EP2029096A1 - Application device for using an application liquid on keratin fibres - Google Patents

Abstract

The object of the present application is an application device (1) for using an application liquid on keratin fibres with at least one container (2) for holding the application liquid, having an application head (3), which is joined to the at least one container (2) and which has a porous application element (31) for applying the application liquid by coating over the fibres, the application liquid containing at least one dye and/or a preliminary dye product and at least one alkyl-phosphoric acid ester.

Description

"Application device for applying an application liquid to keratinic fibers"

The present invention relates to a special application device for applying an application liquid to keratinic fibers, wherein the application liquid contains at least one dye and / or one dye precursor and at least one alkylphosphoric acid ester.

Human hair as an example of a keratin fiber is treated today in many 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 dyes, tinting agents, waving agents and styling preparations. In this case, means for changing or nuancing the color of the head hair play a prominent role.

For temporary dyeings usually dyeing or tinting agents are used which contain as coloring component so-called substantive dyes. 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 dyeings are usually prone to shampooing, so that sometimes after a few washes an undesirable nuance shift or even a visible "discoloration" occurs.

For permanent, intensive dyeings with corresponding fastness properties, so-called oxidation colorants are used. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form under the influence of oxidizing agents or of atmospheric oxygen with one another or with coupling with one or more coupler components, the actual dyes. The oxidation stains are characterized by excellent, long lasting staining results. For naturally acting dyeings, a mixture of a larger number of oxidation dye precursors must usually be used; In many cases, direct dyes are still used for shading.

Finally, another dyeing process has received much attention recently. In this process, 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 coloration can be done with atmospheric oxygen as the sole oxidant, so that no further oxidizing agents must be used. In individuals with originally medium blond to brown hair, the indoline can be used as the sole dye precursor. On the other hand, satisfactory results can often only be achieved for use in persons with originally red and, in particular, dark to black hair color, by using other dye components, in particular special oxidation dye precursors.

Usually, the colorants of the three categories described in the form of creams, gels or solutions are usually applied to the fibers with the aid of a brush. Also available on the market are dyes that are applied to the fibers as a shampoo formulation or conditioner formulation. In all these types of applications, the resulting scalp staining plays a major role, which is considered disadvantageous.

In addition to these more conventional application methods, a wide variety of application devices have also been developed for temporary colorants based on substantive dyes and oxidative colorants based on oxidation dye precursors, with the aid of which the compositions can be applied to the keratinic fibers or to specific areas of the fibers. Application devices containing dyes based on substantive dyes have the disadvantage that the resulting tints do not have a long shelf life; On the other hand, application devices which contain dyeing agents based on oxidation dye precursors have the disadvantage that they have to be of a very complicated construction, since the two components of the dyeing agent must remain separate until immediately before application.

Specifically, DE 199 22 092 A1 describes, for example, a cap-like application device for dyeing hair strands, which is placed on an associated container with hair dye. This application device comprises a plurality of outlet openings for applying the hair dye and adjacent thereto guide prongs, which are drawn during use with combing movements through the hair. In addition, bristles are arranged around the outlet opening in order to achieve a more uniform application of the hair dye. Nevertheless, the outlet openings with the bristles do not allow a sufficiently metered application of the hair dye. In particular, an excessive leakage of the hair dye and thus also an unwanted wetting of the scalp can not be effectively excluded. Furthermore, these means of the state with respect to the Paint lift, that is, not completely convincing in terms of the resulting color intensity.

It was therefore an object of the present invention to develop a dyeing system which is easy to handle and permits intensive coloring of the fibers with little staining of the scalp.

After extensive research it has now surprisingly been found that a special application device in combination with an application liquid based on a dye and / or a dye precursor and an alkyl phosphoric acid ester overcomes the disadvantages of the prior art. With the aid of the application device according to the invention, it is now possible to selectively stain gray areas of hair, in particular at the temples, the contours and the vertex, whereby an intensive staining result is obtained with slight scaling of the scalp.

A first subject of the present invention is therefore an application device (1) for applying an application liquid to keratinic fibers with at least one container (2) for receiving the application liquid, with an application head (3) which is connected to the at least one container (2) and a porous application body (31) for applying the application liquid by sweeping the fibers, wherein the application liquid contains at least one dye and / or a dye precursor and at least one alkyl phosphoric acid ester.

As the first constituent essential to the invention, the application liquids according to the invention contain at least one alkylphosphoric acid ester.

It may be preferred according to the invention if the application liquid contains at least one alkyl phosphoric acid ester of the formula (I)

OR ₃

R ₂ OP ^ O ^

OR ₁ where R ₁ , R ₂ and R ₃ independently of one another represent a hydrogen atom, an alkali metal cation or a radical of the formula (II)

(C ₂ H ₄ O) _n , - (C ₃ H ₆ O) _n -R ₄ (H), where m and n are independently an integer between 0 and 20 and R ₄ is a saturated or unsaturated, branched or unbranched C ₅ . ₂₈ alkyl, with the proviso that at least one of R ₁ , R ₂ or R ₃ is a radical of the formula (II).

Furthermore, it has proved to be preferred if the application liquid contains at least one alkylphosphoric acid ester of the formula (I) in which one of the radicals R ₁ , R ₂ or R _{3 is} a hydrogen atom.

