EP3744821A1 - Use of esterquat compounds in dishwashing, including esterquat compounds and machine dishwashing detergents containing such compounds - Google Patents

Abstract

The description describes the use of compounds of the formula (I) in dishwashing for drying the dishes and / or for cleaning sieve residues where R ₁ C ₁ -C <sub> 6 </ sub > -Alkyl denotes R ₂, R ₃ and R ₄ are each identical or different and hydrogen, C _{1 </ sub > -C ₁₈ -alkyl, C ₂ -C ₁₈ -alkenyl or -CO-R ₅, R ₅ C ₇ -C ₁₉ -alkyl or C ₇ -C ₁₉ -Alkenyl means, with the proviso that at least one of the radicals R ₂, R ₃ and / or R ₄ -CO-R <sub > 5} and forms an ester bond with the oxygen atom of an ethoxy group, m, n and p are each identical or different and denote numbers from 0 to 50, with the proviso that the sum m + n + p is a number of is at least 1, and with the proviso that if one or more of the variables m, n and / or p are 0, the one or more n respective radicals R ₂, R ₃ and / or R ₄ C ₁ -C <sub> 18 < / sub> -alkyl or C ₂ -C ₁₈ -alkenyl, X is a b-valent inorganic or organic anion, b is a number from 1 to 4, and c means a number with the value 1 / b.

Description

The present invention relates to the use of selected esterquat compounds in machine dishwashing for drying the dishes and / or for cleaning sieve residues, in particular for drying the dishes while avoiding or reducing residues in the sieve of the dishwasher, as well as selected esterquat compounds that can be used in particular in automatic dishwashing detergents.

In the context of the present invention, the automatic dishwashing agents according to the invention are understood to mean both automatic dishwashing agents in the classic sense and rinsing agents.

The requirements for machine-washed dishes are very high today, especially when compared to manual dishwashing. In addition to residue-free cleaning, the dishes should be cleaned after the full cleaning program, usually consisting of a pre-wash cycle, a main wash cycle followed by a rinse cycle with a final drying phase, whereby the individual wash cycles are interrupted by intermediate wash cycles, in a streak-free, perfectly shiny and dry Condition. The interior of the machine as well as the machine sieve and the rinse aid chamber should also be in a clean condition. Even if food residues are properly removed from dishes, whitish residues and stains from water hardness or other inorganic or organic salts, which originate from dried-on water droplets and films, often lead to an incorrect assessment of the washing performance. For this reason, rinse aids have long been used successfully for improved rinse aid and drying performance in rinse aids and automatic dishwashing detergents in order to obtain stain-free, streak-free and residue-free dishes. In the case of rinsing agents, the rinse aid is automatically dispensed from a dosing tank into the interior of the dishwasher in the rinse cycle of the cleaning program. In so-called For multifunctional combination products, the rinse aid is already integrated in the dishwasher detergent.

Quaternary ammonium compounds have already been proposed as additives in dishwashing detergents.

So revealed WO-A-01/19948 the use of diquaternary polysiloxanes in automatic dishwashing detergents.

EP-A-171006 describes a dishwashing detergent based on polymeric alkali metal phosphates, alkali metal silicates, alkali metal carbonates and optionally active oxygen-releasing compounds, and low-foaming surfactants which contain enzymes and primary long-chain alkylamines, the latter also being alkoxylated and / or quaternized.

DE-A-19723605 describes quaternized fatty acid amidoamine ethoxylates which can be obtained by condensation of fatty acids with oligoamines, subsequent ethoxylation and quaternization. These compounds can be used as surface-active substances in detergents and cleaning agents, including dishwashing detergents.

DE-A-10060534 discloses quaternized and alkoxylated ammonium compounds that have been modified with fatty acid residues. These compounds contain peroxide bonds or carbonate ester bonds and can be used in dishwasher detergents.

Finally describes WO-A-94/02575 foaming detergent mixtures containing a selected quaternized and ethoxylated methylammonium compound and other surfactants. The methylammonium compound is derived from ethoxylated triethanolamine, which has a total of 3-13 ethoxy groups and thus a low degree of ethoxylation. Two of these (poly) ethoxy groups are esterified with fatty acids and the third of these (poly) ethoxy groups is unesterified. The detergent mixtures are suitable because of their high tendency to foam Use in detergents and cleaning agents, hair shampoos and hand dishwashing detergents.

The cleaning of dishes in dishwashers, especially for domestic use, is subject to continuous changes and improvements. For example, new formats of multifunctional combination products ("all-in-one" dosing systems) are constantly being developed, such as single- or multi-phase tablets, bags and capsules ("pouches, pods, caps") or liquid formats such as multifunctional gels. Such multifunctional combination products require new additives that are effective against staining and film formation, show an advantageous rinse aid performance and / or an advantageous drying performance, and which also prevent the formation of sieve residues during the entire cleaning process or promote the dissolution of sieve residues that have formed.

It has now been found, surprisingly, that selected quaternized and ethoxylated ammonium compounds which contain ethoxy groups, the end groups of which are capped with carboxylic acids, are suitable for increasing the drying performance of dishes and preventing the formation of sieve residues during dishwashing or prevent or slow down the formation of such sieve residues .

Although good washing results are already achieved with the systems described in the prior art, there is still plenty of room for improvements to the previous agents, in particular with regard to improved drying performance in combination with a clean, grease-free machine interior of automatic dishwashing detergents.

The object of the present invention was to provide dishwashing detergents which, in addition to an advantageous cleaning performance, in particular leave behind an advantageous drying performance without grease residues, and which exhibit an advantageous filter cleaning performance.

Another object of the present invention was to provide selected esterquat compounds which, in addition to excellent

Filter cleaning performance show an advantageous drying performance and leave no solid residues when used in the dishwasher.

worin

• R₁ C₁-C₆-Alkyl bedeutet,
• R₂, R₃ und R₄ jeweils gleich oder verschieden sind und Wasserstoff, C₁-C₁₈-Alkyl, C₂-C₁₈-Alkenyl oder -CO-R₅ bedeuten,
• R₅ C₇-C₁₉-Alkyl oder C₇-C₁₉-Alkenyl, vorzugsweise C₇-C₁₇-Alkyl oder C₇-C₁₇-Alkenyl bedeutet, mit der Maßgabe, dass
• mindestens einer der Reste R₂, R₃ und/oder R₄ -CO-R₅ bedeutet und mit dem Sauerstoffatom einer Ethoxygruppe eine Esterbindung ausbildet,
• m, n und p jeweils gleich oder verschieden sind und Zahlen von 0 bis 50 bedeuten, mit der Maßgabe, dass
• die Summe m + n + p eine Zahl von 1 bis 70 bedeutet, und mit der Maßgabe, dass wenn eine oder mehrere der Variablen m, n und/oder p 0 bedeuten, der eine oder die mehreren jeweiligen Reste R₂, R₃ und/oder R₄ C₁-C₁₈-Alkyl oder C₂-C₁₈-Alkenyl darstellen,
• X ein b-wertiges anorganisches oder organisches Anion ist,
• b eine Zahl von 1 bis 4 ist, und
• c eine Zahl mit dem Wert 1/b bedeutet.

The present invention relates to the use of one or more compounds of the formula (I) in dishwashing for drying dishes and / or for cleaning sieve residues, in particular in the sieve of a dishwasher

wherein

• R _{1 is} C ₁ -C ₆ -alkyl,
• R ₂ , R ₃ and R _{4 are} each identical or different and are hydrogen, C ₁ -C ₁₈ -alkyl, C ₂ -C ₁₈ -alkenyl or -CO-R ₅ ,
• R _{5 is} C ₇ -C ₁₉ -alkyl or C ₇ -C ₁₉ -alkenyl, preferably C ₇ -C ₁₇ -alkyl or C ₇ -C ₁₇ -alkenyl, with the proviso that
• at least one of the radicals R ₂ , R ₃ and / or R ₄ -CO-R ₅ and forms an ester bond with the oxygen atom of an ethoxy group,
• m, n and p are each identical or different and are numbers from 0 to 50, with the proviso that
• the sum m + n + p means a number from 1 to 70, and with the proviso that if one or more of the variables m, n and / or p mean 0, the one or more respective radicals R ₂ , R ₃ and / or R _{4 represent} C ₁ -C ₁₈ -alkyl or C ₂ -C ₁₈ -alkenyl,
• X is a b-valent inorganic or organic anion,
• b is a number from 1 to 4, and
• c means a number with the value 1 / b.

If one of the radicals R ₁ , R ₂ , R ₃ , R ₄ and / or R ₅ and the radicals R ₆ , R ₇ and / or R ₈ defined below is alkyl, the alkyl group can be branched as well as unbranched. An alkyl group of these radicals contains the number of carbon atoms specified above.

R ₁ as C ₁ -C ₆ -alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n- butyl, sec -butyl, tert -butyl, pentyl or hexyl, preferably methyl or ethyl and in particular methyl.

Examples of R ₂ , R ₃ and R ₄ as C ₁ -C ₁₈ -alkyl are methyl, ethyl, n-propyl, isopropyl, n- butyl, sec -butyl, tert -butyl, pentyl, hexyl, heptyl, 2- Ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl. Preferred alkyl radicals R ₂ , R ₃ and R ₄ are those having eight to eighteen carbon atoms, and in particular those having twelve to sixteen carbon atoms.

Examples of R ₅ or the radicals R ₆ , R ₇ and / or R ₈ defined below as C ₇ -C ₁₉ -alkyl are heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl , Hexadecyl, heptadecyl, octadecyl or nonadecyl. Preferred alkyl radicals R ₅ are those with seven to seventeen carbon atoms, in particular those with eleven to seventeen carbon atoms, and very particularly those with eleven to thirteen carbon atoms. Particularly preferred alkyl radicals R ₅ have an odd number of carbon atoms, are in particular linear and are very particularly preferably mixtures of linear alkyl groups having 11 and 13 carbon atoms.

If one of the radicals R ₂ , R ₃ , R ₄ and / or R ₅ and the radicals R ₆ , R ₇ and / or R ₈ defined below is alkenyl, the alkenyl group can be branched or unbranched and one or more ethylenic contain unsaturated bonds. An alkenyl group of these radicals contains the number of carbon atoms specified above.

If there are several double bonds in an alkenyl group, they can be conjugated or non-conjugated to one another. Alkenyl radicals preferably contain only one double bond.

Examples of R ₂ , R ₃ and R ₄ as C ₂ -C ₁₈ alkenyl are vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, 2-ethylhexenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl , Hexadecenyl, heptadecenyl or octadecenyl. An example of an alkenyl radical with several ethylenically unsaturated bonds is 1,3-butadienyl.

Preferred alkenyl radicals R ₂ , R ₃ and R ₄ are those with eight to eighteen carbon atoms, and in particular those with twelve to sixteen carbon atoms.

In the compounds of the formula (I) at least one of the radicals R ₂ , R ₃ or R _{4 is} a radical —CO — R ₅ which forms an ester bond with the oxygen atom of an ethoxy group. At least two, in particular all three of the radicals R ₂ , R _{3 and} R _{4 are} preferably a —CO — R ₅ radical, each of which forms an ester bond with the oxygen atoms of ethoxy radicals. Residues of the formula -CO-R ₅ are therefore bonded to groups of the formula -CH ₂ -CH ₂ -O-. If a compound of the formula (I) contains several radicals of the formula -CO-R ₅ , these are all bonded to groups of the formula -CH ₂ -CH ₂ -O-.

Examples of R ₅ or of the radicals R ₆ , R ₇ and / or R ₈ defined below as C ₇ -C ₁₉ alkenyl are heptenyl, ethylhexenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl , Heptadecenyl, octadecenyl or nonadecenyl. Preferred alkenyl radicals R ₅ are those with seven to seventeen carbon atoms, in particular those with eleven to seventeen carbon atoms, and very particularly those with eleven to thirteen carbon atoms. Particularly preferred alkenyl radicals R ₅ have an odd number of carbon atoms, are in particular linear and are very particularly preferably mixtures of linear alkenyl groups with 11 and 13 carbon atoms or an alkenyl group with seventeen carbon atoms, in particular derived from oleic acid.

The positive charge of the quaternary ammonium cation is compensated for by a b-valent anion X. The number of anions is 1 / b, so that the charge balance is taken into account. The valence of the anion X and thus the value of the variable b is in the range from 1 to 4, preferably from 1 to 2 and is in particular 1. In principle, X can be any inorganic or organic anion. Mixtures of anions X can also be present.

