EP1897933A1 - Use of long-chained alkoxylated fatty alcohols as detergent additives for hard surface cleaning - Google Patents

Abstract

Alkoxylated fatty alcohols (I) are used in cleaners for hard surfaces. Alkoxylated fatty alcohols of formula (I) are used in cleaners for hard surfaces. RO(C nH 2nO) mH (I) R : alkyl or alkenyl with at least 19 C atoms; m : 20 or more; n : 2 or 3. Independent claims are also included for: (1) mixtures of (I) and surfactants of formula (II)-(IX) and/or betaines; (2) hard surface cleaners comprising surfactants, water softeners and (I); (3) liquid rinse aid comprising water, a solubilizer, optionally an acid, and 0.1-25 wt.% (I). R 1>O(CH 2CH 2O) xCH 2CH(OM)R 2>(II) R 3>O(CH 2CH 2O) y(CH 2CHCH 3O) zCH 2CH(OH)R 4>(III) R 5>(OC 2H 4) aOH (IV) R 6>CO(OC 2H 4) mOR 7>(V) R 8>O(G) p(VI) HO(CH 2CH 2O) oCH 2CH(R 9>)O(CH 2CH 2O) bH (VII) R 10>CH(OR 11>)CH 2OR 11>(VIII) N(R 13>) 3(IX) R 1>4-22C alkyl or alkenyl orR 2>CH(OH)CH 2; R 2>8-16C alkyl or alkenyl; x : 40-80; M : H or 1-18C alkyl; R 3>8-22C alkyl or alkenyl; R 4>8-16C alkyl or alkenyl; y : 10-35; z : 0-5; R 5>8-22C alkyl or alkenyl; a : 1-20; R 6>7-21C alkyl or alkenyl; m : 11-100; R 7>H or COR 6>; R 8>4-22C alkyl or alkenyl; G : a 5-6C sugar residue; p : 1-10; R 9>4-22C alkyl or alkenyl; o : 1-20; b : 0-20; R 10>8-16C alkyl or alkenyl; R 11>(CH 2CH 2O) rCH 2CH(OH)R 12>; r : 0-50; R 12>8-16C alkyl or alkenyl; R 13>(CH 2CH 2O) sCH 2CH(OH)R 14>or 8-16C alkyl; s : 0-50;.

Description

The present application relates to the use of selected fatty alcohol alkoxylates in detergents and cleaners, preferably those for use in automatic dishwashing processes containing these fatty alcohol alkoxylates.

The cleaning of hard surfaces and especially the washing of dishes makes special demands on the cleaner used. This applies in particular to automatic dishwashing. The three components of the machine system are cleaner, rinse aid and regeneration salt for water softening. Here, the central tasks of the main component cleaners are the soil release, the dirt dispersion, the binding of residual water hardness and the corrosion inhibition. Following the trend towards a simplified application, many manufacturers today offer their customers multifunctional dishwashing detergents, i. that the cleaner additionally contains agents for rinsing and water softening or gloss retention on metallic surfaces or protection against silver discoloration after cleaning, so that the customer does not have to achieve these functions by separate means, but achieved only by a form of supply the desired benefit.

Conventional multifunctional detergents for automatic dishwashing (so-called "ADD" automatic dish detergents) have a poorer drying performance compared to the conventional rinse aid system (detergent, salt and rinse aid as separate products). Drying performance is to be understood in how far a dishwashing item which has been cleaned with a dishwashing detergent still has water, preferably water droplets, on the surface after passing through the dishwashing process.

Due to the increased use of multifunctional agents, the drying performance has become worse compared to the classic rinse aid. It is therefore sought ways to improve the drying performance of cleaning agents for hard surfaces, especially dishwashing detergents. However, additives for cleaning agents must not adversely affect the rinsing and especially the rinsing performance of the cleaners. For example, it may not come to excessive foaming of the cleaner by adding or using the rinse additives. Ideally, an additive should even improve the overall performance of the cleaner.

An essential parameter for dishwashing is the rinse aid performance. It is determined how large the proportion of deposits on the dishes, after they were rinsed. The deposits are essentially mineral compounds, in particular Ca and / or Mg salts, but also surfactant residues. However, lime mainly leads to undesirable deposits for the user. In order to reduce the proportion of these deposits, common dishwashing agents, in particular those for automatic dishwashing, generally contain so-called rinse aid. Commercially available rinse aids are usually mixtures of low foaming nonionic surfactants, typically fatty alcohol polyethylene / polypropylene glycol ethers, solubilizers (eg cumene sulfonate), organic acids (eg citric acid) and solvents (eg ethanol) Means is to influence the interfacial tension of the water so that it can run off in a very thin, coherent film from the items to be washed, so that remain in the subsequent drying process, no drops of water, streaks or films. There are differences between two types of deposits. On the one hand, the so-called "spotting", which is caused by drying drops of water, is examined. On the other hand, the "filming", which are layers that result from the drying of thin water films, is evaluated. It will thus be understood that there is a continuing need for improved rinse aids which not only requires an improvement in rinse aid performance but also avoids the performance problems described above.

It has now been found that the selected long-chain fatty alcohol alkoxylates are able to accomplish this task.

A first subject of the invention relates to the use of alkoxylated fatty alcohols of the general formula (I) RO - (C _n H _2n O) _m -H, where R is a linear branched, saturated or unsaturated alkyl or alkenyl radical having at least 19 C Atoms and m is a number of greater than or equal to 20 and n is 2 or 3, in hard surface cleaners, especially in automatic dishwashing cleaners. This includes the use of the alkoxylates of formula (I) as additives to improve the rinse performance in hard surface cleaners, especially in automatic dishwashing cleaners.

Fatty alcohols are known to be a collective name for the linear, saturated or unsaturated primary alcohols (1-alkanols) having 6-22 carbon atoms obtainable by reduction of the triglycerides, fatty acids or fatty acid methyl esters. As an alternative to the production of fatty alcohols via fats and oils, these products are accessible via the oxo reaction (hydroformylation). In the Alfol process, higher olefins are first prepared by the oligomerization of ethylene as an aluminum-organic compound, which is oxidized in a further step with atmospheric oxygen u. be hydrolyzed to the corresponding fatty alcohols.

