US3803323A

US3803323A - Isothiouronium salts for reducing the excessively oily appearance of the hair and scalp

Info

Publication number: US3803323A
Application number: US00061834A
Authority: US
Inventors: G Kalopissis; C Bouillon
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1969-08-08
Filing date: 1970-08-06
Publication date: 1974-04-09
Anticipated expiration: 1991-04-09
Also published as: GB1286919A; DE2039408B2; FR2057074B1; CH514336A; IT983073B; CA965010A; FR2057074A1; LU59254A1; AT322111B; NL7011583A; SE368336B; BE754560A; DE2039408A1

Abstract

A COSMETIC COMPOSITION FOR REDUCING A DISAGREEABLE EXCESSIVE OILY AND GREASY APPEARANCE OF THE HAIR AND SCALP INCLUDES AS AN ACTIVE INGREDIENT IN A COSMETIC CARRIER OR VEHICLE, AT LEAST ONE COMPOUND HAVING THE FORMULA

NH2-C(=NH2(+))-S-(CH2)N-NH3(+) 2X(-)

WHEREIN X IS CHLORINE OR BROMINE AND N IX 2-3.

Description

United States Patent C 3,803,323 ISOTHIOURONIUM SALTS FOR REDUCING THE EXCESSIVELY OILY APPEARANCE OF THE HAIR AND SCALP Gregoire Kalopissis, Paris, and Claude Bouillon, Eaubonne, France, assignors to LOreal, Paris, France No Drawing. Filed Aug. 6, 1970, Ser. No. 61,834 Int. Cl. A61k 27/00 US. Cl. 424-322 4 Claims ABSTRACT OF THE DISCLOSURE A cosmetic composition for reducing a disagreeable excessive oily and greasy appearance of the hair and scalp includes as an active ingredient in a cosmetic carrier or vehicle, at least one compound having the formula wherein X is chlorine or bromine and n is 2-3.

This invention relates to a cosmetic composition for improving the condition and appearance of the hair and scalp. More particularly, the present invention is concerned with a composition which minimizes or reduces excessive exudation of natural oils by the scalp, which oils can impart a disagreeable excessive oily appearance to the hair and scalp. The present invention also relates to a method and composition for treating the hair and scalp with a cosmetic composition containing as an active ingredient an aminoalkyliosthiouronium salt.

It is known that a hypersecretion of the sebaceous glands of the scalp imparts to the hair a greasy or oily appearance which is generally considered disagreeable and tends to seriously detract from the aesthetic qualities of the hair. It has now been found that the cosmetic composition of this invention substantially reduces or minimizes this disagreeable appearance when applied to the hair and scalp, which in turn remain free from said disagreeable appearance for substantially longer periods of time than the hair and scalp when not treated with the composition of this invention. Without being bound by any particular theory, it is believed that the composition of this invention normalizes the secretion of the sebaceous glands and thereby substantially reduces the oily or greasy appearance of the hair and scalp.

The novel cosmetic composition of this invention contains, as the active ingredient, at least one compound having the formula wherein X is a member selected from the gorup consisting of chlorine and bromine and n is an integer of 2-3, and the tautomeric forms thereof.

Representative of such compounds are the chloride of B-aminoethylisothiouronium hydrochloride having the formula c-s-om-om-zvm 201-, Hill? 3,803,323 Patented Apr. 9, 1974 the bromide of B-aminoethylisothiouronium hydrobromide having the formula the chloride of 'y-aminopropylisothiouronium hydrochloride having the formula The active compound can be present in the cosmetic composition in amounts ranging from 0.5 to 5% and, preferably, from 1.5 to 2.5% by weight of the total composition, the remainder of the composition being a suitable cosmetic carrier or vehicle customarily employed in formulations for application to the hair and scalp.

The pH of the cosmetic composition according to the present invention generally ranges between 3 and 8. In this connection, it is noted that the amidinium group attached to the sulfur atom is very labile and that it can be cut off or exchanged between the sulfur and NH group by the action of a base at regular temperature. Thus, when the pH of the cosmetic composition is between 7 and 8, the compound can be a w-mercaptoalkylguanidine salt having the formula:

wherein X and n have the meanings given above.

