CA1073309A

CA1073309A - Amphoteric surface active agents

Info

Publication number: CA1073309A
Application number: CA261,866A
Authority: CA
Inventors: Robert J. Verdicchio; Louis J. Nehmsmann
Original assignee: GAF Corp
Current assignee: GAF Corp
Priority date: 1976-09-01
Filing date: 1976-09-23
Publication date: 1980-03-11
Also published as: DE2643795A1

Abstract

AMPHOTERIC SURFACE ACTIVE AGENTS

ABSTRACT

Complex phosphate ester surfactants derived from a quaternary dihydroxy compound having the formula:

Description

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This invention relates to amphoteric surfactants, and more particularly to specific ethyoxylated amines which are quaterni~ed and at least partially phosphated: methods of making such surfactants; and to methods of using such surfactants. ~ore particularly, this invention relates to a method comprising treating a metal surface with an aqueous cornposition ! ~ containing an effective cleaning, lubricating, rustproofing ~*~for corrosion proofing amount of an amphoteric surface active agent of the formula:

R \ ~CH2CHO)n 1 X

Rl (CH CHO~ - 2 wherein R is C6 22 alkyl or alkenyl, Rl is lower alkyl or benzyl~ R2 and R3 each represent H or CH3, n is an integer of 1-50, Zl is with the bonded O
atom, a phosphate ester group in acidic or salt form, Z2 is H or Zl~ X is an anion.
Such active agents can be made through reaction (phosphating) of such dihydroxy quaternary compound with a conventional phosphating agent such as P205~ polyphosphoric acid, or POC13 to form amphoteric surface active agents having utility as metal lubricants, heavy duty cleaners, and detergents.
The above active agent may be compounded with other conventional cleaning agents. For example, the composition may contain from about 2 to about 17% by weight of caustic soda, or up to about 10% by weight of tetra-potassium pyrophosphate (TKPP) or a mixture thereof.
In particular, the ultimate complex phosphate ester surfactants themselves, that are derived from phosphating in the manner discussed above, are compositions which are characteri~ed by the following chemical formula or structure ~33~

\ ~ ~ (cH2cHo)n 1 X

R / ~ (CH2CIHO)n - Z2 wherein R is C6 22 alkyl or alkenyl, Rl is lower alkyl or benzyl, R2 and R3 each represent H or C113, n is an integer of 1-50, Zl is with the bonded O
ato~, a phosphate ester group in acidic or salt form, Z2 is H or Zl and X
is an anion such as, ~i ~, - 2 -~6~73~

e g., halogen, sulfate, or alkyl sulfate. Of course, as would be appreciated by those skilled in the art, the diesters and triesters of the above formula can exist in a variety of forms, e.g., in the form of a variety of aliphatic3 cyclic, and polymeric compounds. However, in accordance with the presen~ invention, the major products formed comprise aliphatic monoesters and diesters.
The prior art describes many, and varied, types of amine phosphonates, phosphates, and related compounds.
For example, various hydroxy alkyl and dihydroxyL alkyl derivatives of higher fatty acid amines have been phosphated, but none of these compounds have achieved significant commer-cial acceptance and in none have been found all of the ' desirable properties of the instant invention.
Considerable research has been carried out during the past few years directed towards improving the lubricating and rust and corrosive inhibiting properties of the new synthetic surfactant compositions. Most of the~e surfactant compositions have, as active surfactant ingredient, anionic ions. As representative of the various additives which have been employed for improving the detersive and surfactant properties of such anionic compositions, there may be mentioned alkali metal phosphates, borates, carbonates, sulfates, chlorides, silicates, higher aliphatic alcohols such as lauryl alcohol, and higher fatty ~cid amides and alkylol amides such as lauroyl amide, lauroyl mono and dialkyl amides, ~733~

