WO1993001264A1

WO1993001264A1 - Aqueous surfactant compositions

Info

Publication number: WO1993001264A1
Application number: PCT/EP1992/001444
Authority: WO
Inventors: Reinhard Müller; Hans-Christian Raths; Detlef Hollenberg; Kurt Seidel
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1991-07-04
Filing date: 1992-06-26
Publication date: 1993-01-21
Also published as: MX9203932A; DE4122200A1

Abstract

Proposed are aqueous surfactant compositions containing at least two different anionic surface-active agents. Such compositions behaviour with respect to foaming power and concentratability, and at the same time are kinder to the skin, if at least one of the anionic surface-active agents contains a polyoxyalkylene group added by alkoxylation in the presence of catalytic amounts of double-layer hydroxide compounds, in particular hydrotalcite, which have been made hydrophobic.

Description

"Aqueous preparations of surface-active substances"

The invention relates to aqueous preparations of surface-active substances with improved behavior with regard to foaming capacity and thickenability with simultaneous low skin stress.

There is a constant need for aqueous preparations of surface-active substances which have improved foaming power and improved thickenability and are therefore particularly suitable for use in body cleansers.

In order to enhance the cleaning action of aqueous preparations, these usually contain surface-active compounds. However, an increased cleansing effect is usually associated with increased skin stress. This is especially true for the important class of anionic surfactants.

This increased skin stress should be avoided in the area of body cleansers. Good skin tolerance is particularly important for products that are designed for frequent use, are used to clean the intimate area or come into contact with mucous membranes.

It is known that the use of magnesium ions in anionic surfactants such as fatty alcohol sulfates and fatty alcohol ether sulfates can give products with improved skin tolerance. It is also known that ampholytic and nonionic surfactants are often characterized by improved skin tolerance compared to anionic surfactants. However, these classes of surfactants cannot be used as a replacement for anionic surfactants for many areas of application because they do not achieve their properties in terms of their cleaning action. The foam formation desired for shampoos is generally not guaranteed if amphoteric surfactants are used exclusively or predominantly.

It can be seen from an article published in "Medical Cosmetology 13, 39-45 (1983)" that the skin tolerance of anion / amphoteric surfactant mixtures is in individual cases higher than that of the pure anionic surfactants. Thus, the skin tolerance of surfactant solutions can be increased by partially replacing the anionic surfactants with amphoteric surfactants, but disadvantages must be accepted with regard to important properties such as cleaning action and foaming.

It was therefore the task of finding cleaning agents which are notable for improved foaming capacity and improved thickenability with simultaneously low skin stress.

This object was achieved according to the invention by aqueous preparations of surface-active substances containing at least two different ones

Anionic surfactants, being as anionic surfactants

a) at least one compound (A1) which is a polyoxyalkylene radical having an average degree of alkoxylation of 1 to 15 and 1 or 2 lipophilic radicals having 1 to 22 carbon atoms and 1 to 3 polar radicals selected from the group consisting of carboxylate, sulfate or Contains sulfonate residues, the polyoxyalkylene residue being attached by alkoxylation in the presence of catalytic amounts of a hydrophobicized double-layer hydroxide compound of the general formula (I)

[M (II) _1-x M (III) _χ (OH) ₂ ] A _a B _b * z H ₂ O (I) in the M (II) a divalent metal cation selected from that of magnesium, zinc, calcium, Iron, cobalt, copper, cadmium, nickel and manganese formed group, M (III) is a trivalent metal cation selected from the group formed by aluminum, iron, chromium, manganese, bismuth and cerium, A is the equivalent of a monoanion of an aliphatic monocarboxylic acid having 2 to 34 C atoms or an equivalent of a dianion of an aliphatic Dicarboxylic acid with 4 to 44 carbon atoms and

B is an anion from the group formed by carbonate, hydrogen carbonate, sulfate, nitrate, nitrite, phosphate, hydroxide and halides and in which the conditions

