WO2009010415A2 - Agents comprising an anti-irritant active substance - Google Patents

Agents comprising an anti-irritant active substance

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Publication number
WO2009010415A2
WO2009010415A2 PCT/EP2008/058790 EP2008058790W WO2009010415A2 WO 2009010415 A2 WO2009010415 A2 WO 2009010415A2 EP 2008058790 W EP2008058790 W EP 2008058790W WO 2009010415 A2 WO2009010415 A2 WO 2009010415A2
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WO
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Application
Patent type
Prior art keywords
ch
acid
amino
group
color
Prior art date
Application number
PCT/EP2008/058790
Other languages
German (de)
French (fr)
Other versions
WO2009010415A3 (en )
Inventor
Astrid Kleen
Janie Terrier
Original Assignee
Henkel Ag & Co. Kgaa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/96Cosmetics or similar toilet preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97Cosmetics or similar toilet preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/92Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A61K8/922Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/04Preparations for permanent waving or straightening the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/10Preparations for permanently dyeing the hair

Abstract

The invention relates to agents for changing the color and/or permanently changing the shape of keratin fibers. Said agents comprise, in a cosmetically acceptable substrate, at least one active substance that changes the color and/or permanently changes the shape of the keratin fibers and at least one plant extract, at least one plant oil, at least one unsaponifiable remainder of a plant oil. The agents according to the invention are stable, give satisfying results with respect to the change of color and/or shape and at the same time provoke hardly any irritations of the scalp. The fibers treated with the agents according to the invention have an improved condition.

Description

"Which contains an anti-irritating active ingredient"

The present application color and / or relates to shape-changing means for keratinous fibers containing at least one plant extract, at least one vegetable oil, at least one unsaponifiable residue of a vegetable oil and at least one color and / or shape-changing agent.

Human hair is nowadays treated in diverse ways with hair cosmetic preparations. These include cleaning the hair with shampoos, care and regeneration with rinses and treatments, as well as bleaching, dyeing and shaping the hair using colorants, tints, waving compositions and styling preparations. Here, media play an important role for changing or shading the color of the hair.

The change of shape and color of hair is an important area of ​​modern cosmetics. Thus, the appearance of the hair can be adapted to both current fashion trends and to the individual needs of each person. Here, perm and other hair shape can changing process is nearly independent of the used hair to be treated type. In contrast, dyeing and blonding are restricted to certain output hair colors. The basics of blonding are known in the art and can be used in relevant monographs, eg Kh. Schrader, bases and Formulations of Cosmetics, 2nd edition, 1989, Dr. Alfred Hüthig Verlag, Heidelberg, or W. Limbach (ed.), Cosmetics, 2nd edition, 1995, Georg Thieme Verlag, Stuttgart, New York, be found.

At the same time, there is also often a desire to change the hair color and to achieve together with the hair coloring and lightening of the hair to be dyed.

Conventional hair dyes contain, as color-changing agents usually at least one developing and / or at least one coupler components and optionally direct dyes as shading agents. Coupler and developer components are also referred to as oxidation dye precursors.

Prior to its application to human hair are usually hair coloring and / or - whitening agent in solid or pasty form with a dilute aqueous hydrogen peroxide solution are mixed. The resulting mixture is then applied to the hair and rinsed out again after a certain contact time. The period of action on the hair to achieve complete dyeing or whitening is between about 30 and 40 minutes. It is obvious that when the users of the hair color or hair bleaching is a need to reduce this exposure time.

To achieve a sufficient dyeing and / or bleaching, such agents are usually adjusted highly alkaline, the pH lies from 8 to 10.5. Such high pH values ​​are required in order to ensure opening of the outer scale layer (cuticle) and thus a penetration of the active species (hydrogen peroxide) to enable the hair.

Neither the pasty nor the powdery coloring and / or bleaching that are on the market today can be considered optimal. While the dyeing and / or bleaching can be referred tailored to the hair than on consumer needs, but there are still a number of disadvantages and problems both in production and in the use of these funds.

Due to the highly alkaline conditions and the use of hydrogen peroxide can occur in connection with the color-changing process irritation to the scalp. This can be observed both during exposure to the color-changing agent and after the treatment.

The permanent deformation of keratin fibers is usually performed so that shaping the fibers and mechanically fixing the shape by suitable means. Before and / or after this shaping, the fibers are treated with the aqueous preparation of a keratin-reducing substance and rinsed after a contact time with water or an aqueous solution. In a second step, the fibers are treated with the aqueous preparation of an oxidizing agent. After an exposure time and this is rinsed out and the fiber from the mechanical deformation tools (winders, papillotes) liberated. The aqueous preparation of the keratin-reducing substance is usually adjusted to be alkaline so deprotonated to a sufficient proportion of the thiol groups is present and the other swells the fiber and a deep penetration of the keratin-reducing substance is made possible in the fiber in this manner. The keratin-reducing substance cleaves some of the disulfide bonds of the keratin to -SH groups, so that there will be a relaxation of the peptide and cross-linking due to the tension of the fiber by the mechanical deformation to a reorientation of the keratin structure. Under the influence of the oxidizing agent disulfide bonds are re-attached, and in this way the keratin is re-fixed in the predetermined deformation. A known method is the permanent wave treatment of human hair. This can be applied both to produce curls and waves in straight hair and for straightening curly hair.