Likewise, it has proved to be advantageous if at least one of the radicals R ₁ , R ₂ or R _{3 is} an alkali metal cation, preferably a sodium cation, a potassium cation or a lithium cation. A sodium cation and a potassium cation are most preferred.

Furthermore, it has proved to be preferred if the application liquid contains at least one alkylphosphoric acid ester of the formula (I) in which the radical R _{4 is} a saturated or unsaturated, branched or unbranched C ₁₂ . ₂₂ alkyl, in particular an unsaturated alkyl radical, most preferably an oleyl radical.

Suitable alkyl phosphoric acid esters are for example the diester of phosphoric acid and of ethoxylated lauryl alcohol (INCI name: Dilaureth-4 Phosphate), that sold under the trade name Hostaphat ^® KO 200 from Clariant mixture of mono- and diesters of phosphoric acid and oleyl alcohol (INCI name: Oleyl phosphates), the triesters of phosphoric acid and ethoxylated cetearyl alcohol (INCI name: triceteareth-4 phosphates), the triesters of phosphoric acid and ethoxylated oleyl alcohol (INCI name: trioleth-8 phosphates), the triesters of phosphoric acid and oleyl alcohol (INCI name : Trioleyl Phosphate) and the phosphoric esters with the INCI names Dicetyl Phosphate, Potassium Cetyl Phosphate, Sodium Lauryl Phosphate.

Also preferred are alkyl phosphoric acid esters with partially or perfluorinated alkyl groups, for example those of the general formula (I) in which the radicals R ₁ , R ₂ and R ₃ independently of one another in addition to the abovementioned meanings for a group R _r (CH ₂ ) _x - (OCH ₂ CH ₂ ) _y - may be where R _{f is} a perfluorinated alkyl radical having 4 to 20, preferably 6 to 18 carbon atoms, x is a number from 0 to 4, preferably 2 and y is a number of 0 to 20 stands.

Suitable fluorinated alkylphosphoric acid esters are the reaction products of the reaction of fluorinated, optionally ethoxylated alcohols with phosphoric acid, POCl ₃ , P ₄ O ₁₀ or polyphosphoric acid. For example, the diethanolammonium salt of Perfluoroalkylethyl phosphate, which is sold under the trade name HOE S 2746 by the company Clariant.

In the context of the work underlying this invention, it has also been found to be advantageous if the application liquid contains at least two different alkyl phosphoric acid esters.

Application fluids containing at least one dialkylphosphoric acid ester and / or at least one ethoxylated monoalkylphosphoric acid ester are particularly preferred according to the invention.

If the application liquid contains two different alkylphosphoric acid esters, a ratio of ethoxylated monoalkylphosphoric acid ester to dialkylphosphoric acid ester of from 1: 5 to 5: 1, in particular from 1: 1 to 2: 1, has proven particularly suitable.

A very particularly preferred according to the invention is a combination of Alkylphosphorsäureesterkombination Oleth-5 Phosphate with dioleyl phosphate, such as is for example sold under the trade name Crodafos ^® HCE by the company Croda.

The alkyl phosphoric acid esters are used in application liquids in an amount of preferably 0.01 to 80 wt .-%, particularly preferably in an amount of 0.1 to 10 wt .-%.

Furthermore, it has proven to be particularly preferred if the application liquid is formulated thin liquid. Application fluids which have a viscosity of from 0 to 2000 mPas when mixed with the oxidizer formulation (measured at 22 ° C. in a Brookfield viscometer with spindle 4 and a speed of 4 rpm) have proved to be particularly preferred. A viscosity of 0 to 100 mPas, measured under the conditions mentioned, is particularly preferred according to the invention. A viscosity of 50 to 500 mPas (measured at 20 ^° C. (Brookfield viscometer type RV-T, spindle 4 with a rotation speed of 20 rpm) is very particularly preferred according to the invention.

As a second constituent essential to the invention, the application liquids according to the invention contain at least one dye and / or at least one dye precursor.

In the context of a first preferred embodiment, the application liquid contains at least one dye. The substantive dyes are preferably selected from the nitrophenylenediamines, the nitroaminophenols, the azo dyes, the anthraquinones or the 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-nitrodiphenylam in-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, it may be preferred according to the invention that the agents contain at least one 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 at least one 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 substantive dyes sold under the trademark Arianor® are also very particularly preferred cationic substantive dyes according to the invention. Furthermore, the preparations according to the invention may also contain naturally occurring substantive dyes such as those found in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, sawnwood, madder root, catechu, sedre and alkano root.

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 application fluid.

In the context of this embodiment, it has proved to be very particularly preferred if the application liquid according to the invention contains at least one anionic substantive dye.

In addition to or instead of the dyes, the application fluids of the invention may contain at least one dye precursor. The dye precursors preferred according to the invention include on the one hand the oxidation dye precursors of the developer and coupler type and on the other hand the precursors of naturally-analogous dyes.

As a rule, the application liquids according to the invention contain at least one developer component and at least one coupler component. Accordingly, it has proved to be preferred if the application fluid contains at least one developer component.

