US3808156A

US3808156A - Chemical composition

Info

Publication number: US3808156A
Application number: US00201197A
Authority: US
Inventors: R Gorsich; M Tuvell; W Dewitt
Original assignee: Ethyl Corp
Current assignee: Ethyl Corp
Priority date: 1971-11-22
Filing date: 1971-11-22
Publication date: 1974-04-30
Anticipated expiration: 1991-04-30
Also published as: FR2160886B1; JPS5023841B2; FR2160886A1; JPS4862805A

Abstract

IT IS DISCLOSED THAT GEL FORMATION IN LIQUID DETERGENTS CONTAINING OLEFIN SULFONATES OF 12 TO 16 CARBON ATOMS PER MOLECULE CAN BE AVOIDED BY THE PRESENCE OF ALKALI METAL, AMMONIUM OR ETHANOL AMMONIUM SALTS OF HYDROXYALKANE SULFONIC ACIDS HAVING FROM 2 TO 7 CARBON ATOMS PER MOLECULE IN SAID SYSTEMS. TYPICAL SYSTEMS MAY INCLUDE IN ADDITION TO THE OLEFIN SULFONATE AND THE HYDROXYALKANE SULFONIC ACID SALT, OTHER DETERGENT ACTIVES SUCH AS ALKYL ETHER SULFATES, TERTIARY AMINE OXIDES, AMIDES, ETHANOL AMIDES AND OTHER CONVENTIONAL DETERGENT ACTIVES AND ADJUVANTS.

Description

United States Patent 3,808,156 CHEMICAL COMPOSITION Richard D. Gorsich, Melvin E. Tuvell, and William J.

Dewitt, Baton Rouge, La., assignors to Ethyl Corporation, Richmond, Va. No Drawing. Filed Nov. 22, 1971, Ser. No. 201,197 Int. Cl. Clld 1/14, 1/83, N84 US. Cl. 252-545 12 Claims ABSTRACT OF THE DISCLOSURE It is disclosed that gel formation in liquid detergents containing olefin sulfonates of 12 to 16 carbon atoms per molecule can be avoided by the presence of alkali metal, ammonium or ethanol ammonium salts of hydroxyalkane sulfonic acids having from 2 to 7 carbon atoms per molecule in said systems. Typical systems may include in addition to the olefin sulfonate and the hydroxyalkane sulfonic acid salt, other detergent actives such as alkyl ether sulfates, tertiary amine oxides, amides, ethanol amides and other conventional detergent actives and adjuvants.

BACKGROUND OF THE INVENTION Field of the invention This invention relates to liquid detergent compositions containing olefin sulfonates in aqueous systems and is directed to the avoidance of the gel formation problem characteristic of aqueous systems containing ole-fin sulfonates. In accordance with the teachings of the present invention, the gel formation problem is avoided or materially reduced by using in such aqueous olefin sulfonate systems a soluble salt of a hydroxy-alkane sulfonic acid and in particular one wherein the hydroxy group is an omega hydroxy group and wherein the alkane structure contains form 2 to about 6 carbon atoms.

Description of the prior art Although light duty liquid detergent formulations containing LAS (linear alkyl aryl sulfonate) have been used on a large scale for many years, particularly for dishwashing, it has been discovered that it is not possible to directly substitute olefin sulfonates for the LAS in such prior formulations or in similar ones because the resulting compositions have a tendency toward the formation of gels in storage in containers or in dispensers used for such formulations. The simple inexpensive dispensers familiar to most of the people who use liquid dishwashing detergents contain a metering or restriction arrangement such as an orifice or small diameter passage or port which retains at least a residual quantity of liquid detergent in contact with the air after each usage aggravates the gelling problem. Thus olefin sulfonates have been characterized by unlikely acceptance because of difficulty of use in the conventional manner familiar to the housewife. Despite the attractiveness of an olefin sulfonate based detergent from biodegradability and cost-effectiveness viewpoints, such cannot be used if it cannot be removed from the container in an easy and conventional manner.

