US3098013A

US3098013A - Urea-fatty alcohol adduct dyeing composition and hair dyeing therewith

Info

Publication number: US3098013A
Application number: US15061A
Authority: US
Inventors: William E Austin; Fred A Levin; Theodore H Binaski
Original assignee: Nestle LeMur Co
Current assignee: Nestle LeMur Co
Priority date: 1960-03-15
Filing date: 1960-03-15
Publication date: 1963-07-16
Anticipated expiration: 1980-07-16
Also published as: BE641262A

Description

United States This invention relates to the dyeing of keratinous ma terials. More particularly, it relates to the dyeing of hair for cosmetic purposes.

Coloring preparations for modifying or changing the natural hair color may be classed generally into the permanent colors and the temporary colors. In current practice, permanent colors are oxidation dyes based on certain coal tar intermediates which develop color in the presence of an oxidizing agent, usually hydrogen peroxide. The permanent colors are retained by the hair until the hair grows out, although the original shade may become altered as the result of frequent shampooing, perspiration, exposure to light, use of permanent waves, or other chemical hair treatments.

The temporary colors are used to give color highlights to the hair, to correct yellowish streaks in gray hair, to blend in mixed gray hair, and to brighten and intensify the natural hair color.

The temporary dyes are of several diiferent types. There are acid dyes in conjunction with organic acids such as citric or tartaric, and sometimes with a surfactant. Another type is the cationic or basic dyes combined with buffering salts such as borates, citrates, or phosphates. Still another type comprises the complex dyes which are formed by the interaction of acid dyes (including direct dyes) with cationic surfactants.

The dyes of all these types of temporary dyes impart color to the hair by way of forming a film on the hair surface. The films are of varying durability. Thus, the first mentioned type, the acid dyes, can be completely removed by a single shampooing, while the second mentioned type, the buffered cationic or basic dyes, usually last through a few shampooings.

In recent years, a desire has become manifest for hair colors of the temporary type, but with longer-lasting characteristics, in elfect, a hair coloring which will withstand many shampoo treatments and will be semi-permanent in its lasting properties. The invention is particularly concerned with fulfilling this need.

Accordingly, a principal object of the invention is to provide a suitable semi-permanent hair dye composition. Other objects are to provide suitable dye components for the compositions; to provide suitable ways for formulation of the dyes; and to provide dyeing procedures whereby coloring of the desired permanence can be obtained.

It has been found that certain normally water-insoluble dyes or dye-complexes can be dispersed in a suitable medium and under the requisite conditions of preparation to provide compositions appropriate for coloring hair with long-lasting or semi-permanent temporary color. This result was unexpected since ordinarily dispersions of color produce only superficial films which are quite readily removable from the hair.

According to the invention, a dye composition suitable for imparting semi-permanent color to the hair comprises an aqueous medium having a water-insoluble dye dispersed therein, and further containing as a dispersing agent for the dye in the medium the system of polyoxyethylene ether of fatty alcohol and urea-fatty alcohol adduct.

The water-insoluble dye can be a known disperse dye,

atent or a known solvent dye. Alternatively, the insoluble dye can be a complex of a basic dye and an anionic surface active agent. Such complexes constitute a group of dyes hitherto not described.

Dye dispersions according to the invention, are stable dispersions or suspensions of the dye in the medium and of such character to provide the dye in a form suitable for application to hair.

As between the various dyes operable according to the invention, there is considerable variation in chemical constitution. The dyes have in common, however, insolubility and dispersibility according to the invention. Mere insolubiiity of a dye is not enough. Thus, insoluble vat dyes have given unsatisfactory results since they are not dispersible according to the invention.

The amount of the dye in the composition can be from a small but effective amount, e.g. .25 wt. percent up to about 2 wt. percent. This range is not critical but is pre ferred. In general the dye is present in a minor proportion and the optimum amount for particular conditions can be determined by experiment.

lBy disperse dye and solvent dye is meant, respectively, the disperse dyes of and according to, and the solvent dyes of and according to Colour Index, 4 vols., American Association of Textile Chemists and Colourists, Lowell, Mass. (completed 1958).

Disperse dyes are defined as a class of water-insoluble dyes, originally provided for dyeing cellulose acetate, and applied as a rule from fine aqueous suspensions. They have been used to a limited degree on wool sheepskins and furs for the production of level pastel shades. Also, attempts have been made to apply these dyes to human hair, but the results hitherto have not been satisfactory. =By means of the present invention, suitable semi-permanent color can be imparted to the hair.

