JP2009538875A - Coating device for using coating solution on keratin fibers - Google Patents

Abstract

An object of the present invention is an application device (1) for applying a coating liquid onto keratin fibers, wherein at least one container (2) for receiving the coating liquid and the at least one container (2) And a coating head (3) having a porous coating element (31) for providing a coating solution by overcoating the fibers, the coating solution comprising at least one dye and / or Another object is to provide a coating device comprising a dye precursor and at least one alkyl phosphate ester.

Description

  The present invention relates to a specific application device for using a coating liquid on keratin fibers. Here, the coating solution comprises at least one dye and / or dye precursor and at least one alkyl phosphate ester.

  Human hair as an example of keratin fibers is currently variously processed using hair cosmetic preparations. These treatments include, for example, hair washing using shampoos, care and regeneration using rinses and cures, and hair decoloring, coloring and styling using colorants, dyes, permanent wave lotions and styling preparations. included. Among these, agents that change hair color or give nuance play an important role.

  For temporary coloring, colorants or dyes which contain so-called direct dyes as coloring components are generally used. These are dye molecules that adhere directly to the hair and do not require an oxidation process for color development. These dyes include, for example, henna, which has long been known for coloring the body and hair. Such dyes are generally sensitive to shampooing, with the consequence that undesirable nuance changes or even visible “bleaching” occurs.

  So-called oxidation dyes are used for persistent coloration with corresponding fastness. Such dyes generally comprise an oxidative dye precursor, a “developing component” and a “coupler component”. Under the influence of oxidant or atmospheric oxygen, the developer components combine with each other or with one or more coupler components to form the actual dye. Oxidative dyes are characterized by a significant persistent coloring effect. For natural-looking coloration, a relatively large number of mixtures of oxidative dye precursors must generally be used (often additional direct dyes are also used to provide nuances).

  Finally, a new type of staining method has recently attracted much interest. In this method, precursors of the natural hair dye melanin are applied to the hair, and during the oxidation process in the hair, they form a natural analog dye.

  A product of this type using 5,6-dihydroxyindoline as a dye precursor is disclosed in EP-B1-530229. When an agent containing 5,6-dihydroxyindoline is used, particularly when it is used repeatedly, the natural hair color can be restored in a person with gray hair. In this case, coloring takes place with atmospheric oxygen as the only oxidant, which means that it is not necessary to rely on other oxidants. For people with originally moderate blonde to brown hair, indoline can be used as the only dye precursor. In contrast, when used in humans with red, especially dark to black hair, satisfactory results are often obtained only in combination with further dye components, in particular with specific oxidation dye precursors. .

  Typically, the three categories of colorants are applied to the fibers using a brush, usually in the form of a cream, gel or solution. In addition, colorants are commercially available and they are applied to the fibers as a shampoo preparation or a conditioner formulation. In all these application forms, the scalp coloration obtained plays an important role, which is considered inconvenient.

  In addition to these rather traditional application methods, a great variety of application devices has been developed for temporary colorants based on direct and oxidative dyes. With these devices, the composition could be applied to keratin fibers or specific areas of the fibers. Application devices comprising colorants based on direct dyes have the disadvantage that the colors obtained are not very durable. On the other hand, application devices comprising colorants based on precursors of oxidative dyes must be very elaborately designed because the two components of the colorant must remain separately packaged until just before application. Has inconvenience.

  In an example, DE 199 22 092 A1 describes a cap-like application device for coloring hair strands attached to a container containing a hair dye. The application device includes a plurality of outlet openings for spreading the hair dye and adjacent guide protrusions that are routed through the hair by the movement of the comb during application. Furthermore, bristles are arranged around the outlet opening in order to obtain a more uniform application of the hair dye. Nevertheless, the outlet opening with bristles does not allow a well-metered application of the hair dye. In particular, excessive release of hair dyes can occur, and as a result, undesired scalp wetting cannot be effectively eliminated. Furthermore, these measures from the prior art are not completely satisfactory with regard to coloring, i.e. with respect to the strength of the color obtained.

  The subject of the present invention is therefore to develop a coloring system that is easy to handle and can strongly dye the fibers with little coloring of the scalp.

  As a result of intensive studies, it has surprisingly been found that certain application devices that combine application liquids based on dyes and / or dye precursors with alkyl phosphate esters eliminate the disadvantages of the prior art. From now on, it is possible to selectively stain the gray hair region, in particular, the temporal region, contour portion, and top region, using the coating device of the present invention. Thereby, the coloring of the present invention can be obtained with almost no scalp coloring.

  Accordingly, a first subject of the present invention is an application device (1) for applying a coating liquid onto keratin fibers, comprising at least one container (2) for receiving the coating liquid, An application head (3) connected to one container (2) and having a porous application element (31) for providing an application liquid by overcoating the fibers, the application liquid comprising at least An application device comprising one dye and / or dye precursor and at least one alkyl phosphate ester.

1 shows a perspective view of a general application device of the present invention.

  As a first component essential to the present invention, the coating liquid of the present invention comprises at least one alkyl phosphate ester.

  According to the present invention, the coating liquid has the formula (I):

[Wherein R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, an alkali metal cation, or formula (II):
-(C ₂ H ₄ O) _m- (C ₃ H ₆ O) _n -R ₄ (II)
Wherein m and n independently of each other represent an integer between 0 and 20, and R ₄ is a saturated or unsaturated, branched or unbranched C _5-28 alkyl group. Means.)
Means a group represented by
However, at least one of R ₁ group, R ₂ group or R ₃ group means a group represented by the formula (II). ]
It may be preferred to comprise at least one alkyl phosphate ester represented by

Further, when the coating solution comprises at least one alkyl phosphate ester represented by the formula (I) (wherein one of R ₁ group, R ₂ group or R ₃ group is a hydrogen atom) Has been found to be suitable.

Similarly, it has been found suitable when at least one of the R ₁ , R ₂ or R ₃ groups represents an alkali metal cation, preferably a sodium cation, a potassium cation or a lithium cation. Sodium and potassium cations are particularly preferred.

Further, the coating solution contains at least one alkyl phosphate ester represented by formula (I) (wherein R ₄ group is a saturated or unsaturated, branched or unbranched C _12-22 -alkyl group. In particular, unsaturated alkyl groups, particularly preferably oleyl groups).

  Illustrative suitable alkyl phosphates include diesters of phosphoric acid and ethoxylated lauryl alcohol (INCI name: dilaureth-4 phosphate), phosphoric acid commercially available from Clariant under the trade name Hostaphat® KO 200. Mixtures of monoesters and diesters with oleyl alcohol (INCI name: oleyl phosphate), triesters of phosphoric acid with ethoxylated cetearyl alcohol (INCI name: triceteales-4 phosphate), tris of phosphoric acid with ethoxylated oleyl alcohol Ester (INCI name: trioles-8 phosphate), Triester of phosphoric acid and oleyl alcohol (INCI name: trioleyl phosphate), and phosphate ester having INCI name dicetyl phosphate, potassium cetyl phosphate, sodium lauryl phosphate .

Similarly, an alkyl phosphate ester having a partially or fully fluorinated alkyl group, such as general formula (I) [wherein R ₁ , R ₂ and R ₃ are independently of one another R _f (CH ₂ ) _x- (OCH ₂ CH ₂ ) _y -group (wherein R _f means a fully fluorinated alkyl group having 4 to 20, preferably 6 to 18 carbon atoms) X can also be a number from 0 to 4, preferably 2 and y can be a number from 0 to 20.) ] Is preferable.

Suitable fluorinated alkyl phosphate esters are reaction products from 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 available from Clariant under the trade name HOE S 2746 is suitable.

  In the work on which the present invention is based, it has been found to be advantageous if the coating solution comprises two different alkyl phosphate esters.

  Coating solutions comprising at least one dialkyl phosphate ester and / or at least one ethoxylated monoalkyl phosphate ester are particularly suitable for the present invention.

  If the coating solution comprises two different alkyl phosphate esters in a ratio of ethoxylated monoalkyl phosphate ester to dialkyl phosphate ester of 1: 5 to 5: 1, in particular 1: 1 to 2: 1, It turned out to be particularly suitable.

  A particularly preferred alkyl phosphate ester combination of the present invention is a combination of oleth-5 phosphate and dioleyl phosphate, such as that marketed by Croda under the trade name Crodafos® HCE.

  The alkyl phosphate ester is suitably used in an amount of 0.01 to 80% by weight, particularly preferably in an amount of 0.1 to 10% by weight.

