WO2024110116A1

WO2024110116A1 - Low-water content agent for dyeing keratinous fibers, in particular human hair, containing aminosilicones, pigments, alkylene glycols and cellulose (derivatives)

Info

Publication number: WO2024110116A1
Application number: PCT/EP2023/078598
Authority: WO
Inventors: Constanze KRUCK; Gabriele Weser; Ulrike Schumacher; Sandra Hilbig
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2022-11-21
Filing date: 2023-10-16
Publication date: 2024-05-30
Also published as: DE102022212410A1

Abstract

The present invention relates to an agent for dyeing keratinous fibers, in particular human hair, containing - in relation the total weight of the agent - (a1) at least alkylene glycol of the formula (AG), where x is an integer from 0 to 10,000, y is an integer from 0 to 10,000, Ra and Rb independently of one another represent a hydrogen atom, a C1-C6 alkyl group or a hydroxy-C1-C6 alkyl group, Rc represents a hydrogen atom, a C1-C6 alkyl group, a phenyl group or a benzyl group, with the proviso that x + y is at least 1; (a2) is at least one pigment; (a3) is at least one amino-functionalized silicone polymer; (a4) is less than 10 wt.-% water; and (a5) is cellulose and/or a cellulose derivative.

Description

Low-water agent for dyeing keratin fibers, especially human hair, containing aminosilicones, pigments, alkylene glycols and cellulose (derivatives)

The present application relates to a low-water agent for dyeing keratin fibers, in particular human hair, which contains at least one alkylene glycol of a specific formula (a1), at least one pigment (a2), at least one amino-functionalized silicone polymer (a3) and cellulose and/or a derivative of cellulose (a5).

Another subject matter of this application is a method for dyeing keratin fibers, in particular human hair, wherein the agent described above is applied to previously moistened keratin fibers and optionally rinsed out again after an exposure time of 30 seconds to 45 minutes.

Changing the shape and color of keratin fibers, especially human hair, is an important area of modern cosmetics. Depending on the coloring requirements, experts know of various coloring systems for changing hair color. Oxidation dyes are usually used for permanent, intensive coloring with good fastness properties and good gray coverage. Such dyes contain oxidation dye precursors, so-called developer components and coupler components, which form the actual dyes under the influence of oxidizing agents such as hydrogen peroxide. Oxidation dyes are characterized by very long-lasting coloring results.

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

The use of color pigments is known for short-term color changes on the hair and/or skin. Color pigments are generally understood to be insoluble, color-giving substances. These are present undissolved in the form of small particles in the coloring formulation and are only deposited on the outside of the hair fibers and/or the surface of the skin. Therefore, they can usually be removed without residue by washing them a few times with detergents containing surfactants. Various products of this type are available on the market under the name hair mascara. If the user wants particularly long-lasting coloring, the use of oxidative dyes is currently the only option. However, despite numerous attempts at optimization, an unpleasant ammonia or amine smell cannot be completely avoided with oxidative hair coloring. The hair damage still associated with the use of oxidative dyes also has a detrimental effect on the user's hair. One ongoing challenge is therefore the search for alternative, high-performance dyes and dyeing processes. Recently, the focus has been on dyeing systems based on pigments.

The work carried out on pigment-based dyes has shown that aminosilicones, especially aminosilicones with certain structural features, can immobilize colored pigments very well on the surface of hair.

In further studies it was found that the adhesion of the pigments to the hair surface can be further improved by choosing a suitable cosmetic base. In particular, low-water or water-free compositions based on alkyl glycols have led to good results in this regard.

In WO 2022/223238 A1, for example, it was shown that anhydrous dyes which contain at least one alkylene glycol in addition to a pigment and an aminosilicone lead to dyeings with very good wash fastness properties.

In WO 2022/223236 A1, the wash fastness of pigment-based colorants could also be improved by combining pigment, aminosilicone and polyethylene glycol. In one embodiment of WO 2022/223236 A1, the colorants are low in water.

In both of the above-mentioned low-water or water-free dyes, the formulation is thickened by the alkylene glycols or polyethylene glycols, which control the viscosity of the composition so that the products are thin enough to be evenly distributed on the hair, but are also thick enough to prevent the product from dripping during the exposure time. If these dyes are applied to dry hair, the application takes place without any further problems and no changes in the rheological properties occur during the time the dye is on the head.

However, other studies have shown that it can be beneficial to pretreat the hair before applying the dye. For example, the studies carried out in WO 2021/104701 A1 have shown that pretreating the hair with a pretreatment agent containing anionic surfactants before applying the dye improves both the It can improve both the color intensity and the evenness of the coloring. If a pre-treatment product is applied to the hair and then rinsed off, the hair is damp or towel-dried after rinsing. In order to make the coloring process as short and comfortable as possible for the user, it is a great advantage not to dry the hair after applying the pre-treatment product, but to distribute the coloring product immediately on the towel-dried or damp hair.

However, when the dyes described in WO 2022/223238 A1 or WO 2022/223236 A1 were applied to damp hair, it was found that the addition of additional water caused the thickening of the formulation to collapse and the dye dripped from the test subject's head in an unfavorable manner over the course of the application period. In other words, it has been found that alkylene glycols or polyethylene glycols, which act both as a base carrier and as a thickener in compositions of this type, react very sensitively to a small variation in the water content. These agents therefore had to be further improved for use on damp or towel-dried hair.

The object of the present invention was to provide a colorant based on pigments, aminosilicones and alkylene glycols that produces intensive and uniform colors with good wash fastness. The agents should be particularly easy to use on damp or towel-dried hair, should not change adversely with regard to their rheological properties and should not drip down from the hair during the application period. The other application properties such as hair feel, uniformity of coloring and color intensity should also not be negatively affected when the agents are used.

Surprisingly, it has now been found that this task can be solved very well if keratin fibers, in particular human hair, are dyed with a low-water or anhydrous agent which, in addition to at least one alkylene glycol of the formula (AG), at least one pigment and an amino-functionalized silicone polymer, additionally contains cellulose and/or a derivative of cellulose.

A first subject of the present invention is an agent for dyeing keratin fibers, in particular human hair, containing - based on the total weight of the agent -

(a1) at least alkylene glycol of formula (AG)

where x is an integer from 0 to 10000, y is an integer from 0 to 10000,

Ra, Rb independently represent a hydrogen atom, a Ci-Ce-alkyl group or a hydroxy-O-Ce-alkyl group,

Rc represents a hydrogen atom, a Ci-Ce alkyl group, a phenyl group or a benzyl group, with the proviso that x + y is at least 1, and

(a2) at least one pigment, and

(a3) at least one amino-functionalized silicone polymer, and

(a4) less than 10 wt.% water, and

(a5) Cellulose and/or a cellulose derivative.

These products were particularly easy to handle and had a stable viscosity, especially when applied to pre-treated and therefore still damp or towel-dried hair. No dripping of the product was observed and the resulting colors were very intense and even. keratin fibers

Keratin fibers include hair, wool, fur and feathers. Human hair, eyelashes and eyebrows are preferred among keratin fibers. Human head hair is particularly preferred among keratin fibers.

Coloring agents

The term “coloring agent” is used in the context of this invention for the coloring of keratin fibers, in particular hair, caused by the use of pigments. In this coloring, the pigments are deposited as color-imparting compounds in a particularly homogeneous and uniform film on the surface of the keratin fibers.

According to the invention, the coloring agent is a ready-to-use agent. This ready-to-use agent can, for example, be filled into a container and applied to the keratin fibers in this form without further dilution, mixing or other process steps. For reasons of storage stability, however, it has proven particularly preferable if the ready-to-use cosmetic agent is only used by the hairdresser or user shortly before Application is prepared. To prepare the ready-to-use agent, for example, the mixture or pre-dispersion of alkylene glycol of the formula (AG) (a1), pigment (a2) and cellulose (derivative) (a5) can be carried out with one or more further agents, one of these further agents containing at least one amino-functionalized silicone polymer (a3). However, it is equally conceivable that the ready-to-use agent is prepared by mixing at least three different agents, one of these agents containing at least one alkylene glycol of the formula (AG) (a1) and cellulose or a derivative thereof (a5), another agent containing at least one pigment (a2) and yet another agent containing at least amino-functionalized silicone polymer (a3). The agents can be mixed, for example, by shaking, thus ensuring a particularly even distribution of the dispersed pigments. The resulting ready-to-use agent is characterized in that it contains, based on the total weight of the ready-to-use agent, less than 10% by weight of water (a4).

Alkylene glycols of the formula (AG) (a1)

As the first essential component (a1), the agent according to the invention contains at least one alkylene glycol of the formula (AG)

where x is an integer from 0 to 10000, y is an integer from 0 to 10000,

Ra, Rb independently represent a hydrogen atom, a Ci-Ce-alkyl group or a hydroxy-Ci-Ce-alkyl group,

Rc represents a hydrogen atom, a Ci-Ce alkyl group, a phenyl group or a benzyl group, with the proviso that x + y is at least 1.

Surprisingly, it has been found that the use of at least one special alkylene glycol of the formula (AG) greatly improves the wash resistance of the colorations after application of the agent according to the invention to the keratin fibers.

