Patented July 18, 1939 2,166,127 UNITED STATES PATENT OFFICE 218, SEAM Poo COMPOSTION Frank J

Patented July 18, 1939 2,166,127 UNITED STATES PATENT OFFICE 218, SEAM Poo COMPOSTION Frank J. Cahn and Morris B. Ratnam, Chicago, . No Drawing. Application January Sera No. 184,080 8, 193s, 13 Claims. (C. 8-5) Our invention relates to new and useful im Again, the employment of the thickening provements in solutions, and particularly aqueous agents, hereinafter described in detail, enhances solutions, of certain sulpho-carboxylic acid the stability of the solutions of the organic nitrog esters. enous base salts of the sulpho-carboxylic acid Broadly speaking, sulpho-carboxylic acid esters esters with respect to low temperatures and ap of alcohols are known, having been disclosed in pears to add in preventing crystallization when various publications and patents, among which the solutions are super-cooled. Other advan may be cited United States Patents Nos., 1917,250 tages accrue from the use of thickening agents and 1,917,255. These compounds are generally in accordance with the present invention into O prepared and employed in the form of their which it does not appear to be necessary to go O alkali metal or ammonium salts. We have dis into detail. covered that organic nitrogenous base salts of the The solutions of the organic nitrogenous base sulpho-carboxylic acid esters have markedly salts of the sulpho-carboxylic acid esters, with or increased solubility in water or in aqueous media without the thickening agents, may be employed 15 Over the corresponding sodium, potassium, Oram for various purposes for which surface or inter 15 nonium salts. In addition, we have made the face modifying agents may be employed. They surprising discovery that solutions, particularly nay, for example, be employed in textile treating aqueous solutions, containing at least several and dyeing oaths, in margarine as emulsifying percent of such organic nitrogenous base salts and antispattering agents, in ore flotation and of Sulpho-carboxylic acid esters tolerate super agglomeration methods, and the like. Since cooling to a considerable extent. In other words, many of the organic nitrogenous base salts when such solutions are super-cooled, the esters possess detergent, lathering, sudsing, frothing, dissolved therein do not crystallize out despite foaming, penetrating and wetting properties, the fact that the limit of solubility thereof may their solutions may be employed in the various 25 be exceeded. Instead of crystallization taking arts where such functions are sought. Thus, for 25 place, the solutions merely become more viscous. example, the high lathering and detergent powers Just why this unusual phenomenon takes place of many of said nitrogenous base salts of the has not been fully ascertained. At any rate, it sulpho-carboxylic acid esters enables their solu does occur and the practical importance thereof tions to be employed for general detergent pur 3. is evident so far as the stability of the solutions poses including the cleansing and launderling of 3) is concerned under conditions of storage arid ship textiles and the like, the cleansing of the skin and ment wherein extreme cold is likely to be met. the scalp, the washing or shampooing of hair on We have also found that such solutions may be the human head, the cleansing or the brushing of thickened in a novel and highly satisfactory man the teeth, and the like. In such and similar uses, 35 ner. While an increase in thickness may, in they overcome many of the disadvantages which 35 certain cases, be accomplished by increasing the normally attend the use of soap, particularly concentration of the organic nitrogenous base salt under adverse conditions of Water supply. of the sulpho-carboxylic acid ester in its solvent, It is accordingly an object of our invention to this becomes impracticable in most cases since produce novel and useful solutions, particularly 40 the esters are frequently soluble to only a limited aqueous solutions, of organic nitrogenous base 40 extent in the particular solvent preferred to be Salts of sulpho-carboxylic acid esters. used. In addition, the increase in the concern Another object of our invention is the provi tration of the esters, aside from other disad sion of aqueous solutions containing at least vantages emanating from Such practice, is usually several percent of organic nitrogenous base salts 45 uneconomic since the degree of enhancement of of sulpho-carboxylic acid esters and which have 45 thickness, consistency or increase in viscosity at good lathering, sudsing and detergent proper tainable by such method is insufficient to war ties. rant the substantially greater cost involved. Still another object of our invention is to Solutions, for example, aqueous solutions, con thicken solutions of organic nitrogenous base 50 taining as high as 20% to 25% or more, by weight, salts of sulpho-carboxylic acid esters, particular 50 of some of the organic nitrogenous base salts of ly aqueous solutions which contain at least sev sulpho-carboxylic acid esters are almost as limpid eral percent of such esters and which possess as water. When poured from a bottle and good lathering, sudsing and detergent proper handled, there is a marked tendency for loss of ties. 55 Solution by Spilling. It becomes highly advan Other objects and advantages of our invention 55 tageous in many instances to increase the thick will become apparent as the detailed description ness, consistency or viscosity of such solutions to thereof proceeds. facilitate the handling thereof and minimize the The compounds of the present invention, in loss during pouring and the like from bottles or general, contain a relatively high molecular similar containers or receptacles. Weight lipophile group and a relatively low molec 2,100,127 ular weight hydrophile group, which latter group pared therefron: aliphatic straight chain and comprises sulpho-carboxylic or sulpho-fatty acid branched chain alcohols such as butyl alcohol, radicals. A more complete understanding of what anyl alcohol, hexyl alcohol, heptyl alcohol, octyl may