WO2025082670A1 - Product comprising special surfactant system for preliminary cleaning keratin fibers prior to dyeing - Google Patents

Abstract

The invention relates to a cosmetic product for cleaning keratin fibers, in particular human hair, containing, in a cosmetic carrier, a surfactant system, the surfactant system comprising, relative to the total weight of the surfactant system, (a) 30 to 75 wt.% of one or more anionic sulfate surfactants and/or sulfonate surfactants, (b) 10 to 35 wt.% of one or more surfactants from the group of alkoxylated fatty alcohols, amphoteric surfactants and zwitterionic surfactants, and (c) 5 to 45 wt.% of one or more nonionic sugar surfactants, the amounts of (a), (b) and (c) adding up to a maximum of 100 wt.%.

Description

Agent with a special surfactant system for pre-cleaning keratin fibers before coloring

The present application relates to a cosmetic agent for cleaning keratinic fibers, in particular human hair, comprising a surfactant system in a cosmetic carrier, wherein the surfactant system comprises one or more anionic sulfate and/or sulfonate surfactants, one or more surfactants from the group consisting of alkoxylated fatty alcohols, amphoteric surfactants and zwitterionic surfactants (b) and one or more non-ionic sugar surfactants (c) in each case in specific quantity ranges.

A second subject matter is a method in which the cleaning agent described above is used for pre-cleaning the keratin fibers before a subsequent dyeing step.

A third object of the invention is the use of the cleaning agent for improving the washfastness of keratin fibers that have been dyed with a colorant containing at least one pigment and/or a direct dye.

Altering the shape and color of keratinous material, especially human hair, represents an important area of modern cosmetics. Depending on the coloring requirements, hair coloring specialists are familiar with various coloring systems. For permanent, intense colorings with good fastness properties and good gray coverage, oxidation dyes are typically used. Such dyes contain oxidation dye precursors, so-called developer components, and coupler components, which, under the influence of oxidizing agents such as hydrogen peroxide, form the actual dyes. Oxidation dyes are characterized by very long-lasting coloring results.

When using direct dyes, the fully formed pigments diffuse from the dyeing agent into the hair fiber. Compared to oxidative hair coloring, the colors obtained with direct dyes are less durable and wash out more quickly. Colorations with direct dyes typically remain on the hair for between 5 and 20 washes.

The use of color pigments is known for temporary color changes on hair and/or skin. Color pigments are generally understood to be insoluble, color-imparting substances. These are present undissolved in the form of small particles in the coloring formulation. and are deposited only externally on the hair fibers and/or the skin's surface. Therefore, they can usually be removed without residue after a few washes with surfactant-containing cleansers. Various products of this type are available on the market under the name hair mascara.

Coloring with pigments offers several significant advantages. Because the pigments only attach to the keratin fibers, especially the hair fibers, from the outside, unwanted coloring can be removed quickly and easily without leaving any residue, thus offering the user the opportunity to return to their original hair color immediately and without much effort. This coloring process is therefore particularly attractive for consumers who do not want to recolor their hair regularly.

Despite these many advantages, the pigment-based coloring system still has some disadvantages, which are due to the pigments' limited penetration into the keratin material. Since the pigments do not diffuse into the keratin fibers, but rather merely deposit themselves on the outer surface of the fiber in the form of a shell or film, the washfastness of the colorations produced with this system still requires improvement. Various studies have attempted to bond the pigment(s) more permanently to the hair surface using film-forming materials, usually polymers.

The coloring processes of EP 2168633 B1 utilize organosilicon compounds from the silane group, the molecular structure of which includes at least one hydroxyl group and/or hydrolyzable group. Due to the presence of the hydroxyl groups or hydrolyzable groups, the silanes are reactive substances that hydrolyze, oligomerize, or polymerize in the presence of water. The oligomerization or polymerization of the silanes, initiated by the presence of water, ultimately leads, when applied to the keratin material, to the formation of a film that fixes the color-imparting compounds, thus producing long-lasting colorations.

The use of other polymers to create a film on the surface of the hair is also known from the prior art. For example, in DE 19847883 A1, chitosans are used in combination with pigments for coloring to simultaneously color, condition, and strengthen hair.

To further improve the dyeings produced with silane/pigment or polymer/pigment, further work was carried out, including investigating the effect of various pretreatment agents. For example, WO 2021/121721 A1 attempted to improve the washfastness of dyes based on direct dyes or pigments and silanes. To improve colorations by using a pretreatment agent containing at least one anionic surfactant.

WO 2021/121721 A1 illustrates, by way of example, a pretreatment agent containing sodium lauryl sulfate and/or sodium laureth sulfate as anionic sulfate surfactants. Although initial good results have already been obtained in WO 2021/121721 A1, the washfastness of the dyeings achievable in this way still requires further improvement.

Based on the work conducted in WO 2021/121721 A1, the theory was developed that while the sulfate surfactants sodium lauryl sulfate and/or sodium laureth sulfate already provide a fairly good pre-cleansing effect on the hair, a pretreatment applied prior to coloring should free the surface even more completely and comprehensively of all adhering contaminants. In particular, for a durable film-based coloring, it also appears necessary to remove the covalently bound 18-methyleicosanoic acid (18-MEA) on the hair surface as completely as possible. 18-methyleicosanoic acid (18-MEA) is a branched-chain fatty acid. It is covalently bound, possibly via a thioester or ester bond, to the cuticle surface of the hair fibers. 18-MEA is known to form a hydrophobic surface and, as a boundary lubricant, reduce frictional resistance between hair fibers.

If 18-MEA is removed from the hair surface, the surface becomes more hydrophilic and friction increases. In the literature, the loss of 18-MEA is described as one of the reasons for the increase in friction at the cuticle surface. This can influence the sensory perception of the hair, so that the user or test subject feels that the hair is dry and difficult to comb or run their fingers through. Due to these negative properties, the loss of 18-MEA during daily hair cleansing with shampoo is undesirable. However, if a film-based coloring is performed after cleansing, the roughening of the hair surface initiated by the loss of 18-MEA appears to lead to better adhesion of the film to the surface.

It is therefore assumed that a sulfate surfactant alone does not sufficiently remove 18-methyleicosanoic acid (18-MEA) from the hair fiber, and that a surfactant combination specifically tailored to the surface of the hair could clean the hair more comprehensively and completely, so that a film formed on the hair fiber can wrap around the surface more evenly and without gaps and adhere better to it.

The objective of this application was therefore to find a pretreatment agent that can comprehensively clean keratin fibers prior to coloring and prepare them for subsequent coloring. The keratin fibers or hair be damaged as little as possible. Cleaning involves removing all deposits from the fiber, and in particular the covalently bound 18-methyleicosanoic acid (18-MEA). Dyeing involves surface dyeing, which immobilizes the color-providing compounds via a film on the surface of the keratin fiber. The application of the pre-cleaning agent should enable the creation of a closed and resistant film on the surface, resulting in intensive dyeing with improved washfastness and improved rubbing fastness.

Surprisingly, it has now been found that the color intensity and wash fastness of colored keratinic fibers could be massively improved if the keratinic fibers are treated in a pretreatment step before coloring with a cosmetic cleaning agent that contains a specially tailored surfactant combination of 30 - 75 wt.% of one or more anionic sulfate and/or sulfonate surfactants (a), 10 - 35 wt.% of one or more surfactants from the group of alkoxylated fatty alcohols, amphoteric surfactants and zwitterionic surfactants (b) and 5 - 45 wt.% of one or more non-ionic sugar surfactants (c).

A first subject of the present invention is a cosmetic agent for cleaning keratinic fibers, in particular human hair, containing a surfactant system in a cosmetic carrier, wherein the surfactant system - based on the total weight of the surfactant system - comprises

(a) 30 to 75 wt.% of one or more anionic sulfate and/or sulfonate surfactants,

(b) 10 to 35 wt.% of one or more surfactants selected from the group consisting of alkoxylated fatty alcohols, amphoteric surfactants and zwitterionic surfactants, and

(c) 5 to 45% by weight of one or more non-ionic sugar surfactants, the amounts of (a), (b) and (c) adding up to a maximum of 100% by weight.

The work leading to this invention has shown that particularly intensive and wash-fast color results could be achieved on hair if the hair was first treated with the special cleaning agent and then treated with a colorant based on pigments or direct dyes and a film-forming substance.

In this way, the aforementioned coloring compounds can be permanently fixed to the keratin material, so that extremely washfast colorations with good resistance to abrasion and/or shampooing could be obtained.

Keratin fibers

Keratin fibers include hair, wool, and fur. Human hair is particularly preferred as keratin fibers.

Cleaning products The cleaning agent used for pre-treatment is intended to comprehensively free the keratin fibers from all components localized on the surface of the keratin fiber before coloring and for this purpose contains a surfactant system comprising the special combination of surfactants (a), (b) and (c) in certain quantity ranges.

The cleaning agent contains the surfactant system in a cosmetic carrier. In principle, various carriers are conceivable as cosmetic carriers for the cleaning agent; the cosmetic carrier is particularly preferably an aqueous, alcoholic, or aqueous-alcoholic carrier.

The carrier can also be a cream, emulsion, paste, or even a surfactant-containing foaming solution, such as a shampoo, foam aerosol, foam formulation, or other preparation suitable for application to the hair. Water is the most common solvent in cosmetic products, so in principle, water can also be used as a cosmetic carrier as the main ingredient.

Furthermore, the cosmetic carrier can also comprise one or more solvents from the group consisting of glycerin, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, ethanol, isopropanol, dipropylene glycol, diethylene glycol monoethyl ether, phenoxyethanol, benzyl alcohol, poly-Ci-Ce-alkylene glycols, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate and glycerol carbonate.

Glycerin is alternatively known as 1,2,3-propanetriol and has the CAS number 56-81-5. Phenoxyethanol has the CAS number 122-99-6. 1,2-Propylene glycol is alternatively known as 1,2-propanediol and has the CAS numbers 57-55-6 [(RS)-1,2-dihydroxypropane], 4254-14-2 [(R)-1,2-dihydroxypropane] and 4254-153 [(S)-1,2-dihydroxypropane]. 1,3-Propylene glycol is alternatively known as 1,3-dihydroxypropane or 1,3-propanediol and has the CAS number 504-63-2. 1,2-Butylene glycol can also be called 1,2-butanediol and has the CAS numbers 584-03-2 (racemate), 40348-66-1 ((R)-enantiomer) and 73522-17-5 ((S)-enantiomer).

Dipropylene glycols (or oxydipropanols) form a group of substances derived from glycol ethers. The dipropylene glycol group includes 2,2'-oxydi-1-propanol (CAS No. 108-61-), 2,1,1'-oxydi-2-propanol (CAS No. 110-98-5), and 2-(2-hydroxypropoxy)-1-propanol (CAS No. 106-62-7). The mixture of these three isomers has CAS No. 25265-71-8.

Ethanol has the CAS No. 64-17-5. Isopropanol is also known as 2-propanol and has the CAS No. 67-63-0. Ethylene glycol is also known as 1,2-ethanediol and has the CAS No. 107-21-1. Diethylene glycol monoethyl ether can alternatively be referred to as ethoxydiglycol or ethyldiglycol or 2-(2-ethoxyethoxy)ethanol) and has the CAS No. 111-90-0.

Benzyl alcohol can also be referred to as phenylmethanol and has the CAS No. 100-51-6.

Dimethyl carbonate or dimethyl carbonate has the CAS number 616-38-6. Diethyl carbonate or diethyl carbonate has the CAS number 105-58-8.

Propylene carbonate or alternatively 4-methyl-1,3-dioxolan-2-one is a clear, colorless and easily mobile liquid with the CAS numbers 108-32-7 [(RS)-4-methyl-1,3-dioxolan-2-one], 51260-39-0 [(S)-4-methyl-1,3-dioxolan-2-one] and 16606-55-6 [(R)-4-methyl-1,3-dioxolan-2-one],

Glyceryl carbonate or alternatively glycerol-1,2-carbonate is formally the cyclic ester of carbonic acid with glycerol and has the CAS number 931-40-8.

The water and/or the solvents described above are preferably contained in the cleaning agent in certain quantities.

In a preferred embodiment, a cleaning agent according to the invention is characterized in that it contains - based on the total weight of the cleaning agent - 5.0 to 98.0 wt.%, preferably 20.0 to 95.0 wt.%, more preferably 40.0 to 95.0 wt.% and most preferably 60.0 to 95.0 wt.% of water.

In a further preferred embodiment, a cleaning agent according to the invention is characterized in that it contains - based on the total weight of the cleaning agent - one or more solvents from the group consisting of glycerol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, ethanol, isopropanol, dipropylene glycol, diethylene glycol monoethyl ether, phenoxyethanol, benzyl alcohol, poly-Ci-Ce-alkylene glycols, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate and glycerol carbonate in a total amount of 0.5 to 60.0 wt.%, preferably 1.0 to 40.0 wt.%, more preferably 1.5 to 20.0 wt.% and very particularly preferably 2.0 to 15.0 wt.%.

