EP3897862A1

EP3897862A1 - Method for dyeing keratin material by means of a dyeing agent and an acidic post-treatment agent

Info

Publication number: EP3897862A1
Application number: EP19778956.3A
Authority: EP
Inventors: Constanze Neuba; Sandra Hilbig; Daniela Kessler-Becker; Torsten LECHNER
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2018-12-18
Filing date: 2019-09-25
Publication date: 2021-10-27
Also published as: CN113242749A; JP2022514004A; WO2020126137A1; US20220062156A1; US11529304B2; DE102018222022A1

Abstract

The present invention relates to a method for dyeing keratin material, in particular human hair, comprising the following steps: - applying a dyeing agent (a) to the keratin material, the agent (a) containing: (a1) at least one amino-functionalized silicone polymer, (a2) at least one coloring compound and (a3) at least one non-ionic surfactant; - applying a post-treatment agent (b) to the keratin material, the agent (b) containing: (b1) at least one acid. The present invention also relates to a multi-component packaging unit which contains the two agents (a) and (b) in two separately produced containers.

Description

“Process for dyeing keratinous material with dye and acidic aftertreatment agent”

The present application relates to a method for dyeing keratinous material, in particular human hair, which comprises the use of at least two different agents (a) and (b). The agent (a) contains at least one amino-functionalized silicone polymer (a1) and at least one coloring compound (a2) and at least one nonionic surfactant (a3). Agent (b) is an aftertreatment agent which contains at least one acid (b1).

A second subject of this application is a multi-component packaging unit (kit-of-parts) for dyeing keratinous material, in particular human hair, which, when assembled separately from one another, comprises means (a) and (b) in two different containers.

The change in shape and color of keratinous material, especially human hair, is an important area of modern cosmetics. To change the hair color, the skilled worker knows various dyeing systems depending on the requirements of the coloring. Oxidation dyes are usually used for permanent, intensive dyeings with good fastness properties and good gray coverage. Such colorants contain oxidation dye precursors, so-called developer components and coupler components, which form the actual dyes with one another under the influence of oxidizing agents, such as hydrogen peroxide. Oxidation dyes are characterized by very long-lasting dyeing results.

When using direct dyes, fully-formed dyes diffuse from the colorant into the hair fiber. Compared to oxidative hair dyeing, the dyeings obtained with direct dyes have a shorter shelf life and quicker washability. Colorings with direct dyes usually remain on the hair for a period of between 5 and 20 washes.

The use of color pigments is known for short-term color changes on the hair and / or the skin. Color pigments are generally understood to mean insoluble, color-imparting substances. These are undissolved in the form of small particles in the dye formulation and are only deposited on the outside of the hair fibers and / or the skin surface. Therefore, they can usually be removed by washing them with detergent containing surfactants Remove without residue. Various products of this type are available on the market under the name of hair mascara.

If the user desires particularly long-lasting dyeings, the use of oxidative coloring agents has so far been his only option. However, despite numerous attempts to optimize the oxidative hair coloring, an unpleasant smell of ammonia or amine cannot be completely avoided. The hair damage still associated with the use of the oxidative colorants also has a disadvantageous effect on the hair of the user. A challenge that still remains is the search for alternative, high-performance dyeing processes.

It was the object of the present invention to provide a dyeing system which has fastness properties comparable to those of oxidative dyeing. However, the use of the oxidation dye precursors normally used for this purpose should be avoided. A technology was sought which made it possible to fix the coloring compounds (such as pigments) known from the prior art in an extremely permanent manner on the hair. When using the agents in a dyeing process, intensive dyeing results should be achieved, particularly in fashionable shades. A particular focus was on the creation of fashionable colors with a strong, long-lasting shine

Surprisingly, it has now been found that the aforementioned object can be achieved excellently if keratinous materials, in particular hair, are dyed using a process in which at least two agents (a) and (b) are applied to the keratinous materials (in particular the hair). be applied. The agent (a) contains at least one amino-functionalized silicone polymer (a1), at least one coloring compound (a2) and at least one nonionic surfactant (a3). Agent (b) is an acidic aftertreatment agent and contains at least one acid (b1). When using the two agents (a) and (b) in a dyeing process, it was possible to dye keratinous materials with a high color intensity, which were distinguished by a particularly strong gloss that also lasted for several washes.

A first object of the present invention is a method for dyeing keratinous material, in particular human hair, comprising the following steps:

Applying a coloring agent (a) to the keratinous material, the agent (a) containing:

(a1) at least one amino-functionalized silicone polymer, and

(a2) at least one coloring compound, and

(a3) at least one nonionic surfactant, and

Applying a post-treatment agent (b) to the keratinous material, the agent (b) containing: (b1) at least one acid.

The work leading to this invention has shown that the successive use of colorant (a) and aftertreatment agent (b) leads to colored keratinous material which is distinguished by high color intensities and a particularly long-lasting shine.

Without being restricted to this theory, it is assumed that the amino-functionalized silicone polymer (a1) contained in the colorant (a) forms adhesive bonds with the keratin material, which initially fix the aminosilicone (al) on the keratin material. The coloring compounds (a2) are embedded in or on the aminosilicone (a1) and are also immobilized in this way on the outside of the keratin material.

The adhesive bonds between amino-functionalized silicone polymer (a1) and keratin are presumably based on electrostatic interactions that form between the positively charged amino groups of the silicone polymer (a1) and negative charges on the keratin material.

Surprisingly, it was observed that the coloring compounds (a2) attach to the latter when used simultaneously with the aminosilicone (a1) or form a common layer with the latter. This common layer formation of (a1) and (a2) leads to the fact that dyeings with high color intensity can be obtained even without a diffusion of the coloring compound into the hair fiber being necessary. In an unpredictable way, the layer formed in this way was characterized by a very high gloss, so that it was possible to produce fashionable, highly glossy shades of color. In this connection, it was also found that the hair gloss observed was particularly strong when mainly nonionic components were used on average (a). For this reason, agent (a) also contains at least one nonionic surfactant (a3).

Furthermore, it has been found that when amino aminosilicon (a1) and coloring compound (a2) are deposited together, very stable layers could be formed, in particular, if optimal pH values were selected during the application process. Particularly resistant layers could be achieved if (a1) and (a2) were first applied to the keratin materials in a neutral to basic environment, and the pH was subsequently reduced by using an acidic post-needle additive. The keratin materials treated in this way retained their luster even after several washes (such as hair washes). keratinous material Keratinous material means hair, skin, nails (such as fingernails and / or toenails). Wool, furs and feathers also fall under the definition of keratinous material.

Keratinous material is preferably understood to mean human hair, human skin and human nails, in particular fingernails and toenails. Keratinous material is particularly preferably understood to mean human hair.

Means (a) and (b)

In the context of the method according to the invention, agents (a) and (b) are applied to the keratinous material, in particular human hair. The two means (a) and (b) are different from each other.

In other words, a first object of the present invention is a method for dyeing keratinous material, in particular human hair, comprising the following steps:

(a1) at least one amino-functionalized silicone polymer, and

(a2) at least one coloring compound, and

(a3) at least one nonionic surfactant, and

Applying a post-treatment agent (b) to the keratinous material, the agent (b) containing:

(b1) at least one acid,

the means (a) and (b) being different from one another. Amino-functionalized silicone polymer fal l on average (a)

As the first ingredient (a1) essential to the invention, agent (a) contains at least one amino-functionalized silicone polymer. The amino-functionalized silicone polymer can alternatively also be referred to as aminosilicone or amodimethicone.

Silicone polymers are generally macromolecules with a molecular weight of at least 500 g / mol, preferably at least 1000 g / mol, further 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 determined by the polymerization method co-determined. 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 ^® g / mol and particularly preferably not more than 10 ⁵ g / mol.

The silicone polymers comprise many Si-O repeating units, it being possible for the Si atoms to carry organic radicals, for example alkyl groups or substituted alkyl groups. Alternatively, a silicone polymer is therefore also referred to as polydimethylsiloxane.

Corresponding to 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, very particularly preferably more than 500 Si-O repeat units .

An amino-functionalized silicone polymer is understood to mean a functionalized polydimethylsiloxane which carries at least one structural unit with an amino group. The amino-functionalized silicone polymer preferably carries a plurality of structural units, each having at least one amino group. An amino group means a primary amino group, a secondary amino group and a tertiary amino group. All of these amino groups can be protonated in an acidic medium and are then in their cationic form. These amino groups are uncharged in a neutral to basic environment.

In principle, good effects could be achieved with amino-functionalized silicone polymers (a1) if they carry at least one primary, at least one secondary and / or at least one tertiary amino group. However, colorations with the best color intensity and the highest gloss were observed when an amino-functionalized silicone polymer (a1) was used in the agent (a) which contains at least one secondary amino group.

In a very particularly preferred embodiment, a method according to the invention is characterized in that the agent (a) contains at least one amino-functionalized silicone polymer (a 1) with at least one secondary amino group.

The secondary amino group (s) can be located at different positions of the amino-functionalized silicone polymer. Very particularly good effects were found when an amino-functionalized silicone polymer (a1) was used which has at least one, preferably more, structural units of the formula (Si-amino). -Amino) in the structural units of the formula (Si-amino), the abbreviations ALK1 and ALK2 independently of one another represent a linear or branched, divalent Ci-C2o-alkylene group.

In a further very particularly preferred embodiment, a method according to the invention is characterized in that the agent (a) contains at least one amino-functionalized silicone polymer (a1) which comprises at least one structural unit of the formula (Si-amino),

-Amino) where

ALK1 and ALK2 independently of one another for a linear or branched, divalent Ci

C2o alkylene group.

