DE3939315A1 - ALKYLENOXIDE-CONTAINING AMPHOTERE TENSIDE - Google Patents

Abstract

Novel alkylene oxide-containing amphoteric compounds of the formula <IMAGE> in which R is C6-C22 straight or branched chain alkyl or a group R3-C6H5-, where R3 is C6-C16 straight or branched chain alkyl; R1 is -CH2COOM, where M is hydrogen or a cation selected from alkali metal, alkaline earth metal, ammonium, mono-, di- and tri-C2-C-C4 alkanolammonium and mono-, di-, tri- and tetra-C1-C4 alkylammonium; R2 is hydrogen or-CH2COOM, where M is as defined above; m is O or an integer 1 to 10; n is an integer 2 to 15; and X<-> is an anion, are useful as surface active agents. The novel amphoteric compounds are especially useful in the cosmetics and toiletries areas, e.g., as surfactants in shampoo compositions.

Description

The invention relates to a new class of surfactants. In particular, it relates to certain alkylene oxide-containing amphoterics Compounds and their use as surfactants in a wide range of products. The amphoteric compounds are particularly suitable for use in cosmetics and other Toiletries, e.g. B. as surfactants in shampoo compositions.

One skilled in the art is well aware that for Formulation of shampoo compositions for human hair many aspects have to be considered in a very special way, namely cleaning power, foaming effect, mildness etc. a surfactant selected primarily on the basis of its cleaning effect, and at the expense of a compromise to be accepted, what that Overall product behavior concerns.

Soap-based shampoos have been used in the past. These had the disadvantage that they could build up limescale deposits. and magnesium soap, especially in hard water, the hair dull and made it lackluster. In addition, such deposits have a foaming effect of each shampoo significantly reduced. Given these problems, attempts have been made to achieve these adverse effects to be eliminated by using the soap previously used partly through synthetic organic surfactants like conventional sulfates and replaced sulfonates. However, these shampoos appear Inadequate based on a mixture of synthetic surfactants and soap  to be, they offer little benefit in terms of consumer requirements. For example, such funds Calcium ions brought together from the water, so the formed Lime soaps can be dispersed using the synthetic surfactant. Thus, when such ions are present, it is not just a decay Part of the soap lost for binding the calcium, but it will also part of the synthetic surfactant as a dispersant for the Lime soap that is formed consumes and loses to a certain extent Cleaning person. It should also be borne in mind that even professional Washing hair is normally done using tap water. In recent times, shampoos have been developed that are essential Cleaning component exclusively a synthetic surfactant or contain a mixture thereof. If these preparations too have acceptable washing and foaming properties, it seems the presence of synthetic surfactant the potential for irritation of the shampoo increase, which means the average from a mild point of view is no longer justifiable. This increased intolerance potential of shampoo based on synthetic surfactant in The synthetic surfactant used to get a grip further modified; for example, in the higher alkyl ether sulfate according to formula

R (OCH₂CH₂) _m -OSO₃M,

wherein R is C₁₀-C₁₅ alkyl, m is a number from 1-3 and M is a cation,

the number of ethyleneoxy groups present increases. But it has Change, though to a certain extent, the potential for stimulus attenuates, an adverse effect on the foam properties.

The present invention provides alkylene oxide-containing amphoteric surfactants, particularly in cosmetics Range are applicable. These surfactants can be an essential ingredient for shampoo preparations are used and have excellent washing and foaming properties. In addition, the amphoteric surfactants have a high salt tolerance, which makes it possible to contribute them in a highly active form low viscosity.  

The amphoteric compounds correspond to the formula I

wherein

R is C₆-C₂₂-alkyl that is linear or branched, or the group R₃-C₆H₅-, wherein R₃ is linear or branched C₆-C₁₆-alkyl;
R₁ for -CH₂COOM, where M is hydrogen or a cation from the series alkali metal, alkaline earth metal, ammonium, mono-, di- and tri-C₂-C₄-alkanolammonium and mono-, di-, tri- and tetra-C₁-C₄-alkylammonium ;
R₂ is hydrogen or -CH₂COOM, wherein M is as defined above;
m represents 0 or a number from 1 to 10;
n for a number from 2 to 15; and
X⊖ represent an anion,

or a mixture of these compounds.

