US3696057A - Anti-foaming compositions and cleaning compositions containing them - Google Patents

Abstract

A SYNERGISTIC ANTI-FORMING COMPOSITION CONSISTING OF A MIXTURE OF (A) A REACTION PRODUCT OF ETHYLENEDIAMINE WITH ETHYLENE OXIDE AND PROPYLENE OXIDE IN ANY SEQUENCE, HAVING A TURBIDITY POINT OF FROM 10* C. TO 35* C., AND (B) A FATTY COMPONENT SELECTED FROM THE GROUP CONSISTING OF FATTY ALCOHOLS VAVING 12 TO 18 CARBON ATOMS AND WATERINSOLUBLE REACTION PRODUCTS THEREOF WITH ETHYLENE OXIDE; SAID COMPONENTS (A) AND (B) BEING PRESENT IN A PROPORTION BY WEIGHT SELECTED FROM THE GROUP CONSISTING OF 5:1 TO 20:1 AND 1:5 TO 1:20, AS WELL AS AQUEOUS CLEANING COMPOSITIONS CONTAINING FROM 0.1 TO 1GM. PER LITER OF SAID ANTI-FOAMING COMPOSITION.

Description

United States Patent 3,696,057 ANTI-FOAMING COMPOSITIONS AND CLEANING COMPOSITIONS CONTAINING THEM Hans-Joachim Schussler, Dusseldorf-Holthausen, and Rolf Scharf, Monheim, Germany, assignors to Henkel & Cie G.m.b.H., Dusseldorf-Holthausen, Germany No Drawing. Filed Aug. 20, 1970, Ser. No. 65,721 Claims priority, application Germany, Sept. 3, 1969, P 19 44 569.3 Int. Cl. Clld 7/18 US. Cl. 252-544 10 Claims ABSTRACT OF THE DISCLOSURE A synergistic anti-foaming composition consisting of a mixture of (a) a reaction product of ethylenediamine with ethylene oxide and propylene oxide in any sequence, having a turbidity point of from 10 C. to 35 C., and (b) a fatty component selected from the group consisting of fatty alcohols having 12 to 18 carbon atoms and waterinsoluble reaction products thereof with ethylene oxide; said components (a) and (b) being present in a proportion by weight selected from the group consisting of :1 to 20:1 and 1:5 to 1:20, as well as aqueous cleaning compositions containing from 0.1 to 1 gm. per liter of said anti-foaming composition.

THE PRIOR ART In many cases it is desirable for the aqueous solutions of cleaning compositions to have a strong cleaning action and a low foaming power. For a long time, therefore, poorly foaming wetting agents especially nonionic Wetting agents have been used, provided that the cleaning effect is sufficient. However, it is often still necessary to use additional anti-foaming compositions. This applies particularly to the industrial cleaning of rigid surfaces such as metal, glass and ceramics in automatic cleaning plants. In the cleaning of bottles especially, very large throughputs take place within short periods, and development tends increasingly to shorten the treatment time. The demands on the cleaning power of the solutions are constantly increased simultaneously with the demands on the anti-foaming substances, since the baths readily tend to form foam, not only from the ingredients therein but especially through the impurities which have been introduced into the cleaning bath. The best cleaning action, however, cannot be used in practice if, at the same time, the development of foam has not been sufliciently suppressed. Therefore, it is in many cases desirable to improve further the anti-foaming action.

OBJECTS OF THE INVENTION An object of the invention is to develop an anti-foaming composition which is stable in strongly alkaline solutions and suppresses foam in the use of cleaning baths.

Another object of the invention is to develop a synergistic anti-foaming composition consisting of a mixture of (a) a reaction product of ethylenediamine with ethylene oxide and propylene oxide in any sequence, having a turbidity point of from C. to 35 C., and (b) a fatty component selected from the group consisting of fatty alcohols having 12 to 18 carbon atoms and water-insoluble reaction products thereof with ethylene oxide;

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said components (a) and (b) being present in a proportion by weight selected from the group consisting of 5:1 to 20:1 and 1:5 to 1:20.

A further object of the invention is to develop an aqueous cleaning composition containing customary washing ingredients and from 0.1 to 1 gm. per liter of a synergistic anti-foaming composition consisting of a mixture of (a) a reaction product of ethylenediamine with ethylene oxide and propylene oxide in any sequence, having a turbidity point of from 10 C. to 35 C., and (b) a fatty component selected from the group consisting of fatty alcohols having 12 to 18 carbon atoms and water-insoluble reaction products thereof with ethylene oxide; said components (a) and (b) being present in a proportion by weight selected from the group consisting of 5:1 to 20:1 and 1:5 to 1:20.

