DK167208B1 - HAIR COLOR SEAT AND PROCEDURE FOR DYING HAIR - Google Patents

Description

in DK 167208 B1

The present invention relates to a hair dye set and a method for dyeing hair, especially human hair.

The color of human hair is due to the fact that there are separate particles of natural pigment, the melanins, in the structure of the hair. Investigation of melanins and melanogenesis has intensified in the last forty years, accompanied by a certain interest in dyeing hair with such materials that are most similar to the natural materials that contribute to hair color. Biosynthesis of melanin involves the conversion of tyrosine to melanin via dihydroxy-phenylalanine (dopa) through a number of intermediate stages, including 5,6-dihydro-10-xyindole.

In addition to the general desirability of dyeing hair in a simple manner and with a color that is closest to the material which contributes to the natural dyeing of hair, there is also a requirement for a hair dye which can also serve as a temporary dye if desired. hair dye that can be applied and removed as desired and can be reliably and quickly applied.

A number of patents have been issued relating to aspects of hair dyeing with melanin precursors, e.g. tyrosine, L-dopa, L-dopa esters and 5,6-dihydroxyindole. U.S. Patent Nos. 2,539,202, 2,875,769, and 3,698,852 relate to the use of L-dopa as a starting material. U.S. Patent Nos. 2,934,396, 3,194,734 and 3,993,436 disclose the use of 5,6-dihydroxy-indole as a starting material. The major drawbacks of these systems are the time required for color development, the uncertainty of developing and the lack of control thereof, and the need to add such compounds as p-phenylenediamine and various couplers for nuance control.

In the process described in U.S. Patent No. 2,934,396, hair is first treated with an acidic or neutral solution of 5,6-dihydroxyin-dol, then excess solution is printed and an oxidizing agent or oxidation-inducing solution is applied to the hair. 30 desired shades are evoked. In one of the methods described in the patent, the oxygen is used in the ambient air, the second solution containing an alkalizing agent and a cobalt or manganese oxidation activator. Essentially, however, an ammonia solution of an oxidizing agent such as hydrogen peroxide or an alkali metal or ammonium oodate, periodate or persulfate is used, etc. When the desired hue is elicited, the hair is rinsed, washed, rinsed and dried.

U.S. Patent No. 3,194,734 is characterized as an improvement over the aforementioned U.S. Patent No. 2,934,396 because staining according to the method of the oldest patent, which is the oxidative polymerization of 5.6 -dihydroxyindole to melanin, at the same time competes with an oxidative destruction of the color formed, resulting in a loss of indole which gives dissimilar results to the hair, 5 and it is difficult to determine when the process should be interrupted by rinsing. Therefore, in the later patent, a process is proposed in which an aqueous alkaline agent containing 5,6-dihydroxyindole and ammonia or an amine is contacted with the hair until the desired hue is obtained. Alternatively, certain methyl derivatives of 5,6-dihydroxyindole may be used in a two-step process to obtain lighter shades, in which the hair is first impregnated with an aqueous solution of such methyl derivative in a solution of acidic or neutral pH. after which the hair is briefly dried and the color developed in a second step by application of an aqueous solution containing an oxidizing agent.

The present invention is based in part on the observation that contrary to the prior art, where HgOg or other oxidizing agents are used either in a separate step or together with 5,6-dihydroxyindole to obtain different shades, better results can be obtained. 20 tater using a metal salt to promote melanogenesis.

We have found that a better range of shades and a more reliable hue development can be obtained and, if desired, improved temporary hair coloring by a method of dyeing hair which includes the steps of bringing the hair to be dyed into contact with an alkaline 25 aqueous solution of a metal which promotes melanin formation from 5,6-dihydroxyindole, which metal is in the form of copper and / or iron, after the aforementioned step contacting the hair with an aqueous solution of 5,6-dihydroxyindole with a pH of at least 8, flushes the hair between the two contact steps, maintains contact with the solution used as # 2, until a desired darker color is obtained, rinse or wash the hair, and if desired then bring the hair in contact with an aqueous solution of hydrogen peroxide having a pH of at least 8 for a maximum of 15 minutes until the desired color shade is achieved, and then rinsing the hair again.

In a particularly convenient embodiment of the method of the invention, the method comprises the step of contacting the hair to be stained with an alkaline aqueous solution containing cuprions. After the aforementioned step, the hair is contacted with an aqueous solution of 5,6-dihydroindole with a pH of at least 8, the hair being rinsed between the two contact steps and contact with the solution used as # 2 maintained until a desired darker color is obtained and the hair is rinsed or washed. If a color other than gray or black is desired, the hue is achieved by subsequent treatment with H2O2. Thus, as will be appreciated, there is a fundamental difference between the method of the invention and all previous proposals for dyeing with 5,6-di hydroxyindole, in which case the hair is dyed in all cases except when the desired final color is black. a gray or black color, after which the final desired hue is elicited by brightening with the hydrogen peroxide solution.

