DE1963864A1 - Foam-reducing additives for dishwashing detergents - Google Patents

Description

PATENT LAWYERS DR.-ING. BY KREISLER DR.-ING. SCHONWALD DR.-ING. TH. MEYER DR. FUES D1PL.-CHEM. ALEK VON KREISLER DIPL-CHEM. CAROLA KELLER DR.-ING. KLOPSCH KDLN 1, DEICHMANNHAUS

Cologne, I2.I2.I969 Ke / Ax

Maries-Kuhlmann-Wyandotte,

25, Boulevard de l'Amiral Brulx, Paris l6 (France)

Foam-reducing additives for dishwashing detergents

It is known, as detergents for dishwashers, alkaline detergents and mixtures of alkaline detergents condensed phosphates and alkaline detergents which may contain chlorinated disodium phosphate. For example, see the U.S. Patent 2 689 225 referenced. It is also known that these cleaning agents optionally, but advantageously with suitable Surfactants can be prepared as described in U.S. Patent 2,895,916. Aqueous solutions of the detergents mentioned above have good washing power and remove ugly stains from plastic and ceramic dishes and can be easily rinsed off glasses, dishes and silverware without leaving unwanted items Leaving films, streaks and stains on it. Although these detergents have many beneficial features, however, they have the undesirable property of foaming in the presence of leftover raw eggs. Since the foaming the Effectiveness of the dishwasher by inhibiting the mechanical action of the fine water jets and through Reducing the speed of rotation of the perforated spray arms in certain automatic washers would be it is advantageous if a detergent for dishes

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Dishwashers would not be available in the presence of leftover raw eggs or other proteinaceous materials excessively foams.

According to U.S. Patent 3,514,891, the foam properties are an aqueous solution of a detergent for

1 *

Dishwashers containing alkaline detergents are essential in the presence of proteinaceous food residues less if this detergent is made up as a mixture containing a non-ionic surface-active substance and at least one alkyl phosphate ester with 18 carbon atoms in the alkyl radical, especially an acidic stearyl phosphate or a contains acid oleyl phosphate.

Alkyl phosphates with 18 carbon atoms in the alkyl radical are very effective, but in the nonionic surface-active agent insoluble and poorly dispersible and lead to segregation during storage, which causes problems in the subsequent handling and compounding.

The invention accordingly relates to compounds which, when added to detergents for dishwashers, the Foam formation during their use in the presence of proteinaceous substances and reduce the problems of

Insolubility of alkyl phosphates with 18 carbon atoms in the alkyl radical eliminate or significantly reduce.

According to the invention it has been found that oxyethylated; Fatty amines, namely polyoxyethylene condensates of higher ι Fatty acid amines with about 10 to 20 carbon atoms in the fatty alkyl radical and 1 to about 15 ethenoxy units in the oxyethylene part are effective dispersants for alkyl phosphates with 18 carbon atoms in the alkyl radical. The oxyethylated fatty acid amines are determined by the following structural formulas

009840/2072 owgwal inspected

indicates:

A. CH ₂ -CH ₂ O) _x H R ₂ H (CH ₂ -CH ₂ O) _x H "

(D

Here, R is a fatty alkyl radical with about 10 Ms 20 carbon atoms and χ in formula (1) and χ + y in formula (2) are a number from about 1 to 15.

To ensure complete dispersion of the alkyl phosphate ester achieve, it is essential that the weight ratio of the alkyl phosphate to the oxyethylated fatty acid amine is approximately 2: 1 "to 1: 2. Outside of this range will be no satisfactory dispersion obtained.

The nonionic surface-active substances which are advantageously used in the rinsing agents according to the invention are generally polyoxyalkylene adducts of hydrophobic bases in which the oxygen / carbon Atomic ratio in the oxyalkylene part of the molecule is above 0.40. Among the compounds made with hydrophobic "bases condensed to form a polyoxyalkylene moiety in which the oxygen / carbon atomic ratio is above 0.40 includes ethylene oxide, butadiene dioxide and glycide, mixtures of these alkylene oxides with one another and with small amounts of propylene oxide, butylene oxide, amylene oxide, styrene oxide and other alkylene oxides of higher molecular weight. Ethylene oxide, for example, is condensed with the hydrophobic base in an amount sufficient to to impart dispersibility or solubility in water and surface activity to the molecule to be formed. the the exact amount of ethylene oxide that is condensed with the hydrophobic base depends on the chemical properties of the base used and can be explained by a person skilled in the art

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easily identify this area.

