WO1997023195A1

WO1997023195A1 - Dyeing process and natural dyes

Info

Publication number: WO1997023195A1
Application number: PCT/EP1996/005606
Authority: WO
Inventors: Horst Höffkes; Bettina Bergmann
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1995-12-22
Filing date: 1996-12-13
Publication date: 1997-07-03
Also published as: DE19548291A1; EP0869768A1

Abstract

The invention relates to a process for dyeing keratin fibres, in particular human hair. An agent containing a naturally occurring dye and 0.5-10 wt % natural emulsifier is mixed with water, applied to the hair and rinsed out after being allowed to work into the hair for 20-60 minutes. The invention also relates to suitable agents and formulations thereof.

Description

..Dyeing process and colorants on a natural basis "

The invention relates to a process for dyeing keratin fibers, in particular human hair, with naturally occurring dyes and dyes based on naturally occurring dyes.

Furs are among the keratin fibers. To understand wool, feathers and in particular human hair. Although the colorants according to the invention are primarily suitable for dyeing keratin fibers, there is in principle nothing to prevent their use in other areas.

Hair dyes are an important type of cosmetic. They can be used to shade the natural hair color slightly or more according to the wishes of the person concerned, to achieve a completely different hair color or to cover up unwanted hair tones, such as gray tones. Depending on the desired color or durability of the dyeing, conventional hair colorants are formulated either on the basis of oxidation dyes or on the basis of substantive dyes. Combinations of oxidation dyes and direct dyes are often used to achieve special shades.

Colorants based on oxidation dyes require the use of strong oxidizing agents such as hydrogen peroxide solutions. this leads to often damage to the hair to be colored, which must be counteracted with appropriate care products. In addition, skin contact with these colorants can lead to undesirable reactions in very sensitive individuals. A major disadvantage of colorants based on direct dye is the poor washfastness of the colored hair.

In the course of the advancement of ecological aspects in modern society, natural dyes such as henna, which have been used by mankind for thousands of years, have again become increasingly popular.

While there is a trend towards natural dyes, the user does not want to forego the advantages of the well-known hair dyes. An essential task of modern cosmetics is therefore to formulate products based on natural products in such a way that they correspond to the products known to the user in terms of their effect and application properties.

The coloring components of natural hair dye products are usually powdery plant components. These are made to swell by mixing with water, so that a paste-like mass is formed, which is then applied to the hair. With known agents, especially when the mixture contains large proportions of ground wood, it is of great disadvantage that the dye paste has only a slight suppleness and, consequently, an unsatisfactory adhesion to the hair. Furthermore, due to the relatively large water absorption capacity of the hair, additional water is removed from the pulp during the dyeing process. This often leads to an unpleasant hardening of the dye paste and can be disadvantageous Cases even lead to a partial crumbling. Finally, it is also frequently observed that the shredded parts of plants are only inadequately removed from the hair during the normal rinsing of the hair after the dyeing process.

An attempt was therefore made to remedy these abuses by adding natural thickening agents such as guar gum and carob flour. In fact, the disadvantages mentioned can be alleviated mildly, but the products obtained cannot yet meet the expectations placed by the user.

It has now been found that the disadvantages mentioned can be remedied to a surprisingly high degree if certain amounts of natural emulsifiers are added to the agents used for the dyeing process.

The invention thus relates to a process for dyeing keratin fibers, in particular human hair, in which an agent containing a naturally occurring dye and 0.5-10% by weight of a natural emulsifier, mixed with water, applied to the hair and is rinsed out after an exposure time of 20 to 60 minutes. With regard to their rinsability, these agents have properties which are so advantageous that rinsing out according to a preferred embodiment can be carried out satisfactorily with the aid of clear water.

Means are suitable for this process that must meet special requirements. These can be made up in several ways.

The invention therefore furthermore relates to compositions for dyeing keratin fibers, in particular human hair, on a natural basis occurring dyes containing 0.5-10% by weight of a natural emulsifier.

In the further course of the text, the designations listed are used according to the following definitions:

“Colorant” or “medium” for short is understood to mean the preparation or the total of the preparations which are present before being mixed with water.

If the colorants are made up in the form of several solid or liquid partial preparations, these partial preparations are referred to as “coloring components” or, briefly, as “components”.

"Application mixture" means the ready-to-order preparation after mixing with water.

The colorants according to the invention are preferably in solid form. This can be, for example, in the form of a powder or a granulate, with powders generally being preferred.