The positions marked with an asterisk ( ^* ) indicate the bond to other structural units of the silicone polymer. For example, the silicon adjacent to the star Atom be bound to a further oxygen atom, and the oxygen atom adjacent to the star can be bound to a further silicon atom or also to a Ci-C6-alkyl group.

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

In the case of ALK1, there is a bond 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, there is a bond from the secondary amino group to the ALK2 group, and the second bond is between ALK2 and the primary amino group.

Examples of a linear divalent Ci-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 carbon atoms, divalent alkylene groups can also be branched. Examples of branched, divalent C3-C2o-alkylene groups are (-CH2-CH (CH3) -) and (-CH2-CH (CH3) -CH2-).

In a further particularly preferred embodiment, the structural units of the formula (Si-amino) represent repeating units in the amino-functionalized silicone polymer (a1), so that the silicone polymer comprises several structural units of the formula (Si-amino).

Particularly suitable amino-functionalized silicone polymers (a1) with at least one secondary amino group are listed below.

Colorings with the very best intensities and the highest gloss could be obtained if, in the process according to the invention, at least one agent (a) was applied to the keratinous material which contains at least one amino-functionalized silicone polymer (a1) which has structural units of the formula (Si-I) and of the formula (Si-Il)

In a further explicitly particularly preferred embodiment, a method according to the invention is characterized in that the agent (a) contains at least one amino-functionalized silicone polymer (a1) which comprises structural units of the formula (Si-I) and the formula (Si-I I)

A corresponding amino-functionalized silicone polymer with the structural units (Si-I) and (Sill) is, for example, the commercial product DC 2-8566 or Dowsil 2-8566 Amino Fluid, which is commercially available from 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. In a further preferred embodiment, a method according to the invention is characterized by the use of an agent (a) on the keratinous material, the agent (a) containing at least one amino-functional silicone polymer (a1) of the formula of the formula (Si-III),

in which

m and n are numbers which are chosen such 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 hydroxyl group or a C1-4-alkoxy group,

wherein at least one of the groups R1 to R3 represents a hydroxy group;

Further methods preferred according to the invention are characterized by the use of an agent (a) on the keratinous material, the agent (a) containing at least amino-functional silicone polymer (a1) of the formula of the formula (Si-IV),

in the

p and q mean numbers which are chosen such that the sum (p + q) is in the range from 1 to 1000,

p is a number in the range from 0 to 999 and q is a number in the range from 1 to R1 and R2, which are different, represent a hydroxyl group or a C1-4 alkoxy group, at least one of the groups R1 to R2 signifying a hydroxyl group.

The silicones of the formulas (Si-Ill) and (Si-IV) differ in the grouping on the Si atom which carries the nitrogen-containing group: In formula (Si-Ill) R2 means a hydroxyl group or a C1-4-alkoxy group, while the rest in formula (Si-IV) is a methyl group. The individual Si groups, which are identified by 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, ie in the formulas (Si-Ill) and (Si IV) not every R1-Si (CH3) ₂ group is bound to a - [0-Si (CH3) ₂ ] group.

Processes according to the invention in which an agent (a) which contains at least one amino-functional silicone polymer (a1) of the formula of the formula (Si-V) has also proven to be particularly effective with regard to the desired effects

in the

A represents a group -OH, -0-Si (CH ₃ ) 3, -0-Si (CH ₃ ) ₂ 0H, -0-Si (CH ₃ ) ₂ 0CH ₃ ,

D represents a group -H, -Si (CH ₃ ) 3, -Si (CH ₃ ) ₂ 0H, -Si (CH ₃ ) ₂ 0CH ₃ ,

b, n and c represent integers between 0 and 1000,

with the stipulations

- 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. it does not have to be block copolymers.

Agent (a) may also contain one or more different amino-functionalized silicone polymers which are represented by the formula (Si-VI)

M (RaQbSiO (4-ab) / 2) x (RcSiO (4-c) / 2) yM (Si-Vl) are described, 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 connecting group which is attached to hydrogen and the Radical Z is bonded, 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 which contains at least one amino-functional group; "a" takes values in the range from about 0 to about 2, "b" takes values in the range from about 1 to about 3, "a" + "b" is less than or equal to 3, and "c" is a number in the range from about 1 to about 3, and x is a number in the range from 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 from 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 is 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 residues, benzyl residues, halogenated hydrocarbon residues such as 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl, chlorophenyl and the like, and sulfur-containing residues such as mercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl and the like; preferably R is an alkyl group 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 ) CH2-, phenylene, naphthylene, -CH2CH2SCH2CH 2-, -CH2CH2OCH2-, -OCH2CH2-, -OCH ₂ CH2CH2-, - CH ₂ CH (CH ₃ ) C (0) 0CH2-, - (CH ₂ ) ₃ CC (0) 0CH ₂ CH ₂ -, -CeH ₄ C ₆ H ₄ -, -CeH ₄ CH ₂ C ₆ H ₄ -; and - (CH 2) ₃ C (0) SCH ₂ CH ₂ - a.

Z is an organic, amino-functional radical containing at least one functional amino group. A possible formula for Z is NH (CH2) zNH ₂ , 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 ₂ NH ₂ residue. Another possible formula for Z is - N (CH ₂ ) z (CH ₂ ) zzNX ₂ or -NX ₂ , 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 0 is.

Q is most preferably a polar, amine functional residue of the formula -CH2CH2CH2NHCH2CH2NH 2. In the formulas, "a" takes values in the range from about 0 to about 2, "b" takes values in the range from about 2 to about 3, "a "+" b "is less than or equal to 3, and" c "is a number ranging from 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 range from 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 or more silicones of the above formula used, then the different variable substituents in the above formula can be different for the different silicone components present in the silicone mixture.

In a particularly preferred embodiment, a method according to the invention is characterized by the use of an agent (a) on the keratinous material, the agent (a) being an amino-functional silicone polymer of the formula (Si-VIII)

R'aG ₃ -a-Si (OSiG ₂ ) n- (OSiG _b R ' ₂ - b) m-0-SiG ₃ -a-R'a (Si-Vll), in which means:

- G is -H, a phenyl group, -OH, -0-CH ₃ , -CH ₃ , -O-CH2CH3, -CH2CH3, -O-

CH ₂ CH2CH3, -CH2CH ₂ CH3, -0-CH (CH ₃ ) 2, -CH (CH ₃ ) ₂ , -O-CH2CH2CH2CH3, -

CH2CH2CH2CH3, -0-CH ₂ CH (CH ₃ ) 2, -CH ₂ CH (CH ₃ ) 2, -0-CH (CH ₃ ) CH ₂ CH3, -

CH (CH ₃ ) CH ₂ CH3, -0-C (CH ₃ ) ₃ , -C (CH ₃ ) ₃ ;

- a stands for a number between 0 and 3, in particular 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 is preferably from 0 to 1999 and in particular from 49 to 149 and m is preferably from 1 to 2000, in particular from 1 to 10,

- R ^' is a monovalent residue selected from

o -QN (R ") - CH ₂ -CH ₂ -N (R") 2

o -QN (R ") ₂

o -QN ⁺ (R ") ₃ A- o -QN ⁺ H (R") ₂ A- o -QN ⁺ H ₂ (R ") A- o -QN (R") - CH ₂ -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- stands,

R "for identical or different radicals from the group -H, -phenyl, -benzyl, -CH ₂ - CH (CH3) Ph, the Ci-20-alkyl radicals, preferably -CH3, -CH2CH3, -CH2CH2CH3, - CH (CH ₃ ) ₂ , -CH2CH2CH2H3, -CH ₂ CH (CH ₃ ) 2, -CH (CH ₃ ) CH ₂ CH3, -C (CH ₃ ) ₃ , and A represents an anion, which is preferably selected from chloride, bromide , iodide or methosulfate.

In the context of a further preferred embodiment, a method according to the invention is characterized by the use of an agent (a) on the keratinous material, the agent (a) containing at least one amino-functional silicone polymer (a1) of the formula (Si-VIII), (CH ₃ ) 3Si- [0-Si (CH3) 2] n [0Si (CH3)] m-0Si (CH ₃ ) 3 (Si-Vlla)

CH ₂ CH (CH ₃ ) CH2NH (CH2) 2NH2 where m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n is preferably from 0 to 1999 and in particular from 49 to 149 and m preferably takes values from 1 to 2000, in particular from 1 to 10.

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

In the context of a further preferred embodiment, a method according to the invention is characterized by the use of an agent (a) on the keratinous material, the agent (a) containing at least one amino-functional silicone polymer of the formula (Si-VIIIb)

R- [Si (CH ₃ ) 2-0] ni [Si (R) -0] m- [Si (CH ₃ ) 2] n2-R (Si-Vllb),

Contain (CH2) 3NH (CH ₂ ) 2NH2, where R is -OH, -0-CH3 or a -CH3 group and m, n1 and n2 are numbers, the sum (m + n1 + n2) of between 1 and 2000 , preferably between 50 and 150, the sum (n1 + n2) preferably having values from 0 to 1999 and in particular from 49 to 149 and m preferably having values from 1 to 2000, in particular from 1 to 10.

According to the INCI declaration, these amino-functionalized silicone polymers are referred to as amino dimethicones.

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

Agents (a) which contain a special 4-morpholinomethyl-substituted silicone polymer (a1) are also suitable for use in the process according to the invention. This amino-functionalized silicone polymer comprises structural units of the formulas (SI-VIII) and of the formula (Si-IX)

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

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

A silicone which has structural units of the formulas (Si-VIII), (Si-IX) and (Si-X), for example, can be used as the 4-morpholinomethyl-substituted silicone

in which

R1 represents -CH ₃ , -OH, -OCHS, -0-CH ₂ CH ₃ , -0-CH ₂ CH ₂ CH ₃ , or -0-CH (CH ₃ ) ₂ ;

R2 represents -CH ₃ , -OH, or -OCH ₃ .

