DE2125689B2 - Method for the temporary coloring of hair - Google Patents

Description

acts when the colored connection is a su.fid to the ^^^^ Χ

2. The method according to claim 1, characterized in that the hair is first drawn with the aqueous solution of a compound that the η '^ ⁱⁿ ^ ™ ^{r is applied} to the hair with an aqueous one of a transition metal. ¹ ^ J ^C "Manganese, cobalt or iron solution treated * o possible oxidation * ^ y ° ^ril gg · ^beh ^ ^el ™ ^d and the transition applied to the hair - those on the hair ^ f * ^^

metal with an aqueous permanganate pertorate, bond is oxidized to an insoluble compound and Persulfate or periodate solution oxidizes. that one has to remove the

3. Procedure after a de? To claim 1 or 2, the hair marked with an ^{R "d} f" ° "f" ^ "^^^ characterized in that a chelating agent treated * ₅ ^ when the colored formers and thiourea as a reducing agent compound is an oxide is provided as a chelate, or metabisulfite used with a chelating agent treated when the colored compound cm

Is sulfide. _mj , _ _c ,

According to a preferred embodiment of the combustion 3o, a manganese,

Cobalt or iron compound used after

applying to the hair with an aqueous permanganate, perborate, persulfate or periodate solution is oxidized. The preferred chelating agent

The technique of hair coloring can already be used for 35 wise thiourea and as reducing agents prove prehistoric times. Used under the metabisulfite.

There is a wide range of known dyes. The process can infielen da Hja

There are also a number of coloring systems that color transitional shades so permanently that the metals, especially cobalt, iron, nickel or coloring are not removed during normal washing * _ir d use manganese (»Cosmetics-Science and Techno- 40 When applying of a C ^^ ¹ ^ " ⁵ ""·! logyf [1957], 515 to 524). Most known or one of a reducing agent can be based on the formation of coloration, however, at any time under very tired conditions of metal sulfides«, being easily and quickly "\ ^{f" n} * ^ ^rd ^ ^{'A' ch} for the precipitation of these sulfides conditions ^e either the Keratinschwefel the hair and or hair cingefdrbt in a conventional manner or used with the colorant of added sulfur. Is 45, can be determined by the ^Erfindun f ^'ei ^ ^{ht d} ".J ^h It is also known hair by a reducing agent and reductive precipitation or odereinen.Chela coloring of metal compounds, for example formers, or with only a Chelatb.ldner If the application of a permanganate solution and reduc- colored compound is a sulphide, remove the permanganate to form manganese dioxide

The known processes have different aqueous solutions of a combination of transition disadvantages. Either chemical reactions occur with metal applied to the hair, which does not occur between the coloring agents and the hair itself, the highest possible level of oxidation, as long as they are undesirable because they damage the hair, or only these conditions are water-soluble and which have the colors applied The I-shape and authenticity are not adhered to satisfactorily, or in the other case the manner in which the metal compound is so strongly adhered that it is hardly reapplied or only applied to the hair is not essential. The Uoerrelativ harsh reagents can be removed again, gang metals can be used as salts, in particular as Finally, from FR-PS 11 21 036 a coloring halides, sulfates, nitrates or also in the form system is known, which the interaction between stable halides, sulfates, nitrates or It is also based on metals used in an organic substance and two different forms of stable salts of organic acids. The actual coloring will be in. Among the halides, in particular, this system is brought about by the adduct of a noble compound, the chlorides and, among the salts, the organic metal compound with a polyphenol, acids in particular the acetates. When using a transition metal in this system as an oxide of manganese, this is preferably used as a dating agent. This method has 6 _S in the form of manganese salts, in particular preferably several disadvantages at the same time. The coloring is difficult to remove as manganese sulfate or manganese lond, which sets required polyphencle to result. Iron and cobalt, too, tend to irritate the skin easily and are in the form of the corresponding iron or cobalt salts

lcused. Mixtures of transition metal compounds can of course also be used. The compounds are usually in the form of. 0.26 to 1.05 FLAAR applied to the n-aqueous solutions at moderate temperatures, for example in the range of 10 to 40 ⁰ C, gnd at a pH of about 4 to 10 degrees. If the metal compound is to be applied separately from the application of the 4 solution and then the oxidizing solution, it is preferred to wait 5 to 30 minutes after the application of the metal compound solution so that the metal can also penetrate the inside of the hair.

