Hewitt, Gordon Trent (Upper Montclair, NJ)
Furgal, Henry Paul (Bernardsville, NJ)

05/136274

10/22/1974

04/21/1971

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Colgate-Palmolive Company (New York, NY)

132/202

424/70.310, 510/508, 510/394, 510/503, 424/70.210, 510/494, 510/427, 510/124, 424/70.800, 424/70.190

A61K8/26; A61K8/40; A61K8/46; A61Q5/02; A61K8/19; A61K8/30; A61K7/06

424/70,157 132/7 252/DIG.7,DIG.13,DIG.14,545,547

Chemical Abstracts, Vol. 74, (1971), p. 34556d. .
Sagarin, Cosmetics-Science & Technology (1957), pgs. 717-724..

Turner, Vincent D.

Sylvester, Herbert Miller Richard Connell Ronald S. N. S.

What is claimed is

1. An aqueous shampoo composition useful for treating hair on the scalp to cleanse and decrease static charges and soiling characteristics consisting essentially of about 0.5 percent to 8 percent by weight of a water-soluble astringent salt of aluminum, hafnium, zinc, or zirconium wherein the salt-forming anion is selected from the group consisting of halides, sulfates, sulfamates, halohydrates, and oxyhalides; about 1 percent to 20 percent by weight of a higher alkyl di-lower alkyl amine oxide or mixture thereof; and about 1 percent to 20 percent by weight of an N-higher alkyl, N,N-di-lower alkyl aminopropane sulfonate or N-higher acylamido-lower alkyl, N,N-di-lower alkyl aminopropane sulfonate or mixture thereof in an aqueous medium; said higher alkyl and higher acyl groups containing from 10 to 18 carbon atoms and said lower alkyl groups containing from 1 to 4 carbon atoms; said shampoo having a pH of 3 to 6.5, being free of anionic detergent, and being effective to reduce static charges on the hair and to decrease the rate of re-soiling of the hair.

2. The shampoo composition according to claim 1 wherein the astringent metal salt is an aluminum salt.

3. The shampoo composition according to claim 2 wherein the astringent metal salt is aluminum chlorohydrate.

4. The shampoo composition according to claim 3 wherein the amine oxide is a C₁₀ -C₁₈ alkyl dimethyl amine oxide and the aminopropane sulfonate is an N-C₁₀ -C₁₈ alkyl, N,N-dimethyl aminopropane sulfonate or an N-C₁₀ -C₁₈ acylamido-lower alkyl, N,N-dimethyl aminopropane sulfonate.

5. The shampoo composition according to claim 4 wherein the amine oxide is one in which the higher alkyl is of 12 to 16 carbon atoms and the aminopropane sulfonate is N-higher alkyl, N,N-dimethyl aminopropane sulfonate or N-higher acylamido-lower alkyl, N,N-di-lower alkyl aminopropane sulfonate in which the higher alkyl is of 10 to 16 carbon atoms and the N-higher acylamido is of 10 to 16 carbon atoms.

6. The shampoo composition according to claim 5 wherein the amine oxide is myristyl dimethyl amine oxide and the aminopropane sulfonate is N-cocoyl, N,N-dimethyl aminopropane sulfonate.

7. The shampoo composition according to claim 1 comprising from 2 to 6 percent of aluminum chlorhydroxide, 4 to 10 percent of myristyl dimethyl amine oxide, 4 to 10 percent of N-cocoyl, N,N-dimethyl aminopropane sulfonate and 75 to 90 percent water.

8. A method of treating human hair on the scalp to decrease the static charges and the soiling characteristics thereof which comprises applying to said hair an aqueous solution containing aluminum chlorohydrate in an amount of at least 0.004 percent by weight and which is effective to react with the hair, maintaining such solution in contact with said hair for a period of from 5 seconds to 5 minutes and rinsing the solution from the hair with water, until the pH of the rinse water is at least over 6.

9. The method according to claim 8 wherein the aqueous solution comprises from 2 percent to 6 percent by weight of aluminum chlorohydrate in water.

This invention relates to compositions containing an astringent metal salt for treating the hair and scalp, and more particularly to shampoo compositions containing such salts, and to methods of applying compositions to the hair and scalp.

