EP1858476A1 - Method for increasing the color intensity of colorations on keratin-containing substrates - Google Patents

Abstract

The invention relates to a method for increasing the color intensity of colorations of keratin-containing fibers, especially human hair, by using SiO2 compounds. These colorations are obtained by using the color-imparting substances (a) at least one direct dye and/or (b) at least one combination from (A) at least one reactive carbonyl compound and (B) at least one compound selected from the group including (i) CH-acidic compounds and (ii) compounds carrying a primary or secondary amine group or hydroxy group, selected from the primary or secondary aromatic amines, nitrogenated heterocyclic compounds and aromatic hydroxy compounds.

Description

Color intensification of stains on keratin-containing substrate

The present invention relates to the use of optionally hydrated SiO ₂ compounds for increasing the color intensity, corresponding means for coloring keratin-containing fibers and a hair dyeing process. The funds included

(a) at least one substantive dye and / or

(b) at least one combination of

A is at least one reactive carbonyl compound (component A), and B is at least one compound (component B) selected from the group consisting of (i) CH-acidic compounds and (ii) compounds having a primary or secondary amino group or hydroxy group, selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds and additionally at least one optionally hydrated SiO ₂ compound and is free of oxidizing agents.

Human hair is treated today in a variety of ways with hair cosmetic preparations. These include, for example, the cleansing of hair with shampoos, the care and regeneration with rinses and cures, and the bleaching, dyeing and shaping of the hair with colorants, tinting agents, waving and styling preparations. In this case, means for changing or nuancing the color of the head hair play a prominent role.

For permanent, intensive colorations with corresponding fastness properties, so-called oxidation colorants are used. Such colorants usually contain oxidation dye precursors, of the so-called developer type

(Developer component) and coupler type (coupler component). The developer components form under the influence of oxidants or of atmospheric oxygen with one another or under coupling with one or more Coupler components from the actual dyes. The oxidation stains are characterized by excellent, long lasting staining results.

Finally, further dyeing has received much attention. In this method, precursors of the natural hair dye melanin are applied to the hair; These then form naturally-analogous dyes in the course of oxidative processes in the hair. Such a process with 5,6-dihydroxyindoline as dye precursor was described in EP-B1-530 229. In particular, multiple use of agents with 5,6-dihydroxyindoline, it is possible to reproduce natural hair color to people with graying hair. The permanent coloration can be done with atmospheric oxygen as the sole oxidant, so that no further oxidizing agent must be resorted to.

For temporary dyeings usually dyeing or tinting agents are used which contain so-called direct drawers as a coloring component. These are dye molecules that attach directly to the hair and do not require an oxidative process to form the paint. These dyes include, for example, the henna already known from antiquity for coloring body and hair. These dyes are usually sensitive to shampooing, so that a much undesirable nuance shift or even a visible "discoloration" can occur.

One way to semipermanently keratinate fibers containing keratin provides the use of coloring agents containing a combination of component

A reactive carbonyl compounds, i. Compounds with at least one reactive

Carbonyigruppe, and component

B Compounds selected from (i) CH-acidic compounds, (ii) compounds having primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, (iii) amino acids, (iv) from 2 contain up to 9 amino acids constructed oligopeptides. The aforementioned components A and B are generally not themselves dyes, and therefore are not suitable alone for dyeing keratinhaltiger fibers alone. Components A and B are referred to below as Oxofarbstoffvorprodukte. The oxo dyeing is used for example in the Publications WO-A1 -99 / 18916, WO-A1 -00 / 38638, WO-A1-01 / 34106 and WO-A1-01 / 4,7483.

The publications WO-A2-99 / 18916 and WO-A1 -01 / 47483 disclose the use of onium aldehydes and ketones, in particular of 2- or 4-formyl-1-methylquinolinium compounds, for dyeing keratin-containing fibers which in combination with compounds having a primary or secondary amino group or hydroxyl group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, and / or CH-acidic compounds. ,

Increasing the color intensity of dyeings on keratin-containing substrate is permanently the focus of the development of colorants. Colorants with color intensifying agent are economically interesting. Although a color intensification allows the increase in intensity with the same amount of dye, but a reduction in the dye content in the colorant with the same color result also provides a delightful and economical use of inexpensive Farbintensivierungsagenzien.

So far, some color intensifying agents have been proposed in the art. Many of these agents affect the dye formation during oxidative dyeing and catalyze the oxidative coupling of the oxidation dye precursors. Little is known about a color intensification of non-oxidative dyeing systems with direct dyes or oxo dye precursors.

From the document EP-A1-873 745 hair dyes are known which contain in addition to Oxofarbstoffvorprodukten at least one color enhancer selected from piperidine, pyridine, imidazole, pyrrolidine, pyrrolidone, pyrazole, triazole, piperazidine, their derivatives and their physiologically acceptable salts.

The document EP-A1-1 242 039 relates to oxidative hair dyes which, in addition to oxidation dye precursors, contain at least one optionally hydrated Si (V compound. The agents cause a reduction in the damage to keratinic fibers, in particular human hair, by oxidative processes. The object of the present invention is to provide colorants for keratin-containing fibers, which bring about a color intensification on the basis of non-oxidative dyeing systems.

It has surprisingly been found that colorants without additional oxidant containing at least one substantive dye and / or a combination of at least one component A reactive carbonyl compounds, i. Compounds with at least one reactive

Carbonyl group, and at least one component B compounds selected from (i) CH-acidic compounds, (ii) compounds having primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic

Compounds and aromatic hydroxy compounds, have an increased color intensity, if they additionally contain at least one optionally hydrated SiO ₂ compound.

A first subject of the invention are therefore agents for coloring keratin-containing fibers, in particular human hair, in a cosmetically acceptable carrier as coloring substances

(a) at least one substantive dye and / or

(b) at least one combination of

A is at least one reactive carbonyl compound (component A), and B is at least one compound (component B) selected from the group consisting of (i) CH-acidic compounds and (ii) compounds having a primary or secondary amino group or hydroxy group, selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds and additionally

(C) at least one optionally hydrated SiO ₂ compound, with the proviso that no oxidizing agent for the coloring substances (a) and / or (b) is included.