comprise the lipophile group and the par alcohol, nonyl alcohol, decyl alcohol, undecyl al ticular character of the sulpho-carboxylic or cohol, lauryl alcohol, myristyl alcohol, cetyl al sulpho-fatty acid group will be had as the de cohol, oley alcohol,linoley alcohol, stearyl alcohol, tailed description progresses. ricinoleyl alcohol, palmitolley alcohol, melissyl the function of the sulphonic acid group is to alcohol, Ceryl alcohol, carnaubyl alcohol, myricy impart hydrophilic, that is, water wetting or alcohol, branched chain octyl, decyl, dodecyl, O water attracting properties, to the molecule as a tetradecyl, hexadecyl and octadecyl aliphatic al O whole. The group which are esterified by the cohols as, for example, 2-ethyl hexanol-1, 2-n sulpho-carboxylic or sulpho-fatty acid are, as in butyl octanol-1, 2-butyl tetradecanol-1, and, in dicated, of a lipophile character, the lipophilic general, the higher molecular weight saturated properties being at times relatively strong and at and unsaturated aliphatic straight chain and other times moderately strong. In other words, branched chain alcohols. Preferably, the alco s and as will be seen in greater detail in connection hols which are utilized are those corresponding to with the examples hereinafter set forth, the the fatty acids occurring in triglyceride oils and lipophile group or groups, may be of relatively low fats of vegetable or animal origin, natural or molecular weight or higher molecular weight. hydrogenated, such as corn oil, cottonseed oil, The lithophile groups entering into the no sesame otl, coconut oil, palm kernel oil, sunflower lecular structure of the substances which we seed oil, lard, tallow, soya bean oil and the like, employ herein may be of simple character as, for those alcohols containing from 12 to 18 carbon exampie, in sulpho-acetates of straight chain atoms being preferred. Other alcohols which alcohols such as octyl alcohol, decyl alcohol, lauryl may be employed are the cyclo-aliphatic or ali alcohol and the like, or of similar lower molecular cyclic alcohols such as the sterols, as, for exampie, weight sulpho-carboxylic acid esters of branched cholesterol, so-cholesterol, phytosterol, sitosterol, chain alcohols such as 2-ethylhexanol-1,2-butyl hydro-aromatic alcohols such as abletol, and such octanol-1, and the like. unsaturated alcohols as linalool, citronellol, gera Others of the substances which We employ niol and the like, Also included within the class herein are lower molecular weight sulpho-car of alcohols which may be employed are such com boxylic acid esters of polyhydroxy substances, at pounds as the hydroxy and alpha-hydroxy higher east one hydroxy group of the polyhydroxy sub aliphatic and fatty acids as, for example, ricinoleic stance being esterified with a carboxylic acid acid, alpha-hydroxy stearic acid, alpha-hydroxy containing at least four carbon atoms and prefer lauric acid, di-hydroxy stearic acid, 1-hydroxy ably between eight and eighteen carbon atoms, Stearic acid, alpha-hydroxy palmitic acid, and the It will be understood that, in all cases, the like, as well as esters of hydroxy-fatty acids, such compounds are employed in the form of their as ethyl ricinoleate, castor oil, butyl ox-hydroxy Organic nitrogenous base salts. stearate, cetyl hydroxystearate, and the like. The following are examples of compounds The term "alcohols', as employed herein, is in which we may employ in accordance with the tended to include alcohols which may or may not teachings of our invention: contain other groups such as carboxylic, halogen, (1) Mono-ethanolamine salt of lauryl Sulpho Sulphonic, Sulphate, or other radicals. The al acetate; cohols obtainable by substituting alkyl or acyl (2) Tri-ethanolamine salt of sulpho-acetic acid radicals, preferably of high molecular weight, in ester of coconut oil mixed with fatty alcohols; place of the hydrogen of one or more hydroxy (3) Piperidine salt of myristyl sulpho-propionate; groups of polyhydroxy substances or polyhydric (4) Pyridine salt of monolaurin sulpho-acetate; alcohols, it being understood that at least one (5) Mono-ethanolamine salt of monopalmitin hydroxy group attached to the nucleus of the sulpho-butyrate; polyhydroxy substance or polyhydric alcohol re 50 (6) Mono-ethanolamine salt of monolauric acid mains, are also within the scope of the alcohols ester of diethylene glycol sulpho-acetate; from which the sulpho-carboxylic esters may be (7) Di-ethanolamine salt of monolauryl ether produced. As examples of such alcohols may be of glycerol sulpho-acetate; mentioned, partially esterified or partially etheri fied sugars and Sugar alcohols such as monolauric 55 (8) Ethylene diamine salt of decyl sulphO-ace tate; acid ester of sucrose, monostearic acid ester of (9) Dethyl mono-ethanolamine salt of cetyl dextrose, monopalmitic acid ester of mannitol, di sulpho-acetate; caproic acid ester of maltose, mono-octyl ether of (10) Propanolamine salt of citronellol sulpho sorbitol, monolauryl ether of pentaerythritol, acetate; monolauric acid ester of pentaerythritol, and the (1) Methyl pyridinium salt of lauryl sulpho like; the monoglycerides and di-glycerides, pref propionate; erably of the higher fatty acids, as, for example, (12) Pyridine salt of lauryl sulpho-acetate; monolaurin, monomyristin, monostearin, di stearin, diolein, dicaproin, mono-lauryl ether of (13) Piperidine salt of sulpho-acetic acid ester glycerol, di-cetyl ether of glycerol, monostearic (8.5 of Coconut oil mixed fatty alcohols containing acid ester of diethylene glycol, monolauric acid about 60% of lauryl alcohol. ester of ethylene glycol, and the like. We may select many different types of com It is, of course, obvious that the alcohols from pounds as lipophile groups, particularly those which the sulpho-carboxylic esters are produced having at least eight and preferably at least may be prepared in accordance with any desired 70 twelve carbon atoms, although, in some cases, method. For example, many of these alcohols 70 the lipophile group or groups may contain as low may be prepared by the so-called Bouveault and as four carbon atoms. For