MXPA06008468A - Alkyl ether sulfates - Google Patents

Abstract

The invention relates to alkyl ether sulfates of general formula (I), in which R represents a linear or branched C8-C18 alkyl group or mixtures of different linear or branched C8-C18 alkyl groups;R1 represents an aliphatic group selected from the group consisting of methyl and ethyl;M+ represents a cation selected from the group consisting of alkali metals, NH4+ and HNR23+, wherein R2 is selected from the group consisting of linear or branched alkyl groups, CH2CH2OH and CH2CH(OH)CH3;x represents an average value of 0 - 3;y represents an average value of 1 - 10;z represents an average value of 0 - 30;and the quotient (II) is>1. The invention also relates to the use of said alkyl ether sulfates as anionic surfactant componentsin detergents and cleaning agents, in technical chemical applications or in cosmetic formulations.

Description

Zur Erklarung der Zweibuchstaben-Codes und der anderen Ab-kürzungen wird auf die Erklarungen ("Guidance Notes on Codes and Abbreviations") am Anfang jeeier regularen Ausgabe der PCT-Gazette verwiesen.

SALTS OF ALKYL-ETHER SULPHATE The present invention relates to alkyl ether sulfate salts from alkoxylated alcohols, which are sulfonated, these alkyl ether sulfate salts have, between the alcohol component and the sulfate group, propylene oxide units and / or butylene and, where appropriate, ethylene oxide units and also relates to the use of these alkyl ether sulfate salts in laundry detergents and cleaning compositions. From the prior art, the use of alkyl ether sulfate salts, for example, as surfactants, is already known. EP-A-1354872 relates to a process for preparing salts consisting of amines and sulfuric ethers. The sulfuric esters can carry in the side chain, an average of 0.1 to 10 oxyalkylene units having 2 to 4 carbons. The publication WO 00/58428 describes a cleaning composition, which can be activated by heat, self-thickener, which comprises anionic surfactants, for example salts of alkyl-benzene sulphates, salts of ethoxylated alkyl ether sulfates and salts of propoxylated alkyl ether sulfate.

The publication 99/65972 relates to an aqueous emulsion comprising at least one resin, which contains building blocks including silicone, and is a reaction product of ammonia or a polyfunctional aliphatic or aromatic amine, carboxylic acids or carboxylic anhydrides and nonionic, anionic or amphoteric surfactants. The anionic surfactants present can be ethoxylated and propoxylated derivatives of alkyl sulfate salts, which have an average of 0.5 to 10 ethylene oxide units and / or propylene oxide. WO 95/15408 discloses a process for etching aluminum or aluminum alloys, in a caustic bath comprising an sulphonic or sulphonate anionic surface active agents. JP 06017088 relates to a milky cleaning composition, which has a pearly appearance and good stability for a long period, and an excellent cleaning action, comprising an alkyl glucoside, an anionic surfactant and the salt of a sulfuric ester. of an alcohol-propylene oxide addition element, having an average molecular weight of 400 to 4000. It is an object of the present invention to provide salts of alkyl ether sulfates, which can advantageously be used as anionic surfactants in laundry detergents and cleaning compositions. We have found that this object is achieved, according to the invention, by the alkyl ether sulfate salts of the general formula I: RO- (CH2CH20) x- (CH2-CHR10) and- (CH2CH20) zS03-M + (I), in which: R is a Cg-Cis alkyl radical, unbranched or branched, or mixtures of different C 8 -C 8 alkyl radicals, unbranched or branched; R 'is methyl, ethyl or mixtures thereof M1 is a cation, selected from the group consisting of alkali metals, NH4 + and HNR23 + 'where R2 is selected from the group consisting of the unbranched or branched alkyl radicals, CH2CH2OH and CH2CH (OH) CH3; x has a mean value of 0 to 3, in particular 0; and has an average value of 1 to 10; z has a mean value of 0 to 30; for which, the quotient A of the critical micelle concentration, eme, is eme (RO- (CH2CH20) zS03"M +) A => L eme (RO- (CH2CH20) x- (CH2-CHR10) y- (CH2CH20) zS03" M +) Preferably, in the alkyl ether sulfate salts of the invention, of the general formula I, R, R ', x, y, z and M + have the following meanings: R is a non-branched or branched C10-C? Alkyl radical, or mixtures of different Cι-Cis, unbranched or branched alkyl radicals; R1 is methyl; M + is a cation of the selected group of alkyl metals, NH +, and HNR23 +, where R2 is selected from the group consisting of unbranched or branched alkyl radicals, CH2CH2OH and CH2CH (OH) (CH3 x has a mean value of 0 to 2, in particular 0; and has an average value of 1 to 3; z has a mean value of 0 to 10, and the quotient A is greater than 1.

Particularly preferred, in the alkyl ether sulfate salts, of the general formula I, wherein R, R 1, x, y and z have the following meanings: R is a C10-C15 alkyl radical, unbranched or branched, or mixtures of different C10-C15 alkyl radicals, unbranched or branched; R1 is methyl; x is 0; and has a mean value of 1 to 2; z has a mean value of 0 to 4, and the quotient A is greater than 1.

Very particularly preferred, in the alkyl ether sulfate salts, of the general formula I, wherein R, R ', x, y and z have the following meanings: R is a radical derived from 2-propylheptanol, iC 3 alcohols or mixtures of 2-propyl alcohol and iC 3 alcohols; R1 is methyl; x is 0; and has an average value of 3; z has a mean value of 0, 1 or 3, and the quotient A is greater than 1.

The invention relates to the defined selection of known alkyl ether sulfate salts, which correspond to the general formula I and wherein A has a value which is greater than 1.

