DE202022003085U1 - Agents for the repigmentation of keratin fibers, especially human hair - Google Patents

Abstract

wobei, jeweils unabhängig voneinander,
R¹ Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxy-alkylgruppe bedeutet,
R² Wasserstoff oder eine-COOH-Gruppe bedeutet, wobei die-COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
R³ Wasserstoff oder eine C₁-C₄-Alkylgruppe bedeutet,
R⁴ Wasserstoff, eine C₁-C₄-Alkylgruppe, eine Aminogruppe oder eine Gruppe -CO-R⁶ bedeutet, in der R⁶ eine C₁-C₄-Alkylgruppe bedeutet, und
R⁵ eine der unter R⁴ genannten Gruppen bedeutet,
oder ein physiologisch verträgliches Salz dieser Verbindungen mit einer organischen oder anorganischen Säure;
und 5,6-Dihydroxyindolin-Derivaten der Formel (II),

wobei, jeweils unabhängig voneinander,
R¹ Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxy-alkylgruppe bedeutet,
R² Wasserstoff oder eine-COOH-Gruppe bedeutet, wobei die-COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
R³ Wasserstoff oder eine C₁-C₄-Alkylgruppe bedeutet,
R⁴ Wasserstoff, eine C₁-C₄-Alkylgruppe, eine Aminogruppe oder eine Gruppe -CO-R⁶ bedeutet, in der R⁶ eine C₁-C₄-Alkylgruppe bedeutet, und
R⁵ eine der unter R⁴ genannten Gruppen bedeutet,
oder ein physiologisch verträgliches Salz dieser Verbindungen mit einer organischen oder anorganischen Säure;
und Koffein als Bioaktivstoff;
und mindestens HC Blue 2 als direktziehenden Farbstoff. Cosmetic formulation containing a dye precursor selected from the group consisting of 5,6-dihydroxyindole derivatives of the formula (I)

where, each independently,
R ¹ represents hydrogen, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ hydroxyalkyl group,
R ² represents hydrogen or a COOH group, where the COOH group may also be present as a salt with a physiologically acceptable cation,
R ³ represents hydrogen or a C ₁ -C ₄ alkyl group,
R ⁴ represents hydrogen, a C ₁ -C ₄ alkyl group, an amino group or a group -CO-R ⁶ in which R ⁶ represents a C ₁ -C ₄ alkyl group, and
R ⁵ represents one of the groups mentioned under R ⁴ ,
or a physiologically acceptable salt of these compounds with an organic or inorganic acid;
and 5,6-dihydroxyindoline derivatives of formula (II),

where, each independently,
R ¹ represents hydrogen, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ hydroxyalkyl group,
R ² represents hydrogen or a COOH group, where the COOH group may also be present as a salt with a physiologically acceptable cation,
R ³ represents hydrogen or a C ₁ -C ₄ alkyl group,
R ⁴ represents hydrogen, a C ₁ -C ₄ alkyl group, an amino group or a group -CO-R ⁶ in which R ⁶ represents a C ₁ -C ₄ alkyl group, and
R ⁵ represents one of the groups mentioned under R ⁴ ,
or a physiologically acceptable salt of these compounds with an organic or inorganic acid;
and caffeine as a bioactive substance;
and at least HC Blue 2 as direct dye.

Description

The present invention relates to a cosmetic formulation containing a dye precursor selected from the group consisting of 5,6-dihydroxyindole derivatives and 5,6-dihydroxyindoline derivatives, caffeine and at least HC Blue 2 (2,2'-[[4-[(2-hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol) as a direct dye. The invention further relates to the use of the cosmetic formulation for repigmenting keratin fibers, in particular human hair.

A person's hair color depends on the amount of melanin (eumelanin and pheomelanin) contained in the fiber layer of the hair and produced by melanocytes in the hair follicles. As part of the normal aging process, but also due to certain illnesses, stress, vitamin and mineral deficiencies or excessive alcohol or nicotine consumption, melanin production can decrease, resulting in hypopigmentation. Such hair appears white or colorless to the observer. The visual impression of gray hair results from the mixture of pigmented and pigmentless hair.

The average life cycle of a hair is three to seven years, then the hair falls out and a new hair grows in its place. Gradually, the proportion of white or pigmentless hair predominates and the hair turns grey.

Changing hair color and especially pigmenting or repigmenting gray hair is an important area of modern cosmetics. Good fastness properties and good gray coverage as well as long-lasting coloring are particularly desirable.

Oxidation dyes are traditionally used for permanent, intensive dyeings with good fastness properties and good gray coverage. Such dyes usually contain oxidation dye precursors, so-called developer components and coupler components, which form the actual dyes under the influence of oxidizing agents such as hydrogen peroxide or atmospheric oxygen, or by coupling with one or more coupler components.

However, the use of oxidative dyes is still associated with impairments or damage to the hair and especially its surface structure.

Alternatively, precursors of the natural hair pigment melanin can be applied to the hair, which form practically nature-identical dyes as part of oxidative processes in the hair. The coloring can be done using atmospheric oxygen as the only oxidizing agent, so that no other oxidizing agents are required. Such a process using 5,6-dihydroxyindoline as a dye precursor is used, for example, in EP 0 530 229 B1 described.

In contrast, direct dyes, also known as direct dyes, are used for temporary coloring. These are dye molecules that are absorbed directly into the hair and no longer require an oxidative process to form the color. In comparison to oxidative hair coloring, the colors obtained with direct dyes are less durable and wash out more quickly. Coloring with direct dyes usually remains on the hair for a period of between 5 and 20 washes.

WO 99/66890 describes a dye for dyeing keratin fibers containing a dye precursor, which can be an indoline or indole derivative, e.g. a derivative of 5,6-dihydroxyindoline or 5,6-dihydroxyindole, and an amino acid or an oligopeptide. The color can be formed by means of air oxidation.

DE 10 2018 127 182 A1 relates to a two-component system for artificial hair coloring containing separately an anhydrous carrier medium which comprises an alkane, a fatty alcohol and an alcohol, as well as an aqueous phase which contains hydrogen peroxide. An organosilicon compound from the group of silanes can be included to protect and care for the hair.

DE 10 2007 038 484 A1 describes a hair treatment product for protection against external influences, wherein the hair treatment product contains bacterial ferment(s) from Thermus thermophilus.

WO 2005/007615 A1 relates to 2-(amino- or substituted amino)-5-(substituted oxymethyl)-phenol compounds and compositions for the oxidative dyeing of keratin fibres.

However, the formulations known in the state of the art do not allow sufficiently satisfactory results to be achieved in terms of quality, intensity and duration of the colouring performance while at the same time causing as little impairment or damage to the hair structure as possible.

The resulting color bodies form with the precursors of the natural hair pigment melanin with a significant delay and the color tones cannot be adequately controlled. In addition, the intermediate color tones often turn out to be an unnatural violet. Another disadvantage is the unpigmented hairline that appears as the hair grows back.

In summary, there is still room for improvement, particularly in terms of fastness properties, grey coverage and the duration of dyeing performance.

Based on this, the object of the present invention was to provide a cosmetic formulation which is suitable for pigmenting or repigmenting keratin fibers, in particular human hair, and in particular offers improved authenticity properties of the pigmented or repigmented keratin fibers as well as improved gray coverage. Furthermore, this cosmetic formulation should have improved properties compared to formulations known from the prior art in terms of quality, intensity and duration of the coloring performance.

This object was surprisingly achieved by the formulation according to claim 1 and its use according to claim 11. Preferred embodiments emerge from the dependent claims.