According to the invention, keratin-containing fibers are understood to mean furs, wool, feathers and in particular human hair. Although the inventive Colorants are primarily suitable for dyeing keratinic fibers, is in principle a use in other fields of coloration nothing contrary, as long as doing the technical problem underlying the invention is achieved.

With regard to the optionally hydrated SiO ₂ compounds, the present invention is in principle subject to no restrictions. Preference is given to silicic acids, their oligomers and polymers and their salts. Preferred salts are the alkali salts, especially the potassium and sodium salts. The sodium salts are very particularly preferred.

The optionally hydrated SiO ₂ compounds can be present in various forms. According to the invention, the SiO ₂ compounds are preferably used in the form of silica gels (silica gel) or as water glass.

Particularly preferred according to the invention are water glasses which are formed from an aqueous solution of a silicate of the formula (SiO ₂ ) n (Na ₂ O) _m (K ₂ O) _p , where n is a positive rational number and m and p are independent of one another for a positive rational number or for 0, with the provisos that at least one of the parameters m or p is different from 0 and the ratio between n and the sum of m and p is between 1: 4 and 4: 1.

In addition to the components described by the empirical formula, the water glasses in small amounts may contain other additives, such as phosphates or magnesium salts.

According to the invention particularly preferred water glasses are sold by the company. Henkel sold under the names Ferrosil® ^® 119, soda water glass 40/42, Portil ^® A, Portil ^® AW and Portil ^® W and by Akzo under the name Britesil® ^® C20.

Although even small amounts of the optionally hydrated SiO ₂ compounds cause the color intensification, it may be preferred according to the invention, the optionally hydrated SiO ₂ compounds in amounts of 0.05 wt .-% to 5 wt .-%, particularly preferably in amounts of 0.15 wt .-% to 2 wt .-% and most preferably in amounts of 0.2 wt .-% to 1.5 wt .-%, each based on the total application preparation to use. The quantities given here in each case the content of the SiO ₂ compounds (without water content) in the application preparations again. The direct dyes of the invention are selected from the group formed from nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Particularly preferred substantive dyes are those under the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 well-known compounds as well 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5 -chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine n-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4- Ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

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

(a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,

(b) aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as

(C) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as mentioned for example in EP-A2-998 908, to which reference is explicitly made at this point in claims 6 to 11 are called. Preferred cationic substantive dyes of group (c) are in particular the following compounds:

CH ₃ SO ₄ ^"

Cl ^"

The compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic substantive dyes of group (c).

The cationic direct dyes which are sold under the brand Arianor® ^® are, according to the invention also very particularly preferred cationic direct dyes. The agents according to the invention preferably contain the substantive dyes in an amount of from 0.01 to 20% by weight, based on the total colorant.

Reactive carbonyl compounds as component A according to the invention have at least one carbonyl group as a reactive group which reacts with the compounds of component B to form a covalent bond to the carbonyl carbon atom. Preferred reactive carbonyl compounds are aldehydes and ketones. Furthermore, according to the invention, those compounds are also usable as component A in which the reactive carbonyl group is derivatized or masked in such a way that the reactivity of the carbon atom of the derivatized carbonyl group with the CH-acidic compounds of the formula I is always present. These derivatives are preferably addition compounds a) of amines and their derivatives to form imines or oximes as addition compound b) of alcohols to form acetals or ketals as addition compound c) of water to form hydrates as addition compound (component A is derived in this case c) from an aldehyde) to the carbon atom of the carbonyl group of the reactive carbonyl compound.

Preferred reactive carbonyl compounds of component A are selected from the group consisting of benzaldehyde and its derivatives, naphthaldehyde and its derivatives, cinnamaldehyde and its derivatives, 2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolizine 9-carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, N-ethylcarbazole-3-aldehyde, 2-formylmethylene-1,3,3- trimethylindoline (Fischer's aldehyde or tribasic aldehyde),

2-indolaldehyde, 3-indolaldehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 2- (1 ', 3', 3'-trimethyl-2-indolinylidene) -acetaldehyde, 1-methylpyrrole-2 aldehyde, 4-pyridinealdehyde, 2-pyridinaldehyde, 3-pyridine aldehyde, pyridoxal, antipyrine-4-aldehyde, furfural, 5-nitofurfural, 2-thenoyl-trifluoro-acetone, chromone-3-aldehyde, 3- ( 5'-nitro-2'-furyl) -acrolein, 3- (2'-furyl) -acrolein and imidazole-2-aldehyde, 5- (4-dimethylaminophenyl) -penta-2,4-dienal, 5- (4- Diethylaminophenyl) penta-2,4-dienal, 5- (4-methoxyphenyl) penta-2,4-dienal, 5- (3,4-dimethoxyphenyl) penta-2,4-dienal, 5- (2,4-dimethoxyphenyl ) penta-2,4-dienal, 5- (4-piperidinophenyl) penta-2,4-dienal, 5- (4-morpholinophenyl) penta-2,4-dienal, 5- (4-pyrrolidinophenyl) penta-2, 4-dienal, 5- (4-dimethylamino-1-naphthyl) penta-3,5-dienal, 9-methyl-3-carbazolaldehyde, 9-ethyl-3-carbazolaldehyde, 3-acetylcarbazoI, 3,6-diacetyl 9-ethylcarbazole, S-acetyl-θ-methylcarbazole, 1,4-dimethyl-3-carbazolaldehyde, 1,4,9-trimethyl-3-carbazolaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2.5- Dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid, 4-formyl-1-methylpyridinium, 2-formyl-1-methylpyridinium, 4-formyl-1-ethylpyridine-2-formyl-1 ethyl pyridinium, 4-formyl-1-benzylpyridinium, 2-formyl-1-benzylpyridinium, 4-formyl-1,2-dimethylpyridinium, 4-formyl-1,3-dimethylpyridinium, 4-formyl-1-methylquinolinium , 2-formyl-1-methyl-quinolinium, 5-formyl-1-methyl-quinolinium, 6-formyl-1-methyl-quinolinium, 7-formyl-1-methyl-quinolinium, 8-formyl-1-methyl-quinolinium, 5-formyl i-ethylquinolinium, 6-formyl-i-ethylquinolinium, 7-formyl-1-ethylquinolinium, 8-formyl-i-ethylquinolinium, 5-formyl-1-benzylquinolinium, 6-formyl-i-benzylquinolinium, 7 -Formyl-i-benzylquinolinium, 8-formyl-1-benzylquinolinium, 5-formyl-i-allylquinolinium, 6-formyl-i-allylchino linium, 7-formyl-1-allyl-quinolinium and 8-formyl-i-allyl-quinolinium-benzenesulfonate, p-toluenesulfonate, methanesulfonate, perchlorate, sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfate, trifluoromethanesulfonate, tetrafluoroborate, isatin, 1-methylisatin, 1-allyis isatin, 1-hydroxymethylisatin, 5-chloro-isatin, 5-methoxy-isatin, 5-nitroisatin, 6-nitro- isatin, 5-sulfoisidine, 5-carboxyisatin, quinisatin, 1-methylquinisatin, and any mixtures of the above compounds.