example, the follow Blanc method or, alternatively, by the reduction ing compounds may be utilized as sources of lipo or catalytic reduction with hydrogen of natural phile groups, and sulpho-carboxylic acid esters or hydrogenated animal or vegetable fats and s thereof, such as Sulpho-acetates, may be pre oils in accordance with well known practices. s a,168,127 3 Again the alcohols may be derived from synthetic xylose, arabinose, galactose, fructose, maltose, processes such as by the Oxidation of hydro mannose and the like; sugar alcohols such as carbons or may be prepared by saponification of arabitol, mannito, sorbitol and dulcitol; and waxes and the like. Alternatively, they may be polyhydroxy-carboxylic acids such as tartaric prepared by reduction of aldehydes or by the acid, mucic acid, saccharic acid, gluconic acid, Grignard reaction. . . glucuronic acid, gulonic acid, nannonic acid, tri It is likewise apparent that mixtures of the hydroxyglutaric acid, glyceric acid, carboxylic foregoing or other alcohols may be utilized in the oxidation products of polyglycerols, others of preparation of the sulpho-carboxylic acid esters similar character, and hydroxyethyl and hydroxy O as, for example, the mixture of alcohols result propyl ether derivatives of the above, as, for O ing from the hydrogenation of coconut oil or the example, free fatty acids of coconut oil. Lauryl alcohol m C-O-C-CO (: - (-CH-CHOF comprises about 45% of the total alcohol mixture, the remainling alcohols running from Cs to Cs. <-o-clichot &ti-o-ch-croit s Again, mixtures of alcohols such as are present it-o-cit-Cition &n, in the so-called sperm oil alcohols, as well as b those present in wool-fat, may equally efficacious ly be utilized. Indeed, these higher molecular th weight alcohols are generally offered on the mar &H-0-cr-chon ket in the form of mixtures of different alcohols. &H-O-CH-CH.oh. If desired for any specific purpose, special frac tions which predominate in a certain particular CH-O-C-CHO higher molecular weight alcohol may be utilized tri-o-cl-chon or, if so desired, the products may be prepared from a single, substantially pure alcohol. bi-o-cis-ch,oh So far as the sulpho-carboxylic acid esters are bh-e-cit-chon concerned which are derivatives of polyhydroxy th-o-ch-CH on substances, we may select many different types CH-O-C-CO of compounds as lipophile groups which are to be 30 esterified or etherified with the polyhydroxy sub (For convenience, all hydroxyl groups are written stances, principally compounds having lipophile facing Cne way.) radicals of relatively high molecular weight. For While the organic nitrogenous base derivatives example, the following materials may be utilized Gf the sulpho-carboxylic acid esters may be pre as sources of lipophile groups: straight chain and pared in various ways, we have found that a very branched chain carboxylic, aliphatic, and fatty satisfactory method comprises reacting an alkal acids such as butyric acid, caprylic acid, caproic metal or similar salt of a sulpho-carboxylic acid acid, capric acid, saturated and Linsatuated high cster such as laury potassium sulphoacetate, with er molecular weight aliphatic acids such as the an organic nitrogenous base such as nono higher fatty acids containing at least eight car ethanol annine, and with a compound which rea 4) bon atons and including melissic acid, stearic acts with the cationic constituent of the sulpho acid, oleic acid, ricinoleic acid, linoleic acid, acetate salt to produce a compound more insoluble linolenic acid, lauric acid, myristic acid, palmitic than the sulphoacetate salt whereby the more acid, mixtures of any two or more of the above insoluble compound precipitates out and may be entioned acids or other, acids, mixed higher removed by filtration or the like, leaving the fatty acids derived from animal or vegetable monoethanolamine salt of the sulphoacetate in sources, for example, lard, coconut oil, sesame oil, solution. palm kernel oil, corn oil, cottonseed oil, sardine More specifically, unusually good results are oil, tallow, partially or completely hydrogenated obtained by reacting a sulpho-carboxylic ester animal and vegetable oils such as those men such as laury potassium sulpho-acetate, tartaric SO tioned; hydroxy and alpha-hydroxy higher ali acid, and an organic nitrogenous base such as phatic and fatty, acids such as i-hydroxy stearic monoethanolamine. The reaction which takes acid, dihydroxyStearic acid, alpha-hydroxy stear place results in the formation of potassium acid ic acid, alpha-hydroxy palmitic acid, alpha-hy tartrate which is quite insoluble in cold water droxy lauric acid, alpha-hydroxy coconut oil and precipitates out, leaving the monoethanol 5 mixed fatty acids, and the like; fatty acids de amine salt of laury sulphoacetate. The reaction rived from various waxes such as beeswax, sper may be illustrated by the following equation: maceti, montan wax, and carnauba wax and car boxylic acids derived, by oxidation and other cho methods, from petroleum; hydroaromatic acids cuits-O-G-C H-S ok -tic,to NH www O such as naphthenic acid and abietic acid; aro H natic acids such as benzoic acid and naphthoic CHOH acid, hydroxy aromatic acids such as hydroxy benzoic and naphthoic acid, and the like. cotta-O--ch-s ot-N-H+ Hrcio. In those compounds which are derivatives of O polyhydroxy substances and in which the poly The reaction takes placc when the alkali metal hydroxy substance provides the linkage between or similar salt of the sulpho-carboxylic acid ester the lipophile group and the sulpho-carboxylic is more soluble or less insoluble than the salt or acid radical, the polyhydroxy substances may be the like such as potassium acid tartrate which Selected from a large class and include glycerol; forms during the reaction. Thus, in the specific O glycols such as ethylene glycol, propylene glycol, cxample referred to above, lauryl potassium sul 70 trimethylene glycol; butylene glycol and the phoacetate being more soluble or less insoluble ... like; polyglycols such as diethylene glycol; penta than potassium acid tartrate, the reaction takes