Nevertheless, the coloring can also be carried out in one step with a single solution. A particularly suitable oxidizing agent is an alkali metal peroxodisulfate, in particular sodium peroxodisulfate. Such peroxosulfate solutions are preferably used in connection with MnCl ₂ solutions. Both components are mixed together immediately before application to the hair and then cracked on as a mixture. The rate-determining step of the oxidative effect of the peroxodisulfate is its hydrolysis to hydrogen sulfate with the release of oxygen. However, this reaction proceeds so slowly that the time required for the manganese ions to penetrate the hair strands is ample available before the manganese ions are oxidized.

In the one-step application of the mixed soldering in the manner described above, the concentration of the metal compound in the solution is usually about 0.05 to 0.50 mol / l, while the peroxodisulfate concentration is 0.08 to 0.60 mol / l. The pH of the solution is adjusted to a value in the range from about 0.8 to 10.0. At temperatures in the range from 10 to 40 ^° C., the combined solution remains in contact with the hair for about 5 to 60 minutes.

The oxidizing agents used are preferably permanganates, perborates, peroxodisulfates, periodates, perphosphates and monopersulfates, preferably in the form of the alkali metal salts. The periodates in particular can also be used in the acidic form, specifically as paraperiodic acid, H ₅ JO ₆ . Hydrogen peroxide can also be used as an oxidizing agent. In the two-stage process, the oxidizing agent solutions are preferably used in a concentration of 0.01 to 0.30 mol / l at temperatures of about 10 to 40 ^° C. and a pH of 7.0 to 10.0. The residence time of the oxidizing agent solution on the hair soaked with the metal compound is usually about 1 to 10 minutes, depending on the desired shade.

The various desired color tones and shades are determined by a corresponding Selection of the reaction components and the reaction conditions, in particular the concentrations, the pH values and the residence times, influenced and adjusted.

The solutions used can contain common auxiliaries, for example buffers, wetting agents, fragrances and other additives familiar to the person skilled in the art, contain.

A particular increase in color intensity can be achieved in the presence of ammonium lauryl sulfate in the oxidizing Solution can be achieved. A particularly surprising increase in intensity is observed when the ammonium lauryl sulfate is added to a permanganate solution, which in conjunction with a Manganese salt solution can be used sdII. This effect is all the more surprising as it deals with the conventional lauryl surfactants, such as sodium lauryl sulphate or triethanolamine lauryl sulphate, for example adjusts. The reason for the observed effect has not yet been established.

When adding ammonium lauryl sulfate, however, care must be taken that this is the oxidizing Solution is only added shortly before use, as the tensii is inactivated in the course of about 50 minutes.

After the desired residence time of the combined solution or, in the case of the two-stage process, the oxidizing agent solution, the hair should be washed using a conventional shampoo. Alkali metal metabisulphites, in particular sodium metabisulphite (Na ₂ S ₂ O ₅ ), have proven to be advantageous as reducing agents for bleaching the colored hair. In the same way, other salts of oxygen-sulfur (IV) acids can also be used, for example sodium sulfite (Na ₂ SO ₃ ), sodium thio-sulfite (Na ₂ S ₂ Oj) or sodium hydrogen sulfite (NaHSOj). The reducing agents are applied at a temperature in the case of calibration of about 10 to 40 ⁰ C and a pH of 1.5 to 7, preferably used in a concentration of 0.05 to 0.4 /. 1 Depending on the type of coloring, the hair treated under the conditions mentioned can be completely bleached in the course of about 0.5 to 20 minutes.

Alternatively, the discoloration can also be done with a chelating agent. The preferred chelating agent is Thiourea is used, but other chelating agents with sulfur atoms, Nitrogen atoms or oxygen atoms can be used as donors, especially ethybndiamine tetraacetic acid or citric acid.