Benzaldehyde, cinnamic aldehyde and naphthaldehyde and their derivatives, in particular having one or more hydroxyl, alkoxy or amino substituents, are very particularly preferably used as the reactive carbonyl compound in the agents according to the invention. Again, the compounds according to formula (B-1) are preferred,

wherein R ¹ , R ² and R ³ independently represent a hydrogen atom, a halogen atom, a C _r C ₆ alkyl group, a hydroxy group, a C ₁ -C ₆ alkoxy group, a C ₁ -C ₆ dialkylamino group, a di (C ₂ -C ₆ - hydroxyalkyl) amino group, a DKCrCe-alkoxy-CrCe-alkytyaminoguppe, a C ₁ -C ₆ -hydroxyalkyloxy group, a sulfonyl group, a carboxyl group, a sulfonic acid group, a sulfonamido group, a sulfonamide group, a carbamoyl group, a C ₂ -C ₆ acyl group, a Acetyl group or a nitro group,

Tl is a direct bond or a vinylene group,

• R ⁴ and R ⁵ represent a hydrogen atom or together form, together with the remainder of the molecule, a 5- or 6-membered aromatic or aliphatic ring.

The derivatives of the benzaldehydes, naphthaldehydes or cinnamaldehydes of the reactive carbonyl compound according to component A are preferably selected from A-hydroxy-3-methoxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-hydroxy-1-naphthaldehyde, 4-hydroxy-2 -methoxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 3-bromo-4-hydroxybenzaldehyde, 4-hydroxy 3-methylbenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 5-bromo-4-hydroxy-3-methoxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, coniferylaldehyde, 2-methoxybenzaldehyde , 3-

Methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxy-benzaldehyde, A-hydroxy-2,5-dimethoxy-benzaldehyde, 4-hydroxy-2,6 dimethoxybenzaldehyde, A-hydroxy-2-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 3,5-Diethoxy-4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxy-benzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2-ethoxy-4- hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5- Dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-drmethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3,6-trimethoxybenzaldehyde, 2,4,6- Trimethoxybenzaldehyde, 2,4,5-

Trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,4-dihydroxy-3-methyl-benzaldehyde, 2,4- Dihydroxy-5-methylbenzaldehyde, 2,4-dihydroxy-6-methylbenzaldehyde, 2,4-dihydroxy-3-methoxybenzaldehyde, 2,4-dihydroxy-5-methoxybenzaldehyde, 2,4-dihydroxybenzaldehyde 6-methoxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4- Dihydroxybenzaldehyde, 3,4-dihydroxy-2-methylbenzaldehyde, 3,4-dihydroxy-5-methylbenzaldehyde, 3,4-dihydroxy-6-methylbenzaldehyde, 3,4-dihydroxy-2-methoxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,5, 6-trihydroxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 3,5-dichloro-4- hydroxybenzaldehyde, 4-hydroxy-3,5-diiodobenzaldehyde, 3-chloro-4-hydroxybenzaldehyde, 5-chloro-3,4-dihydroxybenzaldehyde, 5-bromo-3,4-dihydroxybenzaldehyde, 3-chloro-4-hydroxybenzaldehyde 5-methoxybenzaldehyde, 4-hydroxy-3-iodo-5-methoxybenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde , 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, A-dimethylamino-1-naphthaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, A Nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde , 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3-nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2.6 Dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 4,5-dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo 3-nitrosalicylaldehyde, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 4-dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde , 4-diethylamino-cinnamaldehyde, 4-dibutylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4- (1-imidazolyl) benzaldehyde and piperonal. These representatives are also the most preferred additional reactive carbonyl compounds of component A.

As CH-acidic compounds are generally considered those compounds which carry a bound to an aliphatic carbon atom hydrogen atom, wherein due to electron-withdrawing substituents, activation of the corresponding carbon-hydrogen bond is effected. The CH-acidic compounds of component B are preferably selected from the group consisting of with physiologically compatible anions, particularly p- Tpluolsulfonaten, methanesulfonates, hydrogen sulfates, tetrafluoroborates and ^• halides such as the chlorides, bromides and iodides, salts of the 1 formed, 4- Dimethylquinolinium, 1-ethyl-4-methyl-quinolinium, 1-ethyl-2-methylquinolinium, 1, 2,3,3-tetramethyl-3H-indolium, 2,3-dimethylbenzothiazolium, 2,3-dimethylnaphtho [ 1,2-d] thiazolium, 3-ethyl-2-methyl-naphtho [1,2-d] thiazolium, 3-ethyl-2-methylbenzoxazolium, 1,2,3-trimethylquinoxaluminum, 3-ethyl-2- Methyl-benzothiazolium, 1, 2-Dihydro-1, 3,4,6-tetramethyl-2-oxopyrimidinium, 1,2-dihydro-1,3,4-trimethyl-2-oxopyrimidinium, 1, 2 Dihydro-4,6-dimethyl-1,3-dipropyl-2-oxopyrimidinium, 1,2-dihydro-1,3,4,6-tetramethyl-2-thioxopyrimidinium, 1,2-dihydro-1, 3,4,5,6-pentamethyl-2-oxopyrimidinium, 2,5-dimethyl-3- (2-propenyl) -1, 3,4-thiadiazolium, 3-E ethyl 2,5-dimethyl-1,3,4-thiadiazolium, 1,2-dimethylquinolinium and 1,3,3-trimethyl-2-methylenindoline (Fischer's base), oxindole, 3-methyl-1-phenyl-pyrazoline 5-one, indan-1, 2-dione, indan-1, 3-dione, indan-1-one, 2-amino-4-imino-1,3-thiazoline hydrochloride, benzoylacetonitrile, 3-dicyanomethylenindan-1 on, 2- (2-furanoyl) acetonitrile, 2- (2-theonyl) acetonitrile, 2- (cyanomethyl) benzimidazole, 2- (cyanomethyl) benzothiazole and 2- (2,5-dimethyl-3-furanoyl) acetonitrile.

