EP1129172B1 - Clear-rinsing agents for machine dishwashing - Google Patents

Description

The present invention is a rinse aid for automatic dishwashing containing alkoxylated carboxylic acid esters, in particular those obtained by reaction of Carboxylic acid esters and alkylene oxides in the presence of calcined hydrotalcites have been prepared and the use of the alkoxylated carboxylic esters as surfactants for the preparation such rinse aid.

Machine-washed dishes are often subject to higher requirements today than on manually washed dishes. So is also a completely cleaned of leftovers dishes then rated as not flawless, if it still remains after machine dishwashing has whitish spots based on water hardness or other mineral salts, the lack of wetting agents come from dried-up water drops.

In order to obtain glossy and spotless dishes, you are now successfully using rinse aid one. The addition of rinse aid at the end of the wash program ensures that the water As completely as possible runs off the dishes, so that the different surfaces on End of the washing program are residue-free and flawlessly shiny.

Commercially available rinse aids are mixtures of nonionic surfactants, solubilizers (e.g., cumene sulfonate), organic acids (e.g., citric acid) and solvents (e.g. Ethanol), water and possibly preservatives and fragrances. The task of the surfactants in these means is to influence the interfacial tension of the water so that it runs off in a very thin, coherent film from the dishes can, so that during the subsequent drying process no drops of water, stripes or Films remain behind (so-called net effect). Furthermore, the surfactants also have the Task to dampen the foam caused by food particles in the dishwasher. Since the rinse aid contains mostly acids for an improvement of the clear dry effect, In addition, the surfactants used must be relatively hydrolysis-insensitive to acids be.

For use in rinse aid formulations, today only recipe ingredients are added in question, the biologically completely degradable, toxicologically harmless and are as skin-friendly as possible. Accordingly, the surfactants used in the rinse aids must also have these properties.

EP-B1 0 197 434 (Henkel) discloses rinse aids which contain mixed ethers as nonionic surfactants. In the dishwasher, a variety of different materials (glass, metal, silver, plastic, porcelain) is cleaned. This variety of materials must be wetted as well as possible in the rinse cycle. Rinse aid formulations which contain exclusively mixed ethers as the surfactant component, do not meet these requirements or only to a small extent, so that the rinsing or drying effect is unsatisfactory, especially in the case of plastic surfaces.

German Offenlegungsschrift DE- A1-19611999 and international application WO 94/13618 disclose alkoxylated carboxylic esters which are prepared by homogeneous catalysis in the presence of hydroxides and reducing agents or a cocatalyst . According to the two documents, such compounds can be used in detergents, dishwashing detergents and cleaners.

German Offenlegungsschrift DE-A-43 26 112, in turn, describes low-foaming all-purpose cleaners which comprise alkoxylated carboxylic acid esters mixed with alkyl glycosides and optionally other surfactants such as alkyl sulfates, alkyl ether sulfates and fatty alcohol polyglycol ethers. Such general-purpose cleaners are designed for cleaning hard surfaces such as clinker, ceramic tile, enamel, PVC or wooden floors. However, all-purpose cleaners, in contrast to rinse aids, always contain anionic surfactants. In addition, all-purpose cleaners, in contrast to rinse aids have a voluminous initial foam. Finally, other surfactant concentrations are used in all-purpose cleaners. Thus, different requirements are placed on all-purpose cleaners than on rinse aid.

The object of the present invention has been new ecological and toxicological to provide flawless rinse aid, with respect to the application Properties provide at least the same results as marketable rinse aid and the above do not have mentioned disadvantages.

in der R¹CO für einen aliphatischen Acylrest mit 8 bis 18 Kohlenstoffatomen, OAlk für einen O-CH₂-CH₂-Rest, n für Zahlen von 5 bis 15 und R² für einen Methylrest steht.An object of the present invention therefore relates to rinse aid for automatic dishwashing comprising mono- and / or polybasic carboxylic acids, solubilizers and alkoxylated carboxylic acid esters of the formula (I),

where R ^{1 is} CO for an aliphatic acyl radical having 8 to 18 carbon atoms, OAlk for an O-CH ₂ -CH ₂ radical, n is a number from 5 to 15 and R ^{2 is} a methyl radical.

