WO1991015192A1

WO1991015192A1 - Skin-compatible aqueous tenside mixtures

Info

Publication number: WO1991015192A1
Application number: PCT/EP1991/000584
Authority: WO
Inventors: Reinhard Müller; Bernd Fabry; Susanne Deiters; Karl Giede
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1990-04-04
Filing date: 1991-03-26
Publication date: 1991-10-17
Also published as: DE4010876A1; JPH05505803A; EP0523127A1

Abstract

Aqueous tenside mixtures containing: A) a sulphation product of an alkyl or alkenyl glycoside; B) amphoteric or hybrid-ionic tensides; and possibly C) other tensides; are suitable for the production of cosmetic cleaning and care agents which are skin-compatible.

Description

Aqueous surfactant mixtures with good skin tolerance

The invention relates to aqueous surfactant mixtures with good skin tolerance, containing sulfation products of alkyl and alkenyl glycosides, amphoteric or zwitterionic surfactants and, if appropriate, further surfactants, and the use thereof for the production of cosmetic cleaning and care products.

Substances and preparations used for cleaning or caring for the body and hair are subject to high demands in terms of foam and cleansing ability as well as skin compatibility. To improve the foaming and cleaning ability, surface-active substances, in particular anionic surfactants such as. B. alkyl sulfates or alkyl ether sulfates can be used. However, the skin tolerance of these substances is not yet sufficient for a number of application areas.

It is known that the skin compatibility of anionic surfactants can be improved by combining them with amphoteric or zwitterionic surfactants. In many cases, however, adequate skin compatibility is only observed for such mixtures if the proportion of amphoteric or zwitterionic surfactants in the mixtures is more than 25% by weight. Furthermore, the mixing of anionic with amphoteric or zwitterionic surfactants often leads to a decrease in the foaming power.

It is also known that the skin tolerance of anionic surfactants can be improved if they are in the form of their Magnesium salts used [Arztl.Kosmetol., 19, 208 (1989)]. Because of their mostly low water solubility, the use of anionic surfactant magnesium salts for the production of aqueous products is only possible to a limited extent.

Another way to improve the skin tolerance of anionic surfactants is to combine them with protein degradation products [soap-oil-fat waxes, 108, 177 (1982). However, such protein hydrolyzates have no surface-active properties and usually also lead to a deterioration in the foaming power.

The object of the invention was therefore to develop aqueous surfactant mixtures which have high foaming and cleaning properties and good skin compatibility and are free from the disadvantages described.

The invention relates to aqueous surfactant mixtures with good skin tolerance, the components as Tensidko

A) a sulfation product of an alkyl or alkenyl glycoside of the formula (I)

¹ -0- (G) _p , (I)

in which G represents a symbol for a glycose unit derived from a sugar with 5 or 6 carbon atoms, p stands for a number between 1 and 10 and R- stands for an alkyl or alkenyl radical with 6 to 22 carbon atoms, B) an amphoteric or zwitterionic surfactant selected from the group consisting of

Bl) alkyl betaines,

B2) alkylamido betaines,

B3) Imidazolinium betaines and

B4) sulfobetaines

is formed and

C) optionally a further surfactant selected from the group consisting of

Cl) alkyl sulfates,

C2) alkyl ether sulfates,

C3) hydroxy mixed ether sulfates,

C4) alpha-olefin sulfonates,

C5) secondary alkanesulfonates,

C6) internal alkyl ether sulfonates,

C7) ether carboxylic acids,

C8) isethionates,

C9) Taurids,

CIO) sarcosides,

Cll) fatty alcohol (ether) citrates and

C12) fatty alcohol (ether) tartrates

C13) sulfosuccinic acid esters

C14) sulfo fatty acids

is formed

contain. Surprisingly, it was found that a synergistic increase in the foaming power occurs in the case of aqueous surfactant mixtures of the type mentioned. The invention also includes the knowledge that the aqueous surfactant mixtures according to the invention have good skin tolerance.

Mixture component A) is a sulfation product of alkyl or alkenyl glycosides in which the glycose unit G in formula (I) is derived from aldoses or ketoses. Because of the better reactivity, the reducing saccharides, the aldoses, are preferably used. Among the aldoses, glucose is particularly suitable because of its easy accessibility and technical availability. Sulfation products of alkyl or alkenyl glucosides are therefore preferably used as mixture component A).

The index number p in formula (I) indicates the degree of oligomerization, i.e. H. the distribution of mono- and oligoglycosides is present and stands for a number between 1 and 10. While p must always be an integer in a given connection and here can assume the values p = 1 to 6, the value p is for certain alkylglycoside is an analytically determined arithmetic size, which usually represents a fractional number. Alkyl glycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. Particularly preferred are those alkyl glycosides whose degree of oligomerization is less than 1.5 and in particular between 1.1 and 1.4.

The radical R * is derived from primary alcohols having 6 to 22, preferably 12 to 18, carbon atoms and 0 or 1 double bonds. Typical examples are capronic alcohol, caprylic alcohol, capric alcohol alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, petroseline alcohol, behenyl alcohol and erucyl alcohol.

