US2763269A - Foaming hair coloring compositions comprising basic dyes, and method of use - Google Patents

Description

United States Patent C) FOAMING HAIR COLORING COMPOSITIONS COMPRISING BASIC DYES, AND METHOD OF USE Marion Den Beste, Prospect Heights, Ill., asfsignor to Rayette, Inc., a corporation of Minnesota No Drawing. Application February 1, 1952, Serial No. 269,600

4 Claims. (Cl. 132--7) The present invention relates to cosmetic compositions and has particular reference to cosmetic compositions adapted for imparting color to human hair.

From earliest history many people have been dissatisfiied with the natural color of their hair and have sought preparations capable of modifying its color. Numerous color modifying materials and many varied procedures for applying such materials to human hair have been dv' veloped in an attempt to formulate a hair coloring cosmetic preparation suitable for convenient home use by the consumer.

The hair coloring compositions which have been suggested heretofore have certain disadvantages which limit the desirability for their use. A primary disadvantage inherent in prior art preparations is that the color imparted through the use of such preparations is absorbed permanently by the hair. Should the user become dissatisfied with the color there may be nothing that can be done to remove the same except to dye the hair with another color to cover the undesirable shade obtained in the first application.

The dyes or the dye intermediates used in prior art compositions are permanently affixed to the hair through the conjoint use of auxiliary agents, e. g., oxidizing agents, dye precipitating agents or mordanting agents. The application of such auxiliary agents to afiix a dye and thereby develop color on hair is undesirable because such agents also attack and embrittle the hair. In addition to permanently affixing the dye on the hair the use of such agents is also objectionable since many such auxiliary agents are toxic and irritating to the skin.

For many years dye chemists and cosmetic manufacturers have been aware of the above described disadvantages inherent in prior art hair coloring compositions. So far as is known, However, all previous attempts to formulate a preparation for coloring human hair lacking or substantially minimizing the above described disadvantages have been unsuccessful.

The surprising discovery has now been made that novel hair coloring compositions can be prepared which do not possess the disadvantages and limitations of the hair coloring compositions heretofore known. The novel compositions of the present invention comprise foaming hair coloring cosmetic compositions comprising a hair coloring component in admixture with a foaming surface active material.

The hair coloring component comprises at least one non-irritating, non-sensitizing basic dye which is capable of being selectively adsorbed from a solution of the composition by the hair. i

The surface active material employed in these novel compositions comprises foaming surface active agents selected from the group consisting of non-ionic surface active agents and surface active agents obtained by condensing protein degradation products with fatty acyl halides, such being so weakly anionic as to be substantially non-ionic. I

Accor'ding to the present invention the surprising dis- 2,763,269 Patented Sept. 18, 1956 covery has been made that a basic dye suspended in a solution of a foaming surface active agent of the type herein described provides a new and markedly improved composition for coloring human hair. Basic dyes have been found to be suitable for coloring human hair since such dyes are amenable to selective adsorption by the hair from solutions containing the particular type of foaming surface active agents herein described. I

An outstanding feature of the combination of the particular dyes and the surface active agents of this inven-' tion is that the said basic dyes are deposited on the hair in the presence of the particular non-ionic and substantially non-ionic surface active agents herein described and are readily removable therefrom upon subsequent shampooing with an anionic sulfate or sulfona-te type shampoo, e. g., the ammonium salt of the mono-sulfated monoglyceride of coconut oil fatty acids which is more strong ly ionizable than the substantially non-ionic surface active agents herein described.

A further outstanding characteristic of this combination is that the particular dyes may be applied from a foam for optimum distribution for a level coloring or tinting of the hair from a desirably small quantity of fluid. Thus, about two tablespoonsful of the composition are sufficient for level tinting of the whole head of hair as a result of its conversion into a large mass of foam at the time of use.

As indicated hereinbefore the dyes which may be used in the novel compositions of the present invention are non-irritating and non-sensitizing to the skin. A dye which is irritating to the skin, i. e., a cutaneous irritant, is one which will cause dermatitis by direct action on the normal skin at the site of contact. A dye which is sensitizing to the skin, i. e., a cutaneous seusitizer, is one which does not necessarily cause demonstrable cutaneous changes on first contact but one which may eifect such specific changes in the skin that, after 5 to 7 days or more, further contact on the same or other parts of the body will cause dermatitis.