Surprisingly, it has been found that rinse aid containing alkoxylated Carbonsäureestem and especially in admixture with mixed ethers, hydroxy mixed ethers and / or fatty alcohol polypropylene / polyethylene glycol ethers not only have a high ecotoxicological value Compatibility, but the requirements for a branded product in the Fully comply with the performance characteristics. In particular, show Such rinse agents have an excellent wetting agent effect and excellent foam damping.

Alkoxylated carboxylic acid esters

Alkoxylated carboxylic acid esters which are compulsorily contained in the rinse aids according to the invention are known from the prior art. Thus, for example, such alkoxylated carboxylic acid esters are accessible by esterification of alkoxylated carboxylic acids with methanol. However, for the purposes of the present invention, the compounds are prepared by reacting carboxylic acid esters with alkylene oxides using catalysts, in particular using calcined hydrotalcite according to German Offenlegungsschrift DE-A-39 14 131, which provide compounds having a restricted homolog distribution.

Preferred acyl radicals are derived from carboxylic acids having 8 to 18 carbon atoms more naturally or of synthetic origin, in particular of straight-chain saturated and / or unsaturated fatty acids, including technical mixtures thereof, as defined by Fat cleavage from animal and / or vegetable fats and oils are available, for example from coconut oil, palm kernel oil, palm oil, soybean oil, sunflower oil, rapeseed oil, cottonseed oil, Fish oil, beef tallow and lard. Examples of such carboxylic acids are Capric acid, lauric acid, isotridecanoic acid, myristic acid, Palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, Petroselinic, linoleic, linolenic, elaeostearic.

R ² is a methyl radical.

Especially suitable are alkoxylated carboxylic acid esters of the formula (I) with on average 5, 7, 9 or 11 moles of ethylene oxide.

If particularly low-viscosity rinse aid is desired, the use is recommended of alkoxylated carboxylic esters derived from short chain carboxylic acids, in particular those with 8 to 10 carbon atoms, derived. High cleaning performances are included alkoxylated carboxylic acid esters obtained from longer-chain carboxylic acids, in particular those with 12 to 18 carbon atoms, derived.

The alkoxylated carboxylic esters can be used as the sole nonionic surfactant in the rinse aids be contained, preferably in amounts of from 0.5 to 40 wt.%, In particular in amounts from 5 to 35% by weight. However, the alkoxylated carboxylic acid esters are preferably in a mixture with further nonionic surfactants in the rinse aids. Typical examples for other nonionic surfactants which may be considered are mixed ethers, hydroxy mixed ethers, Fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid amide polyglycol ethers, Fatty amine polyglycol ethers, alkoxylated triglycerides, alk (en) yloligoglycosides, Fatty acid N-alkyl glucamides, protein hydrolysates (especially vegetable products Wheat base), polyol fatty acid esters, sugar esters, sorbitan esters and polysorbates. Unless the contain nonionic surfactants polyglycol ether chains, these can be a conventional, but preferably have a narrow homolog distribution. Preferred are as other nonionic surfactants fatty alcohol polyglycol ethers, alkyl oligoglucosides, fatty acid N-alkyl-glucamides, Hydroxy mixed ethers and / or mixed ethers.