As usual in oleochemistry, these alcohols can also be present as technical mixtures, such as those used for. B. by high pressure hydrogenation of fatty acid methyl ester fractions based on natural fats and oils or by reduction of aldehyde cuts from Roelen'sehen oxosynthesis are accessible. However, the radical R * is preferably derived from a coconut alcohol having 12 to 18, in particular 12 to 14, carbon atoms.

The sulfation of the alkyl glycosides can be carried out according to the teachings of European patent application EP-A-0 186 242 and international patent application WO 88/1640 by reaction with gaseous sulfur trioxide in diethyl formamide, dichloroethane, tetrahydrofuran or other inert solvents and subsequent neutralization tion with aqueous bases.

Another method for producing sulfation products of alkyl glycosides is to mix alkyl glycosides with fatty alcohols or fatty alcohol polyglycol ethers and to react them together with gaseous sulfur trioxide. In this case, mixtures of tenides are obtained which contain sulfates of the alkyl glycoside and of the fatty alcohol or fatty alcohol polyglycol ether.

Such mixtures of alkyl glycoside and fatty alcohol or fatty alcohol polyglycol ether for the common sulfation can be produced mechanically by stirring the individual substances in the heat. However, a particularly preferred process consists in technical mixtures of alkyl glycoside and To use fatty alcohol in a ratio of 10:90 to 30:70 in the sulfation, as are obtained as intermediates in the technical production of the alkyl glycosides. In this way, the step of isolating the pure alkyl glycoside can be saved in whole or in part, which is otherwise associated with additional energy expenditure due to the distillative removal of excess fatty alcohol.

The invention includes the knowledge that surfactant mixtures which are obtained by jointly sulfating alkyl glycosides and fatty alcohols or fatty alcohol polyglycol ethers, in combination with amphoteric surfactants, have particularly advantageous foaming power with good skin tolerance.

The surfactants used as mixture components B and C are known substances which can be obtained by the customary methods in organic chemistry. Unless otherwise indicated, processes for their preparation are described, for example, in J. Falbe, U. Hasserodt (ed.), "Catalysts, Surfactants, Mineral Oil Additives", Thieme Verlag, Stuttgart, 1978 or J. Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1986.

As a component Bl) are alkyl betaines that follow the formula (II)

R2 R ³ -N ⁺ - (CH ₂ ) _x -C00- (II) in which R2, R3 and R ⁴ independently of one another represent hydrogen, linear or branched aliphatic hydrocarbon radicals having 1 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and x are integers from 1 to 10. R ^ is preferably an alkyl radical having 12 to 18 carbon atoms, R ³ and R ⁴ are hydrogen or a methyl group, and x is 1 or 2.

Suitable mixture components B2) are alkylamido betaines which follow the formula (III)

CH ₃ R5-CO-NH- (CH2) yN ⁺ - (CH ₂ ) _z C00- (III) CH ₃

in which R5-C0 represents an aliphatic acyl radical having 8 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and y and z are integers from 1 to 10. R-5-CO is preferably derived from coconut or tallow fatty acid, while y is 2 or 3 and z is 1 or 2.

Suitable mixture components B3) are imidazolinium betaines which follow the formula (IV)

-00C- (CH ₂ ) _z N ⁺ CH ₂

R6-C CH ₂ (IV)

N R7

in which R ^ represents an aliphatic hydrocarbon radical having 5 to 21 carbon atoms and 0, 1, 2 or 3 double bonds, R ^{7 represents} hydrogen or a substance optionally substituted with hydroxyl groups tuiert alkyl radical with 1 to 6 carbon atoms and z represents integers from 1 to 10. Ϊ is preferably an alkyl or alkenyl radical with 12 to 18 carbon atoms, 7 7 for a hydroxyethyl radical and z for 1 or 2.

Suitable mixture components B4) are sulfobetaines which follow the formula (V)

CH ₃ R ⁸ -N ⁺ - (CH ₂ ) _q CH-CH ₂ -Sθ3- (V) CH ₃ OH

in which ^~ ß stands for an aliphatic hydrocarbon radical with 8 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and q stands for numbers from 1 to 10. ^~ Is preferably an alkyl or alkenyl radical having 12 to 18 carbon atoms and q is 1.

Suitable mixture components Cl) are alkyl sulfates which follow the formula (VI)

R -0-S0 ₃ X (VI)

in the ^~ 9 for a linear or branched aliphatic hydrocarbon residue with 8 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and X for hydrogen, an alkali or alkaline earth metal, aluminum, an ammonium, alkylammonium or alkanol - ammonium group stands. ^~ Is preferably an alkyl radical having 12 to 18 carbon atoms.