The ammonium salt structure given in formula I represents a possible ionic arrangement. However, it is clear that the solvation of the individual ions taking place in aqueous solution leads to an equilibrium condition in which a zwitterionic form also exists with the solvated ions M _s ⊕ and X _s ⊖ according to the reaction scheme below:

R as linear or branched alkyl preferably contains 8 to 20 C atoms, more preferably 10 to 20 and in particular 12 to 18 C atoms.

If R represents the group R₃-C₆H₅-, the R₃ portion preferably contains 6 to 14 C atoms, more preferably 8 to 12 and particularly preferably 9 up to 12 carbon atoms.  

In the defined for M C₂-C₄ hydroxyalkyl group the hydroxy group is preferably at other than the α-carbon atom. If M contains more than one C₂-C₄-hydroxyalkyl or C₁-C₄-alkyl group, these may be the same or different, but are preferably the same. M expediently contains no more than two tertiary butyl groups. Preferred alkali metals as M are lithium, potassium and sodium, preferred alkaline earth metals are magnesium, calcium, barium and strontium.

The variable m preferably represents 0 or a number from 1 to 5, more preferably 0 or a number from 1 to 3, particularly preferably 0 or a number from 1 to 2.

The variable n preferably means a number from 2 to 12, more preferably a number from 3 to 10 and even more preferably a number from 4 to 9.

The variables m and n , as well as the indices p, q, r, t, u and v defined below, represent average values. However, it is clear that these indices represent integers for each individual compound.

The anion X⊖ is preferably halide, more preferably Chloride or bromide, especially for chloride. Preferred compounds correspond to formula Ia,

wherein

R _{a is} C₈-C₂₀-alkyl which is straight-chain or branched, or the group R _{3 a} -C₆H₅-, wherein R _{3 a is} straight-chain or branched C₆-C₁₄-alkyl;
R _{1 a is} -CH₂COOM _a , wherein M _{a is} hydrogen or a cation from the series alkali metal, alkaline earth metal and ammonium;
R _{2 a is} hydrogen or -CH₂COOM _a , wherein M _{a is} as defined above;
p for 0 or a number from 1 to 5,
q for a number from 2 to 12; and
X _a ⊖ represent a halide,

or a mixture of these compounds of the formula Ia.

Compounds of the formula Ib are more preferred,

wherein

R _{b is} C₁₀-C₂₀ alkyl which is straight-chain or branched, or the group R _3b -C₆H₅-, in which R _3b denotes straight-chain or branched C₈-C₁₂-alkyl;
R _{1 b is} -CH₂COOM _b , wherein M _{b is} hydrogen or a cation from the series alkali metal and ammonium;
R _{2b is} hydrogen or -CH₂COOM _b , wherein M _{b is} as defined above;
r for 0 or a number from 1 to 3,
t for a number from 3 to 10; and
X _b ⊖ represents chloride or bromide,

or a mixture of these compounds of the formula Ib.

Even more preferred are compounds of formula Ic

wherein

R _{c is} C₁₂-C₁₈ alkyl that is linear or branched, or the group R _3c -C₆H₅-, wherein R _{3c is} linear or branched C₉-C₁₂ alkyl;
R _{1c is} -CH₂COOM _c , wherein M _{c is} hydrogen, sodium, potassium or ammonium;
R _{2c is} hydrogen or -CH₂COOM _c , wherein M _{c is} as defined above;
u for 0 or a number from 1 to 2,
v for a number from 4 to 9; and
X _c ⊖ is chloride,

or a mixture of these compounds of the formula Ic.