  Furthermore, it has been found that it is particularly preferred when the coating solution is formulated to have a low viscosity. After mixing with the oxidant preparation, a coating solution showing a viscosity of 0 to 2000 mPas (measured at 22 ° C., Brookfield viscometer, spindle 4, speed 4 rpm) has been found to be particularly suitable. According to the invention, a viscosity of 0-100 mPas (measured under the above conditions) is particularly preferred. According to the invention, a viscosity of 50 to 500 mPas (20 ° C. (measured at Brookfield viscometer type RV-T, spindle 4, rotation speed 20 rpm) is particularly preferred.

As a second component essential to the present invention, the coating liquid of the present invention comprises at least one dye and / or at least one dye precursor.
In a first preferred embodiment, the coating solution comprises at least one dye.

  The direct dye is preferably selected from nitrophenylenediamine, nitroaminophenol, azo dye, anthraquinone or indophenol. Particularly suitable direct dyes are compounds known under the following international 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, and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β -Hydroxyethyl) aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1 -Amino-4- (2'-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino- 2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro- 4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

Furthermore, the agent of the present invention preferably comprises at least one cationic direct dye. Particularly preferred are the following cationic dyes:
(a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14;
(b) aromatic systems substituted by quaternary nitrogen atoms, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17; and
(c) a heterocycle containing at least one quaternary nitrogen atom, as specified for example in claims 6-11 of EP-A2-998908 (expressly incorporated herein by reference) Having a direct dye.

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

Compounds of formula (DZ1) (DZ3) and (DZ5), also known under the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are particularly preferred cationic direct dyes of group (c).
Cationic direct dyes marketed under the trade name Arianor® are also particularly preferred cationic direct dyes according to the invention.

  Further, the preparations of the present invention are present, for example, in henna red, henna natural, henna black, chamomile flowers, sandalwood, tea, barberry bark, sage, logwood, red root, catechu, cedar and arcanna roots. Such naturally occurring dyes can also be included.

  The agent of the present invention contains a direct dye, preferably in an amount of 0.01 to 20% by weight, based on the total coating solution.

  In this embodiment, it has been found that it is particularly preferred that the coating solution of the invention comprises at least one anionic direct dye.

  In addition to or in place of the dye, the coating liquid of the present invention may comprise at least one dye precursor. Dye precursors suitable for the present invention include, firstly, developer-type and coupler-type oxidative dye precursors, and secondly, natural similar dye precursors.

  Usually, the coating liquid of the present invention comprises at least one developer component and at least one coupler component. Therefore, it was found that the coating solution preferably contains at least one developer component.

  Developer components are typically primary aromatic amines having additional free or substituted hydroxy or amino groups in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives, and 2,4, 5,6-tetraaminopyrimidine and its derivatives.

  According to the invention, it is preferred to use a p-phenylenediamine derivative or one of its physiologically compatible salts as the developer component. Particularly preferred are p-phenylenediamine derivatives of the formula (E1):

［式中、
- G¹は、水素原子、C₁〜C₄アルキル基、C₁〜C₄モノヒドロキシアルキル基、C₂〜C₄ポリヒドロキシアルキル基、(C₁〜C₄)アルコキシ(C₁〜C₄)アルキル基、4'-アミノフェニル基であるか、または窒素含有基、フェニル基もしくは4'-アミノフェニル基によって置換されたC₁〜C₄アルキル基であり；
- G²は、水素原子、C₁〜C₄アルキル基、C₁〜C₄モノヒドロキシアルキル基、C₂〜C₄ポリヒドロキシアルキル基、(C₁〜C₄)アルコキシ(C₁〜C₄)アルキル基、または窒素含有基によって置換されたC₁〜C₄アルキル基であり；
- G³は、水素原子、ハロゲン原子、例えば、塩素、臭素、ヨウ素またはフッ素原子、C₁〜C₄アルキル基、C₁〜C₄モノヒドロキシアルキル基、C₂〜C₄ポリヒドロキシアルキル基、C₁〜C₄ヒドロキシアルコキシ基、C₁〜C₄アセチルアミノアルコキシ基、C₁〜C₄メシルアミノアルコキシ基、またはC₁〜C₄カルバモイルアミノアルコキシ基であり；
- G^４は、水素原子、ハロゲン原子またはC₁〜C₄アルキル基であるか；または
- G³およびG⁴が互いにオルト位にある場合、それらは一緒になって架橋α,ω-アルキレンジオキソ基、例えばエチレンジオキシ基を形成しうる。］。

[Where:
-G ¹ is a hydrogen atom, C ₁ -C ₄ alkyl group, C ₁ -C ₄ monohydroxyalkyl group, C ₂ -C ₄ polyhydroxyalkyl group, (C ₁ -C ₄ ) alkoxy (C ₁ -C ₄ ) alkyl group, 4'-aminophenyl group or where a nitrogen-containing group, a phenyl group or a 4'-amino C ₁ -C ₄ alkyl group substituted by a phenyl group;
- G ² is a hydrogen atom, C ₁ -C ₄ alkyl group, C ₁ -C ₄ monohydroxyalkyl radical, C ₂ -C ₄ polyhydroxyalkyl radical, (C ₁ ~C ₄₎ alkoxy (C ₁ -C ₄ ) alkyl group or a C ₁ -C ₄ alkyl group substituted by a nitrogen-containing group;
- G ³ represents a hydrogen atom, a halogen atom, e.g., chlorine, bromine, iodine or fluorine atom, C ₁ -C ₄ alkyl group, C ₁ -C ₄ monohydroxyalkyl radical, C ₂ -C ₄ polyhydroxyalkyl radical, C ₁ -C ₄ hydroxyalkoxy group, a C ₁ -C ₄ acetylamino alkoxy group, C ₁ -C ₄ mesyl aminoalkoxy group or a C ₁ -C ₄ carbamoylamino alkoxy group;
- G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ -C ₄ alkyl group; or
When G ³ and G ⁴ are in the ortho position to each other, they can together form a bridged α, ω-alkylenedioxo group, for example an ethylenedioxy group. ].

Examples of C ₁ -C ₄ alkyl group which is designated as the substituents in the compounds of the present invention include methyl, ethyl, propyl, isopropyl and butyl groups. Ethyl and methyl are preferred alkyl groups. Preferred C ₁ -C ₄ alkoxy groups in the present invention, for example, methoxy or ethoxy group. In addition, preferred examples of C ₁ -C ₄ hydroxyalkyl groups that can be specified are hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl. A 2-hydroxyethyl group is particularly preferred. Particularly preferred are C _{2 to} C ₄ polyhydroxyalkyl groups and 1,2-dihydroxyethyl groups. According to the invention, examples of halogen atoms are F, Cl or Br atoms, with Cl atoms being particularly preferred. According to the invention, other terms used are derived from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) is, in particular, amino groups, C ₁ -C ₄ monoalkylamino group, C ₁ -C ₄ dialkylamino group, C ₁ -C ₄ trialkylammonium group, C ₁ -C ₄ monohydroxyalkylamino groups, imidazolinium and ammonium.

  Particularly preferred p-phenylenediamines of the formula (E1) are selected from the following compounds: p-phenylenediamine, p-toluylenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylene Diamine, 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-phenylene Diamine, 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-phenyl Range amine, 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- (β-hydroxyethyloxy) -p-phenylenediamine, 2- (β-acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p -Phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine, and 5,8-diaminobenzo-1,4-dioxane, and Their physiologically compatible salts.

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

  According to the invention, it is also preferred to use as the developer component compounds having at least two aromatic nuclei substituted by amino groups and / or hydroxyl groups.