The alkoxylates of the fatty alcohols thereby represent a group of nonionic surfactants obtained by alkoxylation, i. Reaction with ethylene oxide (fatty alcohol ethoxylates, FAEO), propylene oxide or butylene oxide, but preferably ethoxylation of primary long-chain fatty or oxo alcohols in the presence of basic or acidic catalysts at temperatures of 120-200 ° C and pressures of 1-10 bar is obtained. In the reaction of the alcohol with the alkylene oxide is formed in a polymerization reaction with the starter fatty alcohol a polyglycol ether mixture of varying degrees alkoxylated homologues their distribution depending on the catalyst and the amount of alkoxide between a statistic corresponding Gauss and a non-selective Schulz Flory Curve may vary. For example, in the presence of sodium hydroxide a wide, using alkaline earth salts, a narrow range (homo) distribution obtained. As a result of the formation of 1,4-dioxane as an undesired by-product, favored by acidic ethoxylation catalysts, and because of the risk of corrosion on the steel of the reaction vessel, preference is given in the art to basic catalysts, e.g. Sodium methylate in methanol or potassium hydroxide in water used.

The fatty alcohol alkoxylates used according to the invention are long-chain, ie the alkyl or in the case of unsaturated alkenyl radicals has at least 19 C atoms, those alkoxylates are preferred whose alkyl or alkenyl radical 19 to 30, preferably 20 to 25 and in particular 21 to Contains 23 C atoms. Very particular preference is given to fatty alcohol alkoxylates based on behenyl alcohol, ie 22 C atoms in the alkyl chain. The radical R in the general formula (I) may be linear or branched, but the linear alkyl or alkenyl chains are preferred. The radical R can therefore be both saturated and monounsaturated or polyunsaturated. Preference is given to compounds of the formula (I) used, whose radical R is saturated. In the selection of suitable compounds of the formula (I), in particular those are preferred whose radical R is linear and saturated.

The compounds of the formula (I) are alkoxylates. This includes compounds which have been prepared either by reaction with ethylene oxide (EO) or propylene oxide, but mixed alkoxylates of EO and PO are also suitable. Particularly preferred are those compounds of formula (I) wherein n is 2, i. the pure ethoxylates. In this case, those alkoxylates which have a narrow homolog distribution can be particularly preferred.

It is essential that the proportion of the alkoxylates, expressed by the index m of the general formula (I) is at least 20, or assumes a larger value. In this case, preference is given to those compounds of the formula (I) in which the index m has the values 20 to 30, preferably 21 to 28 and in particular 22 to 26. Very particular preference is given to alkoxylates with 25 parts of alkoxide, preferably ethylene oxide, per molecule of fatty alcohol. Furthermore, preference is given to those compounds of the general formula (I) in which R is a linear, saturated alkyl radical having 22 carbon atoms, n is the number 2 and m can be taken for values 22 to 26. Very particular preference is given to a behenyl alcohol which has been reacted with 25 parts of ethylene oxide.
In a preferred embodiment of the present invention, the above-described alkoxylates of the formula (I) are used as the sole alkoxylates, ie, for example, in a detergent as alkoxylates exclusively those of the formula (I) are included, preferably alkoxylates of the formula (I) with 22 C atoms find use.

The preparation of the alkoxylates used according to the invention is carried out in a manner known per se. The starting alcohol is z. B. presented in the reactor and melted. An alkaline catalyst, eg NaOMe 30% strength, is then added to the melt with stirring. Then the pressure is reduced, for example to <40 mbar and at elevated temperature, for example 100-120 ° C, evacuated and filled with N ₂ . The desired amount of ethylene oxide is then at further elevated temperatures, for example 160 ° C - 180 ° C and a pressure of max. 5 bar added. After completion of the reaction is cooled to about 100-120 ° C and evacuated again to <40mbar. The product can be neutralized by adding stoichiometric amounts of acid (eg, lactic acid, acetic acid, citric acid, phosphoric acid) and optionally filtered before filling.

The alkoxylates of the formula (I) are used, for example, as additives in cleaning agents, the use preferably being carried out in automatic dishwashing cleaners. The alkoxylates are preferably used in amounts of 0.1 to 25 wt .-%, preferably in amounts of 0.5 to 10 wt .-% and in particular in amounts of 1.0 to 5 wt .-%, based in each case on the Total weight of the cleaner. The alkoxylates can preferably be used in solid cleaners. However, it is not essential whether they are powders, granules, pellets, flakes or shaped articles, ie tablets or e.g. Cleaner in block form is.

However, the fatty alcohol alkoxylates of the general formula (I) are not only suitable for use in cleaning or dishwashing detergents. It is also possible and preferred to use the alkoxylates in rinse aids both in solid and in liquid rinse aids.

The alkoxylates can also be advantageously used in the form of compounds, preferably in combination with nonionic surfactants. Nonionic surfactants from the group of polyethylene glycols are alkyl (oligo) glycosides. Fatty alcohol alkoxylates with the exception of the compounds of formula (I), Polyolhydroxyalkylether and / or Hydroxymischether preferred. For this purpose, the alkoxylates of the formula ( I ) are compounded with the further compounds in a form suitable for the person skilled in the art and can then be further processed in this form. The present invention additionally makes use of the knowledge that the presence of the selected fatty alcohol alkoxylates of the general formula (I) as component a) in combination with structurally different surface-active compounds of the type b) have advantageous drying and / or drying properties the rinse performance of cleaner formulations for hard surfaces, and particularly dishwashing detergents. At least two surface-active compounds are combined, of which one component a) must necessarily be a fatty alcohol alkoxylate as described above and the other component b) is selected from one or more of the compounds b1) to b8) described below:

Surface-active compounds of type b1)

