MX2008005295A - Process for hair dyeing comprising application of composite pigment - Google Patents

Abstract

Disclosed is a process for dyeing of keratin-containing fibers comprising treating the fibers with at least one functionalized particle comprising on the surface an organic chromophore which is bound via a bridge member, wherein the particles are based on SiO2, Al2O3or mixtures thereof, and the functionalized particles carry a positive charge.

Description

PROCESS FOR DYEING HAIR COMPRISING APPLICATION OF COMPOUND PIGMENT Field of the Invention The present invention relates to a process for dyeing keratin-containing fibers, especially human hair, wherein specifically functionalized particles are used as dyes.

BACKGROUND OF THE INVENTION For example, it is known from O 95/01772 that cationic dyes can be used for dyeing keratin-containing fibers. This kind of dyes exhibit very bright shades. However, one disadvantage is their unsatisfactory firmness to hydrolysis and light, their frequently inadequate stability under reducing or oxidizing conditions, and their frequently unsatisfactory storage stability (see: John F. Corbett: "The Chemistry of Hair-Care Products", JSCD August 1976, p.290). Frequently, the spotting of the skin is also a matter. In addition, there is a need to dye hair with compounds that give easy access to the full spectrum of colors.

Description of the Invention The object of the present invention is to provide dyes for the dyeing of fibers containing keratin which are distinguished by intense dyeing and which simultaneously have good firmness properties with respect to washing, light, shampooing and scrubbing, which preferably exhibit satisfactory stability under reducing or oxidating dyeing conditions, and which cause less staining to the skin. The subject of the present invention is based on the idea of using nano-, submicro- or micro-particles of silica or alumina dioxide, modified on the surface with at least one chemically bound dye, which is additionally required a cationic group chemically bound , and if it is required to make them compatible to a solvent, a compatibilizing group. With this approach and by using different colored dyes, it is possible to synthesize rather homodisperse particles with any necessary color. Additionally, the cationic charge does not necessarily have to be part of the dye. The cationic charge can also be introduced by additional groups that allow the load to be adjusted to a desired level. Therefore, the present invention relates to a process for dyeing keratin-containing fibers comprising treating the fibers with at least one functionalized particle comprising on the surface an organic chromophore that is joined by a bridge member, wherein the particles are based on Si02, AI2O3 or mixtures thereof, and the functionalized particles have a positive charge.

Functionalized particles comprising a covalently bound organic chromophore have a positive charge (for example with nitrogen, sulfur or phosphorus as the charge carrying atom). Examples of cationic groups are cationic ammonium, phosphonium or sulfonium groups. It is preferred that the particles comprise a cationic ammonium group. Examples of cationic ammonium groups are those of the formula -N (Ri *) 3, wherein the three radicals Ri * may have the same or different meanings, and Ri * is hydrogen; Ci-Ci2alkyl which may be interrupted by -0- and may be substituted by hydroxyl or phenyl, and wherein the phenyl radical may be further substituted by Ci-Cgalkyl, Ci-C8alkoxy or halogen; phenyl which may be substituted by Ci-Csalkyl, Ci-Csalkoxy or halogen. It is preferred that Ri * is hydrogen, Ci-C ^ alkyl or Ci-Ci2hydroxyalkyl, more preferably hydrogen or Ci-Ci2alkyl, especially Ci-Ci2alkyl. Examples of cationic phosphonium groups are those of the formula -P (Ri *) 3, wherein the three Ci * radicals can have the same or different meanings, and are as defined above. Examples of sulfonium groups are those of the formula -S (Ri *) 2, wherein the two Ri * radicals may have the same or different meanings, and are as defined above. In the context of the present invention, it is going to understand that the cationic groups can also understand the corresponding anionic counterions. Anionic counterions denote, for example, an organic or inorganic anion, such as halide, preferably chloride and fluoride, sulfate, acid sulfate, phosphate, boron tetrafluoride, carbonate, bicarbonate, oxalate or Ci-Cgalkyl sulfate, especially methyl sulfated or ethyl sulfate; Anionic counterion also denotes lactate, formate, acetate, propionate or a complex anion, such as the double salt of zinc chloride. The anionic counterion especially a halide, preferably chloride, fluoride or iodide, sulfate, acid sulfate, methyl sulfate, ethyl sulfate, phosphate, formate, acetate or lactate. The anionic counterion is more especially fluoride, chloride, iodide, methyl sulfate, ethyl sulfate, formate or acetate. As for the organic chromophore, the definitions and preferences given in the following apply for D. Functionalized particles comprising, covalently bound to an oxygen atom on the surface, a radical of the formula are preferred. wherein Ri and R2 are independently from each other hydróg particle surface-O-, or a substituent, B is the direct link or a source member, D is a radical of an organic chromophore, and n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10. Ri and R2 are, for example, independently between hydrogen; Ci-C25alkyl which may be interrupted by -O-, -S- or -N (R3) -; C2-C2Jalkenyl; phenyl; C7-Cgphenylalkyl; -OR5; Rfi I 6 R6 R6 R6 -Si-O- |R. Si-O-Si -O-Si-O- Si-O-Si- I I I I I R, R¾ is hydrogen; Ci-C25alkyl which may be interrupted by -O-, -S- or -N (R3) -; · C2-C24alkenyl; phenyl; C7- Cgphenylalkyl; ; or a particle surface, R6 and R7 independently of each other are hydrogen; Ci-C25alkyl which may be interrupted by -O-, -S- or -N (R3) -; C2-C24alkenyl; phenyl; C7-C9phenylalkyl; or -OR5, and Rg, R9 and Rio independently of each other are hydrogen; Ci ~ C25alkyl which may be interrupted by -O-, -S- or -N (R3) -; C2-C24alkenyl; phenyl; or C7-Cgphenylalkyl. R3 is hydrogen or Ci-Ci2alkyl optionally substituted. R3 as the alkyl radical may be substituted by the cationic groups mentioned above, especially by a cationic ammonium group. Preferably, R3 is hydrogen or Ci-Ci2alkyl, especially hydrogen or Ci-C4alkyl. A highly preferred meaning for R3 it is hydrogen. RIF R2, R5, Re, R7, RS R9 and Rio as Ci-C25alkyl can be a branched or unbranched radical, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1; 3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1, 1,3, 3-tetra-methylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1, 1 3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, .undecyl, 1-methylundecyl, dodecyl, 1, 1,3,3,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl , octadecyl, icosyl or docosyl. The alkyl radicals can be uninterrupted or they can be interrupted by -0-, -S- or -N (R3) -. Alkyl C2-C25alkyl radicals, especially C3-C2alkyl, which are interrupted by -0- or -S- are, for example, CH3-0-CH2CH2-, CH3-S-CH2CH2-, CH3-0-CH2CH2-0 -CH2CH2-, CH3-0-CH2CH2-0-CH2CH2-, CH3- (0-CH2CH2-) 20-CH2CH2-, CH3- (0-CH2CH2-) 30-CH2CH2- or CH3- (0-CH2CH2-) 4O -CH2CH2-. Ci-C ^ alkyl, especially Ci ~, is preferred Csalkyl, alkyl radicals which may be uninterrupted or interrupted by -0-. Ri / R 2 R 5 R 6 R 7 Rs / R 9 Y Rio as alkenyl having 2 to 24 carbon atoms may be a branched or unbranched radical such as, for example, vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, n -2,4- pentadienyl, 3-methyl-2-butenyl,? -2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl,? -2-octadecenyl or n-4-octadecenyl. Preference is given to alkenyl having from 3 to 18, especially from 3 to 12, for example 3 to 6, especially 3 to 4 carbon atoms. Rif R 2, R 5, R 7, R 8 R 9 and Rio as C 7 -C 9 phenylalkyl are, for example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl or 2-phenylethyl. Preference is given to benzyl. R5 is preferably hydrogen, Ci-C4alkyl, or the particle surface, especially the particle surface, such as the surface of A1203 or the surface of SiO2. A highly preferred meaning for R5 is the surface of Si02. R6, R7, Rs, R9 and Rio are preferably Ci- C4alkyl, especially methyl. Preferably Ri and R2 are -OR5; RR RR RK R, R. R- - O-Si-O-R- - O-Si-O-Si-O-R- - O-Si-O-Si-O-Si-OR- 1 5 II 5 III 5 R7. R7 R7. "R7 R7 R7 especially a radical of the formula -OR5, wherein for R5 / R6 and R7 apply the meanings and preferences mentioned above. More preferably, Ri and R2 are a radical of the formula -0R5, wherein R5 is the particle surface, such as the surface of A1203 or the surface of Si02, especially the surface of Si02. n is preferably 1, 2, 3, 4, 5, 6, 7 or 8, preferably 2, 3 or 4, especially 3. B is, for example, the direct bond, -0-, -S-, -N (R3) -, -NH-S02-, -NH-CO-, -NH- CO-NH-CO- or Ci-C25alkylene, alkylene which may be attached and / or interrupted by at least one of the radicals selected from the group consisting of -0-, -S-, -N (R3) -, -N + (R3) 2-, -C0-, -0-C0-, -C0-0-, -N (R3) -C0-, -C0-N (R3) - and phenylene, wherein R3 is hydrogen or Ci- Ci2alkyl optionally substituted. The Ci-C2-alkylene radical can be unsubstituted or substituted, for example by the cationic groups mentioned above or by hydroxy, preferably by hydroxy. The phenylene radical mentioned above can be unsubstituted or substituted, for example by hydroxyl, halogen, carboxy, sulfonate, amino, acetylamino, mono- or di (Ci-Csalkyl) amino or the cationic groups mentioned above. R3 as the alkyl radical may be substituted by the cationic groups mentioned above, especially by a cationic ammonium group. Preferably, R3 is hydrogen or Ci-Ci2alkyl, especially hydrogen or Ci-C4alkyl. 'A highly preferred meaning for R3 is hydrogen. Preferably, B is the direct bond, -0-, -S-, -N (R3) - or a bridge member of the formula -Ai-Ci-C25alkylene-A2-, -Ai-Ci-C25alkylene-phenylene -A2- or -Ai ~ phenylene-Ci-C25alkylene-A2-, wherein the Ci-C2-alkylene can be uninterrupted or interrupted as given above and ?? and A2 are the direct link or radicals as it is given above. The preferred meanings for Ai and A2 are the direct bond, -0-, -S-, -N (R3) -, -C0-, -0- C0-, -C0-0-, -N (R3) -C0 -, -C0-N (R3) -, especially -N (R3) -, -0- or -S-, wherein R3 is as defined above. The 5 highly preferred meanings for ?? and A2 are the direct link or -N (R3) -, especially the direct link or -NH-. As for Ci-C25alkylene, it is preferred that it is uninterrupted or interrupted by at least one of the radicals selected from the group consisting of -0-, N (R3) -, -N + (R3) 2-, -C0-, - C0-0-, -C0-N (R3) - and phenylene, ] or especially -0-, -NH-, -C0-0-, -CO-NH- and phenylene, and more preferably -C0-0-, -CO-NH- and phenylene. Ci ~ C 25 alkylene and phenylene may be substituted as given above, or preferably unsubstituted. In general, for Ci-C25alkylene radicals, C2- * is preferred C25alkylene, especially C2-Ci6alkylene. More preferably, B is a direct bond, -0-, -S-, -N (R3) - or a bridging member of the formula - ?? - C1-C25alkylene-A2-, -A1-Ci-C25alkylene phenylene-A2- or -Ai ~ phenylene-Ci-C25alkylene-A2-, where Ai and A2 are the direct bond • -0-, -S-, -N (R3) -, -C0-, - 0-C0-, -C0-0-, -N (R3) -C0- or -C0-N (R3) -, the radical Ci-C25alkylene radical is uninterrupted interrupted by at least one of the radicals selected from the group consisting of of -0-, -S-, -N (R3) -, -N + (R3) 2-, -C0-, -0-C0-, -C0-0-, -N (R3) -C0-, - C0- N (R3) - and phenylene, and where R3 is as defined above.