A successful shampoo or hair treatment should leave the hair clean, yet manageable, lustrous yet not oily or greasy, and with body, yet not sticky, and it must be mild, not harsh or strong. Furthermore, it should counteract the deposition of dulling films on the hair and should not cause brittleness of the hair or excessive drying of hair or scalp. The various desirable attributes of a shampoo are to some extent self-contradictory, with various shampoo ingredients having favorable properties in some respects and because of those very properties being unacceptable with respect to other characteristics. Thus, an ingredient which cleans very well might also extract so much oil or natural waxes from the hair as to make it excessively dry and brittle. Lustre imparting agents may sometimes contribute to oiliness and often will attract dust or dirt to the hair, necessitating more frequent washings. Of course, with such an increase in frequency of shampooing, it is important that the ingredients of the shampoo have a mild effect on the hair and the scalp.

Heretofore, there has not been any satisfactory composition for washing and treating the hair which would leave the skin of the scalp feeling healthy and firm and which would counteract a tendency towards excessive perspiration in that area, while yet having good hair treatment properties and possessing all the desirable foaming and cleaning attributes of a useful shampoo. Neither was there known a method of treating the hair which would be mild enough to be acceptable and yet which would significantly act to diminish excessive perspiration from the scalp and which would cause the hair to be less easily soiled after treatment.

DESCRIPTION OF THE INVENTION

The present invention contemplates preferred shampoo compositions comprising minor proportions of an astringent metal salt, a higher alkyl di-lower alkyl amine oxide or a higher acylamido lower alkyl di-lower alkyl amine oxide, or mixtures thereof, and an N-higher alkyl, N,N-di-lower alkyl aminopropane sulfonate or an N-higher acylamido lower alkyl, N,N-di-lower alkyl aminopropane sulfonate or mixtures thereof, and an aqueous medium. Such compositions are generally in liquid form, are of an acidic pH, usually from 3 to 6.5, include an aluminum salt as the astringent metal salt and most preferably, employ aluminum chlorhydroxide as the astringent metal salt. Generally, to obtain best results, certain preferred amine oxides and aminopropane sulfonate compounds are used and proportions of the various constituents are regulated to be within preferred ranges. Also within the invention are methods of treating or washing the hair, utilizing aluminum chlorhydroxide or the previously described compositions.

DETAILED DESCRIPTION OF THE INVENTION

The astringent metal salts useful in the present shampoos are known in the art by such designation. They are compounds normally employed in antiperspirant preparations and are mentioned at pages 717 to 724 of the text, Cosmetics: Science and Technology, edited by Edward A. Sagarin and published in 1957 by Interscience Publishers. Such compounds are preferably water soluble salts of aluminum, zirconium, zinc or equivalent metals which have the power to react with the skin and thereby narrow or close perspiration and sebaceous duct openings leading to its surface. The saltforming anions are usually halides, sulfates, sulfamates or other water soluble salts of strong mineral acids, although organic anions may also be employed. It appears that the metal cation is the active factor which causes pore constriction and therefore, importance of the anion is principally in controlling the release of cation and in influencing its astringent properties. The salts that are usable are most preferably employed as their chlorhydroxides or chlorohydrates. For example, using the aluminum compound as illustrative, the aluminum chlorohydrate or chlorhydroxide will nowmally be of the empirical formula Al ₂ (OH) ₆ -n X _n , wherein X is Cl ^- , Br ^- , I ^- or NO ₃ ^- and n is about 1 to 2. Such compounds may be used in the forms of complexes, containing various proportions of water of hydration, preferably about 2 moles thereof. In a similar manner, zirconyl chloride octahydrate ZrOCL ₂ ^. 8H ₂ O), aluminum bromohydroxide, hafnium chlorohydrate, etc. may be used. In a corresponding manner, other such salts of such metals, together with their hydrates, are also usable astringents or antiperspirant components of the present shampoos and are useful in the described methods.