Suitable mixture components C2) are alkyl ether sulfates which follow the formula (VII) Rl0- [0C _n H _2n 0] _πι -0-S0 ₃ X (VII)

in which R 0 is a linear or branched aliphatic hydrocarbon radical with 8 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, n for 2 or 3, m for a number from 1 to 20 and X for hydrogen, an alkali or alkaline earth metal, aluminum, an ammonium, alkylam onium or alkanolammonium group. R 1 preferably represents an alkyl radical with 12 to 18 carbon atoms, n for 2 and m for numbers from 2 to 5. Aqueous surfactant mixtures within the meaning of the invention which have particularly advantageous application properties are obtained if alkyl ether sulfates with a reduced concentration are obtained Homolog distribution proceeds.

Suitable mixture components C3) are hydroxy mixed ether sulfates which follow the formula (VIII)

0S0 ₃ X

in which R ^{11 is} an alkyl radical having 6 to 16 carbon atoms, R ^{12 is} an alkyl radical having 1 to 4 carbon atoms, n is 2 or 3, m is a number from 1 to 10 and X is hydrogen, an alkali or alkaline earth metal, aluminum, is an ammonium, alkylammonium or alkanolammonium group. RÜ is preferably an alkyl radical with 8 to 10 carbon atoms, R ¹² for a butyl radical, n for 2 and for numbers from 2 to 5. The preparation of the hydroxy-ether sulfates is described in German patent application DE-A-37 23 354. Suitable mixture components C4) are alpha-olefin sulfonates which follow one of the formulas (IX) or (X),

R ^ -CH-C ^ -SOsX (IX)

OH

S0 ₃ X

in which R * 3 represents an alkyl radical having 6 to 20 carbon atoms and X represents hydrogen, an alkali or alkaline earth metal, aluminum, ammonium, alkylammonium or alkanolammonium group. R13 is preferably an alkyl radical having 12 to 18 carbon atoms. The alpha-olefin sulfonates can be present as hydroxysulfonates of the formulas (IX) and (X) or in a mixture with the corresponding alkene sulfonates, the composition of which can be derived formally from the formulas (IX) and (X) by splitting off 1 mol Water results.

Secondary alkanesulfonates which follow the formula (XI) are suitable as component C5):

R ^ -CH-R ^ (XI)

S0 ₃ X

in which R ¹⁴ and R * 5 independently of one another are alkyl radicals having 1 to 20, in total 7 to 21 carbon atoms and X is hydrogen, an alkali or alkaline earth metal, aluminum, an ammonium, alkylammonium or alkanolammonium group. R ¹⁴ and R ¹⁵ are preferably alkyl radicals having a total of 12 to 18 carbon atoms. Suitable mixture components C6) are internal alkyl ether sulfonates which follow one of the formulas (XII) or (XIII),

CH ₃ (CH ₂ ) _r CH- (CH ₂ ) _s CH- (CH ₂ ) _t - [0C _n H _2n ] _m -0H (XII) OH S0 ₃ X

CH ₃ (CH ₂ ) _r CH- (CH ₂ ) _s CH- (CH ₂ ) _t - [0C _n H _2n ] _m -0H (XIII) S0 ₃ X OH

in which s for 1 or 2, r and t for numbers from 1 to 17, the sum of s, r and t for numbers from 13 to 19, n for 2 or 3, for numbers from 1 to 10 and X for hydrogen, an alkali or alkaline earth metal, aluminum, an ammonium, alkylammonium or alkanol ammonium group. The alkyl ether sulfates preferably contain 16 to 18 carbon atoms in the carbon chain. The internal alkyl ether sulfonates can be present as hydroxysulfonates according to formulas (XII) and (XIII) or as a mixture with the corresponding alkene sulfonates, the composition of which can be derived formally from formulas (XII) and (XIII) by splitting off 1 mol of water results. The preparation of the substances is described in German patent application DE-A-3725030.

Suitable mixture components C7) are ether carboxylic acids which follow the formula (XIV)

Rl6- [0C _n H _2n ] _m -0-CH ₂ -C00X (XIV)

in R ¹⁶ for an aliphatic hydrocarbon radical with 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, n for 2 or 3, m for numbers from 1 to 10 and X for hydrogen, an alkali

REPLACEMENT LEAF Li or alkaline earth metal, aluminum, an ammonium, alkylammonium or alkanolammonium group. R ¹ ^ is preferably an alkyl radical with 12 to 18 carbon atoms, n for 2 and m for numbers from 2 to 5.

Possible mixture components C8) are isethionates which follow the formula (XV)

0 R17_C-0 (CH ₂ ) ₂ -S0 ₃ X (XV)

in the R ¹ ? represents an aliphatic hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and X represents hydrogen, an alkali or alkaline earth metal, aluminum, an ammonium, alkylammonium or alkanolammonium group. R17 is preferably an alkyl radical having 12 to 18 carbon atoms.