Typical hydrophobic bases that can be condensed with ethylene oxide to form nonionic surfactants Preparing agents are, for example, mono- and polyalkylphenols, Polyoxypropylene condensed with a base, which contains 1 to 6 carbon atoms and at least one reactive hydrogen atom, fatty acids, fatty acid amides and Fatty alcohols. The hydrocarbon ethers, e.g. benzyl ethers or lower alkyl ethers of the surface-active polyoxyethylene condensates are also advantageous in the mixtures used according to the invention.

To the suitable non-ionic surface-active substances include the polyoxyethylene condensates of alkylphenols with about 6 to 20 carbon atoms in the alkyl part and about 5 to 30 ethenoxy groups in the polyoxyethylene radical. as Alkyl substituents on the aromatic ring are octyl, diamyl, n-dodecyl, polymerized propylene, e.g. Propylene tetramers and trimers, isooctyl and nonyl in Embossing. The benzyl ethers of the polyoxyethylene condensates of Monoalkylphenols give the mixtures' according to the Invention good properties. A typical product has the following formula

. ^υ 3 ^η 17 £ \ - (OCH ₂ CHg) ₁
Higher ethoxylated polyalkylphenols of the formula

in which R is a hydrogen atom or an alkyl radical with about

1 2
1 to 12 carbon atoms, R and R alkyl radicals with about

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BATH ORIGINAL

6 to 16 carbon atoms and η has a value of about 10 to 40, are also considered to be nonionic surface-active Medium suitable. A typical oxyethylated polyalkylphenol is the dinonylphenol condensed with 14 moles of ethylene oxide.

Also suitable as nonionic surface-active agents are "cogeneric" mixtures of conjugated ones Polyoxyalkylene compounds which have at least one hydrophobic oxyalkylene chain in their structure in which the oxygen / Carbon atomic ratio does not exceed 0.40, and at least one hydrophilic oxyalkylene chain in which the oxygen / carbon atomic ratio is above 0.40, contain.

Polymers of oxyalkylene residues obtained from propylene oxide, Butylene oxide, amylene oxide or styrene oxide, mixtures of these oxyalkylene groups with one another and with small amounts of Polyalkylene groups obtained from ethylene oxide, butadiene dioxide and glycide are examples of hydrophobic oxyalkylene chains with an oxygen / carbon atomic ratio of not more than 0.40. Polymers of oxyalkylene groups obtained from ethylene oxide, butadiene dioxide and glycide, mixtures these oxyalkylene groups with each other and with small amounts of oxyalkylene groups, obtained from propylene oxide, Butylene oxide, amylene oxide and styrene oxide are examples of hydrophilic oxyalkylene chains with an oxygen / carbon atom ratio greater than 0.40.

The conjugated polyoxyalkylene compounds that can be used in the mixtures according to the invention, include compounds of formula

in which Y is the remainder of an organic compound with about 1 to 6 carbon atoms and a reactive hydrogen

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atom, η has an average value of at least about 6.4 is determined by the hydroxyl number and m has a value such that the Oxyäthylenteil about 10 to 90 wt -. ° / o of the molecule constitutes "These surfactants are described in detail in US ₀ described A. Patent 2,677,700.

Further conjugated polyoxyalkylenes which are extremely advantageous as surface-active agents in the mixtures according to of the invention are the compounds of formula

in which Y is the remainder of an organic compound with about 2 to 6 carbon atoms and χ reactive hydrogen atoms where χ has a value of at least about 2, η one such that the molecular weight of the polyoxypropylene used as the hydrophobic base is at least about Is 900, and m has a value such that the molecule contains about 10 to 90% by weight of oxyethylene. Links, which fall under the definition of Y are, for example, propylene glycol, glycerol, pentaerythritol, tyimethylolpropane and ethylene diamine. As already mentioned, the oxypropylene chains optionally, but advantageously contain small amounts Amounts of ethylene oxide. The oxyethylene chains also contain optionally, but advantageously small amounts of alkylene oxides, e.g. propylene oxide and butylene oxide. These compounds are more fully described in the U.S. Patent 2,674,619.