Examples of inorganic anions X ^b - are halide ions such as fluoride, chloride, bromide or iodide, or hydroxide ions or anions of inorganic acids such as phosphate, sulfate, nitrate, borate, hexafluorophosphate, tetrafluoroborate, perchlorate, chlorate, hexafluoroantimonate, hexafluoroarsenate, cyanide. The sulfate or phosphate anions also include those which have an organic radical, in particular an alkyl radical, very particularly preferably a methyl radical. The methyl sulfate anion CH ₃ -OSO ₃ ^- is preferred.

Examples of organic anions X ^a- are anions of mono- to tetravalent carboxylic acids or mono- to tetravalent sulfonic acids, it being possible for these acids to be saturated or unsaturated. Examples of anions of organic acids are acetate, formate, trifluoroacetate, trifluoromethanesulfonate, pentafluoroethanesulfonate, nonafluorobutanesulfonate, butyrate, citrate, fumarate, glutarate, lactate, malate, malonate, oxalate, pyruvate or tartrate.

Preferred anions X ^b- are halide ions, hydroxy ions, phosphate ions, sulfate ions, perchlorate ions, hexafluorophosphate ions or tetrafluoroborate ions.

X ^b- chloride or a sulfate anion is particularly preferred, chloride or a methyl sulfate anion is very particularly preferred.

The numbers m, n and p describe the number of ethoxy groups in the residues on the ammonium cation. These numbers move in the range from 0 to 50, preferably from 1 to 50, very particularly preferably from 2 to 40, in particular from 3 to 34, and extremely preferably from 3 to 24.

At least one of the radicals R ₂ , R ₃ or R ₄ on the ammonium cation must have at least one ethoxy group. Preferably at least two, in particular all of the R ₂ , R ₃ or R ₄ radicals on the ammonium cation have at least one ethoxy group. In the event that one or two of the radicals R ₂ , R ₃ or R ₄ have no ethoxy group (s) on the ammonium cation, these radicals are C ₁ -C ₁₈ -alkyl or C ₂ -C ₁₈ -alkenyl.

The sum of the numbers m, n and p (m + n + p) in the compounds of the formula (I) used according to the invention is at least 1, preferably 2 to 70, particularly preferably 10 to 70, in particular from 15 to 50, very particularly preferably from 15 to 40 and most preferably from 15 to 30.

The sums of numbers m, n and p given above can be whole numbers. These can describe individual connections. Usually, however, the compounds of the formula (I) are mixtures of compounds with a different degree of ethoxylation. The sum of the numbers m, n and p therefore generally describes a mean value that can vary between the limits specified above.

The compounds of the formula (I) are preferably used in machine dishwashing.

The residues to be removed are preferably greasy sieve residues.

Compounds of the formula (I) which are preferably used are those in which R _{1 is} methyl.

Particular preference is given to using compounds of the formula (I) in which R ₂ , R ₃ and R _{4 are} each identical or different and are hydrogen or —CO — R ₅ , with the proviso that at least one of the radicals R ₂ , R ₃ and / or R _{4 is} -CO-R ₅ ,
m, n and p are each identical or different and are numbers from 1 to 50, the sum of m + n + p being a number from 10 to 70, preferably from 15 to 50.

Very particular preference is given to using compounds of the formula (I) in which b is 1, and in which X ^{- is} selected from the group consisting of H ₃ CO-SO ₃ ^- and halide, preferably is selected from the group consisting of is selected from H ₃ CO-SO ₃ ^- , Cl ^- , Br ^- and I ^- and is particularly preferably selected from the group consisting of H ₃ CO-SO ₃ ^- and Cl ^- .

Compounds of the formula (I) in which the variables m, n and p are each identical or different and are numbers from 3 to 34, preferably numbers from 3 to 24, are also very particularly preferably used.

Compounds of the formula (I) in which the sum of the variables m, n and p is a number from 15 to 40 and preferably a number from 15 to 30 are also very particularly preferably used.

In the case of compounds of the formula (I) which are used with particular preference, R ₅ denotes C ₁₁ -C ₁₇ -alkyl or C ₁₁ -C ₁₇ -alkenyl, in particular C ₁₁ -C ₁₃ -alkyl or C ₁₇ -alkenyl, preferably linear C ₁₁ -C ₁₃ -Alkyl or linear C ₁₇ -alkenyl and particularly preferably a mixture of linear alkyl groups with 11 and 13 carbon atoms or an alkenyl group with seventeen carbon atoms, in particular derived from oleic acid.

The compounds of the formula (I) are preferably used in the form of mixtures of several compounds of the formula (I) in an automatic dishwashing detergent.

These mixtures of several compounds of the formula (I) preferably contain, on a molar average, 1.0 to 3.0 radicals -CO-R ₅ , in particular on a molar average of 1.5 to 2.8 radicals -CO-R ₅ , and particularly preferably on a molar average of 2.3 to 2.8 radicals -CO-R ₅ .

Particular preference is given to using compounds of the formula (I) in which the sum of the variables m, n and p is a number from 5 to 15 and in which the molar average is 1.0 to 1.5 radicals -CO-R ₅ in the Compounds of formula (I) are included.

Very particular preference is given to using compounds of the formula (I) in which the sum of the variables m, n and p is a number from 15 to 70 and im molar mean 1.5 to 3.0 radicals -CO-R _{5 are contained} in the compounds of formula (I) and in which in particular the sum of the variables m, n and p is a number from 17 to 60 and the molar mean is 2 , 0 to 3.0 radicals -CO-R _{5 are contained} in the compounds of the formula (I).

Compounds of the formula (I) in which R _{1 is} methyl, X is methosulfate, R ₂ , R ₃ and R _{4 are} each identical or different and are hydrogen or -CO-R ₅ , R _{5 is} alkyl with 11 are extremely preferred and / or 13 carbon atoms or alkenyl with 11 and / or 13 carbon atoms or an alkenyl group with seventeen carbon atoms, in particular derived from oleic acid, m, n and p are each identical or different and are numbers from 0 to 50, the sum of the variables m, n and p is a number 24 to 26, preferably 25, and the compounds of the formula (I) contain 2.5 radicals -CO-R ₅ on a molar average.

The compounds of the formula (I) described above are distinguished by a very good drying performance when drying the dishes and by a very good cleaning performance when cleaning sieve residues.

It has also been found that compounds of the formula (I) with a high degree of ethoxylation have no tendency to form solid residues in the machine or on the treated dishes.

worin

• R₁ C₁-C₆-Alkyl bedeutet,
• R₂, R₃ und R₄ jeweils gleich oder verschieden sind und Wasserstoff, C₁-C₁₈-Alkyl, C₂-C₁₈-Alkenyl oder -CO-R₅ bedeuten,
• R₅ C₇-C₁₉-Alkyl oder C₇-C₁₉-Alkenyl, insbesondere C₇-C₁₇-Alkyl oder C₇-C₁₇-Alkenyl bedeutet, mit der Maßgabe, dass
• mindestens einer der Reste R₂, R₃ und/oder R₄ -CO-R₅ bedeutet, und mit dem Sauerstoffatom einer Ethoxygruppe eine Esterbindung ausbildet,
• m, n und p jeweils gleich oder verschieden sind und Zahlen von 0 bis 50 bedeuten, mit der Maßgabe, dass
• die Summe m + n + p eine Zahl von 10 bis 70 bedeutet, und mit der Maßgabe, dass wenn eine oder mehrere der Variablen m, n und/oder p 0 bedeuten, der eine oder die mehreren jeweiligen Reste R₂, R₃ und/oder R₄ C₁-C₁₈-Alkyl oder C₂-C₁₈-Alkenyl bedeuten,
• X ein b-wertiges anorganisches oder organischen Anion ist,
• b eine Zahl von 1 bis 4 ist, und
• c eine Zahl mit dem Wert 1/b bedeutet.

The present invention therefore also relates to compounds of the formula (I)

wherein

• R _{1 is} C ₁ -C ₆ -alkyl,
• R ₂ , R ₃ and R _{4 are} each identical or different and are hydrogen, C ₁ -C ₁₈ -alkyl, C ₂ -C ₁₈ -alkenyl or -CO-R ₅ ,
• R _{5 is} C ₇ -C ₁₉ -alkyl or C ₇ -C ₁₉ -alkenyl, in particular C ₇ -C ₁₇ -alkyl or C ₇ -C ₁₇ -alkenyl, with the proviso that
• at least one of the radicals R ₂ , R ₃ and / or R ₄ -CO-R ₅ , and forms an ester bond with the oxygen atom of an ethoxy group,
• m, n and p are each identical or different and are numbers from 0 to 50, with the proviso that
• the sum m + n + p means a number from 10 to 70, and with the proviso that if one or more of the variables m, n and / or p mean 0, the one or more respective radicals R ₂ , R ₃ and / or R _{4 is} C ₁ -C ₁₈ -alkyl or C ₂ -C ₁₈ -alkenyl,
• X is a b-valent inorganic or organic anion,
• b is a number from 1 to 4, and
• c means a number with the value 1 / b.

The compounds of the formula (I) are preferably those which are also used with preference for the uses described above.

The compounds used according to the invention can be prepared by standard methods of organic chemistry.

In one variant of the method, monoethanolamine, diethanolamine or triethanolamine are used as the starting point and an esterification reaction of some or all of the terminal hydroxyl group (s) of the ethoxy group (s) with an acid R ₅ -COOH, its alkyl ester or its acid halide is carried out, whereby one or more - CO-R ₅ residues are introduced into the molecule. Subsequently, remaining free hydroxyl groups on ethoxy radicals are ethoxylated to polyethoxy groups, if appropriate with ethylene oxide. The product obtained is then quaternized, for example with an alkyl halide, to give an N-alkylammonium compound. Instead of monoethanolamine or diethanolamine, one can also start from N, N-dialkylmonoethanolamine or from N-alkyldiethanolamine.

In a further variant of the method, monoethanolamine, diethanolamine or triethanolamine are used as the starting point and some or all of the free hydroxyl groups on ethoxy radicals are ethoxylated with ethylene oxide to give polyethoxy groups. An esterification reaction of some or all of the terminal hydroxyl group (s) of the ethoxy group (s) is then carried out with an acid R ₅ -COOH, its alkyl ester or its acid halide, whereby one or more -CO-R ₅ radicals are introduced into the molecule. The product obtained is then quaternized, for example with an alkyl halide, to give an N-alkylammonium compound. In this variant of the process, N, N-dialkylmonoethanolamine or N-alkyldiethanolamine can also be used instead of monoethanolamine or diethanolamine.

The amount of ethylene oxide in the reaction is chosen so that the desired degree of ethoxylation, expressed by the sum m + n + p, is achieved.

As is customary in such reactions, the esterification reaction is carried out in an acidic or, in particular, in a basic medium.

The compounds of the formula (I) with a high degree of ethoxylation are not only distinguished by their particularly good drying performance and cleaning action of screen residues, but also by a low tendency to foam and are therefore outstandingly suitable for use in automatic dishwashing detergents.

The invention therefore also relates to an automatic dishwashing agent containing one or more compounds of the formula (I) in which the sum m + n + p is a number from 11 to 70.

Another advantage of the invention is that the automatic dishwashing agents according to the invention, in addition to the advantageous properties mentioned above, also show an advantageous rinse aid performance.

Automatic dishwashing detergents containing at least one enzyme in addition to the one or more compounds of the formula (I) are preferred.

Also preferred are automatic dishwashing detergents containing, in addition to the one or more compounds of the formula (I), one or more rinse aid surfactants, in particular EO-PO block copolymers or alkoxylated fatty alcohols and very particularly preferably alkoxylated C ₁₂ -C ₁₅ fatty alcohols that contain Ethoxy groups and / or are alkoxylated with propoxy groups, in particular C ₁₂ -C ₁₅ fatty alcohols which are alkoxylated with 8 ethoxy groups and 4 propoxy groups.

worin

• R₆, R₇ und R₈ jeweils gleich oder verschieden sind und C₇-C₂₄Alkyl oder C₇-C₂₄-Alkenyl, insbesondere C₇-C₁₉Alkyl oder C₇-C₁₉-Alkenyl bedeuten,
• q, r und s jeweils gleich oder verschieden sind und Zahlen von 1 bis 200,
• vorzugsweise von 1 bis 80, und ganz besonders bevorzugt von 2 bis 70 bedeuten, mit der Maßgabe, dass die Summe q + r + s eine Zahl von größer als 5 bedeutet,
• vorzugsweise von 20 bis 70 und ganz besonders bevorzugt von 30 bis 60.