The bottle-cap dispenser is an example of a widelyused type of dispenser that is prone to pluggage due to the formation of gels with olefin sulfonates. To hold costs low, this dispenser usually contains a simple arrangement of a flow passage having a diameter of from several millimeters up to about 10 or 20 millimeters, typically millimeters. The small diameter and exposed position relative to air provides a particularly adverse combination of conditions prone to gellation.

Olefin sulfonate detergents are generally used as formulations containing other detergent materials. A typical 3,808,156 Patented Apr. 30, 1974 containing higher R alkyl groups such as lauryl and myristyl (C H and (C I-I groups. Although the olefin sulfonates may be used in formulations containing only one of the aforementioned AES, amine oxide or amide materials, a particularly preferred formulation is a formulation which contains both ABS and amides or both ABS and amine oxide together with the olefin sulfonates.

Other conventional detergent active and adjuvant materials normally present in light duty formulations such as the foregoing include coupling agents which typically are lower alkanols such as ethanol; dyes; perfumes; water softeners; etc. Such systems are generally made into aqueous systems containing 50-75 wt. percent water providing a liquid detergent which is not prohibitively expensive to transport and is easy and convenient to use except for the problem of gelling which manifests itself usually as pluggage of the small diameter cap metering passage after only several uses; however, some systems such as the amine oxide containing systems are so prone to gelling that they form gels on storage even in the bottle itself.

SUMMARY OF THE INVENTION Once the gelling problem was discovered, attempts were made to solve it using numerous approaches; however, all efforts met with little or no success until it was discovered that the gellation problem could be avoided with the conventional prior art described ADS-containing systems by the addition of a comparatively small amount of a hydroxy alkane sulfonate compound of the formula In this formula, n is 1 to 6, preferably 1 or 2 particularly 1; and M is an alkali metal, ammonium or ethanol ammonium cation. Once this discovery was made, numerous formulations involving wide ranges of proportions of the ingredients discussed were tested including formulations having various percentages and ratios of ABS, amine oxide and amide to determine the proportions of components which can be dispensed through conventional metering cap systems without undue gelling tendencies.

The amount of anti-gelling compound useful for the anti-gelling capability ranges from about 1 to about 15 percent by weight of the liquid detergent formulation. A preferred range is from about 3 to about 10 percent by weight, about 5 percent by weight being particularly preferred. On a ratio basis, the ratio of detergent actives relative to the HOCH (CH ),,SO M is from about 2:1 to about 30:1.

In accordance with the present invention, a particularly preferred anti-gelling additive is sodium isethionate or beta hydroxyethane sulfonic acid sodium salt and which has the formula HOCH CH SO Na. Other typical additives include omega hydroxypropane sulfonic acid potassium salt, omega hydroxyisopropane sulfonic acid sodium salt, omega hydroxybutane sulfonic acid sodium salt, omega hydroxypentane sulfonic acid potassium salt, omega hydroxyhexane sulfonic acid monoethanol ammonium salt, omega hydroxybutane sulfonic acid ammonium salt, beta hydroxyethane sulfonic acid triethanol ammonium salt, omega hydroxypropane sulfonic acid diethanol ammonium salt.

The hydroxyalkane can be produced by any suitable pror art process. For example, the production of beta hydroxyethane sulfonic acid sodium salt is described by Lauer and Hill in Journal of the American Chemical Society, vol. 58, p. 1873 (1936). This compound is produced by reacting NaHSO with ethylene oxide.