The quotient: eme (RO- (CH2CH20) 2S? 3 'M +) A = eme (RO- (CH2CH20) x- (CH2-CHR10) y- (CH2CH20) zS03' M +) describes the ratio of the eme ie the critical micelle concentration of the alkyl ether sulfate salts, which are attached to the long chain alcohol (RO), then have only ethylene oxide units or no units of alkoxide, to the eme of the alkyl ether sulfate salts, which, between the long chain alcohol (RO-) and the sulfate group, optionally have ethylene oxide units and other alkylene oxide units ( CH2-CHR'0) different from ethylene oxide. It has been found that the salts of the alkyl ether sulfate of the general formula I, which form a quotient A, which is greater than 1, exhibit particularly favorable properties when they are used as a component of an anionic surfactant in detergents of laundry and cleaning compositions in chemical applications, or in cosmetic formulations. It is concluded that the alkyl ether sulfate salts of the invention, of the general formula I, compared with the corresponding alkyl ether sulfate salts, which, if appropriate, have only ethylene oxide units or without units of alkoxide, exhibit a lower value for the critical micelle concentration (eme) from which the value of A is greater than 1. This fraction of the alkyl ether sulfate salts can be determined by synthesizing the salts of alkyl sulfate. ether of the invention and synthesizing the corresponding alkyl ether sulfate salts containing, optionally, only ethylene oxide salts or without alkoxide units and comparing the critical micelle concentration (eme). The values of the critical micelle concentration (eme) in moles / liter were determined by means of concentration series using the DeNucy method of measuring the surface tension. The quotient A describing the relationship between the micellar concentrations of the alkyl ether sulfate salts, optionally containing only ethylene oxide units and the alkyl ether sulfate salts of the invention, according to the invention. invention has a value greater than 1 to 100, preferably A has a value greater than 1 to 80, very particularly preferred, A has a value greater than 1 to 20. The quotient A is, within the aforementioned limits, preferably greater than 1.1, particularly greater than 1.2 and very particularly preferred, greater than 1.5. The alkyl ether sulfate salts of the invention are distinguished by the fact that they have a critical micelle concentration, which is to be compared with the eme of the longer chain alcohols. Micelles are aggregates of dissolved molecules, which are formed by association in the narrowest sense, those aggregates are formed of molecules of surfactants in aqueous solutions, above a certain temperature and a characteristic concentration are designated micelles.

This concentration is designated the critical micelle concentration (eme). Obtaining the critical micelle concentration can be recognized by an abrupt change in physical properties. When this critical micelle concentration is exceeded, the concentration of molecules in the solution is virtually constant and the excess molecules form micelles.

It is inferred from this that the salts of alkyl ether sulfate of the invention, due to their concentration of critical micelles, form, at a lower concentration in the aqueous solution, micelles that are necessary for a good surfactant action. As a result, by means of the alkyl ether sulfate salts, the dose of surfactants in laundry detergents and cleaning compositions can be reduced. If one considers the examples of the invention 1 to 6, and the corresponding reference examples 1 to 6, it becomes evident that the eme values of the alkyl ether sulfate salts of the invention 1 to 6 are lower than all that in the corresponding reference examples 1 to 6, each of which have only ethylene oxide and no propylene oxide or butylene oxide directly attached to the corresponding alcohol. The alkyl ether sulfate salts of the invention of the general formula I can be prepared by one of the following methods: The corresponding alcohol alkoxide components can be converted into the alkyl ether sulfate salts of the formula I, by sulfation in a known manner, using sulfuric acid or sulfuric acid derivatives, to give the salts of alkyl ether sulphates. Sulfation reactions of alcohols have already been described, for example in US-A-3, 462, 626, 3,420,875 or 3,524,864- The details for carrying out this reaction are also given in "Ullmann'3 Encyclopedia of Industrial Chemistry ", 5th Edition, Vol. A25 (1994), pages 770-783 and in the literature regencies given there. If the sulfuric acid itself is used for the esterification, 75 to 100% by weight, preferably 85 to 98% strength by weight, of the acid (so-called "concentrated sulfuric acid" or "monohydrate") is suitably used. ). The esterification can be formed in a solvent or diluent if it is desired to control the reaction, for example, the development of heat. Generally, the alcohol reagent is first introduced and the sulfation reagent is added gradually with continuous mixing. If complete esterification of the alcohol alkoxide component is desired, the sulfation reagent and the alcohol alkoxide component are used in a molar ratio of 1: 1 to 1: 1.5, preferably 1: 1 to 1: 1.2. Minor amounts of the sulfation reagent can be advantageous if mixtures of alcohol alkoxylates are used. The esterification is usually carried out at temperatures of 25 to 85 ° C, preferably in the range of 45 to 75 ° C. If appropriate, it may be convenient to carry out the esterification in a water-immiscible, low-boiling solvent, and diluent at its boiling point, the water being formed in the esterification being distilled and azeotropically separated. In place of the sulfuric acid, of the concentration noted above, for sulfation of the alkanol mixtures of the invention, it is also possible to use, for example, sulfur trioxide, sulfur trioxide complexes, sulfur trioxide solutions in sulfuric acid ("oleum"), chlorosulfonic acid, sulfuryl chloride or also sulfamic acid. The reaction conditions must then be modified appropriately. If the sulfur trioxide is used as the sulfation reagent, the reaction can also advantageously be carried out in a falling film reactor, in a countercurrent or concurrent flow and, if appropriate, also continuously. The batches, after esterification, are neutralized by adding alkali and, if appropriate, removing excess alkali metal sulfate and any solvent present, are processed.