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

(Si-Xl)

in the

R1 represents -CHs, -OH, -OCH ₃ , -0-CH ₂ CH ₃ , -0-CH ₂ CH ₂ CH ₃ , or -0-CH (CH ₃ ) ₂ ;

R2 represents -CH ₃ , -OH, or -OCH ₃ .

B represents a group -OH, -0-Si (CH3) 3, -0-Si (CH ₃ ) ₂ 0H, -0-Si (CH ₃ ) ₂ 0CH3,

D represents a group -H, -Si (CH3) 3, -Si (CH ₃ ) ₂ OH, -Si (CH ₃ ) ₂ OCH ₃ ,

a, b and c independently of one another represent integers between 0 and 1000, with the

Requirement a + b + c> 0

m and n independently of one another are integers, numbers between 1 and 1000 with the proviso that

at least one of the conditions B = -OH or D = -H is fulfilled, the units a, b, c, m and n are distributed randomly or in blocks in the molecule.

Structural formula (Si-Xl) is intended to clarify that the siloxane groups n and m do not necessarily have to be bound directly to an end group 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 group B or D is preferably bound to a dimethylsiloxy group. Also in formula (Si-VI) the siloxane units a, b, c, m and n are preferably statistically distributed.

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

B = -0-Si (CH ₃ ) ₂ 0H and D = -Si (CH ₃ ) ₃

B = -0-Si (CH ₃ ) ₂ 0H and D = -Si (CH ₃ ) ₂ OH

B = -0-Si (CH ₃ ) ₂ 0H and D = -Si (CH ₃ ) 20CH ₃

B = -0-Si (CH ₃ ) ₃ and D = -Si (CH ₃ ) ₂ OH

B = -0-Si (CH ₃ ) ₂ 0CH ₃ and D = -Si (CH ₃ ) ₂ OH means. 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 in the case of oxidative treatment.

To produce particularly resistant films, agent (a) contains the amino-functionalized silicone polymer (s) (a2), preferably in certain quantitative ranges.

Particularly robust films were obtained if an agent (a) was used in the process according to the invention which, based on the total weight of agent (a), contains one or more silicone polymers in a total amount of 0.1 to 8.0% by weight, preferably contains 0.2 to 6.0% by weight, more preferably 0.5 to 5.0% by weight and very particularly preferably 1.0 to 3.5% by weight.

In a further preferred embodiment, a method according to the invention is characterized in that the agent (a), based on the total weight of the agent (a), comprises one or more amino-functionalized silicone polymers in a total amount of 0.1 to 8.0% by weight. , preferably 0.2 to 6.0 wt .-%, more preferably from 0.5 to 5.0 wt .-% and very particularly preferably from 1.0 to 3.5 wt .-%. coloring compound (a2) on average (a)

The agent (a) used in the process according to the invention contains at least one coloring compound (a2) as a second constituent essential to the invention.

In the context of the invention, coloring compounds are understood to mean substances which are capable of imparting a color to the keratin material. Particularly suitable coloring compounds can be selected from the group of pigments, direct dyes, photochromic dyes and thermochromic dyes.

In the context of a further preferred embodiment, a method according to the invention is characterized in that the agent (a) contains at least one coloring compound (a2) from the group of pigments, direct dyes, photochromic dyes and thermochromic dyes.

Pigments in the sense of the present invention are understood to mean coloring compounds which, at 25 ° C. in water, have a solubility of less than 0.5 g / L, preferably less than 0.1 g / L, even more preferably less than 0, Own 05 g / L. Water solubility can be achieved, for example, using the method described below: 0.5 g of the pigment is weighed out in a beaker. A stir fish is added. Then a liter of distilled water is added. This mixture is stirred on a magnetic stirrer for heated to 25 ° C for one hour. If undissolved constituents 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 pigments 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 (a) 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, for example, from chalk, ocher, umber, green earth, burnt terra di Siena or graphite. Furthermore, as inorganic color pigments, black pigments such. B. iron oxide black, colored pigments such. B. ultramarine or iron oxide red and fluorescent or phosphorescent pigments can be used.

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 are particularly suitable. 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), ultramarine (sodium aluminum sulfosilicate, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI77289 ), Iron blue (Ferric Ferrocyanide, CI77510) and / or Carmine (Cochineal).

Colored pearlescent pigments are very particularly preferred according to the invention. 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 conjunction 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 pearlescent pigment. Particularly preferred pearlescent pigments are based on natural or synthetic mica (mica) and are coated with one or more of the aforementioned metal oxides. The color of the respective pigments can be varied by varying the layer thickness of the metal oxide (s). In a further preferred embodiment, a method according to the invention is characterized in that the agent (a) contains at least one coloring compound (a2) from the group of inorganic pigments, 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 from colored pigments based on mica or mica, which are coated with at least one metal oxide and / or a metal oxychloride.

By using pearlescent pigments or effect pigments, colorations with a particularly high gloss can be achieved, which is why the use of these pigments is particularly preferred.

In a further very particularly preferred embodiment, a method according to the invention is characterized in that the agent (a) contains at least one coloring compound (a2) from the group of pigments, which is selected from pigments based on mica or mica, with one or more Metal oxides from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and / or brown iron oxide (CI 77491, CI 77499), manganese violet (CI 77742), ultramarine (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) are coated.

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

For example, very particularly preferred color pigments with the trade name Colorona® are:

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

Colorona Passion Orange, Merck, Mica, CI 77491 (Iran 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, CI 77491 (TITANIUM DIOXIDE), MICA, CI 77891 (IRON OXIDES) Colorona Imperial Red, Merck, MICA, TITANIUM DIOXIDE (CI 77891), D&C RED NO. 30 (CI 73360) Colorona Majestic Green, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 77288 (CHROMIUM OXIDE GREENS)

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

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

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

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

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

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

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

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

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

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

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

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

Colorona Mica Black, Merck, CI 77499 (Iran oxides), Mica, CI 77891 (Titanium dioxide)

Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium dioxide), CI 77491 (Iran oxides)

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

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

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

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

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

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

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

Unipure Red LC 381 EM, Sensient CI 77491 (Iran Oxides), silica Unipure Black LC 989 EM, Sensient, CI 77499 (Iran Oxides), silica

Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iran Oxides), silica

In a further embodiment, the agent according to the invention can also contain (a) 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 color varnishes which, for example, from the group of nitroso, nitro, azo, xanthene, anthraquinone, isoindolinone, isoindoline, quinacridone, perinone, perylene -, Diketo-pyrrolopyorrol, indigo, thioindido, dioxazine and / or triarylmethane compounds can be selected.

Suitable organic pigments include, 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 1 1680, CI 1 1710, CI 15985, CI 19140, CI 20040, CI 21 100, CI 21 108, CI 47000, CI 47005, green pigments with the color index numbers CI 61565, CI 61570, CI 74260, orange pigments with the color index numbers CI 1 1725, CI 15510, CI 45370, CI 71 105, red pigments with the color index numbers CI 12085, CI 12120,

CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI

15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and / or CI 75470.

In a further embodiment, a method according to the invention is characterized in that the agent (a) contains at least one coloring compound (a2) from the group of organic pigments, which is selected from the group consisting of carmine, quinacridone, phthalocyanine, sorghum and blue pigments the color index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the color index numbers CI 1 1680, CI 1 1710, CI 15985, CI 19140, CI 20040, CI 21 100, CI 21 108, CI 47000, CI 47005, green pigments with the color index numbers CI 61565, CI 61570, CI 74260, orange pigments with the color index numbers CI 1 1725, CI 15510, CI 45370, CI 71 105, red pigments with the color index numbers

CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI

15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and / or CI 75470.

The organic pigment can also be a colored lacquer. For the purposes of the invention, the term color lacquer is understood to mean particles which comprise a layer of absorbed dyes, the unit consisting of particles and dye being insoluble under the abovementioned conditions. The particles can be, for example, inorganic substrates act, which can be aluminum, silica, calcium borosilicate, calcium aluminum borosilicate or aluminum.

For example, the alizarin color lacquer can be used as the color lacquer.

Because of their excellent light and temperature resistance, the use of the aforementioned pigments in agent (a) of the process according to the invention is very particularly preferred. It is further 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 5.0 to 45 pm, preferably 10 to 40 pm, in particular 14 to 30 pm. The average particle size D50 can be determined, for example, using dynamic light scattering (DLS).

To produce the highest possible gloss, it has proven particularly advantageous to use the pigments in certain quantitative ranges on average (a). The pigment or pigments are preferably present in an amount of 0.001 to 20% by weight, more preferably 0.1 to 8% by weight, even more preferably 0.6 to 6% by weight and very particularly preferably 1 , 0 to 4.5 wt .-%, each based on the total weight of the agent (a), are used.

In a further very particularly preferred embodiment, a method according to the invention is characterized in that the agent (a), based on the total weight of the agent (a), comprises one or more pigments in a total amount of 0.001 to 20% by weight, more preferably of Contains 0.1 to 8% by weight, even more preferably 0.3 to 6% by weight and very particularly preferably 0.5 to 4.5% by weight.

In a further embodiment, which is explicitly very particularly preferred, a method according to the invention is characterized in that the agent (a), based on the total weight of the agent (a), further comprises one or more inorganic pigments in a total amount of 0.001 to 20% by weight preferably from 0.1 to 8% by weight, still more preferably from 0.3 to 6% by weight and very particularly preferably from 0.5 to 4.5% by weight.

The agents (a) used in the process according to the invention can also contain one or more substantive dyes as color-imparting compounds (a2). Direct dyes are dyes that are applied directly to the hair and do not require an oxidative process to form the color. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes or indophenols. The substantive dyes for the purposes of the present invention have a solubility in water (760 mmHg) at 25 ° C. of more than 0.5 g / L and are therefore not to be regarded as pigments. For the purposes of the present invention, the direct dyes preferably have a solubility in water (760 mmHg) at 25 ° C. of more than 1.0 g / l.