The higher alkyl di-lower alkyl amine oxides useful as a detersive constituent of the compositions of the invention are generally of the formula R ¹ R ² R ₃ N➝O, wherein R ¹ and R ² are lower alkyl and R ³ is higher alkyl. Such lower alkyl groups are normally of 1 to 4 carbon atoms, preferably from 1 to 2 carbon atoms and most preferably are methyl groups. Although R ¹ and R ² may be different, preferably they are the same. The higher alkyl, of 10 to 18 carbon atoms is preferably of 12 to 16 carbon atoms and of such alkyls, myristyl is most preferred. Although some branching of both the higher and lower alkyl groups is permitted, it is normally preferably to use the straight chain radicals. Also, although substitution with non-interfering substituents is permissible and even some unsaturation is acceptable, it will normally be most desirable to utilize completely saturated straight chain higher and lower alkyls. Of course, equivalent amine oxides which are compatible with the other shampoo constituents are also useful. Thus when R ³ thereof is replaced in the described amine oxides with a corresponding higher acylamido-lower alkyl, in which the acyl is of the same number of carbon atoms as the higher alkyls or one more, and the lower alkyl is of 1 to 4 carbon atoms, preferably of 2 to 3 carbon atoms, good astringent shampoos are made. Similarly, when R ¹ and R ² represent ends of a cyclic group, such as cycloalkyl of 4 to 5 carbon atoms, the amine oxides are useful in the present compositions. Other groups may also be used to make suitable amine oxides, as is known in the art. However, it is preferred that when amine oxides other than the higher alkyl di-lower alkyl and higher acylamido-lower alkyl amine oxides are used they should be only a minor proportion of the amine oxide content, generally less than 30 percent thereof, although in some cases greater quantities can be used and the product will be a good one.

The N-higher alkyl, N,N-di-lower alkyl aminopropane sulfonates or sulfobetaines are ordinarily of the formula (R ⁴ ) (R ⁵ ) (R ⁶ )-N ⁺ -- CH ₂ CH ₂ CH ₂ SO ₃ ^- or of the corresponding cyclic structure. ##SPC1##

In either the linear or cyclic formulas given above R ⁴ and R ⁵ of 1 to 4 carbon atoms, preferably of 1 to 2 carbon atoms and most preferably they are both methyl. Most preferably also, R ⁴ and R ⁵ are the same but they may be different. R ⁶ is a higher alkyl of 10 to 18 carbon atoms, is preferably of 10 to 16 carbon atoms and most preferably is lauryl. As was the case with R ¹ , R ² and R ³ , it is highly preferred that the mentioned radicals be of straight chain structure and saturated, although some branching and unsaturation are permissible, providing that the effects of the hydrocarbyl radicals used are essentially the same as the straight chain alkyls. As with the amine oxides, the higher alkyl groups may be replaced by higher acylamido alkyls of the same number of carbon atoms or one more in the acyl. Mixed compounds may be utilized. Sulfobetaines or aminopropane sulfonates can be employed wherein R ⁴ and R ⁵ are terminal portions of a cycloaliphatic group, preferably cycloalkyl of 4 to 5 carbon atoms. Other sulfobetaines, betaines and acylamido alkyl betaines can be used, too, but preferably, other than for the described N-higher alkyl, N,N-di-lower alkyl and N-higher acylamido, N,N-di-lower alkyl aminopropane sulfonates, these will be only a minor proportion, preferably less than 30 percent, of the usual combined sulfobetaine+betaine content of the shampoo or hair treating compositions.

The most preferred amine oxide is myristyl dimethyl amine oxide and the most preferred aminopropane sulfonate is N-lauryl, N,N-dimethyl aminopropane sulfonate. Instead of the lauryl radical, the equivalent alkyl radical and, in some cases, the equivalent acyl radical, may be that derived from coconut oil and such are identified in this specification as "cocoyl" or "cocooyl," respectively.

Although it is within the contemplation of this invention that astringent metal salt, amine oxide and aminopropane sulfonate may be compounded together and employed as a mixture, it will usually be preferable to have these constituents dissolved in an aqueous solvent, preferably water. The shampoos of the invention must be formulated to avoid interfering ionic reactions. The combination of astringent salt, amine oxide and aminopropane sulfonate in aqueous solution have been found to be especially compatible.