The developer components are usually primary aromatic amines having a further, located in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives ,

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

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

G ³ represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ - Polyhydroxyalkylrest, a C ₁ - to C ₄ -hydroxyalkoxy, a C ₁ - to C ₄ -Acetylaminoalkoxyrest, a C ₁ - to C ₄ - Mesylaminoalkoxyrest or a C ₁ - to C ₄ -Carbamoylaminoalkoxyrest;

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

Examples of the C ₁ - to C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ -C ₄ -alkoxy radicals 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, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. 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-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4 -Amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) -amino-2 -methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2 Fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N , N- (ethyl .beta., hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (β-hydroxyethyloxy) - p-phenylenediamine, 2- (β-acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazole -1-yl) propyl] amine and 5,8-diaminobenzo-1, 4-dioxane and their physiologically acceptable salts.

Very particular 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 developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.

Among the binuclear developer components 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 radical which is optionally substituted by a C ₁ - to C ₄ -alkyl radical, by a C ₁ - to C ₄ -hydroxyalkyl radical and / or by a bridge Y. or 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 optionally 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 ₁ - 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 developer components of the formula (E2) are in particular: N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-diethyl-N, N ' bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane , N, N'-bis (2-hydroxy-5-aminobenzyl) -piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1, 10-bis (2 ', 5'-diaminophenyl) -1 , 4,7,10-tetraoxadecane and their physiologically acceptable salts.

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

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

in which: G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ alkyl group - (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical, a hydroxy- (C 1 -C ₄ ) -alkylamino radical, a C ₁ - to C ₄ -hydroxyalkoxy radical, a C ₁ - to C ₄ -hydroxyalkyl- (C _{1 to} C ₄ ) -aminoalkyl or a (di-C ₁ - to C ₄ -alkylamino) - (C ₁ to C ₄ ) -alkyl, and

G ¹⁴ is a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a (C ₁ - to C ₄ ) - Alkoxy (C 1 -C ₄ ) -alkyl radical, a C ₁ -C ₄ -aminoalkyl radical or a C ₁ -C ₄ -cyanoalkyl radical,

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- (diethyl-aminomethyl) -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, the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

Further, the developer component may be selected from heterocyclic developer components 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-Amino-pyridine, 2,3-diamino-6-methoxy-pyridine, 2- (β-methoxy-ethyl) -amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

Preferred pyrimidine derivatives are, in particular, the compounds described in German Patent DE 2 359 399, Japanese Laid-Open Patent Publication JP 02019576 A2 or in the published patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy- 2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6- triaminopyrimidine.

Preferred pyrazole derivatives are, in particular, 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-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4.5- Diamino-1, 3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-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:

in which:

G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ - Polyhydroxyalkylrest a (C ₁ - to C ₄ ) alkoxy (C-ι- to C ₄ ) alkyl, a C ₁ - to C ₄ - aminoalkyl, optionally protected by an acetyl-ureide or a sulfonyl radical may be a (C ₁ to C ₄ ) alkylamino (C ₁ to C ₄ ) alkyl, a di - [(C 1 to C ₄ ) alkyl] - (C - to C ₄ ) - aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C ₁ - to C ₄ ) -aminoalkylrest, the X radicals independently of one another represent a hydrogen atom, a C ₁ - to C ₄ - alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ - polyhydroxyalkyl radical, a C ₁ - to C ₄ aminoalkyl radical, a (C ₁ - to C ₄₎ alkylamino (C-ι- to C ₄₎ - alkyl group, a di - [(d- to C ₄₎ alkyl ] - (C ₁ - to C ₄ ) -aminoalkyl, 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 - bis C ₄ -hydroxyalkyl) -aminoalkyl, an amino, 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 Sulfonsäuregrup pe, 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 does not equal 0 is when p + q is 2, n is 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7); wweennnn pp ++ qq gglleeiicchh 11 iisstt, nn ddtwhen WWeerrtt 11 hhaatt, 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 shown, 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-ylamino) ethanol;

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

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

2 - [(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) - (2-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 addition to the developer components, the application liquids according to the invention may contain at least one coupler component.

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

Preferred coupler components according to the invention are m-aminophenol and its derivatives, such as, for example, 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-methylphenyl } amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} -amino) ethanol, 2- [3-morpholin-4-yl-phenyl) -amino] -ethanol, 3-amino- 4- (2-methoxyethoxy) -5-methylphenylamine and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene, o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1 -methylbenzol,

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, for example, 6-hydroxybenzomorpholine and 6-aminobenzomorpholine, quinoxaline derivatives such as, for example, 6-methyl-1,2,3,4-tetrahydroquinoxaline, pyrazole derivatives such as, for example, 1-phenyl-3-methylpyrazol-5-one, indole derivatives such as 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, for example, 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4- methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene and their physiologically acceptable salts.

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

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

In a further embodiment of the present invention, the application liquids according to the invention may contain at least one precursor of a naturally-analogous dye. As precursors of naturally-analogous dyes such indoles and indolines are preferably used which have at least one hydroxy or amino group, preferably as a substituent on the six-membered ring. These groups may carry further substituents, e.g. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group. In a second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.

