US3549543A - Low-foaming washing and cleansing agents - Google Patents

Description

United States Patent ABSTRACT OF THE DISCLOSURE Low-foaming, washing and cleansing compositions particularly for use in mechanical dishwashers 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 small amounts of oxypropylene and oxybutylene radicals, or mixed oxyethylene-oxypropylene glycols having an excess of oxyethylene units, (B) compounds of the formula high molecular weight lipophilic compounds adducted with ethylene oxide and which may also contain small amounts of oxypropylene and oxybutylene units and X is a bivalent linkage selected from the group consisting of Claims wherein A represents and (C) high molecular weight lipophilic radicals adducted with propylene oxide and/ or butylene oxide which may contain small amounts of oxyethylene units, or mixed oxypropylene-oxyethylene glycols having an excess of oxypropylene units.

In an increasing measure, mechanical washing methods are being employed to wash china, glass, procelain, 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 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 effect. 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 the function of the washing apparatus.

3,549,543 Patented Dec. 22, 1970 ice 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:

(A) from 5% to 79.5% by weight of compounds based on ethylene 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 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 75% 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 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 consistmg of (1) oxygen, (2) ethers derived from bifunctional compounds having a carbon chain of at least two carbon atoms capable of forming ether linkages with an alcohol, (3) esters derived from bifunctional compounds capable of forming carboxylic ester linkages with an alcohol, (4) urethanes derived from bifunctional groups capable of linkages with an alcohol, (5) amines derived from chlorine-containing bifunctional compounds capable of forming ether linkages with an alcohol and amine linkages by reaction of the chlorine with an amino compound selected from the group consisting of ammonia and primary amines, (6) sulfides derived from chlorine-containing bifunctional compounds capable of forming ether linkages with an alcohol and sulfide linkage by reaction of the chlorine with a metallic sulfide selected from the group consisting of alkali metal sulfides and alkaline earth sulfides, (7) bifunctional linkages derived from epoxy-containing compounds capable of forming ether linkages with an alcohol, said epoxy-containing compound forming bifunctional linkages with a bifunctional compound selected from the group consisting of dihydroxy compounds and dimercapto compounds, and (8) --O-SO -O-; 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 3 to 5000 and adducted with 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-foamlng washing and cleansing agents, havpreferably 1700 to 3250.

(B) Compounds of the general structural principle wherein A and A signify the radical, of a polyoxyalkylene compound volume, are particularly suitable for mechanical washing and cleaning methods.

The components A, B and C used for the preparation 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 alklene oxides to those higher contain reactive hydrogen through the heteroatoms atoms, bonded O, S or N. The aliphatic comrepresents a bridging link selected from the group consisting of NH, O, S, CONH, SO NH, and COO. The aliphatic-aromatic 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, alklnaphthyl, 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 while a lesser molecular propylene oxide and/or butylenee oxide is then added. The reaction is accomplished in the usual manner, for example, by utilizing pressure in the presence of alkaline catalysts.

Componud A may also molecular weight aliphatic or aliphatic-aromatic commolecular weight cols.

As starting compounds for the preparation of the above compoun Examples for compound A are: The adduct of 15 mols of ethylene oxide with dodecyl alcohol; the adduct of 20 alcohols or alkylphenols.

The above compound A ti ely 0r ried out also by addition of propylene oxide to lower molecular weight hydroxyl and/or amino group containing aliphatic or aromatic compounds containing at least 2 reactive hydrogen atoms. Examples of such compounds are glycol, glycerin, sugar alcohols, ethylene diamine, phenylene diamine, alkanolamine and the like.

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 or 48 mols of propylene oxide and 146 mols of ethylene oxide to ethylene diamine; the adduct of 48 mols of propylene oxide and 42 mols of ethylene oxide to ethylene glycol.

Compounds of group B are formed by the linkage of 2 molecules of polyoxyalkylene compounds containing the high molecular weight radicals of A through their end hydroxyl groups. Preferably, those polyoxyalkylene compounds which contain at least 12 oxyethylene units in the molecule are used.

The following indicates the most significant linkage reactions; however, it should be understood that the invention is not limited hereupon in any manner.

