United States Patent Office Patented Aug
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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.