Machine dishwashing agents containing, in addition to the one or more compounds of the formula (I), one or more ethoxylated glycerol esters of the formula (II) are widely preferred

wherein

• R ₆ , R ₇ and R _{8 are} each identical or different and are C ₇ -C ₂₄ alkyl or C ₇ -C ₂₄ alkenyl, in particular C ₇ -C ₁₉ alkyl or C ₇ -C ₁₉ alkenyl,
• q, r and s are each identical or different and are numbers from 1 to 200,
• preferably from 1 to 80, and very particularly preferably from 2 to 70, with the proviso that the sum q + r + s denotes a number greater than 5,
• preferably from 20 to 70 and very particularly preferably from 30 to 60.

worinOf the compounds of the formula (II), particular preference is given to using those which have been prepared by reacting triglycerides of the formula (III) with ethylene oxide in the presence of a catalyst

wherein

R ₆ , R ₇ and R _{8 are} each identical or different and have the meaning defined above, and in which the catalyst is a compound which is obtained by reacting calcium hydroxide with a carboxylic acid containing 3 to 40 carbon atoms, the molar ratio of calcium hydroxide to the carboxylic acid is from 1: 1 to 1: 3.

Machine dishwashing agents containing one or more polymers in addition to the one or more compounds of the formula (I) are widely preferred.

In addition, automatic dishwashing detergents which contain one or more compounds of the formula (I) and which are in the form of a powder, a tab, a pod, a gel or as a liquid rinse aid are preferred.

Automatic dishwashing detergents which contain one or more compounds of the formula (I) and are packaged in a water-soluble film, in particular in a film containing polyvinyl alcohol, are also preferred.

In this context, “water-soluble film” means that the film consists of at least 90% by weight of water-soluble polymer, copolymer or mixtures thereof. For the purposes of the invention, water-soluble polymers are those polymers which are more than 2.5% by weight soluble in water at 25 ° C.

Preferred materials of the above-mentioned water-soluble films preferably comprise at least partially at least one substance selected from the group consisting of polyvinyl alcohols, acetalized polyvinyl alcohols, polyvinylpyrrolidones, polyethylene oxides, gelatine, polyvinyl alcohols substituted with sulphate, carbonate and / or citrate, polyalkylene oxides, acrylamides, cellulose esters, cellulose ethers, Cellulose amides, cellulose, polyvinyl acetate, polycarboxylic acids and their salts, polyamino acids or peptides, polyamides, polyacrylamides, copolymers of maleic acid and acrylic acid, copolymers of acrylamides and (meth) acrylic acid, polysaccharides, such as starch or guar derivatives, gelatin and the INCI Designations Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27. The water-soluble material particularly preferably comprises polyvinyl alcohol.

In one embodiment of the invention, the material of the water-soluble films comprises mixtures of different substances, for example copolymers. Such mixtures make it possible to adjust the mechanical properties of the film and the containers made from it and can influence the degree of water solubility.

The water-soluble film preferably contains at least one polyvinyl alcohol and / or at least one polyvinyl alcohol copolymer.

In a further embodiment, the invention relates to the use of one or more compounds of the formula (I), preferably in the form of an automatic dishwashing agent, in automatic dishwashing for drying the dishes and / or for cleaning sieve residues, in particular to avoid or reduce residues in the Sieve of the dishwasher, the residues resulting in particular from cleaning the dishes, particularly preferably from cleaning the dishes from greasy soiling.

The automatic dishwashing agents according to the invention preferably contain the one or more compounds of the formula (I) in amounts of 0.1 to 10% by weight, particularly preferably in amounts of 0.5 to 5% by weight, based in each case on the total weight of dishwashing detergent.

The enzyme or enzymes in the automatic dishwashing agent according to the invention are preferably selected from the group consisting of proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases and oxidoreductases. These enzymes are usually of natural origin. Improved variants based on the natural molecules are commercially available for use in automatic dishwashing detergents and are accordingly preferred.

Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'from Carlsberg and their further developed forms, the Protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus , subtilisin DY and the subtilases.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis , from B. amyloliquefaciens , from B. stearothermophilus , from Aspergillus niger and A. oryzae and the improved further developments of the aforementioned amylases for use in dishwasher detergents. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) should be highlighted.

According to the invention, lipases or cutinases can also be used, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtained from Humicola lanuginosa ( Thermomyces lanuginosus ) or further developed, in particular those with the amino acid substitution D96L. Furthermore, for example, the cutinases can be used that were originally isolated from Fusarium solani pisi and Humicola insolens . Lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocma and Fusarium solanii can also be used.

Furthermore, enzymes can be used which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and ß-glucanases.

To increase the bleaching effect, oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention. Advantageously, preferably organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancer) or to increase the activity different redox potentials between the oxidizing enzymes and the soiling to ensure the flow of electrons (mediators).

The enzymes can be used in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and / or with stabilizers.

Alternatively, the enzymes can be encapsulated both for the solid and for the liquid dosage form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example due to the application of polymeric film formers, and due to the coating are stable in storage.

It is also possible to pack two or more enzymes together so that a single granulate has several enzyme activities.

Machine dishwashing agents according to the invention generally contain the enzyme (s) in amounts of 1 ^× 10 ^-6 to 5% by weight, preferably in amounts of ¹ × 10 ^-5 to 3% by weight and particularly preferably in amounts of 1 × 10 ^-4 to 2 % By weight, each based on the total weight of the dishwashing detergent. The amount of the enzyme (s) in the automatic dishwashing detergents according to the invention is also based on active protein. The protein concentration can be determined by known methods such as, for example, the BCA method or the biuret method.

1. A) der/den Verbindung(en) der Formel (I), und
2. B) dem/den Enzym(en) und/oder den Verbindungen der Formel (II) selbstverständlich noch eine oder mehrere weitere Substanzen enthalten.

The automatic dishwashing detergents according to the invention can in addition to

1. A) the compound (s) of the formula (I), and
2. B) the enzyme (s) and / or the compounds of the formula (II) naturally also contain one or more further substances.

• C) einen oder mehrere Gerüststoffe,
• D) ein Bleichsystem,
• E) ein oder mehrere Tenside,
• F) ein oder mehrere Polymere, und/oder
• G) ein oder mehrere weitere Additive, wobei letztere

vorzugsweise ausgewählt sind aus der Gruppe bestehend aus Komplexbildnern, Glaskorrosionsinhibitoren, Wasser, organischen Lösungsmitteln, Verdickern, Schauminhibitoren, Farbpartikeln, Silberschutzmitteln, Mitteln zur Verhinderung des Anlaufens von Silber, Korrosionsinhibitoren, Farbstoffen, Füllstoffen, keimtötenden Mitteln, Hydrotropen, Antioxidantien, Enzymstabilisatoren, Parfümen, Lösungsvermittlern, Trägermaterialien, Verarbeitungshilfsmitteln, Pigmenten und pH-Stellmitteln.Particularly preferably, these further substances optionally contained in the automatic dishwashing agents according to the invention are selected from components C), D), E), F) and / or G):

• C) one or more builders,
• D) a bleaching system,
• E) one or more surfactants,
• F) one or more polymers, and / or
• G) one or more further additives, the latter

are preferably selected from the group consisting of complexing agents, glass corrosion inhibitors, water, organic solvents, thickeners, foam inhibitors, color particles, silver protectants, agents to prevent the tarnishing of silver, corrosion inhibitors, dyes, fillers, germicides, hydrotropes, antioxidants, enzyme stabilizers, perfumes, Solubilizers, carrier materials, processing aids, pigments and pH adjusters.

Machine dishwashing detergents containing, in addition to the above-described compounds of formula (I), formula (II) and one or more enzymes, preferably selected from the group of proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases and / or oxidoreductases, are widely preferred , one or more components of the components C), D), E), F) and / or G) also described above.

The pH of the automatic dishwashing detergents according to the invention is preferably from 8 to 14, particularly preferably from 9 to 11.5 and particularly preferably from 9.5 to 11.5, measured as a 10% strength by weight solution of the inventive dishwasher detergents Automatic dishwashing detergents according to the invention in water.

The substances mentioned and further preferred ingredients of the automatic dishwashing detergents according to the invention are described in more detail below.

Builders

The machine dishwashing agents according to the invention can also contain one or more builders as component C).

The builders and other ingredients that can be used in the automatic dishwashing detergents according to the invention have already been described in detail in the patent literature, e.g. B. in the US 2010/0160204 A1 and in the EP 1 757 676 A1 .

The automatic dishwashing detergents according to the invention preferably contain one or more builders from the group consisting of carbonates, hydrogen carbonates, organic builders, preferably methylglycine diacetic acid (MGDA), silicates, phosphates, phosphonates and alkali metal hydroxides.

Organic builders include polycarboxylates, polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, and dextrins.

Common aminocarboxylic acids preferred within the scope of the present invention are, for example, ethylenediaminetetraacetic acid (EDTA), methylglycinediacetic acid (MGDA) and glutamine diacetic acid (GLDA). Mixtures can also be used. Polymeric aminodicarboxylic acids, their salts or their precursors are also to be mentioned as further preferred builders. Polyaspartic acids, their salts or their derivatives are particularly preferred.

In addition, amphoteric polymers can also be used as builders.

Oxidisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further preferred organic builders, which are often also referred to as co-builders. Ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also preferred as builders or co-builders in this context.

Automatic dishwashing agents according to the invention can contain, as builder C), preferably crystalline layered sodium silicates of the general formula NaMSi _x O _{2x + 1} · yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably 1.9 to 4, particularly preferred values for x being 2, 3 or 4, and y being a number from 0 to 33, preferably from 0 to 20.

The phosphates have proven to be effective builders in terms of cleaning performance. Of the large number of commercially available phosphates, the alkali metal phosphates have the greatest importance in the detergent and cleaning agent industry, in particular pentasodium and pentapotassium triphosphate (sodium or potassium tripolyphosphate).

The automatic dishwashing agents according to the invention can contain one or more phosphonates, which are often also referred to as co-builders, as further builders.

Automatic dishwashing agents according to the invention can contain alkali metal hydroxides as further builders C).

The automatic dishwashing agents according to the invention can contain the aforementioned builders C) both individually and in the form of mixtures of two, three, four or more builders.

In a preferred embodiment of the invention, the automatic dishwashing agents according to the invention do not contain any phosphate builders. The automatic dishwashing agents according to the invention contain the one or more builders of component C) preferably in amounts of 2 to 50% by weight, particularly preferably in amounts of 10 to 30% by weight and particularly preferably in amounts of 10 to 25% by weight. -%, in each case based on the total weight of the automatic dishwashing agent according to the invention.

Bleaching system

The automatic dishwashing detergents according to the invention can also contain a bleach system D).

The bleach system D) of the automatic dishwashing detergents according to the invention preferably contains one or more substances from the group consisting of bleaching agents, bleach activators and bleach catalysts.

The automatic dishwashing agents according to the invention can contain an oxygen bleaching agent as a bleaching agent. Among these oxygen bleaching agents which produce H ₂ O ₂ in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which provide H ₂ O ₂ , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid. Organic bleaches can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are the peroxy acids, such as alkyl peroxy acids and the aryl peroxy acids.

In order to achieve an improved bleaching effect when cleaning at temperatures of about 60 ° C. and below, the automatic dishwashing agents according to the invention can additionally contain one or more bleach activators. The bleach activator or bleach activators are preferably selected from the group consisting of compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Substances that O- and / or Carry N-acyl groups of the stated number of carbon atoms and / or optionally substituted benzoyl groups. Multiply acylated alkylenediamines are preferred, tetraacetylethylenediamine (TAED) having proven particularly suitable.

In addition to the conventional bleach activators or instead of them, so-called bleach catalysts can also be used. These substances are bleach-intensifying transition metal salts or

Transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salen complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands and Co, Fe, Cu and Ru amine complexes can also be used as bleach catalysts.

The bleaching system D) preferably comprises one or more bleaches and one or more substances from the group of the bleach activators and bleach catalysts. The bleach system particularly preferably comprises one or more bleaching agents, one or more bleach activators and one or more bleach catalysts.

The automatic dishwashing detergents according to the invention contain the bleach system of component D) preferably in amounts of 1 to 40% by weight, particularly preferably in amounts of 0.5 to 30% by weight and particularly preferably in amounts of 3 to 25% by weight , in each case based on the total weight of the automatic dishwashing agent according to the invention.

Surfactants

Preferred automatic dishwashing detergents according to the invention can furthermore contain one or more surfactants of component E), the group of surfactants including the nonionic, anionic, cationic and amphoteric surfactants.

The one or more surfactants of component E) of the automatic dishwashing agents according to the invention is preferably selected from the group of nonionic surfactants, in particular the low-foaming nonionic ones Surfactants. All nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants in the context of the present invention.