In a preferred embodiment of the invention, the nonionic surfactants used are alkyl and alkenyl oligoglycosides which follow the formula (II) , R ³ O- [G] _p (II) in which R ^{3 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 is a number 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 (II) 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 here especially If p = 1 to 6 can be assumed, the value p for a given alkyloligoglycoside is an analytically determined arithmetic quantity, which usually represents 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 ³ 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 technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis. 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 ³ 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.

in der R⁵CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R⁴ für einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 12 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Fettsäure-N-alkylpolyhydroxyalkylamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können. Hinsichtlich der Verfahren zu ihrer Herstellung sei auf die US-Patentschriften US 1,985,424, US 2,016,962 und US 2,703,798 sowie die internationale Patentanmeldung WO 92/06984 verwiesen. Eine Übersicht zu diesem Thema von H.Kelkenberg findet sich in Tens.Surf.Deterg. 25, 8 (1988). Another group of preferred further nonionic surfactants are fatty acid N-alkylpolyhydroxyalkylamides which follow the formula (III)

where R ^{5 is} CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{4 is} an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups. The fatty acid N-alkyl polyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. With regard to the processes for their preparation, 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.Deterg. 25 , 8 (1988).

Preferably, the fatty acid N-alkylpolyhydroxyalkylamides are derived from reducing sugars having 5 or 6 carbon atoms, especially glucose. The preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (IV) :

The fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula (IV) in which R ^{4 is} an alkyl group and R ⁵ CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, Oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachidic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures. Particular preference is given to fatty acid N-alkylglucamides of the formula (IV) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C _12/14 coconut fatty acid or a corresponding derivative. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

R⁶ für einen Alkyl- und/oder Alkylenrest mit 8 bis 22 C-Atomen,

MO für einen Propylenoxid- und/oder einen Butylenoxidrest,

p für eine Zahl von 1 bis 15 und

m für 0 oder eine Zahl von 1 bis 10 steht.

Fatty alcohol polyglycol ethers are particularly preferred as further nonionic surfactants. The fatty alcohol polyglycol ethers are addition products of alkylene oxides having 2 to 4 carbon atoms (ethylene oxide, propylene oxide and / or butylene oxide) with fatty alcohols having 6 to 22 carbon atoms. In one embodiment, the fatty alcohol polyglycol ethers are addition adducts of initially ethylene oxide and optionally subsequently propylene oxide and / or butylene oxide with fatty alcohols of the type described. Within this embodiment, suitable fatty alcohol polyethylene glycol / polypropylene glycol or polybutylene glycol ethers are in particular those of the formula (V) R ⁶ O (CH ₂ CH ₂ O) _p [MO] _m H (V) in the

R ^{6 is} an alkyl and / or alkylene radical having 8 to 22 C atoms,

MO is a propylene oxide and / or butylene oxide radical,

p for a number from 1 to 15 and

m is 0 or a number from 1 to 10.

Fatty alcohol polyethylene glycol / polypropylene or polybutylene glycol ethers of the formula (V) can be prepared, for example, in accordance with European Patent Application EP- A2-161,537 or German Offenlegungsschriften DE-A1 39 28 602 and DE-A1-39 28 600 .

Particularly suitable representatives are those of the formula (V) in which R ^{6 is} an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 C atoms, o is a number from 1 to 5 and m is 0. These are adducts of 1 to 5 moles of ethylene oxide with monofunctional alcohols. As monofunctional alcohols are the so-called fatty alcohols such as caproic, caprylic, lauryl, myristyl and stearyl alcohol and their technical mixtures, as obtained in the high pressure hydrogenation of technical methyl esters based on fats and oils suitable. Examples of monofunctional, 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.

Further suitable compounds of the formula (V) are those in which R ^{6 is} an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 C atoms, o is a number from 2 to 7 and m is a number from 3 to 7 stands. These are addition products of initially with 2 to 7 moles of ethylene oxide and then with 3 to 7 moles of propylene oxide and / or butylene oxide alkoxylated monofunctional alcohols of the type already described.

R⁷ für einen Alkyl- und/oder Alkylenrest mit 8 bis 22 C-Atomen,

r für eine Zahl von 1 bis 10 und

q für eine Zahl von 0 bis 15 steht.