The preferred aqueous solvent medium, water, is usually deionized or distilled water or other water of comparatively low hardness. Generally, the hardness will be less than 150 parts per million, as equivalent calcium carbonate, and most preferably will be less than 50 p.p.m. of calcium carbonate. Usually there will be no necessity for any additional solvent material but in some cases it may be desirable, to improve clarity or impart other special properties to the shampoo, to employ co-solvents or additional solvents for the shampoo constituents. Thus, up to about 35 percent of lower alcohol, e.g., ethanol, isopropanol, may be present, with the balance of the aqueous medium being water or other additional solvents, including emollient materials, such as glycerol, polyethylene glycol, polypropylene glycol or sorbitol. Such additional solvent material will normally not be present in excess of 15 percent of the total solvent present, including water and lower alcohol.

The usual types of adjuvants normally employed in shampoos should not be indiscriminately used in the present compositions. However, in suitable circumstances adjuvants will be formulatable with the present products to produce shampoos having additional desirable characteristics. Thus, if a thickened clear shampoo is desired, care will be taken not to utilize a mucilage or gum which would react with any of the shampoo constituents, especially the astringent metal salt. However, keeping this restriction in mind, useful thickening agents can be selected from the materials normally employed for this purpose, including inorganic thickeners and organic colloidal gums or mucilages. Among such materials are included magnesium aluminum silicates, clays, bentonite, carboxyalkyl celluloses, hydroxyalkyl cellulose, carboxypolymethylenes, natural gums, polyvinyl pyrrolidones, startch derivatives, polyvinyl alcohols and dextrans. The preferred thickening agents include sodium carboxymethyl cellulose and hydroxyethyl-- and hydroxypropyl methyl cellulose, ethylene maleic anhydride copolymers, polyvinyl alcohols, polyvinyl pyrrolidones and carrageenan gum. Of course, mixtures of such materials may be used. To make clear products, those thickeners which do not cloud in the solvent system will be selected. Other synthetic or natural organic detergents or surface active adjuvant components of these shampoo compositions should also be non-reactive with the astringent metal salt. Because it appears that most anionic detergents react with the astringent metal ions, these and soaps are generally to be avoided. Although amphoteric, ampholytic, zwitterion, cationic and nonionic surface active materials can make good clear shampoos, generally these do not have the desirable properties of the present amine oxides and aminopropane sulfonates and if used at all, will be employed in relatively small quantities. Nevertheless, nonionic surface active agents such as polyethenoxy ethers of alkyl phenols, polyethenoxy ethers of higher alcohols, polyethenoxy ethers of mercaptans, polyethenoxy esters, polyhydroxy ethers and esters, block and random copolymers of polyethylene oxide and polypropylene oxide, such as the Pluronics, can be useful.

Descriptions of the various surface active agents and detergents employable in the present shampoos are found in the text Nonionic Surfactants, edited by M. J. Schick and published in 1967 by Marcel Dekker, Inc., and Surface Active Agents and Detergents, Vol. II, by A. M. Schwartz, J. W. Perry and J. Berch, published in 1958, by Interscience Publishers.

In addition to the thickeners and surface active agents which may be used as adjuvants, various other shampoo ingredients can be present, including hydrophilic and lipophilic oils, lanolin, lanolin esters and other lanolin derivatives; conditioning agents; foaming agents, e.g., lauric myristic diethanolamide; sequestrants, e.g., ethylene diamine tetraacetic acid; clarifying agents; microbicides, including bactericides and fungicides; preservatives, stabilizers, including ultraviolet absorbers, such as fluorescent dyes; brighteners, which may be fluorescent brighteners; coloring agents; and perfumes. Although it is usually desirable to utilize clear shampoos, emulsifying and clouding agents may be intentionally added to these compositions, either in liquid, flake, solid, gel or other suitable form, to create a creamy product or washing solution. Adjuvants of the various types mentioned above are described at length in the text Cosmetics: Science and Technology, previously mentioned, and examples of such compounds are given at length therein.