Even with the permanent wave treatment, the fibers are exposed to aggressive media, so that even in this area there was a need to improve the means with regard to their caring properties.

Therefore, there has been no lack of attempts in the past to optimize the color and / or shape-changing means in terms of their scalp compatibility. Both methods have been proposed in which the scalp was pre-treated with a protective preparation as well as methods in which the color and / or shape-changing agents themselves contain active ingredients that are intended to minimize the scalp irritation. Nevertheless, the means of the prior art could not fully comply with the existing requirements so far.

More particularly, the active compounds used within the scope of these methods have to meet high demands with respect to their stability, as the coloring creams typically have a high pH and the oxidizing agent preparations a low pH. These active ingredients have to be stable to the reducing conditions of the wave agent. Furthermore, incompatibilities of various active ingredients with one another and thus avoid a short shelf life.

Therefore, there was a need for drugs that can irritate the scalp, which can manifest themselves in the form of tingling, itching and / or redness degrade under the conditions of the oxidative color change, and permanent waving of keratinous fibers and in addition, antimicrobial, anti-inflammatory and / or can act antioxidant. Furthermore, there is an interest in active ingredients that support a structure of the natural minerals ( "mineral building"). It has now surprisingly been found that color and / or shape-changing means, besides the active compound, which the color and / or permanent form the keratin fibers changed, at least one plant extract, at least one vegetable oil and at least one unsaponifiable residue of a vegetable oil containing, are stable, satisfactory with regard to their color and / or shape and at the same time cause less scalp irritation. wise addition, with the inventive treated means fibers have an improved condition on.

therefore a first object of the present application, a means for color and / or permanent change in shape of keratin fibers, comprising, in a cosmetically acceptable support, at least one active ingredient that changes the color and / or permanently, the shape of keratinous fibers, further

- at least one plant extract,

- at least one vegetable oil,

- contains at least one unsaponifiable residue of a vegetable oil and.

are to be understood as "keratin fibers" According to the invention include pelts, wool, feathers and particularly human hair.

The inventive compositions contain, as a first essential component of the invention, at least one plant extract.

Typically these extracts are prepared by extracting the entire plant. but it may in some cases be preferable to the extracts exclusively from flowers, leaves and / or the other components of the plant, as example, to establish branches.

With regard to the inventive preferred plant extracts is made in particular to the extracts listed in the on page 44 of the 3rd edition of the introduction to the ingredient declaration of cosmetic products, published by the Industrial Association, Perfumery and Detergent Association (IKW), Frankfurt, incipient table lists.

According to the invention, the extracts from Moringa Olifeira, Cardiospermum Halicacabum, green tea, oak bark, stinging nettle, witch hazel, hops, henna, chamomile, burdock, horsetail, hawthorn, linden blossom, almond, aloe vera, pine needles, horse chestnut, sandalwood, juniper, coconut , preferably mango, apricot, lemon, wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, lady's smock, wild thyme, yarrow, thyme, lemon balm, Hauhechel, coltsfoot, marshmallow, meristem, ginseng and ginger root.

Particularly preferably, the extracts of Moringa Olifeira, green tea, Cardiospermum Halicacabum, oak bark, stinging nettle, witch hazel, hops, chamomile, burdock, horsetail, lime blossom, almond, aloe vera, coconut, mango, apricot, lemon, wheat, kiwi, melon, are orange, grapefruit, sage, rosemary, birch, lady's smock, wild thyme, yarrow, rest harrow, meristem, ginseng and ginger root.

Particularly suited to the extracts of Moringa Olifeira, green tea, Cardiospermum Halicacabum, almond, aloe vera, coconut, mango, apricot, lemon, wheat, kiwi and melon are.

Furthermore, if the plant extract is obtained from a creeper have the invention particularly advantageous properties. Climbing plants are divided according to their ability to climb itself (Selbstklimmern) or their need for a climbing frame.

Preferred Selbstklimmern include ivy, species / varieties of Virginia creeper, Parthenocissus, Cobea scandens.

Among the inventively preferred scaffold climbing plants include Cardiospermum Halicacabum, clematis, vines, wisteria, honeysuckle, blackberry, climbing rose and pyracantha.

As a particular preference, the extracts obtained from vines such as Cardiospermum Halicacabum, wisteria and honeysuckle have proved invention.

According to the invention most preferably are plant extracts which are obtained from the plant Cardiospermum Halicacabum; wherein again the extracts are particularly preferred which are obtained from the flowers, leaves, and cuttings of the plant Cardiospermum Halicacabum.

As extraction agents for producing the plant extracts mentioned water, alcohols and mixtures thereof can be used. Among the alcohols, lower alcohols such as ethanol and isopropanol, but especially polyhydric alcohols such as ethylene glycol and propylene glycol, both as sole extractant or in a mixture with water, preferably. Plant extracts based on water / propylene glycol in a ratio of 1: 10 to 10: 1 have proved to be particularly suitable. The plant extracts can be used according to the invention both in pure form or in dilute form. If they are used in diluted form, they typically contain ca. 2 - 80 wt .-% of active substance and solvent as the extraction agent used to obtain them or extractant mixture.

Furthermore, it may be preferred to use mixtures of several, more particularly two, different plant extracts in the novel color-changing means.

Furthermore, at least compositions of the invention contain a vegetable oil.