(1) The direct etherification of 2 'mols of polyoxyalkylene compounds containing the high molecular weight radicals of A at elevated temperatures in the presence of catalysts, such as p-toluolsulfonic acid.

(2) The reaction of 2 mols of polyoxyalkylene compounds containing the high molecular weight radicals of A with 1 mol of a bifunctional compound reacting to form ether groups.

Examples of such bifunctional compounds are: aliphatic dihalides such as dichloroethane, dibromoethane; diepoxides such as diepoxybutane; dihydrin halides such as a,m-dichlorohydrin; epihydrin halides such as epichlorohydrin, epibromohydrin, l-chloro-2,3-epoxybutane; compounds containing activated double bonds such as divinylsulfone, etc.

(3) The reaction of 2 mols of polyoxyalkylene compounds containing the high molecular Weight radicals of A with 1 mol of a bifunctional compound reacting to form carboxylic ester groups. As such the following bifunctional compounds may be used: dicarboxylic acids such as oxalic acid, maleic acid, tartaric acid, phthalic acid, malonic acid, succinic acid, and also functional derivatives of dicarboxylic acids such as anhydrides, halides, esters of the aforementioned acids, phosgene and the like.

(4) The reaction of 2 mols of polyoxyalkylene compounds containing the high molecular Weight radicals of A with 1 mol of a bifunctional compound reacting to form urethane groups. Such compounds are aliphatic and aromatic diisocyanates such as hexamethylene diisocyanate. toluylene diisocyanate-(2.4), etc.

(5) The reaction of 2 mols of a halide hydrin ether of a polyoxyalkylene compound containing the high molecular weight radical of A with 1 mol of ammonia or a primary amine or an alkalior alkaline earth sulfide; or the reaction of 2 mols of glycidyl ether of a polyoxyalkylene compound containing the high molecular weight radicals of A with 1 mol of glycol, polyglycol, diphenol or dimercaptan to form the corresponding bridge links containing either N, S or O hetero atoms.

(6) The reaction of 2 mols of polyoxyalkylene compounds containing the high molecular weight radicals of A with 1 mol of bifunctional compounds which introduce as bridge links the radicals of inorganic acids, for example, sulfuryl chloride.

The compounds of group B may also be obtained in a different manner, for example, by esterification of 1 mol of polyalkylene glycols having a molecular weight of about 1000 to 5000 with 2 mols of higher molecular weight aliphatic or aliphatic-aromatic carboxylic acids. The preparation may also be accomplished by reaction of a bischlorohydrin ether of a polyalkylene glycol with higher molecular weight primary or secondary amines or the reaction of a bis-glycidylether of a polyalkylene glycol with higher molecular weight alcohols, mercaptans or alkylphenols.

Examples for compounds of group B are:

(l) The etherification product from 2 mols of an addition product of 20 mols ethylene oxide to nonylphenol; the etherification product from 2 mols of the addition product of 14 mols ethylene oxide and 2 mols propylene oxide to a fatty acid mixture of the chain length C C (2) The reaction product of 2 mols of an addition product of 18 mols ethylene oxide to dodecyclalcohol with 1 mol dibromoethane; the reaction product of 2 mols of the addition product of 14 mols ethylene oxide to isooctylphenol with 1 mol a,a-dichlorohydrin; the reaction product of 2 mols of an addition product of 20 mols ethylene oxide and 1 mol propylene oxide to a fatty acid mixture of the chain length C C with 1 mol divinylsulfone;

(3) The esterification product from 28 mols of the addition product of 30 mols ethylene oxide and 2 mols butylene oxide to dodecylalcohol with 1 mol of phthalic acid; the reaction product of 2 mols of the addition product of 25 mols ethylene oxide to isotridecylalcohol with 1 mol of maleic acid anhydride; the reaction product of 2 mols of the adduct of 20 mols ethylene oxide to dodecylmercaptan with 1 mol of phosgene;

(4) The reaction product of 2 mols of the adduct of 38 mols of ethylene oxide with dodecylalcohol dimerized according to the Guerbet method and 1 mol of hexamethylene diisocyanate-(l,6); the reaction product of 2 mols of the adduct of 12 mols ethylene oxide to a coconut oil fatty acid amide admixture having chain lengths of C -C with 1 mol of toluylene-diisocyanate-(2,4);