The meanings important for B are the direct bond, -O-, -S-, -N (R3) - or a bridge member of the formula -Ai-Ci-C25alkylene-A2-, -A1-C1-C25al ^ uileno phenylene-A2- or -Ai-phenylene-Ci-C25alkylene-A2-, where ?? and A2 are the direct bond -N (R3) -, -O- or -S-, wherein R3 is as defined above, and the Ci-C25alkylene radical is uninterrupted or interrupted by at least one of the radicals selected from the group which consists of -O-, -S-, -NH-, -CO-, -O-CO-, -CO-O-, -NH-CO-, -CO-NH- and phenylene. The very important meanings for E are the direct bond, -O-, -S-, -NH- or a bridge member of the formula -NH-Ci-C25alkylene-A2-, -NH-Ci-C25alkylene-phenylene-A2 - or -NH-phenylene-Ci-C25alkylene-A2-, wherein A2 is the direct bond. -NH-, and the Ci-C25alkylene radical is uninterrupted or interrupted by at least one of the radicals selected from the group consisting of -CO-O-, -CO-NH- and phenylene. Ci-C2-alkylene and phenylene may be substituted as given above, or preferably be unsubstituted. D is preferably the radical of an acridine, anthraquinone, azomethine, monoazo, disazo, polyazo, benzodifuranone, coumarin, diketopyrrolopyrrole, dioxazine, diphenylmethane, formazan, indigoid, methine, polymethine, naphthalimide, naphthoquinone, nitroaryl, oxazine, perinone, perylene, phenazine , phthalocyanine, pirenoquinone, quinacridone, quinoneimine, quinophthalone, stilbene, styryl, thiazine, thioxanthene, triarylmethane, xanthene or metallic complex dye, and more preferably the radical of an anthraquinone, monoazo, azomethine, methine, polymethine, styryl, triarylmethane or metal complex dye. Highly preferred are radicals of an anthraquinone, monoazo, azomethine or complex metallic dye, especially those of a monoazo or azomethine dye. Preferred radicals D of a monoazo dye are the following: B N = N B2 (2), wherein B1 and B2, independently of each other, are optionally substituted phenyl, naphthyl or a heterocyclic group. As heterocyclic groups corresponding to aromatic groups, imidazole, triazole, thiazole, benzothiazole and pyridine type groups are preferred. It is especially preferred that B1 or B2 as a heterocyclic group is a radical of an aromatic unsubstituted or substituted heterocyclic group of the formula where Z2 and Z5 are -0-; -S-; or a radical NRn2, Zi, Z3, Z, Z6, Z7, Z8 and Z9 are each independently of each other N or a radical CRn3; Rioo, Rioi, Ri02, Rivers, RIO6Í Rio8 Rio9? Ruo and Rn3 are independently hydrogen; halogen; hydroxy; Ci-Ci2 substituted or unsubstituted alkyl; substituted or unsubstituted phenyl; nitrile; C2-C4alkanoylamino; carbamoyl; ureido; sulfonylamino; Ci-Ci2alkylthio; or a radical of the formula -N (R114) Rn5, -N (Rn4) (RnsyRn or -ORu4, R103, R104, R107, Rui and Rii2 are independently substituted or unsubstituted Ci-Ci2alkyl hydrogen, or a substituted or unsubstituted phenyl, and Rii4 / Rus and R116 are independently hydrogen, Ci-Ci2 substituted or unsubstituted alkyl, triazinyl or substituted or unsubstituted phenyl, The phenyl or thiazinyl radicals mentioned above under the formulas (3a) to (3j) and Bx and B2 in the meaning as phenyl or naphthyl can be substituted or unsubstituted for example by Ci-C8alkyl; Ci-Cghydroxyalkyl; Ci-C8alkoxy; Ci-C8hydroxyalkoxy; hydroxyl; halogen; or a radical of the formula -N (R114) Rn5, N (Rn4) (Rn5) ii6 or -OR114, wherein Rn4, Rn5 and Rn6 are as defined above The above-mentioned Ci-Ci2 radicals under formulas (3a) to (3j) may be unsubstituted or substituted, for example by Ci-C8alkoxy; C8hydroxyalkoxy, phenyl which may be unsubstituted or substituted mo is given above; hydroxyl; halogen; or a radical of the formula -N (R114) R115, -N (RI) (R115) Rn6 or -OR11, wherein R4, Rus and R116 are as defined above. R100, R101, R102, Rivers, Rio6? Rio 9 R 1 and R 11 3 are preferably independently from each other hydrogen; halogen; hydroxy; Ci-Ci2alkyl; phenyl; C2-C4alkanoylamino; or a radical of the formula -N (RU4) R115, -N (R114) (RU5) RU6 or - 0Rn4- Highly preferred are meanings such as hydrogen; halogen; hydroxy; Ci-Ci2alkyl; or a radical of the formula -N (R114) R115 / -N (Rm) (R115) Rue or -ORn, especially hydrogen. R103, R104, R107, Rui and R112 are preferably unsubstituted or substituted Ci-Ci2alkyl; or unsubstituted or substituted phenyl; especially Ci-Ci2alkyl or phenyl, and more preferably Ci-Ci2alkyl, especially . As for R114, Rus and RUE it is preferred that for these radicals apply the definitions and preferences given above for Ri Zi, Z3, Z4, Z6, Z7, Z8 and Z9 are preferably a radical CR113. As for R113, the meaning is preferred as hydrogen or Ci-Ci2alkyl, especially hydrogen. Z2 is preferably -S- or a radical NRu2, especially a radical NR 2. As for R112, the meaning is preferred as Ci-C ^ alkyl, especially Ci-C4alkyl. Z5 is preferably -S- or a radical n2, especially -S-. As to Rn2, the meaning as Ci-Ci2alkyl, especially Ci-C4alkyl, is preferred. B1 or B2 as a heterocyclic group is more preferably a radical of the formula (3a), (3c), (3e), (3g) or (3i), especially a radical of the formula (3a), (3c) or ( 3e). highly preferred are radicals of the formula (3a) or (3c), especially those of the formula (3a) Furthermore, it is preferred that at least one of B1 and B2 is a phenyl or naphthyl group, especially a phenyl group. Preferred radicals D of a disazo dye are the following: wherein B1 and B2 are as defined above under formula (2) and B3 is a phenylene or naphthylene, each of which may be substituted as given above under formula (2) for B1 and B2 in the meaning as phenyl or naphthyl. The preferred D radicals of an azametin dye are the following: B1 CH = N B2 (5) or B1 CH = N NH B2 (6), wherein B1 and B2 are as defined above under formula (2). It is preferred that B1 is a phenyl or naphthyl radical, especially a phenyl radical. The preferred D radicals of a styryl dye are the following: B1 CH = CH B2 (7), wherein B1 and B2 are as defined above under formula (2). It is preferred that B1 is a phenyl or naphthyl radical, especially a phenyl radical. Preferred D radicals of a triarylmethane dye those of the formula: wherein B4, B5 and B6 independently from each other, are phenyl, naphthyl or a heterocyclic group. With respect to B4, B5 and B6, the definitions and preferences given above apply under formula (2) for B1 and B. Preferably, B4, B5 and B6 are the corresponding phenyl radicals. It is highly preferred that the triarylmetene dyes of f. { formulas (8) contain at least one group, especially at least three groups, of the formula - (Rn4) Rii5 or -N (R114) (R115) R116, wherein Rn4, Rn5 and R116 are as defined above for the formula (2). The preferred D radicals of an anthraquinone dye are the following: (10a), · o wherein Rm, R120 and R123 are hydrogen; or a substituted or unsubstituted Ci-C ^ alkylp, Rim Rii9 R121 and R122 are hydrogen; Ci-Ci2alkyl substituted or unsubstituted; C2-C4alkanoylamino; halogen; carboxy; sulfonate; ureido; carbamoyl; cyano; nitro; hydroxyl or a radical of the formula -N (RU4) R115, -N (R1H) (Rn5) Rn6 or -0Rn4, wherein ii / Rus and Rii6 are as defined above; and R124 is hydrogen; Ci-Ci2 substituted or unsubstituted alkyl; or a substituted or unsubstituted phenyl.

The phenyl radicals mentioned above under the formulas (9), (10a) and (10b) can be unsubstituted or substituted, for example, by Ci-C8alkyl; Ci-C8hydroxyalkyl; Ci-C8alcoxi; Ci-C8hydroxyalkoxy; hydroxyl; halogen; sulfonate; carboxy; or a radical of the formula -N (Rn4) Rn5, -N (R114) (R115) R116 or -ORn4, wherein Ru4, R115 and R116 are as defined above. The Ci-Ci2alkyl radicals mentioned above under the formulas (9), (10a) and (10b) can be unsubstituted or substituted, for example by Ci-C8alkoxy; Ci-C8hydroxyalkoxy; phenyl which may be unsubstituted or substituted as given above; hydroxyl; halogen; or a radical of the formula -N (RU4) Rn5, -N (R114) (R s) R6 or -OR114, wherein Rm, R5 and Ri16 are as defined above. The preferred D radicals of a complex dye Metallic are those that comprise terpyridine ligands. The preferred metals are iron, especially Fe2 +. Preferred terpyridine ligands are those of the formula wherein R125 is hydrogen or Ci-Ci2alkyl; Ri26 R127 and R128 are each independently hydrogen; Ci-Ci2alkyl; Ci-Ci2alkoxy; hydroxy; unsubstituted phenyl substituted by Ci-C8alkyl, Cx-Csalkoxy, phenyl or by hydroxy; hydrazino; Not me; N-mono- or N, N-di-Ci-C4-unsubstituted alkylamino substituted by hydroxyl in the alkyl portion; or an unsubstituted pyrrolidine substituted with Ci-Csalkyl, piperidine, piperazine, morpholine or azepane ring. R125 is preferably Ci-Ci2alkyl, more preferably Ci-C4alkyl. Ri26, R127 and 128 are preferably hydrogen. According to a further embodiment of the present invention, the functionalized particles may further comprise the radical of the formula (1), covalently bound to an oxygen atom on the surface, a radical of the formula R 12 -Si-Rn R 13 (11) ), wherein R12 and Ri3 have the meanings given above under formula (1) for Rx and R2, Rn is Ci-C25alkyl or C2-C24alkenyl, each of which is unsubstituted or substituted by amino, mercapto, phenyl or hydroxyl and is uninterrupted or interrupted by -O-, -S-, -N (Ri4) -, -CO-, -O-CO-, -CO-O-, -N (Ri4) -CO-, -CO -N (R14) -o or phenylene; C5-Ci2cycloalkyl; C5-Ci2cycloalkenyl; or a polymerizable group or a polymer each of which may be linked by a bridge member, and R14 is hydrogen or Ci-Ci2 substituted or unsubstituted alkyl, especially hydrogen, Ci-Ci2alkyl or Ci-Ci2alkyl substituted with hydroxyl, and more preferably hydrogen or Ci-C4alkyl. The radical of formula (11) can be introduced, for example into the particles in order to make the particle compatible with a dispersion medium. With respect to Ri2 and R13, the definitions and preferences given hereinabove apply for Ri and R2. R 14 is preferably hydrogen or methyl, especially hydrogen. With respect to Rn in the meaning as Ci-C25alkyl and C2-C2 alkenyl, the definitions and preferences given above apply for Ri, R2, R5, R6, R7, R8, R9 and Rio- A preferred definition of Rn is C2-Ci2alkyl , especially C2-C8alkyl. Rn as Ci-C25alkyl substituted with hydroxy is a branched or unbranched radical preferably containing 1 to 3, in particular 1 or 2, hydroxyl groups, such as for example, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, -hydroxybutyl, 3-hydroxybutyl, 2- hydroxybutyl, 5-hydroxypentyl, 4-hydroxypentyl, 3-hydroxypentyl, 2-hydroxypentyl, 6-hydroxyhexyl, 5-hydroxyhexyl, 4-hydroxyhexyl, 3-hydroxyhexyl, 2-hydroxyhexyl, 7-hydroxyheptyl, 6-hydroxyheptyl, 5-hydroxyheptyl , 4-hydroxyheptyl, 3-hydroxyheptyl, 2-hydroxyheptyl, I) -hydroxyoctyl, 7-hydroxyoctyl, 6-hydroxyoctyl, 5-hydroxyoctyl, 4-hydroxyoctyl, 3-hydroxyoctyl, 2-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl , 11-hydroxyundecyl, 12-hydroxydecyl, 13-hydroxytridecyl, 14-hydroxytetradecyl, 15-hydroxypentadecyl, 16-hydroxyhexadecyl, 17-hydroxyheptadecyl, 18-hydroxyoctadecyl, 20-hydroxyethicosyl or 22-hydroxycholesyl. A preferred definition of Rn is C2 ~ Ci2alkyl substituted with hydroxyl, especially C4-Caalkyl substituted with hydroxyl. Rn as alkyl which is interrupted by -O-, -S-, -N (Ri4) -, -CO-, -O-CO- or -CO-O- is a corresponding C2-C25alkyl radical, for example, CH3- 0-CH2CH2-, CH3-NH-CH2CH2-, CH3-N (CH3) -CH2CH2-, CH3-S-CH2CH2-, CH3-O-CH2CH2-O-CH2CH2-, CH3-O-CH2CH2-O-CH2CH2- , CH3- (O-CH2CH2-) 2O-CH2CH2-, CH3- (0-CH2CH2-) 3O-CH2CH2-, CH3- (O-CH2CH2-) O-CH2CH2-, CH3- (0-CH2CH2-) 4O- CH2CH2-O (CO) -CH2CH2-, CH3CH2- (O-CH2CH2-) 4O-CH2CH2- 0 (CO) -CH2CH2- or CH3- (CH2) nO (CO) -CH2CH2-. Rn as alkyl which is substituted by hydroxyl and interrupted by -O-, -S-, -N (Ri4) -, -CO-, -O-CO- or -CO-O- is a corresponding C2-C2alkyl radical, by Example, -CH2-CH (OH) -CH2-0-CH3, -CH2-CH (OH) -CH2-0-CH2CH3, CH2-CH (OH) -CH2-0-CH (CH3) 2 or -CH2CH2- CO-0-CH2CH2-0-CO- (CH2) 5-0-C0- (CH2) 5-OH. Rii as alkyl which is substituted by amino-, mercapto- or hydroxyl and is interrupted by -O-, -S-, -N (Rn) -, -CO-, -0-CO- or -CO-O- is a corresponding C2-C25alkyl radical, for example, HO-CH2CH2-0-CH2CH2-, H2NCH2CH2-NH-CH2CH2-, HOCH2CH2-NH (CH3) -CH2CH2-, HOCH2CH2-S-CH2CH2-, H2NCH2CH2-0-CH2CH2-0-CH2CH2-, HOCH2CH2-0-CH2CH2-0-CH2CH2-, HSCH2CH2- (0-CH2CH2-) 20-CH2CH2-, H2NCH2CH2- (0-CH2CH2-) 30-CH2CH2-, H2NCH2CH2- (0-CH2CH2-) 40-CH2CH2-, HSCH2CH2- (0-CH2CH2-) 40-CH2CH2 -0 (CO) -CH2CH2- or HOCH2CH2CH2CH2- (0-CH2CH2-) 40-CH2CH2-0 (CO) -CH2CH2-. R n as C 5 -Ci 2 cycloalkyl is, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl or cyclododecyl. Preference is given to cyclohexyl. Rn as C5-Ci2cycloalkenyl is, for example, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl, cyclodedecenyl or cyclododecenyl. Preference is given to cyclohexenyl. Rn as a polymerizable group is, for example, or Rii as a polymer is the polymerization product when a polymerizable group is polymerized, as for example summarized above. In addition, for Rn as a polymer, polyorganosiloxanes, polydimethylsiloxane type, are considered. Polydimethylsiloxanes of the formula are preferred wherein n is a number from 1 to 100, especially from 10 to 80, and more preferably from 40 to 70. The polymer Rn can be linked via a linking group. With respect to this linking group, it applies the definitions and preferences given above for B. Rn is preferably Ci-C25alkyl which is unsubstituted or substituted by hydroxyl, and is uninterrupted or interrupted by -O-, -S-, -N (Ri4), -CO-, -O-CO-, -CO-O-, -N (Ri4) -CO- or -CO-N (Ri4) -, especially by -N (Ri4) -, -CO- , -O-CO-, -CO-O-, -N (Ri) -CO- or -CO-N (Ri4) -, or Rn is a polyethylene glycol, polypropylene glycol or polyacrylate group that is linked by Ci-C2alkylene, which in turn it can be joined and / or interrupted by at least one of the radicals selected from the group consisting of -O-, -S-, -N (Ri4), -CO-, -O-CO-, - CO-O-, N (Ri4) -CO- or -CO-N (Ri4) -, especially by -NH-, -C'O-, -0-C0-, -CO-0-, -NH-CO- or -CO- NH-. Most preferably R is Ci-Ci2alkyl; Ci ~ Ci2alkyl which is substituted by hydroxy; Ci-Ci2alkyl which is substituted by a polymerizable group, such as those given above; C2-C25alkyl 'which is interrupted by -NH-, -C0-, -0-C0-, -CO-0-, -NH-CO- or -C0-NH- and which is optionally substituted by hydroxy; or a polyethylene glycol, polypropylene glycol and polyacrylate group which is linked by Ci-C25alkylene, which in turn may be attached and / or interrupted by at least one of the radicals selected from the group consisting of -NH-, -C0-, -0-C0-, -CO-0-, -NH-CO- or -CO-NH-. It is preferred that the polymer be linked to the alkylene radical by -0-C0- or -CO-0-. With respect to alkylene, it is preferred that it be directly attached to the Si atom indicated in formula (11). In addition, it is preferred that the alkylene be interrupted by at least one of -0-, -S-, -NH-, -C0-, -0-C0-, -CO-0-, -NH-CO- or -CO -NH-, especially by -NH-, -C0-, -0-C0-, -C0-0-, -NH-CO- or -CO-NH-, and more preferably by -NH-, -0 -C0-, -CO-0-, -NH-CO- or -C0-NH-. According to a further embodiment of the present invention, the functionalized particles may further comprise the radical of the formula (1) or in addition to the radicals of the formulas (1) and (11), covalently attached to an oxygen atom in the surface, a radical of the formula ^ 16 | Si-R 15 ¾17 12), wherein Ri6 and R17 have the meanings given above under formula (1) for Ri and R2, Ri5 is Ci-C25alkyl or C2-C24alkenyl, each of which is unsubstituted or substituted by amino, mercapto, phenyl or hydroxyl and is uninterrupted or interrupted by -O-, - S-, -N (Ri8) -, -N + (R18) 2-, -CO-, -O-CO-, -CO-O-, -N (R18) -CO -, - 10 CO-N (Rig) - or phenylene; C5-Ci2cycloalkyl; C5- Ci2cycloalkenyl; or a polymerizable group or a polymer each of which can be attached by a bridge member, R <8> is hydrogen or Ci-Ci <2> substituted or unsubstituted alkyl, and, wherein R <15> or R <5> additionally comprise a cationic group, especially an ammonium group cationic, such as a group of the formula -N (Rm) (Rii5) Rii6 wherein R1H, 2Q Rii5 and Rii6 are as defined above. The radical of the formula (12) can be introduced into the particles in order to provide the particles with the desired charge. In cases where there are already radicals that provide the charge, such as radical D, the radical of formula (12) can be introduced in order to adjust. the 2 ^ load to a desired level.