Suitable alcohols as starting materials for the preparation of the compounds of the formula I are straight-chain or branched primary alcohols having 6 to 22 carbon atoms; typical representatives with branched Alkyl chains are isodecyl and isostearyl alcohol. It can too Alcohol mixtures are used as they are generally commercially available are available in the form of mixtures of several alcohols. A mixture of is to be mentioned as specific examples C₁₂-C₁₅ straight-chain alcohols, such as those commercially available from Union Carbide is; a mixture of mainly C₁₂-C₁₅ straight chain alcohols with a 20% branched portion, as sold by Shell Chemical Co. is available; and a mixture of alcohols that are at least 70 Contains mol% of branched 1-decanols and from Exxon Chemical Co. can be obtained. If such alcohol mixtures are used, then the specified carbon number represents an average value that by gas chromatography analysis or by determining the hydroxyl number can be determined.

Straight-chain or branched are also suitable as starting compounds Alkylphenols that carry 6-16 carbon atoms in the alkyl part. Typical Examples of alkylphenols with a linear alkyl radical are n-hexylphenol, n-decylphenol, n-dodecylphenol, n-tetradecylphenol, etc .; Representative with a branched alkyl configuration are i-octylphenol and branched Nonylphenol.

The compounds of formula I and mixtures thereof are per se usual methods. You can by carboxyalkylation of the Adduct, as by propoxylation and / or ethoxylation of a straight-chain or branched primary alcohol with 6-22 carbon atoms or a straight-chain or branched alkylphenol with 6-16 C atoms in the alkyl part is obtained, condensation with a suitable Amine and subsequent carboxyalkylation of the amidoamine intermediate are produced, resulting in a compound of the formula I, where R₂ is hydrogen. By further carboxyalkylation the compound thus obtained becomes a compound of formula I prepared in which R₂ is -CH₂COOM.  

The alkoxylations are generally carried out in the presence of an alkaline Catalyst, e.g. B. of alkali metal hydroxides, sodium ethoxide, Sodium methoxide, alkali metal acetates and dimethylamine, or mixtures of which, carried out. Sodium or potassium hydroxide is preferably used in an amount of 0.2-1%, preferably 0.3-0.75% based on the weight of the total reaction mixture.

It is advantageous to use the alcohol or a mixture to be alkoxylated of these or the alkylphenol to add a reducing agent to discolor the reaction products to a minimum. As Suitable reducing agents can be sodium borohydride, lithium aluminum hydride and diborane, preferably sodium borohydride.

If an alcohol or alkylphenol which is first polypropylated and then polyethoxylated is to be used, the calculated amount of propylene oxide which is necessary to achieve the desired degree of propoxylation is first added and allowed to react until the propylene oxide has been consumed, which is followed by Drop in the reaction pressure is noticeable. In an analogous manner, the calculated amount of ethylene oxide is added to complete the alkoxylation reaction. The alkoxylated product is usually aftertreated with a weak acid, for example glacial acetic acid, in order to neutralize all traces of basic catalyst. Each individual alkoxylation step serves to introduce a desired average number of alkylene oxide units per alcohol or alkylphenol molecule. For example, in the initial reaction with propylene oxide, the addition is effected to every molecule of alcohol or alkylphenol. However, it may also be the case that individual alcohol or alkylphenol molecules react with more than m mol of propylene oxide, and some with less than m mol of propylene oxide. In general, however, there are no more than 20 propyleneoxy units and no more than 25 ethyleneoxy units per single molecule. The number of alkyleneoxy units per single molecule is not critical as long as the mean value for each block is within the limit values set for m and n , this mean value need not represent an integer as an average value.

Any alkoxylation is carried out at elevated temperature and pressure carried out. Suitable reaction temperatures are between 120 ° and 220 ° C, preferably between 130 ° and 180 ° C, and in particular between 140 ° and 160 ° C. A suitable reaction pressure is achieved that the reaction vessel with the required amount of propylene oxide or Ethylene oxide, both at the intended reaction temperature have a high vapor pressure. The prevailing Pressure is a measure of how far the response has progressed is; If the pressure drop is no longer detected, the alkoxylation can be considered to have ended.