According to the invention, the object is achieved by providing a cosmetic formulation which contains a dye precursor selected from the group consisting of 5,6-dihydroxyindole derivatives and 5,6-dihydroxyindoline derivatives, caffeine and at least HC Blue 2 (2,2'-[[4-[(2-hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol) as a direct dye.

Surprisingly, it was found that the contrast to the regrowing hair (hairline) is significantly lower, as the natural pigment formation in the hair root is stimulated, while at the same time the already grown-out hair darkens.

Overall, the hair becomes gradually darker, with the color effect building up subtly, gray hairs are clearly covered, and the overall impression of the hair color appears significantly darker.

Thus, the cosmetic formulation according to the invention achieves good grey coverage and excellent fastness properties with long-lasting colouring performance and reduced greying of the hairline.

The caffeine contained in the formulation according to the invention, together with the dye precursor, stimulates the keratinocytes in the hair roots so that they produce more natural pigment again. The caffeine also causes the hair to stay on the head for longer. This delays the loss of hair that is still pigmented and also contributes to the natural repigmentation of hair that is already poorly pigmented or has no pigment. In the context of the present invention, the terms pigmentation and repigmentation are used interchangeably.

The dye precursor contained in the formulation according to the invention, which is a 5,6-dihydroxyindole derivative and/or 5,6-dihydroxyindoline derivative, can carry further substituents on the hydroxy groups, e.g. in the form of an etherification or esterification.

In a preferred embodiment of the invention, the dye precursor is a 5,6-dihydroxyindole derivative.

wobei, jeweils unabhängig voneinander,

• R¹ Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxyalkylgruppe bedeutet,
• R² Wasserstoff oder eine-COOH-Gruppe bedeutet, wobei die-COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• R³ Wasserstoff oder eine C₁-C₄-Alkylgruppe bedeutet,
• R⁴ Wasserstoff, eine C₁-C₄-Alkylgruppe, eine Aminogruppe oder eine Gruppe -CO-R⁶ bedeutet, in der R⁶ eine C₁-C₄-Alkylgruppe bedeutet, und
• R⁵ eine der unter R⁴ genannten Gruppen bedeutet,
• oder ein physiologisch verträgliches Salz dieser Verbindungen mit einer organischen oder anorganischen Säure.

According to the invention, the dye precursor is preferably a derivative of 5,6-dihydroxyindole of the formula (I),

where, each independently,

• R ¹ represents hydrogen, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ hydroxyalkyl group,
• R ² represents hydrogen or a COOH group, where the COOH group may also be present as a salt with a physiologically acceptable cation,
• R ³ represents hydrogen or a C ₁ -C ₄ alkyl group,
• R ⁴ represents hydrogen, a C ₁ -C ₄ alkyl group, an amino group or a group -CO-R ⁶ in which R ⁶ represents a C ₁ -C ₄ alkyl group, and
• R ⁵ represents one of the groups mentioned under R ⁴ ,
• or a physiologically acceptable salt of these compounds with an organic or inorganic acid.

Representatives preferred according to the invention are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole.

In a particularly preferred embodiment, the compound of formula (I) is selected from 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole and their physiologically acceptable salts.

Most preferably, the dye precursor used in the formulation according to the invention is 5,6-dihydroxyindole.

In a further preferred embodiment of the invention, the dye precursor is a 5,6-dihydroxyindoline derivative.

wobei, jeweils unabhängig voneinander,

• R¹ Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxyalkylgruppe bedeutet,
• R² Wasserstoff oder eine-COOH-Gruppe bedeutet, wobei die-COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• R³ Wasserstoff oder eine C₁-C₄-Alkylgruppe bedeutet,
• R⁴ Wasserstoff, eine C₁-C₄-Alkylgruppe, eine Aminogruppe oder eine Gruppe -CO-R⁶ bedeutet, in der R⁶ eine C₁-C₄-Alkylgruppe bedeutet, und
• R⁵ eine der unter R⁴ genannten Gruppen bedeutet,
• oder ein physiologisch verträgliches Salz dieser Verbindungen mit einer organischen oder anorganischen Säure.

According to the invention, the dye precursor is preferably a derivative of 5,6-dihydroxyindoline of the formula (II),

where, each independently,

• R ¹ represents hydrogen, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ hydroxyalkyl group,
• R ² represents hydrogen or a COOH group, where the COOH group may also be present as a salt with a physiologically acceptable cation,
• R ³ represents hydrogen or a C ₁ -C ₄ alkyl group,
• R ⁴ represents hydrogen, a C ₁ -C ₄ alkyl group, an amino group or a group -CO-R ⁶ in which R ⁶ represents a C ₁ -C ₄ alkyl group, and
• R ⁵ represents one of the groups mentioned under R ⁴ ,
• or a physiologically acceptable salt of these compounds with an organic or inorganic acid.

Representatives preferred according to the invention are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindole.

In a particularly preferred embodiment, the compound of formula (II) is selected from 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline and their physiologically acceptable salts.

Most preferably, the dye precursor used in the formulation according to the invention is 5,6-dihydroxyindoline.

In a further particularly preferred embodiment, the dye precursor used in the formulation according to the invention is dihydroxyindoline hydrobromide (2,3-dihydro-1H-indole-5,6-diol hydrobromide).

The 5,6-dihydroxyindole and 5,6-dihydroxyindoline derivatives contained in the agents according to the invention can be used both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, e.g. the hydrochlorides, sulfates and hydrobromides.

The 5,6-dihydroxyindole or 5,6-dihydroxyindoline derivative is usually contained in the formulation according to the invention in an amount of 0.001-5 wt.%, preferably 0.005-2 wt.%, preferably 0.01-2 wt.%, preferably 0.01-1.5 wt.%, preferably in an amount of about 0.05 wt.%, 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1.0 wt.%, 1.5 wt.%, each based on the total weight of the formulation.

In a particularly preferred embodiment, the dye precursor is a 5,6-dihydroxyindole derivative, preferably 5,6-dihydroxyindole, which is contained in the formulation according to the invention in an amount of 0.01-2 wt. %, preferably 0.05-0.6 wt. %, preferably in an amount of 0.08-0.5 wt. %, preferably in an amount of about 0.1-0.5 wt. %, in each case based on the total weight of the formulation.

In a further particularly preferred embodiment, the dye precursor is a 5,6-dihydroxyindoline derivative, preferably 5,6-dihydroxyindoline hydrobromide (2,3-dihydro-1H-indole-5,6-diol hydrobromide), which is contained in the formulation according to the invention in an amount of 0.01-4.0 wt. %, preferably 0.05-2.0 wt. %, preferably in an amount of 0.08-1.0 wt. %, preferably in an amount of about 0.1-0.5 wt. %, in each case based on the total weight of the formulation.

The formulation according to the invention can also contain more than one 5,6-dihydroxyindole or 5,6-dihydroxyindoline derivative or mixtures of 5,6-dihydroxyindole and 5,6-dihydroxyindoline derivatives.

The formation of the pigment from the dye precursor, i.e. the 5,6-dihydroxyindole or 5,6-dihydroxyindoline derivative, occurs by reaction with atmospheric oxygen; no additional oxidizing agent is required.

The caffeine contained in the cosmetic formulation, together with the dye precursor, leads in particular to the keratinocytes in the hair roots being stimulated to produce more natural pigment. In addition, the caffeine causes the hair to stay on the head for longer, which on the one hand delays the loss of hair that is still pigmented and on the other hand contributes to the natural repigmentation of hair that is already poorly pigmented or pigmentless.

