DE102006016817A1 - Brightening and / or colorants with good skin compatibility - Google Patents

Abstract

Means for bleaching human hair, which - based on their weight - 5 to 70 wt .-% of at least one solid peroxo compound selected from ammonium and alkali metal persulfates and peroxide sulfates, and 0.05 to 5 wt .-% of at least one Cyanates of the formula M <SUP> + </SUP> [OCN] <SUP> - </SUP> in the M <SUP> + </SUP> for K <SUP> + </SUP>, Na <SUP> + </SUP>, Li <SUP> + </SUP> or NH <SUB> 4 </SUB> <SUP> + </SUP> or 1 / 2Ca2 +, 1 / 2Mg2 + or 1 / 2Zn2 + and / or 0, 05 to 5% by weight of at least one compound of the formula H <SUB> 2 </SUB> NC (O) -L in which L stands for a group which can be displaced by the anion <SUP> - </SUP> OOH to a reduction in the exposure times and the irritation potential of these agents.

Description

The The invention relates to a bleaching agent for human hair, in particular a bleaching agent for human Hair that is in paste or powder form.

The change The shape and color of the hair represents an important area of the hair This can change the appearance of the hair both current fashion trends as well as the individual wishes adapted to the individual person become. It can Perming and other hair shape changing procedures almost independent of Type of hair to be treated to be used. In contrast, dyeing and in particular bleaching method to certain initial hair colors limited. So are suitable for lightening procedures, the so-called Blondierverfahren, essentially only dark blond or lighter hair. The basics of the Blondierverfahren are known in the art and can in relevant Monographs, z. By Kh. Schrader, basics and recipes Cosmetics, 2nd edition, 1989, Dr. med. Alfred Hüthig Verlag, Heidelberg, or W. Umbach (ed.), Cosmetics, 2nd edition, 1995, Georg Thieme Verlag, Stuttgart, New York, can be read.

So become common solid or pasty Preparations with solid oxidizing agents immediately before use with a diluted one hydrogen peroxide solution mixed. This mixture is then applied to the hair and rinsed out again after a certain exposure time.

The preparations which are mixed with a hydrogen peroxide solution before use, are referred to hereinafter as "Blondiermittel" or "Blondierpulver". All listed Unless otherwise stated, quantities are exclusive these preparations.

Neither the pasty ones still the powdery Bleaching agents that are on the market today may be considered optimal become. While the Blondierwirkung on the hair can be described as satisfactory can, there are still a number of disadvantages and problems both in the manufacture and in the handling of these agents. For pasty Agents that are highly viscous for stability reasons can be adjusted especially the dosage and the mixing behavior in the hydrogen peroxide solution yet do not satisfy. For powdered Means are the dust behavior, both in the packaging as well as in the application, as well as the mixing behavior at the center of the improvement efforts during the application. In addition, the duration of exposure to the hair to achieve a complete color between about 30 and 40 minutes. It is obvious that users have a need to reduce this exposure time.

It it has now been found that certain drug combinations with particular advantage in Blondiermittel and to reduce the exposure times and lead to the irritation potential of these funds.

• a) 5 bis 70 Gew.-% mindestens einer festen Peroxoverbindung, die ausgewählt ist aus Ammonium- und Alkalimetall-persulfaten und -peroxidisulfaten,
• b1) 0,05 bis 5 Gew.-% mindestens eines Cyanats der Formel M⁺[OCN]^– in der M⁺ für K⁺, Na⁺, Li⁺ oder NH₄ ⁺ oder ½ Ca²⁺, ½ Mg²⁺ oder ½ Zn²⁺ steht und/oder
• b2) 0,05 bis 5 Gew.-% mindestens einer Verbindung der Formel H₂N-C(O)-L in der L für eine durch das Anion ^–OOH verdrängbare Gruppe steht.

The invention relates in a first embodiment to a means for bleaching human hair, comprising - in each case based on its weight -

• a) from 5 to 70% by weight of at least one solid peroxy compound selected from ammonium and alkali metal persulfates and peroxydisulfates,
• b1) 0.05 to 5 wt .-% of at least one cyanate of the formula M ⁺ [OCN] ^- in which M ^{+ stands} for K ⁺ , Na ⁺ , Li ⁺ or NH ₄ ⁺ or ½ Ca ²⁺ , ½ Mg ²⁺ or ½ Zn ²⁺ and / or
• b2) from 0.05 to 5% by weight of at least one compound of the formula H ₂ NC (O) -L in which L stands for a group displaceable by the anion ^- OOH.

The Bleaching agent according to the invention contain as the first compelling component a solid peroxo compound, the selected is made of ammonium and alkali metal persulfates and peroxydisulfates. The selection of this peroxo compound is subject in principle no restrictions; usual, peroxo compounds known to the person skilled in the art are, for example, ammonium peroxydisulfate, Potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, Potassium persulfate, sodium persulfate. Among these peroxo compounds, which can also be used in combination, according to the invention are the Peroxidisulfate preferred, in particular combinations of at least two peroxydisulfates.

Preferred agents according to the invention are therefore characterized in that they contain sodium peroxydisulfate and / or potassium peroxodisulfate and / or ammonium peroxodisulfate, preferred agents containing at least two different peroxidisulfates. Furthermore, use within narrower ranges is preferred, so that preferred agents according to the invention are characterized in that they are from 6 to 65 Wt .-%, preferably 7.5 to 60 wt .-%, particularly preferably 8 to 55 wt .-% and in particular 10 to 50 wt .-% peroxydisulfate (s) included.

When additional component can the bleaching compositions according to the invention contain an alkalizing agent, which is used to adjust the alkaline pH of the application mixture is used. This is preferred according to the invention.

According to the invention can the expert also for Blondiermittel known, usual Alkalizing agents such as ammonium, alkali metal and alkaline earth metal hydroxides, carbonates, bicarbonates, hydroxycarbonates, silicates, in particular Metasilicates, and alkali phosphates are used. Also short-chain Amines such as monoethanolamines, 3-amino-2-methylpropanol or alkaline reactive amino acids like arginine, ornithine and lysine are usable. In a preferred embodiment contain the blonding powder according to the invention at least two different alkalizing agents. It can mixtures for example, a metasilicate and a hydroxycarbonate preferred be.

The Bleaching agent according to the invention contain alkalizing agents preferably in amounts of 1-30 wt .-%, in particular from 2 to 25% by weight.

As a second essential ingredient, the bleaching agents according to the invention contain from 0.05 to 5 wt .-% of at least one cyanate of the formula M ⁺ [OCN] ^- in the M ⁺ for K ⁺ , Na ⁺ , Li ⁺ or NH ₄ ⁺ or% Ca ²⁺ , ½ Mg ²⁺ or ½ Zn ²⁺ and / or 0.05 to 5 wt .-% of at least one compound of the formula H ₂ NC (O) -L, in which L is a displaceable by the anion ^- OOH group ,

According to the invention, therefore, cyanates may be potassium cyanate, KOCN, and / or sodium cyanate, NaOCN, and / or lithium cyanate, LiOCN, and / or ammonium cyanate, NH ₄ OCN, and / or calcium cyanate, Ca (OCN) ₂ , and / or magnesium cyanate, Mg ( OCN) ₂ , and / or zinc cyanate, Zn (OCN) ₂ , are used.

According to the invention preferred Agents are characterized by being 0.075 to 4% by weight, preferably 0.1 to 2.5 wt .-% and in particular 0.2 to 1 wt .-% sodium cyanate and / or potassium cyanate and / or ammonium cyanate, wherein sodium cyanate is particularly preferred.

und M für -H, Na, K, NH₄ steht, Q ausgewählt ist aus den aus tertiären Aminen gebildeten quartären Ammoniumresten, Heteroarylresten oder nicht-aromatischen Heterocyclen und R¹ für -H, -CH₃, -CH₂CH₃, -(CH₂)₂CH₃, -CH(CH₃)₂ oder eine andere Alkylgruppe steht.Instead of cyanates or in combination with them, compounds of the formula H ₂ NC (O) -L in which L is a group displaceable by the anion ^- OOH may also be present in the agents according to the invention. Here are preferred agents according to the invention characterized in that they are 0.075 to 4 wt .-%, preferably 0.1 to 3.5 wt .-% and in particular 0.2 to 3 wt .-% of at least one compound of the formula H ₂ NC (O) -L in which L is selected from -S-CH ₂ -COOH, -S- (CH ₂ ) ₃ SO ₃ H, -S- (CH ₂ ) ₂ -NH ₂ , -OCH ₃ , -O- (C ₆ N ₄ ) -SO ₃ M, -Q ⁺ , -NH-OH, -OC (O) -R ¹ , -OC (O) -H, -O-CH (OH) ₂ , -SO ₃ M, -PH (O) OH, -P (O) (OH) ₂ , - (NH-glucosamine) _n , -NH-C (O) -NH ₂ , -NH-NH ₂ , -NH-CN, -P (OH) (O) -C (O) NH ₂ , -SCN, -OCN, -SC (NH) NH ₂ ,

and M is -H, Na, K, NH ₄ , Q is selected from quaternary ammonium radicals, heteroaryl radicals or non-aromatic heterocycles formed from tertiary amines and R ^{1 is} -H, -CH ₃ , -CH ₂ CH ₃ , - (CH ₂ ) ₂ CH ₃ , -CH (CH ₃ ) ₂ or another alkyl group.

• – H₂N-C(O)S-CH₂-COOH
• – H₂N-C(O)-S-(CH₂)₂-NH₂
• – H₂N-C(O)-S-(CH₂)₃SO₃Na
• – H₂N-C(O)-S-(CH₂)₃SO₃K
• – H₂N-C(O)-S-(CH₂)₃SO₃NH₄
• – H₂N-C(O)-SO₃H
• – H₂N-C(O)-SO₃Na
• – H₂N-C(O)-SO₃K
• – H₂N-C(O)-SO₃NH₄
• – H₂N-C(O)-O-(C₆H₄)-SO₃H
• – H₂N-C(O)-O-(C₆H₄)-SO₃Na
• – H₂N-C(O)-O-(C₆H₄)-SO₃K
• – H₂N-C(O)-O-(C₆H₄)-SO₃NH₄
• – H₂N-C(O)-O-C(O)-H
• – H₂N-C(O)-O-C(O)-CH₃
• – H₂N-C(O)-O-C(O)-CH₂CH₃
• – H₂N-C(O)-O-C(O)-(CH₂)₂CH₃
• – H₂N-C(O)-O-C(O)-CH(CH₃)₄
• – H₂N-C(O)-OCH₃
• – H₂N-C(O)-NH-OH
• – H₂N-C(O)-O-CH(OH)₂
• – H₂N-C(O)-PH(O)OH
• – H₂N-C(O)-P(O)(OH)₂
• – H₂N-C(O)-NH-C(O)-NH₂
• – H₂N-C(O)-NH-NH₂
• – H₂N-C(O)-NH-CN
• – H₂N-C(O)-P(OH)(O)-C(O)NH₂
• – H₂N-C(O)-SCN
• – H₂N-C(O)-OCN
• – H₂N-C(O)-S-C(NH)NH₂
• – H₂N-C(O)-N(CH₃)₃ ⁺Cl^–
• – H₂N-C(O)-N(CH₂CH₃)₃ ⁺Cl^–
• – H₂N-C(O)-N((CH₂)₂CH₃)₃ ⁺Cl^–
• – H₂N-C(O)-N(CH(CH₃)₂)₃ ⁺Cl^–
• – H₂N-C(O)-N(C₆H₅)₃ ⁺Cl^–
• – H₂N-C(O)-N(CH₂-Ph)₃ ⁺Cl^–
• – H₂N-C(O)-N(CH₃)₃ ⁺Br^–
• – H₂N-C(O)-N(CH₂CH₃)₃ ⁺Br^–
• – H₂N-C(O)-Ni(CH₂)₂CH₃)₃ ⁺Br^–
• – H₂N-C(O)-N(CH(CH₃)₂)₃ ⁺Br^–
• – H₂N-C(O)-N(C₆H₅)₃ ⁺Br^–
• – H₂N-C(O)-N(CH₂-Ph)₃ ⁺Br^–
• – H₂N-C(O)-N(CH₃)₃ ⁺H₃C-OSO₃ ^–
• – H₂N-C(O)-N(CH₂CH₃)₃ ⁺H₃C-OSO₃ ^–
• – H₂N-C(O)-N((CH₂)₂CH₃)₃ ⁺H₃C-OSO₃ ^–
• – H₂N-C(O)-N(CH(CH₃)₂)₃ ⁺H₃C-OSO₃ ^–
• – H₂N-C(O)-N(C₆H₅)₃ ⁺H₃C-OSO₃ ^–
• – H₂N-C(O)-N(CH₂-Ph)₃ ⁺H₃C-OSO₃ ^–
• – H₂N-C(O)-N(CH₃)₃ ⁺H₃C-CH₂-OSO₃ ^–
• - H₂N-C(O)-N(CH₂CH₃)₃ ⁺H₃C-CH₂-OSO₃ ^–
• – H₂N-C(O)-N((CH₂)₂CH₃)₃ ⁺H₃C-CH₂-OSO₃ ^–
• – H₂N-C(O)-N(CH(CH₃)₂)₃ ⁺H₃C-CH₂-OSO₃ ^–
• – H₂N-C(O)-N(C₆H₅)₃ ⁺H₃C-CH₂-OSO₃ ^–
• – H₂N-C(O)-N(CH₂-Ph)₃ ⁺H₃C-CH₂-OSO₃ ^–

Particularly preferred agents according to the invention contain from 0.075 to 4% by weight, preferably from 0.1 to 3.5% by weight and in particular from 0.2 to 3% by weight of at least one of the compounds listed below:

• - H ₂ NC (O) S-CH ₂ -COOH
• - H ₂ NC (O) -S- (CH ₂ ) ₂ -NH ₂
• - H ₂ NC (O) -S- (CH ₂ ) ₃ SO ₃ Na
• - H ₂ NC (O) -S- (CH ₂ ) ₃ SO ₃ K
• - H ₂ NC (O) -S- (CH ₂ ) ₃ SO ₃ NH ₄
• - H ₂ NC (O) -SO ₃ H
• - H ₂ NC (O) -SO ₃ Na
• - H ₂ NC (O) -SO ₃ K
• - H ₂ NC (O) -SO ₃ NH ₄
• - H ₂ NC (O) -O- (C ₆ H ₄ ) -SO ₃ H
• - H ₂ NC (O) -O- (C ₆ H ₄ ) -SO ₃ Na
• - H ₂ NC (O) -O- (C ₆ H ₄ ) -SO ₃ K
• - H ₂ NC (O) -O- (C ₆ H ₄ ) -SO ₃ NH ₄
• - H ₂ NC (O) -OC (O) -H
• - H ₂ NC (O) -OC (O) -CH ₃
• - H ₂ NC (O) -OC (O) -CH ₂ CH ₃
• - H ₂ NC (O) -OC (O) - (CH ₂ ) ₂ CH ₃
• - H ₂ NC (O) -OC (O) -CH (CH ₃ ) ₄
• - H ₂ NC (O) -OCH ₃
• - H ₂ NC (O) -NH-OH
• - H ₂ NC (O) -O-CH (OH) ₂
• - H ₂ NC (O) -PH (O) OH
• - H ₂ NC (O) -P (O) (OH) ₂
• - H ₂ NC (O) -NH-C (O) -NH ₂
• - H ₂ NC (O) -NH-NH ₂
• - H ₂ NC (O) -NH-CN
• - H ₂ NC (O) -P (OH) (O) -C (O) NH ₂
• - H ₂ NC (O) -SCN
• - H ₂ NC (O) -OCN
• - H ₂ NC (O) -SC (NH) NH ₂
• H ₂ NC (O) -N (CH ₃ ) ₃ ⁺ Cl ^-
• H ₂ NC (O) -N (CH ₂ CH ₃ ) ₃ ⁺ Cl ^-
• - H ₂ NC (O) -N ((CH ₂ ) ₂ CH ₃ ) ₃ ⁺ Cl ^-
• H ₂ NC (O) -N (CH (CH ₃ ) ₂ ) ₃ ⁺ Cl ^-
• H ₂ NC (O) -N (C ₆ H ₅ ) ₃ ⁺ Cl ^-
• H ₂ NC (O) -N (CH ₂ -Ph) ₃ ⁺ Cl ^-
• - H ₂ NC (O) -N (CH ₃ ) ₃ ⁺ Br ^-
• - H ₂ NC (O) -N (CH ₂ CH ₃ ) ₃ ⁺ Br ^-
• - H ₂ NC (O) -Ni (CH ₂ ) ₂ CH ₃ ) ₃ ⁺ Br ^-
• - H ₂ NC (O) -N (CH (CH ₃ ) ₂ ) ₃ ⁺ Br ^-
• - H ₂ NC (O) -N (C ₆ H ₅ ) ₃ ⁺ Br ^-
• - H ₂ NC (O) -N (CH ₂ -Ph) ₃ ⁺ Br ^-
• H ₂ NC (O) -N (CH ₃ ) ₃ ⁺ H ₃ C-OSO ₃ ^-
• H ₂ NC (O) -N (CH ₂ CH ₃ ) ₃ ⁺ H ₃ C-OSO ₃ ^-
• H ₂ NC (O) -N ((CH ₂ ) ₂ CH ₃ ) ₃ ⁺ H ₃ C-OSO ₃ ^-
• H ₂ NC (O) -N (CH (CH ₃ ) ₂ ) ₃ ⁺ H ₃ C-OSO ₃ ^-
• H ₂ NC (O) -N (C ₆ H ₅ ) ₃ ⁺ H ₃ C-OSO ₃ ^-
• H ₂ NC (O) -N (CH ₂ -Ph) ₃ ⁺ H ₃ C-OSO ₃ ^-
• H ₂ NC (O) -N (CH ₃ ) ₃ ⁺ H ₃ C-CH ₂ -OSO ₃ ^-
• H ₂ NC (O) -N (CH ₂ CH ₃ ) ₃ ⁺ H ₃ C-CH ₂ -OSO ₃ ^-
• H ₂ NC (O) -N ((CH ₂ ) ₂ CH ₃ ) ₃ ⁺ H ₃ C-CH ₂ -OSO ₃ ^-
• H ₂ NC (O) -N (CH (CH ₃ ) ₂ ) ₃ ⁺ H ₃ C-CH ₂ -OSO ₃ ^-
• H ₂ NC (O) -N (C ₆ H ₅ ) ₃ ⁺ H ₃ C-CH ₂ -OSO ₃ ^-
• H ₂ NC (O) -N (CH ₂ -Ph) ₃ ⁺ H ₃ C-CH ₂ -OSO ₃ ^-

Farther It has proved to be advantageous if the Blondiermittel invention nonionic surfactant Contain substances. In this case, such surfactants, the one Have HLB value of 5.0 and greater, prefers. For the definition of the HLB value is expressly based on the statements in Hugo Janistyn, Handbuch der Kosmetika und Riechstoffe, III. Tape: The body care products, 2nd edition, dr. Alfred Huthig Verlag Heidelberg, 1973, pages 68-78 and Hugo Janistyn, paperback the modern perfumery and Cosmetics, 4th Edition, Scientific Publishing Company M.B.H. Stuttgart, 1974, pages 466-474, and the cited therein Original works.

Particularly preferred nonionic surfactants are because of the ease of processing substances that are commercially available as solids or liquids in pure form. The definition of purity in this context does not refer to chemically pure compounds. Rather, especially when it comes to products on a natural basis, mixtures may differ ner homologs are used, for example, with different alkyl chain lengths, as obtained in products based on natural fats and oils. Even with alkoxylated products, mixtures of different degrees of alkoxylation are usually present. The term purity in this context refers rather to the fact that the chosen substances should preferably be free from solvents, stabilizers and other impurities.

• – alkoxylierte Fettalkohole mit 8 bis 22, insbesondere 10 bis 16, Kohlenstoffatomen in der Fettalkylgruppe und 1 bis 30, insbesondere 1 bis 15, Ethylenoxid- und/oder Propylenoxid-Einheiten. Bevorzugte Fettalkylgruppen sind beispielsweise Lauryl-, Myristyl-, Cetyl-, aber auch Stearyl-, Isostearyl- und Oleylgruppen. Besonders bevorzugte Verbindungen dieser Klasse sind beispielsweise Laurylalkohol mit 2 bis 4 Ethylenoxid-Einheiten, Oleyl- und Cetylalkohol mit jeweils 5 bis 10 Ethylenoxideinheiten, Cetyl- und Stearylalkohol sowie deren Mischungen mit 10 bis 30 Ethylenoxideinheiten sowie das Handelsprodukt Aethoxal^®B (Henkel), ein Laurylalkohol mit jeweils 5 Ethylenoxid- und Propylenoxideinheiten. Neben den üblichen alkoxylierten Fettalkoholen können auch sogenannte „endgruppenverschlossene" Verbindungen erfindungsgemäß eingesetzt werden. Bei diesen Verbindungen weist die Alkoxygruppe am Ende keine OH-Gruppe auf, sondern ist in Form eines Ethers, insbesondere eines C1-C4-Alkyl-Ethers, „verschlossen". Ein Beispiel für eine solche Verbindung ist das Handelsprodukt Dehypon^®LT 054, ein C_12-18-Fettalkoholol + 4,5 Ethylenoxid-butylether.
• – alkoxylierte Fettsäuren mit 8 bis 22, insbesondere 10 bis 16, Kohlenstoffatomen in der Fettsäuregruppe und 1 bis 30, insbesondere 1 bis 15, Ethylenoxid- und/oder Propylenoxid-Einheiten. Bevorzugte Fettsäuren sind beispielsweise Laurin-, Myristin-, Palmitin-, Stearin-, Isostearin- und Ölsäure.
• – alkoxylierte, bevorzugt propoxylierte und insbesondere ethoxylierte, Mono-, Di- und Triglyceride. Beispiele für bevorzugte Verbindungen sind Glycerinmonolaurat + 20 Ethylenoxid und Glycerinmonostearat + 20 Ethylenoxid.
• – Polyglycerinester und alkoxylierte Polyglycerinester. Bevorzugte Verbindungen dieser Klasse sind beispielsweise Poly(3)glycerindiisostearat (Handelsprodukt: Lameform^®TGI (Henkel)) und Poly(2)glycerinpolyhydroxystearat (Handelsprodukt: Dehymuls^®PGPH (Henkel)).
• – Sorbitan-Fettsäureester und alkoxylierte Sorbitan-Fettsäureester wie beispielsweise Sorbitanmonolaurat und Sorbitanmonolaurat + 20 Ethylenoxid (EO).
• – Alkylphenole und Alkylphenolalkoxylate mit 6 bis 21, insbesondere 6 bis 15, Kohlenstoffatomen in der Alkylkette und 0 bis 30 Ethylenoxid- und/oder Propylenoxid-Einheiten. Bevorzugte Vertreter dieser Klasse sind beipielsweise Nonylphenol + 4 EO, Nonylphenol + 9 EO, Octylphenol + 3 EO und Octylphenol + 8 EO.

Preferred nonionic surfactants are

• - Alkoxylated fatty alcohols having 8 to 22, in particular 10 to 16, carbon atoms in the fatty alkyl group and 1 to 30, in particular 1 to 15, ethylene oxide and / or propylene oxide units. Preferred fatty alkyl groups are, for example, lauryl, myristyl, cetyl, but also stearyl, isostearyl and oleyl groups. Particularly preferred compounds of this class are, for example, lauryl alcohol with 2 to 4 ethylene oxide units, oleyl and cetyl alcohol with 5 to 10 ethylene oxide, cetyl alcohol and stearyl alcohol and mixtures thereof with 10 to 30 ethylene oxide units and the commercial product Aethoxal ^® B (Henkel), Lauryl alcohol with 5 ethylene oxide and 3 propylene oxide units. In addition to the usual alkoxylated fatty alcohols, it is also possible to use so-called "end-capped" compounds according to the invention In these compounds, the alkoxy group has no OH group at the end but is "closed" in the form of an ether, in particular a C 1 -C 4 -alkyl ether. , An example of such a compound is the commercially available product ^® Dehypon LT 054, a C _12-18 -Fettalkoholol + 4.5 ethylene oxide-butyl ether.
• - alkoxylated fatty acids having 8 to 22, in particular 10 to 16, carbon atoms in the fatty acid group and 1 to 30, in particular 1 to 15, ethylene oxide and / or propylene oxide units. Preferred fatty acids are, for example, lauric, myristic, palmitic, stearic, isostearic and oleic acids.
• - alkoxylated, preferably propoxylated and especially ethoxylated, mono-, di- and triglycerides. Examples of preferred compounds are glycerol monolaurate + 20 ethylene oxide and glycerol monostearate + 20 ethylene oxide.
• Polyglycerol esters and alkoxylated polyglycerol esters. Preferred compounds of this class are for example poly (3) glycerol diisostearate (commercial product: Lameform ^® TGI (Henkel)) and poly (2) glycerinpolyhydroxystearat (commercial product: Dehymuls ^® PGPH (Henkel)).
• Sorbitan fatty acid esters and alkoxylated sorbitan fatty acid esters such as sorbitan monolaurate and sorbitan monolaurate + 20 ethylene oxide (EO).
• - Alkylphenols and Alkylphenolalkoxylate having 6 to 21, in particular 6 to 15, carbon atoms in the alkyl chain and 0 to 30 ethylene oxide and / or propylene oxide units. Preferred representatives of this class are, for example, nonylphenol + 4 EO, nonylphenol + 9 EO, octylphenol + 3 EO and octylphenol + 8 EO.

Especially preferred classes of nonionic surfactants the alkoxylated fatty alcohols, the alkoxylated fatty acids as well the alkylphenols and alkylphenol alkoxylates.

When Particularly advantageous agents according to the invention have proven, the nonionic surfactants Contain substances in amounts of 1-5 wt .-%.

Farther can the bleaching compositions according to the invention all known in such preparations active ingredients, additives and excipients contain. In many cases the agents contain at least one surfactant, in principle both anionic as well as zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases However, it proved to be advantageous, the surfactants from anionic, cationic or nonionic surfactants. Anionic surfactants can do this be particularly preferred.

Preferred anionic surfactants are alkyl sulfates, ether carboxylic acid salts having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule such as C ₁₂ H ₂₅ - (C ₂ H ₄ O) ₆ -CH ₂ -COONa and in particular salts of saturated and especially unsaturated C8-C22 carboxylic acids such as oleic acid, stearic acid, isostearic acid and palmitic acid.

These anionic surfactants should preferably be in solid, in particular powder form available. Very particularly preferred are at room temperature solid soaps, in particular sodium stearate. These are preferred in amounts of 5 to 20 wt .-%, in particular 10 to 15 wt .-%, before.

When Nonionic surfactants are particularly suitable C8-C22 alkyl mono- and oligoglycosides and their ethoxylated analogs. Especially the non-ethoxylated compounds have been found to be particularly suitable.

Examples of the cationic Ten usable in the hair treatment compositions of the present invention side are in particular quaternary ammonium compounds. Preference is given to ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. Cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetylmethyl ammonium chloride. Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.

Alkylamidoamines, in particular fatty acid amidoamines, such as the ^{stearylamidopropyldimethylamine} obtainable under the name Tego ^Amid® S 18, are distinguished not only by a good conditioning action but also by their good biodegradability.

Also very good biodegradability are quaternary Esterverbindungen, so-called "esterquats", such as the Distearoylethylhydroxyethylammoniummethosulfat available in a blend with Cetearylalkohle under the name Dehyquart® ^® F 75 miles.

at the compounds used as surfactants with alkyl groups each are uniform substances. However, it is usually preferred in the preparation of these substances of native vegetable or animal raw materials, so that you substance mixtures obtained with different, depending on the raw material alkyl chain lengths.

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane,
• – kationische Polymere wie quaternisierte Celluloseether und andere, als Feststoff stabile bzw. im Handel erhältliche Verbindungen,
• – zwitterionische und amphotere Polymere, die als Feststoffe stabil bzw. bevorzugt als Handelsprodukte erhältlich sind,
• – anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren und Vinylacetat/Crotonsäure-Copolymere, sofern diese als Feststoffe stabil bzw. bevorzugt im Handel erhältlich sind,
• – Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, Gummi arabicum, Karaya-Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, Cellulose-Derivate, z. B. Methylcellulose, Hydroxyalkylcellulose und Carboxymethylcellulose, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, Tone wie z. B. Bentonit oder vollsynthetische Hydrokolloide wie z. B. Polyvinylalkohol,
• – Strukturanten wie Glucose, Maleinsäure und Milchsäure,
• – haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline, sowie Silikonöle
• – Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierte Proteinhydrolysate,
• – Parfümöle, Dimethylisosorbid und Cyclodextrine,
• – Farbstoffe zum Einfärben der Zubereitungen,
• – Wirkstoffe wie Panthenol, Pantothensäure, Allantoin, Pyrrolidoncarbonsäuren und deren Salze,
• – Cholesterin,
• – Fette und Wachse wie Walrat, Bienenwachs, Montanwachs, Paraffine, Fettalkohole und Fettsäureester,
• - Fettsäurealkanolamide,
• - Komplexbildner wie EDTA, NTA und Phosphonsäuren,
• – Quell- und Penetrationsstoffe wie Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,

Other active ingredients, auxiliaries and additives are, for example

• Nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes,
• Cationic polymers such as quaternized cellulose ethers and other solid-stable or commercially available compounds,
• Zwitterionic and amphoteric polymers, which are stable as solids or preferably available as commercial products,
• Anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids and vinyl acetate / crotonic acid copolymers, if these are stable or preferably commercially available as solids,
• Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. As bentonite or fully synthetic hydrocolloids such. For example, polyvinyl alcohol,
• - structurants such as glucose, maleic acid and lactic acid,
• Hair conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins, and silicone oils
• Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates,
• Perfume oils, dimethylisosorbide and cyclodextrins,
• Dyes for coloring the preparations,
• - active substances such as panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and their salts,
• - cholesterol,
• Fats and waxes such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters,
• Fatty acid alkanolamides,
• - complexing agents such as EDTA, NTA and phosphonic acids,
• - swelling and penetrating substances such as carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

The Selection of these other substances will be the skilled person according to the desired Meet properties of the agents.

Next the invention contained Substances can the agents according to the invention contain one or more dye precursors.

Compositions according to the invention, the additional at least one oxidation dye precursor of the developer type and / optionally contain at least one coupler-type oxidation dye precursor, are preferred.

• – Oxidationsfarbstoffvorprodukte vom Entwickler- und/oder Kuppler-Typ, und
• – Vorstufen naturanaloger Farbstoffe, wie Indol- und Indolin-Derivate,

sowie Mischungen von Vertretern dieser Gruppen enthalten.With regard to the further dye precursors which can be used in the bleaching compositions according to the invention, the present invention is not subject to any restrictions. The bleaching agents according to the invention can be used as further dye precursors

• - Developer and / or coupler type oxidation dye precursors, and
• Precursors of nature-analogous dyes, such as indole and indoline derivatives,

and mixtures of representatives of these groups.