According to a further preferred embodiment, fatty alcohol polyglycol ethers are contained, which are adducts of initially propylene oxide and subsequently optionally ethylene oxide. Accordingly, they are fatty alcohol polypropylene glycol / polyethylene glycol ethers, which preferably follow the formula (VI) , R ⁷ O [CH ₂ (CH ₃ ) CHO] r (CH ₂ CH ₂ O) _q H (VI) in the

R ^{7 is} an alkyl and / or alkylene radical having 8 to 22 C atoms,

r for a number from 1 to 10 and

q is a number from 0 to 15.

Such compounds are described, for example, in German Offenlegungsschrift DE-A1-43 23 252 . Particularly preferred representatives of the compounds of the formula (VI) are those in which R ^{7 is} an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 C atoms, r is a number from 1 to 5 and q is a number from 1 to 6 stands. These are preferably adducts of 1 to 5 moles of propylene oxide and from 1 to 6 moles of ethylene oxide with monofunctional alcohols, of the kind already described.

Further particularly preferred further nonionic surfactants are the so-called mixed ethers. The mixed ethers are adducts of ethylene oxide and / or propylene oxide with fatty alcohols, which are end-capped by subsequent reaction with an alkyl chloride in the presence of bases. Particularly suitable mixed ethers are those which have been prepared by end-capping with an alkyl halide having 1 to 8 carbon atoms, in particular having 1 to 4 carbon atoms of the fatty alcohol polyglycol ethers of formula (V) and / or (VI) . Typical examples are mixed ethers based on a technical C _12/18 or C _12/14 cocoalcohol residue, to which 5 to 10 moles of ethylene oxide have been attached and which have been end-capped with a methyl group or with a butyl group, for example Dehypon ^(R) LS-54, LS-104, LT-54, LS-104, LS -531, Henkel KGaA, Dusseldorf / FRG).

R⁸ für einen Alkyl- und/oder Alkylenrest mit 4 bis 18 C-Atomen,

R⁹ für Wasserstoff oder einen Methyl- oder Ethylrest,

R¹⁰ für einen Alkylrest mit 2 bis 22 C-Atomen,

x für 0 oder eine Zahl von 1 bis 10,

y für eine Zahl von 1 bis 30 und

z für die Zahl 1 steht

Further particularly preferred nonionic surfactants are so-called hydroxy mixed ethers which have been prepared by reacting 1,2-epoxyalkanes with monohydric, dihydric and / or polyhydric alcohols which have been alkoxylated. Preferred hydroxy mixed ethers follow the formula (VII), R ⁸ O [CH ₂ CH (CH ₃ ) O] _x (CH ₂ CHR ⁹ O) _y [CH ₂ CH (OH) R ¹⁰ ] _z (VII) in the

R ^{8 is} an alkyl and / or alkylene radical having 4 to 18 C atoms,

R ^{9 is} hydrogen or a methyl or ethyl radical,

R ^{10 is} an alkyl radical having 2 to 22 C atoms,

x for 0 or a number from 1 to 10,

y for a number from 1 to 30 and

z stands for the number 1

Hydroxy mixed ethers of the formula (VII) are known from the literature and are described, for example, in international application WO 96/12001 . They are prepared by reacting 1,2-epoxyalkanes (R ¹⁰ CHOCH ₂ ) with monohydric alcohols which have been alkoxylated. Preferred for the purposes of the invention are those hydroxy mixed ethers which are derived from alkoxylates of monohydric alcohols (z = 1) of the formula R ⁸ -OH. Suitable examples of alcohols have already been described in connection with the fatty alcohol polyglycol ethers.

The alcohols are used in the form of their alkoxylates, which are prepared by reaction of the alcohols with ethylene oxide, propylene oxide and / or butylene oxide in a known manner. Alkoxylates of alcohols are preferably used with 10 to 25 moles of ethylene oxide (R ⁹ = hydrogen, x = 0, y = 10 to 25) or with 1 to 3 moles of propylene oxide and then with 10 to 25 moles of ethylene oxide (R ⁹ = hydrogen , x = 1 to 3, y = 10 to 25) have been alkoxylated.