A yet further object of the invention is the development of a method for suppressing foam in strongly foaming aqueous cleaning compositions which comprises agitating a strongly foaming aqueous cleaning composition and adding thereto from 0.1 to 1 gm. per liter of a synergistic anti-foaming composition consisting of a mixture of (a) a reaction product of ethylenediamine with ethylene oxide and propylene oxide in any sequence, having a turbidity point of from 10 C. to 35 C., and (b) a fatty component selected from the group consisting of fatty alcohols having 12 to 18 carbon atoms and Water-insoluble reaction products thereof with ethylene oxide; said components (a) and (b) being present in a proportion by weight selected from the group consisting of 5:1 to 20: 1 and 1:5 to 1:20.

These and other objects of the invention will become more apparent as the description thereof proceeds.

DESCRIPTION OF THE INVENTION The present invention provides synergistic foam-inhibiting additives and a cleaning composition having said foam-inhibiting additives, comprising an anti-foaming composition a mixture of (a) A reaction product of ethylenediamine with ethylene oxide and propylene oxide in any sequence, and which has a turbidity point in the region of 10 to 35 C., and

(b) A fatty alcohol having 1 to 18 carbon atoms or water-insoluble reaction product thereof with ethylene oxide, wherein the said components (a) and (b) are present in a proportion by weight of 5 :1 to 20:1, or 1:5 to 1:20, respectively.

In the utilization of the reaction products of the ethylenediarnine with ethylene oxide and propylene oxide or propylene oxide and ethylene oxide, it is essential for the turbidity point to lie within the indicated range. Preferably, the turbidity point should lie within the range of 15 to 32 C. The respective turbidity point is found by slowly heating a 1% solution of the compound in question and observing the first easily optically recognizable turbidity. The turbidity points indicated relate to pure solutions of the substances in question. The turbidity point is altered by the addition of other foreign substances.

In the following table the turbidity points of some characteristic compounds are given. The abbreviations ED for ethylene oxide and PO for propylene oxide have been used. The statement ethylenediamine +30 E0 +60 PO.

means that 30 mols of ethylene oxide and after this 60 mols of propylene oxide have been added on per mol of ethylenediamine. Since the addition takes place statisti- TABLE A Ethylene dlamlne+30 E+60 PO" Ethylenedlamtne+30 EO+87 P0..- Ethylenedlamlne-l-iil) E0+118 PO -,Ethylenedtmatne+40 EO+78 PO... Ethyleuedtamine-lto EO+102 P0.. Ethylenedlamlne+40 EO+128 PO Ethylenedlam1ne+45 EO+99 P0. Ethylenedlamlne+46 EO+131 P0..

Ethylenedlamtne+52 PO+8 EO Ethylenedlam1ne+52 PO+18 E0-.-

a. r-u- 0o automates-m It can be seen from the table that, in order to attain the given turbidity point, generally the ratio of ethylene oxide: propylene oxide lies in the range of 1:2 to 1:4 and the ratio of propylene oxide: ethylene oxide lies in the range of 3:1 to 6.5 1. In the given ratios, in each case the alkylene oxide first mentioned is that which was added on first.

Certain gradual dilferences exist in the case of the individual products. A reaction product of ethylenediamine with about 30 mols of ethylene oxide and about 60 mols of propylene oxide has proved especially suitable.

Suitable fatty alcohols are especially dodecyl, tetradecyl, hexadecyl, octadecyl and oleyl alcohols. The waterinsoluble products of ethylene oxide with the said fatty alcohols contain in general not more than 4 mols, preferably 1 to 2 mols, of ethylene oxide per mol of fatty alcohol. Generically, the second component of the synergistic anti-foaming composition of the invention is a waterinsoluble compound having the formula wherein R is a fatty radical having from 12 to 18 carbon atoms selected from the group consisting of alkyl, alkenyl and alkadienyl, and n is an integer from 0 to 4, preferably from 0 to 2. The reaction product of oleyl alcohol with 2 mols of ethylene oxide has proved especially suitable.