In the mixtures according to the invention, conjugated polyoxyalkylenes can also be used as surface-active agents the formula

can be used advantageously. Here, P is the remainder of an organic compound with about 8 to 18 carbon atoms and χ

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reactive hydrogen atoms, where χ stands for 1 or 2 η is such that the molecular weight of the polyoxypropylene portion is at least about 58, and m has such a value that the oxyethylene content of the molecule is about 10 Ms 90% by weight. Are suitable also conjugated polyoxyalkylenes of the formula

in which P is the remainder of an organic compound with about 8 to 18 carbon atoms and χ reactive hydrogen atoms is, where χ stands for 1 or 2, η has such a value, that the molecular weight of the polyoxyethylene moiety is at least about 44, and m has a value such that the oxypropylene content of the molecule is about 10 to 90 percent by weight amounts to. In both cases, the oxypropylene chains can optionally, but advantageously, small amounts of ethylene oxide contain. Likewise, the oxyethylene chains can optionally but advantageously small amounts of alkylene oxides, e.g. propylene oxide, butylene oxide and higher alkylene oxides 8 to 18 carbon atoms in the alkyl chains.

Suitable nonionic surface-active agents are thus cogenic mixtures of conjugated polyoxyalkylene compounds, which in their structure the remainder of an active hydrogen-containing compound, at least one hydrophobic chain of oxypropylene units or oxypropylene-oxyethylene units, wherein the oxygen / carbon atomic ratio is not more than 0.40, and at least a hydrophilic chain of oxyethylene units or oxyethylene-oxypropylene units, in which the oxygen / Carbon atomic ratio is above 0.40.

Further suitable nonionic surface-active agents are the polyoxyethylene esters of higher fatty acids with about 8 to 22 carbon atoms in the acyl radical and about 8 to 30 Ethenoxy units in the oxyethylene part. Typical products are for example the polyoxyethylene adducts of tall oil,

009840/2072 ^ _{0 0} W0.nau

- ο -

Resin acids, lauric acid, stearic acid and oleic acid. Suitable nonionic surfactants are also the condensates of polyoxyethylene with higher fatty acid amides, which contain about 8 to 22 carbon atoms in the fatty acid alkyl radical or-acyl radical and about 10 to 30 ethenoxy units in the oxyethylene part contain »examples of such Products are the coconut oil fatty acid amides condensed with about 10 to 30 mol of ethylene oxide.

Other polyoxyalkylenes that prove to be nonionic surface-active Suitable agents are the alkylene oxide adducts of higher aliphatic alcohols and thioalcohols with about 8 to 22 carbon atoms in the aliphatic part and about 3 to 50 oxyalkylene units in the oxyalkylene part »Typical Products are synthetic fatty alcohols condensed with 3 to 50 moles of ethylene oxide, e.g. n-decyl alcohol, n-undecyl alcohol, n-dodecyl alcohol, n-tridecyl alcohol, n-tetradecyl alcohol, n-hexadecyl alcohol, n-octadecyl alcohol and mixtures of these alcohols, mixtures of normal fatty alcohols which condense with 8 to 20 moles of ethylene oxide and are end-blocked with a benzyl halide or an alkyl halide, mixtures of normal fatty alcohols, which are condensed with 10 to 30 mol of a mixture of ethylene and propylene oxide, mixtures of several fatty alcohols, one after the other with 2 to 20 moles of ethylene oxide and 3 to 10 moles of propylene oxide in any order have been condensed, mixtures of normal fatty alcohols with a mixture of propylene and ethylene oxide, in which the oxygen / carbon atomic ratio is below 0.40, and then with a mixture of Propylene and ethylene oxide, in which the oxygen / carbon atomic ratio is above 0.40, have been condensed, or condensed with 3 to 30 moles of ethylene oxide linear secondary alcohols, linear secondary alcohols condensed with a mixture of propylene and ethylene oxide and with a mixture of ethylene, propylene and

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higher alkylene oxides condensed linear secondary Alcohols.

Preferred alkyl phosphates for the mixtures according to the invention are predominantly made from monostearyl phosphate "existing phosphates, which also include di- and iristearyl phosphates may contain, and monooleyl phosphates, which may also contain di- and trioleyl phosphates.

The commercially available alkyl phosphates are generally mixtures of mono- and dialkyl phosphates, the may also contain some trialkyl phosphate. For the purposes of the invention, preferred are alkyl phosphates that in addition to the monoalkyl phosphate, up to about 50 moles Dialkyl phosphate and up to about 5 wt .- ^ of the trialkyl phosphate may contain. In a preferred embodiment of the invention, there is the acidic stearyl phosphate component at least 50 moles from the monostearyl phosphate.

Of course, the salts, in particular the alkali metal salts, of the alkyl phosphates can also be used. Include accordingly the expressions "acidic stearyl phosphate" and "acidic oleyl phosphate" used here also refer to the salts the acidic stearyl and oleyl phosphates.