Particularly suitable precursors of natural-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (NAV I),

in the independently of each other

dg is hydrogen, a C 1 -C ₄ -alkyl group or a C 1 -C ₄ -hydroxy-alkyl group,

G ₂₀ is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,

G ₂ i is hydrogen or a C 1 -C ₄ -alkyl group,

G ₂₂ is hydrogen, a C 1 -C ₄ -alkyl group or a group -CO-G ₂₄ , in which G ₂₄ is a C 1 -C ₄ -alkyl group, and

- G ₂₃ stands for one of the groups listed under G ₂₂ , and physiologically acceptable salts of these compounds with an organic or inorganic acid.

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

Particularly noteworthy within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5, 6-Dihydroxyindolin.

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

in the independently of each other

G ₂₅ is hydrogen, a C 1 -C ₄ -alkyl group or a C 1 -C ₄ -hydroxyalkyl group,

G ₂₆ is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,

G ₂₇ is hydrogen or a C 1 -C ₄ -alkyl group,

G ₂₈ is hydrogen, a C 1 -C ₄ -alkyl group or a group -CO-G ₃₀ , in which G ₃₀ is a C 1 -C ₄ -alkyl group, and

G ₂₉ is one of the groups mentioned under G ₂₈ , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6- dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole. Emphasized within this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, and especially the 5,6 -Dihydroxyindol.

The indoline and indole derivatives can be used in the colorants of the invention both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, for. As the hydrochlorides, sulfates and hydrobromides are used. The indole or indoline derivatives are contained therein usually in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.

In a further embodiment, it may be preferred according to the invention to use the indoline or indole derivative in colorants in combination with at least one amino acid or an oligopeptide. The amino acid is advantageously an α-amino acid; Very particularly preferred α-amino acids are arginine, ornithine, lysine, serine and histidine, in particular arginine.

A third essential aspect of the present invention is the design of the application device.

An advantageous design of the actual application device provides that the porous applicator has continuous pores to achieve capillary action. The capillary properties of the application body, which is in contact with the application liquid in a wick-like manner, ensure reliable transport of the application liquid out of the container and metered application of the application liquid by sweeping it over the fibers. According to a further developed variant of the application device, the application body preferably has a fibrous, sponge, foam, felt or sintered material-like material structure. This material structure causes the desired capillary action of the application body, so that, for example, an unwanted leakage or dripping of the application liquid from the application body is omitted, but at the same time a reliable fluid delivery is ensured by means of the application body.

As an alternative to a substantially block-shaped design of the porous application body, it can also have a plurality of pin-shaped projections. This increases the effective surface of the application body and thus improves the application of the application liquid. Accordingly, by means of the coating movement of the applicator body over the keratinic fibers, in particular the hair, a better dyeing result is guaranteed both quantitatively and qualitatively. Another useful embodiment of the application device is achieved in that the application head has a plurality of possibly detachably arranged, comb teeth. These comb teeth are arranged in particular adjacent to the application body. The brushing motion of the entire application head during the application initially provides, by means of the comb teeth, for a disentanglement of the fibers or the hair and thus, above all, for a uniform application of the application liquid. Basically, the detachable arrangement of the comb teeth on the application head allows a more versatile use of the application device. It also proves to be advantageous for such an arrangement when the comb teeth protrude from the porous applicator body. In this way it is prevented for an application in hair that in addition to the hair, the skin, especially the scalp, is wetted with the application liquid. A preferred embodiment of the application device is to arrange the comb teeth of the application head in a circle around the application body. Regardless of the respective coating movement direction, the fibers or hair are first unraveled during use in each case before the actual application of the application liquid takes place.

In the context of the present invention, it has proved to be preferred if the application liquid comprises a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purposes of the present invention, such carriers are, for example, creams, emulsions, gels or else surfactant-containing foaming solutions, for example shampoos, foam aerosols or other preparations which are suitable for use on the hair.

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

Particularly preferred according to the invention is a water-containing carrier which contains at least one C ₁ -C ₄ -alkoxy and at least one further organic solvent. It may be preferred according to the invention if the water accounts for 20 to 60 wt .-%, preferably from 30 to 50 wt .-%, the C ₁ -C ₄ -AlkOhOl a proportion of 20 to 60% by weight, preferably from 30 to 50 wt .-%, and the organic solvent, a proportion of 1 to 30 wt .-%, preferably from 5 to 15 wt .-%, each based on the total application liquid have. In the context of this embodiment, a composition containing water, ethanol and propylene carbonate may be particularly preferred. In the context of a first embodiment of the present invention, the application liquid contains substantially only substantive dyes as coloring components, preferably anionic substantive dyes.

In the context of this embodiment, it has proven to be preferred if the application liquid contains a pH of from 1 to 5, preferably from 1, 5 to 3.

To adjust the pH, the application liquid of this embodiment preferably contains at least one organic or inorganic acid. Hydrochloric acid, sulfuric acid and phosphoric acid are to be mentioned in particular as preferred inorganic acids. Preferred organic acids are acetic acid, glycolic acid, citric acid, tartaric acid, lactic acid and malic acid. Malic acid is a particularly preferred acid used.

In the context of a second, likewise preferred embodiment, the application liquid may contain at least one dye precursor.

In the context of this embodiment, the application liquid according to the invention is preferably adjusted to a pH of from 7 to 11, in particular from 8.5 to 10, by means of acids and / or alkalizing agents.