0.1 ≤ x ≤ 0.5

0 <a ≤ 0.5

0 ≤ b ≤ 0.5

0 <a + b ≤ 0.5

0 ≤ z ≤ 10

apply, and

b) at least one compound (A2) which is a polyoxyalkylene radical having an average degree of alkoxylation of 1 to 15 and 1 or 2 lipophilic radicals having 1 to 22 carbon atoms and 1 to 3 polar radicals selected from the group consisting of carboxylate, sulfate or Contains sulfonate residues, the polyoxyalkylene residue being attached by alkoxylation in the presence of catalytic amounts of a hydrophobicized double-layer hydroxide compound of the general formula (I)

or

c) at least one compound (B1) which is a polyoxyalkylene radical having an average degree of alkoxylation of 1 to 15 and 1 or 2 lipophilic radicals having 1 to 22 carbon atoms and 1 to 3 polar radicals selected from the group consisting of carboxylate, sulfate or Contains sulfonate residues and / or

at least one compound (B2) which contains 1 or 2 lipophilic residues with 1 to 22 C atoms and a polar residue selected from the group consisting of carboxylate, sulfate or sulfonate residues,

are contained and the lipophilic residues of the compounds (A1), (A2), (B1) and (B2) together each contain at least 8 carbon atoms.

The polyoxyalkylene radical is understood to mean a group consisting of oxyethylene units - [CH ₂ -CH ₂ -O] - or of oxypropylene units - [CH (CH ₃ ) - CH ₂ -O] - is built up. The average number of oxyethylene or oxypropylene units is referred to as the average degree of alkoxylation.

The aqueous preparations according to the invention can e.g. Combinations of anionic surfactants from the following groups contain:

- (A1) and (A2)

- (A1) and (B1)

- (A1) and (B2)

- (A1) and (B1) and (B2)

Those compounds (I) which are hydrophobicized hydrotalcites are preferred. Hydrotalcite is a natural mineral of the ideal formula Mg _0.75 Al _0.25 (OH) ₂ CO ₃ * 0.5 H ₂ O; Since integer indices were usually preferred in the older literature, the formula Mg ₆ Al ₂ (OH) ₁₆ CO ₃ * 4 H ₂ O is often also found, which is obtained from the first representation by multiplication by a factor of eight.

The structure of hydrotalcite is derived from that of brucite, Mg (OH) ₂ . Brucite crystallizes in a layer structure with the metal ions in octahedron pieces between two layers of densely packed hydroxyl ions, with only every second layer of the octahedron gaps being occupied. In the hydrotalcite, some magnesium ions are replaced by aluminum ions, which gives the layer package a positive charge. This is compensated for by the anions, which are located in the intermediate layers together with zeolitic crystal water. The layer structure is shown in the X-ray powder diagram (ASTM card No. 14-191), which can be used for characterization. The Mg ²⁺ : Al ³⁺ ratio can vary between about 1 and 5 in natural and synthetic hydrotalcites. The ratio of OH-: CO ₃ ^2- can also vary.

The hydrophobicized double-layer hydroxide compounds (I), in particular the hydrophobicized hydrotalcites, are obtained by reacting double-layer hydroxide compounds, for example hydrotalcites, with aliphatic monocarboxylic acids with 2 to 34 C atoms or aliphatic dicarboxylic acids with 4 to 44 C atoms. These reactions can be carried out, for example, in organic solvents such as isopropanol or directly by stirring or kneading both reactants. According to the invention, the compounds (A1), (A2) and (B1) are preferably selected from the group of alkyl and dialkyl ether sulfates, ether carboxylic acids, sulfosuccinic acid half-esters, fatty alcohol ether citrates, fatty alcohol ether tartrates and hydroxyalkyl ether sulfonates, and the compounds (B2) from the group of sulfosuccinic acid half-esters, fatty alcohol sulfates -Olefin sulfonates, secondary alkyl sulfonates, acyl sarcosides, acyl taurides and the sulfation products of unsaturated fatty acids.

The counterions of the carboxylate, sulfate or sulfonate residues are preferably selected from the group of alkali and alkaline earth metals, aluminum, ammonium and alkyl or alkylolammonium groups with 1 to 4 carbon atoms in each alkyl or alkylol group.

The chemical structures and the basic surfactant properties of most of these anionic surfactants are now part of textbook knowledge and therefore require no further explanation. Dialkyl ether sulfates are to be understood as meaning compounds as described in European patent application EP 299 370. Details of the production process and the properties of these compounds can be found in this document. Fatty alcohol ether tartrates are monoester salts of tartaric acid, fatty alcohol ether citrates are mono- and / or diester salts of citric acid with adducts of ethylene oxide and / or propylene oxide with fatty alcohols. Hydroxyalkyl ether sulfonates are the subject of German patent application DE 37 25 030. Details of the production process can be found in patent application DE 37 25 030 mentioned. Sulfonates of unsaturated fatty acids are sulfonation products of fatty acids with 12 to 22 carbon atoms and 1 to 6 double bonds. Such products are known from the literature and are accessible, for example, by reacting these fatty acids with gaseous sulfur trioxide. Using the example of oleic acid, details of the production process can be found in German patent application DE 3926344.