Irritation and sensitization determinations of basic dyes may be made in any convenient manner. According to one method a fii-inch square piece of 4-ply gauze is saturated with the dye and applied to uninflamed skin behind the ear. This is sealed to the skin with adhesive plaster. The gauze or patc is left in place for 24 hours. The reaction-s are read immediately upon removal of the patch and for several days thereafter. Dyes which give negative reaction-s after two patch tests 5 to 7 days apart are both non-irritating and non-sensitizing to the skin and are suitable for use in accordance with this invention.

Representative examples of water soluble basic dyes which are non-irritating and non-sensitizing include:

By blending various dyes, it is possible to produce a complete range of shades which appear natural in color and which are non-injurious to the hair and scalp. The invention is not limited to the use of the particular dyes mentioned, inasmuch as any of the great number of other dyes possessing the definitive characteristics set forth hereinabove may be employed.

It is essential that the surface active materials used in formulating the novel compositions of the present invention be capable of forming relatively large amounts of foam. The foam apparently acts as a vehicle or a carrier for the dye and assures a thorough and uniform distribution of the same upon the individual hair filaments.

Representative examples of suitable non-ionic surface active materials which may be employed in the present invention include those compounds derived from the reaction of fatty acids and alcohols having about 12 to 30 carbon atoms per molecule with sufiicient ethylene oxide groups to form surface active materials having the desired foaming properties described, e. g., polyethylene glycol oleate, polyethylene glycol ether of lauryl alcohol, etc.; the high molecular weight derivatives of polyhydroxy compounds such as polyalkylene glycols and polyglycerols, e. g., alkyl thio-ethers of polyethylene glycol (stearyl thio-ether of polyethylene glycol), sterol ethers of polyethylene glycol (cholesterol ether of polyethylene glycol), alkyl phenol ethers of polyethylene glycol having an average of about 8.5 to oxyethylene groups (n- Nonyl phenyl ether of polyethylene glycol); the corresponding derivatives of polypropylene glycol, polybutylene glycol, and polyglycerol; polyalkylene glycol ethers of partially esterified glycerol (polyethylene glycol ether of monostearin), sorbitol (polyethylene glycol ether of sorbitol oleate), sorbitan (sorbitan monostearate polyoxyethylene); etc.

Additional examples of surface active materials which may be employed in this invention include surface active agents prepared by hydrolyzing waste protein materials of high molecular weight, e. g., scrap leather, glue, or other hydrolyzable collagens, with alkali. The hydrolyzate thus obtained is a complex comprising lower polypeptides and some hydrolytic products thereof, e. g., free amino acids. This complex then is condensed with a fatty acyl halide. During the condensation the amino groups of the polypeptides and of the amino acids are converted to amide derivatives of the fatty acyl halide. The condensation product thus obtained has excellent foaming properties. This product bears a resemblance to anionic surface active agents but is so weakly ionizable as tobe substantially non-ionic in its action in admixture with the basic dyes herein described and is suitable for use in the novel compositions of the present invention.

The particular fatty acyl halides used in the condensation reactions described may be formed by reacting a suitable halide material with either the mixed fatty acids obtained from tallow, coconut oil, peanut oil, soy bean oil, etc., or with any of the individual fatty acids which may be derived from these oils. Suitable fatty acids include those containing about 8 to 24 carbon atoms and preferably those containing 12 to 18 carbon atoms per molecule.

Sufficient surface active material is incorporated in the novel compositions herein disclosed to assure the provision of a composition having the satisfactory foaming characteristics described. It has been found that products containing about 5 to surface active material by weight of the final composition provide completely satisfactory products. Although the surface active material may be present in somewhat higher concentrations, no particular advantages are obtained thereby. Moreover, an increase in the concentration of the surface active material necessarily results in an increase in the cost of the final composition without affording any increase in product quality.

The amount of dye which has been found to be satisfactory for use in compositions having a concentration of surface active material as set forth hereinabove falls within the range of about 0.05 to 2.5% by weight of the finished product.