Particularly preferred is the one or more surfactants of component E) of the automatic dishwashing agents according to the invention selected from the group of nonionic surfactants consisting of fatty alcohol alkoxylates, end-capped fatty alcohol alkoxylates, ethylene oxide-propylene oxide block copolymers, N-acylglucamides and epoxy-capped poly (alkoxylated) alcohols.

R_a

für eine lineare oder verzweigte gesättigte Alkylgruppe mit 8 bis 30 Kohlenstoffatomen oder eine lineare oder verzweigte ungesättigte Alkenylgruppe mit einer oder mehreren Doppelbindungen und 8 bis 30 Kohlenstoffatomen steht,

A

aus der Gruppe bestehend aus -C₂H₄- und -C₃H₆- ausgewählt ist,

x

für eine Zahl von 1 bis 150 steht,

Y

für H, eine lineare oder verzweigte Alkylgruppe mit 1 bis 30 Kohlenstoffatomen oder eine Gruppe -CH(OH)-R_b steht und R_b für eine lineare oder verzweigte Alkylgruppe mit 1 bis 30 Kohlenstoffatomen steht, und wobei die Gruppe -(-AO-)_x- eine oder mehrere -C₂H₄O-Gruppen umfasst und zusätzlich eine oder mehrere -C₃H₆O-Gruppen umfassen kann und dann, wenn die Gruppe -(-AO-)_x- gleichzeitig -C₂H₄O- und -C₃H₆O-Gruppen umfasst, die -C₂H₄O- und -C₃H₆O-Gruppen auf beliebige Weise, vorzugsweise auf statistische, gradientenartige oder blockartige Weise und besonders bevorzugt auf blockartige Weise über die -(-AO-)_x-Gruppe verteilt sein können und die molare Menge der -C₂H₄O-Gruppen in der Gruppe -(-AO-)_x- vorzugsweise größer als die molare Menge der -C₃H₆O-Gruppen ist.

Machine dishwashing agents according to the invention are particularly preferred, the one or more surfactants of component E) being selected from the group of nonionic surfactants of the general formula (IX)

R _a O - (- AO-) _x -Y (IX),

in the

R _a

represents a linear or branched saturated alkyl group with 8 to 30 carbon atoms or a linear or branched unsaturated alkenyl group with one or more double bonds and 8 to 30 carbon atoms,

A.

is selected from the group consisting of -C ₂ H ₄ - and -C ₃ H ₆ -,

x

stands for a number from 1 to 150,

Y

represents H, a linear or branched alkyl group having 1 to 30 carbon atoms or a group -CH (OH) -R _b and R _{b represents} a linear or branched alkyl group having 1 to 30 carbon atoms, and the group - (- AO- ) _x - comprises one or more -C ₂ H ₄ O groups and can additionally comprise one or more -C ₃ H ₆ O groups and if the group - (- AO-) _x - simultaneously -C ₂ H ₄ O and -C ₃ H ₆ O groups, the -C ₂ H ₄ O and -C ₃ H ₆ O groups in any way, preferably in a random, gradient-like or block-like manner and particularly preferably in a block-like manner via the - (- AO-) _x group can be distributed and the molar amount of the -C ₂ H ₄ O groups in the group - (- AO-) _x - preferably greater than the molar amount of the -C ₃ H ₆ O- Groups is.

Examples of the alkyl and alkenyl groups R _{a of} the formula (IX) are, for example, the alkyl and alkenyl groups of the following alcohols R _a -OH: 1-octanol (caprylic alcohol), 2-ethylhexanol, 1-nonanol (pelargon alcohol), 1-decanol (Capric alcohol), 1-undecanol, 1-dodecanol (lauryl alcohol), 1-tridecanol, isotridecanol, 1-tetradecanol (myristyl alcohol), 1-pentadecanol, 1-hexadecanol (cetyl alcohol), cis-9-hexadecen-1-ol (palmitoleyl alcohol ), 1-heptadecanol, 1-octadecanol (stearyl alcohol), cetearyl alcohol, 16-methylheptadecan-1-ol (isostearyl alcohol), 9E-octadecen-1-ol (elaidyl alcohol), cis-9-octadecen-1-ol (oleyl alcohol), Oleylcetyl alcohol (i.e. a mixture of oleyl alcohol and cetyl alcohol), 9Z, 12Z-octadecadien-1-ol (linoleyl alcohol), 9E, 12E-octadecadien-1-ol (elaidolinoleyl alcohol), 9Z, 12Z, 15Z-octadecatrien-1-ol (Linolenyl alcohol), 9E, 12E, 15E-octadecatrien-1-ol (elaidolinolenyl alcohol), 1-nonadecanol, 1-eicosanol (arachidyl alcohol), 1-heneicosanol, 1-docosanol (behenyl alcohol), cis-13-docosen-1-ol (He ucyl alcohol), 1-tetracosanol (lignoceryl alcohol), 1-hexacosanol (ceryl alcohol), 1-octacosanol (montanyl alcohol) and 1-triacontanol (myricyl alcohol) or mixtures thereof.

R _a in formula (IX) preferably represents a linear or branched saturated alkyl group with 8 to 22 carbon atoms or a linear or branched unsaturated alkenyl group with one or more double bonds and 8 to 22 carbon atoms, particularly preferably a linear or branched saturated alkyl group with 8 to 18 carbon atoms or a linear or branched unsaturated alkenyl group with one or more double bonds and 8 to 18 carbon atoms and particularly preferably for a linear or branched saturated alkyl group with 12 to 15 carbon atoms or a linear or branched unsaturated alkenyl group with one or more double bonds and 12 to 15 carbon atoms.

The groups R _a in formula (IX) are preferably alkyl groups.

Preferably, x in formula (IX) is a number from 1 to 50, particularly preferably a number from 1 to 20 and particularly preferably a number from 5 to 20. The examples given above for the alkyl group R _a of the compound of the formula (IX) may be mentioned as examples of the alkyl groups Y and R _{b of} the compounds of the formula (IX). Further examples are the alkyl groups methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, sec-pentyl (2-pentyl), 3 -Pentyl, 2-methylbutyl, iso-pentyl (3-methylbutyl), 3-methylbut-2-yl, 2-methylbut-2-yl, neopentyl (2,2-dimethylpropyl), 1-hexyl, 2-hexyl, 3 -Hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl , 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3.3 -Dimethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, 2-ethyl-1-butyl, 1-heptyl, 2-heptyl, 3-heptyl, 4-heptyl and n-octyl.

If Y in formula (IX) represents a linear or branched alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms.

R _b in formula (IX) preferably represents a linear or branched alkyl group having 8 to 22 carbon atoms.

In a preferred embodiment of the invention, the group - (- AO-) _x - consists of one or more -C ₂ H ₄ O groups and does not contain any -C ₃ H ₆ O groups.

In a further preferred embodiment of the invention, the group - (- AO-) _x - contains one or more -C ₂ H ₄ O groups and one or more -C ₃ H ₆ O groups. In this preferred embodiment of the invention, the molar amount of -C ₃ H ₆ O groups, based on the total amount of -C ₂ H ₄ O and -C ₃ H ₆ O groups, is preferably less than 50%, particularly preferred 45% or less than 45%, particularly preferably 40% or less than 40% and extremely preferably 33% or less than 33%.

In a further preferred embodiment of the invention, Y in formula (IX) is H. In this preferred embodiment of the invention, the molar amount of -C ₃ H ₆ O groups, based on the total amount of -C ₂ H ₄ O- and -C ₃ H ₆ O groups, preferably 20 to less than 50%, particularly preferably 33 to 45% and particularly preferably 33 to 40%.

If Y has a meaning other than H, the molar amount of the -C ₃ H ₆ O groups, based on the total amount of -C ₂ H ₄ O and -C ₃ H ₆ O groups, is preferably 20% or less than 20% and particularly preferably 10% or less than 10%.

In a further preferred embodiment of the invention, Y in formula (IX) represents an alkyl group having 1 to 4 carbon atoms. In this preferred embodiment, the molar amount of the -C ₃ H ₆ O groups, based on the total amount of -C ₂ H ₄ O and -C ₃ H ₆ O groups, is preferably 20% or less than 20% and particularly preferably 10% or less than 10%.

In a further embodiment of the invention, Y in formula (IX) represents the group —CH (OH) —R _b , in which R _{b represents} a linear or branched alkyl group having 8 to 22 carbon atoms. In this preferred embodiment, the molar amount of the -C ₃ H ₆ O groups, based on the total amount of -C ₂ H ₄ O and -C ₃ H ₆ O groups, is preferably 20% or less than 20% and particularly preferably 10% or less than 10%.

In a particularly preferred embodiment of the invention, the one or more nonionic surfactants of component E) of the automatic dishwashing detergents according to the invention contain, on a molar average, 8 -C ₂ H ₄ O groups and 4 -C ₃ H ₆ O groups and R _a is one linear or branched saturated alkyl group having 12 to 15 carbon atoms or a linear or branched unsaturated alkenyl group having one or more double bonds and 12 to 15 carbon atoms. In these nonionic surfactants of component E) of the automatic dishwashing detergents according to the invention, Y is preferably H.

The nonionic surfactant (s) of component E) of the automatic dishwashing agents according to the invention particularly preferably have a cloud point of 40 to 60.degree.

The variable “x” in the one or more compounds of the formula (IX) represents molar agents, ie the automatic dishwashing agents according to the invention can contain several compounds of the formula (IX) with different degrees of alkoxylation.

in der

Rb

für eine lineare oder verzweigte gesättigte Alkylgruppe mit 11 bis 21 Kohlenstoffatomen oder eine lineare oder verzweigte ungesättigte Alkenylgruppe mit einer oder mehreren Doppelbindungen und 11 bis 21 Kohlenstoffatomen steht und

Rc

für Wasserstoff oder eine lineare oder verzweigte gesättigte Alkylgruppe mit 1 bis 4 Kohlenstoffatomen steht.

Machine dishwashing agents according to the invention are also very particularly preferred, the one or more surfactants of component E) being selected from the group of N-acylglucamides, which are also known as N-1-deoxysorbityl fatty acid amides or glucamides, of the formula (X),

in the

Rb

represents a linear or branched saturated alkyl group having 11 to 21 carbon atoms or a linear or branched unsaturated alkenyl group having one or more double bonds and 11 to 21 carbon atoms and

Rc

represents hydrogen or a linear or branched saturated alkyl group having 1 to 4 carbon atoms.

In the one or more N-acylglucamides of the formula (X), Rc is preferably a methyl group.

In the N-acylglucamides of the formula (X), Rb preferably represents a linear or branched saturated alkyl group having 11 to 17 carbon atoms or a linear or branched unsaturated alkenyl group having one or more double bonds and 11 to 17 carbon atoms.

Particularly preferably, Rb in the N-acylglucamide (s) of the formula (X) represents a linear or branched saturated alkyl group having 15 to 17 carbon atoms or a linear or branched unsaturated alkenyl group having one or more double bonds and 15 to 17 carbon atoms.

In a preferred embodiment of the invention, 50% by weight or more, particularly preferably 60 to 99% by weight and particularly preferably 70 to 98% by weight of the groups Rb in the N-acylglucamide (s) of the formula ( X) for linear or branched saturated alkyl groups with 17 carbon atoms.

In a further preferred embodiment of the invention, 0.1 to 50% by weight, particularly preferably 0.5 to 40% by weight and particularly preferably 1.0 to 30% by weight of the groups Rb are in the N- Acylglucamide (s) of the formula (X) for linear or branched saturated alkyl groups with 15 carbon atoms.

In a further preferred embodiment of the invention, 50% by weight or more of the groups Rb in the N-acylglucamide (s) of the formula (X) represent linear or branched unsaturated alkenyl groups with one or more double bonds.

In a particularly preferred embodiment of the invention, 50% by weight or more, particularly preferably 80% by weight or more and extremely preferably 90% by weight or more of the groups Rb are in the N-acylglucamide (s) of the formula (X) for linear or branched alkenyl groups with one or more double bonds and 17 carbon atoms.

In the N-acylglucamide (s) of the formula (X) Rb is particularly preferably a linear group.

In another preferred embodiment of the invention, RbCO in the N-acylglucamide (s) of the formula (X) is derived from lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid or linolenic acid. In a particularly preferred embodiment of the invention, RbCO in the N-acylglucamide (s) of the formula (X) is derived from stearic acid, oleic acid, linoleic acid or linolenic acid. In a particularly preferred embodiment of the invention, in the N-acylglucamide (s) of the formula (X), RbCO is derived from oleic acid, linoleic acid and linolenic acid, and in an exceptionally preferred embodiment of the invention, the N-acylglucamide ( en) of the formula (X) RbCO from oleic acid.

