DE102020211753A1 - Agent for decolorizing keratinous material colored with an organosilicon compound and a pigment - Google Patents

Abstract

The present invention relates to agents for decolorizing colored keratin material, containing (a) at least one fluorine compound, (b) at least one cationic surfactant, (c) at least one acid and (d) water.

Description

The present application is in the field of cosmetics and relates to an agent for decolorizing keratin material which has been colored preferably by using at least one organosilicon compound and at least one pigment. The decolorizing agent is characterized by its content of at least one fluorine compound (a), at least one cationic surfactant (b), at least one acid (c) and water (d).

A second subject matter of the present application is a method for decolorizing colored keratin material, in which a decolorizing agent of the first subject matter of the invention is applied to the colored keratin material and rinsed off again after an exposure time.

A third subject matter of the present application is a multi-component packaging unit which contains a coloring agent and the previously described decolorizing agent in separately made-up containers.

Changing the shape and color of keratin fibers, in particular hair, represents an important area of modern cosmetics. The person skilled in the art knows various coloring systems for changing the hair color, depending on the coloring requirements. Oxidation colorants are usually used for permanent, intensive colorations with good fastness properties and good gray coverage. Such colorants usually 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 coloring agents are characterized by very long-lasting coloring results.

When using substantive dyes, dyes that have already formed diffuse from the dye into the hair fiber. In comparison to oxidative hair coloring, the colorings obtained with substantive dyes are less durable and can be washed out more quickly. Dyes with direct dyes usually remain on the hair for a period of between 5 and 20 hair 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 present in undissolved form in the form of small particles in the coloring formulation and are only deposited from the outside on the hair fibers and/or the surface of the skin. Therefore, they can usually be removed without leaving any residue with a few washes with detergents containing surfactants. Various products of this type are available on the market under the name of hair mascara.

Recently, attention has been paid to a new coloring system in which dyeings are colored by using a combination of a pigment, an organic silicon compound and a polymer. This new staining system is used, for example, in EP 2168633 B1 described.

If these organic silicon compounds are applied to keratin material, a film or a coating is formed on the keratin material, which completely envelops the keratin material and in this way greatly influences the properties of the keratin material. If the application takes place in the presence of a coloring compound, for example a pigment, the pigments are embedded in this film or in the coating. The film colored by the pigment remains on the keratin material or keratin fibers. The colorations obtained in this way are said to be particularly resistant to shampooing.

In this dyeing process, too, it can happen that the dyeing has to be completely or partially reversed for various reasons. Partial removal of the dye may be necessary, for example, if the dyeing result on the fibers turns out to be darker than desired. On the other hand, complete removal of the coloration may be desirable in some cases. For example, it is conceivable that the hair should be dyed or tinted in a specific shade for a specific occasion and the original color should be regained after a few days.

The object of the present invention was therefore to provide a decolorizing agent for decolorizing colored keratinic fibers which have previously been colored by using at least one organosilicon compound, in particular a C ₁ -C ₆ -alkoxysilane, and at least one pigment became. Here, the decolorization should be as complete as possible so that the coloration of the keratin material can ideally be restored to its original state. Furthermore, the bleaching should be long-lasting and even, and the bleached keratin fibers should not suffer from shifts in nuances or unevenness in the color result. In addition, the keratin material should be damaged as little as possible by the decolorizing agent, and the conditions when using the decolorizing agent should be as mild as possible.

Surprisingly, it has now been found that this object can be fully achieved if keratinic material, which has previously been colored with at least one organosilicon compound and at least one pigment, is treated with a decolorizing agent which contains at least one fluorine compound, at least one cationic surfactant , contains at least one acid and water.

1. (a) mindestens eine Fluorverbindung,
2. (b) mindetens ein kationisches Tensid,
3. (c) mindestens eine Säure und
4. (d) Wasser.

A first object of the present invention is a composition for decolorizing colored keratin material containing

1. (a) at least one fluorine compound,
2. (b) at least one cationic surfactant,
3. (c) at least one acid and
4. (d) water.

In the experiments leading to this invention, keratin fibers (hair strands) were used, for example, which had previously been colored with an agent containing various organosilicon compounds (such as organic C ₁ -C ₆ -alkoxysilanes) and various pigments (such as organic and inorganic pigments). contained. After being dyed, these fibers were decolorized again by using a decolorizing agent according to the invention. In this connection, it has surprisingly been found that an aqueous or water-based deinking agent containing the combination of fluorine compound (a), cationic surfactant (b) and acid (c) is capable of removing the colored film formed from the organosilicon compound and pigment almost completely removed from the keratin fiber. In this way, it was possible to restore the original color of the hair and restore the keratin fibers to their original colour. The hair was not damaged by the bleaching process.

Discoloration of keratin material

Keratinic material means hair, skin, nails (such as fingernails and/or toenails). Wool, fur and feathers also fall under the definition of keratin material.

Keratinic material is preferably understood to mean human hair, human skin and human nails, in particular fingernails and toenails. Very particularly preferably, keratin material is understood as meaning human hair.

In the context of this invention, the term “decolorizing agent” means that a coloration on the keratin material that was produced by using at least one organosilicon compound and at least one pigment can be removed again. During coloring, the keratin material or keratin fiber is enveloped by a colored film formed from the organosilicon compounds and the pigments. According to the invention, the decolorizing agent is applied after the coloring agent has been applied, and the decolorizing agent is able to remove this colored film from the keratin material again.

Particularly good decolorizing results were obtained when the decolorizing agent is used on keratinic material which has been colored by using at least one organic C ₁ -C ₆ -alkoxysilane and/or a condensation product thereof and by using at least one pigment.

Coloring using organosilicon compounds

The bleaching agent according to the invention is applied to previously colored keratin material. At least one organosilicon compound is particularly preferably used on the keratin material in the previous coloring.

Organic silicon compounds, alternatively referred to as organosilicon compounds, are compounds that either have a direct silicon-carbon bond (Si-C) or in which the carbon is bonded to the silicon via an oxygen, nitrogen, or sulfur atom. atom is linked. The organic silicon compounds according to the invention are preferably compounds containing one to three silicon atoms. The organic silicon compounds particularly preferably contain one or two silicon atoms.

The decolorizing agent works particularly well on colored keratin material if an organic C ₁ -C ₆ -alkoxy silane was used in the previous coloring.

The organic C ₁ -C ₆ -alkoxysilane or organic, non-polymeric silicon compounds are preferably selected from the group of silanes having one, two or three silicon atoms.

According to the IUPAC rules, the term silane stands for a group of chemical compounds based on a silicon backbone and hydrogen. In the case of organic silanes, some or all of the hydrogen atoms are replaced by organic groups such as (substituted) alkyl groups and/or alkoxy groups.

It is characteristic of the C ₁ -C ₆ -alkoxysilanes according to the invention that at least one C ₁ -C ₆ -alkoxy group is directly bonded to a silicon atom. The C ₁ -C ₆ -alkoxysilanes according to the invention thus comprise at least one structural unit R'R''R'''Si-O-(C ₁ -C ₆ -alkyl) where the radicals R', R'' and R''' stand for the three remaining bond valences of the silicon atom.

The C ₁ -C ₆ -alkoxy group or groups bonded to the silicon atom are very reactive and are hydrolyzed at high speed in the presence of water, the reaction speed also depending, inter alia, on the number of hydrolyzable groups per molecule. If the hydrolyzable C ₁ -C ₆ -alkoxy group is an ethoxy group, the organic silicon compound preferably contains a structural unit R'R''R'''Si-O-CH2-CH3. The radicals R', R'' and R''' again represent the three remaining free valences of the silicon atom.

Even the addition of small amounts of water initially leads to hydrolysis and then to a condensation reaction of the organic alkoxysilanes with one another. For this reason, both the organic alkoxysilanes and their condensation products can be used for coloring purposes.

A condensation product is understood as meaning a product which is formed by reaction of at least two organic C.sub.1 _{-C.sub.6 -alkoxysilanes} with elimination of water and/or elimination of a C.sub.1 _{-C.sub.6 -alkanol} . The condensation products can be, for example, dimers, but also trimers or oligomers, the condensation products being in equilibrium with the monomers. Depending on the amount of water used or consumed in the hydrolysis, the equilibrium shifts from monomeric C ₁ -C ₆ -alkoxysilane to the condensation product.

In a particularly preferred embodiment, the agent according to the invention is therefore characterized in that it is an agent for decolorizing keratin material which is obtained by using at least one organic C ₁ -C ₆ -alkoxysilane and/or a condensation product thereof and by using at least colored with a pigment.

The organic C ₁ -C ₆ alkoxysilanes can be, for example, compounds chosen from silanes containing one, two or three silicon atoms, the organic silicon compound also comprising one or more basic chemical functions.

This basic group can be, for example, an amino group, an alkylamino group or a dialkylamino group, which is preferably linked via a linker with a silicon atom connected is. The basic group is preferably an amino group, a C ₁ -C ₆ -alkylamino group or a di(C ₁ -C ₆ )alkylamino group.

A very particularly preferred decolorizing agent according to the invention is characterized in that it is applied to keratin material which has been colored by using at least one organic C ₁ -C ₆ -alkoxysilane and/or a condensation product thereof and by using at least one pigment, the C ₁ -C ₆ alkoxy silane further comprises one or more basic chemical functions.

Very particularly good results were obtained when the decolorizing agent was used on keratin material which had previously been colored with C ₁ -C ₆ -alkoxysilanes of the formula (SI) and/or (S-II). Since hydrolysis/condensation begins even with traces of moisture, the coloring of the keratin material with C ₁ -C ₆ -alkoxysilanes of the formula (SI) and/or (S-II) also includes the use of their condensation products.

• - R₁, R₂ unabhängig voneinander für ein Wasserstoffatom oder eine C₁-C₆-Alkylgruppe stehen,
• - L für eine lineare oder verzweigte, zweiwertige C₁-C₂₀-Alkylengruppe steht,
• - R₃, R₄ unabhängig voneinander für eine C₁-C₆-Alkylgruppe stehen,
• - a, für eine ganze Zahl von 1 bis 3 steht, und
• - b für die ganze Zahl 3 - a steht, und

(R₅O)_c(R₆)_dSi-(A)_e-[NR₇-(A')]_f-[O-(A'')]_g-[NR₈-(A''')]_h-Si(R₆')_d'(OR₅')_c' (S-II), wobei

• - R5, R5', R5'', R6, R6' und R6'' unabhängig voneinander für eine C₁-C₆-Alkylgruppe stehen,
• - A, A', A'', A''' und A'''' unabhängig voneinander für eine lineare oder verzweigte, zweiwertige C₁-C₂₀-Alkylengruppe stehen,
• - R₇ und R₈ unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine Hydroxy-C₁-C₆-alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine Amino-C₁-C₆-alkylgruppe oder eine Gruppierung der Formel (S-III) stehen,

- (A'''')-Si(R6'')d''(OR5'')c'' (S-III),

• - c, für eine ganze Zahl von 1 bis 3 steht,
• - d für die ganze Zahl 3 - c steht,
• - c' für eine ganze Zahl von 1 bis 3 steht,
• - d' für die ganze Zahl 3 - c' steht,
• - c'' für eine ganze Zahl von 1 bis 3 steht,
• - d'' für die ganze Zahl 3 - c'' steht,
• - e für 0 oder 1 steht,
• - f für 0 oder 1 steht,
• - g für 0 oder 1 steht,
• - h für 0 oder 1 steht,
• - mit der Maßgabe, dass mindestens einer der Reste aus e, f, g und h von 0 verschieden ist.

In another very particularly preferred embodiment, an agent according to the invention is therefore characterized in that it is an agent for decolorizing keratin material, which is obtained by using at least one organic C ₁ -C ₆ -alkoxysilane of the formula (SI) and/or (S-II) and a pigment, R ₁ R ₂ NL-Si(OR ₃ ) _a (R ₄ ) _b (SI) whereby

• - R ₁ , R ₂ independently represent a hydrogen atom or a C ₁ -C ₆ -alkyl group,
• - L represents a linear or branched, divalent C ₁ -C ₂₀ -alkylene group,
• - R ₃ , R ₄ independently represent a C ₁ -C ₆ alkyl group,
• - a, is an integer from 1 to 3, and
• - b is the integer 3 - a, and

(R ₅ O) _c (R ₆ ) _d Si-(A) _e -[NR ₇ -(A')] _f -[O-(A'')] _g -[NR ₈ -(A''') ] _h -Si(R ₆ ') _d' (OR ₅ ') _c' (S-II), whereby

• - R5, R5', R5'', R6, R6' and R6'' independently represent a C ₁ -C ₆ alkyl group,
• - A, A', A'', A''' and A'''' independently represent a linear or branched, divalent C ₁ -C ₂₀ -alkylene group,
• - R ₇ and R ₈ independently represent a hydrogen atom, a C ₁ -C ₆ alkyl group, a hydroxy C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, an amino C ₁ -C ₆ - alkyl group or a group of the formula (S-III),

- (A'''')-Si(R6'')d''(OR5'')c'' (S-III),

• - c, represents an integer from 1 to 3,
• - d stands for the integer 3 - c,
• - c' is an integer from 1 to 3,
• - d' stands for the integer 3 - c',
• - c'' is an integer from 1 to 3,
• - d'' stands for the integer 3 - c'',
• - e stands for 0 or 1,
• - f stands for 0 or 1,
• - g stands for 0 or 1,
• - h stands for 0 or 1,
• - with the proviso that at least one of the radicals from e, f, g and h is different from 0.

The substituents R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₅ ', R ₅ '', R ₆ , R ₆ ', R ₆ '', R ₇ , R ₈ , L, A, A' , A'', A''' and A'''' in the compounds of formula (SI) and (S-II) are exemplified below: Examples of a C ₁ -C ₆ -alkyl group are the groups methyl, ethyl , propyl, isopropyl, n-butyl, s-butyl and t-butyl, n-pentyl and n-hexyl. Propyl, ethyl and methyl are preferred alkyl radicals. Examples of a C ₂ -C ₆ -alkenyl group are vinyl, allyl, but-2-enyl, but-3-enyl and isobutenyl, preferred C ₂ -C ₆ -alkenyl radicals are vinyl and allyl. Preferred examples of a hydroxy-C ₁ -C ₆ -alkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 2-hydroxypropyl, a 3-hydroxypropyl, a 4-hydroxybutyl group, a 5-hydroxypentyl and a 6-hydroxyhexyl group ; a 2-hydroxyethyl group is particularly preferred. Examples of an amino-C ₁ -C ₆ -alkyl group are the aminomethyl group, the 2-aminoethyl group, the 3-aminopropyl group. The 2-aminoethyl group is particularly preferred. Examples of a linear divalent C ₁ -C ₂₀ -alkylene group are, for example, the methylene group (-CH ₂ -), the ethylene group (-CH ₂ -CH ₂ -), the propylene group (-CH ₂ -CH ₂ -CH ₂ - ) and the butylene group (-CH ₂ -CH ₂ -CH ₂ -CH ₂ -). The propylene group (-CH ₂ -CH ₂ -CH ₂ -) is particularly preferred. From a chain length of 3 carbon atoms, divalent alkylene groups can also be branched. Examples of branched divalent C ₃ -C ₂₀ alkylene groups are (-CH ₂ -CH(CH ₃ )-) and (-CH ₂ -CH(CH ₃ )-CH ₂ -).

In the organic silicon compounds of formula (SI) R ₁ R ₂ NL-Si(OR ₃ ) _a (R ₄ ) _b (SI), the radicals R ₁ and R ₂ independently represent a hydrogen atom or a C ₁ -C ₆ -alkyl group. The radicals R ₁ and R ₂ are very particularly preferably both hydrogen atoms.

In the middle part of the organic silicon compound is the structural unit or the linker -L- which stands for a linear or branched, divalent C ₁ -C ₂₀ -alkylene group. The divalent C ₁ -C ₂₀ alkylene group may alternatively also be referred to as a divalent or divalent C ₁ -C ₂₀ alkylene group, by which is meant that each -L- moiety can form two bonds.