The alkylene glycols of the formula (AG) are protic substances with at least one hydroxy group. The substituents Ra, Rb, Rc in the compounds of the formula (AG-I) are explained below by way of example: Examples of a Ci-Ce-alkyl group are the groups methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl and t-butyl, n-pentyl and n-hexyl. Propyl, ethyl and methyl are preferred alkyl radicals. Preferred examples of a hydroxy-Ci-Ce-alkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 2-hydroxypropyl, a 3-hydroxypropyl, a 4-hydroxybutyl group, a 5-hydroxypentyl and a 6-hydroxyhexyl group; the hydroxymethyl group and the 2-hydroxyethyl group are particularly preferred.

By varying the residues Ra, Rb and Rc as well as x and y, the polarity of the alkylene glycol (AG) can be adjusted and the viscosity of the agent according to the invention can be influenced.

In the alkylene glycols (a1) of the formula (AG), x can be an integer from 0 to 10000.

The residue y can be an integer from 0 to 10000. The proviso is that the sum of x and y must be at least 1. If y is 0, the residues Ra and Rb are non-existent in the alkylene glycols of the formula (AG).

The radical R _c stands for a hydrogen atom, a Ci-Ce-alkyl group, a phenyl group or a benzyl group. In this embodiment, it is furthermore particularly preferred if R c stands for a hydrogen atom.

The use of certain alkylene glycols of the formula (AG) has proven to be particularly suitable for producing dyes with good wash fastness and good rub fastness. In this embodiment, the use of polyethylene glycols is particularly preferred.

Polyethylene glycols are alkylene glycols of the formula (AG) in which x is an integer from 1 to 10,000, in particular an integer from 2 to 10,000, and y is the number 0. Rc is a hydrogen atom.

In a further particularly preferred embodiment, an agent according to the invention is characterized in that it

(a1) contains at least alkylene glycol of the formula (AG), where x is an integer from 1 to 10,000, and y is the number 0, and Rc is a hydrogen atom.

The corresponding polyethylene glycols are the compounds of the formula (AG'),

where x' is an integer from 1 to 10000. In the course of the work leading to this invention, it has been found that polyethylene glycols are particularly suitable for improving the fastness properties of the dyes and for optimally adjusting the viscosity of the dyes.

Depending on their chain length, polyethylene glycols are liquid or solid, water-soluble polymers. Polyethylene glycols with a molecular weight between 200 g/mol and 400 g/mol are non-volatile liquids at room temperature. PEG 600 has a melting range of 17 to 22 °C and thus a paste-like consistency. With molecular weights above 3000 g/mol, PEGs are solid substances and are sold as flakes or powder.

The use of low molecular weight polyethylene glycols in particular has proven to be particularly suitable for solving the problem of the invention. In the case of low molecular weight polyethylene glycols in the sense of the present invention, x' (then referred to as x1) is an integer from 1 to 100, preferably an integer from 1 to 80, more preferably an integer from 2 to 60, even more preferably an integer from 3 to 40, even more preferably an integer from 4 to 20 and very particularly preferably an integer from 6 to 15.

(a1) contains at least one alkylene glycol of formula (AG-1), wherein

(AG-1), x1 is an integer from 1 to 100, preferably an integer from 1 to 80, more preferably an integer from 2 to 60, even more preferably an integer from 3 to 40, even more preferably an integer from 4 to 20 and most preferably an integer from 6 to 15.

A particularly preferred low molecular weight polyethylene glycol is, for example, PEG-8. PEG-8 comprises 8 ethylene glycol units (x1 = 8), has an average molecular weight of 400 g/mol and has the CAS number 25322-68-3. PEG-8 is also alternatively referred to as PEG 400 and is commercially available from the company APS, for example.

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 (x1 = 32), has an average molecular weight of 1500 g/mol and has the CAS number 25322-68-3. PEG-32 is also known as PEG 1500 and can be purchased commercially from Clariant, for example.

Furthermore, the use of high molecular weight polyethylene glycols has also proven to be well suited to solving the problem according to the invention.

High molecular weight polyethylene glycols in the sense of the present invention can be represented by the formula (AG-2), where the index number x2 stands for an integer from 101 to 10000

In the case of particularly suitable high molecular weight polyethylene glycols, x2 represents an integer from 101 to 1000, preferably an integer from 105 to 800, more preferably an integer from 107 to 600, even more preferably an integer from 109 to 400 and most preferably an integer from 110 to 200.

(a1) contains at least one alkylene glycol of formula (AG-2), wherein

(AG-2), x2 for an integer from 101 to 1000, preferably for an integer from

105 to 800, more preferably an integer from 107 to 600, even more preferably an integer from 109 to 400 and most preferably an integer from 1 10 to 200.

A particularly suitable high molecular weight polyethylene glycol is PEG 6000, which can be obtained commercially from National Starch (China). The molecular weight of PEG 6000 is 6000 to 7500 g/mol, which corresponds to a x2 value of 136 to 171.

Another suitable polyethylene glycol is PEG 12000, which is sold, for example, under the trade name Polyethylene Glycol 12000 S (or PEG 12000 S) by the company CG Chemicals is sold commercially. The molecular weight of PEG 12000 is given as 10500 to 15000 g/mol, corresponding to a x2 value of 238 to 341 .

Another suitable polyethylene glycol is PEG 20000, which is 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 20000 g/mol, which corresponds to a x2 value of 454.

Surprisingly, it has been found that colorants containing both a low molecular weight alkylene glycol (AG-1) and a high molecular weight alkylene glycol (AG-2) have particularly good application properties, since these agents have both very good fastness properties and are optimized with regard to their rheological profile.

In a further explicitly particularly preferred embodiment, an agent according to the invention is therefore characterized in that it

(a11) contains at least one first alkylene glycol of the formula (AG-1), wherein

x1 for an integer from 1 to 100, preferably for an integer from 1 to

80, more preferably an integer from 2 to 60, even more preferably an integer from 3 to 40, even more preferably an integer from 4 to 20 and most preferably an integer from 6 to 15, and

(a12) contains at least a second alkylene glycol of formula (AG-2), wherein

x2 stands for an integer from 101 to 1000, preferably for an integer from 105 to 800, more preferably for an integer from 107 to 600, even more preferably for an integer from 109 to 400 and most preferably for an integer from 1 10 to 200. Since the agent according to the invention has a low water content or is water-free, components other than water must also be selected for the cosmetic carrier of the agent. In this context, it has proven to be particularly preferred if the alkylene glycol(s) (AG), and in particular the particularly preferred compounds of the formula (AG-1) and/or (AG-2), themselves function as cosmetic carrier substances. For this purpose, the alkylene glycols (AG) are particularly preferably used in the correspondingly high quantity ranges in the agent according to the invention. These amounts of alkylene glycols (AG) used can, for example - based on the total weight of the agent - be in the range from 10.0 to 99.0% by weight, preferably from 30.0 to 99.0% by weight, more preferably from 50.0 to 99.0% by weight and very particularly preferably from 70.0 to 99.0% by weight.

Very particularly preferably, the alkylene glycol(s) of formula (AG-1) and/or the alkylene glycol(s) of formula (AG-2) are also contained in the composition, preferably in certain quantity ranges.

It has been found to be particularly preferred if the agent - based on the total weight of the agent - contains (a1) one or more alkylene glycols of the formula (AG-1) in a total amount of 20.0 to 99.0 wt.%, preferably 40.0 to 95.0 wt.%, particularly preferably 60.0 to 90.0 wt.%.

Furthermore, it has been found to be particularly preferred if the agent - based on the total weight of the agent - contains one or more alkylene glycols of the formula (AG-2) in a total amount of 1.0 to 35.0 wt.%, preferably 3.0 to 30.0 wt.%, particularly preferably 4.0 to 25.0 wt.%.

In a further very particularly preferred embodiment, an agent according to the invention is therefore characterized in that it contains - based on the total weight of the agent - (a1) one or more alkylene glycols of the formula (AG-1) in a total amount of 20.0 to 99.0 wt. %, preferably 40.0 to 95.0 wt. %, particularly preferably 60.0 to 90.0 wt. %, and/or it contains one or more alkylene glycols of the formula (AG-2) in a total amount of 1.0 to 35.0 wt. %, preferably 3.0 to 30.0 wt. %, particularly preferably 4.0 to 25.0 wt. %.

Explicitly very particularly preferred is an agent which - based on the total weight of the agent - (a1) contains one or more alkylene glycols of the formula (AG-1) in a total amount of 20.0 to 99.0 wt. %, preferably 40.0 to 95.0 wt. %, particularly preferably 60.0 to 90.0 wt. %, and it contains one or more alkylene glycols of the formula (AG-2) in a total amount of 1.0 to 35.0 wt. %, preferably 3.0 to 30.0 wt. %, particularly preferably 4.0 to 25.0 wt. %. Furthermore, the agent according to the invention can also contain at least one alkylene glycol of the formula (AG)

(AG), where x stands for the number 1, y stands for the number 0, and Rc stands for a phenvlaruooe.