The IUPAC name of caffeine is 1,3,7-trimethyl-3,7-dihydro-1H-purine-2,6-dione. Alternatively, caffeine is also called 1,3,7-trimethylxanthine. Caffeine is represented by the following chemical formula (III).

Caffeine is a methylxanthine alkaloid belonging to the class of methylxanthines. It is a bitter crystalline substance, can be considered a purine derivative and is chemically related to the adenine and guanine bases of deoxyribonucleic acids and ribonucleic acid.

The caffeine is usually present in the formulation according to the invention in an amount of 0.0001-10 wt.%, preferably 0.01-5 wt.%, preferably 0.05-2 wt.%, preferably 0.1-1.5 wt.%, preferably in an amount of about 0.0001 wt.%, 0.05 wt.%, 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.5 wt.%, 0.7 wt.%, 1.0 wt.%, 1.3 wt.%, 1.4 wt.%, 1.5 wt.%, in each case based on the total weight of the formulation.

The formulations according to the invention further contain at least HC Blue 2 (2,2'-[[4-[(2-hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol) as a direct dye.

It was surprisingly found that the colour effect of a formulation which, in addition to the dye precursor of the 5,6-dihydroxyindole or 5,6-dihydroxyindoline type and caffeine, also contains at least HC Blue 2 (2,2'-[[4-[(2-hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol) as a direct dye, is more intense than would have been expected based on the colour effects of the individual components, dye precursor of the 5,6-dihydroxyindole or 5,6-dihydroxyindoline type and at least HC Blue 2 (2,2'-[[4-[(2-hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol). The darkening effects (repigmentation) are synergistically increased in terms of the speed of color onset and color depth by combining them with at least HC Blue 2 (2,2'-[[4-[(2-Hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol) as direct dyes.

In the presence of a combination of dye precursor of the 5,6-dihydroxyindole or 5,6-dihydroxyindoline type and at least HC Blue 2 (2,2'-[[4-[(2-hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol) as a direct dye, a synergistic effect occurs. Thus, with the cosmetic formulation according to the invention containing a dye precursor of the 5,6-dihydroxyindole or 5,6-dihydroxyindoline type, caffeine and at least HC Blue 2 (2,2'-[[4-[(2-hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol) as a direct dye, a particularly intense color effect is advantageously achieved, with excellent gray coverage and excellent fastness properties, i.e. a highly natural color tone with a long-lasting coloring result.

As mentioned at the beginning, direct dyes are dye molecules that are absorbed directly into the hair and no longer require an oxidative process to produce the color.

Further preferred direct dyes include nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones and indophenols and are preferably selected from the group of dyes known under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, Basic Yellow 57, Basic Yellow 87, HC Orange 1, Disperse Orange 3, Acid Orange 7, Basic Orange 31, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, Acid Red 33, Acid Red 52, Pigment Red 57:1, Basic Red 51, Basic Red 76, HC Blue 2 (2,2'-[[4-[(2-Hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol), HC Blue 12, HC Blue 16, Disperse Blue 3, Acid Blue 7, Basic Blue 99, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, Acid Black 52, Basic Brown 16 und Basic Brown 17 sowie 1,4-Diamino-2-nitrobenzol, 2-Amino-4-nitrophenol, 1,4-Bis-(β-hydroxyethyl)-amino-2-nitrobenzol, 3-Nitro-4-(β-hydroxyethyl)-aminophenol, 2-(2-Hydroxyethyl)amino-4,6-dinitrophenol, 1-(2'-Hydroxyethyl)amino-4-methyl-2-nitrobenzol, 1-Amino-4-(2-hydroxyethyl)-amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1-(2-ureidoethyl)amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'- carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, hydroxyethyl-2-nitro-toluidine, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

HC Blue 2 (2,2'-[[4-[(2-hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol) is usually present in the formulation according to the invention in an amount of 0.001-5 wt.%, preferably 0.05-3 wt.%, preferably 0.1-2 wt.%, preferably 0.1-1.2 wt.%, preferably in an amount of about 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1.0 wt.%, 1.1 wt.%, 1.2 wt.%, 1.3 wt.%, 1.4 wt.%, 1.5 wt.%, 1.6 wt.%, 1.7 wt.%, 1.8 wt.%, 1.9 wt.%, 2.0 wt.%, each based on the total weight of the formulation.

In a particularly preferred embodiment, the formulation according to the invention contains 5,6-dihydroxyindole as a dye precursor and caffeine. 5,6-dihydroxyindole is present in an amount of 0.05-0.6% by weight and caffeine in an amount of 0.8-1.2% by weight, each based on the total weight of the formulation.

In another particularly preferred embodiment, the formulation according to the invention contains 5,6-dihydroxyindole as a dye precursor, caffeine and also at least HC Blue 2 (2,2'-[[4-[(2-hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol) as a direct dye. 5,6-dihydroxyindole is contained in an amount of 0.05-0.6% by weight, caffeine in an amount of 0.8-1.2% by weight and HC Blue 2 (2,2'-[[4-[(2-hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol) in an amount of 0.1-1.2% by weight, each based on the total weight of the formulation.

Furthermore, the cosmetic formulation according to the invention can contain all additives known in such preparations (i.e. active ingredients, additional substances and auxiliary substances).

In one embodiment, the cosmetic formulation comprises a surfactant. The surfactant can be an anionic, nonionic, cationic or zwitterionic surfactant. The surfactant is preferably an anionic or nonionic surfactant, in particular an anionic or nonionic surfactant that is as mild as possible (i.e. particularly skin-friendly). Nonionic surfactants are used according to the invention in particular because of their very good emulsification properties and their excellent skin care properties. Anionic surfactants are preferred because they have a particularly high cleaning performance. They are therefore particularly suitable in cleaning formulations such as shampoos. Cationic surfactants have excellent hair care properties and are used according to the invention in particular in hair care formulations such as in conditioners, shampoos and treatments.

The formulation according to the invention preferably contains surfactants in an amount of 2 to 40 wt.%, in particular 5 to 30 wt.%, preferably 7 to 20 wt.%, particularly preferably 10 to 17 wt.%, in each case based on the total weight of the formulation. Suitable amounts of surfactant are: 8 wt.%; 9 wt.%; 10 wt.%, 11 wt.%; 12 wt.%; 13 wt.%; 14 wt.%, 15 wt.%; 16 wt.%, 17 wt.%; 18 wt.%, 19 wt.%; 20 wt.%; 21 wt.%; 22 wt.%; 23 wt.%, 24 wt.%; 25 wt.%, in each case based on the total weight of the formulation. The cosmetic formulation of the invention particularly preferably contains one or more anionic surfactants in an amount of 0.1 to 20 wt. %, preferably 1 to 17 wt. %, and particularly preferably 5 to 15 wt. %, based in each case on the total weight of the formulation. Suitable amounts of anionic surfactant are: 1 wt. %, 2 wt. %, 3 wt. %, 4 wt. %, 5 wt. %, 6 wt. %, 7 wt. %, 8 wt. %, 9 wt. %, 10 wt. %, 11 wt. %, 12 wt. %, 13 wt. %, 14 wt. %, 15 wt. %, 16 wt. %, 17 wt. %, 18 wt. %, 19 wt. %, 20 wt. %, based in each case on the total weight of the formulation. In these amounts, the surfactants have a particularly high cleaning performance and are extremely well tolerated by the skin, scalp and hair.