The compounds (B1) contain a polyoxyalkylene radical; With regard to the degree of alkoxylation, it generally applies to these compounds that alkoxylation reactions such as, for example, the addition of x mol of ethylene oxide to 1 mol of fatty alcohol in the presence of an alkoxylation catalyst According to the known ethoxylation processes, no uniform adduct, but a mixture of residual amounts of free fatty alcohol and a number of homologous (oligomeric) addition products of 1, 2, 3, ... x, x + 1, x + 2 etc. molecules of ethylene oxide per molecule of fatty alcohol becomes. The average degree of ethoxylation (x) is defined by the starting quantities of fatty alcohol and ethylene oxide. The distribution curve of the homologue mixture usually has a maximum in the range between x-3 and x + 3. Further information on this can be found, for example, in the magazine Soap / Cosmetics / Chemical Specialties, issue January 1988, p. 34.

Furthermore, in addition to the anionic surfactants, the surface-active mixtures according to the invention can additionally contain 0.5-20% by weight, in particular 1-10% by weight, of ampholytic and / or zwitterionic surfactants.

Anpholytic surfactants are surface-active compounds which, in addition to a C ₈ -C 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-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 C. Atoms in the alkyl group.

Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO (-) - or -SO ₃ (-) - group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the coconut alkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the coconut acylaminopropyl dimethylammonium glycinate, and 2-alkyl -3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. The skin-protecting properties of the agents according to the invention come into their own particularly when they are formulated in such a way that they have a pH value close to the neutral point of the skin. Agents with pH values in the range from 5.0 to 7.5, in particular from 5.5 to 7.0, are therefore preferred.

The agents according to the invention can be used in a large number of consumer products such as hair shampoos, bubble baths, shower baths, liquid soaps and manual dishwashing agents.

In addition to the surfactant combination described, these products contain the usual ingredients such as emulsifiers, oil components, fats and waxes, solubilizers, thickeners, superfatting agents, biogenic agents, film formers, fragrances, dyes, pearlescent agents, foam stabilizers, preservatives and pH regulators.

As further emulsifiers, the substances customary in cosmetic preparations, such as. B. fatty acid partial glycerides, fatty acid sorbitan partial esters and their ethoxylates, soaps, fatty alcohol polyglycol ethers, lanolin, wool fatty alcohols and alkyl phosphates can be used.

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

Low monohydric or polyhydric alcohols such as ethanol, isopropanol, 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 also simultaneously serving as foam stabilizers.

Suitable thickeners are, for example, polysaccharides, in particular xanthan gum, guar gum, agar agar, alginates and tyloses, and also car boxymethyl cellulose and hydroxyethyl cellulose, also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinyl pyrrolidone and finally electrolytes such as table salt and ammonium chloride, if desired in combination with alkyl ether sulfates.

Biogenic active substances are understood to mean, for example, plant extracts, protein breakdown products 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.

The substances listed in the annex to the Cosmetics Ordinance are suitable as preservatives.

Particularly suitable pearlescent agents are 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 by Verlag 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 agents according to the invention are fragrances and substances which serve to adjust the pH of the agents.

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 shampoos for washing hair. The following examples serve to illustrate the invention and are not to be interpreted as restrictive.

For example

1. General

1.1. Abbreviations

The addition of HHT to the name of a surfactant means in the following that the ethylene oxide building blocks contained therein have been added using hydrophobized hydrotalcite as a catalyst. The surfactants obtained in this way are referred to as HHT surfactants.

The headers of Tables 1 to 3 show the examples with B1, B2, B3, etc., the comparisons with V1, V2, V3 etc.