The preferred representatives of the compounds of component B which is selected from the compounds having primary or secondary amino group or hydroxyl group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds are mentioned below:

It may be preferred according to the invention to use as component B a p-phenylenediamine derivative or one of its physiologically acceptable salts. Particular preference is given to p-phenylenediamine derivatives of the formula (E1)

(E1) G ¹ represents a hydrogen atom, a C ₁ - to C ₄ alkyl, C ₁ - to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ alkoxy ( C ₁ - to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;

G ² represents a hydrogen atom, a C ₁ - to C ₄ alkyl, C ₁ - to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ alkoxy ( C ₁ - to C ₄ ) -aikylrest or a C ₁ - to C ₄ -alkyl radical which is substituted with a nitrogen-containing group;

G ³ represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ Polyhydroxyalkyl, C ₁ to C ₄ hydroxyalkoxy, C ₁ to C ₄ acetylaminoalkoxy, C ₁ to C ₄ mesylaminoalkoxy or C ₁ to C ₄ carbamoylaminoalkoxy;

G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ - to C ₄ -alkyl radical or, when G ³ and G ⁴ are ortho to one another, they may together form a bridging α, ω-alkylenedioxy group, for example an ethylenedioxy group.

Examples of the C ₁ - to C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ -C ₄ -alkoxy radicals which are preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C ₁ to C ₄ hydroxyalkyl group, there may be mentioned a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ to C ₄ polyhydroxyalkyl group is the 1, 2-dihydroxyethyl group. Examples of halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived according to the invention from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are in particular the amino groups, C ₁ to C ₄ monoalkylamino groups, C ₁ to C ₄ dialkylamino groups, C ₁ to C ₄ trialkylammonium groups, C ₁ to C ₄ monohydroxyalkylamino groups, Imidazolinium and ammonium. Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-rhenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino 3-methyl- (N, N-diethyl) -aniline, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) -amino-2- methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2- Fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2 - (.beta.-hydroxyethyloxy) -p-phenylenediamine, 2- (.beta Acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine and 5,8-diaminobenzo-1, 4-dioxane and their physiologically acceptable salts.

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

It may further be preferred according to the invention to use as component B compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.

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

Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ -ReSt which is optionally substituted by a C ₁ - to C ₄ -alkyl radical, by a C _r to C ₄ -hydroxyalkyl radical and / or by a bridge Y or which is optionally part of a bridging ring system, the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which is one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, Sulfur or nitrogen atoms may be interrupted or terminated and may be substituted by one or more hydroxyl or C ₁ to C ₈ alkoxy radicals, or a direct bond,

G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -hydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a direct compound for bridging Y,

G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a C _r to C ₄ -alkyl radical, with the proviso that the compounds of the formula ( E2) contain only one bridging Y per molecule.

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

Preferred binuclear components B of the formula (E2) are in particular: N, N'-bis- (β-hydroxyethyl-N, N'-bis-C 1 -aminophenyl O-I, S-diamino-propane, -ol, N, N ' Bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) - tetramethylenediamine, N, N ¹ -bis- (.beta.-hydroxyethyl) -N, N'-bis (4-aminophenyl) - tetramethylenediamine, N, N ^l-bis- (4-methyl-aminophenyl)) - tetramethylenediamine, N ₁ N-diethyl-N, N ¹ -bis (4'-amino-3 ^1- methylpyhenyl)) ethyl) -endiamine, bis (2-hydroxy-5-aminophenyl) -methane, N, N'-bis - (4'-aminophenyl) -1,4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) -piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1, 10 Bis (2 ^l , 5'-diaminophenyl) -1, 4,7 ₎ 10-tetraoxadecane and its physiologically acceptable salts.

Very particularly preferred components B binuclear of formula (E2) are N, N'-bis (.beta.-hydroxyethyl) -N, N ^l -bis (4-aminophenyl) -1, 3-diamino-propan-2-ol, Bis- (2-hydroxy-5-aminopheny-O-methane, 1,3-bis (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4-aminophenyl) -1, 4- diazacycloheptane and 1, 10-bis (2,5-diaminophenyl) -1, 4,7, 10-tetraoxadecane or one of their physiologically acceptable salts.

Furthermore, it may be preferred according to the invention to use as component B a p-aminophenol derivative or one of its physiologically acceptable salts. Particular preference is given to p-aminophenol derivatives of the formula (E3)

in which:

G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -mohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalky, a (C ₁ - to C ₄ ) - , alkyl alkoxy (C _r to C ₄₎ a C ₁ - to C ₄ aminoalkyl radical, a hydroxy (C _r -C ₄₎ -a) ky) amino group, a C ₁ - to C ₄ -Hydroxyalkoxyrest, a C ₁ - to C ₄ - Hydroxyalky) - (Crbis C ₄₎ aminoalkyl radical or a (di-C ₁ - to C ₄ -alkylamino) - (C _r to C alkyl group _4), and

G ¹⁴ represents a hydrogen or halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical _; a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ alkoxy (C _r to C ₄₎ alkyl group, a C ₁ - to C ₄ aminoalkyl radical or a C ₁ - to C ₄ - cyanoalkyl, G ¹⁵ is hydrogen, C ₁ - to C ₄ alkyl, C ₁ - to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and

G ¹⁶ is hydrogen or a halogen atom.

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

Preferred p-aminophenols of the formula (E3) are, in particular, p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) -phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino 2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) phenol, 4-amino-2- (α, β-dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2 chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) phenol and their physiologically acceptable salts.