erythritol; polyglycerols such as diglycero, tri place. On the other hand, this particular reac glycerol, tetraglycerol and the like including nix tion does not appear to take place when steary s tures thereof; sugars such as dextrose, sucrose, potassium sulpho-acetate is substituted for lauryl s 4 2,100,187 potassium sulphoacetate, presumably because upon the resulting solution was filtered from the steary potassium sulpho-acetate is less soluble potassium acid tartrate which had precipitated than potassium acid tartrate. In such a case, out. other convenient methods may be employed, as, Approximately 780 cc. of a yellow colored for example, by reacting sulpho-acetic acid with limpid solution were obtained which had excell the desired alcohol to form the sulpho-acetic acid lent foaming, sudsing, lathering and detergent ester of the alcohol, and then neutralizing by properties in hard water as well as in the presence means of the desired organic nitrogenous base. of alkalies and acids. The solution contained a Other methiods of making such compounds will substantial proportion of the pyridine salt of the readily suggest themselves to the skilled chemist sulpho-acetate of lauryl alcohol. in the light of our novel teachings herein. O In order to enable those skilled in the art to Eacaraple W understand the nature of the invention even 173 grams of lauryl potassium sulphO-acetate more fully, the following examples are given by were dissolved in 1050 cc. of boiling water and 5 way of illustration. It will be understood, how mixed with a solution containing 93 grams of ever, that the specific reactants, the proportions tartaric acid, 51 grams of piperidine and 300 cc. 5 thereof, and the times and temperatures may be of water. After cooling to approximately room varied within limits without departing from the temperature, the solution was filtered of from spirit of the invention. The examples, therefore, the precipitated potassium acid tartrate and the are to be taken in an illustrative rather than in solution was then neutralized to a methyl red a limitative sense, the full scope of the invention yellow with 20 grams of piperidine. A water being pointed out in the claims, white viscous liquid was obtained possessing Ecample strong foaming, sudsing, lathering and detergent properties in alkaline or acid aqueous media as A. 200 grams of crystalline lauryl potassium Well as in hard water. sulpho-acetate, prepared from commercial lauryl 25 alcohol, Were dissolved in 400 cc. of Water at 80 Eacample W degrees C. to produce a relatively stiff paste. 453 grams of lauryl potassium sulpho-acetate, B. 150 grams of tartaric acid and 141 grams of prepared from commercial lauryl alcohol con 30 triethanolamine were dissolved in 400 cc. of taining about 75% lauryl alcohol, and contain Water. ing about 40% water Were dissolved in 1810 cc. 30 C. Compositions A and B were then stirred of water previously heated to about 90 degrees C. together at a temperature of about 90 degrees C. To the above solution there was then added, at A heavy precipitate came down and the previ about 90 degrees C., a solution of monoethanol 8. Ously viscous mixture became quite mobile. The amine acid tartrate prepared by mixing together precipitate, which comprises potassium acid a solution of 60.9 grains of monoethanolanine 35 tartrate, was filtered off and the filtrate was then (molecular weight 62.6) in 210 cc. of water with neutralized with 50 grams of triethanolamine. a solution of 146 grams of tartaric acid dissolved The final solution was quite viscous, containing in 210 cc. of water. in the neighborhood of 20% of lauryl triethanol The resulting solution was then allowed to amine sulpho-acetate. It possessed unusually cool for about a day at room temperature and 40 good foaming, sudsing, lathering and detergent was then decanted and filtered from the precipi characteristics. tate of potassium acid tartrate, the latter then Eacantaple II being washed with 50 cc. of water and the wash 133.5 grams of potassium lauryl sulpho-acetate water being added to the filtrate. To the approximately 2660 grams of solution CH-O-C-CH-SOK thus obtained, about 20 grams of monoethanol ( ) amine were added until methylred gave a yellow were dissolved in 700 cc. of boiling water and color. There was then added to said solution 10 were then mixed with a previously prepared cc. of a solution of monoethanolamine sulphate Solution containing 69.4 grams of tartaric acid in order to thicken the solution. and 28.7 grams of monoethanolamine in 200 cc. The solution of monoethanolamine sulphate of water. These two solutions were mixed to was prepared by adding a solution of 325 grams gether at a temperature of about 90 degrees C. of monoethanolamine dissolved in 250 cc. of and the resulting mixture thereof was allowed Water to a solution of a stolchiometrically equiv to cool to room temperature. The liquid was alent amount of 96% sulphuric acid dissolved in then filtered from the precipitated potassium 580 cc. of water. acid tartrate. The filtrate was a viscous, strong ly foaming, substantially Odorless and colorless Eacample VI liquid after having been neutralized with 6.7 An aqueous solution of 8.1 parts, by weight, of grams of monoethanolamine to a litmus blue re acid methylpyridinium tartrate in 17 parts, by action. The solution contained 13.8% of the weight, of water was prepared by mixing one monoethanolamine salt of lauryl sulpho-acetate mol of 0.166 normal methylpyridinium hydroxide and 2.9% of the tartrate of monoethanolamine, solution with an aqueous solution of one mol of The solution had excellent sudsling, foaming, tartaric acid and evaporating down. This solu lathering, and detergent properties. tion was then heated to a temperature of about Eacample III 90 degrees C. and was then added to a previously heated solution, also at about 90 degrees C, con 133 grams of potassium lauryl sulpho-acetate taining 10.4 parts, by weight, of lauryl potassium were dissolved in 700 cc. of boiling Water and the Sulpho-acetate and 50 parts, by weight, of water. o resulting solution was then mixed with a previ The mass was permitted to cool to approximately ously prepared solution containing 69 grams of 25 degrees C. and the acid potassium tartrate tartaric acid, 36.6 grams of pyridine and 200 cc. which had precipitate? out was filtered off. The of water. The two solutions were mixed at a resulting clear filtrate was neutralized to yellow temperature of about 90 degrees C. and were methylred with 20 volume parts of 0.167 normal s then allowed to cool to room temperature where methylpyridinium hydroxide solution. 