Possible mixture components C9) are taurides which follow the formula (XVI)

0 CH ₃ R18_ _C -N- (CH ₂ ) ₂ S0 ₃ X (XVI)

in which R18 is an aliphatic hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and X is hydrogen, an alkali metal or alkaline earth metal, aluminum, an ammonium, alkylammonium or alkanolammonium group. R ¹ ^ is preferably an alkyl radical having 12 to 18 carbon atoms. Suitable mixture components CIO) are sarcosides which follow the formula (XVII)

0 CH ₃ R19_ _C -N-CH ₂ C00X (XVII)

in which R ^{19 represents} an aliphatic hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and X represents hydrogen, an alkali metal or alkaline earth metal, aluminum, an ammonium, alkylammonium or alkanolammonium group. R ¹ ^ is preferably an alkyl radical having 12 to 18 carbon atoms.

Fatty alcohol (ethe) citrates which follow the formula (XVIII) are suitable as the mixture component C1),

C0 (0C _n H _2n ) _m 0R20

RZiOfCnH ^ OJmOC - ^ - C - ^ - COfOCnH ^ OJmOR ²² (XVIII)

OH

in which R 1, R ² * and R ²² independently of one another for an aliphatic hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, R ²¹ and R ²² additionally for hydrogen, an alkali metal or alkaline earth metal , Aluminum, an ammonium, alkylammonium or alkanolammonium group, n is 2 or 3 and m is 0 or numbers from 1 to 10. R ² ^ and R ²¹ are preferably alkyl radicals having 12 to 18 carbon atoms, R ^{22 is}

Sodium, potassium, magnesium or aluminum, n for 2 and m for numbers from 2 to 7. Suitable mixture components C12) are Fetta1koho1 (ether) tartrates which follow the formula (XIX)

OH OH R ²³ 0 (C _n H _2π 0) _m 0C-CH-CH-C0 (0C _n H _n ) _ra 0R ²⁴ (XIX)

in which R ²³ and R ²⁴ independently of one another for an aliphatic hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, R ²⁴ additionally for hydrogen, an alkali metal or alkaline earth metal, aluminum, an ammonium or alkylammo nium or alkanolammonium group, n is 2 or 3 and m is 0 or numbers from 1 to 10. R ²³ is preferably an alkyl radical having 12 to 18 carbon atoms, R ^{24 is} sodium, potassium, magnesium or aluminum, n is 2 and m is a number from 2 to 7.

Suitable mixture components C13) are sulfosuccinic esters which follow the formula (XX)

X0 S-CH-C0 (0C _n H2 _π ), n0R ²⁵ (XX)

CH ₂ -C0 (0C _n H _2n ) _m 0R26

in which R ^ and R ^ independently of one another for an aliphatic hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, R ² ^ additionally for hydrogen, an alkali metal or alkaline earth metal, aluminum, an ammonium , Alkyl ammonium or alkanol ammonium group, n is 2 or 3, 0 or numbers from 1 to 10 and X is hydrogen, an alkali metal or alkaline earth metal, aluminum, an ammonium, alkyl ammonium or alkanol ammonium group. R ² ^ and R ² ^ are preferably alkyl radicals having 12 to 18 carbon atoms. Suitable mixture components C14) are sulfofatty acids which have the formula (XXI),

R ² -CH-C00X (XXI)

S0 ₃ X

in which R ^{27 represents} an aliphatic hydrocarbon radical having 4 to 18 carbon atoms and 0, 1, 2 or 3 double bonds and X represents hydrogen, an alkali or alkaline earth metal, aluminum, an ammonium, alkylammonium or alkanolammonium group. R ²⁷ is preferably an alkyl radical having 10 to 16 or an alkenyl radical having 14 to 16 carbon atoms.

The aqueous surfactant mixtures according to the invention are produced either mechanically at an optionally elevated temperature of 30 to 40 ° C. or by combined reaction of alkyl glycosides with fatty alcohols or fatty alcohol polyglycol ethers with gaseous sulfur trioxide, neutralization with aqueous bases and subsequent mixing of the anionic surfactant mixture with amphoteric or zwitterionic surfactants.

Binary aqueous surfactant mixtures with high foaming power and good skin tolerance contain components A and B in a weight ratio of 90:10 to 10:90, preferably 85:15 to 75:25.

Ternary aqueous surfactant mixtures with high foaming power and good skin tolerance contain components A, B and C in a weight ratio of 5: 15: 80 to 40: 25: 35, preferably 10: 15: 75 to 20: 2555. The skin-protecting properties of the agents according to the invention come into their own when they are formulated in such a way that they have a pH value in the vicinity of the neutral point. Agents with pH values in the range from 5.5 to 7.5, in particular 5.5 to 6.5, are therefore preferred.

The aqueous surfactant mixtures according to the invention are suitable for the production of cosmetic cleaning and care products, such as. B. Sha poos, shower rooms, liquid soaps and the like.

In addition to the surfactant mixtures described, these products can contain conventional constituents of cosmetic preparations such as, for example, emulsifiers, oil components, fats and waxes, solubilizers, thickeners, superfatting agents, biogenic active ingredients, film formers, fragrances, dyes, pearlescent agents, foam stabilizers, Preservatives and pH regulators included.

Common oil components are substances such as paraffin oil, vegetable oils, fatty acid esters, squalane and 2-0ctyldodecanol, while fats and waxes are used, for example, as walrus, beeswax, montan wax, paraffin and cetylstearyl alcohol.