l~uroyl ethanolamide, ~nd lauroyl di-ethanolamide. The use of the aforementioned alkali metal salts, par~icularly the phosphates and borates, genera]ly have resulted in what is known as "built" or "heavy duty" type detergents. While such compositions are partially suitable for use in cleaning machines of various types, ~hey find limi~ed used in appli-cations wherein any degree of metal lubrication and cleaning is involved. H~wever, these additives, which have ~^
thus far been more or less commercially accepted, have ] properties and characteristics which still leave much to be desired with respect to preEerred or favored characteristics such as more universal compatibility and adaptal)ility to different conditions, costs and the like.
Various organic surfactants have achi~v~d considerable commercial success; however, the art is still confronted by the problem of providing surfactant composi-tions which provide dual cationic and anionic functionalities and yet are free from undesirable disadvantages.
It has been found that the compositions according to the instant invention comprise very valuable surface-active agents which may be used either alone or admixed with other cat~onic, anionic or non-ionic surface active agents in the different fields as above referred to.
The instant compositions comprise a very valuable group of surface-active agents, known as amphoteric compounds 9 i.e., chemical agents containing both cationic and anionic groups in a single molecule, and therefore exhibit a h~gh degree of st.ability and renarkable utility in concentrated electrolytic solutions. These compounds also show unusual ~33~3~
chemical stability under prolonged contact with alkaline systems. Products made from the instant compounds have the following advantages: they possess good surface-active properties so that they can be used as detergents (since they have the advantage of preventing the accumulation of electrostatic charges); are well tolerated by ~he skin and, therefore, do not cause any appreciable irritation thereto;
are useful as lubricants, rust inhibitors, corrosion inhibitors, hard surface cleaners, alkali soluble cleaners, agricultural emulsi:Eiers, hydraulic fluids, and in emulsion polymerization.
These amphoterics employ the phosphate ester as the anionic moiety, thereby in addition to providing dual cationic/anionic functionality, offer novel properties such as metal lubrication, and cleaning, enhanced corrosion inhibition, and alkali solubility.
The compo~mds of this invention have the following unexpected combinations of properties: (1) they, unlike phosphates of ethoxylated amines, tolerate the presence of chlorine bleaches; (2) they may be used in shampoos and other cosmetics at pH values of 4.5-8.5, and, under these conditions, are effective cleaning agents, whereas conventional counterparts to these materials do not work well under pH values of 6.0: e.g., conventional amphoterics such as betaines do not work at their isoelectric point (about pH 5.7) since they become insoluble at these pH

~733~

values; ~3) t~e~ are better detergents with sverage or hard water; do not precipitate;and at pHs as low as 4.5, are mild to the eyes and skin and are relatively non-toxic.
In addition, these products are readil~y biodegradable, and as such are ecologically safe. The instant amphoteric -~
eompounds are useful as detergents, weltting, emulgating, and emulsifying agents, and also posse~s a unique combina-tion of properties which provide n~w and improved products for lubricants, pesticide emulsifiers, and hard surface cleaners. They are al80 useful as surface actlve agents in treatin8 natural and synthetic fibers in ~he textile and related fields where they may be employed as syn~hetic detergents, dye assistants, and sof~eners.
These amphoteric surfactants also sh~w an advantage over the prior art and seemingly do not exhibit a pronounced isoelectric poin~ where general surface-active and physical properties such as solubility and foaming are at a minimwm.
As previously noted, the present complex phosph~te surfactants are derived from quaternary dihydroxy compounds previously described above, and, as derived9 are obtained in two major forms- (1) as monoesters, and (2~ as diesters, wi~h minor amounts of triesters (essentially as an impurity) being formed ~733~9 The phosphate ester group may be in the acidic orm or in the form of a salt, for e~ample of the formula Y04 ~ wherein ~1 represents H or a conventional cation such as~ Na, K, Mg, Ca, or Al, preferably Na or K, or a suitable amine such as an alkanol amine or alkylamine, preferably mono-ethanolamine, diethanolamine, or triethanolamine. The X moiety of the quaternary dihydroxy compound, when a halogen, may be chlorine, fluorine, bromine, or iodine, and preferably chlorine. When a sulfate, X can be an alkyl sulfate, preferably ethyl sulfate. In the most pre~erred embodiment ;
R and Rl are dissimilar, one being a long alkyl chain, ~he other being a shorter alkyl chain, the sum total of carbon atoms for R and R , taken to-gether, not being less than 7 carbon atoms. Also disclosed are methods of making same and uses therefor.
The compounds of the instant invention may be prepared from a precursor material by first condensing an alkyl amine, containing 6 to 22 carbon atoms in its alkyl chain, with an alkylene oxide (e.g. ethylene oxide or propylene oxide) in the presence of a conventional base. To produce the quaternized component, a quaternizing agent is added thereto and the alkoxy-lated amine is thereafter quaternized. The quaternized alkoxylated amine is thereafter phosphated so as to produce a quaternary phosphate. The phosphated amphoteric product is generally a mixture containing varying amounts of monophosphate, diphosphate, triphosphate, non-phosphated nonionic (alkoxylate), phosphoric acid, and minor amounts of other materials such . . .
, r~ i _ _.. A.~ 7 ~733~ ~

