WO1999049006A1 - Fatty acid oligo-alkylene glycol ester sulfates in aqueous tenside solutions - Google Patents

Abstract

According to the invention, fatty acid oligo-alkylene glycol ester sulfates of formula (I) R<1>COO(R<2>O)nSO3M, wherein M represents a cation, especially an ammonium ion, and R<1>CO represents a linear or branched, aliphatic, saturated or unsaturated acyl radical with 6 to 22 carbon atoms and wherein R<2> in (R<2>O)n means an alkylene radical, especially CH2CH2 or CH(CH3)CH2 or CH2CH(CH3), n then being a number from 0.5 to 5, preferably 0.7 to 3, especially 0.9 to 2 or wherein (R<2>O)n represents a unit of the type (EO)u(PO)v(EO)w, E representing CH2CH2 and P representing CH(CH3)CH2 or CH2CH(CH3), and 0</=u</=5, 0.1</=v</=5, 0</=w</=5 and u + w > 0, the sum u + v + w being a value of 0.5 to 5, preferably 0.7 to 3, especially 0.9 to 2, can be used to adjust the viscosity of aqueous tenside solutions to a specific value without the usual thickeners, especially in combination with alkylether sulfates. Aqueous tenside solutions with fatty acid oligo-alkylene glycol ester sulfates of formula (I) have degrees of viscosity either greater than 1000 to 10<5> mPa.s at room temperature, preferably at least 5000 mPa.s, especially at least 10000 mPa.s, most preferably at least 20000 mPa.s, or of 0.01 to 1000 mPa.s, preferably 0.1 to 600 mPa.s, especially 0.5 to 300 mPa.s, most preferably 1 to 100 mPa.s.

Description

 "Fatty acid oligoalkylene glycol ester sulfates in aqueous surfactant solutions"

The present invention relates to the use of fatty acid oligoalkylene glycol ester sulfates in aqueous surfactant solutions for adjusting the viscosity and aqueous surfactant solutions of defined viscosity with fatty acid oligoalkylene glycol ester sulfates and alkyl ether sulfates.

Aqueous surfactant solutions, especially those used in the field of cleaning agents used as all-purpose cleaners, dishwashing detergents or carpet care products and in the field of body care as hair shampoos, bubble baths, shower baths, hand washing pastes and the like, usually contain anionic surfactants, for example alkyl ether sulfates. In order to stabilize these clear or disperse systems and to improve their handling for the user, thickening agents are usually added to these surfactant solutions.

A large number of inorganic and organic compounds which are used to increase the viscosity of solutions containing anionic surfactants are already known to the person skilled in the art. Water-soluble electrolyte salts, usually table salt, are generally used as inorganic thickeners.

From the publication and properties of fatty saurepolyglykolestersulfaten (K. Engel, W. Ruback fats, soaps and paints, 1986, 88, 20-25) is the thickened 15 wt .-% aqueous solutions of C _{12 /} i ₄ fatty acid -4EO ester sulfate and C _{12 /} i ₄ fatty alcohol 3EO ether sulfate known by common salt. Figure 9 on page 24 shows that the input Setting a viscosity of 10,000 mPa-s in the case of the solution of the C _{12 /} i ₄ fatty alcohol 3EO ether sulfate 5% by weight NaCl and in the case of the solution of the C _{2 /} i4 fatty acid 4EO ester sulfate even 8%. -% NaCl required.

Examples of organic thickeners are fatty acid alkanolamides, polyethylene glycol difatty acid esters and a number of water-soluble polymers. In most cases it is at most possible to use large amounts to adjust the desired viscosity of the surfactant solution by using only inorganic electrolyte salts. It is therefore generally the way to use organic thickeners in addition to the inorganic salts, but some of them have a number of disadvantages. For example, the surfactant solutions thickened with polyethylene glycol fatty acid diesters often have inadequate viscosity stability during storage, while water-soluble polymers have an undesirable slimy flow behavior with a tendency to become stringy in the thickened surfactant solutions.

In the patents DE 3730179 and DE 3817415 it is therefore proposed to use adducts of ethylene oxide and / or propylene oxide, optionally with a restricted homolog distribution, on saturated and / or unsaturated fatty alcohols to thicken surfactant solutions. Our own studies have shown that fatty acid alkylene glycols are also suitable organic thickeners for aqueous surfactant solutions. These products no longer have the above disadvantages.

However, there is a need for further organic thickeners with an increased thickening effect which, in particular, make it possible to use low levels of organic and inorganic thickeners for a given viscosity of the surfactant solution to be set, or even to dispense with additional thickeners. The present invention was accordingly based on the object of providing compounds for adjusting the viscosity of aqueous surfactant solutions which are at the same time powerful surfactants, preferably anionic surfactants, and require little or no auxiliary use of thickeners.

This object was achieved according to the invention by using fatty acid oligoalkylene glycol ester sulfates, in particular in combination with alkyl ether sulfates.