Direct dyes can be divided into anionic, cationic and nonionic direct dyes.

In a further embodiment, a method according to the invention is characterized in that the agent (a) contains at least one coloring compound (a2) from the group of anionic, nonionic and cationic substantive dyes.

Suitable cationic direct dyes are, for example, Basic Blue 7, Basic Blue 26, HC Blue 16, Basic Violet 2 and Basic Violet 14, Basic Yellow 57, Basic Red 76, Basic Blue 16, Basic Blue 347 (Cationic Blue 347 / Dystar), HC Blue No. 16, Basic Blue 99, Basic Brown 16, Basic Brown 17, Basic Yellow 57, Basic Yellow 87, Basic Orange 31, Basic Red 51 Basic Red 76.

Nonionic nitro and quinone dyes and neutral azo dyes, for example, can be used as nonionic direct dyes. Suitable nonionic direct dyes are those under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 1 1, HC Red 13, HC Red BN, HC Blue 2, HC Blue 1 1, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 known compounds , and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (2-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (2-hydroxyethyl) - aminophenol, 2- (2-

Hydroxyethyl) amino-4,6-dinitrophenol, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-amino-4- (2-hydroxyethyl) amino-5-chloro-2-nitrobenzene , 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 2 - [(4-amino-2-nitrophenyl) amino] -benzoic acid, 6-nitro-1, 2,3, 4-tetrahydroquinoxaline, 2-hydroxy-1, 4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-4-nitrophenol .

In the course of the work leading to this invention, it has been found that agents (a) which contain at least one anionic direct dye (a2) are also suitable.

In a further embodiment, a method according to the invention is therefore characterized in that the agent (a) contains at least one anionic direct dye.

Anionic direct dyes are also known as acid dyes. Acid dyes are direct dyes that have at least one carboxylic acid group (-COOH) and / or a sulfonic acid group (-SO3H). Depending on the pH, the protonated forms (-COOH, -SO3H) of the carboxylic acid or sulfonic acid groups are in equilibrium with their deprotonated forms (-COO, -SO3). The proportion of protonated forms increases with decreasing pH. If direct dyes are used in the form of their salts, the carboxylic acid groups or sulfonic acid groups are in deprotonated form and are neutralized with appropriate stoichiometric equivalents of cations in order to maintain electroneutrality. Acid dyes according to the invention can also be used in the form of their sodium salts and / or their potassium salts.

The acid dyes for the purposes of the present invention have a solubility in water (760 mmHg) at 25 ° C. of more than 0.5 g / L and are therefore not to be regarded as pigments. For the purposes of the present invention, the acid dyes preferably have a solubility in water (760 mmHg) at 25 ° C. of more than 1.0 g / l.

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

An essential feature of the acid dyes is their ability to form anionic charges, the carboxylic acid or sulfonic acid groups responsible for this usually being linked to different chromophore systems. Suitable chromophoric systems can be found, for example, in the structures of nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinone dyes, triarylmethane dyes, xanthene dyes, rhodamine dyes, oxazine dyes and / or indophenol dyes.

In one embodiment, a process for dyeing keratinous material is suitable, which is characterized in that the agent (a) contains at least one anionic direct dye which is selected from the group consisting of the nitrophenylenediamines, the nitroaminophenols, the azo dyes and the anthraquinone dyes , the triarylmethane dyes, the xanthene dyes, the rhodamine dyes, the oxazine dyes and / or the indophenol dyes, where the dyes from the aforementioned group each have at least one carboxylic acid group (-COOH), a sodium carboxylate group (-COONa), a potassium carboxylate group (-COOK ), a sulfonic acid group (-SO3H), a sodium sulfonate group (- SOsNa) and / or a potassium sulfonate group (-SO3K).

As further suitable acid dyes, for example, one or more compounds can be selected from the following group: Acid Yellow 1 (D&C Yellow 7, Citronin A, Ext. D&C Yellow No. 7, Japan Yellow 403, CI 10316, COLIPA n ° B001), Acid Yellow 3 (COLIPA n °: C 54, D&C Yellow N ° 10, Quinoline Yellow, E104, Food Yellow 13), Acid Yellow 9 (C1 13015), Acid Yellow 17 (C1 18965), Acid Yellow 23 (COLIPA n ° C 29, Covacap Jaune W 1 100 (LCW), Sicovit Tartrazine 85 E 102 (BASF), Tartrazine, Food Yellow 4, Japan Yellow 4, FD&C Yellow No. 5), Acid Yellow 36 (CI 13065), Acid Yellow 121 (CI 18690), Acid Orange 6 (CI 14270), Acid Orange 7 (2-naphthol orange, Orange II, CI 15510, D&C Orange 4, COLIPA n ° C015), Acid Orange 10 (Cl 16230; Orange G sodium salt), Acid Orange 1 1 (CI 45370), Acid Orange 15 ( CI 50120), Acid Orange 20 (CI 14600), Acid Orange 24 (BROWN 1; CI 20170; KATSU201; nosodiumsalt; Brown No.201; RESORCIN BROWN; ACID ORANGE 24; Japan Brown 201; D & C Brown No.1) , Acid Red 14 (Cl14720), Acid Red 18 (E124, Red 18; CI 16255), Acid Red 27 (E 123, CI 16185, C-Rot 46, Echtrot D, FD&C Red Nr.2, Food Red 9, Naphtholrot S), Acid Red 33 (Red 33, Fuchsia Red, D&C Red 33, CI 17200), Acid Red 35 (CI Cl18065), Acid Red 51 (CI 45430, Pyrosin B, Tetraiodfluorescein, Eosin J, l odeosin), Acid Red 52 (CI 45100, Food Red 106, Solar Rhodamine B, Acid Rhodamine B, Red n ° 106 Pontacyl Brilliant Pink), Acid Red 73 (CI CI 27290), Acid Red 87 (Eosin, CI 45380), Acid Red 92 (COLIPA n ° C53, CI 45410), Acid Red 95 (CI 45425, Erythtosine, Simacid Erythrosine Y), Acid Red 184 (CI 15685), Acid Red 195, Acid Violet 43 (Jarocol Violet 43, Ext. D&C Violet n ° 2, Cl 60730, COLIPA n ° C063), Acid Violet 49 (CI 42640), Acid Violet 50 (CI 50325), Acid Blue 1 (Patent Blue, CI 42045), Acid Blue 3 (Patent Blau V, CI 42051), Acid Blue 7 (CI 42080), Acid Blue 104 (CI 42735), Acid Blue 9 (E 133, Patent Blue AE, Amido Blue AE, Erioglaucin A, CI 42090, Cl Food Blue 2), Acid Blue 62 (CI 62045 ), Acid Blue 74 (E 132, CI 73015), Acid Blue 80 (CI 61585), Acid Green 3 (CI 42085, Foodgreenl), Acid Green 5 (CI 42095), Acid Green 9 (C.1.42100), Acid Green 22 (C.1.42170), Acid Green 25 (CI 61570, Japan Green 201, D&C Green No. 5), Acid Green 50 (Brillantsäuregrün BS, Cl 44090, Acid Brilliant Green BS, E 142), Acid Black 1 (Black n ° 401, Naphthalene Black 10B, Amido Black 10B, CI 20 470, COLIPA n ° B15), Acid Black 52 (CI 1571 1), Food Yellow 8 (CI 14270), Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 1 1, D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 and / or D&C Brown 1.

The water solubility of the anionic direct dyes can be determined, for example, in the following way. 0.1 g of the anionic direct dye is placed in a beaker. A stir fish is added. Then 100 ml of water are added. This mixture is heated to 25 ° C. with stirring on a magnetic stirrer. It is stirred for 60 minutes. The aqueous mixture is then assessed visually. If there are still undissolved residues, the amount of water is increased - for example in steps of 10 ml. Water is added until the amount of dye used has completely dissolved. If the dye-water mixture cannot be assessed visually due to the high intensity of the dye, the mixture is filtered. If a portion of undissolved dyes remains on the filter paper, the solubility test is repeated with a higher amount of water. If 0.1 g of the anionic direct dye dissolves in 100 ml of water at 25 ° C., the solubility of the dye is 1.0 g / L. Acid Yellow 1 is called 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid disodium salt and has a solubility in water of at least 40 g / L (25 ° C).

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

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

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

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

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

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

Acid Red 92 is the disodium salt of 3,4,5,6-tetrachloro-2- (1, 4,5,8-tetrabromo-6-hydroxy-3-oxoxanthene-9-yl) benzoic acid, its water solubility with more than 10 g / L is specified (25 ° C).

Acid Blue 9 is the disodium salt of 2 - ({4- [N-ethyl (3-sulfonatobenzyl] amino] phenyl} {4 - [(N-ethyl (3-sulfonatobenzyl) imino] -2,5-cyclohexadien-1- ylidene} methyl) -benzenesulfonate and has a water solubility of more than 20 wt .-% (25 ° C).

In a further embodiment, a method according to the invention is therefore characterized in that the agent (a) contains at least one substantive dye (a2) which is selected from the group consisting of Acid Yellow 1, Acid Yellow 3, Acid Yellow 9, Acid Yellow 17 , Acid Yellow 23, Acid Yellow 36, Acid Yellow 121, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 1 1, Acid Orange 15, Acid Orange 20, Acid Orange 24, Acid Red 14, Acid Red, Acid Red 27, Acid Red 33, Acid Red 35, Acid Red 51, Acid Red 52, Acid Red 73, Acid Red 87, Acid Red 92, Acid Red 95, Acid Red 184, Acid Red 195, Acid Violet 43, Acid Violet 49 , Acid Violet 50, Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 104, Acid Blue 9, Acid Blue 62, Acid Blue 74, Acid Blue 80, Acid Green 3, Acid Green 5, Acid Green 9, Acid Green 22, Acid Green 25, Acid Green 50, Acid Black 1, Acid Black 52, Food Yellow 8, Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 1 1, D&C Red 21, D&C Red 27, D & C Red 33, D&C Violet 2 and / or D&C Brown 1.