In a first preferred embodiment contains the bleaching agent further comprises at least one developer component. As developer components are usually primary aromatic Amines with another, in para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used.

wobei

• – G¹ steht für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen 4'-Aminophenylrest oder einen C₁- bis C₄-Alkylrest, der mit einer stickstoffhaltigen Gruppe, einem Phenyl- oder einem 4'-Aminophenylrest substituiert ist;
• – G² steht für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylrest oder einen C₁- bis C₄-Alkylrest, der mit einer stickstoffhaltigen Gruppe substituiert ist;
• – G³ steht für ein Wasserstoffatom, ein Halogenatom, wie ein Chlor-, Brom-, Iod- oder Fluoratom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Hydroxyalkoxyrest, einen C₁ bis C₄-Acetylaminoalkoxyrest, einen C₁- bis C₄-Mesylaminoalkoxyrest oder einen C₁- bis C₄-Carbamoylaminoalkoxyrest;
• – G⁴ steht für ein Wasserstoffatom, ein Halogenatom oder einen C₁ bis C₄-Alkylrest oder
• – wenn G³ und G⁴ in ortho-Stellung zueinander stehen, können sie gemeinsam eine verbrückende α,ω-Alkylendioxogruppe, wie beispielsweise eine Ethylendioxygruppe bilden.

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. Particular preference is given to p-phenylenediamine derivatives of the formula (E1)

in which

• G ¹ represents a hydrogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ alkoxy radical (C ₁ - to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;
• G ² represents a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a (C ₁ - to C ₄ ) -alkoxy- C ₁ to C ₄ ) -alkyl radical or a C ₁ to C ₄ -alkyl radical which is substituted by a nitrogen-containing group;
• G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl, C ₁ - to C ₄ -hydroxyalkoxy, C ₁ to C ₄ -acetylaminoalkoxy, C ₁ - to C ₄ -mesylaminoalkoxy or C ₁ - to C ₄ -carbamoylaminoalkoxy;
• G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ to C ₄ alkyl radical or
• When G ³ and G ⁴ are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.

Examples of the C ₁ - to C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ -C ₄ -alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Further, as preferred examples of a C ₁ to C ₄ hydroxyalkyl group, there may be mentioned a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ to C ₄ polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examples of halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived according to the invention from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are especially the amino groups, C ₁ -C ₄ monoalkylamino, C ₁ - to C ₄ dialkylamino, C ₁ to C ₄ -Trialkylammoniumgruppen, C ₁ to C ₄ -Monohydroxyalkylaminogruppen, imidazolinium and ammonium ,

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4 -Amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (β-hydroxyethyl) amino-2- methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2-fluoro -p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N - (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophe nyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (β-hydroxyethyloxy) -p-phenylenediamine, 2- (β-acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1,4-dioxane and their physiologically acceptable salts.

Very particular according to the invention preferred p-phenylenediamine derivatives of the formula (E1) are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine and N, N-bis (β-hydroxyethyl) -p-phenylenediamine.

It can continue according to the invention be preferred to use as a developer component compounds, which contain at least two aromatic nuclei which are reactive with amino and / or hydroxyl groups are substituted.

wobei:

• – Z¹ und Z² stehen unabhängig voneinander für einen Hydroxyl- oder NH₂-Rest, der gegebenenfalls durch einen C₁- bis C₄-Alkylrest, durch einen C₁- bis C₄-Hydroxyalkylrest und/oder durch eine Verbrückung Y substituiert ist oder der gegebenenfalls Teil eines verbrückenden Ringsystems ist,
• – die Verbrückung Y steht für eine Alkylengruppe mit 1 bis 14 Kohlenstoffatomen, wie beispielsweise eine lineare oder verzweigte Alkylenkette oder einen Alkylenring, die von einer oder mehreren stickstoffhaltigen Gruppen und/oder einem oder mehreren Heteroatomen wie Sauerstoff-, Schwefel- oder Stickstoffatomen unterbrochen oder beendet sein kann und eventuell durch einen oder mehrere Hydroxyl- oder C₁- bis C₈-Alkoxyreste substituiert sein kann, oder eine direkte Bindung,
• – G⁵ und G⁶ stehen unabhängig voneinander für ein Wasserstoff- oder Halogenatom, einen C₁ bis C₄-Alkylrest, einen C₁ bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest oder eine direkte Verbindung zur Verbrückung Y,
• – G⁷, G⁸, G⁹, G¹⁰, G¹¹ und G¹² stehen unabhängig voneinander für ein Wasserstoffatom, eine direkte Bindung zur Verbrückung Y oder einen C₁- bis C₄-Alkylrest, mit den Maßgaben, dass
• – die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten und
• – die Verbindungen der Formel (E2) mindestens eine Aminogruppe enthalten, die mindestens ein Wasserstoffatom trägt.

Among the binuclear developer components which can be used in the compositions according to the invention, mention may be made in particular of the compounds which correspond to the following formula (E2) and their physiologically tolerated salts:

in which:

• - Z ¹ and Z ² independently of one another are a hydroxyl or NH ₂ radical which is optionally substituted by a C ₁ - to C ₄ -alkyl radical, by a C ₁ - to C ₄ -hydroxyalkyl radical and / or by a bridge Y. or is optionally part of a bridging ring system,
• - The bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms may be and may be substituted by one or more hydroxyl or C ₁ - to C ₈ alkoxy, or a direct bond,
• - G ⁵ and G ⁶ are each independently a hydrogen or halogen atom, a C ₁ to C ₄ alkyl, C ₁ -C ₄ monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a direct compound for bridging Y,
• - G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² are each independently a hydrogen atom, a direct bond to the bridge Y or a C ₁ - to C ₄ alkyl, with the provisos that
• The compounds of the formula (E2) contain only one bridge Y per molecule and
• - The compounds of formula (E2) contain at least one amino group which carries at least one hydrogen atom.

The used in formula (E2) substituents are analogous to the invention to the above statements Are defined.

preferred binuclear developer components of the formula (E2) are in particular: N, N'-bis (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-diethyl-N, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine, Bis (2-hydroxy-5-aminophenyl) methane, 1,3-bis (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane and their physiologically tolerable Salts.

Very particularly preferred binuclear developer components of the formula (E2) are N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, bis- (2-hydroxy-5-aminophe nyl) -methane, 1,3-bis- (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane and 1,10-bis - (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane or one of its physiologically acceptable salts.

wobei:

• – G¹³ steht für ein Wasserstoffatom, ein Halogenatom, einen C₁ bis C₄-Alkylrest, einen C₁ bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest, einen Hydroxy-(C₁- bis C₄)-alkylaminorest, einen C₁ bis C₄-Hydroxyalkoxyrest, einen C₁- bis C₄-Hydroxyalkyl-(C₁- bis C₄)-aminoalkylrest oder einen (Di-C₁- bis C₄-Alkylamino)-(C₁- bis C₄)-alkylrest, und
• – G¹⁴ steht für ein Wasserstoff- oder Halogenatom, einen C₁ bis C₄-Alkylrest, einen C₁ bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest oder einen C₁ bis C₄-Cyanoalkylrest,
• – G¹⁵ steht für Wasserstoff, einen C₁- bis C₄-Alkylrest, einen C₁ bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen Phenylrest oder einen Benzylrest, und
• – G¹⁶ steht für Wasserstoff oder ein Halogenatom.

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. Particular preference is given to p-aminophenol derivatives of the formula (E3)

in which:

• G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy - (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical, a hydroxy (C ₁ - to C ₄ ) -alkylamino radical, a C ₁ to C ₄ -hydroxyalkoxy radical, a C ₁ - to C ₄ hydroxyalkyl (C ₁ to C ₄ ) aminoalkyl or a (di-C ₁ to C ₄ alkylamino) (C ₁ to C ₄ ) alkyl, and
• G ¹⁴ is a hydrogen or halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a C ₁ to C ₄ -cyanoalkyl radical,
• G ¹⁵ is hydrogen, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and
• - G ¹⁶ is hydrogen or a halogen atom.

The used in formula (E3) substituents are analogous to the invention to the above statements Are defined.

preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (□ -hydroxyethoxy) -phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino-2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) -phenol, 4-amino-2- (α, β-dihydroxyethyl) -phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) -phenol as well as their physiologically tolerable Salts.

All particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-α, β-dihydroxyethyl) -phenol and 4-amino-2- (diethylaminomethyl) -phenol.

Further For example, the developer component can be selected from o-aminophenol and its derivatives, such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

Farther For example, the developer component may be selected from heterocyclic Developer components, such as the pyridine, pyrimidine, Pyrazole, pyrazole pyrimidine derivatives and their physiologically tolerable Salt.

preferred Pyridine derivatives are in particular the compounds 2,5-diamino-pyridine, 2- (4'-Methoxyphenyl) amino-3-amino-pyridine, 2,3-diamino-6-methoxy-pyridine, 2- (β-methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

preferred Pyrimidine derivatives are in particular 2,4,5,6-tetraaminopyrimidine, 4-Hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.

Preferred pyrazole derivatives are in particular 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'- chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1 , 3-dime thyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl- 3-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4 '-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4 , 5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (α-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5- triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole.

wobei:

• – G¹⁷, G¹⁸, G¹⁹ und G²⁰ unabhängig voneinander stehen für ein Wasserstoffatom, einen C₁ bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest einen (C₁ bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁ bis C₄-Aminoalkylrest, der gegebenenfalls durch ein Acetyl-Ureid- oder einen Sulfonyl-Rest geschützt sein kann, einen (C₁- bis C₄)-Alkylamino-(C₁ bis C₄)-alkylrest, einen Di-[(C₁- bis C₄)-alkyl]-(C₁ bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁- bis C₄-Hydroxyalkyl- oder einen Di-(C₁- bis C₄)-[Hydroxyalkyl]-(C₁- bis C₄)-aminoalkylrest,
• – die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest, einen (C₁- bis C₄)-Alkylamino-(C₁- bis C₄)-alkylrest, einen Di-[(C₁- bis C₄)alkyl]-(C₁- bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁- bis C₄-Hydroxyalkyl- oder einen Di-(C₁- bis C₄-hydroxyalkyl)aminoalkylrest, einen Aminorest, einen C₁ bis C₄-Alkyl- oder Di-(C₁- bis C₄-hydroxyalkyl)aminorest, ein Halogenatom, eine Carboxylsäuregruppe oder eine Sulfonsäuregruppe,
• – i hat den Wert 0, 1, 2 oder 3,
• – p hat den Wert 0 oder 1,
• – q hat den Wert 0 oder 1 und
• – n hat den Wert 0 oder 1, mit der Maßgabe, dass
• – die Summe aus p + q ungleich 0 ist,
• – wenn p + q gleich 2 ist, n den Wert 0 hat, und die Gruppen NG¹⁷G¹⁸ und NG¹⁹G²⁰ belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);
• – wenn p + q gleich 1 ist, n den Wert 1 hat, und die Gruppen NG¹⁷G¹⁸ (oder NG¹⁹G²⁰) und die Gruppe OH belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);

Preferred pyrazole-pyrimidine derivatives are, in particular, the derivatives of the pyrazolo [1,5-a] pyrimidine of the following formula (E4) and its tautomeric forms, if a tautomeric equilibrium exists:

in which:

• - G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a C ₁ to C ₄ alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ Polyhydroxyalkyl radical is a (C ₁ to C ₄ ) -alkoxy (C ₁ to C ₄ ) -alkyl radical, a C ₁ to C ₄ -aminoalkyl radical which may optionally be protected by an acetyl-ureide or a sulfonyl radical, a (C ₁ to C ₄ ) alkylamino (C ₁ to C ₄ ) alkyl radical, a di - [(C ₁ to C ₄ ) alkyl] (C ₁ to C ₄ ) aminoalkyl radical, wherein the Dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C ₁ - to C ₄ ) aminoalkyl,
• - The X radicals independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl, a (C ₁ - to C ₄ ) -alkylamino- (C ₁ - to C ₄ ) -alkyl, a di - [(C ₁ - to C ₄ ) alkyl] - (C ₁ - bis C ₄ ) aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl or a di- (C ₁ - to C ₄ -hydroxyalkyl) aminoalkyl radical, amino, C ₁ to C ₄ alkyl or di (C ₁ to C ₄ hydroxyalkyl) amino, halogen, carboxylic or sulfonic acid,
• - i has the value 0, 1, 2 or 3,
• - p has the value 0 or 1,
• - q has the value 0 or 1 and
• - n has the value 0 or 1, with the proviso that
• The sum of p + q is not equal to 0,
• If p + q equals 2, n has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);
• When p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

The used in formula (E4) substituents are analogous to the invention to the above statements Are defined.

When the pyrazolo [1,5-a] pyrimidine of the above formula (E4) contains a hydroxy group at one of the 2, 5 or 7 positions of the ring system, there is a tautomeric equilibrium shown, for example, in the following scheme:

• – Pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – 2,5-Dimethyl-pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – Pyrazol-[1,5-a]-pyrimidin-3,5-diamin;
• – 2,7-Dimethyl-pyrazol-[1,5-a]-pyrimidin-3,5-diamin;
• – 3-Aminopyrazol-[1,5-a]-pyrimidin-7-ol;
• – 3-Aminopyrazol-[1,5-a]-pyrimidin-5-ol;
• – 2-(3-Aminopyrazol-[1,5-a]-pyrimidin-7-ylamino)-ethanol;
• – 2-(7-Aminopyrazol-[1,5-a]-pyrimidin-3-ylamino)-ethanol;
• – 2-[(3-Aminopyrazol-[1,5-a]-pyrimidin-7-yl)-(2-hydroxy-ethyl)amino]-ethanol;
• – 2-[(7-Aminopyrazol-[1,5-a]-pyrimidin-3-yl)-(2-hydroxy-ethyl)amino]-ethanol;
• – 5,6-Dimethylpyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – 2,6-Dimethylpyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – 3-Amino-7-dimethylamino-2,5-dimethylpyrazol-[1,5-a]-pyrimidin;

sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomers Gleichgewicht vorhanden ist.In particular, among the pyrazolo [1,5-a] -pyrimidines of the above formula (E4):

• - pyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• - pyrazolo [1,5-a] pyrimidine-3,5-diamine;
• 2,7-dimethylpyrazolo [1,5-a] -pyrimidine-3,5-diamine;
• 3-aminopyrazolo [1,5-a] pyrimidin-7-ol;
• 3-aminopyrazolo [1,5-a] pyrimidin-5-ol;
• 2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol;
• 2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol;
• - 2 - [(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) amino] -ethanol;
• - 2 - [(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol;
• 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 3-amino-7-dimethylamino-2,5-dimethylpyrazolo [1,5-a] pyrimidine;

and their physiologically acceptable salts and their tautomeric forms when a tautomeric equilibrium is present.

The Pyrazole- [1,5-a] -pyrimidines of the above formula (E4) can, as described in the literature by cyclization starting from a Aminopyrazole or produced from hydrazine.

In a further preferred embodiment contain the agents of the invention at least one coupler component.