The olefin sulfonate used is typically an alkali metal, ammonium or ethanol ammonium salt of a mixture of alkene and hydroxyalkane sulfonates having from about 12 to about 16 carbon atoms per molecule. It is obtained by reacting olefin with gaseous uncomplexed S in a ratio of about 1 mol of S0 per mol of olefin followed by a saponification with an appropriate base such as NaOH, preferably at temperatures of from about 100 to about 150 C. As disclosed in U.S. Pat. 3,332,876, olefin sulfonates are produced typically by a reaction of the olefin in a liquid S0 diluent system or in a gaseous diluent system. An example of the former is U.S. Pat. 2,061,617 while examples of the latter are U.S. Pats. 2,697,031 and 3,169,- 142.

Preferred sulfonates are those which are predominantly of a structure with a sulfonate group attached to a terminal C atom. Sulfonates whose sulfonate group are attached to non-terminal carbon atoms such as those produced by the sulfonation of internal olefins are also desirable, particularly when such are components of mixed systems containing derivatives of vinyl, vinylidene and internal types of olefins. Such sulfonates are characterized as being of substantially open chain carbon skeleton structures.

Although the derivatives of pure olefins may be used or may be produced separately and blended into mixtures as herein described, the sulfonation of mixtures of olefins is preferred, typically mixtures having up to about 20 percent C 2, up to about 100 percent C and up to about 80 percent C and which contain predominantly straight chain terminal olefins plus from about 3 to about 30 mol percent of beta branched terminal olefins and from about 3 to about 12 mol percent of internal olefins, the latter preferably being predominantly straight chain. Such preferred olefins are typically obtained by the so-called Ziegler process of chain-growth with ethylene on a lower trialkyl aluminum compound to produce a higher alkyl trialkyl aluminum as described in U.S. Pat. 2,826,598, followed by an ethylene displacement liberating the desired higher molecular weight olefins. Such an ethylene displacement is described in U.S. Pat. 3,389,161. The process is also described in Annalen der Chemie, vol. 629, Nos. 1-3, pp. 172-198. The olefins thus obtained are acyclic in structure and almost exclusively mono olefins.

The sulfonates thus produced are essentially acyclic and contain a wide spectrum of open chain compounds in two general classes of unsaturated and hydroxyalkane compounds some of which have two or more sulfonic acid groups and which frequently are called disulfonates. The compounds are predominantly alkene sulfonates and hydroxyalkane sulfonates many of which are described individually or in groups in U.S. Pats. 2,061,617; 2,061,- 618; 2,061,619; 2,061,620; 2,160,343; 2,187,244; 2,365,- 783; 2,383,737; 2,383,738; 2,486,922; 2,529,538; 2,923,- 728; 3,169,142; 3,259,645; 3,270,038; 3,328,460; 3,332,- 880; 3,346,505; 3,350,428; 3,384,597; 3,409,637; 3,420,- 875; 3,424,693; 3,424,694; 3,428,654; 3,444,087; 3,444,- 191; 3,488,384; 3,506,580; 3,531,518; 3,535,339; 3,544,- 475; 3,565,809; and Re. 22,548.

The alcohol ether sulfate component optionally used in compositions in accordance with the present invention is typically obtained as an aqueous system of the product of sulfntion of ethoxylated alcohols with chlorosulfonic acid.

4 The alcohols ethoxylated are pure alkanols or mixtures of As mentioned also in U.S. Pat. 3,332,876, the alkyl ether prior literature, such are less preferred in connection with U.S. Pats. 3,384,651 and 3,415,861. The ethoxylated derivatives preferably average from about 1 to about 5 ethylene oxide units per molecule.

As mentioned also in U.S. Pat. 3,332,876, the alkl ether sulfates can be made by the condensation by known methods of ethylene oxides on to monohydric alcohols from various natural or synthetic sources and having 10 to 18 carbon atoms per molecule. Molar proportions of ethylene oxide to alcohol are generally 1 to 5. The resulting ethoxylated alcohol is then sulfated and neutralized with an appropriate base such as alkali metal hydroxide, ammonium hydroxide of ethanol ammonium base. Although the alkaline earth metal salts are generally discussed in prior literature such are less preferred in connection with the present invention.