If the chlorosulfonic acid is used as the sulfation agent, the corresponding alcohol alkoxide component is charged in an agitated apparatus under inert conditions. Under vigorous stirring, a corresponding amount of chlorosulfonic acid is added in drops. The molar ratio between the alcohol component and chlorosulfonic acid is 0.5: 1 to 1: 0.5, preferably the ratio is 0.75: 1 to 1: 0.75. Very particularly preferred, the molar ratio of the alcohol alkoxide component to the chlorosulfonic acid is 1: 1. After the HCl gas is removed, the reaction batch is adjusted to a slightly alkaline pH, using a sodium hydroxide solution. The invention also relates to the use of the alkyl ether sulfate salts of the invention as an anionic surfactant component in laundry detergents and cleaning compositions. The alkyl ether salts of the invention can be used in laundry detergents and cleaning compositions, as the sole anionic surfactant component, or also in combination with other anionic surfactants, with the customary constituents. Preferred modalities of laundry detergents and cleaning compositions are volvo laundry detergents, compact laundry detergents, super-compact laundry detergents, laundry detergent extrudates, laundry detergent gels, liquid laundry detergents, detergent bags liquid laundry, liquid laundry detergent concentrates, manual dishwashing detergents, dishwashing detergents for washing machines, scrubbing or scouring milks, hand washing pastes or gels, all-purpose cleaners, dishwashing cleaners Glasses, window cleaners, floor cleaners, bathroom cleaners, toilet cleaners, kitchen cleaners, cleaners, car shampoos or metal cleaners. In particular, the alkyl ether sulfate salts of the invention can be used as components of anionic surfactants in laundry detergents or detergents for the manual washing of dishes. Laundry detergents and cleaners of this type have been described many times in the prior art. A very good investigation of the mode of action and composition of laundry cleansers and detergents can be found, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A7 (1986), pages 137 et seq. Laundry detergents and cleaning compositions comprise a surfactant and a plurality of surfactants of the same or different groups and generally other auxiliaries and additives which are required for the final formulation and / or which serve to adapt to cleaning compositions and detergents. laundry for the specific intended purposes of use or the type of application (manual cleaning or by machinery). Constituents which, in addition to the various surfactants, can be used in various combinations and proportions, in many cleaning compositions and laundry detergents, are, for example, formation agents (agents and segregation) and co-formers, H-regulators. , such as inorganic or organic acids, inorganic or organic bases, and regulatory systems, dispersants, thickeners, enzymes, bleaching systems, hydrotropic compounds, as solubilizers, for example urea or alcohols, organic solvents, finely divided abrasive components, example, quartz flour or marble flour, chalk, diatomaceous earth, pumice, polishing or emery dust, foam controllers to stabilize or vaporize the foam, skin protection agents, and anticorrosive, compound or disinfectant systems, for example those that contain iodine or that release chlorine or hypochlorous acid, for example the dichloroisocyanurate salt, perfumes, dyes and biocides. An important proportion of the cleaning action of laundry detergents and cleaning compositions, described in the prior art, are considered in the surfactants present herein. Use is made of ionic surfactants, more precisely not only anionic surfactants, for example alcohol sulphates, salts of alkyl ether sulphates, alkylbenzene sulphonates, α-olefin sulphonates, sulfosuccinates, and also cationic surfactants, for example hydroxide halides. dialkyl (Cs to Cie) -dimethylammonium, dialkoxydimethylammonium halides or imidazolinium salts having a long chain alkyl residue. The use of amphoteric surfactants, for example of secondary or tertiary amine derivatives, for example (C6-C? S) -betaines or (CQ-C15) alkyl-sulphobetaines, or amine oxides, such as alkyldimethylamine oxides as already described. Nonionic surfactants, in particular also the longer chain and long chain alkanoyl and polyglycoside alkoxylates, in particular having 8 to 20 carbon atoms and also alkylamines alkylamines and alkylamides are used in laundry detergents and laundry detergents. cleaning compositions. It is also known, in particular, to use oxo alcohols having from 10 to 13 carbon atoms in the form of their phosphoric or sulfuric esters, and also alkoxylates of these oxo-alcohols or in the form of their phosphoric or sulfuric esters as surfactants in laundry detergents and cleaning compositions. In the interest of the most economical use of the substance, the greatest economic efficiency and the least environmental contamination, manufacturers of cleaning compositions and laundry detergents require a constant improvement in the efficiency of their products and in particular the surfactants. there present. We have now found that the alkyl ether sul salts of the invention, described above, as the component of the anionic surfactant in cleaning compositions and laundry detergents, exhibit a considerably higher efficiency compared to the known compositions. The present invention also relates to the use of the alkyl ether sul salts, described above, of the general formula I, as the component of the anionic surfactant, in laundry detergents and cleaning compositions. Also, the laundry detergent compositions and cleaning compositions comprise the known customary auxiliaries and additives and, if appropriate, additional surfactants. The minimum content of the alkyl ether sul salts of the general formula I of the total weight of the laundry detergents of the invention and the cleaning compositions is sufficiently high that a significant action of this additive is exhibited. Favorably, the content of the alkyl ether sul salts to be used according to the invention is adjusted so that in the interaction with the remaining constituents of the laundry detergent and cleaning composition, an optimal cleaning action results . Generally, a good cleaning action is achieved when the content of the alkyl ether sul salts of the invention, of the formula I in the laundry detergent and the cleaning composition, based on the total weight of the composition, it is from 0.01 to 40% by weight, preferably from 0.1 to 35% by weight, in particular from 0.1 to 30% by weight. The compounds of the general formula I can be unitary substances, but can also be mixtures where different substances, within the general formula I, are mixed together. The components of these mixtures may differ with respect to the meanings of R, R1 and M, and with respect to the values of x, y and z. This means that the analytical values obtained in the elemental analysis of the alkyl ether sul salts of the invention, of the general formula I, for example the values of C and H, obtained for the structural group of oxo-alcohol, and in particular the values of the determination of the alkoxy group in the calculation back to the structural formula, lead to values Fractional for x, y and z. The average values of x, y and z are the average values of the degrees of the alkoxylation of the compounds present in the mixtures. These values are integral values in samples that contain only one compound. Obviously, such mixtures of substances are also compounds of the invention, under the general formula I, which have the advantages described, compared with the prior art. Obviously, the compositions of the cleaners are adapted to the different purposes, as is familiar to those skilled in the art. For this, all the appropriate auxiliaries and additives known from the prior art can be added to the laundry detergent and cleaning compositions, which comprise the alkyl ether sulfate salts of the invention, of the general formula I.