These compounds are so-called hydroxy mixed ethers, or HME for short. Hydroxy mixed ethers follow the broad general formula R'O [AO] _x CH ₂ CH (OM) R ", in which R is a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms, R "is a linear or branched alkyl and / or alkenyl radical having 2 to 22 carbon atoms x is 10 to 80 and AO is an ethylene oxide, Propylene oxide or butylene oxide radical symbolized and M can stand for a hydrogen atom or an alkyl or alkenyl radical Such Hydroxymischether are known from the literature and are for example in the German application DE 197 38 866 described. They are prepared, for example, by reaction of 1,2-epoxyalkanes (R "CHOCH ₂ ), where R" is an alkyl and / or alkenyl radical having 2 to 22, in particular 6 to 16, carbon atoms, with alkoxylated alcohols. Preferred in the context of the invention are those hydroxy mixed ethers which are derived from alkoxylates of monohydric alcohols of the formula R'-OH having 4 to 18 carbon atoms, where R is an aliphatic, saturated, straight-chain or branched alkyl radical, in particular having 6 to 16 carbon atoms , Examples of suitable straight-chain alcohols are butanol-1, caproic, eananthic, caprylic, pelargonic, capric alcohol, undecanol-1, lauryl alcohol, tridecanol-1, myristyl alcohol, pentadecanol-1, palmityl alcohol, heptadecanol-1, stearyl alcohol, nonadecanol- 1, arachidyl alcohol, heneicosanol-1, behenyl alcohol and their technical mixtures, as obtained in the high pressure hydrogenation of technical methyl esters based on fats and oils. Examples of branched alcohols are so-called oxo alcohols, which usually carry 2 to 4 methyl groups as branches and are prepared by the oxo process and so-called Guerbet alcohols which are branched in the 2-position with an alkyl group. Suitable Guerbet alcohols are 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol and / or 2-octyldodecanol. The alcohols are used in the form of their alkoxylates, which are prepared by reaction of the alcohols with ethylene oxide in a known manner.
In addition, other hydroxy mixed ethers are known, namely those which have more than one free hydroxyl group in the molecule. Such compounds can be prepared, for example, by reacting diols, preferably alkylene glycols and their derivatives, preferably polyethylene glycols, each with two moles of an alkyl epoxide (R-CHOCH ₂ ) per mole of the diol.

Surface-active substances of the type b1) according to the formula (IIa )

These are commercially available surfactants of the HME type which follow the general formula (11a):

R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OM) R ² (IIa)

in which R ^{1 is} a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms, or a radical R ^{2 is} -CH (OH) CH ₂ , where R ^{2 is} a linear or branched alkyl and / or Alkenyl radical having 8 to 16 carbon atoms, x represents a number from 40 to 80, and M represents a hydrogen atom or a saturated alkyl radical having 1 to 18 carbon atoms. Advantageously, compounds of the type b1) of the general formula (IIa) which contain at least one free hydroxyl group (= -OH) are used.

Preferred for the purposes of the invention are those hydroxy mixed ethers which are derived from ethoxylates of monohydric alcohols of the formula R ¹ -OH having 6 to 18 carbon atoms, preferably 6 to 16 and especially 8 to 10 carbon atoms, where R ^{1 is} a linear alkyl radical and x for 40 to 60. Furthermore, compounds of the general formula (IIa) are preferred in the mixtures according to the invention, in which the index x stands for a number from 40 to 70, preferably 40 to 60 and in particular from 40 to 50. M is then a hydrogen atom.
Very particular preference is given to hydroxy mixed ethers of the formula (IIa) where R ^{1 is} an alkyl radical having 8 to 10 carbon atoms, in particular based on a native fatty alcohol, R ^{2 is} an alkyl radical having 10 carbon atoms, in particular a linear alkyl radical and x is 40 to 60 stands.
Preference is furthermore given to mixtures which contain as surface-active compound of type b1) a compound of the general formula (IIa) in which R ^{1 is} an alkyl and / or alkenyl radical having 8 to 10 carbon atoms and R ^{2 is} an alkyl radical or alkenyl radical having 8 to 10 carbon atoms and x is a number from 40 to 50, wherein also here M stands for a hydrogen atom.
However, such compounds of the type b1) of the formula (IIa) are suitable in which R ^{1 is} an alkyl or alkenyl radical having 8 to 10 carbon atoms, R ^{2 is} a radical having 8 to 12 carbon atoms and M is a saturated alkyl radical having 1 to 6, preferably 1 to 4 carbon atoms. The latter compound contains no free hydroxyl groups - rather, the hydroxyl functions have been alkylated with suitable reagents, for example alkyl halides.

Surface-active substances of the type b1) according to the formula (IIb)

Also suitable and preferred are compounds of group b1) which follow the general formula (IIb):

R ³ O [CH ₂ CHCH ₃ O] _z [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ⁴ (IIb)

in which R ^{3 is} a linear or branched alkyl and / or alkenyl radical having 8 to 22 carbon atoms, R ^{4 is} a linear or branched alkyl and / or alkenyl radical having 8 to 16 carbon atoms, y is a number of 10 and 35, z is zero or must be a number from 1 to 5. It may be advantageous if R ³ = R ¹ and at the same time R ⁴ = R ² those compounds of the formula b1) are selected in which the index z is at least 1. If mixtures of the surface-active compounds of type a) with those of type b1) are used, only those mixtures within the meaning of the present technical teaching in which the molecules structurally differ from one another are used. So there must always be different structure connections side by side.
Particularly preferred compounds of the type b1) are, for example, those in which in the formula (IIb) the index y stands for a number from 20 to 30, preferably from 20 to 25. Preference is furthermore given to those compounds of the type b1) in which R ³ in the formula (IIb) represents an alkyl radical having 8 to 12, preferably 8 to 10, carbon atoms, R ^{4 is} an alkyl radical having 10 to 12, preferably 10 carbon atoms, y a number from 15 to 35, preferably 20 to 30 and z is a number from 1 to 3, preferably 1 means.
Preference is also given to mixtures which contain as surface-active compound of the type b1) a compound of the general formula (IIb) in which R ^{3 is} an alkyl and / or alkenyl radical having 11 to 18 carbon atoms and R ^{4 is} an alkyl or Alkenyl radical having 8 to 10 carbon atoms and y is a number from 20 to 35.