If y is 0, no structural unit comprising the substituents Ra and Rb exists in the general formula (AG).

In a further embodiment, a particularly preferred agent is characterized in that it contains (a1) at least one alkylene glycol of the formula (AG), where x is the number 1 and y is the number 0, and

Rc stands for a phenyl group.

The compound of this type is phenoxyethanol. In particular, the agent according to the invention contains at least one alkylene glycol of the formula (AG-1) and at least one alkylene glycol of the formula (AG-2) and phenoxyethanol.

The content of phenoxyethanol in the agent according to the invention is - based on the total weight of the agent - preferably from 0.1 to 10.0 wt.%, preferably from 0.2 to 5.0 wt.%, more preferably from 0.3 to 2.5 wt.% and very particularly preferably from 0.4 to 1.5 wt.%.

Furthermore, the agent according to the invention can also contain at least one alkylene glycol of the formula (AG)

where x stands for the number 0, and y stands for the number 1, and

Ra stands for a hydrogen atom, and

Rb stands for a methyl group, and

Rc stands for a hydrogen atom.

In a further embodiment, a particularly preferred agent is characterized in that it contains (a1) at least one alkylene glycol of the formula (AG), where x is the number 0 and y is the number 1, and

Ra stands for a hydrogen atom, and Rb stands for a methyl group, and

Rc stands for a hydrogen atom.

If x is 0, no structural unit -CH2-CH2-O- exists in the compounds of the general formula (AG).

The compound of this type is 1,2-propanediol. The agent according to the invention preferably contains at least one alkylene glycol of the formula (AG-1) and at least one alkylene glycol of the formula (AG-2) and 1,2-propanediol. The agent according to the invention particularly preferably contains at least one alkylene glycol of the formula (AG-1) and at least one alkylene glycol of the formula (AG-2) and phenoxyethanol and 1,2-propanediol.

The content of 1,2-propanediol in the agent according to the invention is - based on the total weight of the agent - preferably from 0.1 to 20.0 wt.%, preferably from 1.0 to 10.0 wt.%, more preferably from 2.0 to 8.0 wt.% and very particularly preferably from 2.5 to 6.5 wt.%.

It is understood that the sum of (a1) all alkylene glycols (AG), pigments (a2) and amino-functionalized silicone polymers (a3) and cellulose (derivatives) (a5) contained in the agent cannot be more than 100% by weight. If a correspondingly small amount of water (a4) and/or other optional ingredients are present in the agent, the total sum of (a1), (a2), (a3) and (a5) is reduced accordingly to values of less than 100% by weight.

Pigments (a2)

As a second essential component, the agent according to the invention contains at least one pigment (a2). Pigments in the sense of the present invention are understood to mean 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, by means of the method described below: 0.5 g of the pigment are weighed in a beaker. A stir bar is added. Then one liter 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 assessed visually due to the high intensity of the pigment, which may be finely dispersed, 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.

Suitable color pigments can be of inorganic and/or organic origin.

In a preferred embodiment, an agent according to the invention is characterized in that it contains at least one coloring compound (a2) from the group of inorganic and/or organic pigments.

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 terra di siena or graphite, for example. Black pigments such as iron oxide black, colored pigments such as ultramarine or iron oxide red as well as fluorescent or phosphorescent pigments can also be used as inorganic color 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 (CI77289), iron blue (ferric ferrocyanide, CI77510) and/or carmine (cochineal).

Colored pearlescent pigments that are also particularly preferred according to the invention are colored pearlescent pigments. These are usually based on mica and/or mica and can be coated with one or more metal oxides. Mica is one of the 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 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 (mica) and are coated with a or several 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, an agent according to the invention is characterized in that it contains at least one inorganic pigment (a2), 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, an agent according to the invention is characterized in that it contains at least one coloring compound (a2) from the group of pigments selected from mica-based pigments coated with one or more metal oxides from the group 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 colour 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 Aborigine 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 DIOXIDE), CI 77510 (FERRIC FERROCYANIDE)

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

Colorona Imperial Red, Merck, MICA, TITANIUM DIOXIDE (Cl 77891), D&C RED NO. 30 (Cl73360)

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

Colorona Light Blue, Merck, MICA, TITANIUM DIOXIDE (Cl 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® are, for example:

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 Magie 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 agent according to the invention can also contain one or more coloring compounds (a2) from the group of organic pigments

The organic pigments according to the invention are correspondingly insoluble, organic dyes or colored lakes which can be selected, for example, from the group of nitroso, nitro, azo, xanthene, anthraquinone, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, 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, an agent according to the invention is characterized in that it contains at least one organic pigment (a2), 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 11725, 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.

The organic pigment can also be a colored lake. For the purposes of the invention, the term colored lake refers to particles which comprise a layer of absorbed dyes, whereby the unit of particle and dye is 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. Due to their excellent light and temperature resistance, the use of the aforementioned pigments in the agent according to the invention is particularly preferred. It is also preferred if the pigments used have a certain 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 from 5.0 to 45 pm, preferably from 10 to 40 pm, in particular from 14 to 30 pm. The average particle size D50 can be determined, for example, using dynamic light scattering (DLS).

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. Coloring based on a substrate plate that contains a vacuum-metallized pigment is also possible.

In a further preferred embodiment, an agent according to the invention is characterized in that it contains at least one pigment (a2) which is 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, particularly 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, particularly 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 as uniform a thickness as possible. Due to the low thickness of the substrate platelets, the pigment has a particularly high hiding power.

The substrate platelets are preferably monolithic in structure. Monolithic in this context means consisting of a single, closed unit without breaks, layers or inclusions, although structural changes can occur within the substrate platelets. The substrate platelets are preferably homogeneous in structure, i.e. no concentration gradient occurs within the platelets. In particular, the substrate platelets are not layered and do not have any particles or particles distributed within them.

The size of the substrate plate can be tailored to the respective application, in particular the desired effect on the keratin material. As a rule, the substrate platelets have an average largest diameter of about 2 to 200 pm, in particular about 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, 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. To prepare the sample, the sample to be examined was predispersed in isopropanol for a period of 3 minutes.

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

They can be of natural origin, but can also be 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 constructed from metal (alloys).

Any metal suitable for metallic luster pigments can be considered as a metal. 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 substrate 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 proportion of scattered light. In addition, pigments based on lamellar substrate platelets do not completely cover the existing color of a keratin material and effects analogous to natural graying can be achieved, for example.

Lenticular (= lens-shaped) substrate platelets have an essentially 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 (VMP) can be obtained, for example, by releasing metals, metal alloys or metal oxides from appropriately coated films. They are characterized by a particularly low thickness of the substrate platelets in the range of 5 to 50 nm and by a particularly smooth surface with increased reflectivity. Substrate platelets which comprise a pigment metallized in a vacuum are also referred to as VMP substrate platelets in the context of this application. VMP substrate platelets made of aluminum can be obtained, for example, by releasing aluminum from metallized films.

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 the incident light to a high degree and produce a light-dark flop. These have proven to be 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, which comprises a vacuum metallized pigment, are available, for example, under the name Alegrace® Marvelous or Alegrace® Aurous from Schlenk Metallic Pigments GmbH.

The pigments (a2) represent the second essential component of the composition according to the invention and are preferably used in the composition in certain quantity ranges.

Particularly good results were obtained when the agent - based on the total weight of the agent - contained one or more pigments (a2) 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. %.

In a further very particularly preferred embodiment, an agent according to the invention is characterized in that the agent contains - based on the total weight of the agent - one or more pigments (a2) in a total amount of 0.01 to 10.0 wt. %, preferably 0.1 to 5.0 % by weight, more preferably from 0.2 to 2.5 % by weight and most preferably from 0.25 to 1.5 % by weight. amino-functionalized silicone polymers (a3)

As a third ingredient essential to the invention, the agent according to the invention contains at least one amino-functionalized silicone polymer (a3). The amino-functionalized silicone polymer can alternatively also be referred to as aminosilicone or amodimethicone.

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.

The silicone polymers comprise many Si-O repeat units, where the Si atoms can carry organic radicals such as alkyl groups 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 repeat units, preferably more than 50 Si-O repeat units and particularly preferably more than 100 Si-O repeat units, most preferably more than 500 Si-O repeat units.

An amino-functionalized silicone polymer is understood to mean a functionalized silicone which carries at least one structural unit with an amino group. The amino-functionalized silicone polymer preferably carries several 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 effects could be achieved with amino-functionalized silicone polymers (a3) if they carry at least one primary, at least one secondary and/or at least one tertiary amino group. However, colorations with the highest color intensities were observed if an amino-functionalized silicone polymer (a3) was used in the agent which contains at least one secondary amino group.

In a particularly preferred embodiment, an agent according to the invention is characterized in that it additionally

(a3) at least one amino-functionalized silicone polymer having at least one secondary amino group.

The secondary amino group(s) can be located at different positions on the amino-functionalized silicone polymer. Particularly good effects were found when an amino-functionalized silicone polymer (a3) was used 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.