The automatic dishwashing agents according to the invention contain the one or more surfactants of component E) preferably in amounts of 0.1 to 15% by weight, particularly preferably in amounts of 0.2 to 10% by weight, and particularly preferably in amounts of 0 , 2 to 5% by weight, based in each case on the total weight of the automatic dishwashing agent according to the invention.

Automatic dishwashing agents according to the invention are also preferred, the one or more surfactants of component E) being selected from the group of zwitterionic surfactants, anionic surfactants and mixtures thereof.

The zwitterionic surfactant is preferably selected from the group consisting of C ₈ to C ₁₈ (preferably C ₁₂ to C ₁₈ ) amine oxides and sulfo- and hydroxyl betaines, such as N-alkyl-N, N-dimethylamino-1-propanesulfonate, where the alkyl group can be C ₉ to C ₁₈ , preferably C ₁₀ to C ₁₄ .

The anionic surfactant is preferably selected from alkyl ethoxysulfates with a degree of ethoxylation of more than 3, particularly preferably 4 to 10 and particularly preferably 6 to 8 and a chain length in the range from C ₈ to C ₁₆ and preferably C ₁₁ to C ₁₅ . In addition, branched alkyl carboxylates have been found useful for purposes of the present invention when the branching occurs in the middle and the average total chain length is 10 to 18 and preferably 12 to 16 with a side chain length of 2 to 4 carbon atoms. An example of this is 2-butyloctanoic acid. The anionic surfactant is usually of a type having good solubility in the presence of calcium. Furthermore, sulfobetaines, alkyl (polyethoxy) sulfates (AES) and short-chain C ₆ -C ₁₀ -alkyl sulfates and sulfonates are such anionic surfactants. It has been shown that straight-chain fatty acids are ineffective because of their sensitivity to calcium.

Polymers

Machine dishwashing agents according to the invention can furthermore contain one or more polymers as component F).

Suitable polymers of component F) are washing or cleaning-active polymers, for example rinse aid polymers and / or polymers that act as fabric softeners. As a rule, according to the invention, the composition for automatic dishwashing can comprise, as polymers of component F), nonionic, cationic, anionic and / or amphoteric polymers.

Cationic polymers in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be achieved, for example, by means of (alkyl) ammonium groups or other positively charged groups in the polymer chain. Particularly preferred cationic polymers come from the groups of the quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternylized derivatives of dialkylammonium and methacrylates, vinylpyrrolidone-methoimidazolinium chloride copolymers, quaternized polyvinyl alcohols or polymers with the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

If cationic polymers are used in component F), they are in particular copolymers which consist of polyalkylene oxide groups and quaternary nitrogen atoms.

The cationic polymers of component F) are preferably containing copolymers
0.1 to 99.9 mol%, preferably 20.0 to 80.0 mol%, particularly preferably 22.0 to 77.6 mol% of one or more cationic structural units (D); and 0.1 to 99.9 mol%, preferably 0.4 to 20.0 mol%, particularly preferably 0.5 to 4.4 mol% of one or more macromonomeric structural units (E).

• worin R¹⁹ und R²¹ gleich oder unterschiedlich sind und unabhängig ausgewählt werden aus Wasserstoff und/oder einer Methylgruppe;
• R²⁰, R²², R²³ und R²⁴ gleich oder unterschiedlich sind und unabhängig voneinander ausgewählt werden aus der Gruppe aus Wasserstoff, aliphatischem Kohlenwasserstoffrest mit 1 bis 20, vorzugsweise mit 1 bis 4 Kohlenstoffatomen, cycloaliphatischem Kohlenwasserstoffrest mit 5 bis 20, vorzugsweise mit 5 bis 8 Kohlenstoffatomen, einer Arylgruppe mit 6 bis 14 Kohlenstoffatomen und/oder Polyethylenglykol (PEG), und werden vorzugsweise ausgewählt aus der Gruppe, die aus Wasserstoff and/oder Methyl besteht, und besonders bevorzugt aus Methyl;
• Y gleich oder verschieden ausgewählt wird aus der Gruppe bestehend aus Sauerstoff, NH und/oder NR²² ausgewählt,
• V gleich oder verschieden ausgewählt wird aus der Gruppe bestehend aus -(CH₂)_x-,
  
• x eine Zahl von 1 bis 6 ist;
• X und X1 gleich oder verschieden ausgewählt werden aus der Gruppe bestehend aus Halogenatom, C₁- bis C₄-Alkylsulfat und C₁- bis C₄-Alkylsulfonat; und die makromonomeren Struktureinheiten (E) werden durch die folgende allgemeine Formel (XIII) dargestellt:
  

worin

• R²⁵ gleich oder verschieden H und/oder Methyl ist;
• Z gleich oder verschieden C = O und/oder O(CH₂)₄ ist, vorzugsweise O(CH₂)₄,
• u im molaren Mittel eine Zahl von 0 bis 7 bedeutet, vorzugsweise von 0 bis 6; und
• v im molaren Mittel eine Zahl von 1 bis 150 ist, vorzugsweise von 11 bis 150, besonders bevorzugt von 12 bis 150.

In the following, the cationic structural units (D) are represented by the general formulas (XI) and / or (XII):

• wherein R ¹⁹ and R ^{21 are the} same or different and are independently selected from hydrogen and / or a methyl group;
• R ²⁰ , R ²² , R ²³ and R ^{24 are the} same or different and are independently selected from the group consisting of hydrogen, aliphatic hydrocarbon radicals with 1 to 20, preferably with 1 to 4 carbon atoms, cycloaliphatic hydrocarbon radicals with 5 to 20, preferably 5 up to 8 carbon atoms, an aryl group with 6 to 14 carbon atoms and / or polyethylene glycol (PEG), and are preferably selected from the group consisting of hydrogen and / or methyl, and particularly preferably methyl;
• Y selected identically or differently is selected from the group consisting of oxygen, NH and / or NR ²² ,
• V is selected identically or differently from the group consisting of - (CH ₂ ) _x -,
  
• x is a number from 1 to 6;
• X and X1, identically or differently, are selected from the group consisting of halogen atom, C ₁ - to C ₄ -alkyl sulfate and C ₁ - to C ₄ -alkyl sulfonate; and the macromonomer structural units (E) are represented by the following general formula (XIII):
  

wherein

• R ^{25 is} identically or differently H and / or methyl;
• Z, identically or differently, is C = O and / or O (CH ₂ ) ₄ , preferably O (CH ₂ ) ₄ ,
• u denotes a number from 0 to 7 on the molar average, preferably from 0 to 6; and
• v is a number from 1 to 150 on the molar average, preferably from 11 to 150, particularly preferably from 12 to 150.

Amphoteric polymers in the context of the present invention have, in addition to positively charged groups, negatively charged groups or monomeric units in the polymer chain. These negatively charged groups or monomeric units are derived, for example, from carboxylic acids, sulfonic acids and phosphonic acids.

Preferred amphoteric polymers which can be used as component F) in the compositions according to the invention are selected from the group consisting of alkyl acrylamide / acrylic acid copolymers, alkyl acrylamide / methacrylic acid copolymers, alkyl acrylamide / methyl methacrylic acid copolymers, alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, alkyl acrylamide / ethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, alkyl acrylamide / alkyl methacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers, and copolymers of unsaturated carboxylic acids unsaturated carboxylic acids with optionally further ionic or non-ionic monomers.

Further particularly preferably used amphoteric polymers are selected from the group consisting of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkaline metal or ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkaline metal or ammonium salts and the methacroylethylmetain / methacrylate copolymers.

If the composition according to the invention for automatic dishwashing contains cationic and / or amphoteric polymers in component F), these polymers are preferably present in amounts of 0.01 to 10% by weight, based on the total weight of the dishwashing detergent. Dishwashing detergents in which the weight fraction of the cationic and / or amphoteric polymers is from 0.01 to 8 wt. %, preferably 0.01 to 4% by weight, particularly preferably from 0.01 to 2% by weight, and very particularly preferably from 0.01 to 1% by weight, based on the total weight of the dishwashing detergent.

Another group of polymers which can preferably be used and which are used in component F) of the automatic dishwashing agent according to the invention are alkoxylated polyalkyleneimines. Alkoxylated polyalkyleneimines have a polyalkyleneimine backbone and alkoxy chains. Preferably, the polyalkyleneimine is polyethyleneimine. The alkoxylated polyalkyleneimine is particularly preferably not quaternized.

If the dishwasher detergent according to the invention contains alkoxylated polyalkyleneimines in component F), the composition preferably contains 1 to 10% by weight, preferably from 1 to 8% by weight, of alkoxylated polyalkyleneimines, based on the total weight of the dishwasher detergent.

The alkoxylated polyalkyleneimine used in component F) preferably contains
0.5 to 40% by weight, preferably 1 to 30% by weight, particularly preferably 2 to 20% by weight of the polyalkyleneimine backbone and
60 to 99% by weight, preferably 60 to 95% by weight, particularly preferably 60 to 90% by weight of the alkoxy chains.

The alkoxy chains preferably contain on average about 1 to about 50, preferably about 2 to about 40, in particular about 3 to about 30, very particularly preferably about 3 to about 20 and extremely preferably about 4 to about 15 alkoxy units, which are preferably ethoxy units. In other suitable alkoxylated polyalkyleneimines for use in component F) the alkoxy chains have on average about 0 to 30, preferably about 1 to about 12, particularly preferably about 1 to about 10 and very particularly preferably about 1 to about 8 propoxy units. Alkoxylated polyethyleneimines in which the alkoxy chains contain a combination of ethoxy and propoxy chains, in particular of polyethyleneimines which contain chains from 4 to 20 ethoxy units and from 0 to 6 propoxy units, are particularly preferred.

The alkoxylated polyalkyleneimine is preferably obtained by alkoxylation, the starting polyalkyleneimine having a weight average molecular weight of from about 100 to about 60,000, preferably from about 200 to about 40,000, particularly preferably from about 300 to about 10,000 g / mol. In a preferred embodiment, a polyethyleneimine with an average molecular weight of 600 g / mol, which is ethoxylated with 20 EO groups per NH group, is used as the alkylated polyalkyleneimine.

Further suitable polyalkylenimines which can be used as component F) in the dishwashing composition according to the invention are compounds with the following general structure: bis - ((C ₂ H ₅ O) (C ₂ H ₄ O) _n ) (CH ₃ ) -N ⁺ -C _x H _2x -N ⁺ - (CH ₃ ) -bis ((C ₂ H ₅ O) (C ₂ H ₄₀ ) _n ), where n is a number from 20 to 30, and x is a number from 3 to 8 means, or sulfated or sulfonated variants thereof.

Additives

The automatic dishwashing detergents according to the invention can contain further ingredients G) which are customarily used in automatic dishwashing agents. In a further preferred embodiment of the invention the automatic dishwashing agents according to the invention contain one or more substances F) selected from the group consisting of complexing agents, glass corrosion inhibitors, water, organic solvents, thickeners, foam inhibitors, color particles, silver protectants, agents for preventing the tarnishing of silver, corrosion inhibitors, dyes, fillers, germicides , Hydrotropes, antioxidants, enzyme stabilizers, perfumes, solubilizers, carrier materials, processing aids, pigments and pH adjusters.

Automatic dishwashing detergents which contain 0.1 to 12% by weight, particularly preferably 0.2 to 10% by weight and particularly preferably 0.5 to 8% by weight of the enzyme preparation are particularly preferred, based in each case on the Total weight of the automatic dishwashing agent according to the invention.

1. A) 0,5 bis 10 Gew.-% der Komponente A),
2. B) 1x10^-6 bis 5 Gew.-% der Komponente B),
3. C) 2 bis 50 Gew.-% der Komponente C),
4. D) 1 bis 40 Gew.-% der Komponente D),
5. E) 0,10 bis 15 Gew.-% der Komponente E) und
6. F) 0 bis 10 Gew.-% der Komponente F),

jeweils bezogen auf das Gesamtgewicht des erfindungsgemäßen maschinellen Geschirrspülmittels.The automatic dishwashing detergents according to the invention particularly preferably contain

1. A) 0.5 to 10% by weight of component A),
2. B) 1x10 ^-6 to 5% by weight of component B),
3. C) 2 to 50% by weight of component C),
4. D) 1 to 40% by weight of component D),
5. E) 0.10 to 15% by weight of component E) and
6. F) 0 to 10% by weight of component F),

each based on the total weight of the automatic dishwashing detergent according to the invention.

In a further preferred embodiment of the invention, the automatic dishwashing agents according to the invention do not contain any phosphate-based builders, and particularly preferably the automatic dishwashing agents according to the invention do not contain any phosphates, i.e. they are phosphate free.