Also preferred are mixtures containing as surface-active compound of type b1) a compound of the general formula (IIb) in which R ^{3 is} an alkyl and / or alkenyl radical having 8 to 12 carbon atoms and R ^{4 is} an alkyl or Alkenyl radical having 8 to 10 carbon atoms and y is a number from 20 to 35 and z is a number from 1 to 3. The compounds of type b1) are also hydroxy mixed ether derivatives which can be prepared by reacting propoxylated and / or ethoxylated fatty alcohols with alkyl epoxides by ring opening in an alkaline medium.

It is in the case of derivatives of type b1) as well as in all other mixed alkoxylates listed in this description, that is to say both a propylene oxide radical CH ₂ CHCH ₃ O (PO) and an ethylene oxide radical CH ₂ CH ₂ O (EO) contain, possible that from the direction of the C atom with the free hydroxyl group first the EO residues and then the PO residues are arranged in blocks, wherein the sequence first PO, then EO is possible. Furthermore, the alkoxide groups can also be randomly distributed (randomized) in the molecule. It is also possible to use both block and random alkoxylates side by side.

Surface-active substances of type b2)

These compounds are known per se fatty alcohol ethoxylates of the general formula (III) R ⁵ - (OC ₂ H ₄ ) _z -OH in which R ^{5 is} linear or branched alkyl and / or alkenyl radicals having 8 to 22 carbon atoms and z is a number from 1 to 20, and preferably from 1 to 15, and especially from 1 to 10. Typical examples are the adducts of on average 1 to 20 moles of caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and Brassidyl alcohol and their technical mixtures, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from the Roelen oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols incurred. Preferred are adducts of 10 to 40 mol ethylene oxide with technical fatty alcohols having 12 to 18 carbon atoms, such as coconut, palm, palm kernel or preferably tallow fatty alcohol. Particularly preferred fatty alcohol ethoxylates are based on tallow alcohols ethoxylated with 2 to 10 and preferably 2 to 5 moles of ethylene oxide per mole of alcohol.

Surface-active compounds of type b3)

These compounds are mono- and / or preferably diesters of glycol and especially polyglycols and are also known and commercially available. They can be described by the formula R ⁶ CO- (OC ₂ H ₄ ) _m -OR ⁷ , where R ^{6 is} an alkyl and / or alkenyl radical having 7 to 21 carbon atoms and m is a number from 11 to 100, and R ^{7 represents} a hydrogen atom or a radical CO-R ⁶ . In this case, symmetrical (R ⁶ = R ⁷ ) and unbalanced connections (R6 # R7) are included. Preferably, compounds of the type b3) are based on polyethylene glycols having molecular weights between 1000 and 10,000 and preferably from 1500 to 6000 and especially from 1500 to 3000 are used in the erfindungemäßen agents. Particular preference is given to diester compounds of type b3). As a result of production, in addition to compounds of type b3), polyglycols may also be present as by-products.

Surface-active compounds of type b4)

These compounds are also known as alky (oligo) glycosides. Alkyl and alkenyl oligoglycosides are known nonionic surfactants which follow the formula R ⁸ O- [G] _p in which R ^{8 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p stands for numbers from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry. The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula indicates the degree of oligomerization (DP), ie the distribution of monoglycerides and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer, and above all the values p = 1 to 6, the value p for a given alkyloligoglycoside is an analytically determined arithmetic size, which is usually a fractional number. Preference is given to using alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred. The alkyl or alkenyl radical R ⁸ can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms: Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, as used, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of hydrogenation of aldehydes from the Roelen oxo synthesis can be obtained. Preference is given to alkyl oligoglucosides of the chain length C ₈ -C ₁₀ (DP = 1 to 3) which are obtained as a feedstock in the distillative separation of technical C ₈ -C ₁₈ coconut fatty alcohol and in a proportion of less than 6% by weight C ₁₂ - Alcohol may be contaminated as well as alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ⁸ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, Oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and technical mixtures thereof which can be obtained as described above. Preference is given to alkyl oligoglucosides based on hydrogenated C _12/14 coconut alcohol having a DP of 1 to 3.

Surface-active compounds of type b5)

in der R¹ für Alkyl- und/oder Alkenylreste mit 6 bis 22 Kohlenstoffatomen, R^II für Wasserstoff oder Alkylreste mit 1 bis 4 Kohlenstoffatomen, R^III für Alkylreste mit 1 bis 4 Kohlenstoffatomen, n für Zahlen von 1 bis 6 und X für ein Alkali- und/oder Erdalkalimetall oder Ammonium steht. Typische Beispiele sind die Carboxymethylierungsprodukte von Hexylmethylamin, Hexyldimethylamin, Octyldimethylamin, Decyldimethylamin, Dodecylmethylamin, Dodecyldimethylamin, Dodecylethylmethylamin, C_12/14-Kokosalkyldimethylamin, Myristyldimethylamin, Cetyldimethylamin, Stearyldimethylamin, Stearylethylmethylamin, Oleyldimethylamin, C_16/18-Talgalkyldimethylamin sowie deren technische Gemische.Betaines are known surfactants which are predominantly produced by carboxyalkylation, preferably carboxymethylation of aminic compounds. Preferably, the starting materials are condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, wherein one mole of salt is formed per mole of betaine. Furthermore, the addition of unsaturated carboxylic acids, such as acrylic acid is possible. Examples of suitable betaines are the carboxyalkylation products of secondary and especially tertiary amines which follow formula (1)

in the R ¹ for alkyl and / or alkenyl radicals having 6 to 22 carbon atoms, R ^{II is} hydrogen or alkyl radicals having 1 to 4 carbon atoms, R ^{III is} alkyl radicals having 1 to 4 carbon atoms, n is from 1 to 6, and X is a Alkali and / or alkaline earth metal or ammonium. Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, dodecylethylmethylamine, C _12/14 cocoalkyldimethylamine, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearylethylmethylamine, oleyldimethylamine, C _16/18 tallowalkyldimethylamine, and technical mixtures thereof.

