3,755,559 United States Patent Office Patented Aug. 28, 1973 1. 2 of 11 to 18 carbon atoms. Soaps of dicarboxylic acids 3,755,559 may also be used such as the soaps of dimerized linoleic HIGH-LATHERNG CONDITIONING SHAMPOO COMPOSTON acid. Soaps of such other higher molecular weight acids Gordon Trent Hewitt, Upper Montclair, N.J., assignor to such as rosin or tall oil acids, e.g. abietic acid, may also Colgate-Palmolive Company, New York, N.Y. be employed. Specific examples include triethanolamine No Drawing. Continuation of abandoned application Ser. myristrate, triethanolamine cocoate, potassium isostearate, No. 816,395, Apr. 15, 1969. This application Aug. 23, potassium myristate and the like. The soap functions as 1971, Ser. No. 174,192 an opacifier and thickener and contributes some condi The portion of the term of the patent subsequent to tioning properties to the instant composition. Since fatty Jan. 16, 1990 has been disclaimed 10 acids are a natural ingredient of the skin, the usefulness Int, Cl, A61k 7/08, C11d 1/84 of soap for cosmetic purposes as an ingredient of a sham U.S. C. 424-70 7 Claims poo is desirable. The water-soluble tertiary amine oxide which con ABSTRACT OF THE DISCLOSURE stitutes the major ingredient of this composition may be This disclosure relates to a stable, creamy-foam sham 15 represented by the general formula: RR2R3N->O where poo comprising a tertiary amine oxide, a higher alkyl in R1 is a higher alkyl radical having from 10 to 18 betaine or sulphobetaine and a soap in the ratio of carbon atoms, such as lauryl, decyl, cetyl, oleyl, stearyl, 2:1:1, respectively. hexadecyl or an amide substituted group, such as 20 RCONHCCH) This application is a continuation of copending appli where RCO is a long chain alkanoyl radical and n is a cation Ser. No. 816,395 filed Apr. 15, 1969, now small whole number; R and R3 are each lower alkyl abandoned. radical such as methyl, ethyl, propyl or a substituted The present invention relates to a clear aqueous, high lower alkyl radical such as hydroxyethyl, hydroxyethoxy lathering shampoo composition capable of simultaneously 25 ethyl, hydroxy polyethoxyethyl etc. Examples of suitable conditioning and cleansing hair. tertiary amine oxides include lauryl dimethyl amine oxide, The formulation of shampoo for human hair is a coconut dimethylamine oxide, dodecyl dimethyl amine specialized field and involves many considerations includ oxide, ing stability and homogeneity of the product, its foaming action, and most important its ability to cleanse without 30 O GH, O GH, diminishing the natural lustre of the hair. Soap-contain coco--N-(CH)--0, tallow- -N-(CH)--0, ing shampoos in the past have had the disadvantage of CH3 CH dulling the hair due to the precipitation thereon of lime and the like. The tertiary nitrogen may also be in the and magnesium soap or the like, especially in hard water form of a cyclic compound such as cocyl morpholine which also reduces the foaming action of the shampoo. oxide, cocyl imidazoline oxide, etc. This has largely been overcome by the substitution of The higher alkyl betaine or sulfobetaine utilized in synthetic organic detergents for the soap. However, many the instant invention renders the soap and tertiary amine synthetic detergents tend to remove the natural oils from oxide compatible and is per se mildly antibacterial. The the hair, leaving it -dy and difficult to manage. A variety betaines may be represented by the following structural of conditioning agents have been added in an attempt to 40 formula: overcome the detrimental effects of natural oil loss and to improve manageability of the hair. The presence of said conditioning agents have had the disadvantage of ad versely affecting the foaming action of the shampoo, whereby the foam volume and/or foam stability were in 45 wherein R1 is a high molecular alkyl radical having from sufficient to effect adequate cleansing of the hair. In 10-18 carbon atoms or the amido radical RCONHCCH)3 addition, the conditioning action of aforesaid agents were wherein R is a higher alkyl radical, R and R are each in many instances inadequate and it was necessary to alkyl radicals having from about 1 to 3 carbon atoms, R4 utilize the additional step of rinsing with a conditioning 50 is an alkylene or hydroxyalkylene radical having from 1 composition. to 4 carbon atoms, and X is an anion selected from the Accordingly, it is an object of the invention to provide group consisting of SOs and COO radicals. R1 and R a high-lathering shampoo with stable, creamy foam in may be a mixture of a high molecular alkyl radical and the presence of hair soil. may contain one or more intermediate linkages such as Another object is to provide a shampoo which leaves ether or polyether linkages or non-functional substituents the hair conditioned, i.e. lustrous, smooth and manageable. 