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

Further, component B may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

Furthermore, the component B may be selected from heterocyclic compounds, such as the pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiologically acceptable salts.

Preferred pyridine derivatives are in particular the compounds described in the patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino-pyridine, 2- (4-methoxyphenyl) -amino-3-arnino-pyridine, 2,3-diamino-6-methoxy-pyridine, 2- (β-

Methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine. Preferred pyrimidine derivatives are, in particular, the compounds described in the German 'patent DE 2 359 399, the Japanese patent application JP 02019576 A2 or in the publication WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, ^ -hydroxy ^ .δ.e-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2 ₎ 4-dihydroxy-5,6-diaminopyrimidine and 2,5,6- triaminopyrimidine.

Preferred pyrazole derivatives are, in particular, the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988, such as 4,5 Diamino-i-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4.5- Diamino-1, 3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-Benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4, 5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole , 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4, 5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3 -methyl-1-isopropylpyrazole, 4-amino-5- (β-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5

Triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole, and 3, 5-diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole.

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

G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ Polyhydroxyalkylrest a (C ₁ - to C ₄ J -oxyalky- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical, which is optionally substituted by an acetyl-ureide or a sulfonyl radical may be protected, a (C ₁ - to C ₄ ) -alkylamino (C _r to C ₄ ) -alkyl radical, a di - [(C _r to C ₄ ) -alkyl] - (Cr to C ₄ ) -aminoalkyl radical, wherein the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C _r to C ₄ ) -aminoalkyl radical, the X radicals independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ - Polyhydroxyalkyl, a C ₁ - to C ₄ -Aminoalkylrest, a (C ₁ - to C ^ -Alkylamino ^ Cr to C ₄ ) alkyl, a di - [(C _r to C ₄ ) alkyl] - (C ₁ - bis C ₄ ) aminoalkyl radical, wherein the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl or a di- (C ₁ - to C ₄ - hydroxyalkyl) aminoalkyl radical , an amino radical, a C ₁ - to C ₄ -alkyl - or di- (C ₁ - to C ₄ -hydroxyalkyl) -amino, a halogen atom, a carboxylic acid group or a sulfonic acid group, i has the value 0, 1, 2 or 3, p has the value 0 or 1, q has the value 0 or 1 and n has the value 0 or 1, with the proviso that the sum of p + q is not 0, if p + q is 2, n is 0, and the groups NG ^{17 are} G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7); when p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

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

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

Among the pyrazolo [1, 5-a] pyrimidines of the above formula (E4) may be mentioned in particular:

Pyrazolo [1,5-a] pyrimidine-3,7-diamine;

2,5-dimethyl-pyrazolo [1,5-a] pyrimidine-3,7-diamine;

Pyrazolo [1,5-a] pyrimidine-3,5-diamine;

2,7-dimethyl-pyrazolo [1,5-a] pyrimidine-3,5-diamine;

3-aminopyrazolo [1,5-a] pyrimidin-7-ol;

3-aminopyrazolo [1,5-a] pyrimidin-5-ol;

2- (3-aminopyrazolo [1,5-a] pyrimidin-7-yl amino) ethanol;

2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol;

2 - [(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol;

2 - [(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol;

5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;

2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;

3-amino-7-dimethylamino-2,5-dimethylpyrazolo [1,5-a] pyrimidine; and their physiologically acceptable salts and their tautomeric forms when a tautomeric equilibrium is present.

The pyrazolo [1, 5-a] pyrimidines of the above formula (E4) can be prepared as described in the literature by cyclization starting from an aminopyrazole or from hydrazine.

In a further preferred embodiment, the colorants according to the invention contain at least one coupler component.

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used. Particularly suitable as coupler substances are 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol cinomonomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2 ' _l 4'-diaminophenoxy) -propane, 2-chloro resorcinol, 4-chloro-resorcinol, 2-chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, ₁ -methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

Furthermore, the following compounds are preferred as component B: m-aminophenol and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4 - aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5 - (2'-hydroxyethyl) -amino-2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1, 3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino-4- methylphenol and 2,4-dichloro-3-aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as, for example, 2,4-diaminophenoxyethanol, 1,3-bis- (2 ', 4'-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1, 3-bis (2 ', 4'-diaminophenyl) -propane, 2,6-bis (2'-hydroxyethylamino ) -1-methylbenzene, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2- methoxy-5-methylphenol yl} amino) ethanol, 2- [3-morpholin-4-ylphenyl) amino] ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine and 1-amino-3-bis- (2'-hydroxyethyl ) - aminobenzene, o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,

Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene, pyridine derivatives such as 2,6-dihydroxypyridine , 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy 4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine, naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2- Hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene, Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,

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

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

Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,

Pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2- Amino-4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or

Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene and their physiologically acceptable salts.

The above-mentioned compounds component A and component B are each preferably used in an amount of 0.03 to 65 mmol, especially 1 to 40 mmol, based on 100 g of the total colorant.

Furthermore, the preparations of the invention may also naturally occurring dyes such as henna red, henna neutral, henna black, chamomile, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and alkano root are included.

It is not necessary that the substantive dyes or the compounds of component B are each uniform compounds. Rather, in the hair colorants according to the invention, due to the production process for the individual dyes, in minor amounts, further components may be included, as far as they do not adversely affect the dyeing result or for other reasons, e.g. toxicological, must be excluded.

With regard to the dyes which can be used in the hair dyeing and tinting compositions according to the invention, reference is expressly made to the monograph Ch. Zviak, The Science of Hair Gare, Chapter 7 (pages 248-250, direct dyes) and Chapter 8, pages 264-267; Oxidation dye precursors), published as Volume 7 of the series "Dermatology" (Editor: Ch., Culnan and H. Maibach), published by Marcel Dekker Inc., New York, Basel, 1986, as well as the "European inventory of cosmetic raw materials", published by the European Community, available in disk form from the Federal Association of German industrial and commercial enterprises for pharmaceuticals, health products and personal care registered association, Mannheim, reference is made.

A cosmetically acceptable carrier is understood in particular to be an otherwise customary carrier of agents for coloring human hair. The colorants according to the invention may be composed with regard to the features essential to the invention according to known colorants or contain them for these conventional ingredients. Examples of further suitable and inventively preferred ingredients are given below.