The amide component used in formulation in accordance with the present invention are fatty acid amides and fatty acid monoand di-lower alkanol amides having from about 10 to about 14 carbon atoms in the fatty acid alkyl groups, particularly those having also lower alkanol groups of from 2 to 6 carbon atoms such as lauryl monoethanol amide, myristyl diethanol amide, myristyl mono isopropanol amide and lauryl diisopropanol amide. In such amides, the alkyl groups present are preferably pure individual or mixed coconut range alkyls, typically a mixed alkyl distribution of a whole cut coconut oil or of a center cut coconut oil.

Suitable amides and their methods of production are well known to those skilled in the art as shown, for example, by U.S. Pats. 2,607,740 and 3,332,878, both of which, like all other patents and literature cited herein are herewith incorporated by reference.

Amine oxides suitable for use in the compositions of the present invention are conventional detergent components Whose structures and methods of preparation are well known to those skilled in the art as disclosed for example by US. Pats. 2,169,976; 3,001,945; 3,234,282; 3,317,430; 3,397,239 and by Canadian Pat. 847,303.

Typical and preferred amine oxides are long chain dimethyl amine oxides such as lauryl dimethyl amine oxide and myristyl dimethyl amine oxide.

To provide a standard of comparison, prior art LAS formulations are discussed in Soap and Chemical Specialties, September 1967, p. 108. Therein are disclosed the following compositions.

Percent LAS 10 25 AES 5 10 Na xylene sulfonate 4 10 Laurie monoethanol amide- 2 5 Ethanol 3 12 Water. Balance Balance Total- 100 DISCUSSION OF THE INVENTION CLAIMED in R and R are lower alkyl radicals or hydroxy alkyl radicals having from 1 to about 4 carbon atoms and R is a saturated aliphatic radical having from about to about 20 carbon atoms, (3) an alkyl ether sulfate having the formula RO(C H O),,SO M, wherein R is an alkyl chain of from about 10 to about 18 carbon atoms; x is a value from 1 to about 5, the cation of said sulfonate and the cation of M of such sulfate being independently selected from the group consisting of alkali metal, ammonium and ethanol ammonium; plus (C) a hydroxyalkane sulfonate of the formula HOCH (CI-I ),,SO M', wherein n is from 1 to about 6 and the cation M is alkali metal, ammonium or ethanol ammonium and (D) water. The composition contains from about to about 60 percent by weight of A+B+C, the proportions of A to B being from about 15:1 to about 1:1 on a weight basis and the weight ratio of A+B to C being from about 2:1 to about 30:1.

In a preferred aspect of the present invention, the hydroxyalkane sulfonate is beta hydroxyethane sulfonic acid, sodium salt.

In preferred embodiments of the present invention a coupling agent is used which preferably is a lower alkanol having up to about 6 carbon atoms per molecule. A preferred alkanol is ethyl alcohol. Other suitable alkanols include normal propyl alcohol, isopropyl alcohol, butyl alcohols, amyl alcohols, and hexyl alcohols. The coupling agent is used in proportions of up to about 15 percent by weight based on the composition, more preferably from about 2 to about 10 percent by weight, on the same basis.

In a preferred aspect of the present invention, the mono olefin sulfonate is the product of the saponification with NaOH of the product of sulfonation of predominantly straight chain terminal olefins with uncomplexed S0,; in proportions of from about 0.9 to about 1.1 mols of S0 per mol of olefin.

In a preferred aspect of the present invention, the predominantly straight chain terminal olefins used in the sulfonation contain from about 3 to about 30 percent on a mol basis of beta-branched terminal olefins and from about 3 to about 12 percent on a mol basis of internal olefins. Preferably the internal olefins are substantially all straight chain.

In a preferred aspect of the present invention, the proportionsof Components A, B and C on a weight basis are from about 15 to about 30 percent, from about 10 to about percent, and from about 1 percent to about 10 percent, respectively.