-L- preferably represents a linear, divalent C ₁ -C ₂₀ -alkylene group. More preferably -L- is a linear divalent C ₁ -C ₆ alkylene group. -L- is particularly preferably a methylene group (-CH ₂ -), an ethylene group (-CH ₂ -CH ₂ -), a propylene group (-CH ₂ -CH ₂ -CH ₂ -) or a butylene group (-CH ₂ - _CH2 - _CH2 - _CH2- ). L is very particularly preferably a propylene group (-CH ₂ -CH ₂ -CH ₂ -).

The organic silicon compounds of the formula (SI) according to the invention R ₁ R ₂ NL-Si(OR ₃ ) _a (R ₄ ) _b (SI), each carry the silicon-containing grouping —Si(OR ₃ ) _a (R ₄ ) _b at one end.

In the terminal structural unit —Si(OR ₃ ) _a (R ₄ ) _b , the radicals R 3 and R 4 independently represent a C ₁ -C ₆ -alkyl group. R ₃ and R ₄ particularly preferably independently represent a methyl group or an ethyl group .

Here, a represents an integer of 1 to 3, and b represents an integer of 3 - a. If a is the number 3, then b is equal to 0. If a is the number 2, then b is equal to 1. If a is the number 1, then b is equal to 2.

The application of the decolorizing agent according to the invention was particularly successful when the keratin material was previously colored with an organic C ₁ -C ₆ -alkoxysilane of the formula (SI) in which the radicals R ₃ , R ₄ independently represent a methyl group or stand for an ethyl group.

Furthermore, the use of the decolorizing agent according to the invention was particularly successful when the keratin material was previously colored with an organic C ₁ -C ₆ -alkoxysilane of the formula (SI) in which the radical a stands for the number 3. In this case, the remainder b stands for the number 0.

• - R₁, R₂ beide für ein Wasserstoffatom stehen, und
• - L für eine lineare, zweiwertige C₁-C₆-Alkylengruppe, bevorzugt für eine Propylengruppe (-CH₂-CH₂-CH₂-) oder für eine Ethylengruppe (-CH₂-CH₂-), steht,
• - R₃ für eine Ethylgruppe oder eine Methylgruppe steht,
• - R₄ für eine Methylgruppe oder für eine Ethylgruppe steht,
• - a für die Zahl 3 steht und
• - b für die Zahl 0 steht.

Within the scope of a particularly preferred embodiment, the agent according to the invention is therefore characterized in that it is an agent for decolorizing keratin material, which is formation of at least one organic C ₁ -C ₆ -alkoxysilane of the formula (I) and/or a condensation product thereof and colored by the use of at least one pigment, R ₁ R ₂ NL-Si(OR ₃ ) _a (R ₄ ) _b (SI), whereby

• - R ₁ , R ₂ both represent a hydrogen atom, and
• - L is a linear, divalent C ₁ -C ₆ -alkylene group, preferably a propylene group (-CH ₂ -CH ₂ -CH ₂ -) or an ethylene group (-CH ₂ -CH ₂ -),
• - R ₃ represents an ethyl group or a methyl group,
• - R ₄ represents a methyl group or an ethyl group,
• - a stands for the number 3 and
• - b stands for the number 0.

• - (3-Aminopropyl)triethoxysilan
  
• - (3-Aminopropyl)trimethoxysilan
  
• - (2-Aminoethyl)triethoxysilan
  
• - (2-Aminoethyl)trimethoxysilan
  
• - (3-Dimethylaminopropyl)triethoxysilan
  
• - (3-Dimethylaminopropyl)trimethoxysilan
  
• - (2-Dimethylaminoethyl)triethoxysilan.
  
• - (2-Dimethylaminoethyl)trimethoxysilan und/oder
  

Silicon compounds of the formula (I) which can be removed particularly well by the subsequent use of the decolorizing agent according to the invention are

• - (3-aminopropyl)triethoxysilane
  
• - (3-aminopropyl)trimethoxysilane
  
• - (2-aminoethyl)triethoxysilane
  
• - (2-aminoethyl)trimethoxysilane
  
• - (3-dimethylaminopropyl)triethoxysilane
  
• -(3-dimethylaminopropyl)trimethoxysilane
  
• - (2-dimethylaminoethyl)triethoxysilane.
  
• - (2-dimethylaminoethyl)trimethoxysilane and/or
  

• - (3-Aminopropyl)triethoxysilan
• - (3-Aminopropyl)trimethoxysilan
• - (2-Aminoethyl)triethoxysilan
• - (2-Aminoethyl)trimethoxysilan
• - (3-Dimethylaminopropyl)triethoxysilan
• - (3-Dimethylaminopropyl)trimethoxysilan
• - (2-Dimethylaminoethyl)triethoxysilan und/oder
• - (2-Dimethylaminoethyl)trimethoxysilan.

In a further preferred embodiment, an agent according to the invention is characterized in that it is an agent for decolorizing keratin material which is obtained by using at least one organic C ₁ -C ₆ -alkoxysilane and/or a condensation product thereof and by using formation of at least one pigment was colored, wherein the organic C ₁ -C ₆ -alkoxysilane is selected from the group consisting of

• - (3-aminopropyl)triethoxysilane
• - (3-aminopropyl)trimethoxysilane
• - (2-aminoethyl)triethoxysilane
• - (2-aminoethyl)trimethoxysilane
• - (3-dimethylaminopropyl)triethoxysilane
• -(3-dimethylaminopropyl)trimethoxysilane
• - (2-dimethylaminoethyl)triethoxysilane and/or
• -(2-dimethylaminoethyl)trimethoxysilane.

The aforementioned organic silicon compounds of the formula (I) are commercially available. For example, (3-aminopropyl)trimethoxysilane is commercially available from Sigma-Aldrich. (3-Aminopropyl)triethoxysilane is also commercially available from Sigma-Aldrich.

In a further embodiment of the agent according to the invention, the keratin material can also be colored beforehand by using one or more organic C ₁ -C ₆ -alkoxysilanes of the formula (S-II), (R ₅ O) _c (R ₆ ) _d Si-(A) _e -[NR ₇ -(A')] _f -[O-(A'')] _g -[NR ₈ -(A''') ] _h -Si(R ₆ ') _d' (OR ₅ ') _c' (S-II).

The organosilicon compounds of the formula (S-II) according to the invention carry the silicon-containing groups (R ₅ O) _c (R ₆ ) _d Si- and -Si(R ₆ ') _d' (OR ₅ ') at both ends _c' .

In the central part of the molecule of formula (S-II) are the groups -(A) _e - and -[NR ₇ -(A')] _f - and -[O-(A'')] _g - and -[ _NR8- (A''')] _h- . Each of the radicals e, f, g and h can independently represent the number 0 or 1, with the proviso that at least one of the radicals e, f, g and h is different from 0. In other words, an organic silicon compound of the formula (II) according to the invention contains at least one group from the group consisting of -(A)- and -[NR ₇ -(A')]- and -[O-(A'')]- and -[NR ₈ -(A''')]-.

In the two terminal structural units (R ₅ O) _c (R ₆ ) _d Si- and - Si(R ₆ ') _d' (OR ₅ ') _c' , the radicals R5, R5', R5" independently stand for a C C ₁ -C ₆ alkyl group. The radicals R6, R6' and R6" independently represent a C ₁ -C ₆ alkyl group.

Here, c is an integer of 1 to 3, and d is an integer of 3 - c. If c is the number 3, then d is equal to 0. If c is the number 2, then d is equal to 1. If c is the number 1, then d is equal to 2.

Similarly, c' represents an integer from 1 to 3 and d' represents the integer 3 - c'. If c' is the number 3, then d' is 0. If c' is the number 2, then d' is 1. If c' is the number 1, then d' is 2.

Dyeings with the best fastness to washing could be obtained if the radicals c and c' both stand for the number 3. In this case, d and d' both represent the number 0.

• - R5 und R5' unabhängig voneinander für eine Methylgruppe oder eine Ethylgruppe stehen,
• - c und c' beide für die Zahl 3 stehen und
• - d und d' beide für die Zahl 0 stehen.

In a further preferred embodiment, an agent according to the invention is characterized in that it is an agent for decolorizing keratin material which is obtained by using at least one organic C ₁ -C ₆ -alkoxysilane of the formula (II) and/or a condensation product thereof and has been colored by using at least one pigment, (R ₅ O) _c (R ₆ ) _d Si-(A) _e -[NR ₇ -(A')] _f -[O-(A'')] _g -[NR ₈ -(A''') ] _h -Si(R ₆ ') _d' (OR ₅ ') _c' (S-II), whereby

• - R5 and R5' independently represent a methyl group or an ethyl group,
• - c and c' both stand for the number 3 and
• - d and d' both stand for the number 0.

When c and c' both represent the number 3 and d and d' both represent the number 0, the organic silicon compounds according to the invention correspond to the formula (S-IIa) (R ₅ O) ₃ Si-(A) _e -[NR ₇ -(A')] _f -[O-(A'')] _g -[NR ₈ -(A''')] _h -Si( OR ₅ ') ₃ (S-IIa).

The radicals e, f, g and h can independently represent the number 0 or 1, where at least one radical from e, f, g and h is different from zero. The abbreviations e, f, g and h therefore define which of the groups -(A) _e - and -[NR ₇ -(A')] _f - and -[O-(A'')] _g - and -[NR ₈ -(A''')] _h -are located in the central part of the organosilicon compound of formula (II).

In this context, the presence of certain groups has proven to be particularly advantageous. Particularly good results can be obtained when at least two of the radicals e, f, g and h are the number 1. Very particularly preferably, e and f both represent the number 1. Furthermore, very particularly preferably, g and h both represent the number 0.

When e and f both represent the number 1 and g and h both represent the number 0, the organic silicon compounds according to the invention correspond to the formula (S-IIb) (R ₅ O) _c (R ₆ ) _d Si-(A)-[NR ₇ -(A')]-Si(R ₆ ') _d' (OR ₅ ') _c' (S-IIb).

The radicals A, A', A'', A''' and A'''' independently represent a linear or branched, divalent C ₁ -C ₂₀ -alkylene group. The radicals A, A′, A″, A″″ and A″″ independently of one another preferably represent a linear, divalent C ₁ -C ₂₀ -alkylene group. More preferably, the radicals A, A′, A″, A″″ and A″″ independently represent a linear divalent C ₁ -C ₆ -alkylene group.

The divalent C ₁ -C ₂₀ alkylene group may alternatively also be referred to as a divalent or divalent C ₁ -C ₂₀ alkylene group, by which is meant that each moiety A, A', A'', A''' and A'''' can form two bonds.

The radicals A, A′, A″, A″″ and A″″ are particularly preferably, independently of one another, a methylene group (-CH ₂ -), an ethylene group (-CH ₂ -CH ₂ -), a propylene group (-CH ₂ -CH ₂ -CH ₂ -) or a butylene group (-CH ₂ -CH ₂ -CH ₂ -CH ₂ -). The radicals A, A′, A″, A″″ and A″″ are very particularly preferably a propylene group (-CH ₂ -CH ₂ -CH ₂ -).

When the radical f is the number 1, the organic silicon compound of the formula (II) according to the invention contains a structural grouping -[NR ₇ -(A')]-.
If the radical h is the number 1, then the organic silicon compound of the formula (II) according to the invention contains a structural grouping -[NR ₈ -(A''')]-.

Here, the radicals R ₇ and R ₈ independently stand for a hydrogen atom, a C ₁ -C ₆ -alkyl group, a hydroxy-C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, an amino-C ₁ - C ₆ alkyl group or a moiety of formula (S-III) - (A'''')-Si(R ₆ '') _d ''(OR ₅ '') _c '' (S-III).

The radicals R7 and R8 are very particularly preferably, independently of one another, a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a group of the formula (S-III).

When the radical f is the number 1 and the radical h is the number 0, the organic silicon compound according to the invention contains the moiety [NR ₇ -(A')] but not the moiety -[NR ₈ -(A''' )]. If the radical R7 now stands for a group of the formula (III), then the organic silicon compound comprises 3 reactive silane groups.

• - e und f beide für die Zahl 1 stehen,
• - g und h beide für die Zahl 0 stehen,
• - A und A' unabhängig voneinander für eine lineare, zweiwertige C₁-C₆-Alkylengruppe stehen und
• - R7 für ein Wasserstoffatom, eine Methylgruppe, eine 2-Hydroxyethylgruppe, eine 2-Alkenylgruppe, eine 2-Aminoethylgruppe oder für eine Gruppierung der Formel (S-III) steht.

In a further preferred embodiment, an agent according to the invention is characterized in that it is an agent for decolorizing keratin material which is obtained by using at least one organic C ₁ -C ₆ -alkoxysilane of the formula (S-II) and/or a condensation product colored by it and by the use of at least one pigment, (R ₅ O) _c (R ₆ ) _d Si-(A) _e -[NR ₇ -(A')] _f -[O-(A'')] _g -[NR ₈ -(A''') ] _h -Si(R ₆ ') _d' (OR ₅ ') _c' (S-II) whereby

• - e and f both stand for the number 1,
• - g and h both stand for the number 0,
• - A and A' independently represent a linear divalent C ₁ -C ₆ alkylene group and
• - R7 represents a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a group of formula (S-III).

• - e und f beide für die Zahl 1 stehen,
• - g und h beide für die Zahl 0 stehen,
• - A und A' unabhängig voneinander für eine Methylengruppe (-CH₂-), eine Ethylengruppe (-CH₂-CH₂-) oder eine Propylengruppe (-CH₂-CH₂-CH₂) stehen, und
• - R7 für ein Wasserstoffatom, eine Methylgruppe, eine 2-Hydroxyethylgruppe, eine 2-Alkenylgruppe, eine 2-Aminoethylgruppe oder für eine Gruppierung der Formel (S-III) steht.

In a further preferred embodiment, an agent according to the invention is characterized in that it is an agent for decolorizing keratin material which is obtained by using at least one organic C ₁ -C ₆ -alkoxysilane of the formula (S-II) and/or a condensation product thereof and was colored by applying at least one pigment, wherein

• - e and f both stand for the number 1,
• - g and h both stand for the number 0,
• - A and A' independently represent a methylene group (-CH ₂ -), an ethylene group (-CH ₂ -CH ₂ -) or a propylene group (-CH ₂ -CH ₂ -CH ₂ ), and
• - R7 represents a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a group of formula (S-III).

• - 3-(Trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamin
  
• - 3-(Triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamin
  
• -N-Methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamin
  
• -N-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamin
  
• - 2-[Bis[3-(trimethoxysilyl)propyl]amino]-ethanol
  
• - 2-[Bis[3-(triethoxysilyl)propyl]amino]-ethanol
  
• - 3-(Trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamin
  
• - 3-(Triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamin
  
• - N1,N1-Bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamin,
  
• - N1,N1-Bis[3-(triethoxysilyl)propyl]-1,2-ethanediamin,
  
• - N,N-Bis[3-(trimethoxysilyl)propyl]-2-propen-1-amin
  
• - N,N-Bis[3-(triethoxysilyl)propyl]-2-propen-1-amin
  

Silicon compounds of the formula (S-II) which can be removed particularly well by the subsequent use of the decolorizing agent according to the invention are

• - 3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine
  
• - 3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine
  
• -N-Methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine
  
• -N-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine
  
• - 2-[bis[3-(trimethoxysilyl)propyl]amino]ethanol
  
• - 2-[bis[3-(triethoxysilyl)propyl]amino]ethanol
  
• - 3-(trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamine
  
• - 3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine
  
• - N1,N1-bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine,
  
• - N1,N1-bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine,
  
• - N,N-bis[3-(trimethoxysilyl)propyl]-2-propen-1-amine
  
• - N,N-bis[3-(triethoxysilyl)propyl]-2-propen-1-amine
  

The above organic silicon compounds of the formula (S-II) are commercially available. For example, bis(trimethoxysilylpropyl)amine with CAS number 82985-35-1 can be purchased from Sigma-Aldrich.
For example, bis[3-(triethoxysilyl)propyl]amine with CAS number 13497-18-2 is commercially available from Sigma-Aldrich.
Alternatively, N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine is referred to as bis(3-trimethoxysilylpropyl)-N-methylamine and is commercially available from Sigma-Aldrich or Fluorochem .
For example, 3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine with CAS number 18784-74-2 can be purchased from Fluorochem or Sigma-Aldrich.