The mixtures according to the invention generally contain from about 95 to 99 »5 wt .- ^ of the nonionic surfactant and a total of about 0.5 to 5.0 wt -. ^C / o alkyl phosphate plus oxyäthyliertes Pettsäureamin. As already mentioned, the ratio of the alkyl phosphate to the oxyethylated fatty acid amine must be about 2: 1 to 1: 2. The mixtures can be easily prepared by mixing the constituents in the proportions mentioned above. The mixture is then added to the dishwashing detergent to reduce foaming in the dishwasher.

009840/2072 bad original

The dishwashing detergents for automatic dishwashers to which the appliances according to the invention are added to the To reduce foaming of aqueous solutions of dishwashing detergents in the presence of leftover raw eggs, generally contain 0 "to 95 weight percent of a condensed alkaline phosphate salt, e.g. tetrasodium pyrophosphate, and polyphosphates complexing such calcium and magnesium ions, their NapO / PpOc ratio ranges from 1: 1 to 1.67: 1 and 5 Ms 100% by weight an alkaline detergent salt such as sodium carbonate, sodium bicarbonate and their mixtures, di- and trisodium orthophosphate, Sodium metasilicate, sodium sesquisilicate, borax, and sodium borate. They also contain detergents often 5 to 25 wt .- ^ chlorinated trisodium phosphate. Instead of chlorinated trisodium phosphate, a mixture of lithium hypochlorite or chlorinated Cyanuric acid and trisodium phosphate can be used. A dishwashing detergent of this type can be made by nian among those disclosed in U.S. Patent 2,895 Conditions described are an aqueous silicate solution to the practically anhydrous sodium tripolyphosphate and then adding chlorinated trinatriurophosphate.

The foam properties of the detergents can be measured · by measuring the speed of rotation of the perforated Spray arms of an automatic dishwasher during a washing process with the remains of raw eggs and the detergent are present in certain quantities, is determined. The rotation speed of the spray arm is natural inversely proportional to the amount of foam present. In the experiments described in the following examples the amount of foam is determined in a Hobart dishwasher "KITCHEN AID". The applied The method is to turn on the machine and turn it off after adding some of the water and then the detergent and possibly the

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Additives and 15 ml of raw egg added. The dishwasher is then switched on again and the rest of the water is added. The water temperature is in the Examples given. After starting the rinsing process a the rotation speed of the perforated spray arm from the first to the second minute and then from the third determined up to the fourth minute. The average of these two speeds is taken as the turning speed of the spray arm for the experiment. A rotation speed of the spray arm of about 70 rpm or more indicates that the foam formation is substantially suppressed.

The invention is further illustrated in the following examples. The acidic stearyl phosphate used here contains 78% by weight of acid monostearyl phosphate, 17% by weight acid distearyl phosphate, remainder acid tristearyl phosphate, phosphoric acid and impurities.

example 1

In a beaker are given 1.5 parts by weight of an acidic stearyl phosphate mixture together with 100 parts by weight of a primary oxyalkylated alcohol (hereinafter referred to as nonionic 1), which is a condensate of a mixture of 25 parts by weight of ethylene oxide and 50 parts by weight. Parts of propylene oxide with 25 parts by weight of a mixture of normal fatty alcohols with 12 to 18 carbon atoms. The beaker is then held for 1 hour at 10O ⁰ C in an oven, is completely melted whereby the acid Stearylphosphatgemisch. After addition of 1.5 parts by weight of oxyethylated fatty acid amine, the beaker is maintained for a further hour in an oven at 100 ⁰ C with constant shaking of the container. The oxyethylated fatty acid amine, hereinafter referred to as oxyethylated fatty acid amine No. 3, has the following formula:

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6AD ORIGINAL

-O

N (CH ₉ -CH ₉ -O -) - H.

When part of the dispersed product is poured into a small jar and six freeze-thaw cycles of each Subjected to 60 minutes duration, "the product remains fully dispersed.

Dispersions containing 1.5 to 3% by weight of the stearyl acid phosphate and contain no oxyethylated fatty acid amine, separate after six freeze-thaw cycles of each 60 minutes duration.

To 0.6 g of the product described above, which contains both the acidic stearyl phosphate and the oxyethylated Fatty acid amine contains 16 g of a detergent, hereinafter referred to as "detergent A "and contains the following components!