The proportions of required components of the present shampoos are important to the obtaining of the desired excellent shampooing properties and effects characteristic of this invention. Thus, minor proportions of the astringent metal salt, amine oxide or mixture and aminopropane sulfonate or mixture will be used for the shampoos and a major proportion of an aqueous medium will be employed. In the absence of such an aqueous medium a major proportion of one of the other three constituents can be present. The amine oxide will usually be employed to the extent of about 1 to 20 percent, with a similar proportion of aminopropane sulfonate. The astringent metal salt or derivative will be present to the extent of about 0.5 to 8 percent. It is considered that preferred proportions within these ranges are from 2 to 6 percent of the astringent metal salt, preferably aluminum chlorhydroxide, 4 to 10 percent of amine oxide, such as myristyl dimethyl amine oxide and 4 to 10 percent of the aminopropane sulfonate, e.g., N-cocoyl, N,N-demethyl aminopropane sulfonate. Within such proportions, the desirable cleaning and conditioning effects of the aminopropane sulfonate compounds are obtained to the best extent, together with the supplementing foaming activity of the amine oxide and hair-treating and pore-restricting properties of the astringent metal salt. In such compositions it is generally found desirable to employ from 50.1 to 97.5 percent of water, most preferably from 75 to 90 percent thereof. However, although such contents of aqueous medium are best to obtain good stable and convenient to use shampoos, in some circumstances less water may be present, especially when additional solvents are also utilized in replacement of parts thereof.

The proportions of adjuvants employed in the present shampoos will be under 25 percent and preferably will be under 10 percent of the total shampoo. Such adjuvants, which include solvents, thickeners and surface active materials, in addition to those materials previously set forth as exemplary of adjuvants, will generally be limited to 10 percent each in the shampoo composition, preferably less than 5 percent. Of course, some adjuvants are employed in very small quantities, as little as 0.001 percent of a dye sometimes being used. Generally however, when an adjuvant is used, there will be from 0.1 to 10 percent thereof present. It will be noted, however, that the proportions of adjuvants to use should be limited so as not to interfere with the activities of the major active ingredients, especially of the astringent metal salt.

In addition to controlling the important conditions of the present shampoos so as to assure that they can be aesthetically successful, by which is meant that they will be of pleasing appearance, perfume, viscosity and of other such desirable physical characteristics, it is primarily important that the shampoos should be maintained under conditions which enable them to act most effectively in washing and treating the hair and scalp. Thus, by maintaining the pH acidic, in the range of 3 to 6.5, the astringent metal salts that are most frequently used, such as the aluminum halides, sulfates and sulfamates, are most stable and effective. Additionally, such acidic conditions improve astringent action. Also, the aminopropane sulfonate compound is an effective, non-interfering surface active material at such a pH and the amine oxide is a good foaming agent. Such effects are not common to many shampoo constituents and such attests to the unexpectedness of the beneficial properties of these specific compositions. Instead of employing a pH of 3 to 6.5, a more preferred pH range is from 3.5 to 5. At such conditions, the activity of the astringent metal salt is even more pronounced than at higher pH's and yet, the shampoo is not unduly acidic. Adjustment of pH may be effected by utilizing buffering agents or mineral acids, such as hydrochloric acid, sulfuric acid or other equivalent acidifying agent, usually dilute, in minor proportion, to control the pH of the final product. If an acid, buffer or other material is employed to adjust the pH of the shampoo, it will normally be used in a proportion from 0.1 to 5% of the composition.

The present shampoos are used in the normal way, with the application of a small proportion, generally from 2 to 10 milliliters, to the hair, followed by diluting with water, foaming and rubbing into the hair and scalp, after which the shampoo is usually rinsed off and re-applied. Since from 2 to 10 milliliters of shampoo will usually be employed to wash the hair, in conjunction with from a cup to a quart of water, the end concentration of the important shampoo active ingredients will be from about 0.5 to 0.02 percent. Even at such low concentrations, which correspond to even lower proportions of astringent metal salt, often from 0.1 to 0.004 percent of astringent salt, there is enough of such salt present and its action is not inhibited by the aminopropane sulfonate, amine oxide and aqueous medium, so that at the pH's mentioned the metal, e.g., aluminum, reacts with the keratin of the hair to a sufficient extent as to make it significantly less anionic in nature, thereby making the hair easier to manage, less receptive to static charges and more readily maintained in clean condition because of the decrease in anionic character, which lowers the tendency of the hair to absorb oil and dirt. Aluminum chlorhydroxide is exceptionally desirable because it hydrolyzes slowly and protectively to release astringent aluminum ion. Thus, even when not employed in shampoo compositions but instead, when used as an aqueous solution, such chlorhydroxides exert useful antiperspirant effects on the scalp and antistatic and anti-soiling effects on the hair, whereby the hair and scalp are kept clean for a longer period of time. Furthermore, the aluminum chlorhydroxide has the very desirable ability to leave the scalp feeling clean and dry. When used apart from the present shampoos, it may be employed in a similar manner, often as a composition comprising from 0.5 to 8 percent aluminum chlorhydroxide, preferably from 2 to 6 percent thereof, with the balance of the composition usually being an aqueous medium, preferably water.

The present invention allows the treatment of the hair and scalp to make it feel good and be clean and tends to keep the hair clean longer. Additionally, secretions of perspiration and sebum are diminished after use of the present compositions or applications of these methods, decreasing the coiling of the hair and counteracting to a significant extent the production of malodorous substances on the hair and scalp. Conditions which may give rise to development of acne are prevented. All this is accomplished with a simple treatment of the hair, which is safe and gentle. It also is achieved by utilization of shampoo compositions containing effective cleaning and treating constituents which are mutually compatible under the conditions of manufacture, storage and use.

The following examples illustrate some embodiments of the present invention. Throughout the specification, unless otherwise indicated, all parts are by weight and all temperatures are in degrees Centigrade.

EXAMPLE 1 ______________________________________ Parts ______________________________________ Aluminum chlorhydroxide 3 Myristyl dimethyl amine oxide 6 N-cocoyl, N,N-dimethyl aminopropane sulfonate (cocoyl dimethyl sulfobetaine) 6.0 Water, deionized 84.7 Hydrochloric acid, 1 Normal 0.1 Perfume 0.2 ______________________________________

The aluminum chlorhydroxide, myristyl dimethyl amine oxide and N-cocoyl, N,N-dimethyl aminopropane sulfonate are separately added to 20, 30 and 34.7 parts, respectively, of the water, at room temperature and each portion of said aqueous medium is stirred until the active material is dissolved therein. The materials are at room temperature and solution is comparatively easy, being completed within 5 minutes stirring time in all cases. Then, the amine oxide and aminopropane sulfonate solutions are admixed, with stirring, and to this clear solution is added the aluminum chlorhydroxide solution. The pH is found to be 5.1 and it is adjusted by the slow addition of the inorganic acid until it is 4.5. Then, the perfume is added slowly and is "dissolved" in the surface active solution to such an extent that the solution appears clear. The product is now ready for packaging or use.

The product is a clear, thickened shampoo, which is free flowing, yet not thin or watery. It is stable on storage and does not separate at room temperature into layers. Because of the use of deionized water and the compatibilities of the ingredients, it is unnecessary to employ sequestrants or other preservatives or stabilizers in this composition.

When used, by applying five milliliters thereof to female "living" hair to be washed, then adding about a pint of warm water and shampooing in the usual way, holding the water solution of shampoo materials in contact with the hair for two minutes, followed by rinsing until a pH of 6.5 is obtained, after which the operation is repeated, it is found that the hair which was previously oily and dirty, is cleaned and that the scalp is also cleaned well, with flakes of dandruff and sebum being completely removed. The hair becomes less prone to static generation, exhibits less "fly-away" and soils less readily, apparently due to reaction of the aluminum chlorhydroxide with the keratin of the hair to chemically modify it, making it less anionic in nature. Also, the lower pH of the shampoo reduces swelling of the hair shaft. The scalp feels desirably and exceptionally clean after shampooing. No irritation of the scalp is apparent, and the shampoo is rated as an excellent product by the user.

After shampooing, setting and drying of the hair, which is, on the average, 12 inches long, it is found that the normal perspiring experienced when the body is subjected to higher temperatures does not occur to as great an extent on the scalp as was formerly the case, before use of the invented shampoo, or aluminum chlorhydroxide treatment. Also, sebum secretions are diminished, with the result that the hair does not become as oily. It is observed that washing of the hair is not required until five days after initial shampooing, whereas with ordinary shampooings, washing is desirable after a shorter time, usually about three days. Thus, the present shampoo acts to prevent resoiling of the hair after use, possibly due to the diminution of secretions from the scalp and chemical modifications of the hair.

When in place of the various active materials described in the above formulas, other equivalents are substituted, comparable results obtain. Thus, when using 2 percent of aluminum sulfamate, 1.5 percent of zirconium tetrachloride, 2 percent of hafnium oxychloride, 3 percent of zirconium oxychloride or 1 percent of zinc sulfate, both astringent and hair-treating effects are observed, although the results are not as good as with the 3 percent aluminum chlorhydroxide. Similarly, dimethyl amine oxides other than the myristyl compound are interchangeable with the myristyl dimethyl amine oxide. For example, the lauryl or palmityl dimethyl amine oxides may be used or such higher alkyl diethyl amine oxides and higher alkyl mixed di-lower alkyl amine oxides. The higher acylamido-lower alkyl di-lower alkyl amine oxides, such as lauroyl amidopropyl dimethyl amine oxide; palmitoyl amidoethyl dimethyl amine oxide; or cocooyl amidopropyl diethyl amine oxide may replace the mentioned amine oxides and mixtures thereof, mixtures of the higher alkyl di-lower alkyl amine oxides or 50:50 mixtures of these types of amine oxides may be employed. In a similar manner, instead of N-cocoyl, N,N-dimethyl aminopropane sulfonate, the corresponding N-lauryl, N,N-dimethyl aminopropane sulfonate or N-decyl, N-methyl, N-ethyl aminopropane sulfonate may be substituted, with good effects. Similarly, the N-higher acylamido-lower alkyl di-lower alkyl aminopropane sulfonates or mixtures thereof may entirely or partially replace the formula aminopropane sulfonate or equivalent sulfonate. For example, N-cocooyl amidopropyl N,N-dimethyl aminopropane sulfonate; N,N-diethyl aminopropane sulfonate or N-palmitoylamidoethyl N,N-dimethyl aminopropane sulfonate can be used in partial or complete substitution for the formula aminopropane sulfonate. In such products the shampoos and aqueous hair treatments are clear, satisfactorily free flowing, stable and mild and effectively clean the hair, leaving it in good, clean state without being excessively oily or electrically chargeable. Instead of water, aqueous-alcoholic media may be employed. Thickeners, including polyvinyl pyrrolidone, polyvinyl alcohol, carrageenan gum and others named in the specification, may be used. Also, an aqueous solution of 3 percent of aluminum chlorhydroxide may be employed to treat the hair after shampooing or even without previous shampooing, to give it improved manageability and to prevent ready re-soiling. Such treatment also imparts antiperspirant activity and helps to keep the scalp and hair clean by diminishing perspiration and sebum excretions. Instead of using an aqueous solution of aluminum chlorhydroxide, aqueous solutions of other water soluble astringent salts such as the salts of aluminum, hafnium, zirconium or zinc may be substituted for part of the aluminum chlorhydroxide.

EXAMPLE 2 ______________________________________ Parts ______________________________________ Aluminum chlorhydroxide 5 C _{10 -14} higher fatty alcohol polyethoxy ethanol* 5 N-cocoyl, N,N-dimethyl aminopropane sulfonate 5 Myristyl dimethyl amine oxide 6 Tallow dimethyl betaine 2 Water, deionized 76.7 Hydrochloric acid, 1 Normal 0.1 Perfume 0.2 ______________________________________ * Polyethoxy ethanol portion is 60% by weight of the compound

The aluminum chlorhydroxide, nonionic surface active agent, aminopropane sulfonate, amine oxide and betaine are separately dissolved or dispersed in approximately equal portions of the water and the aqueous solutions are then admixed, after which hydrochloric acid acidifying agent and perfume are added. Preliminary dissolvings take place at about 40°C. and admixing(s) at 30°C. The perfume is added at 25°C.

The product resulting is an effective astringent shampoo. Because of the increased contents of detersive ingredients, including the nonionic, it is a more effective cleaning formula than that given in Example 1. Also, because of the increased proportion of aluminum chlorhydroxide astringent, the pore-closing and scalp-tightening effects noted are greater. Yet, despite the increased content of astringent, the product is of good shelf stability being stable for more than a year at ordinary ambient temperatures. Hair washed with it according to the method described in the specification and in Example 1 appears to remain clean longer than when treated with an ordinary shampoo. The washed hair is lustrous, controllable and sweet smelling, with no trace thereon of insoluble materials precipitated out from the shampoo.