• - 3-(Trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamin
• - 3-(Triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamin
• - N-Methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamin
• - N-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamin
• - 2-[Bis[3-(trimethoxysilyl)propyl]amino]-ethanol
• - 2-[Bis[3-(triethoxysilyl)propyl]amino]-ethanol
• - 3-(Trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-Propanamin
• - 3-(Triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-Propanamin
• - N1 ,N1-Bis[3-(trimethoxysilyl)propyl]-1,2-Ethanediamin,
• - N1,N1-Bis[3-(triethoxysilyl)propyl]-1,2-Ethanediamin,
• - N,N-Bis[3-(trimethoxysilyl)propyl]-2-Propen-1-amin und/oder
• - N,N-Bis[3-(triethoxysilyl)propyl]-2-Propen-1-amin.

In a further preferred embodiment, an agent according to the invention is characterized in that it is an agent for decolorizing keratin material, which is obtained by using at least one organic C ₁ -C ₆ -alkoxysilane and/or a condensation product thereof and by using at least one pigment was colored, wherein the organic C ₁ -C ₆ alkoxysilane is selected from the group consisting of

• - 3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine
• - 3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine
• - N-Methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine
• - N-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine
• - 2-[bis[3-(trimethoxysilyl)propyl]amino]ethanol
• - 2-[bis[3-(triethoxysilyl)propyl]amino]ethanol
• - 3-(trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamine
• - 3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine
• - N1 ,N1-bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine,
• - N1,N1-bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine,
• - N,N-bis[3-(trimethoxysilyl)propyl]-2-propen-1-amine and/or
• - N,N-bis[3-(triethoxysilyl)propyl]-2-propen-1-amine.

In further coloring/decolorizing experiments, it has also turned out to be particularly advantageous if at least one organic C.sub.1 _{-C.sub.6 -alkoxysilane} of the formula (S-IV) is used to color the keratin material in the process according to the invention R ₉ Si(OR ₁₀ ) _k (R ₁₁ ) _m (S-IV).

The compounds of formula (S-IV) are organic silicon compounds selected from silanes having one, two or three silicon atoms, the organic silicon compound comprising one or more hydrolyzable groups per molecule.

• - R₉ für eine C₁-C₁₂-Alkylgruppe steht,
• - R₁₀ für eine C₁-C₆-Alkylgruppe steht,
• - R₁₁ für eine C₁-C₆-Alkylgruppe steht
• - k für eine ganze Zahl von 1 bis 3 steht, und
• - m für die ganze Zahl 3 - k steht.

The organic silicon compound(s) of the formula (S-IV) can also be referred to as silanes of the alkyl-C ₁ -C ₆ -alkoxysilane type, R ₉ Si(OR ₁₀ ) _k (R ₁₁ ) _m (S-IV), whereby

• - R ₉ represents a C ₁ -C ₁₂ alkyl group,
• - R ₁₀ represents a C ₁ -C ₆ alkyl group,
• - R ₁₁ represents a C ₁ -C ₆ alkyl group
• - k is an integer from 1 to 3, and
• - m is the integer 3 - k.

• - R₉ für eine C₁-C₁₂-Alkylgruppe steht,
• - R₁₀ für eine C₁-C₆-Alkylgruppe steht,
• - R₁₁ für eine C₁-C₆-Alkylgruppe steht
• - k für eine ganze Zahl von 1 bis 3 steht, und
• - m für die ganze Zahl 3 - k steht.

In a further preferred embodiment, an agent according to the invention is characterized in that it is an agent for decolorizing keratin material which is obtained by using at least one organic C ₁ -C ₆ -alkoxysilane of the formula (S-IV) and/or a condensation product colored by it and by the use of at least one pigment, R ₉ Si(OR ₁₀ ) _k (R ₁₁ ) _m (S-IV), whereby

• - R ₉ represents a C ₁ -C ₁₂ alkyl group,
• - R ₁₀ represents a C ₁ -C ₆ alkyl group,
• - R ₁₁ represents a C ₁ -C ₆ alkyl group
• - k is an integer from 1 to 3, and
• - m is the integer 3 - k.

In the organic C ₁ -C ₆ -alkoxysilanes of the formula (S-IV), the radical R ₉ is a C ₁ -C ₁₂ -alkyl group. This C ₁ -C ₁₂ alkyl group is saturated and can be linear or branched. R ₉ is preferably a linear C ₁ -C ₈ -alkyl group. R ₉ preferably represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group or an n-dodecyl group. R ₉ is particularly preferably a methyl group, an ethyl group or an n-octyl group.

In the organic silicon compounds of the formula (S-IV), the radical R ₁₀ is a C ₁ -C ₆ -alkyl group. R ₁₀ particularly preferably represents a methyl group or an ethyl group.

In the organic silicon compounds of the formula (S-IV), the radical R ₁₁ is a C ₁ -C ₆ -alkyl group. R ₁₁ particularly preferably represents a methyl group or an ethyl group.

Further, k is an integer of 1 to 3, and m is an integer of 3 - k. If k is the number 3, then m is equal to 0. If k is the number 2, then m is equal to 1. If k is the number 1, then m is equal to 2.

Very good discoloration results were obtained when the keratin material was first colored with an organic C ₁ -C ₆ -alkoxysilane of the formula (S-IV), in which the radical k stands for the number 3. In this case, the remainder m stands for the number 0.

• - Methyltrimethoxysilan
  
• - Methyltriethoxysilan
  
• - Ethyltrimethoxysilan
  
• - Ethyltriethoxysilan
  
• - n-Propyltrimethoxysilan (auch bezeichnet ans Propyltrimethoxysilan)
  
• - n-Propyltriethoxysilan (auch bezeichnet als Propyltriethoxysilan)
  
• - n-Hexyltrimethoxysilan (auch bezeichnet als Hexyltrimethoxysilan)
  
• - n-Hexyltriethoxysilan (auch bezeichnet als Hexyltriethoxysilan)
  
• - n-Octyltrimethoxysilan (auch bezeichnet als Octyltrimethoxysilan)
  
• - n-Octyltriethoxysilan (auch bezeichnet als Octyltriethoxysilan)
  
• - n-Dodecyltrimethoxysilan (auch bezeichnet als Dodecyltrimethoxysilan) und/oder
  
• - n-Dodecyltriethoxysilan (auch bezeichnet als Dodecyltriethoxysilan).
  

Organic silicon compounds of the formula (S-IV) which are particularly suitable for solving the problem of the invention are

• - methyltrimethoxysilane
  
• - methyltriethoxysilane
  
• - ethyltrimethoxysilane
  
• - ethyltriethoxysilane
  
• - n-propyltrimethoxysilane (also called ans propyltrimethoxysilane)
  
• - n-propyltriethoxysilane (also referred to as propyltriethoxysilane)
  
• - n-hexyltrimethoxysilane (also referred to as hexyltrimethoxysilane)
  
• - n-hexyltriethoxysilane (also referred to as hexyltriethoxysilane)
  
• - n-octyltrimethoxysilane (also referred to as octyltrimethoxysilane)
  
• - n-octyltriethoxysilane (also referred to as octyltriethoxysilane)
  
• - n-dodecyltrimethoxysilane (also referred to as dodecyltrimethoxysilane) and/or
  
• - n-dodecyltriethoxysilane (also referred to as dodecyltriethoxysilane).
  

• - Methyltrimethoxysilan,
• - Methyltriethoxysilan,
• - Ethyltrimethoxysilan,
• - Ethyltriethoxysilan,
• - Propyltrimethoxysilan,
• - Propyltriethoxysilan,
• - Hexyltrimethoxysilan,
• - Hexyltriethoxysilan,
• - Octyltrimethoxysilan,
• - Octyltriethoxysilan,
• - Dodecyltrimethoxysilan, und/oder
• - Dodecyltriethoxysilan.

In a further preferred embodiment, an agent according to the invention is characterized in that it is an agent for decolorizing keratin material, which is obtained by using at least one organic C ₁ -C ₆ -alkoxysilane and/or a condensation product thereof and by using at least one pigment was colored, wherein the organic C ₁ -C ₆ alkoxysilane is selected from the group consisting of

• - methyltrimethoxysilane,
• - methyltriethoxysilane,
• - ethyltrimethoxysilane,
• - ethyltriethoxysilane,
• - propyltrimethoxysilane,
• - propyltriethoxysilane,
• - hexyltrimethoxysilane,
• - hexyltriethoxysilane,
• - octyltrimethoxysilane,
• - octyltriethoxysilane,
• - dodecyltrimethoxysilane, and/or
• - Dodecyltriethoxysilane.

• Hydrolyse von C₁-C₆-Alkoxy-Silan der Formel (S-I) mit Wasser (Reaktionsschema am Beispiel von 3-Aminopropyltriethoxysilan):
  

The corresponding hydrolysis or condensation products are, for example, the following compounds:

• Hydrolysis of C ₁ -C ₆ -alkoxysilane of the formula (SI) with water (reaction scheme using 3-aminopropyltriethoxysilane as an example):
  

bzw.

Depending on the amount of water used, the hydrolysis reaction can also take place several times per C ₁ -C ₆ -alkoxysilane used:

or.

Hydrolysis of C ₁ -C ₆ -alkoxysilane of the formula (S-IV) with water (reaction scheme using methyltrimethoxysilane as an example):

bzw.

Depending on the amount of water used, the hydrolysis reaction can also take place several times per C ₁ -C ₆ -alkoxysilane used:

or.

und/oder

und/oder

und/oder

und/oder

und/oder

und/oder

Examples of possible condensation reactions are (shown using the mixture of (3-aminopropyl)triethoxysilane and methyltrimethoxysilane):

and or

and or

and or

and or

and or

and or

In the above exemplary reaction schemes, the condensation to form a dimer is shown in each case, but more extensive condensations to form oligomers having a plurality of silane atoms are also possible and also preferred.

Partially hydrolyzed as well as fully hydrolyzed C ₁ -C ₆ -alkoxysilanes of the formula (SI) can participate in these condensation reactions, which carry out a condensation with unreacted, partially or completely hydrolyzed C ₁ -C ₆ -alkoxysilanes of the formula (SI) run through. In this case, the C ₁ -C ₆ -alkoxysilanes of the formula (SI) react with themselves.

Furthermore, both partially hydrolyzed and fully hydrolyzed C ₁ -C ₆ -alkoxysilanes of the formula (SI) can also take part in the condensation reactions, which undergo a condensation with unreacted, partially or fully hydrolyzed C ₁ -C ₆ -alkoxysilanes of the formula ( S-IV) go through. In this case, the C ₁ -C ₆ -alkoxysilanes of the formula (SI) react with the C ₁ -C ₆ -alkoxysilanes of the formula (S-IV).

Furthermore, both partially hydrolyzed and fully hydrolyzed C ₁ -C ₆ -alkoxysilanes of the formula (S-IV) can also participate in the condensation reactions, which a condensation with unreacted, partially or fully hydrolyzed C ₁ -C ₆ -alkoxysilanes of the Run through formula (S-IV). In this case, the C ₁ -C ₆ -alkoxysilanes of the formula (S-IV) react with themselves.

Coloring using pigments

The bleaching agent according to the invention is applied to previously colored keratin material. In the case of coloring, it is particularly preferred if, in addition to the at least one organosilicon compound, in particular the organic C ₁ -C ₆ -alkoxysilane, at least one pigment is also used.

For the purposes of the present invention, pigments are understood to mean coloring compounds which have a solubility in water at 25° C. of less than 0.5 g/l, preferably less than 0.1 g/l, even more preferably less than 0. Possess 05 g/L. The water solubility can be determined, for example, using the method described below: 0.5 g of the pigment is weighed out in a glass beaker. A stir bar is added. Then one liter of distilled water is added. This mixture is heated to 25°C with stirring on a magnetic stirrer for one hour. Are in the mix after the If undissolved components of the pigment are still visible during 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 present in finely dispersed form, the mixture is filtered. If a proportion 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 further very particularly preferred embodiment, a method according to the invention is characterized in that the decolorizing agent is applied to keratin material which has been colored by using at least one inorganic and/or organic pigment.

Preferred color pigments are selected from synthetic or natural inorganic pigments. Inorganic color pigments of natural origin can be made from chalk, ochre, umber, green earth, burnt terra di sienna or graphite, for example. 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, metal hydroxides and metal oxide hydrates, mixed-phase pigments, sulfur-containing silicates, silicates, metal sulfides, complex metal cyanides, metal sulfates, metal chromates and/or metal 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), ultramarines (sodium aluminum sulfosilicates, CI 77007, pigment blue 29), hydrated chromium oxide (CI77289 ), Iron Blue (Ferric Ferrocyanide, CI77510) and/or Carmine (Cochineal).

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

As an alternative to natural mica, synthetic mica optionally coated with one or more metal oxide(s) 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, an agent according to the invention is characterized in that it is an agent for decolorizing keratin material which has been colored by using at least one pigment selected from the group of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulphates, bronze pigments and/or mica or mica based colored pigments coated with at least one metal oxide and/or one metal oxychloride.

In a further preferred embodiment, an agent according to the invention is characterized in that it is an agent for decolorizing keratin material which has been colored by using at least one pigment selected from the group consisting of pigments based on mica or mica, which are mixed with one or several metal oxides from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and/or brown iron oxide (CI 77491, CI 77499), manganese violet (CI 77742), ultramarines (sodium Aluminum sulfosilicates, CI 77007, Pigment Blue 29), hydrated chromium oxide (CI 77289), chromium oxide (CI 77288) and/or iron blue (Ferric Ferrocyanide, CI 77510).

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

• Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES)
• Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxides), Alumina
• Colorona Patina Silver, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)
• Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470 (CARMINE)
• Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES)
• Colorona Dark Blue, Merck, MICA, TITANIUM DIOXIDE, FERRIC FERROCYANIDE
• Colorona Chameleon, Merck, CI 77491 (IRON OXIDES), MICA
• Colorona Aborigine Amber, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)
• Colorona Blackstar Blue, Merck, CI 77499 (IRON OXIDES), MICA
• Colorona Patagonian Purple, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE), CI 77510 (FERRIC FERROCYANIDE)
• Colorona Red Brown, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)
• Colorona Russet, Merck, 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 (Iron 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 (Iron oxides), Mica, CI 77891 (Titanium dioxide)
• Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium dioxide), CI 77491 (Iron oxides)
• Colorona Blackstar Gold, Merck, MICA, CI 77499 (IRON OXIDES)

Very particularly preferred color pigments with the trade name Colorona® are, for example:

• Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES)
• Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxides), Alumina
• Colorona Patina Silver, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)
• Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470 (CARMINE)
• Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES)
• Colorona Dark Blue, Merck, MICA, TITANIUM DIOXIDE, FERRIC FERROCYANIDE
• Colorona Chameleon, Merck, CI 77491 (IRON OXIDES), MICA
• Colorona Aborigine Amber, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)
• Colorona Blackstar Blue, Merck, CI 77499 (IRON OXIDES), MICA
• Colorona Patagonian Purple, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE), CI 77510 (FERRIC FERROCYANIDES)
• Colorona Red Brown, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDES)
• Colorona Russet, Merck, CI 77491 (TITANIUM DIOXIDES), 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 (Iron 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 (Iron oxides), Mica, CI 77891 (Titanium dioxide)
• Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium dioxide), CI 77491 (Iron oxides)
• Colorona Blackstar Gold, Merck, MICA, CI 77499 (IRON OXIDES)

• 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.

