US3382176A - Low-foaming washing and cleansing agents - Google Patents

Description

United States Patent 10 Claims. ci. 2s2 s9 ABSTRACT OF THE DISCLOSURE Low foaming, washing and cleansing compositions particularly for use in mechanical dish washers consisting essentially of a mixture of three types of polyoxyalkylene compounds which are: (A) ethylene oxide adducts of high molecular weight lipophilic radicals which adducts may additionally contain oxypropylene and oxyb-utylene radicals (B) compounds of the formula AX wherein A represents high molecular weight lipophilic compounds adducted with ethylene oxide and which may also contain oxypropylene and oxybutylene units and X is a bivalent linkage selected from acetals and ketals and (C) high molecular weight lipophilic radicals containing oxypropylene and/or oxybutylene radicals which may contain oxyethylene units.

This application is a continuation-in-part of our copending United States patent application Ser. No. 423,585, filed Ian. 5, 1965, now abandoned.

In an increasing measure, mechanical washing methods are being employed to wash china, glass, porcelain, ceramic, metal and synthetic articles. Detergents containing specific surface-active compounds are generally utilized. These detergents should be low foaming, so that they do not affect the function of the washing apparatus. A foam formation of too large a volume, caused and increased by -the vigorous motion of the bath in the machine, leads to considerable trouble, as the foam mass decreases the mechanical effect of the liquid sprayed onto the articles to be cleaned and furthermore may cause the bath in the machine to run over.

Recently, developments in washing apparatus have been directed toward further increasing the intensity of the liquor motion as well as the water volume cycled per minute, and in this way to further improve the mechanical cleansing efiect. As a result of such developments, it was found that conventional washing agents,

such as alkylene oxide adducts were no longer satisfactory under these turbulent washing conditions. Instead, due to voluminous foam formation, the conventional washing agents gave rise to the disadvantages mentioned previously.

It is an object of this invention to provide novel compositions of washing and cleansing agents having lowfoaming properties.

Another object of this invention is to provide novel compositions of washing and cleansing agents that exhibit low-foaming properties in high speed mechanical washers.

A further object of the invention is to provide a composition of washing and cleansing agents having lowfoaming properties comprising:

3,382,176 Patented May 7, 1968 ice (A) from 5% to 79.5% by weight of compounds based onethylene oxide adducts selected from the group consisting of (1) high molecular weight lipophilic radicals having a replaceable hydrogen atom adducted with more than 50 mol percent to 100 mol percent of oxyethylene units and the remainder of oxyalkylene units selected from the group consisting of oxypropylene and oxybutylene, (2) an ethylene oxide adduct containing from 35 to 85 mol percent of oxyethylene units adducted to a polypropylene oxide polymer having an average molecular weight in the range of 1,000 to 4,000, and (3) an ethylene oxide adduct containing from 35 to 85 mol percent of oxyethylene units adducted to a propylene oxide adduct of a polyfunctional compound having from 2 to 6 carbon atoms and at least two replaceable hydrogen atoms, said propylene oxide adduct having an average molecular weight in the range of 1,000 to 4,000;

(B) from 0.5% to by weight of dimeric compounds based on ethylene oxide adducts of the formula wherein A represents a high molecular weight lipophilic radical having a replaceable hydrogen atom adducted with more than 50 mol percent to 100 mol percent of oxyethylene units and the remainder of oxyalkylene units selected from the group consisting of oxypropylene and oxybutylene and having a terminal alkylene group derived from an oxyalkylene unit, and X represents a bivalent linkage selected from the group consisting of acetals and ketals; and

(C) from 20% to 94.5% by weight of compounds based on alkylene oxide adducts selected from the group consisting of (1) high molecular weight lipophilic radicals having a replaceable hydrogen atom adducted with more than 50 mol percent to 100 mol percent of oxyalkylene units selected from the group consisting of oxypropylene and oxybutylene and the remainder of oxyethylene units, (2) polypropylene oxide polymers having an average molecular weight in the range of 1000 to 5000 adducted with from 0 to 30 mol percent of oxyethylene units, and (3) propylene oxide adducts of a polyfunctional compound having from 2 to 6 carbon atoms and at least two replaceable hydrogen atoms, said propylene oxide adducts having an average molecular weight in the range of 1000 to 5000 and adducted with 0 to 30 mol percent of oxyethylene units.

These and other objects and advantages will become evident as the description proceeds.

Accordingly, the present invention relates to extraordinarily low-foaming washing :and cleansing agents, having particular utility for the cleansing of dishes in mechanical dishwashers. They are characterized by a mixture comprising the following individual constituents:

(A)(l) compounds containing both polyoxyalkylene radicals and higher molecular weight aliphatic or aliphatic-aromatic radicals, the polyoxyalkylene radicals of said compounds consisting of more than 50 mol percent of oxyethylene units, and a lesser molecular portion consisting of oxypropylene and/or oxybutylene units; and/or (2) ethylene oxide adducts containing 35 to mol percent of oxyethylene units adducted to a propylene oxide polymer with a molecular weight of 1000 to 4000, and preferably 17-00 to 3250.