At a temperature of 10 to 40 ^° C. and a pH in the range from 2.5 to 5.0, the chelating agent is used in a concentration of about 0.1 to 1.0 mol / l. The contact time required for complete removal of the coloration is about 1 to 15 minutes, depending on the type of coloration. When decolorizing sulfidic colorations, somewhat longer contact times and / or higher temperatures are generally required than for oxidic colorations. In exceptional cases, if only one chelating agent is used, treatment times of up to one hour may be necessary in the case of strong sulfidic staining. Such long treatment times are practically only necessary, even in the context of exceptional cases, if the hair has not been colored in the manner described above according to the invention. On the other hand, however, such a discoloration itself is able to remove stubbornly adhering colorations, which have been applied in a manner known per se, in particular by reducing transition metal compounds, within the stated period of time. An example of such a system is coloring with a cobalt or nickel salt from an aqueous solution with subsequent fixation with a dithionite or hyposulfite solution. Also, for example, a color that is produced in a manner known per se by applying potassium per manganate to the hair and reducing it with sodium sulfide or pyrogallol.

21

was made by reduction with metabisulfite or by complex formation with a thiourea solution easily removed.

The invention is described in more detail below on the basis of exemplary embodiments.

Example I.

It became a first solution with the following composition manufactured:

Components by weight

MnCl ₂ 20

NH ₄ Cl 20

H ₂ O 60

100

This solution was brought to pH 8 with NaOH. Human hair was now using this solution treated for a period of 30 minutes at room temperature (21 ° C) and rinsed with water. It was then with an aqueous solution containing 2.1% sodium perborate treated at a pH of 10.2 to 10.4 for 10 minutes again at room temperature. After one wash, the hair showed a warm, dark brown tint.

Changing the pH of the second solution from 10.2 to 2.5 while maintaining the pH of the first solution at 8 resulted in a range of colors or tints from dark warm brown through medium and light warm brown to a medium and light ash blonde. Maintaining the pH of the second solution at 10.2 and changing the pH of the first solution from 2.5 to 8 using NaOH or NH ₄ OH resulted in a range of colors from a dark, warm brown to a light, reddish one Brown.

The method described above can be modified in other ways to deviate Get results. For example, by changing the duration of treatment, different shades of brown can be achieved as indicated in the table below:

Contact time (minutes)

45 Solution 1 5 10 15 20 25 30 35

Solution 2 35 30 25 20 15 10 5
Color LB MB MB MB DB DB DB

LB is a light brown shade, MB is a medium shade, and DB is a dark brown shade.

The task of the ammonium chloride in solution 1 is to allow, with regard to the manganese, that this remains in solution after the solution becomes alkaline. The mechanism arises “Is a complex formation, and so are other ammonium compounds can be added instead.

Example II

A first solution was prepared with the following composition:

Components by weight

MnSO ₄ -H ₂ O 28 ₆ ,

H ₂ O 62

Na lauryl sulfate 10

689 Ψ

The pH of the solution was brought to 6.5 by adding NaOH. Human hair was treated with the solution at room temperature for 7 minutes and then rinsed with water. Then a second solution was freshly prepared with the following composition:

Components by weight

Standard KMnO ₄ solution with

0.44 percent by weight KMnO ₄ 25

H ₂ O 57.5

aqueous solution with 28 percent by weight
Ammonium Lauryl Sulphate 17.5

100.0

This solution was used to apply to the hair for a total of 35 minutes to treat. The hair was then washed with an ordinary commercially available shampoo. It showed a very dark warm brown color.

Increasing the permanganate concentration to twice that specified results in darker ones Colors that go well with warm blacks.

Example III

A solution was prepared with the following composition:

Components by weight

MnCl ₂ 15

Sodium perborate 2

Water + 1 n-HCl at pH 4.5 ... remainder

This solution was applied to human hair for 5 minutes at pH 4.5. The hair was rinsed with water and then an aqueous solution of 0.4% KMnO _{4 was applied} over a period of about 35 minutes at a pH of 10.5. The result was a black color.

When the permanganate was kept at a pH less than 7, only browns resulted Shades unless an extremely porous hair type has been treated. Changes in pH of the manganese solution in the range of 1.0 to 5.7 did not affect the final coloration of the hair.

