homolog distribution or alkyl oligoglucosides and electrolytes such as table salt and ammonium chloride.

superfatting

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

stabilizers

Metal salts of fatty acids, such as e.g. Magnesium, aluminum and / or zinc stearate or ricinoleate can be used.

polymers

Suitable cationic polymers are, for example, cationic cellulose derivatives, such as, for example, a quaternized hydroxyethyl cellulose, which is available from Amerchol under the name Polymer JR 400®, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers, such as, for example, Luviquat® (BASF) , Condensation products of polyglycols and amines, quaternized collagen polypeptides, such as, for example, lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, such as, for example, amodimethicones, copolymers of adipic acid and dimethylaminetetrinoxypropyldiamine (d) aminohydroxyaminol (d) aminohydroxyaminol (d) aminohydroxyaminol (d) aminohydroxyaminol (d) aminohydroxyaminol (d) aminohydroxyaminophenyl (hydroxyethyl) hydroxypropyl amine (D) aminohydroxyaminophenyl (di) aminohydroxyaminol (d) aminohydroxyaminol (di) aminohydroxyaminodi (d) aminohydroxyaminophenyl / hydroxymethyl trinoxydiamine (c) Acrylic acid with dimethyldiallylammonium chloride (Merquat® 550 / Chemviron), polyaminopolyamides, as described, for example, in FR 2252840 A and their crosslinked water-soluble polymers, cationic chitin derivatives such as quaternized chitosan, optionally microcrystalline, condensation products of dihaloalkylene, such as dibromobutane with bisdialkylamines, such as bis-dimethylamino-1,3-propane, cationic guar gum, such as Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from the company Celanese, quaternized ammonium salt polymers, such as Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 from Miranol.

Anionic, zwitterionic, amphoteric and nonionic polymers include, for example, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobomylacrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and their esters, uncrosslinked acrylamide acrylamide and non-crosslinked acrylamide acrylamide and polyethylenethacrylate acrylate and with polyesters, uncrosslinked acrylamide acrylamide and non-crosslinked acrylamide acrylamide and polyamides Copolymers, octylacrylamide / methyl methacrylate / ter.butylaminoethyl methacrylal / 2-hydroxyproyl methacrylate copolymers, polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymers, vinyl pyrrolidone / dimethylaminoethyl methacrylate / vinyl caprolactam terpolymers and optionally derivatized cellulose. Further suitable polymers and thickeners are listed in Cosmetics & Toiletries Vol. 108, May 1993, page 95ff .

silicone compounds

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 can be both liquid and resinous at room temperature. Simethicones, which are mixtures of dimethicones with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates, are also suitable. A detailed overview of suitable volatile silicones can also be found by Todd et al. in Cosm.Toil. 91 , 27 (1976).

Biogenic agents

Examples of biogenic active substances are tocopherol, tocopherol acetate, tocopherol palmitate, Ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, Amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes to understand.

film formers

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 its salts and similar compounds.

swelling agent

Montmorillonites, clay minerals, pemulene and alkyl-modified carbopol types (Goodrich) can serve as swelling agents for aqueous phases. Further suitable polymers or swelling agents can be found in the overview by R. Lochhead in Cosm.Toil. 108 , 95 (1993) .

hydrotropes

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.

Hydrotropes such as ethanol, isopropyl alcohol or polyols can also be used to improve the flow behavior. Polyols that come into consideration here preferably have 2 to 15 carbon atoms and at least two hydroxyl groups. The polyols can also contain further functional groups, in particular amino groups, or be modified with nitrogen. Typical examples are

glycerol;

Alkylene glycols, such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols with an average molecular weight of 100 to 1,000 daltons;

technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10 such as technical diglycerol mixtures with a diglycerol content of 40 to 50% by weight;

Methyl compounds, such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;

Lower alkyl glucosides, in particular those with 1 to 8 carbons in the alkyl radical, such as methyl and butyl glucoside;