(5) The reaction product of 2 mols of the hydrinchloride ether of the addition product of 35 mols ethylene oxide to stearic acid with 1 mol monoethanolamine; the reaction product of 2 mols of the bromohydrin ether of the adduct of 25 mols ethylene oxide to dodecylphenol with 1 mol of calcium sulfide; the reaction product of 2 mols of the glycidylether of the addition product of 20 mols ethylene oxide and 3 mols propylene oxide to a fatty amine admixture having chain lengths of C C with 1 mol diglycol;

(6) The reaction product from 2 mols of the adduct of 18 mols of ethylene oxide with nonylphenol and 1 mol of sulfurylchloride.

Compound B may also be: the esterification product of 1 mol of polyethyleneglycol 1500 with 2 mols of oleic acid; the esterification product of 1 mol of the adduct of 40 mols ethylene oxide to a polypropylene glycol having a molecular Weight of 900 with 2 mols of a coconut oil fatty acid admixture having chain lengths of C C the reaction product of 1 mol of the bis-chlorohydrinether of polyethyleneglycol 2000 with 2 mols of an amine admixture obtained from stearic acids; and the reaction product of 1 mol of the bis-glycidylether of polyethyleneglycol 1000 with 2 mols of dodecylmercaptan.

It is not in all cases necessary to prepare the compounds B in pure form. Frequently, it is practical to convert the polyoxyalkylene compounds containing high molecular weight radicals A only partially into the compounds B, and to use these admixtures directly for the preparation of the admixtures of the washingand cleansing agents.

The preparation of the compounds C also starts with the same higher molecular Weight compounds as used for the structure of compounds A. 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 at least 50 mol percent, Whereas the same or 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, oxypropyleneand/or oxybutylene units, preferably in combination with either a lesser or an identical number of oxyethylene units. In the latter case, the molar ratio of the oxyethylene units to the oxypropyleneand/ or oxybutylene units is 1:33 to 1: 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 mols of propylene oxide to tallow alcohol. 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 to 5000, 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 compounds with 2 to 6 carbon atoms containing at least 2 reactive hydrogen atoms. 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.

In general the washing and cleansing composition of the invention may be composed of 579.5% 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 20-50% by weight of the components A, 2.5 to 20% by weight of the components B, and 3075% 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 0.021.0 g./1., 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 a 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.

Concentrated liquid products, such as those preferably used for dishwashers equipped with automatic metering devices, may be prepared by dissolving the admixtures in water, using organic, water-miscible solvents if necessary. By varying the constituents with respect to composition and quantities, those liquid concentrates may be standardized in such a manner, that they possess a good temperature stability and that they are not inclined to precipitate or separate in layers. In the same way it is possible to vary the dehydration temperature of the admixtures in aqueous solution and to adjust said dehydration temperature to the respective requirements, for example, for the rinsing temperature utilized. The most extreme low-foaming compositions are attained, as a rule when the dehydration temperature of the mixture is below the rinsing temperature of commercial machines.

The following specific embodiments of the invention are illustrative thereof. It is obvious however that other expedients may be employed and the specific embodiments are not to be deemed limitative in any manner.

EXAMPLES The foam behavior of different cleansing admixtures was examined for comparison purposes in a special foam examination apparatus. The startlingly favorable foam behavior of the admixtures of the invention, in particular in comparison to any corresponding 2-component admixtures, may be realized from the test results given in the tables following hereinafter.

The foam apparatus used was constructed in similar manner as a modern dishwasher operating according to the spray system. By means of a rotating pump about liters of water per minute were rotated and sprayed into the metering chamber by means of a rotating spray arm equipped with nozzles. Foam heights from 0 to 280 mm. may be measured in reproducible manner, whereas larger foam volumes cannot be measured accurately, and, therefore, they are indicated in the table as 280. The bath temperature during the tests was 50' C., the hardness of the water used was 16 dH. and the duration of the foam test lasted 5 minutes. The reading of the foam heights was conducted immediately after the apparatus became idle. This foam apparatus is described in Fette, Seifen, Anstrichmittel, 66 (1964), 529 (Fats, Soaps, Paints).

