US3730912A - Ternary foam control systems and detergent compositions containing same - Google Patents

Abstract

A DETERGENT COMPOSITION HAVING AN INVERSE FOAM TO TEMPERATURE RELATIONSHIP IS DISCLOSED, AS WELL AS A TERNARY COMPOSITION FOR ACCOMPLISHING THIS RELATIONSHIP WHEN ADDED TO A DETERGENT SYSTEM. THE INVERSE FOAM TO TEMPERATURE RELATIONSHIP IS PROVIDED BY A SYNERGISTIC MIXTURE OF A FATTY ACID, A POLYETHOXYLATED QUATERNARY AMMONIUM SALT, AND A HIGH MOLECULAR WEIGHT AMIDE OR A PRIMARY, SECONDARY OR TERTIARY AMINE.
D R A W I N G

Description

May 1, 1973 J. T. INAMORATO 3,730,912

TERNARY FOAM CONTROL SYSTEMS AND DETERGENT COMPOSITIONS CONTAINING SAME Filed May 28. 1970 I IDEAL FOAM FULL 000p PROFILE 80F |2o.9o [so 190 DREWASH. HEATING STAGE OFM WASH CYCLE CYCLE WASH CYCLE o.|=.--- -,----o.E--

. 3% SOAP O.F=OVEPFLOW 50 no 90. 150 I90 m 3% SOAP 1%KEMAMINE 3%SOAD 1%QUAT.

INVENTOR. F G- V JACK TfMAS INAMGRATO BY ATTOQNEY United States Patent U.S. Cl. 252528 35 Claims ABSTRACT OF THE DISCLOSURE A detergent composition having an inverse foam to temperature relationship is disclosed, as well as a ternary composition for accomplishing this relationship when added to a detergent system. The inverse foam to temperature relationship is provided by a synergistic mixture of a fatty acid, a polyethoxylated quaternary ammonium salt, and a high molecular weight amide or a primary, secondary or tertiary amine.

This application is a continuation-in-part of copending application, Ser. No. 41,359, filed May 28, 1970.

This invention relates to detergent compositions. More particularly, this invention relates to detergent compositions which have an inverse foam-to-temperature relationship and to means for accomplishing this relationship.

The use of synthetic detergents for washing clothes has assumed worldwide importance, due to the efiiciency and cheapness of such products. Thesedetergents are compounded with various additives to provide compositions having improved and desirable characteristics. Among these characteristics is that of maintaining a proper level of foam for suds.

Foaming, or sudsing, of detergents is an extremely important factor to consider when formulating a detergent composition. It is known, for example, that a detergent which over-foams does not do an efficient job of cleaning in a washing machine. On the other hand, in hand washing there is a desire on the part of most consumers for a substantial amount of foam produced by a detergent. It is therefore necessary to provide a detergent composition which produces enough foam to reassure the consumer but yet not so much foam as to inhibit the detergent action of the composition. This need has been satisfactorily achieved in many ways.

There is, however, another situation which requires a totally different approach to foam control in a detergent system. There are geographical areas where hot water is not readily available for one reason or another. In such areas, as well as others, washing machines are designed with internal water heating systems which begin their cycle with cold water and gradually heat the same to the desired operating temperature which is usually the boil. Such washing machines are used extensively, for instance, in many European countries. It is well known, however, that a detergent system which provides an adequate level of foam when used with hot water will not foam at all in cold water. Conversely, a detergent system which is compounded so that a sufficient level of foam is produced in cold water will over-foam to the extent of overflowing the washing machine when used with hot water. Of course, a detergent system which over-foams can have a foam suppressor included therein. The problem then, naturally, is that such a system will produce no foam when used with cold water. In other words, most detergent systems have essentially a direct relationship between temperature and foam, wherein as the temperature increases the amount of foam increases.

The invention disclosed and claimed in the aforementioned co-pending application, Ser. No. 41,359, filed May 28, 1970, provided the necessary inverse foam-to-temperature relationship through a synergistic binary system of a fatty acid and a polyethoxylated quaternary ammonium salt. It has been found, however, that when extremely high temperatures, i.e., about 200 F., are encountered, over-foaming occurs. The present invention solves this problem by utilizing a ternary system of a fatty acid, a polyethoxylated quaternary ammonium salt and 'a high molecular weight amide or a primary, secondary or tertiary amine.