With respect to Ri6 and R17, the definitions and preferences given herein above apply for Ri and R2. Lanes as alkyl radical can be substituted by the cationic groups mentioned above, especially by a cationic ammonium group, such as the group of the formula -N (Rn4) (R115) Rii6- Preferably, R18 is hydrogen or Ci-Ci2alkyl, especially hydrogen or Ci-C4alkyl. A highly preferred meaning for Ri8 is hydrogen. As for Ri5, the definitions and preferences given hereinabove apply for R. It is to be understood that R15 can be substituted by the cationic groups mentioned above under formula (12). It is preferred that R15 further comprises a cationic ammonium group, such as the group of the formula -N (Rn4) (R115) Rii6- The functionalized particles according to the present invention preferably have a spherical shape. Preferably, the particles have an average particle size of 1 to 1000 nm, especially 1 to 600 nm, more preferably 1 to 400. An average particle size of 1 to 300 nm, especially 1, is preferred. at 200 nm. Very important are the particles having an average particle size of from 1 to 100. As a lower limit of the average particle size, 10 nm, especially 20 nm, is preferred. He Particle size can be determined, for example, by electron microscopy. The organic content of the particles according to the present invention is, for example, from 5 to 90 percent by weight, especially from 20 to 90 percent by weight, and more preferably from 40 to 90 percent by weight, based on the total weight of the | particle '. The particles are typically silicon dioxide, aluminum oxide, a homogeneous mixture thereof or silicon oxide and aluminum as mixed oxides. The particles of silicon and aluminum oxide according to the present invention can show silicon contents between 1 and 99% of metal atoms. It is preferred that the functionalized particle is a silica particle (SiO2) or alumina (AI2O3) especially a silica particle. Unmodified particles, especially these nanoparticles, are commercially available from different suppliers such as Degussa, Hanse Chemie, Nissan Chemicals, Clariant, H.C. Starck, Nanoproducts or Nyacol Nano Technologies as powder or as dispersions. Examples of commercially available silica nanoparticles are Aerosil® from Degussa, Ludox® from DuPont, Snowtex® from Nissan Chemical, Levasil® from Bayer, or Sylysia® from Fuji Silysia Chemical. Examples of commercially available AI2O3 nanoparticles are Nyacol® products from Nyacol Nano Technologies Inc., or Disperal® products from Sasol. The expert is aware of the different well-established processes for accessing particles in different sizes, with different physical properties and with different compositions such as hydrolysis to the flame (Aerosil Process), flame process, arc process and reactor processes hot wall for reactions in gas phase or solid phase or ion exchange process and precipitation process for solution based reactions. preference is given to several references describing the detailed processes, such as EP-A-1, 236, 765, US-B-5, 851, 507, US-B-6, 719, 821, US-A-2004- 178530 or US-B-2,244,325, WO-A-05/026068, EP-A-1, 0 8, 617. The preparation of the functionalized particles comprising on the surface at least one radical of the formula (1) is carried preferably carried out by the reaction of corresponding particles (such as non-functionalized particles of silica or alumina) with a compound of the formula (Ia) where \ I N-R '4 X is oxygen type group, sulfur or / Ro is Ci-C25alkyl, R 'i is hydrogen, R'2 and R'3 independently whether they are hydrogen, Ci-C2salkyl, C3-C25alkyl which is interrupted by oxygen or sulfur or -N (R3) -; C2-C24alkenyl, phenyl, C7-Cgphenylalkyl or -0R'5, R '4 is hydrogen, Ci-C25alkyl or C3-C25alkyl which is interrupted by oxygen or sulfur or -N (R3) -; R '5 is hydrogen or Ci-C25alkyl, and n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12. The reaction of the compound of the formula (Ia) with the particles is It can be carried out in analogy to known processes. The reaction can be carried out, for example, in an organic medium, preferably a mixture of water with an organic medium. As an organic medium, solvents such as alcohols, especially methanol, can be used. It is preferred to carry out the reaction at temperatures such as 20 to 90 ° C, especially 40 to 60 ° C. With respect to the compounds of the formula (la), it is preferred to use those, wherein at least one of Ro, R '2 and R' 3 is methoxy or ethoxy, especially where R0, R '2 and R' 3 are methoxy or ethoxy. It is highly preferred that R0, R '2 and R3 are methoxy. If desired, the obtained products can be re-dispersed in a suitable medium, such as water, ethanol, toluene or xylol. In a further step, the reaction product of the particles with the compound of the formula (la) can be easily derivatized to obtain particles comprising radicals of the formula (1) by processes known as for example esterification, amidation, Michael addition or epoxide opening. In the following, some examples of these reactions are given in general terms: a) Particles, which show active linking groups such as -SH or -N¾ can be easily modified at the surface with educts. having, for example, ester, epoxy, carboxy, carbonyl, acrylic, methacrylic, alkyl halide, alkylsulfate, anhydride, terminal double bond, nitrile and for example α, β-unsaturated carbonyl groups. The chemistry of these substances and molecular organic synthesis (such as nucleophilic substitutions, nucleophilic additions, Michel additions, ring opening reactions, addition of radicals, etc.), are well known and can be easily adapted to organic chemistry in solid phase. b) Particles, which show functional groups on their surfaces, such as ester, epoxy, carboxy, carbonyl, acrylic, methacrylic, alkylhalogenide, alkyl sulfate, anhydride, terminal double bond, nitrile and for example α, β-unsaturated carbonyl groups can be made easily react additionally with educts having -SH, -RNH (R = organic group) 'or group -NH2 with, the chemical reactions mentioned above under a). c) In educts, such as dyes, they can be introduced to a functional group by the use of a dye containing fluoride as the starting compound and introduction of the functional group in analogy to the process as described in WO-A-04/076564 (see especially page 5 to 8 therein). d) Educts that show groups -OH, -RNH (R = organic group) or NH2 can be activated by using acryloyl chloride under basic conditions to generate educt-acrylate (acylation), which can be easily reacted with particles that have -SH or -NH2 groups by using an addition of Michel. Other syntheses which are conducive to functional groups mentioned in a) and b) are well known. e) Educts can be functionalized by using reactive alkoxysilanes that show functional groups and mechanisms as mentioned in a), b), or d) and then grafted to the surface of the particle using a silanization reaction of the state of the art. According to an alternative process for. the preparation of custom particles comprising radicals of the formula (1) corresponding to non-functionalized particles, such as commercially available silica or A1203 particles, can be reacted with a compound of the formula (Ib) Where R0, '2 and R' 3 are as described above under the formula (la) and n, B and D are as previously defined under formula (1). By this route, the particles comprising a radical of the formula (1) can be obtained directly, without additional derivatization. The reaction conditions can be chosen as given above for the reaction of the particles not functionalized with the compound of the formula (Ia), the reaction can be carried out, for example, in analogy to the preparation process described in WO- A-03/002652. The radicals of formulas (11) and (12) can be introduced in analogy to the above preparation processes. These reactions can be carried out simultaneously with the introduction of the radical of the formula (1), or in steps. As for the preparation methods summarized above, it is to be noted that non-functionalized particles (such as silica or alumina particles) comprise free hydroxyl groups on the surface. These groups are reacted in order to obtain functionalized particles used according to the present invention, which can also be described by the following formula: Particle Particle where Z is a radical of the formula (1) and the line vertical corresponds to the surface of the particle. In addition, the radicals of formulas (11) and 70 (12) can be attached to a hydroxyl group in the same manner as given above for Z. A further object of the present invention are novel functionalized particles comprising, covalently bound to an oxygen atom on the surface, a radical of the formula wherein the particles are based on Si02, A1203 or mixtures thereof, the functionalized particles have a positive charge, Ri and R2 are independently of each other, hydrogen, particle surface (0), or a substituent, B is the direct link or a bridge member, N is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, and D is a radical of the formula |, 2 B -N:: N- (2) , -N: (4), B1 CH = N B2 (5), B1 CH = N NH B2 (6) or B1 CH = CH B2 (7), wherein B3 is unsubstituted or substituted phenylene or naphthylene, and B1 and B2, independently of each other, are optionally substituted phenyl, naphthyl or a heterocyclic group of the formula (3j), where Z2 and Z5 are -0-; -S-; or a radical NR 2, Zi, Z3, Z4, Z6, Z7, Z8 and Z9 are independently of each other N or a radical CR113; R100, R101, R102, R105, RIO6Í Rivers Rio9r R110 and R113 are independently hydrogen; hydroxy halogen; Ci-Ci2alkyl unsubstituted or substituted; unsubstituted or substituted phenyl; nitrile; C2-C, alkanoylamino; carbamoyl; ureido; sulfonylamino; Ci-Cxaalkylthio; or a radical of the formula -N (U4) Rn5, -N (Rn) (R115) Riie or -ORu; R103, R104, Ri07, Rui and R112 are independently hydrogen; Ci-Ci2alkyl unsubstituted or substituted; or unsubstituted or substituted phenyl; and Rii f R115 and Rii6 are independently hydrogen; Ci-Ci2alkyl unsubstituted or substituted; triazinyl or unsubstituted or substituted phenyl. With respect to the new functionalized particles comprising a covalently linked radical of the formula (1 '), the definitions and preferences given above apply. It is preferred that in each of the radicals given for D at least one of the radicals B1 and B2 be a heterocyclic group selected from the formulas (3a) to (3j). Additionally, it is preferred that the other of the radicals B1 and B2 be unsubstituted or substituted phenyl. The functionalized particles according to the invention are suitable for dyeing fibers containing keratin, preferably human hair. The dyeings obtained are distinguished by their depth of shade and their good properties of firmness to washing, such as, for example, firmness to light, washing with shampooing and scrubbing. The stability is excellent, in particular the storage stability of the functionalized particles according to the invention. In general, hair dyeing agents in a synthetic base can be classified into three groups: temporary dyeing agents, semi-permanent dyeing agents, and permanent dyeing agents.

The multiplicity of shades of the functionalized particles of the invention can be increased by combination with other dyes. Therefore, the functionalized particles of the present invention can be combined with dyes of the same or different kind of dyes, especially with direct dyes, oxidation dyes; combinations of dye precursors of a coupling compound as well as a diazotized compound, or a marked diazotized compound; and / or cationic reactive dyes. The direct dyes are of natural origin or can be prepared synthetically. These are uncharged, cationic or anionic, such as acid dyes. The functionalized particles of the invention can be used in combination with at least one individual direct dye different from the functionalized particles of the invention. Direct dyes do not require any addition of an oxidizing agent to develop their dyeing effect. Accordingly, the dyeing results are less permanent than those obtained with permanent dyeing compositions. Therefore, direct dyes are preferably used for semi-permanent dyeing of hair. Examples of direct dyes are described in "Dermatology", edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, .Ch.