Low mono- or polyhydric alcohols such as ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, glycerol, 1,3-butylene glycol and diethylene glycol are usually used as solubilizers.

Substances such as polyethoxylated lanolin derivatives, lecithin derivatives and fatty acid alkanolamides can be used as superfatting agents, the latter simultaneously serving as foam stabilizers. Suitable thickeners are, for example, polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and toliosis, carboxymethyl cellulose and hydroxyethyl cellulose, furthermore higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinyl pyrrolidone and electrolytes such as cooking salt and ammonium chloride, if desired in combination with alkyl ether sulfates.

Biogenic active substances are understood to mean, for example, plant extracts, protein hydrolyzates and vitamin complexes.

Common film formers are, for example, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives and similar compounds.

Suitable preservatives are, for example, aldehyde solution, p-hydroxybenzoate or sorbic acid.

Suitable pearlizing agents are, for example, glycol distearic acid esters such as ethylene glycol distearate, but also fatty acid monoglycol esters.

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, published in Ver¬ lag Chemie, Weinheim, 1984. These dyes are usually used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole. If desired, further components of the aqueous surfactant mixtures according to the invention are fragrances and substances which serve to adjust the pH of the compositions.

The mixtures according to the invention are preferably used in products which are used for washing, dyeing, waving or rinsing hair. The mixtures are particularly suitable for producing mild sha poos, for example baby shampoos.

The following examples are intended to explain the subject matter of the invention in more detail without restricting it.

Examples

I. Surfactants used:

AI) C ₂ /14-coconut alkyl glucoside sulfate Na salt, obtained by reacting a coconut alkyl glucoside with gaseous sulfur trioxide in a mixture of dimethylformamide and dichloroethane as a solvent according to European patent application EP-A-0 186 242. The product was used in the form of an aqueous solution with an active substance content of 30% by weight.

A2) Cχ / i4- okosa1ky1g1ucoside sulfate / Cι ₂ / i4-Kokosfetta1ky1su1 - fat-Na-salt mixture, obtained by the joint reaction of a mixture of 20% by weight coconut alkyl glucoside and 80% by weight coconut fatty alcohol (Lorol ( ^R ) S, Hydroxyl number 289, sales product from Henkel) with gaseous sulfur trioxide and subsequent neutralization with aqueous sodium hydroxide solution. The molar ratio between feed and sulfur trioxide was 1: 1.3, the sulfonation temperature 45 ° C. The product was used in the form of an aqueous solution with an active substance content of 30% by weight.

A3) Cι / i4-KokosaIky1glucos dsuIfat / Cj / i4-Kokosfetta1koho1-

2E0 ether sulfate / Na salt mixture obtained by jointly reacting a mixture of 20% by weight coconut alkyl glucoside and 80% by weight of a product from the hydrotaleity-catalyzed addition of 2 moles of ethylene oxide to a coconut fatty alcohol cut (Lorol (R ) S) with gaseous sulfur trioxide and subsequent neutralization with aqueous sodium hydroxide solution. The molar ratio between Substitute and sulfur trioxide was 1: 1.3, the sulfonation temperature 55 ° C. The product was used in the form of an aqueous solution with an active substance content of 30% by weight.

Bl) alkyl betaine, Dehyton ( ^R ) CB, sales product from Henkel. Reaction product of sodium chloroacetate with cetyldimethylamine. The product was used in the form of an aqueous solution with an active substance content of 30% by weight.

B2) Alkyla idobetaine, Dehyton ( ^R ) K, sales product from Henkel. Reaction product of sodium chloroacetate with a condensation product of 1 mol of coconut fatty acid and 1 mol of N, N-dimethyl-propylenediamine. The product was used in the form of an aqueous solution with an active substance content of 30% by weight.

Cl) -C / i4-ocosalkyl sulfate Na salt, obtained by reacting a technical Cι ₂ / i4 coconut fatty alcohol cut with gaseous sulfur trioxide and subsequent neutralization with aqueous sodium hydroxide solution. The product was used in the form of an aqueous solution with an active substance content of 30% by weight.

C2) Cι ₂ / i4-cocoalkyl-2E0-ether sulfate-Ha-salt, obtained by reacting an adduct of an average of 2 moles of ethylene oxide with a technical Cι _2/14 Kokosfettalko- holschnitt with gaseous sulfur trioxide and subsequent neutralization with aqueous sodium hydroxide. The addition of the ethylene oxide to the fatty alcohol was determined according to German patent application DE-A-38 43 713 in Presence of hydrotalcite as an alkoxylation catalyst and led to a fatty alcohol ethoxylate with a low content of free fatty alcohol and a narrow homolog distribution. The product was used in the form of an aqueous solution with an active substance content of 30% by weight.

II. Examples of application technology:

Preparation of the mixtures. To prepare the aqueous surfactant mixtures according to the invention and the comparative mixtures, the components which were in the form of aqueous solutions were added together at room temperature and with stirring in tap water at 18 ° d, the ratio of surfactant: water being chosen so that aqueous solutions with a Solids content of 2% by weight resulted.