Further, the applicants have found that the activity of the isothiouronium salts and the w-Inercaptoalkylguanidine salts compare favorably in minimizing or reducing excessive exudation of natural oils by the scalp and thereby both are effective in improving the appearance of the hair and scalp.

As indicated above the cosmetic vehicle or carrier containing the active ingredient for reducing or minimizing the oily appearance of the hair and scalp can be a material that is conventionally applied to the hair and scalp. Thus, the cosmetic vehicle can be water, an aqueous lower alkanol solution, a detergent composition to provide a shampoo, a hair waving neutralization formulation, a hair dye composition, a hair dye-shampoo composition or the like. The novel composition of the present invention can also be in the form of a cream or gel.

When the active ingredient of the present invention is employed in a hair lotion composition, the base lotion, as the vehicle, can be water containing usual cosmetic adjuvants such as a perfume, or it can be an aqueous lower alkanol solution wherein the alkanol is, preferably, ethanol or isopropanol, usually present in a concentration of 20 to When the active ingredient is employed in a detergent base to provide a shampoo composition, the composition can contain about 5 to 60% detergent in an aqueous medium. The detergent can be anionic, amphoteric, cationic, or nonionic.

Anionic detergents include both the soap and non-soap detergents. Examples of suitable soaps are the sodium, potassium, ammonium and alkanol ammonium salts of higher fatty acids (Cg-C20). Examples of anionic nonsoap detergents are alkyl glyceryl ether sulfonates, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkyl monoglyceride sulfates or sulfonates, alkyl polyethoxy ether sulfates, alkanolamide sulfonates, alkanolamide sulfates, alkyl monosulfosuccinates, acyl sarcosinates, acyl esters of isethionates, acyl N-methyl taurines, alkyl benzene sulfonates and alkyl phenol polyethoxy sulfonates. In these compounds the alkyl and acyl groups, respectively, can contain 8-20 carbon atoms and they can be used in the form of water-soluble salts such as the sodium, potassium, ammonium and alkanolammonium salts.

Suitable examples of cationic detergents are dilauryldimethyl ammonium chloride, diisobutyl phenoxy ethoxy ethyl dimethylbenzyl ammonium chloride, cetyl trimethyl ammonium bromide, N-cetyl pyridinium bromide and benzethonium chloride, lauryl benzyl trimethyl ammonium bromide or chloride, myristil benzyl trimethyl ammonium bromide or chloride and cetyl benzyl trimethyl ammonium bromide or chloride.

Suitable examples of amphoteric detergents are asparagine derivatives, alkyl dimethyl betaine, alkyl betaamino propionates, wherein the alkyl group contains 20 carbon atoms, basic quaternary ammonium compounds derived from 2-alkyl-substituted imidazoline and compounds responding to the formula in which R is a radical derived from fatty acids of copra and radicals (C to C derived from tallow.

Representative nonionic detergents are ethylene oxide adducts of fatty alcohols, long chain aliphatic phenols (e.g. octadecyl phenol), long chain mercaptans or long chain amides, such as lauric alcohol oxyethylenated with 12 moles ethylene oxide and C thiols oxyethylenated with 12 moles of ethylene oxide.

Shampoo formulations can, of course, contain any of the usual shampoo additives such as color, perfume, thickeners, solvents, opacifiers, suds builders, conditioning agents, preservatives, butters and antistatic agents.

When the active ingredient is employed in a dye composition for coloring human hair the dye portion of the composition can be any of those conventionally employed, such as oxidation dyes. Representative oxidation dyes include paraphenylene diamine, 2,5-toluene diamine sulfate, chloroparaphenylene diamine sulfate, nitroparaphenylene diamine, 1,2,4-triamino benzene dihydrochloride, paraaminodiphenyl amine, ortho phenylene diamine, 4-chloro ortho phenylene diamine, 4-nitro ortho phenylene diamine, paraaminophenol, 4-amino-2 methy1 phenol sulfate, 4-amino-3methyl phenol, 4amino-2-nitro-phenol, 2,4-diaminophenol hydrochloride, paramethyl aminophenol, sulfate ortho aminophenol, 4-chloro-2-aminophenol, 4 nitro-Z-aminophenol, S-nitro-Z-aminophenol, 4.6 dinitro 2 aminophenol, 6-chloro-4-nitro-2-aminophenol hydrochloride, 4-amino diphenylamine, 4,4-diamino diphenylamine sulfate, meta phenylene diamine, chloro-meta phenylene diamine, ,nitro-meta phenylene diamine, meta toluylene diamine, 2,4-diamino anisol sulfate, meta amino phenol, 3,5-diaminophenol hydrochloride, diethyl meta amino phenol and para amino-ortho cresol.