The present invention therefore relates to the use of fatty acid oligoalkylene glycol ester sulfates of the formula I for adjusting the viscosity of aqueous surfactant solutions,

R ¹ COO (R ² 0) _n S0 ₃ M (I)

where in formula IM stands for a cation, in particular an ammonium ion, and R ¹ CO for a linear or branched, aliphatic, saturated or unsaturated acyl radical having 6 to 22 carbon atoms and R ² in (R ² 0) "for an alkylene radical, in particular CH ₂ CH ₂ or CH (CH ₃ ) CH ₂ or CH ₂ CH (CH ₃ ), where n then denotes a number from 0.5 to 5, preferably 0.7 to 3, in particular 0.9 to 2 , or (R ² 0) _{n represents} a unit of the type (EO) _u (PO) _v (EO) „, where E is CH ₂ CH ₂ and P is CH (CH ₃ ) CH ₂ or CH ₂ CH (CH ₃ ) and 0 <u <5, 0.1 <v <5, 0 ≤ w ≤ 5 and u + w> 0 and the sum u + v + w is a value from 0.5 to 5, preferably 0.7 to 3, in particular 0.9 to 2.

Another object of the present invention are aqueous surfactant solutions, the fatty acid oligoalkylene glycol ester sulfates of the formula I, R ¹ COO (R ² 0) _n S0 ₃ M (I)

in the M for a cation, in particular an ammonium ion, and R ¹ CO for a linear or branched, aliphatic, saturated or unsaturated acyl radical having 6 to 22 carbon atoms and R ² in (R ² 0) "is an alkylene radical, in particular CH ₂ CH ₂ or CH (CH ₃ ) CH ₂ or CH ₂ CH (CH ₃ ), where n is then a Number from 0.5 to 5, preferably 0.7 to 3, in particular 0.9 to 2, stands or represents (R ² 0) "a unit of the type (EO) _u (PO)" (EO) ", where E is CH ₂ CH ₂ and P is CH (CH ₃ ) CH ₂ and CH ₂ CH (CH ₃ ) as well as 0 <u <5, 0.1 <v <5, 0 <w <5 and u + w> 0 and the sum u + v + w assumes a value of 0.5 to 5, preferably 0.7 to 3, in particular 0.9 to 2, contain and at room temperature a viscosity in the range from greater than 1000 to 10 ⁵ mPa * s, preferably at least 5000 mPa ^ s, in particular at least 10000 mPa-s, most preferably at least 20,000 mPa-s.

In a preferred embodiment of the invention, these surfactant solutions additionally contain alkyl ether sulfates of the formula II,

R ³ 0 CH ₂ CH ₂ 0) _m S0 ₃ M ': ID

in which R ^{3 stands} for a saturated or unsaturated C ₈ -C ₂₂ alkyl group, m for numbers from 1 to 10 and M 'for an alkali or an alkaline earth metal cation or an ammonium ion, in a weight ratio of fatty acid oligoalkylene glycol ester sulfates to alkyl ether sulfates in the range from 1 to 4 to 2 to 1, preferably 1 to 3.5 to 1.5 to 1, in particular 1 to 3 to 1 to 1, or in a ratio in the range from 5 to 1 to 100 to 1, preferably at least 8 to 1, especially at least 10 to 1.

The present invention also relates to aqueous surfactant solutions which contain fatty acid oligoalkylene glycol ester sulfates of the formula I,

R ¹ COO (R ² 0), S0 ₃ M (I) in which M represents a cation, in particular an ammonium ion, and R ¹ C0 represents a linear or branched, aliphatic, saturated or unsaturated acyl radical having 6 to 22 carbon atoms and R ² in (R ² 0) "for an alkylene radical, in particular CH ₂ CH ₂ or CH (CH ₃ ) CH ₂ or CH ₂ CH (CH ₃ ), where n is then a number from 0.5 to 5, preferably 0.7 to 3, in particular 0.9 to 2, or (R ² 0) represents a unit of the type (EO) _u (PO) _v (EO) _v , where E is CH ₂ CH ₂ and P is CH (CH ₃ ) CH ₂ or CH ₂ CH (CH ₃ ) and 0 <u <5, 0.1 <v <5, 0 w w 5 5 and u + w> 0 and the sum u + v + w are from 0.5 to 5, preferably 0.7 to 3, in particular 0.9 to 2, and contain and at room temperature a viscosity in the range from 0.01 to 1000 mPa-s, preferably 0.1 to 600 mPa-s, in particular up to 0.5 to 300 mPa-s, most preferably 1 up to 100 mPa-s.

In a preferred embodiment of the invention, these surfactant solutions additionally contain alkyl ether sulfates of the formula II,

R0 (CH ₂ CH ₂ 0) _m S0 ₃ M '(II)

in which R ^{3 stands} for a saturated or unsaturated C ₈ -C ₂₂ alkyl group, m for numbers from 1 to 10 and M 'for an alkali or an alkaline earth metal cation or an ammonium ion, in a weight ratio of fatty acid oligoalkylene glycol ester sulfates to alkyl ether sulfates in the range from 1 to 1.2 to 12 to 1, preferably 1.3 to 1 to 8 to 1, in particular 2 to 1 to 5 to 1, or in a ratio in the range from 1 to 20 to 1 to 1.9 , preferably 1 to 10 to 1 to 2.1, in particular 1 to 7 to 1 to 2.3.