In many cases, it is favorable to combine the alkyl ether sulfate salts of the invention, of the general formula I, with other nonionic surfactants, for example alkoxy alkoxylate alcohol alkoxylates, alkylamido alkoxylates, alkyl polyglycosides or surfactants ionic, preferably anionic, eg sulfate salts of long-chain alcohols or super-long chains, other than the alkyl ether sulfate salts of the invention, the alkylbenzene sulphonate salts, the sulfonate salts of α-olefins, the sulfosuccinate salts or with amphoteric surfactants, for example the alkylamine oxides or the betaines. In the foregoing, examples of surfactant people of different nature, which are suitable for said combinations, were mentioned. Suitable nonionic surfactants are, for example, (C3-C22), unbranched or branched, alkoxylated, or oxo-alcohol alkoxylates. Alkoxylation can be carried out with ethylene oxide, propylene oxide and / or butylene oxide. The surfactants that can be used are, in this case, all the alkoxylated alcohols which preferably contain, in aggregate form, at least two molecules of a alkylene oxide mentioned above. The block polymers of ethylene oxide, propylene oxide and / or butylene oxide or the addition products containing said alkylene oxides in a random distribution can also be used here. By mole or alcohol of 2 to 50 moles, preferably 3 to 20 moles, of at least one alkylene oxide is used. Preferably, the alkylene oxide used is ethylene oxide. The alcohols preferably have 10 to 18 carbon atoms. Depending on the type of alkoxylation catalyst, alkoxylates having a homologous distribution of alkylene oxide, broad or narrow, can be obtained. A further class of suitable nonionic surfactants are alkylphenol alkoxylates, such as alkylphenol ethoxylates having C to C 14 alkyl chains and from 5 to 30 moles of alkylene oxide units. Another class of nonionic surfactants is the alkyl polyglucosides with 6 to 22, preferably 8 to 18 carbon atoms in the alkyl chain. These compounds usually contain from 1 to 20, preferably from 1 to 5 glucoside units. Another class of nonionic surfactants are the N-alkylglucamates of the general structures: where Ba is (C6-C22) alkyl, B2 is hydrogen or (C1-C4) alkyl and D is a polyhydroxyalkyl radical having from 5 to 12 carbon atoms and at least 3 hydroxyl groups. Preferably B 'is alkyl (Cio-Cis), B2 is C3 and D is a radical C5 to Cs. For example, these compounds are obtained by acylating reducing amine sugars with acid chlorides of carboxylic acids Cio to Cie. Other nonionic surfactants, which may be used, are the end-capped alkoxylates of fatty acid amides of the general formula: R3-CO-NH- (CH2) nO- (AxO) m-R4 in which : R3 is a Cs-C2 alkyl radical? p alkenyl R4 is a C1-C4 alkyl group; A1 is a C2-C4 alkylene; n is a number 2 or 3 and m has a value of 1 to 6. known from publication Wo-A 95/11225.

Examples of such compounds are the reaction products of n-butyl triglycolamine, of the following formula: H2N (CH2-CH2-0) 2-C4H2, with methyl dodecanoate or the reaction products of ethyl tetraglycolamine, of the formula H2N- (CH2-CH2-0) 4-C2H5, with a conventional mixture of methyl esters of unsaturated C5-C? 8 fatty acids. The compounds, which are also suitable as nonionic surfactants, are also block copolymers of ethylene oxide, propylene oxide and / or butylene oxide (Pluronic®etronic® from BASF), polyhydroxy or polyalkoxy fatty acid derivatives , such as the polyhydroxy fatty acid amides, N-alkoxy or N-aryloxy polyhydroxy fatty acid amides, fatty acid amide ethoxylates, in particular end-capped compounds, and also alkane alkoxylates fatty acid lamide. The additional nonionic surfactants are preferably present in those of the invention, in an amount of 0.01 to 40% by weight, in particular 0.1 to 35% by weight, especially 0.5 to 30% by weight. Individual nonionic surfactants or a combination of different nonionic surfactants can be used. A nonionic surfactant of only one class can be used, in particular only C 6 -C 22 alkoxylated alcohols, but mixtures of surfactants of different kinds can also be used. The alkyl ether sulfate salts of the invention can also be used in a mixture with other anionic surfactants. Other suitable anionic surfactants are the sulfonates of Cs-C2 olefins and disulfonates, which may also be mixtures of alkene and hydroxyalkane sulfonates or disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, sulfonates glyceryl esters of fatty acids, alkylphenol polyglycol ether sulfonates, paraffin sulphonates having from about 20 to about 50 carbon atoms (based on paraffin or mixtures of paraffins produced from natural sources), alkyl phosphates, acyl methionates, acyl taurates, acyl methyltaurates, alkylsuccinic acids, alkynylsuccinic acids or their half-esters or semi-amides, alkylsulfosuccinic acids or their amides, mono- and di-esters of sulfosuccinic acids, acyl sarcosinates, sulphated alkyl polyglycosides, polyglycol carboxylates of alkyl, and hydroxyalkyl sarcosinates. The anionic surfactants are preferably added to laundry detergents and cleaning compositions in the form of salts. Suitable cations in these salts are the alkali metal ions, such as sodium, potassium and lithium, and ammonium salts, for example hydroxyethylammonium, dihydroxyethylammonium and tri (hydroxyethyl) ammonium salts. The anionic surfactants are present in the cleaning composition of the invention in amounts up to 40% by weight, especially up to 35% by weight, in particular up to 30% by weight. If the C8-C20 linear alkylbenzene sulphonates (LAS) are used together, they are used in a customary manner in an amount up to 25% by weight, in particular up to 20% by weight. Individual surfactants or a combination of ionic surfactants can be used. In addition, the alkyl ether sulfate salts to be used, according to the invention, of the general formula I, can be combined with cationic surfactants, in customary form in an amount up to 25% by weight, preferably 0.1 to 15% by weight, for example dialkyldimethylammonium halides Cs-Cie, or imidazolinium salts having a long chain alkyl radical and / or anphoretic surfactants, customary in an amount of up to 15% by weight, preferably 0.1 to 10% by weight, for example derivatives of secondary or tertiary amines, such as C6-C6 alkyl betabetaines, or C6-C6 alkylsulfobetaines, or amine oxides, such as alkyltrimethylamine oxides. Generally, the alkyl ether sulfate salts to be used, according to the invention, of the general formula I, are combined with forming agents (segregation agents), for example polyphosphates, polycarboxylates, phosphonates, agents which they form complexes, for example methylglyc- indiacetic acid, and their salts, nitrilotriacetic acid and its salts, ethylenediaminetetraacetic acid, and their salts and, if appropriate, with co-formers. The individual forming substances are highly suitable to be combined with the salts of alkyl ether sulfates, which are to be used, according to the inventionof the general formula I, listed below. Suitable inorganic formers are, in particular, crystalline or amorphous aluminosilicates, which have ion exchange properties, such as, in particular, zeolites. Various types of zeolites are suitable, in particular zeolites A, X, B, P, MAP and HS, in their Na form, or in forms in which Na is partially exchanged for other cations, such as Li, K, Ca, Mg or ammonium. Suitable zeolites are described, for example in US-A 4,904,224.