In order to achieve optimal yields, it is desirable to carry out the alkoxylation to be carried out under as moisture-free conditions as possible and to avoid side reactions in which water is formed. Around the reaction vessel and the feed lines before loading dry with a dry, oxygen-free gas, e.g. B. be flushed with nitrogen. The catalyst used should be as anhydrous as possible; and also the propylene oxide and Ethylene oxide should be cleaned to remove traces of it before use Moisture and other contaminants associated with side reactions Can form water to remove.

The resulting alkyl or alkaryl polyalkoxylene intermediate is then carboxymethylated using the Williamson synthesis, thereby the product with chloro or bromoacetic acid or a salt thereof in the presence of a strong base such as sodium hydroxide or sodium carbonate etc., implemented, or by catalytic oxidation. Such Reactions are usually not complete, so that Reaction product small amounts of non-carboxymethylated alkyl or may contain alkaryl polyalkoxide. Although there are methods to separate this non carboxymethylated material as well as to ensure that the carboxymethylation is essentially complete has expired, these are generally very lengthy and expensive. However, it has been found that small amounts of do not disturb carboxymethylated product and even beneficial could be. With regard to the complete course of carboxymethylation the route via Williamson synthesis is preferred.  

The amidoethylamine intermediates can via a condensation reaction getting produced. The alkyl or alkylphenyl polyoxyalkylene carboxylic acid and the corresponding amine, e.g. B. 2-Aminoethylethanolamine, in approximately equimolar proportions at elevated temperatures between 100 ° and 220 ° C and reduced Pressure is reacted with each other and the water that forms is removed.

The condensation can also be carried out so that one lower alkyl esters of alkyl or alkylphenyl polyoxyalkylene carboxylic acid, e.g. B. the methyl, ethyl, isopropyl ester, etc., or Halide with the corresponding amine in approximately equimolar amounts a temperature in the range of 50 ° -150 ° C. For example the corresponding isopropyl ester can be used, with isopropyl alcohol is released. If the corresponding carboxylic acid halide is used, the reaction is in a molar ratio of 0.45-1.10 Perform carboxylic acid halide to amine. The excess of amine is required to trap the hydrochloric acid formed. Conveniently in this case a basic amine is added to the reaction mixture, for example triethylamine or pyridine, added to the hydrochloric acid to tie. If so, the reactants can be in equimolar ratio can be used. Usually the condensation reaction in an inert organic solvent, such as an aliphatic hydrocarbon, e.g. B. dichloromethane, at one Temperature between 25 ° and 50 ° C carried out.

The amidoethylamine intermediates obtained are then via a nucleophilic substitution to form the ammonium salt carboxymethylated. This reaction takes place without base addition. As a result the amidoethylamine intermediate and a salt of bromo or chloroacetic acid in approximately equimolar amounts in the presence of a conventional Solvent, e.g. B. water or an alcohol, at a temperature in the range 25 ° -100 ° C, preferably between 50 ° -90 ° C, implemented results in a compound of formula I, wherein R₂ is hydrogen. You can also work without a solvent, provided the viscosity the reaction mixture effective stirring and good mass transfer allows.  

The introduction of a further carboxymethyl group can also be carried out in an analogous manner take place for the preparation of a compound of formula I, wherein R₂ is -CH₂COOM; namely through a corresponding substitution reaction as described above, in the presence of a strong Base that deprotonates the ammonium ion and nucleophiles the nitrogen makes against the salt of chloro or bromoacetic acid. The Reaction conditions are essentially the same as above for the preparation of the compounds of formula I with R₂ in importance of hydrogen mentioned.