In order to attain an increased anti-foaming effect it is essential for the reaction products of the ethylenediamine and ethylene oxide and propylene oxide or propylene oxide and ethylene oxide on the one hand, and fatty alcohols or their water-insoluble reaction products with ethylene oxide on the other hand to be present in the given relative proportions of 5:1 to 20:1 and 1:5 to 1:20 respectively. A synergistic etfect is in fact only obtained in the given ranges. It varies from case to case whether the fatty alcohols or their derivatives or the derivatives of the ethylenediamine should be present in excess. If this is not individually indicated in the present application, it can easily be found by a simple experiment. To some case, a synergistic effect occurs with an excess of either one or the other anti-foaming composition. In the other ranges, especially when there are equal parts of the two anti-foaming compositions, no synergistic or even a negative efiect is obtained.

Preferred for the anti-foaming compositions of the invention are mixtures of (a) a reaction product of ethylenediamine with about 30 mols of ethylene oxide and about 60 mols of propylene oxide and (b) a reaction product of oleyl alcohol with 2 mols of ethylene oxide, in a weight ratio of 18:1 to 5:1. When fatty alcohols are employed as component (b) it is usually preferable to utilize them in excess in a weight ratio of component (a) to component (b) of 1:5 to 1:18.

The cleaning compositions may contain the usual wetting agent components, especially anionic wetting agents, particularly the sulfates and sulfonates, such as alkyl sulfates, alkyl sulfonates, alkylbenzene sulfonates and nonionic wetting agents such as the polyglycol ethers, which are obtained by addition of ethylene oxide to fatty alcohols, fatty amines and carboxylic acid amides. Other customary washing compounds are suitable, for example builders and complex-formers such as orthophosphates, polymeric phosphates, silicates, soda ash, potash, gluconates and other complex-forming compounds known as themselves as cleaning substances, such as nitrilo-triacetic acid, ethylenediaminetetraacetic acid or l-hydroxy-alkane- 1,1-diphosphonic acids. The compositions may further contain caustic alkalis such as caustic potash and caustic soda in considerable amounts, especially when they are used for cleaning bottles.

The said substances may be present in the cleaning compositions in the usual concentrations. The concentration of the anti-foaming agent mixture amounts to 0.1 to 1 gm. per liter, based on the solution used.

The new anti-foaming compositions have the advantage of a further reduced foam formation together with a stability against alkalis which, especially in the case of industrial cleaners and preferably bottle cleaning compositions, enables the throughput in automatic cleaning machines to be further increased or the cleaning times to be shortenend. The synergistic effect in the reduction of foaming, which is obtained with the very specific relative proportions of the components to be used, was not to be foreseen, all the more so as no effects or negative results ccurred with other mixing ratios.

The present invention will be further described with reference to the following specific examples which are not to be deemed limitative.

Example 1 In a commercial bottle cleaning plant with an alkaline zone, the hourly output of which amounts to 8000 bottles, and a temperature of 65 C., milk bottles were cleaned with a bottle cleaning mixture having the following composition on a dry basis:

% sodium hydroxide 10% sodium tripolyphosphate 2% sodium silicate (molar ratio Na 0:Si0g=3.35)

3% anti-foaming mixture comprising (a) reaction product of ethylenediamine with 30 mols of ethylene oxide and 60 mols of propylene oxide and (b) reaction product of oleyl alcohol with 2 mols of ethylene oxide, in the .proportions of 9:1.

The concentration of the cleaning solution was 1%. There was a good cleaning action and no development of foam.

Examples 2 In a bottle cleaning machine with 2 immersion baths and an hourly output of 10,000 units, beer and lemonade bottles were cleaned at a treatment temperature of 70 C. The bottle cleaning mixture had the following compositions on a dry basis:

40% finely powdered sodium hydroxide 20% sodium tripolyphosphate 35% sodium sulfate 5% anti-foaming agent mixture comprising (a) reaction product of ethylenediamine with 30 mols of ethylene oxide and 60 mols of propylene oxide and (b) reaction product of oleyl alcohol with 2 mols of ethylene oxide, in the relative proportions of 5 1.

The bottles were provided with paper labels, which usually lead to strong foaming in the plant. When a concentration of 1.5% of the above-mentioned bottle cleaning composition was used, the plant operated for over a week without any tiresome development of foam.

Example 3 In a bottle cleaning plant with 3 separate alkaline baths and an hourly output of 24,000 units, wine bottles were cleaned at a temperature of 65 C. A 1% sodium hydroxide solution was used as a cleaning solution, to which was added 1.5 kg. of a cleaning agent concentrate per cubic meter with the following composition:

80% polymer phosphate (sodium salt) 20% anti-foaming agent mixture comprising (a) reaction product of ethylenediamine with 30 mols of ethylene oxide and 60 mols of propylene oxide and (b) reaction product of oleyl alcohol with 2 mols of ethylene oxide, in the ratio of 18:1.