In a further very particularly preferred embodiment, an agent according to the invention is characterized in that the agent contains at least one amino-functionalized silicone polymer (a3) which comprises at least one structural unit of the formula (Si-amino),

-Amino) where

ALK1 and ALK2 independently represent a linear or branched, divalent C1-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 can be bonded to another oxygen atom, and the oxygen atom adjacent to the star can 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 from the silicon atom to the ALK1 group, and the second bond is between ALK1 and the secondary amino group.

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

Examples of a linear divalent C1-C2o-alkylene group are, for example, 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 C 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 repeat 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.

Colours with the highest colour intensities could be obtained when an agent was applied to the keratin fibres containing at least one amino-functionalised silicone polymer

(a3) which comprises structural units of the formula (Si-I) and the formula (Si-II)

(Si-Il), 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.

In a further embodiment, an agent according to the invention is therefore particularly preferably 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 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 radical R1 in the structural units of the formula (Si-II) is a methyl group or a hydrogen atom. The radical R2 is a Ci-Ce-alkyl group or a Ci-Ce-alkoxy group. The radical R2 is particularly preferably 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 stands for a methyl group and R2 stands for a methyl group.

A particularly suitable amino-functionalized silicone polymer with the structural units (Si-I) and (Si-II), in which R2 stands for a methyl group and R1 stands for a methyl group, is, for example, the commercial product DC 2-8566 or Dowsil 2-8566 Amino Fluid, which is sold commercially by the Dow Chemical Company and which has 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 sold commercially by the Dow Chemical Company. Within the scope of a further embodiment, an agent according to the invention is therefore particularly preferably 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 is a hydrogen atom and R2 is a methyl group.

Another particularly suitable amino-functionalized silicone polymer with the structural units (Si-I) and (Si-II), in which R2 stands for a methyl group and R1 stands for a hydrogen atom, is, for example, the commercial product Wacker Belsil ADM 1370, which is sold by Wacker and which is named as Siloxanes and Silicones, “3-((2-Aminoethyl)amino)propyl Me, di-Me” and has the CAS number 71750-79-3.

Within the scope of a further embodiment, an agent according to the invention is therefore particularly preferably 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 is a hydrogen atom and R2 is a methoxy group.

Another particularly suitable amino-functionalized silicone polymer with the structural units (Si-I) and (Si-II), in which R1 is a hydrogen atom and R2 is a methoxy group, is the commercial product Silamine MUE, which is sold commercially by Tiltech Corp and which has the chemical name "Siloxanes and Silicones, di-Me, [[[3- (2-Aminoethyl)amino]propyl]dimethoxysilyl]oxy-terminated" and has the CAS number 71750-80-6. In Silamine MUE, the structural units of the formula (Si-II) are therefore located at both ends of the amino silicone, and the oxygen atom of the -Si-O- group is part of a second methoxy group within the group (Si-II).

These described suitable and particularly suitable aminosilicones are linear silicone polymers.

Particularly preferred is an agent for dyeing keratin fibers, in particular human hair, containing - based on the total weight of the agent -

(a1) at least alkylene glycol of formula (AG), wherein formula (AG) has been previously described,

(a2) at least one pigment, and

(a3) at least one linear amino-functionalized silicone polymer, and

(a4) less than 10 wt.% water, and

(a5) Cellulose and/or a cellulose derivative.

Linear aminosilicone polymers are macromolecules that consist of only one polymer main chain, i.e. the polymer comprises a main chain of repeating Si-O- Units. The silicon atoms can be part of the structural units (Si-I) and/or (Si-II), but the Si-O chain is not branched, ie there is no branching to further -Si-O- groups at the Si atom.

In a further preferred embodiment, an agent according to the invention is characterized in that it contains at least one amino-functional silicone polymer (a3) of the formula (Si-III),

where m and n are numbers chosen so that the sum (n + m) is in the range from 1 to 1000, n is a number in the range from 0 to 999 and m is a number in the range from 1 to 1000,

R1, R2 and R3, which are the same or different, represent a hydroxy group or a C1-4 alkoxy group, wherein at least one of the groups R1 to R3 represents a hydroxy group;

Further preferred agents according to the invention are characterized by their content of at least one amino-functional silicone polymer (a3) of the formula (Si-IV),

in which p and q are numbers chosen so that the sum (p + q) is in the range 1 to 1000, p is a number in the range 0 to 999 and q is a number in the range 1 to 1000,

R1 and R2, which are different, represent a hydroxy group or a C1-4 alkoxy group, wherein at least one of the groups R1 to R2 represents a hydroxy group.

The silicones of the formulas (Si-III) and (Si-IV) differ in the grouping on the Si atom that carries the nitrogen-containing group: In formula (Si-III), R2 is a hydroxy group or a C1-4 alkoxy group, while the remainder in formula (Si-IV) is a methyl group. The individual Si groups, which are marked with the indices m and n or p and q, do not have to be present as blocks; rather, the individual units can also be statistically distributed, i.e. in the formulas (Si-III) and (Si-IV), not every R1-Si(CH3)2 group is necessarily bound to a -[O-Si(CH3)2]- group.

Agents according to the invention which contain at least one amino-functional silicone polymer (a3) of the formula (Si-V) have also proven to be particularly effective with regard to the desired effects.

in which -OH, -O-Si(CH3)3,-O-Si(CH ₃ )2OH,-O-Si(CH ₃ )2OCH3 represents a group, -H, -Si(CH3)3,-Si(CH3)2OH, -Si(CH3)2OCH3 represents a group, b, n and c represent integers between 0 and 1000, with the provisos

- n > 0 and b + c > 0 at least one of the conditions A = -OH or D = -H is fulfilled.

In the above formula (Si-V), the individual siloxane units with the indices b, c and n are statistically distributed, i.e. they do not necessarily have to be block copolymers.

The agent (a) may further contain one or more different amino-functionalized silicone polymers represented by the formula (Si-VI) M(RaQbSiO(4-ab)/2)x(RcSiO(4-c)/2)yM(Si-VI), wherein in the above formula R is a hydrocarbon or a hydrocarbon radical having 1 to about 6 carbon atoms, Q is a polar radical of the general formula -R ¹ HZ, wherein R ¹ is a divalent linking group bonded to hydrogen and the radical Z composed of carbon and hydrogen atoms, carbon, hydrogen and oxygen atoms, or carbon, hydrogen and nitrogen atoms, and Z is an organic amino-functional radical containing at least one amino-functional group; "a" takes on values in the range of about 0 to about 2, "b" takes on values in the range of about 1 to about 3, "a" + "b" is less than or equal to 3, and "c" is a number in the range of about 1 to about 3, and x is a number in the range of 1 to about 2,000, preferably from about 3 to about 50, and most preferably from about 3 to about 25, and y is a number in the range of about 20 to about 10,000, preferably from about 125 to about 10,000, and most preferably from about 150 to about 1,000, and M is a suitable silicone end group as known in the art, preferably trimethylsiloxy. Non-limiting examples of the radicals represented by R include alkyl radicals such as methyl, ethyl, propyl, isopropyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, isohexyl, and the like; Alkenyl radicals such as vinyl, halovinyl, alkylvinyl, allyl, haloallyl, alkylallyl; cycloalkyl radicals such as cyclobutyl, cyclopentyl, cyclohexyl and the like; phenyl radicals, benzyl radicals, halohydrocarbon radicals such as 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl, chlorophenyl and the like and sulfur-containing radicals such as mercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl and the like; preferably R is an alkyl radical containing 1 to about 6 carbon atoms, and most preferably R is methyl. Examples of R ¹ include methylene, ethylene, propylene, hexamethylene, decamethylene, - CH ₂ CH(CH ₃ )CH ₂ -, phenylene, naphthylene, -CH2CH2SCH2CH 2-, -CH2CH2OCH2-, -OCH2CH2-, -OCH2 CH2CH2-, -CH ₂ CH(CH ₃ )C(O)OCH2-, -(CH ₂ ) ₃ CC(O)OCH ₂ CH ₂ -, -C ₆ H 4C6H4-, -C ₆ H 4CH2C6H4-; and -(CH 2) ₃ C(O)SCH ₂ CH ₂ -.

Z is an organic amino-functional radical containing at least one amino functional group. One possible formula for Z is NH(CH2)zNH2, where z is 1 or more. Another possible formula for Z is -NH(CH2)z(CH 2)zzNH, where both z and zz are independently 1 or more, which structure includes diamino ring structures such as piperazinyl. Z is most preferably a -NHCH2CH 2NH2 radical. Another possible formula for Z is -N(CH2)z(CH2)zzNX2 or -NX2, where each X of X2 is independently selected from the group consisting of hydrogen and alkyl groups having 1 to 12 carbon atoms, and zz is 0.

Q is most preferably a polar, amine-functional radical of the formula -CH2CH2CH2NHCH2CH2NH 2. In the formulas, "a" takes on values in the range of about 0 to about 2, "b" takes on values in the range of about 2 to about 3, "a" + "b" is less than or equal to 3, and "c" is a number in the range of about 1 to about 3. The molar ratio of the R _a Qb SiO(4- _a -b)/2 units to the R _c SiO(4- _C )/2 units is in the range of about 1:2 to 1:65, preferably from about 1:5 to about 1:65, and most preferably from about 1:15 to about 1:20. When one or more silicones of the above formula are used, the various variable substituents in the above formula can be different for the various silicone components present in the silicone mixture.