Disperse dyes include nitro-arylanines, azo dyes, and anthraquinone dyes, and are all characterized by the absence of solubilizing sulfonic acid groups. Specific examples of preferred disperse dyes are disperse violet, Cl. #4, disperse orange, Cl. #5, and disperse blue, 0.1. #29, the designations being those of the aforementioned publication Colour Index. These and other suitable disperse dyes, along with the Colour Index designation and dye class, are set forth in the following table:

TABLE =I.DISPERSE DYES Dye Color Index Class Number Disperse yellow Nitro.

Do Mcthine Disperse orange- Azo. Disperse red Azo.

0 Azo. Disperse violet. Anthraquinone Do zo. Disperse blue Anthraquinone.

D0 Cl. #29

cludes many dyestufi groups, such as azo dyes, xanthene dyes, triarylmethane dyes, thiazine dyes, azine dyes, phthalocyanine dyes; also metallized complexes of azo dyes, complexes formed by the interaction of acid and basic dyes, and many dyes whose chemical constitution is not as yet recorded. Specific examples of preferred solvent dyes are solvent black, Cl. #5 and solvent brown, 01. #19, again the designations being those of the aforementioned publication Colour Index. These and other suitable disperse dyes, along with the Colour Index designations and dye class, are set forth in Table II.

TABLE II.SOLVENT DYES Here again, the enumerated dyes are merely exemplary and the other disperse dyes enumerated in the aforementioned Colour Index can be used.

The novel complexes, which are insoluble materials formed from a basic dye and an anionic surface active agent, can be made by admixing aqueous solutions containing molecular equivalents of the dyestutf and the surfactant. The complex precipitates from the solution and can be separated from the supernatant liquid by decanting. It can then be used directly in wet condition in formulation of the dye composition or can be dried and later employed for the formulation.

The novel complexes are well suited for the purposes of the invention and have the further advantage that they increase the number of possible colors and shades for dyeing [according to the invention. Additionally, they can be used as dye components in compositions comprising an aqueous medium, dye, and dispersant, other than the compositions according to the invention wherein as dispersant there is used the ether-adduct system.

By basic dyes is meant the basic dyes of and according to the aforementioned publication Colour Index. Specific examples of basic dyes are chrysoidine, basic brown, Cl. #1, basic red, CI. #2 and basic orange, Cl. #1, the identification by notation being that of the aforementioned Colour Index publication. Basic dyes suitable for the formation of complex dyes according to the invention are set forth in Table III:

TABLE III.-BASIC DYES Here again, the enumerated dyes are merely exemplary and the other disperse dyes listed in the aforementioned Colour Index can be used.

The anionic surface active agents used for forming the complex dyes are represented by soaps including complex soaps such as the sodium salt of oleyl sarcosine; sulfonated fatty alcohols such as sodium lauryl sulfate and diethanolamine salt of myristyl alcohol sulfate; sulfonated fatty acid amines such as sodium sulfonate of butanolamido stearic acid; sulfonated fatty acid esters such as sodium dihexyl sulfosuccinate; sulfonated derivatives of saturated oil and/or their fatty acids such as sodium sulfonate of stearic acid monoglyceride; and alkyl-aryl sulfonates such as sodium dodecyl benzene sulfonate and sodium dilauryl naphthalene sulfonate. This enumeration of suitable anionic surfactants is merely exemplary. Any relatively highly ionized anionic, as represented by the mentioned materials, can be used.

The polyoxyethylene ether of fatty alcohol serves primarily as a dispersant for the dye. The ether can be an ethoxylated higher fatty alcohol, e.g. an alcohol having from 10-30 carbon atoms, preferably 10-22, formed by treatment of the alcohol with ethylene oxide. Varying amounts of ethylene oxide may be present in the dispersant. Only those compounds, however, containing suflicient ethylene oxide to give hydrophilic-lipophilic balance values (HLB) of 15 or higher have desirable properties for the purpose of the invention. The HLB scale is defined in Emulsions, Paul Beacher, American Chemical Society Monograph #135, pp. 189-96. Suitable ethers are polyoxyethylene oleyl ether of HLB 15.3, polyoxyethylene stearyl ether of HLB 15.3 and polyoxyethylene lauryl ether of HLB 16.9.

The quantity of the ethoxylated higher fatty alcohol which should be employed, depends on the particular dye composition. Suitable quantities can be determined by experiment. In general, for the composition the amount of ether will be in the range of about 0.5-4 wt. percent. Amounts outside this range can be used, but the mentioned range is preferred.