Depending on the desired color intensity, the direct dye or dyes can be used in various amounts on average (a). Particularly good results could be obtained if agent (a) - based on the total weight of agent (a) - had one or more substantive dyes (b) in a total amount of 0.01 to 10.0% by weight, preferably of Contains 0.1 to 8.0% by weight, more preferably 0.2 to 6.0% by weight and very particularly preferably 0.5 to 4.5% by weight. Furthermore, the agent (a) can also contain at least one photochromic or thermochromic dye as the coloring compound (a2).

Photochromic dyes are dyes that react to UV light (sunlight or black light) with a reversible change in color. The UV light changes the chemical structure of the dyes and thus their absorption behavior (photochromism).

Thermochromic dyes are dyes that react to changes in temperature with a reversible change in hue. The change in temperature changes the chemical structure of the dyes and thus their absorption behavior (thermochromism).

The agent (a) - based on the total weight of the agent (a) - one or more photochromic dyes (b) in a total amount of 0.01 to 10.0 wt .-%, preferably from 0.1 to 8.0 % By weight, more preferably from 0.2 to 6.0% by weight and very particularly preferably from 0.5 to 4.5% by weight

The agent (a) - based on the total weight of the agent (a) - one or more thermochromic dyes (b) in a total amount of 0.01 to 10.0 wt .-%, preferably from 0.1 to 8.0 % By weight, more preferably from 0.2 to 6.0% by weight and very particularly preferably from 0.5 to 4.5% by weight, contain nonionic surfactants (a3) on average (a)

As a third component (a3) essential to the invention, agent (a) contains at least one nonionic surfactant. It has been shown that the use of nonionic surfactants synergistically increases the gloss that can be produced by the process according to the invention.

Nonionic surfactants (Tnio) contain e.g. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such connections are, for example

Addition products of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear and branched fatty alcohols with 6 to 30 carbon atoms, the fatty alcohol polyglycol ethers or the fatty alcohol polypropylene glycol ethers or mixed fatty alcohol polyethers,

Addition products of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear and branched fatty acids with 6 to 30 carbon atoms, the fatty acid polyglycol ethers or the fatty acid polypropylene glycol ethers or mixed fatty acid polyethers,

Addition products of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide onto linear and branched alkylphenols having 8 to 15 carbon atoms in the alkyl group, which Alkylphenol polyglycol ethers or the alkylpolypropylene glycol ethers or mixed alkylphenol polyethers,

with a methyl or C2 - C6 alkyl group end capped adducts of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear and branched fatty alcohols with 8 to 30 C atoms, with fatty acids with 8 to 30 C atoms and on alkylphenols having 8 to 15 carbon atoms in the alkyl group, such as the type available under the commercial names Dehydol ^® LS, Dehydol ^® LT (Cognis),

Ci ₂ -C30 fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,

Addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil, polyol fatty acid esters, such as the commercial product Hydagen ^® HSP (Cognis) or Sovermol ^® types (Cognis),

alkoxylated triglycerides,

alkoxylated fatty acid alkyl esters of the formula (T nio-1)

R ¹ CO- (OCH ₂ CHR ² ) _W OR ³ (Tnio-1) in the R ¹ CO for a linear or branched, saturated and / or unsaturated acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or methyl, R ³ represents linear or branched alkyl radicals having 1 to 4 carbon atoms and w represents numbers from 1 to 20,

Amine oxides,

Hydroxy mixed ethers, as described, for example, in DE-OS 19738866, sorbitan fatty acid esters and deposits of ethylene oxide and sorbitan fatty acid esters, such as, for example, the polysorbates,

Sugar fatty acid esters and adducts of ethylene oxide with sugar fatty acid esters, adducts of ethylene oxide with fatty acid alkanolamides and fatty amines,

Sugar surfactants of the alkyl and alkenyl oligoglycoside type according to formula (E4-II),

R ⁴ 0- [G] _P (Tnio-2) in which R ^{4 represents} an alkyl or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. The alkyl and alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably from glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (Tnio-2) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in the individual molecule is always an integer must and here can assume the values p = 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ⁴ can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length C8-CIO (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical Cs-C-is-coconut fatty alcohol by distillation and with a proportion of less than 6% by weight of C-12 -Alcohol can be contaminated as well as alkyl oligoglucosides based on technical C9 / n-oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ¹⁵ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened C12 / 14 coconut alcohol with a DP of 1 to 3 are preferred.

Sugar surfactants of the fatty acid N-alkylpolyhydroxyalkylamide type, a nonionic surfactant of the formula (Tnio-3),

R ⁵ CO-NR ⁶ - [Z] (Tnio-3) in the R ⁵ CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ⁶ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for is a linear or branched polyhydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups. The fatty acid N-alkyl polyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. The fatty acid N-alkylpolyhydroxyalkylamides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (Tnio-4):

R ⁷ CO- (NR ⁸ ) -CH ₂ - [CH (OH)] ₄ - CH ₂ OH (Tnio-4) The preferred fatty acid N-alkylpolyhydroxyalkylamides used are glucamides of the formula (Tnio- 4) in which R ^{8 represents} hydrogen or an alkyl group and R ⁷ CO represents the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid Stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures. Fatty acid N-alkylglucamides of the formula (Tnio-4) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C12 / 14 coconut fatty acid or a corresponding derivative are particularly preferred. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

Further typical examples of nonionic surfactants are fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, mixed ethers or mixed formals, protein hydrolyzates (in particular vegetable products based on wheat) and polysorbates.

The selection of certain nonionic surfactants has proven to be particularly advantageous, since these increase the gloss to a particular degree. Most preferably, agent (a) contains at least one highly ethoxylated fatty alcohol, i.e. a fatty alcohol with a degree of ethoxylation of 80 to 120.

In a further preferred embodiment, an inventive method is characterized in that the means (a) an ethoxylated C8-C contains at least ₂₄ fatty alcohol (a3) with a degree of ethoxylation from 80 to 120.

According to the invention, fatty alcohols are to be understood as meaning saturated or unsaturated, unbranched or branched Cs-C ₂₄ -alkyl groups with hydroxy substitution. Unsaturated fatty alcohols can be mono- or polyunsaturated. In the case of an unsaturated fatty alcohol, their CC double bond (s) can have the cis or trans configuration.

Preferred fatty alcohols are octan-1-ol (octyl alcohol, caprylic alcohol), decan-1-ol (decyl alcohol, capric alcohol), dodecan-1-ol (dodecyl alcohol, lauryl alcohol), tetradecan-1-ol, (tetradecyl alcohol, myristyl alcohol), hexadecane 1-ol (hexadecyl alcohol, cetyl alcohol, palmityl alcohol),

Octadecan-1-ol (octadecyl alcohol, stearyl alcohol), (9Z) octadec-9-en-1-ol (oleyl alcohol), (9 U) - octadec-9-en-1-ol (elaidyl alcohol), (9Z, 12Z ) -Octadeca-9,12-dien-1-ol (linoleyl alcohol), (9Z, 12Z, 15Z) -Octadeca-9,12,15-trien-1-ol (linolenoyl alcohol), eicosan-1-ol (eicosyl alcohol, Arachyl alcohol), (9Z) -Eicos-9-en-1-ol (gadoleyl alcohol), (5Z, 8Z, 11Z, 14Z) -Eicosa-5,8,11, 14-tetraen- 1 -ol (arachidone alcohol), docosan -1-ol (docosyl alcohol, behenyl alcohol), (13E) -docosen-1-ol (brassidyl alcohol) and (13Z) -docos-13-en-1-ol (erucyl alcohol). Within this group again Hexadecan-1-ol (hexadecyl alcohol, cetyl alcohol, palmityl alcohol) and octadecan-1-ol (octadecyl alcohol, stearyl alcohol) are very particularly preferably fatty alcohols.

These fatty alcohols are ethoxylated with a degree of ethoxylation of 80 to 120. Ethoxylation (also oxyethylation) means the reaction of the fatty alcohols with ethylene oxide (EO). By inserting 80 to 120 groupings of the type -CH2-CH2-0- per fatty alcohol molecule, linear polyethers are formed which have a hydroxyl group at one chain end and the C8-C ₂₄ alkyl group of the fatty alcohol at the other chain end.

Preferred highly ethoxylated fatty alcohols (a3) have a degree of ethoxylation of 90 to 110. It is very particularly preferred if ethoxylated fatty alcohols (a3) are used which have a degree of ethoxylation of 100.

In a further very particularly preferred embodiment, a method according to the invention is therefore characterized in that the agent (a) contains at least one ethoxylated fatty alcohol (a3) of the formula (T1)

(T1) wherein R1 is a saturated or unsaturated, unbranched or branched C8-C24 alkyl group, preferably a saturated, unbranched C16 or C18 alkyl group, and n is an integer from 80 to 120, preferably an integer from 90 to 110, more preferably an integer from 95 to 105 and particularly preferably the number 100.

In addition, it has proven to be particularly preferred if the agent (a) also contains a low ethoxyated fatty alcohol, i.e. contains a fatty alcohol with a degree of ethoxylation of 10 to 40.

In a further very particularly preferred embodiment, a method according to the invention is characterized in that the agent (a) contains at least one ethoxylated Cs-C ₂₄ fatty alcohol (a3) with a degree of ethoxylation of 10 to 40.

