US3649159A

US3649159A - Hair coloring method using a peroxydiphosphate oxidant

Info

Publication number: US3649159A
Application number: US733830A
Authority: US
Inventors: Bernard Cohen; Paul Raimond Mucenieks
Original assignee: FMC Corp
Current assignee: FMC Corp
Priority date: 1968-06-03
Filing date: 1968-06-03
Publication date: 1972-03-14
Anticipated expiration: 1989-03-14

Abstract

Hair and other keratinous substances are colored or dyed by being contacted with a mixture containing, as essential ingredients, an ''''oxidation dye'''' and either an ammonium or an alkali metal peroxydiphosphate; said ''''oxidation dye'''' is oxidized and condensed to a colored or natural appearing, substantially water-insoluble state in-situ and remains fixed within said hair or keratinous substance.

Description

United States Patent Cohen et al.

[54] HAIR COLORING METHOD USING A PEROXYDIPHOSPHATE OXIDANT [72] Inventors: Bernard Cohen; Paul Raimond Mucenieks,

[21] Appl. No.: 733,830

[52] US. Cl ..8/10.2, 8/11, 8/32, 8/111, 424/62 [51] Int. Cl. ..A61k 7/12 [58] Field of Search ..8/l0.2, 11, 32, l 1 1.5; 424/62 [56] References Cited UNITED STATES PATENTS 3,011,858 12/1961 Lantzet al ..8/l0.2

3,167,478 1/1965 Charle et a1. ..8/10.2

3,218,234 11/1965 Wilmsmann et a1. ....424/62 X 3,378,444 4/1968 Swanson ..424/62 1 1 Mar. 14, 1972 FOREIGN PATENTS OR APPLICATIONS 451,026 6/1936 Great Britain ..8/l1 1.5 126,795 7/1928 Switzerland ..8/1 11 OTHER PUBLICATIONS Hackh 5 Chemical Dictionary, 3rd Edition, The Blakiston Company, Philadelphia, Pa., 1944), P. 634.

Primary Examiner-Albert T. Meyers Assistant Examiner-Vera C. Clarke Attorney-Eugene G. Seems, Frank lanno and Milton Zucker ABSTRACT Hair and other keratinous substances are colored or dyed by being contacted with a mixture containing, as essential ingredients, an oxidation dye and either an ammonium or an alkali metal peroxydiphosphate; said oxidation dye" is oxidized and condensed to a colored or natural appearing, substantially water-insoluble state in-situ and remains fixed within said hair or keratinous substance.

6 Claims, No Drawings HAIR COLORING METHOD USING A PEROXYDIPHOSPHATE OXIDANT BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to improvements in the process and composition for dyeing human hair and other keratinous substances.

2. Description of the Prior Art It is known that human hair and other keratinous substances can be dyed or otherwise changed in color by treating the hair with dye pigments which either coat the surface of the hair fibers or penetrate the hair fibers and form color particles therein. While certain dyes can be used which merely coat the outside of the hair fibers, the most popular permanent dyeing processes are those which utilize a so-called oxidation dye. These compounds are not in fact true dyes, but dye precursors. They are aromatic organic compounds which are converted to colored derivatives by oxidation, hence the term oxidation dyes; these compounds pass through an intermediate stage as imines or diimines and enter into condensation reactions to form larger, colored molecules.

These oxidation dyes" generally have the structure identified as in which R is an aromatic group which can have one, two or three aromatic rings condensed together and n is at least 1. These amino compounds must be easily oxidizable to imines and must be capable of condensing to form water-insoluble, colored derivatives. A typical example of an oxidation dye" is p-phenylenediamine, and a typical reaction which converts this compound into a higher molecular weight colored molecule is set forth below:

HIN

After the stage of Bandronskys Base, further condensations can take place in a random way to give a large structure of the type:

In the application of the above type oxidation dye to human hair, the dye is mixed with a known oxidant, typically hydrogen peroxide, and immediately applied to the hair fibers. The reaction between the oxidation dye" and the oxidant does not take place immediately, since the reaction proceeds at a relatively slow rate. During this period the oxidation dye" and the oxidant mixture thoroughly penetrate the hair fibers. The oxidation dye and the oxidant then progressively react in-situ within the fiber, e.g., within the cortical layer of the hair fiber (or other keratinous fiber), to produce the xidized form of the dye. In this state, the dye quickly combines into large molecules of a colored dye by the condensation of a number of these molecules. The condensed, enlarged dye molecule, which now has the desired color, is then trapped within the cortical layer of the hair fiber in the form of an insoluble colored solid which cannot be easily removed from the hair. The entire oxidation and condensation reactions take place in from 15 to about 30 minutes, and the excess dye and oxidant, e.g., hydrogen peroxide, are then washed from the hair, leaving the insoluble, colored dye fixed within the hair or keratinous substance.

The most common oxidizing agent which is used in the above process is hydrpgen peroxide, although other oxidizing agents, such as ferric chloride, potassium dichromate and potassium permanganate, and the like, can be used. In many cases ammonium hydroxide is used as an alkalizer along with the hydrogen peroxide to permit the oxidation reaction to take place within a desired pH range. The amount of hydrogen peroxide used must be sufficient to oxidize all the oxidizable groups on the dye molecule.

The use of these dye compositions for coloring the hair has resulted in many difficulties. One of these is that the oxidant which is used in the composition, normally hydrogen peroxide, does not imme;iately react with the oxidation dye" and therefore is present on the hair in an uncombined form. In this state the hydrogen peroxide can and does bleach hair fibers it contacts. This is undesired for a number of reasons. Initially, it lightens the hair and therefore makes the dyeing of the hair to a constant color difficult. Additionally, a portion of the peroxide is used up in bleaching the hair, rather than being utilized for its primary purpose of oxidizing the dye. The remaining peroxide may not be sufficient to oxidize all of the dye to a proper shade or within the desired dyeing time.

Other difficulties are that the hydrogen peroxide must be used in very controlled, dilute solutions to avoid damaging the hair. Thus, sizable excesses of peroxides must be avoided. Also, such oxidizing agents as hydrogen peroxide are relatively unstable and cannot be contained in dilute solution for extended periods. Further, all of the known oxidizing agents are relatively slow in reacting with oxidation dyes and therefore require extended periods of time to complete the dyeing process.

OBJECTS OF THE INVENTION It is an object of the invention to prepare a dyeing composition for dyeing hair and keratinous material with a composition which does not attack or bleach the hair during the dyeing operation.

It is a further object of the present invention to utilize a dyeing composition in which the oxidant components of the dye are stable in either a dry or liquid state and which can be directly mixed with the dyeing composition prior to applica tion of the dyeing composition to the hair.

It is still a further object of the present invention to utilize a dyeing composition in which the oxidant can be used in high concentration, without damaging the hair fibers, and in which the dyeing process is carried out in a shorter period of time than previously possible.

These and other objects will be apparent from the following description of the invention.

SUMMARY OF THE INVENTION It has now been found that improved dyeing of hair or keratinous materials can be carried out with a composition containing an oxidation dye" and an oxidant in which the oxidant contains, as an essential ingredient, either ammonium peroxydiphosphate or an alkali metal peroxydiphosphate.