Accordingly, it is a primary object of the present invention to provide a detergent system free of the aforementioned and other such disadvantages.

It is another object of the present invention to provide a detergent having an inverse foam-to-temperature relationship.

It is still another object of the present invention to provide a detergent system which can be used in an environment wherein it will be subject to cold water as well as hot water and still provide a satisfactory foam level.

It is yet another object of the present invention to provide a composition which will impart an inverse foamto-temperature relationship to a detergent system.

Other objects and advantages of the present invention will become apparent from the following detailed description thereof.

According to the present invention, a composition is provided for regulating the foam profile of a detergent system, comprising a ternary synergistic mixture of a fatty acid, a polyethoxylated quaternary ammonium salt, and a high molecular weight amide or a primary, secondary or tertiary amine.

In another aspect of the present invention, a detergent composition is provided having an inverse foam-to-temperature relationship which comprises an anionic detergent, inorganic builders, and a synergistic mixture of a fatty acid, a polyethoxylated quaternary ammonium salt, and a high molecular weight amide or a primary, secondary or tertiary amine.

The detergent composition could have other additives such as brighteners, germicides, soil suspending agents, anti-oxidants, bleaches, coloring materials, and perfume. It is quite unexpected to find that the mixture of a fatty acid, polyethoxylated quaternary ammonium salt, and an amine or amide provides the inverse foam-to-temperature relationship, since each of the ingredients, when used alone, do not exhibit any such properties.

The useful fatty acids which may be employed in the present invention include those saturated linear acids containing between about 8 and 30 carbon atoms in their alkyl chain. These include: capric acid lauric acid myristic acid palmitic acid stearic acid arachidic acid behenic acid lignoceric acid cerotic acid melissic acid oleic acid linoleic acid as well as various natural and synthetic mixtures thereof.

The preferred fatty acids, however, are those having alkyl chains of from about 14 to 22 carbon atoms. One such preferred fatty acid is stearic acid. Another preferred acid composition is available commercially under the name Hyfac 431. Hyfac 431 is a hydrogenated fish fatty acid having the following approximate composition:

Percent Myristic acid 8 Palmitie acid 29 Stearic acid l8 Arachidic acid 26 Behenic acid 17 Oleic acid 2 Other commercially available mixtures of fatty acids are those which are available under the name Hystrene. For instance, Hystrene 7022 comprises about 70%, C to C fatty acids. Hystrene 9022 comprises about 90% C to C fatty acids. Another such commercial product is Neofat 1858, which is a hydrogenated tallow acid. The fatty acid, used in combination with the polyethoxylated quaternary ammonium salt and the amine or amide, should be present in the final detergent composition in an amount from about 1 to about 6 by weight of the total detergent composition.

The polyethoxylated quaternary ammonium salt component of the synergistic mixture can be any such salt, although a polyethoxylated mono fatty alkyl methyl ammonium salt is preferred. For instance, a polyethoxylated (40 moles of ethylene oxide) dicoco methyl ammonium methyl sulfate has been used. Still more preferred, however, are the polyethoxylated (15 moles of E) mono fatty alkyl methyl ammonium chlorides, which are commercially available under the name Ethoquad. Specifically, the most preferred such salt is Ethoquad 18/25, which is polyethoxylated (15 moles) stearyl methyl ammonium chloride. Other suitable quaternary salts having about to 50 moles ethylene oxide may be used. Any suitable anion can be used including other halides (e.g. bromide), nitrates and sulfates.

The third component of the synergistic ternary foamsuppressing system is a high molecular weight amine or amide. By high molecular weight amine or amide is meant a primary secondary, or tertiary amine or an amide having a saturated or unsaturated alkyl chain of from about 14 to about 22 carbon atoms. In particular, amides which have been found to be useful in the present invention are behenamide and erucamide. Amines which were found particularly useful are products by Humko available under the name Kemamine. Representative of these are:

Kemamine S970di-hydrogenated tallow amine Kemamine S190di-arachidyl/behenyl amine Kemamine Pl90arachidyl/behenyl amine While primary, secondary and tertiary amines all work in the composition of the present invention, the preferred amines are the secondary and tertiary amines. Still more preferred are the secondary amines.