In accordance with a preferred aspect of the present invention, the proportions of Components A, B and C on a weight basis are from about 15 to about 30 percent, from about 10 to about 20 percent, and from about 1 percent to about 15 percent, respectively, and the Component B is a mixture of alkyl ether sulfate as defined in the foregoing and fatty acid monoor di-lower alkanol amide as described in the foregoing in a weight ratio of from about 4:1 to about 2:1 of alkyl ether sulfate relative to amide.

In accordance with a preferred aspect of the present invention, the proportions of A, B and C on a weight basis are from about 15 to about 30 percent, from about 10 to about 20 percent, and from about 1 percent to about 10 percent, respectively, and the Component B is a mixture of alkyl ether sulfate and tertiary amine oxide in weight ratio of from about 4: l to about 2:1 of alkyl ether sulfate relative to tertiary amine oxide.

In a particularly preferred combination in accordance with the present invention, Component A is the product of saponification with NaOH of the product of sulfonation with uncomplexed S0,, of a mixture of predominantly straight chain terminal olefins having from about 12 to about 16 carbon atoms per molecule. In this preferred embodiment, Component B is a mixture of alkyl ether sulfate and lauryl dimethylamine oxide or, alternately,

myristyl dimethyl amine oxide in a weight ratio of about 3:1, and Component C is beta hydroxyethane sulfonic acid, sodium salt. In this preferred embodiment, the proportions of Components A, B and C on a weight basis are about 21 percent, about 16 percent, and about 5 percent, respectively, and the system contains about 5 percent ethyl alcohol as coupling agent. Particularly preferred compositions in accordance with this embodiment contain the usual proportions of other conventional detergent adjuvants and actives including perfume, dye, water softeners, etc. as described in the patents cited herein.

Formulations of olefin sulfonates in accordance with the present invention preferably are made into aqueous systems ranging from about 50 to about 75 percent water on a weight percent basis providing a more or less thick liquid system.

The detergent active ingredients mentioned as well as the hydroxyalkane sulfonic acid Component (C) are for the most part used in the form of solids added to water to ultimately result in a system of the desired water content. An exception to this is the alcohol ether sulfate which is usually obtained in an aqueous solution of about 60 wt. percent AES concentration. On an anhydrous adjuvantfree weight percent basis, preferred compositions of the present invention are expressed broadly as 40-70' percent olefin sulfonate, 5-40 percent alcohol ether sulfate and 1-20 percent amide.

The lower alkanol described as useful as a coupling agent, typically ethanol, may be replaced wholly or partially by humectants such as propylene glycol, glycerine and sorbitol.

EXAMPLES The following detergent formulations were made and tested by dispensing from a 12 oz. plastic bottle having a screw-on cap containing a tubular passage therein of approximately 5 millimeters diameter and 20 millimeters length. grams of each formulation was used for the tests. Three times each day at about 8:00 a.m., 12:00 noon and 4:00 pm. the bottle was inverted and squeezed so as to discharge about 2 cc. of the detergent sample contained therein. Following each discharge, the bottle was replaced in an upright position and allowed to stand, the cap portion being uppermost. This procedure was continued until the discharge passage became blocked with gel or until the contents of the bottle were exhausted. All samples shown as containing beta hydroxyethane sulfonic acid, sodium salt, successfully passed the bottle cap test for gelling. All samples that did not have beta hydroxyethane sulfonic acid, sodium salt failed by pluggage of the discharge passage within two or three days after the start of the test.

The AES was Alfonic l4-12A ether sulfate manufactured by Continental Oil Company. It is based on 3 mols ethoxylate of a mixture of mainly dodecanol and tetradecanol in a 40/60 ratio by weight, as the ammonium salt.

The lauryl dimethyl amine oxide was Aromox (Armour Industrial Chemical Co.) DMMCDW containing 1.0 percent C 70.0 percent C 24 percent C 5 percent C by weight distribution of the long chain alkyl groups.