The automatic dishwashing agents according to the invention can be produced in solid or liquid form and as a combination of solid and liquid available forms. Automatic dishwashing agents according to the invention which are solid at 20 ° C. are preferred. In particular, powders, granules, extrudates or compacts, in particular tablets, in single-phase or multiphase form are suitable as solid supply forms. Tablets are formulated for single dose applications.

The solid agents according to the invention preferably contain less than 20% by weight of water, particularly preferably 0.1 to 20% by weight of water and particularly preferably 0.5 to 5% by weight of water, based in each case on the total weight of the automatic dishwashing agent according to the invention .

In another preferred embodiment of the invention, the automatic dishwashing agents according to the invention are anhydrous.

In a particularly preferred embodiment of the invention, the automatic dishwashing agents according to the invention are in the form of tablets.

In a further preferred embodiment of the invention, the automatic dishwashing agents according to the invention are liquid at 20.degree. The liquid supply forms, preferably based on water and / or organic solvents, can be present in thickened form in the form of gels. Capsules are particularly suitable as a liquid supply form in single-phase or multiphase form. The liquid automatic dishwashing agents according to the invention preferably contain up to 60% by weight of water, particularly preferably from 10 to 60% by weight of water and particularly preferably from 25 to 60% by weight of water, based in each case on the total weight of the liquid machine dishwashing agent according to the invention .

The automatic dishwashing agents according to the invention are advantageously suitable for cleaning dishes in dishwashers, with soiled dishes being treated in a dishwashing machine with an aqueous alkaline composition containing an inventive automatic dishwashing agent.

The invention therefore further provides a method for cleaning dishes in a dishwasher, where soiled dishes are treated in a dishwasher with an aqueous alkaline composition containing an inventive automatic dishwashing agent.

In the dishwashing method of the present invention, the pH of the aqueous alkaline composition is preferably 8 or higher, and more preferably 9 or higher.

The automatic dishwashing agents according to the invention or the one or more esterquat compounds of component A) of the automatic dishwashing agents according to the invention are advantageously used to improve the wettability of dishes, to reduce staining and film formation on dishes, to improve the rinsing performance of an automatic dishwashing agent, preferably an automatic dishwashing agent according to the invention, or to improve the drying performance of an automatic dishwashing agent, preferably an automatic dishwashing agent according to the invention, particularly preferably in a method according to the invention for cleaning dishes in a dishwasher.

The preferred embodiments given above for the automatic dishwashing agents according to the invention also apply correspondingly to the method according to the invention for cleaning dishes in a dishwasher and to the inventive use of the automatic dishwashing agents according to the invention or the one or more compounds of the formula (I) of the machine according to the invention Dishwashing detergent as a rinse aid in automatic dishwashing, to improve the wettability of dishes, to reduce the formation of stains and film formation on dishes, to improve the clear rinse performance of an automatic dishwashing detergent, preferably an automatic dishwashing detergent according to the invention, and to improve the drying performance of an automatic dishwashing agent, preferably an inventive machine Dishwashing detergent.

The invention is explained in more detail below by means of examples without being restricted thereto. Unless explicitly stated otherwise in the examples, the percentages in the examples are to be understood as percent by weight (% by weight).

Examples Preparation of the compounds of the formula (I)

The compounds of the formula (I) were prepared in a three-stage process. A sequence of ethoxylation and esterification (or vice versa) produces ethoxylated triethanolamine fatty acid ester precursors. These compounds were then quaternized with dimethyl sulfate (DMS). All reactions were carried out according to known procedures. The procedures are described in the following sections.

General instructions for the ethoxylation of triethanolamine

All ethoxylation reactions were carried out according to known procedures. The masses used for the respective examples and the analytical data can be found in the table below.

Triethanolamine and NaOH (50% aq.) Were placed in a 3 L autoclave, the mixture was dried at 90 ° C. for 2 hours, the vacuum was compensated for by nitrogen and the reaction mixture was then heated to 140 ° C. At this temperature, the corresponding amount of ethylene oxide was reacted by adding it in portions while the procedure was rendered inert at a total pressure of 2-6 bar. After reaction to constant pressure, the product was cooled to 80 ° C., traces of unreacted ethylene oxide were removed by applying a vacuum for 30 min and the product was isolated. example (m + n + p) Triethanolamine [g] NaOH (50% aq.) [G] Ethylene oxide [g] OH number [mgKOH / g] Total amine number [mgKOH / g] Sample No. 1 (TEA + 5EO) 5 950.00 10.15 1397.7 469 156 Sample No. 2 (TEA + 15EO) 15th 400.00 4.28 1765.5 221 71.3 Sample No. 3 (TEA + 10EO) 10 650.00 11.12 1912.7 305 99.3 Sample No. 4 (TEA + 20EO) 20th 350.00 5.99 2059.8 175 56.8 Sample No. 5 (TEA + 25EO) 25th 330.00 5.29 2427.6 145 45.8

General instructions for the esterification of ethoxylated triethanolamine

All esterification reactions were carried out according to known procedures. The masses used for the respective examples and the analytical data can be found in the table below.

Ethoxylated triethanolamine, fatty acid and phosphinic acid (50% aqueous solution) were weighed into a multi-necked flask equipped with a KPG stirrer, reflux condenser, distillation bridge and N ₂ connection. The reaction mixture was heated to 180 ° C. under nitrogen (5L / hour). The progress of the reaction was followed by measuring the free acid (acid number). After completion, the reaction was cooled to room temperature. example TEA + nEO quantity Fatty acid main comp. quantity Share of TEA / FA Cat. SZ Basic nitrogen [G] [G] [mol / mol] [G] [mgKOH / g] [%] Sample # 6 TEA + 5EO 100.00 C8 / 10 107.84 1.0 / 2.5 0.23 1.25 2.0072 Sample # 7 TEA + 15EO 150.02 C8 / 10 76.30 1.0 / 2.5 0.21 3.41 1.2542 Sample No. 8 TEA + 10EO 150.01 C8 / 10 84.01 1.0 / 2.0 0.22 2.58 1.7133 Sample No. 9 TEA + 5EO 100.00 C12 / 14 84.91 1.0 / 1.5 0.21 1.01 2.1993 Sample # 10 TEA + 5EO 100.01 C12 / 14 141.50 1.0 / 2.5 0.24 4.30 1.6646 Sample No. 11 TEA + 25EO 150.02 C12 / 14 65.62 1.0 / 2.5 0.20 9.68 0.8024 Sample No. 12 TEA + 15EO 150.00 C12 / 14 80.20 1.0 / 2.0 0.22 4.41 1.1904 Sample No. 13 TEA + 10EO 151.47 C16 / 18 112.30 1.0 / 1.5 0.20 3.64 1.4498 Sample # 14 TEA + 10EO 100.01 C16 / 18 123.39 1.0 / 2.5 0.20 4.80 1.1576 Sample # 15 TEA + 20EO 150.00 C16 / 18 85.04 1.0 / 2.0 0.20 5.88 0.9113

Instructions for the ethoxylation of a triethanolamine ester + 10 EO (sample no.16)

The esterification product (300.00 g, 50.8 wt%, 1.0 eq.) Of the reaction of 1.6 eq. Oleic acid with 1.0 eq. Triethanolamine, prepared by known methods for esterification, was treated with sodium methylate (30% by weight in methanol, 1.42 g,
0.24% by weight). The mixture was heated to 100 ° C. under a water jet vacuum and the methanol contained was removed within 2 hours. At 160 ° C., ethylene oxide (289.7 g, 49.1% by weight, 10.0 eq.) Was reacted by adding it in portions while the procedure was rendered inert at a total pressure of 2-6 bar. After reaction to a constant pressure, the product was cooled to 80 ° C., traces of unreacted ethylene oxide were removed by applying a vacuum for 30 min and the product was isolated. The product obtained has an OH number of 99 mgKOH / g.

General procedure for quaternizing ethoxylated triethanolamine fatty acid esters

All quaternization reactions were carried out according to known procedures. The masses used for the respective examples and the analytical data can be found in the table below.

The ester compound prepared in the previous step was weighed into a multi-necked flask equipped with a KPG stirrer, reflux condenser and N ₂ connection. The ester was heated to a reaction temperature of 60 ° C. under a flow of nitrogen (5 L / hour). The required amount of DMS was added dropwise to the reaction at a dosing rate of 0.2 mL / min. After the end of the metering, the reaction mixture was heated to 80.degree. After a Preussmann test was obtained with a negative result, the reaction was cooled to room temperature. example Ester precursor quantity DMS Basic nitrogen Degree of quaternization [G] [G] [%] [%] Sample No. 17 Sample # 6 100.00 17.66 0.0331 98.1 Sample No. 18 Sample # 7 100.00 11.07 0.0175 98.5 Sample No. 19 Sample No. 8 100.00 15.14 0.0199 98.7 Sample # 20 Sample No. 9 100.00 19.42 0.0357 98.1 Sample # 21 Sample # 10 100.00 14.50 0.0287 98.0 Sample # 22 Sample No. 11 100.00 7.08 0.0101 98.7 Sample No. 23 Sample No. 12 100.00 10.51 0.0148 98.6 Sample No. 24 Sample No. 13 100.00 12.74 0.0162 98.7 Sample # 25 Sample No. 14 100.00 10.22 0.0184 98.2 Sample No. 26 Sample no.15 100.00 8.05 0.0161 98.1 Sample No. 27 Sample # 16 103.15 11.62 0.0921 98.2

Example 1: Filter cleaning performance

For the test, a dishwasher filter was heavily soiled with grease and oil. The grease removal in the machine filter was determined gravimetrically and the result indicated by a performance index (0-100; 0 = no cleaning; 100 = complete cleaning). The interior of the machine was assessed according to its aesthetic appearance on a point scale (0-100; 100 = perfect). component Market product with filter cleaning F1% by weight *) F2% by weight *) Trisodium citrate dihydrate 28.5 28.5 sodium 19.5 19.5 Sodium silicate 2.0 2.0 MGDA-Na ₃ 15.0 15.0 Polycarboxylate 10.0 10.0 Sodium percarbonate 9.0 9.0 TAED 2.0 2.0 HEDP 0.9 0.9 Protease 0.9 0.9 Amylase 0.9 0.9 Sample # 22 2.0 2.5 C12 / 14-FA-TEA 25 EO Fatty alcohol alkoxylate 3.5 3.5 Sodium sulfate Ad 100 **) Ad 100 **) Filter cleaning performance 46 54 71 Aesthetic appearance of the machine interior 78 63 73 *) The ingredients are added according to their active ingredient content in% by weight
**) Sodium sulfate is added as a filler for a constant mass balance of the automatic dishwashing detergent without any function and without affecting the performance of the automatic dishwasher detergent

It can be seen from the results of Table A above that the use of the inventive automatic dishwashing detergents F2 leads to advantageous values for the filter cleaning performance and the aesthetic appearance of the interior of the machine compared to comparative formulation F1 and a market product.

Example 2: drying performance in combination with a clean machine interior

The drying performance of the formulations F5-F8 according to the invention was investigated. The drying performance of formulations F3 and F4, which in the case of F3 only contained fatty alcohol alkoxylate and in the case of F4 only modified fatty alcohol alkoxylate, were tested as comparative examples. Test conditions: Dishwasher: Miele G 1222 SC GSL-2 Test dishes: 10 starter knives 10 starter forks 10 starter spoons 10 teaspoons 2 vegetable spoons 12 drinking glasses 10 porcelain cups 25 porcelain plates 3 SAN plates 3 polypropylene plates 6 polypropylene bowls Dishwashing program: P4R0 without pre-wash Main rinse at 50 ° C Rinse cycle at 65 ° C Water hardness: 21 ° dH Water softening: no Detergent dosage: 18 g, placed in the tablet collecting tray immediately after opening the dosing chamber Dirt: 50 g frozen dirt, added immediately after opening the dosing chamber Rinse aid: none Cleaning cycles: 4th

All items were treated once with demineralized water, Neodisher A 8, citric acid and again demineralized water.

Evaluation:

The evaluation of the test dishes was started 30 minutes after the end of the dishwashing cycle. During this time, the dishwasher door remained closed. Dishwashing cycles 2-4 were assessed in each test. The assessment was carried out with an illumination of 1000-1500 lux.