In a particularly preferred embodiment, the cleaning agent according to the invention is characterized in that the cosmetic carrier is an aqueous or an aqueous-alcoholic carrier and the agent contains - based on the total weight of the agent - 0.1 to 30 wt.%, preferably 0.5 to 25 wt.% and particularly preferably 1.0 to 20 wt.% of the surfactant system. A surfactant system refers to all of the surfactants contained in the cleaning agent. The amount of surfactant system in percent by weight is based on the total weight of the cleaning agent, which means that, for example, 100 g of an agent containing 10% by weight of the surfactant system contains 10% by weight of a mixture of surfactants. If the cleaning agent contains only surfactants (a), (b), and (c) as surfactants and no other surfactants, then the combination of (a), (b), and (c) makes up 10% of the weight of the cleaning agent. If the cleaning agent contains an optional additional surfactant (d) or two additional optional surfactants (d) and (e), then with a surfactant system content of 10% by weight, the agent contains the mixture of surfactants (a) to (d) or (a) to (e) in a weight proportion of 10 percent, based on the total weight of the agent. anionic sulfate and/or sulfonate surfactants (a) in the surfactant system

As the first component (a) essential to the invention, the surfactant system according to the invention contains - based on the total weight of the surfactant system - 30 to 75 wt.% of one or more anionic sulfate and/or sulfonate surfactants.

Anionic sulfate or sulfonate surfactants are characterized by the presence of at least one sulfate or sulfonate group, which, depending on the pH prevailing in the cleaning agent, can be present in the form of their free acid or in the form of their physiologically acceptable salt. Examples of physiologically acceptable salts of sulfate groups include the sodium salts, potassium salts, and ammonium salts of sulfates. Examples of physiologically acceptable salts of sulfonate groups include the sodium salts, potassium salts, and ammonium salts of sulfonates.

The molecular structure of the anionic sulfate or sulfonate surfactants does not contain any cationic or cationizable groups, i.e. the structure of these surfactants does not include either (substituted) amino or (substituted) ammonium groups.

In the tests carried out, particularly good pre-cleaning was observed when the surfactant system contained in the cleaning agent contained at least one anionic sulfate and/or sulfonate surfactant (a) from the group consisting of

- Dialkyl sulfosuccinates whose two alkyl groups are selected from identical or different, branched or unbranched C2 to C12 alkyl groups,

- Alkyl sulfates and alkyl polyglycol ether sulfates of the formula R9-O-(CH2-CH2O) _n -SO3X, in which R9 preferably represents a straight-chain or branched, saturated or mono- or polyunsaturated alkyl or alkenyl radical having 8 to 22 carbon atoms, n represents 0 or 1 to 12, and X represents an alkali or alkaline earth metal ion or profaned triethanolamine or the ammonium ion,

- straight-chain or branched, saturated or mono- or polyunsaturated alkylsulfonates with 8 to 22 C atoms, - linear alpha-olefin sulfonates with 8 to 22 C atoms,

- Acyl isethionates whose acyl group is selected from a branched or unbranched Cs to C22 alkyl group,

- N-acyl taurates, whose acyl group is selected from a branched or unbranched Ca to C22 alkyl group, and/or the salts of the aforementioned compounds.

In one embodiment, therefore, a cosmetic agent for cleaning keratin fibers, in particular human hair, containing a surfactant system in a cosmetic carrier is particularly preferred, wherein the surfactant system - based on the total weight of the surfactant system - comprises

(a) 30 to 75% by weight of one or more anionic sulfate and/or sulfonate surfactants selected from the group consisting of

- Dialkyl sulfosuccinates whose two alkyl groups are selected from identical or different, branched or unbranched C2 to C12 alkyl groups,

- Alkyl sulfates and alkyl polyglycol ether sulfates of the formula R9-O-(CH2-CH2O) _n -SOaX, in which R9 preferably represents a straight-chain or branched, saturated or mono- or polyunsaturated alkyl or alkenyl radical having 8 to 22 carbon atoms, n represents 0 or 1 to 12, and X represents an alkali or alkaline earth metal ion or profaned triethanolamine or the ammonium ion,

- straight-chain or branched, saturated or mono- or polyunsaturated alkylsulfonates with 8 to 22 C atoms,

- linear alpha-olefin sulfonates with 8 to 22 C atoms,

- Acyl isethionates whose acyl group is selected from a branched or unbranched Cs to C22 alkyl group,

- N-acyl taurates, whose acyl group is selected from a branched or unbranched Cs to C22 alkyl group, and/or the salts of the aforementioned compounds,

(b) 10 to 35 wt.% of one or more surfactants selected from the group consisting of alkoxylated fatty alcohols, amphoteric surfactants and zwitterionic surfactants, and

(c) 5 to 45% by weight of one or more non-ionic sugar surfactants, the amounts of (a), (b) and (c) adding up to a maximum of 100% by weight.

In a particularly preferred embodiment, the cleaning agent according to the invention is characterized in that it contains a surfactant system which, based on the total weight of the surfactant system, comprises

(a) 30 to 70 wt.% of one or more anionic sulfate or sulfonate surfactants selected from the group consisting of - Dialkyl sulfosuccinates whose two alkyl groups are selected from identical or different, branched or unbranched C2 to C12 alkyl groups,

- Alkyl sulfates and alkyl polyglycol ether sulfates of the formula Rg-O-(CH2-CH2O) _n -SO3X, in which R9 preferably represents a straight-chain or branched, saturated or mono- or polyunsaturated alkyl or alkenyl radical having 8 to 22 carbon atoms, n represents 0 or 1 to 12, and X represents an alkali or alkaline earth metal ion or profaned triethanolamine or the ammonium ion,

- straight-chain or branched, saturated or mono- or polyunsaturated alkylsulfonates with 8 to 22 C atoms,

- linear alpha-olefin sulfonates with 8 to 22 C atoms,

- Acyl isethionates whose acyl group is selected from a branched or unbranched Ca to C22 alkyl group,

- N-acyl taurates, whose acyl group is selected from a branched or unbranched Ca to C22 alkyl group, and/or the salts of the aforementioned compounds.

A suitable anionic sulfate surfactant is sodium laureth sulfate, which is a mixture of ethoxylated, sulfated C12-C14 fatty alcohols whose sulfate groups are present in the form of the sodium salt. Sodium laureth sulfate has the CAS number 68891-38-3, and the raw material is commercially available, for example, under the trade name Texapon N 70.

Another suitable anionic sulfate surfactant is sodium lauryl sulfate, also known as sodium dodecyl sulfate, which is obtained by sulfation of dodecanol. In sodium lauryl sulfate, the sulfate group is present in the form of its sodium salt; the substance has the CAS number 151-21-3.

Particularly good results in pre-cleaning were obtained with anionic sulfonate surfactants, especially with sulfosuccinate surfactants.

In a further particularly preferred embodiment, therefore, a cosmetic agent for cleaning keratinic fibers, in particular human hair, containing a surfactant system in a cosmetic carrier is particularly preferred, wherein the surfactant system - based on the total weight of the surfactant system - comprises

(a) 30 to 75 wt.% of one or more anionic sulfonate surfactants,

(b) 10 to 35 wt.% of one or more surfactants selected from the group consisting of alkoxylated fatty alcohols, amphoteric surfactants and zwitterionic surfactants, and

(c) 5 to 45% by weight of one or more non-ionic sugar surfactants, the amounts of (a), (b) and (c) adding up to a maximum of 100% by weight. In an explicitly particularly preferred embodiment, the cleaning agent according to the invention is therefore characterized in that it contains a surfactant system which - based on the total weight of the surfactant system - comprises

(a) 30 to 70 wt.% of one or more anionic sulfonate surfactants selected from the group of dialkyl sulfosuccinates whose two alkyl groups are selected from the same or different, branched or unbranched C2 to C12 alkyl groups, and/or the salts of these compounds,

(b) 10 to 35 wt.% of one or more surfactants selected from the group consisting of alkoxylated fatty alcohols, amphoteric surfactants and zwitterionic surfactants, and

(c) 5 to 45% by weight of one or more non-ionic sugar surfactants, the amounts of (a), (b) and (c) adding up to a maximum of 100% by weight.

Particularly suitable examples are ethoxylated monoalkyl sulfosuccinates, diisodecyl sulfosuccinates, sodium dioctyl sulfosuccinates, disodium lauryl sulfosuccinates, and butane diacid sulfoalkyl esters. Diethylhexyl sulfosuccinate and its salts are the most suitable.

Sodium ethylhexyl sulfosuccinate, also known as sulfosuccinic acid bis(2-ethylhexyl) ester, sodium salt, sodium bis(2-ethylhexyl) sulfocuccinate, or docusate sodium salt, is commercially available. This surfactant is also known by the abbreviation AOT, has the CAS number 577-11-7, and is a compound of the formula (AOT).

The anionic sulfonate surfactant, in particular the dialkyl sulfosuccinate(s) and/or salts thereof, particularly preferably 1,4-bis(2-ethylhexyl) sulfosuccinate sodium salt, are - based on the total weight of the surfactant system - preferably contained in the surfactant system in an amount of 30 to 70 wt.%, preferably 35 to 68 wt.%, more preferably 40 to 66 wt.% and very particularly preferably 50 to 65 wt.%.

In a further particularly preferred embodiment, the cleaning agent according to the invention is characterized in that it contains a surfactant system which, based on the total weight of the surfactant system, comprises (a) 30 to 70% by weight, preferably 35 to 68% by weight, more preferably 40 to 66% by weight and most preferably 50 to 65% by weight of one or more dialkyl sulfosuccinates and/or salts thereof, most preferably 1,4-bis(2-ethylhexyl) sulfosuccinate in the form of its sodium salt.

In a further particularly preferred embodiment, therefore, a cosmetic agent for cleaning keratinic fibers, in particular human hair, containing a surfactant system in a cosmetic carrier is particularly preferred, wherein the surfactant system - based on the total weight of the surfactant system - comprises

(a) 30 to 70 wt.%, preferably 35 to 68 wt.%, more preferably 40 to 66 wt.% and most preferably 50 to 65 wt.% of one or more dialkyl sulfosuccinates and/or salts thereof, particularly preferably 1,4-bis(2-ethylhexyl) sulfosuccinate in the form of its sodium salt,

(b) 10 to 35 wt.% of one or more surfactants selected from the group consisting of alkoxylated fatty alcohols, amphoteric surfactants and zwitterionic surfactants, and

(c) 5 to 45% by weight of one or more non-ionic sugar surfactants, the amounts of (a), (b) and (c) adding up to a maximum of 100% by weight.

Surfactants (b) from the group of alkoxylated fatty alcohols, amphoteric surfactants and zwitterionic surfactants

As a second essential component (b), the surfactant system contained in the cleaning agent according to the invention comprises - based on the total weight of the surfactant system - 10 to 35 wt. % of one or more surfactants from the group of alkoxylated fatty alcohols, preferably from the group of ethoxylated fatty alcohols, particularly preferably from the group of ethoxylated Ca-C22 alcohols with 1 to 15 EO, in particular Ci2-C18 alcohols with 7 EO.

In interaction with the surfactants or surfactant groups (a) and (c), the surfactants of group (b) enable a particularly effective and comprehensive removal of the components that are adhesively and covalently bound to the surface of the keratin fibers.

Alkoxylated fatty alcohols are alkylene oxide addition products with saturated or unsaturated linear fatty alcohols, each containing 1 to 120 moles of ethylene oxide (EO) per mole of fatty alcohol. Particularly suitable fatty alcohols are C8-C22 alcohols with 1 to 15 EO, especially C12-C18 alcohols with 6 to 9 EO (calculated in moles of EO per mole of fatty alcohol).

The abbreviation EO stands for ethylene oxide.

Fatty alcohols that can be subjected to alkylation or, in particular, ethoxylation are, for example, 1-octanol, 1-decanol, 1-lauryl alcohol, 1-myristyl alcohol, 1-cetyl alcohol and/or 1-steryl alcohol or even 1-stearyl alcohol. The fatty alcohols can each be a single substance. However, it is generally preferred to produce these Substances are derived from native plant or animal raw materials, so that mixtures of substances with different alkyl chain lengths are obtained, depending on the respective raw material.

For surfactants that are addition products of ethylene and/or propylene oxide with fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. "Normal" homolog distribution refers to mixtures of homologs obtained from the reaction of fatty alcohols and alkylene oxides using alkali metals, alkali metal hydroxides, or alkali metal alkoxides as catalysts. Narrow homolog distributions, on the other hand, are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides, or alkoxides are used as catalysts. The use of products with a narrow homolog distribution may be preferred.

A very suitable surfactant of this type bears the trade name Brij S 100 or Brij S 100 PA SG. This is stearyl alcohol ethoxylated with 100 EO, which is commercially available from Croda and has the CAS number 9005-00-9.