Obviously, other hair dye compositions can also be employed such as anthraquinone type dyes including for instance 1-hydroxy-2,4-di-(p-trimethylammoniumphenylamino) anthraquinone methosulfate and l-hydroxy-2,4- di(p trimethylammoniumphenylamino) anthraquinone iodide and the like.

The active ingredient of this invention can also be employed in the neutralizing composition used to fix the hair in a permanent waving operation. Generally such neutralizers include peroxides, bromates and perborates, with hydrogen peroxide being generally employed.

Regardless of the specific cosmetic carrier or vehicle employed, be it water, an aqueous lower alkanol solution, a detergent, a dye, a detergent-dye or a permanent wave neutralizer or any other formulation conventionally applied to the hair and scalp, the active ingredient defined herein effectively reduces or minimizes a disagreeable oily appearance of the hair and scalp.

In the case of lotion, cream or gel a daily application during 15 to 20 days of about 15 to 20 cm. of the cosmetic composition according to the present invention is suflicient to reduce or minimize the oily appearance of the hair and scalp.

In the case of shampoo composition, 10 to 20 cm. of the shampoo composition once a week during about 4 weeks are suflicient to get the same result.

The active ingredient employed in the cosmetic compositions of this invention can be prepared in accordance with known procedures such as are disclosed by Doherty, Shapira and Burnett, J. Amer. Chem. Soc., 1957, 79, 5667.

The following examples are given to illustrate the pres ent invention.

EXAMPLE 1 A cosmetic hair and scalp treating composition is made according to the present invention by dissolving:

Chloride of f3 aminoethylisothiouronium hydrochloride g 0.82 Perfumed distilled water sufficient for cc The resulting solution is applied to the hair and scalp which, prior to application, exhibited an excessively oily appearance. After application and drying the hair, the hair and scalp remained significantly less oily in appearance for a substantially longer period of time than did the hair and scalp without treatment with the above cosmetic composition.

EXAMPLE 2 Another hair and scalp cosmetic is made in accordance with this invention by dissolving 1.5 grams of chloride of 1 -aminopropylisothiouronium hydrochloride in 100 cc. of 50% dilute alcohol solution, the alcohol being ethanol.

This resulting composition is employed as outlined in The hair dressing lotion is applied to the hair and scalp and inhibits or reduces an excessive oily or greasy appearance.

EXAMPLE 4 A liquid shampoo is made in accordance with the present invention by mixing together the following materials: G.

Sodium lauryl sulfate oxyethylenated with 2.2 moles of ethylene oxide 5 Sodium monolanryl sulfosuccinate 1 Polyethylene glycol distearate 1.5 Iauryl diethanolamide 2.5 Chloride of y-aminopropylisothiouronium hydrochloride Perfume 0.2 Lactic acid, sufiicient for pH 6.5 Water, sufiicient for 100 The hair and scalp which initially exhibited an excessively oily and greasy appearance were thoroughly washed with the above shampoo composition. Thereafter the hair and scalp remained free from such an excessively oily and greasy appearance for a substantially longer period of time than did the hair and scalp without the above shampoo treatment.

EXAMPLE 5 Another liquid shampoo composition is made in accordance with this invention by mixing together the following ingredients:

G. Sodium lauryl sulfate oxyethylenated with 2 moles of ethylene oxide 6 Sodium monolauryl sulfosuccinate 1 Polyethylene glycol distearate 1 Lauryl diethanolamide 2.5 Bromide of ,B-aminoethylisothoronium hydrobromide 5 Perfume 0.3 Lactic acid, suflicient for pH 6 Water, suflficient for 100 This shampoo composition is applied to the hair and scalp as outlined in Example 4 with substantially equally favorable results.

EXAMPLE 6 A cream shampoo composition is made in accordance with the present invention by mixing together the following materials:

The hair and scalp which exhibited a greasy and oily appearance were washed with the above shampoo composition essentially as outlined in Example 4 and equally favorable results were achieved.