When Coupler components are usually m-phenylenediamine derivatives, Naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives used. Particularly suitable coupling agents are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, Resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2 ', 4'-diaminophenoxy) -propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2-chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

• – m-Aminophenol und dessen Derivate wie beispielsweise 5-Amino-2-methylphenol, N-Cyclopentyl-3-aminophenol, 3-Amino-2-chlor-6-methylphenol, 2-Hydroxy-4-aminophenoxyethanol, 2,6-Dimethyl-3-aminophenol, 3-Trifluoroacetylamino-2-chlor-6-methylphenol, 5-Amino-4-chlor-2-methylphenol, 5-Amino-4-methoxy-2-methylphenol, 5-(2'-Hydroxyethyl)amino-2-methylphenol, 3-(Diethylamino)-phenol, N-Cyclopentyl-3-aminophenol, 1,3-Dihydroxy-5-(methylamino)-benzol, 3-Ethylamino-4-methylphenol und 2,4-Dichlor-3-aminophenol,
• – o-Aminophenol und dessen Derivate,
• – m-Diaminobenzol und dessen Derivate wie beispielsweise 2,4-Diaminophenoxyethanol, 1,3-Bis-(2',4'-diaminophenoxy)-propan, 1-Methoxy-2-amino-4-(2'-hydroxyethylamino)benzol, 1,3-Bis-(2',4'-diaminophenyl)-propan, 2,6-Bis-(2'-hydroxyethylamino)-1-methylbenzol und 1-Amino-3-bis-(2'-hydroxyethyl)aminobenzol,
• – o-Diaminobenzol und dessen Derivate wie beispielsweise 3,4-Diaminobenzoesäure und 2,3-Diamino-1-methylbenzol,
• – Di- beziehungsweise Trihydroxybenzolderivate wie beispielsweise Resorcin, Resorcinmonomethylether, 2-Methylresorcin, 5-Methylresorcin, 2,5-Dimethylresorcin, 2-Chlorresorcin, 4-Chlorresorcin, Pyrogallol und 1,2,4-Trihydroxybenzol,
• – Pyridinderivate wie beispielsweise 2,6-Dihydroxypyridin, 2-Amino-3-hydroxypyridin, 2-Amino-5-chlor-3-hydroxypyridin, 3-Amino-2-methylamino-6-methoxypyridin, 2,6-Dihydroxy-3,4-dimethylpyridin, 2,6-Dihydroxy-4-methylpyridin, 2,6-Diaminopyridin, 2,3-Diamino-6-methoxypyridin und 3,5-Diamino-2,6-dimethoxypyridin,
• – Naphthalinderivate wie beispielsweise 1-Naphthol, 2-Methyl-1-naphthol, 2-Hydroxymethyl-1-naphthol, 2-Hydroxyethyl-1-naphthol, 1,5-Dihydroxynaphthalin, 1,6-Dihydroxynaphthalin, 1,7-Dihydroxynaphthalin, 1,8-Dihydroxynaphthalin, 2,7-Dihydroxynaphthalin und 2,3-Dihydroxynaphthalin,
• – Morpholinderivate wie beispielsweise 6-Hydroxybenzomorpholin und 6-Amino-benzomorpholin,
• – Chinoxalinderivate wie beispielsweise 6-Methyl-1,2,3,4-tetrahydrochinoxalin,
• – Pyrazolderivate wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on,
• – Indolderivate wie beispielsweise 4-Hydroxyindol, 6-Hydroxyindol und 7-Hydroxyindol,
• – Pyrimidinderivate, wie beispielsweise 4,6-Diaminopyrimidin, 4-Amino-2,6-dihydroxypyrimidin, 2,4-Diamino-6-hydroxypyrimidin, 2,4,6-Trihydroxypyrimidin, 2-Amino-4-methylpyrimidin, 2-Amino-4-hydroxy-6-methylpyrimidin und 4,6-Dihydroxy-2-methylpyrimidin, oder
• – Methylendioxybenzolderivate wie beispielsweise 1-Hydroxy-3,4-methylendioxybenzol, 1-Amino-3,4-methylendioxybenzol und 1-(2'-Hydroxyethyl)amino-3,4-methylendioxybenzol.

According to preferred coupler components are

• - M-aminophenol and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl 3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino 2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino-4-methylphenol and 2,4-dichloro-3 aminophenol,
• O-aminophenol and its derivatives,
• - 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 , 1,3-bis (2 ', 4'-diaminophenyl) -propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene,
• O-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,
• Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
• Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3, 4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,
• Naphthalene derivatives such as, for example, 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,
• Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
• Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,
• Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,
• Pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino -4-hydroxy-6-me thylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or
• - Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.

Particularly according to the invention preferred coupler components are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, Resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

When Precursors of naturally-analogous dyes are preferably those indoles and indolines containing at least one hydroxy or amino group, preferably as a substituent on the six-membered ring. These groups can bear further substituents, for. B. in the form of an etherification or Esterification of the hydroxy group or alkylation of the amino group. In a second preferred embodiment, the means include at least one indole and / or indoline derivative.

in der unabhängig voneinander

• – R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxy-alkylgruppe,
• – R² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• – R³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• – R⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-R⁶, in der R⁶ steht für eine C₁-C₄-Alkylgruppe, und
• – R⁵ steht für eine der unter R⁴ genannten Gruppen,

sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.Particularly suitable precursors of naturally-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (IIIa),

in the independently of each other

• R ¹ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxy-alkyl group,
• R ² is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
• R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
• R ⁴ is hydrogen, a C ₁ -C ₄ -alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C ₁ -C ₄ -alkyl group, and
• R ⁵ is one of the groups mentioned under R ⁴ ,

and physiologically acceptable salts of these compounds with an organic or inorganic acid.

Especially preferred derivatives of indoline are the 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

Especially noteworthy within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and in particular the 5,6-dihydroxyindoline.

in der unabhängig voneinander

• – R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxyalkylgruppe,
• – R² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• – R³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• – R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-R⁶, in der R⁶ steht für eine C₁-C₄-Alkylgruppe, und
• – R⁵ steht für eine der unter R⁴ genannten Gruppen,
• – sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.

Also suitable as precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindole of the formula (IIIb),

in the independently of each other

• R ¹ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxyalkyl group,
• R ² is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
• R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
• - R ¹ is hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C ₁ -C ₄ alkyl group, and
• R ⁵ is one of the groups mentioned under R ⁴ ,
• - As well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

Especially preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.

Within of this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular the 5,6-dihydroxyindole.

The Indoline and indole derivatives can in the used in the context of the method according to the invention Means both as free bases and in the form of their physiological acceptable Salts with inorganic or organic acids, e.g. The hydrochlorides, the sulfates and hydrobromides used. The indole or Indoline derivatives are common in these in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.

In a further embodiment it may be preferred according to the invention be the indoline or Indolderivat in hair dyes in combination with at least one amino acid or an oligopeptide. The amino acid is advantageous an α-amino acid; all particularly preferred α-amino acids Arginine, ornithine, lysine, serine and histidine, especially arginine.

preferred inventive agent are characterized in that they at least one dye precursor from the groups of aromatic and heteroaromatic diamines, Aminophenols, naphthols, polyphenols CH-acidic coupler components and their derivatives in amounts of from 0.01 to 25% by weight, preferably from 0.5 to 10 wt.%, In particular from 1 to 5 wt .-%, each based on the entire remedy, included.

Next the invention contained Substances can the agents according to the invention for shading one or more substantive dyes.

Substantive Dyes are common Nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are the under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 Compounds as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

Corresponding agents according to the invention, which are characterized in that they contain at least one substantive dye from the group of cationic (basic) dyes, preferably Basic Blue 6, CI-No. 51,175; Basic Blue 7, CI-No. 42.595; Basic Blue 9, CI-No. 52.015; Basic Blue 26, CI-No. 44.045; Basic Blue 41, CI-No. 11.154; Basic Blue 99, CI-No. 56.059; Basic Brown 4, CI-No. 21.010; Basic Brown 16, CI-No. 12.250; Basic Brown 17, CI-No. 12.251; Basic Green 1, CI-No. 42.040; Basic Orange 31; Basic Red 2, CI-No. 50.240; Basic Red 22, CI-No. 11.055; Basic Red 46; Basic Red 51; Basic Red 76, CI-No. 12.245; Basic Violet 1, CI-No. 42.535; Basic Violet 2; Basic Violet 3, CI-No. 42.555; Basic Violet 10, CI-No. 45.170; Basic Violet 14, CI-No. 42.510; Basic Yellow 57, CI-No. 12.719; Basic Yellow 87 and / or the anionic (acidic) dyes, and / or the nonionic dyes, preferably Acid Black 1, CI-No. 20.470; Acid Black 52; Acid Blue 7; Acid Blue 9, CI-No. 42.090; Acid Blue 74, CI-No. 73.015, Acid Red 18, CI-No. 16.255; Acid Red 23; Acid Red 27, CI-No. 16.185; Acid Red 33; Acid Red 52; Acid Red 87, CI-No. 45,380; Acid Red 92, CI-No. 45,410; Acid Orange 3; Acid Orange 7; Acid Violet 43, CI-No. 60.730; Acid Yel low 1, CI-No. 10.316; Acid Yellow 10; Acid Yellow 23, CI-No. 19,140; Acid Yellow 3, CI-No. 47.005; Acid Yellow 36; D & C Brown no. 1, CI-No. 20.170 (Acid Orange 24); D & C Green no. 5, CI-No. 61,570 (Acid Green G); D & C Orange No. 4, CI-No. 15.510 (Acid Orange II); D & C Orange No. 10, CI-No. 45.425: 1 (Solvent Red 73); D & C Orange No. 11, CI-No. 45.425 (Acid Red 95); D & C Red No. 21, CI-No. 45.380: 2 (Solvent Red 43); D & C Red No. 27, CI-No. 45.410: 1 (Solvent Red 48); D & C Red No. 33, CI-No. 17,200 (Acid Red 2A, Acid Red B); D & C Yellow No. 7, CI-No. 45.350: 1 (Solvent Yellow 94); D & C Yellow No. 8, CI-No. 45,350 (Acid Yellow 73); FD & C Red No. 4, CI-No. 14,700 (Food Red 4); FD & C Yellow No. 6, CI-No. 15,985 (Food Yellow 3); Food Green 3; Pigment Red 57-1; Disperse Black 9; Disperse Blue 1; Disperse Blue 3; Disperse Violet 1; Disperse Violet 4; HC Orange 1; HC Red 1; HC Red 3; HC Red 13; HC Yellow 2; HC Yellow 4; Sodium Pikramat; 1,4-bis- (2'-hydroxyethyl) amino-2-nitro-p-phenylenediamine; HC Yellow 5; HC Blue 2; HC Blue 12; 4-amino-3-nitrophenol; HC Yellow 6; HC Yellow 12; 2-nitro-1- (2'-hydroxyethyl) amino-4-methyl benzene; 2-nitro-4-amino-diphenylamine-2-carboxylic acid; 2-amino-6-chloro-4-nitrophenol; HC Red BN; 6-nitro-1,2,3,4-tetranitrochinoxalin; o-nitro-p-phenylenediamine; p-nitro-m-phenylenediamine; HC Red B 54; HC Red 10; HC Red 11; HC Red 13; 2- (2'-hydroxyethyl) amino-1-hydroxy-4,6-dinitrobenzene; 4-ethylamino-3-nitrobenzoic acid; 2-chloro-6-ethylamino-4-nitrophenol; 2-hydroxy-1,4-naphthoquinone; amine-1-propene (4-amino-2-nitrophenyl); isatin; N-methylylisatin; HC Violet 1; HC Violet 2; 4-Nitrophenyl-aminoethyl urea in amounts of 0.01 to 25 wt.%, Preferably from 0.5 to 10 wt.%, In particular from 1 to 5 wt .-%, each based on the total agent included, are preferred embodiments of the present invention.

Under Some of the dyes mentioned above are particular preferred, which is why further preferred agents according to the invention, which are characterized in that they have at least one direct puller, selected Basic Blue 7, Basic Blue 99, Basic Violet 14, Basic Brown 16, Basic Brown 17, Basic Orange 31, Basic Red 46, Basic Red 51, Basic Red 76, Basic Yellow 57, Basic Yellow 87, Acid Black 1, Acid Blue 7, Acid Red 23, Acid Red 52, Acid Orange 7, Acid Yellow 1, Acid Yellow 10, Acid Yellow 36, Food Green 3, Pigment Red 57-1, Disperse Black 9, Disperse Blue 1, Disperse Blue 3, Disperse Violet 1, Disperse Violet 4, HC Orange 1, HC Red 1, HC Red 3, HC Red 13, HC Yellow 2, HC Yellow 4, Na picakrate, 1,4-bis (2'-hydroxyethyl) amino-2-nitro-p-phenylenediamine, HC Yellow 5, HC Blue 2, HC Blue 12, 4-amino-3-nitrophenol, HC Yellow 6, HC Yellow 12, 2-nitro-1- (2'-hydroxyethyl) amino-4-methylbenzene, 2-nitro-4-amino-diphenylamine-2-carboxylic acid, 2-amino-6-chloro-4-nitrophenol, HC Red BN; 6-nitro-1,2,3,4-tetranitroquinoxaline, o-nitro-p-phenylenediamine, p-nitro-m-phenylenediamine, HC Red B 54, HC Red 10, HC Red 11, HC Red 13, 2- (2'-hydroxyethyl) amino-1-hydroxy-4,6-dinitrobenzene, 4-ethylamino-3-nitrobenzoic acid, 2-chloro-6-ethylamino-4-nitrophenol, 2-hydroxy-1,4-naphthoquinone, 1-propene- (4-amino-2-nitrophenyl) amine, Isatin, N-Methylylisatin, HC Violet 1, HC Violet 2, 4-Nitrophenyl-aminoethyl urea in amounts of from 0.01 to 25% by weight, preferably from 0.5 to 10% by weight, in particular from 1 to 5 wt .-%, each based on the total Means, contained, are preferred.

• (a) kationische Triphenylmethanfarbstoffe, wie beispielsweise Basic Blue 7, Basic Blue 26, Basic Violet 2 und Basic Violet 14,
• (b) aromatischen Systeme, die mit einer quaternären Stickstoffgruppe substituiert sind, wie beispielsweise Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 und Basic Brown 17, sowie
• (c) direktziehende Farbstoffe, die einen Heterozyklus enthalten, der mindestens ein quaternäres Stickstoffatom aufweist, wie sie beispielsweise in der EP-A2-998 908, auf die an dieser Stelle explizit Bezug genommen wird, in den Ansprüchen 6 bis 11 genannt werden.

Furthermore, the agents according to the invention may contain a cationic substantive dye. Particularly preferred are

• (a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,
• (b) aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as
• (c) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as mentioned, for example, in EP-A2-998 908, which is incorporated herein by reference, in claims 6 to 11.

Preferred cationic substantive dyes of group (c) are in particular the following compounds:

The Compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also available under the terms Basic Yellow 87, Basic Orange 31 and Basic Red 51 are very particularly preferred cationic substantive Dyes of group (c).

The cationic direct dyes, which are sold under the trademark Arianor ^®, according to the invention are also very particularly preferred cationic direct dyes.

The agents according to the invention according to this embodiment contain the substantive dyes preferably in an amount from 0.01 to 20 wt .-%, based on the total agent.

Furthermore, the preparations of the invention may also be present in nature dyes such as, for example, henna red, henna neutral, henna black, chamomile flower, sandalwood, black Tea, buckthorn bark, sage, bluewood, madder root, catechu, sedre and alkano root are included.