Another particularly suitable surfactant of this type is ceteareth-30. Ceteareth-30 is a mixture of cetyl alcohol and stearyl alcohol, each ethoxylated with 30 units of ethylene oxide. The mixture of cetyl alcohol and stearyl alcohol is called cetearyl alcohol. Ceteareth-30 has the CAS number 68439-49-6 and is commercially available from BASF, for example, under the trade name Eumulgin B3.

Another particularly suitable raw material is Dehydol LT 7, a C12-C18 fatty alcohol, ethoxylated with 7 EO (or 7 mol ethylene oxide per mol fatty alcohol).

In a further embodiment, a cosmetic agent for cleaning keratin fibers, in particular human hair, containing a surfactant system in a cosmetic carrier is particularly preferred, wherein the surfactant system - based on the total weight of the surfactant system - comprises

(a) 30 to 75 wt.% of one or more anionic sulfate and/or sulfonate surfactants,

(b) 10 to 35 wt.% of one or more surfactants from the group of alkoxylated fatty alcohols of the formula (Tl)

(T-1) wherein Ra represents a saturated or unsaturated, unbranched or branched Cs-C24 alkyl group, preferably a saturated, unbranched C12 to C18 alkyl group, and n represents an integer from 1 to 120, preferably an integer from 1 to 30, more preferably an integer from 1 to 15, and most preferably an integer from 6 to 9, and

(c) 5 to 45% by weight of one or more non-ionic sugar surfactants, the amounts of (a), (b) and (c) adding up to a maximum of 100% by weight.

In a further particularly preferred embodiment, a cosmetic agent for cleaning keratin fibers, in particular human hair, containing a surfactant system in a cosmetic carrier is particularly preferred, wherein the surfactant system - based on the total weight of the surfactant system - comprises

(a) 30 to 75 wt.% of one or more anionic sulfonate surfactants,

worin Ra für eine gesättigte oder ungesättigte, unverzweigte oder verzweigte Cs-C24-Alkylgruppe, bevorzugt für eine gesättigte, unverzweigte C12- bis C18- Alkylgruppe, steht und n für eine ganze Zahl von 1 bis 120, bevorzugt für eine ganze Zahl von 1 bis 30, weiter bevorzugt für eine ganze Zahl von 1 bis 15 und ganz besonders bevorzugt für eine ganze Zahl von 6 bis 9 steht, und (b) 10 to 35 wt.% of one or more surfactants from the group of alkoxylated fatty alcohols of the formula (Tl)

wherein Ra represents a saturated or unsaturated, unbranched or branched Cs-C24 alkyl group, preferably a saturated, unbranched C12 to C18 alkyl group, and n represents an integer from 1 to 120, preferably an integer from 1 to 30, more preferably an integer from 1 to 15, and most preferably an integer from 6 to 9, and

(c) 5 to 45% by weight of one or more non-ionic sugar surfactants, the amounts of (a), (b) and (c) adding up to a maximum of 100% by weight.

In addition to or instead of the ethoxylated fatty alcohols (b), the surfactant system contained in the cleaning agent according to the invention can also contain at least one amphoteric and/or zwitterionic surfactant, wherein all surfactants of group (b) are contained in the surfactant system in a total amount of 10 to 35 wt.%. Ampholytic or amphoteric surfactants are surface-active compounds that, in addition to a C5-C24 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO5H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic or amphoteric surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids, and alkylaminoacetic acids, each with approximately 8 to 24 carbon atoms in the alkyl group. Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.

Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C12-Cis-acylsarcosine.

Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO° - or -SO ^{2 O} - group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N,N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acyl-aminopropyl-N,N-dimethylammonium glycinates, for example cocoacylaminopropyl dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines, each with 8 to 18 C atoms in the alkyl or acyl group, as well as cocoacylaminoethyl hydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

The surfactant(s) of group (b) are present in the surfactant system in an amount of 10 to 35 wt.%, based on the total weight of the surfactant system. With these surfactant amounts, the cleaning agents already exhibit very good surface cleaning. These results could be further improved when the surfactants of group (b) were present in the surfactant system in an amount range of 15 to 34 wt.%, preferably 18 to 33 wt.%, more preferably 21 to 32 wt.%, and even more preferably 24 to 31 wt.%.

In a further particularly preferred embodiment, therefore, a cosmetic agent for cleaning keratinic fibers, in particular human hair, containing a surfactant system in a cosmetic carrier is particularly preferred, wherein the surfactant system - based on the total weight of the surfactant system - comprises

(a) 35 to 68% by weight, more preferably 40 to 66% by weight and most preferably 50 to 65% by weight of one or more anionic sulfonate surfactants,

(b) 15 to 34 wt.%, preferably 18 to 33 wt.%, more preferably 21 to 32 wt.%, even more preferably 24 to 31 wt.% and most preferably 27 to 30 wt.% of one or more ethoxylated Cs-C22 alcohols having 1 to 30 EO, and (c) 5 to 45% by weight of one or more non-ionic sugar surfactants, the amounts of (a), (b) and (c) adding up to a maximum of 100% by weight.

In a further particularly preferred embodiment, therefore, a cosmetic agent for cleaning keratinic fibers, in particular human hair, containing a surfactant system in a cosmetic carrier is particularly preferred, wherein the surfactant system - based on the total weight of the surfactant system - comprises

(a) 35 to 68% by weight, more preferably 40 to 66% by weight and most preferably 50 to 65% by weight of one or more anionic sulfonate surfactants,

(b) 15 to 34 wt.%, preferably 18 to 33 wt.%, more preferably 21 to 32 wt.%, even more preferably 24 to 31 wt.% and most preferably 27 to 30 wt.% of one or more ethoxylated Ca-C22 alcohols having 1 to 15 EO, and

(c) 5 to 45% by weight of one or more non-ionic sugar surfactants, the amounts of (a), (b) and (c) adding up to a maximum of 100% by weight.

In a further particularly preferred embodiment, the cleaning agent according to the invention is characterized in that it contains a surfactant system which, based on the total weight of the surfactant system, comprises

(b) 15 to 34 wt.%, preferably 18 to 33 wt.%, more preferably 21 to 32 wt.%, even more preferably 24 to 31 wt.% and most preferably 27 to 30 wt.% of one or more ethoxylated Ca-C22 alcohols having 1 to 15 EO.

Non-ionic sugar surfactants (c)

As a third essential component (c), the surfactant system contained in the cleaning agent according to the invention comprises - based on the total weight of the surfactant system - 5 to 45 wt.% of one or more non-ionic sugar surfactants.

Nonionic sugar surfactants are uncharged, i.e., neither cationic nor cationizable, nor anionic or anionizable surfactants whose molecular structure includes at least one sugar unit. Suitable sugar surfactants (c) are, for example, alkyl polyglycosides, which are esters of fatty acids with sugars or sugar derivatives.

Alkylglucosides, alkylpolyglucosides can be described by the structural formula (T-II)

wobei

where

Rb represents a linear or branched Ce-C24 alkyl radical and p represents an integer from 1 to 100, preferably from 1 to 30 and particularly preferably from 1 to 10.

Alkylpolyglucosides are also known to those skilled in the art by the abbreviation APG.

Particularly preferred are decyl polyglucoside and lauryl polyglucoside, which are marketed by BASF under the trade names Plantacare 2000, Plantaren 2000, and Plantaren 1200, respectively. Lauryl glucoside is commercially available from BASF under the trade names Plantacare 1200 UP or NP in the form of an approximately 51% aqueous solution. The CAS numbers for lauryl glucoside are 59122-55-3, 27836-64-2, 110615-47-9, and 113976-90-2.

Furthermore, particularly good results were obtained in the pre-cleaning of the keratin fibers with surfactants (c) from the group of mannosylerythritol lipids, which the expert also knows under the abbreviation MEL or MEL surfactants.

Mannosylerythritol lipids (MELs) are surface-active substances consisting of a hydrophilic moiety, 4-ObD-mannopyranosyl-meso-erythritol, and a hydrophobic moiety, which is a fatty acid or an acetyl group. They are obtained by fermentation from various microorganisms, primarily Pseudozyma sp., but also from Ustilago sp. and Schizonella melanogramma. Due to their origin, they are classified as biosurfactants. The MELs used according to this invention are particularly preferably compounds of the general formula (T-III)

wobei

where

Rc and Rd independently represent a hydrogen atom or an acetyl group, r is an integer from 6 to 10 and s is an integer from 6 to 10.

A distinction is made between

MEL-A: Rc = Rd = Ac

MEL-B: Rc = Ac, Rd = H

MEL-C: Rc= H, Rd = Ac

MEL-D: Rc = Rd = H.

In a preferred embodiment, a mixture of MEL-A and MEL-B is used in the surfactant system according to the invention.

In a further embodiment, a cosmetic agent for cleaning keratin fibers, in particular human hair, containing a surfactant system in a cosmetic carrier is very particularly preferred, wherein the surfactant system - based on the total weight of the surfactant system - comprises

(a) 30 to 75 wt.% of one or more anionic sulfonate surfactants,

(b) 10 to 35 wt.% of one or more surfactants from the group of alkoxylated fatty alcohols, and

(c) 5 to 45% by weight of one or more non-ionic sugar surfactants from the group consisting of alkyl polyglucosides and mannosylerythritol lipids, the amounts of (a), (b) and (c) adding up to a maximum of 100% by weight. In a further particularly preferred embodiment, the cleaning agent according to the invention is characterized in that it contains a surfactant system which, based on the total weight of the surfactant system, comprises

(c) 5 to 45 wt.% of one or more non-ionic sugar surfactants selected from the group consisting of alkyl (poly)glucosides (APG) and mannosyl erythritol lipids (MEL).

Other suitable sugar surfactants include nonionic surfactants of the sugar fatty acid ester or alkyl sugar ester type. These are esters of C1-C24 fatty acids and sugars or alkyl sugars.

Methyl glucoside monostearate is a corresponding product sold under the name GRILLOCOSE IS by the company GRILLOWERKE.

Methyl glucoside sesquistearate is sold under the name GLUCATE SS by AMERCHOL.

Ethyl 6-glucoside decanoate is sold under the name BIOSURF 10 by NOVO. A mixture of ethyl 6-glucoside mono- and dicocoate (82/7), like the product sold under the name BIOSURF COCO by NOVO.

The mixture of ethyl 6-glucoside mono- and dilaurate (84/8) is sold under the name BIOSURF 12 by NOVO.

C-fatty acid monoesters of butyl glucoside, such as butyl glucoside monocoat, are sold by REWO under the names REWOPOL V3101 or REWOSAN V3101. Butyl glucoside monocoat, polyoxyethylated with 3 mol of ethylene oxide, is sold by REWO under the name REWOPOL V3122.

The surfactant(s) of group (c) are present in the surfactant system in an amount of 4 to 45 wt.%, based on the total weight of the surfactant system. With these surfactant amounts, the cleaning agents already exhibit very good surface cleaning. These results could be further improved when the surfactants of group (c) were present in the surfactant system in an amount of 6 to 40 wt.%, preferably 7 to 35 wt.%, more preferably 8 to 30 wt.%, and even more preferably 9 to 25 wt.%.

The best cleaning effects were achieved with alkyl(poly)glucosides (APG) as surfactant (c). Therefore, it is particularly preferred if the surfactant system—based on the total weight of the surfactant system—(c) comprises 6 to 40 wt.%, preferably 7 to 35 wt.%, more preferably 8 to 30 wt.%, even more preferably 9 to 25 wt.% of alkyl(poly)glucosides (APG).

In a further particularly preferred embodiment, the cleaning agent according to the invention is characterized in that it contains a surfactant system which, based on the total weight of the surfactant system, comprises (c) 6 to 40 wt.%, preferably 7 to 35 wt.%, more preferably 8 to 30 wt.%, even more preferably 9 to 25 wt.% and most preferably 10 to 20 wt.% of alkyl(poly)glucosides (APG).

In a further particularly preferred embodiment, therefore, a cosmetic agent for cleaning keratinic fibers, in particular human hair, containing a surfactant system in a cosmetic carrier is particularly preferred, wherein the surfactant system - based on the total weight of the surfactant system - comprises

(a) 35 to 68% by weight, more preferably 40 to 66% by weight and most preferably 50 to 65% by weight of one or more anionic sulfonate surfactants,

(b) 15 to 34 wt.%, preferably 18 to 33 wt.%, more preferably 21 to 32 wt.%, even more preferably 24 to 31 wt.% and most preferably 27 to 30 wt.% of one or more ethoxylated Ca-C22 alcohols having 1 to 30 EO, and

(c) 6 to 40% by weight, preferably 7 to 35% by weight, more preferably 8 to 30% by weight, even more preferably 9 to 25% by weight and most preferably 10 to 20% by weight of one or more non-ionic sugar surfactants, the amounts of (a), (b) and (c) adding up to a maximum of 100% by weight.

In a further particularly preferred embodiment, therefore, a cosmetic agent for cleaning keratinic fibers, in particular human hair, containing a surfactant system in a cosmetic carrier is particularly preferred, wherein the surfactant system - based on the total weight of the surfactant system - comprises

(a) 40 to 66 wt.% of one or more anionic sulfonate surfactants,

(b) 18 to 33 wt.% of one or more ethoxylated Ca-C22 alcohols with 1 to 30 EO, and

(c) 7 to 35% by weight of one or more non-ionic sugar surfactants, the amounts of (a), (b) and (c) adding up to a maximum of 100% by weight.

In a further particularly preferred embodiment, therefore, a cosmetic agent for cleaning keratinic fibers, in particular human hair, containing a surfactant system in a cosmetic carrier is particularly preferred, wherein the surfactant system - based on the total weight of the surfactant system - comprises

(a) 50 to 65 wt.% of one or more anionic sulfonate surfactants,

(b) 27 to 30 wt.% of one or more ethoxylated C8-C22 alcohols having 1 to 30 EO, and

(c) 10 to 20 wt.% of one or more non-ionic sugar surfactants, the amounts of (a), (b) and (c) adding up to a maximum of 100 wt.%.

Composition of the surfactant system The cleaning agent according to the invention contains a surfactant system which

(a) 30 to 75 wt.% of one or more anionic sulfate and/or sulfonate surfactants,

(b) 10 to 35 wt.% of one or more surfactants selected from the group consisting of alkoxylated fatty alcohols, amphoteric surfactants and zwitterionic surfactants, and

(c) 5 to 45 wt% of one or more non-ionic sugar surfactants.

Here, the amounts of surfactant groups (a), (b), and (c) add up to a maximum of 100 wt.%. If the contents of (a), (b), and (c) in the surfactant system add up to 100 wt.%, the surfactant system consists only of the three surfactant groups (a), (b), and (c), which, for the purposes of the present invention, means that the surfactant system of the cleaning agent does not comprise any surfactants other than (a), (b), and (c). In this embodiment, the cleaning agent then also contains no surfactants other than (a), (b), and (c).

In principle, the surfactant system of the cleaning agent can optionally also comprise additional surfactants other than (a), (b), and (c). This may be particularly the case if, in addition to the primarily desired cleaning effect, additional properties are desired. In this case, the surfactant system can, for example, also contain a cationic surfactant or another non-ionic and/or anionic surfactant other than (a), (b), and (c).

However, since the surfactant system of (a), (b) and (c) is specifically tailored to detach or remove as comprehensively as possible all components located on the surface of the keratin fiber, it is particularly preferred if the surfactant system of the cleaning agent either does not comprise any further surfactants other than (a), (b) and (c) or if it contains them only in very small quantities that do not significantly influence the cleaning performance.

For this reason, it is very particularly preferred if the surfactants (a), (b) and (c) make up a proportion of at least 65% by weight, preferably at least 75% by weight, more preferably at least 85% by weight, even more preferably at least 95% by weight and particularly preferably at least 99% by weight of the total surfactant content of the agent.

In a further very particularly preferred embodiment, the cleaning agent according to the invention is characterized in that the surfactants (a), (b) and (c) make up a proportion of at least 65% by weight, preferably of at least 75% by weight, more preferably of at least 85% by weight, even more preferably of at least 95% by weight and particularly preferably of at least 99% by weight of the total surfactant content of the agent. If surfactants (a), (b), and (c) make up at least 95% by weight of the total surfactant content of the cleaning agent, then the agent contains a surfactant system consisting of at least 95% by weight of surfactants (a), (b), and (c). Other surfactants other than (a), (b), and (c) then make up a maximum of 5% by weight of the surfactant system.

Particularly preferably, the cleaning agent contains no further surfactants apart from surfactants (a), (b) and (c).

In a further very particularly preferred embodiment, the cleaning agent according to the invention is characterized in that it contains no further surfactants apart from the surfactants (a), (b) and (c).

This means that the surfactant system of the cleaning agent does not comprise any surfactants other than (a), (b) and (c) and that the cleaning agent does not contain any surfactants other than (a), (b) and (c).

Selection of surfactants (a), (b) and (c)

A semi-empirical model was used to identify the best surfactant blends for removing oils and 18-MEA from keratin fibers, and specifically from hair. Using this model, various surfactants were selected and their ratios determined. The surfactant blends suggested by the model were experimentally tested using phase diagram studies. Those surfactant blends that form a microemulsion with specific oils were considered the best candidates for pre-cleansing hair and were investigated in further trials with regard to their suitability as pretreatment agents for use before a subsequent coloring step.

The concept of hydrophilic-lipophilic deviation (HLD) was used to find the surfactant mixtures particularly suitable for pre-cleaning.

In contrast to the HLB (hydrophilic-lipophilic balance) concept, the HLD model also takes into account formulation-related parameters such as the oil type, temperature and salt content of a formulation.

The concept of hydrophilic-lipophilic deviation (HLD) was described by Salager et al. as a formulation aid for the development of surfactant/oil/water systems. This semi-empirical model incorporates experimental parameters such as salt concentration and temperature and calculates the chemical potential difference during the transfer of a surfactant from the oil to the aqueous phase. Through further research, it became possible to describe the chemical potential difference mathematically by incorporating some formulation-related parameters such as the (estimated) The alkane carbon number of the oil phase, the temperature of the system, or the water/oil ratio (WOR) were taken into account. (3) The general HLD equation can be formulated as follows:

F(s): function for salinity

EACN: estimated carbon chain length of the oil used k: scaling factor

T: Temperature in degrees Celsius a (alpha) surfactant-specific temperature factor.

Cc: characteristic curvature of the surfactant or its hydrophilic/hydrophobic

Character f(a) Influence of polar oils and/or co-surfactants.

For different surfactants, the following parameters are obtained:

Further formulas for calculating the HLD value can be found in the literature, for example Acosta, Bhakta, J. Surfact. Deterg. (2009) 12:7-19 or Chen et al., Colloids Surf. A: Physicochem. Eng. Asp. 634 (2022) 127599.

During the pre-cleaning of the keratin fibers, the oils, hydrophobic substances, and 18-MEA present on the surface of the keratin fibers must be removed. The hydrophilic-lipophilic divergence (HLD) concept was used to search for a reproducibly usable model substance to represent these oils. It turned out that a mixture of hexane and glyceryl stearate is a good model for the lipids deposited on the keratin fibers. In the work carried out within the scope of this invention, it has been found that the surfactant systems in particular show particularly good cleaning performance, have an HLD value (Hydrophilic Lipophilic Deviation) of -4 to 0.5, preferably of -3.5 to 0 and particularly preferably of -2 to 0.

In a further particularly preferred embodiment, the cleaning agent according to the invention is characterized in that it contains a surfactant system which has an HLD value (Hydrophilic Lipophilic Deviation) of -4 to 0.5, preferably of -3.5 to 0 and particularly preferably of -2 to 0. Further optional components of the cleaning agent

The cleaning agent may optionally also contain one or more other cosmetic ingredients.

The cosmetic ingredients that can optionally be used in cleaning agents can be any suitable components to impart additional beneficial properties to the product. For example, the cleaning agent may contain thickening or film-forming polymers, preservatives, or fragrances, as well as fatty components such as Cs-Cs0 fatty alcohols, hydrocarbon compounds, fatty acid esters, acids and bases belonging to the group of pH regulators, plant extracts, and/or protein hydrolysates.

In a further particularly preferred embodiment, the cleaning agent according to the invention is characterized in that it additionally contains at least one further component selected from the group consisting of anionic polymers, cationic polymers, non-ionic polymers, preservatives and fragrances.

The expert will select these additional substances based on the desired properties of the product. Regarding further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the expert.

Process for coloring keratin fibers

The cleaning agent described above is primarily used for pre-treatment before coloring keratin fibers in order to comprehensively clean the keratin fibers and thus prepare them for coloring, in which a pigment and/or a direct dye is deposited on or near the surface of the keratin fiber and immobilized there by forming a film. A second subject of the present application is therefore a process for dyeing keratin fibers, in particular human hair, comprising the following steps in the order given:

(1) Application of a cleaning agent as disclosed in detail in the description of the first subject matter of the invention for pre-cleaning the keratin fibers, and

(2) Application of a colorant (F), wherein the colorant contains at least one colorant compound from the group of pigments and direct dyes.

Coloring agents

In the context of this invention, the term "coloring agent" refers to the coloring of keratin fibers, particularly hair, achieved through the use of pigments or direct dyes. During this coloring, the pigments or direct dyes are deposited on or near the surface of the keratin fiber.

Following application of the cleaning agent, the colorant is applied to the keratin material in the process according to the invention. The colorant contains at least one color-imparting compound from the group of pigments and direct dyes.

Pigments within the meaning of the present invention are understood to be coloring compounds which have a solubility in water at 25°C of less than 0.5 g/L, preferably less than 0.1 g/L, even more preferably less than 0.05 g/L. The water solubility can be determined, for example, using the method described below: 0.5 g of the pigment is weighed into a beaker. A stirring bar is added. Then one liter of distilled water is added. This mixture is heated to 25°C for one hour while stirring on a magnetic stirrer. If undissolved components of the pigment are still visible in the mixture after this period, the solubility of the pigment is below 0.5 g/L. If the pigment-water mixture cannot be visually assessed due to the high intensity of the pigment, which may be present in finely dispersed form, the mixture is filtered. If a portion of undissolved pigment remains on the filter paper, the solubility of the pigment is below 0.5 g/L.

Preferred color pigments are selected from synthetic or natural inorganic pigments. Inorganic color pigments of natural origin can be made from chalk, ochre, umber, green earth, burnt sienna, or graphite, for example. Other inorganic color pigments that can be used include black pigments such as iron oxide black, colored pigments such as ultramarine or iron oxide red, as well as fluorescent or phosphorescent pigments. Particularly suitable are colored metal oxides, hydroxides, and oxide hydrates, mixed-phase pigments, sulfur-containing silicates, silicates, metal sulfides, complex metal cyanides, metal sulfates, chromates, and/or molybdates. Particularly preferred color pigments are black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI 77491), manganese violet (CI 77742), ultramarines (sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), iron blue (ferric ferrocyanide, CI 77510), and/or carmine (cochineal).

Also particularly preferred color pigments according to the invention are colored pearlescent pigments. These are typically based on mica and/or mica and can be coated with one or more metal oxides. Mica belongs to the class of layered silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite, and margarite. To produce the pearlescent pigments in combination with metal oxides, the mica, predominantly muscovite or phlogopite, is coated with a metal oxide.

As an alternative to natural mica, synthetic mica, optionally coated with one or more metal oxides, can also be used as a pearlescent pigment. Particularly preferred pearlescent pigments are based on natural or synthetic mica and coated with one or more of the aforementioned metal oxides. The color of the respective pigments can be varied by varying the layer thickness of the metal oxide(s).

In a further preferred embodiment, a process according to the invention is characterized in that the colorant contains at least one inorganic pigment, which is preferably selected from the group of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments and/or colored pigments based on mica or mica, which are coated with at least one metal oxide and/or one metal oxychloride.

In a further preferred embodiment, a process according to the invention is characterized in that the colorant contains at least one pigment selected from mica- or mica-based pigments coated with one or more metal oxides from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and/or brown iron oxide (CI 77491, CI 77499), manganese violet (CI 77742), ultramarines (sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288) and/or iron blue (ferric ferrocyanide, CI 77510).