The invention further relates to a hair color set containing in a single package several containers comprising a first container containing an alkaline aqueous solution of an effective amount of a metal which promotes melanin formation, which metal is in the form of copper and / or iron, a second and third containers, the contents of which are mixed to a solution having a pH of at least 8, wherein the second container contains a solution of an effective amount of 5,6-dihydroxyindo! with an acidic pH and, above the solution in the second container, an air space containing a non-oxidizing gas is maintained and the third container contains an alkalizing agent, the air space of the second container having a sufficient volume to accommodate the third container. the contents of the container or the third container, and optionally a fourth container containing an aqueous solution of hydrogen peroxide having a pH of at least 8.

The invention further relates to a hair color kit containing in a single package several containers comprising a first container containing an alkaline aqueous solution of an effective amount of a metal which promotes melanin formation, which metal is in the form of copper and / or iron. a second container containing an alkaline solution wherein in the second container an air space above the solution is maintained, a third container containing a solution of an effective amount of 5,6-dihydro-xyindole with acidic pH, the air space of the second container. has a sufficient volume to accommodate the contents of the third container or third container and provide a total solution with a pH of at least 8, and optionally a fourth container containing an aqueous solution of hydrogen peroxide with a pH of at least 8.

In a particular embodiment of the hair color set of the invention, the metal is copper.

According to the invention, unless a black or gray nuance is desired, a clearing of it with melanin from 5,6-dihydroxyindole is made. dyed hair with a hydrogen peroxide-containing solution. As used in the specification and claims, the term "hydrogen peroxide" is intended to mean hydrogen peroxide or any other ingredient which, in an aqueous solution, forms hydrogen peroxide such as urea peroxide. This brightening or color nuance setting is different from the conventional oxidation treatment used in conventional bleaching of hair. In conventional bleaching, the natural color of the hair is removed by bleaching when it is desired to color it to a shade lighter than the natural color of the hair. In this case, the natural color of the hair is bleached over a long period of time with a strong oxidizing solution, usually containing hydrogen peroxide and further bleaching enhancement, at a pH of about 10. This bleaching step generally tends to weaken the hair or otherwise damage it. In the leaching step of the process of the invention, it is not the conventional type of bleaching because the hydrogen peroxide solution used in the process of the invention does not contain added bleaching agents such as persaltes, it is suitably used at a pH below 10, suitably about pH 9 and the clearing requires only up to approx. 15 minutes for the lightest shades. Thus, the luminous, color-inducing oxidation step of the method of the invention is considerably faster than conventional bleaching and is not used to bring the luminance further than the natural color or color it had before the method of the invention was applied.

Without being bound by the following explanation, we believe that the difference between the brightness of the process of the invention and conventional bleaching can be attributed to the new staining step of the method of the invention. In naturally colored hair, the melanin pigment is distributed throughout the cortex, ie. the inner core of the hair shaft.

This means that when bleaching the natural melanin color of the hair with a strong bleach such as hydrogen peroxide, enhanced by the addition of persalt, a considerable time is required for the bleach to penetrate the unpigmented periphery or cuticle and into the hair shaft. By the process of the invention, the dye is believed to be substantially disposed along the periphery of the hair shaft, and the luminous hydrogen peroxide in. ·: Does not exhibit the first absence of potent agents in the form of per-compounds and prolonged exposure to reach and for To bleach the dye. P.g.a. the shorter exposure and the peripheral penetration, the brightening step of the method according to the invention does not tend to damage or weaken the hair, as is the case with conventional bleaching.

It is further believed that the dyes produced are unique in that the melanogenesis-promoting metal forms a complex with the melanin formed during the staining. The affinity of the complexed metal is considered to be greater for melanin than for the keratin in hair. Therefore, the melanin-metal complex dye has greater reactivity with hydrogen peroxide than melanin without the metal. This is confirmed by the observation that the produced melanin / copper complex can be brightened faster with hydrogen peroxide than a natural melanin, even if a copper salt is dissolved in the hydrogen peroxide used to brighten the natural melanin.

Therefore, not only does the metal promote melanin formation in the color step of the process of the invention, but it is believed to contribute to the ease and speed with which the brightening step takes place. For this reason, we distinguish between the leaching step of the process of the invention, which can be completed in less than 15 minutes, and conventional bleaching which is of a different type and generally requires a time of well over 20 times and requires bleach reinforcing agents. in addition to hydrogen peroxide.