Example IV

Human hair was treated with a solution of the following composition:

Components by weight

MnCl ₂ 15

CoCl ₂ 5

Water rest

at a pH of about 5.0 at room temperature and for a period of about 15 minutes. After bobbin winding, the hair _{was treated with 0.4% aqueous KMnO 4} for about 5 minutes. The resulting color was brown, but significantly less warm (less red) than could be observed when cobalt was omitted.

Example V

The procedure of Example I was repeated but the first solution was a simple one

10% aqueous solution of MnCl ₂ . The treatment with this solution was carried out at pH 4.7 for a period of 30 minutes at room temperature. The oxidizing solution was an aqueous solution containing 2.1% sodium perborate at a pH of 10.2 and room temperature. After 5 minutes of contact, the hair turned a medium ash brown color. A decrease in the perborate concentration resulted in lighter colors with a medium ash brown at 1%, light ash brown at 0.05% and ash blonde at 0.25%. The colors from these perborate treatments generally tended to be more yellowish gray than similar treatments using permanganate.

Example VI

A solution was prepared with the following composition:

Components by weight

CoCl ₂ -OH ₂ O 25

NaBO ₃ -4H ₂ O 4

Water rest

with enough 0.5 N-HCl for a pH of 1.6. Three bleached human hair swatches (Nos. 1, 2 and 3) were treated and rinsed with water for periods of 45, 10 and 20 minutes, respectively. They were then treated with a 0.44% strength aqueous KMnO ₄ solution for a period of 10, 10 or 20 minutes, washed with shampoo and tested. Sample No. 1 was dark brown; No. 2 very dark brown and No. 3 black.

If a 10% alkaline potassium persulfate solution with a pH of 10.5 in place of the Permanganatlösunp is used, you get a reddish brown to red color, which can be adjusted by adjusting the pH of the cobalt from 2.5 to 11.0. An addition of 1% potassium persulfate and Iu% urea to the cobalt solution leads to an ίο intense red color.

B e i s ρ i e 1 e VII to XVI

These examples are summarized to illustrate the gamut or range of colors that which is achieved in accordance with the invention. In all the folds there were stains Performed on dark brown hair that was initially bleached to a pale yellow state became. In all cases the hair was treated with solution 1,

ao as shown in the table below, while the Treated the specified time, rinsed with water and then with Solution 2 during the specified Treated length of time. It was then washed with a commercially available shampoo and dried. In general, Examples VIl through X gave ash colors while Examples 11 through II led to warm colors. The intensity of the colors seems to be proportional to the porosity of the hair, which is enhanced by bleaching. Lighter ones, d. That is, lighter colors should be expected if treating hair that has been bleached to a lesser extent. Black can under these circumstances can nevertheless be achieved by increasing de; Part of perborate in solution 1.

Solution 1 VII VIII IX X XI XII XIII XlV XV XVI black Solution 1 MnCl ₂ · _{4H 2} O 19% 6% 10% 10% - 10% 6% Λ 0 /
⁰ Zo ⁰ /O 6% 28% NH ₄ Cl 19th 13th - - - - 13th 13th 13th 13th - H ₂ O + In-NaOh 61 81 - - - - 81 81 81 81 - H ₂ O - - 90 90 90 90 - - - - - FeSO ₄ · 7 K ₂ O - - - - 10 - - - - - - NaBO ₃ · 4 H ₂ O - - - - - - - - - 1.5 H ₂ O 4-In • HCl - - - - - - - - - 70.5 pH, solution 1 7.9 7.9 5.0 5.0 3.5 5.0 7.9 7.9 7.9 7.9 1 to 5.7 Duration in solution 1, 30th 30th 15th 30th 30th 15th 30th 30th 30th 30th 5 min Solution 2 NaBO ₃ · 4 H ₂ O 3 - 0.5 - - - - - - - H ₂ O 4-In-HCl 97 - - - - - - - - NaBO ₃ saturated - 100 - 100 100 - 100 100 100 100 - solution H ₂ O - - 99.5 - - 99 - - - - 99.6 KMnO ₄ - - - - - - - - - - 0.4 H ₅ JO ₆ - - - - - 1 pH, solution 2 5.0 7.2 10.1 10.1 10.1 2.0 7.4 7.6 to
7.8 8.0 to
8.2 9.0 to
10.5 10.5 Duration in solution 2, 10 10 10 5 5 5 10 10 10 10 35 min

colour

Blond medium light average reddish. Red. Light middle dark very black Blond brown brown blond borrowed brown brown brown dark