An essential advantage of the invention is to achieve a desired effect, ie a certain viscosity, without using a component that is only useful for this purpose, but moreover is more harmful than useful and therefore undesirable per se, usually a thickener, but through the skilful use of the properties or the interaction of the core components of a surfactant solution, namely the surfactant. The invention thus makes surfactant solutions of defined viscos also accessible without the use of a thickener.

The use of conventional thickeners that thicken by definition, i.e. act to increase viscosity, the invention is also superior in that it also serves to adjust low viscosities or to provide low viscosity solutions.

The aqueous surfactant solutions according to the invention are notable for their skin-friendliness and are suitable as cleaning agents. Preferred surfactant solutions according to the invention are, for example, high-performance hand dishwashing detergents whose viscosity can be adjusted in a wide range in a targeted manner solely by metering the fatty acid oligoalkylene glycol ester sulfates or the weight ratio of fatty acid oligoalkylene glycol ester sulfate to alkyl ether sulfate, without appreciably impairing the cleaning action and without adding an additional thickening agent (see examples).

Another advantage of the surfactant solutions according to the invention is their good emulsifying power. An increasing proportion of fatty acid oligoalkylene glycol ester sulfate (A) results in an increasing stability of the emulsion, whereby in combination with alkyl ether sulfate (B) a surprisingly high increase in stability can be found even with a weight ratio A to B of 1 to 1 (see examples).

The fatty acid oligoalkylene glycol ester sulfates (FSES) of the formula I according to the invention are known compounds which are distinguished by excellent skin compatibility and by sulfating fatty acid oligoalkylene glycol esters of the formula R ¹ C00 (R ² 0) _n H, in which R ¹ , R ² and n or . (R ² 0) _{n have} the same meaning as in formula I, are accessible (cf. K. Engel, W. Ruback Fette, Seifen und Anstrichmittel 1986, 88, 20-25). As described in the unpublished German patent application P 19736906.5, the sulfation is preferably carried out with sulfur trioxide in a molar ratio of 1 to 1 to 1 to 1.3, in particular 1 to 1.05 to 1 to 1.1, on a continuously working falling film reactor preferably at temperatures of at least 5 to 10 ° C. above the melting point of the fatty acid oligoalkylene glycol esters, followed by neutralization of the acidic ester obtained with alkali metal hydroxides, alkaline earth metal hydroxides, ammonia and / or water-soluble organic amines, preferably NaOH, KOH and / or NH ₃ , in the form of their 20 to 50% by weight aqueous solutions, the pH in a range from 5 to 9, preferably 6 to 8, and the temperature preferably between 10 and 40 ° C., in particular 20 and 35 ° C. , is held.

The fatty acid oligoalkylene glycol esters used in the sulfation can be prepared, for example, according to application P 19736906.5 above by basic homogeneously catalyzed addition of ethylene oxide and / or propylene oxide to fatty acids. The use of amines such as alkanolamines, preferably monoethanolamine or diethanolamine, in particular triethanolamine, in amounts, based on the amount of fatty acids, of 0.1 to 5% by weight, preferably 0.5 to 1.5% by weight, described there. %, as a catalyst it is now also possible to obtain selectively low-alkoxylated, in particular low-ethoxylated, products with a narrow homolog distribution and a low proportion of by-products. The alkoxylation of the fatty acids with 0.5 to 5, preferably 1 to 2 equivalents, based on the amounts of material, ethylene oxide, propylene oxide or an ethylene oxide / propylene oxide mixture can be carried out in a known manner at temperatures from 80 to 180 ° C., preferably 100 to 120 ° C, under autogenous pressure of 1 to 5 bar, preferably 2 to 3 bar. FSES with conventional as well as preferably with narrowed homolog distribution are suitable according to the invention. The FSES according to the invention can - if necessary for production reasons - to a lesser extent glycol mono- and glycol disulfa- te, fatty acid soaps, unsulfated parts and / or inorganic sulfates.

According to the invention, the FSES are sulfates of alkoxylated aliphatic carboxylic acids of the formula R ^ -COOH, in which R ^x CO is an aliphatic, linear or branched acyl radical having 6 to 22, preferably 12 to 18, carbon atoms and 0, 1, 2 or 3 double bonds. Typical examples are the oligoalkyl ester sulfates of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, linoleic acid, linoleic acid, linoleic acid, lauric acid, lauric acid, lauric acid, lauric acid, lauric acid, lauric acid, lauric acid, lauric acid, lauric acid, lauric acid, lauric acid, lauric acid, lauric acid, elauric acid, Gadolic acid, behenic acid and erucic acid as well as their technical mixtures, which occur, for example, in the pressure splitting of natural fats and oils. Technical fatty acids with 12 to 18 carbon atoms such as coconut, palm, palm kernel or tallow fatty acid are preferred.

According to the invention, the sulfates of the formula I with an average degree of alkoxylation n or (u + v + w) of 0.7 to 3, preferably 0.9 to 2 are preferred. The sulfates of the propoxylated and in particular the ethoxylated carboxylic acids or their ammonium salts, especially those of lauric acid oligoalkylene glycol ester sulfates, most preferably the ammonium salt of lauric acid + IEO ester sulfate. Further cations M according to the invention (formula I) are alkali and alkaline earth metal cations, in particular Mg ²⁺ .