The monoethanol amide was Stepan Ninol AA-62 Extra.

The beta hydroxyethane sulfonic acid, sodium salt was GAF Sodium Isethionate manufactured by General Aniline and Film Company.

The A08 was a C /C olefin derivative.

The A08 used was the product of saponification at C. with NaOH of the product of sulfonation with gaseous S0 in a falling-film reactor at 30 C. of olefins (Wt. percent C 0.4; C -66.2; C 33.4; average C No. 14.6, average MW 205) (mol percent by NMR vinyl79.2; vinylidene12.5; internal-8.2) produced by displacement of the product of chain growth of ethylene or triethyl aluminum.

EXAMPLE I [Weight percent of components shown] A B C D E F G H I J AES 12. 7 s 12 o 12. 7 s. o 0 12. 0 o Ethanol- 6.0 e o. 0 e s. 9 6.0 s. o 6.0 a. 0 s. 9

LMMEA- 0 0 6.3 0 0 0 0 6.3 0 0 Amine oxide 0 0 0 4 5. 0 0 0 0 4. 0 5. 0

Beta hydroxy ethane sulfonlc acid, sodium salt.... 8. 0 6 6. 0 6 5. 9 0 0 0 0 0 A09 25. 3 18 31. 7 21 28. 1 25. 3 18. 0 31. 7 2l. 0 28. 1 Watm- Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Total 100. 0 100 100. 0 100 100. 0 100. o 100. 0 100. 0 100. 0 100. 0

EXAMPLE II (C) a hydroxyalkane sulfonate of the formula: A quick screening test was provided for determining 2 z)n s the gelling characteristics of detergent formulations. The wherein n is from 1 to about 6, and the cation M components of the formulations were as described in Example I. A glass plate approximately 70 cm. in length was placed with one end thereof 17.5 centimeters higher than the other forming an inclined plane surface. A portion of the detergent formulation to be tested was placed upon the glass plate near the upper end and the flow characteristics that resulted were evaluated. In those instances where a smooth substantially straight downward flow along the plate was obtained, the material under test was rated as having a satisfactory performance with regard to anti-gelling, the results correlating closely with the bottle cap test. An unsatisfactory performance with regard to anti-gelling was indicated by the presence of a very irregular flow pattern as a gel film formed on the forward edge of the downward flowing stream causing the material to fiow sideways to by-pass the obstructions resulting from the gel formation. Again in every instance tabulated herein the compositions using beta hydroxyethane sulfonic acid, sodium salt were found to produce test results indicative of suitable non-gelling properties for the sodium isethionate-containing compositions in contrast to unsatisfactory gelling properties for the similar compositions that did not contain beta hydroxyethane sulfonic acid, sodium salt.

is alkali metal, ammonium or ethanol ammonium, and

(D) water, said composition containing from about 15 to about 60 percent by weight of A+B+C, the proportions of A to B being from about 15:1 to about 1:1 on a wt. basis and the weight ratio of A plus B to C being from about 2:1 to about 30:1.

2. The composition of claim 1 wherein the hydroxy alkyl sulfonate is beta hydroxyethane sulfonic acid, sodium salt.

3. The composition in accordance with claim 1 containing a coupling agent in proportions of up to about 15 percent by weight of the composition.

4. The composition of claim 3 wherein the coupling agent is ethyl alcohol.

5. The composition of claim 1 wherein the monoolefin sulfonate is the product of the saponification with NaOH of the product of sulfonation of predominantly straight chain terminal olefins with uncomplexed 80;, in proportions of from about 0.9 to about 1.1 mols of S0 per mol of olefin.