For this purpose, preferred alkalizing agents are alkali or alkaline earth hydroxides, ammonia or organic amines. The organic amines are preferably selected from the group consisting of monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1, 3-propanediol, 2-amino-2-ethyl-1 , 3-propanediol, 2-amino-2-methylbutanol and triethanolamine. In particular, monoethanolamine, triethanolamine and 2-amino-2-methyl-propanol and 2-amino-2-methyl-1, 3-propanediol are preferred within the scope of this group. Also, the use of amino acids and / or oligopeptides such as ω-aminocaproic acid as the alkalizing agent is preferred in the context of the present invention.

Furthermore, preference is given to using those amino acids and oligopeptides whose 2.5% strength by weight solutions have a pH of 9 or greater in water. Such an amino acid is arginine which is preferably used.

With regard to the acids preferred according to the invention, reference is explicitly made to the above statements at this point. The application fluids according to the invention of both mentioned embodiments may furthermore in principle contain all active ingredients, additives and auxiliaries known in such preparations. Although it has been found to be particularly preferred if the application liquids are formulated free of surfactants, in another embodiment the inventive application liquids may also contain at least one surfactant, with both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has proved to be advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants. Anionic surfactants may be very particularly preferred.

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 with about 10 to 22 C-men men. 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 as well as mono-, di- and trialkanol ammonium salts with 2 or 3 C atoms in the alkanol group, linear fatty acids having 10 to 22 C atoms (Soap),

Ethercarbonsäuren 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 C atoms in the acyl group,

Acyltaurides having 10 to 18 C atoms in the acyl group,

Acyl isethionates having 10 to 18 C atoms in the acyl group,

Sulfobernsteinsäuremono- and -dialkylester having 8 to 18 carbon atoms in the alkyl group and

Sulfosuccinic acid mono-alkylpolyoxyethyl 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 α-olefin sulfonates having 12 to 18 C atoms,

Alpha-sulfofatty acid methyl esters of fatty acids containing 12 to 18 carbon 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 carbon 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. A polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. 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 on

Alkylphenols having 8 to 15 C atoms in the alkyl group,

C ₁₂ -C ₂₂ fatty acid mono- and diesters of addition products of 1 to 30 moles 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 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. Particular preference is given to those alkylpolyglycosides in which R ¹ consists essentially of C ₈ and C ₁₀ -alkyl groups, essentially of C ₁₂ and C ₁₄ -alkyl groups, essentially of C ₈ - to C ₁₆ -alkyl groups or 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 ingredient of the preparations according to the invention in the event that an action 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 surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ⁽⁾ or -SO ₃ ⁽⁾ group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammoniumglycinates, for example cocoacylaminopropyldimethylammonium glycinate, and Alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and Kokosacylaminoethylhydroxyethyl- carboxymethylglycinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine. Also particularly suitable as co-surfactants are ampholytic surfactants. Ampholytic surfactants are understood as meaning those surface-active compounds which contain, in addition to a C ₈ -C -alkyl or acyl group in the molecule, 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-coconut alkylaminopropionate, cocoacylaminoethyl aminopropionate and C _{12-i 8} acyl sarcosine.

According to the invention, the cationic surfactants used are, in particular, those of the quaternary ammonium compound type, the esterquats and the amidoamines.

Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. For example, 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 ester quats 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 marketed under the trade names Stepantex® ^{®, ®} and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, 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 is that available under the name Tegoamid ^® S 18 commercially stearamidopropyl dimethylamine. Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolyzates, the protein hydrolyzate on which the animal is based, for example from collagen, milk or keratin, from the plant, for example from wheat, corn, rice, potatoes, soy or almonds, from marine life forms, for example from fish collagen or algae, or biotechnologically derived protein hydrolysates. The protein hydrolyzates on which the cationic derivatives which can be used according to the invention can be obtained from the corresponding proteins by chemical, in particular alkaline or acid hydrolysis, by enzymatic hydrolysis and / or a combination of both types of hydrolysis. The hydrolysis of proteins usually results in a protein hydrolyzate having a molecular weight distribution of about 100 daltons up to several thousand daltons. Preference is given to those cationic protein hydrolyzates whose underlying protein content has a molecular weight of 100 to 25,000 daltons, preferably 250 to 5000 daltons. Furthermore, cationic protein hydrolyzates are to be understood as meaning quaternized amino acids and mixtures thereof. The quaternization of the protein hydrolyzates or amino acids is often carried out using quaternary ammonium salts such as N, N-dimethyl-N- (n-alkyl) -N- (2-hydroxy-3-chloro-n-propyl) ammonium halides. Furthermore, the cationic protein hydrolysates may also be further derivatized. As typical examples of the cationic protein hydrolysates and derivatives according to the invention, those mentioned under the INCI names in the "International Cosmetic Ingredient Dictionary and Handbook", (seventh edition 1997, The Cosmetic, Toiletry and Fragrance Association 1 101 17 ^th Street, NW, Suite 300, Washington, DC 20036-4702) and commercially available products called: Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Casein, Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Hair Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Rice Protein, Cocodimonium Hydroxypropyl Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, Hydroxypropyl Arginine Lauryl / Myristyl Ether HCl, Hydroxypropyltrimonium Gelatin, Hydroxypropyltrimonium Hydrolyzed Casein, Hydroxypropyltrimonium Hydrolyzed Collagen, Hydroxypropyltrimonium Hydrolyzed Conchio Hydroxypropyltrimonium Hydrolyzed Keratin, Hydroxypropyltrimonium Hydrolyzed Rice Bran Protein, Hydroxypropyltrimonium Hydrolyzed Soy Protein, Hydroxypropyl Hydrolyzed Vegetable Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein / Siloxysilicate, Laurdimonium Hydroxypropyl Hydrolyzed Soy Protein, Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein, Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein / Siloxysilicate, Lauryldimonium Hydroxypropyl Hydrolyzed Casein, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen, Lauryldimonium Hydroxypropyl Hydrolyzed Keratin, Lauryldimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Casein, Steardimonium Hydroxypropyl Hydrolyzed Collagen, Steardimonium Hydroxypropyl Hydrolyzed Keratin, Steardimonium Hydroxypropyl Hydrolyzed Rice Protein, Steardimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Vegetable Protein, Steardimonium Hydroxypropyl Hydrolyzed Wheat Protein, Steartrimonium Hydroxyethyl Hydrolyzed Collagen, Quaternium-76 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Keratin, Quaternium-79 Hydrolyzed Milk Protein, Quaternium-79 Hydrolyzed Soy Protein, Quaternium-79 Hydrolyzed Wheat Protein.

Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning, 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; di- quaternary 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 Gluceth-10 Hydroxypropyl Dimonium Chloride".

The compounds used as surfactant with alkyl groups may each be uniform substances. However, it is usually preferred to start from the production of these substances from native plant or animal raw materials, so as to obtain substance mixtures with different, depending on the particular raw material alkyl chain lengths.

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. By "normal" homolog distribution are meant 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 are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alkoxides are used as catalysts. The use of products with narrow homolog distribution may be preferred.

Furthermore, the agents used in the process according to the invention may preferably also contain a conditioning agent selected from the group consisting of cationic surfactants, cationic polymers, silicones, alkylamidoamines, paraffin oils, vegetable oils and synthetic oils. Cationic polymers may be preferred as conditioning agents. These are in the

Rule Polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group.

Preferred cationic polymers are, for example, quaternized cellulose derivatives, such as are available under the names of Celquat ^® and Polymer JR ^® commercially. The compounds Celquat ^® H 100, Celquat L 200 and Polymer JR ^{® ®} 400 are preferred quaternized cellulose derivatives. polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and esters and amides of acrylic acid and methacrylic acid. The products obtainable under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)), Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) and Merquat ^® 280 (dimethyldiallylammonium chloride-acrylic acid copolymer are examples of such cationic polymers. Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and - methacrylate such as, for example, quaternized with diethyl sulfate, vinylpyrrolidone dimethylaminomethacrylate copolymers such compounds are available under the names Gafquat ^® 734 and Gafquat ^® 755 commercially..

Vinylpyrrolidone-Methoimidazoliniumchlorid copolymers, such as those available under the name Luviquat ^® , quaternized polyvinyl alcohol and those under the names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and

Polyquaternium 27 known polymers with quaternary nitrogen atoms in the polymer main chain.

Particular preference is given to cationic polymers of the four first-mentioned groups, very particular preference to polyquaternium-2, polyquaternium-10 and polyquaternium-22.

I may furthermore be preferred as conditioning agents silicone oils and / or silicone gums.

Silicones or silicone gums which are suitable according to the invention are in particular dialkyl and alkylaryl siloxanes, for example dimethylpolysiloxane and methylphenylpolysiloxane, and also their alkoxylated, quaternized or else anionic derivatives.

Examples of such silicones are: Oligomeric polydimethylcyclosiloxanes (INCI name: Cyclomethicone), in particular the tetrameric and pentameric compounds sold as commercial products DC 344 and DC 345, respectively, by Dow Corning,

Hexamethyl disiloxane (INCI name: Hexamethyldisiloxane), z. B. the product sold under the name Abil ^® K 520,

Polydimethylsiloxane polymers (INCI name: Dimethicone), z. As the products sold under the name DC 200 by Dow Corning products, polyphenylmethylsiloxanes (INCI name: Phenyl Trimethicone), z. B. the commercial product DC 556 fluid from Dow Corning,

Silicone glycol copolymers (INCI name: Dimethicone Copolyol), z. The commercial products DC 190 and DC 193 from Dow Corning,

Esters and partial esters of silicone glycol copolymers, such as, for example, by the company Fanning under the trade name LIM Fancorsil ^®: marketed, (INCI designation dimethicone copolyol Meadowfoamate)

Hydroxy-terminated dimethylsiloxanes (INCI name: dimethiconol), e.g. Dow Corning's commercial products DC 1401 and Q2-1403, aminofunctional polydimethylsiloxanes, and hydroxylamine-modified silicones (INCI name: Amodimethicone and Quaternium-80, among others), such as the commercial products XF42-B1989 (manufactured by GE Toshiba Silicones) Q2-7224 (manufacturer: Dow Corning, a stabilized trimethylsilylamodimethicone), Dow ^Corning® 939 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), anionic silicone oils, such as the product Dow Corning ^® 1784 amino-modified organosilicones, such as the product Abil soft A843 (manufactured by Osi Specialties).