in der R^IV CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen und 0 oder 1 bis 3 Doppelbindungen, m für Zahlen von 1 bis 3 steht und R^II, R^III, n und X die oben angegebenen Bedeutungen haben. Typische Beispiele sind Umsetzungsprodukte von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, namentlich Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Gemische, mit N,N-Dimethylaminoethylamin, N,N-Dimethylaminopropylamin, N,N-Diethylaminoethylamin und N,N-Diethylaminopropylamin, die mit Natriumchloracetat kondensiert werden. Bevorzugt ist der Einsatz eines Kondensationsproduktes von C_8/18-Kokosfettsäure-N,N-dime-thylaminopropylamid mit Natriumchloracetat.Also suitable are carboxyalkylation products of amidoamines which follow the formula (2),

in which R ^IV CO is an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, m is a number from 1 to 3 and R ^II , R ^III , n and X have the meanings given above. Typical examples are reaction products of fatty acids having 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate. The use of a condensation product of C _8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate is preferred.

in der R^V für einen Alkylrest mit 5 bis 21 Kohlenstoffatomen, R⁶ für eine Hydroxylgruppe, einen OCOR^V- oder NHCOR^V-Rest und m für 2 oder 3 steht. Auch bei diesen Substanzen handelt es sich um bekannte Stoffe, die beispielsweise durch cyclisierende Kondensation von 1 oder 2 Mol Fettsäure mit mehrwertigen Aminen, wie beispielsweise Aminoethylethanolamin (AEEA) oder Diethylentriamin erhalten werden können. Die entsprechenden Carboxyalkylierungsprodukte stellen Gemische unterschiedlicher offen-kettiger Betaine dar. Typische Beispiele sind Kondensationsprodukte der oben genannten Fettsäuren mit AEEA, vorzugsweise Imidazoline auf Basis von Laurinsäure oder wiederum C_12/14Kokosfettsäure, die anschließend mit Natriumchloracetat betainisiert werden.Further suitable starting materials for the betaines to be used in the context of the invention are imidazolines which follow the formula (3),

in which R ^{V is} an alkyl radical having 5 to 21 carbon atoms, R ^{6 is} a hydroxyl group, an OCOR ^V or NHCOR ^V radical and m is 2 or 3. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines, such as, for example, aminoethylethanolamine (AEEA) or diethylenetriamine. The corresponding carboxyalkylation products are mixtures of different open-chain betaines. Typical examples are condensation products of the abovementioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C _12/14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.

Surface-active compounds of type b6)

in der R⁹ für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen und o für eine Zahl von 1 bis 20 und der Index p für Null oder Zahlen von 1 bis 20 steht.These nonionic compounds, which are also known, are prepared, for example, by reacting alkyl epoxides with ethylene glycol and then with further ethylene oxide. These are also commercially available substances. They follow the general formula (IV)

in which R ^{9 is} a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms and o is a number from 1 to 20 and the subscript p is zero or numbers from 1 to 20.

Surface-active compounds of type b7)

These compounds, which are also to be referred to as hydroxy mixed ethers, follow the general formula (V):

R ¹⁰ CH (OR ¹¹ ) CH ₂ -OR ¹¹ (V)

in which R ^{10 is} a saturated or unsaturated, branched or unbranched alkyl or alkenyl radical having 8 to 16 carbon atoms, and R ¹¹ each independently of one another symbolizes a radical (CH ₂ CH ₂ O) _r CH ₂ CH (OH) R ¹² , wherein r in each R ^{11 is} independently zero or a number from 1 to 50 and R ^{12 is} a saturated or unsaturated, branched or unbranched alkyl or alkenyl radical of 8 to 16 carbon atoms. These compounds are prepared, for example, by reacting compounds of type (III) with further alkylene oxide having carbon chains in the range of 8 to 18 carbon atoms under the conditions of alkaline catalysis.

Surface-active compounds of type b8)

These are nitrogen-containing compounds of the general formula (VI):

NR ¹³ ₃ (VI)

wherein R ¹³ independently of one another is a radical (CH ₂ CH ₂ O) _s -CH ₂ CH (OH) R ¹⁴ or an alkyl radical having 8 to 16 carbon atoms and s is independently zero for each individual radical R ¹³ , or a number from 1 to 50. Compounds of type b8) are, for example obtainable by ethoxylation of alkylamines or of triethanolamine and subsequent reaction with alkylene oxides with alkyl chains having 8 to 18 carbon atoms under alkaline catalysis conditions.

The compounds b1) to b8) can each be combined alone with at least one compound of the type a). Particularly preferred are binary mixtures of a) and a compound of type b) and in particular the compounds of type b1). However, it is also possible to combine mixtures of different substances of type class b) with those of type a). It may be advantageous for mixtures containing a plurality of different compounds of type b) to use these compounds in a weight ratio of 1: 1.

The compounds of the type a) and b) are preferably present in a weight ratio of 10: 1 to 1:10 side by side in the mixtures according to the invention. However, preference may be given to those mixtures in which the surface-active compounds of the type a) and b) in a weight ratio of 5: 1 to 1: 5, in particular from 3: 1 to 1: 3 and particularly preferably from 2: 1 to 1: 2 and most preferably 1: 1 are present side by side. The compounds of type b1) to b8) can - as stated above - also be present side by side in any mixtures. Preferably, however, the mixtures consist only of a compound of type a) and a compound of type b).

The mixtures described above are preferably suitable for use in cleaners, in particular in dishwashing detergents and in particular in automatic dishwashing detergents. The mixtures can be used to improve the drying performance and / or the rinsing performance of cleaning agents and in particular for dishwashing detergents, preferably dishwasher detergents for automatic dishwashing. The solid preparations according to the invention can in principle be prepared in any manner known to the person skilled in the art.

• durch Sprühkühlung (Prilling) der Schmelze in einem Sprühturm
• durch Pastillierung der Schmelze auf einem Kühlband
• durch das Erstarren der Schmelze in einer Wirbelschicht
• durch das Vertropfen der Schmelze, z.B. Droppo Line der Fa. Rieter; Microspheres der
• Fa. Brace; Jet Priller der Fa. Gouda)
• durch das Erstarren der Schmelze auf Kühlwalzen

Such waxy and preferably anhydrous or low-water raw materials for applications in detergents as described above, which, like the alkoxylates according to the invention are obtained as a melt in the synthesis, can be converted into powders or granules, for example, by the following methods known to those skilled in the art:

• by spray cooling (prilling) the melt in a spray tower
• by pasting the melt on a cooling belt
• by the solidification of the melt in a fluidized bed
• by the dripping of the melt, eg Droppo Line from Rieter; Microspheres the
• Fa. Brace; Jet Priller of the company Gouda)
• by the solidification of the melt on cooling rollers

In order to set a desired particle size distribution, this process may optionally follow a milling step.