The agents according to the invention preferably contain the components according to the invention in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose of hair coloring, such carriers are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions, such as, for example, shampoos, foam aerosols or other preparations which are suitable for use on the hair. But it is also conceivable to integrate the dye precursors in a powdered or tablet-shaped formulation.

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

The colorants of the invention may further contain all known for such preparations active ingredients, additives and excipients. In many cases, the colorants contain at least one surfactant, wherein in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proved to be advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants. Suitable anionic surfactants in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic 'group such. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and the mono-, di- and Trialkanolammoniumsalze with 2 or 3 C atoms in the alkanol group, linear fatty acids having 10 to 22 carbon atoms (soaps ), Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group having 10 to 22 C atoms and x = 0 or 1 to 16,

Acylsarcosides having 10 to 18 carbon atoms in the acyl group, acyl taurides having 10 to 18 carbon atoms in the acyl group, acyl isethionates having 10 to 18 carbon atoms in the acyl group, sulfosuccinic acid mono- and dialkyl esters having 8 to 18 carbon atoms in the acyl group Alkyl group and sulfosuccinic acid monoalkylpolyoxyethyl esters having 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 12 to 18 C atoms, linear alpha-olefin sulfonates having 12 to 18 C atoms, alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 C atoms, alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group having 10 to 18 C atoms and x = 0 or 1 to 12,

Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene-propylene glycol ethers according to DE-A-37 23 354,

Sulfonates of unsaturated fatty acids having 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,

Esters of tartaric acid and citric acid with alcohols which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 carbon atoms. Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid , Isostearic acid and palmitic acid.

Nonionic surfactants contain as hydrophilic group z. B, a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such compounds are, for example

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,

C ₂ -C ₂₂ -fatty acid mono- and diesters of addition products of 1 to 30 mol of ethylene oxide with glycerol,

C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs and

Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil.

Preferred nonionic surfactants are alkyl polyglycosides of the general formula R ¹ O- (Z) _x . These connections are identified by the following parameters.

The alkyl radical R ¹ contains 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and methyl-branched in the 2-position aliphatic see radicals. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. When using so-called "oxo-alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The alkyl polyglycosides which can be used according to the invention can contain, for example, only one particular alkyl radical R ¹ . Usually, however, these compounds are prepared starting from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the particular work-up of these compounds. Particularly preferred are those alkylpolyglycosides in which R ¹ -, substantially from C ₈ - and C-io-alkyl groups, ^ - consisting essentially of C ₁₂ - and C ₁₄ -alkyl groups, consisting essentially of C ₈ - to C ₁₆ -alkyl groups or. consists essentially of C ₁₂ - to C ₁₆ -alkyl groups.

As sugar building block Z it is possible to use any desired mono- or oligosaccharides. Usually, sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain on average from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. Very particular preference is given to alkyl glycosides in which x is 1: 1 to 1, 4.

In addition to their surfactant action, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. The person skilled in the art will therefore prefer to use this substance class as a further constituent of the preparations according to the invention in the event that an effect of the perfume oil on the hair which exceeds the duration of the hair treatment is desired.

The alkoxylated homologs of said alkyl polyglycosides can also be used according to the invention. These homologs may contain on average up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.

Furthermore, zwitterionic surfactants can be used, in particular as cosurfactants. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ^H or -SO ₃ ^H group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N, N-dimethylammonium glycinates, for example the cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinates, for example the cocoacylaminopropyldimetic acid. thylammonium glycinate, and 2-alkyl-3-carboxy-methyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethyl hydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Also particularly suitable as co-surfactants are ampholytic surfactants. Ampholytic surfactants are understood as meaning surface-active compounds which, in addition to a C ₈ -C ₁₈ -alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and for the formation of internal Salts are capable. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkyl aminopropionate, cocoacylaminoethyl aminopropionate and C ₂ i ₈ acyl sarcosine.

According to the invention, the cationic surfactants used may in particular be those of the quaternary ammonium compounds, esterquats and amidoamines type.

Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred esterquats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are, for example, under the brand names Stepantex® ^{®, ®} and Dehyquart® Armocare® ^® distributed. The products Armocare ^® VGH-70, a N, N-bis (2-Palmitoyloxy- efhyl) dimethylarrιmoniumchlorid, as well as Dehyquart ^® F-75 and Dehyquart ^® AU-35 are examples of such esterquats.

The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. An inventively particularly suitable compound from this group of substances that available under the brand Tegoamid ^® S 18 commercially stearamidopropyl dimethylamine is.

Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.

Also suitable in the present invention are cationic silicone oils such as the commercially available products Q2-7224 (manufactured by Dow Coming, a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® - Quat 3270 and 3272 (manufacturer: Th Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80.).

An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ^® 100, according to INCI nomenclature a "lauryl methyl GIu- Ceth-10 hydroxypropyl dimonium chloride".

The compounds used as surfactant with alkyl groups may each be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that substance mixtures having different alkyl chain lengths depending on the respective raw material are obtained.

In the case of the surfactants which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. Under "normal" homolog distribution are thereby Mixtures of homologs obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrowed homolog distributions, on the other hand, are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with narrow homolog distribution may be preferred.