In a further preferred embodiment, an agent according to the invention is characterized in that it contains at least one amino-functional silicone polymer of the formula (Si-VII),

R'aG3-a-Si(OSiG 2)n-(OSiG b '2- b)m-O-SiG3-a-R'a (Si-Vll), where:

- G is -H, a phenyl group, -OH, -O-CH3, -CH3, -O-CH2CH3, -CH2CH3, -O-

CH ₂ CH2CH3,-CH2CH ₂ CH3, -O-CH(CH ₃ )2, -CH(CH ₃ )2, -O-CH2CH2CH2CH3, - CH2CH2CH2CH3, -O-CH ₂ CH(CH ₃ )2, -CH ₂ CH(CH ₃ )2, -O-CH(CH ₃ )CH ₂ CH3, - CH(CH ₃ )CH ₂ CH3, -OC(CH ₃ )3, -C(CH ₃ )3 ;

- a stands for a number between 0 and 3, especially 0;

- b stands for a number between 0 and 1 , in particular 1 ,

- m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n preferably assumes values from 0 to 1999 and in particular from 49 to 149 and m preferably assumes values from 1 to 2000, in particular from 1 to 10,

- R' is a monovalent radical selected from o -QN(R")-CH ₂ -CH ₂ -N(R")2 o -QN(R") ₂ o -QN ⁺ (R")3A- o -QN ⁺ H(R") ₂ A- o -QN ⁺ H ₂ (R")A- o -QN(R")-CH2-CH ₂ -N ⁺ R"H ₂ A- , where each Q represents a chemical bond, -CH2-, -CH2-CH2-, -CH2CH2CH2-, -C(CH3)2- , -CH2CH2CH2CH2-, -CH ₂ C(CH ₃ )2-, -CH(CH ₃ )CH ₂ CH2-,

R" stands for identical or different radicals from the group -H, -phenyl, -benzyl, -CH2- CH(CH3)Ph, the Ci-20-alkyl radicals, preferably -CH3, -CH2CH3, -CH2CH2CH3, - CH(CH ₃ )2, -CH2CH2CH2H3, -CH ₂ CH(CH3)2, -CH(CH3)CH ₂ CH3, -C(CH ₃ )3, and A represents an anion which is preferably selected from chloride, bromide, iodide or methosulfate. In a further preferred embodiment, an agent according to the invention is characterized in that it contains at least one amino-functional silicone polymer (a3) of the formula (Si-Vlla),

(CH3)3Si-[O-Si(CH ₃ )2]n[OSi(CH3)]m-OSi(CH ₃ )3 (Si-Vlla),

CH ₂ CH(CH3)CH ₂ NH(CH2)2NH2 wherein m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n preferably assumes values from 0 to 1999 and in particular from 49 to 149 and m preferably assumes values from 1 to 2000, in particular from 1 to 10.

According to the INCI declaration, these silicones are called trimethylsilylamodimethicones.

In a further preferred embodiment, an agent according to the invention is characterized in that it contains at least one amino-functional silicone polymer of the formula (Si-Vllb)

R-[Si(CH3) ₂ -O]ni[Si(R)-O]m-[Si(CH3) ₂ ]n2-R (Si-Vllb),

(CH2)3NH(CH ₂ ) ₂ NH2, in which R is -OH, -O-CHs or a -CHs group and m, n1 and n2 are numbers whose sum (m + n1 + n2) is between 1 and 2000, preferably between 50 and 150, the sum (n1 + n2) preferably assuming values from 0 to 1999 and in particular from 49 to 149 and m preferably assuming values from 1 to 2000, in particular from 1 to 10.

These amino-functionalized silicone polymers are called amodimethicones according to the INCI declaration.

Regardless of which amino-functional silicones are used, agents according to the invention are preferred which contain an amino-functional silicone polymer (a3) whose amine number is above 0.25 meq/g, preferably above 0.3 meq/g and in particular above 0.4 meq/g. The amine number represents the milliequivalents of amine per gram of the amino-functional silicone. It can be determined by titration and also given in the unit mg KOH/g. Furthermore, agents containing a special 4-morpholinomethyl-substituted

Silicone polymer (a3). This amino-functionalized silicone polymer comprises

Structural units of the formulas (Sl-Vlll) and (Si-IX)

Corresponding 4-morpholinomethyl-substituted silicone polymers are described below.

Another suitable amino-functionalized silicone polymer is known under the name Amodimethicone/Morpholinomethyl Silsesquioxane Copolymer and is commercially available in the form of the raw material Belsil ADM 8301 E from Wacker.

For example, a silicone having structural units of the formulas (Si-VIII), (Si-IX) and (Si-X) can be used as a 4-morpholinomethyl-substituted silicone

in which

R1 is -CH3, -OH, -OCH3, -O-CH2CH3, -O-CH2CH2CH3, or -O-CH(CH ₃ ) ₂ ;

R2 stands for -CH3, -OH, or -OCH3.

Particularly preferred agents according to the invention contain at least one 4-morpholinomethyl-substituted silicone of the formula (Si-Xl)

(Si-Xl) in the

R1 is -CH ₃ , -OH, -OCH3, -O-CH2CH3, -O-CH2CH2CH3, or -O-CH(CH ₃ ) ₂ ;

R2 stands for -CH3, -OH, or -OCH3.

B represents a group -OH, -O-Si(CH3)3,-O-Si(CH ₃ )2OH,-O-Si(CH ₃ )2OCH3,

D stands for a group -H, -Si(CH3)3, -Si(CH3)2OH, -Si(CH3)2OCH3, a, b and c independently stand for integers between 0 and 1000, with the proviso that a + b + c > 0 m and n independently stand for integers between 1 and 1000, with the proviso that at least one of the conditions B = -OH or D = -H is met, the units a, b, c, m and n are distributed statistically or in blocks in the molecule.

Structural formula (Si-XI) is intended to illustrate that the siloxane groups n and m do not necessarily have to be directly bonded to an end grouping B or D. Rather, in preferred formulas (Si-VI) a > 0 or b > 0 and in particularly preferred formulas (Si-VI) a > 0 and c > 0, i.e. the terminal grouping B or D is preferably bonded to a dimethylsiloxy grouping. In formula (Si-VI) too, the siloxane units a, b, c, m and n are preferably distributed statistically.

The silicones used according to the invention and represented by formula (Si-VI) can be trimethylsilyl-terminated (D or B = -Si(CH3)3), but they can also be dimethylsilylhydroxy-terminated on two sides or dimethylsilylhydroxy- and dimethylsilylmethoxy-terminated on one side. Silicones used particularly preferably in the context of the present invention are selected from silicones in which

B = -O-Si(CH ₃ ) ₂ OH and D = -Si(CH ₃ ) ₃

B = -O-Si(CH ₃ ) ₂ OH and D = -Si(CH ₃ ) ₂ OH

B = -O-Si(CH ₃ ) ₂ OH and D = -Si(CH ₃ ) ₂ OCH3

B = -O-Si(CH ₃ ) ₃ and D = -Si(CH ₃ ) ₂ OH

B = -O-Si(CH ₃ ) ₂ OCH3 and D = -Si(CH ₃ ) ₂ OH These silicones lead to exorbitant improvements in the hair properties of the hair treated with the agents according to the invention, and to a significantly improved protection during oxidative treatment.

It has been found to be particularly advantageous if the agent according to the invention contains the amino-functionalized silicone polymer(s) (a3) in certain quantity ranges. Particularly good results were obtained if the agent contains - based on the total weight of the agent - a total amount of 0.1 to 8.0 wt.%, preferably 0.2 to 5.0 wt.%, more preferably 0.3 to 3.0 wt.% and very particularly preferably 0.4 to 2.5 wt.%.

In a further particularly preferred embodiment, an agent according to the invention is characterized in that it contains - based on the total weight of the agent - one or more amino-functionalized silicone polymers (a3) in a total amount of 0.1 to 8.0% by weight, preferably 0.2 to 5.0% by weight, more preferably from 0.3 to 3.0% by weight and very particularly preferably from 0.4 to 2.5% by weight.

Low-water or water-free agent

The agent according to the invention is characterized in that it contains less than 10% by weight of water (a4) based on its total weight. The water content is therefore on average a maximum of 9.9% by weight and preferably less, so that the agent is low in water or anhydrous. In the case of a low-water agent, small amounts of water, for example 2.0 to 7.0, preferably 2.0 to 6.0% by weight, can be added to the agent. In the context of the present invention, the term anhydrous is understood to mean that no water is intentionally added to the agent as a separate component. In order to achieve certain desired application properties, however, it can be advantageous to add ingredients to the agent that are hygroscopic or that contain water as an unavoidable secondary component. In this case, anhydrous is understood to mean that the agent contains less than 1.0% by weight of water, preferably less than 0.5% by weight of water, more preferably less than 0.1% by weight of water and very particularly preferably less than 0.01% by weight of water based on its total weight.