Examples of further 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.

• Unipure Red LC 381 EM, Sensient CI 77491 (Iron Oxides), Silica
• Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica
• Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iron Oxides), Silica

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

• Unipure Red LC 381 EM, Sensient CI 77491 (Iron Oxides), Silica
• Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica
• Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iron Oxides), Silica

In a further embodiment, the agent according to the invention can also be an agent for decolorizing keratin material, in which case the keratin material has also been colored with at least one organic pigment before application of the decolorizing agent.

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

Particularly suitable organic pigments are, for example, carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the Color Index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the Color Index numbers CI 11680 , CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, Cl 21108, CI 47000, CI 47005, green pigments with the Color Index numbers CI 61565, CI 61570, CI 74260, orange pigments with the Color Index numbers CI 11725 , CI 15510, CI 45370, CI 71105, red pigments with the Color Index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and/or CI 75470.

In a further preferred embodiment, an agent according to the invention is characterized in that it is an agent for decolorizing keratin material which has been colored by using at least one organic pigment selected from the group consisting of carmine, quinacridone, phthalocyanine, sorghum, and blue pigments with the Color Index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the Color Index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108 , CI 47000, CI 47005, green pigments with the Color Index numbers CI 61565, CI 61570, CI 74260, orange pigments with the Color Index numbers CI 11725, CI 15510, CI 45370, CI 71105, red pigments with the Color Index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 261008, CI 261008 CI 45410, CI 58000, CI 73360, CI 73915 and/or CI 75470.

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

Alizarin color lake, for example, can be used as the color lake.

Due to their excellent light and temperature stability, coloring with the aforementioned pigments is particularly preferred. Furthermore, it is preferred if the pigments used have a specific particle size. On the one hand, this particle size leads to a uniform distribution of the pigments in the polymer film formed and, on the other hand, avoids a rough feel on the hair or skin after the cosmetic agent has been applied. It is therefore advantageous according to the invention if the at least one pigment has an average particle size Dso of from 1.0 to 50 μm, preferably from 5.0 to 45 μm, preferably from 10 to 40 μm, in particular from 14 to 30 μm. The mean particle size Dso can be determined, for example, using dynamic light scattering (DLS).

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

The substrate flakes of this type have an average thickness of at most 50 nm, preferably less than 30 nm, particularly preferably at most 25 nm, for example at most 20 nm. The average thickness of the substrate flakes is at least 1 nm, preferably at least 2.5 nm, particularly preferably at least 5 nm, for example at least 10 nm. Preferred ranges for the thickness of the substrate flakes are 2.5 to 50 nm, 5 to 50 nm, 10 to 50nm; 2.5 to 30nm, 5 to 30nm, 10 to 30nm; 2.5 to 25 nm, 5 to 25 nm, 10 to 25 nm, 2.5 to 20 nm, 5 to 20 nm and 10 to 20 nm. Each substrate plate preferably has a thickness which is as uniform as possible.

Due to the small thickness of the substrate flakes, the pigment has a particularly high hiding power.

The substrate plates have a monolithic structure. In this context, monolithic means consisting of a single, self-contained unit without fractures, layers or inclusions, although structural changes can occur within the substrate platelets. The substrate flakes are preferably of homogeneous structure, i.e. there is no concentration gradient within the flakes. In particular, the substrate flakes are not built up in layers and have no particles or particles distributed therein.

The size of the small substrate can be adjusted to the respective application, in particular the desired effect on the keratin material. As a rule, the substrate flakes have an average largest diameter of about 2 to 200 μm, in particular about 5 to 100 μm.

In a preferred embodiment, the form factor (aspect ratio), expressed as the ratio of the average size to the average thickness, is at least 80, preferably at least 200, more preferably at least 500, particularly preferably more than 750. The mean size of the uncoated substrate flakes is the d50 value of the uncoated substrate flakes. Unless otherwise stated, the d50 value was determined using a Sympatec Helos device with Quixel wet dispersion. To prepare the sample, the sample to be examined was predispersed in isopropanol for a period of 3 minutes.

The substrate flakes can be constructed from any material that can be formed into flake form.

They can be of natural origin, but also produced synthetically. Materials from which the substrate flakes can be constructed are, for example, metals and metal alloys, metal oxides, preferably aluminum oxide, inorganic compounds and minerals such as mica and (semi)precious stones, and plastics. The substrate flakes are preferably constructed from metal (alloys).

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

Lamellar substrate platelets are characterized by an irregularly structured edge and are also referred to as "cornflakes" due to their appearance.

Due to their irregular structure, pigments based on lamellar substrate flakes generate a high proportion of scattered light. In addition, the pigments based on lamellar substrate flakes do not completely cover the existing color of a keratinic material and, for example, effects analogous to natural graying can be achieved.

Lenticular (= lens-shaped) substrate flakes have an essentially regular round edge and are also referred to as “silver dollars” because of their appearance. Due to their regular structure, the proportion of reflected light predominates in the case of pigments based on lenticular substrate plates.

Vacuum metallized pigments (vacuum metallized pigments, VMP) can be obtained, for example, by releasing metals, metal alloys or metal oxides from appropriately coated foils. They are characterized by a particularly low thickness of the substrate flakes in the area from 5 to 50 nm and a particularly smooth surface with increased reflectivity. In the context of this application, substrate flakes which comprise a pigment metallized in a vacuum are also referred to as VMP substrate flakes. Aluminum VMP substrate flakes can be obtained, for example, by releasing aluminum from metallized foils.

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

Uncoated lamellar, lenticular and/or VPM substrate flakes, in particular those made of metal or metal alloy, reflect the incident light to a large extent and produce a light-dark flop, but no color impression.

A color impression can be generated, for example, due to optical interference effects. Such pigments can be based on substrate flakes coated at least once. These show interference effects due to the superimposition of differently refracted and reflected light beams.

Correspondingly, preferred pigments are pigments based on a coated lamellar substrate platelet. The substrate flake preferably has at least one coating B made of a high-index metal oxide with a coating thickness of at least 50 nm. There is preferably another coating A between the coating B and the surface of the small substrate.

Suitable materials for the coatings A, B and C are all substances which can be applied in the form of a film and permanently to the substrate flakes and, in the case of layers A and B, have the required optical properties. In general, a coating of part of the surface of the substrate flakes is sufficient to obtain a pigment with a glossy effect. For example, only the upper and/or lower side of the substrate flakes can be coated, with the side surface(s) being omitted. The entire surface of the optionally passivated substrate flakes, including the side surfaces, is preferably covered by coating B. The substrate flakes are thus completely encased by coating B. This improves the optical properties of the pigment and increases the mechanical and chemical resilience of the pigments. The above also applies to layer A and preferably also to layer C, if present.

Although several coatings A, B and/or C may be present in each case, the coated substrate flakes preferably have only one coating A, B and, if present, C each.

The coating B is made up of at least one metal oxide with a high refractive index. Materials with a high refractive index have a refractive index of at least 1.9, preferably at least 2.0 and particularly preferably at least 2.4. The coating B preferably comprises at least 95% by weight, particularly preferably at least 99% by weight, of high-index metal oxide(s).

The coating B has a thickness of at least 50 nm. The thickness of coating B is preferably no more than 400 nm, particularly preferably at most 300 nm.

High-index metal oxides suitable for coating B are preferably selectively light-absorbing (ie colored) metal oxides, such as iron(III) oxide (a- and γ-Fe2O3, red), cobalt(II) oxide (blue), chromium(III) oxide (green ), titanium(III) oxide (blue, usually found in a mixture with titanium oxynitrides and titanium nitrides) and vanadium(V) oxide (orange) and mixtures thereof. Colorless, high-index oxides such as titanium dioxide and/or zirconium oxide are also suitable.

The coating B can contain a selectively absorbing dye, preferably 0.001 to 5% by weight, particularly preferably 0.01 to 1% by weight, based in each case on the total amount of the coating B. Organic and inorganic dyes which are stable incorporated into a metal oxide coating.

The coating A preferably has at least one metal oxide and/or metal oxide hydrate with a low refractive index. Coating A preferably comprises at least 95% by weight, particularly preferred at least 99% by weight low-index metal oxide (hydrate). Materials with low refractive index have a refractive index of at most 1.8, preferably at most 1.6.

The low-index metal oxides suitable for coating A include, for example, silicon (di)oxide, silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, boron oxide, germanium oxide, manganese oxide, magnesium oxide and mixtures thereof, silicon dioxide being preferred. The coating A preferably has a thickness of 1 to 100 nm, particularly preferably 5 to 50 nm, particularly preferably 5 to 20 nm.

The distance between the surface of the substrate flakes and the inner surface of coating B is preferably at most 100 nm, particularly preferably at most 50 nm, particularly preferably at most 20 nm. The fact that the thickness of coating A and thus the distance between the surface of the substrate flakes and Coating B is in the range given above, it can be ensured that the pigments have high hiding power.

If the pigment based on a lamellar substrate platelet has only one layer A, it is preferred that the pigment has a lamellar substrate platelet made of aluminum and a layer A made of silicon dioxide. If the pigment based on a lamellar substrate flake has a layer A and a layer B, it is preferred that the pigment has a lamellar substrate flake made of aluminum, a layer A made of silicon dioxide and a layer B made of iron oxide.

According to a preferred embodiment, the pigments have a further coating C of a metal oxide (hydrate) which is different from the underlying coating B on. Examples of suitable metal oxides are silicon(di)oxide, silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, zinc oxide, tin oxide, titanium dioxide, zirconium oxide, iron(III) oxide and chromium(III) oxide. Silicon dioxide is preferred.

The coating C preferably has a thickness of 10 to 500 nm, particularly preferably 50 to 300 nm. By providing the coating C, for example based on TiO ₂ , a better interference can be achieved, with a high covering power remaining guaranteed.

Layers A and C are used in particular as protection against corrosion and also for chemical and physical stabilization. Layers A and C particularly preferably contain silicon dioxide or aluminum oxide, which are applied by the sol-gel process. This method comprises dispersing the uncoated lamellar substrate flakes or the lamellar substrate flakes already coated with layer A and/or layer B in a solution of a metal alkoxide such as tetraethyl orthosilicate or aluminum triisopropoxide (usually in a solution of organic solvent or a mixture of organic solvent and water with at least 50% by weight organic solvent such as a C1 to C4 alcohol), and adding a weak base or acid to hydrolyze the metal alkoxide, thereby forming a film of the metal oxide on the surface of the (coated) substrate flakes.

Layer B can be produced, for example, by hydrolytic decomposition of one or more organic metal compounds and/or by precipitation of one or more dissolved metal salts and, if appropriate, subsequent post-treatment (for example converting a hydroxide-containing layer formed into the oxide layer by tempering).

Although each of the coatings A, B and/or C may be composed of a mixture of two or more metal oxide (hydrate)s, each of the coatings is preferably composed of a metal oxide (hydrate).

The pigments based on coated lamellar or lenticular substrate flakes or the pigments based on coated VMP substrate flakes preferably have a thickness of 70 to 500 nm, particularly preferably 100 to 400 nm, particularly preferably 150 to 320 nm, for example 180 to 290 nm, on. Due to the small thickness of the substrate flakes, the pigment has a particularly high hiding power. The small thickness of the coated substrate flakes is achieved in particular by the fact that the thickness of the uncoated substrate flakes is small, but also by the fact that the thicknesses of the coatings A and, if present, C are set to the smallest possible value. The thickness of coating B determines the color impression of the pigment.

The adhesion and abrasion resistance of pigments based on coated substrate plates in the keratin material can be significantly increased by modifying the outermost layer, layer A, B or C depending on the structure, with additional organic compounds such as silanes, phosphoric acid esters, titanates, borates or carboxylic acids will. The organic compounds are bound to the surface of the outermost layer A, B or C, which preferably contains metal oxide. The outermost layer refers to the layer that is spatially furthest away from the lamellar substrate plate. The organic compounds are preferably functional silane compounds which can bond to the layer A, B or C containing metal oxide. These can be either monofunctional or bifunctional compounds. Examples of bifunctional organic compounds are methacryloxypropenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-acryloxyethyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2-acryloxyethyltriethoxysilane, 3-methacryloxypropyltris(methoxyethoxy)tris(methoxyethoxy)silane Methacryloxypropyltris(butoxyethoxy)silane, 3-methacryloxypropyltris(propoxy)silane, 3-methacryloxypropyltris(butoxy)silane, 3-acryloxypropyltris(methoxyethoxy)silane, 3-acryloxypropyltris(butoxyethoxy)silane, 3-acryloxypropyltris(butoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylethyldichlorosilane, vinylmethyldiacetoxysilane, vinylmethyldichlorosilane, vinylmethyldiethoxysilane, vinyltriacetoxysilane, vinyltrichlorosilane, phenylvinyldiethoxysilane, or phenylallyldichlorosilane. Furthermore, a modification with a monofunctional silane, in particular an alkyl silane or aryl silane, can take place. This has only one functional group which can bond covalently to the surface of pigment based on coated lamellar substrate flakes (ie to the outermost layer containing metal oxide) or, if the coverage is not quite complete, to the metal surface. The hydrocarbon residue of the silane points away from the pigment. Depending on the type and nature of the hydrocarbon residue of the silane, a different degree of hydrophobicization of the pigment is achieved. Examples of such silanes are hexadecyltrimethoxysilane, propyltrimethoxysilane, etc. Pigments based on silicon dioxide-coated aluminum substrate flakes are particularly preferably surface-modified with a monofunctional silane. Octyltrimethoxysilane, octyltriethoxysilane, hecadecyltrimethoxysilane and hecadecyltriethoxysilane are particularly preferred. The changed surface properties / water repellency can improve adhesion, abrasion resistance and orientation in the application.

Suitable pigments based on a lamellar substrate flake include, for example, the pigments from Eckart's VISIONAIRE series.

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

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

Coloring using polymers

When coloring the keratin material, in particular the keratin fibers, at least one film-forming polymer can also be used in addition to the organosilicon compound or compounds, in particular the organic C ₁ -C ₆ -alkoxysilanes and the at least one pigment.

It has been found that the colorations obtained by using the combination of organic C ₁ -C ₆ -alkoxysilane, pigment and film-forming polymer are particularly resistant and therefore also particularly difficult to decolorize. Surprisingly, it has been found that the use of the decolorizing agent according to the invention is also excellent at decolorizing these colors again.

In a further preferred embodiment, an agent according to the invention is characterized in that it is an agent for decolorizing keratin material, which is obtained by using at least one organic C ₁ -C ₆ -alkoxysilane and/or a condensation product thereof, by using at least one pigment and colored by application of at least one film-forming polymer.

Polymers are understood to be macromolecules with a molecular weight of at least 1000 g/mol, preferably at least 2500 g/mol, particularly preferably at least 5000 g/mol, which consist of identical, repeating organic units. In the polymers of the present According to the invention, the polymers can be synthetically produced, which are produced by the polymerization of one type of monomer or by the polymerization of different types of monomers which are structurally different from one another. If the polymer is made by polymerizing one type of monomer, it is called a homo-polymer. If structurally different types of monomers are used in the polymerization, the resulting polymer is referred to as a copolymer.

The maximum molecular weight of the polymer depends on the degree of polymerization (number of polymerized monomers) and the batch size and is also determined by the polymerization method. For the purposes of the present invention, it is preferred if the maximum molecular weight of the film-forming, hydrophobic polymer (c) is not more than 10 ⁷ g/mol, preferably not more than 10 ⁶ g/mol and particularly preferably not more than 10 ⁵ g/mol amounts to.