Furthermore, the colorants of the invention can be further active ingredients, auxiliary and

Additives, such as, for example, nonionic polymers, for example vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes,

cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl-ammonium chloride copolymers, diethyl sulfate-quaternized dimethylaminoethylmethacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as Acrylamidopropyltri- methyTammoniumchlorid / acrylate copolymers ^"and Octylacryfamid / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers,

anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert. Butyl acrylamide terpolymers,

amphiphilic polymers, such as, for example, the polymers according to the INCI names Acrylates / Beheneth-25 Methacrylate Copolymer, Acrylates / C10-30 Alkyl Acrylate Crosspolymer, Acrylates / Ceteth-20 Itaconate Copolymer, Acrylates / Ceteth-20 Methacrylate Copolymer, Acrylates / Laureth- 25 Methacrylate Copolymer, Acrylates / Palmeth-25 Acrylate Copolymer, Acrylates / Palmeth-25 Itaconate Copolymer, Acrylates / Steareth-50 Acrylate Copolymer, Acrylates / Steareth-20 Itaconate Copolymer, Acrylates / Steareth-20 Methacrylates Copolymer, Acrylates / Stearyl Methacrylate Copolymer, Acrylates / Vinyl Isodecanoate Crosspolymer,

Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. Bentonite or fully synthetic hydrocolloids such as e.g. polyvinyl alcohol,

Structural agents such as maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins,

Protein hydrolysates, in particular elastin, collagen, keratin, milk protein,

Soy protein and wheat protein hydrolysates, their condensation products with

Fatty acids and quaternized protein hydrolysates,

Perfume oils, dimethylisosorbide and cyclodextrins,

Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,

- Fiber structure improving agents, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate

Defoamers like silicones,

Antidandruff active ingredients such as Piroctone Olamine, zinc Omadine and Climbazole, light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,

Substances for adjusting the pH, such as, for example, customary acids, in particular edible acids and bases,

Active ingredients such as allantoin, pyrrolidonecarboxylic acids and their salts, and bisabolol,

Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,

Plant extracts such as extracts of green tea, oak bark, stinging nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, lime blossom, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, Coconut, mango, apricot, lime, wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, toadstool, coltsfoot, marshmallow, meristem, ginseng and ginger root ,.

- cholesterol,

Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as spermaceti, beeswax, montan wax and paraffins,

Fatty acid alkanolamides,

Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids, swelling and penetrating substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers, pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate, pigments,

Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,

- Antioxidants, included.

With regard to further optional components as well as the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, eg. B. Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig book publisher, Heidelberg, 1989, referenced.

The application temperatures of the composition according to the invention can be in a range between 15 ^' and 40 ^° C. After a contact time of usually 5 to 45 minutes, the hair dye is removed by rinsing of the hair to be dyed. The washing with a shampoo is omitted if a strong surfactant-containing carrier, such as a dyeing shampoo was used.

A second subject matter of the present invention is a process for coloring keratinic fibers, in which a hair colorant according to the invention is applied to the fibers and rinsed off again after a contact time. A third object is the use of optionally hydrated SiO ₂ compounds to increase the color intensity of dyeings of keratin-containing fibers, in particular human hair, with the coloring substances

(a) at least one substantive dye and / or

(b) at least one combination of

, A at least one reactive carbonyl compound and

B is at least one compound selected from the group consisting of (i) CH-acidic compounds and (ii) compounds having primary or secondary amino or hydroxy groups selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, obtained without the influence of an additional oxidizing agent for the coloring substances (a) and / or (b).

B e i s p e e l e

1.0 Color intensification of substantive dyes

The following commercially available hair dye preparations based on substantive dyes were used:

F1 Poly Palette Foam Tinting; Nuance intensive red (Schwarzkopf & Henkel)

F2 poly palette foam tinting; Nuance Cassis (Schwarzkopf & Henkel)

F3 Color Color Softtonder; Nuance wild cherry (Schwarzkopf & Henkel)

F4 LIVE Softtöner; Nuance Blue-Black (Schwarzkopf & Henkel)

F5 LIVE Softtöner; Nuance Purple Whisper (Schwarzkopf & Henkel)

For each hair dye preparation, the following application mixture was prepared immediately before use:

A1 1, 6 g of the above hair coloring was mixed with 0.4 g of a 10% - sodium Britesil ^® offset C20 solution (Akzo.) And homogeneously mixed by stirring.

A2 1.6 g of one of the abovementioned hair dye preparations were mixed with 0.4 g of deionized water and mixed homogeneously by stirring.

2.0 g of A1 were applied to 1.0 g of a strand of hair (Kerling Naturweiß, Kerling). After 30 minutes exposure time at 32 ° C, the hair was rinsed, washed with a conventional shampoo and then dried.

The same dyeing process was carried out with the agent A2.

The stained with the respective agent A2 strands already showed for the appearance of a stronger color.

The color was additionally measured colorimetrically with the Dataflash SF450 from Datacolor and the Lab values were determined. The listed ClELab coordinates are a measure of L (brightness), a (color red-green component), b (color yellow). Blue component). The color difference ΔE was calculated according to the following color difference formula:

AE = V ((Δi) ² + (Δα) ² + (Ab) ² )

The color difference is a measure of the color change. The values of the respective colorations are summarized in Table 1.

Table I

2.0 Color intensification of oxo stains

The following oxo dye precursors were used in the colorants F:

F1 component A1: Vanillin

Component B1: 1,2-dihydro-1,3,4,6-tetramethyl-2-oxopyrimidinium hydrogen sulfate F2 Component A2: 3,5-dimethoxy-4-hydroxybenzaldehyde

Component B2: 1, 2-dihydro-1, 3,4,6-tetramethyl-2-oxopyrimidinium hydrogen sulfate F3 Component A3: 4-hydroxy-2-methoxybenzaldehyde

Component B3: 1, 2-dihydro-1, 3,4,6-tetramethyl-2-oxopyrimidinium hydrogen sulfate

For each hair dye F, the following application mixtures were prepared immediately before use on the hair: An1 0.98 g of a 0.1 molar aqueous solution of the above-mentioned component A and 0.98 g of a 0.1 molar aqueous solution of the corresponding component B of one of the above-mentioned hair colorant F were mixed with 0.04 g of a 10% Britesil ^® solution () with stirring and the pH adjusted with sodium hydroxide to pH 9.

An2 1, 0 g of a 0.1 molar aqueous solution of the above component A and 1, 0 g of a 0.1 molar aqueous solution of the corresponding component B each one of the o.g. Hair dye F were added with stirring and the pH was adjusted to pH 9 with sodium hydroxide solution.

2.0 g of An1 were applied to 1.0 g of an unstained hair strand (Kerling Naturweiss, Kerling). After 30 minutes exposure time at 32 ⁰ C, the hair was rinsed, washed with a conventional shampoo and then dried.

The same dyeing process was carried out with the application mixture An2.

The stained with the respective agent An2 strands of the corresponding hair colorant F already showed for the appearance of a stronger color than the stained with the application mixture An1 hair colorant F strand.