as polymers of the foregoing phosphates.
The alkyl portion of the amine can be saturated or unsaturated, substituted or free from substitution. A
pure source of alkyl amine to be employed can vary in carbon length from 6 to 22 carbon atoms; examples of pure saturated acids which can be used as precursors for such an amine are caproic, caprylic, capric, lauric, myristic, palmitic, stearic, arachidic, and behenic. Unsaturated pure fatty acid precursors include those such as oleic~
lauroleic, and palmitolic. An example of a substituted fatty acid useful in this invention is ricinoleic.
Mixtures of the above fatty acids, commonly found in vegetable oils, animal fats and oils, and the marine fats and oils, may also be used successfully as precursors.
Examples of vegetable sources of useful precursor fatty acids containing mixtures in various proportions are coconut oil, linseed oil, olive oil, palm oil, peanut oil, tung oil, and rape seed oil. Animal and marine sources of fatty acids containing saturated and unsaturated fatty acid substituents are lard, tall~w, and sardine oil. Any fatty acid or mixtures of fatty acids, whether pure or from impure sources, may be employed as an amine precursor without departing from the spirit o the invention so long as they contain from 6 to 22 carbon atoms in their chain length.

~:3i7330~

Preferred fatty acids are those contained in coconut vegetable oil. A typical coconut vegetable oil may contain fatty acids varying in length from 8 to 18 carbon atoms. These fatty acids from coconut oil can be saturated or unsaturated.
The alkyl amines used in this invention can also be derived from the esters of the atty acids without departing from the scope of the invention. The methyl or ~;
ethyl esters of the fatty acids can be easily condensed with 10 ~ the polyamines.~su~stituted polyamines with ready removal of methanol or ethanol occurring.
The fatty acid amine precursor is prepared in accordance with procedures well known in the art and~ ~ -accordingly, that reaction and reac~ion product per se, form no part of the instant invention.
The thus-produced alkyl amine is then subjected to an alkoxylation reaction in accordance with procedures well known in the art, such as, for example, by reacting the amine with the required number of moles of ethylene oxide to produce the ethoxylated amine employed in the instant invention. This oxyethylatlon reaction is well ;
known in the art. The reaction is preferably carried out at elevated temperatures and pressures, and may be catalyzed by quaternary hydroxides, amines, acids and/or coordinating type compounds, although strong alkaline catalyst such as KOH or NaOH and the like are preferred because of the fewer by-products formed and the more easily controllable Y33~9 r reaction conditions under which they can react. Since the reaction is substantially quantitative, the molecular proportions of the ethylene oxide and amine employed determine the average oxyeth~lene chain length of the resulting ethoxylated amine, although it will be understood ~hat the product is a mixture of ethoxylated amines of varying oxyethylene chain length. As stated above, sufficient ethylene oxide is employed to produce an ethoxylated amine containing by weight about 25 to 90 percent of combined ethylene oxide. The optimum oxyethylene chain length wlll, in any particular instance, be determined mainly by the particular amine being oxyethylated, the particular detergent with which it is to be admixed, the hardness o~ the water in which the detergent is to be employed, the desired efficacy of the finished product for the particular application, and the like.
Throughout the specification, the invention is describcd with reference to the phosphated quaternized alkoxylated amine. It is to be understood, however, that ~ the amine as well as the alkoxylated amine are products kn~wn in the art. The alkoxylated amine may be used per se or the amine may be alkoxylated in accordance with procedures well known in the art.

~1~7330~

The product of the invention is then conveniently prepared by reaoting appropria~e proportions of alkoxylated monoalkyl amine in the presence of said hypophosphorousacld and a quaternizing agent, such as diethysulfate~ the la~ter being present in the amount of 50 to 100 mole %, preferably 90 to 100 mole %.
The alkoxylated monoalkyl amine starting materials prepared by alkoxylating primary amines, have the ~2 general structure / (CH2CH0~-H
R-N
--(CH2~otH

wherein R2 and R3 are H or CH3 as above descrlbed and n is a positive integer having an average value of from 1-50, compounds with n-2 to 15 being preferred.
After completion of the reaction, the alkoxylated monoalkyl amine is therea~ter submitted to treatment conducive to quaternization of the tertiary amino group, utilizing a conventional quaternizing agent. Thus, noting the above structural formula, suitable quaterllizing agents include: dialkyl sulfates, e.g. dimethyl sulfate and diethyl sulfate; benzyl or substituted benzyl halides, e.g. benzyl chloride, benzyl bromide, and benzyl iodide;
and alkyl halides, e.g. methyl chloride. Accordingly, any conventional quaternizing agent can be advantageously employed in the production of the quaternary alkoxyla~ed monoalkyl amines used herein.