When the aluminum chlorhydroxide content is replaced in whole or in part, preferably in part, with less than 50 percent replacement thereof, with aluminum sulfamate, aluminum chloride, zinc sulfate, zirconium sulfate or zirconium oxychloride, a satisfactory shampoo with the mentioned desired properties is also obtained. Similarly, when the myristyl dimethyl amine oxide is replaced with myristoylamidopropyl dimethylamine oxide or with n-hexadecanoylamidoethyl diethylamine oxide and when the tallow dimethyl betaine is replaced with cocodimethyl betaine, a good shampoo is obtained. This is also the case when the nonionic is replaced with nonylphenol polyoxyethylene ethanol ("Igepal" CO-630). Also, when the sulfobetaine and the betaine are replaced by corresponding acylamidopropyl-- or acyl-amidoethyl sulfobetaine or betaines, in which the acyl group is of the same length as the tallow or coco alkyl, excellent shampoos are produced.

EXAMPLE 3 ______________________________________ Parts ______________________________________ Aluminum chlorhydroxide 3 Aluminum sulfamate 1 Zirconium oxychloride 1 Cocoyl dimethyl amine oxide 8 Cocoyl dimethyl sulfobetaine 5 N-cocooylamidopropyl, N,N-dimethyl amino propane sulfonate 2 Water, deionized 79.7 Perfume 0.3 ______________________________________

The various ingredients are separately dissolved in the water at approximately room temperature and the solutions are admixed at the same temperature, after which the perfume is added. The pH of the product is about 5 to 6 and the shampoo made is clear. When used in the manner previously mentioned, especially in Example 1, the stable shampoo washes human hair well and continued use thereof has the effect of reducing scalp perspiration and the spread of scalp sebum, thus decreasing developments of odor, oiliness and greasiness of the hair.

To produce a thickened, but free flowing shampoo product, 0.5 percent of a 50:50 mixture of polyvinyl alcohol and hydroxypropyl methyl cellulose is added to the shampoo by first dissolving it in a portion of water, at a temperature of 40°-50°C., cooling to room temperature and admixing with the detergent solutions. Also, when it is desired to produce a creamy shampoo, opacifying agents of known types may be employed, such as behenic and other higher fatty acids and glycerides, providing that they are not unduly reactive with the cation of the astringent compound. Usually from 0.1 to 0.5 percent of opacifier will be sufficient.

Changes may be made in proportions and various active ingredients, in accordance with the teachings of the specification, without significantly adversely affecting the utility of the product.

EXAMPLE 4

A shampoo is made according to the method of Examples 2 and 3, which comprises 4 percent by weight of aluminum chlorhydroxide, 5 percent myristyl dimethyl amine oxide and 6 percent of N-cocoyl, N,N-dimethyl amine propane sulfonate in 85 percent of a 75:10 solution of water:ethanol. A clear shampoo of a pH of about 5 is obtained. For pH adjustment, hydrochloric acid, sulfuric acid or sodium hydroxide is employed. The aluminum chlorhydroxide does not react detrimentally with the other constituents and accordingly, the product made is stable.

Approximately 5 milliliters of shampoo are applied to the hair and water is added to it to work up a lather. Although some water applied is lost from the hair, the use of about a pint of water is typical and the shampoo is diluted accordingly. It is left on the hair for about a minute, after which it is rinsed off and another application is made in similar manner. Generally, warm water, at about 40°-50°C. is used. After the second application of the shampoo, and working of it into the hair to produce a copious lather, it is allowed to remain on the hair for approximately three minutes, after which it is rinsed off so that the final wash water is about neutral, usually with a pH of about 6 or slightly more. The hair is washed in this manner twice a week and after a month of use it is noted that perspiration and the transfer of sebum from the scalp onto the hair are both diminished. The washed hair is clean, shiny and non-oily.

When the detergent constituents are omitted and the aluminum chlorhydroxide, in solution or suspension, is applied to the hair in the same concentrations, it also produces diminished perspiration of the scalp and oilness of the hair. Although such treatment is useful, especially after shampooing of the hair, it is not as satisfactory as application of the astringent in the described shampoo composition.

The invention has been described with respect to various examples and illustrations thereof but it is evident that it is not to be limited to them, because it will be apparent to one of skill in the art that substitutes and equivalents may be employed without departing from the spirit of the invention of the scope of the claims.