The number of adhering residual water droplets was counted for each test piece of utensils in a specified order and with a specified time limit. Depending on the number of drops counted, the following rating results for each test piece of crockery: Grading for porcelain, stainless steel and glass: 0 dry, no water drops 1 1 drop of water 2 2 drops of water 3 3 drops of water 4th 4 drops of water 5 5 drops of water 6th more than 5 drops of water 0 dry, no water drops 1 1 drop of water 2 2 drops of water 3 3 drops of water 4th 4 drops of water 5 5 drops of water 6th 6 drops of water 7th 7 drops of water 8th more than 7 water drops

In this assessment scheme, a grade of 0 stands for the best performance and a grade of 6 or 8 for the worst performance for each test piece of utensils. For each dishwashing cycle 2, 3 and 4, the sum of the marks for all test dishes was formed. To compare the various formulations F3-F8, the average score of all sums of dishwashing cycles 2-4 was averaged. This leads to a theoretical maximum value with the worst drying performance of 630 and a theoretical minimum value with the best drying performance of 0.

The results are shown in Table B below.

In addition, the grease residues on plastic parts (machine sieve, rinse aid compartment) in the machine were rated (scale 1-7; 1 = strong residues and 7 = no residues). The results are also shown in Table B.

Compositions:

The compositions of the formulations F3-F8 are given in Table B below.

Example 3: Final rinse performance of automatic dishwashing detergents

The rinsing performance of the formulation F7 according to the invention was investigated. As comparison examples, the rinsing performance of formulations F3 and F4, which in the case of F3 only contained fatty alcohol alkoxylate and in the case of F4 only modified fatty alcohol alkoxylate, was tested. Test conditions: Dishwasher: Miele G 1222 SC GSL Test dishes (8 groups): 6 drinking glasses (higher quality) 6 drinking glasses (lower quality) 3 polypropylene bowls 3 melamine plates 3 butter dishes + 4 knives (stainless steel; lower quality) 4 knives (stainless steel; higher quality) 3 porcelain plates (higher quality) 3 porcelain plates (lower quality) Dishwashing program: Program 4, R = 2 without pre-wash Main rinse at 50 ° C Rinse cycle at 65 ° C Water hardness: 21 ° dH Water softening: no Detergent dosage: 18 g, added to the dosing chamber before starting the test Dirt: 100 g frozen dirt, added immediately after opening the dosing chamber Rinse aid: none Cleaning cycles: 4th

All dishes except the polypropylene bowls were treated once with demineralized water, Neodisher A 8, citric acid and again demineralized water.

Evaluation:

Assessment of the test dishes was started at the earliest 30 minutes after the dishwasher door had been opened after the dishwashing cycle had ended. Dishwashing cycles 2-4 were assessed in each test. The assessment was made according to the following rating:

Final rinse effects considered for visual grading:

stains

Spots of different sizes and intensities

Attachment points

Stains from contact points between dishes and parts of the dishwasher

Stripes

Rinse aid strips

Film formation

Continuous film evenly distributed over the test harness

Structure film formation

Scattered, cracked film

Solid residue

Solid powder or crystalline residues

Fat residues

Drops or films of fat

Iridescence

Iridescence, iridescence

Visual grading:

10

Perfect

9

Perfect to just visible

8th

Just visible

7th

Just visible to visible

6th

Visible

5

Visible to annoying

4th

Annoying

3

Disturbing or not acceptable

2

Unacceptable

1

Absolutely not acceptable

The combination of the eight clear rinse effects listed above results in a grade of 1 - 10 according to the visual grading above for each piece of crockery, with a grade of 1 for the worst performance and a grade of 10 for the best performance. For each of the 8 test dishes groups listed above, the average rating for all dishes of a respective material group was calculated for each dishwashing cycle, then the sum of all material groups was formed for each dishwashing cycle and finally the average for all three dishwasher cycles 2 - 4 was determined. The resulting average rating was used as the overall rinsing performance to compare the various formulations F3, F4 and F7. This leads to a theoretical maximum value with the best final rinse performance of 80.0 and a theoretical minimum value with the worst final rinse performance of 8.0.

The results are shown in Table B below. Table B: Compositions, drying performance, grease residues and rinsing performance for formulations F3 - F8 component F3% by weight * ⁾ F4% by weight * ⁾ F5% by weight * ⁾ F6% by weight * ⁾ F7% by weight * ⁾ F8% by weight * ⁾ Trisodium citrate dihydrate 29.0 29.0 29.0 29.0 29.0 29.0 sodium 20.0 20.0 20.0 20.0 20.0 20.0 Sodium silicate 2.0 2.0 2.0 2.0 2.0 2.0 MGDA-Na ₃ 15.0 15.0 15.0 15.0 15.0 15.0 Polycarboxylate 10.0 10.0 10.0 10.0 10.0 10.0 Sodium percarbonate 9.0 9.0 9.0 9.0 9.0 9.0 TAED 2.0 2.0 2.0 2.0 2.0 2.0 HEDP 0.9 0.9 0.9 0.9 0.9 0.9 Protease 1.0 1.0 1.0 1.0 1.0 1.0 Amylase 1.0 1.0 1.0 1.0 1.0 1.0 Fatty alcohol alkoxylate 3.5 3.5 3.5 3.5 Modified fatty alcohol ethoxylate 3.5 Sample # 22 3.5 1.0 2.0 3.5 2.5 C12 / 14-FA-TEA 25 EO Sodium sulfate Ad 100 ** ⁾ Ad 100 ** ⁾ Ad 100 ** ⁾ Ad 100 ** ⁾ Ad 100 ** ⁾ Ad 100 ** ⁾ Drying performance 194 134 88 175 136 170 Rinsing performance 47.5 55.9 49.3 Fat residues 6th 3 6th 7th 7th 7th *) The ingredients are added according to their active ingredient content in% by weight.
**) Sodium sulfate is added as a filler for a constant mass balance of the automatic dishwashing detergent without any function and without affecting the performance of the automatic dishwashing detergent.

It can be seen from the results of Table B above that the use of the automatic dishwashing detergents F5-F8 according to the invention leads to advantageous values for the drying performance compared to the use of the comparative formulation F3. The use of the inventive automatic dishwashing detergent F5 leads to advantageous values for the drying performance compared to the use of the comparative formulations F3 and F4 and also to fewer grease residues in the machine interior compared to F4. Using the drying values of the inventive dishwashing detergents F6, F7 and F8, it can be shown that the addition of the inventive esterquat compounds to a formulation containing fatty alcohol alkoxylate can significantly improve the drying performance of the automatic dishwashing detergents compared to the automatic dishwashing detergent F3. The addition of the esterquat compounds according to the invention to automatic dishwashing detergents which contain fatty alcohol alkoxylates does not adversely affect the rinse aid performance (cf. F3 and F6).

Example 4: drying performance of automatic dishwashing detergents

The drying performance of the formulations F9-F19 and F21-F22 according to the invention was investigated. As a comparative example, the drying performance of formulation F20, which only contained fatty alcohol alkoxylate, was tested. Test conditions: Dishwasher: Bosch SMS86 Test dishes: 6 starter knives 10 starter forks 10 starter spoons 10 teaspoons 2 vegetable spoons 6 drinking glasses 5 porcelain cups 19 porcelain plates 2 SAN plates 2 polypropylene plates 4 polypropylene bowls Dishwashing program: Eco 50 Variospeed Plus without pre-wash Main rinse at 50 ° C Rinse cycle at 62 ° C Drying phase at 70 ° C Water hardness: 21 ° dH Water softening: no Detergent dosage: 18 g, placed in the tablet collecting tray immediately after opening the dosing chamber Dirt: 100 g frozen dirt, added immediately after opening the dosing chamber Rinse aid: none Cleaning cycles: 1

All items were treated once with demineralized water, Neodisher A 8, citric acid and again demineralized water.

Evaluation:

The evaluation of the test dishes was started 30 minutes after the end of the dishwashing cycle. During this time, the dishwasher door remained closed. The dishwashing cycle is assessed in each test. The assessment was made in each case with an illumination of 1000-1500 lux.

The number of adhering residual water droplets was counted for each test piece of utensils in a specified order and with a specified time limit. Depending on the number of drops counted, the following rating results for each test crockery part: Grading: 0 dry, no water drops 1 1 drop of water 2 2 drops of water 3 3 drops of water 4th 4 drops of water 5 5 drops of water 6th more than 5 drops of water

In this assessment scheme, a grade of 0 stands for the best performance and a grade of 6 for the worst performance for each test piece of utensils. For the dishwashing cycle, the sum of the marks for all test dishes is calculated. To compare the various formulations F9-F22, the sums were formed in each case. This leads to a theoretical maximum value with the worst drying performance of 456 and a theoretical minimum value with the best drying performance of 0.

The results are shown in Tables C1-C3 below.

Compositions:

The compositions of formulations F9-F22 are shown in Tables C1-C3. Table C1: Compositions and drying performance for formulations F9-F14 component F9% by weight * ⁾ F10% by weight * ⁾ F11% by weight * ⁾ F12% by weight * ⁾ F13% by weight * ⁾ F14% by weight * ⁾ Trisodium citrate dihydrate 29.0 29.0 29.0 29.0 29.0 29.0 sodium 20.0 20.0 20.0 20.0 20.0 20.0 Sodium silicate 2.0 2.0 2.0 2.0 2.0 2.0 MGDA-Na ₃ 15.0 15.0 15.0 15.0 15.0 15.0 Polycarboxylate 10.0 10.0 10.0 10.0 10.0 10.0 Sodium percarbonate 9.0 9.0 9.0 9.0 9.0 9.0 TAED 2.0 2.0 2.0 2.0 2.0 2.0 HEDP 0.9 0.9 0.9 0.9 0.9 0.9 Protease 1.0 1.0 1.0 1.0 1.0 1.0 Amylase 1.0 1.0 1.0 1.0 1.0 1.0 Sample No. 17 3.5 2.5 C8 / 10-FA-TEA 5 EO Sample No. 18 3.5 2.5 C8 / 10-FA-TEA 15 EO Sample No. 19 3.5 2.0 C8 / 10-FA-TEA 10 EO Sample # 20 3.5 1.5 C12 / 14-FA-TEA-5 EO Sample # 21 3.5 2.5 C12 / 14-FA-TEA 5 EO Sample # 22 3.5 2.5 C12 / 14-FA-TEA 25 EO Sodium sulfate Ad 100 ** ⁾ Ad 100 ** ⁾ Ad 100 ** ⁾ Ad 100 ** ⁾ Ad 100 ** ⁾ Ad 100 ** ⁾ Drying performance 30th 29 28 30th 37 29 *) The ingredients are added according to their active ingredient content in% by weight.
^**) Sodium sulfate is added as a filler for a constant mass balance of the automatic dishwashing detergent without any function and without any influence on the performance of the automatic dishwashing detergent. component F15% by weight ^*) F16% by weight ^*) F17% by weight ^*) F18% by weight ^*) F19% by weight ^*) F20% by weight ^*) Trisodium citrate dihydrate 29.0 29.0 29.0 29.0 29.0 29.0 sodium 20.0 20.0 20.0 20.0 20.0 20.0 Sodium silicate 2.0 2.0 2.0 2.0 2.0 2.0 MGDA-Na ₃ 15.0 15.0 15.0 15.0 15.0 15.0 Polycarboxylate 10.0 10.0 10.0 10.0 10.0 10.0 Sodium percarbonate 9.0 9.0 9.0 9.0 9.0 9.0 TAED 2.0 2.0 2.0 2.0 2.0 2.0 HEDP 0.9 0.9 0.9 0.9 0.9 0.9 Protease 1.0 1.0 1.0 1.0 1.0 1.0 Amylase 1.0 1.0 1.0 1.0 1.0 1.0 Sample No. 23 3.5 2.0 C12 / 14-FA-TEA 15 EO Sample No. 24 3.5 1.5 C16 / 18-FA-TEA 10 EO Sample # 25 3.5 2.5 C16 / 18-FA-TEA 10 EO Sample No. 26 3.5 2.0 C16 / 18-FA-TEA 20 EO Sample No. 27 3.5 Oleyl FA-TEA 10 EO Fatty alcohol alkoxylate 3.5 Sodium sulfate Ad 100 ^**) Ad 100 ^**) Ad 100 ^**) Ad 100 ^**) Ad 100 ^**) Ad 100 ^**) Drying performance 21st 17th 19th 34 28 253 ^*) The ingredients are added according to their active ingredient content in% by weight.
^**) Sodium sulfate is added as a filler for a constant mass balance of the automatic dishwashing detergent without any function and without any influence on the performance of the automatic dishwashing detergent. component F21% by weight ^*) F22% by weight ^*) Trisodium citrate dihydrate 29.0 29.0 sodium 20.0 20.0 Sodium silicate 2.0 2.0 MGDA-Na ₃ 15.0 15.0 Polycarboxylate 10.0 10.0 Sodium percarbonate 9.0 9.0 TAED 2.0 2.0 HEDP 0.9 0.9 Protease 1.0 1.0 Amylase 1.0 1.0 Sample # 22 1.5 2.5 2.5 C12 / 14-FA-TEA 25 EO Sodium sulfate Ad 100 ^**) Ad 100 ^**) Drying performance 73 90 ^*) The ingredients are added according to their active ingredient content in% by weight.
^**) Sodium sulfate is added as a filler for a constant mass balance of the automatic dishwashing detergent without any function and without any influence on the performance of the automatic dishwashing detergent.