5 9,180,127 . . . 5 The resulting solution, containing. a substan pho-carboxylic esters prepared from the product tial proportion of the methylpyridinium salt of known as 'oro Technical' which comprises a laury sulpho-acetate, was water-white, relatively mixture of fatty alcohols derived from the hy viscous, substantially odorless, and had excellent drogenation of coconut oil or the free fatty acids foaming, sudsing, lathering, and detergent prop of coconut oil. Lauryl alcohol comprises about S erties in hard water as well as in aqueous acidu 60% of the total alcohol mixture, the remaining lated media. - . alcohols running from C to Cus. Similarly, it is Those skilled in the art will readily be able to apparent, that mixtures of different organic carry out the invention and make diverse varia nitrogenous bases, such as mixtures of those re 10 tons all of which, however, are within the spirit ferred to hereinabove, may be employed with to of the invention in view of the detailed explana eficacious results. Indeed, in order to obtain tion and guiding principles set out herelnabove. varied solubility and other characteristics mix We have obtained unusually good results with tures of different organic nitrogenous bases may organic nitrogenous base salts of sulpho-acetic. be employed with mixtures of different sulpho. is acid esters of lauryl alcohol or higher molecular carboxylic acid esters. 5 weight aliphatic alcohol mixtures containing at As we have indicated above, it frequently be least 40% of lauryl alcohol and, preferably, from comes quite desirable to increase the thickness, 60% to 80% or more of lauryl alcohol, the alkylol consistency or viscosity of the aforementioned amine salts such as monoethanolamine and tri solutions. As a result of considerable research ethanolamine being outstandingly satisfactory. work, a large class of thickening agents has been The preparation of the alkali metal sulpho discovered which are of marked utility for thick acetates or the like, which are employed in the ening solutions, particularly aqueous solutions, specific examples set forth hereinabove whereby of sulpho-carboxylic acid esters, including those the organic nitrogenous base derivatives are pro having good sudsing and detergent properties. ges duced, may be effected, for example, as disclosed These 'thickeners may be characterized as salts es in said patents, by initially reacting a higher of organic nitrogenous bases, notably, salts of molecular weight alcohol, such as lauryl alco such bases with water-soluble acids. Particularly hol, with chloracetic or bromacetic acid or the useful are the salts of the alcohol amines, and - like to produce the chloracetic or bromacetic ester of unusual utility are the salts of mono-ethanol so of lauryl alcohol. The resulting product, prefer amine, especially monoethanolamine sulphate. so ably washed free of the formed hydrochloric acid In place of monoethanolamine, other organic and the unreacted chloracetic acid or the like, is nitrogenous bases may be employed, as, for ex then treated with an aqueous solution of an ample, alcohol amines and alkylolamines, includi alkali metal sulphite, such as K2SO3, in accord ing diethanolamine, triethanolamine, propano is ance with the so-called Strecker reaction to pro amines, butanolamines, pentanolamines, hexanol- is duce the alkali metal sulpho-acetate which may, amines, glycerolamines, dibutyl ethanolamine, if desired, be purified in accordance with prac diethanol ethyl amine, cyclohexyl ethanolamine, tices Well known in the art. . . . . alkylol polyamines such as alkylol derivatives of It will be appreciated, for example, that other ethylene diamine, mono-methyl mono-ethanol organic nitrogenous bases may be employed in amine, diethyl monoethanolamine, mono-, di-, 40 place of those described herelnabove. Illustrative and trlethyl triethanolamine, 1-amino-2, 3-pro of bases of this type are, for example, alcohol panediol, 12-diamine propanol; alkylamines such anines and alkylolamines including mono-, dir, as butylamine, dimethylamine, ethylene diamine, and tri-ethanolamine and mixtures thereof such diethylene triamine, triethylene tetra-amine, is as are, for example, present in so-called commer mono-methyl ethylene diamine, monoethyl di- is clal trlethanolamine, propanolamines, butanol ethylene tetra-amine, aromatic and heterocyclic amines, pentanolamines, hexanolamines, glycerol bases such as pyridine, guinaldine, piperidine, andnes, dibutyl ethanolamine, diethanol ethyl methylpyridine, and homologues and derivatives amine, cyclohexyl ethanolamine, diethanol ethyl thereof, quaternary ammonium bases or hydrox in amine, cyclohexyl ethanolamine, alkylol polya ides such as tetra-methyl ammonium hydroxide, so mines such as alkylol derivatives of ethylene di tetra-ethyl ammonium hydroxide, quaternary amine, mono-methyl mono-ethanolamine, diethyl ammonium bases with dissimilar alkyl radicals mono-ethanolamine, mono-, di-, and tri-ethyl such as methyl-triethyl ammonium hydroxide, triethanolamine, 1-amino-2, 3-propanediol, 1,2- propyl-trimethyl ammonium hydroxide, mixtures 56 diaminopropanol: alkylamines such as butyla of any two or more thereof, and the like. It is mine, dimethylamine, ethylene diamine, diethylene will be understood that these organic nitrog triamine, triethylene tetra-amine, mono-methyl enous bases may be employed in pure, impure or ethylene diamine, mono-ethyl diethylene tetra commercial form such as, for example, com amine, aromatic and heterocyclic bases such as mercial triethanolamine which contains minor 60 pyridine, quinaldine, methylpyridine, and homo proportions of mono- and di-ethanolamine. 