The letters A, B and C indicate the types of compounds corresponding with the description text.

TABLE I Ex (gortcen- Foam ra 10 No. Composition of the admixture g./ I iri iii n i 1a--.- A. Nonlyphenol adducted with 20 mols O. 12 280 of ethylene oxide. B. Reaction product from 2 mols of a fatty 0.01

alcohol CITCIS plus 20 mols of ethylene oxlde and 1 mol of divinylsulfone. 1b.... A. Nonylphenol adducted with 20 mols 0. 12 280 of ethylene oxide. 0. Fatty alcohol C 0; adducted with 0. 12

5 mols of ethylene oxide plus 13 mols of propylene oxide. 10.... A. Nonylphenol adducted with 20 mols 0.12

of ethylene oxide. B. Reaction product from 2 mols of a fatty O. 01 35 alcohol 012-01 plus 20 mols of ethylene oxide and 1 mol of divinylsulfone. 0. Fatty alcohol Ctr-O15 adducted with 0.12

5 mols of ethylene oxide plus 13 mols of propylene oxide.

2a.... A. Nonylphenol adducted with with 20 0.12 280 mols of ethylene oxide. B. Reaction product from 2 mols of 0. 01

nonylphcnol addueted with 20 mols of ethylene joxide and 1 mol of divinyl sulfone. 2b.... A. Nonylphcnol adducted with 20 mols 0. 12

of ethylene oxide. B. Reaction product from 2 mols of nonyl- 0. 01 20 phenol adducted with 20 mols of ethylene oxide and 1 mol of divinylsulfone.

TABLE IContin'ued TABLE I-Contin-ued 5 mols of ethylene oxide plus 13 mols of propylene oxide.

- Concen- Foam Concen- Foam Ex. tration, height; Ex; tration height No. Composition of the admixture g./I. in mm. No. Composition of the admixture g./I. in mm.

0. Fatty alcohol C adducted with 0.12 8a A1. Nonylphcnol adducted with 20 mols 0.05

mols of ethylene oxide plus 13 mols 5 of ethylene oxide. of propylene oxide. A2. Fatty alcohol Cit-Cit adducted with 0.05 280 C20rmoflls oi ethyllele ocxidead at y a coho 12 18a noted with 5 0.13 g gg gfig gg gg with 20 mols 280 mols of ethyltliine oxide plus 13 moles of 0. Fatty alcohol 012-01. adducted with 5 0. i2 propy mols 01f ethyletrile oxide plus 13 mols of 1 O g g w gggy j l with 20 mols O5 propy cne oxl e. 3b A+B. Etherification product from n011y1- 0.12 20 Estenficatim Pmduc" 1 m of a fatty alcohol Cit-Cit adducted with phenol adducted with 20 mols of ethylene oxide containing 60% of 20 mols of ethylene oxide and 0.25 mol starting product and 40% ether. cofFpmhahc acld' 0. Fatty alcohol 012-0.. adducted with 5 0.12 alcohol 9" addumd 5 13 mols of ethylene oxide plus 13 mols of g g g gg f ggg oxide plus 13 mols of e x e. propylene oxide 15 8o- A1. Nonylplleuol adducted with 20 mols of 0. 05

ethylene oxide. 4a A. Nonylphenol adducted with 20 mols of 0.12 28 A2- Fatty alcohol Cit-On adducted with 0.05

ethylene oxide. 20 mols of ethylene oxide. 0. Fatty alcohol ou-cmadducted with 5 0.12 Duster from p yet y g ycol 50 0. 5