The urea-fatty alcohol adduct has several desirable effects on the composition. It facilitates dispersion of the dyes in the medium; increases the viscosity so that handling of the composition for application to the hair is made more convenient; provides improvement in operation of the dye composition in that the luster and condition of the hair is improved; and, most important, it improves effectiveness of the dye composition in that it increases penetration of the dye into the hair and this results in a fuller and longer lasting color.

The adduct functions as an adjuvant having pronounced effectiveness in imparting to the dye compositions the desired semi-permanent properties, and it activates the composition to provide penetration and improved appearance.

The fatty alcohol component of the adduct can be a higher fatty alcohol, for example having about 10-30, preferably 10-22, carbon atoms. Suitable alcohols are lauryl, cetyl, myristyl and stearyl. The adducts are microcrystalline or amorphous powders. They can be included in the composition in such form, or, as is more particularly described hereinafter, they can be formed in situ.

The adduct can be used in the composition in the amount of about 2-10 wt. percent of the dye composition. Where the adduct is formed in situ the alcohol can be about 1-5 wt. percent and the urea about 2-8 wt. percent. The proportion of urea to fatty alcohol, when the adduct is added as such to the composition can be that set forth for the in situ formation of the adduct. While the limits mentioned are not critical, they are preferred.

The dye compositions of the invention can be formed by admixing the dye, water medium and dispersant. Advantageously, the polyoxyethylene ether is liquified at about 50-60 C., and the other components are then blended therein with agitation.

Where the fatty alcohol-urea adduct is formed in situ, the dye components comprising the water, dye, polyoxyethylene ether and the urea-fatty alcohol adduct, are admixed and the adduct is provided therein by separate addition of the urea and fatty alcohol for the in situ formation of the adduct in the composition. Desirably, the fatty alcohol and urea are added to the polyoxyethylene ether of fatty alcohol. Thus, the fatty alcohol can be added to the polyoxyethylene ether and an aqueous solution of the urea can be then added to the ether-fatty alcohol admixture.

When the complex of a basic dye and anionic surfactant is formed in situ, 'a like procedure can be followed with respect to the complex precursor ingredients, i.e., the basic dye and the anionic surfactant. Also, both the in situ formation of the adduct and the in situ formation of the complex can be practiced in the same dye composition formulation.

In application of dyes according to the invention, the hair can first be shampooed in the usual manner, then rinsed and towel dried. The dye composition is then applied directly to the hair, either by pouring on and distributing with :a comb to all parts of the hair, or by means of a brush or applicator or cotton swab. Enough is used to cover the entire hair, and usually 1 ounce or less is suiiicient. The composition is allowed to remain on the hair for 5 to 15 minutes, according to the intensity of color desired. The dyeing is then complete and the dyed hair can be rinsed, set, and dried in the usual manner.

The range of shade attainable with the color compositions comprises all the desired hair colors. The diversity of color may be extended if desired, by combining two or more compositions made from the different classes of dye materials.

The coloring imparted to the hair according to the invention is a semiperrnanent color as distinct from permanent and temporary color as is now commonly used. Thus, whereas in general permanent colors are displaced by hair growth and temporary colors are removed by one or two shampooings, the semi-permanent dyes of the invention withstand several, commonly 5-6, shampooings.

The invention is further described in the following examples, where formulations for dyes and dye compositions are set forth in parts by Weight. The pH for the dye compositions in the examples are the natural pHs thereof. The dye compositions are stable dispersions and remain such under normal conditions of use, shipment, storage, etc.

Example 1 In this example, a dye composition based on a disperse dye is prepared. The formula for the composition is as follows:

Parts Polyoxyethylene lauryl ether 2.0 Lauryl alcohol 2.0 Disperse violet, CI. #4 1.0 Urea 4.0 Water 91.0

Example 2 In this example, a dye composition based on a solvent dye is prepared. The formula for the composition is as follows:

Parts Polyoxyethylene oleyl ether 1.5 Solvent black, Cl. #5 0.5 Urea-cetyl alcohol adduct 5.0

Water 93.0

and an anionic surface active agent. The composition formulation is as follows:

Parts Polyoxyethylene stearyl ether 0.5 Myristyl alcohol 2.5 Diethanol lauryl sulfate (30%) 3.0 Basic brown, C1. #1 1.0 Basic red, Cl. #2 5.0 Urea 5.0

Water 87.5

A melt of the ether and myristyl alcohol at 55 C. is stirred to provide a uniform blend. The anionic surfactant, diet-hanol lauryl sulfate, and the urea are dissolved in 40 parts of water at C. and the resulting solution is stirred into the melt of ether and fatty alcohol. The dye is dissolved in the balance of the water at 85 C. and the resulting solution is added to the previously prepared aqueous admixture. Stirring is continued while the composition cools to room temperature. The dye composition produces on white hair a full auburn shade.