The useful detergents which may be used in conjunction with the foam profile regulating composition of the present invention include anionic detergents such as alkylbenzene-sulfonic acid and its salts, and compounds of the formula alkyl-phenyl-SO M, wherein alkyl is an alkyl radical of a fatty acid and M is hydrogen or an alkali metal, which compounds comprise a well-known class of anionic detergents and include sodium dodecylbenzene sulfonate, potassium dodecylbenzenesulfonate. Others are the alkali metal dialkyl sulfosuccinates, e.g., sodium dioctylsulfosuccinate, and sodium dihexylsulfosuccinate, sodium sulfoethylphthalate, sodium lauryl-panisidinesulfonate; sodium tetradecanesulfonate; sodium diisopropylnaphthalenesulfonate; sodium octylphenoxyethoxyethylsulfonate, etc.; and the alkali metal alkyl sulfates, e.g., sodium lauryl sulfate.

Among the above noted alkylbenzene-sulfonic acid and salts thereof, the preferred compounds included those which are biodegradable and which are particularly characterized by a linear alkyl substituent of from C to C and preferably from C to C It is, of course, understood that the carbon chain length represents, in general, an average chain length since the method for producing such products usually employs alkylating reagents of mixed chain length. It is clear, however, that substantially pure olefins as well as alkylating compounds used in other techniques can and do give alkylated benzene sulfonates wherein the alkyl moiety is substantially (i.e., at least 99%) of one chain length; i.e., C C C or C The linear alkyl benzene sulfonates are further characterized by the position of the benzene ring in the linear alkyl chain, with any of the position isomers (i.e., alpha to omega) being operable and contemplated.

The linear alkyl benzene sulfonates are generally and conveniently prepared by sulfonating the corresponding alkyl benzene hydrocarbons which in turn may be prepared by alkylating benzene with a linear alkyl halide, a l-alkene or a linear primary or secondary alcohol. Pure isomers (of the l-phenyl isomer) are prepared by reduction of the acylated benzene (alkyl phenyl ketone) using a modification of the Wollf-Keshner reaction. The 2-phenyl isomer is obtained from n-undecyl phenyl ketone and methyl magnesium bromide to form the tertiary alcohol which is dehydrated to the alkene and then hydrogenated. The S-phenyl isomer is obtained similarly from a n-heptyl phenyl ketone and n-butyl magnesium bromide. The other isomers are obtained in a similar manner from the appropriate n-alkyl phenyl ketone and n-alkyl magnesium bromide.

In addition to the benzene sulfonates, one may also employ the lower alkyl (C to C analogs of benzene such as toluene, xylene, the trimethyl benzenes, ethyl benzene, isopropyl benzene, and the like. The sulfonates are generally employed in the water soluble salt form which include as the cation the alkali metals, ammonium, and lower amine and alkanolamine.

Examples of suitable linear alkyl benzene sulfonates are:

sodium n-decyl benzene sulfonate sodium n-dodecyl benzene sulfonate sodium n-tetradecyl benzene sulfonate sodium n-pentadecyl benzene sulfonate sodium n-hexadecyl benzene sulfonate and the lower corresponding lower alkyl substituted homologues of benzene, as well as the salts of the cations previously referred to. Mixtures of these sulfonates may, of course, also be used with mixtures which may include compounds wherein the linear alkyl chain is smaller or larger than indicated herein, provided that the average chain length in the mixture conforms to the specific requirements of C to C Other anionic detergents are the olefin sulfonates, including long chain alkene sulfonates, long chain hydroxyalkane sulfonates or mixtures of alkenesulfonates and hydroxylalkanesulfonates. These olefin sulfonate detergents may be prepared, in known manner, by the reaction of S0 with long chain olefins (of 825, preferably l2-2l, carbon atoms) of the formula RCH=CHR where R is alkyl and R is alkyl or hydrogen, to produce a mixture of sultones and alkenesulfonic acids, which mixture is then treated to convert the sultones to sulfonates.

The linear paraffin sulfonates are also a well-known group of compounds and include water soluble salts (alkali metal, amine, alkanolamine, and ammonium) of:

l-decane sulfonic acid l-dodecane sulfonic acid l-tridecane sulfonic acid l-tetradecane sulfonic acid l-pentadecane sulfonic acid l-hexadecane sulfonic acid as well as the other position isomers of the sulfonic acid group.

In addition to the parafiin sulfonates illustrated above, others with the general range of C to C alkyls may be used, with the most preferable range being from C to C20.