1.2. Substances used

N25: aqueous solution of sodium lauryl ether sulfate; Active substance content: 28% by weight ("Texapon ^(R) N25"; Fa. Henkel / Düsseldorf)

Dehyton K: Aqueous solution of a fatty acid amide derivative with betaine structure of the formula R-CONH- (CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ -COO-; CTFA name: Cocamidopropyl Betaine; Active substance content: 30% by weight; NaCl content: 5% by weight (Henkel / Düsseldorf)

Dehyton CB: fatty amine derivative with betaine structure; CTFA name: Coco betaine; Active substance content: 31% by weight; NaCl content 5% by weight (from Henkel / Düsseldorf).

Comperlan LS: Mixture of coconut fatty acid diethanolamide (approx. 70%) and an adduct of 2 moles of ethylene oxide with lauryl alcohol (approx. 20%); Balance: water, free amine, free fatty acid, ester. (Henkel / Düsseldorf).

K14S: aqueous solution of lauryl / myristyl ether sulfate, Na salt; Active substance content: 28% by weight ("Texapon ^(R) K14S-Spezial"; Fa. Henkel / Düsseldorf). SB3: aqueous solution of a sulfosuccinic acid semi-ester based on an alkyl polyglycol ether, di-Na salt, CTFA name: disodium laureth, (C12, 12 (3 EO)) sulfosuccinates; Active substance content: 40% by weight ("Texapon ^(R) SB3; from Henkel / Düsseldorf) HMS: Aqueous solution of a dialkyl ether sulfate of the formula (III) in which R ^{2 is} an n-decyl radical, R ^{3 is} an n-octyl radical, R ^{4 is} hydrogen, m is the number 2 and b is the number 4; Active substance content: 40% by weight.

AKYP: aqueous solution of an ether carboxylic acid salt of the formula C _12/14 - (O-CH ₂ -CH ₂ ) ₁₀ -OCH ₂ -COONa, active substance content: 22% by weight ("Akypo ^(R) -Soft 100 NV"; Chemy -Y)

HOES: Aqueous solution of a mixture of hydroxyalkyl ether sulfates according to the formulas (VIII) and (IX), which, analogously to the procedure disclosed in Examples 2.1 and 2.2 of German Patent Application 3725030, consists of an adduct of 10 mol ethylene oxide with technical oleyl alcohol with an iodine number of 94 and has a hydroxyl number of 210 and in which M ^{6 is} sodium; Active substance content: 32% by weight.

ÖDS: Aqueous solution of oleic acid sulfonate, disodium salt, produced by sulfonation of technical oleic acid with gaseous sulfur trioxide according to German patent application DE 39 26 344; the oleic acid No. 1 (ex beef tallow) identified on page 4 of this application was used. Active substance content: 51% by weight.

APG600: C _12/14 fatty alcohol glucoside with a degree of oligomerization of 1.45 (from Henkel / Düsseldorf).

HHT surfactants: With the exception of the ethoxylation step, the preparation of the HHT surfactants was identical to the preparation of the analogue compound of the same empirical formula. The hydrophobicized hydrotalcite used as the ethoxylation catalyst was obtained as follows: 50 g of hydrotalcite (commercial quality) were suspended in 250 ml of isopropanol and added within 30 minutes with 33.2 g of lauric acid (molar ratio of hydrotalcite: oleic acid 1: 2) in 200 ml of isopropanol Room temperature offset. During the heating to reflux temperature, CO ₂ evolution started. After the evolution of gas had ended, the mixture was left to react for 1 to 2 hours, cooled and the suspension was filtered. The filter cake was washed with isopropanol and dried to constant weight in a drying cabinet at 105 ° C. and 100 hPa. Yield 56.4 g; Lauric acid content approx. 26.4% by weight based on the total weight; Carbonate content: 6.9% by weight. For the ethoxylation, the corresponding alcohol was placed in a pressure reactor and treated with the hydrophobized hydrotalcite. The reactor was purged with nitrogen and at a temperature of 100 ° C for 30 minutes evacuated. The temperature was then raised to 180 ° C. and the desired amount of ethylene oxide was injected at a pressure of 400 to 500 kPa (4-5 bar). After the reaction had ended, the mixture was left to react for 30 minutes. The desired ethoxylate was obtained after filtering off the catalyst.