(B) compounds of the general structural principle 3 wherein A and A signify the radical, of a polyoxyalkylene compound according to A(l) wherein said compound contains both polyoxyalkylene radicals and higher molecular weight aliphatic or aliphatic-aromatic radicals, the polyoxyalkylene radicals of said compounds consisting of more than 50 mol percent of oxyethylene units, and a lesser molecular portion consisting of oxypropyleneand/or oxybutylene units, reduced at its end to a hydroxyl group and wherein R represents hydrogen or a hydrocarbon and R represents a hydrocarbon, particularly the acetals or ketals of compound A(l).

(C)(1) compounds containing polyoxyalkylene radicals and higher molecular aliphatic or aliphatic-aromatic radicals, the polyoxyalkylene units of said compounds consisting of more than 50 mol percent of oxypropyleneand/or oxybutylene units and a lesser molecular portion consisting of oxyethylene units; and/or acetals or ketals of these compounds; and/or (2) propylene oxide polymers with a total molecular weight of 1000 to 5000, preferably 1700 to 4100, to which up to 30 mol percent of ethylene oxide may be adducted.

The mixtures possess a remarkable cleansing, degreasing and draining effectiveness and due to their low-foam volume, are particularly suitable for mechanical washing and cleaning methods.

The components A, B and C used for the preparation of the mixtures are known or are obtainable according to well known processes.

The preparation of the compounds A may be accomplished by an addition of alkylene oxides to those higher molecular weight aliphatic or aliphatic-aromatic compounds, which contain reactive hydrogen atoms, bonded through the hcteroatoms O, S or N. The aliphatic compounds possess higher molecular weight radicals with 8 to 36, and preferably 10 to 20 carbon atoms and are preferably of the formula wherein R represents a radical having from 8 to 36 carbon atoms selected from the group consisting of alkyl, alkenyl, alkadieuyl and hydroxy-alkenyl, H represents a replaceable hydrogen and Y represents a bridging link selected from the group consisting of The aliphatic-aromatic compounds possess higher molecular weight radicals with 12 to 22, and preferably 14 to 18 carbon atoms and are preferably of the formula wherein Y and H have the above assigned values and R represents a radical having 12 to 22 carbon atoms selected from the group consisting of alkylphenyl, alkylnapthyl, alkoxyphenyl and alkylcyclohexyl. The hydrocarbon radicals R and R may contain conventional substituents such as hydroxyl groups, halide atoms, or alkyl side chains.

The alkylene oxides to be added consist of more than 50 mol percent of ethylene oxide, while a lesser molecular portion may consist of propylene oxide and/ or butylene oxide. When various alkylene oxides are used, as a rule ethylene oxide is added in the first step and thereafter propylene oxide and/or butylene oxide is then added. The reaction is accomplished in the usual manner, for example, by utilizing pressure in the presence of alkaline catalysts.

Compound A may also be prepared by reacting higher molecular weight aliphatic or aliphatic-aromatic compounds with compounds containing prepared polyoxyalkylene chains, for example, the esterification of higher molecular weight carboxylic acids with polyethylene glycols or the etherification of higher molecular weight alcohols with polyethylene glycols.

As starting compounds for the preparation of the above compound A, the following may be utilized: higher A molecular weight aliphatic alcohols, carboxylic acids, mercaptans, amines, carboxylic acid amides or carboxylic acid alkanolamides, sulfonic acid amides and the like, as well as alkylphenols. The polyoxyalkylene derivatives obtained from these compounds contain 4 to 60, and preferably 10 to 40 oxyethylene units. Insofar as propylene oxide and/or butylene oxide are added, the molar ratio of ethylene oxide to propylene or butylene oxide is advantageously from 120.03 to 1:0.3.

Examples for compound A are: the adduct of 15 mols of ethylene oxide with dodecyl alchohol; the adduct of 20 mols of ethylene oxide with a fatty alcohol mixture of the chain length C C the adduct of 35 mols of ethylene oxide with stearyl alcohol; the adduct of 15 mols of ethylene oxide with oleyl alcohol; the adduct of 37 mols of ethylene oxide with a dodecyl alcohol dimerized according to the Guerbet method; the adduct of 25 mols of ethylene oxide with isotridecyl alchohol; the adduct of 30 mols of ethylene oxide with nonylphenol; the adduct of 10 mols ethylene oxide with a coconut oil fatty acid amide mixture of the chain length C -C the esterification product of 1 mol of a polyethylene glycol (molecular weight 2200) with 2 mols of a fatty acid mixture of the chain length C -C a fatty amine mixture of the chain length C -C reacted with 15 mols of ethylene oxide; the adduct of 21 mols of ethylene oxide and 5 mols of propylene oxide with nonylphenol; the adduct of 40 mols of ethylene oxide with an alcohol mixture obtained by the reduction of dimerized fatty acids of the chain length C the addition product of 20 mols of ethylene oxide and 7 mols of propylene oxide with oleyl alcohol; the adduct of 30 mols ethylene oxide and 2 mols butylene oxide with a fatty alcohol mixture of the chain length (E -C the adduct of 20 mols ethylene oxide with dodecylmercaptan. Of special interest are the alkylene oxide adducts with higher molecular Weight fatty alcohols or alkylphenols.