According to the invention, preferred examples of such oils are sunflower oil, olive oil, soybean oil, echium oil, rapeseed oil, almond oil, jojoba oil, orange oil, wheat germ oil, peach kernel oil and the liquid fractions of coconut oil. Suitable but other triglyceride oils such as the liquid fractions of beef tallow and synthetic triglyceride oils.

According to the invention the vegetable oils have proven particularly preferably also derived from a flowering plant; wherein the class of dicotyledonous Dreifurchenpollen- is particularly preferred.

Within this class, the oils are that can be obtained for example from asters and button-like; a particularly preferred source of novel vegetable oils is the (Echium).

As a third essential ingredient, the inventive compositions comprise at least one unsaponifiable residue of another vegetable oil.

Under the unsaponifiable residue of a vegetable oil, the proportion is understood according to the invention, which resists saponification reaction. The unsaponifiable residue contains inter alia specific plant phytosterols and fat-soluble vitamins.

According to all vegetable oils are in principle as a source of unsaponifiable residue in question. but it is essential to the invention that the source of unsaponifiable rest of the vegetable oil does not coincide with the also required vegetable oil. In the context of the present invention have particularly good effects shown unsaponifiable residues which is obtained from a plant of the Korbblütengewächse a vegetable oil.

A particularly preferred genus Asteraceae is the genus of sunflowers.

An example of a particularly preferred active substance, which contains the above combination of active ingredients is the product marketed under the trade name Defensil ® mfd. By Rahn. This product has the INCI designation octyldodecanol, Cardiospermum Halicacabum Flower / Leaf / Vine Extract, Echium Plantagineum Seed OiI, Helianthus annuus (Sunflower) Seed OiI Unsaponifiables.

In the colorants the active ingredient combination according to the invention is preferably contained in an amount of at least 0.01 up to 20 wt .-%. Preference is given to amounts of from 0.01 up to 10 wt .-%, very particularly preferably amounts of from 0.01 to 5 wt .-%, based on the total composition.

Furthermore, it has proven in the context of this application work underlying that the advantageous properties of the compositions of the invention described above could be further enhanced if they contain at least one bioactive glass.

The term "bioactive glasses" includes in the context of the present application glasses which are biologically active and / or biologically active. The biological activity of a glass can be seen for example in its antimicrobial properties, bioactive glass differs from conventional lime-sodium silicate jars before in that it binds to living tissue. As biologically active glass, for example, designates a glass, which forms a strong bond with body tissue, wherein a hydroxylapatite layer is formed. Under bioactive glass is also meant a glass, the antimicrobial and / or shows anti-inflammatory effect The glass powders exhibit biocidal or biostatic effect against a bacteria, fungi and viruses,. are tolerated by the skin, toxicologically acceptable and are also particularly suitable for consumption in contact with humans.

contain the inventive bioactive glass or glass powder or glass ceramic powder or composite materials which comprise such a bioactive glass. Under glass powders are understood granules and glass beads in the context of the present application. Because of the demands on the toxicological safety of the glass, the glass powder should be particularly pure, preferably. Exposure to heavy metals is preferably low. Thus, the maximum concentration is in the field of cosmetic formulations, preferably for Pb <20 ppm, Cd <5 ppm, As <5 ppm, Sb <10 ppm, Hg <1 ppm, Ni <10 ppm.

The unceramized starting glass which is directly included in compositions of the invention or is optionally used for the production of a glass ceramic according to invention, containing SiO 2 as a network former, preferably between 35-80 wt .-%. At lower concentrations, the spontaneous tendency to crystallize increases strongly and the chemical resistance sharply. At higher SiO 2 values the crystallization stability may decrease, and the processing temperature is significantly increased, so that the hot-forming properties deteriorate. Na 2 O is used as a flux during melting of the glass. At concentrations less than 5%, the melting behavior is adversely affected. Sodium is a component of the forming during ceramization phases and must, if high crystalline phase portions to be adjusted by the ceramization be contained in appropriately high concentrations in the glass. K 2 O acts as a flux in melting the glass. In addition, potassium is released in aqueous systems. Are high potassium concentrations in the glass, potassium-containing phases such as potassium silicates are also eliminated. About the P 2 O 5 content, the chemical durability of the glass and thus the release of ions in aqueous media can be adjusted in silicate glasses, glass ceramics, or composites. In Phospahtgläsern P 2 O 5 network images. The P 2 O 5 content is preferably between 0 and 80 wt .-%. In order to improve the meltability, the glass may contain up to 25% by weight B 2 O 3. AI 2 O 3 is used to adjust the chemical durability of the glass.

To enhance the antimicrobial, in particular antibacterial properties of the glass-ceramic ion antimicrobial such can. As Ag, Au, I, Ce, Cu, Zn be included 5 wt .-% at concentrations less.

Colorants such ions. B. Mn, Cu, Fe, Cr, Co, V, may be included individually or in combination, preferably in a total concentration less than 1 wt .-%. Typically, the glass or the glass ceramic is used in powder form. Ceramization can be done either with a glass block or glass ribbons or with glass powder. After ceramization, the glass ceramic blocks or ribbons must be ground to powder. the powder was ceramified must possibly also be ground again in order to remove agglomerates arise on during Keramisierungsschrittes. The millings can both dry and be carried out in aqueous or non-aqueous grinding media. Typically, the particle sizes are less than 500 microns. Be expedient particle sizes have proven to <100 microns or <20 microns. Particularly suitable are particle sizes of <10 microns and less than 5 microns and less than 2 microns, see below.