Suitable crystalline silicates as formers are, for example, disilicates or sheet silicates, for example d-Na2Si205 ß-Na2Si205 (SKS 6 and SKS 7). The silicates can be used in the form of their alkali metal salts, alkaline earth metal salts or ammonium salts, preferably as Na, Li and Mg silicates. Amorphous silicate, for example, sodium metasilicate, which has an amorphous polymeric or disilicate structure (Britesil® H 20, manufacturer: Akzo) are similarly usable. Suitable inorganic forming substances, based on carbonate, are carbonates and hydrogencarbonates. They can be used in the form of their alkali metal salts, alkaline earth metal salts or ammonium salts. Preferably, use is made of the carbonates or hydrogen carbonates of Na, Li and Mg, in particular sodium carbonate and / or sodium hydrogencarbonate. Customary phosphates used as inorganic formers are alkali metal orthophosphates and / or polyphosphates, for example pentasodium triphosphate. Said forming components can be used individually or in mixtures with each other. In a preferred embodiment, the laundry detergents and the cleaning compositions comprising the alkyl ether sulfate salts of the invention, of the general formula I, in addition to the inorganic formers, comprise from 0.05 to 20% by weight, in in particular from 0.1 to 10% by weight, of organic co-formers, in the form of oligomeric or polymeric carboxylic acids, of low molecular weight. In particular, the polycarboxylic acids or the phosphonic acids or their salts, in particular, the Na or K. salts. Low molecular weight carboxylic acids or phosphonic acids which are suitable as organic co-formers are, for example: Phosphonic acids, such as 1-hydroxyethane-1,1-diphosphonic acid, amino-tris (methylene phosphonic) acid, ethylene diamine tetra (methylene phosphonic acid), hexamethylene diaminotetra (methylene phosphonic acid) and diethylenetriamine penta (methylene phosphonic acid). C4-C2o di-, tri- and tetracarboxylic acids, for example succinic acid, propan-tricarboxylic acid, butacarboxylic acid, cyclopentane-tratracarboxylic acid and alkyl- and alkenyl-succinic acids, having C2 to C6 radicals - alkyl or alkenyl; C4 to C20 hydroxycarboxylic acids, for example malic acid, tartaric acid, gluconic acid, gutárico acid, citric acid, lactobiónico acid and saccharose monodi and tricarboxílicos acids, aminopolicarboxílicos acids, for example nitrilotriacetic acid, ß-alanindiacetic acid, ethylenediaminetetraacetic acid , and serindiacetic acid, isoserindiacetic acid, alkylethylenediaminetriacetate, N, N-bis (carboxymethyl) glutamic acid, ethylene diaminodisuccinic acid and N- (2-hydroxyethyl) iminodiacetic acid, and methyl- and ethyl-glycine diacetic acid. Oligomeric or polymeric carboxylic acids which are suitable as organic co-formers are, for example: oligomalie acids, as described, for example, in EP-A 451508, and EP-A 396303, copolymers and terpolymers of unsaturated C4-C8-carboxylic acids, in which as comonomers, monoethylenically unsaturated monomers of group (i), given below, can be copolymerized in amounts up to 95% by weight, group (ii) in amounts of up to 60% by weight and group (iii) in amounts up to 20% by weight. Suitable Cs-Cs, unsaturated dicarboxylic acids are, for example, maleic acid, fumaric acid, itaconic acid and citraconic acid. Preference is given to maleic acid. Group (i) comprises C3-C8, monocarboxylic, monoethylenically unsaturated acids, for example acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid. Preferably, acrylic acid and methacrylic acid are used from group (i). Group (ii) comprises C2-C22, monoethylenically unsaturated olefins, vinyl-alkyl ethers having C? -C8 alkyl groups, styrene, vinyl ethers of carboxylic acids Ci-Cs, (meth) acrylamide and vinylpyrrolidone. Preferably, from the group (iii) use is made of the C2-C6 olefins, vinyl alkyl ethers having C de-C4 alkyl groups, vinyl acetate and vinyl propionate. If the polymers of group (ii) contain polymerized vinyl esters, they may also be present, fully or partially hydrolyzed, to vinyl alcohol structural units. Suitable copolymers and terpolymers are, for example, those described in US-A 3887806 and also in DE-A 4313909. Group (iii) comprises (meth) acrylic esters of Ci-Cs (meth) acrylonitrile alcohols, (meth) acrylamides of C? -C8 amines, N-vinylformamide and N-vinylimidazole. Homopolymers of C3 ^ C8 monoethylenically unsaturated monocarboxylic acids which are suitable as organic co-formers are, for example, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid, in particular acrylic acid and methacrylic acid, copolymers of dicarboxylic acids, for example copolymers of maleic acid and acrylic acid, in a weight ratio of 10:90 to 95: 5, particularly preferred in a weight ratio of 30:70 to 90:10, having molar masses of 1000 to 140,000; terpolymers of maleic acid, acrylic acid and C 1 -C 3 carboxylic acid vinyl ester, in a weight ratio of 10 (maleic acid): 90 (acrylic acid + vinyl ester) to 95 (maleic acid): 10 ( acrylic acid + vinyl ester), in this case the weight ratio of the acrylic acid to the vinyl ester can vary in the range of 30:70 to 70:30; copolymers of maleic acid with C2-C8 olefins in a molar ratio of 40:60 to 80:20, in this case, particular preference is given to copolymers of maleic acid with ethylene, propylene, isobutene or diisobutene, in a molar ratio of 50.50. Graft polymers of unsaturated carboxylic acids in low molecular weight carbohydrates, or hydrogenated carbohydrates, see US-A 5227446, DE-A 4415623 and DE-A 4313909, are similarly suitable as organic co-formers. Suitable unsaturated carboxylic acids are, in this case, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid, and also mixtures of acrylic acid and maleic acid, which they are grafted in amounts of 40 to 95% by weight, based on the component to be grafted. For the modification, also up to 30% by weight, based on the component to be grafted, of monoethylenically unsaturated monomers, can be polymerized.