The cleaning was satisfactory with only a small development of foam.

Example 4 For the preparation of a degreasing bath for steel parts a metal cleaning mixture of the following composition, on the dry basis, was used:

75% sodium hydroxide 19% trisodium phosphate 3 sodium tripolyphosphate 2% dodecylbenzenesulfonate (Na salt) 1% anti-foaming agent mixture comprising (a) reaction product of ethylenediamine with 30 mols of ethylene oxide and 60 mols of propylene oxide and (b) stearyl alcohol, in the ratio of 1 :5.

The bath concentration was 5% and the treatment temperature 80 C. The very greasy steel parts were cleaned in 15 seconds. In spite of the high content of stronglyfoaming fatty impurities introduced, no development of foam occurred.

Example 5 Machine finished parts were treated in a one-chamber spraying apparatus with a neutral liquid cleaning mixture of the following composition:

15% dodecylbenzenesulfonate (Na salt) 5% reaction product of nonyl phenol with 9 mols of ethylene oxide and 5 mols of propylene oxide 10% anti-foaming agent mixture comprising (a) reaction product of ethylenediamine with 52 mols of propylene oxide and 8 mols of ethylene oxide and (b) dodecyl alcohol, in the relative proportions of 1:5. 70% water The concentration of the cleaning composition used was 1% and the spraying temperature was 40 C. In spite of the spray pressure of 1.5 atm., no objectionable foam development resulted. Example 6 For the cleaning of work clothes in a commercial washmg machine, a cleaning mixture of the following composition was used:

30% sodium tripolyphosphatc 15% sodium perborate 10% sodium silicate (molar ratio Na O:SiO =3.3)

10% dodecylbenzenesulfonate (Na salt) 25 sodium sulfate 10% anti-foaming agent mixture comprising (a) reaction product of ethylenediamine with 46 mols of ethylene oxide and 131 mols of propylene oxide and (b) reaction product of oleyl alcohol with 2 mols of ethylene oxide, in the ratio of 5:1.

The concentration of the cleaning composition used was 0.5%. A satisfactory cleaning result could be obtained in the washing machine without any troublesome development of foam.

Example 7 In order to test the anti-foaming action, test solutions were prepared which contained diiferent amounts (given in p.p.m.) of tetrapropylenebenzenesulfonate in the form of the triethanolamine salt as the foam-producing agent tested.

The churning apparatus according to DIN 53903 was used as the test apparatus. In the following tables the results of the tests are given in cc. of foam which were obtained under the difierent conditions with the antifoaming compositions indicated in each case. In the left hand column the amount of foamer tested is noted, then the foam numbers without anti-foaming composition and after that the results with addition of the anti-foaming composition alone and in various mixing proportions (given in p.p.m.). The individual components are denoted by I and II and correspond to the data at the top of the table. The notations E0 for ethylene oxide and PO for propylene oxide were used as previously defined. Ocenol is a commercial oleyl alcohol.

TABLE 1 Ethylenedlamlne 30 mol E0 mol PO (I) /ocenol 2 mol E0 (II), test temperature 0.

Volume of foam (ml.)

Without antifoaming composition or mixture 250 p.p.m. 200 p.p.m. 150 p.p.m. 100 p.p.m: Test foamer of such 300 I; 50 I; 100 I; 150 I; 200 300 (p.p.m.) compositions p.p.m. I p.p.m. II p.p.m. II p.p.m. II p.p.m. II p p.111. II

TABLE 2 Ethylenediamine 30 mol E0 60 mol P0 (DIIatty alcohol 012 (II), test temperature 65 0.

Volume of loam (ml.)

Without antiioaming composition or mixture 250 p.p.m. 200 p.p.m. 150 p.p.m. p.p.m. Test foamer of such 300 I; 50 I; 100 I; 150 I; 200 300 (p.p.m.) compositions p pm. I p.p.m. II p.p.m. II p.p.m. II p.p.m. II p.p.m. II

TABLE 3 Ethylenedlamine 30 mol E 60 21101 6P5? gflfatty alcohol Cm (II), test temperaura Volume of foam (ml.)