60 logues and derivatives thereof, quaternary am As stated, these organic nitrogenous bases are monium bases or hydroxides such as tetra-methyl employed in the form of their salts such as su ammonium hydroxide, tetra-ethyl ammonium hy phates, phosphates, nitrate, acetates, chlorides, droxide, quaternary ammonium bases with dis bromides, iodides, borates, lactates, citrates, tar is similar alkyl radicals such as methyl-triethyl trates, and the like or mixtures of any two or 5 ... ammonium hydroxide, propyl-trimethyl am more thereof. The salts may be made in ways monium hydroxide, mixtures of any two or more known in the art, for example, by neutralizing thereof, and the like. It will be understood that the base or mixtures of bases with the equivalent these organic nitrogenous bases, as in the case of amount of acid or any desired mixture of two or To triethanolamine, for example, may be employed more acids. For example, monoethanolamine to in pure, impure, or commercial form. . . acetate may be prepared by mixing equal molec As previously pointed out, and as is evident, ular quantities of monoethanolamine and glacial pure or single sulpho-carboxylic esters need not acetic acid. The glacial acetic acid is added drop by drop to the monoethanolamine while con to leastbe employed. equally efficacious Mixtures as, are, for in example, many cases, the sul at . stantly stirring the latter, the flask of the like 5 6 9,100,187 containing the monoethanolamine being sur tion with respect to the thickening of aqueous rounded by an ice bath to insure that the ten solutions of the sulpho-carboxylic acid esters, it perature does not rise too high And too rapidly. must not be inferred that the invention is so The monoethanolamine acetate is a brownish, limited. Alcoholic or other organic solvents may viscous liquid. Trlethanolamine acetate is made be employed, as well as aqueous-organic solvent in the same manner and has the same general mixtures, but for economic and other obvious appearance as monoethanolamine acetate. reasons Water is preferred, Monoethanolamine sulphate may be prepared in Besides the salts of Organic nitrogenous bases solution, for example, by adding a solution of which are employed as thickeners, we have alse 0 325 grams of monoethanolamine dissolved in 250 found that various electrolytes such as annoni cc. of water to a solution of a stoichiometrically un sulphate, sodium sulphate, magnesium sul O equivalent amount of 96% sulphuric acid dis phate, disodium hydrogen phosphate treated solved in 580 cc. of Water. with sufficient sulphuric acid to give a neutral As illustrative of thickeners falling within the reaction to litmus, and the like, may be utilized scope of the invention may be mentioned, by Way for a similar purpose although not nearly so sat 15 of example, monoethanolamine acetate, mono isfactorily as the salts of the organic nitrogenous 5 ethanolamine sulphate, diethanolamine acetate, bases. trlethanolamine acetate, 1-amino-2, 3 propane While the thickening effect increases with in diol acetate, 1,3-diaminopropanol acetate, nono creasing concentrations of the sulpho-carboxylic ethanolamine phosphate, trlethanolamine phos acid esters and while it commences to become phate, ethylenediamine sulphate, butylamine appreciable, in most cases, at concentrations of acetate, and the like. the order of magnitude of several percent or It is convenient to prepare a solution of the five to ten percent, nevertheless the invention thickener and add it in the desired amounts to is applicable, as well, at concentrations of said the interface modifying agent solution although esters substantially below and beyond the above 25 the manner of incorporation is optional and may mentioned range. Indeed the invention is ap be accomplished in various ways as, for example, plicable to the treatment of solutions of said in situ during the preparation of the solution of esters of as low as about 0.5% strength and as the sulpho-carboxylic acid ester. Since, in the high as 25% or 30% strength, or even higher. 30 main, aqueous solutions of sulpho-carboxylic Many of the sulpho-carboxylic acid esters em acid esters are employed, the thickeners utilized ployed herein may be represented by the gen in such solutions will be water-soluble. It will era formula be understood that in all cases the thickener must be soluble in the solution of the interface R-COO-Ri modifier in which it is employed. SS While, as stated and is obvious, the amount wherein R. denotes a lower molecular weight all of thickener which may be employed is variable phatic radical containing at least one sulphonic within relatively wide ranges of proportions, in acid radical the hydrogen of which is replaced order to indicate the remarkable and unusual by the radical of an organic nitrogenous base, aspects of this phase of the invention, the fol and Ra denotes a radical of a higher molecular lowing facts should be understood. Aqueous so weight mono- or polyhydric alcohol. lutions of many of the thickening agents which Many of the sulpho-carboxylic acid esters uti are disclosed herein, even in concentrations as lized herein may also be represented by the general high as 50%, are of a very limpid character with formula viscosity practically identical with or not much greater than that of ordinary water. Never o theless, the addition of relatively small propor R-o-c-x-sao Y tions of such limpid solutions to solutions of ( Yo-mwy ) sulpho-carboxylic acid esters results in an en tirely unexpected increase in thickness and vis wherein R is a radical comprising or containing cosity of said latter solutions. That this hap a lipophile group with at least four carbon atons pens in the face of and notwithstanding the mu and preferably from twelve to eighteen carbon tual dilution which simultaneously occurs is all atoms, X is the carbon-hydrogen residue of the the more remarkable. The following table illus sulpho-carboxylic acid, Y is an organic nitroge trates the nature of the results which have been nous base cation, and D is a small whole number, obtained: at least one.