The above compound A may be substituted either entirely or partly by an ethylene oxide adduct, containing 35 to mol percent of oxyethylene radicals, adducted to a propylene oxide polymer having a molecular weight of 1000 to 4000, preferably 1700 to 3250. The propylene oxide polymers having a molecular weight of 1000 to 4000 contain from 17 to 69 oxypropylene units in the molecule.

The ethylene oxide adducts to propylene oxide polymers, to be used in compound A are well known compounds. For example, they can be obtained by polymerization of propylene oxide in the presence of alkaline catalysts, such as sodium hydroxide, sodium methylate and others, to give a polypropylene glycol and subsequently adducted under the same conditions with 35 to 85 mol percent of ethylene oxide based on the total number of the alkylene oxide radicals in the molecule. The preparation of the propylene oxide polymers may be carried out also by addition of propylene oxide to lower molecular weight aliphatic or aromatic compounds having 2 to 6 carbon atoms containing hydroxyl and/or amino groups and at least 2 reactive hydrogen atoms. Examples of such compounds are glycol, glycerin, sugar alcohols, ethylene diamine, phenylene diamine, alkanolamines and the like. The propylene oxide adducts of the lower molecular weight aliphatic or armoatic compounds having 2 to 6 carbon atoms containing hydroxyl and/or amino groups and at least 2 reactive hydrogen atoms having a molecular weight of 1000 to 4000 contain from 15 to 67 oxypropylene units in the molecule.

Examples of compounds of the above type are the adducts of 17, 60 or 159 mols of ethylene oxide to a polypropylene glycol with a molecular weight of 1750 or having about 30 oxypropylene units; the adduct of 51 mols of ethylene oxide to a polypropylene glycol with a molecular weight of 2250; the adduct of 250 mols of ethylene oxide to a polypropylene glycol consisting of 48 oxypropylene radicals; the adduct of 295 mols of ethylene oxide to a polypropylene glycol consisting of 56 oxypropylene radicals; the adduct of 30 mols of propylene oxide and 26.5 mols of ethylene oxide or 48 mols of propylene oxide and 42 mols of ethylene oxide to ethylene diamine; the adduct of 48 mols of propylene oxide and 42 mols of ethylene oxide to ethylene glycol.

The compounds of group B are obtained by reaction of 2 mols of polyoxyalkylene compounds containing high molecular weight radicals A with 1 mol of either an aldehyde or a ketone. For the formation of an acetal, primarily formaldehyde and acetaldehyde are to be considered, however, other aldehydes such as propionaldehyde, benzaldehyde, acrolein, glycolaldehyde and glyoxal, may be used. Ketones suitable for the formation of the ketals are for example acetone, acetophenone, methyl ethylketone, etc.

Examples for suitable acetals or ketals are the formaldehyde acetals of the following adducts: nonylphenol adducted with mols of ethylene oxide; fatty alcohol admixture C -C adducted with 20 mols of ethylene oxide; dodecylalcohol adducted with 12 mols of ethylene oxide; dodecylalcohol adducted with 5 mols of propylene oxide-lmols of ethylene oxide; myristic acid monoethanolamide adducted with 10 mols of ethylene oxide; linolenic acid adducted with 20 mols of ethylene oxide; alkane-l,2-diol admixture of the chain lengths C C adducted with 20 mols of ethylene oxide; also the acetaldehyde acetal of an adduct of dodecylphenol with mols of ethylene oxide; the ketal of acetone and an adduct of nonylphenol with 25 mols of ethylene oxide. Preferably the formaldehyde and/or acetaldehyde acetals of the alkylene oxide addition products of higher molecular fatty alcohols and alkylphenols are used.

It is not in all cases necessary to prepare the acetals or the ketals in pure form. Frequently it is practical, to convert the alkylene oxide adducts of higher molecular weight compounds according to A only partially into the acetal or ketal, and to use these admixtures directly for the preparation of the end products.