Examples of particularly suitable color pigments are commercially available under the trade names Rona®, Colorona®, Xirona®, Dichrona® and Timiron® from Merck, Ariabel® and Unipure® from Sensient, Prestige® from Eckart Cosmetic Colors and Sunshine® from Sunstar. Particularly preferred color pigments with the trade name Colorona® are, for example:

Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES)

Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxides), Alumina

Colorona Patina Silver, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)

Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470 (CARMINE)

Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES)

Colorona Dark Blue, Merck, MICA, TITANIUM DIOXIDE, FERRIC FERROCYANIDE

Colorona Chameleon, Merck, CI 77491 (IRON OXIDES), MICA

Colorona Aboriginal Amber, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)

Colorona Blackstar Blue, Merck, CI 77499 (IRON OXIDES), MICA

Colorona Patagonian Purple, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM

DIOXIDES), CI 77510 (FERRIC FERROCYANIDES)

Colorona Red Brown, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)

Colorona Russet, Merck, CI 77491 (TITANIUM DIOXIDE), MICA, CI 77891 (IRON OXIDES)

Colorona Imperial Red, Merck, MICA, TITANIUM DIOXIDE (CI 77891), D&C RED NO. 30 (CI 73360)

Colorona Majestic Green, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 77288 (CHROMIUM OXIDE GREENS)

Colorona Light Blue, Merck, MICA, TITANIUM DIOXIDE (CI 77891), FERRIC FERROCYANIDE (Cl 77510)

Colorona Red Gold, Merck, MICA, Cl 77891 (TITANIUM DIOXIDE), Cl 77491 (IRON OXIDES)

Colorona Gold Plus MP 25, Merck, MICA, TITANIUM DIOXIDE (Cl 77891), IRON OXIDES (Cl 77491)

Colorona Carmine Red, Merck, MICA, TITANIUM DIOXIDE, CARMINE

Colorona Blackstar Green, Merck, MICA, Cl 77499 (IRON OXIDES)

Colorona Bordeaux, Merck, MICA, Cl 77491 (IRON OXIDES)

Colorona Bronze, Merck, MICA, Cl 77491 (IRON OXIDES)

Colorona Bronze Fine, Merck, MICA, Cl 77491 (IRON OXIDES)

Colorona Fine Gold MP 20, Merck, MICA, Cl 77891 (TITANIUM DIOXIDE), Cl 77491 (IRON OXIDES)

Colorona Sienna Fine, Merck, Cl 77491 (IRON OXIDES), MICA

Colorona Sienna, Merck, MICA, Cl 77491 (IRON OXIDES)

Colorona Precious Gold, Merck, Mica, Cl 77891 (Titanium dioxide), Silica, Cl 77491 (Iron oxides), Tin oxide

Colorona Sun Gold Sparkle MP 29, Merck, MICA, TITANIUM DIOXIDE, IRON OXIDES, MICA, Cl 77891, Cl 77491 (EU)

Colorona Mica Black, Merck, Cl 77499 (Iron oxides), Mica, Cl 77891 (Titanium dioxide) Colorona Bright Gold, Merck, Mica, Cl 77891 (Titanium dioxide), Cl 77491 (Iron oxides)

Colorona Blackstar Gold, Merck, MICA, Cl 77499 (IRON OXIDES)

Other particularly preferred color pigments with the trade name Xirona® include:

Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide

Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide

Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide

Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide.

In addition, particularly preferred color pigments with the trade name Unipure® are, for example:

Unipure Red LC 381 EM, Sensient CI 77491 (Iron Oxides), Silica

Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica

Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iron Oxides), Silica

In a further embodiment, the applied colorant may also contain one or more organic pigments.

The organic pigments according to the invention are correspondingly insoluble, organic dyes or lakes which can be selected, for example, from the group of nitroso, nitro, azo, xanthene, anthraquinone, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyorrole, indigo, thioindido, dioxazine and/or triarylmethane compounds.

Particularly suitable organic pigments are, for example, carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the color index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the color index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with the color index numbers CI 61565, CI 61570, CI 74260, orange pigments with the color index numbers CI 1 1725, CI 15510, CI 45370, CI 71105, red pigments with the color index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and/or CI 75470.

In a further particularly preferred embodiment, a process according to the invention is characterized in that the colorant contains at least one organic pigment, which is preferably selected from the group consisting of carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the Color Index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the color index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with the color index numbers CI 61565, CI 61570, CI 74260, orange pigments with the color index numbers CI 1 1725, CI 15510, CI 45370, CI 71 105, red pigments with the color index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and/or CI 75470.

The organic pigment can also be a colored lake. For the purposes of the invention, the term colored lake refers to particles comprising a layer of absorbed dyes, the particle-dye unit being insoluble under the above-mentioned conditions. The particles can be, for example, inorganic substrates, which can be aluminum, silica, calcium borosilicate, calcium aluminum borosilicate, or even aluminum.

Alizarin varnish, for example, can be used as a colored varnish.

Pigments with a specific shape can also be used to color the keratin fibers. For example, a pigment based on a lamellar and/or lenticular substrate plate can be used. Furthermore, coloring based on a substrate plate containing a vacuum-metallized pigment is also possible.

In a further preferred embodiment, a process according to the invention is characterized in that the colorant contains at least one pigment selected from the group of pigments based on a lamellar substrate platelet, pigments based on a lenticular substrate platelet and vacuum metallized pigments.

The substrate platelets of this type have an average thickness of at most 50 nm, preferably less than 30 nm, more preferably at most 25 nm, for example at most 20 nm. The average thickness of the substrate platelets is at least 1 nm, preferably at least 2.5 nm, more preferably at least 5 nm, for example at least 10 nm. Preferred ranges for the thickness of the substrate platelets are 2.5 to 50 nm, 5 to 50 nm, 10 to 50 nm; 2.5 to 30 nm, 5 to 30 nm, 10 to 30 nm; 2.5 to 25 nm, 5 to 25 nm, 10 to 25 nm, 2.5 to 20 nm, 5 to 20 nm and 10 to 20 nm. Each substrate platelet preferably has a thickness that is as uniform as possible. Due to the low thickness of the substrate platelets, the pigment has particularly high hiding power.

The substrate platelets are preferably monolithic in structure. Monolithic in this context means consisting of a single, closed unit without fractures, stratification or Inclusions exist, although structural changes may occur within the substrate platelets. The substrate platelets are preferably homogeneous in structure, meaning that no concentration gradient occurs within the platelets. In particular, the substrate platelets are not layered and do not contain any particles or particles distributed within them.

The size of the substrate platelet can be tailored to the specific application, especially the desired effect on the keratinous material. Typically, the substrate platelets have an average diameter of approximately 2 to 200 pm, particularly approximately 5 to 100 pm.

In a preferred embodiment, the aspect ratio, expressed as the ratio of the average size to the average thickness, is at least 80, preferably at least 200, more preferably at least 500, and particularly preferably more than 750. The average size of the uncoated substrate platelets is understood to be the d50 value of the uncoated substrate platelets. Unless otherwise stated, the d50 value was determined using a Sympatec Heios device with Quixel wet dispersion. For sample preparation, the sample to be tested was predispersed in isopropanol for 3 minutes.

The substrate platelets can be made of any material that can be formed into platelets.

They can be of natural origin or synthetically produced. Materials from which the substrate platelets can be constructed include metals and metal alloys, metal oxides, preferably aluminum oxide, inorganic compounds and minerals such as mica and (semi-)precious stones, as well as plastics. The substrate platelets are preferably made of metal (alloys).

Any metal suitable for metallic luster pigments can be considered. Such metals include iron and steel, as well as all air- and water-resistant (semi)metals such as platinum, zinc, chromium, molybdenum, and silicon, as well as their alloys such as aluminum bronze and brass. Preferred metals are aluminum, copper, silver, and gold. Preferred substrate platelets are aluminum platelets and brass platelets, with aluminum platelets being particularly preferred.

Lamellar substrate platelets are characterized by an irregularly structured edge and are also called "cornflakes" due to their appearance. Due to their irregular structure, pigments based on lamellar substrate platelets generate a high degree of scattered light. Furthermore, pigments based on lamellar substrate platelets do not completely cover the existing color of a keratinous material, and effects similar to natural graying can be achieved, for example.

Lenticular (= lens-shaped) substrate platelets have a generally regular, round edge and are also called "silver dollars" due to their appearance. Due to their regular structure, the proportion of reflected light predominates in pigments based on lenticular substrate platelets.

Vacuum metallized pigments (VMPs) can be obtained, for example, by releasing metals, metal alloys, or metal oxides from appropriately coated foils. They are characterized by a particularly thin substrate platelet thickness in the range of 5 to 50 nm and a particularly smooth surface with increased reflectivity. Substrate platelets comprising a vacuum-metallized pigment are also referred to as VMP substrate platelets in this application. VMP substrate platelets made of aluminum can be obtained, for example, by releasing aluminum from metallized foils.

The substrate plates made of metal or metal alloy can be passivated, for example by anodizing (oxide layer) or chromating.

Uncoated lamellar, lenticular, and/or VPM substrate plates, especially those made of metal or metal alloy, reflect incident light to a high degree and produce a light-dark flop. These have proven particularly preferred for use in the colorant.

Suitable pigments based on a lamellar substrate platelet include, for example, the pigments of the VISIONAIRE series from Eckart.

Pigments based on a lenticular substrate platelet are available, for example, under the name Alegrace® Gorgeous from Schlenk Metallic Pigments GmbH.

Pigments based on a substrate platelet comprising a vacuum metallized pigment are available, for example, under the name Alegrace® Marvelous or Alegrace® Aurous from Schlenk Metallic Pigments GmbH.

Due to their excellent light and temperature resistance, the use of the aforementioned pigments in the agent according to the invention is particularly preferred. Furthermore, It is preferred if the pigments used have a specific particle size. It is therefore advantageous according to the invention if the at least one pigment has an average particle size D50 of 1.0 to 50 pm, preferably of 5.0 to 45 pm, more preferably of 10 to 40 pm, in particular of 14 to 30 pm. The average particle size D50 can be determined, for example, using dynamic light scattering (DLS).

The colorant can also contain at least one substantive dye as a coloring compound. Substantive dyes are dyes that absorb directly into the hair and do not require an oxidative process to develop the color. Substantive dyes are typically nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes, or indophenols.

Direct dyes can be non-ionic, cationic or anionic.

Anionic direct dyes are also referred to as acid dyes. Acid dyes are defined as direct dyes that contain at least one carboxylic acid group (-COOH) and/or one sulfonic acid group (-SO3H) and/or one sulfate group (-OSO3H). Depending on the pH, the profaned forms (-COOH, -SO3H) of the carboxylic acid or sulfonic acid groups exist in equilibrium with their deprotonated forms (-COO-, -SCh, or -OSC>3'). As the pH decreases, the proportion of profaned forms increases. If direct dyes are used in the form of their salts, the carboxylic acid or sulfonic acid groups are present in deprotonated form and are neutralized with corresponding stoichiometric equivalents of cations to maintain electroneutrality. Acid dyes according to the invention can also be used in the form of their sodium salts and/or their potassium salts.

The alkaline earth metal salts (such as calcium and magnesium salts) and aluminum salts of acid dyes often have lower solubility than the corresponding alkali metal salts. If the solubility of these salts is below 0.5 g/L (25 °C, 760 mmHg), they do not fall under the definition of a direct dye.

A key feature of acid dyes is their ability to form anionic charges, with the carboxylic acid or sulfonic acid groups responsible for this being typically linked to various chromophoric systems. Suitable chromophoric systems can be found, for example, in the structures of nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinone dyes, triarylmethane dyes, xanthene dyes, rhodamine dyes, oxazine dyes, and/or indophenol dyes. Examples of acid dyes that can be mentioned are: Acid Yellow 1 (D&C Yellow 7, Citronin A, Ext. D&C Yellow No. 7, Japan Yellow 403, CI 10316, COLIPA n° B001), Acid Yellow 3 (COLIPA n°: C 54, D&C Yellow N° 10, Quinoline Yellow, E104, Food Yellow 13), Acid Yellow 9 (CI 13015), Acid Yellow 17 (C1 18965), Acid Yellow 23 (COLIPA n° C 29, Covacap Jaune W 1 100 (LCW), Sicovit Tartrazine 85 E 102 (BASF), Tartrazine, Food Yellow 4, Japan Yellow 4, FD&C Yellow No. 5), Acid Yellow 36 (CI 13065), Acid Yellow 121 (CI 18690), Acid Orange 6 (CI 14270), Acid Orange 7 (2-Naphthol orange, Orange II, C1 15510, D&C Orange 4, COLIPA n° C015), Acid Orange 10 (Cl 16230; Orange G sodium salt), Acid Orange 11 (Cl 45370), Acid Orange 15 (Cl 50120), Acid Orange 20 (Cl 14600), Acid Orange 24 (BROWN 1 ;CI20170;KATSU201 ;nosodium salt;Brown No.201 ;RESORCIN BROWN;ACID ORANGE 24;Japan Brown 201 ;D & C Brown No.1), Acid Red 14 (C.1.14720), Acid Red 18 (E124, Red 18; Cl 16255), Acid Red 27 (E 123, Cl 16185, C-Red 46, Real Red D, FD&C Red No.2, Food Red 9, Naphthol Red S), Acid Red 33 (Red 33, Fuchsia Red, D&C Red 33, Cl 17200), Acid Red 35 (Cl Cl18065), Acid Red 51 (Cl 45430, Pyrosine B, Tetraiodofluorescein, Eosin J, lodeosin), Acid Red 52 (Cl 45100, Food Red 106, Solar Rhodamine B, Acid Rhodamine B, Red n° 106 Pontacyl Brilliant Pink), Acid Red 73 (Cl 27290), Acid Red 87 (Eosin, Cl 45380), Acid Red 92 (COLIPA n° C53, Cl 45410), Acid Red 95 (Cl 45425, Erythtosine.Simacid Erythrosine Y), Acid Red 184 (Cl 15685), Acid Red 195, Acid Violet 43 (Jarocol Violet 43, Ext. D&C Violet n° 2, Cl 60730, COLIPA n° C063), Acid Violet 49 (Cl 42640), Acid Violet 50 (Cl 50325), Acid Blue 1 (Patent Blue, Cl 42045), Acid Blue 3 (Patent Blue V, Cl 42051), Acid Blue 7 (Cl 42080), Acid Blue 104 (Cl 42735), Acid Blue 9 (E 133, Patent Blue AE, Amido Blue AE, Erioglaucin A, Cl 42090, Cl Food Blue 2), Acid Blue 62 (Cl 62045), Acid Blue 74 (E 132, Cl 73015), Acid Blue 80 (Cl 61585), Acid Green 3 (Cl 42085, Foodgreenl), Acid Green 5 (Cl 42095), Acid Green 9 (C.1.42100), Acid Green 22 (C.1.42170), Acid Green 25 (Cl 61570, Japan Green 201, D&C Green No. 5) 14270), Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 11, D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 and/or D&C Brown 1.