According to a first preferred embodiment, the entire colorant is packaged in the form of a single preparation. The user can mix an appropriate amount of this preparation with water and apply the application mixture thus obtained to the hair. To facilitate the mixing, preferably heated water, in particular boiling water, is used. In a second preferred embodiment, the colorant is made up in the form of several, in particular two, components. In the case of this form of packaging, it is preferred to provide the natural dyes and the natural emulsifiers in separate components. In principle, the other ingredients of the colorant can be divided up among the individual components in any way, whereby they can either be incorporated into only one component or into several components. In a first preferred variant of this embodiment, the colorant consists of two components, the first component consisting only of the naturally occurring dyes, while all further ingredients are contained in the second component. In a second preferred variant of this embodiment, the colorant likewise consists of two components, the first component, however, consisting only of the natural emulsifiers, while all further ingredients are contained in the second component. The person skilled in the art will select this variant in particular if the natural emulsifiers are compounds which are sensitive to oxidation and in which undesired reactions with other constituents of the colorant may occur in the course of longer storage times.

In this form of assembly it is further preferred that at least one component is in solid form. In the event that only one component is in solid form, it will preferably either consist of the naturally occurring dye or contain it. In a further preferred variant of this form of preparation, the first component consists only of the naturally occurring dyes present in solid form, while the second component consists of a liquid mixture or liquid aqueous solution of the remaining ingredients of the colorant. The application mix is made available by the user immediately before use.

If the colorant consists of only one component, it only needs to be mixed with water. If, on the other hand, the colorant consists of two or more components, in a preferred first embodiment these are first mixed together and then mixed with water. According to a further preferred embodiment, only one component of the colorant is mixed with the amount of water necessary for mixing; the second and optionally further components of the colorant are then added to this preparation. The order in which the individual components may be added will be determined by the person skilled in the art on the basis of the ingredients present in each case.

The following comments on the individual ingredients apply regardless of the selected form of packaging. If special forms of assembly are desired, the person skilled in the art will select the ingredients which are particularly suitable for this, e.g. with regard to the state of matter at room temperature or the compatibility of the individual raw materials, based on his specialist knowledge. Unless otherwise noted, the quantities given for the individual ingredients always relate to the colorant.

The agents according to the invention contain a naturally occurring dye as the first mandatory ingredient. Such substances, which are also referred to as natural dyes below, are, for example, henna red, henna black (Indigofera argentea), henna neutral, chamomile flowers, sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and alkanna root. zel. Preferred naturally occurring dyes for the agents according to the invention are henna red, henna black, henna neutral, chamomile flowers, sandalwood and black tea. The natural dyes are usually present in the colorants according to the invention in amounts of about 50-99.5% by weight, preferably in amounts of 70-95% by weight. The proportion of the individual natural dyes is usually not less than 1% by weight, in particular not less than 3% by weight.

In a preferred embodiment, the colorants according to the invention contain only natural dyes as coloring components. However, it is also possible to add conventional synthetic oxidation dye precursors, so-called developer and coupler components, and / or substantive dyes to these agents in preferably minor amounts.

Primary aromatic amines with a further free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives can be used as developer components, for example be used. Specific representatives are, for example, p-toluenediamine, 2,4,5, 6-tetraaminopyrimidine, p-aminophenol, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) -ethanol, 1 -phenyl-3-carboxyamido-4-amino-pyrazolon-5 and 4-amino-3-methylphenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2, 4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-4-hydroxypyrimidine.

Preferred coupler components are m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols. det. Suitable coupling substances are, in particular, α-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol. Resorcinol monomethyl ether, m-phenylenediamine, l-phenyl-3-methyl-pyrazolone-5. 2,4-dichloro-3-aminophenol, 1, 3-bis (2,4-diaminophenoxy) propane, 4-chlororesorcinol, 3-amino-2-chloro-6-methylphenol and 2-methylresorcinol.

The developer and coupler components can generally be used in free form. For substances with amino groups, however, it may be preferred to use them in salt form, in particular in the form of the hydrochlorides and hydrobromides. Furthermore, it is preferred to use oxidation dye precursors which are capable of the appropriate colorations solely due to air oxidation or in the presence of suitable enzymes in combination with the corresponding substrates, even in the absence of relatively high concentrations of hydrogen peroxide.

Direct dyes which can be used according to the invention are, for example, nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, such as those with the international names or trade names HC Yellow 2, HC Yellow 4, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Nitro Blue, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16, Picramic Acid and Rodol 9 R known compounds as well as 4-Amino-2 -nitro-diphenylamine-2'-carboxylic acid and 6-nitro-1,2,3,4-tetrahydroquinoxaline.

It is not necessary that the oxidation dye precursors or the direct dyes each represent uniform compounds. Rather, in the colorants according to the invention, due to the production process for the individual dyes, in minor amounts Other components may be included, provided that they do not adversely affect the coloring result or must be excluded for other reasons, such as toxicological ones.

The synthetic oxidation dye precursors or substantive dyes are preferably present in the colorants according to the invention in amounts of about 1-10% by weight.