  Among the binuclear developers that can be used in the coloring composition of the present invention, specifically mentioned are compounds represented by the following formula (E2) and physiologically compatible salts thereof:

［式中、
- Z¹およびZ²は、互いに独立して、ヒドロキシル基またはNH₂基であって、C₁〜C₄アルキル基、C₁〜C₄ヒドロキシアルキル基および／または架橋Yによって任意に置換されていてよく、または任意に、架橋環系の一部であってよく；
- 架橋Yは、炭素原子1〜14個を有するアルキレン基、例えば、直鎖または分岐鎖アルキレン基またはアルキレン環であって、1個以上の窒素含有基および／または1個以上のヘテロ原子、例えば、酸素、硫黄または窒素原子により中断されるか、または末端化されてもよく、かつ、1個以上のヒドロキシル基またはC₁〜C₈アルコキシ基によって置換されている場合もある、またはYは直接結合であり；
- G⁵およびG⁶は、互いに独立して、水素またはハロゲン原子、C₁〜C₄アルキル基、C₁〜C₄モノヒドロキシアルキル基、C₂〜C₄ポリヒドロキシアルキル基、C₁〜C₄アミノアルキル基、または架橋Yへの直接結合であり；
- G⁷、G⁸、G⁹、G¹⁰、G¹¹およびG¹²は、互いに独立して、水素原子、架橋Yへの直接結合、またはC₁〜C₄アルキル基であり；
但し、
- 式(E2)の化合物は、1分子につき唯1つの架橋Yを有するものとする。］。
本発明によれば、式(E2)における置換基は、前記と同様に定義される。

[Where:
-Z ¹ and Z ² are, independently of each other, a hydroxyl group or NH ₂ group, optionally substituted by a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ hydroxyalkyl group and / or a bridge Y Or may optionally be part of a bridged ring system;
The bridge Y is an alkylene group having 1 to 14 carbon atoms, for example a linear or branched alkylene group or an alkylene ring, wherein one or more nitrogen-containing groups and / or one or more heteroatoms, for example , oxygen, or is interrupted by sulfur or nitrogen atom, or may be terminated, and, in some cases, which is substituted by one or more hydroxyl groups or C ₁ -C ₈ alkoxy group, or Y is a direct A bond;
- G ⁵ and G ⁶ are independently of one another, a hydrogen or halogen atom, C ₁ -C ₄ alkyl group, C ₁ -C ₄ monohydroxyalkyl radical, C ₂ -C ₄ polyhydroxyalkyl radical, C ₁ -C ₄ aminoalkyl groups, or a direct bond to the bridge Y;
-G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² are, independently of one another, a hydrogen atom, a direct bond to the bridge Y, or a C ₁ -C ₄ alkyl group;
However,
-The compound of formula (E2) shall have only one bridge Y per molecule. ].
According to the invention, the substituents in formula (E2) are defined as above.

  Preferred dinuclear developer components of formula (E2) are in particular the following compounds: N, N′-bis (β-hydroxyethyl) -N, N′-bis (4′-aminophenyl) -1, 3-diaminopropan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetra Methylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N , N'-Diethyl-N, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-amino Phenyl) -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 compatible salts.

  Particularly preferred dinuclear developer component of formula (E2) is N, N′-bis (β-hydroxyethyl) -N, N′-bis (4′-aminophenyl) -1,3-diaminopropane-2 -Ol, bis (2-hydroxy-5-aminophenyl) methane, 1,3-bis (2,5-diaminophenoxy) propan-2-ol, N, N'-bis (4'-aminophenyl) -1 1,4-diazacycloheptane, and 1,10-bis (2 ′, 5′-diaminophenyl) -1,4,7,10-tetraoxadecane, or one of their physiologically compatible salts.

  Furthermore, according to the invention, it is also preferred to use a p-aminophenol derivative or one of its physiologically compatible salts as the developer component. Particularly preferred are p-aminophenol derivatives of the formula (E3):

［式中、
- G¹³は、水素原子、ハロゲン原子、C₁〜C₄アルキル基、C₁〜C₄モノヒドロキシアルキル基、C₂〜C₄ポリヒドロキシアルキル基、(C₁〜C₄)アルコキシ(C₁〜C₄)アルキル基、C₁〜C₄アミノアルキル基、ヒドロキシ(C₁〜C₄)アルキルアミノ基、C₁〜C₄ヒドロキシアルコキシ基、C₁〜C₄ヒドロキシアルキル(C₁〜C₄)アミノアルキル基、または(ジ- C₁〜C₄アルキルアミノ)(C₁〜C₄)アルキル基であり；
- G¹⁴は、水素またはハロゲン原子、C₁〜C₄アルキル基、C₁〜C₄モノヒドロキシアルキル基、C₂〜C₄ポリヒドロキシアルキル基、(C₁〜C₄)アルコキシ(C₁〜C₄)アルキル基、C₁〜C₄アミノアルキル基、またはC₁〜C₄シアノアルキル基であり；
- G¹⁵は、水素、C₁〜C₄アルキル基、C₁〜C₄モノヒドロキシアルキル基、C₂〜C₄ポリヒドロキシアルキル基、フェニル基またはベンジル基であり；
- G¹⁶は、水素またはハロゲン原子である。］。
本発明によれば、式(E3)における置換基は、前記と同様に定義される。

[Where:
- G ¹³ is a hydrogen atom, a halogen atom, C ₁ -C ₄ alkyl group, C ₁ -C ₄ monohydroxyalkyl radical, C ₂ -C ₄ polyhydroxyalkyl radical, (C ₁ -C ₄₎ alkoxy (C ₁ -C ₄₎ alkyl group, C ₁ -C ₄ aminoalkyl group, hydroxy (C ₁ ~C ₄₎ alkylamino group, C ₁ -C ₄ hydroxyalkoxy group, C ₁ -C ₄ hydroxyalkyl (C ₁ -C ₄ ) aminoalkyl groups, or, (di - C ₁ -C ₄ alkylamino) (C ₁ -C ₄₎ an alkyl group;
- G ¹⁴ is hydrogen or halogen atom, C ₁ -C ₄ alkyl group, C ₁ -C ₄ monohydroxyalkyl radical, C ₂ -C ₄ polyhydroxyalkyl radical, (C ₁ ~C ₄₎ alkoxy (C ₁ ~ C ₄₎ alkyl group, a C ₁ -C ₄ aminoalkyl radical or C ₁ -C ₄ cyanoalkyl radical;
- G ¹⁵ is hydrogen, C ₁ -C ₄ alkyl group, C ₁ -C ₄ monohydroxyalkyl radical, C ₂ -C ₄ polyhydroxyalkyl radical, a phenyl group or benzyl group;
-G ¹⁶ is a hydrogen or halogen atom. ].
According to the invention, the substituents in formula (E3) are defined as above.

  Preferred p-aminophenols of the formula (E3) are in particular the following compounds: 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-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (β-hydroxyethylaminomethyl) 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 Physiological Compatibility salt.

  Particularly preferred compounds of 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.

  Furthermore, the developer component can also 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 can also be selected from heterocyclic developer components such as pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives, and physiologically compatible salts thereof.

  Preferred pyridine derivatives are in particular the compounds disclosed in GB 1026978 and GB 1153196, for example 2,5-diaminopyridine, 2- (4′-methoxyphenyl) amino-3-aminopyridine, 2,3-diamino- Selected from 6-methoxypyridine, 2- (β-methoxyethyl) amino-3-amino-6-methoxypyridine and 3,4-diaminopyridine.

  Preferred pyrimidine derivatives are in particular the compounds disclosed in German patent DE 2359399, Japanese publication JP 02019576 A2 or international publication WO 96/15765, for example 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 disclosed in patents DE 3843892, DE 4133957 and patent applications WO 94/08969, WO 94/08970, EP-740931 and DE 19543988, for example the following compounds: 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-methylpyra 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 following formula (E4) pyrazolo [1,5-a] pyrimidines and their tautomeric forms when a tautomeric equilibrium exists:

［式中、
- G¹⁷、G¹⁸、G¹⁹およびG²⁰は、互いに独立して、水素原子、C₁〜C₄アルキル基、アリール基、C₁〜C₄ヒドロキシアルキル基、C₂〜C₄ポリヒドロキシアルキル基、(C₁〜C₄)アルコキシ(C₁〜C₄)アルキル基、C₁〜C₄アミノアルキル基(アセチルウレイドまたはスルホニル基によって任意に保護されていてよい)、(C₁〜C₄)アルキルアミノ(C₁〜C₄)アルキル基、ジ[(C₁〜C₄)-アルキル](C₁〜C₄)アミノアルキル基(該ジアルキル基は、5または6個の鎖員と共に炭素環または複素環を任意に形成してよい)、C₁〜C₄-ヒドロキシアルキルまたはジ(C₁〜C₄)[ヒドロキシアルキル](C₁〜C₄)アミノアルキル基であり；
- X基は、互いに独立して、水素原子、C₁〜C₄アルキル基、アリール基、C₁〜C₄ヒドロキシアルキル基、C₂〜C₄ポリヒドロキシアルキル基、C₁〜C₄アミノアルキル基、(C₁〜C₄)アルキルアミノ(C₁〜C₄)アルキル基、ジ[(C₁〜C₄)-アルキル](C₁〜C₄)アミノアルキル基(該ジアルキル基は、5または6個の鎖員と共に炭素環または複素環を任意に形成してよい)、C₁〜C₄ヒドロキシアルキルまたはジ(C₁〜C₄ヒドロキシアルキル)アミノアルキル基、アミノ基、C₁〜C₄アルキルまたはジ(C₁〜C₄ヒドロキシアルキル)アミノ基、ハロゲン原子、カルボン酸基またはスルホン酸基であり；
- iは、0、1、2または3の数値であり；
- pは、0または1の数値であり；
- qは、0または1の数値であり；
- nは、0または1の数値であり；
但し、
- p+qの合計は0でないものとし；
- p+qが2の場合、nは0の数値であり、NG¹⁷G¹⁸基およびNG¹⁹G²⁰基は、(2,3)、(5,6)、(6,7)、(3,5)または(3,7)の位置にあるものとし；
- p+qが1の場合、nは1の数値であり、NG¹⁷G¹⁸(またはNG¹⁹G²⁰)基およびOH基は、(2,3)、(5,6)、(6,7)、(3,5)または(3,7)の位置にあるものとする。］。
本発明によれば、式(E4)における置換基は前記と同様に定義される。

[Where:
-G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ are each independently a hydrogen atom, a C ₁ -C ₄ alkyl group, an aryl group, a C ₁ -C ₄ hydroxyalkyl group, a C ₂ -C ₄ polyhydroxyalkyl Groups, (C ₁ -C ₄ ) alkoxy (C ₁ -C ₄ ) alkyl groups, C ₁ -C ₄ aminoalkyl groups (optionally protected by acetylureido or sulfonyl groups), (C ₁ -C ₄ ) Alkylamino (C ₁ -C ₄ ) alkyl group, di [(C ₁ -C ₄ ) -alkyl] (C ₁ -C ₄ ) aminoalkyl group (the dialkyl group is carbon with 5 or 6 chain members) ring or may a heterocyclic ring optionally form), C ₁ ~C ₄ - hydroxyalkyl or di (C ₁ ~C ₄₎ [hydroxyalkyl] (C ₁ ~C ₄₎ aminoalkyl radical;
- X groups are independently of one another, a hydrogen atom, C ₁ -C ₄ alkyl group, aryl group, C ₁ -C ₄ hydroxyalkyl group, C ₂ -C ₄ polyhydroxyalkyl radical, C ₁ -C ₄ aminoalkyl group, (C ₁ -C ₄₎ alkylamino (C ₁ -C ₄₎ alkyl group, a di [(C ₁ ~C ₄₎ - alkyl] (C ₁ ~C ₄₎ aminoalkyl group (said dialkyl groups, 5 or may optionally form a carbocyclic or heterocyclic ring with six chain members), C ₁ -C ₄ hydroxyalkyl or di (C ₁ -C ₄ hydroxyalkyl) aminoalkyl group, an amino group, C ₁ -C ₄ alkyl or di (C ₁ -C ₄ hydroxyalkyl) amino group, halogen atom, carboxylic acid group or sulfonic acid group;
-i is a number 0, 1, 2 or 3;
-p is a number 0 or 1;
-q is a number 0 or 1;
-n is a number 0 or 1;
However,
-The sum of p + q shall be non-zero;
-When p + q is 2, n is a numerical value of 0, and NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ are (2,3), (5,6), (6,7), (3 , 5) or (3,7);
-When p + q is 1, n is the number 1, and the NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and OH groups are (2,3), (5,6), (6,7 ), (3,5) or (3,7). ].
According to the invention, the substituents in formula (E4) are defined as above.

  When the pyrazolo [1,5-a] pyrimidine of the above formula (E4) has a hydroxyl group at one of the 2, 5 or 7 positions of the ring system, for example, tautomeric equilibrium as shown by the following formula Exists:

Among the pyrazolo [1,5-a] pyrimidines of the above formula (E4), mention may be made in particular of the following compounds:
-Pyrazolo [1,5-a] pyrimidine-3,7-diamine;
-2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
-Pyrazolo [1,5-a] pyrimidine-3,5-diamine;
-2,7-dimethylpyrazolo [1,5-a] pyrimidine-3,5-diamine;
-3-aminopyrazolo [1,5-a] pyrimidin-7-ol;
-3-aminopyrazolo [1,5-a] pyrimidin-5-ol;
-2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol;
-2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol;
-2-[(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) (2-hydroxyethyl) amino] ethanol;
-2-[(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) (2-hydroxyethyl) amino] ethanol;
-5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
-2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
-3-amino-7-dimethylamino-2,5-dimethylpyrazolo [1,5-a] pyrimidine;
As well as their physiologically compatible salts, and their tautomeric forms when a tautomeric equilibrium exists.

  As described in the literature, the pyrazolo [1,5-a] pyrimidines of the above formula (E4) can be prepared by cyclization starting from aminopyrazoles or hydrazines.

  In another preferred embodiment, the colorant of the present invention comprises at least one coupler component.

  The coupler components used are generally m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives. Suitable coupler materials are in particular the following materials: 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-methylpyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2 ', 4'-diaminophenoxy) propane, 2- Chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5- Aminophenol.

According to the invention, preferred coupler components are the following substances:
m-aminophenol and its derivatives, such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2 -Methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) benzene, 3-ethylamino-4-methylphenol and 2,4-dichloro-3-aminophenol;
-o-aminophenol and its derivatives;
-m-diaminobenzene and its derivatives such as 2,4-diaminophenoxyethanol, 1,3-bis (2 ′, 4′-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2′-hydroxy Ethylamino) 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-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;
As well as their physiologically compatible salts.

  According to the invention, particularly preferred coupler components are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino. -3-hydroxypyridine, resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3 , 4-Dimethylpyridine.

  The dye composition of the present invention comprises a developer component and a coupler component in an amount of 0.005 to 20% by weight, preferably 0.1 to 5% by weight, respectively, based on the total oxidation dye composition. preferable. In this case, the developer component and the coupler component are generally used in approximately molar amounts relative to each other. Although molar use has proven convenient, the specific excess of the individual oxidative dye precursors is not inconvenient, since the developer and coupler components are in a molar ratio of 1: 0.5 to 1: 3, In particular, it means that it can exist in 1: 1 to 1: 2.

  In another embodiment of the present invention, the coating liquid of the present invention contains at least one precursor of a natural similar dye as a dye precursor (DP). The natural analogue dye precursors used are preferably indoles and indolines having at least one hydroxy or amino group, preferably as a substituent on the 6-membered ring. These groups can have further substituents, for example in the form of etherification or esterification of hydroxy groups or alkylation of amino groups. In a second preferred embodiment, the colorant contains at least one indole and / or indoline derivative.

  Particularly suitable as a precursor for natural analogue hair dyes is the formula (NAV I):

[Wherein independently of each other,
- G ₁₉ is hydrogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkyl group;
- G ₂₀ is hydrogen or -COOH group, the -COOH group can also be present as salts with physiologically compatible cation;
- G ₂₁ is hydrogen or C ₁ -C ₄ alkyl group;
- G ₂₂ is hydrogen, C ₁ -C ₄ alkyl radical or -CO-G ₂₄ group, wherein G ₂₄ is an C ₁ -C ₄ alkyl group;
- G ₂₃ is one of the groups given for G _22. ]
And the physiologically compatible salts of these compounds with organic or inorganic acids.

  Particularly preferred indoline derivatives 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.

  Of particular importance within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 -Dihydroxyindoline, especially 5,6-dihydroxyindoline.

  A particularly suitable natural hair dye precursor is of formula (NAV II):

[Wherein independently of each other,
- G ₂₅ is hydrogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkyl group;
G ₂₆ is hydrogen or a —COOH group, which can also be present as a salt with a physiologically compatible cation;
- G ₂₇ is hydrogen or C ₁ -C ₄ alkyl group;
- G ₂₈ is hydrogen, C ₁ -C ₄ alkyl radical or -CO-G ₃₀ group, wherein G ₃₀ is an C ₁ -C ₄ alkyl group;
- G ₂₉ is one of the groups given for G _28. ]
As well as physiologically compatible salts of these compounds with organic or inorganic acids.

  Particularly preferred indole derivatives 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.