DESCRIPTION OF THE INVENTION AND THE PREFERRED EMBODIMENTS In carrying out the present invention, one or more oxidation dyes is made up into an aqueous solution, containing from 1 to about 3 weight percent of the dye. In some cases the dyes are insoluble in water and a solvent which is miscible with water must be used to obtain a water solution of the dyes. The term oxidation dye" as used in this application and in the claims refers to those compounds having the structure wherein R is an aromatic group having from 1 to 3 aromatic rings and n is at least 1. Further, the aromatic groups can be unsubstituted or substituted with groups such as, methyl, methoxy, sulfonate, sulfonic acid, nitro, ethyl, ethoxy, phenol, etc. These oxidation dyes also must have the property of being readily oxidizable to imines and further must be capable of condensing into insoluble colored compounds having a higher average molecular weight than the nonoxidized precursor amines. Among the oxidation dyes which have been found suitable, are the following: p-aminodiphenylamine, paminophenylamine hydrochloride, p-aminodiphenylaminesulfonic acid, 2-amino-4-nitrophenol, 4-amino-2-nitrophenol, o-aminophenol, p-aminophenol, p-aminophenol hydrochloride, p-aminophenol sulfate, 2-aminophenol-4-sulfonic acid, 4-aminophenoI-2-sulfonic acid, N-(p-aminophenyl)glycine, o-anisidine, 2,4-diaminoanisole, 2,4- diaminoanisole sulfate, p,p'-diaminodiphenylamine, p,p'- diaminodiphenyl aminesulfonic acid, p,p'-diaminodiphenyl methane, 1,8diaminonaphthalene, 2,4-diaminophenetole, 2,4- diaminophenol, 2,4-diaminophenol hydrochloride, 2,5- diaminophenol-4-sulfonic acid, N,N-dimethyl-p-phenylenediamine, 4,6-dinitro2-aminophenol, N-(p-hydroxyphenyl)glycine, N-(Z-hydroxy-S-nitrophenyl)glycine, pmethylaminophenol sulfate, 4-nitro-o-phenylenediamine, 2- nitro-p-phenylenediamine, N-(p-nitrophenyl)glycine, o-phenylenediamine, m-phenylenediamine, m-phenylenediamine hydrochloride, p-phenylenediamine, p-phenylenediamine hydrochloride, p-phenylenediamine sulfate, mtolylenediamine, ptolylenediamine, 2,4,6-trinitroaniline.

In addition to the oxidation dyes many modifiers which are not amines may be used to modify and stabilize the shades obtained when the above dyes are oxidized. Among these modifiers may be mentioned pyrocatechol, catechol( 1,2- dihydroxy benzene), resorcinol and pyrogallol. Others include, for example, alpha and beta naphthols, diaminophenetole and diamino-anisole. Many of these modifiers are essential in order to produce the currently popular grayish tones, also termed silver, smoke, steel, etc., when these specific tones are desired. The dye formulations also may include antioxidants to prevent oxidation of the dyes due to atmospheric oxygen, and alkalizers to adjust the pH to those values in which the dyes operate best. Suitable alkalizers include sodium carbonate, ammonium hydroxide, ammonium bisulfite, etc.

In the present state of the art, the dye formulations normally contain a mixture of several oxidation dyes and/or modifiers which are used together to impart desirable highlights and/or shades to the basic oxidation dyes. These mixtures of dyes, and/or oxidants, and/or modifiers are well known in the art and form no part of the instant invention.

In accordance with the present invention, the above dye solution is mixed with an ammonium peroxydiphosphate or an alkali metal peroxydiphosphate, to form a thoroughly blended aqueous solution. The peroxydiphosphate salts are added in effective amounts sufficient to oxidize all of the oxidizable groups contained in the dye. Normally at least one mole of the peroxydiphosphate salt is necessary per mole of oxidizable amino group in the dye. The peroxydiphosphate salt can be added to the dye as an aqueous solution having a concentration of from 1-30 percent by weight. In the makeup of the final dyeing solution, the dye materials can be mixed as a solid with the solid peroxydiphosphate salts and both dissolved in water, or either of the components, i.e., the dye materials or the peroxydisulfate, can be dissolved in water and the other added thereto. In all events, the peroxydiphosphate oxidizer and the dye mixture must be in contact with each other in an aqueous solution, in order to achieve proper dyeing of the hair or other keratinous material.