55 such as hydroxyl or halogen radicals which do not affect It has now been found that soap can be combined with the hydrophobic character. of the radical. The ionic neu a tertiary amine oxide and a higher alkyl betaine or sulfo trality of the betaines over a wide pH range permits both betaine in an alkaline aqueous medium to yield a cleans foaming and adsorption thereof from the washing solu ing and conditioning shampoo having high and stable 60 tion. Examples of betaines useful herein include the high foaming capabilities. - - - alkyl betaines, such as coco dimethyl carboxymethyl Soaps utilized in the composition include the water solu betaine, lauryl dimethyl carboxymethyl betaine, lauryl ble salts of higher fatty acids of naturally occurring veg dimethyl alpha-carboxy-ethyl betaine, cetyl dimethyl car etable or animal fats and oils. Examples are sodium, boxymethyl betaine, lauryl bis-(2 hydroxyethyl) carboxy potassium, ammonium, monoethanolamine, diethanol methyl betaine, stearyl bis-(2 hydroxypropyl) carboxy amine, triethanolamine salts, morpholine, diglycolamine, 65 methyl betaine, oleyl dimethyl gamma-carboxy-propyl etc. of fatty acids occurring in coconut oil, soy bean oil, betaine, lauryl bis-(2 hydroxypropyl) alphacarboxyethyl castor oil, tallow, or synthetically produced fatty acids. betaine, etc. The sulfobetaines may be represented by The acid portion of the soap is advantageously that of a coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfo fatty acid such as lauric, myristic, stearic, oleic, elaidic, propyl betaine, lauryl bis-(2 hydroxyethyl) sulfopropyl isostearic, palmitic, undecylenic, tridecylenic, penta 70 betaine and the like, amido betaines and amidosulfo decylenic or other saturated or unsaturated fatty acid betaines, wherein the RCONHCCH) radical is attached 3,755,559 3. 4. to the nitrogen atom of the betaine are also useful in deposition of conditioning surfactants thereon. This sub this invention. It is sometimes preferable to use the sulfo stantivity can be exploited in the formulation of hair betaine because of their better solubility and compata coloring shampoos by the addition of direct dyes and bility with synthetic detergents, wherein the betaines are polyethylen imine to the instant compositions. desirable in the preparations of an opaque composition Various adjuvant materials may be added to these because of their thickening properties. foaming, aqueous, detergent compositions such as small The mixture of higher alkyl betaine, soap and tertiary amounts of viscosity builders and conditioning agents amine oxide should be suitably proportioned at proper inclusive of gums, hydroxypropyl methyl cellulose and pH values in an aqueous solution to yield foaming alkanolamides such as lauric myristic diethanolamide, cleansing compositions which yield a strong adsorption O monoalkanolamides, isopropanolamides. Other ingre onto hair, scalp and skin. By suitably selecting the ingre dients may include alkaline or acid buffers to aid in the dients, clear aqueous solutions with low cloud points are adjustment and maintenance of the desired pH of the obtainable at alkaline pH, preferably at pH 8-9. Although finished product such as borax, various inorganic water the proportions of ingredients can be varied over a wide soluble phosphates, sodium hydroxide, citric acid, etc. range, it is desirable that the sum of amine oxide plus 5 Other additions include optical brighteners, bleaches, betaine should be greater than the amount of soap, and germicides, fungicides, bactericides, colorants, perfumes, the preferred ratio is 2 parts amine oxide: 1 part betaine: etc. in minor amounts which do not interfere with the 1 part soap. In general, the tertiary amine oxide ingre conditioning properties of the composition. dient constitutes the major detergent in the composition in In the manufacture of the shampoo in aqueous forms, amounts