Suitable modified monomers are the aforementioned monomers of groups (ii) and (iii). Suitable graft bases are interrupted polysaccharide slabs, for example starches interrupted in acid or enzymatic form, inulins or cellulose, protein hydrolysates and reduced interrupted polysaccharides (hydrogenated or hydrogenated-amines), for example mannitol, sorbitol, aminosorbitol and N-glucamine, and also polyalkylene glycols having molar masses up to Mw = 5000, for example polyethylene glycols, block copolymers of ethylene oxide / propylene oxide or ethylene oxide / butylene oxide or ethylene oxide / propylene oxide / butylene oxide and alkoxylated monohydric or polyhydric C?-C22 alcohols (see ÜS-A-5,756,456). Polyglyxyl acids suitable as organic co-formers are, for example, described in EP-B-001003, US-A-5,399,286, DE-A-4105366 and EP-A-656014. The end groups of the polyglyoxyl acids may have different structures. Polyamidocarboxylic acids are modified polyamidocarboxylic acids, which are suitable as organic co-formers, are described, for example, in EP-A-454126, EP-B-522037, WO-A.94 / 01486 and EP-A-58142. As organic co-formers, use is made in particular of the polyaspartic or co-condensed acids of aspartic acid with other amino acids, monocarboxylic or dicarboxylic acids C? -C26 and / or monoamines or C4-C24 diamines Particularly preferred use is made of polyaspartic acids Prepared in phosphorus-containing acids, modified with mono- or dicarboxylic acids C6_C22; or modified with mono- and di-amines C6-C22. Suitable organic co-formers are also iminodisucinic acid, oxydisuccinic acid, aminopolycarboxylates, alkylpolyaminocarboxylate, aminopolyalkylene phosphonates, polyglutamates, hydrophobically modified citric acid, for example agaricic acid, poly-a-hydroxyaryl acid, N-acylethylenediaminetriacetals, such as lauorylethylenediamine- alkylamide triacetate of ethylenediaminetetraacetic acid, for example tallow amide EDTA.

Likewise, oxidized starches can also be used as organic co-formers. In a preferred embodiment, the laundry detergents and cleaning compositions comprising the alkyl ether sulfate salts of the invention, may additionally, in particular in addition to the inorganic formers, the anionic surfactants and / or nonionic surfactants, that comprise 0.5. 20% by weight, in particular from 1 to 10% by weight, of glycine-N, N-diacetic acid derivatives, for example those described in WO 97/19259. Frequently, it is also favorable to add to laundry detergents and cleaning compositions, which comprise alkyl ether sulfate salts, bleach systems consisting of bleach, such as perborate, percarbonate and, if appropriate, bleach activators, for example tetraacetylethylenediamine + bleaching stabilizers. In these cases, the laundry detergents and cleaning compositions comprising the alkyl ether sulfate salts additionally comprise from 0.5 to 30% by weight, in particular from 5 to 28% by weight, especially from 10 to 25% by weight , of bleach in the form of percarboxylic acids, for example, diperoxoddecanedicarboxylic acid, phthalimidopercaphoic acid or monoperoxophthalic acid or monoperoxoterephthalic acid, addition elements of hydrogen peroxide to inorganic salts, for example sodium perborate monohydrate, tetrahydrate sodium perborate, sodium carbonate perhydrate or sodium phosphate perhydrate, elements for the addition of hydrogen peroxide to organic compounds, for example urea perhydrate or inorganic peroxo salts, for example the alkali metal persulfates or peroxodisulfates of metals alkaline, if appropriate, in combination with the 0 to 15% by weight, preferably from 0.1 to 15% by weight, in particular from 0.5 to 8% by weight of bleach activators. Suitable bleach activators are: - polyacylated sugars, for example petacetylglucose; acyloxybenzenesulfonic acids and their alkali metal and alkaline earth metal salts, for example sodium p-nonanoyloxybenzenesulfonate or sodium p-benzoyloxybenzenesulfonate; - NN-diacylated amines and N, N, N ', N'-tetraacylated amines, for example N, N, N', N '-tetraacetylmethylenediamine and N, N, N', N'-tetraacetylethylenediamine (RAED), N, N-diacetylaniline, NN-diacetyl-p-toluidine or 1,3-diacylated hydantoins, such as 11 1,3-diacetyl-5,5-dimethylhydantoin; - N-alkyl-N-sulfonylcarbonamides, for example N-methyl-N-mesylacetamide or N-methyl-N-mesylbenzamide; - N-acetylated cyclic hydrazides, triazoles or acylated urazoles, for example the hydrazide of monoacetylmalic acid; 0, N, N-trisustitide hydroxylamines, for example 0-benzoyl-N-succinylhydroxylamine, 0-acetyl-N, N-succinylhydroxylamine or 0, N, N-triacetylhydroxylamine; - N, N'-diacetylsulfonilamidss, for example N, N-dimethyl-N, N'-diacetylsulfuryl amide or N, N '-diethi-N, N'-dipropionylsulfonylamide; acylated lactams, for example acetylcaprolactam, octanoylcaprolactam, benzoylcaprolactam or carbonyl bis-caprolactam; - anthranil derivatives, for example 2-methylanthranil or 2-phenylantanyl; - triacylcyanurates, for example triacetylcyanurate or tribencoylcyanurate; oxime esters and bisoxime esters, for example 0-acetylacetone oxime or bisisopropyiminocarbonate; - carboxylic anhydrides, for example acetic anhydride, benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride; esters of enol, for example isopropenyl acetate; - 1, 2-diacyl-4, 5-diacyloxyimidazolines, for example 1,3-diacetyl-4,5-diacetoxy-imidazoline; tetraacetylglycoluril and tetrapropionylglioluril; 2, 5-diacylated diketopiperzines, for example, 1,4-diacetyl-2, 5-diketopiperazine; - nitriles substi tuted with ammonium, for example N-methyl morpholinium acetonitrile methylsulfate; - acylation products of propylene diurea and 2,2-dimethylpropylene diurea, for example tetraacetyl propylene diurea; - α-acyloxypolyazylmalonamides, for example a-acetoxy-N, N-diacetylmalonamide; diaceyldioxohezahydro-1,3,5-triazines, for example 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine; - benz (4H) -1, 3-oxazin-4-ones having alkyl radicals, for example, methyl radicals or aromatic radicals, for example phenyl, in the 2-position.