mols of ethylene oxide plus 13 mols of and 2 mo s of fatty acid Ci-i-Glllpropylene oxide, C. Fatty alcohol Cir-C13 adducted Wlth 5 0. 13 4b A. Nonylphenol adducted with mols of 0. l2 20 mols h e e oxide p 18 mols p ethylene oxide. pylene oxide. B. Reaction product from? mols of non- 0.015 30 g ghleho. atlg c te c l 17513211823330? of The following three component combinations are exg g 2.12 ,g g f g g' ceptlonal low-foam mixtures, which, when used at con- C.5Fat1ty al c t ht l CITQAB addut -ged v itll 0.1 r centrations of from 0.1-0.5 g./l. in 50 C. water, of any L ,38 5. gf e p us mo hardness, under practical conditions, form no closed foam 40--" A gg lp l z u with 20 mols layer on the cleansing liquors. They do not develop more y en OX1 B. Reaction product from 2n1ols of non- 0.015 20 than foam 1n the foam test pp ylphenoladductedwith 30 mols of ethyl- TABLE II ene olxidle), 2tniols of epichlorohydrin and mo 0 u y amine. E 0. F tt akiphol cit-p 18 addutlzted vtiith5 0.12 30 ,3533% $335. 5; 3 on 0 plus 3 m s 0 A. a ty alc hol cit-0n adducted with 30 mols of 40 4a.-.- A. Nonylphenol adducted with 20 mols 0.12

of ethylene oxide B. Esteilficat on product from 2 mols of nonylphenol 20 B. Reaction product from 2mols ofa tal- 0.015 20 adducted 111015 0f ethylene Oxide and 1 low fatty alcohol adducted with 20 mols acldof ethylene oxide, 2 mols of epich10mhy 0. Fatty alcohol C 0 adducted with 7 mols of 40 (mm and 1 mol of monoethanolamme d ethylene oxide plus 13 mols of propylene oxide. 0. Fatty alcohol ci ca adducted with 5 [0, 12 10...- A. Nonylphenol adducted with 20 mols of ethylene 40 mols of ethylene oxide plus 13 mols of made l 231015 of propylene Oxldepropylene oxide B. Reaction product from 2 mols of nonylphenol 20 adducted with 20 mols of ethylene oxide and lmol cf toluylene diisocyanate (2,4). Adduct f 20 mols f ethylene oxide to 12 280 40 0. Fatty alcohol 012-018 adducted with 9 mols of 40 a dimerization product f decylalcohol ethylene oxide plus 16 mols of propylene oxide. prepared according to Guerbet 11 A. Fatty alcohol Cit-Cit adducted with 20 mols of 40 o. Nonylphenol adducted with 9 mols of 0.12 y e oxide ethyqene oxide plus 10111015 oipmpylene B. Reaction product from 2 mols of nonylphenol 20 oxide adducted with 20 mols of ethylene oxide and 1 mol 5b..-- A. Adduct of 20 mols of ethylene oxide to 0.12 Of sulfurylchlondea dimemation product of decylalcohol C. Nonylphenol adducted with 7 mols of ethylene 40 prepared according to Guerbet. oxlde D1115 13 mols of p py (Wide; 13 Reaction d t from 1 l of t 0 02 25 12...- A1. Secondary alcohol 015 adducted with 20 mols of 9 adduct A, 1 mol of epichlorohydrin and ethylene OXldB- I d 5 l of but lamjne. A2. Fatty alcohol Cn-C13 adducted with 20 mols of 9 C. Nonylphenol adducted with 9 mols of 0.12 y e O e.

ethylene oxide plus 10 15 of propylene B. Reaction product from 2 mols 0f nonylphenol 32 1d adducted with 35 mols of ethylene oxide, 2 mols of epichlorohydrin and 1 mol of butylamine. 0. Fatty alcohol 012*013 adducted with 5 mols of 50 6a--.- A. Fatty alcohol 016-01 adducted with 0.12 280 y ene o d D1l1$13 mols of propylene e.

15 mols of ethylene oxide. l3 A. Nouylpllenol adducted with 20 mols of ethylene 4t 0. Nonylphenol adducted with 9 mols of 0. 12 o do.

ethylene oxide plus 10 ols of propylene B. Reaction product from 2 mols of nonylphenol 6 oxide, adducted with 20 mols of ethylene oxide and 1 mol 6b.... A+B. Reaction product from 1 mol of 0. 12 25 ofhexamethylcne diisocyanate-(l,6).