The method of the invention can also be used for dyeing hair which is pre-dyed with conventional permanent or semi-permanent hair colors. As long as the original color is stable to the lightening solution which is milder than conventional hair bleaches, the color and brightening steps of the present process do not destroy the hair color of the hair within the time periods used for lightening, regardless of whether the hair color is natural color or not. Accordingly, hair dyed by the present method can be re-lightened to this starting color, regardless of whether the re-lighting occurs the next day or a considerable time later.

If the method of the invention is intended to dye hair to a new shade which is lighter than the natural hue of the hair or lighter than a hue to which the hair has been dyed by conventional techniques, the hair must first be bleached lighter or even bleached completely before the method according to the invention is used. In this case, the lightening treatment can be continued to any shade darker than the initially bleached hue, and the hair may then be lightened to any intermediate hue or the bleached shade may be restored if desired. .

If the desired shade is a lighter shade, it is not necessary to color the hair completely black, but it will suffice to color it 5 to a lighter or darker gray. When the color is then lightened in a subsequent step, it will initially lighten to a lighter or darker brown hue, depending on whether the hair was colored to a lighter or darker gray color in the initial steps. Of all the tested melanogenic 2+ se enhancers, only Cu was found to promote melanin formation all the way to an intense black color. The other tested metal activators are only found to help stain for lighter or darker shades of gray. In our experiment, longer exposure of the hair or greater concentrations of the metal activator did not result in an increase in the resulting color depth.

The metal salts used as melanogenesis promoters can be used either alone or in admixture. Apart from cupri solutions, it was found that it is generally necessary to use a chelating agent such as citric acid, a citrate, ethylenediaminetetraacetic acid, ascorbic acid or the like to keep the metal in solution.

Designations such as "melanogenesis-promoting agent", "melanogenesis-promoting metal salt" and variants of such terms used in the specification and claims refer to solutions of copper and / or iron which will promote hair color formation within a maximum period of time. of 20 minutes after contacting the hair with a solution of 5,6-di hydroxyindole.

The flour anogenesis promoter that was found to be best 2+ suitable is Cu, which provides a significantly faster staining, and 2+ the resulting color can go all the way to deep black. Although the Fe ion will also work well, it is less preferred than copper due to solubility problems at certain pH levels and other considerations. Furthermore, when using the cupri ion at a pH of about 9 or greater, suitably at pH 9.5, no chelating agent is required because no trace of insoluble materials can be found in the solution. Monoethanolamine or other nitrogen-containing alkaline agents such as other alkanoamines, ammonia ac, etc. can be suitably used to adjust the desired pH. All potassium hydroxides work well only if a chelating agent is used to maintain the solution. The basic pH value has the additional advantage of causing the hair to swell up, which allows DK 167208 B1 7 a better color absorption. If using the cupri ion, it is definitely preferable first to impregnate the hair with the cupri ion-containing solution and after rinsing or imprinting the hair to impregnate it with the 5,6-dihydroxyindole solution. The intermediate rinse or imprinting of the hair surface is necessary to avoid a superficial washable color formation since a color formation is desired in the hair shaft itself. As used in the specification and claims, the term "rinsing" in this context must include imprinting, wiping, and other methods for removing a solution from the hair surface. It requires approx.

10 to 20 minutes to dye the hair to the maximum achievable color depth when using a metal salt activator for melanogenesis, but when using the cupri ion, the required time is even at the shorter end of this short time interval. As can be seen, the use of the cupri ion therefore offers more advantages than those obtainable with other melanogenesis-promoting agents.

The 5,6-dihydroxyindole-containing solution has a pH of 8 or greater. Preferably, the pH should not exceed 9.5, as the solutions are progressively unstable at elevated pHs. When the dyeing of the hair to black or gray is complete, hair washing is preferred over simple rinsing. The reason for this is that dye that may have formed on the hair surface may not be able to peel off and may later be rubbed off the surface. A hair wash will remove such a surface color and thus prevent rubbing.

The concentration of the 5,6-dihydroxyindole is not critical, but a concentration of approx. 0.5 to approx. 2% by weight for economic reasons and due regard for appropriate control over the staining rate. As shown, the concentration of the respective constituents is not critical. Therefore, whenever a concentration in the specification and claims is characterized as an "effective amount", this characterization means that the amount used is sufficient for the desired purpose. Such purposes may be as diverse as different shade depth, better economics in terms of ingredient spending, different reaction rate, solution stability, and the like. Whatever the purpose, the business of determining the amount of an ingredient can be determined by routine experimentation. All percentages in the specification and claims are by weight unless otherwise stated.