In a preferred embodiment of the invention, the fatty acid oligoalkylene glycol ester sulfates are used to adjust the viscosity of aqueous surfactant solutions in which C ₈ -C ₂₂ -alkyl ether sulfates according to formula II are used as a further surfactant component. In a likewise preferred embodiment of the invention, the aqueous surfactant solution contains 1 to 70% by weight, in particular 3 to 50% by weight, extremely preferably 6 to 30% by weight, of fatty acid oligoalkylene glycol ester sulfates.

Furthermore, the aqueous surfactant solutions according to the invention necessarily contain C ₈ -C ₂₂ -alkyl ether sulfates according to formula II in amounts, based on the composition, of usually 0.1 to 40% by weight, preferably 0.1 to 20% by weight, in particular 1 to 13% by weight, most preferably 2 to 9% by weight.

These substances are also known chemical compounds which can be obtained by sulfating C ₈ -C ₂₂ alcohol polyglycol ethers. Also C ₈ -C ₂₂ alkyl ether sulfates with a narrow homolog distribution (NRE = narrow range ethoxylates), as described, for example, in international patent application WO 91/05764 and in the review by DL Smith (J. Am. Oil. Chem. Soc. 1991, 68, 629) can be used.

Typical examples are the sulfation products of adducts of 0.5 to 10 mol ethylene oxide (conventional or restricted homolog distribution) with 1 mol capryl alcohol, caprinal alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol , Arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol as well as their technical mixtures or also with 1 mole of a petrochemical alcohol such as the commercially available C _{ι2 /} ι ₃ oxo alcohols Neodol 23 ^® or Lial 123 ^® . Sulfates of adducts of 1 to 7 moles of ethylene oxide with saturated coconut oil alcohols in the form of their sodium, potassium and / or magnesium salts and ammonium salts, such as monoisopropanolammonium salts, are preferred. For example, alkyl ether sulfates can be used, which are derived from corresponding fatty alcohol polyglycol ethers, which in turn are present in the presence of calcined or, in particular, hydrogenated phobicized hydrocalcite have been produced and therefore have a particularly advantageous narrow homolog distribution.

As further anionic surfactants, the surfactant solutions according to the invention can be C ₈ -C ₂₂ carboxamide amide sulfates of the formula R-CO-NH (CH ₂ CH ₂ 0) _j -S0 ₃ X, in which R represents a saturated or unsaturated C ₈ -C ₂₂ - Alkyl group, j are numbers from 1 to 10 and X is an alkali metal, alkaline earth metal or quaternary ammonium ion.

C ₈ -C ₂₂ carboxylic acid amide ether sulfates are known anionic surfactants which have a pronounced foaming capacity and low sensitivity to hardness (cf. A. Reng Parf. And Kosmetik 1980, 61, 87-97). They can be produced by methods known from the prior art (cf. J. Falbe Surfactants in Consumer Products 1987, Springer Verlag, p. 93 ff.).

Typical examples of C ₈ -C ₂₂ carboxylic acid amide ether sulfates are the sulfated adducts of 1 to 10 moles of ethylene oxide (conventional or narrowed homolog distribution) with 1 mole of carboxylic acid real alkanolamide, such as, for example, the amide of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitolemic acid , Stearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, lmoleic acid, arachic acid, gadoleic acid, behenic acid and erucic acid. As is customary in fat chemistry, the fatty acid component of the amides can also be derived from technical fatty acid cuts, such as those that occur in the pressure splitting of natural fats and oils, for example palmol, palm kernel oil, coconut oil, rubol or beef tallow. Preferred feedstocks are the carboxylic acid amide ether sulfates of coconut fatty acid.

The C ₈ -C ₂₂ -carboxylic acid amide ether sulfates can be used in the surfactant solutions according to the invention in amounts of 0.01 to 60% by weight, based on the finished solution, preferably 0.1 to 40% by weight, in particular 0.2 to 25% by weight, most preferably 0.5 to 15% by weight, can be contained. As further anionic surfactants, for example, alkyl sulfates with 8 to 22 carbon atoms in the alkyl radical, n-alkylbenzenesulfonates with 9 to 16 carbon atoms in the alkyl radical, alkanesulfonates with 10 to 20 carbon atoms in the alkyl radical and / or olefin sulfonates with 12 to 16 carbon atoms in the alkyl radical can be present in the surfactant solutions according to the invention .

Soaps, ie alkali or ammonium salts of saturated or unsaturated C ₈ -C ₂₂ fatty acids, are preferably not contained in the surfactant combinations according to the invention because of their foam-suppressing properties.

The feature "preferably not included" is intended to mean that very small amounts of soap of up to 2% by weight, based on the total solution, can still be tolerated in the sense of the invention.

The preferred nonionic surfactants are alkyl polyglycosides (APG) of the formula III,

R ⁴ 0 [G] _x im;

in which R ^{4 is} a linear or branched, saturated or unsaturated alkyl radical having 8 to 22 carbon atoms, [G] is a glycosidically linked sugar radical and x is a number from 1 to 10.