It can be seen from the results of the above Tables C1-C3 that the use of the inventive automatic dishwashing detergents F9-F19 and F 21-F22 leads to advantageous values for the drying performance compared to the use of the comparative formulation F20.

Furthermore, the inventive automatic dishwashing detergents F5-F19 and F21-F22 show very good cleaning performance in the above example.

Claims (37)

Use of one or more compounds of the formula (I) in dishwashing for drying dishes and / or for cleaning sieve residues, in particular in the sieve of a dishwasher

wherein R _{1 is} C ₁ -C ₆ -alkyl, R ₂ , R ₃ and R _{4 are} each identical or different and are hydrogen, C ₁ -C ₁₈ -alkyl, C ₂ -C ₁₈ -alkenyl or -CO-Rs, R _{5 is} C ₇ -C ₁₉ -alkyl or C ₇ -C ₁₉ -alkenyl, with the proviso that at least one of the radicals R ₂ , R ₃ and / or R _{4 is} -CO-Rs, and with the oxygen atom of an ethoxy group forms an ester bond, m, n and p are each identical or different and are numbers from 0 to 50, with the proviso that the sum m + n + p means a number of at least 1, and with the proviso that if one or more of the variables m, n and / or p is 0, which represents one or more of the respective radicals R ₂ , R ₃ and / or R ₄ C ₁ -C ₁₈ -alkyl or C ₂ -C ₁₈ -alkenyl, X is a b-valent inorganic or organic anion, b is a number from 1 to 4, and c means a number with the value 1 / b. Use according to Claim 1, characterized in that the compounds of the formula (I) are used in automatic dishwashing and that the residues are greasy sieve residues. Use according to at least one of Claims 1 or 2, characterized in that R _{1 is} methyl. Use according to at least one of Claims 1 to 3, characterized in that the sum m + n + p means a number from 2 to 70. Use according to at least one of claims 1 to 4, characterized in that R ₂ , R ₃ and R _{4 are} each identical or different and are hydrogen or -CO-Rs, with the proviso that at least one of the radicals R ₂ , R ₃ and / or R _{4 is} -CO-R ₅ ,
m, n and p are each identical or different and are numbers from 1 to 50, the sum of m + n + p being a number from 10 to 70, preferably from 15 to 50. Use according to at least one of claims 1 to 5, characterized in that b is 1 and that X ^{- is} selected from the group consisting of H ₃ CO-SO ₃ ^- and halide, preferably is selected from the group consisting of H ₃ CO -SO ₃ ^- , Cl ^- , Br ^- and I ^- and is particularly preferably selected from the group consisting of H ₃ CO-SO ₃ ^- and Cl ^- . Use according to at least one of Claims 1 to 6, characterized in that the variables m, n and p are each identical or different and mean numbers from 3 to 34, preferably numbers from 3 to 24. Use according to at least one of Claims 1 to 7, characterized in that the sum of the variables m, n and p means a number from 15 to 40 and preferably a number from 15 to 30. Use according to at least one of Claims 1 to 8, characterized in that R _{5 is} C ₇ -C ₁₇ -alkyl or C ₇ -C ₁₇ -alkenyl, in particular C ₁₁ -C ₁₇ -alkyl or C ₁₁ -C ₁₇ -alkenyl. Use according to claim 9, characterized in that R _{5 is} C ₁₁ -C ₁₃ -alkyl or C ₁₇ -alkenyl, preferably linear C ₁₁ -C ₁₃ -alkyl or linear C ₁₇ -alkenyl and particularly preferably a mixture of linear alkyl groups with 11 and 13 carbon atoms or an alkenyl group with seventeen carbon atoms, in particular derived from oleic acid. Use according to at least one of Claims 1 to 10, characterized in that mixtures containing several compounds of the formula (I) are used in an automatic dishwashing detergent. Use according to claim 11, characterized in that the mixtures of several compounds of the formula (I) contain on average 1.0 to 3.0 residues -CO-R ₅ , preferably on average 1.5 to 2.8 residues - CO-Rs, and particularly preferably 2.3 to 2.8 radicals -CO-Rs on a molar average. Use according to at least one of claims 1 to 11, characterized in that the sum of the variables m, n and p is a number from 5 to 15 and a molar average of 1.0 to 1.5 radicals -CO-Rs in the compounds of Formula (I) are included. Use according to at least one of claims 1 to 13, characterized in that the sum of the variables m, n and p is a number from 15 to 70 and a molar average of 1.5 to 3.0 radicals -CO-Rs in the compounds of Formula (I) are included and that the sum of the variables m, n and p is preferably a number from 17 to 60 and on a molar average contain 2.0 to 3.0 radicals -CO-Rs in the compounds of formula (I) are. Use according to at least one of claims 1 to 14, characterized in that R _{1 is} methyl, X is methosulfate, R ₂ , R ₃ and R _{4 are} each identical or different and are hydrogen or -CO-Rs, R _{5 is} alkyl with 11 and / or 13 carbon atoms or alkenyl with 11 and / or 13 carbon atoms or an alkenyl group with seventeen carbon atoms, in particular derived from oleic acid, m, n and p are each the same or different and denote numbers from 0 to 50, the sum of Variables m, n and p is a number 24 to 26, preferably 25, and the compounds of the formula (I) contain 2.5 radicals —CO — Rs on a molar average. Compounds of formula (I)

wherein R _{1 is} C ₁ -C ₆ -alkyl, R ₂ , R ₃ and R _{4 are} each identical or different and are hydrogen, C ₁ -C ₁₈ -alkyl, C ₂ -C ₁₈ -alkenyl or -CO-Rs, R _{5 is} C ₇ -C ₁₉ -alkyl or C ₇ -C ₁₉ -alkenyl, with the proviso that at least one of the radicals R ₂ , R ₃ and / or R _{4 is} -CO-R ₅ , and one with the oxygen atom Ethoxy group forms an ester bond, m, n and p are each identical or different and denote numbers from 0 to 50, with the proviso that the sum m + n + p is a number from 10 to 70, and with the proviso that if one or more of the variables m, n and / or p are 0, the one or more respective radicals R ₂ , R ₃ and / or R _{4 is} C ₁ -C ₁₈ -alkyl or C ₂ -C ₁₈ -alkenyl, X is a b-valent inorganic or organic anion, b is a number from 1 to 4, and c means a number with the value 1 / b. Compounds according to claim 16, characterized in that R _{1 is} methyl. Compounds according to at least one of claims 16 to 17, characterized in that R ₂ , R ₃ and R _{4 are} each identical or different and are hydrogen or -CO-R ₅ , with the proviso that at least one of the radicals R ₂ , R ₃ and / or R _{4 is} -CO-R ₅ ,
m, n and p are each identical or different and are numbers from 1 to 50, the sum of m + n + p being a number from 10 to 70, preferably from 15 to 50. Compounds according to at least one of claims 16 to 18, characterized in that b is 1 and that X ^{- is} selected from the group consisting of H ₃ CO-SO ₃ ^- and halide, preferably is selected from the group consisting of H ₃ CO -SO ₃ ^- , Cl ^- , Br ^- and I ^- and is particularly preferably selected from the group consisting of H ₃ CO-SO ₃ ^- and Cl ^- . Compounds according to at least one of Claims 16 to 19, characterized in that the variables m, n and p are each identical or different and denote numbers from 3 to 34, preferably numbers from 3 to 24. Compounds according to at least one of Claims 16 to 20, characterized in that the sum of the variables m, n and p means a number from 15 to 40 and preferably a number from 15 to 30. Compounds according to at least one of claims 16 to 21, characterized in that R _{5 is} C ₇ -C ₁₇ -alkyl or C ₇ -C ₁₇ -alkenyl, in particular C ₁₁ -C ₁₇ -alkyl or C ₁₁ -C ₁₇ -alkenyl. Compounds according to claim 22, characterized in that R _{5 is} C ₁₁ -C ₁₃ -alkyl or C ₁₇ -alkenyl, preferably linear C ₁₁ -C ₁₃ -alkyl or linear C ₁₇ -alkenyl and particularly preferably a mixture of linear alkyl groups with 11 and 13 carbon atoms or an alkenyl group with seventeen carbon atoms, particularly derived from oleic acid. Compounds according to at least one of Claims 16 to 23, characterized in that they contain mixtures of several compounds of the formula (I). Compounds according to claim 24, characterized in that the mixtures of several compounds of the formula (I) have a molar average of 1.0 to 3.0 -CO-R ₅ radicals contain, preferably on average 1.5 to 2.8 -CO-R ₅ radicals, and particularly preferably 2.3 to 2.8 -CO-R ₅ radicals on molar mean. Compounds according to at least one of claims 16 to 25, characterized in that the sum of the variables m, n and p is a number from 15 to 70 and on a molar average 1.5 to 3.0 radicals -CO-Rs in the compounds of Formula (I) are included and that the sum of the variables m, n and p is preferably a number from 17 to 60 and a molar average of 2.0 to 3.0 radicals -CO-R ₅ in the compounds of the formula (I) are included. Compounds according to at least one of claims 16 to 26, characterized in that R _{1 is} methyl, X is methosulfate, R ₂ , R ₃ and R _{4 are} each identical or different and are hydrogen or -CO-R ₅ , R _{5 is} alkyl with 11 and / or 13 carbon atoms or alkenyl with 11 and / or 13 carbon atoms or alkenyl with 17 carbon atoms, m, n and p are each identical or different and denote numbers from 0 to 50, the sum of the variables m, n and p is a number 24 to 26, preferably 25, and the compounds of the formula (I) contain 2.5 radicals -CO-Rs on a molar average. Automatic dishwashing detergent containing one or more compounds of the formula (I) according to one or more of Claims 16 to 27. Automatic dishwashing agent according to Claim 28, characterized in that it contains at least one enzyme in addition to the one or more compounds of the formula (I). Machine dishwashing detergent according to at least one of claims 28 to 29, characterized in that it contains one or more rinse aid surfactants, in particular EO-PO block copolymers or alkoxylated fatty alcohols and very particularly preferably alkoxylated C ₁₂ -C ₁₅ fatty alcohols containing ethoxy groups and / or are alkoxylated with propoxy groups. Machine dishwashing detergent according to at least one of Claims 28 to 30, characterized in that it contains one or more ethoxylated glycerol esters of the formula (II)

wherein R ₆ , R ₇ and R _{8 are} each identical or different and are C ₇ -C ₂₄ -alkyl or C ₇ -C ₂₄ -alkenyl, q, r and s are each identical or different and are numbers from 1 to 200, preferably from 1 to 80, and very particularly preferably from 2 to 70, with the proviso that the sum q + r + s denotes a number greater than 5, preferably from 20 to 70 and very particularly preferably from 30 to 60. Machine dishwashing detergent according to Claim 31, characterized in that the ethoxylated glycerol esters of the formula (II) have been prepared by reacting triglycerides of the formula (III) with ethylene oxide in the presence of a catalyst

wherein
R ₆ , R ₇ and R _{8 are} each identical or different and have the meaning defined in claim 31, and in which the catalyst is a compound which is obtained by reacting calcium hydroxide with a carboxylic acid containing 3 to 40 carbon atoms, the molar ratio being from calcium hydroxide to carboxylic acid is from 1: 1 to 1: 3. Machine dishwashing detergent according to at least one of Claims 28 to 32, characterized in that it contains one or more polymers. Machine dishwashing detergent according to at least one of Claims 28 to 33, characterized in that it is in the form of a powder, a tab, a pod, a gel or as a liquid rinse aid. Machine dishwashing detergent according to at least one of Claims 28 to 34, characterized in that it is packaged in a water-soluble film. Use of one or more compounds of the formula (I) according to at least one of claims 16 to 27, preferably in the form of an automatic dishwashing agent according to at least one of claims 28 to 35, in automatic dishwashing for drying dishes and / or for cleaning sieve residues, in particular for drying dishes while avoiding or reducing residues in the dishwasher sieve. Use according to Claim 36, characterized in that the residues result from cleaning the dishes, particularly preferably from cleaning the dishes from greasy soiling.