The present invention, in the broadest aspects thereof, contemplates that the novel hair coloring compositions may be prepared and marketed in any desired physical form, e. g., in an aqueous form such as a liquid, paste, or

gel; as a dry powder; etc. When sold as a paste or gel or in a dry powder form the compositions are preferably dissolved by the user in an aqueous solvent medium, similar to that employed when manufacturing the compositions in liquid form, prior to, application to the hair. Such a medium is requisite for the provision of a hair coloring composition having satisfactory foaming properties. Water (tap water, distilled water, deionized water, etc.) has been found to be a satisfactory medium for the particular surface active materials and dyes herein described. The amount of the aqueous solvent employed generally should amount to at least about 80% and preferably about to of the total weight of the finished composition.

In order to indicate even more fully the advantages and capabilities of the novel compositions of the present invention, the following specific examples of representative hair coloring cosmetic compositions are set forth. The formulations have been set forth for illustrative purposes only and they are not intended to limit the scope of the invention in any manner.

Example I A hair coloring cosmetic composition capable of imparting a silver color to white or grey hair comprises:

Per cent Protein condensate with oleyl chloride 8.0 Calcozine Orange RS 0.04 Benzyl Violet DSC H 0.027 Basic Blue FN Ex 0.027 Safranine T Ex 0.007 Sodium alginate 1.0 Perfume 0.1 Boric acid U. S. P. powder 0.960 Water Balance Example II A hair coloring cosmetic composition capable of im parting a grey color to white or grey hair comprises:

Per cent Protein condensate with oleyl chloride 8.0 Calcozine Orange RS 0.120 Benzyl Violet DSC 0.080 Basic Blue FN Ex 0.080 Safranine T Ex 0.020 Sodium alginate 1.0 Perfume 0.1 Boric acid U. S. P. powder 0.960 Water Balance Example III A hair coloring cosmetic composition capable of imparting a black color to light or dark colored hair comprises:

Product obtained by condensing a higher fatty acid with 2 moles of diethanolamine.

Example IV A hair coloring cosmetic composition capable of imparting a silver color to white or grey hair comprises:

Per cent iso-Octyl phenoxy heptaethylene glycol 14.000 Calcozine Orange RS 0.040 Benzyl Violet DSC 0.027 Basic Blue FN Ex 0.027 Safranine T F 0.027 Water Balance Y Exa'mple V A hair coloring cosmetic composition capable of imparting a silver color to White or grey hair comprises:

. Percent n-Nony-l phenoxy nonaethylene glycol 7.600 CalooZin-e Orange RS 0.040 Benzyl Violet DSC 0.0 Basic Blue -FN Ex 0 .016 Safranine T EX 0.004 Perfume 0.050 Water Balance Example VI A hair coloring cosmetic composition capable of imparting a grey or a steel grey color to grey or predomi nantly grey hair comprises:

7 Percent Polyethylene glyco tert-dodecyl thio ether 10.200 Basic Brown GXP 0.093 Cyper Black IA 0.1 16 Safranine T EX 0.046 Methylene Blue ZX 0.046 Water Balance Example VII A hair coloring cosmetic composition capable of imparting a black color on light or dark colored hair com prises:

Percent Polyethylene glyco tert-dodecyl thio ether 8.000 Cyper Black IA 0.660 Basic Brown GXP 1.000 Safr-anine T Ex 0.400 Methylene Blue ZX 0.440 Water Balance Example VIII A hair coloring cosmetic composition capable of imparting a black color on light or dark colored hair comprises:

A hair coloring cosmetic composition capable of imparting a dark brown color on light or dark colored hair comprises:

Percent n-Nonyl phenoxy nonaethylene glycol 5.80 Basic Brown GXP 0.75 Benzyl Violet DSC 0.115 Methylene Blue ZX 0.:' Safranine T Ex 0.15 Water Balance Exalmple X A hair coloring cosmetic composition capable of im parting a dark brown color on medium or dark brown hair comprises:

Per cent iso-Octyl phenoxy heptaethylene glycol 11.00- Basic Brown GXP 1.57 Benzyl Violet DSC 0.31 Methylene Blue ZX 0.31 Sarfranine T EX 0.31 Water Balance Example XI A hair coloring cosmetic composition capable of parting reddish-brown highlights on brown or medium brown hair comprises:

Per cent n-Nonyl phenoxy decaethylene glycol 9.20 Basic Brown GXP 0.20 Calcozine Orange RS 0.15 Basic Blue FN 0.05 Safranine T Ex 0.05 Methylene Blue ZX 0.02 Boric acid U. S. P. powder 1.00 Perfume 0.10 Water Balance Example XII A hair coloring cosmetic composition capable of imparting reddish-gold highlights to light blonde or ash blonde hair comprises:

. Per cent n-Nonyl phenoxy nonaethylene glycol 5.00 Safranine T Ex 0.01 Oalcozine Orange RS 0.06 Boric acid U. S. P. powder 1.00 Perfume 0.10 Water Balance Example XIII A hair coloring cosmetic composition capable of imparting auburn highlights on auburn or dark bnown hair comprises:

Percent Protein condensate with oleyl chloride 8.500 Basic Brown GXP 0.625 Basic Blue EN 0.050 Benzyl Violet DSC 0.050 Safranine T Ex 0.275 Sodium alginate 1.000 Perfume 0.100 Boric acid U. S. P. powder 0.960 Water Balance Example XIV v A hair coloring cosmetic composition capable of imparting a brown color to light auburn, dark auburn or dark brown hair comprises:

The novel hair coloring compositions of the present invention are adapted for convenient home use by the consumer. Prior to using any one of these compositions the hair preferably is given a thorough cleansing treatment by washing with a good quality non-soap shampoo. After substantially all dirt, grease and the like has been removed a lustrous new hair color may be obtained upon a single application of the compositions herein described.

Any desired tint or color may be imparted to the hair by applying thereto, in several small portions, the particular coloring composition whose color is desired. The portions are applied around the top of the head about one-half inch from the scalp, each portion being worked into a foam before applying the next portion. After all the portions have been applied the foam is worked throughout the entire head of hair to insure even distribution. The hair is then rinsed thoroughly with water and then toweled-dry.

By using the novel compositions of this invention color is imparted to the hair immediately upon contact, i. e., no Waiting or setting period is required. The compositions, When correctly applied, will not rub off on clothing or pillows. Furthermore, the color imparted, while resistant to attack by the sun, rain, etc., may be removed satisfactorily and the hair restored to its natural color upon subsequent shampooing with anionic sulfate or sulfonate type shampoo compositions. The simplicity of the process makes it obvious that no expert beauty parlor application is necessary.

The addition of various adjuvant materials to the novel hair coloring compositions is contemplated by the present invention. Thus, the compositions ordinarily will contain a perfume which should be selected so as to be compatible with the character of the finished product. Also, ingredients which impart further desired qualities to the hair may be incorporated in the present compositions. Hair conditioners, for example, or superfatting materials or foam boosters such as lanolin, lecithin, fatty amides, etc., generally may be used in minor proportions. Furthermore, small amounts of thickening agents such as sodium alginate may be included to reduce the fluidity of the product. Moreover, suitable preservatives may be incorporated in minor amounts as needed to prevent or substantially minimize the formation of mold.

In preparing the novel composition of the present invention in aqueous form the formula amounts of the dyes are dispersed in about 70% of the water. The mix is heated to a temperature around 110 to 120 F. and

thoroughly agitated until all of the dye is dispersed. Should any dye particles remain undispersed, the same may be removed in any convenient manner, e. g., by filtration, decantation or the like. The surface active material then is introduced into the mix with moderate agitation and at a rate slow enough to prevent lumping and the incorporation of air. Any compatible perfume and preservatives are then added.

While there has been disclosed and described What is at present considered to be the preferred embodiment of the present invention, it will be understood, of course, that many modifications and changes and substitutions may be made therein Without departing from the true scope of the invention as defined in the appended claims.