APG are non-ionic surfactants and are known substances that can be obtained using the relevant methods of preparative organic chemistry.

The index number x in the general formula III indicates the degree of oligomerization (DP degree), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While x in a given compound must always be an integer must and here can assume the values x = 1 to 6, is the Value x for a certain alkyl glycoside is an analytically calculated value, which usually represents a fractional number. Alkyl glycosides with an average degree of oligomerization x of 1.1 to 3.0 are preferably used. From an application point of view, those alkyl glycosides are preferred whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.6. Glucose and xylose are preferably used as glycosidic sugars.

The surfactant solutions according to the invention preferably contain APG in amounts of 0.1 to 20% by weight, in particular 0.5 to 10% by weight, extremely preferably 1 to 5% by weight, and / or in a ratio to the total amount of anionic surfactant from 1: 8 to 1: 4, in particular 1: 7 to 1: 5.

The alkyl or alkenyl radical R ⁴ (formula III) can be derived from primary alcohols having 8 to 18, preferably 8 to 14, carbon atoms. Typical examples are capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as those obtained in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from RoELEN's oxo synthesis.

However, the alkyl or alkenyl radical R ⁴ is preferably derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol. Elaidyl alcohol, petroselinyl alcohol, arachidyl alcohol, gadolinyl alcohol, behenyl alcohol, erucyl alcohol and their technical mixtures are also to be mentioned.

Further suitable nonionic surfactants are C ₈ -C ₁₈ alcohol alkoxylates of the formula R'O- (CH ₂ CH _{2 0),} -H are used, wherein R 'is a saturated or unsaturated C ₈ -Cι ₈ alkyl group, and i for Numbers from 1 to 20 stands. The fatty alcohol alkoxylates are known compounds which can be obtained by alkoxylating the fatty alcohols. Alcohol alkoxylates ^¬ The fat may be present in an amount of 0.1 to 15 wt .-% in the surfactant solution according to the invention.

Other nonionic surfactants that can be used are fatty acid alkanolamides, for example CIO _{/ 22} fatty acid monoethanolamide or addition products of 4 to 20, preferably 4 to 10, moles of C ₂ -C ₃ -alkylene oxide, preferably ethylene oxide to C ₀ -C ₂₀ , preferably C ₂ -C _{2 8} -alkanols, as well as the adducts of ethylene oxide and propylene glycols, which are known under the name Pluronics ^®, as well as addition products of 1 to 7 moles of ethylene oxide with 1 to 5 moles of propylene oxide converted C suitable ₁₂ -C ₁₈ alkanols. Fatty alkyl amine oxides are also suitable.

Fatty acid N-alkylpolyhydroxyalkylamides can also be used as nonionic surfactants, which are also known substances which are usually obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, one Fatty acid alkyl esters or a fatty acid chloride can be obtained. With regard to the processes for their production, reference is made to US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798 and international patent application WO 92/06984. An overview of this topic by H. Kelkenberg can be found in Tens. Surf. Det. 1988, 25, 8. Preferred fatty acid N-alkylpolyhydroxyalkylamides are the fatty acid N-alkylglycamides derived from reducing sugars with 5 or 6 carbon atoms, in particular glucose.

Betaine compounds of the formula IV,

(R ⁵ ) (R ⁶ ) (R ⁷ ) N-CH ₂ COO ^~ (IV)

in the R ^5, optionally by heteroatoms or hetero- alkyl groups interrupted by atomic groups and having 8 to 25, preferably 10 to 21 carbon atoms and R ⁶ and R ^{7 are} identical or different alkyl radicals having 1 to 3 carbon atoms. Preferred are -C ₀ -C ₈ -alkyl-dimethylcarboxymethyl-betaine and Cn--C- ₇ -Alkylamidopropyl-dimethylcarboxymethyl-betaine.

The betaine compounds of the formula IV are preferably present in an amount of 0.1 to 14% by weight, in particular 1 to 8% by weight, of the surfactant solutions according to the invention.

The total surfactant content in the surfactant solutions according to the invention is preferably above 15% by weight, based on the total solution, but not above 75% by weight, in particular not above 50% by weight.

The solvents to be added if necessary are preferably low molecular weight alkanols having 1 to 4 carbon atoms in the molecule, in particular ethanol and isopropanol. Other solution mediators, for example for dyes and perfumes, can optionally be, for example, alkanolamines, polyols such as ethylene glycol, propylene glycol, glycerol and alkylbenzenesulfonates having 1 to 3 carbon atoms in the alkyl radical, in particular cumene, toluene and xylene sulfonates.

The pH of the surfactant solutions according to the invention is preferably between 5 and 9, in particular between 6 and 8, most preferably between 6 and 7. The pH is optionally adjusted by means of conventional pH regulators such as citric acid or sodium hydroxide. To stabilize the storage, antimicrobial agents or pH buffers can be added in amounts of up to 10% by weight based on the active substance content of fatty acid oligoalkylene glycol ester sulfate (s).