As a second mandatory ingredient, the colorants according to the invention contain a natural emulsifier. Preferred natural emulsifiers are, for example, phosphohpides, saponins, tannic acid, bile acids and their derivatives and abietic acid. Among the natural emulsifiers, phosphophides such as lecithins, partially hydrolyzed lecithins and cephalins are preferred. Egg and soy lecithin are particularly preferred. The preferred bile acids and their derivatives according to the invention include cholic acid, dexoxycholic acid, lithocholic acid and taurocholic acid. According to the invention, the acids mentioned can also be used in the form of their physiologically tolerable salts, in particular their alkali metal and ammonium salts. Of course, the colorants according to the invention can also contain several natural emulsifiers. Quantities of 1-3% by weight of natural emulsifiers have proven to be particularly advantageous.

Organic acids preferred according to the invention exhibit at room temperature, i.e. at 20 ° C, a water solubility of at least 1 wt .-%.

A particularly suitable class of organic acids are α-hydroxycarboxylic acids. Preferred α-hydroxycarboxylic acids are lactic acid, Citric acid. Malic acid, ascorbic acid and gluconic acid. Lactic acid and citric acid are particularly preferred.

The organic acids in the agents according to the invention are preferably in amounts of 0.5-5% by weight, in particular 1-3% by weight. contain.

Especially when using phospholipids as natural emulsifiers, the colorants already show excellent properties if they only contain these emulsifiers in combination with organic acids and the natural dyes. When using other natural emulsifiers, the properties of the colorants according to the invention can be impressively improved if they contain at least one further ingredient, selected from natural waxes and natural thickeners.

Waxes used according to the invention can be of animal (such as beeswax) as well as of vegetable or mineral origin. Waxes of vegetable or mineral origin are preferred. Such waxes are, for example, candelilla wax, jojoba oil, Japanese wax and montan wax. Preferred waxes are jojoba oil and candelilla wax.

The waxes mentioned are contained in the agents according to the invention preferably in amounts of 0.5-10% by weight, in particular 2-5% by weight.

Examples of natural thickeners for the agents according to the invention are guar gum, locust bean gum, agar agar, guar gum and alginates. Xanthan gum, gum arabic, karaya gum, linseed gums, dextrans, starch fractions and derivatives such as amylose, amylopectin and dextrins and clays such as e.g. B. bentonite in question. Natural thickeners for the purposes of the present invention are also cellulose derivatives, such as. B. methyl cellulose, hydroxyalkyl cellulose and Carboxy¬ methyl cellulose.

The natural thickener is preferably present in the colorants according to the invention in amounts of 1-10% by weight, in particular in amounts of 2-5% by weight.

In principle, the agents according to the invention can be prepared by simply mixing the individual constituents by the customary processes. However, it is also possible, for example, to produce granules by the known processes. In this case, however, it is generally necessary for the agents to contain the organic thickeners mentioned above.

Furthermore, the colorants according to the invention can contain all active substances, additives and auxiliaries known in such preparations. In many cases, the colorants contain at least one surfactant, both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has proven to be advantageous to select the surfactants from anionic, cationic or nonionic surfactants. Anionic surfactants can be very particularly preferred.

Preferred anionic surfactants are alkyl sulfates, ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and specially unsaturated C8-C22 carboxylic acids such as oleic acid, stearic acid, isostearic acid and palmitic acid. These anionic surfactants can preferably be in solid, in particular powder form. These are preferably in amounts of 5 to 20% by weight. in particular 10 to 15% by weight.

Particularly suitable nonionic surfactants are C8-C22 alkyl mono- and oligoglycosides and their ethoxylated analogs. In particular, the nonethoxylated compounds, which are also commercially available in powder form, have proven to be particularly suitable.

Examples of the cationic surfactants which can be used in the hair treatment compositions according to the invention are, in particular, quaternary ammonium compounds. Ammonium halides such as alkyltrimethylammonium chlorides are preferred. Dialkyldimethylammoniumchloride and Trialkylmethylammoniumchloride, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. The quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.

Alkylamidoamines, especially fatty acid amidoamines such as that

® Tungo Amid S 18 available stearylamidopropyldimethylamine, apart from a good conditioning effect, are particularly characterized by their good biodegradability.

Quaternary ester compounds, so-called

® called "Esterquats", like the one under the name Dehyquart F 75 in Ab- Mixture of distearoylemylhydroxyethylammonium methosulfate available with cetearyl alcohol.

The compounds with alkyl groups used as surfactants can each be uniform substances. However, it is generally preferred to start from natural vegetable or animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained.