EXAMPLE 7 A dye-shampoo is made in accordance with the present invention .by combining the following materials:

G. Bromide of p-aminoethylisothiorium hydrobromide 5 Ammonium lauryl sulfate oxyethylenated with 2 This product is mixed with 1000 g. of volume hydrogen peroxide. Hair containing 20% white hair is impregnated with the resulting mixture and a chestnut coloring is imparted thereto. The thus dyed hair remained free from an excessively oily or greasy appearance for a substantially longer period of time than did the hair and scalp without the above dye-shampoo treatment.

6 EXAMPLE 3- A hair-setting dye lotion intended for application to white hair having a greasy appearance is prepared according to the following formula:

G. Polyvinyl pyrrolidone (mol. Wt. about 40,000) 0.4 Resin 28.1310 sold by National Starch 0.2 [Vinyl acetate-crotonic acid copolymer (mol. wt.

20000)] Alcohol (isopropanol) sufiicient for 50 Chloride of -aminopropylisothiouronium hydrochloride 0.7 Aminopropylamino-l anthraquinone 0.03 Picramic acid 0.017 N-y-aminopropylamino-4 N-methy1 amino-1- anthraquinone 0.040 Water, sulficient for Triethanolamine, suflicient to adjust the pH to 7.

The resulting hair-setting lotion is applied to white hair and imparts thereto a smoky gray glint and clearly improves the initial greasy appearance of the hair which remained free from an excessively greasy appearance for a substantially longer period of time than did the hair without benefitof the above treatment.

EXAMPLE 9 oxide g 0.8 Ammonia, solution, sufficient for N 0.7 Water, sufiicient for g 100 After contact with the hair for a suitable period of time, i.e. about 10 to 40 minutes, a neutralizing composition originally packaged in two parts is applied thereto. The first part of the neutralizing composition contains:

Hydrogen peroxide, sufl'icient for volumes 6.6 Citric acid g 0.1 Water, sufficient for cc 100 The second part of the neutralizer is a powder made up of:

Chloride of p-aminoethylisothiorniurn hydrochloride 5 The powder constituting the second part of the neutralizer is dissolved in the hydrogen peroxide solution and the hair treated in the first stage, after being wound on curlers, is treated with the neutralizer composition for a period of about 15 to 30 minutes.

After the hair has been rinsed, removed from the curlers and then dried, a good holding permanent is obtained. The hair was much less greasy than before and remained that way for a period of time substantially longer than did the hair absent the above treatment with the composition of the present invention.

What is claimed is:

1. A process for treating the hair and scalp to substantially reduce disagreeable oily and greasy appearance thereof comprising applying to the hair and scalp an effective amount to reduce said disagreeable oily and greasy appearance of a cosmetic composition comprising in a solvent selected from the group consisting of water and an aqueous solution of a lower alkanol selected from the group consisting of ethanol and isopropanol, 0.5-5% by weight of an active compound of the formula wherein X represents a member selected from the group consisting of chlorine and bromine and n is an integer of 2-3 or the tautomeric forms thereof.

2. The process of claim 1 wherein said active compound is selected from the group consisting of the chloride of p-aminoethylisothiouronium hydrochloride, the bromide of fi-aminoethylisothiouronium hydrobromide and the chloride of -aminopropylisothiouronium hydrochloride.

3. The process of claim 1 wherein said active compound in present in amounts of about 1.52.$% by weight of the total composition.

4. The process of claim 1 wherein said composition has a pH of 3-8.

References Cited Doherty et al., Journal of the American Chemical 5 Society, vol. 79, pp. 5667-5671.

JEROME D. GOLDBERG, Primary Examiner VERA C. CLARKE, Assistant Examiner US. Cl. X.R.

8l0.1, 10.2; 424Digests 2 and 4, 70, 71, 72, 326

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,803, 323 Dated April 9, 1974 Inventor(s) Gregoire Kalopissis and Claude Bouillon It is certified that error appeafs in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Signed and sealed this 1st day of October 1974.

(SEAL) Attest:

McCOY M. GIBSON JR. Attesting Officer C. MARSHALL DANN I Commissioner of Patents