The linear alkyl sulfates which are contemplated in this invention comprise the range of C to C Specific examples include sodium n-decyl sulfate; sodium ndodecyl sulfate; sodium n-octadecyl sulfate; and the ethoxylated (l to moles ethylene oxide) derivatives; and, of course, the other water soluble salt-forming cations mentioned above.

Thecomposition of the present invention may also include in addition to the foam profile regulating compounds and conventional anionic detergent compositions builders, brighteners, hydrotropes, germicides, soil suspending agents, anti-redeposition agents, antioxidants, bleaches, coloring materials (dyes and pigments), perfumes,'water soluble alcohols, non-detergent alkali metal benzene sulfonates, fabric softening compounds, enzymes, etc.

The builder is, generally, a water soluble, inorganic salt which may be a neutral salt, e.g., sodium sulfate or an alkaline builder salt such as phosphates, silicates, bicarbonates, carbonates, and borates. The preferred builders are those characterized as condensed phosphates such as polyphosphates and pyrophosphates. Specific examples of alkaline salts are: tetrasodium pyrophosphates, pentasodium tripolyphosphate (either Phase I or Phase II), sodium hexametaphosphate, and the corresponding potassium salts of these compounds, sodium and potassium silicates, e.g., sodium metasilicate and alkaline silicates (Na O; 2Si0 and Na O; 3SiO sodium carbonate, potassium carbonate and sodium and potassium bicarbonate. Other salts may also be used Where the compounds are water soluble. These include the general class of alkali metal, alkaline earth metal, amine, alkanolamine, and ammonium salts. Other builders which are salts of organic acids may also be used, and in particular the water soluble (alkali metal, ammonium, substituted ammonium and amine) salts of aminopolycarboxylic acids such as:

ethylene diamine tetra-acetic acid nitrilo triacetic acid diethylene triamine penta-acetic acid N-(2-hydroxyethyl)-ethylene diamine triacetic acid 2-hydroxyethyliminodiacetic acid 1,2diaminocyclohexane diacetic acid,

and the like.

In addition to the above ingredients, one may as previously delineated, employ hydrotropes in connection with the compositions of the instant invention. The useful hydrotropes include such compounds as sodium xylene sulfonate, potassium xylene sulfonate, sodium and potassium toluene sulfonates, in the position isomers thereof, and ethyl benzene sulfonate.

It has now been found, quite unexpectedly, that when the synergistic mixture of a fatty acid, a polyethoxylated quaternary ammonium salt, and an amine or amide, as disclosed above, is added to a conventional detergent system, or is used in combination with the above detergents and other conventional detergent additives, an inverse foam-to-temperature relationship is exhibited by the resultingrsystem.

In the composition for regulating the foam profile of a detergent according to the present invention, there is employed from about 20 to 80 percent fatty acid, from about 10 to 60 percent polyethoxylated quaternary ammonium salt and from about 10 to about 60 percent amine or amide. Preferably, there is employed from about 35 to 60 percent fatty acid, from about 20 to P percent polyethoxylated quaternary ammonium salt, and from about 20 to about 40 percent amine or amide. In terms of the total detergent system, there is employed from about 1 to 6 percent fatty acid, from about 1 to 6 percent polyethoxylated quaternary ammonium salt, and from about 1 to about 6 percent amine or amide; and preferably from about 2 to 5 percent fatty acid, from about 1 to 3 percent polyethoxylated quaternary ammonium salt, and from about 1 to about 3 percent amine or amide. All of said percentages are by weight, based on the total amount of the composition being used. In the case of the detergent systems, the percentages are based on an anionic detergent concentration of about 8 to 18 percent by weight. When less anionic detergent is present in the system, a correspondingly lesser amount of each of the fatty acid, the polyethoxylated quaternary ammonium salt, and the amine or amide can be used. Builders, when used, may range from 10-85 wt. percent.

The present invention will now be illustrated by the following, more detailed examples thereof. It is noted, however, that the present invention is not deemed as being limited thereto.

The following examples demonstrate the foam profiles of various detergent systems under the conditions of use to be encountered in Europe. The detergent compositions were tested in a Miele automatic washing machine, which is of German manufacture. The machine is a front-loading, tumbler type washing machine equipped with a heater that raises the Water temperature from room temperature to the boil. The machine operates on 220 volts, 5O cycle alternating current. In each instance, the machine was set on the white clothes setting, and a five-pound load of clean clothing was used. The water capacity is 11 liters. A detergent concentration of 0.5% was used in each cycle. This detergent concentration was provided by using 56 grams of detergent.