Another object of the present application relates to cleaning compositions for hard surfaces, containing surfactants, water softeners and optionally other ingredients, characterized in that the cleaning agent alkoxylated fatty alcohols of the general formula (I) RO- (C _n H _2n O) _m -H, wherein R is a linear branched, saturated or unsaturated alkyl or alkenyl radical having at least 19 C atoms and m is a number greater than or equal to 20 and n is 2 or 3, contain. These are finished cleaning agents, preferably dishwasher detergents for automatic dishwashing. These contain the alkoxylates of the general formula (I) according to the invention, preferably in amounts of from 0.1 to 25% by weight, based on the total weight of the cleaning agent. The cleaning agents according to the invention additionally contain other, other surfactants, which are preferably selected from the classes of polyethylene glycols, the alkyl (oligo) glycosides, the fatty alcohol alkoxylates with the exception of the compounds of formula (I), the Polyolhydroxyalkylether and the Hydroxymischether. Details can be found in the above description of the compound types b1) to b8), which are all suitable, alone or in combination with one another, to find use as surfactants in the cleaners according to the invention. The cleaning agents preferably contain the mixtures of surfactants of groups a) and b) as described above. In this case, those agents are preferred which contain these surfactant mixtures in amounts of 0.1 to 50 wt .-%, preferably 0.5 to 30 wt .-% and in particular in amounts of 2 to 25 wt .-%.

The detergents themselves may furthermore preferably comprise as water softeners phosphates and / or polyacrylates, preferably in amounts of from 1 to 80% by weight, based on the total weight of the cleaning agents. The cleaners according to the invention may additionally contain enzymes, enzyme activators, bleaches, bleach boosters, complexing agents, disintegrants, dyes, biocides, solubilizers, fragrances or perfumes, inorganic Salts, carriers, soil repellents, corrosion inhibitors, and / or defoamers. Suitable inorganic or organic carriers are, for example, zeolites, alkali metal phosphates, alkali metal carbonates, alkali metal sulphates, alkali metal bicarbonates, alkali metal silicates, alkali metal citrates, polysaccharides and their derivatives or polymers and mixtures thereof.

Preference is given to detergents according to the invention which are present in solid form, ie as granules, flakes, powders, pellets or lozenges or as shaped articles, such as tablets, and in particular as granules or as shaped articles. The preparation of the solid detergents can be carried out by methods such as grinding, scaling, pelleting, extrusion, prilling, dropping and / or drying and granulation in the thin-layer (flash-dryer). Optionally, several of these methods can be combined. A preferred embodiment uses the ethoxylates of the general formula (I) as granules, which is then formulated together with the other ingredients to the finished detergent. Particularly preferred preparation processes for ready-formulated detergents are granulation in the fluidized bed and extrusion.

The detergents according to the invention are preferably present as multifunctional agents, i. that they include in a fixed supply form means for cleaning, means for rinsing and, where appropriate, additional means for water softening and / or metal cleaning or metal protection (so-called "2 in 1" or "3 in 1" or even "5 in 1" products ).

A final object of the invention relates to a liquid rinse aid comprising at least water, a solubilizer and optionally an acid, preferably an organic acid, characterized in that in the rinse aid compounds of the general formula (I) in amounts of 0.1 to 25 wt. -% is included. As a solubilizer, all substances known to those skilled in the art can be used, for example short-chain alcohols, such as ethanol or propanol, or fatty acid esters and similar compounds. Ethanol is particularly preferred here.
Preferred organic acids are preferably hydroxycarboxylic acids and in particular citric acid or its derivatives, for example esters or alkoxylates of citric acid. Preference is given to those liquid agents which contain compounds of the formula (I) in amounts of from 0.2 to 20% by weight, preferably from 1.0 to 15% by weight and in particular from 1.5 to 10% by weight. The liquid agents can be adjusted in their viscosity and different on the one hand be low viscosity (such as water), but also present thickened, for example in the form of oils or gels or in paste form.

Examples 1. Dishwashing performance

The rinse aid is evaluated digitally using a method developed by Cognis for the quantitative measurement of deposits on solid surfaces. The method is described in European Patent Application 1 635 167 A1 , Plane materials made of glass, stainless steel, ceramics and various plastics are rinsed under defined conditions (water at 2 °, 16 ° and 21 ° dH (depending on the application) and 50 g of a standard stain *) in a household dishwasher. Thereafter, the items to be washed are measured in the measuring apparatus after staining and coating formation. The results are given as "significantly better / better than / worse than standard".
The experimental results are shown in Table 1 below, experiments I to III showing comparative experiments (= standard formulation with C16 / 18 fatty alcohol + 40 EO) and formulations IV and V representing the examples according to the invention.

The following formulation was used as a basis for an automatic dishwashing agent (= ADD) of the "3-in-1" type (data in% by weight of active substance): 7% by weight Sodium disilicate (SKS 6 Fa. Clariant), 27.5% by weight Sodium, 4% by weight Polycarboxylate, sodium salt (Acusol ^® 587) 2.5% by weight TAED 8% by weight sodium, 2% by weight ethoxylated fatty alcohol ad 100% by weight sodium tripolyphosphate * Standard soiling: Based on 1000 g: 25 g each of ketchup, mustard and gravy, 300 g margarine, 150 g drinking milk, 15 g potato starch, 9 g egg yolk, 3 g benzoic acid, balance: water. Table 1: composition I II III IV V C16 / 18 fatty alcohol + 25 EO 2 C 16/18 fatty alcohol + 40 EO 2 C22 fatty alcohol + 10 EO 2 C22 fatty alcohol + 25 EO 2 C22 fatty alcohol + 25 EO granules 2 Rinse aid on ++: significantly better cutlery 0 - + ++ ++ +: better porcelain 0 - 0 + + 0: comparable read 0 - + ++ ++ -: worse than standard plastic 0 0 - + +

It can be seen from Table 1 that the "3 in 1" ADD formulations IV and V according to the invention are far better than the comparison formulation in terms of their performance properties. This is particularly evident in the rinse aid on glass and stainless steel.