If the desired hue is not black, the hair after dyeing and possibly hair washing is subjected to a clearing step by bringing it into contact with a dilute hydrogen peroxide solution until the desired hue is obtained. In this step, any suitable hydrogen peroxide solution useful for bleaching or lightening hair can be used; however, it was found that a H 1% 5 to approx. 6% is sufficient. When lightening hair from black or gray, the color will go through various gradually lighter shades, and the process can be terminated by rinsing the hair once it has reached the desired shade. The natural shade can be easily restored when a previous darker shade is no longer desired. The aqueous hydrogen peroxide solution 10 is used at a pH above 8, suitably at a pH of 9. The relatively slow but not too slow lightening rate of up to 15 minutes gives the user sufficient control to be able to stop at any desired hue or at the natural shade of hair. In this way, the competing staining and bleaching reactions of the prior art and the ensuing disadvantages are excluded and a better, more positive control over the whole process is provided, whether the staining is performed by the hairdresser or by the user.

The method of the present invention also allows for a selective staining of various hair regions for the purpose of providing contrasts, streaks and other special cosmetic effects.

In order to maintain stability, the 5,6-dihydroxyindole solution is suitably kept at an acidic pH, preferably about pH 4.5. In addition, the solution with the acidic pH should be suitably maintained under anaerobic conditions, such as under nitrogen, whereby the atmosphere above the solution in the bottle during the packing is established with nitrogen rather than with air. One method of solving the problem is to maintain a small volume of nitrogen over the solution in the bottle, this space being sufficient to allow the addition of an all calibrating agent before use. However, this may be inconvenient and, therefore, suitably a concentrated, such as a 12.5%, aqueous alcoholic or fully alcoholic solution of the 5,6-dihydroxyindole in which the substance is readily soluble can be maintained at an acidic pH in a small, full container until used. Immediately before use, the contents of this small bottle can be transferred to a larger bottle which may contain a pre-thickened alkaline solution to obtain the alkaline 5,6-dihydroxyindole solution immediately prior to its use. Another method is to keep all the calibration media in a small bag made of a selectively soluble material; the entire bag can then be dumped into the compartment above the acidified 5,6-dihydroxyindole-containing solution to prevent the user from having to deal with a possibly highly alkaline agent. Alternatively, when a small, concentrated solution of the acidified 5,6-dihydroxyindole may be added to an alkaline solution, the former may be kept in a selectively soluble bag which may be wholly transferred to the aqueous alkaline solution to prevent the user from will have to pour a liquid from one container to another.

It has been found that adding a small amount, such as 1% by weight, of a surfactant such as sodium lauryl sulfate to at least one of the metal and 5,6-dihydroxyindole solutions can improve the flow properties of the preparations so as to facilitate application to the hair. . Similarly, scalp staining can be reduced and the desired flow properties of the solutions can be improved by adding a small amount, such as 0.5% by weight, of a thickener to both solutions, such as carbomer 940, a polymer of acrylic acid crosslinked with a polyfunction. 15 commercial agent and marketed by The Goodrich Chemical Company under the name "Carbopol 940". The identity of other agents for setting desirable flow properties can be determined by routine experimentation, since such agents for setting flow properties are well known in the art, formulation of hair treatment compositions. It is also known in the art that certain additives for altering flow properties may be incompatible with certain compositions. It became, for example. found that additives such as cocamidopropyl hydroxysultain, marketed by Lonza Chemical Co. under the designation "Lonzaine C $" and hydroxypropyl methyl cellulose, sold by Dow Chemical Co. under the designation "Methocel", 25 did not appear to be compatible with the compositions referred to here, because the resulting color was not so deep when these materials were included. Other ingredients known per se such as conditioners, perfumes, anti-static agents and the like. may be included in the formulations or may be applied to the hair later.

The following examples serve to illustrate the invention.

Unless otherwise stated, the percentages are by weight.

Example 1

The following activation preparation was prepared: 35

CuS04.5H2O 1% carbomer 940 0.5% sodium lauryl sulphate 1% DK 167208 B1 10 monethanolamine up to pH 9.5 water q.s. to 100

The following color preparation was prepared: 5 sodium acetate 1.2% 5,6-dihydroxyindole 1.2% carbomer 940 0.47% ethanol 19.7% 10 sodium hydroxide until pH 8.5 Hair was saturated with the catalytic preparation for 5 minutes and then rinsed with water. Then the hair was saturated with the 5,6-dihydroxyindole-containing composition for a period of 5 minutes. The resulting black colored hair was washed to remove melanin from the hair surface.