The surfactants of the present invention are found in, among others, Book “Surfactants and interfacial phenomena”, by Milton Rosen and Joy Kunjappu, John Wiley & Sons, Inc.-Verlag, 2012, 4 . edition described.

In a preferred embodiment, the surfactant is an anionic surfactant selected from alkyl carboxylates, alkyl sulfonates, alkyl sulfates, alkyl ether sulfates, alkyl phosphates, alkyl sarcosinates, alkyl taurates, amino acid surfactants and mixtures thereof. The surfactant is particularly preferably selected from alkyl carboxylates, alkyl sulfates, alkyl sarcosinates, alkyl taurates, alkyl glutamate, such as sodium cocoyl glutamate/disodium cocoyl glutamate, alkyl glycinate, alkyl alaninate, such as sodium cocoyl alaninate and mixtures thereof. Also preferred due to their cleaning performance are fatty alcohol polyglycerol ether sulfates, monoglyceride sulfates, mono- and/or dialkyl sulfosuccinates, fatty acid isethionates and α-olefin sulfonates.

Alkyl carboxylates have the generic formula RCO ₂ M, alkyl sulfates have the generic formula ROSO ₃ M, alkyl sarcosinates have the generic formula RC(O)N(CH ₃ )CH ₂ CO ₂ M, and alkyl taurates have the generic formula RC(O)N(CH ₃ )CH ₂ CH ₂ SO ₃ M, where R is a C ₄ -C ₂₆ alkyl or C ₄ -C ₂₆ alkenyl and M is a water-soluble cation such as ammonium, sodium or potassium. Preferably M is sodium cation. Preferably R is C ₁₂ -C ₁₆ alkyl or a C ₁₂ -C ₁₈ alkyl.

In one embodiment, the surfactant is a nonionic surfactant (also referred to as a nonionic emulsifier). Non-limiting examples include glycerol fatty acid esters, fatty alcohols, polyoxyethylene ethers of one or more fatty alcohols, alkoxylated fatty acid alkyl esters, polyglycerol ethers of fatty alcohols, polyglycerol esters of fatty acids, polyethylene glycol and/or polypropylene glycol ethers, fatty acid amides, alkylphenol polyglycol ethers, amine oxides, and alkyl polyglucosides.

In one embodiment, the surfactant is selected from the group of glycerol fatty acid esters, fatty alcohols, polyoxyethylene ethers of one or more fatty alcohols, polyglycerol ethers of fatty alcohols, polyglycerol esters of fatty acids and mixtures thereof.

In the present invention, the term "glycerol fatty acid ester" refers to a glycerol mono- or glycerol difatty acid ester. Glycerol difatty acid esters have the formula R ³ -COO-(CH ₂ CH(OH)CH ₂ )-OOR ⁴ or R ³ -COO-(CH ₂ CH(OOR ⁴ )CH ₂ )-OH. Glycerol monofatty acid esters have the formula R ³ -COO-(CH ₂ CH(OH)CH ₂ )-OH or HO-(CH ₂ CH(OOR ³ )CH ₂ )-OH. R ³ and R ⁴ are independently selected from C ₆ -C ₂₈ alkyl and C ₆ -C ₂₈ alkenyl. Glycerol monofatty acid esters contain a glycerol group which is bonded to a single fatty acid via an ester bond. Examples are glycerin monostearate, glycerin monobehenate, glycerin monocaprylate, glycerin monocaprate and glycerin monolaurate.

Fatty alcohols (saturated) are compounds of the formula H ₃ C-(CH ₂ ) _n -CH ₂ -OH, where n is an integer between 4 and 20, preferably an integer between 6 and 16.

Polyoxyethylene ethers are compounds of the formula R ⁵ (OC ₂ H ₃ ) _n OH, where R ⁵ is selected from C ₆ -C ₂₈ alkyl, C ₆ -C ₂₈ alkenyl, substituted and unsubstituted phenoxy groups; and n is an integer greater than 1. Preferably, the polyoxyethylene ether of one or more fatty alcohols is selected from the group of steareth-2, steareth-21, macrogol-cetostearyl ether 12, ceteareth-25, macrogol-cetostearyl ether 20 and mixtures of the aforementioned compounds. Even more preferably, the polyoxyethylene ether is a compound selected from the group of ceteareth-25, macrogol-cetostearyl ether 20 and mixtures of the aforementioned compounds.

The term "polyglycerol ethers of fatty alcohols" refers to a compound of the formula R ⁶ O-(C ₃ H ₆ O ₂ ) _n -H, where R ⁶ is a branched or linear C ₆ -C ₂₈ alkyl or C ₆ -C ₂₈ alkenyl and n is an integer greater than 1, preferably an integer from 2 to 10. It is preferred that the formulation contains 0.01 to 15.0 wt.%, 0.1 to 10.0 wt.%, or 1 to 5.0 wt.% polyglycerol ether.

The term "polyglycerol esters of fatty acids" refers to compounds containing both a polyglycerol moiety and at least one C ₆ -C ₂₆ alkyl or C ₆ -C _{26 alkenyl} carboxylic acid moiety. These compounds may have the formula R ⁷ -R ⁸ -(C ₃ H ₆ O ₂ ) _n -H, where R ⁷ is a C ₆ -C ₂₆ alkanoate or C ₆ -C ₂₆ alkenoate moiety and R ⁸ is a suitable linking molecule or direct bond. Thus, the polyglycerol moiety and the C ₆ -C ₂₆ alkyl or C ₆ -C ₂₆ alkenyl carboxylic acid moiety may be directly linked by an ester bond or may contain a linking moiety linking these two moieties together. Non-limiting examples of this group are polyglyceryl-3-methylglucose distearate, polyglycerol polycrinoleate, polyglyceryl dimerate isostearate, polyglyceryl-2-laurate, polyglyceryl-2-sesquiisostearate, polyglyceryl-3-distearate (Cremophor GS 32), polyglyceryl-3-oleate, polyglyceryl-3-methylglycose distea arate, polyglyceryl-4-caprate (polyglycerol caprate T2010190), polyglyceryl-4-diisostearate / polyhydroxystearate / sebacate (Isolan GPS) and polyglyceryl-4-isostearate.

In one embodiment, the surfactant comprises a cationic surfactant, such as a quaternary surfactant. Quaternary surfactants contain at least one N atom that is covalently bonded to 4 alkyl or aryl groups. This leads to a positive charge, regardless of the pH value. Alkyl betaine, alkylamidopropyl betaine and alkylamidopropyl hydroxysulfaine are advantageous. The cationic surfactants used according to the invention can also preferably be selected from the group of quaternary ammonium compounds, in particular benzyltrialkylammonium chlorides or bromides, such as benzyldimethylstearylammonium chloride, and also alkyltrialkylammonium salts, for example cetyltrimethylammonium chloride or bromide, alkyldimethylhydroxyethylammonium chlorides or bromides, Dialkyldimethylammonium chlorides or bromides, alkylamideethyltrimethylammonium ether sulfates, alkylpyridinium salts, for example lauryl or cetylpyrimidinium chloride, imidazoline derivatives and compounds with cationic character such as amine oxides, for example alkyldimethylamine oxides or alkylaminoethyldimethylamine oxides. Cetyltrimethylammonium salts are particularly advantageous to use.

In a further embodiment, the formulation according to the invention contains at least one additive. Preference is given to additives which are usually used in shampoos, conditioners and emulsions for treating the skin, scalp and hair. The at least one additive can be present in a proportion of 0.01% by weight to 12.0% by weight, more preferably from 0.25% by weight to 10.0% by weight, in particular from 1.0 to 7.0% by weight.