The preparation of the compounds C also starts with the same higher molecular weight compounds as used for the structure of compounds A containing higher molecular weight radicals. The preparation is likewise accomplished preferably by addition of alkylene oxides. However, in compound C the portion of propylene oxide and/or butylene oxide amounts to more than 50 mol percent, whereas a lesser portion may consist of ethylene oxide. When various alkylene oxides are used, ethylene oxide generally is added first and thereafter propylene oxide and/or butylene oxide. The polyoxyalkylene derivatives thus obtained contain 4 to 40, preferably 7 to 25, oxypropylene and/or oxybutylene units, preferably in combination with a lesser number of oxyethylene units. In the latter case, the molar ratio of the oxyethylene units to the oxypropylene and/or oxybutylene units is 1:33 to 121.1.

Examples for compounds of group C are the following: the adduct of 7 mols of ethylene oxide and 10 mols of propylene oxide or of 9 mols of ethylene oxide and 16 mols of propylene oxide to a fatty alcohol admixture of the chain lengths C C the adduct of 4 mols of ethylene oxide and 12 mols of propylene oxide to a fatty acid ethanolamide admixture with the chain lengths C C the adduct of 7 mols of ethylene oxide and 10 mols of propylene oxide to nonylphenol; and the addition product of 9 mols of ethylene oxide and 9.5 mols of propylene oxide to tallow alcohol; the adduct of 8 mols of ethylene oxide, 20 mols of propylene oxide and 2 mols of butylene oxide to nonylphenol; furthermore the formaldehyde acetal of a fatty alcohol admixture of the chain lengths C C reacted with 5 mols of ethylene oxide and 13 mols of propylene oxide; the formaldehyde acetal of an adduct of nonylphenol with 8 mols of ethylene oxide and 15 mols of propylene oxide. The addition products of ethylene oxide and propylene oxide to higher molecular fatty alcohols or alkylphenols are of particular interest.

The above compound C may be substituted either entirely or partially by a propylene oxide polymer having a total molecular weight of 1000 to5000, preferably 1700 to 4100, to which up to 30 mol percent of ethylene oxide may be added. The propylene oxide polymers having a molecular weight of 1000 to 5000 contain from 17 to 86 oxypropylene units in the molecule. These compounds C not containing high molecular weight radicals are obtained similarly as are the compounds A not containing high molecular weight radicals by polymerization of propylene oxide or by the addition of propylene oxide to lower molecular weight compounds with '2 to 6 carbon atoms containing at least 2 reactive hydrogen atoms. The propylene oxide adducts of the lower molecular weight compounds containing at least 2 reactive hydrogen atoms having a molecular weight of 1000 to 5000 contain from 15 to 84 oxypropylene units in the molecule. Preferably, up to 30 mol percent of ethylene oxide, based on the total number of the alkylene oxide radicals in the molecule are added to the resultant propylene oxide polymer.

Examples of compounds C not containing high molecular weight radicals are: the adduct of 4.5 mols of ethylene oxide to a polypropylene glycol with a molecular weight of 1750; the adduct of 7 or 16 mols of ethylene oxide to a polypropylene glycol with a molecular weight of 2750; the adduct of 8.5 mols of ethylene oxide to a polypropylene glycol consisting of 56 oxypropylene radicals; the adduct of 35 mols of propylene oxide to glycerin; the adduct of 48 mols of propylene oxide and 7 mols of ethylene oxide to ethylene diamine.

It has been proven (see Example 3 a-c below) that a combination of the compounds A, as used until now (as an example nonylphenol adducted with 20 mols of ethylene oxide) on one hand with a compound C (as an example the adduct of 5 mols of ethylene oxide and 13 mols of propylene oxide to a fatty alcohol admixture (D -C or on the other hand with a compound B (as an example the formaldehyde acetal of the adduct of 20 mols of ethylene oxide with nonylphenol) leads to considerable foam volumes. These combinations are unsuited for practical use for instance of a fast rotating dishwasher. However, when these three compounds according to A, B and C are combined, a very distinct foam decrease is observed in surprising manner. The occuring foam masses are so insignificant, that even under extreme mechanical operation conditions no upsets will arise due to foam formation. Furthermore, an excellent cleansing effect and a perfect clear-drying effect are attained.

In general the washing and cleansing composition of the invention may be composed of 5 to 79.5% by weight of the components A; 0.5 to 75% by weight of the components B, and 20 to 94.5% by weight of the components C. Preferably mixtures of 20 to 50% by weight of the components A, 5 to 20% by weight of the components B, and 30 to 75% by weight of the components C are utilized. The amounts used of these admixtures in the cleansing bath are within the concentration zone of about 0.02 to 1.0 g./l., preferably 0.05 to 0.3 g./l., based on the total amount of the components A, B and C.

When utilized in washing and cleansing compositions in the above proportions other commonly employed materials in such agents may also be employed.