The bioactive glasses present in the novel compositions or glass powder or glass-ceramic powder or composite compositions comprise glasses, which preferably comprise the following components: SiO 2: 35-80 wt .-%, Na 2 O: 0-35% by weight, P 2 O 5: 0-80 wt .-%, MgO: 0-5 wt .-%, Ag 2 O: 0-0.5 wt .-%, AgI: 0-0.5% by weight, NaJ: 0-5 wt .-% TiO 2: 0-5 wt .-%, K 2 O: wt .-%, ZnO 0-35: 0-25: 0-10 wt .-%, Al 2 O 3 .-% and B 2 O 3: 0-25 wt .-%.

Furthermore, the base glass according to the above composition to achieve further effects, such as color, or UV-filtering can ions such as Fe, Co, Cr, V, Ce, Cu, Mn, Ni, Bi, Sn, Ag, Au, J individually or in total up are added to 10 wt .-%. A further glass composition may be as follows: SiO 2: 0-5 wt: 35-80 wt .-%, Na 2 O: 0-35 wt .-%, P 2 O 5: 0- 80 wt .-% MgO .-%, Ag 2 O: 0-0.5 wt .-%, AgI: 0-0.5 wt .-%, NaJ: 0-5 wt .-% TiO 2: 0-5 wt .-% , K 2 O: 0-35 wt .-%, ZnO: 0-10 wt .-%, Al 2 O 3: 0-25 wt .-%, B 2 O 3: 0- 25 wt .-%, SnO : 0-5 wt .-%, CeO 2: 0-3 wt%, and Au: 0.001-0.1 wt .-%.

Particularly preferred agents according to the invention are characterized in that the bioactive glass - based on its weight - has the following composition:

SiO 2 35 to 60 wt .-%, preferably 40 to 60 wt .-%,

Na 2 O 0 to 35 wt .-%, preferably 5 to 30 wt .-%,

K 2 O 0 to 35 wt .-%, preferably 0 to 20 wt .-%,

P 2 O 5 0 to 10 wt .-%, preferably 2 to 10 wt .-%,

MgO 0 to 10 wt .-%, preferably 0 to 5 wt .-%,

CaO 0 to 35 wt .-%, preferably 5 to 30 wt .-%,

Al 2 O 3 0 to 25 wt .-%, preferably 0 to 5 wt .-%,

B 2 O 3 0 to 25 wt .-%, preferably 0 to 5 wt .-%,

TiO 2 0 to 10 wt .-%, preferably 0.1 to 5 wt .-%.

In this case, such glasses have proved particularly suitable which represent a mixture of the oxides of silicon, calcium, sodium and phosphorus. Such glasses are available under the INCI name Sodium calcium phosphosilicates commercially. Furthermore, it has proved to be advantageous if these glasses are used in a mixture with the known under the INCI name Mica. A mixture of 94-97Gew.-% Sodium calcium phosphosilicates and 3-6Gew .-% Mica has according to the invention proved to be very particularly preferred. Such a mixture is sold for example under the name Actysse ® premiere BG by Engelhard.

As mentioned above, the bioactive glass is preferably used in particulate form. Highly preferred colorant of the invention are characterized in that the antimicrobial glass particle sizes <10 microns, preferably from 0.5 to 4 .mu.m, particularly preferably from 1 to 2 microns, having.

In the compositions, the bioactive glass is preferably contained in an amount of at least 0.01 up to 20 wt .-%. Preferred are amounts of the bioactive glass from 0.01 up to 10 wt .-%, very particularly preferably amounts of from 0.01 to 5 wt .-%, based on the total composition.

As a further essential component the invention, the colorants comprise at least one color-modifying active ingredient.

As part of a first preferred embodiment, wherein the color-changing agent to a dye precursor.

Regarding the useable in the inventive coloring dye precursors, the present invention is subject to no restrictions. The colorants according to the invention can be used as dye precursors

• oxidation dye precursors of the developer and / or coupler type, and

contain • precursors of nature-analogous dyes, such as indole and indoline derivatives, and mixtures of representatives of these groups.

As part of a first preferred embodiment of the present invention, compositions of the invention contain at least one dye precursor of the developer and / or

Intermediate type.

It may be preferable in the invention as a developer component a p

Phenylenediamine derivative or one of its physiologically acceptable salts.

Particularly preferably p-phenylenediamine derivatives of formula (E1) are in which

G 1 represents a hydrogen atom, a (Ci to C4) alkyl, a (Ci to C 4) - monohydroxyalkyl radical, a (C 2 to C 4) polyhydroxyalkyl radical, a (Ci-C 4) alkoxy- (C to C 4) alkyl group, a 4'-aminophenyl or (Ci to C4) alkyl which is substituted with a nitrogenous group, a phenyl group or a 4'-aminophenyl radical;

G 2 represents a hydrogen atom, a (C 1 to C 4) alkyl radical, a (C 1 to C 4) - monohydroxyalkyl radical, a (C 2 to C 4) polyhydroxyalkyl radical, a (C 1 to C 4) alkoxy alkyl group (C-ι-C 4) or a (C 1 to C 4) alkyl which is substituted with a nitrogenous 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, a (C 2 to alkoxy Acetylaminoalkoxyrest, a Mesylamino- (C-ι-C 4) or a (C 1 to C 4) - C 4) - polyhydroxyalkyl radical, a (C 1 to C 4) -Hydroxyalkoxyrest, a (C 1 to C 4) - Carbamoylaminoalkoxyrest;