It it is not necessary that the oxidation dye precursors or the direct dyes in each case uniform compounds represent. Rather, you can in the agents according to the invention, due to the production process for the individual dyes, be contained in minor amounts still other components as far as these are not the dyeing result adversely affect or for other reasons, eg. B. toxicological, must be excluded.

Regarding the in the hair dyeing and -tönungsmitteln applicable dyes is still expressly on the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pp. 248-250; Dyes) and chapter 8, pages 264-267; Oxidation dye precursors) appeared as volume 7 of the series "Dermatology" (ed. Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, as well as the "European Inventory of cosmetic raw materials ", issued by the European Community, available in diskette form from the German Association of Industrial and Trade Companies for Medicines, Health food and personal care products e.V., Mannheim.

• A Verbindungen, die eine reaktive Carbonylgruppe enthalten mit Komponente
• B Verbindungen, ausgewählt aus (a) CH-aciden Verbindungen, (b) Verbindungen mit primärer oder sekundärer Aminogruppe oder Hydroxygruppe, ausgewählt aus primären oder sekundären aromatischen Aminen, stickstoffhaltigen heterozyklischen Verbindungen und aromatischen Hydroxyverbindungen, (c) Aminosäuren, (d) aus 2 bis 9 Aminosäuren aufgebauten Oligopeptiden.

In a further embodiment, the agent according to the invention additionally contains a combination of component

• A compounds containing a reactive carbonyl group with component
• B Compounds selected from (a) CH-acidic compounds, (b) compounds having primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, (c) amino acids, (d) from 2 up to 9 amino acids oligopeptides.

• a) Aminen und deren Derivate unter Bildung von Iminen oder Oximen als Kondensationsverbindung
• b) von Alkoholen unter Bildung von Acetaten oder Ketalen als Kondensationsverbindung.

Compounds according to the invention having a reactive carbonyl group (also referred to below as reactive carbonyl compounds or component A) have at least one carbonyl group as reactive group which reacts with the compounds of component B to form a chemical bond linking both components. Furthermore, those compounds according to the invention are also included as component A in which the reactive carbonyl group is derivatized or masked in such a way that the reactivity of the carbon atom of the derivatized or masked carbonyl group with respect to component B is always present. These derivatives are preferably condensation compounds of reactive carbonyl compounds with

• a) amines and derivatives thereof to form imines or oximes as a condensation compound
• b) of alcohols to form acetates or ketals as a condensation compound.

Component A is preferably selected from the group consisting of acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 3-hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3-hydroxybutyrophenone, 4-hydroxybutyrophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,3,4-trihydroxyacetophenone, 3,4,5-trihydroxyacetophenone, 2,4,6-trihydroxyacetophenone, 2,4, 6-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone diethyl ketal, 4-hydroxy-3-methoxy-acetophenone, 3,5-dimethoxy-4-hydroxyacetophenone, 4-aminoacetophenone, 4- Dimethylaminoacetophenone, 4-morpholinoacetophenone, 4-piperidinoacetophenone, 4-imidazolinoacetophenone, 2-hydroxy-5-bromo-acetophenone, 4-hydroxy-3-nitroacetophenone, acetophenone-2-carboxylic acid, acetophenone-4-carboxylic acid, benzophenone, 4-hydroxybenzophenone, 2-aminobenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4 , 4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2-hydroxy-1-acetonaphthone, 1-hydroxy-2-acetonaphthone, chromone, chromone-2-carboxylic acid, flavone, 3-hydroxyflavone, 3,5,7- Trihydroxyflavone, 4 ', 5,7-trihydroxyflavone, 5,6,7-trihydroxyflavone, quercetin, 1-indanone, 9-fluorenone, 3-hydroxyfluorenone, anthrone, 1,8-dihydroxyanthrone,
Vanillin, coniferylaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxy-benzaldehyde, 4-hydroxy-2,5-dimethoxy benzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxybenzaldehyde 2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde, 3,5-diethoxy 4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3 Ethoxy-4-hydroxybenzaldehyde, 4-ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6- Dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde hyd, 2,3,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3- Dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2, 3,6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino 2-hydroxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1- naphthaldehyde, 2,4-dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehy d, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-hydroxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 2-methoxycinnamaldehyde, 4-methoxycinnamaldehyde, 4-hydroxy-3-methoxy-cinnamaldehyde, 3,5-dimethoxy-4-hydroxy-cinnamaldehyde, 4-dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino cinnamaldehyde, 4-dibutylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 4- (1-imidazolyl) benzaldehyde, piperonal, 2,3,6,7-tetrahydro-1H, 5H-benzo [ ij] quinolizine-9-carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, N-ethylcarbazole-3-aldehyde, 2-formylmethylene-1, 3,3-trimethylindoline (Fischer's aldehyde or tribasic aldehyde),
2-indolealdehyde, 3-indolealdehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 1-acetylindole-3-aldehyde, 3-acetylindole, 1-methyl-3-acetylindole, 2- (1 ', 3 ', 3'-trimethyl-2-indolinylidene) -acetaldehyde, 1-methylpyrrole-2-aldehyde, 1-methyl-2-acetylpyrrole, 4-pyridine aldehyde, 2-pyridine aldehyde, 3-pyridine aldehyde, 4-acetylpyridine, 2-acetylpyridine , 3-acetylpyridine, pyridoxal, quinoline-3-aldehyde, quinoline-4-aldehyde, antipyrin-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyl-trifluoro-acetone, chromon-3-aldehyde, 3- (5 'Nitro-2'-furyl) acrolein, 3- (2'-furyl) acrolein and imidazole-2-aldehyde,
1,3-diacetylbenzene, 1,4-diacetylbenzene, 1,3,5-triacetylbenzene, 2-benzoyl-acetophenone, 2- (4'-methoxybenzoyl) -acetophenone, 2- (2'-furoyl) -acetophenone, 2- (2'-pyridoyl) acetophenone and 2- (3'-pyridoyl) acetophenone,
Benzylideneacetone, 4-hydroxybenzylideneacetone, 2-hydroxybenzylideneacetone, 4-methoxybenzylideneacetone, 4-hydroxy-3-methoxybenzylideneacetone, 4-dimethylaminobenzylideneacetone, 3,4-methylenedioxybenzylideneacetone, 4-pyrrolidinobenzylideneacetone, 4-piperidinobenzylideneacetone, 4-morpholinobenzylideneacetone, 4-diethylaminobenzylideneacetone, 3 Benzylidene-2,4-pentanedione, 3- (4'-hydroxybenzylidene) -2,4-pentanedione, 3- (4'-dimethylaminobenzylidene) -2,4-pentanedione, 2-Benzylidene-cyclohexanone, 2- (4'-hydroxybenzylidene) cyclohexanone, 2- (4'-dimethylaminobenzylidene) cyclohexanone, 2-benzylidene-1,3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -1,3-cyclohexanedione, 3- (4'-dimethylaminobenzylidene) -1, 3-cyclohexanedione, 2-benzylidene-5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxy-3 -methoxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-dimethylaminobenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2-benzylidenecyclopentanone, 2 '- (4-hydroxybenzylidene) - cyclopentanone, 2- (4'-dimethyl aminobenzylidene) -cyclopentanone,
5- (4-dimethylaminophenyl) penta-2,4-dienal, 5- (4-diethylaminophenyl) penta-2,4-dienal, 5- (4-methoxyphenyl) penta-2,4-dienal, 5- (3, 4-dimethoxyphenyl) penta-2,4-dienal, 5- (2,4-dimethoxyphenyl) penta-2,4-dienal, 5- (4-piperidinophenyl) penta-2,4-dienal, 5- (4-morpholinophenyl ) penta-2,4-dienal, 5- (4-pyrrolidinophenyl) penta-2,4-dienal,
6- (4-Dimethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-diethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-methoxyphenyl) hexa-3,5 -dien-2-one, 6- (3,4-dimethoxyphenyl) hexa-3,5-dien-2-one, 6- (2,4-dimethoxyphenyl) hexa-3,5-dien-2-one, 6 - (4-piperidinophenyl) hexa-3,5-dien-2-one, 6- (4-morpholinophenyl) hexa-3,5-dien-2-one, 6- (4-pyrrolidinophenyl) hexa-3,5- diene-2-one, 5- (4-dimethylamino-1-naphthyl) penta-3,5-dienal, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldehyde , 4-chloro-3-nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3 -methoxy-5-nitrobenzaldehyde, 4,5-dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 9-methyl-3-carbazolaldehyde, 9-ethyl-3 carbazolaldehyde, 3-acetylcarbazole, 3,6-diacetyl-9-ethylcarbazole, 3-acetyl-9-methylcarbazole, 1,4-dimethyl-3-carbazolaldehyde, 1,4,9-trimethyl-3-carbazolaldehyde, 4-formyl 1-methylpyridinium, 2-formyl-1-methylpyridinium, 4-formyl-1-ethylpyridinium, 2-formyl-1-ethylpyridinium, 4-formyl-1-benzylpyridinium, 2-formyl-1-benzylpyridinium, 4-formyl-1,2-dimethylpyridinium, 4-formyl-1,3-dimethylpyridinium, 4-formyl-1-methylquinolinium, 2-formyl-1-methylquinolinium, 4-acetyl-1-methylpyridinium, 2 Acetyl-1-methylpyridinium, 4-acetyl-1-methylquinolinium, 5-formyl-1-methylquinolinium, 6-formyl-1-methylquinolinium, 7-formyl-1-methylquinolinium, 8-formyl-1 methylquinolinium, 5-formyl-1-ethylquinolinium, 6-formyl-1-ethylquinolinium, 7-formyl-1-ethylquinolinium, 8-formyl-1-ethylquinoline 5-formyl-1-benzyl-quinolinium, 6-formyl-1-benzyl-quinolinium, 7-formyl-1-benzyl-quinolinium, 8-formyl-1-benzyl-quinolinium, 5-formyl-1-allyl-quinolinium, 6-formyl 1-allyl-quinolinium, 7-formyl-1-allyl-quinolinium and 8-formyl-1-allyl-quinolinium, 5-acetyl-1-methyl-quinolinium, 6-acetyl-1-methyl-quinolinium, 7-acetyl-1-methyl-quinolinium, 8-acetyl-1-methylquinolinium, 5-acetyl-1-ethylquinolinium, 6-acetyl-1-ethylquinolinium, 7-acetyl-1-ethylquinolinium, 8-acetyl-1-ethylquinolinium, 5-acetyl-1-benzylquinolinium , 6-acetyl-1-benzyl-quinolinium, 7-acetyl-1-benzyl-quinolinium, 8-acetyl-1-benzyl-quinolinium, 5-acetyl-1-allyl-quinolinium, 6-acetyl-1-allyl-quinolinium, 7-acetyl 1-allyl-quinolinium and 8-acetyl-1-allyl-quinolinium, 9-formyl-10-methylacridinium, 4- (2'-formyl-vinyl) -1-methyl-pyridinium, 1,3-dimethyl-2- (4'-formyl-phenyl) benzimidazolium, 1,3-dimethyl-2- (4'-formylphenyl) imidazolium, 2- (4'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-acetylphenyl) -3-methylbenzothiazolium, 2 (4'-formylphenyl) -3-methylbenzoxazolium, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium, 2- (5'-Formyl-2'-thienyl) -3-methylbenzothiazolium, 2- (3'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-formyl-1-naphthyl) -3-methylbenzothiazolium , 5-chloro-2- (4'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-formylphenyl) -3,5-dimethylbenzothiazolium benzenesulfonate, p-toluenesulfonate, methanesulfonate, perchlorate, sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfate, trifluoromethanesulfonate, tetrafluoroborate, isatin, 1-methyl-isatin, 1-allyl-isatin, 1-hydroxymethyl-isatin, 5-chloro-isatin, 5-methoxy -isatin, 5-nitroisatin, 6-nitroisatin, 5-sulfoisoisine, 5-carboxyisatin, quinisatin, 1-methylquinisatin, and any mixtures of the above compounds.

When CH-Acids are generally considered to be compounds which a hydrogen atom bonded to an aliphatic carbon atom carry, due to electron-withdrawing substituents one Activation of the corresponding carbon-hydrogen bond causes becomes. According to the invention, CH-acidic compounds also include enamines. by alkaline treatment of quaternized N-heterocycles with a conjugated to quaternary nitrogen CH-acid Alkyl group arise.

The CH-acidic compounds of component B are preferably selected from the group consisting of 1,2,3,3-tetramethyl-3H-indolium iodide, 1,2,3,3-tetramethyl-3H-indolium p-toluenesulfonate, 1,2,3,3-tetramethyl-3H-indolium methanesulfonate, 1,3,3-trimethyl-2-methylenindoline (Fischer's base), 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium p-toluenesulfonate, 2,3-dimethylnaphtho [1,2-d] thiazolium p-toluenesulfonate, 3-ethyl-2-methyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, rhodanine, Rhodanine-3-acetic acid, 1,4-dimethylquinolinium iodide, 1,2-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1,3-dimethylthiobarbituric acid, 1,3-diethylthiobarbituric acid, 1,3-diethylbarbituric acid, oxindole, 3-indoxylacetate, 2-coumaranone, 5-hydroxy-2-cumaranone, 6-hydroxy-2-cumaranone, 3-methyl-1-phenylpyrazolin-5-one, indan-1,2-dione, indan-1,3-dione, Indan-1-one, benzoylacetonitrile, 3-dicyanomethylenedan-1-one, 2-amino-4-imino-1,3-thiazoline hydrochloride, 5,5-dimethylcyclohexane-1,3-dione, 2H-1,4-benzoxazin-4H-3-one, 3-ethyl-2-methyl-benzoxazolium iodide, 3-ethyl-2-methylbenzothiazolium iodide, 1-ethyl-4-methylquinolinium iodide, 1-ethyl-2-methylquinolinium iodide, 1,2,3-trimethylquinoxalinium iodide, 3-ethyl-2-methylbenzoxazolium p-toluenesulfonate, 3-ethyl-2-methyl-benzothiazolium-p-toluenesulfonate, 1-ethyl-4-methyl-quinolinium-p-toluenesulfonate, 1-ethyl-2-methyl-quinolinium-p-toluenesulfonate, and 1,2,3-trimethylquinoxaluminum p-toluenesulfonate.

In addition, the agents according to the invention contain additional ingredients. A use of certain metal ions For example, or complexes may be preferred to be intense colorations to obtain. Here, agents according to the invention are preferred which additionally contain Cu, Fe, Mn, Ru ions or complexes of these ions.

Preferred bleaching agents according to the invention additionally contain Cu, Fe, Mn, Co, Ce, V, Ru ions or complexes of these ions, with particularly preferred agents being from 0.0001 to 2.5% by weight, preferably from 0.001 to 1 wt .-% of at least one compound from the group copper chloride (CuCl ₂ ), copper sulfate (CuSO ₄ ), iron (II) sulfate, manganese (II) sulfate, manganese (II) chloride, cobalt (II) chloride, cerium sulfate, cerium chloride , Vanadium sulfate, manganese dioxide (MnO ₂ ).

When further ingredient can the compositions of the invention at least one ammonium compound from the group ammonium chloride, Ammonium carbonate, ammonium bicarbonate, ammonium sulfate and / or ammonium carbamate in an amount of 0.5 to 10, preferably 1 to 5 wt .-%, based on contain the total composition of the agent.