According to a preferred embodiment, the preparations according to the invention contain a combination of a volatile and a nonvolatile silicone. Volatile in the context of the invention are those silicones which have a volatility which is equal to or greater than the volatility of the cyclic, pentameric dimethylsiloxane. Such combinations are also available as commercial products (eg, Dow ^Corning® 1401, Dow ^Corning® 1403, and Dow ^Corning® 1501, each containing mixtures of a cyclomethicone and a dimethiconol).

According to a particularly preferred embodiment, the preparation contains a dialkylpolysiloxane or one of its derivatives. Preferably, the alkyl groups are methyl, ethyl, i-propyl and n-propyl. Dimethylpolysiloxane or one of its derivatives is particularly preferably used. Preference is given to the derivatives of dimethylpolysiloxane which are amino-functional. One Very particularly preferred derivative is commercially available under the INCI name Amodimethicone. Within the scope of the work on which this application is based, it has been possible to show that the active ingredient combination of alkylphosphoric acid ester and dialkylpolysiloxane, in particular of alkylphosphoric acid ester and amodimethicone, achieves the object according to the invention in a very particularly high degree.

The preparations according to the invention preferably contain the silicones in amounts of from 0.01 to 10% by weight, in particular from 0.1 to 5% by weight, based on the total application preparation.

Also suitable as conditioning active ingredients are silicone oils, in particular dialkyl and alkylaryl siloxanes, for example dimethylpolysiloxane and methylphenylpolysiloxane, and also their alkoxylated and quaternized analogs. Examples of such silicones are the Dow Corning under the names DC 190, DC 200, DC 344, DC 345 and DC 1401 products sold and the commercial products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silyl amodimethicone), Dow Corning ^® 929 emulsion (containing a hydroxylamino-modified silicone which is also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th Goldschmidt, di-quaternary polydimethylsiloxanes, quaternium-80).

Also usable as conditioning active ingredients are paraffin oils, synthetically prepared oligomeric alkenes and vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil and peach kernel oil.

Likewise suitable hair-conditioning compounds are phospholipids, for example soya lecithin, egg lecithin and cephalins.

Further active agents, auxiliaries and additives are, for example, nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, zwitterionic and amphoteric polymers such as acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate ^ -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,

Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. Methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and

Derivatives such as amylose, amylopectin and dextrins, clays such. B. 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,

Perfume oils, dimethylisosorbide and cyclodextrins,

Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, fiber-structure-improving agents, especially 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,

Dyes for staining the agent,

Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,

Light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,

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

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,

Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,

Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates,

Hydrogencarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers

Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,

pigments

Stabilizer for hydrogen peroxide and other oxidants,

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

Antioxidants.

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 constituents of the water-containing carrier are used to prepare the inventive application liquid in amounts customary for this purpose; for example, emulsifiers in concentrations of 0.5 to 30 wt .-% and thickening agents in concentrations of 0.1 to 25 wt .-% of the total colorant used.

According to a preferred embodiment, the formation of the dyeing takes place with atmospheric oxygen as the sole oxidizing agent.

B e i s p e e l e

Other features of the invention will become apparent from the single drawing, which shows a generic application device in perspective and will be explained in more detail below.

The application device 1 shown in FIG. 1 is designed for use with a liquid hair dye. In principle, however, such an application device 1 can also generally serve for the application of any application fluid for keratinic fibers, the application fluid being applied by brushing movements to the fibers. The application device 1 has a container 2 which receives the hair dye or the application liquid and stores it until it is used. For this purpose, it may be useful to provide an absorbent storage element in the interior of the container, which is designed, for example, as a fibrous or sponge-shaped, in order to receive the hair dye or the application liquid. An application head 3, by means of which the hair dye is applied to the hair, is fastened to an open container end. The application head 3 essentially comprises a porous application body 31 and a plurality of comb teeth 33, which in turn are advantageously integrally connected to at least one comb element 34. FIG. 1 shows the application device 1 in the ready-to-use operating position, ie. H. with open application head 3. Outside the application times, the application head 3 is covered by a cap, not shown, which is attached, for example, to a thread 4 on the container 2. Thus, the application head 3 is sealed from the environment, so that drying of the liquid hair dye is effectively prevented.

Specifically, the applicator body 31 communicates with the liquid hair dye or the application liquid to promote the liquid in the manner of a wick by capillary action from the container and to provide for applying to the hair. For this purpose, the porous application body 31 has a material structure with continuous pores in order to achieve the corresponding capillary action. The application body 31 consists in particular of a fibrous, sponge, foam, felt or sintered material-like material. The advantage of such a designed applicator body 31 is not only in the reliable promotion of the hair dye but also in the high fluid absorbency. Namely, the high liquid absorption capability prevents unwanted leakage or dripping of the hair dye from the application device 1. Geometrically, the application body 31 is preferably block-shaped (not shown) or designed with a plurality of pin-shaped projections 32. In particular, the embodiment with a plurality of pin-shaped projections 32 increases the effective surface of the application body 31, so that better coloring results are achieved when sweeping the hair. The comb teeth 33, which are likewise formed immediately adjacent to the applicator body 31 on the application head 3, are used for unraveling the hair during application of the application device 1. This disentangling of the hair results in a more uniform application of color to the hair. In particular, the individual comb teeth 33 are integrally connected to at least one comb element 34 in order to simplify handling and production in general. Furthermore, it makes sense to attach the comb teeth 33 or comb elements 34 detachably to the application head 3, in order to permit an application without comb teeth 33 or comb elements 34, depending on the particular case of use. In general, the comb teeth 33 protrude in the longitudinal direction of the application device 1 with respect to the application body 31 in order to prevent contact of the scalp with the application body 31 or the application fluid, especially in hair applications.