Within the quantitative proportions given above, the composition of the admixtures is variable without running the risk that the outstanding advantage of low foam would be lost. In this way it is possible to render the admixture suitable for the specific requirements of practical use. Thus, agents with exceptionally good cleaning and wetting effect are obtained, when are relatively large portion of the components A, which in themselves are inclined to greater foam formation, is present in the admixture. The draining and clear-drying effect, which is important for the appearance of the articles cleaned and dried, may also be favorably influenced, when the portion of the component A is relatively high.

8 Example 2 A liquid, concentrated cleansing agent suitable for commercial dishwashers was formed with the following composition:

Concentrated liquid products, such as those preferably B wer ht ercen used for dishwashers equlpped with automatic metering y P t devices, may be prepared by dissolvlng the admixtures in Fatty alcohol admixture 312- 18 adducted Wlth 20 water, using organic, water-miscible solvents if necessary. H1018 of ethylene oxide 16 These concentrates contain preferably about 20 to 70% Formaldehyde acetal of a fatty alcohol admixture of the components A, B and C. By varying the constituents 10 C C adducted with 20 mols of ethylene oxide 4 with respect to composition and quantities, those liquid Nonylphenol adducted with 9 mols of ethylene oxide concentrates may be standardized in such a manner, that mols of propylene oxide 40 they possess a good temperature stability and that they Ethanol 5 are not inclined to precipitate or separate in layers. In Water 35 the Same Way it.is possible to vary dehydration i 15 The agent was measured as to its amount by means of i of the aqmlxtures m aqueous solution i to adlust an automatic metering device in relation to the hot rinsing 531d dehydration temperature to the respectwe reqmre' water with a temperature of 70 to 90 C in the dishwasher ments for example for nnsmg PP i in quantities of 0.2 to 0.3 g./l. The rinsing water, contain- The most extreme low-foaming compositlons are attained, in the mduct and fiowin in the Washtank Still resulted as a rule when the dehydration temperature of thfi in no disturbing foam forriation in spite of intensive liqtltllgihiirslesbelow the rmsmg temperature of commerclal uor Circulation. 1

The following specific embodiments of the invention Examp e 3 are illustrative thereof. It is obvious however that other The foam behavior of different cleansing admixtures ex edients may be employed and the specific embodiments was examined for comparison purposes in a special foam P are not to be deemed lrmrtatrve 1n any manner. examination apparatus. The startlingly favorable foam be- 1 1 havior of the admixtures claimed, in particular in com- Examp e parison to any corresponding 2-component-admixtures, A detergent, suitable for household dishwashers was may be realized from the table following hereinafter. The formed with the following composition: cleansing and clear drying effect is satisfactory in all agents of the following table. By Weight Percent The foam apparatus as used was constructed in simi- Nonylphenol adducted wlth 20 mols of ethylene lar manner as a modern dishwasher operating according to oxide 1l the 1et spray system. By means of a pump about 170 liters Formaldehyde acetal of nonylphenol adducted with of water per minute were rotated and sprayed into the N 20 8 gz a 1:33: ,i' 'g 'gj 'g 'i 'g'z ag metering chamber by means of a rotating spray-arm prog; us l O y 11 vided with nozzles. Foam heads from 0 to 280 mm. may j' s o propy cm X e 10 be measured in reproducible manner, whereas larger foam W 63 volumes can no longer be measured accurately, and, a er 40 therefore, they are indicated in the table as 280. The The admixture was used in a concentration of 0.2 to liquor temperature during the tests was C., the hard- 0.4 g./l., preferably between 50 and C. and developed, ness of the water used was 16 dH and the duration of even under extreme conditions, no appreciable amount of the foam test lasted 5 minutes. The reading of the foam foam. On the other hand it had an exceptional wetting height was done immediately after the machine came to a and cleansing effect so that dishes of clean appearance 45 standstill. The foam apparatus is described in Fette, and a clear luster were the result. Seifen, Anstrichmittel,. 66 (1964), 529.

TABLE I Test Type 0! Concentration Foam N0. Cleansing Agent Compound of the liquor, heigh g. mm.

(a) Nopylphenoligdducted with 20 mols of A 0.12 280 e y 6118 OK e. The formaldehyde acetal of nonylphenol B 0. 05

adidiucted with 20 mols of ethylene 0 6. (b) Nogylphenoliidducted with 20 mols of A 0.12 280 en X1 e. F;tty a1c h%lCu-C;4 adducted with 5 C 0.13

111211; tigfighgitglee oxide plus 13 mols of (o) N glghenohgdducted with 20 mols of A 0. 24 30 yen 0X1 e. The fonna ldehyde acetal of nonylphenol B 0. 05

addlucted with 20 mols of ethylene 1 e. Fatty alcohol-CW0 adducted with 5 C 0.13

315,1; 3% relghggiee oxlde plus 13 mols of (d) Nofiylphenoligddiicted with 20 mols of A 0.12 40 e 116 O 8. The f rinaldihyde acetal of nonylphenol B 0. 007

addiucted with 20 mols of ethylene 0 1 Fat ty Zlcohok-Crz-Cn adducted with 5 C 0.13

grrglgyolggghggiee oxide plus 13 mols of (e) Fatty alc0hol-C iCrraddncted with 20 A 0.16 280 mols of ethylene oxide. Fatty alcohol-GT0 adducted with 7 C 0.12

mols of ethylene oxide plus 13 mols ol propylenepxide.