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane,
• – kationische Polymere wie quaternisierte Celluloseether, Polysiloxane mit quaternären Gruppen, Dimethyldiallylammoniumchlorid-Polymere, Acrylamid-Dimethyldiallyl-ammoniumchlorid-Copolymere, mit Diethylsulfat quaternierte Dimethylamino-ethylmethacrylat-Vinylpyrrolidon-Copolymere, Vinylpyrrolidon-Imidazolinium-methochlorid-Copolymere und quaternierter Polyvinylalkohol,
• – zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyl-trimethylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methyl-methacrylat/tert-Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere,
• – anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Malein-säureanhydrid-Copolymere und Acrylsäure/Ethylacrylat/N-tert.Butyl-acrylamid-Terpolymere,
• – Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, Gummi arabicum, Karaya-Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, Cellulose-Derivate, z. B. Methylcellulose, Hydroxyalkylcellulose und Carboxymethylcellulose, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, Tone wie z. B. Bentonit oder vollsynthetische Hydrokolloide wie z. B. Polyvinylalkohol,
• – Strukturanten wie Maleinsäure und Milchsäure,
• – haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline,
• – Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierte Proteinhydrolysate,
• – Parfümöle, Dimethylisosorbid und Cyclodextrine,
• – Lösungsmittel und -vermittler wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin und Diethylenglykol,
• – faserstrukturverbessernde Wirkstoffe, insbesondere Mono-, Di- und Oligosaccharide wie beispielsweise Glucose, Galactose, Fructose, Fruchtzucker und Lactose,
• – quaternierte Amine wie Methyl-1-alkylamidoethyl-2-alkylimidazolinium-methosulfat
• – Entschäumer wie Silikone,
• – Farbstoffe zum Anfärben des Mittels,
• – Antischuppenwirkstoffe wie Piroctone Olamine, Zink Omadine und Climbazol,
• – Lichtschutzmittel, insbesondere derivatisierte Benzophenone, Zimtsäure-Derivate und Triazine,
• – Substanzen zur Einstellung des pH-Wertes, wie beispielsweise übliche Säuren, insbesondere Genußsäuren und Basen,
• – Wirkstoffe wie Allantoin, Pyrrolidoncarbonsäuren und deren Salze sowie Bisabolol,
• – Vitamine, Provitamine und Vitaminvorstufen, insbesondere solche der Gruppen A, B₃, B₅, B₆, C, E, F und N,
• – Pflanzenextrakte wie die Extrakte aus Grünem Tee, Eichenrinde, Brennessel, Hamamelis, Hopfen, Kamille, Klettenwurzel, Schachtelhalm, Weißdorn, Lindenblüten, Mandel, Aloe Vera, Fichtennadel, Roßkastanie, Sandelholz, Wacholder, Kokosnuß, Mango, Aprikose, Limone, Weizen, Kiwi, Melone, Orange, Grapefruit, Salbei, Rosmarin, Birke, Malve, Wiesenschaumkraut, Quendel, Schafgarbe, Thymian, Melisse, Hauhechel, Huflattich, Eibisch, Meristem, Ginseng und Ingwerwurzel,.
• – Cholesterin,
• – Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• – Fette und Wachse wie Walrat, Bienenwachs, Montanwachs und Paraffine,
• – Fettsäurealkanolamide,
• – Komplexbildner wie EDTA, NTA, β-Alanindiessigsäure und Phosphonsäuren,
• – Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
• – Trübungsmittel wie Latex, Styrol/PVP- und Styrol/Acrylamid-Copolymere
• – Perlglanzmittel wie Ethylenglykolmono- und -distearat sowie PEG-3-distearat,
• – Pigmente,
• – Stabilisierungsmittel für Wassserstoffperoxid und andere Oxidationsmittel,
• – Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft,
• – Antioxidantien,

enthaltenFurthermore, the bleaching according to the invention other active ingredients, auxiliaries and additives, such as

• Nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes,
• Cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyl diallylammonium chloride polymers, acrylamide-dimethyldiallyl-ammonium chloride copolymers, diethyl sulfate quaternized dimethylaminoethylmethacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers, and quaternized polyvinyl alcohol,
• Zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers,
• Anionic polymers, for example polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
• Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. As bentonite or fully synthetic hydrocolloids such. For example, polyvinyl alcohol,
• - structurants such as maleic acid and lactic acid,
• Hair-conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins,
• Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates,
• Perfume oils, dimethylisosorbide and cyclodextrins,
• Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
• Fiber-structure-improving active substances, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose,
• Quaternized amines such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate
• Defoamers like silicones,
• Dyes for staining the agent,
• Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,
• - light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
• Substances for adjusting the pH, such as, for example, customary acids, in particular edible acids and bases,
• - active substances such as allantoin, pyrrolidonecarboxylic acids and their salts, and bisabolol,
• Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and N,
• - Plant extracts such as extracts of green tea, oak bark, stinging nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, Kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, toadstool, coltsfoot, marshmallow, meristem, ginseng and ginger root ,.
• - cholesterol,
• Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
• - fats and waxes such as spermaceti, beeswax, montan wax and paraffins,
• Fatty acid alkanolamides,
• Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,
• - swelling and penetrating substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
• Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
• Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,
• - pigments,
• Stabilizer for hydrogen peroxide and other oxidizing agents,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - antioxidants,

contain

Regarding further optional components as well as the amounts of these components used expressly on the specialist manuals known to those skilled in the art, eg. B. Kh. Schrader, Basics and formulations of cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989, referenced.

The compositions of the invention may contain the ingredients in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose of hair coloring such carriers are, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair. But it is also possible to provide a powdery or tablet-shaped formulation, which is preferred for Blondiermittel.

For the purposes of the present invention, aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing from 3 to 70% by weight of a C ₁ -C ₄ -alcohol, in particular ethanol or isopropanol. The compositions according to the invention may additionally contain further organic solvents, for example methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. Preference is given to all water-soluble organic solvents.

preferred inventive agent are characterized in that they additionally a non-aqueous solvent contain, with particularly preferred compositions according to the invention the solvent in a concentration of 0.1-30% by weight, preferably in a concentration of 1-20% by weight, most preferably in a concentration of 2-10% by weight, respectively on the means included.

In furthermore preferred agents according to the invention is the solvent selected from ethanol, n-propanol, Isoropanol, n-butanol, propylene glycol, n-butylene glycol, glycerol, Diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, Phenoxyethanol and benzyl alcohol and their mixtures.

Of the pH value of the agents according to the invention can by suitable ingredients such as Acidifizierungsmittel or Alkalizing agent can be adjusted in a wide range.

A oxidative staining The fibers may be in the presence of oxidation dye precursors in principle done with atmospheric oxygen. However, preference is given to a chemical Oxidizing agent used, especially if in addition to the staining a Whitening effect on human hair is desired. This whitening effect can be independent from the staining method required be. The presence of oxidation dye precursors is accordingly no mandatory requirement for an employment of oxidizing agents in the agents according to the invention. The oxidizing agents are persulfates, chlorites and in particular Hydrogen peroxide or its addition products to urea, Melamine and sodium borate in question.

However, according to the invention the oxidation colorant also be applied to the hair together with a catalyst, the oxidation of the dye precursors, eg. B. by atmospheric oxygen, activated. Such catalysts are z. As metal ions, iodides, Quinones or certain enzymes.

Suitable metal ions are, for example, Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ , Mn ⁴⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al ³⁺ . Particularly suitable are Zn ²⁺ , Cu ²⁺ and Mn ²⁺ . The metal ions can in principle be used in the form of any physiologically acceptable salt or in the form of a complex compound. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, both the formation of the dyeing can be accelerated and the color shade can be specifically influenced.

• – Pyranose-Oxidase und z. B. D-Glucose oder Galactose,
• – Glucose-Oxidase und D-Glucose,
• – Glycerin-Oxidase und Glycerin,
• – Pyruvat-Oxidase und Benztraubensäure oder deren Salze,
• – Alkohol-Oxidase und Alkohol (MeOH, EtOH),
• – Lactat-Oxidase und Milchsäure und deren Salze,
• – Tyrosinase-Oxidase und Tyrosin,
• – Uricase und Harnsäure oder deren Salze,
• – Cholinoxidase und Cholin,
• – Aminosäure-Oxidase und Aminosäuren.

Suitable enzymes are z. As peroxidases, which can significantly increase the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the aid of atmospheric oxygen, such as, for example, the laccases, or generate small amounts of hydrogen peroxide in situ and thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, for. B.

• - pyranose oxidase and z. D-glucose or galactose,
• Glucose oxidase and D-glucose,
• - glycerol oxidase and glycerin,
• Pyruvate oxidase and pyruvic acid or its salts,
• Alcohol oxidase and alcohol (MeOH, EtOH),
• Lactate oxidase and lactic acid and their salts,
• Tyrosinase oxidase and tyrosine,
• Uricase and uric acid or their salts,
• - choline oxidase and choline,
• - amino acid oxidase and amino acids.

at An application of oxidants becomes the actual colorant expediently immediately before use by mixing the preparation of the Oxidizing agent with the preparation containing the compounds of formula 1 and optionally dye precursors. The resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6 to 12 have. Particularly preferred the application of hair dye in a slightly alkaline environment. The application temperatures can in a range between 15 and 40 ° C. After an exposure time of 5 to 45 minutes will be the hair dye by rinsing of which to be colored Hair removed. The washing with a shampoo is eliminated, if a strong surfactant-containing carrier, z. B. a dyeing shampoo, has been used.

Especially in hard-to-dye Hair may be an agent of the invention optionally with additional Dye precursors but also without prior mixing with the Oxidation component to be applied to the hair. After a Einwirkdauer of 20 to 30 minutes will then - if necessary after a Intermediate rinse - the oxidation component applied. After another exposure time of 10 to 20 minutes is then rinsed and if desired shampooed. In this embodiment, according to a first variant, in which the previous application of the dye precursors to effect a better penetration into the hair, the corresponding Medium adjusted to a pH of about 4 to 7. According to one second variant is first an air oxidation, with the applied agent being preferred has a pH of 7 to 10. At the subsequent accelerated Post-oxidation may be the use of acidified peroxydisulfate solutions as Oxidizing agent may be preferred.

For the application the agents according to the invention on the hair, the Blondiermittel immediately before applying with a hydrogen peroxide solution mixed. The concentration of this hydrogen peroxide solution is on the one hand by the legal requirements and on the other hand by the desired Effect determined; usually 6- to 12-percent solutions in Water used. The proportions Bleaching agent and hydrogen peroxide solution are usually in the range 1: 1 to 1: 2, with an excess of hydrogen peroxide solution in particular then chosen if not too pronounced Blondierwirkung desired is.

According to the invention preferred is also the use of so-called complexing agents. Complex images are Substances that can complex metal ions. Preferred complexing agents are so-called chelate complexing agents, ie substances with metal ions form cyclic compounds, wherein a single ligand more than occupying a coordination site on a central atom, i. H. at least "bidentate". In this case Thus, normally stretched compounds by complexation on a Ion closed to rings. The number of bound ligands depends on the coordination number of the central ion.

common and in the context of the present invention, preferred chelate complex images Examples are polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA), Nitrilotriacetic acid (NTA) and hydroxyethanediphosphonic acids or their alkali metal salts. Also complexing polymers, ie polymers, either in the main chain itself or sideways too carry functional groups which can act as ligands and react with suitable metal atoms usually to form chelate complexes, are used according to the invention. The polymer-bound ligands of the resulting metal complexes can with only one macromolecule or belong to different polymer chains. The latter leads to Crosslinking of the material, unless the complexing polymers already above covalent bonds were crosslinked.

complexing Groups (ligands) more common complexing polymers are iminodiacetic acid, hydroxyquinoline, thiourea, Guanidine, dithiocarbamate, hydroxamic, amidoxime, aminophosphoric, (cycl.) Polyamino, mercapto, 1,3-dicarbonyl and crown ether residues with z. T. very specific. Activities towards ions different metals. Many base polymers are also commercially available important complexing polymers are polystyrene, polyacrylates, Polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethylenimines. Also natural Polymers such as cellulose, starch or chitin are complexing polymers. In addition, these can provided by polymer-analogous transformations with other ligand functionalities become.

• (i) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,
• (ii) stickstoffhaltigen Mono- oder Polycarbonsäuren,
• (iii) geminalen Diphosphonsäuren,
• (iv) Aminophosphonsäuren,
• (v) Phosphonopolycarbonsäuren,
• (vi) Cyclodextrine.

In the context of the present invention, it is particularly preferable to use one or more chelating agents from the groups of

• (i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,
• (ii) nitrogen-containing mono- or polycarboxylic acids,
• (iii) geminal diphosphonic acids,
• (iv) aminophosphonic acids,
• (v) phosphonopolycarboxylic acids,
• (vi) cyclodextrins.

• a) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt wie Gluconsäure,
• b) stickstoffhaltige Mono- oder Polycarbonsäuren wie Ethylendiamintetraessigsäure (EDTA), N-Hydroxyethylethylendiamintriessigsäure, Diethylentriaminpentaessigsäure, Hydroxyethyliminodiessigsäure, Nitridodiessigsäure-3-propionsäure, Isoserindiessigsäure, N,N-Di-(β-hydroxyethyl)glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)asparaginsäure oder Nitrilotriessigsäure (NTA),
• c) geminale Diphosphonsäuren wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP), deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon und 1-Aminoethan-1,1-diphosphonsäure, deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon,
• d) Aminophosphonsäuren wie Ethylendiamintetra(methylenphosphonsäure), Diethylentriaminpenta(methylenphosphonsäure) oder Nitrilotri(methylenphosphonsäure),
• e) Phosphonopolycarbonsäuren wie 2-Phosphonobutan-1,2,4-tricarbonsäure sowie
• f) Cyclodextrine.

In the context of the present invention, all complexing agents of the prior art can be used. These can belong to different chemical groups. Preferably, used individually or in admixture with each other:

• a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid,
• b) nitrogen-containing mono- or polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserinediacetic acid, N, N-di (β-hydroxyethyl) glycine, N- (1,2-dicarboxy 2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA),
• c) geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), their higher homologues having up to 8 carbon atoms and hydroxy- or amino-containing derivatives thereof and 1-aminoethane-1,1-diphosphonic acid whose higher homologues with up to 8 carbon atoms and hydroxyl- or amino-containing derivatives thereof,
• d) aminophosphonic acids, such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) or nitrilotri (methylenephosphonic acid),
• e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid and
• f) cyclodextrins.

When polycarboxylic a) in the context of this patent application also carboxylic acids Monocarbonsäuren- understood, in which the sum of carboxyl and contained in the molecule Hydroxyl groups is at least 5. Complexing agent from the Group of nitrogen-containing polycarboxylic acids, in particular EDTA, are prefers. In the invention required alkaline pH values of the treatment solutions are these complexing agents at least partially as anions. It does not matter if they are in the form of acids or in the form of salts. In case of use Salts are alkali, ammonium or alkylammonium salts, in particular Sodium salts, preferred.

As well As further preferred complexing agents are polymeric aminodicarboxylic acids whose Salts or their precursors to call. Particular preference is given to polyaspartic acids or their salts and derivatives, in addition to cobuilder properties also have a bleach-stabilizing effect.

Further suitable complexing agents are polyacetals, which by reaction of dialdehydes with polyol carboxylic acids containing 5 to 7 carbon atoms and at least 3 hydroxyl groups can be obtained. preferred Polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic receive.