. .

~37330~

The above quaternized composition ls then preferably but not neces~arily s~ripped of any unreacted quaternizing agent and thereafter r~acted with a phosphating agent so as to convert the quaternized alkoxylated monoalkyl amine into a quaternlzed phosphate ester product. Suitable phosphating agents include phosphorus plentoxide;
polyphosphoric acid; phosphorus oxychloride; and mixtures thereof.
In accordance with a preferred procedure of the present invention, the alkoxylated fatty amine and poly-phosphoric acid are mixed together and heated to about 90-100C. under vacuum. The product thereof ls thereafter cooled to 20 to 90C., preferably to 30C., and thereto there is added 50 to 100 mole /O~ preferably 90 to 100 mole %, of a quaternizing agent, and the mixture is thereafter heated so as to effect quaternization of the alko~ylated fatty acid amine. Any unreacted quaternizing agent m~y be stripped away at elevated temperature and under vacuum.
The remaining product is thereafter cooled and there is slowly added thereto the phosphating agent in am~unts of 10 to 200 mole %, preferably 90 to 110 mole %3 at temperatures of 20 to 110C~, preferably 40 to 50~C. If phosphorus j oxychloride~K~h~ is used as the phosphating agent, the .~
reaction mixture is bubbled with nitrogen at such temperature until a desired degree of chloride ion is reached, preferably 0.01 to 1.0%. The phosphorus oxychloride reaction product is then drowned lnto water and base and there is thereafter obtained the surfactant solution .... ...

~(3733~9 containing the instant product.
The nature of the invention ~y perhaps be best understood by the detailed procedure set forth in the examples herebelow for preparing a typical member of the phosphated quaternized ethoxylated amphoterics; all parts, proportions and percentages in these examples, as well as in the appended claims, are by weight unless indicated otherwise. Ethylene oxide throughout these examples is referred to as "E0".

EXAMPLE I
. ~.~
Charge into a l-liter flask equipped with an agitator, thermometer and gas inlet, 320 parts (0.5 mole) of cocoamine + lOE0 and 2 parts of 50% hypophosphorous acid. Dry the mixture under vacuum (10-15 mm.) at 80-100C.
Cool under dry nitrogen to 40-50C. and add 80 parts (0 52 mole) of diethyl sulfate at 40-50C. over two hours.
Strip any unreacted diethyl sulfate at 90-100C.
under good vacuum. Cool to 30-40C., and, under a

2.0 nitrogen blanket, add 35.5 parts of phosphorus pentoxide and stir at 100C. for 5 hours. Cool to 80-85C., add 5 parts water, and stir for 2 hours. There is obtained 433 parts of active surfactant. Thls represents a 99%
yield.

~13-~733[)~ ~

EX~MPLE II
Operating as in Examplc I, 460 parts (0.4 mole) of tallowamine (Armean-TD- a distilled tallow amine made by and available from Armak3 + 20EO and 2 par~s of 50%
hypophosphorous acid are charged to a l-liter flaskO The mixture is driPd at 90-100C. under a good vacuum, cooled to 30-40C., and 60 parts of diethyl sulfate are added over 2 hours. The mixture o quaternized amine ethoxylate is phosphated in the following manner. Hypopho~phorous acid (50%) 1 part, is added at 40-50C. followecl by 29 parts of phosphoru9 pentoxide at 50-60C. The mixture is heated to 100C. for 5 hours under a nitrogen blanket, cooled to 80-85C., and 5 parts water are addcd. The system is stirred for 2 hours at 80-85C. There i8 obtained 553 par~s of 100% active surfactant EXAMPLE III
Accord~ng to Example I, 460 parts of tallow-amine ~ 20E0, 2 parts of 50% hypophosphorous acid, and 60 parts of diethyl sulfate are reacted to form 520 parts of quaternized tallowamine ~ 20E0, To this mixture, 1 part 50% hypophQsphorous acid is added at 40-60Co~
followed by 170 parts of 115% polyphosphoric acid at 40-60Co under a nitrogen blanket. The phosphating mix-ture i~ heated at 100C. for 5 hours, then cooled to 8~-85C., and 5 parts of water are added. Ater two hours at 80-35C., 1 part of 35% hydrogen peroxide is added to yield 697 parts of 100% active ~urfact~nt.