Measurement method. For the production of a particularly fine-pored foam, as is desired in personal cleansing and personal care products, a blow foam apparatus was used, such as that used for. B. is known from DIN 53902.

340 ml of the aqueous surfactant mixture were transferred to the whipped foam apparatus. Foam was generated by 10 blows with a perforated plate with 1 mm bores (speed: 50 blows / min, stroke: 13 cm) and the foam volume was determined in ml after 1, 3 and 5 min.

Default. For a better comparison of the foam properties of the aqueous surfactant mixtures according to the invention and of the comparative mixtures, all measurements were evaluated against a good-foaming standard which had the following composition and corresponds to a common surfactant mixture for personal care products on the market: 12% by weight Texapon ( ^R ) N, commercial product from Henkel,

(Cι / i4-fatty alcohol-2E0-sulfate-Na salt)

3% by weight Dehyton ( ^R ) K, commercial product from Henkel,

(Reaction product of sodium chloroacetate with a condensation product of 1 mol of coconut fatty acid with 1 mol

N, N-dimethyl-propylenediamine) 1% by weight Comperlan ( ^R ) KD, commercial product from Henkel, (coconut fatty acid diethanolamide)

The standard mixture provided the following foam values under the conditions mentioned:

after 1 min: 230 ml after 3 min: 220 ml after 5 min: 180 ml

These foam values were set at 100%; all following measurements represent relative percentages to this standard.

Examples 1 - 8. Comparative Examples 1 - 3:

Tab. 1: Relative foaming power of aqueous surfactant mixtures Specification of the mixing ratio in weight - Specification of the amount of foam in ml

A: B: C = mixing ratio of components A, B and C. II. Skin compatibility test

The in vitro method developed by Zeidler and Reese was used to determine the skin tolerance of the aqueous surfactant mixtures [Arztl.Kosmetol., 13, 39 (1983)].

The swelling of pig epidermis served as a measure of the skin tolerance of the surfactant mixtures. The required epidermis was obtained immediately after young pigs were slaughtered and stored frozen.

For the measurement, punched-out epidermis strips measuring 1 cm × 6 cm were immersed for 30 minutes in the surfactant solutions, each containing 2% by weight of active substance, heated to 39 ° C. and adjusted to pH = 6.5. After a short rinse and removal of the adhering water, the weight of the swollen strips was determined by gently squeezing under defined conditions. The strips were then dewatered over calcium chloride for 24 h and weighed again. In order to eliminate influences that are based on specific properties of the respective animal or the place of removal (back, side), a standard measurement was carried out in each case. An immediately adjacent strip of epidermis was treated in the same way with water instead of the surfactant solution.

The measured values t for the surfactant treatment and w for the treatment with water result from the relationship:

Weight (g _e q _U0 ] _ene epider is) - Weight (-dried epidermis) t, w =

Weight (dry epidermis) The standardized, relative swelling change Q is finally defined as

Q = (t / w - 1) ^• 100%

The Q value of the skin treated only with water is therefore by definition 0%; negative values indicate swelling-inhibiting properties. The results of the epidermal swelling are summarized in Table 2.

Tab. 2: E idermis uellun water-based surfactant mixtures

Legend: Comp. = Component

A: B: C = mixing ratio of components A, B and C.

Claims

1. Aqueous surfactant mixtures with good skin tolerance, characterized in that they are used as surfactant components

A) a sulfation product of an alkyl or alkenyl glycoside of the formula (I)

MGj _p , (i)

in which G represents a symbol for a glycose unit derived from a sugar with 5 or 6 carbon atoms, p stands for a number between 1 and 10 and R * stands for an alkyl or alkenyl radical with 6 to 22 carbon atoms,

B) an amphoteric or zwitterionic surfactant selected from the group consisting of

Bl) alkyl betaines,

B2) alkylamido betaines,

B3) I idazolinium betaines and

B4) sulfobetaines

is formed and

C) optionally a further surfactant selected from the group consisting of

Cl) alkyl sulfates,

C2) alkyl ether sulfates, C3) hydroxy mixed ether sulfates,

C4) alpha-olefin sulfonates,

C5) secondary alkanesulfonates,

C6) internal alkyl ether sulfonates,

C7) ether carboxylic acids,

C8) isethionates,

C9) Taurids,

CIO) Sarcosinates,

Cll) fatty alcohol (ether) citrates,

C12) fatty alcohol (ether) tartrates

C13) sulfosuccinic acid esters and

C14) sulfo fatty acids

is formed

are included.

2. Aqueous surfactant mixtures according to claim 1, characterized in that the glycose unit G in formula (I) is derived from aldoses or ketoses, in particular glucose, p is a number from 1.1 to 3.0, in particular 1.1 to 1,4, and R- represents an alkyl radical having 12 to 18 carbon atoms.