TABLE ICon-tinued A Test Type of Concentration Foam N o. Cleansing Agent Compound of the liquor, height,

g./l. mm. o Fatty alcohol-C ro adducted with 20 A 0. 1e 20 mols of ethylene oxide. The formaldehyde aoetal of fatty aleo- B 0.08

holCi2-Ci4 adduoted with 20 mols of ethylene oxide. Fatty alcoholC o-C|4 adduoted with 7 C 0. 12

mols of ethylene oxide plus 18 mols of propylene oxide. (g) Nonylphenol edducted with 20 mols of A 0.24 280 ethylene oxide. N onylphenol addueted with 9 mols of C 0. 12

ethylene oxide plus 15 mols oipropylene oxide. (h) Nonylphenol adducted with mols oi A 0.22 20 ethylene oxide. The aeetaldehyde acetal of nonylphenol B O. 02

addiucted with 20 mols of ethylene ox! e. Nonylphenol adducted with 9 mols of C 0. l2

ethylene oxide plus 15 mols ofpropyl-. ene oxide.

The same testing device as employed in Example -I II TABLE ontmued was also utilized in the following examples of compara- F tive results wherein part or all of components A and/ or 13x. Composition of the Admjxmre g Q C containing higher molecular weight radicals were regJl. in mm. placed by polyalkylene oxide derivatives also classed as 70 Nonylphenol addumd with 20 mols 0'12 components A B T ll e 1 513 i i d' a t 1 f 1 tt 0 02s The letters .A, B and C signify the types of compounds gfi f fl f ff f i fi 8 mols of eth lene oxide. conformmg to the descr text 0. Glycerin dtlduoted with mols of 0.24

propylene oxide.

8a- A. N onylphenol adducted with 20 mols 0. 12 280 TAB LE H c i d ii i t e f' i th 1 id t Concem Foam no 0 m0 s o e y ene ox e o 0. 24 11313. Composition of the Admixture tration, Height 35 g ggggop y lg ieglycol of molecular sh--. A. liplglfllhenbl aidueted with 20 mols 0. 12 4a.... A: Adduct of mols of ethylene oxide to 0. 24 160 o 9 Y ene 0x1 ttiit iiiiii iizzii iixiiitiit iihiiti ethylene oxide. Eggflfigfl ifi fiifig ffi gggg 12 C. Adduct of 6 mols of ethylene oxide to 0. 24 5 oxide plus 13 mols of propylene oxide. 40 a R gg gg g molecular 4b-... A. Adduct of 40 mols of ethylene oxide to 0.24 welg o I g g g gggg iege mlecular 9a- A. g att aio ih co-cli odduoted with 0.12 280 mosoe yeneoxi e. g ga fifgg g s fi g 38 3 025 0 C. Adduet of 4.5 mols of ethylene oxide 0.24

Ethylene oxkm I to a plglytplrc alpigleneglycol of molecular won; 0 gggghgei i g'g ggfi ii .5533: 9b-..- A. F atty alcohol-Cn-C 1; addueted with o. 12 Hide plus 13 pmpylene B. rh l n n old hy d ifo t o l'oi nonylo. 03 5a- A. Adduet of 40 mols of ethylene oxide to 0.12 160 g igf gi gg gg with 20 111915 of g gf gggg igfg of mdecular v C. Adduet of 4.5 mols of ethylene oxide 0. 24 45 0. Coconut oil fatty 9.1C0h01-'C1zC1a 0. 24 to gg f ig of molecular addiuoted wl isth 5115110? of ethylene d welg 0 i on e p us 1110 o propy ene oxi e. 5h A. Adduct oi 4o mols oi ethylene oxide to 0.12 f of 129 1111018 i ig pp gg griy lgleglycol oi molecular 53 g er 61165 W 0 W we1g 0 1 i i B. The formaldehyde aeetal of a fatty 0. 05 0 ldducll; of f etlllylfene f 05 alcohol-CW0 addueted with 20 g fi'glfig elleg 3' 0 1110 9611 C giifif fi? ig f fi gjy 24 10b... A. Adduct of 129 mols of ethylene oxide 0.12