ranging from 5% to 40% and preferably 10% 20 the soap component may be prepared in advance or in to 20% by weight of the total. The amount of the betaine situ by dissolving the soap fatty acid in warm amine ingredient should be sufficient to effect compatability oxide plus betaine or sulfobetaine. The neutrailizing base between the tertiary amine oxide and the soap, usually such as triethanolamine, potassium hydroxide or the like about 6% and preferably about one half the amine oxide is added until the pH is sufficiently alkaline, preferably content, and more specifically about 5% to 10% by 25 8-9. The resultant solutions are clear, moderately vis weight of the total composition. The amount of soap is cous shampoos and retain their clarity when cooled to less than the sum of the amine oxide and the betaine, 34 F. at pH's above 8.3. At pH's below 8.5. it has been usually about 6% and preferably one half of the amine found that the amine oxide and the soap are particularly oxide content, and more specifically about 5% to 10% inclined to precipitate, but the precipitation is definitely by weight of the total product. 30 retarded by the presence of the betaine or sulfobetaine Formulations embraced by this invention are stable, component. homogeneous aqueous shampoos which lather properly. The following specific examples are further illustrative These compositions have the dual function of washing of the nature of the present invention, and it is to be and conditioning the hair, leaving the hair soft and more understood that the invention is not limited thereto. All manageable after shampooing. The need for frequent 35 parts are by weight unless otherwise indicated. combing is minimized and the act of combing the hair is accomplished with greater facility due to the elimination EXAMPLE of tangled hair. The hair is rendered significantly anti Ingredients: Static and exhibits good sheen or luster and curl retention. Lauryl dimethyl amine oxide ------12.0% Other important advantages include a desirable modifica 40 Coco Sulfobetaine' ------6.0%. tion of the foaming power so that there is achieved su Triethanolamine myristate ------6.0%. perior foam volume and stability in the presence of fatty Triethanolamine ------To pH 8.0. acid soaps. Perfume ------0.3%. Foam tests on prototype hair conditioning shampoos Water ------To 100%. have indicated that the foam stabilization contribution oralia: of alkanolamide so clearly beneficial in anionic-based shampoos, is not needed in the betaine-amine oxide-fatty pH, acid soap compositions. Both foam volumes and foam RNCHCH-CHsor consistencies of these novel compositions are superior to CH prior art formulations as evidenced by a higher volume 50 of foam which was more stable, and slower to break The above ingredients are mixed together with agita down or drain out of the hair and scalp. In addition, other tion yielding a clear moderately viscous solution partic soap-containing shampoos are more susceptible to the ularly useful as a high foaming shampoo, effects of hard water, rendering the instant products more EXAMPLE II versatile under myriad conditions. The unusual foam 55 In lieu of the triethanolamine myristate ingredient of stability of the amine oxide and betaine in the presence Example I, 4% isostearic acid is added to a warm solu of soap renders these ternary formulations useful as soap tion of the amine oxide and sulfobetaine and sufficient bars and as bubble bath compositions with foam which triethanolamine is used to obtain a pH of 8.6. This com is not destroyed by the use of conventional bath soap. position remains clear when cooled to 34° F. The result The compatability exhibited by the betaine, soap and 60 ant product is a superior, clear, foaming, conditioning amine oxide ingredients, and the excellent protein ad shampoo. sorption of the betaine-amine oxide-soap complex at EXAMPLE III alkaline pH render these formulations particularly useful as conditioning shampoos. This is unexpected since prior To the composition of Example II is added 3.0% lauric art formulations containing anionic surfactants including 65 myristic diethanolamide. This composition is more vis soap and alkanolamides do not leave the hair conditioned cous than the solutions of Examples I and II, and remains and do not give evidence of any deposition and residual clear when cooled to 34 F. This shampoo product