Detergent A Gew «- $

Tetrasodium pyrophosphate 4-4

Sodium tripolyphosphate 19

Sodium Metasilicate Hydrate 12

Chlorinated trisodium phosphate 25

The detergent of the above composition is based on the foam properties in the presence of residual raw egg evaluated in a Hobart dishwasher in the manner described above. The received Results are given in Table I below. The specified speed is the average of the rotational speeds the spray arms during the second and fourth minutes of a rinsing process.

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Table I. Medium speed, rpm

49 ⁰ G 74

6O ⁰ C 88

71 ⁰ C 91

The results in Table I show that the equipment according to the invention when added to a conventional dishwashing detergent had a good suds suppressing effect in the presence of scraps of raw egg. In all cases lay the mean speed above 70 rpm, i.e. the mixture cut when compared with the results given in the Examples of U.3.A. patent 3 314 891 are given, cheap from. As "however, the stability tests show the mixture containing the oxyethylated fatty acid amine has a high stability in nonionic surface-active substances Agents, while the mixture, which is otherwise the same but does not contain the oxyethylated amine, does not is stable.

Examples 2 to 18

Further foam-inhibiting mixtures according to the invention are made from the non-ionic substances mentioned in Table II below surfactants, acid stearyl phosphate and the oxyethylated fatty acid amines mentioned in Table II in the proportions given in Table II (in wt. ~ $). 0.6 g each of the foam-inhibiting mixtures of Examples 2 to 18 are used with 16 g of the basic cleaning agent referred to in Example 1 as "cleaning agent A" mixed. These detergents are all put in a Hobart "KITCHEN AID" dishwasher on the above described way checked. The results as the average number of revolutions during the first and third minutes Bind named in Table II below.

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The following in Table II with the numbers 1 "to 3 designated non-ionic surfactants ■ are used:

Nonionic 1 is described in Example 1 above.

Nonionio 2 is a "heteric" conjugated polyoxyalkylene polyol, which is prepared as follows: A mixture of 90 wt .- ^ propylene oxide and 10 wt .- ^ ethylene oxide is condensed with trimethylolpropane in such a way that a hydrophobic base is formed which has a molecular weight of about 3200 has. A mixture of 90 wt .- $ ethylene oxide and 10 wt .- $ propylene oxide is then condensed with the hydrophobic base so that a hydrophilic part, which has a molecular weight of about 1280 is formed.

Nonionic 3 is the polyoxyethylene adduct of a hydrophobic one Polyoxypropylene base having a molecular weight of about 1750 and an oxyethylene content of about 20% by weight des Molecule. The oxyethylated synthetic fatty acid amines denoted by the numbers 1 to 3 have the following composition:

The fatty acid amine # 1 has the general formula

0 _% y (CH ₂ -OH ₂ -O-) ₅ H OH ₃ (GHg) ₁₀ C ^ 0- N <^

(CH ₂ -CH ₂ -O-) ₅ H

The fatty acid amine # 2 is a tertiary amine "with a fatty acid alkyl radical derived from tallow and two polyoxyethylene groups bonded to nitrogen. It has general formula

(CH ₂ -CH ₂ O) _x H.
(CH ₂ CH ₂ 0) _y H

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in which R is the residue derived from tallow and the sum of χ + y = 5.

Fatty acid amine # 3 is above in connection with Example 1 has been described. Excellent results are also obtained here, especially when used of amine no.2, in whose formula R represents the lauryl radical.

Table II

at
game
No. Nonionic
No. $> 97 Oxyethylated acid
Fatty acid amine stearyl
No * $> phosphate 1.5 1.5 Mid-
Turn
number
Rpm water
tempe
rature,
⁰ C 2 1 97 1 1.5 1.5 88 38 3 1 97 ' 2 1.5 1.5 91 60 4th 1 97 2 1.5 1.5 90 49 VJI 1 97 2 1.5 1.5 - 90 71 6th 1 97 3 1.5 1.5 87 71 7th 1 97 3 1.5 1.5 91 60 8th 1 97 3 1.5 1.5 87 49 9 1 97 3 1.5 1.5 79 38 10 2 97 3 1.5 1.5 74 49 11th 2 97 3 1.5 1.5 88 60 12th 2 96 3 2.0 2.0 91 71 13th 1 98 3 1.0 1.0 87 60 14th 2 98 · 3 1.0 1.0 86 60 15th 3 97 3 1.5 1.5 81 60 16 3 96 3 2.0 2.0 84 60 17th 3 98 3 1.0 1.0 86 60 18th 1 3 75 38

All cleaning agents listed in Table II are stable, i.e. there is no segregation when left to stand.