3. Aqueous surfactant mixtures according to one of claims 1 and 2, characterized in that the alkyl betaines (B1) follow the formula (II),

R ² R ³ -N ⁺ - (CH ₂ ) _x -C00- (II)

^~ A in which R ² , R ³ and R ⁴ independently of one another represent hydrogen, linear or branched aliphatic hydrocarbon radicals having 1 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and x are integers from 1 to 10.

4. Aqueous surfactant mixtures according to one of claims 1 and 2, characterized in that the alkyl idobetaines (B2) follow the formula (III),

CH ₃

R5-C0-NH- (CH ₂ ) _y -N ⁺ - (CH ₂ ) _z C00- (III)

CH ₃

in which R-5-C0 is an aliphatic acyl radical having 8 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and y and z are integers from 1 to 10.

5. Aqueous surfactant mixtures according to one of claims 1 and 2, characterized in that the imidazolinium betaines (B3) follow the formula (IV),

-00C- (CH) _z -N CH ₂

R ⁶ -C CH ₂ (IV)

N R7

in which R ^{6 is} an aliphatic hydrocarbon radical having 5 to 21 carbon atoms and 0, 1, 2 or 3 double bonds, R ^{7 is} hydrogen or an alkyl radical which is optionally substituted by hydroxyl groups and has 1 to 6 carbon atoms and z is an integer from 1 to 10 stands.

6. Aqueous surfactant mixtures according to one of claims 1 and 2, characterized in that the sulfobetaines (B4) follow the formula (V),

CH ₃ R8-N ⁺ - (CH ₂ ) _q CH-CH ₂ -S0 ₃ - (V) CH ₃ OH

in which R-S represents an aliphatic hydrocarbon radical having 8 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and q represents numbers from 1 to 10.

7. Aqueous surfactant mixtures according to at least one of the claims

1 to 6, characterized in that the alkyl sulfates (Cl) follow the formula (VI),

R9-0-S0 ₃ X (VI)

in the R9 for a linear or branched aliphatic hydrocarbon radical with 8 to 22 carbon atoms and 0, 1,

2 or 3 double bonds and X represents hydrogen, an alkali or alkaline earth metal, aluminum, an ammonium, alkylammonium or alkanolammonium group.

8. Aqueous surfactant mixtures according to at least one of claims 1 to 6, characterized in that the alkyl ether sulfates (C2) follow the formula (VII),

in the R * 0 for a linear or branched aliphatic hydrocarbon radical with 8 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, n for 2 or 3, m for a number from 1 to 20 and X for hydrogen, an alkali or Erdalkalime¬ tall, aluminum, an ammonium, alkyl ammonium or alkanol ammonium group.

9. Aqueous surfactant mixtures according to at least one of claims 1 to 6, characterized in that the hydroxy mixed ether sulfates (C3) follow the formula (VIII),

R ¹¹ -CH-CH2- [0C _π ll2n] ιr0- ^Rl2 ( ^vπι ) 0S0 ₃ X

in the RÜ for an alkyl radical with 6 to 16 carbon atoms, R * ² for an alkyl radical with 1 to 4 carbon atoms, n for 2 or 3, m for numbers from 1 to 10 and X for hydrogen

Alkali or alkaline earth metal, aluminum, an ammonium, alkyl ammonium or alkanol ammonium group.

10. Aqueous surfactant mixtures according to at least one of claims 1 to 6, characterized in that the alpha-olefin sulfonates (C4) follow one of the formulas (IX) or (X),

Rl3.-CH-CH ₂ -S0 ₃ X (IX)

OH

R ¹³ -CH-CH ₂ -0H (X)

S0 ₃ X in which R ^{13 represents} an alkyl radical having 6 to 20 carbon atoms and X represents hydrogen, an alkali or alkaline earth metal, aluminum, an ammonium, alkylammonium or alkanolammonium group.

11. Aqueous surfactant mixtures according to at least one of claims 1 to 6, characterized in that the secondary alkanesulfonates (C5) follow the formula (XI),

R ¹⁴ -CH-Rl5 (XI) so ₃ times

in which R ¹⁴ and R ¹ ^ independently of one another are alkyl radicals having 1 to 20, in total 7 to 21 carbon atoms and X is hydrogen, an alkali metal or alkaline earth metal, aluminum, an ammonium, alkylammonium or alkanolammonium group.

12. Aqueous surfactant mixtures according to at least one of claims 1 to 6, characterized in that the internal alkyl ether sulfonates (C6) follow one of the formulas (XII) or (XIII),

CH ₃ (CH ₂ ) _r CH- (CH ₂ ) _s CH- (CH ₂ ) _t - [0C _π H _2n ] _πι -0H (XII) OH S0 ₃ X

CH ₃ (CH ₂ ) _r CH- (CH ₂ ) _s CH- (CH ₂ ) t- [0C _n H _2n ] _ιπ -0H (XIII) S0 ₃ X OH

in which s for 1 or 2, r and t for numbers from 1 to 17, the sum of s, r and t for numbers from 13 to 19, n for 2 or 3, for numbers from 1 to 10 and X for hydrogen, an alkali or alkaline earth metal, aluminum, an ammonium, alkylammonium or alkanolammonium group.