is conditioning surfactants as is shown by the instant com" found to lather profusely and to wash and condition hair. positions, as demonstrated by the substantive deposition In addition to the usual and conventional soaps, as of Rubine W. S. dye by the shampooed and rinsed hair. 70 described above, there may also be employed other types Normally, substrate such as hair will not retain Rubine of fatty carboxylates such as the (1) N-alkanoyl sarcosin W. S. dye, a water-soluble anionic dye, unless first treated ates e.g. with cationic surfactants. However, it has now been found that untreated hair shampooed with the instant composi R -N-(c H)COOMt. tion does retain the Rubine dye; illustrating the effective 75 O Ri 3,755,559 5 6 wherein R is e.g. Co to Cao (decyl, dodecyl, tetradecyl, acid; said salt being selected from the group consisting hexadecyl, octadecyl, eicosyl, etc.); R is hydrogen, alkyl of sodium, potassium, ammonium, monoethanolamine, di or cycloalkyl e.g. methyl, ethyl, propyl, hexyl, octyl, cy ethanolamine, triethanolamine, diglycolamine, and mor clohexyl, cyclopentyl substituted cyclohexyls, etc.; x is 1 pholine; and the balance being water; said shampoo hav to 4 and M is a conventional cation, e.g., Nat, Kt and ing a pH of from 8 to 8.6. NH; (2) compounds of the type 5 2. A composition in accordance with claim wherein the amine oxide is lauryl dimethylamine oxide. R (O (CH2)).O(CH2) -COOM 3. A composition in accordance with claim wherein wherein R1 is alkyl or alkaryl of e.g. C to Cao, n is 2 or the soap is a triethanolamine soap. 3, n is 1 to 50 and preferably 1 to 10 and t is 1, 2 or 3; 4. A composition in accordance with claim 1 wherein M is a conventional cation e.g. Na+, K+ NH, O said higher alkyl betaine is present in an amount of 5% to 10% by weight, said soap is present in an amount of NHCHCHOH, 5% to 10% by weight, and the sum of said betaine and NH(CHCHOH), said amine oxide being greater than the amount of soap. N(CH2CHOH), 5. The composition in accordance with claim 4 where etc. in the ratio of amine oxide: betaine: soap is 2:1:1. Although the present invention has been described with 6. A composition in accordance with claim 1 wherein reference to particular embodiments and examples it will the betaine ingredient is cocosulfobetaine. be apparent to those skilled in the art that variations and 7. A composition in accordance with claim 6 wherein modifications of this invention can be made and that the amine oxide is lauryl dimethylamine oxide and the equivalents can be substituted therefor without departing 20 Soap is a triethanolamine soap. from the principles and true spirit of the invention. I claim: References Cited 1. A clear, aqueous, high-lathering shampoo composi UNITED STATES PATENTS tion for simultaneously cleansing and conditioning hair 3,499,930 3/1970 Wakeman et al. 260-584 in a single operation which consists essentially of 5% to 3,400,198 9/1968 Lang ------252-528 X 20% by weight of a higher alkyl betaine having the struc 3,280,179 10/1966 Ernst ------. 260-501.12. tural formula 3,086,943 4/1963 Lang ------252-547 FOREIGN PATENTS R 30 680,670 10/1966 Belgium ------252-117

3 OTHER REFERENCES wherein R1 is Cio-C8 alkyl or Cio-Cia alkyl amidopropyl, "The Sulfobetaine” Technical Bulletin, printed by Texi R2 and R3 are each alkyl or hydroxyalkyl radicals having Lana Corporation, 1966. from about 1 to 3 carbon atoms, R is an alkylene or "Fatty Amine Oxides” by E. Jungermann and M. E. hydroxyalkylene radical having from 1 to 4 carbons, and Ginn, Soap & Chemical Specialties, September 1964, pp. X is an anion selected from the group consisting of SO 59-62. and CO; 10% to 20% by weight of a higher alkyl "Recent Advances in Fatty Amine Oxides” by T. P. amine oxide having the general formula RR2RN->O 40 Matson, Journal American Oil Chemists' Society, vol. 40, wherein R1 is Co-C18 alkyl or Co-C18 alkyl amidopropyl November 1963, pp. 640-642. and R2 and R3 are each selected from the group consist ing of C1-C alkyl, C1-C3 hydroxyalkyl and C1-C3 hy LEOND. ROSDOL, Primary Examiner droxyalkyloxyalkyl or R3 and R3 together with the amino D. L. ALBRECHT, Assistant Examiner nitrogen form a morpholino or imidazole group; from 5% 45 to 20% by weight of a water-soluble soap selected from U.S. C. X.R. the group consisting of salts of a saturated C1-Cia fatty 252-117, 545, 546, 547, DIGEST 13, DIGEST 4.