For the purposes of the invention, a film-forming polymer is a polymer which is able to form a film on a substrate, for example on a keratin material or a keratin fiber. The formation of a film can be demonstrated, for example, by observing the keratin material treated with the polymer under a microscope.

The film-forming polymers previously used in the coloring step can be hydrophilic or hydrophobic.

In a further preferred embodiment, an agent according to the invention is characterized in that it is an agent for decolorizing keratin material, which is obtained by using at least one organic C ₁ -C ₆ -alkoxysilane and/or a condensation product thereof, by using at least one pigment and colored by application of at least one film-forming hydrophobic polymer.

A hydrophobic polymer is understood to mean a polymer that has a solubility in water at 25° C. (760 mmHg) of less than 1% by weight.

The water solubility of the film-forming hydrophobic polymer can be determined, for example, in the following way. 1.0 g of the polymer is placed in a beaker. Water is made up to 100 g. A stir bar is added and the mixture is warmed to 25°C on a magnetic stirrer with stirring. Stir for 60 minutes. The aqueous mixture is then assessed visually. If the polymer-water mixture cannot be assessed visually due to a high level of turbidity in the mixture, the mixture is filtered. If some undissolved polymer remains on the filter paper, the solubility of the polymer is less than 1% by weight.

Mention may be made here in particular of polymers of the acrylic acid type, polyurethanes, polyesters, polyamides, polyureas, cellulosic polymers, nitrocellulose polymers, silicone polymers, polymers of the acrylamide type and polyisoprenes .

Particularly suitable film-forming, hydrophobic polymers are, for example, polymers from the group of copolymers of acrylic acid, copolymers of methacrylic acid, homopolymers or copolymers of acrylic acid esters, homopolymers or copolymers of methacrylic acid esters, homopolymers or copolymers of acrylic acid amides, homopolymers or methacrylic acid amide copolymers, vinylpyrrolidone copolymers, vinyl alcohol copolymers, vinyl acetate copolymers, ethylene homopolymers or copolymers, propylene homopolymers or copolymers, styrene homopolymers or copolymers, polyurethanes, polyesters and/or or the polyamides.

In a further preferred embodiment, an agent according to the invention is characterized in that it is an agent for decolorizing keratin material which has been colored by using at least one film-forming, hydrophobic polymer selected from the group consisting of acrylic acid copolymers and methacrylic acid copolymers , homopolymers or copolymers of acrylic acid esters, homopolymers or copolymers of methacrylic acid esters, homopolymers or copolymers of acrylic acid amides, homopolymers or copolymers of methacrylic acid amides, copolymers of vinylpyrrolidone, copolymers of vinyl alcohol, copolymers of vinyl acetate, ethylene homopolymers or copolymers, propylene homopolymers or copolymers, styrene homopolymers or copolymers, polyurethanes, polyesters and/or polyamides.

In particular, the film-forming hydrophobic polymers which are selected from the group of synthetic polymers, polymers obtainable by free-radical polymerization or natural polymers have proven to be well suited for coloring.

Other particularly well suited film-forming hydrophobic polymers can be selected from the homopolymers or copolymers of olefins, such as cycloolefins, butadiene, isoprene or styrene, vinyl ethers, vinyl amides, the esters or amides of (meth)acrylic acid with at least one C ₁ -C ₂₀ - alkyl group, an aryl group or a C ₂ -C ₁₀ hydroxyalkyl group.

Other film-forming hydrophobic polymers can be selected from the homo- or copolymers of isooctyl (meth)acrylate; isononyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; lauryl (meth)acrylate); isopentyl (meth)acrylate; n-butyl (meth)acrylate); isobutyl (meth)acrylate; ethyl (meth)acrylate; methyl (meth)acrylate; tert-butyl (meth)acrylate; stearyl (meth)acrylate; hydroxyethyl (meth)acrylate; 2-hydroxypropyl (methacrylate; 3-hydroxypropyl (meth)acrylate and/or mixtures thereof.

Other film-forming hydrophobic polymers can be selected from the homo- or copolymers of (meth)acrylamide; N-alkyl (meth) acrylamides, in particular those with C2-C18 alkyl groups, such as N-ethyl acrylamide, N-tert-butyl acrylamide, le N-octyl-acrylamide; N -Di(C1-C4)alkyl(meth)acrylamide.

Further preferred anionic copolymers are, for example, copolymers of acrylic acid, methacrylic acid or their C ₁ -C ₆ -alkyl esters, as are marketed under the INCI declaration Acrylates Copolymers. A suitable commercial product is, for example, ^Aculyn® 33 from Rohm & Haas. However, preference is also given to copolymers of acrylic acid, methacrylic acid or their C ₁ -C ₆ -alkyl esters and the esters of an ethylenically unsaturated acid and an alkoxylated fatty alcohol. Suitable ethylenically unsaturated acids are, in particular, acrylic acid, methacrylic acid and itaconic acid; suitable alkoxylated fatty alcohols are, in particular, steareth-20 or ceteth-20.

Very particularly preferred polymers on the market are, for example, _Aculyn® 22 (acrylates/steareth-20 methacrylate copolymer), _Aculyn® 28 (acrylates/beheneth-25 methacrylate copolymer), Structure _2001® (acrylates/steareth-20 itaconate). Copolymer), Structure 3001 _® (Acrylates/Ceteth-20 Itaconate Copolymer), Structure Plus _® (Acrylates/Aminoacrylates C10-30 Alkyl PEG-20 Itaconate Copolymer), Carbopol® 1342, 1382, Ultrez 20, Ultrez 21 (Acrylates/C10- 30 Alkyl Acrylate Crosspolymer), Synthalen W 2000® (Acrylates/Palmeth-25 Acrylate Copolymer) or the Soltex OPT (Acrylates/C12-22 Alkyl methacrylate Copolymer) sold by Rohme and Haas.

Examples of suitable polymers based on vinyl monomers are the homo- and copolymers of N-vinylpyrrolidone, of vinylcaprolactam, of vinyl-(C1-C6-)alkyl-pyrrole, of vinyl-oxazole, of vinyl-thiazole, of vinylpyrimidine, of vinylimidazole.

The copolymers octylacrylamide/acrylates/butylaminoethyl methacrylate copolymers, such as those sold commercially by NATIONAL STARCH under the trade names AMPHOMER® or LOVOCRYL® 47, or the copolymers of acrylates/octylacrylamide under the trade names DERMACRYL® LT and DERMACRYL® 79 are sold by NATIONAL STARCH.

Examples of suitable polymers based on olefins are the homo- and copolymers of ethylene, propylene, butene, isoprene and butadiene.

In a further embodiment, the film-forming hydrophobic polymers used can be block copolymers which comprise at least one block of styrene or the derivatives of styrene. These block copolymers can be copolymers which, in addition to a styrene block, contain one or more other blocks, such as styrene/ethylene, styrene/ethylene/butylene, styrene/butylene, styrene/isoprene, styrene/butadiene. Corresponding polymers are sold commercially by BASF under the trade name “Luvitol HSB”.

In another embodiment, the film-forming polymers previously used in the coloring step can also be hydrophilic.

In a further particularly preferred embodiment, a method according to the invention is characterized in that the decolorizing agent is applied to keratin material which has been produced by using at least one organic C ₁ -C ₆ -alkoxysilane and/or a condensation product thereof, by using at least one pigment and colored by application of at least one film-forming hydrophilic polymer.

A hydrophilic polymer is understood as meaning a polymer that has a solubility in water at 25° C. (760 mmHg) of more than 1% by weight, preferably more than 2% by weight.

The water solubility of the film-forming hydrophilic polymer can be determined, for example, in the following way. 1.0 g of the polymer is placed in a beaker. Water is made up to 100 g. A stir bar is added and the mixture is warmed to 25°C on a magnetic stirrer with stirring. Stir for 60 minutes. The aqueous mixture is then assessed visually. A completely dissolved polymer appears macroscopically homogeneous. If the polymer-water mixture cannot be assessed visually due to a high level of turbidity in the mixture, the mixture is filtered. If no undissolved polymer remains on the filter paper, then the solubility of the polymer is greater than 1% by weight.

Nonionic, anionic and cationic polymers can be used as film-forming, hydrophilic polymers.

Suitable film-forming, hydrophilic polymers can be, for example, from the group of polyvinylpyrrolidone (co)polymers, polyvinyl alcohol (co)polymers, vinyl acetate (co)polymers, carboxyvinyl (co)polymers, acrylic acid (co)polymers, methacrylic acid (co)polymers, natural gums, polysaccharides and/or acrylamide (co)polymers.

Furthermore, it is very particularly preferred to use polyvinylpyrrolidone (PVP) and/or a copolymer containing vinylpyrrolidone as the film-forming hydrophilic polymer.

In a further preferred embodiment, an agent according to the invention is characterized in that it is an agent for decolorizing keratin material which has been colored by using at least one film-forming, hydrophilic polymer selected from the group consisting of polyvinylpyrrolidone (PVP) and the copolymers of polyvinylpyrrolidone.

It is also preferred if the agent according to the invention contains polyvinylpyrrolidone (PVP) as the film-forming, hydrophilic polymer. Particularly suitable polyvinylpyrrolidones are available, for example, under the name Luviskol® K from BASF SE, in particular _Luviskol® K 90 or _Luviskol® K 85 from BASF SE.

The polymer PVP K30, which is marketed by the Ashland company (ISP, POI Chemical), can also be used as a further polyvinylpyrrolidone (PVP) that is explicitly particularly well suited. PVP K 30 is a polyvinylpyrrolidone that is very readily soluble in cold water and has the CAS number 9003-39-8. The molecular weight of PVP K 30 is around 40000 g/mol.

Other very particularly suitable polyvinylpyrrolidones are the substances known under the trade names LUVITEC K 17, LUVITEC K 30, LUVITEC K 60, LUVITEC K 80, LUVITEC K 85, LUVITEC K 90 and LUVITEC K 115 and are available from BASF.

The use of film-forming hydrophilic polymers from the group of polyvinylpyrrolidone copolymers has also led to particularly good results.

In this connection, vinylpyrrolidone-vinyl ester copolymers, such as those sold under the trade name ^Luviskol® (BASF), can be mentioned as particularly suitable film-forming, hydrophilic polymers. ^Luviskol® VA 64 and ^Luviskol® VA 73, each vinyl pyrrolidone/vinyl acetate copolymers, are particularly preferred nonionic polymers.

Of the vinylpyrrolidone-containing copolymers, a styrene/VP copolymer and/or a vinylpyrrolidone-vinyl acetate copolymer and/or a VP/DMAPA acrylates copolymer and/or a VP/vinyl caprolactam/DMAPA acrylates copolymer are very particularly preferably used in the cosmetic compositions .

Vinylpyrrolidone-vinyl acetate copolymers are sold by BASF SE under the name Luviskol® VA. For example, a VP/vinyl caprolactam/DMAPA acrylates copolymer is sold by Ashland Inc. under the trade name Aquaflex® SF-40. For example, a VP/DMAPA acrylates copolymer sold by Ashland under the name Styleze CC-10 is a highly preferred vinylpyrrolidone-containing copolymer.

Other suitable copolymers of polyvinylpyrrolidone are the copolymers obtained by reacting N-vinylpyrrolidone with at least one other monomer from the group consisting of V-vinylformamide, vinyl acetate, ethylene, propylene, acrylamide, vinylcaprolactam, vinylcaprolactone and/or vinyl alcohol .

In a further preferred embodiment, an agent according to the invention is characterized in that it is an agent for decolorizing keratin material which has been colored by using at least one film-forming, hydrophilic polymer which is selected from the group of polyvinylpyrrolidone (PVP), vinylpyrrolidone/vinyl acetate Copolymers, vinylpyrrolidone/styrene copolymers, vinylpyrrolidone/ethylene copolymers, vinylpyrrolidone/propylene copolymers, vinylpyrrolidone/vinylcaprolactam copolymers, vinylpyrrolidone/vinylformamide copolymers and/or vinylpyrrolidone/vinyl alcohol copolymers.

Another suitable copolymer of vinylpyrrolidone is the polymer known under the INCI name maltodextrin/VP copolymer.

Furthermore, intensely colored keratin material, in particular hair, could be bleached again with very good results if a nonionic, film-forming, hydrophilic polymer was used as the film-forming, hydrophilic polymer.

In a first embodiment, it can be preferred if the keratin material was colored with at least one nonionic, film-forming, hydrophilic polymer in the previous coloring step.

According to the invention, a nonionic polymer is a polymer which, under standard conditions, in a protic solvent--such as water, for example--does not carry any structural units with permanently cationic or anionic groups which have to be compensated for by counterions while maintaining electroneutrality. Cationic groups include, for example, quaternized ammonium groups, but not protonated amines. Anionic groups include, for example, carboxyl and sulfonic acid groups.

• - Polyvinylpyrrolidon,
• - Copolymeren aus N-Vinylpyrrolidon und Vinylestern von Carbonsäuren mit 2 bis 18 Kohlenstoffatomen, insbesondere aus N-Vinylpyrrolidon und Vinylacetat,
• - Copolymeren aus N-Vinylpyrrolidon und N-Vinylimidazol und Methacrylamid,
• - Copolymeren aus N-Vinylpyrrolidon und N-Vinylimidazol und Acrylamid,
• - Copolymeren aus N-Vinylpyrrolidon mit N,N-Di(C₁ bis C₄)-Alkylamino-(C₂ bis C₄)-alkylacrylamid.

The agents used for coloring can contain, for example, at least one polymer selected from the group consisting of as nonionic, film-forming, hydrophilic polymer

• - polyvinylpyrrolidone,
• - Copolymers of N-vinylpyrrolidone and vinyl esters of carboxylic acids having 2 to 18 carbon atoms, in particular of N-vinylpyrrolidone and vinyl acetate,
• - Copolymers of N-vinylpyrrolidone and N-vinylimidazole and methacrylamide,
• - Copolymers of N-vinylpyrrolidone and N-vinylimidazole and acrylamide,
• - Copolymers of N-vinylpyrrolidone with N,N-di(C ₁ to C ₄ )alkylamino-(C ₂ to C ₄ )alkylacrylamide.

If copolymers of N-vinylpyrrolidone and vinyl acetate are used, it is preferred if the molar ratio of the structural units from the monomer N-vinylpyrrolidone to the structural units of the polymer from the monomer vinyl acetate is in the range from 20:80 to 80:20, in particular from 30 to 70 to 60 to 40. Suitable copolymers of vinylpyrrolidone and vinyl acetate are available, for example, under the trade names Luviskol® VA 37, Luviskol® VA 55, Luviskol® VA 64 and Luviskol® VA 73 from BASF SE.

Another particularly preferred polymer is selected from the polymers of the INCI designation VP/methacrylamide/vinyl imidazole copolymer, which are available, for example, under the trade name Luviset Clear from BASF SE.

Another very particularly preferred nonionic, film-forming, hydrophilic polymer is a copolymer of N-vinylpyrrolidone and N,N-dimethylaminopropylmethacrylamide, which, for example, with the INCI designation VP/DMAPA Acrylates Copolymer e.g. B. is sold under the trade name Styleze® CC 10 by the company ISP.

A cationic polymer according to the invention is the copolymer of N-vinylpyrrolidone, N-vinylcaprolactam, N-(3-dimethylaminopropyl)methacrylamide and 3-(methacryloylamino)propyllauryldimethylammonium chloride (INCI name: Polyquaternium-69), which is available, for example, under the trade name ^AquaStyle® 300 (28-32% by weight of active substance in an ethanol-water mixture, molecular weight 350,000) is sold by ISP.

• - Vinylpyrrolidon-Vinylimidazoliummethochlorid-Copolymere, wie sie unter den Bezeichnungen Luviquat^® FC 370, FC 550 und der INCI-Bezeichnung Polyquaternium-16 sowie FC 905 und HM 552 angeboten werden,
• - Vinylpyrrolidon-Vinylcaprolactam-Acrylat-Terpolymere, wie sie mit Acrylsäureestern und Acrylsäureamiden als dritter Monomerbaustein im Handel beispielsweise unter der Bezeichnung Aquaflex^® SF 40 angeboten werden.