Without cntlfoaming composition or mixtures 250 p.p.m. 200 p.p.m. 50 p.p.m.

of such 300 I; 50 I; 100 I; 250 300 compositions p.p.m. I p.p.m. II p.p.m. II p.p.m. II p.p.m. II

TABLE 4 Ethylenediamiue mol E0 60 mol PO (I)/fatty alcohol C'is (II), test temperature 65 (J.

Volume of Ioam (ml.)

Without antifoaming composition or mixture 250 p.p.m. 200 ppm. 100 p.p.m. 5O p.p.m. Test foamer of such 300 I; I; 100 I; 200 I; 250 300 (p.p.m.) compositions p.p.m. I ppm. II ppm. 11 p.p.m. II p.p.m. II p.p.m. II

TABLE 5 Ethylencdiamiue 52 11101 PO 8 mol E0 (1)/ocenol 2 mol E0 (11), test temperature 0.

Volume of foam (ml.)

Without antitoaming composition or mixture 250 p.p.m. 200 p.p.m. 100 ppm. 60 p.p. Test ioamer of such 300 I; 50 I; 100 I; 200 I; 250 300 (p.p.m.) compositions p.p.m. I p.p.m. II p.p.m II p.p.m. II ppm. II p.p.m. II

TABLE 6 Ethylenediamino 52 moi P0 8 mol E0 (Dlfatty alcohol C (II), test temperature 65 0.

Volume of foam (1111.)

Without entifoaming composition or mixture 200 p.p.m. 150 p.p.m. 100 p.p.m. 50 p.p.m. Test foamer of such 300 I; 100 I; 150 I; 200 I; 250 300 (p.p.m.) compositions p.p.m. I p.p.m. II p.p.m. II p.p.m. II p.p.m. II ppm. II

TABLE 7 Ethylenediamine 46 mol E0 131 mol Pgfi flglocenol 2mol E0 (II), test temperature Volume of foam (mL) Without autifoaming composition or mixture 250 p.p.m. 50 ppm.

of such 300 I; 250 300 Test Ioamer (p.p.pm) compositions p.p.m. I p.p.m. II p.p.m.I1 p.p.m. II

TABLE 8 Ethylenediamine 52 mol PO 18 mol E (D/ocenol 2 mol E0 (II), test temperature 65 0.

Volume of foam (mL) Without autiioaming composition or mixture 250 p.p.m. 200 ppm. 100 ppm. 50 ppm. Test foamer of such I; 50 I; 100 I; 200 I; 250 3 (p.p.m.) compositions p.p.m. I p.p.m. II ppm. II p.p.m. II p.p.m. II p.p.m. II

The preceding specific embodiments are illustrative of the practice of the invention. It is to be understood, however, that other expedients known to those skilled in the art may be employed without departing from the spirit of the invention or the scope of the appended claims.

We claim:

1. A synergistic anti-foaming composition consisting of a mixture of (a) an oxyalkylation reaction product of ethylenediamine with ethylene oxide and propylene oxide in any sequence, where, when the ethylene oxide is reacted first, the ethylene oxide: propylene oxide ratio is from 1:2 to 1:4 and when propylene oxide is reacted first, the propylene oxide:ethylene oxide ratio is from 3:1 to 6.5 :1, said oxyalkylation reaction product having a turbidity point of from 15 C. to 32 C., and (b) a water-insoluble fatty component having the formula wherein R is a fatty radical having 12 to 18 carbon atoms selected from the group consisting of alkyl, alkenyl and alkadienyl and n is an integer from 0 to 2; said components (a) and (b) being present in a proportion by weight of :1 to 20:1.

2. The composition of claim 1 wherein component (a) is the reaction product of ethylenediamine with about 30 mols of ethylene oxide and about 60 mols of propylene oxide and component (b) is the reaction product of oleyl alcohol with 2 mols of ethylene oxide.

3. The composition of claim 1 having from 5 to 18 parts by weight of the reaction product of ethylenediamine with about 30 mols of ethylene oxide and about 60 mols of propylene oxide as component (a) and 1 part by weight of the reaction product of oleyl alcohol with 2 mols of ethylene oxide as component (b).

