EP2934685A2

EP2934685A2 - Gentle dyeing method

Info

Publication number: EP2934685A2
Application number: EP13792660.6A
Authority: EP
Inventors: Matthias Schweinsberg; Jisook Baek; Astrid Kleen; Erik Schulze Zur Wiesche; Antje Gebert; Monika Nebel
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2012-12-19
Filing date: 2013-11-15
Publication date: 2015-10-28
Also published as: US8814952B2; US20140165302A1; WO2014095181A2; DE102012223805A1; WO2014095181A3

Abstract

The invention concerns a method for oxidatively dyeing keratin fibres, in particular hair, wherein: (a) a pre-treatment agent containing at least one 4-morpholinomethyl-substituted silicone of formula (V) is applied to the keratin fibres, in particular hair; and (b) subsequently, within a period of between one second and 24 hours after step (a), a hair dye is applied to the keratin fibres, the dye containing at least one oxidation dye precursor of the developer type and at least one oxidation dye precursor of the coupler type, and at least one oxidizer.

Description

"Hair-gentle dyeing process"

The present invention relates to a gentle process for oxidative hair coloring, in which keratinic fibers are protected from oxidative influences.

The oxidative dyeing of hair poses the problem that scalp irritation and damage to the keratin fiber may occur due to the aggressive agents. In particular, the natural hydrophobicity of the keratinic fiber is reduced because the Färbebzw. Lightening agent must make the hair first penetrate to develop their effect. The water-repellent effect is on the one hand a natural protection of the hair, on the other hand, the consumer desired parameters such as shine, suppleness, grip and "falling" of the hair are closely linked to her.

In order to overcome the mentioned disadvantages, so-called pre-treatment agents are on the market, which should protect the hair from the aggressive influence. However, these often complicate the hair or impair the success of the subsequent lightening or coloring of the hair; in particular, the washfastness of the dyeing may be degraded by the pretreatment agent.

It is an object of the present invention to provide a process for oxidative hair dyeing with a hair-protecting pretreatment which overcomes the mentioned disadvantages, without counteracting the success of a subsequent oxidative dyeing treatment. In particular, a method should be provided in which the hair is not weighted and even with a not immediately before the oxidative dyeing pretreatment achieve the desired effect, whereby the time between pre-treatment and dyeing can be extended.

The use of aminated silicones in hair care is state of the art. These are widely used in shampoos and especially in conditioners to develop nurturing effects there. Thus, EP 1771 144 B1 discloses hair conditioning agents with amino-functional silicones. The agents described there are aftertreatment agents.

The European patents EP 1312334 B1 (aminosilicone and thickener) and EP 1312335 B1 (aminosilicone and conditioner) also disclose hair aftertreatment agents. In the former document also extremely water-rich formulations are disclosed.

It has now been found that a pretreatment of the keratinic fibers with special 4-morpholinomethyl-substituted silicones within a certain period of time before an oxidative dyeing treatment not only leads to markedly improved hair protection without impairing the results of the oxidative dyeing treatment but also particularly good dyeing results , in particular dyeings having a high wash fastness achieved. Hair protection in the sense of the application is understood in particular so that the structure of the keratinic fiber, in particular of the hair, is less affected by the oxidizing agent, so that the surface of the fiber or the hair is roughened less strongly, the hair ends less Splattered, and / or less hair breakage occurs.

The present invention is in a first embodiment, a method for the oxidative coloring of keratinic fibers, in particular of hair, in which

a) a pretreatment agent containing at least one 4-morpholinomethyl-substituted silicone of the formula (V),

for a structural unit (I), (II) or (III) attached via an -O-

or represents an oligomeric or polymeric radical containing an -O- radical, containing structural units of the formulas (I), (II) or (III), or represents half of a connecting O atom to a structural unit (III) or -OH .

* for a bond to one of the structural units (I), (II) or (III) or for a

End group B (Si-bonded) or D (O-linked), B is a group -OH, -O-Si (CH ₃ ) ₃ , -O-Si (CH ₃ ) ₂ OH, -O-Si (CH ₃ ) ₂ OCH ₃ stands,

D is a group -H, -Si (CH ₃ ) ₃ , -Si (CH ₃ ) ₂ OH, -Si (CH ₃ ) ₂ OCH ₃ , a, b and c are integers from 0 to 990, with the proviso a + b + c> 0 m, n and o are integers from 2 to 990,

is applied to the keratinic fibers, especially the hair,

(b) thereafter, within a period of one second to 24 hours after step a), a hair dye is applied to the keratinic fibers containing at least one oxide developer-type dye dye precursor and at least one coupler-type oxidation dye precursor and at least one oxidizing agent.

Pre-treatment agents preferably used in accordance with the invention are characterized in that they comprise the at least one 4-morpholinomethyl-substituted silicone of the formula (V), which in each case has at least one of the structural units of the formulas (I), (II) and (III), in a total amount of 0.001 to 5 wt .-%, preferably 0.005 to 2 wt .-%, particularly preferably 0.01 to 1 wt .-%, most preferably 0.02 to 0.1 wt .-%, each based on the total weight of the pretreatment agent , contain.

Pre-treatment agents preferably used according to the invention are characterized in that they contain the at least one 4-morpholinomethyl-substituted silicone of the formula (V) in water-emulsified form. Pre-treatment agents used with particular preference contain 30-98% by weight, preferably 40-90% by weight, more preferably 50-85% by weight, most preferably 60-80% by weight of water, in each case based on the total weight of the pretreatment agent ,

Pre-treatment agents used with particular preference are in the form of an oil-in-water emulsion in which the number-average size of the silicone particles in the emulsion is in the range from 3 to 500 nm, preferably in the range from 5 to 60 nm.

The structural units of the formulas (I), (II) and (III) can be present randomly distributed in the molecule, but the silicones used according to the invention can also be block copolymers of blocks of the individual structural units, wherein the blocks can again be present statistically distributed.

The ^* at the free valences of the structural units (I), (II) or (III) stands for a bond to one of the structural units (I), (II) or (III) or for an end group B (Si-bonded) or D (O-linked).

The silicones used according to the invention can be trimethylsilyl-terminated on both sides (D = -Si (CH ₃ ) ₃ B = -O-Si (CH ₃ ) ₃ ), but they can also be dimethylsilylhydroxy- or dimethylsilylmethoxy-terminated one or two-sided. Silicones particularly preferably used in the context of the present invention have at least one terminal dimethylsilylhydroxy group, ie are selected from silicones in which

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

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

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

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

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

means. These silicones lead to exorbitant improvements in the hair properties of the hair treated by the method according to the invention, in particular to a serious reduction in the contact angle.

In the structural unit (III), the radical A

for a structural unit (I), (II) or (III) or a group bonded via an -O- or an oligomeric or polymeric radical bonded via an -O- and containing structural units of the formulas (I), (II) or (III)

- or half of a connecting O atom to a structural unit (III) or for -OH. In the former case, the structural unit (III) becomes one of the structural units (IIIa), (IIIb) or (

with m = n = o = 1 and A or D as defined above.

In the second case, in the above-mentioned formulas (IIIa), (IIIb) and (Never), the subscripts m, n and o may stand for integers of 2 to 990. However, the second case also covers oligomeric or polymeric radicals which contain at least two different structural units of the formulas (I), (II) or (III), as shown in formula (IIId):

in the a, b and c are integers from 0 to 990, with the proviso a + b + c> 0 and n and o are integers from 1 to 990. In the third case A is half of a connecting O atom to a structural unit (III) (represents in the structural unit (Never) or for -OH (shown in the structural unit (Nif)

As already mentioned, the structural units of the formulas (I), (II) and (III) can preferably be present in random distribution. Pre-treatment agents preferably used according to the invention contain at least one 4-morpholinomethyl-substituted silicone of the formula (V)

in the

A is a structural unit (I), (II) or (III) attached via an -O- or an oligomeric or polymeric radical bonded via an -O- containing structural units of the formulas (I), (II) or (III) or Half of a connecting O atom to a structural unit (III) or is -OH,

B is a group -OH, -O-Si (CH ₃ ) ₃ , -O-Si (CH ₃ ) ₂ OH, -O-Si (CH ₃ ) ₂ OCH ₃ ,

D for a group -H; -Si (CH ₃ ) ₃ , -Si (CH ₃ ) ₂ OH, -Si (CH ₃ ) ₂ OCH ₃ ,

a, b and c are integers from 0 to 990, with the proviso that a + b + c> 0

n and o stand for integers from 1 to 990.

Structural formula (V) is intended to make it clear that the siloxane groups n and o do not necessarily have to be bound directly to an end grouping B or D, respectively. Rather, in preferred formulas (V) a> 0 or b> 0 and in particularly preferred formulas (V) a> 0 and b> 0, i. the terminal moiety B or D is preferably attached to a dimethylsiloxy moiety. Also in formula (V), the siloxane units a, b, c, n and o are preferably randomly distributed.

The silicones used according to the invention represented by formula (V) may also be trimethylsilyl-terminated on both sides (D = -Si (CH ₃ ) ₃ B = -O-Si (CH ₃ ) ₃ ), but they may also be on or be bilaterally dimethylsilylhydroxy- or dimethylsilylmethoxy-terminated. Silicones particularly preferably used in the context of the present invention have at least one terminal dimethylsilylhydroxy group, ie are selected from silicones in which

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

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

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

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

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

means. These 4-morpholinomethyl-substituted silicone of the formula (V), which in each case has at least one of the structural units of the formulas (I), (II) and (III), lead to surprisingly high improvements in the hair properties of the hair treated according to the method according to the invention, in particular to a dramatically improved hair protection and color protection in oxidative hair coloring.

Also in formula (V), the radical A

for a structural unit (I), (II) or (III) or a group bonded via an -O- or

an oligomeric or polymeric radical bonded via an -O- and containing structural units of the formulas (I), (II) or (III)

- or half of a connecting O atom to a structural unit (III) or for -OH.

Analogous to the comments on the structural unit (III), formula (V) is thus specified to one of the formulas (Va), (Vb), (Vc), (Vd), (Ve) or (Vf):

(Va)

IVD)

The structural unit (III) or the siloxane units o in the formulas (V) can form via the group A nest or partial cage structures, if A stands for a half of a connecting O atom to a structural unit (III). Inventive pretreatment agents containing silicones with corresponding 4-morpholinomethyl-substituted silsesquioxane partial structures are preferred according to the invention, since these silicones result in enormously improved hair protection in the oxidative dyeing treatment.

Pre-treatment agents preferably used according to the invention are characterized in that they contain at least one 4-morpholinomethyl-substituted silicone which has structural units of the formula (VI)

in the

R ₁ , R ₂ , R ₃ and R 4, independently of one another, denote -H, -CH ₃ , a group D, a structural unit (I), (II) or (III) or an oligomeric or polymeric radical comprising structural units of the formulas (I), (II ) or (III) or

two of the radicals R1, R2, R3 and R4 for a structural unit -Si (R6) (R5) - with

R 5 = -CH ₃ or a structural unit of the formula (I) or (II) or (III) or an oligomeric or polymeric radical containing structural units of the formulas (I), (II) or (III)

R 6 = -OH, -CH ₃ , or a structural unit of the formula (I) or (II) or (III) or an oligomeric or polymeric radical containing structural units of the formulas (I), (II) or (III).

In preferred silicones of the formula (VI), at least one of the radicals R 1, R 2, R 3 or R 4 is an oligomeric or polymeric radical containing structural units of the formulas (I), (II) or (III). In further preferred silicones of the formula (VI), at least one of the radicals R 1, R 2, R 3 or R 4 is an oligomeric or polymeric radical containing structural units of the formulas (I) and (II). In still further preferred silicones of the formula (VI), at least one of the radicals R 1, R 2, R 3 or R 4 is an oligomeric or polymeric radical containing structural units of the formulas (I) and (II) and (III).

Preferably, at least one of the radicals R _1, R _2, R ₃ or R _{4 is} a - [- Si (CH ₃ ) ₂ -O] _m - grouping, ie an oligo- or polymer of the structural unit (I). In addition, the structural unit (II) or an oligo- or polymer thereof is preferably never alone, but always bound in a random distribution with further structural units of the formula (I) as one of the radicals R 1, R 2, R 3 or R 4 in the molecule.

Preferred silicones of the formula (VI) can be described by the formula (VI a)

in the

R ₁ , R ₂ and R 4, independently of one another, denote -H, -CH ₃ , a group D, a structural unit (I), (II) or (III) or an oligomeric or polymeric radical comprising structural units of the formulas (I), (II) or (III) stand or

two of the radicals R1, R2 and R4 for a structural unit -Si (R6) (R5) - with

R 6 = -OH, -CH ₃ , or a structural unit of the formula (I) or (II) or (III) or an oligomeric or polymeric radical containing structural units of the formulas (I), (II) or (III)

a, b and c are integers from 0 to 990, with the proviso that a + b + c> 0, n and o are integers from 1 to 990.

Further preferred silicones of the formula (VI) can be described by the formula (VI b)

in which the radicals and indices are as defined above.

Particularly preferred silicones of the formula (VI) can be described by the formula (VIc)

in which the radicals and indices are as defined above and the indices d and e stand for integers from 0 to 990.

In the formulas (VI a), (VI b) and (VI c) n, preferably at least one of the groupings D is -Si (CH ₃ ) ₂ OH.

The silsesquioxane structures can be even more pronounced in the 4-morpholinomethyl-substituted silicones used according to the invention, which enhances the advantageous effects. Particularly preferred pretreatment agents used according to the invention are characterized in that they comprise at least one 4-morpholinomethyl-substituted silicone which has structural units of the formula (VII),

in the

R is a residue 4-morpholinomethyl,

R6 is -H or the grouping

stands,

wherein the siloxane units m, n and o or a, b, c, x and y are present randomly distributed.

Particularly preferably used pretreatment agents according to the invention contain at least one silicone of the following formula (VII a),

(VII a) with the definitions as for formula (VII).

Very particularly preferred pretreatment agents used according to the invention contain at least one silicone of the following formula (VII b)

(VII b) with the definitions as for formula (VII).

In the formulas (VII), (VII a) and (VII b), the bridging oxygen atoms between the morpholinomethyl-substituted silicon atoms can also be represented by a - [- Si (CH ₃ ) ₂ -O] _m grouping, ie an oligo- or polymer of the structural unit (I), be extended. Corresponding pretreatment agents used according to the invention are those which contain at least one 4-morpholinomethyl-substituted silicone which has structural units of the formula (VIII)

in the

A represents a structural unit (I), (II) or (III) attached via an -O- or an oligomeric or polymeric radical bonded via an -O-, containing structural units of the formulas (I), (II) or (III) or is half of a connecting O atom to a structural unit (III) or for -OH,

G1 to G9 independently of one another represent --O- or a group - [- Si (CH ₃ ) ₂ -O] _m - where m = 1 to

200 stand,

R is a residue 4-morpholinomethyl,

R6 is -H or the grouping

stands,

wherein the siloxane units m, n and o or a, b, c, x and y are present randomly distributed. Particularly preferred pretreatment agents used according to the invention comprise at least one silicone of the following formula (VIII a)

(VIII a) with the definitions as for formula (VIII).

Very particularly preferred pretreatment agents used according to the invention comprise at least one silicone of the following formula (VIII b)

(VIII b) with the definitions as for formula (VIII). Regardless of which particular 4-morpholinomethyl-substituted silicone is included in the pretreatment agents used in the invention, pretreatment agents containing a 4-morpholinomethyl-substituted silicone in which more than 50 mol% of the structural units are dimethylsiloxy units are preferred for the process according to the invention are, ie in which the structural unit (I) makes up at least half of all structural units of the silicone used.

In other words, silicones are preferred in which m> (n + o) or (a + b + c)> (n + o).

Still further preferred pretreatment agents used in the present invention include a 4-morpholino methyl substituted silicone in which more than 87.5 mole percent of the structural units are dimethylsiloxy units, i. in which the structural unit (I) makes up more than 875 thousandths of all the structural units of the silicone used.

In other words, silicones are preferred in which m> 8 (n + o) or (a + b + c)> 8 (n + o). Still further preferred pretreatment agents used in the present invention include a 4-morpholino methyl-substituted silicone in which more than 96 mole percent of the structural units are dimethylsiloxy units, i. in which the structural unit (I) is at least ninety-six hundredths of all the structural units of the silicone used.

In other words, silicones are preferred in which m> 25 (n + o) or (a + b + c)> 25 (n + o). Still further preferred pretreatment agents used in the present invention include a 4-morpholino methyl substituted silicone in which more than 98.7 mole percent of the structural units are dimethylsiloxy units, i. in which the structural unit (I) makes up at least nine hundred and seventy-seven thousandths of all the structural units of the silicone used.

In other words, silicones are preferred in which m> 77 (n + o) or (a + b + c)> 77 (n + o). Still further preferred pretreatment agents used in the present invention include a 4-morpholino methyl substituted silicone in which more than 99.5 mole percent of the structural units are dimethylsiloxy units, i. in which the structural unit (I) is at least nine hundred and ninety-five thousandths of all the structural units of the silicone used.

In other words, silicones are preferred in which m> 200 (n + o) or (a + b + c)> 200 (n + o).

In summary, preferred pretreatment agents used according to the invention are characterized in that they contain at least one 4-morpholinomethyl-substituted silicone in which

m> (n + o) or (a + b + c)> (n + o), preferably

m> 8 (n + o) or (a + b + c)> 8 (n + o), more preferably

m> 25 (n + o) or (a + b + c)> 25 (n + o), more preferably

m> 77 (n + o) or (a + b + c)> 77 (n + o) and in particular

- m> 200 (n + o) or (a + b + c)> 200 (n + o).

Another method preferred according to the invention is characterized in that the pretreatment agent used in step a) comprises hydroxy-terminated (s) 4-morpholinomethyl-substituted containing silicone (s) in which the molar ratio hydroxy / alkoxy in the range of 0.2: 1 to 0.4: 1, preferably in the range of 1: 0.8 to 1: 1, 1 lies.

Another preferred process according to the invention is characterized in that the weight-average molar mass of the 4-morpholinomethyl-substituted silicone of the formula (V) used in step a is in the range from 2,000 to 1,000,000 gmol ¹ , preferably in the range from 5,000 to 200,000 gmol ^-1 lies.

The average molar masses of amino-substituted silicones can be measured, for example, by gel permeation chromatography (GPC) at room temperature in polystyrene. As columns Styragel columns μ, as eluent THF and as flow rate 1 ml / min can be selected. The detection is preferably carried out by means of refractometry and UV meter.

Particularly preferred 4-morpholinomethyl-substituted silicones of the formula (V) according to the invention are contained in the raw material Belsil ADM 8301 E (ex Wacker Silicones) under the name amodimethicone / morpholinomethyl silsesquioxane. Belsil ADM 8301 E is a microemulsion and consists of the following constituents: amodimethicone / morpholinomethyl silsesquioxane (10% by weight); Trideceth-5 (5 wt%); Glycerin (2.5% by weight), phenoxyethanol (0.45% by weight) and water (82.05% by weight).

It has been found that the process according to the invention can be further improved if certain nonionic components are likewise present in the pretreatment agents used according to the invention. In addition, these nonionic components have positive effects on the storage stability of the pretreatment agent used in the invention. Nonionic components which are particularly suitable here are ethoxylates of decanol, undecanol, dodecanol, tridecanol, myristyl alcohol, cetyl alcohol and / or stearyl alcohol. Particularly suitable ethoxylated tridecanols have proven to be incorporated with particular preference in the pretreatment agent used in the invention. Particularly preferred are branched ethoxylated tridecanols, in particular branched tridecanols having 3 to 5 ethylene oxide units in the molecule. Pre-treatment agents used particularly preferably according to the invention contain, based in each case on their weight, from 0.001 to 5% by weight, preferably from 0.005 to 3.5% by weight, particularly preferably from 0.01 to 2% by weight, more preferably from 0.05 to 1 wt .-% and in particular 0.1 to 0.5 wt .-% branched, ethoxylated tridecanol, particularly preferably 0.001 to 5 wt .-%, preferably 0.005 to 3.5 wt .-%, particularly preferably 0.01 to 2 wt .-%, more preferably 0.05 to 1 wt .-% and in particular 0, 1 to 0.5 wt .-% branched, ethoxylated tridecanol having 3 to 5 ethylene oxide units in the molecule.

Further surfactants and emulsifiers are preferably not present in the pretreatment agents used according to the invention or only in small amounts. Pre-treatment agents preferably used according to the invention comprise, based on the total weight of the composition, from 0.001 to at most 6% by weight of surfactant (s), the abovementioned ethoxylates of decanol, undecanol, dodecanol, tridecanol, myristyl alcohol, cetyl alcohol and / or stearyl alcohol being included.

Preferably, the pretreatment agent used in the invention are low viscosity, the is, with a viscosity (measured at 20 ° C) in the range of 10 - 2000 mPas, preferably 20 - 1000 mPas, more preferably 50 - 800 mPas formulated. It has also been shown that thickening polymers can attenuate the effect according to the invention, so that preferred pretreatment agents used according to the invention are characterized in that they contain thickening polymers in a total amount of <2.5% by weight, preferably <1% by weight. , more preferably <0.5 wt .-% and in particular <0.01 wt .-%, each based on the weight of the pretreatment agent.

The pretreatment agents used according to the invention may contain further ingredients. Preference is given here to the use of polyhydric alcohols which have moisturizing properties. Preferred pretreatment agents used according to the invention are those which contain at least one polyhydric alcohol, preferably selected from the group of sorbitol and / or glycerol and / or 1,2-propylene glycol or mixtures thereof, in a total amount of from 0.05 to 15% by weight, preferably 0, 1 to 10 wt .-%, particularly preferably 0.15 to 5 wt .-% and in particular 0.15 to 1 wt .-%, each based on the weight of the pretreatment agent. For certain applications, it may be advantageous to use only one of the three preferred polyhydric alcohols mentioned above. In most cases, glycerin is preferred. However, in other applications, mixtures of two of the three polyhydric alcohols or all three polyhydric alcohols may be preferred. Here, a mixture of glycerol, sorbitol and 1,2-propylene glycol in a weight ratio of 1: (0.5-1): (0.1-0.5) has proved particularly advantageous.

In addition to sorbitol, glycerol and 1, 2-propylene glycol are suitable as further polyhydric alcohols are those having at least 2 OH groups, preferably mannitol, xylitol, polyethylene glycol, polypropylene glycol and mixtures thereof. Among these compounds, those having 2 to 12 OH groups, and especially those having 2, 3, 4, 5, 6 or 10 OH groups are preferred.

Polyhydroxy compounds having 2 OH groups are, for example, glycol (CH ₂ (OH) CH ₂ OH) and other 1, 2-diols such as H- (CH ₂ ) _n -CH (OH) CH ₂ OH where n = 2, 3, 4 , 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20. Also 1,3-diols such as H- (CH ₂ ) _n -CH (OH) CH ₂ CH ₂ OH with n = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, 15, 16, 17, 18, 19, 20 can be used according to the invention. The (n, n + 1) or (n, n + 2) diols with non-terminal OH groups can also be used. Important representatives of polyhydroxy compounds having 2 OH groups are also the polyethylene and polypropylene glycols. As preferred further polyhydric alcohols may, for. As xylitol, propylene glycols, polyethylene glycols, especially those having average molecular weights of 200-800, are used. Particularly preferred is the use of glycerol, so that agents which contain no other polyhydric alcohols other than glycerol are particularly preferred.

With regard to the pretreatment prior to an oxidative dyeing treatment, the use of certain care substances in the pretreatment compositions of the process according to the invention is preferred. Pre-treatment agents preferably used according to the invention are characterized in that they additionally contain care substance (s) in a total amount of 0.001 to 10 wt.%, Preferably 0.005 to 7.5 wt.%, Particularly preferably 0.01 to 5 wt in particular from 0.05 to 2.5% by weight, in each case based on the total weight of the pretreatment agent. Preferred care substances are selected from at least one of the following groups:

i-L-carnitine and / or its salts;

ii. Taurine and / or its salts;

iii. niacinamide;

iv. ubiquinone;

V. Ectoin;

vi. vitamins;

vii. Flavonoids.

As a further ingredient, the pretreatment agents used according to the invention may with particular preference contain one or more amino acids. Particularly preferred amino acids which can be used according to the invention are from the group glycine, alanine, valine, leucine, isoleucine, phenylalanine, tyrosine, tryptophan, proline, aspartic acid, glutamic acid, asparagine, glutamine, serine, threonine, cysteine, methionine, lysine, arginine, histidine , β-alanine, 4-aminobutyric acid (GABA), betaine, L-cystine (L-Cyss), L-carnitine, L-citrulline, L-theanine, 3 ', 4-dihydroxy-L-phenylalanine (L-dopa) , 5'-Hydroxy-L-tryptophan, L-homocysteine, S-methyl-L-methionine, S-allyl-L-cysteine sulfoxide (L-alliin), L-frans-4-hydroxyproline, L-5-oxoproline (L-pyroglutamic acid), L-phosphoserine, creatine, 3-methyl-L-histidine, L-ornithine, whereby both the individual amino acids and mixtures can be used.

Preferred pretreatment agents used according to the invention comprise one or more amino acids in narrower ranges. Here, pretreatment agents used according to the invention are characterized in that they contain as care substance 0.01 to 5 wt .-%, preferably 0.02 to 2.5 wt .-%, particularly preferably 0.05 to 1, 5 wt .-%, further preferably 0.075 to 1 wt .-% and in particular 0, 1 to 0.25 wt .-% amino acid (s), preferably from the group glycine and / or alanine and / or valine and / or lysine and / or leucine and / or Threonine, each based on the total weight of the pretreatment agent.

The pretreatment agent used according to the invention may be formulated as a low-viscous water-based emulsion, as a spray, as a cream, gel, lotion, paste, shampoo or conditioner. The method according to the invention comprises the application of a pretreatment agent to keratinic fibers and an oxidative dyeing treatment following this within a period of one second to 24 hours.

A great advantage of the pretreatment agents used in step a) is that they are not only effective if they are applied immediately before the oxidative dyeing treatment, but can be applied up to 24 hours in advance without a weakening of the effect due to external influences to be feared. In this way it is possible, for example in the morning after shampooing to carry out step a) of the method according to the invention and the oxidative dyeing treatment only in the evening.

Preferred methods according to the invention are characterized in that the time between method steps a and b is from 2 seconds to 20 minutes, preferably 30 Seconds to 10 minutes, more preferably 1 to 5 minutes.

Further inventively preferred processes are characterized in that the pretreatment agent applied in process step a is allowed to act on the hair for a period of 2 seconds to 120 minutes, preferably 5 seconds to 10 minutes, before beginning process step b.

Further inventively preferred processes are characterized in that the pretreatment agent applied in process step a is allowed to act on the hair for a period of 2 seconds to 120 minutes, preferably 5 seconds to 10 minutes, before at least one of the following process steps a) i), starting before step b) is started: rinsing the hair;

Drying the hair in the air;

Dry-drying the hair,

Drying the hair with a drying hood;

Dry the hair with a towel.

The drying process can take place at a temperature of 20 ° C to 150 ° C.

The drying process or the dry processes is preferably preceded by no rinsing of the hair. However, according to the invention it may also be preferred to first rinse the hair after step a) and then to dry it before the dyeing step b takes place.

The process according to the invention is further characterized in that step b) comprises applying a hair colorant containing at least one developer type oxidation dye precursor and at least one coupler type oxidation dye precursor and at least one oxidant.

The first binding ingredient used in step b) of this method according to the invention hair dyeing therefore contain at least one oxidizing agent. Preferred oxidizing agents are selected from peroxo compounds, preferably selected from hydrogen peroxide, solid addition compound of hydrogen peroxide to inorganic or organic compounds such as sodium perborate, sodium percarbonate, magnesium percarbonate, sodium percarbamide, polyvinylpyrrolidone n H ₂ 0 ₂ (n is a positive integer greater than 0), urea peroxide and melamine peroxide, further selected from diammonium peroxodisulfate (also referred to as ammonium persulfate), Dinatnumperoxodisulfate (also referred to as sodium persulfate) and dipotassium peroxodisulfate (also referred to as potassium persulfate) and mixtures of these oxidizers. Oxidants which are very particularly preferably used according to the invention are aqueous hydrogen peroxide solutions. The concentration of a hydrogen peroxide solution is determined on the one hand by the legal requirements and on the other hand by the desired effect; preferably 6-12% by weight solutions in water are used. Preferred processes according to the invention are characterized in that the hair dyes used in step b) - based on their weight - 0.5 to 12 wt .-%, preferably 2 to 10% by weight, particularly preferably 3 to 6 wt .-% hydrogen peroxide (calculated as 100% H ₂ 0 ₂ ). Oxidative dyeing processes on keratin fibers usually take place in an alkaline medium. However, in order to preserve the keratin fibers as well as the skin as much as possible, the setting of too high a pH value is not desirable. Therefore, it is preferred if the pH of the hair dye used in step b) in the range of 7 and 1 1, in particular in the range of 8 and 10.5, is. For the purposes of the present invention, the pH values are pH values which were measured at a temperature of 22 ° C.

The alkalizing agents which can be used according to the invention for adjusting the preferred pH can be selected from the group of ammonia, basic amino acids, alkali metal hydroxides, alkanolamines, alkali metal metasilicates, alkali metal phosphates and alkali metal hydrogenphosphates. The alkali metal ions used are preferably lithium, sodium, potassium, in particular sodium or potassium.

The basic amino acids which can be used as alkalizing agents are preferably selected from the group consisting of L-arginine, D-arginine, D, L-arginine, L-lysine, D-lysine, D, L-lysine, particularly preferably L-arginine, D-arginine, D, L-arginine used as an alkalizing agent according to the invention. The alkali metal hydroxides which can be used as alkalizing agents are preferably selected from the group consisting of sodium hydroxide and potassium hydroxide.

The alkanolamines which can be used as alkalizing agents are preferably selected from primary amines having a C ₂ -C ₆ -alkyl basic body which carries at least one hydroxyl group. Particularly preferred alkanolamines are selected from the group formed from 2-amino-ethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol , 1-Aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropane-1 -ol, 1-amino-2-methylpropan-2-ol, 3-aminopropane-1, 2-diol, 2-amino-2-methylpropane-1, 3-diol. Very particularly preferred alkanolamines according to the invention are selected from the group consisting of 2-aminoethane-1-ol, 2-amino-2-methylpropan-1-ol and 2-amino-2-methylpropane-1,3-diol.

For a coloring that requires a strong lightening of very dark hair, the use of hydrogen peroxide or its addition products to organic or inorganic compounds is often not sufficient. In these cases, a combination of hydrogen peroxide and Peroxodisulfatsalzen (persulfate salts) is usually used. Preferred persulfate salts are ammonium peroxydisulfate, potassium peroxodisulfate, sodium peroxodisulfate, and mixtures thereof.

The at least one persulfate salt is preferably contained in a total amount of 0.1 to 25% by weight, more preferably in a total amount of 1 to 15% by weight, based on the weight of the ready-to-use colorant.

As further obligatory ingredients, the colorants used in step b) of the process of the invention contain at least one oxidation dye precursor of the developer type and at least one oxidation dye precursor of the coupler type.

Due to their reaction behavior, oxidation dye precursors can be divided into two categories, so-called developer components and coupler components. Coupler components do not form a significant color within the framework of the oxidative dyeing alone, but always require the presence of developer components. Developer components can form the actual dye with themselves.

The developer and coupler components are usually used in free form. In the case of substances having amino groups, however, it may be preferable to use them in salt form, in particular in the form of the hydrochlorides or hydrobromides or of the sulfates.

Surprisingly, it has been found that with the process according to the invention using at least one oxidation dye precursor of the developer type and at least one coupler type oxidation dye precursor hair dyeings having a particularly high wash fastness could be obtained. A particularly good washfastness improvement was observed for formulations with the developer / coupler combination 1-hydroxyethyl-4,5-diaminopyrazole / 3-amino phenol. The reduction of hair damage was surprisingly high.

Particularly preferred developer components are selected from at least one compound from the group formed from p-phenylenediamine, p-toluenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, 2- (1, 2-dihydroxyethyl) -p-phenylenediamine , N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazole) 1-yl) propyl] amine, N, N'-bis (2-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1, 3-diamino-propan-2-ol, bis (2 - hydroxy-5-aminophenyl) methane, 1, 3-bis (2,5-diaminophenoxy) propan-2-ol, N, N'-bis (4-aminophenyl) -1, 4-diazacycloheptane, 1 , 10-bis (2,5-diaminophenyl) -1, 4,7,10-tetraoxadecane, p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2 - (1, 2-dihydroxyethyl) phenol and 4-amino-2- (diethylaminomethyl) phenol, 4,5-diamino-1- (2-hydroxyethyl) pyrazole, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy -2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, the physiologically acceptable salts of these compounds and mixtures of these developer components and developer component salts.

Very particularly preferred developer components are selected from 4,5-diamino-1- (2-hydroxyethyl) pyrazole, p-toluenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N- (4 -Amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine and mixtures of these compounds and their physiologically acceptable salts. Extraordinary preference is given to 4,5-diamino-1- (2-hydroxyethyl) pyrazole and its physiologically tolerated salts.

The developer components are preferably used in a total amount of 0.005 to 10 wt .-%, particularly preferably 0.1 to 5 wt .-%, each based on the weight of the ready dye.

For the purposes of this application, the term "ready-to-use colorant" is understood as meaning the mixture of all oxidation dye precursors and all oxidizing agents, if appropriate in combination with a suitable cosmetic carrier, for example a cream base, and optionally in combination with at least one substantive dye.

Coupler components according to the invention allow at least one substitution of a chemical residue of the coupler by the oxidized form of the developer component. This forms a covalent bond between the coupler and the developer component. Couplers are preferred cyclic compounds bearing on the cycle at least two groups selected from (i) optionally substituted amino groups and / or (ii) hydroxyl groups. When the cyclic compound is a six-membered ring (preferably aromatic), said groups are preferably in ortho position or meta position to each other.

Preferred processes according to the invention are characterized in that the at least one coupler-type oxidation dye precursor is selected from one of the following classes:

3-aminophenol (m-aminophenol) and / or its derivatives,

3-aminoaniline (m-diaminobenzene) and / or its derivatives,

2-aminoaniline (1, 2-diaminobenzene, o-diaminobenzene) and / or its derivatives,

2-aminophenol (o-aminophenol) and / or derivatives thereof,

Naphthalene derivatives having at least one hydroxy group,

Di- or trihydroxybenzene and / or derivatives thereof,

- pyridine derivatives,

- pyrimidine derivatives,

Monohydroxyindole derivatives and / or monoamine indole derivatives,

Monohydroxyindoline derivatives and / or monoaminoindoline derivatives,

Pyrazolone derivatives such as 1-phenyl-3-methylpyrazol-5-one,

Morpholine derivatives, such as, for example, 6-hydroxybenzomorpholine or 6-aminobenzomorpholine,

Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,

Mixtures of two or more compounds from one or more of these classes are also preferred according to the invention in the context of this embodiment.

Particularly preferred additional coupler components according to the invention are selected from 3-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro 2-methylphenol, 5- (2-hydroxyethyl) amino-2-methylphenol, 2,4-dichloro-3-aminophenol, 2-aminophenol, 3-phenylenediamine, 2- (2,4-diaminophenoxy) ethanol, 1, 3-bis (2,4-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene (= 2-amino-4-hydroxyethylaminoanisole), 1, 3-bis (2,4- diaminophenyl) propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2- ( {3 - [(2-Hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2 - [3-morpholin-4-yl-phenyl) -amino] -ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis (2-hydroxyethyl) aminobenzene, resorcinol, 2 Methyl resorcinol, 4-chlororesorcinol, 1, 2,4-trihydroxybenzene, 2-amino-3-hyd roxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-phenyl-3-methylpyrazole-5 on, 1-naphthol, 1, 5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline or mixtures of these compounds or the physiologically acceptable salts of the aforementioned compounds.

Very particularly preferred are 3-aminophenol, resorcinol, 2-methylresorcinol, 5-amino-2-methylphenol, 2- (2,4-diaminophenoxy) ethanol, 1, 3-bis (2,4-diaminophenoxy) propane, 1 methoxy-2 amino-4- (2'-hydroxyethylamino) benzene, 2-amino-3-hydroxypyridine and 1-naphthol and their physiologically acceptable salts and mixtures of the said components.

The at least one coupler component is preferably used in a total amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the weight of the ready oxidation dye.

In the context of the present invention, the following combinations of oxidation dye precursors of the developer type and of the coupler type are particularly preferred, wherein the amine compounds and the nitrogen heterocycles may also be present in the form of their physiologically tolerated salts:

p-toluenediamine / resorcinol;

p-toluenediamine / 2-methylresorcinol;

p-toluenediamine / 5-amino-2-methylphenol;

p-toluenediamine / 3-aminophenol;

p-toluenediamine / 2- (2,4-diaminophenoxy) ethanol;

p-toluenediamine / 1,3-bis (2,4-diaminophenoxy) propane;

p-toluenediamine / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene;

p-toluenediamine / 2-amino-3-hydroxypyridine;

p-toluenediamine / 1-naphthol;

2- (2-hydroxyethyl) -p-phenylenediamine / resorcinol;

2- (2-hydroxyethyl) -p-phenylenediamine / 2-methylresorcinol;

2- (2-hydroxyethyl) -p-phenylenediamine / 5-amino-2-methylphenol;

2- (2-hydroxyethyl) -p-phenylenediamine / 3-aminophenol;

2- (2-hydroxyethyl) -p-phenylenediamine / 2- (2,4-diaminophenoxy) ethanol;

2- (2-hydroxyethyl) -p-phenylenediamine / 1,3-bis (2,4-diaminophenoxy) propane;

2- (2-hydroxyethyl) -p-phenylenediamine / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene;

2- (2-hydroxyethyl) -p-phenylenediamine / 2-amino-3-hydroxypyridine;

2- (2-hydroxyethyl) -p-phenylenediamine / 1-naphthol;

2-methoxymethyl-p-phenylenediamine / resorcinol;

2-methoxymethyl-p-phenylenediamine / 2-methylresorcinol;

2-methoxymethyl-p-phenylenediamine / 5-amino-2-methylphenol;

2-methoxymethyl-p-phenylenediamine / 3-aminophenol;

2-methoxymethyl-p-phenylenediamine / 2- (2,4-diaminophenoxy) ethanol;

2-methoxymethyl-p-phenylenediamine / 1, 3-bis (2,4-diaminophenoxy) propane;

2-methoxymethyl-p-phenylenediamine / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene;

2-methoxymethyl-p-phenylenediamine / 2-amino-3-hydroxypyridine;

2-methoxymethyl-p-phenylenediamine / 1-naphthol;

N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine / resorcinol;

N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine / 2-methylresorcinol;

N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine / 5-amino-2-methylphenol; N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) -propyl] amine / 3-aminophenol;

N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine / 2- (2,4-diaminophenoxy) ethanol; N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine / 1, 3-bis (2,4-diaminophenoxy) propane;

N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene;

N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine / 2-amino-3-hydroxypyridine;

N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine / 1-naphthol;

4,5-diamino-1- (2-hydroxyethyl) pyrazole / resorcinol;

4,5-diamino-1- (2-hydroxyethyl) pyrazole / 2-methylresorcinol;

4,5-diamino-1- (2-hydroxyethyl) pyrazole / 5-amino-2-methylphenol;

4,5-diamino-1- (2-hydroxyethyl) pyrazole / 3-aminophenol;

4,5-diamino-1- (2-hydroxyethyl) pyrazole / 2- (2,4-diaminophenoxy) ethanol;

4,5-diamino-1- (2-hydroxyethyl) pyrazole / 1,3-bis (2,4-diaminophenoxy) propane;

4,5-diamino-1- (2-hydroxyethyl) pyrazole / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene;

4,5-diamino-1- (2-hydroxyethyl) pyrazole / 2-amino-3-hydroxypyridine;

4,5-diamino-1- (2-hydroxyethyl) pyrazole / 1-naphthol.

Particularly preferred according to the invention are the combinations 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 3-aminophenol and p-toluenediamine / 3-aminophenol. Highly preferred, especially with regard to the improvement of wash fastness, the combination is 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 3-aminophenol.

In order to achieve a balanced and subtle nuance formation, it is preferred according to the invention if further coloring components are contained in the colorant used in step b) of the process according to the invention.

In a further embodiment, the agents used in step b) of this variant of the method according to the invention may additionally contain at least one substantive dye. These are dyes that raise directly on the hair and do not require an oxidative process to form the color. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.

A further preferred process according to the invention is characterized in that the dyeing agent applied in step b is rinsed off the fibers after a time of 5-60 minutes, preferably 30-45 minutes.

The colorant used in step b according to the invention is preferably prepared from a two-component agent, one component containing the oxidation dye precursors and the other components containing the oxidizing agent or agents. The ready-for-use colorant for step b is then prepared by mixing both components directly before the application step b. Separation into multicomponent systems is particularly suitable where incompatibilities of the ingredients are to be expected or to be feared.

Another object of the present application is the use of at least one 4-morpholinomethyl-substituted silicone of the formula (V),

for a structural unit (I), (II) or (III) attached via an -O-

* for a bond to one of the structural units (I), (II) or (III) or for a

for improving the wash fastness of an oxidative hair dyeing obtained from at least one developer type oxidation dye precursor and at least one coupler type oxidation dye precursor and at least one oxidizing agent.

A preferred use according to the invention is characterized in that the oxidative hair coloring with a hair dye containing the combination of 4,5-diamino-1- (2-hydroxyethyl) pyr-azole and 3-aminophenol and at least one oxidizing agent was obtained.

The comments made on preferred embodiments of the method according to the invention apply mutatis mutandis mutandis for the inventively preferred uses.

embodiments

example 1

Hair tresses were immersed for one minute in an aqueous emulsion of 4-morpholinomethyl substituted silicone of formula (V) containing 0.01% by weight of 4-morpholinomethyl substituted silicone (s) of formula (V) and 0.005 wt .-% branched trideceth-5, further 0.006 wt .-% glycerol and water ad 100 wt .-%, immersed and then dry-blown.

Subsequently, a freshly prepared coloring cream oxidizer mixture was applied to the tresses and allowed to act for 30 minutes. Subsequently, the colorant was rinsed with water. For the color measurements, the strands were dry-blown. The combing tests were performed on strands which had been combed three times after rinsing the dye cream-oxidizer mixture.

Coloring creams (in% by weight):

Ingredient 5-0 6-88 12-0

1-hydroxyethyl 4,5-diamino-pyrazole sulfates - 1, 5 -

Toluene-2,5-diamines Sulfates 1, 4 - 0.02

3-aminophenol 0.2 0.6 -

Resorcinol 0.7 - -

2-amino-4-hydroxyethylaminoanisole sulfates 0.02 0.02

(1-Methoxy-2-amino-4- (2'-hydroxyethylamino) benzenesulfate)

4-amino-2-hydroxytoluene - 0.3 0.01

4-amino-m-cresol - 0, 18 -

Cetearyl Alcohol 14 14 14

Glyceryl stearates 1, 4 1, 4 1, 4

Ammonium hydroxides 3.4 3.4 6.8

Ceteareth-20 3,5 3,5 3,5

Octyldodecanol 1 1 1

Sodium Laureth Sulfate 0.5 0.5 0.5

1,3-Butylene glycol 3,5 3,5 3,5

Sodium Cetearyl Sulfate 1, 0 1, 0 1, 0

Ethanolamine 0.7 0.6 -

Oleic acid 0, 1 0, 1 0.1

Perfume (Fragrance) 0,5 0,5 0,5 Potassium Stearate 0.5 0.5 0.5

Sodium sulphite 0.2 0.2 0.2

Tetrasodium EDTA 0.3 0.3 0.3

Carbomer 0.3 0.3 0.3

Polyquaternium-39 (ex Merquat 3330) 0.05 0.05 0.05

Potassium Hydroxide 0.06 0.08 0.08

Ascorbic acid 0.02 0.02 0.02

Linoleamidopropyl PG-Dimonium Chloride Phosphate 0, 1 0, 1 0.1

Sodium sulfate 0, 1 0, 1 0.1

Citric Acid 0.002 0.002 0.002

Cl 77891 (Titanium Dioxide) 0.3 0.3 0.3

Aqua (Water, Eau) ad 100 ad 100 ad 100

The above-mentioned coloring creams 5-0 and 6-88 were each mixed in a weight ratio of 1: 1 with the developer dispersion No. 1 shown below to give ready-to-use colorants. The above-mentioned Dye Cream 12-0 was mixed in a weight ratio of 1: 1 with the developer dispersion No. 2 shown below to a ready-to-use colorant. Subsequently, the respective colorant was applied to the test strands, each 4 g of colorant per gram of hair for the tests on combability, split ends, hair breakage and sensors and 5 g of colorant per gram of hair for the tests for wash fastness. The stains remained on the tress for 30 minutes each. The strands were then rinsed with 32 ° C tap water at a flow rate of 0.5 liters per minute for 2 minutes.

Developer dispersions used (amounts in% by weight):

Ingredients No. 1 No. 2

Cetearyl alcohol 4.0 4.0

Dipicolinic acid 0, 1 0.1

Disodium Pyrophosphate 0, 1 0.1

Potassium hydroxide 0, 1 0.1

1, 2-propylene glycol 1, 0 1, 0

1-Hydroxyethane-1,1-diphosphonic acid (Etidronic acid) 0, 1 0.1

Paraffin Liquidum 0,5 0,5

STEELTRIMONIUM CHLORIDE 0,5 0,5

Ceteareth-20 1, 0 1, 0

H ₂ 0 ₂ (active matter) 6.0 12.0 Water ad 100 ad 100

wet combing; Combing work in mJ

By means of the pretreatment with the 4-morpholinomethyl-substituted silicone of the formula (V) according to the invention, the hair damage to the oxidative dyeing without pretreatment according to the invention was markedly reduced, that is, the wet combing work was simplified (lower combing work is equivalent to less hair damage) and split ends and hair breakage were reduced by about half. The sensory evaluation of the hair by trained hairdressers also proved that the hairs treated according to the invention feel softer and smoother than the untreated hairs. Wash fastness after 36 washing cycles; Specification of L from color difference ΔΕ

ΔΕ- E _before washing ^- ^ after washing

The washfastness tests after 36 washing cycles also show that the difference between the starting color and the color after 36 washing cycles is significantly lower for the hairs treated according to the invention, ie less color was washed out than for the untreated hairs.

Claims

claims:

1. A process for the oxidative dyeing of keratinic fibers, in particular of hair, characterized in that

for a structural unit (I), (II) or (III) attached via an -O-

* for a bond to one of the structural units (I), (II) or (III) or for a

End group B (Si-bonded) or D (O-linked),

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

a, b and c are integers from 0 to 990, with the proviso that a + b + c> 0

m, n and o are integers from 1 to 990,

is applied to the keratinic fibers, especially the hair, b) then, within a period of one second to 24 hours after step a), a hair dye is applied to the keratinic fibers containing at least one developer-type oxidation dye precursor and at least one coupler-type oxidation dye precursor and at least one oxidizing agent.

A method according to claim 1, characterized in that the pretreatment agent used in step a contains at least one 4-morpholinomethyl-substituted silicone of the formula (V), in which

m> (n + o) or (a + b + c)> (n + o), preferably

m> 8 (n + o) or (a + b + c)> 8 (n + o), more preferably

m> 25 (n + o) or (a + b + c)> 25 (n + o), more preferably

m> 77 (n + o) or (a + b + c)> 77 (n + o) and in particular

m> 200 (n + o) or (a + b + c)> 200 (n + o).

Method according to one of claims 1 or 2, characterized in that the pretreatment agent used in step a, based on its weight, 4-morpholinomethyl-substituted (s) silicone (s) in a total amount of 0.001 to 5 wt .-% , preferably 0.005 to 2% by weight, particularly preferably 0.01 to 1 wt .-%, most preferably 0.02 to 0, 1 wt .-%, each based on the total weight of the pretreatment agent contains.

Method according to one of claims 1, 2 or 3, characterized in that the pretreatment agent used in step a, based on its weight, at least one 4-morpholino nomethyl-substituted silicone of formula (V), each of at least one of the structural units of Formulas (I), (II) and (III), in a total amount of 0.001 to 5 wt .-%, preferably 0.005 to 2 wt .-%, particularly preferably 0.01 to 1 wt .-%, most preferably 0 , 02 - 0, 1 wt .-%, each based on the total weight of the pretreatment agent contains.

Method according to one of claims 1 to 4, characterized in that the pretreatment agent used in step a contains hydroxy-terminated (s) 4-morpholinomethyl-substituted (s) silicone (s), in which the molar ratio hydroxy / alkoxy in the range of 0 , 2: 1 to 0.4: 1, preferably in the range of 1: 0.8 to 1: 1, 1.

Method according to one of claims 1 to 5, characterized in that the weight average molecular weight of the used in step a 4-morpholinomethyl-substituted silicone of formula (V) in the range of 2,000 to 1,000,000 gmol ¹ , preferably in the range of 5,000 to 200,000 gmol ^"1 lies.

7. The method according to any one of claims 1 to 6, characterized in that the used in step a 4-morpholinomethyl-substituted silicone of the formula (V) is in the form of an oil-in-water emulsion in which the number average size of the silicone particles in the Emulsion preferably in the range of 3 to 500 nm, more preferably in the range of 5 to 60 nm.

8. The method according to any one of claims 1 to 7, characterized in that the applied in step b combination of at least one oxidation dye precursor of the developer type and at least one oxidation dye precursor coupler type is selected from at least one of the following combinations, wherein the amine compounds and the nitrogen heterocycles also in May be present form of their physiologically acceptable salts: p-toluenediamine / resorcinol;

p-toluenediamine / 2-methylresorcinol;

p-toluenediamine / 5-amino-2-methylphenol;

p-toluenediamine / 3-aminophenol;

p-toluenediamine / 2- (2,4-diaminophenoxy) ethanol;

p-toluenediamine / 1,3-bis (2,4-diaminophenoxy) propane;

p-toluenediamine / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene;

p-toluenediamine / 2-amino-3-hydroxypyridine;

p-toluenediamine / 1-naphthol;

2- (2-hydroxyethyl) -p-phenylenediamine / resorcinol;

2- (2-hydroxyethyl) -p-phenylenediamine / 2-methylresorcinol;

2- (2-hydroxyethyl) -p-phenylenediamine / 5-amino-2-methylphenol;

2- (2-hydroxyethyl) -p-phenylenediamine / 3-aminophenol;

2- (2-hydroxyethyl) -p-phenylenediamine / 2- (2,4-diaminophenoxy) ethanol;

2- (2-hydroxyethyl) -p-phenylenediamine / 1,3-bis (2,4-diaminophenoxy) propane;

2- (2-hydroxyethyl) -p-phenylenediamine / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene; 2- (2-hydroxyethyl) -p-phenylenediamine / 2-amino-3-hydroxypyridine;

2- (2-hydroxyethyl) -p-phenylenediamine / 1-naphthol;

2-methoxymethyl-p-phenylenediamine / resorcinol;

2-methoxymethyl-p-phenylenediamine / 2-methylresorcinol;

2-methoxymethyl-p-phenylenediamine / 5-amino-2-methylphenol;

2-methoxymethyl-p-phenylenediamine / 3-aminophenol;

2-methoxymethyl-p-phenylenediamine / 2- (2,4-diaminophenoxy) ethanol;

2-methoxymethyl-p-phenylenediamine / 1, 3-bis (2,4-diaminophenoxy) propane;

2-methoxymethyl-p-phenylenediamine / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene; 2-methoxymethyl-p-phenylenediamine / 2-amino-3-hydroxypyridine;

2-methoxymethyl-p-phenylenediamine / 1-naphthol;

N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine / 2-methylresorcinol; N- (4-amino-3-methylphenyl) - ^■ N - [3- - (1 H -imidazol- ^■ 1-yl) propyl] amine / 5-amino-2-methyl phenol;

N- (4-amino-3-methylphenyl) - ^■ N - [3- - (1 H- imidazol ^■ ^■ 1-yl) propyl] amine / 3-aminophenol;

N- (4-amino-3-methylphenyl) - ^■ N - [3- - (1 H- imidazol ^■ ^■ 1-yl) propyl] amine / 2- (2,4-diamino-phenoxy) - ethanol;

N- (4-amino-3-methylphenyl) - ^■ N - [3- - (1 H- imidazol ^■ ^■ 1-yl) propyl] amine / 1, 3-bis (2,4-diaminophenoxy) - propane ;

N- (4-amino-3-methylphenyl) - ^■ N - [3- ^■ (1 H- imidazol ^■ ^■ 1-yl) propyl] amine / 1-methoxy-2-amino-4- (2-hydroxyethylamino )benzene;

N- (4-amino-3-methylphenyl) - ^■ N - [3- ^■ (1 H- imidazol ^■ ^■ 1-yl) propyl] amine / 2-Am ino-3-hyd roxy py rid in;

N- (4-amino-3-methylphenyl) - ^■ N - [3- ^■ (1 H- imidazol ^■ ^■ 1-yl) propyl] amine / 1-naphthol;

4,5-diamino-1 - (2-hydroxyethyl

9. The method according to any one of claims 1 to 8, characterized in that the at least one applied in step b oxidation dye precursor of the developer type 4,5-diamino-1 - (2-hydroxyethyl) pyrazole.

10. The method according to any one of claims 1 to 9, characterized in that the period between the process steps a and b of 30 seconds to 20 minutes, preferably 45 seconds to 10 minutes, more preferably 1 to 5 minutes.

1 1. A method according to any one of claims 1 to 10, characterized in that the applied colorant in step b after a time of 5-60 minutes, preferably 30 - 45 minutes, rinsed from the fiber.

12. Use of at least one 4-morpholinomethyl-substituted silicone of the formula (V), for a structural unit (I), (II) or (III) attached via an -O-

* for a bond to one of the structural units (I), (II) or (III) or for a

End group B (Si-bonded) or D (O-linked),

a, b and c are integers from 0 to 990, with the proviso that a + b + c> 0

m, n and o are integers from 1 to 990,

13. Use according to claim 12, characterized in that the oxidative hair coloring with a hair dye containing the combination of 4,5-diamino-1- (2-hydroxyethyl) pyrazole and 3-aminophenol and at least one oxidizing agent was obtained.