Sugar alcohols with 5 to 12 carbon atoms, such as sorbitol or mannitol,

Sugars with 5 to 12 carbon atoms, such as glucose or sucrose;

Aminosugars such as glucamine;

Dialcohol amines, such as diethanolamine or 2-amino-1,3-propanediol.

preservative

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, Pentanediol or sorbic acid and those listed in Appendix 6, Parts A and B of the Cosmetics Ordinance other substance classes.

perfume oils

Perfume oils include mixtures of natural and synthetic fragrances. natural Fragrance substances are extracts from flowers (lily, lavender, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peels (Bergamot, lemon, oranges), roots (mace, angelica, celery, cardamom, costus, iris, Calmus), woods (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, Lemongrass, sage, thyme), needles and twigs (spruce, fir, pine, mountain pine), resins and balms (Galbanum, Elemi, Benzoe, Myrrh, Olibanum, Opoponax). Animal raw materials also come such as civet and castoreum. Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, Linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, Benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. the Jonone, α-isomethylionon and methylcedryl ketone, to the alcohols anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes and balms. However, preference is given to using mixtures of different fragrances that work together create an appealing fragrance. Also essential oils of lower volatility, mostly as aroma components are used as perfume oils, e.g. Sage oil, chamomile oil, clove oil, Melissa oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, Labolanum oil and Lavandin oil. Bergamot oil, dihydromyrcenol, lilial, lyral, Citronellol, phenylethyl alcohol, α-hexyl cinnamaldehyde, geraniol, benzylacetone, cyclamenaldehyde, linalool, Boisambrene Forte, Ambroxan, indole, Hedione, Sandelice, lemon oil, mandarin oil, orange oil, Allylamylglycolat, Cyclovertal, Lavandinöl, Muscatel Sage Oil, β-Damascone, Geraniumöl Bourbon, Cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, Evemyl, Iraldein gamma, phenylacetic acid, Geranyl acetate, benzyl acetate, rose oxide, romilllate, irotyl and floramat alone or in mixtures, used.

dyes

The dyes which can be used are the substances which are suitable and approved for cosmetic purposes, as compiled, for example, in the publication "Cosmetic Dyes" by the Dye Commission of the German Research Foundation, Verlag Chemie, Weinheim, 1984, pp . 81-106 . These dyes are usually used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole.

The total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40% by weight on the middle - amount. The agents can be produced by customary cold or hot processes; the phase inversion temperature method is preferably used.

Examples

Liquid soap preparations were prepared (Examples 1 to 3 are according to the invention, V1 is used for comparison) and their foaming behavior and storage stability with (-) = poor, (+) = satisfactory, (++) = good to (+++) = very well rated. The Brookfield viscosity (20 ° C., 10 rpm, spindle 5, mPas) was also measured. The results are summarized in Table 1. Liquid soaps - compositions and properties (quantities as% by weight) component 1 2 3 V1 Edenor® K 12-18 coconut oil fatty acid 10 7 8th 10 Texapon® N70 Sodium Laureth Sulfate 9 12 10 9 Plantacare® 1200 UP Lauryl Glucoside 6.5 6.5 6 10 Dehyton® G fatty acid amide derivative with amphoteric structure 4 3 5 4 Lamesoft® PO 65 35.7% by weight Coco Glucoside (and) 26.3% by weight Glyceryl Oleate 5 7 10 - NaCl 0.5 0.6 0.8 0.5 NaOH, 50% by weight 3.9 4.3 4.0 3.7 water ad 100 PH value 9.1 9.3 8.8 9.1 viscosity 5500 7250 9500 900 Foaming power (ml) 390 410 420 350 Creaminess of the foam ++ +++ +++ + Total irritation scores ++ ++ +++ - storage stability +++ +++ +++ +++