2. Determination of the foaming behavior

The foaming behavior of the surfactants and surfactant mixtures was determined using a motorized blow-foam apparatus based on DIN 53902. 340 ml of surfactant solution (2% by weight of active substance in tap water from Düsseldorf-Holthausen at 18 ° dH) were prepared for this purpose. The foam was generated at room temperature with a perforated plate (holes of 1 mm in diameter, 10 impacts at a frequency of 50 impacts / min, 13 cm stroke); it was very fine-pored and thus largely corresponded to a foam that formed on the head when shampooing. The measurements were carried out as a duplicate determination without grease contamination of the surfactant solution.

The foam behavior of a mixture known to be good foaming was compared

(a) 42% by weight of Texapon N 25 (= 12% active substance),

(b) 10% by weight of Dehyton K (= 3% active substance),

(c) 1% by weight Comperlan LS (= 1% active substance) and

(d) 47 weight percent water

certainly. This standard mixture was diluted with water and also used in the form of a solution with 2% by weight of active substance. The following amounts of foam were measured:

- after 1 minute: 240 ml

- after 3 minutes: 210 ml

- after 5 minutes: 190 ml

The measured foam amounts of the surfactant solutions according to the invention are given in Table 1 in percent based on the foam amount of the comparison mixture. It is striking that those surfactant mixtures which contain at least one NRE surfactant are clearly superior to the corresponding NRE-free comparisons with regard to the amount of foam. Table 1: relative amount of foam

V1 B1 B2 V2 B3 B1 V3 B5 B6 B7 V4 B8 V5 B9 V6 B10

K14S 60 - - - - - 40 - 40 - - - - - 80 -

K14S / HHT - 60 40 - - - - 40 - 40 - - - - - 80

SB3 - - - 40 - - - - - - BO - - - - -

SB3 / HHT - - - - 40 30 - - - - - 80 - - - - HMS - - - - - - 60 60 - - - - - - - -

HMS / HHT - - - - - - - - 60 • 60 - - - - - -

AKYP - - - - - - - - - - - - 40 - - -

AKYP / HHT - - - - - - - - - - - - - 40 - -

HOES - - - - - - - - - - 20 20 60 60 - -

ÖDS 40 40 20 60 60 40 - - - - - - - - - -

DEHYTON K - - - - - - - - - - - - - - 20 20

APG600 - - 40 - - 30 - - - - - - - - - -

Foam 1 '70 80 100 50 66 100 91 98 98 97 91 96 78 88 98 119

Foam 3 '40 44 100 22 58 100 85 95 95 96 86 91 80 90 90 105

Foam 5 '12 12 99 12 42 106 89 92 92 105 94 99 72 82 87 106 (1) The information in the upper block of the table relates to the weight ratio of the surfactants at a total concentration of 2% by weight of active substance.

The information in the lower block of the table indicates the percentage of foam in comparison to the standard.

3. Thickenability of mixtures with ampholytic or

zwitterionic surfactants

The thickenability of selected surfactant mixtures was measured at 20 ° C. using a Brookfield viscometer using spindle 3 at 20 revolutions per minute. The results are shown in Table 2. It should be noted that the viscosities of Examples B11 to B14 are clearly superior to the corresponding comparisons V7 to V10.

Table 2: Thickenability ⁽¹⁾

Substance V7 V8 V9 V10 B11 B12 B13 B14

N25 12.0 12.0 12.0 - - - - -

N25 / HHT - - - - 12.0 12.0 12.0 -

K14S - - - 12.0 - - - -

K14S / HHT - - - - - - - 12.0

Dehyton CB 3.0 3.0 3.0 - 3.0 3.0 3.0 -

Dehyton K - - - 3.0 - - - 3.0

NaCl - 1.0 5.0 5.0 - 1.0 5.0 5.0

Viscosity [Pas] 1.1 22.4 2.0 9.4 2.8 130.0 8.4 25.2

(1) Unless otherwise stated, the information in the table relates to% by weight of active substance.

4. Skin tolerance tests

The in vitro method developed by Zeidler and Reese was used to determine the skin tolerance of the surfactant mixtures, and is described in detail in the journal Ärzte Cosmetologie 13, 39-45 (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 hours and weighed again. In order to eliminate influences that go back to specific properties of the respective animal or the place of removal (back, side), a standard measurement was carried out. An immediately adjacent strip of epidermis is 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 (swollen epidermis) - weight (dry 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 water-treated skin is therefore by definition 0%; negative values indicate anti-swelling properties.

The results of the swelling measurements are summarized in Table 3. The test numbers given in the header correspond to those in Table 1 with regard to the composition of the surfactant mixtures.