Urea, sodium chloride, magnesium sulfate or chloride, ammonium chloride or polysaccharides and the like, which are also used in combination, can be included as thickeners can be. Substances such as gelatin or casein can also be used to adjust the viscosity of the surfactant solution. In a particularly preferred embodiment of the invention, in order to adjust the viscosity of the aqueous surfactant solution, the additional use of a conventional thickening agent is dispensed with.

Examples of preservatives that can be mentioned are sodium benzoate, formaldehyde and sodium sulfite. The surfactant solutions according to the invention can also contain conventional disinfectants.

Finally, the surfactant solutions according to the invention can contain, as further constituents, perfume, dyes and opacifiers, as well as skin protection components, such as those e.g. are known from the document EP 0 522 756.

In the following, examples of formulations of the surfactant solutions according to the invention are given, which were obtained by stirring the individual components together in any order and allowing the mixture to stand until there were no bubbles.

B e i s p i e l e

The agents E1 to E33 according to the invention and the comparison agents V0 to V3 were produced (composition in% by weight according to Tables 1 to 3). The pH was adjusted between 6.2 and 6.6 with citric acid. Water in Tables 1 to 3 means water and pH regulator (s). The following surfactant components were used: A lauric acid + IEO estersulfate NH ₄ salt (FSES), B lauryl ether sulfate Na salt (AES), CC _{8 14} alkyl polyglucoside (APG) and D coconut fatty acid amidopropyl betaine.

Determination of the viscosity of fatty acid oligoalkylene glycol ester sulfate and alkyl ether sulfate-containing surfactant solutions

The viscosity of the surfactant solutions E1 to E5 and V0 and VI was determined. The measurements were carried out using a Broc / cfield LV viscometer of the type LVDV-II + in a Brookfield Small Sample Adapter (measuring tube for sample volumes from 2 to 16 ml) at 20 ° C. and a measuring time of 2 minutes, with spindle and Speed was chosen so that the measured viscosity was in the recommended measuring range. The type numbers of the spindles used and the vicissosites obtained are given in Table 1. The rotation frequency was 30 revolutions per minute.

Table 1

VO El E2 E3 E4 E5 VI

A 13.8 10.3 9 8 6.9 3.5 -

B - 3.5 4.8 5.8 6.9 10.3 13.8

C 2.3 2.3 2.3 2.3 2.3 2.3 2.3

D 5.0 5.0 5.0 5.0 5.0 5.0 5.0

Ethanol 5.0 5.0 5.0 5.0 5.0 5.0 5.0

Water adlOO AdlOO adlOO adlOO adlOO adlOO adlOO

A: B 1: 0 3: 1 1.9: 1 1.4: 1 1: 1 1: 3 0: 1

η [mPa-s] 3632 160 260 320 598 6016 880Spindle 25 30 30 30 30 25 30

η [mPa-s] 3632 160 260 320 598 6016 880

The viscosity can be set in a very wide range from 160 to 6016 mPa ^• s. Viscosities that are significantly lower than those of solution VI without fatty acid oligoalkylene glycol ester sulfate (E1 to E4, table 1) and one that is significantly greater than that of solution V0 without alkyl ether sulfate (E5, table 1) can be set here.

The viscosities of further aqueous surfactant solutions E6 to E19 and V2 (composition according to Table 2) which, apart from FSES (A) and / or AES (B), contain no further surfactant components, and E20 to E33 and V3 (composition according to Table 3), which in addition to FSES (A) and / or AES (B) containing alkyl polyglycoside (C) as an additional surfactant component, were also determined. The type numbers of the spindles used, the rotation frequencies v (revolutions per minute) and the viscosities η obtained are shown in Tables 2 and 3.

Table 2 AB c water spindle V f]

[% By weight] [% by weight] [% by weight] [% by weight] [min ^"1 ] [mPa-s]

V2 - 14 0 adlOO 18 60 5

E6 1 13 0 adlOO 18 60 5

E7 2 12 0 adlOO 18 60 6

E8 3 11 0 adlOO 31 60 20

E9 4 10 0 adlOO 31 30 172

E10 5 9 0 adlOO 31 12 1705

Express 6 8 0 adlOO 25 30 10560

E12 7 7 0 adlOO 31 3 8330

E13 8 6 0 adlOO 31 30 534

E14 9 5 0 adlOO 31 30 235

E15 10 4 0 adlOO 31 60 106

E16 11 3 0 adlOO 31 60 72

E17 12 2 0 adlOO 31 30 321

E19 14 - 0 adlOO 31 6 4480 E18 13 1 0 adlOO 31 12 2280

E19 14 - 0 adlOO 31 6 4480

Table 3

A B C water spindle V

[% By weight] [% by weight] [% by weight] [% by weight] [mm ^"1 ] [mPa-s]

V3 - 14 2.3 adlOO 18 60 8

E20 1 13 2.3 adlOO 18 60 9

E21 2 12 2.3 adlOO 31 60 25

E22 3 11 2.3 adlOO 31 30 175

E23 4 10 2.3 adlOO 31 6 2590

E24 5 9 2.3 adlOO 25 30 10520

E25 6 8 2.3 adlOO 25 12 27 600

E26 7 7 2.3 adlOO 31 12 2182

E27 8 6 2.3 adlOO 31 30 410

E28 9 5 2.3 adlOO 31 30 210

E29 10 4 2.3 adlOO 31 60 126

E30 11 3 2.3 adlOO 31 60 80

E31 12 2 2.3 adlOO 31 60 89

E33 14 - 2,3 adlOO 25 12 6280E32 13 1 2.3 adlOO 25 12 4280

E33 14 - 2.3 adlOO 25 12 6280

If the aqueous system contains only FSES and AES as surfactant components, an FSES: AES ratio of 1: 2.5 (E9) to 1.8: 1 (E14) is a marked increase in viscosity with a maximum of 1: 1 , 3 (rush) to watch (Table 2).