Example 4 In this example a complex of a basic dye and an anionic surface active agent is employed. The formula of the composition is as follows:

Parts 'Po'lyoxyethylene lauryl ether 1.0 Stcaryl alcohol 1.5

Complex of basic orange, Cl. #1, and dodecyl benzene sodium sulfonate 1.5 Urea 4.0 Water 92.0

Example 5 In this example, the dye composition includes a disperse dye and a solvent dye. The formula for the composition is as follows:

Parts Polyoxyethylene stearyl ether 1.5 Disperse orange, Cl. #5 0.5 Solvent brown, Cl. #19 0.5 Solvent black, Cl. #5 0.1 Urea-lauryl alcohol adduct 5.0 Water 92.4

The ether is liquefied by heating to 55 C., and the disperse dyes and both solvent dyes are then stirred into the ether. The urea adduct is dissolved in the water at 85 C. and the resulting solution is slowly added with constant stirring to the dye-containing mixture. Stirring is continued to room temperature. On white hair the dye composition produces a medium ash blonde shade.

Example 6 In this example, there is made a dye composition including a disperse dye and a complex dye of a basic dye and anionic surface active agent. The formula for the composition is as follows:

Parts Polyoxyethylene lauryl ether 1.0 Myristyl alcohol 2.0 Disperse blue, Cl. #29 0.5 Sodium oleyl sarcosinate 1.5 Urea 5.0 Basic brown, Cl. #1 1.0 Basic red, Cl. #2 0.2

Water 88.8

The ether and myristyl alcohol are blended together at 55 C., and the disperse dye is stirred into the resulting admixture. The sodium oleyl sarcosinate and urea are then dissolved in 40 parts of water at 85 C. and the resulting urea-surfactant aqueous mixture is added slowly to the disperse dye-containing mixture, with stirring. The basic dyes are dissolved in the balance of the water at 85 C. and the resulting aqueous mixture is added to the first described aqueous material, with stirring. Stirring is continued until the composition cools to room temperature. The resulting dye composition imparts to white hair a chestnut brown color.

Exa m pl e 7 In this example, there is made a complex of a basic dye and an anionic surface active agent.

A11 aqueous solution of 2.5 grams of chrysoidine (molecular Weight 248.7) in 100 cc. of Water and an aqueous solution of 2.8 grams of sodium lauryl sulfate in 100 cc. of Water are mixed together. The complex forms and precipitates. It can be separated and dried and stored for future use, or it can be separated by decanting and then used for formulation of dye compositions according to the invention.

In the foregoing examples, in place of the disperse dyes, solvent dyes and complex dyes, the corresponding other dyes disclosed herein as operable for the purposes of the invention can be used.

While the invention has been described in detail with reference to specific embodiments thereof, various changes and alternatives will occur to those skilled in the art, and it is desired to secure by these Letters Patent all such modifications as are within the scope of the appended claims.

What is claimed is:

1. A composition suitable for use as a hair coloring comprising an aqueous medium, an insoluble dye dispersed in the medium, and as dispersing agent for the dye in the medium the system of polyoxyethylene ether of a C to C fatty alcohol and urea-C to C fatty alcohol adduct.

2. A composition according to claim 1, the polyoxyethylene ether of fatty alcohol having a hydrophilic-lipophilic balance of at least 15 and the fatty alcohol of the ureafatty alcohol adduct having about 10-30 carbon atoms.

3. A composition according to claim 1, the dye being selected from the group consisting of disperse dyes, solvent dyes, complexes of cationic dyes with anionic surfactants, and mixtures thereof.

4. The method of dyeing hair which comprises contacting the hair with a coloring composition comprising an aqueous medium, an insoluble dye dispersed in the medium, and as dispersing agent for the dye in the medium the system of polyoxyethylene ether of a C to C fatty alcohol and urea-C to C fatty alcohol adduct, and continuing the contacting for a time sufiicient for development of color in the hair.

5. The method of claim 4, the polyoxyethylene ether of fatty alcohol having a hydrophilic-lipophilic balance of at least 15 and the fatty alcohol of the urea-fatty alcohol adduct having about 1030 carbon atoms.