Within the scope of a further embodiment, a process according to the invention is characterized in that the colorant contains at least one acid dye which is selected from the group consisting of Acid Yellow 1, Acid Yellow 3, Acid Yellow 9, Acid Yellow 17, Acid Yellow 23, Acid Yellow 36, Acid Yellow 121, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 11, Acid Orange 15, Acid Orange 20, Acid Orange 24, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 33, Acid Red 35, Acid Red 51, Acid Red 52, Acid Red 73, Acid Red 87, Acid Red 95, Acid Red 184, Acid Red 195, Acid Violet 43, Acid Violet 49, Acid Violet 50, Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 104, Acid Blue 9, Acid Blue 62, Acid Blue 74, Acid Blue 80, Acid Green 3, Acid Green 5, Acid Green 9, Acid Green 22, Acid Green 25, Acid Green 50, Acid Black 1, Acid Black 52, Food Yellow 8, Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 1 1, D&C Red 21 , D&C Red 27, D&C Red 33, D&C Violet 2 and/or D&C Brown 1 . Since alkaline earth metal salts (such as calcium and magnesium salts) or aluminum salts of acid dyes are less soluble than the corresponding alkali metal salts, an organic dye that, in the form of its alkali metal salt, is considered an acid dye can also exist in the form of a pigment if the counterion for the acid group(s) is not an alkali metal ion, but rather an alkaline earth metal or an analogous, correspondingly more highly charged counterion. If the solubility of these salts is below 0.5 g/L (25 °C, 760 mmHg), the compounds do not fall under the definition of a direct dye.

The water solubility of anionic direct dyes can be determined, for example, as follows: 0.1 g of the anionic direct dye is placed in a beaker. A stir bar is attached. Then 100 ml of water is added. This mixture is heated to 25 °C on a magnetic stirrer while stirring. It is stirred for 60 minutes. The aqueous mixture is then visually assessed. If undissolved residues remain, the amount of water is increased – for example, in 10 ml increments. Water is added until the added amount of dye has completely dissolved. If the dye-water mixture cannot be visually assessed due to the high intensity of the dye, the mixture is filtered. If a portion of undissolved dye remains on the filter paper, the solubility test is repeated using a larger amount of water. If 0.1 g of the anionic direct dye dissolves in 100 ml of water at 25 °C, the solubility of the dye is 1.0 g/L.

Acid Yellow 1 is called 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid disodium salt and has a solubility in water of at least 40 g/L (25°C).

Acid Yellow 3 is a mixture of the sodium salts of mono- and disulfonic acids of 2-(2-quinolyl)-1H-indene-1,3(2H)-dione and has a water solubility of 20 g/L (25 °C).

Acid Yellow 9 is the disodium salt of 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid, its water solubility is above 40 g/L (25 °C).

Acid Yellow 23 is the trisodium salt of 4,5-dihydro-5-oxo-1-(4-sulfophenyl)-4-((4-sulfophenyl)azo)-1H-pyrazole-3-carboxylic acid and is readily soluble in water at 25 °C.

Acid Orange 7 is the sodium salt of 4-[(2-hydroxy-1-naphthyl)azo]benzenesulfonate. Its water solubility is greater than 7 g/L (25 °C).

Acid Red 18 is the trisodium salt of 7-hydroxy-8-[(E)-(4-sulfonato-1-naphthyl)-diazenyl)]-1,3-naphthalenedisulfonate and has a very high water solubility of more than 20 wt%.

Acid Red 33 is the disodium salt of 5-amino-4-hydroxy-3-(phenylazo)-naphthalene-2,7-disulfonate, its water solubility is 2.5 g/L (25 °C).

Acid Red 92 is the disodium salt of 3,4,5,6-tetrachloro-2-(1,4,5,8-tetrabromo-6-hydroxy-3-oxoxanthen-9-yl)benzoic acid, whose water solubility is stated to be greater than 10 g/L (25 °C). Brilliant Blue FCF, alternatively known as Food Blue 2 or Acid Blue 9, is known as disodium 2-[(Z)-{4-[ethyl(3-sulfonatobenzyl)amino]phenyl}{(4Z)-4-[ethyl(3-sulfonatobenzyl)iminio]-2,5-cyclohexadien-1-ylidene}methyl]benzenesulfonate in its disodium salt and has the CAS number 3844-45-9. The disodium salt of Acid Blue 9 has a water solubility of more than 20 wt.% (25 °C).

Acid Blue 74 is also known as indigo carmine, Food Blue 1, or FD&C Blue 2 and has the chemical name indigo-5,5'-disulfonic acid, disodium salt, or disodium 5,5'-(2-(1,3-dihydro-3-oxo-2H-indazol-2-ylidene)-1,2-dihydro-3H-indol-3-one)disulfonate. Acid Blue 74 in the form of the disodium salt has a solubility in water of 10 g/L at 25 °C.

The coloring compound(s) are preferably used in the colorant in specific quantity ranges. Particularly good results were obtained when the colorant contained one or more coloring compounds from the group consisting of pigments and direct dyes in a total amount of 0.01 to 10.0 wt. %, preferably 0.1 to 5.0 wt. %, more preferably 0.2 to 2.5 wt. %, and most preferably 0.25 to 1.5 wt. %, based on the total weight of the colorant. Film-forming compounds in the colorant

Particularly preferably, the colorant also contains at least one film-forming substance, which results in a film that is as homogeneous, even and smooth as possible being applied around the surface of the keratin fibers and in this way holds the color-providing compounds there.

The film-forming compound can be, for example, organic Ci-Ce alkoxysilanes, aminosilicones or film-forming polymers.

Particularly resistant films were obtained by using organic Ci-Ce alkoxysilanes. For this reason, it is particularly preferred if the colorant contains at least one organic silicon compound selected from the group consisting of (3-aminopropyl)triethoxysilane, (3-aminopropyl)trimethoxysilane, (2-aminoethyl)triethoxysilane, (2-aminoethyl)trimethoxysilane, (3-dimethylaminopropyl)triethoxysilane, (3-dimethylaminopropyl)trimethoxysilane, (2-dimethylaminoethyl)triethoxysilane, (2-dimethylaminoethyl)trimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, octadecyltrimethoxysilane and Octadecyltriethoxysilane and/or their hydrolysis and/or condensation products. Organic compounds particularly suitable for solving the problem according to the invention

Silicon compounds are

- (3-Aminopropyl)triethoxysilane

- (3-Aminopropyl)trimethoxysilane

- (2-Aminoethyl)triethoxysilane

- (2-Aminoethyl)trimethoxysilane

1-(2-Aminoethyl)silanetriol

- (3-Dimethylaminopropyl)triethoxysilane

- (3-Dimethylaminopropyl)trimethoxysilane

1-(3-Dimethylaminopropyl)silanetriol

- (2-Dimethylaminoethyl)triethoxysilane.

- (2-Dimethylaminoethyl)trimethoxysilane and

1-(2-Dimethylaminoethyl)silanetriol

Furthermore, organic silicon compounds which are particularly suitable for solving the problem according to the invention are

- Methyltrimethoxysilane

- Ethyltriethoxysilan

- Ethyltrimethoxysilane

- Ethyltriethoxysilane

- n-Hexyltriethoxysilane

- n-octyltriethoxysilane

- n-dodecyltrimethoxysilane and/or

n-Octadecyltrimethoxysilan und/oder n-Octadecyltriethoxysilan. - n-Dodecyltriethoxysilane.

n-octadecyltrimethoxysilane and/or n-octadecyltriethoxysilane.

In a further particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) additionally contains at least one organic silicon compound which is selected from the group consisting of (3-aminopropyl)triethoxysilane, (3-aminopropyl)trimethoxysilane, (2-aminoethyl)triethoxysilane, (2-aminoethyl)trimethoxysilane, (3-dimethylaminopropyl)triethoxysilane, (3-dimethylaminopropyl)trimethoxysilane, (2-

Dimethylaminoethyl)triethoxysilane, (2-dimethylaminoethyl)trimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane,

Propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane,

Octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, octadecyltrimethoxysilane and octadecyltriethoxysilane and/or their hydrolysis and/or condensation products. In an explicitly particularly preferred embodiment, a method is characterized in that a coloring agent (F) is applied to the keratinic fibers, which contains at least one organic silicon compound of the formula which is selected from the group consisting of (3-aminopropyl)triethoxysilane and (3-aminopropyl)trimethoxysilane, and additionally contains at least one further organic silicon compound of the formula which is selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, hexyltrimethoxysilane and hexyltriethoxysilane.

It has been found to be preferred if the colorant (F) - based on the total weight of the colorant (F) - contained one or more organic silicon compounds in a total amount of 0.1 to 20 wt.%, preferably 1 to 15 wt.% and particularly preferably 2 to 12 wt.%.

In the case of the previously described organic silicon compounds or silanes, even the addition of small amounts of water leads to hydrolysis or oligomerization and/or polymerization. The extent of oligomerization or polymerization depends on the amount of water that comes into contact with the previously described silane(s). The aim of the process according to the invention is that the formation of the colored film, i.e. the final polymerization originating from the silanes, takes place when the colorant is already on the keratin fibers. However, due to the high reactivity of the silanes, oligomerization or pre-condensation may have already taken place before the colorant (F) is applied, and the silanes may already be hydrolyzed, oligomerized, or even polymerized to a small extent in the colorant (F).

For this reason, both the silanes and their hydrolysis products, oligomers, and/or condensation products can be present in the colorant (F). According to the invention, the term "silanes" therefore also encompasses their hydrolysis products, oligomers, and/or condensation products.

To form the film, the dye can also contain one or more film-forming polymers. Chitosans, in particular, have proven to be particularly suitable polymers in this context.

In a further particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) additionally contains at least one chitosan and/or a chitosan derivative. Chitosan, also known as polyglusam, poly-D-glucosamine, or polyglucosamine, is a naturally occurring biopolymer derived from chitin, which is composed of ß-1,4-glycosidically linked N-acetylglucosamine residues (more precisely, 2-acetamido-2-deoxy-ß-D-glucopyranose residues), and is thus, like chitin, a polyaminosaccharide. To produce chitosan, chitin is deacetylated, so that the molecule ultimately consists of only approximately 2,000 linearly linked 2-amino-2-deoxy-ß-D-glucopyranose or glucosamine monomers. Chitosan has the CAS number 9012-76-4.

Chitosan is preferably produced from the chitin found in shellfish or crustaceans. Chitosan is industrially obtained from chitin by deacetylation. This can be achieved, for example, using (hot) sodium hydroxide solution or enzymatically. Both processes are used industrially, but the alkaline procedure is clearly the most commonly used. The degree of resulting deacetylation can vary considerably: deacetylation can be complete or partial, resulting in a distribution of highly deacetylated regions alongside less deacetylated regions, or a homogeneous deacetylation distribution. At the same time, this chemical intervention can decrease the chain length of the polymer (depolymerization). The molecular weight of chitosan can vary over a wide range, for example, from 20,000 to approximately 5 million g/mol.

Chitosan derivatives are compounds with a chitosan base structure in which at least some of the functional groups present have been chemically modified. Chitosan derivatives are also based on a poly-D-glucosamine or polyglucosamine structure.

For example, a chitosan with a molecular weight of 20,000 to 800,000 g/mol, preferably 50,000 to 600,000 g/mol, more preferably 80,000 to 450,000 g/mol and most preferably 100,000 to 300,000 g/mol is very suitable.

In a further very particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one chitosan and/or a chitosan derivative (F-1) with a molecular weight of 20,000 to 800,000 g/mol, preferably of 50,000 to 600,000 g/mol, more preferably of 80,000 to 450,000 g/mol and very particularly preferably of 100,000 to 300,000 g/mol.

In a further very particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one chitosan (F-1) with a molecular weight of 20,000 to 800,000 g/mol, preferably of 50,000 to 600,000 g/mol, more preferably of 80,000 to 450,000 g/mol and very particularly preferably of 100,000 to 300,000 g/mol. Chitosan with a molecular weight of 100,000 to 300,000 g/mol can be purchased commercially from Sigma Aldrich, for example.

A chitosan with a lower molecular weight of 10,000 to 30,000 g/mol (or Dalton) is commercially available in pharmaceutical grade from BioLog Heppe (Kraeber), for example. The degree of deacetylation of this chitosan is 88-95%.