4. An aqueous cleaning composition containing customary washing ingredients selected from the group consisting of anionic sulfate wetting agents, anionic sulfonate wetting agents, non-ionic wetting agents, builders and complex-formers, and caustic alkalis and from 0.1 to 1 gm. per liter of a synergistic anti-foaming composition consisting of a mixture of (a) an oxyalkylation reaction product of ethylenediamine with ethylene oxide and propylene oxide in any sequence, where, when ethylene oxide is reacted first, the ethylene oxide:propylene oxide ratio is from 1:2 to 1:4 and when propylene oxide is reacted first, the propylene oxide:ethylene oxide ratio is from 3:1 to 6.5 :1, said oxyalkylation reaction product having a turbidity point of from C. to 32 C., and (b) a fatty component having the formula wherein R is a fatty radical having 12 to 18 carbon atoms selected from the group consisting of alkyl, alkenyl and alkadienyl and n is an integer from 0 to 2; said components (a) and (b) being present in a proportion by weight of 5:1 to :1.

5. The aqueous cleaning composition of claim 4 wherein component (a) is the reaction product of ethylenediamine with about mols of ethylene oxide and about 60 mols of propylene oxide and component (b) is the reaction product of oleyl alcohol with 2 mols of ethylene oxide.

6. The aqueous cleaning composition of claim 4 wherein said anti-foaming composition contains from 5 to 18 parts by weight of the reaction product of ethylenediamine with about 30 mols of ethylene oxide and about 60 mols of propylene oxide as component (a) and 1 part by weight of the reaction product of oleyl alcohol with 2 mols of ethylene oxide as component (b).

7. A synergistic anti-foaming composition consisting of a mixture of (a) an oxyalkylation reaction product of ethylene diamine with about 30' mols of ethylene oxide and about 60 mols of propylene oxide, having a turbidity point of from 20 C. to 30 C., and (b) a fatty component having the formula wherein R is a fatty radical having 12 to 18 carbon atoms selected from the group consisting of alkyl, alkenyl and alkadienyl and n is an integer from 0 to 2; said components (a) and (b) being present in a proportion 1:5 to 1:20.

8. A synergistic anti-foaming composition consisting of a mixture of (a) an oxyalkylation reaction product of ethylenediamine with ethylene oxide and propylene oxide in any sequence, where, when ethylene oxide is reacted first, the ethylene oxide:propylene oxide ratio is from 1:2 to 1:4 and when propylene oxide is reacted first, the propylene oxide:ethylene oxide ratio is from 3:1 to 65:], said oxyalkylation reaction product having a turbidity point of from 15 C. to 32 C., and (b) a water-insoluble fatty component having the formula wherein R is a fatty radical having 12 to 18 carbon atoms selected from the group consisting of alkyl, alkenyl and alkadienyl and n is an integer from 0 to 2 said components (a) and (b) being present in a proportion by weight of 1:5 to 1:20.

9. The composition of claim 8 wherein component (a) is the reaction product of ethylenediamine with about 30 mols of ethylene oxide and about 60 mols of propylene oxide and in components (b), n is 0 and said components (a) and (b) are present in a proportion of 1:5 to 1:18.

10. An aqueous cleaning composition containing customary washing ingredients selected from the group consisting of anionic sulfate wetting agents, anionic sulfonate wetting agents, non-ionic wetting agents, builders and complexformers, and caustic alkalis and from 0.1 to 1 gm. per liter of a synergistic anti-foaming composition consisting of a mixture of (a) an oxyalkylation reaction product of ethylenediamine with ethylene oxide and propylene oxide in any sequence, where, when ethylene oxide is reacted first, the ethylene oxide:propylene oxide ratio is from 1:2 to 1:4 and when propylene oxide is reacted first, the propylene oxide:ethylene oxide ratio is from 3:1 to 6.5 :1, said oxyalkylation reaction product 11 12 having a turbidity of from 15 to 32 C., and (b) a fatty 3,356,613 12/1967 Gedge 252-137 component having the formula 3,382,176 5/1968 Jakobi et a1. 252-89 c 3,463,737 8/1969 Kasperl et a] 252-153 R 3,557,003 1/1971 Morris et a1. 252-90 wherein R 1s a fatty radical having 12 to 18 carbon atoms 5 selected from the group consisting of aikyl, alkenyl and FOREIGN PATENTS alkadienyl and n. is an integer from 0 to 2; said compo- 830 875 3/1960, Great Britain nents (a) and (b) being present in a proportion of 1:5 to 1120- MAYER WEINBLA'IT, Primary Examiner References Cited 10 UNITED STATES PATENTS 2,867,585 1/1959 Vitale 252-135 1 252-89, 321, 358, 357, 525, Dig. 14

3,312,626 4/1967 Hooker 252-152