The compounds of the formula I are used as surface-active Agents, they are suitable for use as emulsifiers, dispersants, Cleaning agents, wetting agents, leveling agents u. in the Textile, leather, paper, paint industry, in personal care for Toiletries and cosmetics etc. and in the rubber industry. So you can use it, for example, as a wetting agent or cleaning agent Treatment and finishing of textiles; as well as for the transfer of liquid or solid substances insoluble in water (such as Hydrocarbons, higher alcohols, oils, fats, waxes and resins) in creamy emulsions, clear solutions or fine stable dispersions be applied.

In addition, the compounds of formula I are valuable Emulsifiers for insecticide compositions and agrochemical sprays (such as DDT, 2,4-D etc.); they are suitable as additives for petrochemical Products, hydraulic fluids, lubricating oils, cutting oils and greases; as an aid in the manufacture of coatings with hydrophilic, film-forming colloid; as an adhesive in the adhesive layer of adhesive tapes, e.g. B. in the photo industry; such as as a foam-providing and emulsifying agent in a wide range the food industry.

The amphoteric compounds of the present invention are particularly effective However, the invention as a surface-active agent in hair shampoo preparations. Their addition not only improves the cleaning and foam properties of the shampoo, but also the  Touch characteristics. Such shampoo preparations usually contain about 5 to 55% of amphoteric compound of formula I, preferred about 10-45%, and more preferably about 10-40% (based on the total weight of the agent). Although the amphoteric compounds can be used as the sole surfactant according to the invention, d. H. the usual anionic surfactants such as alkyl EO sulfates completely replace, it is more preferred that the latter only partially are replaced, so the compounds of formula I preferably in Can be used in combination with commonly used surfactants. Such shampoo preparations are normally 20-50 percent by weight (based on the total weight of the mixture) included, preferred 30-45%.

The shampoo preparations can also contain other usual ingredients contain, for example fatty alkanolamides to support the Foam stabilization and for increased foam formation as well as Ensuring a viscosity that is acceptable for cosmetic purposes. in the is generally a C₈-C₁₈ mono- or dialkanolamide with a 1: 1 ratio (prepared by reacting equimolar amounts of the methyl ester a suitable carboxylic acid and the mono- or dialkanolamine) used. A suitable monoalkanolamide is e.g. B. coconut monoethanolamide, suitable dialkanolamides are e.g. B. Lauryl diethanolamide and Coconut diethanolamide.

Also conditioning agents in the form of quaternary ammonium compounds such as dimethyl distearyl ammonium chloride and cationic polymers such as Cartaretin F-23 (Sandoz Corporation) and Polymer JR (Union Carbides) can be added. These additives are said to be combing and Shaping damaged hair and ease the electrostatic charge lessen hair that has dried after washing.

To add shine to washed hair, use shampoo an oil can be added, for example a silicone oil (such as dimethylpolysiloxane or another common polysiloxane), olive oil or a light mineral oil.  

The content of water or aqueous vehicle depends on that for the final product Desired consistency: viscous, lotion or gel. It inorganic salts such as sodium chloride can also be added to to have the viscosity under control.

Other possible additives, typical for shampoos, are the following: Oily fragrances that mask the smell of the composition and give a cosmetic coat; non-toxic and dyes compatible with the mixture, provided the coloring of the Preparation is desired; Preservatives like methyl paraben, Propyl paraben and formaldehyde; Sunscreens such as octyl-dimethyl-p-aminobenzoic acid; and anti-dandruff agents based on zincomadine (Olin).

The following examples, in which all parts are by weight and the temperatures in degrees Celsius are used for Illustration of the invention.

example 1 N- [2- (N′-carboxymethyl-N ′ - (2-hydroxyethyl) ammonium) ethyl] lauryl-tetraethoxyacetamide chloride a) Preparation of N- [2- (2-hydroxyethylamino) ethyl] lauryl-tetraethoxyacetamide

282.6 parts of lauryltetraethoxyacetic acid are placed in a reaction flask submitted and heated to 70 ° C under vacuum (with water suction). Nitrogen is bubbled through and the mixture is cooled to 25 ° C. Under Stirring at 25 ° C under nitrogen are then in a continuous stream 52.07 parts of 2-aminoethyl ethanolamine were added. The reaction temperature is gradually increased to 49 ° C within an hour, then the reaction mixture is heated to 160 ° C. under a stream of nitrogen. After 10 parts of water have been collected, the heating is stopped and the reaction product obtained is cooled to 25 ° C. It results in a liquid product, which has the formula

comes to.