Zviak, The Science of Hair Care, chapter 7, p. 248-250., And in "Europáisches Inventar der Kosmetikrohstoffe", 1996, published by The Europeán Commission, obtainable in the form of disc of the Bundesverband der deutschen Industri- und Handelsunternehmen für Arzneimittel, Reformwaren und Kórperpflegemittel e.V., Mannheim. The most preferred direct dyes which are useful for combination with at least one functionalized particle of the invention, especially for semi-permanent dyeing, are: 2-amino-3-nitrophenol, 2-amino-4-hydroxyethylamino-anisole sulfate, 2 -amino-6-chloro-4-nitrophenol, 2-chloro-5-nitro-N-hydroxyethylene-p-phenylenediamine, 2-hydroxyethyl-picramic acid, 2,6-diamino-3- ((pyridin-3-yl) azo) pyridine, 2-nitro-5-glyceryl-methylaniline, 3-methylamino-4-nitro-phenoxyethanol, 4-amino-2-nitrodiphenylene-2'-carboxylic acid, 6-nitro-1, 2, 3, , -tetrahydroquinoxaline, 4-N-ethyl-1,4-bis (2'-hydroxyethylamino-2-nitrobenzene, l-methyl-3-nitro-4- (2'-hydroxyethyl) -aminobenzene hydrochloride, 3-nitro- p-hydroxyethyl-aminophenol, 4-amino-3-nitrophenol, 4-hydroxypropylamino-3-nitrophenol, hydroxyanthylaminopropylmethyl-morpholino-methosulfate, 4-nitrophenyl-aminoethylurea, 6-nitro-p-toluidine, Blue Acid 62, Blue Acid 9, Red Acid 35, Red Acid 87 (Eosin), Violet Acid 43, Yellow Acid 1, Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 12, Basic Blue 26, Basic Blue 99, Basic Coffee 16, Basic Coffee 17, Basic Red 2, Basic Red 22, Basic Red 76, Basic Violet 14, Basic Yellow 57, Basic Yellow 9, Scattered Blue 3, Scattered Orange 3, Dispersed Red 17, Scattered Violet 1, Scattered Violet 4, Scattered Black 9 , Fast Green FCF, Blue HC 2, Blue HC 7, Blue HC 8, Blue HC 12, Orange HC 1, Orange HC 2, Red HC 1, Red HC 10-11, Red HC 13, Red HC 16, Red HC 3 , Red HC BN, Red HC 7, Violet HC 1, Violet HC 2, Yellow HC 2, Yellow HC 5, Yellow HC 5, Yellow HC 6, Yellow HC 7, Yellow HC 9, Yellow HC 12, Red HC 8, Hydroxyethyl -2-nitro-p-toluidine,?,? - Bis- (2-Hydroxyethyl) -2-nitro-p-phenylenediamine, Violet HC BS, Picramic Acid, Green Solvent 7. In addition, the functionalized particles of the invention with at least one cationic azo dye, for example, the compounds described in GB-A-2,319,776 as well as the oxazine dyes described in DE-A-299,12,327 and mixtures thereof with the other direct dyes mentioned in US Pat. and even more preferred with cationic dyes such as Basic Yellow 87, Basic Orange 31 or Basic Red 51, or with cationic dyes as described in O 01/66646, especially example 4, or with cationic dyes as described in WO 02. / 31056, especially example 6 (compound of formula 106); or the cationic dye of the formula (3) as described in EP-A-714,954, or with a yellow cationic dye of the formula (DD1), wherein Ri and R2 are each independently of one another Ci-Cealkyl; or an unsubstituted or substituted benzyl; R3 is hydrogen; Ci-Csalquilo; Ci-C8alcoxi; cyanide; or halide; preferably hydrogen; and X "is an anion, and preferably a compound of the formula (DD1), wherein Ri is methyl, R2 is benzyl, R3 is hydrogen, and X ~ is an anion, or where Ri is benzyl, R2 is benzyl, R3 is hydrogen, and X "is an anion; or where Ri is benzyl; R2 is methyl; R3 is hydrogen; and X "is an anion.In addition, the cationic nitroaniline and anthraquinone dyes are useful for a combination with a functionalized particle of the invention, for example, the dyes as described in the following patent specifications: US-5, 298 , 029, especially in column 2, line 33 to column 5, line 38, US-5,360,930, especially in column 2, line 38 to column 5, line 49, US-5, 169, 403, especially in column 2, line 30 to column 5, row 38, US-5, 256, 823, especially in column 4, row 23 to column 5, row 15, US-5, 135, 543, especially in column 4, row 24 a column 5, row 16; EP-A-818, 193, especially on p. 2, line 40 to p. 3, row 26; US-5 486,629, especially in column 2, row 34 to column 5, row 29; and EP-A-758, 547, especially on p. 7, line 48 to p. 8, line 19. The functionalized particles of the invention can also be combined with acidic dyes, for example, agents that are known from international names (color index), or trademarks. Preferred acid dyes which are useful for the combination of the functionalized particles of the invention are described in U.S. Patent No. 6,248,314. Include Color Red No. 120, Color Yellow No. 4, Color Yellow No. 5, Color Red No. 201, Color Red No. 227, Color Orange No. 205, Color Coffee No. 201, Color Red No. 502, Color Red No. 503, Color Red No. 504, Color Red No. 506, Color Orange No. 402, Color Yellow No. 402, Color Yellow No. 406, Color Yellow No. 407, Color Red No. 213, Color Red No 214, Color Red No. 3, Color Red No. 104, Color Red No. 105 (1), Color Red No. 106, Color Green No. 2, Color Green No. 3, Color Orange No. 207, Color Yellow No. 202 (1), Color Yellow No. 202 (2), Color Blue No. 202, Color Blue No. 203, Color Blue No. 205, Color Blue No. 2, Color Yellow No. 203, Color Blue No. 201, Color Green No. 201, Color Blue No. 1, Color Red No. 230 (1), Color Red No. 231, Color Red No. 232, Color Green No. 204, Color Green No. 205, Color Red No 401, Color Yellow No. 403 (1), Color Green No. 401, Color Green No. 402, Color Black No. 401 and Color Purple No. 401, especially Color Black No. 401, Color Purple 401, Color Orange No. 205. These Acid dyes can be used either as an individual component or in any combination thereof. Hair dye compositions comprising an acid dye are known. For example they are described in "Dermatology", edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, chapter 7, p. 248-250, especially on p. 253 and 254. Hair dye compositions comprising an acid dye have a pH of 2-6, preferably 2-5, more preferably 2.5-4.0. The functionalized particles of the invention can also be easily used in combination with acidic dyes and / or adjuvants, for example. acid dyes and an alkylene carbonate, as described in US Pat. No. 6,248,314, especially in Examples 1 and 2; acid hair dye compositions comprising various classes of organic solvents represented by benzyl alcohol as a penetrating solvent having good penetrability in the hair, as described in Japanese Patent Applications Revealed Numbers Nos. 210023/1986 and 101841/1995; acid hair dye compositions with a water soluble polymer or the like to prevent dropping or dripping of the hair dye composition, as described for example in Japanese Patent Laid-Open Applications Nos. 87450/1998, 255540/1997 and 245348/1996; acid hair dye compositions with a water soluble polymer of aromatic alcohols, lower alkylene carbonates, or the like as described in Japanese Patent Application No. 53970/1998 and Japanese Invention Patent No. 23911 / 1973. The functionalized particles of the invention can also be combined with uncharged dyes, for example, selected from the group of nitroanilines, nitrophenylenediamines, nitroaminophenols, anthraquinones, indophenols, phenazines, phenothiazines, bispyrazones, or bispyrazole-aza derivatives and methines. Additionally, the functionalized particles of the invention can also be used in combination with oxidation dye systems. The oxidation dyes, which, in the initial state, are not dyes but the dye precursors are classified according to their chemical properties in the developer and coupler compounds. Suitable oxidation dyes are described for example in DE 19 959 479, especially in column 2, row 6 to column 3, row 11; "Dermatology", edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, chapter 8, on p. 264-267 (oxidation dyes); Preferred developer compounds are, for example, primary aromatic amines, which are substituted in the para-or-ortho position with a substituted or unsubstituted hydroxy or amino residue, or diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives, 2, 4 derivatives. , 5,6-tetraaminopyrimidine or unsaturated aldehydes as described in DE 19,717,224, especially in p. 2, line 50 to l. 66 and on p. 3 row 8 to row 12, or cationic developer compounds as described in WO 00/43367, especially in p., 2 row 27 to p. 8, line 24, in particular on p. 9, line 22 to p. 11, line 6. Additionally, developer compounds can be used in the form of addition of compatible and physiological acid such as hydrochloride or sulfate. The developer compounds, which have aromatic OH radicals are also suitable in their salt form together with a base, such as alkali metal phenolates. Preferred developer compounds are described in DE 19959479, p. 2, line 8-29.

The most preferred developer compounds are p-phenylenediamine, p-toluylenediamine, p-, m- or-aminophenol,?,? -bis- (2-hydroxyethyl) -p-phenylenediamine sulfate, 2-amino-4-hydroxyethylaminoanisole sulfate, hydroxyethyl-3,4-methylenedioxyaniline, 1- (2'-Hydroxyethyl) -2,5-diaminobenzene, 2,6-dimethoxy-3,5-diamino-pyridine, hydroxypropylbis- (N-hydroxyethyl-p-phenylenediamine) hydroxyethyl hydroxyethyl-p-phenylenediamine -sulfate, 4-amino-3-methylphenol, 4-methylaminophenol sulfate, 2-aminomethyl-4-aminophenol, 4,5-diamino-1- (2-hydroxyethyl) -1H-pyrazole, 4-amino-m-cresol , 6-amino-m-cresol, 5-amino-6-chloro-cresol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine or 4-hydroxy-2, 5,6 -triaminopyrimidine-sulfate. Preferred coupling compounds are derivatives of m-phenylenediamine, naphthol, resorcin and resorcinol derivatives, pyrazolone and m-aminophenol derivatives, and more preferably coupling compounds described in DE 19959479, p.l, row 33 to p. 3, line 11. The functionalized particles of the invention can also be used together with unsaturated aldehydes as described in DE 19,717,224 (p.2, row 50 to row 66 and in p.3, row 8 to row 12) which can be used. use as direct dyes, or alternatively together with oxidation dye precursors. Additionally preferred for a combination with the functionalized particles of the invention are the following oxidation dye precursors: the developer / coupler combination, 2,4,5,6-tetraaminopyrimidine and 2-methylresorcin for evaluation of red hues; - p-toluenediamine and 4-amino-2-hydroxytoluene for evaluation of blue-violet shades; p-toluenediamine and 2-amino-4-hydroxyethylaminoanisole for evaluation of blue shades; - p-toluenediamine and 2,4-diamino-phenoxyethanol for evaluation of blue shades; methyl-4-aminophenol and 4-amino-2-hydroxytoluene for evaluation of orange shades; - p-toluenediamine and resorcin for evaluation of coffee-green shades; - p-toluenediamine and 1-naphthol for evaluation of blue-violet shades, or p-toluenediamine and 2-methylresorcin for evaluation of brown-golden shades. Additionally, autooxidable compounds can be used in combination with the functionalized particles of the invention. Self-oxidizable compounds are aromatic compounds with more than two substituents on the aromatic ring, which may have a very low reduction-oxidation potential and will therefore oxidize when exposed to air. The dyeings obtained with these compounds are very stable and resistant to washing with shampoo. The autoxidizable compounds are for example benzene, indole or indolite, especially derivatives of 5,6-dihydroxyindole or 5,6-dihydroxyindoline as described in WO 99/20234, especially in p. 26, line 10 to p. 28, row 15, or in WO 00/28957 on p. 2, third paragraph. The preferred autogenous benzene derivatives are 1,2,4-tr'ihydroxybenzene, l-methyl-2,4,5-trihydroxybenzene, 2, -diamino-6-methylphenol, 2-amino-4-methylaminophenol, 2, 5 diamino-4-methyl-phenol, 2,6-diamino-4-diethylaminophenol, 2,6-diamino-1,4-dihydroxybenzene, and salts of these compounds, which are accessible with acid. Preferred auto-oxidized indole derivatives are 5,6-dihydroxyindole, 2-methyl-5,6-dihydroxyindole, 3-methyl-5,6-dihydroxyindole, 1-methyl-5,6-dihydroxyindole, 2,3-dimethyl-5 , 6-dihydroxyindole, 5-methoxy-6-dihydroxyindole, 5-acetoxy-6-hydroxyindole, 5,6-diacetoxyindole, 5,6-dihydroxyindole-2-carbon acid, and salts of these compounds, which are accessible with acid. The functionalized particles of the invention can also be used in combination with dyes that occur naturally, such as red henna, neutral henna, black henna, chamomile flower, sandalwood, black tea, Rhamnus frángula bark, sage, Campeche wood. , blonde root,. catecú, sedre, and alkanet root. These dyes are described, for example, in EP-A-404, 868, especially on p. 3, line 55 to p. 4, line 9. Additionally, the functionalized particles of the invention can also be used in combination with capped diazotized compounds. Suitable diazotized compounds are for example the compounds of the formula (I) - (4) in WO 2004/019897 (linking pages 1 and 2) and the corresponding water-soluble coupling components (I) - (IV) as it is described in the same reference. In addition, preferred dyes or dye combinations that are useful for combination with the functionalized particles of the invention are described in (DC-01): WO 95/01772, wherein mixtures of at least two cationic dyes, especially p. 2, line 7 to p. 4, line 1, preferably p. 4, line 35 to p. 8, row 21; formulations p. 11, last paragraph - p. 28, row 19; (DC-02): US Pat. No. 6,843,256, wherein cationic dyes are described, especially the compounds of formulas (1), (2), (3) and (4) (col.1, line 27 - col.3, line) 20, and preferably the compounds as prepared in examples 1 to 4 (col.10, r.42 to col. 13, row 37; formulations col. 13, row 38 to col. 15, row 8; (DC-03 ): EP 970,685, where direct dyes are described, especially page 2, line 44 to page 9, line 56 and preferably page 9, line 58 to page 48, line 12; processes for dyeing fibers containing keratin especially p. 50, line 15 to 43; formulations p. 50, line 46 to p. 51, line 40; (DC-04): DE-A-19, 713, 698, where direct dyes are described, especially in p. 2, line 61 to p. 3, row 43; formulations p. 5, line 26 to 60; (DC-05): US 6,368,360, where direct dyes are described (col 4, row 1 to col 6, row 31) and oxidizing agents (col 6, row 37-39); col. formulations 7, line 47 to col. 9, row 4; (DC-06): EP 1,166,752, wherein cationic dyes are described (p.3, row 22 - p.4, row 15) and anionic UV absorbers (p.4, row 27-30); formulations p. 7, row 50 - p. 9, row 56; (DC-07): EP 998,908, wherein oxidation dyes comprising a cationic direct dye and pyrazolo- [1,5-a] -pyrimidines (p.2, row 48-p.4, row 1) are described; dyeing formulations p. 47, line 25 to p. 50, row 29; (DC-08): FR-2788432, wherein combinations of cationic dyes with Arianres are described, especially p. 53, line 1 to p. 63, line 23, more especially p. 51 to 52, more especially, Basic Coffee 17, Basic Coffee 16, Basic Red 76 and Basic Red 118, and / or at least one Basic Yellow 57, and / or at least one Basic Blue 99; or combinations of arianoren and / or oxidative dyes, especially p. 2, row 16 a p. 3, row .16; dyeing formulations on p. 53, line 1 to p. 63, row 23; (DC-09): DE-A-19, 713, 698, wherein the combinations of direct dyes and fixed permanent waving are described comprising an oxidation agent, an oxidation dye and a direct dye; especially p. 4, line 65 to p. 5, row 59; (DC-10): EP 850,638, wherein developer compounds and oxidizing agents are disclosed; especially p. 2, line 27 to p. 7, row 46 and preferably p. 7, line 20 to p. 9, row 26; dyeing formulations on p. 2, line 3-12 and line 30 to p. 14, and p. 28, line 35 - p. 30, row 20; preferably p. 30, line 25 -p. 32, row 30; (DC-11): US 6,190,421 wherein extemporaneous mixtures of a composition (A) containing one or more dye precursors of. oxidation and optionally one or more couplers, of a composition (B), in powder form, containing one or more direct dyes (col .5, row 40-col 7, row 14), optionally dispersed in a pulpy excipient organic and / or a mineral powdery excipient, and a composition (C) containing one or more oxidizing agents; col. formulations 8, row 60 -col. 9, row 56; (DC-12): US Pat. No. 6,228,129, where a ready-to-use composition comprising at least one oxidation base, at least one direct cationic dye and minus one enzyme of the two-electron oxidoreductase type in the presence of at least one donor for the same enzyme; especially col. 8, row 17 - col. 13, row 65; dyeing formulations in col. 2, line 16 to col. 25, row 55, a multi-compartment dyeing device is described in col. 26, row 13-24; (DC-13): WO 99/20235, wherein compositions of at least one cationic dye and at least one dye of benzene nitrated with direct cationic dyes and direct nitrobenzene dyes are described; in P. 2, line 1 to p. 7, line 9, and p. 39, line 1 to p. 40, line 11, preferably p. 8, line 12 to p. 25, row 6, p. 26, line 7 to p. 30, row 15; p. 1, line 25 to p. 8, row 5, p. 30, line 17 to p. 34, row 25, p. 8, line 12 to p. 25, row 6, p. 35, line 21 to 27, especially on p. 36, line 1 to p. 37; (DC-14): WO 99/20234, wherein compositions comprising at least one direct cationic dye and at least one autoxid dye are described, especially benzene, indole and indolite derivatives, preferably direct dyes on p. 2, line 19 to p. 26, row 4, and autooxidizable dyes as described especially in p. 26, line 10 to p. 28, row 15; dyeing formulations especially in p. 34, line 5 to p. 35, row 18; (DC-15): EP 850,636, wherein oxidation dyeing compositions comprising at least one direct dye and at least one metallurgical derivative are described. aminophenol as a coupler component and at least one developer compound and an oxidizing agent, especially p. 5, line 41 to p. 7, row 52, dyeing formulations on p. 19, row 50 - p. 22, row 12; (DC-16): EP-A-850 637, wherein oxidation dyeing compositions comprising at least one oxidation base selected from para-phenylenediamines and bis (phenyl) alkylenediamines, and the acid addition salts of the same, at least one coupler selected from meta-diphenols, and the acid addition salts thereof, at least one direct cationic dye, and at least one oxidizing agent, especially p. 6, line 50 to p. 8, line 44 are described; dyeing formulations p. 21, row 30 - p. 22, row 57; (DC-17): WO 99/48856, wherein oxidation dyeing compositions comprising cationic couplers, especially p. 9, row 16-p. 13, line 8, and p. 11, line 20 - p. 12, row 13; dyeing formulations p. 36, row 7 - p. 39, line 24; (DC-18): DE 197, 172, 24, wherein dyeing agents are described comprising unsaturated aldehydes and couplers and compounds of primary and secondary amino groups, heterocyclic nitrogen-containing compounds, amino acids, oligopeptides, aromatic hydroxy compounds, and / or at least one CH-active compound, e.g. 3, row 42 - p. 5, row 25; dyeing formulations p. 8, line 25 - p. 9, line 61. In the dye combinations described in the references (DC-01-DC-18) above, the functionalized particles of the invention can be added to dye combinations or dyeing formulations or can be replaced with at least a functionalized particles of the invention. The present invention also relates to formulations, which are used for dyeing keratin-containing fibers, and more preferably human hair, comprising at least one functionalized particle of the invention. The functionalized particles of the invention can be incorporated in the formulation in amounts of 0 ... 1-5% by weight (indicated below only as "%"), particularly 0.005-4%, more particularly 0.2-3% , based on the total weight of the formulation. The formulations can be applied to the fiber containing keratin, preferably human hair in different technical forms. The technical forms of formulations are for example a solution, especially an aqueous or aqueous thickened alcohol solution, a cream, foam, shampoo, powder, gel or emulsion. Usually, the dyeing compositions are applied to the fiber containing keratin in an amount of 50 to 100 g.