Preferred fatty alcohols are analogous to octan-1-ol (octyl alcohol, caprylic alcohol), decan-1-ol (decyl alcohol, capric alcohol), dodecan-1-ol (dodecyl alcohol, lauryl alcohol), tetradecan-1-ol, (tetradecyl alcohol, myristyl alcohol), hexadecane -1-ol (hexadecyl alcohol, cetyl alcohol, palmityl alcohol), octadecan-1-ol (octadecyl alcohol, stearyl alcohol), (9Z) -octadec-9-en-1-ol (oleyl alcohol), (9E) -octadec-9-en- 1-ol (elaidyl alcohol), (9Z, 12Z) -Octadeca-9,12-dien-1-ol (Linoleyl alcohol), (9Z, 12Z, 15Z) -Octadeca-9, 12, 15-trien-1-ol (linolenoyl alcohol), eicosan-1-ol (eicosyl alcohol, arachyl alcohol), (9Z) -Eicos-9-en- 1-ol (gadoleyl alcohol), (5Z, 8Z, 1 1 Z, 14Z) -eicosa- 5,8, 1 1, 14-tetraen-1-ol (arachidone alcohol), docosan-1-ol (docosyl alcohol, behenyl alcohol), (13E) - Docosen-1-ol (brassidyl alcohol) and (13Z) -Docos-13-en-1-ol (erucyl alcohol). Within this group, in turn, hexadecan-1-ol (hexadecyl alcohol, cetyl alcohol, palmityl alcohol) and octadecan-1-ol (octadecyl alcohol, stearyl alcohol) are very particularly preferably fatty alcohols.

These fatty alcohols are ethoxylated with a degree of ethoxylation of 10 to 40. Ethoxylation (also oxyethylation) means the reaction of the fatty alcohols with ethylene oxide (EO). By inserting 10 to 40 groups of the type -CH2-CH2-0- per fatty alcohol molecule, linear polyethers are formed which have a hydroxyl group at one chain end and the C8-C24 alkyl group of the fatty alcohol at the other chain end.

Preferred low ethoxylated fatty alcohols (a3) have a degree of ethoxylation of 12 to 30.

In a further very particularly preferred embodiment, a method according to the invention is characterized in that the agent (a) contains at least one ethoxylated fatty alcohol (a3) of the formula (T-II), wherein R2 is a saturated or unsaturated, unbranched or branched C8-C24 alkyl group, preferably a saturated, unbranched C16 or C18 alkyl group, and m is an integer from 10 to 40, preferably an integer from 12 to 30, stands.

It has proven to be particularly effective to use, on average (a), both a highly ethoxylated Cs-C ₂₄ fatty alcohol and a low-ethoxylated Cs-C ₂₄ fatty alcohol as the nonionic surfactants (a3).

The alkylene oxide adducts with fatty acids, each with 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid, and the sugar surfactants have proven to be suitable nonionic surfactants. Preparations with excellent properties are also obtained if they contain fatty acid esters of ethoxylated glycerol as nonionic surfactants.

These connections are characterized by the following parameters. The alkyl radical R contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear and methyl-branched aliphatic radicals in the 2-position are preferred. Such alkyl radicals are, for example 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred. When using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

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

For the surfactants, which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrowed homolog distribution can be used. “Normal” homolog distribution is understood to mean mixtures of homologues which are obtained as catalysts from the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates. On the other hand, narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be preferred.

Nonionic surfactants have also proven useful as additives for further improving the skin feel during and after use, the additional use of which can therefore be recommended for the preparation of the compositions according to the invention. Compositions according to the invention are therefore particularly preferred with an additional content of 0.1-20% by weight of nonionic surfactants with an HLB value of 2-18. Such products can be added by adding ethylene oxide to e.g. B. fatty alcohols with 6 - 30 C atoms, on fatty acids with 6 - 30 C atoms or on glycerol or sorbitan fatty acid partial esters based on Ci2-Ci8 fatty acids or on fatty acid alkanolamides. The HLB value means the proportion of hydrophilic groups, e.g. B. on glycol ether or polyol groups based on the total molecule and it is calculated according to the relationship

HLB = 1/5 x (100 wt .-% L), where wt .-% L is the weight fraction of lipophilic groups, ie z. B. represents alkyl or acyl groups with 6-30 carbon atoms in the surfactant molecule.

In the course of the work leading to this invention it has been found that the use of nonionic surfactants improves the gloss of the colored keratin materials. Other nonionic components have also proven to be advantageous in this regard. So it has been shown that the gloss increases the more the proportion of non-ionic components on average (a).

In this context, it has proven to be particularly preferred if the proportion by weight of all nonionic constituents in average (a), based on the total weight of agent (a), is 80% by weight, preferably 85% by weight, more preferably 90% by weight and very particularly preferably 99% by weight. In other words, agent (a) in the context of this embodiment consists of 80% by weight, preferably 85% by weight, more preferably 90% by weight and very particularly preferably 99% by weight, of nonionic constituents.

In the context of a further very particularly preferred embodiment, a method according to the invention is characterized in that the weight fraction of all nonionic constituents in the average (a) - based on the total weight of the average (a) - is at least 80% by weight, preferably at least 85% by weight .-%, more preferably at least 90 wt .-% and very particularly preferably at least 98 wt .-%.

In other words, the method according to the invention of this particularly preferred embodiment is characterized in that the total weight fraction of all nonionic constituents contained in agent (a) - based on the total weight of agent (a) - is at least 80% by weight, preferably at least 85 % By weight, more preferably at least 90% by weight and very particularly preferably at least 98% by weight.

Example: Contain 100 g of an agent (a)

10 g cetearyl alcohol (non-ionic fat component)

5.0 g Paraffinum Liquidum (non-ionic fat component)

1.5 g ceteareth-30 (nonionic surfactant)

0.5 g ceteareth-100 (nonionic surfactant)

2.0 g pearlescent pigment (non-ionic pigment)

2.0 g ethanol (non-ionic solvent)

2.0 g amino silicone (non-ionic amino silicone)

ad 100 g water (non-ionic solvent)

The proportion by weight of all nonionic components - based on the total weight of the agent (a) - is 100% by weight.

Example: Contain 100 g of an agent (a)

15 g cetearyl alcohol (non-ionic fat component)

10.0 g Paraffinum Liquidum (non-ionic fat component)

2.5 g ceteareth-30 (nonionic surfactant) 1.5 g ceteareth-100 (nonionic surfactant)

1.5 g pearlescent pigment (nonionic pigment)

6.0 g phenoxyethanol (non-ionic solvent)

2.0 g amino silicone (non-ionic amino silicone)

0.5 g sodium hydroxide (salt, ionic)

ad 100 g water (non-ionic solvent)

The proportion by weight of all nonionic components - based on the total weight of the agent (a) - is 99.5% by weight. pH of the agent (a)

The colorant (a) is preferably adjusted to a neutral to alkaline pH. The colorant (a) is very particularly preferably adjusted to an alkaline pH. Under basic conditions, the amino-functionalized silicone polymer (a1) can be dissolved or dispersed particularly well and without protonation.

To set the desired pH, agent (a) preferably contains at least one alkalizing agent. The pH values in the sense of the present invention are pH values that were measured at a temperature of 22 ° C.

Agent (a) can contain, for example, ammonia, alkanolamines and / or basic amino acids as alkalizing agents.

The alkanolamines which can be used in the agent according to the invention are preferably selected from primary amines having a C2-C6-alkyl base which carries at least one hydroxyl group. Preferred alkanolamines are selected from the group formed from 2-aminoethane-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropane -2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1 -Amino-2-methylpropan-2-ol, 3-aminopropan-1, 2-diol, 2-amino-2-methylpropan-1, 3-diol.

Alkanolamines which are particularly preferred according to the invention are selected from 2-aminoethan-1-ol and / or 2-amino-2-methylpropan-1-ol. A particularly preferred embodiment is therefore characterized in that the agent according to the invention contains as alkali agent an alkanolamine selected from 2-aminoethan-1-ol and / or 2-amino-2-methylpropan-1-ol.

An amino acid in the sense of the invention is an organic compound which contains at least one protonatable amino group and at least one -COOH or an -SOsH group in its structure. Preferred amino acids are aminocarboxylic acids, in particular a- (alpha) -amino-carboxylic acids and w-aminocarboxylic acids, with a-aminocarboxylic acids being particularly preferred. According to the invention, basic amino acids are understood to mean those amino acids which have an isoelectric point p1 of greater than 7.0.

Basic a-aminocarboxylic acids contain at least one asymmetric carbon atom. In the context of the present invention, both possible enantiomers can be used equally as a specific compound or also mixtures thereof, in particular as racemates. However, it is particularly advantageous to use the naturally preferred isomer form, usually in the L configuration.

The basic amino acids are preferably selected from the group which is formed from arginine, lysine, ornithine and histidine, particularly preferably from arginine and lysine. In a further particularly preferred embodiment, an agent according to the invention is therefore characterized in that the alkalizing agent is a basic amino acid from the group arginine, lysine, ornithine and / or histidine.

In addition, the agent can contain further alkalizing agents, in particular inorganic alkalizing agents. Inorganic alkalizing agents which can be used according to the invention are preferably selected from the group formed from sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate and potassium carbonate.

Very particularly preferred alkalizing agents are ammonia, 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2- methylpropan-2-ol, 3-aminopropan-1, 2-diol, 2-amino-2-methylpropan-1, 3-diol, arginine, lysine, ornithine, histidine, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, Sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate and potassium carbonate.