If an APG (C) is contained as a further surfactant component, a significantly higher increase in viscosity occurs with an almost tripled maximum value, while the position of the maximum (E25) or distribution (E22 to E28) remains essentially unchanged.

The proportion of FSES in this case results in an exceptionally high thickening of the aqueous surfactant systems, without the need to add further thickeners, such as, for example, inorganic salts. But even beyond the maximum viscosity in terms of increasing FSES content, very low viscosities of less than 100 mPa-s can be set (E16, Table 2; E30, E31, Table 3).

Determination of the cleaning power of fatty acid oligoalkylene glycol ester sulfate and alkyl ether sulfate-containing surfactant solutions

The cleaning ability of the aqueous surfactant compositions E1 to E5 and V0 and VI as hand dishwashing detergent was tested in a mechanized plate test on beef tallow soil (c = 0.15 g / 1) and on mixed soiling (c = 0.12 g / 1). The cleaning ability of mixture VI was set as the standard (cleaning ability = 100%). The percentage cleaning power obtained with respect to the VI standard is shown in Table 4.

Table 4

V0 El E2 E3 E4 E5 VI

87 116 121 126 124 108 100Beef tallow soiling 93 114 121 114 121 100 100 Mixed soiling

87 116 121 126 124 108 100

With a consistently good cleaning capacity of El to E5 between 100 and 126%, the viscosity can be set in a very wide range from 160 to 6016 mPa-s.

In addition, the rinse power of the compositions E1 to E5, which contain components A and B, is synergistically superior to that of the comparative solutions V0 and VI containing only one of these two components.