' fatty alcohol Cid-C18 adducted with 15 0. Fatty alcohol ClZGiS adducted with 5 mols of 50 mols of ethylene oxide, 0.2 mol of epiethylene oxide plus 13 mols of propylene oxide. chlorohydrin and 0.1 mol of butylarnine. I 14"-. A. )leylalcohol adducted with 20 mols of ethylene 62. 5 O. Nonylphenol adducted with 9 mols of 0. l2 oxide.

ethylene oxide plus 10 mols of propylene B. Reaction product from 2 mols of nonylphenol 12. 5 oxide. adducted with 35 mols of ethylene oxide and toluylcne diisocyanate-(l,4). 0. Octylcresol adducted with 10 mols of ethylene 25 7a A. Nonylpllenol adducted with 20 mols 0.12 280 oxide plus 18 mols of propylene oxide.

of ethylene oxide. dd t 2 '5 fitil' oiie ti yiet ggi eiiiugie gngi i 15) Adrnixtures with essentially similar properties are 7b p igpyl ne oxii iead t d H120 i I 0 12 obtained, when in Examples 8 to 13 component A is subgi ggg gfif e m0 5 stituted by tallow fatty alcohol adducted with 15 to 25 B. ite tc ti h rotln ct il'(It| /H:12I1 1t0fiS2%faf8itt} 0. 05 15 mols of ethylene oxide or fatty alcohol C -C adducted aooo 12-186 uce wi moso ethylene oxide, 2 mols of epichlorohy- Wlth 15 to {Hols of Fthylene Oxlde' d 2 Sa e fi m 0 12 (16) A liquid Washing agent composition, which 15 5115015 0? i hlflfine gii e 2:111: ia mgis oi extraordinarly low foaming even under very unfavorable 7 p gp e g i t d m 20 1 f o 12 mechanical dishwasher conditions and which is suitable gig g 5 3f e for all types of commercial dishwashers, has the follow- B. Reactionproductfrom2mols ofnonyl- 0.05 20 ring composition;

phenolgddzucteld with mtfis gtethy ene oxl e, mo so epic oro y rinan 1 molofcalcium sulfidm 20% of the adduct of 20 mols of ethylene oxide to nonyl 0. Fatty alcohol circle adducted with 0.12 phenol 4% of the reaction product from 2 mols of the addition product of 20 mols of ethylene oxide to a fatty alcohol admixture of the chain lengths C C and 1 mol of divinylsulfone 30% of the addition product of 5 mols of ethylene oxide and 13 mols of propylene oxide to a fatty alcohol admixture of the chain lengths C C 10% of ethanol and 36% of Water.

The agent can be easily measured into the supply water of the dishwasher by means of an automatic dosing device. The concentration used is about 0.2 to 0.4 g./l.

(17) An exceptionally low-foaming, liquid washing agent for dishwashers in ordinary households has the following composition:

10% of the adduct of 20 mols of ethylene oxide to nonylphenol 5% of the reaction product from 2 mols of the chlorohydrin ether of the adduct of 20 mols of ethylene oxide to a fatty alcohol admixture of the chain lengths C C and 1 mol of monoethanolamine 15% of the adduct of 7 mols of ethylene oxide and 13 mols of propyleneoxide to nonylphenol 10% of ethanol 60% of water.

The product possessed an excellent heat and cold stability. Using 0.l-0.3 g./l. of said product in the wash water, a good water drainage for the articles to be washed was obtained without any drop formation. In the foam examination apparatus the admixture, when 0.3 g./l. of product were used, did not develop more than 15 mm. of foam height. In; practical use no closed foam layer occurred on the washing liquors.

The following examples demonstrate admixtures containing components A, B and C wherein either component A and/ or component C does not contain a high molecular weight radical.

The foam-testing apparatus is that described previously in connection with Table I.

TAB LE III Foam height in mm.

Concentration, g./l.

Ex. No. Composition of the admixture 18a... A. Nonylphenol adducted with 20 mols of ethylene oxide.

C. Adduct of 6 mole of ethylene oxide to a polypropylene glycol of molecular weight 2,250.

181)... A. Nonylphenol adducted with 20 mols of ethylene oxide.

B. Reaction product from 2 mols of nonylphenol adducted with 20 mols of pthylene oxide and 1 mol of divinylsulne. 0. Adduct of 6 mols of ethylene oxide to a polypropylene glycol of molecular Weight 2,250.