Other suitable film-forming, hydrophilic polymers are, for example

• - Vinylpyrrolidone-vinylimidazolium methochloride copolymers, such as those offered under the names Luviquat ^® FC 370, FC 550 and the INCI name Polyquaternium-16 as well as FC 905 and HM 552,
• - Vinylpyrrolidone-vinylcaprolactam-acrylate terpolymers, such as those commercially available with acrylic acid esters and acrylic acid amides as the third monomer building block, for example under the name ^Aquaflex® SF 40.

Polyquaternium-11 is the reaction product of diethyl sulfate with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate. Suitable commercial products are available, for example, from BASF SE or Gafquat 440, Gafquat 734, Gafquat 755 or Gafquat 755N from Ashland Inc. under the names Dehyquart® CC 11 and Luviquat® PQ 11 PN.

Polyquaternium-46 is the reaction product of vinylcaprolactam and vinylpyrrolidone with methylvinylimidazolium methosulfate and is available, for example, under the name Luviquat® Hold from BASF SE. Polyquaternium-46 is preferably used in an amount of 1 to 5% by weight, based on the total weight of the cosmetic composition. It is most preferred that Polyquaternium-46 is used in combination with a cationic guar compound. In fact, it is highly preferred that Polyquaternium-46 is used in combination with a cationic guar compound and Polyquaternium-11.

Examples of suitable anionic, film-forming, hydrophilic polymers that can be used are acrylic acid polymers, which can be present in uncrosslinked or crosslinked form. Corresponding products are sold commercially, for example, under the trade names Carbopol 980, 981, 954, 2984 and 5984 by the company Lubrizol or under the names Synthalen M and Synthalen K by the company 3V Sigma (The Sun Chemicals, Inter Harz).

Examples of suitable film-forming, hydrophilic polymers from the group of natural gums are xanthan gum, gellan gum and carob gum.

Examples of suitable film-forming, hydrophilic polymers from the group of polysaccharides are hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl cellulose and carboxymethyl cellulose.

Examples of suitable film-forming, hydrophilic polymers from the group of acrylamides are polymers which are prepared from monomers of (methy)acrylamido-C1-C4-alkylsulfonic acid or the salts thereof. Corresponding polymers can be selected from the polymers of polyacrylamidomethanesulfonic acid, polyacrylamidoethanesulfonic acid, polyacrylamidopropanesulfonic acid, poly2-acrylamido-2-methylpropanesulfonic acid, poly-2-methylacrylamido-2-methylpropanesulfonic acid and/or poly-2-methylacrylamido-n-butanesulfonic acid.

Preferred polymers of poly(meth)arylamido-C1-C4-alkylsulfonic acids are crosslinked and at least 90% neutralized. These polymers can be crosslinked or uncrosslinked.

Crosslinked and completely or partially neutralized polymers of the poly-2-acrylamido-2-methylpropanesulfonic acid type are known by the INCI names “ammonium polyacrylamido-2-methylpropanesulphonate” or “ammonium polyacryldimethyltauramide”.

Another preferred polymer of this type is the crosslinked poly-2-acrylamido-2methyl-propanesulphonic acid polymer sold by Clamant under the trade name Hostacerin AMPS, which is partially neutralized with ammonia.

In a further preferred embodiment, an agent according to the invention is characterized in that it is an agent for decolorizing keratin material, which is obtained by using at least one organic C ₁ -C ₆ -alkoxysilane and/or a condensation product thereof, by using at least one pigment and colored by application of at least one film-forming anionic polymer.

wobei
M für ein Wasserstoffatom oder für Ammonium (NH₄), Natrium, Kalium, ½ Magnesium oder ½ Calcium steht.In this context, the best results have been obtained when the decolorizing agent is applied to keratin material which has been produced by using at least one organic C ₁ -C ₆ -alkoxysilane and/or a condensation product thereof, by using at least one pigment and by using at least a film-forming, anionic polymer, wherein the film-forming, anionic polymer comprises at least one structural unit of formula (PI) and at least one structural unit of formula (P-II).

whereby
M is a hydrogen atom or ammonium (NH ₄ ), sodium, potassium, ½ magnesium or ½ calcium.

When M is a hydrogen atom, the structural unit of formula (P-I) is based on an acrylic acid moiety.

When M is an ammonium counterion, the structural unit of formula (P-I) is based on the ammonium salt of acrylic acid.

When M is a sodium counterion, the structural unit of formula (P-I) is based on the sodium salt of acrylic acid.

When M is a potassium counterion, the structural unit of formula (P-I) is based on the potassium salt of acrylic acid.

When M represents a half equivalent of a magnesium counterion, the structural unit of formula (P-I) is based on the magnesium salt of acrylic acid.

When M is half an equivalent of a calcium counterion, the structural unit of formula (P-I) is based on the calcium salt of acrylic acid.

fluorine compounds (a)

The decolorizing agent according to the invention contains one or more fluorine compounds (a) as the first constituent essential to the invention.

In the context of the present invention, the term “fluorine compound” is understood to mean compounds which contain at least one fluorine atom. These compounds can be inorganic or organic fluorine compounds. The fluorine compounds are preferably understood as meaning salts which contain at least one fluoride anion.

Sodium, potassium and zinc salts of fluoride, fluorophosphates and fluorosilicates are advantageously used according to the invention. Preferred decolorizing agents according to the invention are therefore characterized in that they contain at least one fluorine compound (a) selected from the group consisting of tetrabutylammonium fluoride, sodium fluoride, potassium fluoride, sodium monofluorophosphate, zinc fluoride, tin fluoride, sodium fluorosilicate, cetylamine hydrofluoride and bis(hydroxyethyl)aminopropyl-N-hydroxyethyl -octadecylamine-dihydrofluoride

In a further preferred embodiment, an agent according to the invention is characterized in that it contains at least one fluorine compound (a) which is selected from the group consisting of Potassium fluoride, sodium fluoride, tetrabutylammonium fluoride, sodium monofluorophosphate, zinc fluoride, tin fluoride, sodium fluorosilicate, cetylamine hydrofluoride and bis(hydroxyethyl)aminopropyl-N-hydroxyethyloctadecylamine dihydrofluoride.

Potassium fluoride is a white, hygroscopic powder that has the CAS number 7789-23-3 and can be purchased commercially, for example, from Merck.

Sodium fluoride is commercially available, for example, under the trade name Sodium fluoride 98/100% or Sodium fluoride Tech Pure from Brenntag GmbH.

Tetrabutylammonium fluoride has the CAS number 22206-57-1 and can be purchased commercially in the form of its hydrate from Sigma Aldrich.

Cetylamine hydrofluoride has the CAS number 3151-59-5 and can be purchased commercially, for example, from Merck. Cetylamine hydrofluoride is known by the trade name Hetaflur.

Bis(Hydroxyethyl)aminopropyl-N-hydroxyethyl-octadecylamine-dihydrofluoride has the CAS number 6818-37-7. Alternative names are N,N,N'-tris(2-hydroxyethyl)-N'-octadecyl-1,3-diaminopropane dihydrofluoride and N,N,N'-tris(2-hydroxyethyl)-N'-octadecyl-1,3 -diaminopropane dihydrofluoride. This fluorine compound can be purchased commercially, for example, in a mixture with propylene glycol under the trade name RonaCare Olafluor from Merck.

The at least one fluorine compound is preferably used in specific quantity ranges in the decolorizing agent in order to ensure adequate effectiveness. The decolorizing agent therefore advantageously contains—based on its total weight—one or more fluorine compounds (a) in a total amount of from 0.5 to 9.0% by weight, preferably from 1.5 to 8.0% by weight, more preferably from 2.0 to 7.0% by weight and most preferably from 2.5 to 6.0% by weight.

In a further preferred embodiment, a decolorizing agent according to the invention is therefore characterized in that it - based on its total weight - one or more fluorine compounds (a) in a total amount of 0.5 to 9.0 wt .-%, preferably from 1.5 to 8.0% by weight, more preferably from 2.0 to 7.0% by weight and most preferably from 2.5 to 6.0% by weight.

Cationic surfactants (b)

The decolorizing agent according to the invention contains at least one cationic surfactant (b) as the second component essential to the invention.

Cationic surfactants are understood as meaning surfactants, ie surface-active compounds, each with one or more positive charges. Cationic surfactants only contain positive charges. These surfactants are usually made up of a hydrophobic part and a hydrophilic head group, with the hydrophobic part usually consisting of a hydrocarbon skeleton (e.g. consisting of one or two linear or branched alkyl chains), and the positive charge(s) located in the hydrophilic head group. Cationic surfactants adsorb at interfaces and aggregate in aqueous solution above the critical micelle concentration to form positively charged micelles.

• -quartäre Ammniumverbindungen, die als hydrophobe Reste ein oder zwei Alkylketten mit einer Kettenlänge von 8 bis 28 C-Atomen tragen können
• -quartäre Phosphoniumsalze, substituert mit einer oder mehreren Alkylketten mit einer Kettenlänge von 8 bis 28 C-Atomen oder
• - tertiäre Sulfonium-Salze.

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 having 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 (e.g. 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 other uncharged functional groups, as is the case with esterquats, for example.

wobei

RT1, RT2

unabhängig voneinander für eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe oder eine Hydroxy-C₂-C₆-alkylgruppe stehen,

RT3

für eine Hydroxy-C₂-C₆-alkylgruppe, eine C₁-C₇-Alkylgruppe, eine C₈-C₃₀-Alkylgruppe, oder für eine C₂-C₆-Alkenylgruppe steht,

RT4

für eine C₈-C₃₀-Alkylgruppe steht und

XT"

für ein physiologisch verträgliches Anion steht.

Within the group of cationic surfactants, the cationic ammonium compounds of the formula (II) have proven to be particularly suitable because of their particularly good effectiveness in the decolorizing agent

whereby

RT1, RT2

independently represent a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group or a hydroxy-C ₂ -C ₆ alkyl group,

RT3

represents a hydroxy-C ₂ -C ₆ -alkyl group, a C ₁ -C ₇ -alkyl group, a C ₈ -C ₃₀ -alkyl group, or a C ₂ -C ₆ -alkenyl group,

RT4

stands for a C ₈ -C ₃₀ alkyl group and

xt"

stands for a physiologically tolerable anion.

wobei

RT1, RT2

unabhängig voneinander für eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe oder eine Hydroxy-C₂-C₆-alkylgruppe stehen,

RT3

für eine Hydroxy-C₂-C₆-alkylgruppe, eine C₁-C₇-Alkylgruppe, eine C₈-C₃₀-Alkylgruppe oder für eine C₂-C₆-Alkenylgruppe steht,

RT4

für eine C₈-C₃₀-Alkylgruppe steht und

XT''

für ein physiologisch verträgliches Anion steht.

In a further preferred embodiment, a decolorizing agent according to the invention is therefore characterized in that it contains at least one cationic surfactant which is selected from cationic surfactants of the general formula (T-1),

whereby

RT1, RT2

independently represent a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group or a hydroxy-C ₂ -C ₆ alkyl group,

RT3

represents a hydroxy-C ₂ -C ₆ -alkyl group, a C ₁ -C ₇ -alkyl group, a C ₈ -C ₃₀ -alkyl group or a C ₂ -C ₆ -alkenyl group,

RT4

stands for a C ₈ -C ₃₀ alkyl group and

XT''

stands for a physiologically tolerable anion.

RT1 and RT2 are preferably each independently a C ₁ -C ₆ -alkyl group. It is particularly preferred if RT1 and RT2 independently represent a methyl group, an ethyl group or an n-propyl group. In a very particularly preferred embodiment, RT1 and RT2 both represent a methyl group or both represent an ethyl group.

RT4 and optionally RT3 stand for a C ₈ -C ₃₀ alkyl group. These alkyl groups can be branched or unbranched, saturated or unsaturated. If the C ₈ -C ₃₀ -alkyl group is unsaturated, it can be mono- or polyunsaturated, ie it can have one or more double bonds.

RT3 is preferably a hydroxy-C ₂ -C ₆ -alkyl group. RT3 is very particularly preferably a 2-hydroxyethyl group.

If RT4 stands for a linear, saturated C ₁₆ -C ₂₂ -alkyl group, this has a particularly advantageous effect on the deinking performance of the deinking agent. RT4 is therefore preferably a linear, saturated C ₁₆ -C ₂₂ -alkyl group. It is very particularly preferred if RT4 stands for a linear, saturated C ₁₆ -C ₁₈ -alkyl group.

RT1, RT2

unabhängig voneinander für eine C₁-C₆-Alkylgruppe, bevorzugt für eine Methylgruppe oder für eine Ethylgruppe, stehen,

RT3

für eine Hydroxy-C₂-C₆-alkylgruppe oder für eine C₁-C₇-Alkylgruppe, bevorzugt für eine Methylgruppe, eine Ethylgruppe oder für eine 2-Hydroxyethylgruppe, steht,

RT4

für eine C₁₂-C₃₀-Alkylgruppe, bevorzugt für eine C₁₂-C₂₂-Alkylgruppe, weiter bevorzugt für eine C₁₂-C₁₈-Alkylgruppe und ganz besonders bevorzugt für eine C₁₆-Alkylgruppe oder für eine C₁₈-Alkylgruppe steht, und

XT-

für ein physiologisch verträgliches Anion aus der Gruppe aus Dihydrogenphosphat, Hydrogenphosphat, Phosphat, Chlorid, Bromid, Fluorid, Acetat, Lactat, Methylsulfat, Ethylsulfat, p-Toluolsulfonat, Citrat, Tartrat, Maleat oder Fumarat steht.

In a further very particularly preferred embodiment, a decolorizing agent according to the invention is therefore characterized in that it contains at least one cationic surfactant of the general formula (T-1), where

RT1, RT2

independently represent a C ₁ -C ₆ -alkyl group, preferably a methyl group or an ethyl group,

RT3

represents a hydroxy-C ₂ -C ₆ -alkyl group or a C ₁ -C ₇ -alkyl group, preferably a methyl group, an ethyl group or a 2-hydroxyethyl group,

RT4

stands for a C ₁₂ -C ₃₀ alkyl group, preferably for a C ₁₂ -C ₂₂ alkyl group, more preferably for a C ₁₂ -C ₁₈ alkyl group and very particularly preferably for a C ₁₆ alkyl group or for a C ₁₈ alkyl group , and

XT

stands for a physiologically tolerable anion from the group consisting of dihydrogen phosphate, hydrogen phosphate, phosphate, chloride, bromide, fluoride, acetate, lactate, methyl sulfate, ethyl sulfate, p-toluenesulfonate, citrate, tartrate, maleate or fumarate.

RT1, RT2

beide für eine Methylgruppe stehen,

RT3

für eine Methylgruppe steht,

RT4

für eine lineare, gesättigte C₁₆-C₁₈-Alkylgruppe steht.

In a further very particularly preferred embodiment, a decolorizing agent according to the invention is characterized in that it contains at least one cationic surfactant (b) of the general formula (T-1), where

RT1, RT2

both stand for a methyl group,

RT3

stands for a methyl group,

RT4

stands for a linear, saturated C ₁₆ -C ₁₈ alkyl group.

Particularly preferred cationic surfactants of the formula (T-1) are, for example, physiologically tolerable salts of cetyltrimethylammonium. A particularly suitable cationic surfactant of this type is, for example, trimethylhexadecylammonium chloride, which can alternatively also be referred to as N,N,N-trimethyl-1-hexadecanaminium chloride, commercially available from BASF under the trade name Dehyquart A CA.

Other likewise preferred cationic surfactants of the formula (T-1) are physiologically tolerable salts of hexadecyl(2-hydroxyethyl)dimethylammonium. For example, the raw material hexadecyl(2-hydroxyethyl)dimethylammonium dihydrogen phosphate (CAS number 85563-48-0) is sold commercially by BASF under the trade name Luviquat Mono CP.

Also preferred are salts of trimethylstearylammonium, in particular trimethylstearylammonium chloride, which is also commercially available under the trade name Genamin STAC. Further particularly preferred cationic surfactants of the formula (I) are salts of trimethyl-1-eicosanaminium, in particular trimethyl-1-eicosanaminium chloride, and salts of trimethyl-1-docosanaminium, in particular trimethyl-1-docosanaminium chloride. A mixture of both compounds is available under the trade name Genamin KDMP from Clariant.

Other suitable cationic surfactants (b) can also be selected from the group of cationic imidazolium compounds. Within the group of cationic imidazolium compounds, compounds of the formula (T-II) have likewise proven to be particularly advantageous with regard to use in a decolorizing process.

worin

RT5

für eine C₁-C₆-Alkylgruppe steht

RT6, RT7

unabhängig voneinander für eine C₇-C₂₇-Alkylgruppe stehen und

XT-

für ein physiologisch verträgliches Anion steht.

In a further embodiment, a decolorizing agent according to the invention is characterized in that it contains at least one cationic surfactant of the formula (T-II),

wherein

RT5

stands for a C ₁ -C ₆ alkyl group

RT6, RT7

independently represent a C ₇ -C ₂₇ alkyl group and

XT

stands for a physiologically tolerable anion.

RT6 and RT7 each independently represents a C ₇ -C ₂₇ alkyl group. These alkyl groups can be branched or unbranched, saturated or unsaturated. If the C ₇ -C ₂₇ alkyl group is unsaturated, it can be mono- or polyunsaturated, ie it can have one or more double bonds.

RT5 is a C ₁ -C ₆ -alkyl group, very particularly preferably RT5 is a methyl group or an ethyl group.

RT5

für eine Methylgruppe steht,

RT6, RT7

unabhängig voneinander für eine C₈-C₂₇-Alkylgruppe stehen und

X'

für ein physiologisch verträgliches Anion steht.

The deinking agent of the present invention gave particularly good results when it contained a cationic surfactant of the formula (T-II) in which

RT5

stands for a methyl group,

RT6, RT7

independently represent a C ₈ -C ₂₇ alkyl group and

X'

stands for a physiologically tolerable anion.

Particularly preferred compounds of the formula (T-II) are known under the INCI name Quaternium-87, which are also marketed under the trade names Varisoft W 575 PB or Revoquat PG 75.

worin

RT8, RT9

unabhängig voneinander für eine C₁-C₆-Alkylgruppe oder eine C₂-C₆-Hydroxyalkylgruppe stehen,

RT10, RT11

unabhängig voneinander für eine C₇-C₂₇-Alkylgruppe stehen und

XV'T

für ein physiologisch verträgliches Anion steht.

In addition, a decolorizing agent with high performance with regard to the color print could be obtained if at least one compound from the group of ester quats was used as the cationic surfactant. The name esterquats is a collective term for cationic surface-active compounds with two hydrophobic groups linked via ester bonds to a quaternized di- or triethanolamine or an analogous compound. Very particularly suitable esterquats are the compounds of the formula (T-III),

wherein

RT8, RT9

independently represent a C ₁ -C ₆ -alkyl group or a C ₂ -C ₆ -hydroxyalkyl group,

RT10, RT11

independently represent a C ₇ -C ₂₇ alkyl group and

XV'T

stands for a physiologically tolerable anion.

worin

RT8, RT9

unabhängig voneinander für eine C₁-C₆-Alkylgruppe oder eine C₂-C₆-Hydroxyalkylgruppe stehen,

RT10, RT11

unabhängig voneinander für eine C₇-C₂₇-Alkylgruppe stehen und

XT-

für ein physiologisch verträgliches Anion steht.

In a further particularly preferred embodiment, a decolorizing agent according to the invention is characterized in that it contains at least one cationic surfactant of the formula (T-III),

wherein

RT8, RT9

independently represent a C ₁ -C ₆ -alkyl group or a C ₂ -C ₆ -hydroxyalkyl group,

RT10, RT11

independently represent a C ₇ -C ₂₇ alkyl group and

XT

stands for a physiologically tolerable anion.

The substituents of the compound of formula (TI) to (T-III) are exemplified below: Examples of a C ₁ -C ₆ alkyl group are the groups methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl and t -butyl, n-pentyl and n-hexyl. Propyl, ethyl and methyl are preferred alkyl radicals. Examples of a C ₂ -C ₆ -alkenyl group are vinyl, allyl, but-2-enyl, but-3-enyl and isobutenyl, preferred C ₂ -C ₆ -alkenyl radicals are vinyl and allyl. Preferred examples of a hydroxy-C ₁ -C ₆ -alkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 2-hydroxypropyl, a 3-hydroxypropyl, a 4-hydroxybutyl group, a 5-hydroxypentyl and a 6-hydroxyhexyl group ; a 2-hydroxyethyl group is particularly preferred.

XT ^- in the formulas (TI) to (T-III) each represents a physiologically tolerable anion. Suitable physiologically tolerable anions are phosphate, hydrogen phosphate, dihydrogen phosphate, halide, hydrogen sulfate, sulfate, benzenesulfonate, p-toluenesulfonate, acetate, citrate, lactate, tartrate, methyl sulfate (H ₃ COSO ₃ ^- ), methyl sulfonate or trifluoromethane sulfonate. A ^- is particularly preferably chloride, bromide or methyl sulfate (H ₃ COSO ₃ ^- ).

By choosing the optimized amounts of one or more cationic surfactants (b) used in the decolorizing agent according to the invention, its performance properties can be further improved. The decolorizing agent preferably contains—based on its total weight—one or more cationic surfactants (b) in a total amount of from 0.1 to 20.0% by weight, preferably from 0.5 to 12.0% by weight, more preferably from 1.0 to 6.0% by weight and most preferably from 1.2 to 3.5% by weight.

In a further preferred embodiment, a decolorizing agent according to the invention is therefore characterized in that - based on the total weight of the decolorizing agent - it contains one or more cationic surfactants (b) in a total amount of from 0.1 to 20.0% by weight, preferably from 0 5 to 12.0% by weight, more preferably from 1.0 to 6.0% by weight and very particularly preferably from 1.2 to 3.5% by weight.

Acids in the decolorizing agent

The decolorizing agent according to the invention contains one or more acids (c) as the third ingredient essential to the invention.

Suitable acids can be selected from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid, citric acid, tartaric acid, malic acid, lactic acid, acetic acid, methanesulfonic acid, benzoic acid, malonic acid, oxalic acid and 1-hydroxyethane-1,1-diphosphonic acid.

In a further particularly preferred embodiment, a decolorizing agent according to the invention is characterized in that it contains at least one acid (c) from the group consisting of sulfuric acid, Hydrochloric acid, phosphoric acid, citric acid, tartaric acid, malic acid, lactic acid, acetic acid, methanesulfonic acid, benzoic acid, malonic acid, oxalic acid and 1-hydroxyethane-1,1-diphosphonic acid, particularly preferably sulfuric acid.

The use of sulfuric acid (c) is explicitly very particularly preferred.

The use of the acid(s) in the agent (c) ensures that a pH value is set in the acidic range, which has proved to be particularly advantageous with regard to the further improvement in the deinking performance.

A particularly good decolorizing effect was observed when the decolorizing agent according to the invention was adjusted to a pH in the range from 1.0 to 6.5, preferably from 2.0 to 6.0, more preferably from 2.5 to 5.5 and completely particularly preferably from 3.0 to 5.5.

In a further particularly preferred embodiment, a decolorizing agent according to the invention is characterized in that it has a pH of from 1.0 to 6.5, preferably from 2.0 to 6.0, more preferably from 2.5 to 5.5 and most preferably from 3.0 to 5.5.

water content

The decolorizing agents according to the invention are further characterized in that they contain water (d) as the fourth ingredient essential to the invention.

The deinking performance can be further improved by adjusting the water content to very specific quantity ranges. For this reason, it has turned out to be particularly preferred if the decolorizing agent—based on its total weight—contains 50 to 95% by weight, preferably 55 to 95% by weight, more preferably 60 to 95% by weight preferably 65 to 95% by weight and very particularly preferably 70 to 95% by weight of water (d).

Within the scope of a further embodiment, a particularly preferred agent according to the invention is characterized in that, based on the total weight of the agent, it contains 50 to 95% by weight, preferably 55 to 95% by weight, more preferably 60 to 95% by weight , more preferably 65 to 95% by weight and very particularly preferably 70 to 95% by weight of water (d).

1. (a) mindestens eine Fluorverbindung, und
2. (b) mindestens ein kationisches Tensid der allgemeinen Formel (T-1),
   
   wobei

   RT1, RT2

   unabhängig voneinander für eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe oder eine Hydroxy-C₂-C₆-alkylgruppe stehen,

   RT3

   für eine Hydroxy-C₂-C₆-alkylgruppe, eine C₁-C₇-Alkylgruppe, eine C₈-C₃₀-Alkylgruppe oder für eine C₂-C₆-Alkenylgruppe steht,

   RT4

   für eine C₈-C₃₀-Alkylgruppe steht und

   XT'

   für ein physiologisch verträgliches Anion steht, und

3. (c) Schwefelsäure und/oder Salzsäure und
4. (d) Wasser.

Within the scope of a further embodiment, an agent for decolorizing colored keratin material is preferred

1. (a) at least one fluorine compound, and
2. (b) at least one cationic surfactant of general formula (T-1),
   
   whereby

   RT1, RT2

   independently represent a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group or a hydroxy-C ₂ -C ₆ alkyl group,

   RT3

   represents a hydroxy-C ₂ -C ₆ -alkyl group, a C ₁ -C ₇ -alkyl group, a C ₈ -C ₃₀ -alkyl group or a C ₂ -C ₆ -alkenyl group,

   RT4

   stands for a C ₈ -C ₃₀ alkyl group and

   XT'

   stands for a physiologically tolerable anion, and

3. (c) sulfuric acid and/or hydrochloric acid and
4. (d) water.

1. (a) mindestens eine Fluorverbindung, und
2. (b) mindestens ein kationisches Tensid der allgemeinen Formel (T-1),
   
   wobei

   RT1, RT2

   unabhängig voneinander für eine C₁-C₆-Alkylgruppe stehen,

   RT3

   für eine C₁-C₇-Alkylgruppe steht,

   RT4

   für eine C₈-C₃₀-Alkylgruppe steht und

   XT-

   für ein physiologisch verträgliches Anion steht, und

3. (c) Schwefelsäure und/oder Salzsäure, und
4. (d) Wasser.

Within the scope of a further embodiment, an agent for decolorizing colored keratin material is preferred

1. (a) at least one fluorine compound, and
2. (b) at least one cationic surfactant of general formula (T-1),
   
   whereby

   RT1, RT2

   independently represent a C ₁ -C ₆ alkyl group,

   RT3

   stands for a C ₁ -C ₇ -alkyl group,

   RT4

   stands for a C ₈ -C ₃₀ alkyl group and

   XT

   stands for a physiologically tolerable anion, and

3. (c) sulfuric acid and/or hydrochloric acid, and
4. (d) water.

Other cosmetic ingredients in the decolorizing agent

In addition to the ingredients that are essential to the invention and can be used optionally, the decolorizing agent can also contain one or more other cosmetic ingredients.

The person skilled in the art will select these further substances in accordance with the desired properties of the agents. With regard to other optional components and the amounts of these components used, express reference is made to the relevant handbooks known to those skilled in the art.

Process for decolorizing colored keratin material

The decolorizing agent described above is used in the decolorization of colored keratinous material, in particular keratin fibers, particularly preferably human hair.

A second subject of the present invention is a method for decolorizing colored keratin material, wherein a decolorizing agent, as disclosed in the description of the first subject of the invention in detail, applied to the colored keratin material and after an exposure time of 1 to 60 minutes, preferably from 1 to 50 minutes, more preferably from 2 to 45 minutes and most preferably from 5 to 20 minutes is rinsed off again.

A method for decolorizing human hair is preferred, in which a decolorizing agent, which was disclosed in detail in the description of the first subject of the invention, is applied to the colored hair and after an exposure time of 1 to 60 minutes, preferably 1 to 50 minutes, more preferred from 2 to 45 minutes and most preferably from 5 to 20 minutes.

In one embodiment, a process for decolorizing keratinic material that has been colored by using at least one organic C ₁ -C ₆ -alkoxysilane and/or a condensation product thereof and by using at least one pigment is particularly preferred, with a decolorizing agent , as disclosed in detail in the description of the first subject of the invention, applied to the colored keratin material and after an exposure time of 1 to 60 minutes, preferably 1 to 50 minutes, more preferably 2 to 45 minutes and very particularly preferably 5 to Rinse off again after 20 minutes.

Within the method according to the invention, the decolorizing agent is applied to the colored keratin material and rinsed off again after a contact time. Since the decolorizing agent is applied to the colored keratin material or hair, the decolorizing agent must be applied to the keratin material after the application of the coloring agent described above.

In other words, the decolorizing agent is applied to the keratinous material after the coloring agent has been rinsed out and the keratinous material preferably dried to accurately determine the color result.

The application can take place, for example, with the (glove-protected) hand or with the aid of an applicator, such as a brush or an aplicet, or else a brush or a comb.

Depending on whether the user wants a complete discoloration, or whether only certain parts or. If strands are to be decolorized, the decolorizing agent can be applied either to the entire keratinous material (such as the entire head of hair) or to specific portions or corresponding strands of the keratinous material or keratin fibers.

The exact point in time at which the decolorizing agent is used is determined by the user's desire to remove the unwanted or no longer required coloring. For example, the decolorizing agent can be applied to the stained keratin material 12 to 24 hours after application of the coloring agent. In a further embodiment, the user can wear the colored keratin materials, in particular the hair, but also for a period of several days to weeks until he decides to change the coloring again or the user wants to have his original hair color back.

After application or application, the decolorizing agent is allowed to act on the keratin material for a certain period of time. For example, the exposure time of 1 to 60 minutes, preferably 1 to 50 minutes, more preferably 2 to 45 minutes and very particularly preferably 5 to 20 minutes, can be rinsed off again. The action of the decolorizing agent on the keratin material can be carried out at room temperature or at body temperature. However, to support or accelerate the color print, the keratin material to which the decolorizing agent has been applied can also be exposed to elevated temperatures. It is in accordance with the invention if the decolorizing agent is applied to the colored keratin material, the keratin material is heated to a temperature of 25 to 70°, preferably 25 to 60° C., more preferably 30 to 55° C. and very particularly preferably while the decolorizing agent is acting on it 40 to 55 °C is heated.

• - das Entfärbemittel auf das gefärbte Keratinmaterial aufgetragen wird
• - das Keratinmaterial während des Einwirkens des Entfärbemittels auf eine Temperatur von 25 bis 70 °, bevorzugt von 25 bis 60 °C, weiter bevorzugt von 30 bis 55 °C und ganz besonders bevorzugt von 40 bis 55 °C erhitzt wird, und dann
• - das Entfärbemittel wieder abgespült wird.

As part of a further b embodiment, a method according to the invention is characterized in that

• - the decolorizing agent is applied to the colored keratin material
• - the keratinous material is heated to a temperature of 25 to 70°C, preferably 25 to 60°C, more preferably 30 to 55°C and very particularly preferably 40 to 55°C during the action of the bleaching agent, and then
• - the decolorizing agent is rinsed off again.

In addition to the thermal support of the bleaching process, it is also possible to subject the keratin material to which the bleaching agent has applied mechanical stress in order to improve the detachment of the film formed on the keratin material during staining. For example, the keratin material can be massaged with the hands or combed with a comb or brush during the bleaching process. Also any other mechanical stress that is suitable is to improve the detachment of the colored film from the keratin material under the action of the decolorizing agent is conceivable and encompassed by the method according to the invention.

• - das Entfärbemittel auf das gefärbte Keratinmaterial aufgetragen wird,
• - das Keratinmaterial während des Einwirkens des Entfärbemittels gekämmt, massiert, gebürstet oder auf eine andere Weise einer mechanischen Krafteinwirkung ausgesetzt wird, und dann
• - das Entfärbemittel wieder abgespült wird.

In a further preferred embodiment, a method according to the invention is characterized in that

• - the decolorizing agent is applied to the colored keratin material,
• - combing, massaging, brushing or otherwise subjecting the keratinous material to mechanical force during exposure to the decolorizing agent, and then
• - the decolorizing agent is rinsed off again.

As already described above, the decolorizing agent according to the invention can be used to decolorize keratin material which has been colored by using at least one organosilicon compound and at least one pigment. For example, if the user finds after coloring that the color result is not what he wants, he can use this as an opportunity to remove the coloring by using the decolorizing agent.

Furthermore, the user can also plan coloring and later decolorization from the outset, for example if he wants to color his hair for a specific occasion and then decolorize it again. For this purpose, the user can also be provided with all the means or formulations that are necessary both for coloring and for decolorizing.

• (1) Auftragen eines Färbemittels auf die Haare, wobei das Färbemittel ein oder mehrere organische C₁-C₆-Alkoxy-Silane und/oder deren Kondensationsprodukte, und ein oder mehrere Pigmente enthält,
• (2) Einwirkenlassen des Färbemittels auf die Haare,
• (3) Ausspülen des Färbemittels aus den Haaren,
• (4) Auftragen eines Entfärbemittels, wie es bei der Beschreibung des ersten Erfindungsgegenstands im Detail offenbart wurde, auf die Haare,
• (5) Einwirkenlassen des Entfärbemittels auf die Haare und
• (6) Ausspülen des Entfärbemittels aus den Haaren.

Another subject of the present invention is therefore a method for coloring and later decolorizing human hair, comprising the following steps:

• (1) applying a coloring agent to the hair, the coloring agent containing one or more organic C ₁ -C ₆ -alkoxysilanes and/or their condensation products and one or more pigments,
• (2) allowing the dye to act on the hair,
• (3) rinsing the dye from the hair,
• (4) applying a bleaching agent as disclosed in detail in the description of the first aspect of the invention to the hair,
• (5) allowing the hair to act with the bleach and
• (6) Rinsing the decolorizing agent from the hair.

• (1) Auftragen eines Färbemittels auf die Haare, wobei das Färbemittel ein oder mehrere organische C₁-C₆-Alkoxy-Silane und/oder deren Kondensationsprodukte, und ein oder mehrere Pigmente enthält,
• (2) Einwirkenlassen des Färbemittels auf die Haare,
• (3) Ausspülen des Färbemittels aus den Haaren,
• (4) Auftragen eines Nachbehandlungsmittels auf die Haare, wobei das Nachbehandlungsmittel mindestens ein filmbildendes Polymer enthält,
• (5) Einwirkenlassen des Nachbehandlungsmittels auf die Haare,
• (6) Ausspülen des Nachbehandlungsmittels aus den Haaren,
• (7) Auftragen eines Entfärbemittels, wie bei der Beschreibung des ersten Erfindungsgegenstand im Detail offenbart wurde, auf die Haare,
• (8) Einwirkenlassen des Entfärbemittels auf die Haare und
• (9) Ausspülen des Entfärbemittels aus den Haaren.

Another subject of the present invention is therefore a method for coloring and later decolorizing human hair, comprising the following steps:

• (1) applying a coloring agent to the hair, the coloring agent containing one or more organic C ₁ -C ₆ -alkoxysilanes and/or their condensation products and one or more pigments,
• (2) allowing the dye to act on the hair,
• (3) rinsing the dye from the hair,
• (4) applying an aftertreatment agent to the hair, the aftertreatment agent containing at least one film-forming polymer,
• (5) allowing the aftertreatment agent to act on the hair,
• (6) rinsing the after-treatment agent out of the hair,
• (7) applying a bleaching agent as disclosed in detail in the description of the first subject of the invention to the hair,
• (8) allowing the hair to act with the bleach and
• (9) Rinsing the decolorizing agent from the hair.

• (4) Auftragen eines Färbemittels auf die Haare, wobei Färbemittel ein oder mehrere Pigmente und ein oder mehrere filmbildende Polymere enthält.

Within the scope of a further embodiment, preference is also given to a corresponding method comprising the

• (4) applying a colorant to the hair, the colorant containing one or more pigments and one or more film-forming polymers.

• (1) Auftragen eines Vorbehandlungsmittels auf die Haare, wobei das Vorbehandlungsmittel ein oder mehrere organische C₁-C₆-Alkoxy-Silane und/oder deren Kondensationsprodukte enthält,
• (2) Einwirkenlassen des Vorbehandlungsmittels auf die Haare,
• (3) Ausspülen des Vorbehandlungsmittels aus den Haaren,
• (4) Auftragen eines Färbemittels auf die Haare, wobei Färbemittel ein oder mehrere Pigmente enthält,
• (5) Einwirkenlassen des Färbemittels auf die Haare,
• (6) Ausspülen des Färbemittels aus den Haaren,
• (7) Auftragen eines Entfärbemittels, wie es bei der Beschreibung des ersten Erfindungsgegenstands im Detail offenbart wurde, auf die Haare,
• (8) Einwirkenlassen des Entfärbemittels auf die Haare und
• (9) Ausspülen des Entfärbemittels aus den Haaren.

Another subject of the present invention is also a method for coloring and later decolorizing human hair, comprising the following steps:

• (1) Application of a pretreatment agent to the hair, the pretreatment agent containing one or more organic C ₁ -C ₆ -alkoxysilanes and/or their condensation products,
• (2) allowing the pre-treatment agent to act on the hair,
• (3) rinsing the pre-treatment agent from the hair,
• (4) applying a colorant to the hair, the colorant containing one or more pigments,
• (5) allowing the dye to act on the hair,
• (6) rinsing the dye from the hair,
• (7) applying a bleaching agent as disclosed in detail in the description of the first aspect of the invention to the hair,
• (8) allowing the hair to act with the bleach and
• (9) Rinsing the decolorizing agent from the hair.

The organic C ₁ -C ₆ -alkoxysilanes and/or their condensation products have already been disclosed in detail in the description of the first subject of the invention. The pigments have already been disclosed in detail in the description of the first subject of the invention. The decolorizing agent has already been disclosed in detail in the description of the first subject of the invention.

• (4) Auftragen eines Färbemittels auf die Haare, wobei Färbemittel ein oder mehrere Pigmente und ein oder mehrere filmbildende Polymere enthält.

In the context of a further embodiment, a corresponding method is preferred, comprising

• (4) applying a colorant to the hair, the colorant containing one or more pigments and one or more film-forming polymers.

The film-forming polymers have already been disclosed in detail in the description of the first subject of the invention.

Regarding the other preferred embodiments of the method according to the invention, what was said about the methods according to the invention applies mutatis mutantis.

Multi-component packaging unit

It is particularly convenient for the user if the corresponding coloring and decolorizing agents are made available to him in the form of a multi-component packaging unit.

• - einen ersten Container mit einem Mittel, welches ein oder mehrere organische C₁-C₆-Alkoxy-Silane und/oder deren Kondensationsprodukte enthält,
• - einen zweiten Container mit einem Mittel, welches mindestens ein Pigment enthält, und
• - einen dritten Container, welcher ein Entfärbemittel enthält, wie es bei der Beschreibung des ersten Erfindungsgegenstand im Detail offenbart wurde.

A further object of the present invention is therefore a multi-component packaging unit (kit-of-parts) for coloring and decolorizing keratin material, comprising made up separately from one another:

• - a first container with an agent containing one or more organic C ₁ -C ₆ -alkoxysilanes and/or their condensation products,
• - a second container with an agent containing at least one pigment, and
• - a third container containing a decolorizing agent as disclosed in detail in the description of the first subject of the invention.

• - einen ersten Container mit einem Mittel, welches ein oder mehrere organische C₁-C₆-Alkoxy Silane und/oder deren Kondensationsprodukte enthält,
• - einen zweiten Container mit einem Mittel, welches mindestens ein Pigment enthält,
• - einen dritten Container, welcher ein Entfärbemittel enthält, wie es bei der Beschreibung des ersten Erfindungsgegenstand im Detail offenbart wurde, und
• - gegebenenfalls einen vierten Container mit einem Mittel, welches mindestens ein filmbildendes Polymer enthält.

A further object of the present invention is therefore a multi-component packaging unit (kit-of-parts) for coloring and decolorizing keratin material, comprising made up separately from one another:

• - a first container with an agent containing one or more organic C ₁ -C ₆ -alkoxy silanes and/or their condensation products,
• - a second container with an agent containing at least one pigment,
• - a third container containing a decolorizing agent as disclosed in detail in the description of the first subject of the invention, and
• - optionally a fourth container with an agent containing at least one film-forming polymer.

The organic C ₁ -C ₆ -alkoxysilanes and/or their condensation products have already been disclosed in detail in the description of the first subject of the invention. The pigments have already been disclosed in detail in the description of the first subject of the invention. The decolorizing agent has already been disclosed in detail in the description of the first subject of the invention.

With regard to the other preferred embodiments of the multi-component packaging unit according to the invention, the statements made regarding the agents and methods according to the invention apply mutatis mutantis.

examples

The following decolorizing agents were prepared (all data, unless otherwise stated, in % by weight) Discolorant 1 wt% potassium fluoride 4.0 cetyltrimethylammonium chloride 2.5 Polyquaternium-37 2-(Trimethylammonio)ethyl methacrylate chloride homopolymer 4.0 Hydrochloric acid 37% 2.2 Euxyl PE 9010 (phenoxyethanol, ethylhexylglycerol, Schülke & Mayr) 1.0 water (distilled) to 100 destainer 2 wt% sodium fluoride 4.0 cetyltrimethylammonium chloride 2.5 Polyquaternium-37 2-(Trimethylammonio)ethyl methacrylate chloride homopolymer 4.0 Hydrochloric acid 37% 2.2 Euxyl PE 9010 (phenoxyethanol, ethylhexylglycerol, Schülke & Mayr) 1.0 water (distilled) to 100 decolorizer 3 wt% potassium fluoride 4.0 cetyltrimethylammonium chloride 2.5 hydroxyethyl cellulose 1.5 Hydrochloric acid 37% 2.2 Euxyl PE 9010 (phenoxyethanol, ethylhexylglycerol, Schülke & Mayr) 1.0 water (distilled) to 100 destainer 4 wt% sodium fluoride 4.0 cetyltrimethylammonium chloride 2.5 hydroxyethyl cellulose 1.5 Hydrochloric acid 37% 2.2 Euxyl PE 9010 (phenoxyethanol, ethylhexylglycerol, Schülke & Mayr) 1.0 water (distilled) to 100

QUOTES INCLUDED IN DESCRIPTION

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

Patent Literature Cited

• EP 2168633 B1 [0007]

Claims (13)

Composition for decolorizing colored keratin material containing (a) at least one fluorine compound, (b) at least one cationic surfactant, (c) at least one acid and (d) water. means after claim 1 , characterized in that it is an agent for decolorizing keratinous material which has been colored by using at least one organic C ₁ -C ₆ -alkoxysilane and/or a condensation product thereof and by using at least one pigment. Means after one of Claims 1 until 2 , characterized in that it contains at least one fluorine compound (a) selected from the group consisting of potassium fluoride, sodium fluoride, tetrabutylammonium fluoride, sodium monofluorophosphate, zinc fluoride, tin fluoride, sodium fluorosilicate, cetylamine hydrofluoride and bis(hydroxyethyl)aminopropyl-N-hydroxyethyloctadecylamine dihydrofluoride . Means after one of Claims 1 until 3 , characterized in that it - based on its total weight - one or more fluorine compounds (a) in a total amount of 0.5 to 9.0 wt .-%, preferably from 1.5 to 8.0 wt .-%, further preferably from 2.0 to 7.0% by weight and most preferably from 2.5 to 6.0% by weight. Means after one of Claims 1 until 4 , characterized in that it contains at least one cationic surfactant (b) of the formula (T-1),

where RT1, RT2 independently stand for a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group or a hydroxy-C ₂ -C ₆ -alkyl group, RT3 for a hydroxy-C ₂ -C ₆ -alkyl group, a C ₁ -C ₆ alkyl group, a C ₈ -C ₃₀ alkyl group, or a C ₂ -C ₆ alkenyl group, RT4 stands for a C ₈ -C ₃₀ alkyl group and XT ^- stands for a physiologically tolerable anion . means after claim 5 , characterized in that it contains at least one cationic surfactant (b) of the formula (T-1), where RT1, RT2 independently represent a C ₁ -C ₆ -alkyl group, preferably a methyl group or an ethyl group, RT3 represents a C ₁ -C ₆ -alkyl group or a hydroxy-C ₂ -C ₆ -alkyl group, preferably a methyl group, an ethyl group or a 2-hydroxyethyl group, RT4 represents a C ₁₂ -C ₃₀ -alkyl group, preferably a C ₁₂ -C ₂₂ -alkyl group, more preferably a C ₁₂ -C ₁₈ -alkyl group and very particularly preferably a C ₁₆ -alkyl group or a C ₁₈ -alkyl group, and XT- stands for a physiologically tolerable anion from the group of chloride, bromide, fluoride, dihydrogen phosphate, hydrogen phosphate, phosphate, acetate, lactate, methyl sulfate, ethyl sulfate, p-toluenesulfonate, citrate, tartrate, maleate or fumaric species. Means after one of Claims 1 until 6 , characterized in that - based on the total weight of the agent - one or more cationic surfactants (b) in a total amount of 0.1 to 20.0 wt .-%, preferably from 0.5 to 15.0 wt .-%. %, more preferably from 1.0 to 9.0% by weight and most preferably from 1.5 to 3.5% by weight. Means after one of Claims 1 until 7 , characterized in that it contains at least one acid (c) from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid, citric acid, tartaric acid, malic acid, lactic acid, acetic acid, methanesulfonic acid, benzoic acid, malonic acid, oxalic acid and 1-hydroxyethane-1,1-diphosphonic acid, particularly preferably sulfuric acid. Means after one of Claims 1 until 8th , characterized in that it has a pH of 1.0 to 6.5, preferably from 2.0 to 6.0, more preferably from 2.5 to 5.5 and very particularly preferably from 3.0 to 5, 5 owns. Means after one of Claims 1 until 9 , characterized in that it - based on the total weight of the agent - 50 to 95 wt .-%, preferably 55 to 95 wt .-%, more preferably 60 to 95 wt .-%, even more preferably 65 to 95 wt .-%. % and very particularly preferably 70 to 95% by weight of water (d). A method for decolorizing colored keratin material, wherein a decolorizing agent according to any one of Claims 1 until 10 applied to the colored keratin material and rinsed off again after an exposure time of 1 to 60 minutes, preferably 1 to 50 minutes, more preferably 2 to 45 minutes and very particularly preferably 5 to 20 minutes. Process for dyeing and later bleaching human hair, comprising the following steps: (1) applying a dye to the hair, the dye containing one or more organic C ₁ -C ₆ -alkoxysilanes and/or their condensation products, and one or contains a plurality of pigments, (2) allowing the hair to act with the colorant, (3) rinsing the hair of the colorant, (4) applying a bleaching agent as described in any of Claims 1 until 10 was defined, on the hair, (5) allowing the hair to act with the bleach and (6) rinsing the hair with the bleach. Multi-component packaging unit (kit-of-parts) for coloring and decolorizing keratin material, comprising made up separately from one another: - a first container with an agent which contains one or more organic C ₁ -C ₆ -alkoxysilanes and/or their condensation products , - a second container with an agent containing at least one pigment, and - a third container containing a decolorizing agent as it is one of Claims 1 until 10 was defined.