G 4 represents a hydrogen atom, a halogen atom or a (C 1 to C 4), or if G 3 and G are in ortho-position to each other 4 alkyl radical, they may together form a bridging α, ω-alkylenedioxo group, such as an ethylenedioxy ,

Especially preferred p-phenylenediamines of formula (E1) are selected from one or more compounds of the group which is formed from p-phenylenediamine, p-tolylenediamine, 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 (.beta.-hydroxyethyl) -p-phenylenediamine, 4-N, N bis (.beta.-hydroxyethyl) amino-2-methylaniline, A- N, N-bis (.beta.-hydroxyethyl) amino-2-chloroaniline, 2- (beta-hydroxyethyl) -p-phenylenediamine, 2- ( α, ß-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (beta-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl, ß-hydroxyethyl) -p-phenylenediamine, N- (ß, γ-dihydroxypropyl) - p-phenylenediamine, N- (4'-aminophenyl) - p-phenylenediamine, N-phenyl- p-phenylenediamine, 2- (.beta.-hydroxyethyloxy) -p-phenylenediamine, 2- (beta-Acetylaminoethyloxy) -p-phenylenediamine, N- (ß-methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl ) -N- [3- (1 H-imidazol-1-yl) propyl] amine, 5,8-diaminobenzo-1, 4-dioxane, as well as their physiologically acceptable salts.

According to the invention particularly preferred p-phenylenediamine derivatives of formula (E1) are selected from at least one of the group of p-phenylenediamine, p-toluylenediamine, 2- (beta-hydroxyethyl) -p-phenylenediamine, 2- (α, ß-dihydroxyethyl) - p-phenylenediamine, N, N-bis (.beta.-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1 H-imidazol-1-yl) propyl] amine as well as the physiologically compatible salts of these compounds.

It may according to the invention further be preferred to use as the developer component compounds containing 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 coloring compositions according to the invention may in particular be mentioned the compounds corresponding to the following formula (E2), and their physiologically tolerable salts:

in which:

Z 1 and Z 2 independently of one another, are a hydroxyl or NH 2 radical, which is optionally substituted by a (Ci to C 4) alkyl, by a (Ci -C 4) hydroxyalkyl 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, by one or more nitrogenous groups and / or one or more hetero atoms such as oxygen , sulfur or nitrogen atoms may be interrupted or terminated, and possibly by one or more hydroxyl or (Ci to C8) -alkoxy radicals may be substituted, or a direct bond,

G 5 and G 6 are each independently a hydrogen or halogen atom, a (C 1 to C 4) alkyl radical, a (C 1 to C 4) monohydroxyalkyl, a (C 2 to C 4) - polyhydroxyalkyl radical, a ( Ci to C 4) -Anninoalkylrest or a direct bond to the bridge Y,

G 7, G 8, G 9, G 10, G 11 and G 12 are each independently a hydrogen atom, a direct bond to the bridge Y or a (C 1 to C 4) alkyl, with the proviso that the compounds of formula (E2) comprise only one bridge Y per molecule.

In formula (E2) substituents used in the present invention are defined analogously to the above embodiments.

Preferred binuclear developer component of the formula (E2) are in particular selected from at least one of the following compounds: N, N'-bis (.beta.-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1, 3-diamino -propan-2-ol, N, N'-bis (.beta.-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) - ethylenediamine, N, N'-bis (4'-aminophenyl) - tetramethylenediamine, N, N'-bis (.beta.-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) tetramethylenediamine, N, N'-bis (4- (methylamino) phenyl) - 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 compatible salts.

Very particularly preferred double bases of formula (E2) are chosen from N, N'-bis (.beta.-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, 1, 10-bis (2,5-diaminophenyl) -1, 4,7,10-tetraoxadecane or one of the physiologically acceptable salts of these compounds.

It may also be preferable in the invention to use as the developer component is a p-aminophenol derivative or one of its physiologically acceptable salts. Particularly preferably p-aminophenol derivatives of formula (E3) are

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, a (C 2 to C 4) polyhydroxyalkyl radical, a (C 1 to C 4 ) alkoxy- (C-ι-C 4) alkyl, a (Ci to C 4) -Anninoalkylrest, -alkylanninorest a hydroxy (Ci to C 4), a (C 1 to C 4) -Hydroxyalkoxyrest, a ( (aminoalkyl C-ι-C 4) or a (di - [(d to C4) alkyl] C 1 to C 4) hydroxyalkyl amino) - (C 1 -C 4) alkyl, and

G 14 represents a hydrogen or halogen atom, a (C 1 to C 4) alkyl radical, a (C 1 to C 4) monohydroxyalkyl, a (C 2 to C 4) polyhydroxyalkyl radical, a (C 1 to C 4 ) alkoxy- (C-ι-C 4) alkyl, a (C 1 to C 4) aminoalkyl radical or a (C 1 to C 4) -Cyanoalkylrest,

G 15 is hydrogen, a (C 1 to C 4) alkyl radical, a (C 1 to C 4) - monohydroxyalkyl radical, a (C 2 to C 4) polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and

G 16 is hydrogen or a halogen atom.