The at least one additive can further be selected from the group consisting of hair conditioning agents, refatting agents, preservatives, stabilizers, fragrances, antioxidants, rheology modifiers, thickeners, care agents, dyes, pearlizing agents, lightening agents, solvents, setting compounds, anti-dandruff agents, vitamins, alkalizing agents or pH adjusters and combinations thereof.

Hair conditioning agents can reduce static electricity in hair by neutralizing electrical charges on its surface. Examples of hair conditioning agents are quaternary ammonium compounds.

Refatting agents, also called refatting agents or superfatting agents, are lipophilic substances that can prevent a disruptive effect on the epidermal barrier function. Examples of refatting agents are wool wax, squalene, liquid paraffin, vegetable oils, silicones and cetyl palmitate.

Preservatives are substances that are used for preservation by killing microorganisms that decompose the formulation and/or inhibiting their growth. The preservatives can preferably be selected from the group consisting of benzoic acid, benzoic acid derivatives, sorbic acid, sorbic acid derivatives, salicylic acid, salicylic acid derivatives, phenoxyethanol, parabens and combinations thereof. In a preferred embodiment, sodium benzoate and/or potassium sorbate are used as preservatives in the formulation according to the invention. In a slightly acidic environment, sodium benzoate releases benzoic acid and potassium sorbate releases sorbic acid. Both acids are said to have an antimicrobial effect.

Stabilizers can protect light-sensitive components against radiation and are preferably UV absorbers such as benzophenone derivatives.

The addition of fragrances can give the formulation a pleasant smell. Examples include perfumes, which are familiar to those skilled in the art.

An antioxidant or antioxidant agent is a chemical compound that slows down or completely prevents the oxidation of other components in the formulation according to the invention. Examples of possible antioxidants include citric acid, ascorbic acid, sodium sulfite and butylhydroxyanisole.

Rheology modifiers and thickeners can help to improve the application properties of the formulation according to the invention. The addition of table salt (sodium chloride) can be considered as a rheology modifier and thickener. By adding table salt, the flowability of the formulation according to the invention can be influenced within certain limits and adjusted to the required level. Naturally occurring gelling agents can also be used as thickeners, which are preferably selected from agar, xanthan gum, cellulose and/or cellulose derivatives or alginic acid.

For the purposes of the application, care products are understood to mean substances that care for the hair and/or scalp. Hydrolyzed wheat protein, panthenol and allantoin have a caring effect on the scalp and hair. Hydrolyzed wheat protein has mainly moisturizing properties.

The formulation according to the invention can contain colorants as additional dyes, for example to give the formulation a visually appealing color. The formulation according to the invention can contain, for example, CI 47005 as a suitable colorant.

The solvent used can be a solvent or solvent mixture that is common to the person skilled in the art. Preferred solvents are ethanol or butylene glycol, in particular 1,4-butylene glycol, propylene glycol and isopropyl alcohol. Ethanol or propylene glycol is preferred. These solvents can preferably be present in the formulation according to the invention in an amount of 0.1 to 70% by weight. They are most preferably present in an amount of 0.1 to 5.0% by weight.

Strengthening compounds are preferably selected from the group consisting of waxes, synthetic polymers and mixtures thereof. Suitable strengthening compounds are known to the person skilled in the art and are described, for example, in Goddard, E. Desmond; Gruber, James V. (1999), “Principles of polymer science and technology in cosmetics and personal care”, Series: Cosmetic science and technology series : v. 22., New York (Marcel Dekker, INC.); Schrader, Karlheinz (1989), “Fundamentals and formulations of cosmetics” (2nd edition), Chapter 3.7, Heidelberg (Hüthig); and Scott, Richard (2017), “ingredients focus: cosmetic waxes and butters”, Personal Care Europe 10(3), 46-47 described.

Anti-dandruff agents are used to control excessive dandruff formation on the scalp. Suitable anti-dandruff agents are known to the expert and are available, for example, in Trüeb, RM (2009). “Treating dandruff successfully.” Akt Dermatol 35(01/02): 19-24; Trueb, RM (2007). “Shampoos: ingredients, efficacy and adverse effects.” J. Dtsch. Dermatol. Ges. 5(5): 356-365; Sanfilippo, A. and J. English (2006). “An overview of medicated shampoos used in dandruff treatment.” P AND T 31(7): 396; and Futterer, E. (1981). “Evaluation of efficacy of antidandruff agents.” J Soc Cosmet Chem 32: 327-338 described.

Vitamins and minerals such as niacinamide (vitamin B3), vitamin E or zinc are used to achieve a positive effect on the growth and repair of hair damage. Suitable vitamins and minerals are known to the expert and can be found, for example, in Pietrzik K, Golly I, Loew D, Handbook of Vitamins, Elsevier GmbH, Urban & Fischer Verlag, Munich 2008; H. Lautenschläger, Vitamins in Cosmetics, medical Beauty Forum 2020 (3), 14-17; and Martini MC, Chivot M., Peyrefitte G., Textbook of Cosmetics: Basics - Basic Ingredients - Basic Techniques, Hogrefe AG, Bern 2001 described.

Alkalizing agents or pH adjusters are used to adjust the pH of the formulation to a desired range. Suitable alkalizing agents or pH adjusters include sodium hydroxide, monoethanolamine 0.1-5%, phosphoric acid and citric acid.

Example compositions are shown in the following table: ingredient Amount in wt.% Aqua [water] ad 100 sodium lauryl ether sulfate 5-15 sodium myreth sulfate 0-5 sodium cocoamphoacetate 0-5 Laureth-2 0-5 Cocoamidopropyl betaine 0-5 disodium lauryl sulfosuccinate 0-5 sodium lauroyl glutamate 0-5 panthenol 0-5 caffeine 0.1-5 sodium chloride 0-5 phenoxyethanol 0-5 wheat protein hydrolysate 0-3 cocoglucoside 0-3 glyceryl oleate 0-3 phosphoric acid 0-3 sodium benzoate 0-3 PEG-120 Methylglucose dioleate 0-3 potassium sorbate 0-3 HC Blue 2 (2,2'-[[4-[(2-Hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol) 0.1-2 allantoin 0-3 PEG-40 hydrogenated castor oil 0-3 menthol 0-2 Polyquaternium-7 0-2 sodium hydroxide 0-2 disodium EDTA 0-2 dihydroxyindole 0.01-2 tocopherol 0-2 citric acid 0-2 niacinamide 0-2 zinc PCA 0-2 dye / coloring agent 0-2

According to the invention, the composition is applied topically. Topical application is understood to mean external application, in particular local, external application. Compositions according to the invention are preferably hair care products (i.e. treatment agents such as shampoos, conditioners or treatments).

In a preferred embodiment, the formulation according to the invention is present as a shampoo, conditioner, treatment or color treatment, in particular as a shampoo or color treatment.

The cosmetic formulation of the present invention is particularly suitable for pigmenting and/or repigmenting keratin fibers.

Accordingly, in a further embodiment, the present invention relates to the use of the cosmetic formulation comprising a dye precursor selected from the group consisting of 5,6-dihydroxyindoline derivatives and 5,6-dihydroxyindole derivatives, and caffeine as a bioactive substance for pigmenting and/or repigmenting keratin fibers and at least HC Blue 2 (2,2'-[[4-[(2-hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol) as a direct dye.

For the purposes of the present invention, “keratin fibers” are understood to mean hair, in particular human hair. The term “human hair” includes in particular head hair and beard hair.