Example 2

Light brown hair was stained black by the procedure of Example 1. Then the hair was saturated with a 6% aqueous solution of hydrogen peroxide 20 at pH 9. After 10 minutes, when the original light brown hue of the hair was reached, the hair was rinsed. The same procedure was repeated, but the hair was lightened for 6 minutes to a darker brown hue. After three weeks, the hair was further lightened for 3¾ minutes to its original pale brown hue.

25

Example 3

The same procedure as in Example 1 was carried out on blond hair except that the concentration of the 5,6-dihydroxyindole was only 0.5%.

Staining was carried out for only 2 minutes to a light gray to medium gray color. After washing, a 6% aqueous hydrogen peroxide solution of pH 9 was used to brighten the hair to a light brown hue within 6 minutes.

Example 4

The copper sulfate solution of Example 1 was replaced using 0.25% FeSOO based on the preparation previously mixed with citric acid in an amount suitable to avoid precipitation of the iron at alkaline pH and monethanolamine was used to adjust the pH. the value to 9.5.

DK 167208 B1 11

The procedure of Example 1 was repeated except that no carbomer 940 was contained in the 5,6-dihydroxyindole-containing solution. The hair was exposed to the catalyst solution for 10 minutes, then rinsed and saturated with the 5,6-dihydroxyindole-containing solution for 10 minutes, until the initially light brown hair color became significantly darker.

Example 5

The same procedure as in Example 1 was repeated except that the 5,6-dihydroxyindole-containing solution was first applied, and then, after rinsing, the catalyst-containing solution was applied. The resulting hair color was less intense than in Example 1.

Claims (11)

A method of dyeing hair, characterized in that it comprises the steps of contacting the hair to be dyed with an alkaline aqueous solution of a metal which promotes melanin formation from 5,6-dihydroxyindole, which metal is in the form of copper and / or iron, after the aforementioned step contacts the hair with an aqueous solution of 5,6-dihydroxyindole with a pH of at least 8, flushes the hair between the two contact steps, maintains contact with the 2 used solution, 10 until a desired darker color is obtained, rinses or washes the hair, and if desired then contacts the hair with an aqueous solution of hydrogen peroxide having a pH of at least 8 for a maximum of 15 minutes until the desired color hue is achieved , and then rinses the hair again. 2. A process according to claim 1, characterized in that, as a metal solution, an alkaline aqueous solution containing cuprous ions is used. 3. A process according to claim 2, characterized in that the pH of the cuprionate containing solution is at least 9. 4. A process according to claim 2 or 3, characterized in that at least one of the solutions containing 5,6-dihydroxyindole and cuprions, respectively, further contains at least one of the following: a thickener, a surfactant, an antistatic additive and a perfume. Process according to one or more of the preceding claims, characterized in that the pH of the solution of the metal is at least 8. Process according to one or more of claims 1-5, characterized in that the pH of the 5,6-dihydroxyindole-containing solution is 8-9.5. A method according to one or more of the preceding claims, 35 characterized in that the concentration of 5,6-dihydroxyindole in the aqueous solution is from approx. 0.5 to approx. 2% by weight. A process according to one or more of the preceding claims, characterized in that the concentration of H 2 O 2 in the hydrogen peroxide solution is from approx. 1% by weight to approx. 6% by weight. 9. Hair color kit, characterized in that in a single package, it contains several containers comprising a first container containing an alkaline, aqueous solution of an effective amount of a metal which promotes melanin formation, which metal is in the form of copper and / or iron, a second and a third container, the contents of which are mixed to a solution having a pH of at least 8, wherein the second container contains a solution of an effective amount of 5,6-dihydroxyindole with an acidic pH and above the solution in the second container maintains an air space containing a non-oxidizing gas and the third container contains an alkalizing agent, the air space in the second container having a sufficient volume to accommodate the third container or the third container, and optionally a fourth container containing an aqueous solution of hydrogen peroxide having a pH of at least 8. 10. Hair color kit, characterized in that it contains in a single package several containers comprising a first container containing an alkaline, aqueous solution of an effective amount of a metal which promotes flour formation, which metal is in the form of copper. and / or iron, a second container containing an alkaline solution wherein in the second container an air space is maintained above the solution, a third container containing a solution of an effective amount of 5,6-dihydroxyindole at 25 acid pH, the air space of the the second vessel has a sufficient volume to accommodate the contents of the third vessel or the third vessel and provide a total solution having a pH of at least 8, and optionally a fourth vessel containing an aqueous solution of hydrogen peroxide having a pH of at least 8. 30 11. Hair color set according to claim 9 or 10, characterized in that the metal is copper. 35