In the formula (E3) substituents used in the present invention are defined analogously to the above embodiments.

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

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

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.

The developer component can be selected from heterocyclic developer components such as, for example, pyrimidine derivatives, pyrazole derivatives, pyrazolopyrimidine derivatives and their physiologically acceptable salts.

Preferred pyrimidine derivatives according to the invention are selected from compounds of formula (E4) or their physiologically acceptable salts, wherein

G 17, G 18 and G 19 independently represents a hydrogen atom, a hydroxy group, a (Ci to C4) alkoxy group or an amino group and

G 20 represents a hydroxy group or a group -NG 21 G 22, wherein G 21 and G 22 are independently a hydrogen atom, a (Ci to C 4) alkyl group, a (C 1 to C 4) -monohydroxyalkyl, with the proviso that at most two of the groups G 17, G 18, G 19 and G 20 represents a hydroxy group and at most two of the radicals G 17, G 18 and G 19 represent a hydrogen atom. Here it is again preferred if the formula (E4) at least two groups of G 17, G 18, G 19 and G represent a group -NG G and are at most two groups of G, G, G and G represents a hydroxy group.

Particularly preferred pyrimidine derivatives are in particular the compounds 2,4,5,6-tetra-aminopyrimidine, 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 according to the invention are selected from compounds of formula (E5),

wherein

G, G, G are, independently, a hydrogen atom, a (C 1 to C 4) - alkyl group, a (C 1 to C 4) monohydroxyalkyl, a (C 2 to C 4) -polyhydroxyalkyl group, an optionally substituted aryl group or an optionally substituted aryl (C-ι-C 4) alkyl group, with the proviso that if G 25 is a hydrogen atom, G 26 in addition to the above-mentioned groups may additionally represent a group NH 2,

G 26 represents a hydrogen atom, a (C 1 to C 4) alkyl group, a (C 1 to C 4) - monohydroxyalkyl group or a (C 2 to C 4) -polyhydroxyalkyl group, and G 27 represents a hydrogen atom, an optionally substituted aryl group, a (Ci to C 4) alkyl group or a (C 1 to C 4) -monohydroxyalkyl, especially for a hydrogen atom or a methyl group.

Preferably, the radical G binds in -NG formula (E5) to the 5 position and the radical G to the 3- position of the Pyrazolzyklus.

Particularly preferred pyrazole derivatives are in particular the compounds which are selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (ß-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 -phenylpyrazol, 4-amino-1, 3-dimethyl-5-hydrazinopyrazol, 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- (ß-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-methyl-pyrazol, 4, 5-diamino-3-hydroxymethyl-1-isopropylpyrazol, 4,5-diamino-3-methyl-1-isopropylpyrazol, 4-amino-5- (beta-aminoethyl) amino-1, 3-dimethylpyrazole, and their physiologically acceptable salts thereof.

Preferred pyrazolopyrimidine derivatives which are derivatives of pyrazolo [1, 5- a] pyrimidine are in particular the following formula (E6) and its tautomeric forms, provided a tautomeric equilibrium exists:

in which:

G 28, G 29 and G 30, G 31 are independently a hydrogen atom, a (Ci to C 4) alkyl radical, an aryl radical, a (Ci to C 4) monohydroxyalkyl, a (C 2 to C 4 ) - a polyhydroxyalkyl (Ci to C 4) alkoxy (Ci -C 4) alkyl, a (Ci to C 4) - aminoalkyl radical, which may be optionally protected by an acetyl ureide or a sulfonyl residue, a (C 1 to C 4) alkylamino (C-ι-C 4) alkyl, a di-I (C 1 to C 4) alkyl] - (C-ι-C 4) aminoalkyl, wherein the dialkyl residues optionally form a carbocycle or a heterocycle with 5 or 6 chain links, a (C 1 to C 4) -Monohydroxyalkyl- or a di [(C-ι-C 4) hydroxyalkyl] - (C-ι-C 4) aminoalkyl, the X radicals are each independently a hydrogen atom, a (Ci to C 4) - alkyl radical, an aryl radical, a (C 1 to C 4) monohydroxyalkyl, a (C 2 to C 4) - polyhydroxyalkyl a (C 1 to C 4) aminoalkyl radical, a (C 1 to C 4) alkylamino (C 1 to C 4) - alkyl group, a di - [(C-ι-C 4) alkyl] - (C-ι-C 4) aminoalkyl, wherein the dialkyl residues optionally form a carbocycle or a heterocycle with 5 or 6 chain links, a (C 1 to C 4) hydroxyalkyl or a di - [(C-ι-C 4) hydroxyalkyl] amino- (C 1 to C 4 ) - alkyl radical, an amino radical, a (C 1 to C 4) alkyl or di - [(d to C4) hydroxyalkyl] amino group, a halogen atom, a carboxylic acid group or a sulfonic acid group, i has the value 0, 1, 2 or 3, p has the value q is 0 or 1 is 0 or 1 and n has the value 0 or 1, with the proviso that the sum of p + q is not 0 when p + q is equal to 2 , n is 0, and the groups NG 28 NG G 29 and G 30 31 occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7); when p + q is equal to 1, n has the value 1, and the groups NG 28 G 29 (or 30 NG G 31) and the group OH occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7);

In formula (E7) substituents used in the present invention are defined analogously to the above embodiments.