Preferred forms of formulations are ready-to-use compositions or multi-compartment staining "equipment" devices or any of the multi-compartment package systems with behaviors as described for example in US 6,190,421, col. 2, line 16 to 31. The pH value of the ready-to-use dyeing compositions is usually from 2 to 11, preferably from 5 to 10. Preferably, the dyeing compositions, which are not stable to reduction, they are prepared with compositions free of oxidizing agent just before the dyeing process. A preferred embodiment of the present invention relates to the formulation of dyes, wherein the functionalized particles of the invention are in powder form. Powdered formulations are preferably used if problems of stability and / or solubility as for example are described in DE 197.13,698, p. 2, line 26 to 54 and p. 3, line 51 to p. 4, row 25, and p. 4, line 41 to p. 5, line 59. Suitable hair care, cosmetic formulations are hair treatment preparations, for example, hair-washing preparations in the form of shampoos and conditioners, hair care preparations, eg pre-treatment preparations. -treatment or products to put such as sprays, cream, gels, lotions, oils and oils, hair toners, styling creams, styling gels, ointments, hair rinses, treatment packages, intensive hair treatments, hair structuring preparations, for example, wavy preparations of hair for permanent wavy (hot corrugated, medium corrugated, cold corrugated), hair straightening preparations, liquid hair hardening preparations, hair foams, hair sprays, bleaching preparations, for example, hydrogen peroxide solutions , lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary dyes, semi-permanent or permanent hair, preparations containing self-oxidizing dyes, or natural hair dyes, such as henna or chamomile. For use in human hair, the dyeing compositions of the present invention can usually be incorporated into an aqueous cosmetic carrier. Suitable aqueous cosmetic carriers include, for example, W / O, O /, O / W / O, W / O / W or PIT emulsions and all kinds of microemulsions, creams, sprays, emulsions, gels, powders and also solutions foamers containing surfactant, for example, shampoos or other preparations, which are suitable for use in keratin-containing fibers. These forms of use are described in detail in Research Disclosure 42448 (August 1999). Yes it is necessary, it is also possible to incorporate the dyeing compositions into anhydrous carriers, as described, for example, in US-3, 369, 970, especially column 1, line 70 to column 3, line 55. The dyeing compositions in accordance The invention is also excellently suited for the dyeing method described in DE-A-3, 829, 870 using a dyeing comb or a dyeing brush. The constituents of the aqueous carrier are present in the dyeing compositions of the present invention in customary amounts, for example emulsifiers may be present in the dyeing compositions in concentrations of 0.5 to 30% b. . and thickeners in concentrations of 0.1 to 25% b.w. of the total dyeing composition. Additional carriers for dyeing compositions are described for example in "Dermatology", edited by Ch. Culnan, H. Maibach, Verlag Arcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, The Scie nce of Hair Care, chapter 7, pages 248-250, especially on page 243, row 1 to page 244, row 12. A shampoo has, for example, the following composition: 0.01 to 5% b.w. of the dye of the formula (1); 8% b.w. of PEG-5-laurylcitrate-disodium sulfosuccinate, sodium laureth sulfate; 20% b.w. of sodium cocoanfoacetate; 0. 5% b.w. of methoxy-PEG / PPG-7/3-aminopropyl-dimethicone; 0.3% b.w. of hydroxypropyl guar-hydroxypropitrimony chloride; 2.5% b.w. of PEG-200, hydrogenated glyceryl palmate; glyceryl-cocoate PEG-7; 0.5% b.w. of PEG-150 distearate; 2.2% b.w. of citric acid; perfume, conservatives; and additional water at 100%. The functionalized particles of the invention can be stored in a liquid paste-like preparation (aqueous or non-aqueous) or in the form of a dry powder. When the functionalized particles of the invention and adjuvants are stored readily in a liquid preparation, the preparation should be substantially anhydrous in order to reduce the reaction of the compounds. The dyeing compositions according to the invention may comprise any known active ingredient, additive or adjuvant for these preparations, such as surfactants, solvents, bases, acids, perfumes, polymeric adjuvants, thickeners and light stabilizers. The following adjuvants are preferably used in the hair dyeing compositions of the present invention: - non-ionic polymers, for example, copolymers of vinylpyrrolidone / vinyl acrylate, polyvinyl-pyrrolidone and copolymers of vinylpyrrolidone / vinyl acetate and polysiloxanes; cationic polymers, such as quaternized cellulose ethers, polysiloxanes having quaternary groups, dimethyldiallylammonium chloride polymers, dimethyldiallylammonium chloride copolymers and acrylic acid, as are commercially available under the name Merquat ™ 280 and the use thereof in hair dyeing as it is described, for example, in DE-A-4, 421, 031, especially page 2, line 20 to 49, or EP-A-953, 334; copolymers of acrylamide / dimethyldiallylammonium chloride, copolymers of dimethylaminoethyl methacrylate quaternized with diethyl sulfate / vinylpyrrolidone, copolymers of vinylpyrrolidone / imidazolinium-metachloride; - quaternized polyvinyl alcohol; zwitterionic and amphoteric polymers, such as copolymers of arrylamido-propyltrimethylammonium chloride / acrylate and copolymers of octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate; anionic polymers, such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, copolymers of vinyl acrylate / butyl maleate / isobornyl acrylate, copolymers of methyl vinyl ether / maleic anhydride and terpolymers of acrylic acid / ethyl acrylate / N-tert-butyl-acrylamide; thickeners, such as sugar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, acacia flour, flaxseed gum, dextrans, cellulose derivatives, for example, methyl cellulose, hydroxyalkyl cellulose and carboxymethyl -cellulose, starch fractions and derivatives, such as amylase, amylopectin and dextrins, clays, for example, bentonite or fully synthetic hydrocolloids such as, for example, polyvinyl alcohol; structuring agents, such as glucose and maleic acid; - hair conditioning compounds, such as phospholipids, for example soy lecithin, egg lecithin, cephalins, silicone oils, and conditioning compounds, such as those described in DE-A-19,729,080, especially page 2, line 20 to 49 , EP-A-834,303, especially page 2, row 18 - page 3, row 2, or EP-A-312, 343, especially page 2, row 59 - page 3, row 11. protein hydrolysates, especially elastin, collagen , keratin, milk protein, soy protein and wheat protein hydrolyzate, condensation products thereof with fatty acids and also hydrolysates of quaternized proteins; perfume oils, dimethyl-isosorbitol and cyclodextrins, - solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, anti-dandruff active ingredients, such as pyroctones, olamines and zinc Omadine, - substances for adjusting the value of the pH; - panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and salts thereof, plant extracts and vitamins; - cholesterol; - light stabilizers and UV absorbers as listed in the Table below: Table 1: UV absorbers that can be used in the dyeing compositions of the present invention The use of UV absorbers can effectively protect the natural hair and dye it from the harmful rays of the sun and increase the fineness to the wash of the dyed hair. Additionally, the following UV absorbers or combinations can be used in the dyeing compositions according to the invention: UV absorbents of cationic benzotriazole as described for example in O 01/36396, especially page 1, line 20 to page 2, line 24 and preferred on pages 3 to 5, on pages 26 to 37; - Cationic benzotriazole UV in combination with antioxidants as described in WO 01/36396, especially on page 11, line 14 to 18; UV absorbers in combination with antioxidants as described in U.S. Patent No. 5,922,310, especially in column 2, row 1 to 3; UV absorbers in combination with antioxidants as described in U.S. Patent No. 4,786,493, especially in column 1, 42 to column 2, row 7, and preferred in column 3, 43 to column 5, row 20; - combination of UV absorbers as described in U.S. Patent No. 5,830,441, especially in column 4, line 53 to 56; - combination of UV absorbers as described in WO 01/36396, especially on page 11, row 9 to 13; or - triazine derivatives as described in WO 98/22447, especially on page 1, line 23 to page 2, line 4, and preferred on page 2, line 11 to page 3, line 15 and more preferred on page 6 to 7 and 12 to 16. Suitable cosmetic preparations may usually contain from 0.05 to 40% b. ., preferably from 0.1 to 20% b.w., based on the total weight of the composition, of one or more UV absorbers. The additional ingredients may be: - consistency regulators, such as sugar esters, polyol esters or polyol-alkyl ethers; - fats and waxes, such as whale sperm, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters; - fatty alkanolamides; - polyethylene glycols and polypropylene glycols having a molecular weight of 150 to 50,000, for example such as those described in EP-A-801, 42, especially page 13, line 44 to 55, - complexing agents, such as EDTA, NTA and phosphonic acids, swelling and penetration substances, such as polyols and polyol ethers, as extensively listed, for example in EP-A-962, 219, especially page 27, row 18 to 38, for example glycerol, propylene glycol, ether monoethylic propylene glycol, butyl glycol, benzyl alcohol, carbonates, acid carbonates, guanidines, ureas and also primary, secondary and tertiary phosphates, imidazoles, tannins, pyrrole; - opacifiers, such as latex; pearlescent agents, such as ethylene glycol mono- and di-stearate; propellants, such as mixtures of propane-butane, N20, dimethyl ether, CO2 and air; antioxidants; preferably the phenolic antioxidants and hindered nitroxyl compounds described in ip.com (IPC0M # 000033153D); - polymers containing sugar, as described in EP-A-970,687 - quaternary ammonium salts, as described in WO 00/10517; bacterial inhibitory agents, such as preservatives having a specific action against gram-negative bacteria, such as, 4, 4 '-trichloro-2' -hydroxydiphenyl-ether, chlorhexidine (1,6-di (-chlorophenyl-diguanide) hexane) or TCC (3,4-trichlorocarbanilide). A large number of aromatic substances and etheric oils also have antimicrobial properties. Typical examples are the active ingredients, eugenol, menthol and thymol in garlic clove oil, peppermint oil, and thyme oil. A natural deodorizing agent of interest is the terpene alcohol, farnesol (3,7,11-trimethyl-2, 6, 10-dodecatrien-1-ol), which is present in lemon blossom oil. Glycerol monolaurate has also proven to be a bacteriostatic agent. The amount of additional agents and inhibitors of bacteria, present, is usually 0.1 to 2% b. ., based on the solids content in the preparations. The dyeing compositions according to the present invention generally comprise at least one surfactant. Suitable surfactants are zwitterionic or ampholytic surfactants, or more preferably anionic, nonionic and / or cationic surfactants. Suitable anionic surfactants in The dyeing compositions according to the present invention include all the anionic surface active substances which are suitable for use in the human body. These substances are characterized by an anionic group imparting solubility in water, for example a carboxylate, sulfate, sulfonate or phosphate group, and a lipophilic alkyl group having approximately 10 to 22 carbon atoms. In addition, the glycol- or polyglycol ether groups, ester, ether and amide groups and also hydroxy groups may be present in the molecule. The following are examples of suitable anionic surfactants, each in the form of sodium, potassium salts 0 ammonium or mono-, di- or tri-alkanolammonium salts having from 2 to 3 carbon atoms in the alkanol group; linear fatty acids having from 10 to 22 carbon atoms (soaps), ether carboxylic acids of the formula RO- (CH2-CH2-0) x-CH2-COOH, in which R is a linear alkyl group having of 10 to 22 carbon atoms and x = 0 or of 1 to 16, acyl sarcosides having from 10 to 18 carbon atoms in the acyl group, acyl taurides having from 10 to 18 carbon atoms in the acyl group, acyl isothionates having from 10 to 18 carbon atoms in the acyl group, - mono- and di-alkyl sulfosuccinic ethers having from 8 to 18 carbon atoms in the alkyl group and the monoalkyl polyoxyethyl sulfosuccinic esters having from 8 to 18 carbon atoms in the alkyl group and from 1 to 6 linear oxygenated, linear alkane sulphonate groups having 12 to 18 carbon atoms in the alkyl group; to 18 carbon atoms, linear α-olefin sulphonates having from 12 to 18 carbon atoms, fatty acid methyl esters of fatty acids having from 12 to 18 carbon atoms, alkyl sulfates and sulfates of alkyl polyglycol ether of the formula R '-0 (CH2-CH2-0) x-S03H, en. which R 'is a preferably linear alkyl group: having from 10 to 18 carbon atoms and x' = 0 or from 1 to 12, mixtures of surface-active hydrosulfonates according to DE-A-3, 725, 030; glycolic ethers of hydroxyalkylpolyethylene and / or hydroxyalkylenepropylene sulphated according to DE-A-3,723,354, especially page 4, line 42 to 62, sulfonates of unsaturated fatty acids having from 12 to 24 carbon atoms and from 1 to 6 double bonds of according to DE-A-3, 926, 344, especially page 2, row 36 to 54, - esters of tartaric acid and citric acid with alcohols which are addition products of approximately 2 to 15 molecules of ethylene oxide and / or oxide of propylene with fatty alcohols having 8 to 22 carbon atoms, or anionic surfactants, as described in WO 00/10518, especially page 45, line 11 to page 48, line 3. Preferred anionic surfactants are alkyl sulfate, alkyl polyglycol ether sulfate and ether carboxylic acids which they have from 10 to 18 carbon atoms of the alkyl group and up to 12 glycol ether groups in the molecule, and also especially salts of saturated and especially unsaturated C8-C22 acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid. Surface-active compounds having at least one quaternary ammonium group and at least one -COO "or -SO3" group in the molecules are terminated zwitterionic surfactants. Preference is given to so-called betaines, such as N-alkyl-N, N-dimethylammonium glycinates, for example, cocoalkyldimethylamine glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example, cocoacylaminopropyldimethylammonium glycinate, and -alkyl-3-carboxymethyl-3-hydroxyethylimidazoline having 8 to 18 carbon atoms in the alkyl or acyl group and also cococylaminoethylhydroxyethylcarboxymethyl glycinate. A preferred zwitterionic agent is the amide derivative of the fatty acid known by the CTFA name of cocoamidopropyl betaine.