20a-.- A. Adduct of 48 mols of propylene oxide and 146 mols of ethylene oxide to ethylene diarnine.

0. Coconut oil fatty alcohol 012-015 adducted with mols of ethylene oxide plus 13 mols of propylene oxide.

20b A. Adduct of 48 mols of propylene oxide and 146 mols of ethylene oxide to ethylene diamine.

B. Reaction product from 2 mols of the chlorohydrin ether of coconut oil iatty alcohol (312-015 adducted with 20 mols of ethylene oxide and 1 mol of monoethanolainine.

C. Coconut oil alcohol 012-018 adducted with 5 mols of ethylene oxide plus 13 mols of propylene oxide.

TABLE III'C-ontinued Foam height in mm.

Concentration, g./l.

Ex. No.

Composition of the admixture A. Nonylphenol adducted with 20 mols of ethylene oxide.

C. Glycerin adducted with 35 mols of propylene oxide.

A. Nonylphenol adducted with 20 mols of ethylene oxide.

B. Reaction product from 2 mols of the chlorohydrin ether of nonylphenol adducted with 35 mols of ethylene oxide and 1 mol of butylamine.

C. Glycerin adducted with 35 mols of propylene oxide.

A. Nonylphenol adducted with 20 mols of ethylene oxide.

0. Adduct of 6 mols of ethylene oxide to a polypropylene glycol of molecular weight 2,260.

A. Nonylphenol adducted With 20 mols of ethylene glycol.

B. Reaction product from 2 mols of the chlorohydrin other of nonylphenol adducted with 20 mols of ethylene oxide and 1 mol of sodium sulfide.

C. Adduct from 6 mols of ethylene oxide to a polypropylene glycol of molecular weight 2,260.

A. Adduct of 265 mols of ethylene oxide to a polypropylene glycol of molecular Weight 3,240.

0. Fatty alcohol Ciz-Cis adducted with 5 mols of ethylene oxide plus 13 mols of propylene oxide.

A. Adduct of 265 mols of ethylene oxide to a polypropylene glycol of molecular weight 3,240.

B. Diester of coconut oil fatty alcohol Crz-Cn adducted with 20 mols of ethylene oxide and phthalic acid.

0. Fatty alcohol Cit-Cm adducted with 5 mols of ethylene oxide plus 13 mols of ropylene oxide.

A. Nonylphenol adducted with 20 mols of ethylene oxide.

C. Glycerin adducted with 35 mols of propylene oxide.

A. N onylphenol adducted with 20 mols of ethylene oxide.

B. Diurethane of nonylphenol adducted with 20 mols of ethylene oxide and hexamethylene diisocyanate (1,6).

0. Glycerin adducted with 35 mols of propylene oxide.

A. Nonylphenol adducted with 20 mols of ethylene oxide.

B. Diurethane of nonylphenol adducted with 35 mols of ethylene oxide and toluylene diisoeyanate (technical product).

C. Glycerin adducted with 35 mols of propylene oxide.

A. Adduct of 265 mols of ethylene oxide to a polypropylene glycol of molecular weight 3,240.

O. Glycerin adducted with 35 mols of propylene oxide.

A. Adduet of 265 mols of ethylene oxide to a polypropylene glycol of molecular weight 3,240.

B. Diurethane 0t nonylphenol adducted with 20 mols of ethylene oxide and toltuylene diisocyanate (technical produ C. Glycerin adducted with 35 mols of propylene oxide.

(27) In a dishwasher for commercial kitchens, with precleansing and rinsing chambers, the dishes were precleansed with an alkaline detergent comprising polyphosphates, soda and waterglass, and if necessary additions of sodium hypochlorite. Subsequently, the articles to be cleansed were then passed through the clear rinsing area, wherein a clear rinsing agent of the following composition at amounts of 0.5 gm./l. was introduced by means of an automatic dosing device. The temperature of the rinsing bath was about 80 C.