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EX~MPLE IV
As in Example I, 586 part~ o oleylamine + 7E0 and 2 parts of 50% hypophosphorous acid are dried and ~ reacted with 286 parts of oleyl chloride at 60-70C. ~or 10 hours~ The quaternized amine ethoxylate mixture is mixed with 1 part 50% hypophosphorous acid and 28 parts water. Phosphorus pentoxide, 142 parts, is added ~lowly under a nitrogen blanket at 40-50C. over 2 hours. The reaction mixture is heated for 3 hours at 90C., and then 5 parts of water are added. The resulting surfact~nt is heated an additional 2 hours at 80-90C., cooled to 60C., and then 1 part 35% hydrogen peroxide is added. There is obtained 1,042 parts of surfactant.

EXAMPLE V
As in Example I, 708 parts of stearyl amine +
lOE0, 2 parts of 50% hypophosphorous acid, and 126 parts of benzyl chloride are reacted at 70-80C. to form the quaternized amine ethoxylate. This material is then ~ !
reacted with 75 parts of phosphorus oxychloride at 40-50C. over ~ hours. The hydrogen chloride is removed by nitrogen bubbling to a constant chloride ion content.
The phosphated acid mixture was drowned into 120 parts of 50% caus~ic soda, to obtain 980 parts of surfactant solu~ion.

-~5-7 ~ 3 ~ ~

EXAMPLE VI
The following surfactant compositions can be employed for different end uses, specified bel~w, in accordance with ~he following table, Table 1, wherein all 5parts mentioned are defined in terms of weight %.

Liquid Hard Drain Steam Surface Cleaner Degreaser Cleaner 10-Phosphate ester amphoteric of Example 1 1.0 1.0 1.0 NaOH 9.0 17.0 2.0 TKPP --- - lo.o Water 90.0 82.0 87.0 Totals 100.0 100.0 100.0 EXAMPLES VII-XII
The present compounds are also applicable as alkaline hard surface cleaners, exhibiting excellent caustic stability depending upon the degree of ethoxylation, anionic functionality, and hydrophobe. Alkali solub-llity is sh~wn in Table 2.

330~ ~ ~

Caustic Solubility - 1% Surfactant Soluble From O to 100C In ~ % NaO~
Example No. CO~POUND % NaO~
7Sodium Phosphate of Cocoamine + 5EO
diethyl sulfate 9.4 8Sodium Phosphate of Cocoamine ~ lOEO
diethyl sulfate 6.6 9Sodium Phosphate of Cocoamine ~ 15EO
diethyl sulfate 4.9 10Sodium Phosphate of Cocoamine ~ 20Eo diethyl sulfate 4.25 11Sodiwm Phosphate of Cocoamine ~ 30EO
diethyl sulfa~e 3.2 12Sodium Phosphate of Cocoamine + 50EO
diethyl sulfate 2.4 EXAMPLE XIII
.
Fabric softeners and detergenttsofteners and sanitizers can be prepared for use on textiles, and Table 3 bel~w sets forth typical formulations (wherein all ingredients are in parts by weight %) for such purposes:
TABLE

Present amphoteric surfactant 3-7 10-30 10-30 Distearyl dimethyl ammonium halide -- 3-7 3-7 (n-alkyl dimethyl benzyl) -- ---- 5.10 ammonium halide Sodium acetate 1-2 ---- ----Water to 100% to 100% to 100%

. .

1~733ai9 EXAMPLE XIV
This exampLe is intended to sh~w that khe present surfactants can be effectively employed in textile soten-ing compositions. In this example, 5 parts by weight of the present amphoteric surfactant in 95 parts by weight of water are neutralized with sodium hydroxide to a pH of 5.5.
This solution, as noted, is a very efficient softener/
antistatic agent for textiles.
In a typical application, the solut~on ~s cliluted l:lO with distilled water.
Conventional textile fabric substrates are thsn treated with th0 dilute surfactant solution during conventional padding of such substrates. The fabrics thus softened sh~w excellent softness, i.e., pliable to feel, and complete elimination of static electricity upon drying.
The advantage of this softener over conventional cationic softeners is that it can be washed out during subsequent laundering, whereas the cationic softeners tend to build up over repeated applica~ions.

:
. ~

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.