According to a further embodiment not shown, the comb teeth 33 are arranged in a circle around the applicator body 31 lying around on the application head 3. Thus, the hair is first unraveled during the application of the application device 1, regardless of the respective coating movement direction, before the actual application of the hair dye takes place. This gives improved staining results.

By means of the application devices described above, the following application liquids were applied to the hair in the visible region (apex, contours and temples) (the amounts are by weight):

Crodafos ^ HCE Complex mixture of ethoxylated oleyl alcohol with approx. 5 EO units and dioleyl phosphate (INCI name: Oleth-5 Phosphate, Dioleyl Phosphate) (Croda)

SME 253 (Silicon) Aminofunctional Silicone Microemulsion (INCI name: Amodimethicone and Cn_i ₅ Pareth-7 and Laureth-9 and Glycerol and Trideceth-12) (GE Silicones)

Subsequently, the hair was dried without washing the product and dressed as usual. The following colorations were obtained:

Formulation 1: Medium Blonde Formulation 2: Red Brown Formulation 3: Dark Brown Formulation 4: Black

Claims

Patent claims

1. Application device (1) for applying an application liquid to keratinic fibers with at least one container (2) for receiving the application liquid, with an application head (3) which is connected to the at least one container (2) and a porous applicator body (31) has for applying the application liquid by sweeping the fibers, characterized in that the application liquid contains at least one dye and / or a dye precursor and at least one alkyl phosphoric acid ester.

2. Application device (1) according to claim 1, characterized in that the application liquid contains at least one Alkylphoshorsäureester of formula (I)

OR ₃

R ₂ OP ^ O ^(l)

OR ₁ where R ₁ , R ₂ and R ₃ independently of one another represent a hydrogen atom or a radical of the formula (II)

(C ₂ H ₄ O) _n , - (C ₃ H ₆ O) _n -R ₄ (H), where m and n are each independently an integer between 0 and 20 and R ₄ is a saturated or unsaturated, branched or unbranched C _5-28 -alkyl radical, with the proviso that at least one of the radicals R _1, R ₂ or R ₃ is a radical of formula (II).

3. Application device (1) according to claim 2, characterized in that at least one of the radicals R ₁ , R ₂ or R _{3 is} a hydrogen atom.

4. Application device (1) according to any one of claims 2 or 3, characterized in that the radical R ₄ is a saturated or unsaturated, branched or unbranched C _{12th 22} alkyl radical.

5. Application device (1) according to any one of claims 2 to 4, characterized in that R ₄ is an unsaturated alkyl radical, preferably an oleyl radical.

6. Application device (1) according to any one of claims 1 to 5, characterized in that the application liquid contains at least two different alkyl phosphoric acid ester.

7. Application device (1) according to one of claims 1 to 6, characterized in that the application liquid contains at least one Dialkylphoshorsäureester.

8. Application device (1) according to any one of claims 1 to 7, characterized in that the application liquid contains at least one ethoxylated Monoalkylphosphorsäureester.

9. Application device (1) according to any one of claims 1 to 8, characterized in that the application liquid contains at least one anionic substantive dye.

10. Application device (1) according to one of claims 1 to 9, characterized in that the application liquid contains at least one organic solvent.

1 1. Application device (1) according to one of claims 1 to 10, characterized in that the application liquid contains at least one polymer.

12. Application device (1) according to claim 11, characterized in that the polymer is nonionic.

13. Application device (1) according to one of claims 1 to 12, characterized in that the application liquid has a pH value between 2 and 5.

14. Application device (1) according to any one of claims 1 to 13, characterized in that the porous applicator body (31) has continuous pores to achieve a capillary action.

15. Application device (1) according to one of claims 1 to 14, characterized in that the application body (31) preferably has a fibrous, sponge, foam, felt or sintered material-like material structure.

16. Application device (1) according to one of claims 1 to 15, characterized in that the porous application body (31) has a plurality of pin-shaped projections (32).

17 comprises application device (1) according to one of claims 1 to 16, characterized in that the application head (3) has a plurality, optionally releasably arranged, comb teeth (33).

18. Application device (1) according to claim 17, characterized in that the comb teeth (33) protrude with respect to the porous applicator body (31).

19. Application device (1) according to any one of claims 17, 18, characterized in that the comb teeth (33) of the application head (3) are arranged in a circle around the applicator body (31) around.

20. Application device (1) according to any one of claims 1 to 19, characterized in that the application liquid has a viscosity of 50 to 500 mPas (measured at 20 ⁰ C (Brookfield viscometer type RV-T, spindle 4 with a rotational speed of 20 U / min).