A provide another substance class with complexing properties the phosphonates. These are in particular hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates is the 1-hydroxyethane-1, l-diphosphonate (HEDP) of particular importance. It is preferably used as the sodium salt, wherein the disodium salt neutral and the tetrasodium salt alkaline (pH 9). When Aminoalkane phosphonates are preferably ethylenediamine tetramethylene phosphonate (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) and their higher Homologous in question. They are preferably in the form of neutral reacting Sodium salts, e.g. B. as hexasodium salt of EDTMP or hepta- and octa-sodium salt of DTPMP. As a complexing agent is from the class of phosphonates preferred HEDP used. The Aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly It may, especially if the agents also contain bleach, preferred be to use Aminoalkanphosphonate, in particular DTPMP, or Use mixtures of the above phosphonates. These substances are described below.

According to the invention preferred Chelating agents are phosphonates, preferably hydroxyalkane or aminoalkanephosphonates and in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) or its Di- or tetrasodium salt and / or ethylenediamine tetramethylenephosphonate (EDTMP) or its Hexasodium salt and / or Diethylentriaminpentamethylenphosphonat (DTPMP) or its hepta- or octasodium salt.

• (a) Nitrilotriessigsäure (NTA),
• (b) Diethylenetriaminpentaesigsäure (DTPA),
• (c) Ethylendiamindibernsteinsäure (EDDS),
• (d) Ethylenediamindiglutarsäure (EDGA),
• (e) 2-Hydroxypropylendiamindibernsteinsäure (HPDS),
• (f) Glycinamid-N,N'-dibernsteinsäure (GADS),
• (g) Ethylendiamin-N-N'-diglutarsäure (EDDG),
• (h) 2-Hydroxypropylendiamin-N-N'-dibernsteinsäure (HPDDS),
• (i) Ethylendiamintetraessigsäure (EDTA),
• (j) Ethylendicysteinsäure (EDC),
• (k) Diaminoalkyldi(sulfobernsteinsäure) (DDS),
• (l) Ethylendiamine-N-N'-bis(ortho-hydroxyphenylesigsäure (EDDHA),
• (m) N-2-hydroxyethyl-N,N-diessigsäure,
• (n) Glyceryliminodiessigsäure,
• (o) Iminodiessigsäure-N-2-hydroxypropylsulfonsäure,
• (p) Asparaginsäure-N-carboxymethyl-N-2,5-hydroxypropyl-3-sulfonsäure,
• (q) 8-Alanin-N,N'-diessigsäure,
• (r) Asparaginsäure-N,N'-diessigsäure,
• (s) Asparaginsäure-N-monoessigsäure,
• (t) Dipicolinsäure,
• (u) sowie deren Salze und/oder Derivate

From the above-mentioned groups of substances, some representatives are particularly preferred in the context of the present invention. Particularly preferred agents according to the invention contain one or

• (a) nitrilotriacetic acid (NTA),
• (b) diethylenetriaminepentaacetic acid (DTPA),
• (c) ethylenediamine disuccinic acid (EDDS),
• (d) ethylenediamine-diglutaric acid (EDGA),
• (e) 2-hydroxypropylenediamine disuccinic acid (HPDS),
• (f) glycinamide-N, N'-disuccinic acid (GADS),
• (g) ethylenediamine-N-N'-diglutaric acid (EDDG),
• (h) 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS),
• (i) ethylenediaminetetraacetic acid (EDTA),
• (j) ethylene dicysteic acid (EDC),
• (k) diaminoalkyldi (sulfosuccinic acid) (DDS),
• (l) ethylenediamine-N-N'-bis (ortho-hydroxyphenylacetic acid (EDDHA),
• (m) N-2-hydroxyethyl-N, N-diacetic acid,
• (n) glyceryliminodiacetic acid,
• (o) iminodiacetic acid N-2-hydroxypropylsulfonic acid,
• (p) aspartic acid-N-carboxymethyl-N-2,5-hydroxypropyl-3-sulfonic acid,
• (q) 8-alanine-N, N'-diacetic acid,
• (r) aspartic acid-N, N'-diacetic acid,
• (s) aspartic acid N-monoacetic acid,
• (t) dipicolinic acid,
• (u) and their salts and / or derivatives

• (i) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,
• (ii) stickstoffhaltigen Mono- oder Polycarbonsäuren,
• (iii) geminalen Diphosphonsäuren,
• (iv) Aminophosphonsäuren,
• (v) Phosphonopolycarbonsäuren,
• (vi) Cyclodextrine

enthalten, wobei bevorzugte Mittel Phosphonate, vorzugsweise Hydroxyalkan- bzw. Aminoalkanphosphonate und insbesondere 1-Hydroxyethan-1,1-diphosphonat (HEDP) bzw. dessen Di- oder Tetranatriumsalz und/oder Ethylendiamintetramethylenphosphonat (EDTMP) bzw. dessen Hexanatriumsalz und/oder Diethylentriaminpentamethylenphosphonat (DTPMP) bzw. dessen Hepta- oder Octanatriumsalz, enthalten.Agents preferred according to the invention are characterized in that they additionally comprise one or more chelate complexing agents from the groups of

• (i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,
• (ii) nitrogen-containing mono- or polycarboxylic acids,
• (iii) geminal diphosphonic acids,
• (iv) aminophosphonic acids,
• (v) phosphonopolycarboxylic acids,
• (vi) cyclodextrins

Preferred agents include phosphonates, preferably hydroxyalkane or aminoalkanephosphonates and in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) or its di- or tetrasodium salt and / or ethylenediamine tetramethylenephosphonate (EDTMP) or its hexasodium salt and / or diethylenetriaminepentamethylenephosphonate ( DTPMP) or its hepta- or octasodium salt.

• – Carbonate und/oder
• – Monoalkylcarbonate (Kohlensäuremonoester) und/oder
• – Kohlensäuremonoamide und/oder
• – Silylcarbonate und/oder
• – Silylcarbamate

In addition to the ingredients mentioned, the use of carbonates and crabonate analogues in the compositions according to the invention has proven to be preferred. Accordingly, preferred agents according to the invention additionally contain 0.1 to 25 wt.%, Preferably 0.5 to 20 wt.%, Particularly preferably 1 to 15 wt.% And in particular 1.5 to 10 wt.% Of at least one substance from the groups of

• - Carbonates and / or
• Monoalkyl carbonates (carbonic acid monoesters) and / or
• - carbonic acid monoamides and / or
• - Silyl carbonates and / or
• - silyl carbamates

When Carbonates are especially ammonium, alkali metal and Alkaline earth metal carbonates and bicarbonates. Especially preferred For example, sodium bicarbonate, sodium carbonate.

In addition to Carbonates or in their place may agents of the invention preferably also at least one carbonic acid monoester and / or at least a carbonic acid monoamide contain. These substances are described in detail below.

Agents preferred according to the invention are characterized in that they contain at least one carbonic acid monoester of the formula (I) ROC (O) -OH (I) in which R represents a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical, or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.

In formula (I), R preferably represents a substituted or unsubstituted, straight-chain or branched alkyl, alkenyl or alkynyl radical, preference being given to hydroxy, amino, nitro, sulfonic acid groups or halogens as substituents. Further preferred radicals R are phenyl and benzyl radicals and further substituted representatives. More preferably, R is a C _1-6 alkyl group. Examples of C ₁ -C ₆ -alkyl groups according to the invention are the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl and hexyl.

Particularly according to the invention preferred agents are characterized in that the remainder R is selected in formula (I) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, tert-butyl and hydroxymethyl and hydroxyethyl radicals.

As an alternative to the carbonic acid monoester or in conjunction with it, the compositions according to the invention may contain carbonic acid monoamides. Here, preferred agents according to the invention are characterized in that they contain at least one carbonic acid monoamide of the formula (II) R-NH-C (O) -OH (II) in which R is a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical, or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.

In formula (II), R preferably represents a substituted or unsubstituted, straight-chain or branched alkyl, alkenyl or alkynyl radical, preference being given to hydroxy, amino, nitro, sulfonic acid groups or halogens as substituents. Further preferred radicals R are phenyl and benzyl radicals and further substituted representatives. More preferably, R is a C _1-6 alkyl group. Examples of C ₁ -C ₆ -alkyl groups according to the invention are the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl and hexyl.

Particularly according to the invention preferred agents are characterized in that the remainder R is selected in formula (II) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, tert-butyl and hydroxymethyl and hydroxyethyl radicals.

The Acid H atom of carbonic acid monoester or monoamides may also be present in neutralized form, i. it can According to the invention also salts of carbonic acid monoesters or carbonic acid monoamides be used. Here, agents according to the invention are preferred which the Kohlensäuremonoester or the carbonic acid monoamide in completely or partially neutralized form, preferably in the form its alkali metal, ammonium, alkaline earth metal or aluminum salt and especially in the form of its sodium salt.

Independently of, whether the agents according to the invention one or more carbonic acid monoesters and / or one or more carbonic acid monoamides included are means of the invention preferably, the or the carbonic acid monoesters and / or carbonic acid monoamides in amounts of from 0.1 to 20% by weight, preferably from 0.5 to 18% by weight, particularly preferably from 2 to 15% by weight and in particular from 5 to 12% by weight, based in each case on the total agent.

In addition to Carbonates and / or carbonic acid monoesters and / or carbonic acid monoamides or in their place the agents according to the invention preferably also at least one silyl carbonate and / or at least contain a silyl carbamate. These substances will be below described in detail.

enthalten, in der die Reste R¹, R² und R³ unabhängig voneinander für ein Wasserstoffatom, einen gesättigten oder ungesättigten, geradkettigen, verzweigten, oder cyclischen, substituierten oder unsubstituierten Kohlenwasserstoffrest oder für eine Trialkylsilylgruppe, vorzugsweise eine Trimethylsilylgruppe oder für eine substituierte oder unsubstituierte Arylgruppe bzw. einen substituierten oder unsubstituierten Heterocyclus oder für ein Halogen, eine substituierte oder unsubstituierte Hydroxy-, Oxo-, Amino-, Iminogruppen stehen und der Rest R⁴ für eine chemische Bindung zum Si-Atom oder zu einem der Reste R¹, R² oder R³, ein Wasserstoffatom, einen gesättigten oder ungesättigten, geradkettigen, verzweigten, oder cyclischen, substituierten oder unsubstituierten Kohlenwasserstoffrest oder für eine substituierte oder unsubstituierte Silyl- oder Aluminylgruppe oder für eine substituierte oder unsubstituierte Arylgruppe bzw. einen substituierten oder unsubstituierten Heterocyclus steht.Agents preferred according to the invention are characterized in that they contain at least one silyl carbonate of the formula (III)

in which the radicals R ¹ , R ² and R ³ independently of one another represent a hydrogen atom, a saturated or unsaturated, straight-chain, branched or cyclic, substituted or unsubstituted hydrocarbon radical or a trialkylsilyl group, preferably a trimethylsilyl group or a substituted or unsubstituted one Aryl group or a substituted or unsubstituted heterocycle or a halogen, a substituted or unsubstituted hydroxy, oxo, amino, imino groups and the radical R ^{4 is} a chemical bond to the Si atom or to one of the radicals R ¹ , R ² or R ³ , a hydrogen atom, a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical or a substituted or unsubstituted silyl or alumino group, or a substituted or unsubstituted aryl group or a substituted or unsubstituted het erocyclus stands.

Preferred radicals R ¹ , R ² and R ³ in the abovementioned formula (III) are substituted or unsubstituted, straight-chain or branched alkyl radicals. Among these, the alkyl radicals having 1 to 5 carbon atoms and the hydroxyalkyl radicals are preferred, so that preferred agents according to the invention are characterized in that the radicals R ¹ , R ² and R ³ in formula (I) are selected from methyl, ethyl, n Propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, hydroxymethyl and hydroxyethyl radicals.

Preferred radicals R ⁴ in the abovementioned formula (III) are hydrogen, substituted or unsubstituted, straight-chain or branched alkyl radicals and trialkylsilyl radicals. Among them, preferred are hydrogen, methyl, ethyl, tert-butyl and trimethylsilyl radicals.

The acidic H atom of the silyl carbonate (R ⁴ = -H in formula III) can also be present in neutralized form, ie according to the invention it is also possible to use salts of silyl carbonates. Here, agents according to the invention are preferred which comprise at least one silyl carbonate in completely or partially neutralized form, preferably in the form of its alkali metal, ammonium, alkaline earth metal or aluminum salt and in particular in the form of its sodium salt.

In addition to the silyl carbonates or in their place, the agents of the invention Silylcarbamate included.

enthalten, in der enthält, in der die Reste R¹, R² und R³ unabhängig voneinander für ein Wasserstoffatom, einen gesättigten oder ungesättigten, geradkettigen, verzweigten, oder cyclischen, substituierten oder unsubstituierten Kohlenwasserstoffrest oder für eine Trialkylsilylgruppe, vorzugsweise eine Trimethylsilylgruppe oder für eine substituierte oder unsubstituierte Arylgruppe bzw. einen substituierten oder unsubstituierten Heterocyclus oder für ein Halogen, eine substituierte oder unsubstituierte Hydroxy-, Oxo-, Aminogruppen stehen und die Rest R⁴ und R⁵ unabhängig voneinander für eine chemische Bindung zum Si-Atom oder zu einem der Reste R¹, R² oder R³, ein Wasserstoffatom, einen gesättigten oder ungesättigten, geradkettigen, verzweigten, oder cyclischen, substituierten oder unsubstituierten Kohlenwasserstoffrest oder für eine substituierte oder unsubstituierte Silyl- oder Aluminylgruppe oder für eine substituierte oder unsubstituierte Arylgruppe bzw. einen substituierten oder unsubstituierten Heterocyclus stehen.Agents preferred according to the invention are characterized in that they contain a silyl carbamate of the formula (IV)

containing, in which the radicals R ¹ , R ² and R ³ independently of one another represent a hydrogen atom, a saturated or unsaturated, straight-chain, branched or cyclic, substituted or unsubstituted hydrocarbon radical or for a trialkylsilyl group, preferably a trimethylsilyl group or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle or a halogen, a substituted or unsubstituted hydroxy, oxo, amino groups and the radicals R ⁴ and R ⁵ independently of one another for a chemical bond to the Si atom or to a the radicals R ¹ , R ² or R ³ , a hydrogen atom, a saturated or unsaturated, straight-chain, branched or cyclic, substituted or unsubstituted hydrocarbon radical or a substituted or unsubstituted silyl or alumino group or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.

Preferred radicals R ¹ , R ² and R ³ in the abovementioned formula (IV) are substituted or unsubstituted, straight-chain or branched alkyl radicals. Among these, the alkyl radicals having 1 to 5 carbon atoms and the hydroxyalkyl radicals are preferred, so that preferred agents according to the invention characterized in that the radicals R ¹ , R ² and R ³ in formula (II) are selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, tert-butyl - As well as hydroxymethyl and hydroxyethyl radicals.

Preferred radicals R ⁴ and R ⁵ in the abovementioned formula (IV) are hydrogen, substituted or unsubstituted, straight-chain or branched alkyl radicals and trialkylsilyl radicals. Among them, preferred are hydrogen, methyl, ethyl, tert-butyl and trimethylsilyl radicals.

Independently of, whether the agents according to the invention one or more silyl carbonates and / or one or more silyl carbamates included are means of the invention preferably the silyl carbonate (s) and / or silyl carbamate (s) in amounts of from 0.1 to 25% by weight, preferably from 0.5 to 20% by weight, particularly preferably from 1 to 15% by weight and in particular from 1.5 to 10% by weight, in each case based on the total agent.

The agents according to the invention preferably have a pH of 5.0 to 9.0, preferably from 5.5 to 8.0, more preferably from 6.0 to 7.7, more preferably from 6.2 to 7.2 and especially from 6.5 to 6.8.

preferred inventive agent are formulated low in water or anhydrous. Particularly according to the invention preferred agents are characterized by being less as 5% by weight, preferably less than 2% by weight, more preferably less than 1% by weight and in particular less than 0.5% by weight of water contain, with preferred agents are anhydrous.