addueted with 5 mols of ethylene gg g of molecular Plus 13 pmpylene B. The formaldehyde aeetal of IlOnyl- 0. 016 15 ea. A. Ethylenediamine adduoted with is 0.12 g fi gi gflg igg Wlth mols of gigig ggg g gg? Plus 146 mm o. Adduet of 4.5 mols of ethylene oxide 0.06 c. Fatt alwh0lC1zC1s addueted with 0.06 200 %g of molecular 5 fmo s 011 ethyleinie oxide plus 13 mols weig o o propy ene ox e. 6b A. Ethylenediamine adduoted with is 0.12 g of f 1111018 f ethlyiiime e I 20 255 nolishoflprop l ane oxide plus 146 mols weig 23 2 V00 0 9011 a oe yeneoxie. I B. The formaldehyde aeetal of nonyl- 0. 007 5 g g f ff gggg with 35 111915 16 ggfigi gii gs wlth 2O mols of llb. A. Adduct of 40 mols of ethylene oxide 0. 20 0. Fatty tioohoi-GIT addueted with 0.06 w gg g z of molecular g gggf g ggflfii oxlde plus 13 mols B. The formaldehyde aeetal of nonyl- 0.025 20 phenol adducted with 20 mols of A' i g i i'g with 20 mols 12 C l y i 'lgg g eted with 35 mols of 0 16 o e y ene ox e.

propylene oxide. iggfgggggggf 35 24 155 11e- A. Adduet of 40 mols of ethylene oxide 0.20 7b.... 14. g oi i i henol iigducted with 20 mols 0.12 fg i gg g figg 01111018611121 1 'd tlirtt 005 55 B. The formaldehyde acetal of nonyl- 0.025 10 The forma deny e we a o F a y i m oi addugted with 20 mols o1 gl g g -g g gg g Wlth mols e y ene 0x1 e. t C Glycerin t d ith 35 l f 0 24 C. Glycerin fidducted with 30 111015 0! 0. l6

propylene oxide.

propylene oxide.

1 1 Example 12 An exceptionally low-foaming liquid washing agent for household dishwashers has the following composition:

Percent Add'uct of 159 mols of ethylene oxide to a polypropyleneglycol of molecular weight of 1740 (A) 18.5 Adduct of 4.5 mols of ethylene oxide to a polypropyleneglycol of molecular weight of 1740 (C) 9.0 Formaldehyde acetal of an adduct of 20 mols of ethylene oxide to nonylphenol (B) 2.5 Ethanol 10.0 Water 60.0

Using from 0.3 to 0.5 g./l. of the above composition, a good water drainage from the articles to be washed is attained without any drop formation, even with hard water. No disturbing foam volume is produced.

Example 13 oxide 12 Acetaldehyde acetal of nonylphenol adducted with 20 mols of ethylene oxide 2.5

Glycerin adducted with 35 mols of propylene oxide Isopropanol Water 51.5

The admixture was liquid and had a turbidity point of 40. It was measured by means of an automatically operating dosing device into the rinsing bath in amounts of 0.2 to 0.4 g./l., the liquor temperature being about 80. A rapid drying of the dishes after the rinsing was obtained. The ready rinsed dishes were glossy-clear and showed no drops or spots. Even in high-capacity machines with considerable water circulation no annoying foam affecting the cleansing process, occurred, neither at the start of the cold machine nor during the continuous process in the hot machine.

While certain specific examples and preferred modes of practice of the invention have been set forth, it will be understood that this is solely for the purpose of illustration and that various changes and modifications may be made without departing from the spirit of the disclosure and the scope of the appended claims.

We claim:

1. A composition of washing and cleansing agents having low foaming properties consisting essentially of:

(A) from 20% to 79.5% by weight of compounds based on ethylene oxide adducts selected from the group consisting of (1) an ethylene oxide adduct containing from 4 to 60 oxyethylene units of a high molecular weight lipophilic radical of the formula selected from the group consisting of wherein R represents a radical having from 8 to 36 carbon atoms selected from the group consisting of alkyl, 'alkenyl, and mono-hydroxy-alkenyl, R represents alkylphenyl having from 12 to 22 carbon atoms, and Y represents a bridging link selected from the group consisting of O, S, NH, CONH and COO; adducted first with oxyethylene units and thereafter with oxyalkylene units selected from the group consisting of oxypropylene and oxybutylene, said oxyethylene units being in a ratio to said oxyalkylene units selected from the group consisting of 1 to 0 and 1 to 0.03 to 1 to 0.3, (2) an ethylene oxide adduct containing from 35 to mol percent of oxyethylene units adducted to a polyoxypropylene glycol having an average number of oxypropylene units of between 17 and 69, the total number of oxypropylene units and oxyethylene units in said adduct being mol percent, and (3) an ethylene oxide adduct containing from 35 to 85 mol percent of oxyethylene units adducted to a propylene oxide adduct of a hydrocarbon compound having from 2 to 6 carbon atoms and at least two reactive hydrogen atoms, selected from the group consisting of alkanes and benzene, substituted with substituents selected from the group consisting of hydroxy, amino and mixtures thereof, said propylene oxide adduct having an average number of oxypropylene units of between 15 and 67, the total number of oxypropylene units and oxyethylene units in said adduct being 100 mol percent;