The machine operates on two cycles, a pre-wash cycle and a Wash cycle. In the pre-wash cycle, the temperature of the water climbs from 70 to F., and the total cycle is 12 to 14 minutes. The drum rotates for about 10 seconds, rests for 4 seconds, reverses direction, and the operation is repeated. At the end of the cycle, the machine stops, drains, and remains motionless until the wash cycle starts.

The wash cycle is divided into two stages, the heating stage and the washing stage. In the heating stage, cold water washes a second charge of detergent into the drum. During this 30-minute stage, the temperature climbs from about 90 F. to over F. The drum rotates for 4 to 5 seconds, rests for 10 seconds, reverses direction, and re peats the operation. At the end of the heating period, the machine changes its drum action and goes into the washing stage.

The washing stage lasts 18 minutes. During this time, the drum action is the same as that described for the prewash cycle. The temperature fluctuates between 190 and 200 F. during the whole washing stage.

EXAMPLE 1 Ingredients Following the foam profile test procedure outlined, the above four formulations give the results shown in FIGS. 1-4 respectively.

The vast improvement and performance of formulation 1 versus formulations 2, 3 and 4 are evident from the profile curves.

EXAMPLE 2 Example 1 is repeated, replacing in formulation 1, the amine (Armeen 2HT) as follows:

Formulation:

(5) 1% Kemamine 8-190 (6) 1.5% Kemamine 8-190 (7) 2.0% Kemamine 8-190 (8) 2.2% Kemamine P-190 (9) mixture of 1% each Kenamine 8-190 and 8-970;

results are comparable to formulation 1.

7 EXAMPLE 3 Example 1 is again repeated, replacing in formulation 1, the Ethoquad as follows:

Formulation:

(13) 4% dicoco methyl ammonium methyl sulfate +40 In the description and claims, reference to fatty acids or the like includes the corresponding water-soluble soaps thereof, preferably the alkali metal soaps such as sodium and potassium. In general, the fatty acids per se and soaps thereof may be used interchangeably depending upon economics, method of manufacture of the composition with other ingredients and its use in washing. For example, fatty acids may exist in the product when post-added to a detergent powder; or partly or wholly in the form of soap when added to a slurry or solution during manufacture of detergent products in the presence of alkaline materials or in alkaline washing solutions.

Accordingly, it is clear that the objects of this invention set forth at the outset of the specification, have been successfully achieved. The invention has been disclosed and described with respect to certain preferred embodiments and various modifications thereof will become obvious to one skilled in the art. It is to be understood that such modifications and variations are to be included within the spirit and scope of the invention which is not limited to the exemplary embodiments, but is defined only by the claims.

What is claimed is:

1. A composition for regulating the foam profile of a detergent system consisting essentially of (1) from about 20 to 80% by weight of C to C fatty acid, (2) from about 10 to 60% by weight of polyethoxylated mono fatty alkyl quaternary ammonium halide, nitrate or sulfate containing from about 10 to about 50 moles of ethylene oxide and (3) from about 10 to about 60% by weight of C -C fatty amine or amide.

2. A composition according to claim 1 wherein said fatty acid contains from about 14 to 22 carbon atoms.

3. A composition according to claim 2 wherein said fatty acid is hydrogenated. fish fatty acid.

4. A composition according to claim 2 wherein said fatty acid is hydrogenated tallow fatty acid.

5. A composition according to claim 1, wherein said fatty acid is present in from about 35 to 60 percent by weight of said composition.

6. A composition according to claim 1, wherein said polyethoxylated mono fatty alkyl quaternary ammonium halide, nitrate or sulfate is a polyethoxylated (15 mole) mono fatty alkyl methyl ammonium chloride.

7. A composition according to claim 6, wherein said polyethoxylated mono fatty alkyl quaternary ammonium halide, nitrate or sulfate is polyethoxylated (15 mole) stearyl methyl ammonium chloride.

8. A composition according to claim 1, wherein said polyethoxylated mono fatty alkyl quaternary ammonium halide, nitrate or sulfate salt is present in from about to 40 percent by Weight of said composition.