In a preferred embodiment, the present invention relates to the use of the cosmetic formulation for pigmenting and/or repigmenting human hair.

The formula is preferably distributed in wet or dry hair and rinsed out after a residence time of between 1 and 30 minutes.

The cosmetic formulation according to the invention for the pigmentation and/or repigmentation of keratin fibers, in particular human hair, causes the hair to be slowly and gently colored permanently and at the same time the keratinocytes in the hair roots are stimulated so that they again produce increased natural pigment.

Thus, in a further embodiment, the invention relates to the use of the cosmetic formulation for the pigmentation and/or repigmentation of human hair, whereby the hair is slowly and gently dyed permanently and at the same time the keratinocytes in the hair roots are stimulated so that they again produce increased natural pigment.

The following formulations are intended to clarify the invention without, however, wishing to restrict it to the specific examples.

character description

• 1 Comparison photos of strands washed with example formula 2 (D1/D2) or comparison formula (E1/E2)
• 2 Comparison of the color preview for the two shampoos used Example Recipe 2 or Comparison Recipe
• 3 Change in color depth when using the shampoos example formulation 2 or comparison formulation as absolute values dL*
• 4 Total color change dE* when using the shampoos example recipe 2 or comparison recipe
• 5 Change in color depth when washing with color shampoo (5 washes) or washing out with neutral formula (14 washes)
• 6 Change in color depth when washing with color shampoo (10 washes) or washing out with neutral formula (15 washes)
• 7 Change in color depth when washing with color shampoo (15 washes) or washing out with neutral formula (15 washes)
• 8 Comparison of the color change for the two shampoos used on a single strand after 15 washes, followed by 15 washes
• 9 Comparison of the color preview for the shampoos used Example Formula 1 or Example Formula 2 or Comparison Formula on a single strand each after 15 washes
• Figure 10 Change in color depth when using the shampoos Example Recipe 1 or Example Recipe 2 or Comparison Recipe as absolute values dL*
• 11 Total color change dE* when using the shampoos example recipe 1 or example recipe 2 or comparison recipe

experimental part

recipes

The following recipes were prepared by methods known to those skilled in the art.

comparative recipe

The comparison formulation contains caffeine and HC Blue 2 (2,2'-[[4-[(2-Hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol) as a direct dye. ingredient amount in wt.% Aqua [water] ad 100 sodium lauryl ether sulfate 11.5 sodium cocoamphoacetate 3 cocamidopropyl betaine 1.7 caffeine 1.1 panthenol 0.92 sodium chloride 1 phenoxyethanol 0.7 cocoglucoside 0.5 glyceryl oleate 0.5 phosphoric acid 0.4 PEG-120 Methylglucose dioleate 0.3 HC Blue 2 0.22 menthol 0.2 Polyquaternium-7 0.2 sodium hydroxide 0.15 niacinamide 0.1 zinc PCA 0.1 dye / coloring agent 0.1 citric acid 0.06

Example Recipe 1

Example formulation 1 contains dihydroxyindole and caffeine. ingredient amount in wt.% Aqua [water] ad 100 sodium lauryl ether sulfate 8.0 sodium myreth sulfate 2.5 Laureth-2 2 panthenol 1.7 sodium chloride 1.65 disodium lauryl sulfosuccinate 1.5 sodium lauroyl glutamate 1.3 caffeine 1.1 PEG-120 Methylglucose dioleate 0.75 wheat protein hydrolysate 0.7 dihydroxyindole 0.49 allantoin 0.4 citric acid 0.38 sodium benzoate 0.36 propylene glycol 0.3 potassium sorbate 0.3 PEG-40 hydrogenated castor oil 0.18 cocoglucoside 0.18 glyceryl oleate 0.17 Polyquaternium-7 0.17 disodium EDTA 0.15 zinc PCA 0.1 niacinamide 0.1 tocopherol 0.06

Example Recipe 2

Example formulation 2 contains dihydroxyindole, caffeine and HC Blue 2 (2,2'-[[4-[(2-Hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol) as a direct dye. ingredient amount in wt.% Aqua [water] ad 100 sodium lauryl ether sulfate 11.5 sodium cocoamphoacetate 3 cocamidopropyl betaine 1.7 caffeine 1.1 panthenol 0.92 sodium chloride 1 phenoxyethanol 0.7 cocoglucoside 0.5 glyceryl oleate 0.5 phosphoric acid 0.4 PEG-120 Methylglucose dioleate 0.3 HC Blue 2 0.22 menthol 0.2 Polyquaternium-7 0.2 sodium hydroxide 0.15 dihydroxyindole 0.2 niacinamide 0.1 zinc PCA 0.1 dye / coloring agent 0.1 citric acid 0.06

Example Recipe 3

Example formulation 3 contains dihydroxyindole, caffeine and HC Blue 2 (2,2'-[[4-[(2-Hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol) as a direct dye. ingredient amount in wt.% Aqua [water] ad 100 sodium lauryl ether sulfate 9 sodium myreth sulfate 3 sodium cocoamphoacetate 1 Laureth-2 2 disodium lauryl sulfosuccinate 1 sodium lauroyl glutamate 2 caffeine 0.9 sodium chloride 1 wheat protein hydrolysate 0.7 phosphoric acid 0.3 sodium benzoate 0.5 potassium sorbate 0.2 HC Blue 2 1 allantoin 0.4 PEG-40 hydrogenated castor oil 0.4 Polyquaternium-7 0.2 disodium EDTA 0.2 dihydroxyindole 0.3 tocopherol 0.02

Example Recipe 4

Example formulation 4 contains dihydroxyindole, caffeine and HC Blue 2 (2,2'-[[4-[(2-Hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol) as a direct dye. ingredient amount in wt.% Aqua [water] ad 100 sodium lauryl ether sulfate 11 sodium myreth sulfate 2 Laureth-2 3 Cocoamidopropyl betaine 2 disodium lauryl sulfosuccinate 1 sodium lauroyl glutamate 1 panthenol 0.5 caffeine 1 sodium chloride 0.9 phenoxyethanol 0.5 wheat protein hydrolysate 0.5 cocoglucoside 0.3 glyceryl oleate 0.4 phosphoric acid 0.25 sodium benzoate 0.2 PEG-120 Methylglucose dioleate 0.1 potassium sorbate 0.5 HC Blue 2 0.8 allantoin 0.1 PEG-40 hydrogenated castor oil 0.2 menthol 0.2 sodium hydroxide 0.1 disodium EDTA 0.2 dihydroxyindole 0.1 citric acid 0.03 niacinamide 0.2 zinc PCA 0.2 dye / coloring agent 0.1

Example Recipe 5

Example formulation 5 contains dihydroxyindole and caffeine. ingredient amount in wt.% Aqua [water] ad 100 sodium lauryl ether sulfate 12 sodium cocoamphoacetate 2 Cocoamidopropyl betaine 2 panthenol 1 caffeine 1.1 sodium chloride 0.9 phenoxyethanol 0.8 cocoglucoside 0.4 glyceryl oleate 0.3 phosphoric acid 0.3 PEG-120 Methylglucose dioleate 0.2 menthol 0.2 Polyquaternium-7 0.1 sodium hydroxide 0.2 disodium EDTA 0.1 dihydroxyindole 0.2 citric acid 0.06 niacinamide 0.2 zinc PCA 0.2 dye / coloring agent 0.5

neutral formulation

The neutral formula contains neither caffeine nor DHI nor HC Blue 2 (2,2'-[[4-[(2-Hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol). ingredient amount in wt.% Aqua [water] ad 100 sodium lauryl ether sulfate 10 Laureth-2 1.9 disodium lauryl sulfosuccinate 1.5 sodium chloride 1.3 sodium lauroyl glutamate 1.3 panthenol 1.2 PEG-120 Methylglucose dioleate 0.5 wheat protein hydrolysate 0.49 citric acid 0.4 sodium citrate 0.35 propylene glycol 0.2 menthol 0.2 PEG-40 hydrogenated castor oil 0.2 potassium sorbate 0.19 Polyquaternium-7 0.17 disodium EDTA 0.11 sodium benzoate 0.1 zinc PCA 0.06 niacinamide 0.055 tocopherol 0.032 dye / coloring agent 0.0005

application examples

To evaluate the dyeing performance in terms of quality, intensity and duration, the following washing tests (wash-up and wash-out tests) were carried out.