Chitosan in the form of its hydrochloride can be purchased as vegan chitosan from Sandream Impact. The chitosan hydrochloride is a chitosan derivative according to the invention.

Chitosan 027 is a suitable high molecular weight chitosan from Polymar, which has a molecular weight of 100,000 - 2,000,000 g/mol.

It has proven particularly advantageous if the colorant contains the chitosans and/or chitosan derivatives (in certain quantity ranges). Particularly good results were obtained if the colorant contained - based on the total weight of the colorant - one or more chitosans and/or chitosan derivatives in a total amount of 0.1 to 10.0 wt.%, preferably 0.2 to 8.0 wt.%, more preferably 0.5 to 6.0 wt.% and most preferably 0.7 to 2.0 wt.%.

The colorant can also contain at least one aminosilicone as a film-forming compound. The aminosilicone can alternatively be referred to as an amino-functionalized silicone polymer or amodimethicone.

In a further particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) additionally contains at least one amino-functionalized silicone polymer.

Silicone polymers are generally macromolecules having a molecular weight of at least 500 g/mol, preferably at least 1000 g/mol, more preferably at least 2500 g/mol, particularly preferably at least 5000 g/mol, which comprise repeating organic units.

The maximum molecular weight of the silicone polymer depends on the degree of polymerization (number of polymerized monomers) and the batch size, and is also determined by the polymerization method. For the purposes of the present invention, it is preferred if the maximum molecular weight of the silicone polymer is not more than 10 ⁷ g/mol, preferably not more than 10 ⁶ g/mol, and particularly preferably not more than 10 ⁵ g/mol. Silicone polymers comprise many Si-O repeating units, where the Si atoms may carry organic residues such as alkyl or substituted alkyl groups. Alternatively, a silicone polymer is therefore also referred to as polydimethylsiloxane.

In accordance with the high molecular weight of the silicone polymers, these are based on more than 10 Si-O repeating units, preferably more than 50 Si-O repeating units and particularly preferably more than 100 Si-O repeating units, most preferably more than 500 Si-O repeating units.

An amino-functionalized silicone polymer is a functionalized silicone that carries at least one structural unit with an amino group. The amino-functionalized silicone polymer preferably carries multiple structural units, each with at least one amino group. An amino group is understood to mean a primary amino group, a secondary amino group, and a tertiary amino group. All of these amino groups can be protonated in an acidic environment and are then present in their cationic form.

In principle, good results could be achieved with amino-functionalized silicone polymers containing at least one primary, at least one secondary, and/or at least one tertiary amino group. However, the highest color intensities were observed when an amino-functionalized silicone polymer containing at least one secondary amino group was used in the product.

In a particularly preferred embodiment, a colorant according to the invention is characterized in that it additionally contains at least one amino-functionalized silicone polymer having at least one secondary amino group.

-Amino) The secondary amino group(s) can be located at various positions on the amino-functionalized silicone polymer. Particularly good results were found when using an amino-functionalized silicone polymer that has at least one, preferably several, structural units of the formula (Si-amino).

-Amino)

In the structural units of the formula (Si-Amino), the abbreviations ALK1 and ALK2 independently represent a linear or branched, divalent Ci-C2o-alkylene group.

-Amino) wobei In a further particularly preferred embodiment, a colorant is characterized in that it contains at least one amino-functionalized silicone polymer (which comprises at least one structural unit of the formula (Si-Amino),

-Amino) where

ALK1 and ALK2 independently represent a linear or branched, divalent Ci-C2o-alkylene group.

The positions marked with an asterisk (*) indicate the bond to other structural units of the silicone polymer. For example, the silicon atom adjacent to the star atom may be bonded to another oxygen atom, and the oxygen atom adjacent to the star may be bonded to another silicon atom or to a Ci-Ce alkyl group.

A divalent Ci-C2o-alkylene group can alternatively be referred to as a divalent or divalent Ci-C2o-alkylene group, which means that each group ALK1 or AK2 can form two bonds.

In the case of ALK1, one bond is formed from the silicon atom to the ALK1 group, and the second bond is formed between ALK1 and the secondary amino group.

In the case of ALK2, one bond is formed from the secondary amino group to the ALK2 moiety, and the second bond is formed between ALK2 and the primary amino group.

Examples of a linear divalent C3-C2o-alkylene group include the methylene group (-CH2-), the ethylene group (-CH2-CH2-), the propylene group (-CH2-CH2-CH2-), and the butylene group (-CH2-CH2-CH2-CH2-). The propylene group (-CH2-CH2-CH2-) is particularly preferred. From a chain length of 3 carbon atoms, divalent alkylene groups can also be branched. Examples of branched, divalent C3-C2o-alkylene groups are (-CH2-CH(CH3)-) and (-CH2-CH(CH3)-CH2-).

In a further particularly preferred embodiment, the structural units of the formula (Si-amino) represent repeating units in the amino-functionalized silicone polymer (a3), so that the silicone polymer comprises several structural units of the formula (Si-amino).

Particularly suitable amino-functionalized silicone polymers (a3) with at least one secondary amino group are listed below.

Colorations with the highest color intensities could be obtained when an agent was applied to the keratin fibers containing at least one amino-functionalized silicone polymer comprising structural units of the formula (Si-I) and the formula (Si-II)

wobei

where

R1 represents a methyl group or a hydrogen atom, and

R2 represents a Ci-Ce-alkyl group, in particular a methyl group, or a Ci-Ce-alkoxy group, in particular a methoxy group.

wobei Within the scope of a further embodiment, a colorant according to the invention is therefore particularly preferably characterized in that it contains at least one amino-functionalized silicone polymer which comprises structural units of the formula (Si-I) and the formula (Si-II)

where

R1 represents a methyl group or a hydrogen atom, and R2 represents an O-Ce-alkyl group, in particular a methyl group, or a Ci-Ce-alkoxy group, in particular a methoxy group.

In the amino-functionalized silicone polymers (a3), the R1 radical in the structural units of formula (Si-II) represents a methyl group or a hydrogen atom. The R2 radical represents a C1-C8 alkyl group or a C1-C8 alkoxy group. Particularly preferably, the R2 radical represents a methyl group or a methoxy group.

In a further particularly preferred embodiment, an agent according to the invention is therefore characterized in that it contains at least one amino-functionalized silicone polymer (a3) which comprises structural units of the formula (Si-I) and the formula (Si-II), where R1 represents a methyl group and R2 represents a methyl group.

A particularly suitable amino-functionalized silicone polymer, in which R2 represents a methyl group and R1 represents a methyl group, is, for example, the commercial product DC 2-8566 or Dowsil 2-8566 Amino Fluid, which is marketed by the Dow Chemical Company and which bears the name "Siloxanes and Silicones, 3-[(2-Aminoethyl)amino]-2-methylpropyl Me, Di-Me-Siloxane" and the CAS number 106842-44-8. Another amino-functionalized silicone polymer with the structural units (Si-I) and (Si-II) is, for example, the commercial product DOWSIL™ AP-8568 Amino Fluid, which is also marketed by the Dow Chemical Company.

Cosmetic carrier of the colorant (F)

The colorant particularly preferably contains the coloring compounds in a cosmetic carrier. In one embodiment, the colorant (F) can be formulated with a low water content or without water. In another embodiment, however, the cosmetic carrier can also be water or a mixture of water with a solvent.

Particularly suitable solvents include compounds from the group consisting of poly-Ci-Ce-alkylene glycols, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, phenoxyethanol, and benzyl alcohol. Poly-Ci-Ce-alkylene glycols, especially polyethylene glycols, have demonstrated particularly good suitability in this regard.

wobei p für eine ganze Zahl von 1 bis 1000, bevorzugt 1 bis 100, besonders bevorzugt 2 bis 50, steht. In a further particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one solvent from the group consisting of poly-Ci-Ce-alkylene glycols, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, phenoxyethanol and benzyl alcohol, very particularly preferably from ethylene glycols. Suitable poly-Ci-Ce-alkylene glycols include, in particular, the polyethylene glycols as described, for example, by the formula (AG)

where p is an integer from 1 to 1000, preferably 1 to 100, particularly preferably 2 to 50.

The alkylene glycols of formula (AG) are protic substances with at least one hydroxyl group, which, due to their repeating unit -CH2-CH2-O-, can also be referred to as polyethylene glycols, provided p represents a value of at least 2. In the alkylene glycols of formula (AG), p represents an integer from 1 to 10,000. The work leading to this invention has shown that these polyethylene glycols are particularly suitable for improving the fastness properties of colorants and for optimally adjusting the viscosity of the agents.

1,2-Propylene glycol is alternatively also called 1,2-propanediol and has the CAS numbers 57-55-6 [(RS)-1,2-dihydroxypropane], 4254-14-2 [(R)-1,2-dihydroxypropane] and 4254-153 [(S)-1,2-dihydroxypropane], 1,3-Propylene glycol is alternatively also called 1,3-dihydroxypropane or as

It is called 1,3-propanediol and has the CAS number 504-63-2. 1,2-butylene glycol can also be called 1,2-butanediol and has the CAS numbers 584-03-2 (racemate), 40348-66-1 ((R)-enantiomer), and 73522-17-5 ((S)-enantiomer).

Dipropylene glycols (or oxydipropanols) form a group of substances derived from glycol ethers. The dipropylene glycol group includes 2,2'-oxydi-1-propanol (CAS No. 108-61-), 2,1,1'-oxydi-2-propanol (CAS No. 110-98-5), and 2-(2-hydroxypropoxy)-1-propanol (CAS No. 106-62-7). The mixture of these three isomers has CAS No. 25265-71-8.

Ethanol has the CAS No. 64-17-5. Isopropanol is also known as 2-propanol and has the CAS No. 67-63-0. Ethylene glycol is also known as 1,2-ethanediol and has the CAS No. 107-21-1.

Diethylene glycol monoethyl ether can alternatively be referred to as ethoxydiglycol or ethyldiglycol or 2-(2-ethoxyethoxy)ethanol) and has the CAS No. 111-90-0. Glycerin is also known as 1,2,3-propanetriol and has the CAS number 56-81-5. Phenoxyethanol has the CAS number 122-99-6. Benzyl alcohol can also be known as phenylmethanol and has the CAS number 100-51-6.

All solvents described above are commercially available from various chemical suppliers such as Aldrich or Fluka.

(EG-F), wobei y für eine ganze Zahl von 1 bis 10000 , bevorzugt für eine ganze Zahl von 2 bis 500, weiter bevorzugt für eine ganze Zahl von 3 bis 100 und ganz besonders bevorzugt für eine ganze Zahl von 5 bis 30 steht. A particularly suitable solvent for the colorant (F) is ethylene glycol, which belongs to the group of poly-Ci-Ce-alkylene glycols and contains repeating -CH2-CH2-O units. Ethylene glycols are compounds of the formula (EG-F)

(EG-F), where y is an integer from 1 to 10000, preferably an integer from 2 to 500, more preferably an integer from 3 to 100 and most preferably an integer from 5 to 30.

If y stands for the number 1, the ethylene glycol of formula (EG-F) is ethylene glycol itself, which is alternatively also called 1,2-ethanediol and has the CAS number 107-21-1.

A particularly preferred low-molecular-weight polyethylene glycol is PEG-8. PEG-8 contains an average of 8 ethylene glycol units (y1 = 8), has an average molecular weight of 400 g/mol, and bears the CAS number 25322-68-3. PEG-8 is also referred to as PEG 400 and is commercially available, for example, from APS.

Other suitable low molecular weight polyethylene glycols include PEG-6, PEG-7, PEG-9 and PEG-10.

Another suitable polyethylene glycol is PEG-32. PEG-32 contains 32 ethylene glycol units (y1 = 32), has an average molecular weight of 1500 g/mol, and carries the CAS number 25322-68-3. PEG-32 is also known as PEG 1500 and can be purchased commercially, for example, from Clariant. A particularly suitable high-molecular-weight polyethylene glycol is PEG 6000, which is commercially available from National Starch (China). The molecular weight of PEG 6000 is between 6000 and 7500 g/mol.

Another suitable polyethylene glycol is PEG 12000, which is marketed commercially by CG Chemicals under the trade name Polyethylene Glycol 12000 S (or PEG 12000 S). The molecular weight of PEG 12000 is stated to be between 10,500 and 15,000 g/mol.

Another suitable polyethylene glycol is PEG 20000, which is commercially available from Clariant under the trade name Polyglycol 20000 P or under the alternative name PEG-350. PEG 20000 has an average molecular weight of 20,000 g/mol.

The solvent(s) are preferably used in specific quantity ranges in the colorant (F). The colorant (F) preferably contains - based on the total weight of the colorant (F) - one or more solvents from the group consisting of water, poly-Ci-Ce-alkylene glycols, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, phenoxyethanol and benzyl alcohol in a total amount of 10.0 to 99.0 wt.%, preferably from 30.0 to 99.0 wt.%, more preferably from 50.0 to 99.0 wt.% and most preferably from 70.0 to 99.0 wt.%.