Very particularly suitable hydroxy mixed ethers of the formula (VII) are those in which R ^{8 is} a saturated straight-chain alkyl radical having 8 to 14 C atoms, R ^{9 is} hydrogen, R ^{10 is} a saturated straight-chain alkyl radical having 8 to 12 C atoms, x stands for 0 or for numbers from 1 to 3 and y for numbers from 10 to 25 and z for the number 1. Such hydroxy mixed ethers are described in DE-A1 37 23 323 exactly.

The rinse aids according to the invention may comprise the alkoxylated carboxylic acid esters and the others nonionic surfactants, in particular the mixed ethers, hydroxy mixed ethers and fatty alcohol polyglycol ethers in a weight ratio of 10:90 to 80:20, especially of 30: 70 to 40: 60 included. The weight ratio of the other nonionic surfactants among each other is less critical.

The rinse aid formulations according to the invention contain, in addition to those already described Surfactants as the most important additives mono- and / or polyvalent carboxylic acids, preferably Hydroxy carboxylic acids. Typical examples are malic acid (monohydroxy succinic acid), Tartaric acid (dihydroxysuccinic acid), saturated aliphatic dicarboxylic acids such as oxalic acid, Malonic acid, succinic acid, glutaric acid, adipic acid, gluconic acid (hexane-pentahydroxy-1-carboxylic acid), preferably, however, anhydrous citric acid. You can in quantities of about 1 to 50, preferably from about 5 to 30 wt .-% used in the rinse aid become. Other additives include, in particular, dyes, fragrances and preservatives in question, preferably in amounts of from 0 up to 1% by weight. In addition, solubilizers are included in the rinse aids. When Solubilizer recommends cumene sulfonate in amounts of 0 to 25, in particular of 0.2 to 15% by weight - calculated as the active substance content. If desired, hydrotropes may additionally be present in the rinse aid. Hydrotropes are ethanol and / or isopropanol in amounts of from 0 to 25% by weight. The ad 100% by weight missing balance is water.

Industrial Applicability

The rinse aids according to the invention contain ecotoxicologically particularly compatible ingredients, show an excellent wetting capability over a wide variety of materials as well as excellent foam damping behavior.

Another object of the invention relates to the use of alkoxylated carboxylic acid esters as a surfactant for the preparation of rinse aids for automatic dishwashing.

The alkoxylated carboxylic acid esters used show an excellent solubility in water, without going through a gel phase. The rinse aid can both in the household area as well as in the institutional field.

Examples

Rinse aid was prepared according to the compositions given in Table 1 (% by weight). based on the active substance) and evaluated for rinse effect. Of the Rinse effect was determined visually by the number of limescale spots on glasses, Cutlery and plates were observed after the glasses, cutlery and plates in one commercial household dishwasher were cleaned at 65 ° C. The Household dishwasher was with the rinse aid according to the invention or with a Comparison formulation (= standard) filled.

When at least 4 out of 5 people visually assessed a lower number of limescale spots, the rinse effect was rated "better than standard". The results are also summarized in Table 1. rinse aid ingredients default Ex.1 Ex. 2 Example 3 Example 4 C _8/18 CO (EO) ₁₀ CH ₃ - 15 2.0 5.0 5.0 hydroxy mixed - - 5.0 10.0 - C _12/14 -FA + 5EO + 4PO 15.0 - 8.0 - 10.0 cumene 8.0 5.0 3.0 2.0 5.0 citric acid 5.0 5.0 5.0 5.0 5.0 ad 100% by weight of water rinse effect + better than better than better than better than default default default default

Claims (11)