  Of particular importance within this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6- Dihydroxyindoles, in particular 5,6-dihydroxyindole.

  Indoline and indole derivatives are used in the colorants of the invention as free bases or in the form of inorganic or organic acids and physiologically compatible salts thereof, such as hydrochlorides, sulfates and hydrobromides. sell. Indole or indoline derivatives are present in the colorants of the invention in an amount of 0.05 to 10% by weight, preferably 0.2 to 5% by weight.

  In a further embodiment, it may be suitable for the present invention to use indoline or indole derivatives in combination with at least one amino acid or oligopeptide in a hair dye composition. The amino acid is preferably an α-amino acid. Particularly preferred α-amino acids are arginine, ornithine, lysine, serine and histidine, especially arginine.

A third important aspect of the present invention is the development of coating devices.
An advantageous design of the actual application device is arranged such that the porous application element has continuous pores in order to achieve capillary action. The capillary properties of the application element communicated by the application liquid being carried by capillary action ensures reliable transport of the application liquid from the container as well as metered application of the application liquid by overcoating across the fiber. To do. According to a further developed application device variant, the application element preferably has a fiber, sponge, foam, felt or sintered type material structure. This material structure, for example, reduces the required capillary action of the application element so that no undesired leakage or dripping of the application liquid from the application element occurs and at the same time reliable liquid transport is ensured by the application element. give.

  As an alternative to the essentially block-like design of the porous application element, the element may also have a plurality of pencil-like protrusions. This increases the active surface of the application element, thereby improving the application of the coating liquid. As a result, a better coloring result is ensured quantitatively and qualitatively by the stroke movement of the application element over the keratin fibers (especially the hair).

  A further preferred embodiment of the application device is achieved in an application head having a plurality of comb teeth which can be removed as required. These comb teeth are arranged in particular close to the application head. With the comb teeth, the stroke movement of the entire application head during use initially gives the fibers or hairs to unravel, and thus in particular gives a uniform application of the application liquid. The removable arrangement of the comb teeth on the application head essentially allows more versatile use of the application device. This type of arrangement has also been found to be advantageous when the comb teeth protrude from the porous application element. When used on the hair, this avoids that the skin (especially the scalp) close to the hair gets wet with the coating solution. A preferred embodiment of the application device consists in that the comb teeth of the application head are arranged annularly around the application element. Independent of the direction of each stroke movement, the fiber or hair is usually first unwound during application, after which the actual application of the application liquid occurs.

  In the present invention, it has been found suitable when the coating solution contains a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purposes of the present invention, such carriers are, for example, creams, emulsions, gels or surfactant-containing foaming solutions such as shampoos, foaming aerosols or other preparations suitable for use on the hair. .

In the context of the present invention, an aqueous-alcoholic solution is understood to mean an aqueous solution comprising 3 to 70% by weight of C ₁ -C ₄ alcohol (especially ethanol or isopropanol). The composition of the present invention may further comprise an additional organic solvent such as propylene carbonate, ethylene carbonate, methoxybutanol, benzyl alcohol, ethylene diglycol or 1,2-propylene glycol. Here, preferably all water-soluble organic solvents are provided.

An aqueous carrier comprising at least one C ₁ -C ₄ alcohol and at least one further organic solvent has been found to be particularly suitable for the present invention. In this regard, the water content is 20 to 60% by weight, preferably 30 to 50% by weight, based on the total coating solution, respectively, and the C ₁ -C ₄ alcohol content is 20 to 60% by weight, preferably 30 to 50% by weight. % And the organic solvent content is 1-30% by weight, preferably 5-15% by weight. In this embodiment, a composition comprising water, ethanol and propylene carbonate may be particularly suitable.

  In the first embodiment of the present invention, the coating liquid essentially comprises only a direct dye (preferably an anionic direct dye) as a coloring component.

  In this embodiment, it was found that the coating solution had a pH of 1 to 5, preferably 1.5 to 3.

  The coating liquid of this embodiment preferably comprises an organic acid or an inorganic acid for adjusting the pH. Hydrochloric acid, sulfuric acid and phosphoric acid are particularly mentioned as suitable inorganic acids. Acetic acid, glycolic acid, citric acid, tartaric acid, lactic acid and malic acid are particularly mentioned as suitable organic acids. Malic acid is a particularly preferably added acid.

  In a second, similarly preferred embodiment, the coating solution may contain at least one dye precursor.

  In this embodiment, the coating solution of the present invention is adjusted to a pH of 7 to 11, particularly 8.5 to 10, preferably with an acidifying agent and / or an alkylating agent.

  For this purpose, suitable alkylating agents are alkali metal hydroxides or alkaline earth metal hydroxides, ammonia or organic amines. In this regard, the organic amine is preferably monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl- Selected from the group consisting of 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 this group. In the present invention, it is also preferable to use amino acids and / or oligopeptides such as ω-aminocaproic acid as alkalizing agents.

Furthermore, those amino acids and oligopeptides are preferably used. Its 2.5 wt% aqueous solution shows a pH of 9 and higher. Arginine is preferably used as this type of amino acid.
With respect to the acids suitable for the present invention, reference is made explicitly to the above embodiments.

  In principle, the coating liquids of both embodiments of the invention can further comprise all active substances, additives and auxiliaries known for such preparations. Although it has been found that it is particularly suitable when the coating liquid is formulated to be free of surfactants, in another embodiment, the coating liquid of the present invention also includes at least one surfactant. Can be. Here, in principle, not only anionic but also zwitterionic, amphoteric, nonionic and cationic surfactants are suitable. However, in many cases it has proved advantageous to select a surfactant from among anionic, zwitterionic or nonionic surfactants. In this regard, anionic surfactants may be particularly suitable.

Suitable anionic surfactants for the preparation of the present invention are any anionic surfactant suitable for use in the human body. They are characterized by water-soluble anionic groups such as carboxylate groups, sulfate groups, sulfonate groups or phosphonate groups, and lipophilic alkyl groups having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups, and hydroxyl groups can also be present in the molecule. Examples of suitable anionic surfactants are, in each case, in the form of sodium, potassium and ammonium salts, and mono-, di- and trialkanol ammonium salts having 2 or 3 carbon atoms in the alkanol group ;
-Linear fatty acids (soaps) with 10 to 22 carbon atoms:
An ether carboxylic acid of the formula RO— (CH ₂ —CH ₂ O) _x —CH ₂ —COOH, wherein R is a linear alkyl group having 10 to 22 carbon atoms and x is 0 or 1 to 16 It is. ];
An acyl sarcoside having 10 to 18 carbon atoms in the acyl group;
An acyl tauride having 10 to 18 carbon atoms in the acyl group;
An acyl isethionate having 10 to 18 carbon atoms in the acyl group;
-Sulfosuccinic acid mono- and dialkyl esters having 8 to 18 carbon atoms in the alkyl group, and monoalkyl polyoxysulfosuccinic acid having 1 to 6 oxyethyl groups having 8 to 18 carbon atoms in the alkyl group Ethyl ester;
A linear alkanesulfonate having 12 to 18 carbon atoms;
A linear α-olefin sulfonate having 12 to 18 carbon atoms;
-Α-sulfo fatty acid methyl esters of fatty acids having 12 to 18 carbon atoms;
- wherein _{RO (CH 2 -CH 2 O)} x -SO 3 H alkyl sulfates and alkyl polyglycol ether sulfates [Formula, R represents preferably a linear alkyl group having 10 to 18 carbon atoms And x is 0 or 1-12. ];
-Mixtures of surface-active hydroxysulfonates according to DE-A-3725030;
-Sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ether, as in DE-A-3723354;
-Sulfonates of unsaturated fatty acids having 12 to 24 carbon atoms and 1 to 6 double bonds, as in DE-A-3926344;
-Esters of tartaric acid and citric acid with alcohols (addition products of about 2 to 15 molecules of ethylene oxide and / or propylene oxide to 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, In particular, salts of saturated, in particular unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.

The nonionic surfactant contains, for example, a polyol group, a polyalkylene glycol ether group, or a combination of a polyol group and a polyglycol ether group as a hydrophilic group. Such compounds are for example the following compounds:
-2 to 30 mol of ethylene oxide and / or 0 of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, fatty acids having 12 to 22 carbon atoms and alkylphenols having 8 to 15 carbon atoms in the alkyl group ~ 5 mol of addition product;
- addition products of ethylene oxide 1~30mol to glycerol, C ₁₂ -C ₂₂ fatty acid mono- - and diesters;
- C ₈ -C ₂₂ alkyl mono - and oligoglycosides and their ethoxylated analogs; and
-Addition product of 5-60 mol of ethylene oxide to castor oil and hydrogenated castor oil.