Parts by weight Nonylphenol adducted with 20 mols of ethylene oxide Diurethane of nonylphenol adducted with 20* mols of ethylene oxide and hexamethylene dissocyanate- 6 Glycerin adducted with 35 mols of propylene oxide 6 Ethanol 15 Water 55 The above clear-rinsing agent is fluid and has a turbidity temperature of about 35 C. The rinsing water ran smoothly oif the rinsed dishes. The remaining thin water film dried completely during the short passage of the dishes from the rinsing area to the removal point without drop formation and without leaving any traces. No disturbing foam formation was observed in the dishwasher.

(28) For a household dishwasher of high capacity a detergent of the following composition is suitable:

ethanolamine Coconut oil alcoholC C adducted with 5 mols of ethylene oxide +13 mols of propylene oxide 9 Isopropanol Water 58 The liquid product is used in amounts of about 0.5 gm./l. For dishes, which are not too soiled, the concomitant usage of an alkaline detergent may be omitted. A prevention of the progress of rinsing due to foam development did not occur.

The preceding specific embodiments are illustrative of the invention. It is obvious, however, that other expedients may be employed without departing from the spirit of the invention or the scope of the appended claims.

We claim:

1. A composition of washing and cleansing agents having low-foaming properties consisting 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 R-Y-H and R'-O-H 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 (a) 1 to 0 and (b) 1 to 0.03 to 1 to 0.3, (2) an ethylene oxide adduct containing from to 85 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 100 mol percent, and (3) an ethylene oxide adduct selected from the group consisting of an adduct of 30 mols of propylene oxide and 26.5 mols of ethylene oxide to ethylene diamine, an adduct of 48 mols of propylene oxide and 42 mols of ethylene oxide to ethylene diamine, an adduct of 48 mols of propylene oxide and 146 mols of ethylene oxide to ethylene diamine and an adduct of 48 mols of propylene oxide and 42 mols of ethylene oxide to ethylene glycol; (B) from 2.5 to 20% by weight of dimeric compounds based on ethylene oxide adducts of the formula wherein X is a bivalent linkage selected from the group consisting of wherein R" is a member selected from the group consisting of CH -CH CH -CH=CH-,

and phenylene, R'" is a member selected from the group consisting of hydrogen, hydroxyethyl and butyl and R is a member selected from the group consisting of hexamethylene and toluylene; and A and A which may be same or different, represent 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 R-Y-H and R-O-H 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 ratio to said oxyalkylene units selected from the group consisting of (a) 1 to 0 and (b) 1 to 0.03 to l to 0.3, and having a terminal methylene group derived from said oxyalkylene oxide units; (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 R-Y-H and R'-O-H wherein R represents a radical having from 8 to 36 carbon atoms selected from the group consisting of alkyl, alkenyl and monohydroxy-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 oxyalkylene units selected from the group consisting of (a) 0 to 1 and (b) 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 mol percent, and (3) a propylene oxide adduct selected from the group consisting of an adduct of 35 mols of propylene oxide to glycerine and an adduct of 48 mols of propylene oxide and 7 mols of ethylene oxide to ethylene diamine.

2. Composition of claim 1, wherein X of ingredient B is 3. Composition of claim 1 wherein ingredient A contains at least 12 oxyethylene units.

4.. Composition of claim 1 wherein R of ingredient A contains from 10 to 20 carbon atoms.

5. Composition of claim 4 wherein R of ingredient A contains from 14 to 18 carbon atoms.

6. Composition of claim wherein ingredient A contains from to 40 oxyethylene units.

7. Composition of claim 1 wherein ingredient A( 1) 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 1:03.

8. Composition of claim 1 wherein ingredient C contains from 1 to oxyethylene units and 4 to oxypropylene units in a molar ratio of oxyethylene to oxypropylene of 1:33 to 1:1.

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

10. 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.

16 References Cited UNITED STATES PATENTS 2,850,535 9/1958 Lane 260613 3,081,354 3/1963 Gaertner et al. 260-609 3,118,000 1/1964 Dupr et a1 260584 3,382,176 5/1968 Jakobi et al. 252152X FOREIGN PATENTS 1,135,122 8/1962 Germany 252152X MAYER WEINBLATT, Primary Examiner M. HALPERN, Assistant Examiner US. Cl. X.R.