Ampholytic surfactants are surface active compounds that, in addition to a Ca-Ciealkyl or -acyl group and contain at least one free amino group and at least one -COOH or -S03H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants include N-alkylglycins, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and acids. alkylaminoacetics, each having about 8 to 18 carbon atoms in the alkyl group. The amphoteric surfactants to which special preference is given are N-cocoalkylaminopropionate, cocoalkylaminoethylaminopropionate and Ci2-Cigacilsarcosine. Suitable nonionic surfactants are described in WO 00/10519, especially page 45, row 11 to page 50, line 12. The nonionic surfactants contain, as a hydrophilic group, for example, a polyol group, a polyalkylene glycol ether group , or a combination of polyol and polyglycol ether groups. These compounds are, for example: - addition product of 2 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols having from 8 to 22 carbon atoms, with fatty acids having of 12 to 22 carbon atoms and with alkylphenols having from 8 to 15 carbon atoms in the alkyl group, - mono- and di-esters of Ci2-C22 acid greases of products of addition of 1 to 30 mol of ethylene oxide with glycerol, C8-C22alkyl-mono- and -oligo-glycosides and ethoxylated analogs thereof, - addition products of 5 to 60 mol of ethylene oxide with castor oil and hydrogenated castor oil, - addition products of ethylene oxide with sorbitan fatty acid esters, - addition products of ethylene oxide with acid alkanolamides fatty. The surfactants which are addition products of ethylene oxide and / or propylene with fatty alcohols or derivatives of these addition products can be either products having "normal" homologous distribution or products having a restricted homologous distribution. The "Normal" homologous distribution are mixtures of homologs obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides, or alkali metal alcolates as catalysts. Restricted homologous distributions, on the other hand, are obtained when, for example, hydrotalcite catalysts, alkali metal salts of carboxylic ether-acids, oxides, hydroxides or alkali metal alcolates are used.

The use of products that have restricted homologous distribution may be preferred. Examples of cationic surfactants that can be used in the dyeing compositions according to the invention are especially quaternary ammonium compounds. Preference is given to ammonium halides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, for example, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethyl-ammonium chloride, lauryldimethylammonium chloride, lauryl dimethylbenzylammonium chloride and trichloethyl ammonium chloride. . The additional cationic surfactants that can be used according to the invention are quaternized protein hydrolysates. Also suitable are cationic silicone oils, such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning 929 emul (comprising a silicone modified with hydroxylamino, which is also referred to as amodimethicone) ), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and also AbilMR-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; dicuternary polydimethylsiloxanes, quaternium-80), or silicones, as described in WO 00/12057, especially page 45, row 9 to page 55, row 2.

Also preferred are alkylamidoamines, especially fatty acid amidoamines, such as stearylaminopropyl-dimethylamine obtainable under the name Tego Amid ™ 18 as surfactants in the present dyeing compositions. It is distinguished not only by a good conditioning action but also especially by its good biodegradability. Quaternary ester compounds, called "esterquats", such as methylhydroxyalkyl dialkoyloxyalkylammonium methosulfate marketed under the tradename Stepantex ™, are also very readily biodegradable. An example of a quaternary sugar derivative which can be used as a cationic surfactant is the commercial product Glucquat ™ 100, in accordance with the CTFA nomenclature a "laurel-methyl-gluceth-10-hydroxypropyl-dimonium chloride". The compounds containing alkyl groups used as surfactants may be individual substances, but in general the use of natural raw materials of animal or vegetable origin is preferred in the preparation of these substances, as a result of the mixture of substances obtained having different lengths of alkyl chains according to the particular starting material used.Usually, the dyeing compositions are applied to the fiber containing keratin in an amount from 50 to 100 g. The functionalized particles of the invention are suitable for dyeing throughout the hair, which is said when the hair is dyed on a first occasion, and also for subsequent re-dyeing, or dyeing of locks or parts of the hair. The functionalized particles of the invention are applied to the hair, for example by hand massage, a comb, a brush or a bottle, or a bottle, which is combined with a comb or a nozzle. In the processes for dyeing according to the invention, whether or not the dyeing is carried out in the presence of an additional dye, it will depend on the hue of the color to be obtained. Further preferred is a process for dyeing keratin-containing fibers comprising treating the keratin-containing fiber with at least one functionalized particle of the invention, a base and an oxidizing agent. The oxidation dyeing process usually comprises rinsing, ie comprising applying to the fibers containing keratin, a mixture of basic pH of base and aqueous solution of hydrogen peroxide, leaving the chopped mixture to rest on the hair and then rinsing the hair. It allows, particularly in the case of hair dyeing, that the melanin and the hair to be dyed be lightened.

The lightening of melanin has the advantageous effect of creating a unified dyeing in the case of gray hair, and in the case of naturally pigmented hair, of brightening the color, ie of making it more visible. In general, the composition containing oxidizing agent is left in the fiber for 0 to 15 minutes, in particular for 0 to 5 minutes at 15 ° to 45 ° C, usually in amounts of 30 to 200 g. Oxidizing agents are, for example, dilute solutions of hydrogen peroxide or persulfate, emulsions of hydrogen peroxide or hydrogen peroxide gels, alkaline earth metal peroxides, organic peroxides, such as urea peroxides, melamine peroxides, or bromate fixations. Alkali metal are also applicable if a dimming powder is used in the base of direct semi-permanent hair dyes. The further preferred oxidizing agents are oxidizing agents for achieving clarified staining, as described in WO 97/20545, especially page 9, row 5 to 9, - oxidizing agents in the form of permanent waving fixing solution, as described in DE-A-19,713,698, especially page 4, line 52 to 55, and line 60 and 61 or EP-A-1062940, especially page 6, line 41 to 47 (and in WO 99/40895 equivalent) The oxidizing agent further preferred is hydrogen peroxide, preferably used in a concentration- about 2 to 30%, and more preferably about 3 to 20%, and more preferably 6 to 12% b. . the corresponding composition. The oxidizing agents may be present in the dyeing compositions according to the invention preferably in an amount of 0.01% to 6%, especially 0.01% to 1%, based on the total dyeing composition. In general, dyeing with an oxidizing agent is carried out in the presence of a base, for example, ammonia, alkali metal carbonate, carbonates. of alkaline earth metals (potassium or lithium), alkanolamines, such as mono-, di- or tri-ethanolamine, alkali metal (sodium) hydroxides, alkaline earth metal hydroxides or compounds of the formula R is a propylene residue, which may be substituted with OH or Ci-C4alkyl, R3, R4, R5 and R6 are independently or in a manner dependent on hydrogen, Ci-C4alkyl or hydroxy- (Ci-Cj) alkyl. The pH value of the oxidizing agent containing the composition is usually from about 2 to 7, and in particular about from 2 to 5. A preferred method for applying formulations comprising the functionalized particles of the invention in the keratin-containing fiber, preferably the hair is by using a multi-component dyeing device or "equipment" or any other multi-component packaging system, as described for example in WO 97/20545 on page 4, row 19 to row 27. The first compartment contains for example at least one functionalized particle of the invention and optionally further direct dyes and a basification agent, and in the second compartment, an oxidizing agent; or in the first compartment at least one functionalized particle and optionally additional direct dyes, in the second compartment a basification agent and in the third compartment an oxidizing agent. In general, the hair is rinsed, after treatment with the dye solution and / or permanent waving solution. A further preferred embodiment of the present invention relates to a method for dyeing the hair with oxidative dyes, comprising a. mixing at least one functionalized particle of the invention and optionally at least one coupling compound and at least one developer compound, and an oxidizing agent, optionally containing at least one additional dye, and b. contact the keratin containing fibers with the mixture as prepared in step a. The pH value of the oxidizing agent-free composition is usually from 3 to 11, and in particular from 5 to 10, and more particularly near 9 to 10. Preferably, a ready-to-use composition is prepared according to a first preferred embodiment by a process comprising a preliminary step comprising storing separately, on the one hand, a composition (A) comprising, in a medium which is suitable for dyeing, at least one developer compound, selected especially from para-phenylenediamines and bis (phenyl) -alkylenediamines, and the addition salts of acid thereof, at least one coupler, especially selected from meta-phenylenediamines and the acid addition salts thereof, and at least one functionalized particle of the invention, on the other hand, a composition (B) containing, in a medium which is suitable for dyeing, at least one oxidizing agent and mixing (A) and (B) together immediately before applying this mixture to the fibers <3ue contain keratin. According to a second preferred embodiment for the preparation of the ready-to-use dye composition, the process includes a preliminary step comprising separately storing, on the one hand, a composition (A) comprising, in a medium that is suitable for dyeing, at least one developer compound, especially selected from para-phenylenediamines and bis (phenyl) alkylenediamines, and the acid addition salts thereof, at least one coupler compound, especially selected from meta-phenylenediamines and the acid addition salts thereof; on the other hand, a composition (A ') comprising, in a medium that is suitable for dyeing, at least one functionalized particle of the invention, and finally, a composition (B) containing, in a medium that is suitable for dyeing , at least one oxidizing agent as defined above, and mixing them together at the time of use immediately before applying this mixture to the fibers containing keratin. The composition (A ') used according to this second embodiment may optionally be in the powder form, the functionalized particles of the invention (by itself) which constitute, in this case, the entire composition (A') or which are optionally dispersed in a powdery organic and / or inorganic excipient. When present in the composition (A '), the organic excipient can be of synthetic or natural origin and is selected in particular from synthetic and cross-linked and non-crosslinked polymers, polysaccharides such as cellulose and modified or unmodified starches, as well as natural products such as sawdust and recétal rubbers (guar gum, taraxacum gum, xanthan gum, etc. When it is present in the composition (A '), the Inorganic excipient may contain metal oxides such as titanium oxides, aluminum oxides, kaolin, talc, silicates, mica, and silicas. A very suitable excipient in the dyeing compositions according to the invention is sawdust. Powdered compositions (A ') may also contain binders or coating products in an amount not preferably exceeding about 3% b.w. in relation to the total weight of the composition (A '). These binders are preferably selected from oils and liquid fatty substances of inorganic, synthetic, animal or vegetable origin. Additionally, the present invention relates to a process for dyeing keratin-containing fibers of the functionalized particles of the invention with auto-oxidizable compounds and optionally additional dyes. Additionally, the present invention relates to a process for dyeing keratin containing fibers with the functionalized particles of the invention and topped diazotized compounds, comprising a. treating the keratin-containing fibers under alkaline conditions with at least one capped diazotised compound and a coupler compound, and optionally a developer compound and optionally an oxidizing agent, and optionally in the presence of an additional dye; and optionally with at least one functionalized particle of the invention; and b. adjusting the pH in the range of 6 to 2 by treatment with an acid, optionally in the presence of an additional dye, and optionally at least one dye of the formula (1), with the proviso that at least in step a. or b., at least one functionalized particle of the invention is present. The capped diazotised compound and the coupler compound and optionally the oxidizing agent and the developer compound can be applied in any desired order, successively, or simultaneously. Preferably, the capped diazotised compound and the coupling compound are applied simultaneously, in a single composition. "Alkaline conditions" denote a pH in the range of 8 to 10, preferably 9-10, especially 9.5-10, which are achieved by the addition of bases, for example sodium carbonate, ammonia or sodium hydroxide. The bases can be added to the hair, to the dye precursors, the diazotized capped compound and / or water-soluble coupling component, or to the dyeing compositions comprising the dye precursors. The acids are for example tartaric acid or citric acid, or citric acid gel, or a suitable buffer solution with optionally an acid dye.

The ratio of the amount of alkaline dyeing composition applied in the first stage to that of the acid dyeing composition applied in the second stage is preferably about 1: 3 to 3: 1, especially about 1: 1. The following examples serve to illustrate the present invention without limiting the present invention to these. Unless otherwise specified, the parts and percentage are related to the weight. The amount of dyes specified are in relation to the material that is colored.

Examples A - Preparation Process Example Al: Silica Nanoparticles Modified with 3-Aminopropyl Silane 510 g of Ludox TMA (Helm AG, 34% nanosilicate dispersion in water) are mixed with 2490 g of ethanol (EtOH). 345 g of 3-aminopropyltrimethoxysilane (Fluka purum) are added dropwise to this homogeneous mixture. After the addition, this mixture is heated at 50 ° C for 18 hours. The volume of this mixture is then reduced to approximately 1 liter by evaporating EtOH / H20 in the rotary evaporator. A total of 4 liters of hexane are added, the mixture is stirred vigorously and the two phases are separated in a separating funnel to remove the unreacted aminosilane. The lower aqueous / ethanolic phase is concentrated to a wet paste in the rotary evaporator in vacuo and then re-suspended in 1 liter of ethanol. A total of 1199 g of solution with a solids content of 27.3% by weight are obtained.

Analysis: Thermogravimetric analysis (TGA, heating rate: 10 ° C / min from 50 ° C to 600 ° C): Weight loss: 25.2% corresponding to the original material Elemental analysis: Found: C: 17.68%, H: 4.65 %, N: 6.73%: corresponding to an organic content of 28.1% in relatively good agreement with the TGA value. Transmission Electron Microscopy (TEM): An average diameter of 35-40 nm is obtained for the individual nanoparticles. Dynamic light scattering (DLS): Average diameter d = 90 = 119 nm.

Example A2: Nanoparticles Modified with 3-Aminopropyl-Silane 150 g of alumina nanoparticles are mixed (Nyacol Corp., Nyacol A120 DW, nanoalumin dispersion at 22% in water) with 250 ml of ethanol (EtOH). 27 g of 3-aminopropyltrimethoxysilane (Fluka purum) are added dropwise to this homogeneous mixture. After the addition, the mixture is heated at 50 ° C for 15 hours. The volume of this mixture is then reduced to approximately 1 liter by evaporating EtOH / H20 in the rotary evaporator. The solid obtained is redispersed in EtOH to an opaque dispersion at 11.4% by weight.