Of the Water content of the funds can be For example, determine by titration Karl Fischer.

• – gewünschtenfalls ein Vorbehandlungsmittel M1 auf die Faser aufgebracht wird, dann
• – ein Mittel M2 auf der Faser zur Anwendung kommt, wobei gewünschtenfalls dem Mittel M2 vor der Anwendung ein weiteres Mittel M3 zugegeben wird,
• – dieses Mittel M2 nach einer Zeit von 5-30 Minuten von der Faser abgespült wird
• – und nach der Behandlung gegebenenfalls ein Nachbehandlungsmittel M4 auf die Faser aufgetragen und nach einer Einwirkzeit von einigen Minuten wieder abgespült wird,

wobei mindestens eines der Mittel M1, M2 oder M3 ein erfindungsgemäßes Mittel ist.A second object of the present invention is a process for whitening keratin fibers, in particular human hair, in which

• - If desired, a pretreatment agent M1 is applied to the fiber, then
• A means M2 is applied to the fiber, wherein, if desired, an additional agent M3 is added to the agent M2 before use,
• - This agent M2 is rinsed from the fiber after a time of 5-30 minutes
• - and after the treatment optionally a post-treatment agent M4 applied to the fiber and rinsed again after a contact time of a few minutes,

wherein at least one of the means M1, M2 or M3 is an agent according to the invention.

The agents according to the invention can accordingly as one-component agent (bleaching agent M2 or aftertreatment agent M4), as a two-component agent (M2 + M3) or as a three-component agent (M2 + M3 + M4) and applied accordingly. A Separation in multicomponent systems is particularly useful there where incompatibilities the ingredients are to be expected or feared; the one to be used Means is in such systems by the consumer directly before the Application made by mixing the component.

One Whitening method in which the whitening cream and the oxidizing agent first are present separately, is preferred. Another item The present invention therefore provides a process for lightening of human hair containing an aqueous composition, containing hydrogen peroxide, with an agent according to the invention mixed into a homogeneous composition, and this on the Hair is applied.

In preferred processes of this type according to the invention, the aqueous composition contains from 1 to 20% by weight, preferably from 2 to 10% by weight and in particular from 3 to 6% by weight of hydrogen peroxide, calculated as 100% H ₂ O ₂ .

Further preferred method according to the invention of this type are characterized in that the composition is water-based, containing hydrogen peroxide, with an agent according to the invention in weight ratio 1: 5 to 10: 1, preferably 1: 2 to 5: 1 and especially 1: 2 to 2: 1 mixed to a homogeneous composition, and this on the hair is applied.

Alternatively, as mentioned above, a three-component system may also be used. Another object of the present invention is therefore a process for whitening human hair, in which an aqueous-based composition containing hydrogen peroxide, with a further agent comprising preferably at least one alkalinity donor and / or substantive hair dye and / or at least one oxidation dye precursor, and an agent according to the invention mixed to form a homogeneous composition, and this is applied to the hair.

Regarding further preferred embodiments the inventive method mutatis mutandis applies to the means of the invention said.

• a) mindestens einer festen Peroxoverbindung, die ausgewählt ist aus Ammonium- und Alkalimetall-persulfaten und -peroxidisulfaten,
• b1) mindestens einem Cyanat der Formel M⁺ [OCN]^– in der M⁺ für K⁺, Na⁺, Li⁺ oder NH₄ ⁺ oder ½ Ca²⁺, ½ Mg²⁺ oder % Zn²⁺ steht und/oder
• b2) mindestens einer Verbindung der Formel H₂N-C(O)-L in der L für eine durch das Anion ^–OOH verdrängbare Gruppe steht,

in Blondiermitteln, vorzugsweise in schwach alkalischen bis neutralen Blondiermitteln.Another object of the present invention is the use of mixtures of

• a) at least one solid peroxo compound selected from ammonium and alkali metal persulfates and peroxydisulfates,
• b1) at least one cyanate of the formula M ⁺ [OCN] ^- in which M ^{+ stands} for K ⁺ , Na ⁺ , Li ⁺ or NH ₄ ⁺ or ½ Ca ²⁺ , ½ Mg ²⁺ or% Zn ²⁺ and / or
• b2) at least one compound of the formula H ₂ NC (O) -L in which L stands for a group displaceable by the anion ^- OOH,

in bleaching agents, preferably in weakly alkaline to neutral bleaching agents.

• i. Steigerung der Aufhell- bzw. Blondierleistung und/oder
• ii. Steigerung der Hautverträglichkeit von Aufhell- bzw. Blondiermitteln.

Particularly preferably, the use of the mixtures serves to achieve certain advantageous effects. Preferred according to the invention are uses for

• i. Increase in the whitening or bleaching performance and / or
• ii. Increase the skin compatibility of brightening or bleaching agents.

With regard to more preferred uses according to the invention mutatis mutandis, the one that applies to the preferred means applies.

Examples:

a) Bleaching pastes:

Britesil^®C20 Fällungskieselsäure (INCI-Bezeichnung: Silica) (PQ)
Texapon^® K12 P Natriumdodecylsulfat, Pulver (INCI-Bezeichnung: Sodium Lauryl Sulfate Silica) (Cognis)
Elfan^® AT 84 Natriumcocoylisethionat (INCI-Bezeichnung Sodium Cocoyl Isethionate) (Julius Hoesch)
Cetiol^® 868 Ethylhexylstearat (INCI-Bezeichnung: Ethyl Hexyl Stearate) (Cognis)
Lorol^® tech. C_12-18-Fettalkohol (INCI-Bezeichnung: Coconut alcohol) (Cognis)
Cutina^® GMS Glycerinmono/dipalmitat/stearat (INCI-Bezeichnung: Glyceryl Stearate) (Cognis)
Eutanol^® G 2-Octyldodecylalkohol (INCI-Bezeichnung: Octyldodecanol) (Cognis)
Aerosil^®200 pyrogene Kieselsäure (INCI-Bezeichnung: Silica) (Degussa)
Cekol^® Carboxymethylcellulose (INCI-Bezeichnung Cellulose Gum) (CP Kelco)Three bleaching pastes were prepared, the composition of which (in g) are given in Table 1:

Britesil ^® C20 precipitated silica (INCI name: Silica) (PQ)
Texapon ^® K12 P sodium dodecyl sulfate, powder (INCI name: Sodium Lauryl Sulfate Silica) (Cognis)
Elfan AT 84 ^® sodium cocoyl isethionate (INCI name Sodium Cocoyl Isethionate) (Julius Hoesch)
Cetiol ^® 868 ethylhexyl stearate (INCI name: Ethyl hexyl Stearate) (Cognis)
Lorol® ^® tech. C _12-18 fatty alcohol (INCI name: Coconut alcohol) (Cognis)
Cutina ^® GMS glycerol mono / dipalmitate / stearate (INCI name: Glyceryl Stearate) (Cognis)
Eutanol ^® G 2-octyldodecyl alcohol (INCI name: Octyldodecanol) (Cognis)
Aerosil ^® 200 fumed silica (INCI name: Silica) (Degussa)
Cekol carboxymethyl cellulose ^® (INCI designation Cellulose Gum) (CP Kelco)

In addition, a developer dispersion of the following composition was prepared: Texapon N28 2.0% by weight Turpinal SL 1.5% by weight hydrogen peroxide 12.0% by weight Ammonia solution; 25% strength 0.65% by weight Acrysol 33 12.0% by weight water ad 100% by weight Texapon.RTM ^® N28 Lauryl ether sulfate sodium salt (at least 26.5% active ingredient content, INCI name: Sodium Laureth Sulfate) (Cognis) Turpinal® ^® SL 1-hydroxyethane-1,1-diphosphonic acid (about 58-61% active ingredient content, INCI name: Etidronic Acid, Aqua (Water)) (Solutia) Acrysol ^® 33 Acrylic polymer (about 28% solids in water, INCI name: acrylates copolymer)

The Formulations 1 to 3 were in the weight ratio 1: 3 with the developer dispersion mixed and after mixing with phosphoric acid to a pH between 7 and 7.5 set.

On medium blond and dark brown hair of codes Fischbach and Miller 6923 or Kerling 2/0 (45 minutes, 32 ° C, weight ratio application mixture / hair = 4: 1) resulted in significantly better lightening than in the corresponding formulations without sodium cyanate.

b) bleaching powder:

Britesil^®C20 Fällungskieselsäure (INCI-Bezeichnung: Silica) (PQ)
Aerosil^®200 pyrogene Kieselsäure (INCI-Bezeichnung: Silica) (Degussa)
Cetiol^® OE Dioctylether (INCI-Bezeichnung: Dicaprylylether) (Cognis)A comparative bleaching powder according to the invention was prepared, the composition of which (in g) is given in Table 1:

Britesil ^® C20 precipitated silica (INCI name: Silica) (PQ)
Aerosil ^® 200 fumed silica (INCI name: Silica) (Degussa)
Cetiol ^® OE dioctyl (INCI name: dicaprylyl) (Cognis)

ever 50 g of the powders were mixed with 50 g of the developer dispersion from a) mixed. The comparative mixture had a pH of 10, the mixture with powder E4 was made up with phosphoric acid a pH of 7.0 set. With these mixtures were hair strands of each 0.5 g weight of the codes Kerling 2/0 (dark brown) and Fischbach and Miller 6923 (dark blond) (45 minutes, 32 ° C, weight ratio application mixture / hair = 4: 1) dyed out.

Both Formulations gave excellent brightening results, i. with a neutral and significantly less hair damaging pH were the Results of conventional reached high alkaline Blondungen.

Claims (13)

Bleaching agent for human hair, containing - in relation to its weight - b. From 5 to 70% by weight of at least one solid peroxy compound selected from ammonium and alkali metal persulfates and peroxydisulfates, b1) from 0.05 to 5% by weight of at least one cyanate of the formula M ⁺ [OCN] ^- in which M ^{+ stands} for K ⁺ , Na ⁺ , Li ⁺ or NH ₄ ⁺ or% Ca ²⁺ , ½ Mg ²⁺ or ½Zn ²⁺ and / or b2) 0.05 to 5 wt .-% of at least one compound the formula H ₂ NC (O) -L in which L stands for a group displaceable by the anion ^- OOH. Agent according to claim 1, characterized in that it comprises 6 to 65 wt .-%, preferably 7.5 to 60 wt .-%, particularly preferably 8 up to 55% by weight and in particular from 10 to 50% by weight of peroxydisulfate (e) contains. Agent according to one of claims 1 or 2, characterized that it Sodium peroxydisulfate and / or potassium peroxodisulfate and / or ammonium peroxydisulfate contains preferred agents being at least two different peroxidisulfates contain. Agent according to one of claims 1 to 3, characterized that it 0.075 to 4 wt .-%, preferably 0.1 to 2.5 wt .-% and in particular 0.2 to 1% by weight of sodium cyanate and / or potassium cyanate and / or ammonium cyanate contains wherein sodium cyanate is particularly preferred. Agent according to one of claims 1 to 4, characterized in that it contains 0.075 to 4 wt .-%, preferably 0.1 to 3.5 wt .-% and in particular 0.2 to 3 wt .-% of at least one compound of the formula H ₂ NC (O) -L in which L is selected from -S-CH ₂ -COOH, -S- (CH ₂ ) ₃ SO ₃ H, -S- (CH ₂ ) ₂ -NH ₂ , -OCH ₃ , -O- (C ₆ H ₄ ) -SO ₃ M, -Q ⁺ , -NH-OH, -OC (O) -R ¹ , -OC (O) -H, -O-CH (OH) ₂ , -SO ₃ M, -PH (O) OH, -P (O) (OH) ₂ , - (NH-glucosamine) _n , -NH-C (O) -NH ₂ , -NH-NH ₂ , -NH-CN, -P (OH) (O) -C (O) NH ₂ , -SCN, -OCN, -SC (NH) NH ₂ ,

and M is -H, Na, K, NH4, Q is selected from quaternary ammonium radicals, heteroaryl radicals or non-aromatic heterocycles formed from tertiary amines and R ^{1 is} -H, -CH ₃ , -CH ₂ CH ₃ , - ( CH ₂ ) ₂ CH ₃ , -CH (CH ₃ ) ₂ or another alkyl group. Agent according to one of claims 1 to 5, characterized in that it additionally contains Cu, Fe, Mn, Co, Ce, V, Ru ions or complexes of these ions, preferred agents being 0.0001 to 2 , 5 wt .-%, preferably 0.001 to 1 wt .-% of at least one compound from the group copper chloride (CuCl ₂ ), copper sulfate (CuSO ₄ ), iron (II) sulfate, manganese (II) sulfate, manganese (II) chloride , Cobalt (II) chloride, cerium sulfate, cerium chloride, vanadium sulfate, manganese dioxide (MnO ₂ ). Agent according to one of claims 1 to 6, characterized that it additionally one or more chelating agents from the groups of (I) polycarboxylic in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, (Ii) nitrogenous mono- or polycarboxylic acids, (iii) geminal diphosphonic acids, (Iv) aminophosphonic, (V) phosphonopolycarboxylic, (Vi) cyclodextrins contains preferred agents include phosphonates, preferably hydroxyalkane or aminoalkane phosphonates and in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) or its di- or tetrasodium salt and / or ethylenediamine tetramethylenephosphonate (EDTMP) or its hexasodium salt and / or Diethylentriaminpentamethylenphosphonat (DTPMP) or its hepta- or Octa sodium salt, included. Agent according to one of claims 1 to 7, characterized that it additionally 0.1 to 25 wt.%, Preferably 0.5 to 20 wt.%, Particularly preferably 1 to 15 wt.% And in particular 1.5 to 10 wt.% Of at least one Substance from the groups of - Carbonates and / or - monoalkyl carbonates (Kohlensäuremonoester) and or - Carbonic acid monoamides and or - Silyl carbonates and or - silyl carbamates contains. Agent according to one of claims 1 to 8, characterized that it a pH of 5.0 to 9.0, preferably 5.5 to 8.0, especially preferably from 6.0 to 7.7, more preferably from 6.2 to 7.2 and in particular from 6.5 to 6.8. Agent according to one of claims 1 to 9, characterized that it less than 5% by weight, preferably less than 2% by weight, especially preferably less than 1% by weight and in particular less than 0.5 Wt .-% water, preferred agents being anhydrous. Method for whitening keratin fibers, in particular human hair, characterized in that If desired, a pretreatment agent M1 is applied to the fiber, then - a medium M2 on the fiber is used, if desired the agent M2 before use another agent M3 added becomes, - this one Means M2 is rinsed off the fiber after 5-30 minutes - and after the treatment optionally an M4 after treatment Fiber applied and after a contact time of a few minutes rinsed off again where at least one of the means M1, M2 or M3 is an agent according to one of the claims 1 to 10 is. Use of mixtures of a) at least one solid peroxo compound selected from ammonium and alkali metal persulfates and peroxydisulfates, b1) at least one cyanate of the formula M ⁺ [OCN] ^- in which M is K, Na or NH ₄ and / or b2) at least one compound of the formula H ₂ NC (O) -L in which L stands for a group displaceable by the anion ^- OOH, in bleaching agents, preferably in slightly alkaline to neutral bleaching agents. Use according to claim 12 for - increase the whitening or bleaching performance and / or - increase the skin compatibility of whitening or bleaching agents.