9. A composition according to claim 1, wherein said fatty amide is behenamide or erucamide.

10. A composition according to claim 1 wherein said amine is a primary amine.

11. A composition according to claim 1 wherein said amine is dihydrogenated tallow amine.

12. A composition according to claim 1 wherein said amine is a secondary amine.

13. A composition according to claim 12 wherein said amine is arachedyl-behenyl amine.

14. A composition according to claim 1 wherein said amine is a tertiary amine.

15. A composition according to claim 14 wherein said amine is di-arachedyl behenyl amine.

16. A composition according to claim 1 wherein 1) is a tallow fatty acid,

(2) is a polyethoxylated stearyl methyl ammonium salt, and

(3) is a dihydrogenated tallow amine.

17. A composition according to claim 1 wherein said polyethoxylated mono fatty alkyl quaternary ammonium halide, nitrate or sulfate is polyethoxylated (10 mole) dicoco methyl ammonium methyl sulfate or polyethoxylated (40 mole) dicoco methyl ammonium methyl sulfate.

18. A detergent composition having an inverse foamto-temperature relationship consisting essentially of (1) from about 1 to 6% by weight of C 'C fatty acid, (2) from about 1 to 6% by weight of polyethoxylated mono fatty alkyl quaternary ammonium halide, nitrate or sulfate containing from about 10 to 50 moles of ethylene oxide, (3) from about 1 to 6% by weight of C -C fatty amine or amide, (4) from about 818% by weight of anionic detergent and (5 from about 10 to by weight of a water soluble neutral or alkaline builder.

19. A composition according to claim 18, wherein said anionic detergent is a linear alkyl benzene sulfonate having about 8 to 22 carbon atoms in the alkyl group.

20. A composition according to claim 19 wherein said alkyl group has about 10 to 15 carbon atoms.

21. A composition according to claim 18, which includes about 8 to 18% linear alkyl benzene sulfonate, and builder salts selected from the group consisting of alkali metal and ammonium polyphosphates, silicates, borates, sulfates, and combinations thereof.

22. A composition according to claim 18 wherein said fatty acid contains from about 14 to 22 carbon atoms.

23. A composition according to claim 22 wherein said fatty acid is hydrogenated fish fatty acid.

24. A composition according to claim 22 wherein said fatty acid is hydrogenated tallow fatty acid.

25. A composition according to claim 18, wherein said fatty acid is present in from about 2 to 5 percent by weight of said composition.

26. A composition according to claim 18, wherein said polyethoxylated mono fatty alkyl quaternary ammonium halide, nitrate or sulfate is a polyethoxylated (15 mole) mono fatty alkyl methyl ammonium chloride.

27. A composition according to claim 26, wherein said polyethoxylated mono fatty alkyl quaterary ammonium halide, nitrate or sulfate is polyethoxylated (15 mole) stearyl methyl ammonium chloride.

28. A composition according to claim 18, wherein said polyethoxylated mono fatty alkyl quaternary ammonium halide, nitrate or sulfate is present in from about 1 to 3 percent by weight of said composition.

29. A composition according to claim 18, wherein said amide is behenamide or erucamide.

30. A composition according to claim 18, wherein said amine is dihydrogenated tallow amine.

31. A composition according to claim 18 wherein said amine is arachedyl behenyl amine.

32. A composition according to claim 18 wherein the fatty acid is a tallow fatty acid, the polyethoxylated mono fatty alkyl quaternary ammonium halide, nitrate or sulfate is a polyethoxylated stearyl methyl ammonium chloride and the amine is dihydrogenated tallow amine.

33. A composition according to claim 32 wherein the anionic detergent is a sodium dodecyl or tridecyl benzene sulfonate detergent.

34. A composition according to claim 18 wherein said polyethoxylated mono fatty alkyl quaternary ammonium halide, nitrate or sulfate is polyethoxylated 10 mole) dicoco methyl ammonium methyl sulfate or polyethoxy- 9 lated (40 mole) dicoco methyl ammonium methyl sulfate.

35. A composition according to claim 18 said anionic detergent is 'C C alkyl benzene sulfonic acid or salt thereof, C -C olefin sulfonate, C -C paraflin sulfonate or C -C linear alkyl sulfate or polyethoxylated derivative thereof containing from 1 to 100 moles of ethylene oxide.

References Cited UNITED STATES PATENTS 10 3,231,508 1/1966 Lew 252137 X 3,325,414 6/1967 Inamorato 252137 FOREIGN PATENTS 1,066,025 4/ 1967 Great Britain.

DIG 14, DIG 15

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