1. Water-based rinse agents for machine dishwashing containing mono- and/or polybasic carboxylic acids, solubilizers and alkoxylated carboxylic acid esters corresponding to formula (I):

   

   in which R¹CO is an aliphatic acyl group, OAlk stands for an O-CH₂CH₂ group, n is a number of 5 to 15 and R² is a methyl group.
2. Rinse agents as claimed in claim 1, characterized in that they contain alkoxylated carboxylic acid esters corresponding to formula (I) which have been produced by reaction of carboxylic acids with alkylene oxides in the presence of calcined hydrotalcite.
3. Rinse aids as claimed in any of claims 1 to 2, characterized in that the alkoxylated carboxylic acid esters are present in quantities of 0.5 to 40% by weight.
4. Rinse agents as claimed in any of claims 1 to 3, characterized in that the alkoxylated carboxylic acid esters are present in admixture with other nonionic surfactants selected in particular from the group of fatty alcohol polyglycol ethers, alkyl oligoglucosides, fatty acid-N-alkyl glucamides, hydroxy mixed ethers and/or mixed ethers.
5. Rinse agents as claimed in claim 4, characterized in that alkoxylated carboxylic acid esters are present in admixture with alkyl polyglycosides corresponding to formula (II): R³O-[G]_p   (II) in which R³ is an alkyl and/or alkenyl group containing 4 to 22 carbon atoms, G is a sugar unit containing 5 or 6 carbon atoms and p is a number
6. Rinse agents as claimed in claim 4, characterized in that alkoxylated carboxylic acid esters are present in admixture with fatty acid-N-alkyl polyhydroxyalkylamides corresponding to formula (III):

   

   where R⁵CO is an aliphatic acyl group containing 6 to 22 carbon atoms, R⁴ is an alkyl or hydroxyalkyl group containing 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group containing 3 to 12 carbon atoms and 3 to 10 hydroxyl groups.
7. Rinse agents as claimed in claim 4, characterized in that alkoxylated carboxylic acid esters are present in admixture with fatty alcohol polyethylene glycol/polypropylene or polybutylene glycol ethers corresponding to formula (V): R⁶O(CH₂CH₂O)_p[MO]_mH   (V) in which R⁶ is an alkyl and/or alkylene group containing 8 to 22 carbon atoms, MO is a propylene oxide and/or a butylene oxide unit, p is a number of 1 to 15 and m is 0 or a number of 1 to 10.
8. Rinse agents as claimed in claim 4, characterized in that alkoxylated carboxylic acid esters are present in admixture with fatty alcohol polypropylene glycol/polyethylene glycol ethers corresponding to formula (VI): R⁷O[CH₂(CH₃)CHO]_r(CH₂CH₂O)_qH   (VI) in which R⁷ is an alkyl and/or alkenyl group containing 8 to 22 carbon atoms, r is a number of 1 to 10 and q is a number of 0 to 15.
9. Rinse agents as claimed in claim 4, characterized in that alkoxylated carboxylic acid esters are present in admixture with hydroxy mixed ethers corresponding to formula (VII): R⁸O[CH₂CH(CH₃)O]_x(CH₂CHR⁹O)_y[CH₂CH(OH)R¹⁰]_z   (VII) in which R⁸ is an alkyl and/or alkylene group containing 4 to 18 carbon atoms, R⁹ is hydrogen or a methyl or ethyl group, R¹⁰ is an alkyl group containing 2 to 22 carbon atoms, x is 0 or a number of 1 to 10, y is a number of 1 to 30 and z is the number 1.
10. Rinse agents as claimed in any of claims 4 to 9, characterized in that the alkoxylated carboxylic acid esters and the other nonionic surfactants are present in a ratio by weight of 10:90 to 80:20.
11. Rinse agents as claimed in any of claims 1 to 10, characterized in that they contain mono- and/or polybasic carboxylic acids, preferably citric acid, in quantities of 1 to 50% by weight.