Preferred nonionic surfactants are alkyl polyglycosides of the general formula R ¹ O— (Z) _x . These compounds are characterized by the following parameters:

The alkyl group R ¹ has 6 to 22 carbon atoms and may be linear or branched. Primary aliphatic groups that are straight-chain or methyl-branched at the 2-position are preferred. Such alkyl groups 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 and 1-myristyl. When so-called “oxoalcohols” are used as starting materials, compounds having an odd number of carbon atoms in the alkyl group are predominant.

The alkyl polyglycoside used in the present invention can have, for example, a single predetermined alkyl group R ¹ . In general, however, these compounds can be produced starting from natural fats or mineral oils. In this case, the alkyl group R is present as a mixture corresponding to the starting compound or corresponding to the workup of each compound.

Particularly preferred are alkyl polyglycosides in which R ¹ consists of:
-Essentially C ₈ -and C ₁₀ -alkyl groups;
-Essentially C ₁₂ -and C ₁₄ -alkyl groups;
- essentially C ₈ -C ₁₆ - alkyl group; or
- essentially C ₁₂ -C ₁₆ - alkyl group.

  The sugar building block Z that can be used is any monosaccharide or oligosaccharide. In general, sugars having 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, with glucose being particularly preferred.

  The alkyl polyglycosides that can be used in the present invention have an average of 1.1 to 5 sugar units. Alkyl polyglycosides having an x value of 1.1 to 1.6 are preferred. Particularly preferred are alkyl glycosides where x is 1.1 to 1.4.

  In addition to its surfactant activity, alkyl glycosides can also act to improve the fixation of scent components in the hair. Thus, if the effect of perfume oil on the hair lasting beyond the hair treatment period is desired, the person skilled in the art preferably uses this type of substance as an additional component of the preparation of the invention.

  Alkoxylated homologues of certain alkyl polyglycosides can also be used in the present invention. These homologues can have an average of up to 10 ethylene oxide units and / or propylene oxide units per alkyl glycoside unit.

Furthermore, zwitterionic surfactants can also be used in particular as cosurfactants. Zwitterionic surfactants are surfactant compounds that have at least one quaternary ammonium group and at least one —COO 2 ^— or —SO ₃ ^— group in the molecule. Particularly suitable zwitterionic surfactants are so-called betaines such as N-alkyl-N, N-dimethylammonium glycinate (eg cocoalkyldimethylammonium glycinate), N-acylaminopropyl-N, N-dimethylammonium. Glycinate (e.g. cocoacylaminopropyldimethylammonium glycinate), and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazoline, wherein the alkyl or acyl group has 8 to 18 carbon atoms, and cocoa Silaminoethyl hydroxyethyl carboxymethyl glycinate. A preferred zwitterionic surfactant is a fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Amphoteric surfactants are also particularly suitable as auxiliary surfactants. The amphoteric surfactant has at least one free amino group and at least one —COOH or —SO ₃ H group in the molecule in addition to the C _{8 to} C ₁₈ alkyl or acyl group, and has an inner salt. It is understood to mean a surface-active compound that can be formed. Examples of suitable amphoteric surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyl Taurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid, each having about 8-18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N- cocoalkyl aminopropionate, cocoa sill aminoethyl aminopropionate and C ₁₂ ~ 18 acyl sarcosine.

  According to the invention, quaternary ammonium compound types, ester quart types and amidoamine types are used in particular as cationic surfactants.

  Suitable quaternary ammonium compounds are ammonium halides, especially ammonium chloride and ammonium bromide such as alkyltrimethylammonium chloride, dialkyldimethylammonium chloride and trialkylmethylammonium chloride such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, chloride Distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, and imidazolium compounds known under the INCI names quaternium-27 and quaternium-83. The long alkyl chain of the surfactant preferably has 10 to 18 carbon atoms.

  Ester quats are known substances that contain both at least one ester functional group and at least one quaternary ammonium group as constituents. Preferred ester quats are quaternized ester salts of fatty acids and triethanolamine, quaternized ester salts of fatty acids and diethanolalkylamine, and quaternized fatty acids with 1,2-hydroxypropyl dialkylamine. Ester salt. Such products are marketed, for example, under the trade names Stepantex®, Dehyquart® and Armocare®. The products Armocare® VGH-70, N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, and Dehyquart® F-75 and Dehyquart® AU-35 are such esters. An example of a quote.

  Alkylamidoamines are generally prepared by amidation with natural or synthetic fatty acids and fatty acid fractions with dialkylaminoamines. A compound from this group of substances that is particularly suitable for the present invention is stearamidopropyldimethylamine, marketed under the trade name Tegoamido® S18.

  Quaternized protein hydrolyzate represents a cationic surfactant that can be used in the present invention, where the basic protein hydrolyzate is animal (eg collagen, milk or keratin), plant (eg wheat) Corn, rice, potato, soybean or almond), marine organisms (eg fish collagen or algae), or biotechnologically obtained protein hydrolysates.

  Protein hydrolysates based on the cationic derivatives according to the invention are obtained from the corresponding proteins chemically, in particular by alkaline or acid hydrolysis, by enzymatic hydrolysis and / or by a combination of both hydrolysis. Protein hydrolysis generally results in protein hydrolysates with a molecular weight distribution of about 100 daltons to thousands of daltons. Preference is given to cationic protein hydrolysates based on proteins having a molecular weight of 100 to 25000 daltons, preferably 250 to 5000 daltons. Furthermore, cationic protein hydrolysates are understood to include quaternized amino acids and mixtures thereof. Quaternization of protein hydrolysates or amino acids can be achieved by quaternary ammonium salts such as N, N-dimethyl-N (n-alkyl) -N- (2-hydroxy-3-chloro-n-propyl) ammonium. Often done using halides. Furthermore, the cationic protein hydrolyzate can be further derivatized.

  Common examples of cationic protein hydrolysates and derivatives of the present invention include commercially available products and the "International Cosmetic Ingredient Dictionary and Handbook" (7th edition, 1997, The Cosmetic, Toiletry, and Fragrance Association 1101 17th Street, NW, Suite 300, Washinton, DC 20036-4702):

Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Casein, Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Hair Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Keratin, Cocodimonium Hydroxy Propyl hydrolyzed rice protein, cocodimonium hydroxypropyl hydrolyzed soy protein, cocodimonium hydroxypropyl hydrolyzed wheat protein,

Hydroxypropylarginine lauryl / myristyl ether HCl, hydroxypropyltrimonium gelatin, hydroxypropyltrimonium hydrolyzed casein, hydroxypropyltrimonium hydrolyzed collagen, hydroxypropyltrimonium hydrolyzed conchiolin protein, hydroxypropyltrimonium hydrolyzed keratin, hydroxypropyl Trimonium hydrolyzed rice bran protein, hydroxypropyltrimonium hydrolyzed soy protein, hydroxypropyl hydrolyzed vegetable protein, hydroxypropyltrimonium hydrolyzed wheat protein, hydroxypropyltrimonium hydrolyzed wheat protein / siloxysilicate,

Raurdimonium hydroxypropyl hydrolyzed soy protein, Raurdimonium hydroxypropyl hydrolyzed wheat protein, Raurdimonium hydroxypropyl hydrolyzed wheat protein / siloxysilicate, lauryl dimonium hydroxypropyl hydrolyzed casein, lauryl dimonium hydroxypropyl hydrolyzed collagen , Lauryl dimonium hydroxypropyl hydrolyzed keratin, lauryl dimonium hydroxypropyl hydrolyzed soy protein,

Stearidimonium hydroxypropyl hydrolyzed casein, stearidimonium hydroxypropyl hydrolyzed collagen, stearidimonium hydroxypropyl hydrolyzed keratin, stearidimonium hydroxypropyl hydrolyzed rice protein, stearidimonium hydroxypropyl hydrolyzed soy protein, stearidimonium 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.

  Cationic silicone oils such as the following commercial products are also suitable for the present invention: Q2-7224 (Manufacturer: Dow Corning; Stabilized Trimethylsilyl Amodimethicone), Dow Corning 929 Emulsion (Hydroxylamino modified, also referred to as Amodimethicone). SM-2059 (Manufacturer: General Electric), SLM-55067 (Manufacturer: Wacker), and Abil®-Quat 3270 and 3272 (Manufacturer: Th. Goldschmidt; Diquaternary) Polydimethylsiloxane, quaternium-80).