Application Example 1

Kerling strands were subjected to a wash-up test with a shampoo containing 5,6-DHI, caffeine and HC Blue 2 (2,2'-[[4-[(2-hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol) (example formulation 2) or with a shampoo containing HC Blue 2 (2,2'-[[4-[(2-hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol) and caffeine (comparison formulation) to investigate the dyeing performance in terms of quality and intensity.

• - Strähnen 30 s mit lauwarmem Wasser befeuchten, überschüssiges Wasser zwischen zwei Fingern ausstreichen
• - Pro 5 Strähnen insgesamt 5 g Shampoo 1 min einmassieren
• - Insgesamt 5 Minuten einwirken lassen
• - 1 Minute mit lauwarmem Wasser ausspülen, anschließend in Küchenrolle ausdrücken
• - Kämmen, einzeln ausgebreitet an der Luft trocknen
• - Am nächsten Tag Strähnen mit dem Konica (Konica-Minolta Spectrophotometer CM600d, Messgeometrie d/8°, Specular Component Excluded (SCE), Normlichtart D65, Gesichtsfeld 10°) einlesen (alle 5 Waschgänge Beispielsträhnen fotografieren); dann Waschzyklus wiederholen

Washing protocol:

• - Moisten strands with lukewarm water for 30 seconds, then rub excess water between two fingers
• - Massage 5 g of shampoo into 5 strands for 1 minute
• - Leave to work for a total of 5 minutes
• - Rinse with lukewarm water for 1 minute, then squeeze out with kitchen roll
• - Comb, spread out individually and let air dry
• - The next day, scan the strands with the Konica (Konica-Minolta Spectrophotometer CM600d, measuring geometry d/8°, Specular Component Excluded (SCE), standard illuminant D65, field of view 10°) (take photos of sample strands every 5 washes); then repeat the wash cycle

• Kerling weiß selektiert, Klebetresse 2 cm breit, 12 cm lang, 3 g/St., Ch. 1719

Hair strands used:

• Kerling white selected, adhesive braid 2 cm wide, 12 cm long, 3 g/pc., Ch. 1719

• Beispielrezeptur 2 Strähnen D1-D5
• Vergleichsrezeptur Strähnen E1-E5

Shampoos used:

• Example recipe 2 strands D1-D5
• comparison recipe strands E1-E5

5 strands were used per product and 28 washes were carried out.

1 shows a comparison of strands D1/D2 treated with example recipe 2 with strands E1/E2 treated with the comparison recipe.

The comparison of the color preview for the two shampoos used is in 2 shown. The 3 and 4 show the change in color depth as absolute values dL* ( 3 ) or as total color change dE* ( 4 ). The figures show the gradual build-up of the colour effect with repeated application as well as the improved colouring result compared to the comparison formulation.

Application Example 2

Kerling strands were subjected to a wash-on and wash-out test with a shampoo containing 5,6-DHI, caffeine and HC Blue 2 (2,2'-[[4-[(2-hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol) (example formulation 2) or with a shampoo containing HC Blue 2 (2,2'-[[4-[(2-hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol) and caffeine (comparison formulation) to investigate the dyeing performance in terms of quality, intensity and duration.

• - Strähnen 30 s mit lauwarmem Wasser befeuchten, überschüssiges Wasser zwischen zwei Fingern ausstreichen
• - Pro 5 Strähnen insgesamt 5 g Shampoo 1 min einmassieren
• - Insgesamt 5 Minuten einwirken lassen
• - 1 Minute mit lauwarmem Wasser ausspülen, anschließend in Küchenrolle ausdrücken
• - Kämmen, einzeln ausgebreitet an der Luft trocknen
• - Am nächsten Tag Strähnen mit dem Konica (Konica-Minolta Spectrophotometer CM600d, Messgeometrie d/8°, Specular Component Excluded (SCE), Normlichtart D65, Gesichtsfeld 10°) einlesen, fotografieren; dann Waschzyklus wiederholen

Washing protocol:

• - Moisten strands with lukewarm water for 30 seconds, then rub excess water between two fingers
• - Massage 5 g of shampoo into 5 strands for 1 minute
• - Leave to work for a total of 5 minutes
• - Rinse with lukewarm water for 1 minute, then squeeze out with kitchen roll
• - Comb, spread out individually and let air dry
• - The next day, scan the strands with the Konica (Konica-Minolta Spectrophotometer CM600d, measuring geometry d/8°, Specular Component Excluded (SCE), standard illuminant D65, field of view 10°), photograph them; then repeat the washing cycle

Hair strands used:

Kerling white selected, adhesive braid 2cm wide, 12cm long

Coloring shampoos used:

• Example recipe 2 strands B1-B15
• comparison recipe strands C1-C15
• The neutral formula was used for washing out.
• For each product, 15 strands were treated in portions of 5 each.

• - jeweils 5 Waschgänge mit Färbeshampoo zum Aufwaschen, gefolgt von 14 Waschgängen mit Neutralrezeptur (5)
• - jeweils 10 Waschgänge mit Färbeshampoo zum Aufwaschen, gefolgt von 15 Waschgängen mit Neutralrezeptur (6)
• - jeweils 15 Waschgänge mit Färbeshampoo zum Aufwaschen, gefolgt von 15 Waschgängen mit Neutralrezeptur (7).

The color change was monitored over the following wash-up and wash-out cycles:

• - 5 washes each with coloring shampoo to wash off, followed by 14 washes with neutral formula ( 5 )
• - 10 washes each with coloring shampoo to wash off, followed by 15 washes with neutral formula ( 6 )
• - 15 washes each with coloring shampoo to wash off, followed by 15 washes with neutral formula ( 7 ).

The 5-7 show the change in color depth when washing with color shampoo or washing out with a neutral formula according to the protocols given above. 8 shows the comparison of the color change for the two shampoos used on a single strand of hair after 15 wash-ups, followed by 15 wash-outs, measured with the Konica measuring device (Konica-Minolta Spectrophotometer CM600d, measuring geometry d/8°, Specular Component Excluded (SCE), standard illuminant D65, field of view 10°). The figures show the gradual build-up of the color effect with repeated use and the improved coloring result compared to the comparison formula. After discontinuing treatment with the shampoo according to the invention, the color effect also lasts longer than when using the comparison formula.

Application Example 3

White Virgin strands (Imhair) were subjected to a wash-up test with a shampoo containing 5,6-DHI and caffeine (example recipe 1) or with a shampoo containing 5,6-DHI, caffeine and HC Blue 2 (2,2'-[[4-[(2-hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol) (example recipe 2) or with a shampoo containing HC Blue 2 (2,2'-[[4-[(2-hydroxyethyl)amino]-3-nitrophenyl]imino]bisethanol) and caffeine (comparison recipe) in order to investigate the dyeing performance in terms of quality and intensity.