It turns out that mixtures which contain an HHT surfactant have at least equally good, in many cases even improved, swelling values in comparison with mixtures free of HHT surfactant. With regard to Table 1, it is thus clear that the surfactant mixtures according to the invention Compared to the comparisons are characterized by an improved foaming capacity with at least equally good swelling values.

Table 3; Swelling measurements ⁽¹⁾

Substance V1 B1 V2 B3 V3 B6 V4 B8 V5 B9

K14S 60 - - - 40 - - - - -

K14S / HHT - 60 - - - 40 - - -

SB3 - - 40 - - - 80 - - -

SB3 / HHT - - - 40 - - - 80 - -

K14S - - - - - - - - - -

HMS - - - - 60 - - - - -

HMS / HHT - - - - - 60 - - - -

AKYP - - - - - - - - 40 -

AKYP / HHT - - - - - - - - - 40

HOES - - - - - - 20 20 60 60

ÖDS 40 40 60 60 - - - - - -

Source value ⁽²⁾ 39 39 39 33 62 22 30 16 29 9

(1) The information in the upper block of the table relates to the weight ratio of the surfactants at a total concentration of 2% by weight of active substance.

The information in the lower block of the table relates to the experimentally determined swelling value Q.

(2) The error limits for tests V1, B1 and V3 were ± 10, for tests V2 and B3 ± 13 and for tests B6, V4, B8, V5 and B9 ± 7.

Claims

1. Aqueous preparations of surface-active substances containing at least two different anionic surfactants, characterized in that as anionic surfactants

[M (II) _1-x M (III) _x (OH) ₂ ] A _a B _b * z H ₂ O (I) in the M (II) a divalent metal cation selected from that of magnesium, zinc, calcium, Iron, cobalt, copper, cadmium, nickel and manganese formed group,

M (III) is a trivalent metal cation selected from the group formed by aluminum, iron, chromium, manganese, bismuth and cerium,

A is the equivalent of a monoanion of an aliphatic monocarboxylic acid with 2 to 34 C atoms or for an equivalent of a dianion of an aliphatic dicarboxylic acid with 4 to 44 C atoms and

B is an anion from the group formed by carbonate, hydrogen carbonate, sulfate, nitrate, nitrite, phosphate, hydroxide and halides

and in the the conditions

0.1 ≤ × ≤ 0.5

0 <a≤ 0.5

0 ≤ b ≤ 0.5

0 <a + b ≤ 0.5

0≤ z ≤ 10

apply, and

b) at least one compound (A2) which has a polyoxyalkylene radical with an average degree of alkoxylation of 1 to 15 and 1 or 2 lipo contains phile residues with 1 to 22 carbon atoms and 1 to 3 polar residues selected from the group consisting of carboxylate, sulfate or sulfonate residues, the polyoxyalkylene residue being attached by alkoxylation in the presence of catalytic amounts of a hydrophobized double-layer hydroxide compound of the general formula (I ) or

c) at least one compound (B1) which is a polyoxyalkylene radical having an average degree of alkoxylation of 1 to 15 and 1 or 2 lipophilic radicals having 1 to 22 carbon atoms and 1 to 3 polar radicals selected from the group consisting of carboxylate, sulfate or Contains sulfonate residues

and or

2. Aqueous preparations according to claim 1, characterized in that the compound of general formula (I) is a hydrophobicized hydrotalcite.

3. Aqueous preparations according to claim 1 or 2, characterized in that the compounds (A1) and (A2) are selected from the group consisting of alkyl and dialkyl ether sulfates, ether carboxylic acids, sulfosuccinic acid semiesters, hydroxyalkyl ether sulfonates, alkyl ether citrates and alkyl ether tartrates.

4. Aqueous preparations according to one of claims 1 to 3, characterized in that the compound (B1) is selected from the group consisting of alkyl and dialkyl ether sulfates, ether carboxylic acids, sulfosuccinic acid semiesters, hydroxyalkyl ether sulfonates, alkyl ether citrates and alkyl ether tartrates.

5. Aqueous preparations according to one of claims 1 to 4, characterized in that the compound (B2) is selected from the group the, alkyl sulfates, α-olefin sulfonates, secondary alkyl sulfonates, acyl sarcosides, acyl taurides, acyl isethionates and the sulfonates of unsaturated fatty acids.