Other active ingredients, auxiliaries and additives are, for example

nonionic polymers such as, for example, vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers and other compounds which are stable as solids or are commercially available, zwitterionic and amphoteric polymers or are used as solids are preferably available as commercial products, anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids and vinyl acetate / crotonic acid copolymers, provided they are stable or preferably commercially available as solids, structurants such as glucose, maleic acid and lactic acid, hair-conditioning compounds such as silicone oils

Protein hydrolyzates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, their condensation products with fatty acids and quaternized protein hydrolyzates, perfume oils, dimethyl isosorbide and cyclodextrins, Active ingredients such as panthenol, pantothenic acid. Allantoin,

Pyrrolidone carboxylic acids and their salts, cholesterol,

Fats and waxes such as whale, paraffins, fatty alcohols and fatty acid esters. Fatty acid alkanolamides,

Complexing agents such as EDTA, NTA and phosphonic acids, swelling and penetration substances such as carbonates, especially soda. Hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

The person skilled in the art will select these further substances according to the desired properties of the agents.

Finally, the invention also relates to the use of natural emulsifiers in amounts of 0.5-10% by weight for the production of agents based on natural dyes for dyeing keratin fibers, in particular human hair.

The following examples are intended to explain the subject of the invention further.

- 1 b -

Examples

The following recipes were examined:

Component: 1 2 3 4

- henna, red 40 - 94 40

- chamomile flower - 10 - -

- Sandalwood - - - 40

- Henna, black (Indigofera argentea) 50 - - 4

- henna, neutral - 70 - -

- Tea, black - 10 - 5

® 1

- Phospholipon P - 2 3 2

- Saponin 2 - - -

- Citric acid - 2 3 2

- Candelilla wax 4 3 - -

- Japanese wax - - - 2

- guar flour 4 3 - 5

deoiled soy lecithin (Rhone-Poulenc)

After mixing with boiling water and cooling to body temperature, all formulations resulted in supple dispersions which were very easy to distribute on the hair, adhered well there for the entire exposure time of approx. 45 minutes and then rinsed off excellently. Recipes 2 and 4 showed particularly good properties. The coloring on light blonde natural hair strands resulted in the following nuances for the individual recipes:

Nuance recipe

1 reddish light brown

2 honey blonde

3 intense red-orange

4 light red with orange tones

Claims

Patent claims

1. A process for dyeing keratin fibers, in particular human hair, characterized in that an agent containing a naturally occurring dye and 0.5-10% by weight of a natural emulsifier, mixed with water, applied to the hair and after an exposure time of 20 to 60 minutes.

2. The method according to claim 1, characterized in that the rinsing is carried out with clear water.

3. Means for dyeing keratin fibers, in particular human hair, based on naturally occurring dyes, characterized in that it contains 0.5-10% by weight of a natural emulsifier.

4. Means according to claim 3, characterized in that it is in solid form.

5. Composition according to claim 3 or 4, characterized in that it is in the form of two separate components, of which the first component contains the naturally occurring dye and the second component contains the natural emulsifier.

6. Composition according to claim 5, characterized in that at least one of the two components is in solid form.

7. Composition according to claim 6, characterized in that a fixed Component contains only the naturally occurring dye.

8. Composition according to one of claims 3 to 7, characterized in that the natural emulsifier is selected from phospholipids. Saponins, tannic acid, cholic acid, deoxycholic acid. Lithocholic acid. Taurocholic acid and abietic acid as well as the alkali metal and ammonium salts of these acids.

9. Composition according to claim 8, characterized in that the natural emulsifier is a phospholipid, in particular a lecithin, a partially hydrolyzed lecithin or a cephalin.

10. Agent one of claims 3 to 9, characterized in that the natural emulsifier is contained in amounts of 1 - 3 wt .-%.

1 1. Agent according to one of claims 3 to 10, characterized in that it further contains an organic acid.

12. A composition according to claim 1 1, characterized in that the organic acid has a water solubility of at least 1 wt .-% at room temperature.

13. Composition according to claim 1 1 or 12, characterized in that the organic acid is an α-hydroxycarboxylic acid.

14. Composition according to claim 13, characterized in that the α-hydroxycarboxylic acid is selected from lactic acid, tartaric acid, malic acid, citric acid. Ascorbic acid and gluconic acid.

15. Composition according to one of claims 1 1 to 14, characterized in that the organic acid in amounts of 0.5 - 5 wt .-%. in particular in amounts of 1-3% by weight.

16. Composition according to one of claims 3 to 15, characterized in that it further contains a natural wax.

17. Composition according to claim 16, characterized in that the natural wax is selected from mineral and in particular vegetable waxes.

18. Composition according to claim 16 or 17, characterized in that the natural wax is contained in amounts of 0.5-10% by weight, in particular 2-5% by weight.

19. Composition according to one of claims 3 to 18, characterized in that it further contains a natural thickener.

20. Use of a natural emulsifier in amounts of 0.5-10% by weight for the production of agents based on a natural dye for dyeing keratin fibers, in particular human hair.