Claims

P aent to sp 1 . Use of fatty acid oligoalkylene glycol ester sulfates of the formula I, R ¹ COO (R ² 0) "S0 ₃ M: D in which M is a cation, in particular an ammonium ion, and R ¹ CO is a linear or branched, aliphatic, saturated or unsaturated acyl radical having 6 to 22 carbon atoms, and R ² in (R ² 0) is an alkylene radical, in particular CH ₂ CH ₂ or CH (CH ₃ ) CH ₂ or CH ₂ CH (CH ₃ ), where n is a number from 0.5 to 5, preferably 0.7 to 3, in particular 0.9 to 2, or (R ² 0) _Λ a unit of the type (EO) _u (PO) v (EO) ", where E for CH ₂ CH ₂ and P for CH (CH ₃ ) CH ₂ or CH ₂ CH (CH ₃ ) are and 0 <u <5, 0.1 <v ≤ 5, 0 <w ≤ 5 and u + w> 0 and the sum u + v + w assumes a value from 0.5 to 5, preferably 0.7 to 3, in particular 0.9 to 2, to adjust the viscosity of aqueous surfactant solutions. 2. Use according to claim 1, characterized in that in the surfactant solution as a further surfactant component alkyl ether sulfates of the formula II, R ³ 0 (CH ₂ CH ₂ 0) _ra S0 ₃ M '(St. in which R ^{3 represents} a saturated or unsaturated C ₈ -C ₂₂ alkyl group, m represents numbers from 1 to 10 and M 'represents an alkali or an alkaline earth metal. 3. Use according to claim 1 or 2, characterized in that no conventional thickeners are used. 4. Use according to claim 1 or 2, characterized in that conventional thickeners are used. 5. Aqueous surfactant solution, characterized in that it contains fatty acid oligoalkylene glycol ester sulfates of the formula I, R ¹ COO (R ² 0) _r S0 ₃ M (I) in which M represents a cation, in particular an ammonium ion, and R ¹ C0 represents a linear or branched, aliphatic, saturated or unsaturated acyl radical having 6 to 22 carbon atoms, and R ² in (R ² 0) _{n represents} an alkylene radical, in particular CH ₂ CH ₂ or CH (CH ₃ ) CH ₂ or CH ₂ CH (CH ₃ ), where n is a number from 0.5 to 5, preferably 0.7 to 3, in particular 0.9 to 2, or (R ² 0) _n a unit of the type (EO) _u (PO) _v (EO) ", where E for CH ₂ CH ₂ and P for CH (CH ₃ ) CH ₂ or CH ₂ CH (CH ₃ ) and 0 <u <5, 0.1 <v <5, 0 <w 5 5 and u + w> 0 and the sum u + v + w assumes a value of 0.5 to 5, preferably 0.7 to 3, in particular 0.9 to 2, and contains one at room temperature Viscosity in the range of greater than 1000 to 10 ⁵ mPa-s, preferably at least 5000 mPa-s, in particular at least 10000 mPa-s, extremely preferably at least 20,000 mPa-s. 6. surfactant solution according to claim 5, characterized in that it contains alkyl ether sulfates of the formula II, R ^J 0 (CH ₂ CH ₂ 0) _m S0 ₃ M ': n: in which R stands for a saturated or unsaturated C ₈ -C ₂₂ alkyl group, m for numbers from 1 to 10 and M 'for an alkali or an alkaline earth metal cation or an ammonium ion, in a weight ratio of fatty acid oligoalkylene glycol ester sulfates to alkyl ether sulfates im Range from 1 to 4 to 2 to 1, preferably 1 to 3.5 to 1.5 to 1, in particular 1 to 3 to 1 to 1, or in a ratio in the range from 5 to 1 to 100 to 1, preferably at least 8 to 1, in particular at least 10 to 1, contains. . Aqueous surfactant solution, characterized in that it contains fatty acid oligoalkylene glycol ester sulfates of the formula I, R ¹ COO (R ² 0) _fl S0 ₃ M (I) where M is a cation, in particular an ammonium ion, and R ^x CO is a linear or branched, aliphatic, saturated or unsaturated acyl radical having 6 to 22 carbon atoms, and R ² in (R ² 0) _{n is} an alkylene radical, in particular CH ₂ CH ₂ or CH (CH ₃ ) CH ₂ or CH ₂ CH (CH ₃ ), where n is a number from 0.5 to 5, preferably 0.7 to 3, in particular 0.9 to 2, or (R ² 0) _n a unit of the type (EO) _{U represents} (P0) _v (EO) ", where E is CH ₂ CH _; and P for CH (CH ₃ ) CH ₂ or CH ₂ CH (CH ₃ ) are as well as 0 <u <5, 0.1 <v <5, 0 <w <5 and u + w> 0 and the sum u + v + w has a value from 0.5 to 5, preferably 0, 7 to 3, in particular 0.9 to 2, and contains and at room temperature a viscosity in the range from 0.01 to 1000 mPa-s, preferably 0.1 to 600 mPa * s, in particular up to 0.5 to 300 mPa-s, most preferably 1 to 100 mPa-s. 8. surfactant solution according to claim 7, characterized in that it contains alkyl ether sulfates of the formula II, R ^J 0 (CH ₂ CH ₂ 0) _m S0 ₃ M '(II) in which R ^{3 stands} for a saturated or unsaturated C ₈ -C ₂₂ alkyl group, m for numbers from 1 to 10 and M ¹ for an alkali metal or an alkaline earth metal cation or an ammonium ion, in a weight ratio of fatty acid oligoalkylene glycol ester sulfates to alkyl ether sulfates in the range from 1 to 1.2 to 12 to 1, preferably 1.3 to 1 to 8 to 1, in particular 2 to 1 to 5 to 1, or in a ratio in the range of 1 to 20 to 1 to 1.9, preferably 1 to 10 to 1 to 2.1, in particular 1 to 7 to 1 to 2.3, contains. 9. surfactant solution according to one of claims 5 or 8, characterized in that it contains the fatty acid oligoalkylene glycol sulfates in amounts of 1 to 70 wt .-%, preferably 3 to 50 wt .-%, in particular 6 to 30 wt .-% . 10. surfactant solution according to one of claims 5 to 9, characterized in that it contains alkyl ether sulfates in amounts of 0.1 to 40 wt .-%, preferably 0.1 to 20 wt .-%, in particular 1 to 13 wt .-%, most preferably 2 to 9 wt .-%, contains. 11. surfactant solution according to one of claims 5 to 10, characterized in that it additionally contains alkyl polyglycosides of the formula III, R 0 [G] _. [HD in the R ⁴ for a linear or branched, saturated or unsaturated alkyl radical having 8 to 22 carbon atoms, [G] for a glycosidically linked sugar radical and x for a number from 1 to 10, preferably 1.1 to 3, in particular 1.2 to 1.6, preferably in amounts of 0.1 to 20% by weight, in particular 0.5 to 10% by weight, most preferably 1 to 5% by weight, and / or in a ratio to the total amount of anion - Contains surfactant from 1: 8 to 1: 4, in particular 1: 7 to 1: 5. 12. Surfactant solution according to one of claims 5 to 11, characterized in that it additionally contains betaine compounds of the formula IV, (R ⁵ ) (R ⁶ ) (R ⁷ ) N-CH ₂ COO ^~ (IV) in which R ^{5 is} an alkyl radical with 8 to 25, preferably 10 to 21 carbon atoms and optionally interrupted by heteroatoms or heteroatom groups and R ⁶ and R ^{7 are} identical or different alkyl radicals with 1 to 3 carbon atoms, preferably in amounts of 0.1 to 14 % By weight, in particular 1 to 8% by weight, contains. 13. Surfactant solution according to one of claims 5 to 12, characterized in that it additionally contains solvents, preferably low molecular weight alkanols with 1 to 4 carbon atoms, in particular ethanol.