As a further experiment, different ethoxylated fatty alcohols in amounts of 2% by weight were added to a commercially available "3-in-1" ADD formulation and the rinse results were determined as described above. Experiment I represents the comparison product, the experiments II and III are according to the invention. Table 2: composition I II III C16 / 18 fatty alcohol + 25 EO C16 / 18 fatty alcohol + 40 EO 2 C22 fatty alcohol + 10 EO C22 fatty alcohol + 25 EO 2 C22 fatty alcohol + 25 EO granules 2 Rinse aid on ++: much better cutlery 0 + + +: better porcelain 0 0 + 0: comparable Glass 0 + + -: worse than standard plastic 0 0 0

Table 2 shows that the "3 in 1" ADD formulations according to the invention are better than the comparison formulation. This is particularly evident in the rinse aid on glass and stainless steel.

Another attempt involved a commercial "5-in-1" formulation for an ADD. Again, 2% by weight of ethoxylated fatty alcohol was added and the rinse power determined as described above. The results are shown in Table 3: Table 3: Composition in% AS I II III C16 / 18 fatty alcohol + 25 EO C16 / 18 fatty alcohol + 40 EO 2 C22 fatty alcohol + 10 EO C22 fatty alcohol + 25 EO 2 C22 fatty alcohol + 25 EO granules 2 Rinse aid on ++: much better cutlery 0 + ++ +: better porcelain 0 0 0 0: comparable Glass 0 + + worse than standard plastic 0 0 0

Table 3 shows that the "5 in 1" ADD formulations II and III according to the invention are far better than the comparison formulation. This is particularly evident in the rinse aid on glass and stainless steel.

In a further experiment, a further commercial "4 in 1" formulation was investigated as described above (addition of 2% by weight of fatty alcohol ethoxylate). The results of the rinse aid tests are listed in Table 4. Table 4: Composition in% AS I II III C16 / 18 fatty alcohol + 25 EO C _16/18 fatty alcohol + 40 EO 2 C22 fatty alcohol + 10 EO C22 fatty alcohol + 25 EO 2 C22 fatty alcohol + 25 EO granules 2 Rinse aid on ++: much better cutlery 0 ++ ++ +: better porcelain 0 ++ ++ 0: comparable Glass 0 ++ ++ -: worse than standard plastic 0 + +

Table 4 shows that the "4 in 1" ADD formulations II and III according to the invention are better than the comparative formulation I. This can be seen in the rinse aid on all surfaces. Compared to the incorporated melt, the granular form of C22 fatty alcohol + 25 EO tends to give better rinsing performance on stainless steel, glass and ceramics.

2. Foaming behavior

The assessment of the foam behavior is carried out by means of the free-fall circulation method. 500mL of distilled water is placed in a double-walled 2 liter graduated cylinder of the free-fall circuit apparatus. The liquid is heated to 20 ° C ± 1 ° C. To the circulating pumped water 0.2mL of the substance to be tested or formulation with 0.2mL of active substance are pipetted. The stopwatch is started at the same time. The resulting total volume (foam and liquid) is recorded at the corresponding temperature after 30 ", 1 ', 2', 3 ', 5', 10 ', 20', and 30 'and the target temperature of the Julabo F12-MB Thermostat after 1 minute at 32 ° C, after 10 minutes at 45 ° C and after 20 minutes at 55 ° C set.
The results are given as "significantly better / better / same / worse than standard". Table 5 shows the test results, where I represents a comparative experiment (= standard, formulation with C16 / 18 fatty alcohol + 20 EO) and II and III represent the examples according to the invention. Table 5: Foam behavior by means of free-fall circulation method Composition in% AS I II III C16 / 18 fatty alcohol + 20 EO 0.2 C22 fatty alcohol + 25 EO 0.2 C22 fatty alcohol + 25 EO granules 0.2 Foaming behavior after ++: much weaker 0.5 min 0 + ++ +: weaker 2 min 0 + ++ 0: comparable 5 min 0 + ++ -: stronger than standard 10 min 0 ++ ++ 20 min 0 ++ ++

It can be clearly seen from Table 5 that the C ₂₂ fatty alcohol ethoxylates according to the invention foam much more weakly than the comparison product, which represents an important property for use in the ADD range. This is particularly evident after a time of more than 10 minutes and higher temperatures of 45 - 55 ° C, which corresponds to the conditions in the dishwasher. Compared to the pre-dissolved melt, the granular form of C ₂₂ fatty alcohol + 25 EO shows even weaker foaming behavior.

Claims (25)

Use of alkoxylated fatty alcohols of the general formula (I) RO- (C _n H _2n O) _m -H, where R is a linear branched, saturated or unsaturated alkyl or alkenyl radical having at least 19 C atoms and m is a number from is greater than or equal to 20 and n is 2 or 3, in hard surface cleaners, especially in automatic dishwashing detergents. Use according to claim 1, characterized in that R in the general formula (I) is a linear branched, saturated or unsaturated alkyl or alkenyl radical having 19 to 30, preferably 20 to 25 and in particular 21 to 23 C-atoms. Use according to claims 1 to 2, characterized in that m in the general formula (I) stands for a number from 20 to 30, preferably 21 to 28 and in particular from 22 to 26. Use according to claims 1 to 3, characterized in that n in the general formula (I) is 2. Use according to claims 1 to 4, characterized in that compounds of the general formula (I) are used, in which R stands for a linear, saturated alkyl radical having 22 C atoms, n is the number 2 and m is for values 22 to 26 can take. Use according to claims 1 to 5, characterized in that the compounds of general formula (I) in amounts of 0.1 to 25 wt.%, Preferably in amounts of, 0.5 to 10 wt .-% and in particular in amounts from 1.0 to 5 wt .-% - based on the cleaning agent - are used. Use of compounds of the general formula (I) according to Claim 1 as additives for improving the rinsing performance in hard surface cleaners, in particular in automatic dishwashing cleaners. Use of compounds of the general formula (I) according to Claim 1 in liquid or solid rinse aids. Use according to claims 1 to 8, characterized in that the alkoxylated fatty alcohols of the formula (I) formulated together with other nonionic surfactants to form a compound and introduced as a compound in the detergent. Use according to claim 9, characterized in that other nonionic surfactants selected are polyethylene glycols, alkyl (oligo) glycosides, fatty alcohol alkoxylates with the exception of the compounds of the formula (I), polyol hydroxyalkyl ethers and / or hydroxy mixed ethers. Mixtures comprising at least two different surface-active substances from groups a) and b), wherein the surface-active compound a) is selected from compounds of general formula (I) according to claim 1, and the surface-active substance b) is selected from the group of b1) Compounds of the following formulas (IIa) and / or (IIb)