Establishment of the title connection

102.15 parts of the compound produced under 1a) are in 180.3 Dissolved parts of distilled water. Add 17.55 with stirring Parts of monochloroacetic acid as sodium salt. The reaction mixture is heated to 70 ° C and left at this temperature for five hours. The Heating is then stopped and a solution is obtained which is 40% Contains active substance. After cooling, the title compound is called Get clear yellow gel.  

Example 2 N- [2- (N ′, N′-bis (carboxymethyl) -N ′ - (2-hydroxyethyl) - ammonium) ethyl] p-nonylphenoxy-nonaethoxyacetamide chloride a) Preparation of N- [2- (2-hydroxyethylamino) ethyl] p-nonyl-phenoxy-nonaethoxyacetamide

Instead of lauryl-tetraethoxyacetic acid, the approximately equivalent Amount of p-nonylphenoxynonaethoxyacetic acid used and otherwise essentially according to the method described in Example 1a) worked, you get the compound of the formula

Establishment of the title connection

218 parts of the compound produced under 2a) are in 416 parts distilled water dissolved. The solution with stirring 30.2 Parts of monochloroacetic acid added as the sodium salt. The reaction mixture is then heated to 75 ° C and during this temperature left for four hours. After cooling to 50 ° C, 20.8 parts 50% sodium hydroxide solution added. It is stirred for 30 minutes then 30.2 parts of monochloroacetic acid as the sodium salt admitted. The mixture is allowed to react overnight, the Temperature is kept at 50 ° C. The title connection results as a light yellow, aqueous solution containing approximately 40% active ingredient.  

Example 3 N- [2- (N ′, N′-bis (carboxymethyl) -N ′ - (2-hydroxyethyl) - ammonium) ethyl] isodecyl-dipropoxyhexaethoxyacetamide chloride a) Preparation of N- [2- (2-hydroxyethylamino) ethyl] isodecyl-dipropoxy-hexaethoxyacetami-d

Is the Lauryltetraäthoxyacetic acid used in Example 1a) by the approximately equivalent amount of isodecyl-dipropoxy-hexaethoxyacetic acid replaced and otherwise according to that described in Example 1a) Method worked, so you get the compound of the formula

Establishment of the title connection

Is essentially according to the last step in the synthesis of the Compound of Example 2 worked, being instead of the compound from Example 2a) the compound prepared under 3a) is used the title compound is obtained as a light yellow aqueous solution, which contains about 40% of active substance.  

Example 4 N- [2- (N ′, N′-bis (carboxymethyl) -N ′ - (2-hydroxyethyl) - ammonium) ethyl] lauryl-tetraethoxyacetamide chloride

Is essentially according to the last stage in the process of Preparation of the compound of Example 2 worked, instead of the compound produced under example 2a) is approximately equivalent Amount of the compound prepared under Example 1a) used , the title compound is obtained as a pale yellow aqueous Solution containing approximately 40% active ingredient.

For all of the examples above, it should be made clear that those for the Propyleneoxy and ethyleneoxy units set numerical Indices represent averages.  

Example 5

To the high degree of salt insensitivity, which the amphoteric Associated with compounds of the present invention is to illustrate became the compound of Example 3 together with Miranol C2M (a commercial amphoteric surfactant with a hydrophobic coconut residue with an average chain length of 12 carbon atoms) tested. Test samples were provided containing 20% active surfactant and a different sodium chloride content between 3 and 13% contained. The resulting viscosity was measured on a Brookfield LVT viscometer determined at 60 rpm.