The solution of the peroxydiphosphate oxidizer and the dye components are then applied to hair or keratinous fibers and permitted to stand. The mixtures can be applied at any temperature from 32 to 212 F., but for ease of application, room temperatures are normally employed. In the case of dyeing human hair, the temperature of the final dyeing solution should be controlled so as not to injure the scalp tissues, e.g., 50 F. to F. is acceptable. The dye and peroxydiphosphate mixture is vigorously rubbed into the hair fibers so that both the peroxydiphosphate salt and the dye component penetrate into the inner structure of the hair fibers, e.g., the cortical layer. Thereafter, the peroxydiphosphates commence to oxidize the dye components in-situ in the hair fibers. During this oxidation the oxidation dye" is oxidized to the imine form and rapidly commences to condense into larger molecules which give the desired color. The color-forming, high-molecular weight molecules thus formed become fixed within the hair fibers because they are water-insoluble and because their large size traps them within the fibrous structure of the hair. In general, the rate at which color development commences is dependent upon the pH, and the higher the pH, i.e., the more alkaline the solution, the slower is the rate of reaction and the emergence of color.

The instant peroxydiphosphate salts can be used to oxidize dye components in hair or keratinous materials at pHs ranging from 1 to l 1. However, in the process of bleaching human hair, the preferred pH of the dye solution should be maintained within 6 to 9 to avoid damage to the hair. In many instances, the optimum pH is dependent upon the solubility of the dye material. Many are soluble only under alkaline or neutral conditions.

In the present process, the preferred alkali metal peroxydiphosphates are the tetrasodium peroxydiphosphate, the tetrapotassium peroxydiphosphate and protonated salts such as K H P O KI-I P O K HP O Na H P O NaH P o or Na HP O. No difference in the oxidizing ability has been found between the potassium, sodium or ammonium peroxydiphosphate compounds. All work equally well.

In the makeup of the dyeing solution, the peroxydiphosphate should be added just prior to utilizing the dye solution for coloring hair, otherwise the peroxydiphosphate oxidizes the dye components prematurely. When this occurs, effective dyeing no longer can take place, since the oxidation and condensation of the dye molecule takes place outside of the hair fibers. If the resulting dye is applied to the hair, it will not penetrate the hair fibers and yield a fast dye which cannot be washed or rinsed out during normal shampooing.

In using the instant dyeing solution on hair, a water-soluble thickener is generally added to the dyeing composition in order to obtain a thick consistency for easy application to the hair. Among the suitable water-soluble thickeners are compounds such as calcium carbonate, magnesium carbonate, Plaster of Paris and other inert fillers such as talc, kaolin and bentonite. A light magnesium carbonate has been found most suitable for this purpose. Other ingredients can also be used along with the thickeners to facilitate application, such as wetting agents, solvents, buffering agents, and the like. Optimum results have been obtained when bleaching human hair with the present dyeing composition when the pH is maintained between 5 and 9 and preferably at a pH range of about 7 to 8. The pH can be maintained by incorporating a suitable level of a buffering agent, for instance, a salt of a strong alkali and a weak acid. Among the buffering compounds which can be used are ammonium bicarbonate, ammonium bisulfate, potassium hydrogen phthalate, tartaric acid, ammonium hydrogen tartrate and acid ammonium salts of polybasic inorganic and organic acids such as, for example, diammonium phosphate.

In the present dyeing system, the use of buffers to adjust the pH is generally not necessary, since the added peroxydiphosphate oxidizers maintain the pH within the range of 6 to 9. However, if added buffers are desired, these can be added to either raise or lower the pH of the dye composition to specified values.

mum-I rune 1n the above embodiment of the invention, the dye components were mixed with only a peroxydiphosphate salt in an aqueous solution and applied to the hair just prior to dyeing. However, in another embodiment of the present invention, the oxidizer may contain a mixture of a peroxydiphosphate salt and a conventional oxidizing agent such as hydrogen peroxide or compounds that give off 11 0 in aqueous solution, e.g., alkali metal perborates such as sodium perborate, potassium perborate, ammonium perborate, sodium carbonate peroxide, sodium pyrophosphate peroxide, urea peroxide and melamine peroxide. By utilizing these conventional oxidizers at low levels with a peroxydiphosphate, any bleaching or other attack on the hair by these oxidizers is minimized. In all events, the oxidizing agent must contain, as an essential ingredient, either an ammonium or an alkali metal peroxydiphosphate in order to come within the purview of the present invention.