sulpho-Carboryito Acid Ester Solution Addition Agent Results 10cc. of E. aqueous solution of triethanolamine sat of laury su grain monoethanolamine acetate------Considerable increase phoacetate. in viscosity. 10 cc. of a 10% aqueous solution of triethanolamine salt of lauryl 2grams monoethanolamine sulphate------. Do, : ideausolutionce oar aqueous solution oaerowoffatherlow viscostyco tes 26% Several drops of a 50% aqueous solution of Considerable thicken of the EEE salt of laurylsulphoacetate and 17 43 monoethanolamine phosphate. ing. triathanolanine phosphate. 5cc. of a 15% aqueous solution of monoethanolamine salt of lauryl focc, of a 50% aqueous solution of butyla- D0. sulphoacetate. nine acetate. 6 20 cc. of a 12% aqueous solution of 5 cc. of a 50% aqueous solution of mono Considerable hacrease ethanolarine sulphate. in viscosity, O 2 70 cut-i-o-OH-OH-0--CE-6 o ONEde-CEOs. n

s While it is preferred to carry out the inven Again, various of the sulpho-carboxylic acid s 2,166,127 7 . esters which may be employed herein may be rep wherever employed in the claims, will be unders resented by the general formula stood to mean at least eight carbon atoms and, conconitantly, the term "lower' will mean less o than eight carbon atoms. The present application is a continuation-in- S l Yoy part of prior application, Serial No. 166,388, fled - (-3. ) September 29, 1937. wherein R is the residue of a polyhydroxy sub What we claim as new. and desire to protect by stance in which the hydrogen of at least one hy Letters Patent of the United States is: droxyl group is substituted by an alkyl or acyl 1. A shampoo composition comprising an aque- O O group containing at least four carbon atoms and ous solution of at least 5% of a lower molecular preferably between eight and eighteen carbon weight sulpho-fatty acid ester of a higher no atoms, X is the carbon-hydrogen residue of the lecular weight alcohol, the hydrogen of the sul sulpho-carboxylic acid, Y is an organic nitroge phonic group of which is replaced by the radical nous base cation, and w is a small whole num of an organic nitrogenous base, the lower mo- is 5 ber, at least one. lecular weight sulpho-fatty acid radical contain So far as the sulpho-carboxylic or sulpho-fatty ing less than eight carbon atoms and the higher acid group of the compounds is concerned, it may molecular weight alcohol radical containing- at be a sulpho-acetate, a sulpho-proponate, sul least eight carbon atoms, said shampoo being sta pho-butyrate, or other similar groups containing ble against crystallization on being super-cooled. 0 not more than seven carbon atoms and contain 2. A shampoo composition comprising an aque ing a sulphonic acid radical whose hydrogen is ous solution of at least 5% of a lower molecular replaced by an organic nitrogenous base cation. weight sulpho-fatty acid ester of a higher molec In general, the sulpho-acetates are particularly ular weight aliphatic alcohol corresponding to the useful' and they possess the advantage of being higher fatty acids present in triglyceride oils and S 25 relatively inexpensively produced from commer fats and waxes, the hydrogen of the sulphonic cally available substances. group of which is replaced by the radical of an The term "sulpho-carboxylic acid' or "sulpho organic nitrogenous base, the lower molecular fatty acid', as employed throughout the specif weight Sulpho-fatty acid radical containing less cation and claims is used in a strictly rigorous than eight carbon atoms and the higher molecu- O sense to cover an aliphatic linkage containing at lar weight alcohol radical containing at least least one eight carbon atoms, said shampoo being stable against crystallization on being super-cooled. NSc-sao 4' 3. A shampoo composition comprising an aque 1 Yo ous solution of at least 5% of a sulpho-acetic acid as ester of a mixture of higher aliphatic alcohols group, the various examples given being clear containing a predominant amount of lauryl alco in this feature. r hol, the hydrogen of the sulphonic group of which The term "residue", as used herein, is employed is replaced by the radical of an organic nitroge in its ordinarily understood chemical significance. nous base, Said shampoo being stable against 0 For example, where one of the hydroxyl groups crystallization on being super-cooled. of glycerine is esterified with a higher fatty acid 4. A composition in accordance with claim 3, and another of the hydroxyl groups of the glyc wherein the Organic nitrogenous base comprises a erine is esterified with a sulpho-carboxylic acid, member selected from the group consisting of that which remains of the glycerine molecule, monoethanolamine, diethanolamine, trethanola- 5 for example mine, and mixtures thereof. C 5. A shampoo composition comprising an aqueous solution of at least 5% of lauryl mono bHoH ethanolamine sulphoacetate, said shampoo being &H,- stable against crystallization on being super- 0 is the residue of the polyhydroxy substance, in cooled. this case, glycerine. 