In a further very particularly preferred embodiment, a process according to the invention is characterized in that the colorant (a) comprises at least one alkalizing agent from the group consisting of ammonia, 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4- Aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentane 4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropan-1, 2-diol, 2-amino-2-methylpropan-1, Contains 3-diol, arginine, lysine, ornithine, histidine, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate and potassium carbonate. Particularly good results were obtained when the agent (a) was adjusted to a pH of from 7.0 to 11.5, preferably from 8.0 to 11.0, and particularly preferably from 8.5 to 10.5.

In a further very particularly preferred embodiment, a method according to the invention is characterized in that the agent (a) contains water and a pH of 7.0 to 11.5, preferably 8.0 to 11.0, and particularly preferably from 8.5 to 10.5.

Acid (b1) on average (b)

After the application of the colorant (a) on the keratin material, the aftertreatment agent (b) is applied. The aftertreatment agent (b) is an acidic solution, dispersion or emulsion. The aftertreatment agent (b) therefore contains at least one acid (b1) as an ingredient essential to the invention.

Here, certain acids have proven to be very particularly suitable for setting the desired pH. These acids can be selected, for example, from the group consisting of citric acid, tartaric acid, malic acid, lactic acid, acetic acid, methanesulfonic acid, benzoic acid, malonic acid, oxalic acid, 1-hydroxyethane-1, 1-diphosphonic acid, sulfuric acid, hydrochloric acid and phosphoric acid.

In a further very particularly preferred embodiment, a process according to the invention is characterized in that the agent (b) contains at least one acid (b1) which is selected from the group consisting of citric acid, tartaric acid, malic acid, lactic acid, acetic acid, methanesulfonic acid, benzoic acid and malonic acid , Oxalic acid, 1-hydroxyethane-1, 1-diphosphonic acid, sulfuric acid, hydrochloric acid and phosphoric acid.

As soon as the aftertreatment agent (b) is applied, it comes into contact with the aminosilicones (a1) and coloring compounds (a2) deposited on the keratin material. Since the agent (b) is acidic, it also lowers the pH in the immediate vicinity of the aminosilicone (a1). In this context, it is assumed that the reduction in pH causes protonation of the previously uncharged aminosilicone (a1), as a result of which the adhesive forces to the keratin material are further increased and the coloring compounds (a2) are bound even more strongly to the hair. As a result, the washfastness of the resulting dyeing is massively improved while maintaining the hair shine. For this reason, the aftertreatment agent (b) is preferably adjusted to an acidic pH in the range from 1.5 to 5.5, preferably from 2.0 to 4.8, and particularly preferably from 2.5 to 4.5. In a further very particularly preferred embodiment, a method according to the invention is characterized in that the agent (b) contains water and a pH of 1.5 to 5.5, preferably 2.0 to 4.8, and particularly preferably 2 , 5 to 4.5.

Within the scope of the work leading to this invention, the choice of the point in time at which the pH value is lowered has proven to be essential for the production of stable layers on the keratin material. It is essential to the invention that the pH of the aminosilicone (a1) is lowered after it has been applied to the keratin fiber. With the simultaneous use of amino silicone (a1) and acid, there is no significant increase in the binding to the keratin. For this reason, it is essential to the invention to incorporate the acid (b1) into the aftertreatment agent (b).

It was found that the better the pH value in the vicinity of the aminosilicone (a1) is reduced, the greater the improvement in wash fastness. In other words, the dyeings were particularly stable when the colorant (a) was set to be comparatively strongly alkaline and the aftertreatment agent (b) had a relatively acidic pH.

Other ingredients in agents (a) and (b)

Agents (a) and (b) described above can also contain one or more optional ingredients.

From the constituents listed below, the nonionic constituents are particularly preferably selected for the agent (a).

Agents (b) can additionally contain one or more surfactants. The term surfactants means surface-active substances. A distinction is made between anionic surfactants consisting of a hydrophobic residue and a negatively charged hydrophilic head group, amphoteric surfactants, which carry both a negative and a compensating positive charge, cationic surfactants, which in addition to a hydrophobic residue have a positively charged hydrophilic group, and nonionic surfactants, which have no charges but strong dipole moments and are highly hydrated in aqueous solution.

Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO ^(_) - or -S03 ^(_) - group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the cocosacylaminopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl- imidazolines each with 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants are surface-active compounds which, in addition to a Cs-C24-alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -SCbH group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 24 C. Atoms in the alkyl group. Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, amino propionates, aminoglycinates, imidazolinium betaines and sulfobetaines.

Particularly preferred ampholytic surfactants are N-coconut alkylaminopropionate, coconut acylaminoethylaminopropionate and C12-Cis-acylsarcosine.

Agents (b) can also additionally contain at least one nonionic surfactant. Suitable nonionic surfactants are alkyl polyglycosides and alkylene oxide adducts with fatty alcohols and fatty acids, each with 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Preparations with good properties are also obtained if they contain, as nonionic surfactants, fatty acid esters of ethoxylated glycerol which have been reacted with at least 2 moles of ethylene oxide. The nonionic surfactants are used in a total amount of 0.1 to 45% by weight, preferably 1 to 30% by weight and very particularly preferably 1 to 15% by weight, based on the total weight of the particular agent.

The agents (b) can also additionally comprise at least one cationic surfactant. Cationic surfactants are understood to mean surfactants, that is to say surface-active compounds, each having one or more positive charges. Cationic surfactants contain only positive charges. These surfactants are usually composed of a hydrophobic part and a hydrophilic head group, the hydrophobic part generally consisting of a hydrocarbon skeleton (for example consisting of one or two linear or branched alkyl chains), and the positive charge (s) are located in the hydrophilic head group. Examples of cationic surfactants are

quaternary ammonium compounds which can carry one or two alkyl chains with a chain length of 8 to 28 carbon atoms as hydrophobic radicals,

- Quaternary phosphonium salts substituted with one or more alkyl chains with a chain length of 8 to 28 carbon atoms or

- Tertiary sulfonium salts. Furthermore, the cationic charge can also be part of a heterocyclic ring (for example an imidazolium ring or a pyridinium ring) in the form of an onium structure. In addition to the functional unit that carries the cationic charge, the cationic surfactant can also contain further uncharged functional groups, as is the case, for example, with esterquats. The cationic surfactants are used in a total amount of 0.1 to 45% by weight, preferably 1 to 30% by weight and very particularly preferably 1 to 15% by weight, based on the total weight of the particular agent.

The agents (b) according to the invention can also comprise at least one anionic surfactant. Anionic surfactants are surface-active agents with exclusively anionic charges (neutralized by a corresponding counter cation). Examples of anionic surfactants are fatty acids, alkyl sulfates, alkyl ether sulfates and ether carboxylic acids with 12 to 20 carbon atoms in the alkyl group and up to 16 glycol ether groups in the molecule.

The anionic surfactants are used in a total amount of 0.1 to 45% by weight, preferably 1 to 30% by weight and very particularly preferably 1 to 15% by weight, based on the total weight of the particular agent.

The agents can also contain other active ingredients, auxiliaries and additives, such as solvents, fat components such as the Cs-C30 fatty alcohols, the C8-C30 fatty acid triglycerides, the Cs-Cso fatty acid monoglycerides, the Cs-Cso fatty acid diglycerides and / or the hydrocarbons; Polymers; Structurants 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; active ingredients that improve fiber structure, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose; Dyes for coloring the agent; Anti-dandruff agents such as piroctone olamine, zinc omadine and climbazole; Amino acids and oligopeptides; Animal and / or vegetable-based protein hydrolyzates, as well as in the form of their fatty acid condensation products or, optionally, anionically or cationically modified derivatives; vegetable oils; Light stabilizers and UV blockers; Active ingredients such as panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidinone carboxylic acids and their salts and bisabolol; Polyphenols, especially hydroxycinnamic acids, 6,7-dihydroxycoumarins, hydroxybenzoic acids, catechins, tannins, leukoanthocyanidins, 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 penetration substances such as glycerol, 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 blowing agents such as propane-butane mixtures, N2O, dimethyl ether, CO2 and air.

Those skilled in the art will select these further substances in accordance with the desired properties of the agents. With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art. The additional active substances and auxiliaries are preferably used in the preparations according to the invention in amounts of in each case from 0.0001 to 25% by weight, in particular from 0.0005 to 15% by weight, based on the total weight of the particular agent.

Process for coloring keratin materials

In the context of the method according to the invention, agents (a) and (b) are applied to the keratinous materials, in particular to human hair. The agent (b) is an aftertreatment agent and is consequently applied after the coloring agent (a).

A method for dyeing keratinous material, in particular human hair, comprising the following steps in the order given is therefore very particularly preferred:

in a first step, application of a coloring agent (a) to the keratinous material, the agent (a) containing:

(a1) at least one amino-functionalized silicone polymer, and

(a2) at least one coloring compound, and

(a3) at least one nonionic surfactant, and

in a second step application of an aftertreatment agent (b) on the keratinous material, the agent (b) containing:

(b1) at least one acid.

The agents (a) and (b) are particularly preferably used within one and the same dyeing process, which means that there is a maximum period of a few hours between the agents (a) and (b).

In the context of a further preferred embodiment, a method according to the invention is characterized in that agent (a) is applied first and agent (b) is then used, the period between the application of agents (a) and (b) at maximum 24 hours, preferably a maximum of 12 hours and particularly preferably a maximum of 6 hours. In the process according to the invention, the keratin materials, in particular human hair, are first treated with colorant (a). Subsequently, the aftertreatment agent (b) is added to the keratin materials, which lowers the pH on the surface of the keratin material and fixes or immobilizes the active ingredients contained in the agent (a) on the keratin in this way. Agent (b) itself preferably contains no dyes or no coloring compounds.

The application properties of the resulting dyeing can be further improved by choosing the optimal process conditions.