  An example of a cationic surfactant quaternary sugar derivative is the commercially available product Glucquat (registered trademark) 100, the INCI name “lauryl methyl glutes-10 hydroxypropyl dimonium chloride”.

  For compounds with alkyl groups used as surfactants, they can each be a pure substance. However, for the production of these materials, it is usually preferred to start with natural plant or animal raw materials and as a result obtain substance mixtures with different alkyl chain lengths depending on each raw material.

  For these surfactants which are addition products of ethylene oxide and / or propylene oxide to fatty alcohols or derivatives of these addition products, products having a “normal” homolog distribution, as well as a narrow homolog distribution The product can be used. The term “ordinary” homolog distribution is understood to mean a mixture of homologs resulting from the reaction of a fatty alcohol and an alkylene oxide using an alkali metal, alkali metal hydroxide or alkali metal alcoholate as a catalyst. Is done. On the other hand, a narrow homolog distribution is obtained when, for example, hydrotalcite, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products having a narrow homolog distribution is preferred.

Furthermore, the agent used in the method of the present invention is preferably another conditioning active product selected from the group consisting of cationic surfactants, cationic polymers, alkylamidoamines, paraffin oils, vegetable oils and synthetic oils. Can be included.
A suitable conditioning active product may be a cationic polymer. These are usually polymers comprising quaternary nitrogen atoms, for example in the form of ammonium groups.

Suitable cationic polymers are, for example:
-Quaternized cellulose derivatives. These are commercially available under the names Celquat® and Polymer JR®. The compounds Celquat® H 100, Celquat® L 200 and Polymer JR® 400 are suitable quaternized cellulose derivatives.
-Polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and esters and amides of acrylic and methacrylic acid. Commercial products Merquat (Merquat® 100 (poly (dimethyldiallylammonium chloride) chloride), Merquat® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) and Merquat® 280 (dimethyldiallylammonium chloride-acrylic acid) Copolymer) is an example of such a cationic polymer.
-Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and dialkylaminomethacrylate, such as dimethylaminoethyl methacrylate copolymer quaternized with vinylpyrrolidone-diethyl sulfate. Such compounds are commercially available under the trade names Gafquat® 734 and Gafquat® 755.
-Vinylpyrrolidone-methymidazolinium chloride copolymer. These are offered under the trade name Luviquat®.
-Quaternized polyvinyl alcohol,
As well as known polymers containing quaternary nitrogen atoms in the polymer backbone,
-Polyquaternium-2,
-Polyquaternium-17,
-Polyquaternium-18, and
-Polyquaternium-27.

  The first four groups of cationic polymers are particularly preferred, with polyquaternium-2, polyquaternium-10 and polyquaternium-22 being particularly preferred.

  In addition, silicone oils and / or silicone gums may be suitable as conditioning actives.

According to the invention, suitable silicones or silicone gums are, inter alia, dialkyl and alkylallyl siloxanes, such as dimethylpolysiloxanes and methylphenylpolysiloxanes and their alkoxylated, quaternized and anionic derivatives.
Examples of such silicones include the following:
-Polydimethylcyclosiloxane oligomers (INCI name: cyclomethicone), in particular tetramer and pentamer compounds marketed by Dow Corning under the names DC 344 and DC 345,
-Hexamethyldisiloxane (INCI name: hexamethyldisiloxane), for example a commercial product with the name Abil® K 520,
-Polydimethylsiloxane polymer (INCI name: dimethicone), for example the commercial product by Dow Corning under the name DC 200,
-Polyphenylmethylsiloxane (INCI name: phenyltrimethicone), for example the commercial product by Dow Corning under the name DC 566 Fluid,
-Silicone-glycol copolymers (INCI name: dimethicone copolyol), for example the commercial product by Dow Corning under the names DC 190 and DC 193,
-Esters and partial esters of silicone-glycol copolymers: marketed by Fanning under the name Fancorsil® LIM (INCI name: dimethicone copolyol medoformate),
-Hydroxy-terminated dimethylsiloxane (INCI name: dimethiconol), for example DC 1401 and Q2-1403 which are commercial products by Dow Corning,
-Amino-functional polydimethylsiloxane and hydroxyamino modified silicone (INCI names: inter alia Amodimethicone and Quotanium-80), for example the commercial product XF42-B1989 (manufacturer: GE Toshiba Silicone), Q2-7224 (manufacturer: Dow Corning, Stabilized trimethylsilylamodimethicone), Dow Corning® 939 Emulsion (containing hydroxyamino-modified silicone, also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) ) And Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt),
An anionic silicone oil, eg the product Dow Corning® 1784;
-Amino-modified organosilicone, for example the product Abil Soft A843 (manufacturer: Osi Specialities).

  In a preferred embodiment, the preparation of the present invention contains volatile and non-volatile silicones. In the present invention, a volatile silicone is a silicone that exhibits a volatility equal to or higher than that of a cyclic pentamer dimethylsiloxane. Such combinations can also be obtained as commercial products (for example, Dow Corning® 1401, Dow Corning® 1403 and Dow Corning® 1501, which are mixtures of cyclomethicone and dimethiconol, respectively).

  According to a particularly preferred embodiment, the preparation according to the invention comprises a dialkylpolysiloxane or one of its derivatives. The alkyl groups methyl, ethyl, i-propyl and n-propyl are preferred. Particularly preferred is dimethylpolysiloxane or one of its derivatives. Amino-functional derivatives of dimethylpolysiloxane are particularly preferred. The most preferred derivative is commercially available under the INCI name of amodimethicone. In the research on which this application is based, the combination of active substances of alkyl phosphate esters and dialkyl polysiloxanes, in particular the combination of active substances of alkyl phosphate esters and amodimethicone, solves the problem of the present invention to a particularly high degree. Was able to show.

  The composition according to the invention preferably comprises silicone in an amount of 0.01 to 10% by weight, in particular 0.1 to 5% by weight, based on the end use preparation.

  Silicone oils, particularly dialkyl and alkylaryl siloxanes such as dimethylpolysiloxane and methylphenylpolysiloxane, and their alkoxylated and quaternized analogs are suitable conditioning active products. Examples of such silicones are those from Dow Corning under the trade names DC 190, DC 200, DC 344, DC 345 and DC 1401, and the commercial product Q2-7224 (manufacturer: Dow Corning; stabilized trimethylsilyl amo Dimethicone), Dow Corning® 929 emulsion (comprising hydroxyamino-modified silicone, also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker), and Abil ® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxane, quaternium-80).

  As conditioning active ingredients it is likewise possible to use paraffin oils, synthetically prepared alkene oligomers and vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil and apricot oil.

  Likewise suitable hair conditioning compounds are phospholipids such as soy lecithin, egg lecithin and kephalin.

Examples of further active ingredients, auxiliaries and additives are as follows:
Non-ionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes;
-Zwitterionic and amphoteric polymers such as acrylamidopropyltrimethylammonium chloride / acrylate copolymer and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymer;
-Anionic polymers such as polyacrylic acid, crosslinked polyacrylic acid, vinyl acetate / crotonic acid copolymer, vinyl pyrrolidone / vinyl acrylate copolymer, vinyl acetate / butyl maleate / isobornyl acrylate copolymer, methyl vinyl ether / maleic anhydride copolymer And acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymer;
-Thickeners such as agar, guar gum, alginate, xanthan gum, gum arabic, karaya gum, locust bean flour, linseed gum, dextran, cellulose derivatives such as methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, amylose, amylopectin and dextrin starch Fractions and derivatives, clays such as bentonite, or synthetic hydrophilic colloids such as polyvinyl alcohol;
-Structurants, such as maleic acid and lactic acid;
-Hair conditioning compounds such as phospholipids such as soy lecithin, egg lecithin and cephalin;
-Perfume oil, dimethyl isosorbide and cyclodextrin;
-Solvents and solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol;
-Active ingredients that improve the fiber structure, in particular monosaccharides, disaccharides and oligosaccharides, such as glucose, galactose, fructose, fructose and lactose;
A quaternized amine, for example methyl-1-alkylamidoethyl-2-alkylimidazolium methosulfate;
-Antifoaming agents, for example silicone;
-Dyes for coloring compositions;
-Anti-dandruff active ingredients such as piroctone olamine, zinc omazine and crimbazole;
-Photoprotective agents, in particular derivatized benzophenones, cinnamic acid derivatives and triazines;
pH adjusting substances such as common acids, in particular edible acids and bases;
-Active ingredients such as allantoin, pyrrolidone carboxylic acid and its salts, and bisabolol;
-Cholesterol;
-Consistency regulators such as sugar esters, polyol esters or polyol alkyl ethers;
-Fats and waxes, such as whale wax, beeswax, montan wax and paraffin;
-Fatty acid alkanolamides;
Complexing agents such as EDTA, NTA, β-alanine diacetate and phosphonic acid;
-Swelling and osmotic substances such as glycerol, propylene glycol monoethyl ether, carbonate, hydrogen carbonate, guanidine, urea, and primary, secondary and tertiary phosphates;
-Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers;
-Pearlescent agents such as ethylene glycol mono- and distearate, and PEG-3 distearate;
-Pigments;
-Stabilizers for hydrogen peroxide and other oxidants;
-Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air;
- Antioxidant.