• - Strähnen 30 s mit lauwarmem Wasser befeuchten, überschüssiges Wasser zwischen zwei Fingern ausstreichen
• - Pro 3 Strähnen insgesamt 2 g Shampoo 30 s einmassieren
• - Insgesamt 5 Minuten einwirken lassen
• - 1 Minute mit lauwarmem Wasser ausspülen
• - Kämmen, an der Luft trocknen
• - Am nächsten Tag Strähnen mit dem Konica einlesen, fotografieren; dann Waschzyklus wiederholen

Washing protocol:

• - Moisten strands with lukewarm water for 30 seconds, then rub excess water between two fingers
• - Massage 2 g of shampoo into 3 strands for 30 seconds
• - Leave to work for a total of 5 minutes
• - Rinse with lukewarm water for 1 minute
• - Comb, air dry
• - The next day, scan strands with the Konica, photograph them, then repeat the washing cycle

• White Virgin (Fa. Imhair)

Hair strands used:

• White Virgin (Fa. Imhair)

Shampoos used:

• Example recipe 1 strands 1-3
• Example recipe 2 strands 4-6
• Comparison recipe strands 7-9

3 strands were used per product and 15 washes were carried out each time.

The comparison of the color preview for the shampoos used is for a single strand of hair in 9 shown. The 10 and 11 show the change in color depth as absolute values dL* ( 10 ) or as total color change dE* ( 11 ). The figures show the gradual build-up of the colour effect with repeated application as well as the improved colouring result compared to the comparison formulation.

Application Example 4

To examine the dyed shade over time, the Kerling white and Imhair bleached strands were dyed for 15 minutes with 10 g of sample formula 2, rinsed for 1 minute and air dried for 1.5 hours (any residual moisture was then blow-dried). Measurements were taken on the day of treatment after 15 minutes of exposure time (initial shade) and after 1, 2, 3, 8, 9, 10, 11, 14 and 15 days. strand Kerling, white starting shade L*(D65) a*(D65) b*(D65) dL*(D65) da*(E65) db*(D65) dE*ab(D65) 76.58 2.15 21 - - - - (after 15 minutes of exposure time) 62.32 1.58 5.02 -14.27 -0.57 -15.98 21.43 read after 1d 62.11 2.05 5.23 -14.48 -0.1 -15.77 21.41 read after 2d 63.06 2.22 4.59 -13.52 0.07 -16.42 21.27 read in 3d 63.02 2.44 5.09 -13.56 0.29 -15.91 20.91 read after 8 days 62.95 2.53 5.57 -13.64 0.38 -15.44 20.6 read after 9d 62.86 2.35 5.5 -13.73 0.21 -15.51 20.71 read after 10d 62.63 2.57 5.87 -13.95 0.42 -15.13 20.58 read after 11d 62.59 2.61 5.47 -14 0.46 -15.53 20.91 read after 14 days 63.16 3.1 6.34 -13.43 0.95 -14.67 19.91 read after 15 days 63.59 3.16 6.26 -12.99 1.02 -14.74 19.68 L*(D65) a*(D65) b*(D65) dL*(D65) da*(E65) db*(D65) dE*ab(D65) strand Imhair, bleached 76.9 3.5 24.61 - - - - Initial shade (after 15 minutes exposure time) 51.51 1.01 2.73 -25.38 -2.49 -21.88 33.61 read after 1d 51.71 1.6 2.8 -25.19 -1.9 -21.82 33.38 read after 2d 52.11 1.61 2.79 -24.78 -1.89 -21.82 33.08 read in 3d 51.57 2.06 3.23 -25.33 -1.43 -21.38 33.17 read after 8 days 52.21 2.22 3.78 -24.68 -1.28 -20.84 32.33 read after 9d 51.98 2.13 3.84 -24.92 -1.36 -20.78 32.47 read after 10d 52 2.29 4.16 -24.9 -1.21 -20.46 32.24 read after 11d 52.11 2.29 4.16 -24.79 -1.21 -20.46 32.16 read after 14 days 52.69 2.65 4.86 -24.21 -0.84 -19.75 31.25 read after 15 days 53.23 2.68 5.01 -23.67 -0.82 -19.61 30.74

The measured values demonstrate a - also visually perceptible - shift in nuance from the original graphite to a more natural, brownish color.

QUOTES INCLUDED IN THE DESCRIPTION

This list of documents listed by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions.

Cited patent literature

• EP 0530229 B1 [0007]
• WO 9966890 [0009]
• DE 102018127182 A1 [0010]
• DE 102007038484 A1 [0011]
• WO 2005/007615 A1 [0012]

Cited non-patent literature

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Claims (9)

Cosmetic formulation containing a dye precursor selected from the group consisting of 5,6-dihydroxyindole derivatives of the formula (I)

where, in each case independently of one another, R ¹ is hydrogen, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ hydroxyalkyl group, R ² is hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically acceptable cation, R ³ is hydrogen or a C ₁ -C ₄ alkyl group, R ⁴ is hydrogen, a C ₁ -C ₄ alkyl group, an amino group or a group -CO-R ⁶ , in which R ⁶ is a C ₁ -C ₄ alkyl group, and R ⁵ is one of the groups mentioned under R ⁴ , or a physiologically acceptable salt of these compounds with an organic or inorganic acid; and 5,6-dihydroxyindoline derivatives of the formula (II),

where, in each case independently of one another, R ¹ is hydrogen, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ hydroxyalkyl group, R ² is hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically acceptable cation, R ³ is hydrogen or a C ₁ -C ₄ alkyl group, R ⁴ is hydrogen, a C ₁ -C ₄ alkyl group, an amino group or a -CO-R ⁶ group, in which R ⁶ is a C ₁ -C ₄ alkyl group, and R ⁵ is one of the groups mentioned under R ⁴ , or a physiologically acceptable salt of these compounds with an organic or inorganic acid; and caffeine as a bioactive substance; and at least HC Blue 2 as a direct dye. Cosmetic formulation according to claim 1 , where the dye precursor is a 5,6-dihydroxyindole derivative. Cosmetic formulation according to claim 2 , wherein the compound of formula (I) is selected from 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole and their physiologically acceptable salts. Cosmetic formulation according to claim 1 , where the dye precursor is a 5,6-dihydroxyindoline derivative. Cosmetic formulation according to claim 4 , wherein the compound of formula (II) is selected from 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline and their physiologically acceptable salts. Cosmetic formulation according to one of the Claims 1 - 5 , wherein further direct dyes are selected from the group consisting of 2-amino-6-chloro-4-nitrophenol, 1,4-bis-(β-hydroxyethyl)-amino-2-nitrobenzene, Basic Yellow 57, Basic Red 76, Basic Brown 16, Basic Brown17, Basic Blue 99, HC Blue 12, HC Blue 16 and Acid Violet 43. Use of the cosmetic formulation according to one of the preceding claims for the repigmentation of keratin fibers, in particular human hair. Use after claim 7 for the repigmentation of human hair, whereby the formulation is distributed in wet or dry hair and rinsed out after a residence time of between 1 and 30 minutes. Use after claim 7 or claim 8 for the repigmentation of human hair, whereby the hair is slowly and gently colored permanently and at the same time the keratinocytes in the hair roots are stimulated so that they produce more natural pigment again.