R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OM) R ² (IIa)

in which R ^{1 is} a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms, or a radical R ^{2 is} -CH (OH) CH ₂ , where R ^{2 is} a linear or branched alkyl and / or Alkenyl radical having 8 to 16 carbon atoms, x is a number from 40 to 80, and M is a hydrogen atom or a saturated alkyl radical having 1 to 18 carbon atoms, and / or

R ³ O [CH ₂ CH ₂ O] _y [CH ₂ CHCH ₃ O] _z CH ₂ -CH (OH) R ⁴ (IIb)

in which R ^{3 is} a linear or branched alkyl and / or alkenyl radical having 8 to 22 carbon atoms, R ^{4 is} a linear or branched alkyl and / or alkenyl radical having 8 to 16 carbon atoms, y is a number of 10 and 35, Z means zero or a number from 1 to 5, with the proviso that if R ³ = R ¹ and at the same time R ⁴ = R ² , then that z must be at least 1 and / or b2) ethoxylated fatty alcohols of the general formula (III) R ⁵ - (OC ₂ H ₄ ) _z -OH in which R ^{5 is} linear or branched alkyl and / or alkenyl radicals having 8 to 22 carbon atoms and z is a number from 1 to 20 stands, and / or b3) R ⁶ CO- (OC ₂ H ₄ ) _m -OR ⁷ , where R ^{6 is} an alkyl and / or alkenyl radical having 7 to 21 carbon atoms and m is a number from 11 to 100, and R ^{7 is} a hydrogen atom or a Rest CO-R ⁶ means, and / or b4) alkyl (oligo) glycosides of the general formula R ⁸ O- [G] _p in the R ⁸ for an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G for a sugar radical having 5 or 6 carbon atoms and p for numbers of 1 to 10, and / or b5) Betaine and / or b6) compounds of the general formula (IV)

in which R ^{9 is} a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms and o is a number from 1 to 20 and the subscript p is zero or numbers from 1 to 20, and / or b7) compounds of the general formula (V)

R ¹⁰ CH (OR ¹¹ ) CH ₂ -OR ¹¹ (V)

in which R ^{10 is} a saturated or unsaturated, branched or unbranched alkyl or alkenyl radical having 8 to 16 carbon atoms, and R ¹¹ each independently of one another symbolizes a radical (CH ₂ CH ₂ O) _r CH ₂ CH (OH) R ¹² , wherein r in each radical R ^{11 is} independently zero or a number from 1 to 50 and R ^{12 is} a saturated or unsaturated, branched or unbranched alkyl or alkenyl radical having 8 to 16 carbon atoms, and / or b8) compounds of the general formula (VI)

NR ¹³ ₃ (VI)

wherein R ¹³ independently of one another is a radical (CH ₂ CH ₂ O) _s -CH ₂ CH (OH) R ¹⁴ or an alkyl radical having 8 to 16 carbon atoms and s is independently zero for each individual radical R ¹³ , or a number from 1 to 50. Mixture according to Claim 11, characterized in that the weight ratio between the surface-active substances a) and b) is in the range from 10: 1 to 1:10. Detergents for hard surfaces, containing surfactants, water softeners and optionally other ingredients, characterized in that the detergents alkoxylated fatty alcohols of general formula (I) RO- (C _n H _2n O) _m -H, wherein R is a linear branched, saturated or unsaturated alkyl or alkenyl radical having at least 19 C atoms and m is a number greater than or equal to 20 and n is 2 or 3 is. Cleaning agent according to claim 13, characterized in that the alkoxylated fatty alcohols in amounts of 0.1 to 25 wt .-%, based on the detergent are included. Detergent according to claims 13 to 14, characterized in that as surfactants nonionic surfactants, preferably selected from the group of polyethylene glycols, the alkyl (oligo) glycosides, the fatty alcohol alkoxylates with the exception of the compounds of formula (I), the Polyolhydroxyalkylether and the Hydroxymischether included are. Cleaning agent according to claims 13 to 15, characterized in that it contains surfactant mixtures according to claims 11 to 12. Detergent according to claim 16, characterized in that it contains the surfactant mixtures in amounts of 0.1 to 50 wt .-%, preferably 0.5 to 30 wt .-% and in particular in amounts of 2 to 25 wt .-%. Cleaning agent according to claims 13 to 17, characterized in that the surfactants according to formula I in amounts of 0, 1 to 25 wt .-% are included. Detergent according to claims 13 to 18, characterized in that the agents preferably contain as water softeners phosphates and / or polyacrylates. Detergent according to claims 13 to 19, characterized in that the agents contain the water softener in amounts of 1 to 80 wt .-%. Cleaning agent according to claims 13 to 20, characterized in that it is solid, preferably as granules or as a shaped body. Detergent according to claims 13 to 21, characterized in that the additional enzymes, enzyme activators, bleaching agents, bleach boosters, complexing agents, disintegrants, dyes, biocides, solubilizers, fragrances or perfumes, inorganic salts, carriers, soil repellents, corrosion inhibitors, and / or defoamers contains. Detergent according to claims 13 to 22, characterized in that it is designed as a detergent for automatic dishwashing. Detergent according to claims 13 to 23, characterized in that it comprises in a solid offer form means for cleaning, means for rinsing and optionally additionally means for softening the water and / or metal cleaning or metal protection. Liquid rinse aid containing at least water, a solubilizer and optionally an acid, preferably an organic acid, characterized in that in the rinse aid compounds of general formula (I) according to claim 1 in amounts of 0.1 to 25 wt .-% are included ,