When the pyrazolo [1, 5-a] pyrimidine of the above formula (E6) containing a hydroxy group at any of positions 2, 5 or 7 of the ring system, a tautomeric equilibrium exists represented, for example, in the following scheme:

Among the pyrazolo [1, 5-a] pyrimidines of the above formula (E7) 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-diannin;

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

3-amino-pyrazolo [1, 5-a] pyrimidin-5-ol;

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

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

2 - [(3-amino-pyrazolo [1, 5-a] pyrinnidin-7-yl) - (2-hydroxy-ethyl) -annino] ethanol;

2 - [(7-amino-pyrazolo [1, 5-a] pyrinnidin-3-yl) - (2-hydroxy-ethyl) -annino] ethanol;

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

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

3-Amino-7-dinnethylannino-2,5-dinnethylpyrazolo [1, 5-a] pyrinnidin; and their physiologically tolerable salts and their tautomeric forms when a tautomeric equilibrium exists.

The pyrazolo [1, 5-a] pyrimidines of the above formula (E6) may be prepared from an aminopyrazole or hydrazine starting as described in the literature by cyclization.

Very particularly preferred developer components are selected from at least one compound from the group which is formed from p-phenylenediamine, p-toluylenediamine, 2- (.beta.-hydroxyethyl) -p-phenylenediamine, 2- (α, ß-dihydroxyethyl) -p phenylenediamine, N, N-bis (.beta.-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1 H-imidazol-1-yl) propyl] amine, N, N'-bis (.beta.-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, 1, 10-bis (2, 5-diaminophenyl) -1, 4,7,10-tetraoxadecane, p-aminophenol, A- amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, ß-dihydroxyethyl) -phenol and 4-amino-2- (diethylaminomethyl) -phenol, 4,5-diamino-1- (ß-hydroxyethyl) pyrazole, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine , 2-hydroxy-4,5,6-triaminopyrimidine, and the physiologically compatible salts of these compounds.

In the following, examples of the substituents as the compounds of formulas (E1) referred to (E6) residues are enumerated:

Examples of (C 1 to C 4) -alkyl radicals are the groups -CH 3, -CH 2 CH 3, -CH 2 CH 2 CH 3, -CH (CH 3) 2, -CH 2 CH 2 CH 2 CH 3, -CH 2 CH (CH 3) 2, -CH (CH 3) CH 2 CH 3, -C (CH 3 J. 3 Inventive examples of (C 1 to C 4) alkoxy groups are -OCH 3, -OCH 2 CH 3, -OCH 2 CH 2 CH 3, -OCH (CHs) 2, -OCH 2 CH 2 CH 2 CH 3, -OCH 2 CH (CH 3) 2, -OCH (CH 3) CH 2 CH 3, - OC (CH 3) 3, in particular a methoxy or an ethoxy group. In addition, preferred examples of (Ci to C 4) monohydroxyalkyl group -CH 2 OH,

-CH 2 CH 2 OH, -CH 2 CH 2 CH 2 OH, -CHCH (OH) CH 3, -CH 2 CH 2 CH 2 CH 2 OH, wherein the group -

CH 2 CH 2 OH being preferred.

A particularly preferred example of (C 2 to C 4) polyhydroxyalkyl group is the 1, 2-

Dihydroxyethyl.

Examples of halogen atoms are F, Cl or Br atoms, chlorine atoms are particularly preferred examples.

Examples of nitrogen-containing groups are especially -NH 2, (C 1 to C 4) -

Monoalkylamino, (Ci to C 4) dialkylamino, (Ci to C 4) -

Trialkylammoniunngruppen, (Ci to C 4) -Monohydroxyalkylaminogruppen, imidazolinium and -

NH 3 +.

Examples of (Ci to C 4) monoalkylamino groups are -NHCH 3, -NHCH 2 CH 3,

-NHCH 2 CH 2 CH 3, -NHCH (CH 3). 2

Examples of (Ci to C 4) dialkylamino group are -N (CH 3) 2, -N (CH 2 CH 3). 2

Examples of (Ci to C4) are -Trialkylamnnoniunngruppen -N + (CH 3) 3, -N + (CH 3) 2 (CH 2 CH 3),

-N + (CH 3) (CH 2 CH 3). 2

Examples of (Ci to C 4) -Hydroxyalkylaminoreste are -NH-CH 2 CH 2 OH, -NH-CH 2 CH 2 OH,

-NH-CH 2 CH 2 CH 2 OH 1 -NH-CH 2 CH 2 CH 2 OH.

Examples of (C 1 to C 4) alkoxy alkyl groups are (C-ι-C 4) the groups -CH 2 CH 2 -O-CH 3,

-CH 2 CH 2 CH 2 -O-CH 3, -CH 2 CH 2 -O-CH 2 CH 3, -CH 2 CH 2 CH 2 -O-CH 2 CH 3, -CH 2 CH 2 -O-CH (CH 3),

-CH 2 CH 2 CH 2 -O-CH (CH 3).

Examples of hydroxy (C, to C 4) alkoxy groups are -0-CH 2 OH, -0-CH 2 CH 2 OH, -0-CH 2 CH 2 CH 2 OH,

-0-CHCH (OH) CH 3, -0-CH 2 CH 2 CH 2 CH 2 OH.