It has been found that particularly suitable agents are those which contain - based on the total weight of the agent - 0.001 to less than 9.0 wt.%, preferably 0.01 to less than 8.0 wt.%, more preferably 0.1 to less than 7.0 wt.% and particularly preferably 1.0 to less than 5.0 wt.% of water.

It has been found that particularly suitable agents are those which contain - based on the total weight of the agent - 0.001 to 8.9 wt.%, preferably 0.01 to 7.9 wt.%, more preferably 0.1 to 6.9 wt.% and particularly preferably 1.0 to 4.9 wt.% of water. In a further very particularly preferred embodiment, an agent according to the invention is characterized in that it contains - based on the total weight of the agent - less than 9% by weight of water (a4), preferably less than 8% by weight of water, more preferably less than 7% by weight of water and very particularly preferably less than 5% by weight of water.

Cellulose or cellulose derivatives

As a further component essential to the invention, the agents according to the invention contain cellulose and/or at least one derivative of cellulose (a5).

The addition of cellulose or cellulose derivatives ensures that the low-water product, which also contains the ingredients (a1), (a2) and (a3), does not become thinner when applied to damp hair and does not drip down from the hair during the exposure period.

In other words, the presence of cellulose (or the cellulose derivative) (a5) can prevent the liquefaction of the dye caused by the addition of water and stabilize its viscosity. In the presence of less than 10% by weight of water, the agent according to the invention is therefore hardly thickened and can be applied evenly to the keratin fibers, and after application to damp hair, the viscosity of the agent remains sufficiently high. A negative change in the other application properties was also not observed in the presence of cellulose (a5).

What was surprising was the observation that other polysaccharides do not show these effects. For example, it has been found that xanthan cannot be incorporated evenly into a product with a low water content. If xanthan and the respective amount of water are mixed together when producing the product according to the invention, the small amount of water available in the product leads to a lumpy and uneven formulation, which means that the formulation could not be applied evenly to the hair and was not suitable for use. In contrast, the incorporation of the cellulose (derivatives) into the product was very even even with small amounts of water and the color obtained when the product was used was homogeneous.

Formulations that contained an acrylate-based polymer instead of cellulose were also unable to produce dyes that met the desired requirements. For example, it was found that a dye that contained the acrylate polymer hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer instead of a cellulose polymer thickened the formulation well, but at the same time disproportionately impaired the uniformity of the resulting dye and led to dyes with reduced intensity and poor fastness to washing. Cellulose in the sense of this invention is understood to mean both cellulose itself and a derivative thereof, ie a chemically or physically modified cellulose.

Cellulose is made up of ß-1,4-glycosidically linked D-glucopyranose units. In the solid state, crystalline regions in cellulose alternate with those of low order (amorphous regions). Natural and manufacturing-related impurities, such as in particular the presence of carboxy groups, are typically in the range of approx. 1%.

Cellulose that can be used according to the invention preferably has a degree of polymerization (DP), i.e. a chain length of glucopyranose units, of 10 to about 8000.

So-called microcrystalline cellulose in particular shows advantageous effects. Microcrystalline cellulose is obtained by partial alkaline or acidic hydrolysis of cellulose, in which only the amorphous areas of the partially crystalline cellulose are attacked and completely dissolved. The initial result is microfine cellulose, which is deaggregated into microcrystalline cellulose in an aqueous suspension under the influence of mechanical force.

The degree of polymerization (also known as leveling-off polymerization degree = LODP) of the microcrystalline cellulose remaining after hydrolysis is preferably in the range of approximately 30-400. Preferred celluloses are therefore microcrystalline celluloses and have a degree of polymerization of 30 to 400.

In another particularly preferred embodiment, cellulose in the form of cellulose fibers is used in the agent according to the invention.

The term "fiber" made of cellulose refers to an object with a length L and a diameter D, where the length L is greater than the diameter D. Whether a fiber is in fiber form can be determined, for example, by microscopic examination of the fiber.

The length L indicates the length of a fiber and D its diameter D, where D can be simplified as the diameter of a circle. The ratio of L to D can also be referred to as the form factor and is, for example, in the range from 3.5 to 2000, preferably from 5 to 500, more preferably from 5 to 150.

Particularly preferred fibers are stretched, flexible structures made of fiber with a length to diameter ratio of more than 3:1, preferably more than 5:1 and in particular more than 10:1. Fibers cannot absorb compressive forces in the longitudinal direction, but only tensile forces. For example, the fibers may have a length range from 1 µm (micrometer) to 10 mm (millimeter), for example from 0.1 mm to 5 mm, such as from 0.3 mm to 3 mm. Their cross-section may be within a circle with a diameter in the range from 2 nm to 900 pm, preferably in the range from 100 nm to 700 pm. The weight or yarn count of the fibers is often given in denier or decitex, and represents the weight in grams per 9 km of yarn. For example, the fibers may, as per the present disclosure, have a yarn count in the range from 1 to 3 0.01 denier to 10 denier, for example from 0.1 denier to 2 denier, such as from 0.3 denier to 0.7 denier.

Cellulose fibers can be of organic origin and can be obtained from plant fibers, for example. Plant fibers occur in plants as vascular bundles in the stem, trunk, bark or as seed processes. Plant fibers usually consist mainly of cellulose.

Particularly suitable cellulose fibers can be purchased commercially, for example, from CFF GmbH & Co. KG under the trade name Sensocel® fibers. The cellulose fibers in the Sensocel® range are cellulose-based plant fibers that are obtained from beech, bamboo, wheat, oats and sugar cane, for example. The following types are particularly suitable:

For the purposes of this invention, a cellulose is also understood to mean a derivative of a cellulose, i.e. the cellulose can be provided with substituents by reaction with a chemical agent and/or carry further chemical functional groups.

A suitable cationic cellulose is, for example, sold under the name Polymer JR® 400 by Amerchol and has the INCI name Polyquaternium-10. Another cationic cellulose has the INCI name Polyquaternium-24 and is sold under the trade name Polymer LM-200 by Amerchol or Quatrisoft® LM 200. Other commercial products are the compounds Celquat® H 100, Celquat® and L 200. The commercial products mentioned are preferred cationic celluloses.

Non-ionic celluloses are particularly preferred. These can be selected, for example, from the group of hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxybutyl methyl cellulose, hydroxyethyl ethyl cellulose, hydroxypropyl methyl cellulose, methyl ethyl cellulose and ethyl cellulose.

Also well suited to solving the problem according to the invention are the non-ionic celluloses from the group of cellulose ethers, from the group of hydroxyethyl cellulose, hydroxypropyl cellulose and hydroxypropyl methyl cellulose. These are sold, for example, under the trademarks Culminal® and Benecel® and Natrosol® types by the companies Aqualon, Hercules or Ashland.

A hydroxypropyl cellulose with a molecular weight of 30,000 to 50,000 g/mol, which is sold, for example, under the trade name Nisso Sl® by Lehmann & Voss, Hamburg, is also particularly suitable. Suitable anionic celluloses are, for example, carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate propionate carboxylate and/or their physiologically acceptable salts.

In a further very particularly preferred embodiment, an agent according to the invention is characterized in that it contains at least one cellulose (a5) and/or a derivative thereof which is selected from the group consisting of cellulose, cellulose fibers, microcrystalline cellulose, cellulose gum, hydroxyethyl cellulose, carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxybutyl methyl cellulose, hydroxyethyl ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, sodium cellulose sulfate, cellulose acetate propionate carboxylate, cetyl hydroxyethyl cellulose and/or hydroxypropyl methyl cellulose stearoxy ether, particularly preferably from the group consisting of cellulose, cellulose fibers and microcrystalline cellulose.

In a further explicitly particularly preferred embodiment, an agent according to the invention is characterized in that it contains cellulose fibers (a5).

The celluloses and/or cellulose derivatives are preferably used in certain quantity ranges in the agent according to the invention. Particularly good results were obtained when the agent - based on its total weight - contains one or more compounds from the group of celluloses and cellulose derivatives in a total amount of 0.1 to 10.0 wt.%, preferably 0.3 to 7.5 wt.%, more preferably from 1.0 to 5.0 wt.% and most preferably from 2.5 to

4.5 wt.%.

In a further particularly preferred embodiment, an agent according to the invention is characterized in that it contains one or more compounds from the group of celluloses and cellulose derivatives in a total amount of 0.1 to 10.0% by weight, preferably 0.3 to 7.5% by weight, more preferably from 1.0 to 5.0% by weight and very particularly preferably from

2.5 to 4.5 wt.%.

In a further particularly preferred embodiment, an agent according to the invention is characterized in that it contains 0.1 to 10.0 wt. %, preferably 0.3 to 7.5 wt. %, more preferably 1.0 to 5.0 wt. %, and very particularly preferably 2.5 to 4.5 wt. % cellulose fibers.

MQ resins

In a further embodiment, it may be preferred if the agent does not contain any MQ silicone resins. MQ silicone resins are branched silicone polymers, where "M" stands for MesSiO and "Q" stands for SiC. MQ resins therefore contain at least one silicon atom, which represents a branching point and is located in proximity to four different oxygen atoms.