13. Aqueous surfactant mixtures according to at least one of claims 1 to 6, characterized in that the ether carboxylic acids (C7) follow the formula (XIV),

R ¹ 6- [0C _n H _2n ] _m -0-CH ₂ -C00X (XIV)

in R ¹⁶ for an aliphatic hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, n for 2 or 3, m for numbers from 1 to 10 and X for hydrogen, an alkali or alkaline earth metal, aluminum, a Ammonium, alkylammonium or alkanolammonium group.

14. Aqueous surfactant mixtures according to at least one of claims 1 to 6, characterized in that the isethionates (C8) follow the formula (XV),

0 R ¹⁷ -C-0 (CH ₂ ) ₂ -S0 ₃ X (XV)

in which R ^{17 represents} an aliphatic hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and X represents hydrogen, an alkali or alkaline earth metal, aluminum, an ammonium, alkylammonium or alkanolammonium group.

15. Aqueous surfactant mixtures according to at least one of claims 1 to 6, characterized in that the taurides (C9) follow the formula (XVI), 0 CH ₃ _R 18_c-H- (CH ₂ ) ₂ S0 ₃ X (XVI)

in which Rl8 represents an aliphatic hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and X represents hydrogen, an alkali or alkaline earth metal, aluminum, an ammonium, alkylammonium or alkanolammonium group.

16. Aqueous surfactant mixtures according to at least one of claims 1 to 6, characterized in that the sarcosides (CIO) follow the formula (XVII),

0 CH ₃ R19_C-N-CH ₂ C00X (XVII)

in which R * 9 represents an aliphatic hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and X represents hydrogen, an alkali or alkaline earth metal, aluminum, an ammonium, alkylammonium or alkanolammonium group.

17. Aqueous surfactant mixtures according to at least one of claims 1 to 6, characterized in that the fatty alcohol (ether) citrates (Cll) follow the formula (XVIII),

COfOCnH ^ JmO ² ** R ²¹ 0 (C _n H _2n O) _m 0C-CH ₂ -C-CH ₂ --C0 (OCnH ₂ n0) _I n0R ²² (XVIII)

OH in the R ²⁰ , R ²¹ and R ²² independently of one another for an aliphatic hydrocarbon radical with 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, R ² * and R ²² additionally for hydrogen, an alkali or alkaline earth metal , Aluminum, an ammonium, alkylammonium or alkanolammonium group, n is 2 or 3 and m is 0 or numbers from 1 to 10.

18. Aqueous surfactant mixtures according to at least one of claims 1 to 6, characterized in that the fatty alcohol (ether) tartrates (C12) follow the formula (XIX),

OH OH R ²³ 0 (CnH ₂ n0) _m 0C-CH-CH-C0 (0C _n H ₂ n) ιιι0R ²⁴ (XIX)

in which R 3 and R ²⁴ independently of one another for an aliphatic hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, R ²⁴ additionally for hydrogen, an alkali metal or alkaline earth metal, aluminum, an ammonium -, Alkylammonium or Alkanolammoniumgruppe, n stand for 2 or 3 and for 0 or numbers from 1 to 10.

19. Aqueous surfactant mixtures according to at least one of claims 1 to 6, characterized in that the sulfosuccinic acid esters (C13) follow the formula (XX),

X0 ₃ S-CH-C0 (0C _n H _2n ) m0R ²⁵ (XX)

CH ₂ -C0 (0C _n H _2n ) _m 0R ² 6

in which R ² ^ and R ² ^ independently of one another for an aliphatic hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, R ²⁶ additionally for water material, an alkali or alkaline earth metal, aluminum, an ammonium, alkyl ammonium or alkanol ammonium group, n for 2 or 3, m for 0 or numbers from 1 to 10 and X for hydrogen, an alkali or alkaline earth metal, aluminum, an ammonium - Alalkylammonium- or Alkanolammoniumgruppe stand.

20. Aqueous surfactant mixtures according to at least one of Claims 1 to 6, characterized in that the sulfofatty acids (C14) follow the formula (XXI),

R ²⁷ -CH-C00X (XXI) so-x

in which R ^{27 is} an aliphatic hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and X is hydrogen, an alkali metal or alkaline earth metal, aluminum, an ammonium, alkylammonium or alkanolammonium group.

21. Aqueous surfactant mixtures according to at least one of claims 1 to 20, characterized in that they contain components A and B in a weight ratio of 10:90 to 90:10.

22. Aqueous surfactant mixtures according to at least one of Claims 1 to 20, characterized in that they contain components A, B and C in a weight ratio of 5: 15: 80 to 40: 25: 35.

23. Use of the aqueous surfactant mixtures according to at least one of claims 1 to 22 for the production of hair cleansing and hair care products with good skin tolerance.

24. Use of the aqueous surfactant mixtures according to at least one of claims 1 to 22 for the production of personal cleansing and personal care products with good skin tolerance.