6. The composition of claim 1 wherein the predominantly straight chain terminal olefins used in the sulfona- EXAMPLE H [Weight percent of components shown] A B C D E F G H I .1

[UPS 16 3 10 9 6 16 3 10 9 6 Ethanol 12 6 15 10 15 12 6 15 10 15 T.MM1 A 0 0 4 0 0 0 0 4 0 0 LMDF A 6 9 0 2 4 6 9 0 2 4 Beta hydroxy ethane sulionic acid, sodium salt-... 4 6 8 6 7 0 0 0 0 0 AOS 1e 20 25 25 2c 16 20 25 25 2e Wam- Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Total 100 100 100 100 100 100 100 100 100 100 What is claimed is: 1. A gel resistant liquid detergent composition consisting essentially of:

(A) a monoolefin sulfonate having from about 12 to about 16 carbon atoms in the molecule; (B) at least one of:

(1) fatty acid monoor di-lower alkanol amide, the fatty acid groups containing from about 10 to about 14 carbon atoms, (2) tertiary amine oxide of the formula tion contain from about 3 to about 30 percent on a mol basis of beta branched terminal olefins and from about 3 to about 12 percent on a mol basis of internal olefins.

7. A composition in accordance with claim 1 wherein the proportions of Components A, B and C on a weight basis are from about 15 to about 30 percent, from about 10 to about 20 percent, and from about 1 percent to about 10 percent, respectively.

8. A composition in accordance with claim 1 wherein the proportions of Components A, B and C on a weight basis are from about 15 to about 30 percent, from about 10 to about 20 percent, and from about 1 percent to about 15 percent, respectively and wherein the Component B is a mixture of 3 and 1 in weight ratio of from about 4:1 to about 2:1.

9. A composition in accordance with claim 1 wherein the proportions of Components A, B and C on a weight basis are from about 15 to about 30 percent, from about 10 to about 20 percent, and from about 1 percent to about 10 percent, respectively and wherein the Component B is a mixture of 3 and 2 in weight ratio of from about 4: 1 to about 2:1.

10. A composition in accordance with claim 1 wherein Component A is the product of saponification with NaOH of the product of sulfonation with uncomp exed of a mixture of predominantly straight chain terminal olefins having from about 12 to about 16 carbon atoms per molecule, wherein Component B is a mixture of alkyl ether sulfate and lauryldimethyl amine oxide in a wt. ratio of about 3:1, wherein Component C is beta hydroxyethane sulfonic acid, sodium salt, wherein the proportions of Components A, B and C on a weight basis are about 21 percent, about 16 percent, and about 5 percent, respectively and wherein the system contains about 5 percent ethyl alcohol as coupling agent.

11. The composition in accordance with claim 1 containing a lower alaknol having up to about 6 carbon atoms per molecule in proportions of up to about 15 percent by weight of the composition.

12. The composition of claim 11 wherein the lower alkanol is ethyl alcohol.

References Cited UNITED STATES PATENTS LEON D. ROSDOL,

Sweeney 252-55 5 Primary Examiner P. E. WILLIS, Assistant Examiner US. Cl. X.R.

ran STATES PATENT OFFICE QEREEFECATE CE CCRECTEON Inventor(s)' Richard D. Gors ich, Melvin E. Tuvell and William J. Dewitt 7 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

T "I Column 2, line 7, reads amines oxide", should read amine oxide; line 9, reads "amides should read amides Column 5, line 7 reads pror", should read prior- Column i, lines 1-6, should read The alcohols ethoxylated are pure alkanols or mixtures of alcohols ranging from about 10 to about 18 carbon atoms per molecule. Typical mixtures of alcohols are center cut or whole cut coconut alcohols of natural or synthetic origin, preferably synthetic as produced in accordance with U. S. Patents 5,584,651 and 3,415,861. The ethoxylated derivatives preferably average from about 1 to about 5 ethylene oxide units per molecule -5 line 7, reads "alkl", should read alkyl Column 9, line 12, reads "alaknol", should read alkanol Signed and sealed this 12th day of November 1974.

(SEAL) Attest:

McCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents