WO2015096936A1

WO2015096936A1 - Method for shaping and colouring fibres containing keratin

Info

Publication number: WO2015096936A1
Application number: PCT/EP2014/074846
Authority: WO
Inventors: Birgit Rautenberg-Groth; Stephan Schwartz
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2013-12-23
Filing date: 2014-11-18
Publication date: 2015-07-02
Also published as: DE102013227122A1

Abstract

Methods involving (i) providing a treatment composition A comprising at least one alkalifying substance, (ii) providing a treatment composition B comprising at least one keratin colouring substance, (iii) mixing together treatment compositions A and B and also optionally further active ingredients to give a treatment composition C having a pH of between 10 and 14, (iv) applying the treatment composition C to the keratinous fibres, (v) thereafter mechanically straightening and rinsing the keratinous fibres, (vi) subsequently treating the fibres optionally with an oxidizing agent and thereafter rinsing them again, are suitable for the simultaneous straightening and colouring of keratinous fibres, more particularly human hair.

Description

PROCESS FOR GLOWING AND STAINING KERATINE-CONTAINING FIBERS

The application relates to the technical field of reshaping and coloring keratin-containing fibers, in particular human hair. As keratin-containing fibers, in principle all animal hair, e.g. Wool, horsehair, angora hair, furs, feathers and products made therefrom or textiles. However, the agents and methods according to the invention are preferably used in the context of hair shaping, in particular the smoothing of curly human hair and wigs made therefrom.

A permanent deformation keratinhaltiger fibers is usually carried out so as to mechanically deform the fiber and determines the deformation by suitable means. Before and / or after this deformation, the fiber is treated with a keratin reducing preparation. After a rinsing operation, the fiber is then treated with an oxidizing agent preparation in the so-called fixing step, rinsed and freed from the forming aids (e.g., winders, papillots) after or during the fusing step. When the keratin reducing component is a mercaptan, e.g. Ammonium thioglycolate is used, this part of the disulfide bridges of the keratin molecule cleaves to -SH groups, so that there is a softening of keratin fibers. In the later oxidative fixation again disulfide bridges are knotted in the hair keratin, so that the Keratingefüge is fixed in the predetermined deformation. Alternatively, it is known to use sulfite instead of the mercaptans for hair styling. By bisulfite solutions and / or sulfite solutions and / or disulfite solutions, disulfide bridges of keratin in a sulfitolysis according to the equation

R - S - S - R + HSO3H ► R - SH + R - S - SO3H and thus achieved a softening of the keratin fibers. Hydrogen sulfite, sulfite or disulfite containing reducing agents do not have the strong odor of the mercaptan-containing agents. The cleavage can be reversed as described above in a fixing step using an oxidizing agent to form new disulfide bridges.

The permanent smoothing of keratin-containing fibers is achieved analogously by the use of keratin reducing and oxidizing compositions. In a similar process, the curly hair is either wound on large diameter worms, usually greater than 15 mm, or the hair is smoothed combed under the action of the keratin reducing composition. Instead of the winder it is also possible to place the fiber on a smoothing board smooth down. Smoothing boards are usually rectangular boards, for example made of plastic. Preferably, the fiber is wetted with the keratin reducing preparation.

Another way of hair straightening is the smoothing with a flat iron after previous use of alkaline products. Such alkaline reshaping agents, in contrast to reshaping with keratin reducing and oxidizing compositions, do not result in reshaping of the disulfide bridges, but in destruction of the disulfide bridges to form monosulfide bridges. Depending on the concentration and duration of use of the alkaline reforming agent and protein chains are hydrolytically cleaved. The pH of the alkaline reforming agent is usually in the range of 11-14, preferably 12-13.

In general, the known forming methods, especially in the case of smoothing, have the disadvantage that the keratin-containing fiber is charged electrostatically. In addition, the deformation result of the known methods in terms of the degree of deformation and the uniformity of the deformation is in need of improvement. When an improvement in the degree of deformation is achieved, this is usually accompanied by an increased damage to the keratin-containing fiber.

This is especially the case if, in addition to the transformation, a coloring of the keratinic fibers is desired. In particular, in the case of an oxidative dyeing, but also when using direct dyes, this leads to an extreme stress on the fibers. Moreover, such a procedure is very time consuming.

Methods for simultaneous reshaping and staining of keratinic fibers have been described in the literature. For example, DE 197 13 698 C1 discloses a method in which an oxidation dye precursor and / or a direct dye is added to the oxidizing agent used to fix the transformed hair.

EP 352 375 A1, EP 1 287 812 A2 and DE 10 2005 061 023 A1 disclose processes for the simultaneous shaping and dyeing of hair, in which a keratin-reducing preparation is used which already contains the necessary dyes and / or dye precursors. These methods described in the prior art are in need of improvement, both in terms of their deformation result and in terms of the dyeing result. In addition, the deformation and colorants used are characterized by a low chemical and physical stability. The object of the application is therefore to provide a forming and dyeing process for keratin fibers, especially for human hair, which provides a very good and lasting deformation and dyeing results, the fiber maintains and protects the structure of the fiber. The funds used should also be characterized by a good chemical and physical stability.

Surprisingly, it has been found that the object can be achieved by the combination and at the same time application of two compositions, one of which contains an agent which modifies the disulfide bridges of the hair and the other a dye.

A first subject of the application is therefore a process for smoothing and coloring keratin-containing fibers, in particular human hair, in which

(i) a treatment agent A containing at least one alkalizing agent is provided,

(ii) a treating agent B containing at least one keratin-coloring substance is provided,

(iii) the treatment agents A and B and optionally further active ingredients are mixed together to form a treatment agent C having a pH of between 10 and 14,

(iv) the treatment agent C is applied to the keratin-containing fibers,

(v) the keratin-containing fibers are subsequently mechanically smoothed and rinsed,

(vi) the fibers are then optionally treated with an oxidizing agent and subsequently rinsed again.

The treatment agent A used in the method according to the invention and the treatment agent C obtained in step (iii) contain at least one alkalizing agent. As stated above, the addition of alkalizing agent serves to break the disufide bridges of the keratinic fibers and thus allow their transformation. For this reason, the pH of the treatment agent C is between 10 to 14, with pH values of 1 1 to 14, in particular of 12 to 13 are preferred.

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 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-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1 Aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol , 1-amino-2-methylpropan-2-ol, 3-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-methyl-propane-1,3-diol.

The alkali metal hydroxides which can be used as alkalizing agents are preferably selected from the group consisting of sodium hydroxide and potassium hydroxide. These alkalizing agents are particularly suitable for the adjustment of strongly alkaline pH values. Methods using treating agents A which contain at least one alkalizing agent selected from the group consisting of sodium hydroxide and potassium hydroxide are preferred.

Very particularly preferred methods according to the invention are characterized in that the fibers in step (iv) are subjected to a treatment with a treatment agent C which - based on its weight - 1 to 5 wt .-%, preferably 1, 5 to 4.5 wt .-%, more preferably 2 to 4 wt .-% and in particular 2.5 to 3.5 wt .-% sodium hydroxide and / the potassium hydroxide, vorugsweise sodium hydroxide.

An alternative to the strongly alkaline alkalizing agents sodium hydroxide and potassium hydroxide are lithium hydroxide, calcium hydroxide and guanidine hydroxide, which is formed in situ from calcium hydroxide and guanidine carbonate. Because of their lower alkalinity, these alkalizing agents damage the keratinic fibers subjected to forming to a lesser extent than the aforementioned hydroxides of sodium and potassium. Preferred processes according to the invention are therefore characterized in that the treatment agent A comprises at least one alkalizing agent selected from the group consisting of lithium hydroxide, calcium hydroxide and guanidine carbonate.

Further particularly preferred methods according to the invention are characterized in that the fibers in step (iv) are subjected to a treatment with a treatment agent C, which based on its weight - 0.5 to 2.5 wt .-%, preferably 0.75 to 2.25 wt .-%, more preferably 1 to 2 wt .-% and in particular 1, 25 to 1, 75 wt. - contains% calcium hydroxide.

Further particularly preferred methods according to the invention are characterized in that the fibers in step (iv) are subjected to a treatment with a treatment agent C, which - based on its weight - 0.5 to 2.5 wt .-%, preferably 0.75 to 2.25 wt .-%, more preferably 1 to 2 wt .-% and in particular 1, 25 to 1, 75 wt .-% guanidine carbonate.

Particularly preferred processes according to the invention are characterized in that the fibers in step (iv) are subjected to a treatment with a treatment agent C which, based on its weight, is 0.5 to 2.5% by weight, preferably 0.75 to 2.25 wt .-%, more preferably 1 to 2 wt .-% and in particular 1, 25 to 1, 75 wt .-% calcium hydroxide and 0.5 to 2.5 wt .-%, preferably 0.75 to 2 , 25 wt .-%, more preferably 1 to 2 wt .-% and in particular 1, 25 to 1, 75 wt .-% guanidine carbonate.

The treatment agent B used in the process according to the invention and the treatment agent C obtained in step (iii) contain at least one keratin-dyeing substance. The proportion by weight of the keratin-coloring substance in the total weight of the treatment agent C is preferably from 0.1 to 20% by weight, preferably from 0.15 to 10% by weight, particularly preferably from 0.2 to 5.0% by weight and in particular 0 , 25 to 2.0% by weight.

Preferred keratin-coloring substances are selected from the group of substantive dyes and the oxidative colorants (oxidation dye precursors). Particularly preferred are those process variants in which the treatment agent B contains at least one keratin-dyeing substance from the group of oxidative colorants. The proportion by weight of the keratin-coloring substance in the total weight of the treating agent C is preferably 0.01 to 4.0% by weight, preferably 0.1 to 2.0% by weight, preferably 0.2 to 1.0% by weight. and in particular from 0.25 to 0.8% by weight

In a further preferred embodiment, the compositions B and C used in the process according to the invention comprise at least one oxidative dye (oxidation dye precursor).

According to the invention, oxidative colorants are to be understood to mean hair color-modifying agents which cause a permanent coloration of the fibers by oxidation of oxidation dye precursors. With regard to the usable dye precursors, the present invention is not subject to any restrictions. The compositions used according to the invention may contain, as dye precursors, oxidation dye precursors of the developer and / or coupler type, and precursors of naturally-analogous dyes, such as indole and indoline derivatives, and mixtures of representatives of these groups.

In a first preferred embodiment of the present invention, the compositions used according to the invention contain at least one oxidation dye precursor of the developer and / or coupler type.

It may be preferred according to the invention to use as the developer component a p-phenylenediamine derivative or one of its physiologically acceptable salts.

Particularly preferred p-phenylenediamines are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine and N-phenyl-p-phenylenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine and their physiologically acceptable salts.

It may further be preferred according to the invention to use as developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups. Preferred binuclear developer components are in particular: N, N'-bis (2-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol and bis (2-hydroxy) Hydroxy-5-aminophenyl) -methane and their physiologically acceptable salts.

Furthermore, it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts.

Preferred p-aminophenols are in particular p-aminophenol, N-methyl-p-aminophenol, and 4-amino-3-methyl-phenol and their physiologically acceptable salts.

Further, the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-5-methylphenol and its physiologically acceptable salts.

Furthermore, the developer component may be selected from heterocyclic developer components, such as the pyridine, pyrimidine, pyrazole, pyrazolo-pyrimidine derivatives and their physiologically acceptable salts. Preferred pyrimidine derivatives are in particular 2,4,5,6-tetraaminopyrimidine and 4-hydroxy-2,5,6-triaminopyrimidine and their physiologically acceptable salts.

A preferred pyrazole derivative is 4,5-diamino-1- (2-hydroxyethyl) pyrazole and its physiologically acceptable salts.

In a further preferred embodiment, the compositions B contain at least one coupler component.

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used. Suitable coupler substances are, in particular, 1-naphthol, 1, 5- and 2,7-dihydroxynaphthalene, 1-acetoxy-2-methoxynaphthalene, resorcinol, 4-chloro-resorcinol and 2-amino-3-hydroxypyridine and their physiologically tolerated salts.

According to preferred coupler components are

(A) m-Aminophenol and its derivatives such as 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5- (2'-hydroxyethyl ) -amino-2-methylphenol and 2,4-dichloro-3-aminophenol,

(B) o-aminophenol and its derivatives, for example 2-amino-5-ethylphenol,

(C) m-diaminobenzene and its derivatives such as 2,4-diaminophenoxyethanol, 1,3-bis (2 ', 4'-diaminophenoxy) -propane, 1-methoxy-2-amino-4- (2' -hydroxyethylamino) benzene, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, and 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol,

(D) o-diaminobenzene and its derivatives,

(E) di- or trihydroxybenzene derivatives such as, for example, 2-methylresorcinol and 1,2,4-trihydroxybenzene,

(F) pyridine derivatives such as 3-amino-2-methylamino-6-methoxypyridine, 2,6-diaminopyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2-amino-3-hydroxypyridine and 3,5-diamino 2,6-dimethoxy,

(G) naphthalene derivatives such as 1-naphthol and 2-methyl-1-naphthol,

(H) morpholine derivatives such as 6-hydroxybenzomorpholine,

(I) quinoxaline derivatives,

(J) pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,

(K) indole derivatives such as 6-hydroxyindole,

(L) pyrimidine derivatives or (M) Methylenedioxybenzene derivatives such as 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene

and their physiologically acceptable salts.

Particularly preferred coupler components according to the invention are 1-naphthol, 1,5- and 2,7-dihydroxynaphthalene, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol, 2-methylresorcinol and 2,6- Dihydroxy-3,4-dimethylpyridine and its physiologically acceptable salts.

The compositions B and C used according to the invention, in particular the compositions C, contain both the developer components and the coupler components preferably in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the total weight the means. In this case, developer components and coupler components are generally used in approximately molar amounts to each other. Although the molar use has proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2 , may be included.

In a further embodiment of the present invention, the oxidation dye precursor compositions used according to the invention contain at least one precursor of a naturally-analogous dye. As precursors of naturally-analogous dyes such indoles and indolines are preferably used which have at least one hydroxy or amino group, preferably as a substituent on the six-membered ring. Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline and 2,3-dioxoindoline (isatin) and their physiologically acceptable salts. A particularly preferred derivative of indole is 5,6-dihydroxyindole and its physiologically acceptable salts.

The agents used according to the invention preferably contain the indole or indoline derivatives in an amount of 0.05-10% by weight, preferably 0.2-5% by weight, in each case based on their total weight.

Direct dyes can be subdivided into anionic, cationic and nonionic substantive dyes. The substantive dyes are preferably selected from the nitrophenylenediamines, the nitroaminophenols, the azo dyes, the anthraquinones or the indophenols and their physiologically tolerated salts.

2,4-dinitro-1-naphthol-7-sulfonic acid disodium salt (Cl 10,316, Acid Yellow 1, Food Yellow No. 1), 2- (indan-1, 3-dione-2) are particularly suitable as anionic substantive dyes. yl) quinoline-x, x-sulfonic acid (mixture of mono- and disulfonic acid) (Cl 47.005, D & C Yellow No. 10, Food Yellow No. 13, Acid Yellow 3, Yellow 10), 5-hydroxy-1 - (4- sulfophenyl) -4 - [(4-sulfophenyl) azo] pyrazole-3-carboxylic acid trisodium salt (Cl 19, 140; Food Yellow No. 4; Acid Yellow 23), 3 - [(4-phenylamino) phenyl] azobenzenesulfonic acid sodium salt ( Cl 13.065; Ki406; Acid Yellow 36), 4 - [(2-hydroxynaphth-1-yl) azo] -benzenesulfonic acid, sodium salt (Cl 15.510, Acid Orange 7), 6-hydroxy-5- [(4-sulfonaphth-1 -yl) azo] -2,4-naphthalenedisulfonic acid trisodium salt (Cl 16,255; Ponceau 4R; Acid Red 18); 8-amino-1-hydroxy-2- (phenylazo) -3,6-naphthalenedisulfonic acid disodium salt (Cl 17,200; Acid Red 33; Red 33), N- [6- (diethylamino) -9- (2,4-disulfophenyl) -3H-xanthen-3-ylidene] -N-ethyl-urethane ammonium hydroxide, inner salt, sodium salt (Cl 45,100; Acid Red 52), 2 ', 4', 5'J'-tetrabromo-4,5,6,7-tetrachloro-3 ', 6'-dihydroxyspiro [isobenzofuran-1 (3H), 9' [ 9H] xanthene] -3-one-disodium salt (Cl 45.410; Acid Red 9 2), 3-hydroxy-4 - [(4-methyl-2-sulfonphenyl) azo] -2-naphthalenecarboxylic acid calcium salt (Cl 15,850: 1; Pigment Red 57: 1), 1,4-bis [(2-sulfo-4-methylphenyl) amino] -9,10-anthraquinone disodium salt (Cl 61, 570; Acid Green 25), bis [4- (dimethylamino) phenyl] - (3,7-disulfo-2-hydroxynaphth-1-yl) carbenium inner salt, sodium salt (Cl 44.090, Food Green No. 4, Acid Green 50), N- [4 - [(2,4-) Disulfophenyl) [4- [ethyl (phenylmethyl) amino) phenyl] methylene] -2,5-cyclohexadiene-1-ylidene] -N-ethylbenzene methanaminium hydroxide, inner salt, sodium salt (CI 42,080, Acid Blue 7), (2- Sulfophenyl) di [4- (ethyl ((4-sulfophenyl) methyl) amino) phenyl] -carbenium disodium salt betaine (CI 42.090, Acid Blue 9, FD & C Blue No. 1), 1-amino-4- (cyclohexylamino) - 9,10-anthraquinone-2-sulfonic acid, sodium salt (Cl 62045; Acid Blue 62), 1-hydroxy-4 - [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone sodium salt (Cl 60.730; D & C Violet No. 2; Acid Violet 43), 5-amino-4-hydroxy-6- [(4-nitrophenyl) -azo] -3- (phenylazo) -2,7-naphthalenedisulfonic acid disodium salt (Cl., 20, 440 Acid Black 1), 3-hydroxy-4 - [(2-hydroxynaphth-1-yl) azo] -7- nitro-1-naphthalenesulfonic acid-chromium complex (3: 2) (Cl 15.71 1; Acid Black 52), 3 ', 3 ", 4,5,5', 5", 6,7-octabromophenolsulfonephthalein (tetrabromophenol blue).

Preferred anionic substantive dyes are those having the international designations or trade names Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52, Pigment Red 57: 1, Acid Blue 7 , Acid Green 50, Acid Violet 43, Acid Black 1 and Acid Black 52 known compounds.

Suitable cationic substantive dyes are, in particular, di [4- (diethylamino) phenyl] [4- (ethylamino) naphthyl] carbenium chloride (CI 42,595, Basic Blue 7), di [4- (dimethylamino) phenyl] [4- (phenylamino ) naphthyl] carbenium chloride (Cl 44.045; Basic Blue 26), 8-amino-2-bromo-5-hydroxy-4-imino-6 - [(3- (trimethylammonio) phenyl) amino] -1 (4H) - naphthalene chloride (Cl 56.059, Basic Blue No. 99), tri (4-amino-3-methylphenyl) carbenium chloride (Cl 42.520, Basic Violet 2), di (4-aminophenyl) (4-amino-3-) methylphenyl) carbenium chloride (CI 42.510 Basic Violet 14), 1 - [(4-aminophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride (Cl 12.250, Basic Brown 16), 1 - [(4-amino-3-nitrophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride (Cl 12,251, Basic Brown 17), 3 - [(4-amino-2,5-dimethoxyphenyl) azo] -N, N, N-trimethylbenzylaminium chloride (Cl 12,605, Basic Orange 69), 2 - [((4-dimethylamino) phenyl) azo ] -1,3-dimethyl-1H-imidazolium chloride (Basic Red 51), 2-hydroxy-1 - [(2-methoxyphenyl) azo] -7- (trimethylammonio) naphthalene chloride (CI 12,245; Basic Red 76) , 2- [4-Aminophenyl] azo] -1,3-dimethyl-1 H -imidazolium chloride (Basic Orange 31), 3-methyl-1-phenyl-4 - [(3- (trimethylammonio) phenyl) azo] pyrazol-5-one chloride (Cl 12,719, Basic Yellow 57), 1-methyl-4- ((methylphenylhydrazono) methyl) -pyridinium methylsulfate (Basic Yellow 87), 1- (2-morpholinium-propylamino) -4 -hydroxy-9,10-anthraquinone methylsulfate, 4-formyl-1-methylquinolonium p-toluenesulfonate and substantive dyes containing a heterocycle having at least one quaternary nitrogen atom.

Suitable nonionic substantive dyes are in particular nonionic nitro and quinone dyes and neutral azo dyes.

Particularly suitable blue nitro dyes are 1,4-bis [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Violet BS), 1- (2-hydroxyethyl) amino-2-nitro-4- [di (2-hydroxyethyl) amino] -benzene (HC Blue 2), 4- [di (2-hydroxyethyl) amino] -1 - [(2-methoxyethyl) amino] -2-nitrobenzene (HC Blue 1: 1), 4- [ethyl (2 -hydroxyethyl) - amino] -1 - [(2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue 12), 1- (2-hydroxyethyl) amino-2-nitro-4-N-ethyl-N- (2-hydroxyethyl) aminobenzene (HC Blue 15), 1-amino-3-methyl-4 - [(2-hydroxyethyl) amino] -6-nitrobenzene (HC Violet 1), 1- (3-hydroxypropylamino) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzene (HC Violet 2).

Suitable red nitro dyes are in particular 1-amino-4 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red 7), 2-amino-4,6-dinitrophenol (pikramic acid) and their salts, 1, 4-diamino -2-nitrobenzene (Cl 76.070), 4-amino-2-nitro-diphenylamine (HC Red 1), 1-amino-4- [di (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Red 13) , 1-amino-4 - [(2-hydroxyethyl) amino] -5-chloro-2-nitrobenzene, 4-amino-1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red 3), 4 - [(2-hydroxyethyl) amino] -3-nitrotoluene, 4-amino-3-nitrophenol, 4 - [(2-hydroxyethyl) amino] -3-nitrophenol, 4 - [(2-nitrophenyl) amino] phenol (HC Orange 1), 1 - [(2-aminoethyl) amino] -4- (2-hydroxyethoxy) -2-nitrobenzene (HC Orange 2), 1-amino-5-chloro-4 - [(2,3- dihydroxypropyl) amino] -2-nitrobenzene (HC Red 10), 5-chloro-1,4- [di (2,3-dihydroxypropyl) amino] -2-nitrobenzene (HC Red 1 1), 2 - [(2 Hydroxyethyl) amino] -4,6-dinitrophenol and its salts, 4-ethylamino-3-nitrobenzoic acid, 2 - [(4-amino-2-nitrophenyl) amino] benzoic acid, 2-chloro-6-ethylamino-4-ni trophenol, 2-amino-6-chloro-4-nitrophenol, 4 - [(3-hydroxypropyl) amino] -3-nitrophenol (HC Red BN), 1,2,3,4-tetrahydro-6-nitroquinoxaline, 6- Hydroxy-5 - ((2-methoxy-5-methyl-4-sulfophenyl) azo) -2-naphthalenesulfonic acid (Curry Red). Suitable yellow nitro dyes are in particular 1, 2-diamino-4-nitrobenzene (Cl 76.020), 1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Yellow 2), 1- (2-hydroxyethoxy) -2- [ (2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 4), 1-amino-2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 5), 4 - [(2,3-dihydroxypropyl ) -amino] -3-nitro-1-trifluoromethylbenzene (HC Yellow 6), 2 - [(2-hydroxyethyl) amino] -1-methoxy-5-nitrobenzene, 2-amino-4-nitrophenol, 1 - ( 2-hydroxyethoxy) -3-methylamino-4-nitrobenzene, 2,3- (dihydroxypropoxy) -3-methylamino-4-nitrobenzene, 3 - [(2-aminoethyl) amino] -1-methoxy-4-nitrobenzene hydrochloride ( HC Yellow 9), 1-chloro-2,4-bis [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 10), 2 - [(2-hydroxyethyl) amino] -5-nitrophenol (HC Yellow 1 1), 1 - [(2'-Ureidoethyl) amino] -4-nitrobenzene, 1-amino-4- [(2-aminoethyl) amino] -5-methyl-2-nitrobenzene, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-chloro-4 - [(2-hydroxyethyl) amino] -3-nitrobenzene (HC Yellow 12), 4 - [(2-hydroxyethyl) amino] -3 -nitro-1-trifluoromethylbenzene (HC Yellow 13).

Suitable quinone dyes are, in particular, 1 - [(2-hydroxyethyl) amino] -4-methylamino-9,10-anthraquinone (Cl 61, 505, Disperse Blue 3), mixtures of 1,4-bis [(2-hydroxyethyl) amino] anthra-9,10-quinone with 1 - [(2-hydroxyethyl) amino] -4 - [(3-hydroxypropyl) amino] anthra-9,10-quinone and 1,4-bis [(3-hydroxypropyl) amino] anthra-9,10-quinone (Disperse Blue 377), 1, 4-diamino-9,10-anthraquinone (Cl. 61, 100, Disperse Violet 1), 1-amino-4- (methylamino) -9,10- anthraquinone (Cl 61, 105, Disperse Violet 4, Solvent Violet No. 12), 2-hydroxy-1,4-naphthoquinone (Lawsone, Cl. 75,480, Natural Orange 6), 1,4-bis [(2,3- dihydroxypropyl) amino] -9,10-anthracenedione (HC Blue 14).

Suitable neutral azo dyes are in particular 1 - [di (2-hydroxyethyl) amino] -3-methyl-4 - [(4-nitrophenyl) azo] benzene (Cl 11, 210, Disperse Red 17), 1 - [Di ( 2-hydroxyethyl) amino] -4 - [(4-nitrophenyl) azo] benzene (Disperse Black 9), 4 - [(4-aminophenyl) azo] -1 - [di (2-hydroxyethyl) amino] -3- methylbenzene (HC Yellow 7), 2,6-diamino-3 - [(pyridin-3-yl) azo] -pyridine, 4 - [(4-nitrophenyl) azo] -aniline (Cl 1, 005; Disperse Orange 3 ).

Preferred process variants are characterized in that the treatment agent C contains no xanthene dye.

To improve the conversion and dyeing results, it has proven to be advantageous if the treatment agent C contains at least one swelling agent. As swelling agent b) is preferably a compound from the group urea and urea derivatives, guanidine and its derivatives, arginine and its derivatives, water glass, imidazole and its derivatives, histidine and its derivatives, benzyl alcohol, glycerol, glycol and glycol ethers, propylene glycol and propylene glycol, for example Propylene glycol monoethyl ether, carbonates, bicarbonates, diols and triols, and in particular 1,2-diols and 1,3-diols, for example 1,2-propanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-dodecanediol, 1,3-propanediol, 1,6-hexanediol, 1, 5-pentanediol, 1, 4-butanediol but also sorbitol or pyrrolidonecarboxylic acid used. A particularly advantageous hair straightening and especially advantageous dyeing results are achieved by the use of a swelling agent b) from the group urea (urea), glycerol (propane-1,2,3-triol), sorbitol (D-glucitol) and / or pyrrolidonecarboxylic acid (5- Oxopyrrolidine-2-carboxylic acid), especially urea. The use of these specific swelling agents is preferred according to the invention.

The proportion by weight of the swelling agent b) in the total weight of the treatment agent C is preferably 0.2 to 15 wt .-%, preferably 1, 0 to 12 wt .-% and in particular 2.0 to 10 wt .-%.

Furthermore, the composition containing the keratin reducing substance may contain surfactants, especially those from the group of anionic, amphoteric, zwitterionic and nonionic surfactants. These surfactants have the task of promoting the wetting of the keratin surface by the treatment solution, but above all to solubilize any existing fragrances or to emulsify stably.

Nonionic surfactants contain as hydrophilic group e.g. a polyol group, a polyalkylene glycol ether group, or a combination of polyol and polyglycol ether groups. Preferred nonionic surfactants are

- Addition products of 2 to 100 moles of ethylene oxide and / or 1 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the Alkyl group, in particular

- Addition product of 15 to 100 moles of ethylene oxide, in particular from 15 to 50 moles of ethylene oxide to a linear or branched (especially linear) fatty alcohol having 8 to 22 carbon atoms

- With a methyl or (C2 to Ce) -alkyl radical endgruppenverschlossene addition products of 2 to 50 moles of ethylene oxide and / or 1 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 C Atoms and alkylphenols having 8 to 15 C atoms in the alkyl group,

C 12 -C 30 -fatty acid mono- and diesters of addition products of 1 to 30 mol of ethylene oxide with glycerol,

Adducts of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil,

Polyol fatty acid esters, such as the commercial product Hydagen® HSP (Cognis) or Sovermol types (Cognis),

- alkoxylated triglycerides, alkoxylated fatty acid alkyl esters of the formula (E4-I)

R ¹ CO- (OCH ₂ CHR ² ) wOR ³ (E4-I)

in the R ¹ CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or methyl, R ^{3 is a} linear or branched alkyl radical having 1 to 4 carbon atoms and w is a number from 1 to 20 stands,

- amine oxides,

Sorbitan fatty acid esters and adducts of ethylene oxide with sorbitan fatty acid esters such as the polysorbates,

Sugar fatty acid esters and addition products of ethylene oxide with sugar fatty acid esters,

Adducts of ethylene oxide with fatty acid alkanolamides and fatty amines,

- sugar surfactants of the alkyl and alkenyl oligoglycoside type of the formula R40- [G] p in which R ^{4 is} an alkyl or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10 stands. They can be obtained by the relevant methods of preparative organic chemistry.

With regard to the care effect of the method according to the invention, it is preferred if the composition C additionally contain at least one cationic surfactant. Again, cationic surfactants selected from quaternary ammonium compounds, esterquats and amidoamines or mixtures thereof are preferred. The cationic surfactants are contained in the compositions C preferably in amounts of 0.05 to 10 wt .-%, based on the total agent. Amounts of 0.1 to 5 wt .-% are particularly preferred.

Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkyl methylammonium chlorides, eg. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms. Very particularly preferred methods according to the invention are characterized in that the treatment agent C, based on its total weight, 0.01 to 1 wt .-%, preferably 0.025 to 0.75 wt .-%, more preferably 0.05 to 0.5 wt % and in particular 0.1 to 0.25 wt .-% (C12 to Cie) - alkyltrimethylammonium salt (s).

Within the scope of one embodiment, it is preferred to additionally employ in the agent according to the invention at least one setting polymer selected from at least one compound the group formed from strengthening nonionic polymers, fortifying anionic polymers, strengthening amphoteric polymers, and setting cationic polymers. Firming polymers contribute to the maintenance and / or build-up of the hair volume and hair fullness of the overall hairstyle. These polymers are at the same time also film-forming polymers and therefore generally typical substances for shaping hair treatment agents such as hair fixatives, hair foams, hair waxes, hair sprays. The film formation can be quite selective and connect only a few fibers.

Another preferred ingredient of the compositions C are cationic polyemes. The additional strengthening cationic polymers have at least one structural unit containing at least one permanently cationized nitrogen atom. Permanently cationized nitrogen atoms are to be understood as meaning those nitrogen atoms which carry a positive charge and thereby form a quaternary ammonium compound. Quaternary ammonium compounds are most commonly prepared by reacting tertiary amines with alkylating agents, e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also produced ethylene oxide. Depending on the tertiary amine used, the following groups are known in particular: alkylammonium compounds, alkenylammonium compounds, imidazolinium compounds and pyridinium compounds.

Preferred processes are characterized in that the treatment agent C, based on its total weight, is from 0.2% by weight to 10.0% by weight, very particularly preferably from 0.5% by weight to 5.0% by weight. containing, setting, cationic polymer.

Suitable cationic polymers are

cationic, quaternized cellulose derivatives such as are prepared, for example, by the reaction of hydroxyethyl cellulose with a dimethyl diallyl ammonium reactant (especially dimethyl diallyl ammonium chloride) optionally in the presence of other reactants; particularly suitable are cationic celluloses with the INCI name Polyquaternium-4;

Copolymers of diethyl sulfate quaternized dimethylaminoethyl methacrylate, with N-vinylpyrrolidone, for example copolymers with the INCI name Polyquaternium-1 1;

- Copolymers of methacryloylaminopropyllauryldimethylammonium chloride with N-vinylpyrrolidone and dimethylaminopropylmethacrylamide, for example copolymers with the INCI name;

- Copolymers of methacryloylaminopropyllauryldimethylammonium chloride with N-vinylpyrrolidone, N-vinylcaprolactam and dimethylaminopropylmethacrylamide, for example copolymers with the INCI name Polyquaternium-69; Copolymers of N-methylvinylimidazole and vinylpyrrolidone copolymers, for example copolymers with the INCI name Polyquaternium-16 or Polyquaternium-44;

Copolymers of N-methylvinylimidazole, vinylpyrrolidone and vinylcaprolactam, for example copolymers with the INCI name Polyquarternium-46;

Copolymers of N-methylvinylimidazole, vinylpyrrolidone, vinylimidazole and methacrylamide copolymers, for example copolymers with the INCI name Polyquaternium-68;

The composition according to the invention preferably contains at least one strengthening nonionic polymer as additional strengthening polymer. The strengthening nonionic polymers are preferably present in the composition according to the invention in an amount of from 0.1% by weight to 20.0% by weight, particularly preferably from 0.2% by weight to 15.0% by weight, completely particularly preferably from 0.5 wt .-% to 10.0 wt .-%, each based on the total weight of the inventive composition.

The compositions A, B and C preferably contain the ingredients in a cosmetically acceptable carrier. Preferred cosmetically acceptable carriers are aqueous, alcoholic or aqueous-alcoholic media. Aqueous alcoholic media preferably contain at least 10% by weight of water, in particular at least 30% by weight of water, in each case based on the total agent. As alcohols, it is possible in particular to include the lower alcohols having 1 to 4 carbon atoms (in particular (C 1 to C 4) monohydroxyalkanes) customarily used for cosmetic purposes, such as, for example, ethanol and isopropanol. It is inventively preferred to use at least one (Ci to C4) monohydroxyalkane in the inventive compositions, wherein amounts of 1 to 50 wt .-%, in particular from 5 to 30 wt .-% are preferred.

The cosmetically acceptable carrier of the agent according to the invention very particularly preferably contains at least 10% by weight of water and 0 to 50% by weight of at least one (C 1 to C ₄ ) monohydroxyalkane, in particular at least 30% by weight of water and optionally 5 to 30 % By weight of at least one (C 1 to C ₄ ) monohydroxyalkane, in each case based on the total weight of the agent according to the invention. As additional co-solvents, organic solvents or a mixture of solvents having a boiling point below 400 ° C. may be present in an amount of from 0.1 to 15% by weight, preferably from 1 to 10% by weight, based on the total agent according to the invention. Particularly suitable as additional co-solvents are unbranched or branched hydrocarbons such as pentane, hexane, isopentane and cyclic hydrocarbons such as cyclopentane and cyclohexane. Further, particularly preferred water-soluble solvents are glycerol, ethylene glycol and 1, 2-propylene glycol in an amount of up to 30 wt .-% based on the total agent. In summary, preferred methods according to the invention are characterized in that the treatment agent C, based on its total weight, contains at least 10% by weight of water and 0 to 50% by weight of at least one (O to C4) monohydroxyalkane.

The keratinic fibers are smoothed in step (v) of the method according to the invention.

The keratinic fibers, in particular the human hair, are preferably mechanically smoothed during or after the end of the reaction time. The smoothing is preferably carried out without heat. For smoothing, for example, the combing or the application of a, preferably unheated smoothing boards are. According to preferred methods are characterized in that the smoothing in step v) takes place without heat. Smoothing and rinsing of the keratinic fibers in step v) can in principle be carried out in any order. For the smoothing and staining results, however, it has proven to be advantageous first to smooth the keratinic fibers in step (v) and then to rinse them.