  With regard to further optional components and their usage, reference is made in particular to relevant handbooks known to the person skilled in the art, for example the monograph by K. Schrader, Grundlagen und Rezepturen der Kosmetika, 2nd edition, Huethig Buch Verlag, Heidelberg (1989). The

  The components of the aqueous carrier are added in the usual amounts for producing the coating liquid of the present invention. For example, the emulsifier is added at a concentration of 0.5-30% by weight based on the total colorant, and the thickener is added at a concentration of 0.1-25% by weight based on the total colorant.

  According to a preferred embodiment, the color is formed by oxygen from the air as the only oxidant.

  Further features of the present invention will become apparent from one drawing showing a general application device in perspective view. Further features of the invention are also described in detail below.

  The application device 1 shown in FIG. 1 is designed for the application of liquid hair dyes. However, this type of applicator device 1 can also be used normally for the application of any coating solution for essentially keratin fibers. Here, the coating liquid is spread on the fiber by a stroke motion. The application device 1 has a container 2 that receives a hair dye or application liquid and stores it until use. It may be suitable to provide an absorbent storage element on the inside of the container, for example in the form of fibers or sponges, for absorbing hair dyes or coating liquids. The application head 3 is fixed on the open end of the container and serves to spread the hair dye on the hair. The application head 3 essentially comprises a plurality of comb teeth 33 which are joined together in a porous application element 31 and advantageously at least one comb element 34. In FIG. 1, the application device 1 is shown ready for use, i.e. with the application head 3 open. When not in use, the application head 3 is covered with a cap (not shown) which is fixed firmly on the container, for example by means of threads 4. In this way, the application head 3 is separated from the environment so as to effectively prevent the liquid hair dye from drying.

  Specifically, in preparation for spreading on the hair, the application head 31 remains in contact with the liquid hair dye or application liquid to carry the liquid from the container by carrying it by a kind of capillary action. In this regard, the porous application element 31 has a material structure that incorporates continuous pores in order to achieve proper capillary action. The application element 31 consists in particular of fiber-, sponge-, foam-, felt- or sintered material. The advantage of such a design of the application element 31 is not only reliable delivery of the hair dye composition, but also high liquid absorption capacity. That is, the high liquid absorption capacity prevents any undesired leakage or dripping of the hair dye from the application device 1. The geometric shape of the application device 31 preferably has a block-like (not shown) or a plurality of pencil-like protrusions 32. Primarily, embodiments having a plurality of pencil-like protrusions 32 increase the effective surface of the application element 31 to achieve better coloring results when stroking through the hair.

  The comb teeth 33 on the application head 3 which are also in the immediate vicinity of the application element 31 serve to unravel the hair when using the application device 1. This unraveling of the hair allows a more uniform color application to the hair. The individual comb teeth 33 are usually connected integrally to at least one comb element 34, in order to simplify handling and manufacture. Furthermore, the comb teeth 33 or the comb elements 34 are removably fixed on the application head 3 in order to enable application without using the comb teeth 33 or the comb elements 34 for special cases. It is preferable. Overall, the comb teeth 33 project longitudinally from the application element 31 to the application device 1 so as to avoid any contact between the scalp and the application element 31 or the application liquid mainly during application to the hair.

  According to a further variant of the embodiment (not shown), the comb teeth 33 are arranged annularly around the application element 31 on the application head 3. In this way, when using the applicator device 1, independently of the direction of each stroke movement, normally the hair is first unwound and then the actual application of the application liquid occurs. This gives improved coloring results.

  Using the application device, the following application liquid was spread over the hair in the visible region (top, contour and temporal) (amounts are weight percent):

Crodafos® HCE: a complex mixture of ethoxylated oleyl alcohol and dioleyl phosphate having about 5 EO units (INCI name: Ores-5 phosphate, dioleyl phosphate) (Croda)

SME 253 (Silicone)): Amino-functional silicone microemulsion (INCI name: Amodimethicone and C _11-15 Palace-7 and Laureth-9 and Glycerin and Trideceth-12) (GE Silicones)

The hair was then dried without washing off the product and the hair was combed as usual. The following coloration was obtained:
Formulation 1: Medium blonde Formula 2: Reddish brown Formulation 3: Dark brown Formula 4: Black

Claims (20)

An application device (1) for applying an application liquid onto keratin fibers,
At least one container (2) for receiving the coating solution;
An application head (3) connected to the at least one container (2), and having a porous application element (31) for providing an application liquid by overcoating the fibers;
The coating solution comprises at least one dye and / or dye precursor and at least one alkyl phosphate ester.
Application device. The coating solution is of formula (I):

[Wherein R ₁ , R ₂ and R ₃ are each independently a hydrogen atom or formula (II):
-(C ₂ H ₄ O) _m- (C ₃ H ₆ O) _n -R ₄ (II)
Wherein m and n independently of each other represent an integer between 0 and 20, and R ₄ is a saturated or unsaturated, branched or unbranched C _5-28 alkyl group. Means.)
Means a group represented by
However, at least one of R ₁ group, R ₂ group or R ₃ group means a group represented by the formula (II). ]
The applicator device (1) according to claim 1, comprising at least one alkyl phosphate ester of formula (1). The coating device (1) according to claim 2, wherein at least one of R ₁ , R ₂ or R ₃ represents a hydrogen atom. _4. The applicator device (1) according to claim 2 or 3, wherein the R4 group means a saturated or unsaturated, branched or unbranched _C12-22 alkyl group. Application device (1) according to any of claims 2 to ₄ , wherein R ₄ represents an unsaturated alkyl group, preferably an oleyl group.   The coating device (1) according to any of claims 1 to 5, wherein the coating solution comprises at least two different alkyl phosphate esters.   The coating device (1) according to any one of claims 1 to 6, wherein the coating liquid comprises at least one dialkyl phosphate ester.   The coating device (1) according to any one of claims 1 to 7, wherein the coating solution comprises at least one ethoxylated monoalkyl phosphate ester.   The coating device (1) according to any of claims 1 to 8, wherein the coating liquid comprises at least one anionic direct dye.   The coating device (1) according to any one of claims 1 to 9, wherein the coating solution comprises at least one organic solvent.   The coating device (1) according to any of claims 1 to 10, wherein the coating solution comprises at least one polymer.   12. The applicator device (1) according to claim 11, wherein the polymer is non-ionic.   The coating device (1) according to any of claims 1 to 12, wherein the pH of the coating solution is between 2 and 5.   14. An applicator device (1) according to any of the preceding claims, wherein the porous applicator element (31) has continuous pores to achieve capillary action.   15. The applicator device (1) according to any of claims 1 to 14, wherein the applicator element (31) preferably has a fiber-, sponge-, foam-, felt- or sintered material structure.   The applicator device (1) according to any of the preceding claims, wherein the porous applicator element (31) has a plurality of pencil-like protrusions (32).   17. The applicator device (1) according to any of claims 1 to 16, wherein the applicator head (3) has a plurality of comb teeth (33) that can be removed as required.   18. An applicator device (1) according to claim 17, wherein the comb teeth (33) protrude from the porous applicator element (31).   19. The applicator device (1) according to claim 17 or 18, wherein the comb teeth (33) of the applicator head (3) are arranged annularly around the applicator element (31).   The viscosity (Brookfield viscometer type RV-T, spindle 4, rotation speed 20 rpm) measured at 20 ° C of the coating solution is between 50 mPas and 500 mPas. Application device (1).

Images