The present peroxydiphosphate compounds have many advantages over prior art oxidizers. Initially, they are most stable and can be handled as solids or in concentrated or dilute aqueous solutions without decomposing on extended storage. Further, the peroxydiphosphate oxidizer permits faster oxidation of the oxidation dyes than conventional oxidizers, e.g., hydrogen peroxide. This permits the dyes to be set and thus form the desired colors in shorter periods of time. Most importantly, the present oxidizers operate well at low temperatures, particularly at normal ambient temperatures used in dyeing hair, i.e., about 50 to about 100 F. Accordingly, no increase in the temperatures of the dyeing solution need be used to obtain a fast dye with the present oxidizing system.

Of particular importance in the present dyeing application is the fact that the peroxydiphosphate compounds when used as oxidizers do not attack hair or degrade it in any way, even in high concentrations. This is considered most unusual, since H 0 and other peroxygen oxidizers normally cause some undesired degradation of the hair during the dyeing process. The present peroxydiphosphate oxidizer is most selective in that it permits better dyeing in shorter amounts of time with no increase in the attack on the hair fibers. Also, the peroxydiphosphates are not toxic, and no special handling problems present themselves in the use of these oxidizer compositions.

Another advantage of the present oxidizers is that they can be mixed directly with a dye composition in a dry form and can remain standing for limited periods without substantially reacting with the dyes. Thereafter, in order to use the dyeing composition, water is added thereto to dissolve the ingredients, and the composition is then immediately applied to the hair.

The following examples are given to illustrate the present invention and are not deemed to be limiting thereof.

EXAMPLE 1 A 3 percent aqueous solution of a medium brown dye base was made up consisting of the following:

Ingredients I: by Weight p-phenylenediamine 2.00 p-aminodiphenylamine 0.16 o aminophenol 0.25 4-nitro-l,Z-diaminobenzene 0.20 Resorcinol 1.50 Ammonium hydroxide q.s. (to pH Sodium sulfite q.s. (to stabilize dyes) Dye base, to make 10000 with water for several minutes. The color in the lock of hair was found to be fast and not altered in intensity or luster by the water washing.

EXAMPLE 2 Three grams of the dye mixtures set forth in Example 1, but without the ammonium hydroxide, was mixed with 30 grams of tetrapotassium peroxydiphosphate (14,150,). The two solids were thoroughly blended together and then dissolved in sufficient water to give a 1.5 percent dye concentration having a pH of 7.0. The resulting mixture was then immediately applied to a lock of brown-gray hair as set forth in Example l. The color was found to be fast and substantially the same as that set forth in Example 1.

EXAMPLE 3 The process of Example 1 was repeated on wool and muskrat fur samples and similar fast dyeing was obtained. No significant differences in the rate of color development were noted.

EXAMPLE 4 The procedure of Example 3 was repeated except that these samples each were dyed with dyeing solution having pH values of 1.6, 7.2 and 1 1.2, respectively. Dyeing with these solutions resulted in the same color as that set forth in Example 3 except that the development time was decreased to as little as 5 minutes when dyeing was carried out at a pH of 1.6.

EXAMPLE 5 The procedure of Example 1 was repeated except that in place of the tetrapotassium peroxydiphosphate the equivalent sodium and ammonium salts of the peroxydiphosphate were used. The resulting hair samples showed the same color development and color shade as that obtained in Example 1 when the tetrapotassium peroxydiphosphate was utilized.