The stability of formulations 1 and V1 was determined on the basis of the pH, the acid, saponification and peroxide number over a period of 3 months. The results are summarized in Table 2. The increase in acid number from 1.1 to 1.6 at 40 ° C for recipe 1 can only be seen as a slight trend. Since the other key data and the appearance do not change, we can assume a stable wording here. Stability of liquid soaps 1 and V1 time investigation Recipe V1 Recipe 1 8 ° C 20 ° C 40 ° C 8 ° C 20 ° C 40 ° C begin PH value 9.1 9.1 9.1 9.1 9.1 9.1 acid number 1.3 1.3 1.3 1.1 1.1 1.1 saponification 1.5 1.5 1.5 3.4 3.4 3.4 peroxide 0.1 0.1 0.1 0.1 0.1 0.1 PH value 9.1 9.1 9.1 9.1 9.1 9.0 after 1 month acid number 1.1 1.1 1.0 1.0 1.0 1.2 saponification 1.6 1.5 1.5 3.4 3.5 3.5 peroxide 0.1 0.1 0.1 0.1 0.1 0.1 PH value 9.0 9.0 9.1 9.1 9.1 9.1 after 3 months acid number 1.1 1.1 1.0 1.0 1.1 1.6 saponification 1.5 1.5 1.6 3.5 3.5 3.5 peroxide 0.1 0.1 0.1 0.1 0.1 0.1

Claims (7)

1. Liquid soaps containing

   (a) 0.1 to 20% by weight sugar surfactants selected from the group consisting of (a1) alkyl and/or alkenyl oligoglycosides and/or (a2) fatty acid-N-alkyl polyhydroxyalkyl amides,

   (b) 0.1 to 20% by weight fatty acid partial glycerides corresponding to formula (III):

   

   in which R⁴CO is a linear or branched, saturated and/or unsaturated acyl group containing 12 to 18 carbon atoms, R⁵ and R⁶ independently of one another have the same meaning as R⁴CO or represent OH and the sum (m+n+p) is 0 or a number of 1 to 100, with the proviso that at least one of the two substituents R⁵ and R⁶ represents OH,

   (c) 0.5 to 34% by weight co-surfactants selected from the group consisting of alkoxylated carboxylic acid esters, monoglyceride (ether) sulfates, olefin sulfonates, betaines and fatty acid polyglycol ester sulfates and mixtures thereof,

   (d) 0.5 to 30% by weight fatty acids.

   with the proviso that the quantities mentioned add up to 100% by weight with water and optionally other auxiliaries and additives.
2. Liquid soaps as claimed in claim 1, characterized in that they contain as component (a1) alkyl and alkenyl oligoglycosides corresponding to formula (I): R¹O-[G]_p    (I) in which R¹ is an alkyl and/or alkenyl group containing 4 to 22 carbon atoms, G is a sugar unit containing 5 or 6 carbon atoms and p is a number of 1 to 10.
3. Liquid soaps as claimed in claims 1 and/or 2, characterized in that they contain as component (a2) fatty acid-N-alkyl polyhydroxyalkyl amides corresponding to formula (II):

   

   in which R²CO is an aliphatic acyl group containing 6 to 22 carbon atoms, R³ is hydrogen, an alkyl or hydroxyalkyl group containing 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group containing 3 to 12 carbon atoms and 3 to 10 hydroxyl groups.
4. Liquid soaps as claimed in at least one of claims 1 to 3, characterized in that they contain as component (d) fatty acids corresponding to formula (X): R¹⁴CO-OH   (X) in which R¹⁴CO is an aliphatic, linear or branched acyl group containing 6 to 22 carbon atoms and 0 and/or 1,2 or 3 double bonds.
5. Liquid soaps as claimed in at least one of claims 1 to 4, characterized in that they have a water content of 40 to 60% by weight, based on the concentration as a whole.
6. Liquid soaps as claimed in at least one of claims 1 to 5, characterized in that they have a pH of 7 to 11.
7. The use of the liquid soaps claimed in claim 1 in liquid soap preparations.