Brown

509 545/36

Example XVII

A solution of the following composition was produced:

Components by weight

MnSO ₄ -H ₂ O 1.6

NH ₄ NO ₃ 7.0

K ₈ S ₂ O ₈ 10.6

Aminonium Lauryl Sulphate (28-30%) 13.3

NH ₄ OH (28-30%) 2.5

Water 65.0

The solution has a pH of about 9.0. The solution was immediately applied to bleached items human hair for a period of 60 minutes at room temperature, whereupon the hair washed with a common shampoo and dried. It was a warm black color.

Example XVIII

Hair colored in accordance with Example XVI was made with a 1.0% aqueous solution Sodium Metabisulfite (Na ^ -A) for a period of time of 5 minutes at room temperature and at a pH of 4.4 and then treated with Rinsed with water. The hair swatches were of the bleached color they showed before dyeing.

Example XIX

Hair dyed in accordance with Example VI was made with an aqueous solution of sodium metabisulphite at room temperature and at pH 4.4 for a period of 5 minutes treated. Again, the hair has been returned to its original color.

Example XX

A solution of the following composition was prepared:

Components by weight

1. Thiourea 8.0

2. Lactic acid 16.0

3 Sodium Lauryl Sulphate (28 to 30%) .. 50.0 4. Water ■ 26.0

100.0

Hair colored in accordance with Examples VI, XI and XVl was made with the above solution treated for a period of 5 minutes (15 minutes for Example XT) at a pH of 2.5. The paint was completely removed in each case.

Example XXI

Human hair was treated with a 10% solution of nickel acetate (made alkaline to a pH of 9.8 with 28% NH ₄ OH) at room temperature for a period of 50 minutes. It was then rinsed with water and treated with a 10% sodium dithionite solution at pH 5.7 for 10 minutes. It resulted in black color from precipitation of nickel sulfide in the hair. If the pH of the nickel solution is kept at 9.8 and that of the dithionite is increased to 9.0, a medium brown is obtained. A change in the pH of nickel in either direction will also result in a brown.

Hair treated in accordance with this example was then treated with a thiourea solution of Example XX for a period of 15 minutes at room temperature with the result of complete removal of the color. The same result was achieved ^{at 40 ° C. within 3 minutes.}

The examples given above illustrate that in accordance with the invention Hair can be colored in a wide range of permanent colors, and those colors as well such as paints obtained conventionally, easily with simple and low cost causing reagents can be removed. In the examples, in which the color is due to oxidation is formed by a manganese salt, it can be assumed that the color is due to the formation of Manganese dioxide is produced. Similarly, where cobalt or iron salts are oxidized, the color is evident as a result of the formation of one or more oxides in which the metal or some of these, has a higher valence ah two.

In all of these examples, unless otherwise stated, the treatments were carried out at approximately room temperature (20 ^° C.), although the temperatures of the solutions themselves may have been somewhat higher in certain cases as a result of the heat of reaction.

The hair treated in the examples was _{bleached with H 2} O ₂ , unless otherwise stated, in order to remove the natural color prior to dyeing.

Claims (1)

matologi-h not harmless, whereby the use η ♦ ♦ - u of platinum-gold ode. · Silver compounds additional patent claims: are extremely expensive components. With 1.Process for the temporary coloring of hair, color tones achievable with this system are further- d.by characterized by the fact that one * ^^^^ state of the art is the the hair first with the aqueous solution of a tinting ^u , a process for Compound of a transition metal, which is not the invention, in its highest possible oxidation state before the ^temp ^^ ° ^ "" di ^ temporary real thing lies, treated and applied to the hair * ^> ™ * ^^ ο £ ΐ without affecting the hair itself Transition metal compound to an insoluble »color benJ ° n hair allows Compound is oxidized, and that for removing chemically angegnnen wirajj _{colorations, each} the color applied in this way changes the hair with a Hch and wob ι ^ ^F ^^ Reducing agent and / or a chelate time effortlessly and under s.nr