EXAMPLE XV
In this example there were prepared, according to the procedure of Example 1 (except for ~he identity and amount of amine reactant used), (a) the sodium phosphate of tallowamine + 5E0 diethyl sulfate and (b) the sodium phosphate of oleylamine ~ 5E0 diethyl sulfate. With respeet to (a~ 240 parts by weight (0.5 mole) of tallowamine + 5E0 (Ethomeen T/15 of Armak) was used (instead o~ the 0 5 mole of cocoamine + lOE0 o Example I), and, w~th respect to (b), 25û parts (0.5 mole) of oleylam~ne ~ 5EO (Ethomeen 0/15 of Armak) was used (instead of the 0.5 mole of cocoamine ~ lOE0 of Example I).
Then, 0.4% aqueous solutions of (a) and (b) were prepared, their pH values were adjusted to pH 8.5 with triethanolamine, and the pH-adjusted solutions evaluated for use as water-based lubricants. The Falex Load Test was used to determine the lubricating properties of the respective solutions, and the foll~wlng results, set forth below in Table 4, were obtained.

Sample Load a~ Failure (l) 0 4% aq. sodium phosphate of tall~wamine + 5E0 diethyl sulfate4,000 lbs.
(2) 0.4% aq. sodium phosphate of oleylamine + 5E0 diPthyl sulfate4,250 lbs.

(3) Water (control) 550 lbs.

~733~9~

. These results indicate excellent lubricant properties.
The products of the instant invent~on may also be further compounded with other ingredients to provi~e for the foll~wing uses:
Liquid steam cleaning compounds, floor maintenance products, wax removers 9 automobile care products, waterless hand cleaners~ oil tank degreaser, aluminum cleaner, hand washing compound, sanitizing hand dis~washing or light duty cleaning compound, pet shampoos, rug and upholstery shampoos, mothproofing, and the like.
It is obvious that numerous changes and modifica-tions can be made in the inventlon without departing from the spirit and scope thereof, and all such obvious modifications are considered to be within the scope of the invention.
For example, in a preferred embodiment of this invention, it has been previously stated that the desired end products comprise mainly a monoester product and a diester product. As would be apparent to those skilled in the art, in view of the foregoing description of this invention, the mono s~er product would be obtained predominately when about 2.0 moles of phosphating agent we~e used per mole of quaternary alkoxylated monoalkyl amine.
Alternatively, the diester product would tend to be the major product when about 1.0 moles of phosphating agent were used per mole of quaternary alkoxylated monoal.kyl ~9733~9 amine. And likewise, the triester product would tend to be the major product when about 0.5 mole of phosphating agent was used per mole of quaternary alkoxylated monoalkyl amine. :~
As one used an increasing excess of phosphating agent beyond about 2.0 moles of phosphating agent, it would be apparent to those skilled in the art that correspondingly increased polymerization products would result. Thu~, it can be seen that obtainment of the numerous, varied types of phosphated amphoteric product mixtures that are possible with the practice of this invention can vary considerably within the scope of this invention, as, e.g., with the amounts of phosphating and oxyalkyla~ing agents used, but all this would represent mere routine experimentation by and to those skilled in the art.
~5

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A method comprising treating a metal surface with an aqueous composition containing an effective cleaning, lubricating, rustproofing or corrosion proofing amount of an amphoteric surface active agent of the formula:
X-wherein R is C6-22 alkyl or alkenyl, R1 is lower alkyl or benzyl, R2 and R3 each represent H or CH3, n is an integer of 1-50, Z1 is with the bonded 0 atom, a phosphate ester group in acidic or salt form, Z2 is H or Z
X is an anion.

2. A method as defined in claim 1 in which R2 and R3 are each H.

3. A method as defined in claim 1 in which Z1 is in the form of the Na or K salt.

4. A method as defined in any of claims 1-3 wherein X is a halide or lower alkyl sulfate.

5. A method as defined in any of claims 1-3 wherein R is derived from oleylamine.

6. A method as defined in any of claims 1-3 wherein R is derived from stearylamine.

7. A method as defined in any of claims 1-3 wherein R is derived from cocoamine.

8. A method as defined in any of claims 1 - 3 wherein R is derived from tallowamine.

9. A method as defined in any of claims 1 3 wherein said composition also contains about 2 to about 17% by weight of caustic soda.

10. A method as defined in any of claims 1 - 3 wherein said composition also contains about 2 to about 17% by weight of caustic soda and about 10% by weight of tetrapotassium pyrophos-phate.