6. A viscous liquid shampoo in accordance with Similarly, the term "carbon-hydrogen residue' claim 1, and a salt of an alcohol amine as a thick of a sulpho-carboxylic acid is employed as in con ening agent. SS wentional chemical nomenclature. Thus, for ex 7. A viscous liquid shampoo in accordance with ample, if sulpho-acetic acid (HOOC-(CH-SO3H) claim 3, and a salt of an alcohol amine as a thick is esterifled with glycerine, the group -CH3- is ening agent. the 'carbon hydrogen residue' of the sulpho 8. A viscous hair shampoo comprising an aque acetic acid. Ous solution of at least 5% of lauryl mono The term "lipophile group', as employed here ethanolamine sulpho-acetate and monoethanol- 0 in, is intended to cover any radical having an amine sulphate as a thickening agent, said affinity for oleaginous material such as oils, fats, shampoo being stable against Crystallization on hydrocarbons and the like and may comprise being super-cooled. radicals such as hydrocarbon radicals, acyl or 9. A viscous liquid shampoo comprising an 65 alkyl groups derived from aliphatic or fatty acids aqueous solution of at least 5% of sulpho-acetic 88 or their corresponding alcohols, and the like. acid esters of a mixture of higher fatty alcohols The "hydrophile group' or groups, in other containing at least 40% of lauryl alcohol, the hya Words, the groups having an affinity for aqueous drogen of the sulpho-acetic acid radical being materials are, as fully set forth hereinabove, sul replaced by the radical of an organic nitrogenous O pho-carboxylic or sulpho-fatty acid groups. base, and a salt of an alcohol amine as a thick- 70 The term "solution" as employed herein and in ener, said shampoo, being stable against crystal the appended claims is employed in a broad sense lization on being super-cooled. to include not only true solutions but also colloidal 10. A composition in accordance with claim 9 wherein the organic nitrogendus base is a men Unless otherwise indicated, the term "higher", ber selected from the group consisting of mono 9,160,187 ethanolanine, dethanolamine, trlethanolamine, by weight, of the monoethanolamine salt of the and mixtures thereof, and the thickener is a salt sulpho-acetic acid ester of a mixture of higher of a strong inorganic acid with an urganic nitrog aliphatic alcohols containing in excess of 40% of enous base. lauryl alcohol, said shampoo being stable against 11. A shampoo composition comprising an crystallization on being super-cooled. aqueous solution of at least 5% of lauryl alkylol 13. A viscous liquid shampoo Comprising an amine lower molecular weight sulpho-fatty acid aqueous solution of between 5% and 20% of esters, the lower molecular weight sulpho-fatty lauryl monoethanolamine sulpho-acetate, and acid radical containing less than eight carbon monoethanolamine sulphate as a thickener, said O atoms, said shampoo being stable against crys shampoo being stable against crystallization on 10 tallization on being super-cooled. being super-cooled. 12. A shampoo composition comprising an FRANK. J. CABN, aqueous solution of between about 5% and 20%, MORRIS B, KAZMAN.

CERTIFICATE OF CORRECTION. Patent No. 2,166, lat. July 18, 1939. FRANK J. CAHN, ET AL. It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, first column, line ll, for the word "group" read groups; line 20, for "lithophile" read lipophile line lb., strike out "with"; and that the said Letters Pat ent should be read with this correction therein that the same may conform to the record of the case in the Patent Office. Signed and sealed this l9th day of September, A. D. l959.

Henry Wan Arsdale, (Seal) Acting Commissioner of Patents. 9,160,187 ethanolanine, dethanolamine, trlethanolamine, by weight, of the monoethanolamine salt of the and mixtures thereof, and the thickener is a salt sulpho-acetic acid ester of a mixture of higher of a strong inorganic acid with an urganic nitrog aliphatic alcohols containing in excess of 40% of enous base. lauryl alcohol, said shampoo being stable against 11. A shampoo composition comprising an crystallization on being super-cooled. aqueous solution of at least 5% of lauryl alkylol 13. A viscous liquid shampoo Comprising an amine lower molecular weight sulpho-fatty acid aqueous solution of between 5% and 20% of esters, the lower molecular weight sulpho-fatty lauryl monoethanolamine sulpho-acetate, and acid radical containing less than eight carbon monoethanolamine sulphate as a thickener, said O atoms, said shampoo being stable against crys shampoo being stable against crystallization on 10 tallization on being super-cooled. being super-cooled. 12. A shampoo composition comprising an FRANK. J. CABN, aqueous solution of between about 5% and 20%, MORRIS B, KAZMAN.

Henry Wan Arsdale, (Seal) Acting Commissioner of Patents.