The diagram according to FIG. 1, which shows the dependence of the viscosity on the salt content, clearly shows that the compound from Example 3 has a clearly lower viscosity for each salt content examined. In addition, the viscosity of the compound from Example 3 responds less strongly to an increase in the salt content than is the case for the viscosity of Miranol C2M. It can be concluded from this that the compound from Example 3 is more suitable than Miranol C2M for the formulation of products which have a high content of ionic material. In addition, it can also be deduced from the above test that the compounds from Example 3 would be significantly more effective than Miranol C2M when used in tertiary oil recovery, which takes place under conditions of high salt content.

Example 6

The following are typical formulations used as shampoos are suitable.

Claims (9)

1. Compounds of formula I whereinR is C₆-C₂₂-alkyl that is linear or branched, or the group R₃-C₆H₅-, wherein R₃ is linear or branched C₆-C₁₆-alkyl;
R₁ for -CH₂COOM, where M is hydrogen or a cation from the series alkali metal, alkaline earth metal, ammonium, mono-, di- and tri-C₂-C₄-alkanolammonium and mono-, di-, tri- and tetra-C₁-C₄-alkylammonium ;
R₂ is hydrogen or -CH₂COOM, wherein M is as defined above;
m represents 0 or a number from 1 to 10;
n for a number from 2 to 15; and
X⊖ represent an anion, or a mixture of these compounds. 2. Compounds according to claim 1, which of the formula Ia correspond in whichR _{a is} C₈-C₂₀-alkyl which is straight-chain or branched, or the group R _3a -C₆H ,-, in which R _3a denotes straight-chain or branched C₆-C₁₄-alkyl;
R _{1a is} -CH₂COOM _a , wherein M _{a is} hydrogen or a cation from the series alkali metal, alkaline earth metal and ammonium;
R _{2a is} hydrogen or -CH₂COOM _a , wherein M _{a is} as defined above;
p for 0 or a number from 1 to 5,
q for a number from 2 to 12; and
X _a ⊖ stand for a halide, or a mixture of these compounds of the formula Ia. 3. Compounds according to claim 2, which of the formula Ib correspond in which R _{b is} C₁₀-C₂₀ alkyl which is straight-chain or branched, or the group R _3b -C₆H₅-, in which R _3b denotes straight-chain or branched C₈-C₁₂-alkyl;
R _{1b is} -CH₂COOM _b , wherein M _{b is} hydrogen or a cation from the series alkali metal and ammonium;
R _{2b is} hydrogen or -CH₂COOM _b , wherein M _{b is} as defined above;
r for 0 or a number from 1 to 3,
t for a number from 3 to 10; and
X _b ⊖ is chloride or bromide, or a mixture of these compounds of the formula Ib. 4. Compounds according to claim 3, which of the formula Ic in which R _{c is} C₁₂-C₁₈ alkyl which is linear or branched, or the group R _3c -C₆H₅- in which R _{3c is} linear or branched C₉-C₁₂ alkyl;
R _{1c is} -CH₂COOM _c , wherein M _{c is} hydrogen, sodium, potassium or ammonium;
R _{2c is} hydrogen or -CH₂COOM _c , wherein M _{c is} as defined above;
u for 0 or a number from 1 to 2,
v for a number from 4 to 9; and
X _c ⊖ is chloride, or a mixture of these compounds of formula Ic. 5. Shampoo preparation, the 5-55 percent by weight A compound according to any one of claims 1-4 or a mixture thereof as contains essential surfactant component. 6. Preparation according to claim 5, which 10-45 percent by weight Contains surfactant component. 7. Shampoo preparation, which as a surfactant component Mixture of anionic surfactant and a compound of formula I. according to claim 1, the latter in an amount of 20-50 Weight percent based on the weight of the mixture is present. 8. A preparation according to claim 7, in which the compound of Formula I in an amount of 30-45 weight percent based on that Weight of the mixture is present. 9. Preparation according to claim 8, in which as the compound of formula I the compound of formula is present.