(B) from 0.5% to 20% by weight of dimeric compounds of the formula A-o-f:o-A

RIII

wherein A represents an ethylene oxide adduct containing from 4 to 60 oxyethylene units of a high molecular weight lipophilic radical of the formula selected from the group consisting of wherein R represents a radical having from 8 to 36 carbon atoms selected from the group consisting of alkyl, alkenyl, and mono-hydroxy-alkenyl, R represents alkylphenyl having from 12 to 22 carbon atoms, and Y represents a bridging link selected from the group consisting of O, S, NH, CONH and COO; adducted first with oxyethylene units and thereafter with oxyalkylene units selected from the group consisting of oxypropylene and oxybutylene units; said oxyethylene units being in a ratio to said oxyalkylene units selected from the group consisting of 1 to 0 and 1 to 0.03 to 1 to 0.3, and having a terminal methylene group derived from said oxyalkylene oxide units, R represents a member selected from the group consisting of hydrogen and methyl, and R is selected from the group consisting of hydrogen, methyl, ethyl, phenyl, vinyl and hydroxymethyl; and

(C) from 30% to 75% by weight of compounds based on alkylene oxide adducts selected from the group consisting of (1) an alkylene oxide adduct of a high molecular weight lipophilic radical of the formula selected from the group consisting of wherein R represents a radical having from 8 to 36 carbon atoms selected from the group consisting of alkyl, 'alkenyl and mono-hydroxy-alkenyl, -R' represents alkylphenyl having from 12 to 22 carbon atoms, and Y represents a bridging link selected from the group consisting of O, S, NH, CONH and COO; adducted first with oxyethylene oxide units and thereafter with oxyalkylene oxide units selected from the group consisting of oxypropylene and oxybutylene, said oxyethylene units being in a ratio to said pxyalkylene units selected from the group consisting of to 1 and 1 to 33 to 1 to 1.1, from 4 to 40 oxypropylene units and oxybutylene units being present in said adduct, (2) a polyoxypropylene glycol having an average number of oxypropylene units of between 17 and 86 adducted with from 0 to 30 mol percent of oxyethylene units, the total number of oxypropylene units and oxyethylene units in said adduct being 100 mol percent, and (3) a propylene oxide adduct of a hydrocarbon compound having from 2 to 6 carbon atoms and at least two reactive hydrogen atoms selected from the group consisting of alkanes and benzene, substituted with substituents selected from the group consisting of hydroxy, amino and mixtures thereof, said propylene oxide adduct having an average number of oxypropylene units of between 15 and 84, adducted with from 0 to 3-0 mol percent of oxyethylene units, the total number of oxypropylene units and oxyethylene units in said adduct being 100 mol percent, with the proviso that the total amount of ingredients A, B and C in said composition is 100% by weight.

2. The composition of claim 1 wherein ingredient A contains from 10 to 40 oxyethylene units.

3. The composition of claim 1 wherein ingredient A(l) contains from 4 to 60 oxyethylene units and 1 to 20 oxypropylene units in 'a molar ratio of oxyethylene units to oxypropylene units of 1:0.03 to 1:033.

4. The composition of claim 1 wherein ingredient C(l) contains from 1 to 30 oxyethylene units and 4 to 40 oxypropylene units in a molar ratio of oxyethylene to oxypropylene of 1:33 to 1:1.1.

5. Aqueous low-foaming compositions containing from 25% to 60% of the composition of claim 1.

6. The method of rinsing of solid articles which comprise rinsing said solid articles with water containing from 0:02 to 1 gram per liter of the composition of claim 1;

7. The composition of claim 1 wherein said ethylene oxide adducts of (A) are ethylene oxide adducts of high molecular weight lipophilic radicals of the formula 8. The composition of claim 1 wherein said ethylene oxide adducts of (A) are ethylene oxide adducts of high molecular weight lipophilic radicals of the formula 9. The composition of claim 1 wherein said ethylene oxide adducts of (A) are ethylene oxide adducts of alkanols having from 10 to 20* carbon atoms adducted' with from 4 to oxyethylene units.

10. The composition of claim 1 wherein said ethylene oxide adducts of (A) are ethylene oxide adducts of alkylphenols having from 14 to 18 carbon atoms adducted with from 4 to 60 oxyethylene units.

References Cited MURRAY KATZ, Primary Examiner.

LEO-N D. ROSDOL, Examiner.

S. D. SCHNEIDER, S. E. DARDEN,

Assistant Examiners.