Claims

Pa tentanspr che

1. means for coloring keratin fibers, in particular human hair, in a cosmetically acceptable carrier as coloring substances

(a) at least one substantive dye and / or

(b) at least one combination of

A is at least one reactive carbonyl compound and B is at least one compound selected from the group consisting of (i) Cl-lacid compounds; and (ii) primary or secondary amino group or hydroxy group compounds selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, and in addition

(C) at least one optionally hydrated SiO ₂ compound, with the proviso that no oxidizing agent for the coloring substances (a) and / or (b) is included.

2. Composition according to claim 1, characterized in that the optionally hydrated SiO ₂ compound is a silica gel.

3. Composition according to one of claims 1 or 2, characterized in that the optionally hydrated SiO ₂ compound is an aqueous solution of a silicate of the formula (SiO ₂ ) n (Na ₂ O) _m (K ₂ θ) p, where n stands for a positive rational number and m and p stand independently for a positive rational number or for 0, with the provisos that at least one of the parameters m or p is different from 0 and the ratio between n and the sum of m and p between 1: 4 and 4: 1.

4. Composition according to one of claims 1 to 3, characterized in that the substantive dyes are selected from the group formed, from Nitrophenylendiaminen, Nitroaminophenolen, azo dyes, anthraquinones and indophenols.

5. Composition according to one of claims 1 to 4, characterized in that it contains at least one cationic substantive dyes.

6. Agent according to one of claims 1 to 5, characterized in that the reactive carbonyl compound is selected from the group which is formed from benzaldehyde and its derivatives, naphthaldehyde and its derivatives, cinnamaldehyde and its derivatives, 2,3,6, 7-Tetrahydro-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, N-ethylcarbazole 3-aldehyde, 2-formylmethylene-1, 3,3-trimethylindoline (Fischer's aldehyde or tribasic aldehyde), 2-indolaldehyde, 3-indolaldehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 2- (1 ^L , 3 ', 3 ^L -trimethyl-2-indolinylidene) - acetaldehyde, 1-methylpyrrole-2-aldehyde, 4-pyridine aldehyde, 2-pyridine aldehyde, 3-pyridine aldehyde, pyridoxal, antipyrine-4-aldehyde, furfural, 5 Nitrofurfural, 2-thenoyltrifluoroacetone, chromone-3-aldehyde, 3- (5'-nitro-2'-furyl) acrolein, 3- (2'-furyl) acrolein and imidazole-2-aldehyde, 5- (4-dimethylaminophenyl) penta-2,4-dienal, 5- (4-diethylaminophenyl) penta-2,4-diene al, 5- (4-methoxyphenyl) penta-2,4-dienal, 5- (3,4-dimethoxyphenyl) penta-2,4-dienal, 5- (2,4-dimethoxyphenyl) penta-2,4-dienal , 5- (4-Pipe-dinophenyl) -penta-2,4-dienal, 5- (4-morpholinophenyl) -penta-2,4-dienal, 5- (4-pyrrolidinophenyl) -penta-2,4-dienal, 5- (4 -Dimethylamino-1-naphthyl) penta-3,5-dienal, 9-methyl-3-carbazolaldehyde, 9-ethyl-3-carbazolaldehyde, 3-acetylcarbazole, 3,6-diacetyl-9-ethylcarbazoi, 3-acetyl-9 -methylcarbazole, 1,4-dimethyl-3-carbazolaldehyde, 1,4,9-trimethyl-3-carbazolaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3 -nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid, 4-formyl-1-methylpyridinium, 2-formyl-1-methylpyridinium, 4-formyl-1-ethylpyridinium, 2-formyl-1-ethylpyridinium, 4-formyl 1 -benzylpyridinium, 2-formyl-1-benzylpyridinium, 4-formyl-1, 2-dimethylpyridinium, 4-formyl-1, 3-dimethylpyridinium, 4-formyl-1-methyl-quinolinium, 2- Formyl 1-methylquinolinium, 5-formyl-1-methylquinolinium, 6-For myl-1-methylquinolinium, 7-formyl-1-methyl-quinolinium, 8-formyl-1-methylquinolinium, 5-formyl-1-ethylquinolinium, 6-formyl-1-ethylquinolinium, 7-formyl-1-ethyichinolinium , 8-formyl-1-ethylquinolinium, 5-formyl-1-benzylquinolinium, 6-formyl-1-benzylquinolinium, 7-formyl-1-benzylquinolinium, 8-formyl-1-benzylquinolinium, 5-formyl-1 allyl-quinolinium, 6-formyl-1-allyl-quinolinium, 7-formyl-1-allyl-quinolinium and 8-formyl-1-allyl-quinolinium-benzenesulfonate, p-toluenesulfonate, methanesulfonate, perchlorate, sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfate, trifluoromethanesulfonate, tetrafluoroborate, isatin, 1-methylisatin, 1-allyl-isatin, 1-hydroxymethyl-isatin, 5-chloro-isatin, 5-methoxy-isatin, 5 Nitroisatin, 6-nitro-isatin, 5-sulfoisoisine, 5-carboxyisatin, quinisatin, 1-methylquinisatin, as well as any mixtures of the above compounds.

7. Composition according to one of claims 1 to 6, characterized in that it additionally contains at least one surfactant selected from the group consisting of anionic surfactants, zwitterionic surfactants, ampholytic surfactants, nonionic surfactants and cationic surfactants.

8. Composition according to one of claims 1 to 7, characterized in that it additionally contains at least one polymer selected from the group of anionic polymers, cationic polymers, amphoteric polymers and amphiphilic polymers.

9. A process for coloring keratinous fibers, wherein an agent according to any one of claims 1 to 8 is applied to the fibers and rinsed again after a contact time.

10. Use of optionally hydrated SiO ₂ compounds to increase the color intensity of dyeings of keratin-containing fibers, in particular human hair, with the coloring substances

(a) at least one substantive dye and / or

(b) at least one combination of

A is at least one reactive carbonyl compound and B is at least one compound selected from the group consisting of (i) CH-acidic compounds and (ii) compounds having primary or secondary amino or hydroxy groups selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds without the influence of an additional oxidizing agent for the coloring substances (a) and / or (b), are obtained.