The smoothing and staining results achieved by means of the method according to the invention can be improved by repeating the method steps (iv) and (v). Particularly preferred process variants are therefore characterized by repeating the process steps (iv) and (v) twice, preferably three times.

In order to improve the care effect of the methods according to the invention, it is preferred to subject the keratinic fibers to an oxidative treatment after step (v).

The compositions, uses, and methods of the invention, and some of their preferred embodiments, are characterized by the following items:

1 . Process for smoothing and coloring keratin-containing fibers, in particular human hair, in which

(i) a treatment agent A containing at least one alkalizing agent is provided,

(iv) the treatment agents A and B and optionally further active ingredients are mixed together to give a treatment agent C having a pH of between 10 and 14,

(iv) the treatment agent C is applied to the keratin-containing fibers,

(vi) the fibers are then optionally treated with an oxidizing agent and subsequently rinsed again. A method according to claim 1, characterized in that the treatment agent A at least one alkalizing agent from the group sodium hydroxide and potassium hydroxide. Method according to one of the preceding claims, characterized in that the treatment agent A contains at least one alkalizing agent from the group lithium hydroxide, calcium hydroxide and guanidine carbonate. Method according to one of the preceding claims, characterized in that the treatment agent B contains at least one keratin-coloring substance from the group of oxidative coloring agents. Method according to one of the preceding points, characterized in that the treatment agent C contains no xanthene dye. Experienced according to one of the preceding points, characterized in that the weight fraction of the keratin coloring oxidative colorant in the total weight of the treating agent C 0.01 to 4.0 wt .-%, preferably 0.1 to 2.0 wt .-%, preferably 0.2 to 1, 0 wt .-% and in particular 0.25 to 0.8 wt .-% is. Method according to one of the preceding points, characterized in that the treatment agent C at least one swelling agent, preferably a swelling agent from the group urea (urea), glycerol (propane-1, 2,3-triol), sorbitol (D-glucitol) and / or pyrrolidonecarboxylic acid (5-oxopyrrolidine-2-carboxylic acid). Method according to one of the preceding points, characterized in that

the proportion by weight of the swelling agent b) in the total weight of the treatment agent C is from 0.2 to 15% by weight, preferably from 1 to 0 to 12% by weight and in particular from 2.0 to 10% by weight. Method according to one of the preceding points, characterized in that the treatment agent C, based on its total weight, 0.01 to 1 wt .-%, preferably 0.025 to 0.75 wt .-%, more preferably 0.05 to 0.5 Wt .-% and in particular 0.1 to 0.25 wt .-% (C12 to Ci8) -Alkyltrimethylammoniumsalz (e). Method according to one of the preceding points, characterized in that the treatment agent C, based on its total weight of 0.2 wt .-% to 1 0.0 wt .-%, most preferably from 0.5 wt .-% to 5, 0 wt .-%, consolidating, cationic polymer. Method according to one of the preceding points, characterized in that the treatment agent C, based on its total weight at least 10 wt .-% water and 0 to 50 wt .-% of at least one (Ci to C4) -Monohydroxyalkans. Method according to one of the preceding points, characterized in that the smoothing in step v) takes place without the action of heat. Method according to one of the preceding points, characterized in that the keratinic fibers are first smoothed in step (v) and then rinsed. Method according to one of the preceding points, characterized in that the method steps (iv) and (v) are repeated at least twice, preferably at least three times. Method according to one of the preceding points, characterized in that the keratinic fibers are subjected to an oxidative treatment following step (v).

Claims

claims:

(i) a treatment agent A containing at least one alkalizing agent is provided,

(v) the treatment agents A and B and, if appropriate, further active ingredients are mixed together to form a treatment agent C having a pH of between 10 and 14,

(iv) the treatment agent C is applied to the keratin-containing fibers,

2. The method according to claim 1, characterized in that the treatment agent A contains at least one alkalizing agent from the group of sodium hydroxide and potassium hydroxide.

3. The method according to any one of the preceding claims, characterized in that the treatment agent A contains at least one alkalizing agent from the group lithium hydroxide, calcium hydroxide and guanidine carbonate.

4. The method according to any one of the preceding claims, characterized in that the treatment agent B contains at least one keratin-coloring substance from the group of oxidative colorants.

5. The method according to any one of the preceding claims, characterized in that the weight fraction of the keratin coloring oxidative colorant in the total weight of the treating agent C 0.01 to 4.0 wt .-%, preferably 0.1 to 2.0 wt .-% , preferably 0.2 to 1, 0 wt .-% and in particular 0.25 to 0.8 wt .-% is.

6. The method according to any one of the preceding claims, characterized in that the treatment agent C is a swelling agent, preferably a swelling agent from the group urea (urea), glycerol (propane-1, 2,3-triol), sorbitol (D-glucitol) and or pyrrolidonecarboxylic acid (5-oxopyrrolidine-2-carboxylic acid).

7. The method according to any one of the preceding claims, characterized in that the smoothing in step v) takes place without heat.

8. The method according to any one of the preceding claims, characterized in that the keratinic fibers are first smoothed in step (v) and then rinsed.

9. The method according to any one of the preceding claims, characterized in that the process step (iv) and (v) are repeated at least twice, preferably at least three times.

10. The method according to any one of the preceding claims, characterized in that the keratinischen fibers are subjected to an oxidative treatment after step (v).