Having thus described the invention, What is claimed 1. A cosmetic composition which in aqueous form is adapted for coloring human hair which comprises about 0.05% to about 2.5% of at least one non-irritating, nonsensitizing water soluble basic dye capable of being selectively adsorbed from an aqueous solution of the composition by hair, about 5% to about 15% of a foaming surface active material, said foaming surface active material being selected from the group consisting of nonionic surface active agents and substantially non-ionic surface active agents obtained by condensing protein degradation products with fatty acyl halides.

2. A foaming hair coloring composition in liquid form comprising in combination about 0.05 to about 2.5 of at least one non-irritating, non-sensitizing water soluble basic dye capable of being selectively adsorbed from a solution of the composition by hair, about 5% to about 15% of a foaming surface active material, a major proportion of an aqueous solvent medium, and small but effective amounts of a preservative and a thickener, said foaming surface active material being selected from the group consisting of non-ionic surface active agents and substantially non-ionicsurface active agents obtained by condensing protein degradation products with fatty acyl halides.

3. A process for coloring hair which comprises shampooing the hair with a strongly ionizable anionic surface active agent, rinsing the hair with water to remove said anionic surface active agent, applying to the hair a foaming hair coloring composition which comprises about 0.05% to 2.5% of at least one non-irritating, non-sensitizing, water soluble basic dye and about 5 to 15 of foaming surface active material selected from the group consisting of non-ionic surface active agents and substantially non-ionic surface active agents obtained by condensing protein degradation products with fatty acyl halides, working said coloring composition throughout the hair, and thereafter rinsing the hair with water.

4. A non-irritating, non-sensitizing, cosmetic composition adapted for coloring human hair comprising an aqueous medium having dissolved therein about 0.5% to about 2.5% of at least one water soluble basic dye and about 5% to about 15% of a foaming surface active material selected from the group consisting of non-ionic surface active agents and substantially non-ionic surface active agents obtained by condensing protein degradation products with fatty acyl halides, said basic dye being capable of being selectively adsorbed by hair from said aqueous medium.

References Cited in the file of this patent UNITED STATES PATENTS 1,930,853 Kollek Oct. 17, 1933 1,970,578 Schoeller Aug. 21, 1934 2,015,912 Sommer Oct. 1, 1935 2,100,090 Sommer Nov. 23, 1937 2,151,241 Sommer a- Mar. 21, 1939 2,208,594 Orelup July 23, 1940 2,643,211 Den Beste June 23, 1953 2,695,259 Charle Nov. 23, 1954 FOREIGN PATENTS 240,909 Switzerland May 16, 1946 197,425 Switzerland Aug. 1, 1938 307,944 Great Britain Mar. 11, 1929 531,153 Germany Aug. 6, 1931 397,219 Germany June 17, 1924 OTHER REFERENCES Janistyn: Riechstofie, Seifen, Kosmetika, Alfred Huthig Verlag, Heidelberg, 1950, vol. 2, pp. 455 and 456, especially F. Shampoo mit Haarfarben.

Redgrove: Hair-Dyes and Hair-Dyeing," Chemical Publishing Co., N. Y., 1939, p. 104.

Bennett: Cosmetic Formulary, Chemical Publishing Co., N. Y., 1937, p. 127.

Claims (1)

1. A COSMETIC COMPOSITION WHICH IN AQUEOUS FORM IS ADAPTED FOR COLORING HUMAN HAIR WHICH COMPRISES ABOUT 0.05% TO ABOUT 2.5% OF AT LEAST ONE NON-IRRITATING, NONSENSITIZING WATER SOLUBLE BASIC DYE CAPABLE OF BEING SELECTIVELY ADSORBED FROM AN AQUEOUS SOLUTION OF THE COMPOSITION BY HAIR, ABOUT 5% TO ABOUT 15% OF A FOAMING SURFACE ACTIVE MATERIAL, SAID FOAMING SURFACE ACTIVE MATERIAL BEING SELECTED FROM THE GROUP CONSISTING OF NONIONIC SURFACE ACTIVE AGENTS AND SUBSTANTIALLY NON-IONIC SURFACE ACTIVE AGENTS OBTAINED BY CONDENSING PROTEIN DEGRADATION PRODUCTS WITH FATTY ACYL HALIDES.