As already mentioned, the mixtures according to the invention can be used with all commercially available dishwashing detergents will. Examples of such dishwashing detergents are

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hereinafter referred to as:

Detergent B

Sodium tripolyphosphate trisodium phosphate decahydrate Sodium Metasilicate Anhydrous Sodium Sulphate Sodium chloride

Cleaning agent G

Sodium tripolyphosphate Sodium carbonate Anhydrous sodium metasilicate

Cleaning agent D

Trisodium phosphate sodium tetraborate pentahydrate Sodium Metasilicate Anhydrous Sodium Carbonate

Cleaning agent E.

Trisodium phosphate Chlorinated trisodium phosphate Sodium tetraborate pentahydrate Sodium Metasilicate Anhydrous Sodium Carbonate

Parts by weight 41.80 11.30 14.70

0.51

0.12

60 20 20

20 25 20 35

20 5 25 20 30

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Claims (7)

Sponsorship claims 1.) Containing additives to detergents for dishwashers which reduce foam formation A) from about 95 to 99 * 5% wt. Of a nonionic surfactant and B) about 0.5 to 5 weight percent of one a) alkyl phosphate with 18 carbon atoms in the alkyl radical and b) oxyethylated fatty acid amine with about 10 to 20 carbon atoms in the fatty acid alkyl radical and 1 to about 15 Ethenoxy units in the oxyethylene radical, wherein the weight ratio of the alkyl phosphate to the oxyethylated Fatty acid amine is about 2: 1 to 1: 2. 2.) additives according to claim 1, characterized in that the alkyl phosphate component consists essentially of up to about 50 mol. <£ dialkyl phosphate, about 5 wt. % Trlalkylphosphat and the remainder monoalkylphosphate. J.) additives according to claim 1 or 2, characterized in that that the nonionic surfactant from polyoxyalkylene adducts hydrophobic bases having an oxygen / carbon atom ratio in the oxyalkylene part of more is 0.40 and the alkyl phosphate is stearyl or oleyl acid phosphate. 4.) additives according to claim 1 to 3, characterized in, that it is used as a non-ionogenic surfactant a) Polyoxyethylene condensates of alkylphenols with about 6 to 20 carbon atoms in the alkyl part or the benzyl ethers these polyoxyethylene condensates of alkylphenols, b) cogenic mixtures of conjugated polyoxyalkylene compounds, the structure of which is the remainder of a active hydrogen containing compound and at least one hydrophobic chain of oxypropylene and 009840/2072 Oxypropylene-oxyethylene units with an oxygen / carbon atom ratio of not more than 0.40 and at least one hydrophilic chain of oxyethylene and oxyethylene-oxypropylene units with an oxygen / carbon atom ratio of more than 0.40 ^! c) Polyoxyethylene esters of higher fatty acids with about 8 to 22 carbon atoms in the acyl radical, d) Polyoxyethylene condensates of higher fatty acid amides with about 8 to 22 carbon atoms in the fatty acid acyl radical or e) alkylene oxide adducts of higher aliphatic alcohols or Thioalcohols with about 8 to 22 carbon atoms in the aliphatic part contain. 5 ·) additives according to claim 4, characterized in that they as oxyethylated fatty acid amines, compounds of the formulas (CH ₂ -CH ₂ O) _x H R ₂ N (CH ₂ -CH ₂ O) _x H RN contain, in which R is a fatty acid alkyl radical with about 10 to 20 carbon atoms and χ in formula 1 and χ + y in formula 2 are values between approximately 1 and 15. 6.) Use of the additives according to claim 1 to 5 in amounts of about 0.1 to 20 wt.% In an in the presence of protein substances low-foaming detergents for automatic dishwashers, further 80 to 99 * 9% wt. Of a mixture of 5 Contains up to 100 % of an alkaline detergent salt and 0 to 95% by weight of an alkaline condensed phosphate salt. 009840/2072 7.) Use of additives according to claim 1 to 5 according to claim 6 in detergents containing sodium carbonate, sodium bicarbonate, di- or trisodium orthophosphate as the alkaline detergent salt, Sodium metasilicate, sodium sesquisilicate, water glass, borax, sodium borate or mixtures thereof and as the alkaline condensed phosphate salt, tetrasodium pyrophosphate or such polyphosphates of contain complexing calcium or magnesium ions, their Na ^ / P ^ O ^ ratio in the range between 1: 1 and 1.6γ.: 1. 009840/2072