6. The method of claim 4, the dye being selected from the group consisting of disperse dyes, solvent dyes, complexes of cationic dyes with anionic surfactants, and mixtures thereof.

7. The method of making a hair coloring composition including as components thereof an aqueous medium, an insoluble dye dispersed in the medium, polyoxyethylene ether of a C to C fatty alcohol as a dispersant and a urea-C to C fatty alcohol adduct as an adjuvant, which comprises admixing said components and providing therein said adduct by separate addition of the urea and fatty alcohol for in situ formation of the adduct in the composition.

8. The method of making a hair coloring composition including as components thereof an aqueous medium, as dye dispersed in the medium a water-insoluble complex of a basic dye and an anionic surface active agent, polyoxyethylene ether of a C to C fatty alcohol as a dispersant, and an urea-C to C fatty alcohol adduct as an adjuvant, which comprises admixing said components and providing therein said dye by separate addition of the basic dye thereof and the anionic surface active agent thereof for in situ formation of the complex dye in the composition.

9. The method of making a hair coloring composition including as components thereof an aqueous medium, as dye dispersed in the medium a water-insoluble complex of a basic dye and an anionic surface active agent, polyoxyethylene ether of a C to C fatty alcohol as a dispersant, and an urea-C to C fatty alcohol adduct as an adjuvant, which comprises admixing said components and providing therein said dye by separate addition of the basic dye thereof and the anionic surface active agent thereof for in situ formation of the complex dye in the composition, and further providing therein said adduct by separate addition of the urea and fatty alcohol for in situ formation of the adduct in the composition.

10. The method of preparing a hair coloring composition which comprises admixing in an aqueous medium for the composition an insoluble dye and as a dispersing agent for the dye in the medium the system of polyoxyethylene ether of a C to C fatty alcohol and urea-C to C fatty alcohol adduct, to disperse the dye in the medium as a stable dispersion thereof.

11. The method of claim 10, the polyoxyethylene ether of fatty alcohol having a hydrophilic-lipophilic balance of at least 15 and the fatty alcohol of the urea-fatty alcohol adduct having about 10-30 carbon atoms.

12. The method of claim 10, the dye being selected from the group consisting of disperse dyes, solvent dyes, complexes of cationic dyes with anionic surfactants, and mixtures thereof.

13. A composition suitable for use as a hair coloring comprising a major amount of an aqueous medium, 0.25 to 2 Weight percent of an insoluble dye dispersed in said aqueous medium, said dye being selected from the group consisting of dispersed dyes, solvent dyes, and waterinsoluble complexes of cationic dyes with anionic surfactants, and as a dispersing agent for the dye in the aqueous medium the system of 0.5 to 4 weight percent of polyoxyethylene ether of a C to C fatty alcohol and 2 to 10 Weight percent of a urea-C to C fatty alcohol adduct.

14. The method of making a hair coloring composition which comprises adding to a major amount of an aqueous medium 0.25 to 2 weight percent of an insoluble dye selected from the group consisting of dispersed dyes, solvent dyes, and complexes of cationic dyes with anionic surfactants, and maintaining in said aqueous medium as dispersing agent for the dye the combination of 0.5 to 4 weight percent of polyoxyethylene ether of a.

9 10 C to C fiamty alcohol and 2 to 10 Weight percent of OTHER REFERENCES urea-C to C fatty alcohol adduct- Diserens: Chemical Technology of Dyeing and Printing, vol. l1, pp. 8-22, publ. by Reinhold Pub. Co., 1948.

References Cited in the file of this patent Colour Index, v01. 1, 2nd Ed., 1956, Am. Assoc. of 5 Textile Chemists and Oolorists, pp. 1655-6; v01. 2, 2nd UNITED STATES PATENTS Ed., 1956, Am. Assoc. of Textile Chemists and Colorists, 2,163,043 K 't h k J 20, 1939 P 2,695,259 c f iii 5: 23, 1954 Goldem-berg: J. Soc. Cosmetic Chemists, 10:5, Septem- 2,848,369 Seemuller Aug. 19,1958

Claims

1. A COMPOSITION SUITABLE FOR USE AS A HAIR COLORING COMPRISING AN AQUEOUS MEDIUM, AN INSOLUBLE DYE DISPERSED IN THE MEDIUM, AND AS DISPERSING AGENT FOR THE DYE IN THE MEDIUM THE SYSTEM OF POLYOXETHYLENE ETHER OF A C10 TO C30 FATTY ALCOHOL AND UREA-C10 TO C30 FATTY ADDUCT.