The described blanching system of bleaches and bleach activators may, if appropriate, also comprise bleach catalysts. Suitable bleach catalysts are, for example, the quaternized imines and sulfonimines, which are described, for example, in US-A-5,360,569 and EP-A-453 003. Particularly active bleach catalysts are the manganese complexes described, for example in WO-A 94/21777. Such compounds, when used in cleaning compositions, are incorporated at most in amounts of up to 1.5% by weight, in particular up to 0.5% by weight and in the case of highly active manganese complexes, amounts up to 0.1% by weight. In addition to the described bleaching system of bleaching agents, whitening activators and, if appropriate, benzene catalysts, it is also possible for laundry detergents and cleaning compositions to comprise the alkyl ether sulfate salts of the invention, general formula I, to use systems that have liberation of enzymatic peroxide or photoactivated bleaching systems. For a number of applications, it is favorable that the laundry detergents and the cleaning compositions comprising the alkyl ether sulfate salts of the invention, of the general formula I, comprise enzymes. Preferred enzymes used in laundry detergents and cleaning compositions are proteases, amylases, lipases and cells. From ? the enzymes, preferably amounts of 0.1 to 2.5% by weight, in particular, preferably 0.2 to 1.5% by weight of the formulated enzyme are added. Suitable proteases are, for example, Sevinase and Esperase (manufacturer: Novo Nordisk). A suitable lipase is, for example, Lipolse (manufacturer, Novo Nordisk), A suitable cellulase is, for example, Celluzym (manufacturer: Novo Nordisk). The use of proxidases to activate the bleaching system is also possible. Individual enzymes or a combination of different enzymes may be used If appropriate, the laundry detergent and cleaning composition, comprising the alkyl ether sulfate salts of the invention, may further comprise the enzyme stabilizers, for example the Calcium propionate, sodium or boric acid form or its salts and / or oxidation inhibitors. The constituents of laundry detergents and cleaning compositions are known in principle to those skilled in the art. The above and following lists of suitable constituents give only one example of the known suitable attendant.

Laundry detergents and cleaning compositions, comprising the alkyl ether sulfate salts of the invention, of the general formula I, can, in addition to the aforementioned principal components, also comprise the following customary additives in customary amounts of the same: known dispersants, for example the condensates of naphthalenesulfonic acid, or polycarboxylates, compounds that regulate the pH, for example alkalis (NaO, KOH, pentasodic metasilicate) or acids (hydrochloric acid, phosphoric acid, amidosulfuric acid, citric acid), systems regulators, for example acetate or phosphate regulators, perfumes, dyes, biocides, for example sothiazolinones 2-bromo-2-nitro-l, 3-propanediol, solubilizers / hydrotropes, for example cumenesulfonates, toluenesulfonates, short chain fatty acids, urea, alcohols or esters of alkyl / aryl phosphoric, phosphoric esters of alkyl / aryl polyglycol, solvents, by example, short chain alkyl oligoglycols, such as butyl glycol, butyl diglycol, propylene glycol monomethyl ether, alcohols, such as ethanol, isopropanol, aromatic solvents, such as toluene, xylene, N-alkylpyrrolidones or alkylene carbonates , thickeners, for example lightly crosslinked polysaccharides and / or polycarboxylics (for example Goodrich Carbopol®), finely divided abrasive components, for example quartz flour, marble flour, chalk, diatomaceous earth, pumice stone or also polishing or emery powder, foam controllers to stabilize or vaporize the foam, skin protectors and anticorrosives, compounds or disinfectant systems, for example , those that release chlorine or hypochlorous acid, for example dichloroisocyanurate salt, or that contain iodine. Laundry detergent and cleaning compositions are usually, but not only, aqueous and are in the form of microemulsions, emulsions or solutions. When they are in powder form, it is also possible to make use of conventional flow control agents, which impart good flowability, dosing and solubility and / or which prevent the formation of doughs and powders, for example sodium sulphate or magnesium sulfate. In the case of laundry detergents and tablet cleaning compositions, they can also use tableting aids, for example polyethylene glycols, having molar masses greater than 1000 g / mol, dispersions of polymers and tablet disintegrants, for example cellulose derivatives, entangled poivinylpyrrolidone, crosslinked polyacrylates or combinations of acids and bases, for example citric acid and sodium bicarbonate, to name a few, are required. Laundry detergents and cleaning compositions, comprising the alkyl ether sulfate salts of the invention, of the general formula I, are surprisingly superior in their cleaning action, comparable to comparable laundry detergent and cleaning compositions. Likewise, the present invention relates to the use of the alkyl ether sulfate salts of the invention, of the general formula I, in chemical engineering applications. In particular, the present invention relates to the use of alkyl ether sulfate salts of the invention, of the general formula I, in textile auxiliaries, auxiliary for the manufacture of paper and auxiliaries of leather, foams for extinguishing fire, formulations pesticides, in emulsion polymerizations, for the pretreatment of metals, as auxiliaries in the ceramic industry, as cooling lubricants or in the emulsification processes. The present invention also relates to the use of the alkyl ether sulfate salts of the invention, of the general formula I, in cosmetic applications.