Analysis: Thermogravimetric analysis (TGA, heating rate: 10 ° C / min from 50 ° C to 800 ° C): Weight loss: 27.9% by weight corresponding to the organic material. Elemental analysis: Found: N: 4.16% by weight: corresponding to an organic content of 17.3% by weight. The difference between the results of TGA and EA is due to the loss of water from the inorganic matrix and the water generated from the condensation processes on the surface during the thermal treatment. Transmission Electron Microscopy (TEM): An average diameter of 50 to 60 nm is obtained for the individual primary nanoparticles. Dynamic light scattering (DLS): Average diameter d = 164 nm.

Example A3: a) Anthraquinone dye preparation of the formula (101) A mixture of 6.0 g of 1-fluoro-anthraquinone, 3.4 g of hexane-amine (FLUKA) and 4.0 g of potassium carbonate is heated with stirring at 95 ° C for 25 hours until the starting fluoride is consumed. The reaction mixture is then filtered. The red residue is taken up in ethyl acetate and extracted successively with 1 N hydrogen chloride (3 times), saturated sodium chloride solution and brine. Evaporation of the solvent leaves a red residue which is purified on a short column of silica gel (230-400 mesh, FLUKA) and eluent (hexane-ethyl acetate 10: 2 (v / v) to give 6.3 g of the red alcohol desired of the formula (101). 1 H-NMR (CDCl 3, 300 MHz): 1.40-1.81 (m, 8 H); 3.26 (ddd, 2 H); 3.66 (t, 2 H); 6.98 (dd, 1 H); 7.45 (ddd, 1 H); 7.50 (dd, 1 H); 7.62-773 (m, 2 H); 8.15 - 8.22 (m, 2 H). 1 H-NMR (CDCl 3, 75 MHz): 25.85; 27.29; 29.34; 32.79; 43.06; 62.70; 112.94; 115.76; 118.11; 126.78; 126.83; 133.05; 133.13; 134.13; 134.74; 135.18; 135.45; 151.78; 184.06; 184.99.

Anthraquinone dye preparation of the formula (102) The compound of the formula (101) is esterified in the presence of the NOVO 435 biocatalyst (Novozymes, Denmark). At 50 ° C and a vacuum at about 450 mbar, 10.0 g of the compound of the formula (101), 22.2 ml of methyl ester of acrylic acid and 5.0 g of the biocatalyst are reacted in 75 ml of toluene for 24 hours until It consumes all the starting compound of the formula (101). The mixture is then filtered, washed with dichloromethane and the solvent is evaporated. After drying under vacuum, 11.5 g of the desired red acrylic ester of the formula (102) are obtained. RM ^ H (CDC13, 300 MHz): 1.35-1.77 (m, 8 H); 3.25 (dt, 2 H); 4.10 (t, 2 H); 5.73 (dd, 1 H); 6.04 (dd, 1 H); 6.28 (dd, 1 H); 6.96 (dd, 1 H); 7.44 (dd, 1 H); 7.50 (dd, 1 H); 7.60 dt, 1 H); 7.66 (dt, 1 H); 8.14 (m, 2 H); 9.64 (broad, t, 1 H). 1 H-NMR (CDCl 3, 75 MHz): 26.15; 27.23; 28.93; 29.40; 43.19; 64.77; 113.11; 115.77; 117.98; 126.83; 126.88; 128.78; 130.67; 133.04; 133.22; 134.06; 134.87; 135.22; 135.43; 151.90; 166.40; 183.87; 185.04.

Example 4A: a) Anthraquinone dye preparation of the formula (103) [precursor] 1.0 g of 1-N-methyl, 4-bromo-anthraquinone, 1.0 g of 6-aminohexanol (FLUKA), 0.6 g of potassium carbonate and 0.2 g of copper powder at 100 ° C in 5 ml of toluene are heated. 26 hours The reaction mixture is filtered, washed with acetone and the residue is dissolved in dichloromethane. The blue solution is applied to a column of silica gel (230-400 mesh, FLUKA) and eluted with dichloromethane-methanol 10: 2 (v / v) to give 0.5 g of the desired blue alcohol of the formula (103). 1 H-NMR (CDC13, 300 MHz): 1.32-1.61 (m, 6 H); 1.69 (quint., 2 H); 2.99 (d, 3 H); 3.29 (q, 2 H); 3.58 (t, 2 H); 7.10 (dd, 2 H); 7.60 (dd, 2 H); 8.21 (dd, 2 H); 10.51 (broad, 1 H); 10.64 (broad t, 1 H). NMR ^ H (CDCl 3, 75 MHz): 25.86; 27.27; 29.83; 29.88; 32.95; 43.11; 63.04; 109.90; 110.09 123.24; 123.69; 126.17 (2 x C); 132.10 (2 x C); 134.03; 134.68; 146.34; 147.03; 182.35 (2 x C).

Anthraquinone dye preparation of the formula (104) In analogy to Example A3 b), 5.0 g of the alcohol of the formula (103) is converted to the ester of the formula (104) in the presence of 4.0 g of biocatalyst and methacrylic acid methyl ester. The ester of the formula (104) is obtained in 5.8 g of filtration of the catalyst and washing with the biocatalyst with the biocatalyst with dichloromethane. 1 H-NMR (CDCl 3, 300 MHz): 1.35-1.76 (m, 8 H); 3.02 (d, 3 H); 3.32 (dt, 2 H); 4.09 (t, 2 H); 5.74 (dd, 1 H); 6.04 (dd, 1 H); 6.28 (dd, 1 H); 7.15 (s, 2 H); 7.61 (m, 2 H); 8.23 (m, 2 H); 10.53 (broad q, 1 H); 10.66 (broad 5 t, 1 H).

Example 5: Silica Nanoparticles Modified with Anthraquinone with Cationic Surface Groups Reaction Scan The synthesis is carried out in a round bottom flask. 3.25 g of a dimethyl-acetamined (DMA) dispersion containing 26.2% by weight of silica nanoparticles modified with 3-aminopropyl-xylan (obtainable according to Example A above, N: 6.73% by weight) are mixed with a solution of 0.775 g of the anthraquinone compound of the formula (102) in 10 g of DMA. The reaction mixture is stirred for 15 hours at 50 ° C. Subsequently, 0.59 g of 2- (dimethylamino) ethyl acrylate is added to the reaction dispersion and stirred again for 15 hours at 50 ° C. After this time, The acrylic groups can not be analyzed by NMR ^ H. Then, 0.6 g of methyl iodide is slowly added to the dispersion and the reaction is carried out for 15 hours at 50 ° C. After cooling, the solvent of the red colored reaction dispersion is evaporated using a rotary evaporator. A dark red resin is obtained which is easily redispersible in water.

Thermogravimetric Analysis (TGA); heating rate (TGA: heating rate 10 ° C / min from 50 ° C to 800 ° C): Weight loss: 85.1% by weight corresponding to the organic material. Dynamic light scattering (DLS): Average diameter d = 65nm.

Example A6: Silica Nanoparticles Modified with Anthraquinone with Cationic Surface Groups Reaction Scheme: The synthesis is carried out in a round bottom flask. 3.25 g of a dispersion of DMA containing 26.2% by weight of silica nanopatics modified with 3-aminopropyl-silane (obtainable according to Example A above, N: 6.73% by weight) are mixed with a solution of 0.775 g of the compound of anthraquinone of the formula (102) in 10 g of DMA. The reaction mixture is stirred for 15 hours at 50 ° C. Subsequently, the reaction mixture is cooled to 0 ° C using an ice / water bath. Then, 0.405 g of the following compound of the formula (105) are added. and 0.43 g of 1,3-dicyclohexylcarbodiimide to the reaction dispersion and stirred for 5 hours at 9 ° C. After this time, the reaction dispersion is brought to temperature ambient. A red dispersion is obtained. After evaporating the solvent with a rotary evaporator, the obtained resin is redispersed in 50 ml of a 1: 1 water / acetone mixture and centrifuged at 2000 rpm for 20 minutes. The solvent is separated from the solid and fresh solvent is added. The cleaning procedure when using centrifugation is repeated 5 times. Subsequently, the red product is redispersed in water to obtain a dispersion with a solids content of 5% by weight.

Analysis: Thermogravimetric analysis (TGA: heating rate: 10 ° C / min from 50 ° C to 800 ° C): Weight loss: 60% by weight corresponding to the organic material. Dynamic light scattering (DLS): Average diameter d = 127 nm.

Example A7: Silica Nanoparticles Modified with Anthraquinone with Cationic Surface Groups. 1.12 g of a dispersion containing 26.2% by weight of silica nanoparticle modified with 3-aminopropylsilane (obtainable according to Example Al, N: 6.73% by weight) are mixed with 1.9 g of MPEG (8) acrylate (= poly ( ethylene glycol) methyl ether-acrylate, CAS 32171-39-4, Aldrich, MW = 454 and a 0.3 g solution of the anthraquinone acrylate dye of the formula (104) (obtainable from agreed to example A) in 30 ml of ethanol. The reaction mixture is stirred for 15 hours at 50 ° C. Subsequently, the reaction mixture is cooled to room temperature. After this time, a small signal can be analyzed that is related to acrylic groups by NMR-1 !. The dispersion is washed using centrifugation at 3000 rpm for 15 minutes. The blue solid is washed with ethanol, redispersed in water / ethanol and centrifuged again. This washing procedure is repeated until no free acrylic bonds can be observed in the 1 H-NMR analysis. The product is then redispersed in water and 1 ml of 2 mol / 1 HC1 solution is added. The pH of the final blue dispersion is 2.

Analysis: Thermogravimetric analysis (TGA, heating rate: 10 ° C / min from 50 ° C to 800 ° C): Weight loss: 59% by weight corresponding to the organic material. Dynamic light scattering (DLS): Average diameter d = 225 nm.

Example A8: Silica Nanoparticles Modified With Anthraquinone with Cationic Surface Groups 3.25 g of a dispersion containing 26.2% by weight of silica nanoparticles modified with 3-aminopropylsilane (obtainable according to Example Al, N: 6.73% by weight) are mixed with 0.93 g of MPEG (8) acrylate (= poly (ethylene glycol) methyl ether-acrylate, CAS 32171-39-4, Aldrich MW = 454) and a solution of 0.78 g anthraquinone dye acrylate of the formula (102) (obtainable according to Example A3 ) in 40 mL of ethanol. The reaction mixture is stirred for 15 hours at 50 ° C. Subsequently, the reaction mixture is cooled to room temperature. After this time, a small signal can be analyzed that is related to acrylic groups by NMR ^ H. The dispersion is washed using centrifugation at 3000 rpm for 15 minutes. The red solid is washed with ethanol, redispersed in water / ethanol and again centrifuged. This washing procedure is repeated until no free acrylic bonds can be observed in the RMN-1? Analysis. The product is then redispersed in water and 2 mol / 1 HCl solution is added to adjust the pH value to 2.

Analysis: Thermogravimetric analysis (TGA: heating rate: 10 ° C / min from 50 ° C to 800 ° C): Weight loss: 62% by weight corresponding to the organic material. Dynamic light scattering (DLS): average diameter d = 180 nm. UV / VIS (water): A ™ ax 518 (pH 2), 524 nm (pH 5).

Example A9: Nanoparticles of Modified Silicas in the Surface with Cationic Surface Groups and Complex Groups of Fe2 +.

Reaction scheme: The synthesis described below is carried out in a round bottom flask. 3 g of a dispersion containing 26.2% by weight of silica nanoparticles modified with 3-aminopropylsilane (obtainable according to Example Al, N: 6.73% by weight) are mixed with 1.2 MPEG (8) acrylate (= poly (ethylene glycol) ) methyl-ether-acrylate, CAS 32171-39-4, Aldrich MW = 454) and a solution of 0.425 g of ligand (I) [with respect to the structure of this ligand see the above reaction scheme] in 30 g of THF. The reaction is stirred for 15 hours at 50 ° C. Subsequently, the reaction mixture is cooled to room temperature. After this time, they can not be analyzed by NMR-1 !! in an acrylic group. After evaporating the solvent with a rotary evaporator, the resin obtainable is redispersed in a mixture of 85 g of water and 3 g of ethanol. In parallel, a fresh 60 mmol solution of Fe3 + is prepared using FeCl3 '6 H20. In addition, a fresh solution B of 60 mmol of vitamin C is prepared. After adding every 18 ml of solution A and B to the dispersion to the nanoparticle, the color changes immediately from milky white to violet. Using ultrasonic treatment, the reaction and complex formation is forced which leads to a dispersion of dark violet nanoparticles.

Analysis: Thermogravimetric analysis (TGA, heating speed: 10 ° C / min from 50 ° C to 800 ° C): weight loss: 79% by weight corresponding to the organic material. Dynamic light scattering (DLS): average diameter d = 91 nm. UV / VIS (water): A ™ ax = 571 nm.

Example A10: Silica Nanoparticles Modified with AZO Dye Reaction Scheme: The ethanolic suspension obtained according to Example Al is concentrated to dryness in vacuo and re-suspended in isopropanol to obtain a suspension with a solids content of 27.8% by weight. In a round bottom flask, equipped with a reflux condenser and a dropping funnel, 5 g of this suspension is heated to the reflux temperature. Then, a solution of 1.0 g of the compound of the formula is added. (106) [prepared as described in WO 2004/076564] in 40 ml of isopropanol for a period of 6 hours at reflux temperature. The resulting red precipitate is filtered and subjected to reflux for 2 hours with 50 ml of isopropanol. After filtration, the product is dried in vacuo to obtain 2.7 g of a red powder, which can be redispersed in water.

Analysis: Elemental Analysis: Found: C: 33.22% | en weight, H: 4.57% by weight, N: 12.75% by weight, corresponding to an organic content of 50.54% by weight. Dynamic light scattering (DLS): Average diameter d = 69 nm. Electronic Scanning Microscope (SEM): The size of the observed particles was in the range of 30 to 70 nm. UV / VIS (water): A ^ ax 505 nm. If in Example A10 the fluoro-substituted dye of formula (106) is replaced by the methoxy-substituted dye of formula (107) (prepared as in US2004187231) under the same reaction conditions, an identical product can be obtained. If, in Examples A5 to A10, aluminum nanoparticles modified with 3-aminopropylsilane (obtainable according to Example A2) are used instead of silica nanoparticles modified with 3-aminopropylsilane, the corresponding functionalized alumina nanoparticles can be obtained.