EXAMPLE 6 A dye formulation was made up containing the following;

Ingredients 1: by Weight p-phenylenediamine 1.70 2,4-diarninoanisole 0.60 4-arnino-2-nitrophenol 0.12 p-aminophenol 0.15 Z-niIm-pphenylenediamine 0.05 Pyrogallol 0.30 Resorcinol 1.70 Ammonium hydroxide q.s. (pH 10) Sodium sull'lte q.s. (to stabilize dyes) Dye Base. to make 100.00

EXAMPLE 7 Example 6 was repeated using 0.1 percent of a wetting agent, Triton X-lOO (alkyl phenoxy polyethoxy ethanol) supplied by Rohm and Haas Company. The results were equivalent to that set forth in Example 6, except that the wetting agent allowed easier application of the peroxydiphosphate solution.

EXAMPLE 8 The procedure of Example 7 was repeated except that 0.2 percent of hydroxyethyl cellulose was used as a thickening agent. The'results were the same as obtained in Example 7, except that the thickening agent allowed easier application of the dyeing solution. I

EXAMPLE 9 EXAMPLE 10 The procedure of Example 6 was repeated using percent sodium perborate monohydrate mixed with 5 percent tetrapotassium peroxydiphosphate. The results were substantially the same as those obtained in Example 6. Further, no noticeable degradation of the hair resulted from the use of this oxidation mixture.

Pursuant to the requirements of the Patent Statutes, the principle of this invention has been explained and exemplified in a manner so that it can be readily practiced by those skilled in the art, such exemplification including what is considered to represent the best embodiment of the invention. However, it should be clearly understood that, within the scope of the appended claims, the invention may be practiced by those skilled in the art, and having the benefit of this disclosure otherwise than as specifically described and exemplified herein.

What is claimed is:

1. In the process of coloring a member selected from the group consisting of human hair and keratinous fibers by contacting said member with a composition containing as essential ingredients, an oxidation dye and an oxidant for said dye in an aqueous medium, the improvement which comprises using as said oxidant an effective amount of a member selected from the group consisting of ammonium peroxydiphosphate and an alkali metal peroxydiphosphate.

2. Process of claim 1 wherein said alkali metal peroxydiphosphate is tetrapotassium peroxydiphosphate 3. Process of claim 1 wherein said alkali metal peroxydiphosphate is tetrasodium peroxydiphosphate.

4. Process of claim 1 wherein the peroxydiphosphate oxidant is present in said composition in amounts sufficient to have at least 1 mole of said peroxydiphosphate oxidant per mole of oxidizable amine group present in said dye.

5. Process of claim 1 wherein the peroxydiphosphate oxidant is present within said composition as an aqueous solution containing from about i to about 30 weight percent of said peroxydiphosphate oxidant.

6. In the process of coloring a member selected from the group consisting of human hair and keratinous fibers by contacting said member with a composition containing as essential ingredients, an oxidation dye and an oxidant for said dye in an aqueous medium, the improvement which comprises using as said oxidant an effective amount of a member selected from the group consisting of ammonium peroxydiphosphate and an alkali metal peroxydiphosphate, and a peroxygen compound selected from the group consisting of hydrogen peroxide and an alkali metal perborate.

Claims

2. Process of claim 1 wherein said alkali metal peroxydiphosphate is tetrapotassium peroxydiphosphate.
3. Process of claim 1 wherein said alkali metal peroxydiphosphate is tetrasodium peroxydiphosphate.
4. Process of claim 1 wherein the peroxydiphosphate oxidant is present in said composition in amounts sufficient to have at least 1 mole of said peroxydiphosphate oxidant per mole of oxidizable amine group present in said dye.
5. Process of claim 1 wherein the peroxydiphosphate oxidant is present within said composition as an aqueous solution containing from about 1 to about 30 weight percent of said peroxydiphosphate oxidant.
6. In the process of coloring a member selected from the group consisting of human hair and keratinous fibers by contacting said member with a composition containing as essential ingredients, an oxidation dye and an oxidant for said dye in an aqueous medium, the improvement which comprises using as said oxidant an effective amount of a member selected from the group consisting of ammonium peroxydiphosphate and an alkali metal peroxydiphosphate, and a peroxygen compound selected from the group consisting of hydrogen peroxide and an alkali metal perborate.