In particular, the present invention relates to the use of the alkyl ether sulfate salts of the invention, of the general formula I, in shower gels, hair shampoos, bath additives, lotions, oils / perfumes, soaps handwashing liquids and emulsifiers or creams. The present invention furthermore relates to laundry detergents and cleaning compositions or cosmetic formulations, which comprise the alkyl ether sulfate salts of the general formula I, in which case the quotient A, as defined above, is greater than 1.

EXAMPLES General protocol for sulfating alcohols / alcohol alkoxylates. The alcohol component, whose composition is described in Table 1, was charged in a stirred apparatus and with an inert nitrogen blanket. With vigorous stirring, an equimolar amount of chlorosulfonic acid was added in drops, over the course of 4 hours. The temperature remained below 20 ° C during this. 1 nitrogen was passed through the viscous solution overnight, at room temperature, to expel the residual HCl. Then, an equimolar amount of 50% NaOH outside was added in droplets to the reaction batch, such that the temperature did not increase above 45 ° C. The pH can be set at 8-9 using 50% strength NaOH or 50% strength H2S04 PO = propylene oxide; EO = ethylene oxide, WAS = washing active substances; eme = critical micelsa concentration; A = eme (Ref.- Ex. X) / eme (Ex. X) The values of the critical micelle concentration (eme) in millimoles / liter were determined by means of series of concentrations using the DeNuoy method of the measurement of surface tension.

Claims (8)

1. An alkyl ether sulfate salt of the general formula I: RO- (CH2CH20) x- (CH2-CHR10) and- (CH2CH20) zS03 'M + (I), in which: R is a C10-C15 alkyl radical, unbranched or branched, or mixtures of different C10-C15 alkyl radicals, unbranched or branched; R 'is methyl; M1 is a cation, selected from the group consisting of alkali metals, NH4 + and HNR23 + 'wherein R3 is selected from the group consisting of the unbranched or branched alkyl radicals CH2CH2OH and CH2CH (OH) CH3; and has a mean value of 1 to 2; z has a mean value of 1 to 4; for which, the quotient A of the critical micelle concentration, eme, is eme (RO- (CH2CH20) zS03"M +) A => i eme (RO- (CH2CH20) x- (CH2-CHR10) y- ( CH2CH20) zS03"M +)

2. The use of the alkyl ether sulfate salts, as claimed in claim 1, as a component of anionic surfactant, in laundry detergents and cleaning compositions.

3. The use, as claimed in claim 2, in which laundry detergents and cleaning compositions are selected from the group consisting of laundry detergents in powder form, compact laundry detergents, super-compact laundry detergents, detergent extrudates laundry, laundry detergent gels, liquid laundry detergents, liquid laundry detergent bags, liquid laundry detergent concentrates, manual dishwashing detergents, mechanical dishwashing detergents, scouring cleaners or scrubbing milks hand washing pastes or gels, all-purpose cleaners, glass cleaners, window cleaners, floor cleaners, bathroom cleaners, toilet cleaners, kitchen cleaners, butcher cleaners, car shampoos and cleansers metals

4. The use of alkyl ether sulfate salts, as claimed in claim 1, as anionic surfactant components, in chemical engineering applications.

5. The use, as claimed in claim 4, is that the engineering applications are selected from the group consisting of textile auxiliaries, auxiliary for the manufacture of paper and auxiliaries for leather, foams for extinguishing fires, pesticidal formulations, uses in polymerizations in emulsion, for the preliminary treatment of metals, as auxiliaries in the ceramic industry, as cooling lubricants and in emulsifying processes.

6. The use of the alkyl ether sulfate salts, as claimed in claim 1, in cosmetic applications.

7. The use, as claimed in claim 6, in which the cosmetic applications are selected from the group consisting of shower gels, hair shampoos, bath additives, lotions, perfume oils / oils, liquid laundry soaps the hands and emulsifiers for creams.

8. A laundry detergent or a composition or cleaning or formulation of cosmetics, comprising sulfate salts of alkyl ethers, as claimed in claim 1. SUMMARY OF THE INVENTION The present invention relates to sulfate salts of alkyl ethers of the general formula I: RO- (CH2CH20) x- (CH2-CHR10) and- (CH2CH20) zS03"M + (1), in which: R is an unbranched or branched Cs-C? 8 alkyl radical, or mixtures of different C8-C? 8 alkyl radicals, unbranched or branched; R 'is an aliphatic radical, selected from the group consisting of methyl and ethyl M1 is a cation, selected from the group consisting of alkali metals, NH4 + and HNR23 + 'wherein R3 is selected from the group consisting of the unbranched or branched alkyl radicals CH2CH2OH and CJ2CH (OH) CH3; x has a mean value of 0 to 3; and has an average value of 1 to 10; z has a mean value of 0 to 30; and the quotient eme (RO- (CH2CH20) zS03- M +) A = > 1. eme (RO- (CH2CH20) x- (CH2-CHR10) y- (CH2CH20) zS03"M +) and its use as an anionic surfactant component in laundry detergents and cleaning compositions, in chemical engineering applications or in cosmetic formulations.