Sequence of procedural steps

As previously described, the cleanser is applied to pre-clean the keratin fibers and thus prior to the application of the colorant (F). In this context, it has proven particularly preferable to apply the cleanser to the keratin material, allow it to work for a certain period of time, and then rinse it off with water.

Particularly preferred is therefore a method for coloring keratin fibers, in particular human hair, comprising the following steps in the given order:

(l a) applying the cleaning agent, as disclosed in detail in the description of the first subject matter of the invention, to the keratin fibers,

(l b) allowing the cleaning agent applied in step (1) to act on the keratin fibers for a period of 2 to 45 minutes, preferably from 2 to 30 minutes and particularly preferably from 2 to 20 minutes,

(l c) Rinse out the cleaning agent with water,

(2a) applying the colorant (F) to the keratin fibers, and (2b) Exposing the colorant applied in step (4) to the keratin fibers for a period of 15 seconds to 45 minutes, preferably 30 seconds to 30 minutes, and particularly preferably 1 to 15 minutes.

In principle, the user can now freely choose the period of time between the application of the two remedies.

However, it may be preferred that no further agents, such as other conditioners, shampoos or styling agents, are applied between the application of the two agents. For this reason, the maximum period of time between the application of the two agents (V) and (F) is particularly preferably limited to a time interval of a maximum of 24 hours.

It has been found to be preferable if there is a period of maximum 24 hours, preferably maximum 12 hours, more preferably maximum 6 hours and most preferably maximum 3 hours between the application of the cleaning agent and the coloring agent (F).

Furthermore, it has also been found to be preferable if there is a period of maximum 24 hours, preferably maximum 12 hours, more preferably maximum 6 hours and most preferably maximum 3 hours between rinsing out the cleaning agent with water and applying a coloring agent (F) to the keratin fibers.

In a further preferred embodiment, a method according to the invention is characterized in that between the pre-cleaning of the keratin fibers in step (1) and the application of the coloring agent in step (2) there is a period of maximum 24 hours, preferably of maximum 12 hours, more preferably of maximum 6 hours and most preferably of maximum 3 hours.

In a further preferred embodiment, a process according to the invention is characterized in that step (2a) takes place directly after step (1c). Step (2a) involves the application of the colorant.

The action of the colorant (F) on the keratin fibers in step (2b) can, for example, take place for a period of 15 seconds to 30 minutes, preferably for a period of 30 seconds to 15 minutes, particularly preferably for a period of 1 to 15 minutes.

Use of the cleaning agent to improve wash fastness

The cleaning agents of the first subject matter of the invention described above improve the washfastness of keratinic fibers or hair that has been dyed with a colorant (F) containing at least one pigment and/or a direct dye. The washfastness of a color shade refers to the color change of a strand of hair dyed with that shade after multiple washes. This color change can involve either a shift in the color toward another shade or a fading of the color. Both color changes are equally undesirable for the user. Color shades with good washfastness show little or no color change even after repeated washes.

For the purposes of the present invention, an improvement in washfastness means that keratin fibers dyed with the colorant (F) have a higher color intensity when using the cleaning agent after a defined number of hair washes than without using the cleaning agent.

The improvement in washfastness can be quantified, for example, through colorimetric measurements (measurement of L, a, and b values) and calculation of the color difference. The smaller the color difference between washed and unwashed hair, the better the washfastness or color retention.

A third subject of the present invention is therefore the use of a cleaning agent, as disclosed in detail in the description of the first subject of the invention, for improving the washfastness of keratin fibers, in particular human hair, which have been dyed with a colorant containing at least one pigment and/or a direct dye.

Examples

1 . Cleaning agents

The following surfactant systems were prepared (all data in wt.% unless otherwise stated):

The following cleaning agents were produced using the surfactant systems prepared in this way:

V = Comparison E = Invention

The cleaning agent 1 tested for comparison contains a surfactant combination as found in a variety of commercially available shampoos.

2. Dye (F)

The following dye was prepared (all values in wt%)

3. Application to strands

Cleansing agents 1 to 4 were each applied to strands of hair (Kerling). 1.0 g of cleanser per gram of hair was applied to the strands, massaged in, and left to work at room temperature for 15 minutes. The strands were then rinsed with water.

Immediately afterward, the dye (F) was applied to the still-damp strands of hair (4.0 g of dye (F) per gram of hair) and massaged into each strand for 30 seconds. Another 4 g of water was added to the hair while the dye was still applied, and the hair was massaged again. After a 5-minute application time, each strand was rinsed under running water for 30 seconds and dried.

Reference strands were treated directly with the colorant (F) without the use of a cleaning agent. Before applying the colorant (F), the reference strand was moistened only with water, then the colorant was applied according to the procedure described above. These strands were also visually assessed by a trained person under a daylight lamp.

Following coloring, each colored strand underwent 20 manual washes. For each wash, the strand was moistened, then a commercially available shampoo (Schwarzkopf, Schauma 7 Herbs) was massaged into the strand for 25 seconds (0.25 g of shampoo per gram of hair). The strand was then rinsed with lukewarm tap water for 30 seconds and dried.

After 20 hair washes, each strand was again visually assessed under a daylight lamp.

The hair strands were assessed for their color intensity using a scale from 1 (very low color intensity) to 5 (very high color intensity).

0 HW = Color result directly after coloring

5 = high intensity 1 = low intensity

The strands dyed using the methods according to the invention showed improved washfastness compared to the corresponding dyeing without pre-cleaning.

The strands dyed with the methods according to the invention also showed improved washfastness and higher color intensity after 20 hair washes compared to the pretreatment with the cleaning agents 1 not according to the invention.

4. Measuring the roughness of the hair surface

Durch die Vorbehandlung mit allen Reinigungsmitteln 1 bis 4 konnte die Haaroberfläche im Vergleich zur nicht gereinigten Strähne aufgeraut werden. To measure the surface roughness of hair strands, the strands (Kerling Euronaturhaar white and Kerling 9.0) were treated with cleaning agents 1 to 4 as described above, then washed and dried. The cleaned strands were then examined under an Olympus OLS5100 laser microscope. Roughness was determined by image analysis using the software supplied with the microscope. The following roughness values were measured:

Pre-treatment with all cleaning agents 1 to 4 roughened the hair surface compared to the uncleaned strand.

The use of cleaning agents 2, 3, and 4 resulted in greater roughness than the use of cleaning agent 1. The greatest roughness was achieved with cleaning agents 2 and 4, especially with cleaning agent 4.

Claims

Patent claims 1. A cosmetic agent for cleaning keratin fibers, in particular human hair, containing a surfactant system in a cosmetic carrier, wherein the surfactant system - based on the total weight of the surfactant system - comprises (a) 30 to 75 wt.% of one or more anionic sulfate and/or sulfonate surfactants, (b) 10 to 35 wt.% of one or more surfactants selected from the group consisting of alkoxylated fatty alcohols, amphoteric surfactants and zwitterionic surfactants, and (c) 5 to 45% by weight of one or more non-ionic sugar surfactants, the amounts of (a), (b) and (c) adding up to a maximum of 100% by weight. 2. Agent according to claim 1, characterized in that the cosmetic carrier is an aqueous or an aqueous-alcoholic carrier and the agent contains - based on the total weight of the agent - 0.1 to 30 wt.%, preferably 0.5 to 25 wt.% and particularly preferably 1.0 to 20 wt.% of the surfactant system. 3. Agent according to one of claims 1 to 2, characterized in that it contains a surfactant system which, based on the total weight of the surfactant system, comprises (a) 30 to 70 wt.% of one or more anionic sulfate or sulfonate surfactants selected from the group consisting of - Dialkyl sulfosuccinates whose two alkyl groups are selected from identical or different, branched or unbranched C2 to C12 alkyl groups, - Alkyl sulfates and alkyl polyglycol ether sulfates of the formula R9-O-(CH2-CH2O) _n -SO3X, in which R9 preferably represents a straight-chain or branched, saturated or mono- or polyunsaturated alkyl or alkenyl radical having 8 to 22 carbon atoms, n represents 0 or 1 to 12, and X represents an alkali or alkaline earth metal ion or profaned triethanolamine or the ammonium ion, - straight-chain or branched, saturated or mono- or polyunsaturated alkylsulfonates with 8 to 22 C atoms, - linear alpha-olefin sulfonates with 8 to 22 C atoms, - Acyl isethionates whose acyl group is selected from a branched or unbranched Ca to C22 alkyl group, - N-acyl taurates, whose acyl group is selected from a branched or unbranched Ca to C22 alkyl group, and/or the salts of the aforementioned compounds. 4. Agent according to one of claims 1 to 3, characterized in that it contains a surfactant system which, based on the total weight of the surfactant system, comprises (a) 30 to 70% by weight, preferably 35 to 68% by weight, more preferably 40 to 66% by weight and most preferably 50 to 65% by weight of one or more dialkyl sulfosuccinates and/or salts thereof, most preferably 1,4-bis(2-ethylhexyl) sulfosuccinate in the form of its sodium salt. 5. Agent according to one of claims 1 to 4, characterized in that it contains a surfactant system which, based on the total weight of the surfactant system, comprises (b) 10 to 35% by weight of one or more surfactants from the group of alkoxylated fatty alcohols, preferably from the group of ethoxylated fatty alcohols, particularly preferably from the group of ethoxylated Ca-C22 alcohols with 1 to 15 EO, in particular Ci2-C18 alcohols with 7 EO. 6. Agent according to one of claims 1 to 5, characterized in that it contains a surfactant system which, based on the total weight of the surfactant system, comprises (b) 15 to 34 wt.%, preferably 18 to 33 wt.%, more preferably 21 to 32 wt.%, even more preferably 24 to 31 wt.% and most preferably 27 to 30 wt.% of one or more ethoxylated C8-C22 alcohols having 1 to 15 EO. 7. Agent according to one of claims 1 to 6, characterized in that it contains a surfactant system which, based on the total weight of the surfactant system, comprises (c) 5 to 45 wt.% of one or more non-ionic sugar surfactants selected from the group consisting of alkyl (poly)glucosides (APG) and mannosyl erythritol lipids (MEL). 8. Agent according to one of claims 1 to 7, characterized in that it contains a surfactant system which, based on the total weight of the surfactant system, comprises (c) 6 to 40 wt.%, preferably 7 to 35 wt.%, more preferably 8 to 30 wt.%, even more preferably 9 to 25 wt.% and most preferably 10 to 20 wt.% of alkyl(poly)glucosides (APG). 9. Agent according to one of claims 1 to 8, characterized in that the surfactants (a), (b) and (c) make up a proportion of at least 65% by weight, preferably at least 75% by weight, more preferably at least 85% by weight, even more preferably at least 95% by weight and particularly preferably at least 99% by weight of the total surfactant content of the agent. 10. Agent according to one of claims 1 to 9, characterized in that it contains no further surfactants apart from the surfactants (a), (b) and (c). 11. Agent according to one of claims 1 to 10, characterized in that it contains a surfactant system which has an HLD value (hydrophilic lipophilic deviation) of -4 to 0.5, preferably of -3.5 to 0 and particularly preferably of -2 to 0. 12. Agent according to one of claims 1 to 11, characterized in that it additionally contains at least one further component selected from the group consisting of anionic polymers, cationic polymers, non-ionic polymers, preservatives and fragrances. 13. A process for dyeing keratin fibers, in particular human hair, comprising the following steps in the specified order: (1) Application of an agent according to any one of claims 1 to 12 for pre-cleaning the keratin fibers, and (2) Application of a colorant (F), wherein the colorant contains at least one coloring compound from the group of pigments and direct dyes. 14. The method according to claim 13, characterized in that the colorant (F) additionally contains at least one organic silicon compound selected from the group consisting of (3-aminopropyl)triethoxysilane, (3-aminopropyl)trimethoxysilane, (2-aminoethyl)triethoxysilane, (2-aminoethyl)trimethoxysilane, (3-dimethylaminopropyl)triethoxysilane, (3-dimethylaminopropyl)trimethoxysilane, (2-dimethylaminoethyl)triethoxysilane, (2-dimethylaminoethyl)trimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, Octadecyltrimethoxysilane and octadecyltriethoxysilane and/or their hydrolysis and/or condensation products. 15. The method according to any one of claims 13 to 14, characterized in that the coloring agent (F) additionally contains at least one chitosan and/or a chitosan derivative. 16. The method according to any one of claims 13 to 15, characterized in that the colorant (F) additionally contains at least one amino-functionalized silicone polymer. 17. The method according to any one of claims 13 to 16, characterized in that between the pre-cleaning of the keratin fibers in step (1) and the application of the coloring agent in step (2) there is a period of a maximum of 24 hours, preferably a maximum of 12 hours, more preferably a maximum of 6 hours and most preferably a maximum of 3 hours. 18. Use of an agent according to any one of claims 1 to 12 for improving the washfastness of keratin fibers, in particular human hair, which have been dyed with a colorant containing at least one pigment and/or a direct dye.