In another particularly preferred embodiment, an agent according to the invention is characterized in that it is free of MQ silicone resins.

In a further particularly preferred embodiment, an agent according to the invention is characterized in that it contains - based on its total weight - less than 0.1% by weight, preferably less than 0.01% by weight and particularly preferably less than 0.001% by weight and very particularly preferably 0% by weight of MQ silicone resins. Other ingredients in the agent

The agents can also contain other active ingredients, auxiliaries and additives, such as structuring agents such as glucose, maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example lecithin and cephalins; perfume oils, dimethyl isosorbide and cyclodextrins; polymers such as anionic, non-ionic and cationic polymers; surfactants such as anionic, non-ionic, cationic, zwitterionic and amphoteric surfactants, fat components, fibre structure-improving active ingredients, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose; dyes for colouring the agent; anti-dandruff active ingredients such as piroctone olamine, zinc omadine and climbazole; amino acids and oligopeptides; protein hydrolysates of animal and/or plant origin, as well as in the form of their fatty acid condensation products or optionally anionically or cationically modified derivatives; vegetable oils; Sunscreens and UV blockers; active ingredients such as panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidinonecarboxylic acids and their salts and bisabolol; polyphenols, in particular hydroxycinnamic acids, 6,7-dihydroxycoumarins, hydroxybenzoic acids, catechins, tannins, leucoanthocyanidins, anthocyanidins, flavanones, flavones and flavonols; ceramides or pseudoceramides; vitamins, provitamins and vitamin precursors; plant extracts; fats and waxes such as fatty alcohols, beeswax, montan wax and paraffins; swelling and penetrating agents such as glycerine, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates; opacifiers such as latex, styrene/PVP and styrene/acrylamide copolymers; Pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate; as well as propellants such as propane-butane mixtures, N2O, dimethyl ether, CO2 and air.

The expert will select these additional substances according to the desired properties of the agent. With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the expert. The additional active ingredients and auxiliary substances are used in the preparations according to the invention preferably in amounts of 0.0001 to 25 wt.%, in particular 0.0005 to 15 wt.%, based on the total weight of the respective agent.

Process for dyeing keratin fibers

The agents described above can be used excellently in processes for dyeing keratin fibers, especially human hair.

A second subject matter of the present invention is therefore a method for dyeing keratin fibers, in particular human hair, in which an agent as described in claims 1 to 15 is applied to keratin fibers, in particular to moist keratin fibers, and optionally rinsed out again after an exposure time of 30 seconds to 45 minutes.

In other words, a second subject of the invention is a method for dyeing keratin fibers, in particular human hair, comprising the following steps:

(1) Applying a pre-treatment agent to the keratin fibers,

(2) if necessary, application of the pretreatment agent

(3) Rinse out the pretreatment agent with water,

(4) applying a dye to the still wet or towel-dried keratin fibers, the dye being an agent as disclosed in detail in the description of the first subject matter of the invention,

(5) Exposure of the dye to the keratin fibres and

(6) Rinse out the dye with water.

In step (1) of the method according to the invention, a pretreatment agent is applied to the keratin fibers, which can be a shampoo or a conditioner, for example. The application of the pretreatment agent is intended to remove all fatty substances or residues on the keratin fibers so that the pigments on the surface of the keratin fiber can be embedded in the aminosilicone in a uniform film.

Optionally, the pretreatment agent can be allowed to take effect, with the exposure time ranging from 15 seconds to 10 minutes, for example.

The pretreatment agent is then rinsed out of the keratin fibers.

Immediately after the pretreatment, in step (4) the dye according to the invention is applied to the still wet keratin fibers. Steps (3) and (4) of the process are therefore within a maximum period of 30 minutes, preferably a maximum of 15 minutes, particularly preferably a maximum of 5 minutes.

Wet, moistened or towel-dried keratin fibers or hair are keratin fibers (or hair) that have been completely wetted with water, for example at the sink or in the shower, then squeezed out and rubbed dry with a towel (e.g. for 30 seconds). Moisturized or towel-dried hair is therefore no longer dripping wet, but still moist.

In step (5) of the method according to the invention, the agent is then allowed to act on the keratin fibers after it has been applied. In this context, various exposure times of, for example, 30 seconds to 60 minutes are conceivable.

However, a major advantage of the coloring system according to the invention is that an intensive color result can be achieved even in very short periods of time after short exposure times. For this reason, it is advantageous if the application mixture only remains on the keratin fibers for a comparatively short period of time of 30 seconds to 15 minutes, preferably 30 seconds to 10 minutes, and particularly preferably 1 to 5 minutes after application.

After the dye has acted on the keratin fibres, they are finally rinsed with water in step (6) of the process.

Process for dyeing keratin fibers, in which the ready-to-use agent is first prepared.

As already described above, the agent of the first subject matter of the invention is a ready-to-use agent which is either made available to the user directly in its ready-to-use form or which is prepared by mixing different agents shortly before use.

In order to ensure a particularly fine distribution of the pigments, it has proven particularly preferable to prepare the ready-to-use agent shortly before use by mixing two or three different agents.

In a particularly preferred embodiment, the ready-to-use agent is prepared by mixing at least two different agents, the first of these two agents comprising the mixture of at least alkylene glycol of formula (AG) (a1) and pigment(s) (a2) and cellulose (derivative) (a5). For example, the mixture of alkylene glycol of formula (AG) (a1) and pigment(s) (a2) can represent a pre-dispersion. The second agent contains at least one amino-functionalized silicone polymer (a3). To prepare the To prepare the ready-to-use agent, the two aforementioned agents are then shaken or stirred together.

A further subject matter of the present application is therefore a method for dyeing keratin fibers, in particular human hair, comprising the following steps:

(1) Provision of an agent (I), the agent (I) containing:

(a1) at least one alkylene glycol of formula (AG) and

(a2) at least pigment, and

(a5) cellulose and/or a cellulose derivative,

(2) Providing an anhydrous agent (II), said agent (II) containing:

(a3) at least one amino-functionalized silicone polymer.

(3) preparing an application mixture by mixing the agents (I) and (II), the resulting application mixture containing - based on the total weight of the application mixture - less than 10% by weight of water (a4),

(4) Applying the application mixture prepared in step (3) to keratin fibers, preferably wet keratin fibers,

(5) Applying the application mixture applied in step (4) to the keratin fibres and

(6) Rinsing the application mixture with water, wherein the ingredients (a1), (a2), (a3) and (a5) have already been disclosed in detail in the description of the first subject matter of the invention.

The agent (I) preferably represents a predispersion of the pigments (a2) in the alkylene glycol(s) of the formula (AG) (a1) and the cellulose or the cellulose derivative (a5).

If the agents (I) and (II) are mixed, the predispersion of the pigments (a2) in the alkylene glycol of the formula (AG) (a1) and the cellulose or the cellulose derivative (a5) ensures a particularly fine distribution of the pigments, which is retained in the ready-to-use agent even after mixing the two agents (I) and (II).

Finally, in a further embodiment, it may prove advantageous to separate the components (a1), (a2) and (a3) from one another, so that the three previously separated components (a1), (a2) and (a3) are mixed together when the ready-to-use agent is produced. This form of production can be advantageous, for example, if the pigment(s) (a2) are to be used in smaller quantities and/or in the form of a powder. Packaging the pigments in powder form simplifies the quantitative transfer of the pigments into a mixing vessel or other container. A further subject matter of the present application is therefore a method for dyeing keratin fibers, in particular human hair, comprising the following steps:

(1) Provision of an agent (I), the agent (I) containing:

(a1) at least one alkylene glycol of formula (AG), and

(a5) cellulose and/or a cellulose derivative,

(2) Provision of a means (II), the means (II) containing:

(a2) at least pigment,

(3) Provision of a means (III), the means (III) containing:

(a3) at least one amino-functionalized silicone polymer,

(4) preparing an application mixture by mixing the agents (I) and (II) and (III), the resulting application mixture containing - based on the total weight of the application mixture - less than 10% by weight of water (a4),

(5) Applying the application mixture prepared in step (4) to the keratin fibers,

(6) Applying the application mixture applied in step (5) to the keratin fibres and

(7) Rinse the application mixture with water, whereby the ingredients (a1), (a2), (a3) and (a5) in the description of the first

subject matter of the invention have already been disclosed in detail.

The agent (I) contains at least one alkylene glycol of the formula (AG) (a1) and cellulose and/or a derivative of cellulose (a5).

The agent (II) contains at least one pigment (a2). In one possible form of packaging, the pigment is provided, for example, in the form of a powder.

The agent (III) contains at least one amino-functionalized silicone polymer (a3) and is preferably in the form of a concentrate.

Multi-component packaging unit

To increase user convenience, the above-described agents can be made available to the user in the form of a multi-component packaging unit.

A further subject matter is therefore a multi-component packaging unit (kit-of-parts) for dyeing keratin fibers, in particular human hair, comprising separately packaged

- a first container with an agent (I), the agent (I) containing:

(a1) at least one alkylene glycol of formula (AG) and (a2) at least pigment, and (a5) Cellulose and/or a cellulose derivative.