Example All: A mixture of tetraethoxysilane (18 g), ammonia (25% solution in water, 8.9 g) and ethanol (210 g) is stirred overnight at room temperature. Then (3-aminopropyl) trimethoxysilane (5.20 g) is added to 110 g of the initial dispersion and the mixture is heated at 55 ° C overnight. The mixture is then cooled to room temperature and evaporated ¾ from the solvents. An equal volume of hexane is added, and the mixture is centrifuged. The resulting mother liquor is decanted and the white solid is washed again with hexane. These functionalized silica particles are then re-dispersed in ethanol. The mixture is heated overnight to a mixture of this dispersion (10 ml, 0.17 g of solid material) and the compound of the formula (106) (0.2 g) and isopropanol (10 ml). This mixture is then cooled to room temperature and the red precipitate is filtered and washed with ethanol followed by acetone to give the nanoparticles functionalized with cationic dye as a red powder (0.155 g). DLS and SEM show monodisperse particles with an average diameter of 90 nm and approximately 70 nm, respectively. TGA shows loss of 44.065%, which corresponds to the organic material and the elemental analysis gives 27.71% (C; H; N) UV / VIS (water): ax 505 nm.

Examples A12 to A16: The variation of the silane / ammonia / ethanol ratios in the above method of Example All gives different sizes of silica nanoparticles. The reaction of these particles of different size in the same manner as before in Example All gives the nanoparticles functionalized with cationic dye of the following approximate diameters: * technical grade used ethanol ** 18.75 ml of H20 EA was also added = elemental analysis of the total of C, H and N in% by weight based on the weight of the product.

Example A17 to A18: The variation in the amount of the dye of the formula (106) used in Example A10 gives substituted particles as a mixture of aminopropyl groups and cationic dyes.

Reaction scheme: A mixture of aminopropyl substituted nanoparticles obtainable according to Example Al, the dye of the formula (106) and isopropanol are heated at reflux overnight. The mixture is then cooled to room temperature, filtered and washed with isopropanol. The solid is refluxed in isopropanol for one hour, then cooled to room temperature, filtered and washed with isopropanol followed by diethyl ether. This gives the product as a dark red solid.

Example A19: Reaction scheme: The cationic dye and the amino-substituted nanoparticles obtainable according to Example A10 (250 mg) dimethyl sulfate (1715 g), potassium carbonate (2257 g) and methanol (100 ml) are heated at reflux overnight. The mixture is then cooled to room temperature and the white precipitate is filtered. Then diethyl ether (200 ml) is added and the white precipitate is filtered again. At rest for 1 hour, the filtrate forms a dark red precipitate, which is filtered and washed with diethyl ether to give the product as a dark red solid (170 mg).

Examples A20 and A21: Under the same reaction conditions of Example A19, the products obtainable according to Examples A17 and A18 are treated with dimethyl sulfate (DMS).

Example A22: Reaction scheme: A mixture of the product obtainable according to Example A10 (300 mg) and acetic anhydride (10 ml) is heated at 110 ° C for 2 hours. The mixture is then cooled to room temperature, acetone (30 ml) is added and the formed precipitate is filtered and washed with more acetone followed by diethyl ether to give the product as a red solid (240 mg). The elemental analysis shows C, 27.68; H, 4.31; N, 10.54%.

Example A23: Step 1: Preparation of the compounds of the formula (108) to (110) A dye mixture of the formula (107 (2.0 g), 1,3-diaminopropane (2.22 g) and acetonitrile (15 ml) is heated at 55 ° C for 3 hours.The mixture is then cooled to room temperature, added 50 ml of diethyl ether and the red precipitate is filtered and washed with more diethyl ether to give the aminopropyl-substituted dye.This aminopropyl-substituted dye (500 mg) is then treated with chloroacetyl chloride (220 mg) and triethylamine (327). mg) in acetonitrile (10 ml) and stirred overnight at room temperature, evaporation of the solvent followed by column chromatography (SiO2, eluent H20 / EtOAc / n-BuOH / HC02H) gives the chloroacetamide of the formula (108) as a red solid (320 mg) The compounds of the formulas (109) and (110), with chains of & and Ci2 respectively, are prepared in a similar manner.

Step 2: Preparation of the compound of the formula Cl A mixture of aminopropyl-substituted nanoparticles obtainable according to Example Al (0.4 g, 26.2% dispersion in ethanol), chloroacetamine of the formula (108) (200 mg), potassium carbonate (72 mg) and isopropanol (15 ml) ) is heated at 90 ° C overnight. The mixture is then cooled to room temperature and the precipitate is filtered and washed with isopropanol, acetone and then water. This gives the bound particles of the above formula as a red solid (189 mg). TEM shows monodisperse particles with an average diameter of approximately 40 nm. TGA shows loss of 47.46%, which corresponds to the organic material and the elemental analysis gives C, 24.59; H, 3.68; N, 9.68%.

And A24: Cl The above compound is prepared in analogy to Example A23 using the compound of the formula (110). TGA shows a loss of 41.74%, which corresponds to the organic material. The elemental analysis shows C, 22.93; H, 3.05; N, 4.13. In the additional washing with water, the elemental analysis shows C36.54; H 4.89; N, 6.72%. The TEM analysis shows uniform spheres of 30-40 nm in diameter.

Example A25: Cl The above compound is prepared in analogy to Example A23 using the compound of the formula (109). TGA shows a loss of 38.44%, which corresponds to the organic material. The elemental analysis shows C, 29.62; H, 4.22; N, 8.70%. TEM shows uniform spheres of 30-40 nm.

Example B / Application The firmness to washing the dyed hair is analyzed using the Grays scale according to: Industrial Organic Pigments, Herbst & Hunger, 2nd ed. engl. p. 61, no. 10: DIN 54001-8-1982, "Herstellung und Be derung der Anderung der Farbe", ISO 105-A02-1993.

Example Bl: 50 mg of the functionalized particle is dispersed obtainable according to Example A6 above in 50 g of water. This red dyeing agent is applied to dry hair (two blonde tresses, two medium blondes and two braids on damaged hair) and left to stand for 20 minutes at room temperature. Then, the strands are rinsed under tap water and dried for 12 hours.

Firmness to washing: 10 X washing with shampoo. Results: In the same way, the application of the following dyes to hair gives the following results: Dye of Example A10 Example B3: Example Dye All Example B4: Dye of Example A14 Dye of Example A17 110 Example B6: Dye of Example A21 Example B7: Dye of Example A20 Example B8: Example Dye twenty

Claims (21)

1. CLAIMS 1. Process for dyeing fibers containing keratin, characterized in that it comprises treating the fibers with at least one functionalized particle comprising on the surface an organic chromophore that is joined by a bridge member, wherein the particles are based on SIO2, AI2O3 or mixtures thereof, and the functionalized particles have a positive charge.
2. 2. Process in accordance with the claim 1, characterized in that the functionalized particles comprise, covalently bound to an oxygen atom in the surface, a radical of the formula wherein Ri and R2 are independently hydrogen, particle surface-O-, or a substituent, B is the direct bond or a source member, D is a radical of an organic chromophore, and n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10.
3. Process according to claim 1, characterized in that Ri and R2 are independently hydrogen; Ci-C25alkyl which may be interrupted by -O-, -S- or -N (R3) -; C2-C2-alkenyl; phenyl; C7-Cgphenylalkyl; -OR5; -OR- R5 is hydrogen; Ci-C25alkyl which may be interrupted by -O-, -S- or -N (R3) -; C2-C24alkenyl; phenyl; C7- R8 I8 -S-R9 R Cgphenylalkyl; 10; or a particle surface, R6 and R7 independently of each other are hydrogen; Ci-C25alkyl which may be interrupted by -O-, -S- or -N (R3) -; C2-C24alkenyl; phenyl; C7-C9phenylalkyl; or -OR5, and R8, R9 and Rio independently of each other are hydrogen; Ci-C25alkyl which may be interrupted by -O-, -S- or -N (R3) -; C2-C24alkenyl; phenyl; or C7-C9phenylalkyl.
4. 4. Process according to claim 2 or 3, characterized in that N is 1, 2, 3, 4, 5, 6, 7, or 8, preferably 3.
5. Process according to any of claims 2 to 4, characterized in that B is the direct bond, -O-, -S-, -N (R3) - or a bridge member of the formula -A1-Ci-C25alkylene-A2-, -Ai-Ci-C25alkylene-phenylene -A2- or - ?? - phenylene-Ci-C25alkylene-A2-, where Ai and A2 are the direct bond -O-, -S-, -N (R3) -, -CO-, -O-CO- , -CO-O-, -N (R3) -CO-, -CO-N (R3) -, the Ci-C2-alkylene radical, is uninterrupted or interrupted by at least one of the radicals selected from the group consisting of -O -, -S-, -N (R3) -, -N + (R3) 2-, -CO-, -O-CO-, -CO-0-, -N (R3) -CO-, -CO-N (R3) - and phenylene, and wherein R3 is hydrogen, Ci-Ci2alkyl or Ci-Ci2alkyl substituted with hydroxyl.
6. Process according to any of claims 2 to 5, characterized in that D is preferably the radical of an acridine, anthraquinone, azomethine, monoazo, disazo, polyazo, benzodifuranone, coumarin, diketopyrrolopyrrole, dioxazine, diphenylmethane, formazan, indigoid, methine , polymethine, naphthalimide, naphthoquinone, nitroaryl, oxazine, perinone, perylene, phenazine, phthalocyanine, pyrenequinone, quinacridone, quinoneimine, quinophthalone, stilbene, styryl, thiazine, thioxanthene, triarylmethane, xanthene or a metallic complex dye.
7. Process according to any of claims 2 to 6, characterized in that D is a radical of anthraquinone, monoazo, azomethine, styryl, methine, polymethine, triarylmethane or a metal complex dye.
8. Process according to any of claims 1 to 7, characterized in that the functionalized particles further comprise, covalently bound to an oxygen atom on the surface, a radical of the formula (11) wherein R12 and R13 have the meanings given above under formula (1) for Ri and R2, Rn is Ci-C25alkyl or C2-C24alkenyl, each of which is unsubstituted or substituted by amino, mercapto, phenyl or hydroxyl and is uninterrupted or interrupted by -0-, -S-, -N (Ri4) -, -C0-, -0-C0-, -C0-0-, -N (Ri4) -C0-, -C0-N (Ri4) ) - or phenylene; C5_Ci2cycloalkyl; C5-Ci2cycloalkenyl; or a perimerizable group or a polymer each of which may be linked by a bridge member, and Ri4 is hydrogen or Ci-Ci2 substituted or unsubstituted alkyl.
9. 9. Process according to any of claims 1 to 8, characterized in that the functionalized particles further comprise, covalently bound to an oxygen atom on the surface, a radical of the formula (12) where Ri6 and 17 have the meanings given under formula (1) for Ri and R2, Ri5 is Ci-C25alkyl or C2-C24alkenyl, each of which is unsubstituted or substituted by amino, mercapto, phenyl or hydroxyl and is uninterrupted or interrupted by -0-, -S-, -N (Ri8) -, -N + (R18) 2-, -C0-, -0- C0-, -C0-0-, -N (Ri8) -C0-, -C0-N (Ri8) - or phenylene; C5-Ci2cycloalkyl; C5-Ci2cycloalkenyl; or a polymerizable group or a polymer each of which can be linked by a bridge member, Ri8 is hydrogen or Ci-Ci2 substituted or unsubstituted alkyl, and, wherein Ri5 or Ri8 further comprise a cationic group, preferably a cationic ammonium group .
10. 10. Process according to any of claims 1 to 9, characterized in that the functionalized particles have at least one cationic ammonium group of the formula -N (Ri *) 3, where the three radicals Ri * may have the same or different meanings, and Ri * is hydrogen; Ci-Ci2alkyl which may be interrupted by -0- and which may be substituted by hydroxyl, phenyl, and wherein the phenyl radical may be further substituted by Cx-C8alkyl, Ci-C8alkoxy or halogen; or phenyl which may be substituted by Ci-C8alkyl, Ci-C8alkoxy or halogen.
11. 11. Process according to claim 10, characterized in that Ri * is hydrogen or Ci-Ci2alkyl.
12. 12. Process according to any of claims 1 to 11, characterized in that the functionalized particles have a spherical shape.
13. 13. Process according to any of claims 1 to 12, characterized in that the functionalized particles have an average particle size of 1 to 1000 nm, preferably 1 to 600 nm.
14. Process according to any of claims 1 to 13, characterized in that the functionalized particles have an average particle size of 1 to 20 nm, preferably 1 to 100 nm.
15. 15. Process according to any of claims 1 to 14, characterized in that the functionalized nanoparticles are based on Si02.
16. Process according to any of claims 1 to 15, characterized in that the keratin-containing fibers are treated with at least one functionalized particle as defined in claim 1, or an oxidizing agent and, optionally, an additional direct dye.
17. Process according to any of claims 1 to 16, characterized in that the keratin fibers are treated with at least one functionalized particle as defined in claim 1 and at least one oxidative dye, or the keratin fibers are treated with at least one functionalized particle as defined in claim 1 and at least one oxidative dye and an oxidative agent.
18. 18. Process according to any of claims 1 to 17, characterized in that the fiber containing keratin is a human hair.
19. 19. Functionalized particles, characterized in that they comprise, covalently bound to an oxygen atom on the surface, a radical of the formula wherein the particles are based on Si02, AI2O3 or mixtures thereof, the functionalized particles have a positive charge, Ri and R2 are independently of each other, hydrogen, particle surface (O), or a substituent, B is the direct link or a bridge member, N is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, and D is a radical of the formula -N = NB (2), -N = N B? N = N B2 (4), CH = N B2 (5), CH = N NH B2 (6) B1 CH = CH B2 (7), wherein B3 is unsubstituted or substituted phenylene or naphthylene, and B1 and B2, independently of each other, are optionally substituted phenyl, naphthyl or a heterocyclic group of the formula where Z2 and Z5 are -0-; -S-; or a radical NRn2, Zi, Z3 Z4, Z6, Z7, Z8 and Z9 are independently of each other N or a radical CR113; R100, Rioi, R102, Ri05, Rio6f Ri08 / Rio9 / R110 and Rii3 are independently hydrogen; hydroxy halogen; Ci-Ci2alkyl unsubstituted or substituted; unsubstituted or substituted phenyl; nitrile; C2-C4alkanoylamino; carbamoyl; ureido; sulfonylamino; Ci-Ci2alkylthio; or a radical of the formula -N (Rm) Rn5, -N (Rn4) (Rn5) Rne or -ORu4; R103, R104, R107, Rui and R112 are independently hydrogen; Ci-Ci2alkyl unsubstituted or substituted; or unsubstituted or substituted phenyl; and Rii4í R115 and R116 are independently of each other hydrogen; Ci-Ci2alkyl unsubstituted or substituted; triazinyl or unsubstituted or substituted phenyl.
20. 20. Functionalized particles according to claim 19, characterized in that at least one of the radicals B1 and B2 is a heterocyclic group selected from the formulas (3a) to (3j).
21. 21. Functionalized particles according to claim 19 or 20, characterized in that Ri03, R104, Rio? / Rm and R112 are Ci-Ci2alkyl, preferably Ci-C4alkyl.