Within the scope of a further embodiment, a method comprising the following steps in the specified order is very particularly preferred

(1) application of the colorant (a) to the keratinous material,

(2) allowing agent (a) to act for a period of from 10 seconds to 10 minutes, preferably from 10 seconds to 5 minutes,

(3) optionally rinsing the keratinous material with water,

(4) application of the aftertreatment agent (b) to the keratinous material,

(5) allowing agent (b) to act for a period of from 30 seconds to 30 minutes, preferably from 30 seconds to 10 minutes, and

(6) Rinse the keratinous material with water.

According to the invention, rinsing out the keratinous material with water in steps (3) and (6) of the method means that only water is used for the rinsing-out process, without further agents other than the means (a) and (b) would be used.

In a step (1), the agent (a) is first applied to the keratin materials, in particular the human hair.

After application, agent (a) is allowed to act on the keratin materials. The process according to the invention permits the production of colorations with particularly good intensity and fastness to washing even with a short exposure time of the agent (a). In this connection, exposure times of 10 seconds to 10 minutes, preferably from 20 seconds to 5 minutes and very particularly preferably from 30 seconds to 2 minutes on the hair have proven to be particularly advantageous.

In the context of a preferred embodiment of the method according to the invention, the agent (a) can now be rinsed out of the keratin materials before the agent (b) is applied to the hair in the subsequent step. Particularly intense and shiny colorations were obtained when agent (b) was applied to the keratin materials which were still exposed to agent (a).

In step (4), agent (b) is now applied to the keratin materials. After application, agent (b) is now allowed to act on the hair.

The process according to the invention permits the production of colorations with particularly good intensity and high gloss even when the agent (b) has a short exposure time. Exposure times from 10 seconds to 10 minutes, preferably from 20 seconds to 5 minutes and very particularly preferably from 30 seconds to 3 minutes on the hair have proven to be particularly advantageous.

In step (6) the agent (b) (and any agent (a) still present) is then rinsed out of the keratin material with water.

(1) applying agent (a) to the keratinous material,

(3) no rinsing

(4) applying agent (b) to the keratinous material,

(6) Rinse the keratinous material with water.

In the context of this embodiment, the sequence of steps (1) to (6) is preferably carried out within 24 hours.

Multi-component packaging unit (kit-of-parts)

To increase user comfort, the user is preferably provided with all the means required in the form of a multi-component packaging unit (kit-of-parts).

A second object of the present invention is therefore a multi-component packaging unit (kit-of-parts) for dyeing keratinous material, which is made up separately from one another

a first container with a coloring agent (a), the agent (a) containing:

(a1) at least one amino-functionalized silicone polymer, and

(a2) at least one coloring compound, and

(a3) at least one nonionic surfactant a second container with an agent (b), the agent (b) containing:

(b1) at least one acid,

wherein the ingredients (a1), (a2), (a3) and (b1) were already disclosed in detail in the description of the first subject matter of the invention.

The amino-functionalized silicone polymers (a1) contained in agent (a) of the kit correspond to the amino-functionalized silicone polymers (a1) which were also used in agent (a) of the previously described method.

The coloring compounds (a2) contained in the agent (a) of the kit correspond to the coloring compounds (a2) which were also used in agent (a) of the method described above.

The nonionic surfactants (a3) optionally contained in the agent (a) of the kit correspond to the nonionic surfactants (a3) which were also used in agent (a) of the process described above.

The acids (b1) contained in the agent (b) of the kit correspond to the acids (b1) which were also used in agent (b) in the process described above.

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

Examples

1. Formulations

The following formulations were prepared (unless otherwise stated, all data are in% by weight)

Colorant (a)

Aftertreatment agent (b)

2. Application

Agent (a) was applied to a strand of hair (Kerling, Euro natural hair white, liquor ratio: 4 g of composition (a) per g of strand of hair) and then left to act for one minute. The lock of hair was then immersed in the aftertreatment agent (b) and left in it for 1 minute. Each strand of hair was then washed thoroughly with water (1 minute), dried and assessed visually under the daylight lamp. To determine the wash fastness, the previously colored strands of hair were placed in an ultrasonic bath which was filled with a 1% solution of a commercially available shampoo (foam, 7 herbs). Then the strands of hair were treated with ultrasound using a standardized procedure, which corresponds to 6 washes. After this period, the strands were removed from the ultrasound bath, dried and visually assessed again under the daylight lamp.

To determine the wash fastness, the previously colored strands of hair were placed in an ultrasonic bath which was filled with a 1% solution of a commercially available shampoo (Schauma, 7 herbs). Then the strands of hair were treated with ultrasound using a standardized procedure, which corresponds to 3 washes. After this period, the strands were removed from the ultrasound bath, dried and visually assessed again under the daylight lamp.

Color intensity: - = undyed + = low ++ = medium +++ = very good

Claims

1. A method for dyeing keratinous material, especially human hair, comprising the following steps:

(a1) at least one amino-functionalized silicone polymer, and

(a2) at least one coloring compound, and

(a3) at least one nonionic surfactant

(b1) at least one acid.

2. The method according to claim 1, characterized in that the agent (a) contains at least one amino-functionalized silicone polymer (a1) with at least one secondary amino group.

3. The method according to any one of claims 1 to 2, characterized in that the agent (a) contains at least one amino-functionalized silicone polymer (a1) 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.

4. The method according to any one of claims 1 to 3, characterized in that the agent (a) contains at least one amino-functionalized silicone polymer (a1) which comprises structural units of the formula (Si-I) and the formula (Si-Il)

5. The method according to any one of claims 1 to 4, characterized in that the agent (a) - based on the total weight of the agent (a) - one or more amino-functionalized silicone polymers (a1) in a total amount of 0.1 to 8.0 % By weight, preferably 0.2 to 6.0% by weight, more preferably from 0.5 to 5.0% by weight and very particularly preferably from 1.0 to 3.5% by weight.

6. The method according to any one of claims 1 to 5, characterized in that the agent

(a) contains at least one coloring compound (a2) from the group of pigments, direct dyes, photochromic dyes and thermochromic dyes.

7. The method according to any one of claims 1 to 6, characterized in that the agent (a) contains at least one coloring compound (a2) from the group of inorganic pigments, 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 from colored pigments based on mica or mica, which are coated with at least one metal oxide and / or a metal oxychloride.

8. The method according to any one of claims 1 to 7, characterized in that the agent (a) contains at least one coloring compound (a2) from the group of pigments, which is selected from pigments based on mica or mica, with one or more Metal oxides from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and / or brown iron oxide (CI 77491, CI 77499), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicate, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288) and / or iron blue (Ferric Ferrocyanide, CI 77510) are coated.

9. The method according to any one of claims 1 to 8, characterized in that the agent (a) - based on the total weight of the agent (a) - one or more inorganic pigments in a total amount of 0.001 to 20 wt .-%, further preferred contains from 0.1 to 8% by weight, even more preferably from 0.3 to 6% by weight and very particularly preferably from 0.5 to 4.5% by weight.

10. A method according to any one of claims 1 to 9, characterized in that the means (a) an ethoxylated C8-C contains at least ₂₄ fatty alcohol (a3) with a degree of ethoxylation from 80 to 120.

1 1. The method according to any one of claims 1 to 10, characterized in that the agent (a) contains at least one ethoxylated fatty alcohol (a3) of the formula (Tl),

12. The method according to any one of claims 1 to 1 1, characterized in that the agent (a) contains at least one ethoxylated fatty alcohol (a3) with a degree of ethoxylation of 10 to 40.

13. The method according to any one of claims 1 to 12, characterized in that the agent (a) contains at least one ethoxylated fatty alcohol (a3) of the formula (T-II), wherein R2 stands for a saturated or unsaturated, unbranched or branched C8-C24 alkyl group, preferably for a saturated, unbranched C16 or C18 alkyl group, and m represents an integer from 10 to 40, preferably an integer from 12 to 30.

14. The method according to any one of claims 1 to 13, characterized in that the weight fraction of all nonionic components in the average (a) - based on the total weight of the agent (a) - at least 80 wt .-%, preferably at least 85 wt. %, more preferably at least 90% by weight and very particularly preferably at least 98% by weight.

15. The method according to any one of claims 1 to 14, characterized in that the agent (a) contains water and a pH of 7.0 to 1 1, 5 preferably from 8.0 to 1 1, 0, and particularly preferably from 8.5 to 10.5.

16. The method according to any one of claims 1 to 15, characterized in that the agent (b) contains at least one acid (b1) which is selected from the group consisting of citric acid, tartaric acid, malic acid, lactic acid, acetic acid, methanesulfonic acid, benzoic acid, malonic acid , Oxalic acid, 1-hydroxyethane-1, 1-diphosphonic acid, sulfuric acid, hydrochloric acid and phosphoric acid.

17. The method according to any one of claims 1 to 16, characterized in that the agent (b) contains water and a pH of 1.5 to 5.5, preferably from 2.0 to 4.8, and particularly preferably from 2 , 5 to 4.5.

18. The method according to any one of claims 1 to 17, characterized in that the agent (a) is applied first, then the agent (b) is applied, the period between the application of the agents (a) and (b) at maximum 24 hours, preferably a maximum of 12 hours and particularly preferably a maximum of 6 hours.

19. The method according to any one of claims 1 to 18, comprising the following steps in the order given

(1) application of the colorant (a) to the keratinous material,

(3) optionally rinsing the keratinous material with water,

(4) application of the aftertreatment agent (b) to the keratinous material,

(6) Rinse the keratinous material with water.

20. Multi-component packaging unit (kit-of-parts) for coloring keratinous material, comprising separately assembled

a first container with a coloring agent (a), the agent (a) containing:

(a1) at least one amino-functionalized silicone polymer, and

(a2) at least one coloring compound, and

(a3) at least one nonionic surfactant

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

(b1) at least one acid,

in which

- The ingredients (a1), (a2), (a3) and (b1) were defined in one of claims 1 to 17.