- a second container with an agent (II), the agent (II) containing:

(a3) at least one amino-functionalized silicone polymer, wherein the ingredients (a1), (a2), (a3) and (a5) have already been disclosed in detail in the description of the first subject matter of the invention and wherein the water content in the agents (I) and

(II) is selected such that the application mixture resulting from the mixing of the two agents contains - based on the total weight of the application mixture - less than 10 wt.% water (a4).

A further subject matter of the present application is a multi-component packaging unit (kit-of-parts) for dyeing keratin fibers, in particular human hair, comprising separately packaged

- a first container with an agent (I), the agent (I) containing:

(a1) at least one alkylene glycol of formula (AG), and (a5) cellulose and/or a derivative of cellulose,

- a second container with an agent (II), the agent (II) containing:

(a2) at least pigment,

- a third container with an agent (III); the agent (III) containing:

(a3) at least one amino-functionalized silicone polymer, wherein the ingredients (a1), (a2), (a3) and (a5) have already been disclosed in detail in the description of the first subject matter of the invention, wherein the water content in the agents (I), (II) and

(III) is selected such that the application mixture resulting from the mixing of the three agents contains - based on the total weight of the application mixture - less than 10 wt.% water (a4).

With regard to the further preferred embodiments of the methods according to the invention and the multi-component packaging unit according to the invention, what has been said about the agent according to the invention applies mutatis mutantis.

Examples

1 . Formulations

The following ready-to-use dyes were prepared (all data in weight percent unless otherwise stated):

In a container, the cellulose (Sensocel BC 20) (or in the comparative formulations the xanthan gum or the acrylate copolymer) was mixed with the specified amount of water, and this mixture was left to stand for 30 minutes while stirring. The other formulation components were then added while stirring, except for the aminosilicone and hexamethyldisiloxane. The aminosilicone and hexamethyldisiloxane were mixed together in a separate vessel.

Then both premixes were combined and the resulting application mixture was stirred well.

2. Application

Strands of hair (Kerling company, type "Euronatur-haarweiß" (ENH)) were pre-washed with a standard commercial shampoo (Schauma 7-Kräuter). The shampoo was washed out under running water. The hair was then rubbed dry with a towel for 30 seconds so that it was no longer wet, but still towel-damp.

Immediately afterwards, the previously prepared ready-to-use products were applied to the towel-dried hair strands and left to work for three minutes.

The strands of hair that had been treated with the dye were hung on a rack and left to hang freely for 5 minutes. A bowl was placed under each strand and the amount of liquid that dripped down from the strand was collected and weighed. The higher the amount of liquid that dripped down from the strand, the worse the applicability of the dye.

* Weight of the towel-damp strand after shampooing

** percentage of water in the towel-damp strand

After application, the V1 formulation dripped down onto the towel-damp hair strands.

Formulation V2 was so lumpy that the production of a homogeneous formulation was not possible. was possible. V2 could not be applied to hair strands. Formulation V3 was thicker, but could be applied to the hair strands. No dripping was observed with V3. Formulation E was thin, homogeneous and could be easily and evenly distributed on the previously moistened hair strands. No dripping was observed with formulation E.

2. Dyeing results

The dyed strands were compared visually with regard to their color properties under a daylight lamp. The color intensity of the strands was rated according to the following scale:

0 = very weak intensity, barely colored 5 = very high color intensity

The evenness of the coloring was assessed visually under a daylight lamp. If the strand was evenly colored, no unevenness in the coloring was visible to the naked eye. If the coloring was poor, different intensities of coloring were visible to the naked eye at different points on the strand.

To measure wash fastness, a commercially available shampoo (0.25 g shampoo (Schauma 7 herbs) per 1 g hair) was applied to each strand of colored hair and massaged in with the fingers for 30 seconds. The shampoo was then rinsed out under running, lukewarm water for 1 minute and the strand of hair was dried. The process described above corresponds to one hair wash. The process was repeated for each subsequent hair wash. After the corresponding number of hair washes, the strands were visually assessed again under the daylight lamp and classified according to the following scale:

0 = very weak intensity, barely colored 5 = very high color intensity

Claims

Patent claims

1. Agent for dyeing keratin fibres, in particular human hair, containing - based on the total weight of the agent -

(a1) at least alkylene glycol of formula (AG)

where x is an integer from 0 to 10000, y is an integer from 0 to 10000,

(a2) at least one pigment, and

(a3) at least one amino-functionalized silicone polymer, and

(a4) less than 10 wt.% water, and

(a5) Cellulose and/or a cellulose derivative.

2. Agent according to claim 1, characterized in that it

(a1) contains at least alkylene glycol of the formula (AG), where x is an integer from 1 to 10,000, and y is the number 0, and

Rc stands for a hydrogen atom.

3. Agent according to one of claims 1 to 2, characterized in that it

(a1) contains at least one alkylene glycol of formula (AG-1), wherein

(AG-1), x1 is an integer from 1 to 100, preferably an integer from 1 to 80, more preferably an integer from 2 to 60, even more preferably an integer from 3 to 40, even more preferably an integer from 4 to 20 and most preferably an integer from 6 to 15. Agent according to one of claims 1 to 3, characterized in that it

(a1) contains at least one alkylene glycol of formula (AG-2), wherein

(AG-2), x2 represents an integer from 101 to 1000, preferably an integer from 105 to 800, more preferably an integer from 107 to 600, even more preferably an integer from 109 to 400, and most preferably an integer from 110 to 200. Agent according to one of claims 1 to 4, characterized in that it contains - based on the total weight of the agent - (a1) one or more alkylene glycols of the formula (AG-1) in a total amount of 20.0 to 99.0 wt. %, preferably from 40.0 to 95.0 wt. %, particularly preferably from 60.0 to 90.0 wt. %, and/or it contains one or more alkylene glycols of the formula (AG-2) in a total amount of 1.0 to 35.0 wt. %, preferably from 3.0 to 30.0 wt. %, particularly preferably from 4.0 to 25.0 wt. %,. Agent according to one of claims 1 to 5, characterized in that it contains (a1) at least one alkylene glycol of the formula (AG), where x is the number 1 and y is the number 0, and

Rc is a phenyl group. Agent according to one of claims 1 to 6, characterized in that it contains (a1) at least one alkylene glycol of the formula (AG), where x is the number 0 and y is the number 1, and

Ra stands for a hydrogen atom, and

Rb stands for a methyl group, and

Rc is a hydrogen atom. Agent according to one of claims 1 to 7, characterized in that it - based on the

Total weight of the product - one or more pigments (a2) in a total amount of 0.01 to 10.0% by weight, preferably 0.1 to 5.0% by weight, more preferably from 0.2 to 2.5% by weight and most preferably from 0.25 to 1.5% by weight. Agent according to one of claims 1 to 8, characterized in that it contains at least one amino-functionalized silicone polymer (a3) which comprises at least one structural unit of the formula (Si-amino),

-Amino) where

ALK1 and ALK2 independently of one another represent a linear or branched, divalent Ci-C2o-alkylene group. Agent according to one of claims 1 to 9, 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)

( _Si -ll), where

R1 represents a methyl group or a hydrogen atom, and

Agent according to one of claims 1 to 10, characterized in that it contains - based on the total weight of the agent - one or more amino-functionalized silicone polymers (a3) in a total amount of 0.1 to 8.0 wt.%, preferably 0.2 to 5.0 wt.%, more preferably from 0.3 to 3.0 wt.% and very particularly preferably from 0.4 to 2.5 wt.%.

Agent according to one of claims 1 to 11, characterized in that it contains - based on the total weight of the agent - less than 9 wt.% water (a4), preferably less than 8 wt.% water, more preferably less than 7 wt.% water and very particularly preferably less than 5 wt.% water.

Agent according to one of claims 1 to 12, characterized in that it contains at least one cellulose (a5) and/or a derivative thereof which is selected from the group consisting of cellulose, cellulose fibers, microcrystalline cellulose, cellulose gum, hydroxyethyl cellulose, carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxybutyl methyl cellulose, hydroxyethyl ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, sodium cellulose sulfate, cellulose acetate propionate carboxylate, cetyl hydroxyethyl cellulose and/or hydroxypropyl methyl cellulose stearoxy ether, particularly preferably from the group consisting of cellulose, cellulose fibers and microcrystalline cellulose. Agent according to one of claims 1 to 13, characterized in that it contains one or more compounds from the group of celluloses and cellulose derivatives in a total amount of 0.1 to 10.0 wt. %, preferably 0.3 to 7.5 wt. %, more preferably 1.0 to 5.0 wt. % and very particularly preferably 2.5 to 4.5 wt. %. Agent according to one of claims 1 to 14, characterized in that it is free from MQ silicone resins. Method for coloring keratin fibers, in particular human hair, in which an agent as described in claims 1 to 15 is applied to keratin fibers, in particular to moist keratin fibers, and optionally rinsed out again after an exposure time of 30 seconds to 45 minutes.