Examples of (C 1 to C 4) -Acetylaminoalkoxyreste are -0-CH 2 NHC (O) CH 3, -O-

CH 2 CH 2 NHC (O) CH 3,

-0-CH 2 CH 2 CH 2 NHC (O) CH 31 -O-CH 2 CH (NHC (O) CH 3) CH 31 -O-CH 2 CH 2 CH 2 CH 2 NHC (O) CH 3.

Examples of (C 1 to C 4) -Carbamoylanninoalkoxyreste are -0-CH 2 CH 2 -NH-C (O) -NH 2,

-0-CH 2 CH 2 CH 2 -NH-C (O) -NH 21 -O-CH 2 CH 2 CH 2 CH 2 -NH-C (O) -NH 2.

Examples of (C 1 to C 4) -aminoalkyl are -CH 2 NH 2, -CH 2 CH 2 NH 2, -CH 2 CH 2 CH 2 NH 2,

-CH 2 CH (NH 2) CH 31 -CH 2 CH 2 CH 2 CH 2 NH 2.

Examples of (C 1 to C 4) -Cyanoalkylreste are -CH 2 CN 1 -CH 2 CH 2 CN 1 -CH 2 CH 2 CH 2 CN.

Examples of (C 1 to C 4) -Hydroxyalkylamino- (C 1 to C 4) alkyl groups are -CH 2 CH 2 NH-CH 2 CH 2 OH 1 -

CH 2 CH 2 CH 2 NH-CH 2 CH 2 OH 1 -CH 2 CH 2 NH-CH 2 CH 2 CH 2 OH 1 -CH 2 CH 2 CH 2 NH-CH 2 CH 2 CH 2 OH.

Examples of di [(d to C4) -hydroxyalkyl] amino- (C 1 to C 4) alkyl groups are

CH 2 CH 2 N (CH 2 CH 2 OH) 21

-CH 2 CH 2 CH 2 N (CH 2 CH 2 OH) 21 -CH 2 CH 2 N (CH 2 CH 2 CH 2 OH) 21 -CH 2 CH 2 CH 2 N (CH 2 CH 2 CH 2 OH) 2 ,

An example of aryl is phenyl. Examples of aryl- (Ci to C4), the benzyl and the 2-phenylethyl group are alkyl groups.

Intermediates formed during the oxidative dyeing alone no significant staining of but always need the presence of developer components. Therefore, it is preferable in the invention that when using at least one developer component in addition is at least one coupler component used.

Intermediates for the purposes of the invention allow at least one substitution of a chemical moiety of the coupler with the oxidised form of the developer component. In this case, a covalent bond between coupler and developer component is formed. Couplers are preferably cyclic compounds, which carry at least two groups on the cycle selected from (i) optionally substituted amino groups, and / or (ii) hydroxyl groups. If the cyclic compound is a six-membered ring (preferably aromatic), so the said groups are preferably each in the ortho-position or meta-position.

Coupler components according to the invention are preferably used as at least one compound selected from one of the following classes:

- m-aminophenol and / or its derivatives,

- m-diaminobenzene and / or its derivatives,

- o-diaminobenzene and / or its derivatives,

- o-aminophenol derivatives such as o-aminophenol,

- naphthalene derivatives containing at least one hydroxy group,

- di- or trihydroxybenzene and / or derivatives thereof,

- pyridine derivatives,

- pyrimidine derivatives,

- monohydroxyindole derivatives and / or derivatives Monoaminoindol,

- Monohydroxyindolin derivatives and / or derivatives Monoaminoindolin,

- pyrazolone derivatives such as 1-phenyl-3-methylpyrazole-5-one,

- morpholine derivatives such as 6-hydroxybenzomorpholine or 6-amino benzomorpholine,

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

Mixtures of two or more compounds of one or more of these classes are also according to the invention in the context of this embodiment.

The usable in this invention m-aminophenols or their derivatives are preferably selected from at least one compound of the formula (K1) and / or at least one physiologically acceptable salt of a compound according to Formula (K1),

) wherein

- G 1 and G 2 independently represent a hydrogen atom, a (C 1 to C 4) alkyl group, a (C 3 -C 6) cycloalkyl group, a (C 2 to C 4) alkenyl group, a (C 1 to C 4) monohydroxyalkyl, a (C 2 to C 4) -polyhydroxyalkyl group, a (C 2 to C 4) - perfluoroacyl group, an aryl (C-ι-C 6) alkyl group, a AmJnO- (C 1 to C 6) alkyl group, a (C 1 to C 6) dialkylamino (C 1 to C 6) alkyl or a (C 1 to C 6) alkoxy (C-ι-C 6) - alkyl group, wherein G 1 and G may form a five-membered, six-membered or seven-membered ring 2 together with the nitrogen atom,

- G 3 and G 4 independently represent a hydrogen atom, a halogen atom, a (C 1 to C 4) alkyl group, a (C 1 to C 4) alkoxy group, a hydroxy group, a (C 1 to C 4) - monohydroxyalkyl, a (C 2 to C 4) -polyhydroxyalkyl group, a hydroxy (C 1 to C 4) alkoxy, (C 1 to C 6) -Alkyox- (C 2 to C 6) alkoxy group, an aryl group or a heteroaryl group.

Particularly preferred m-aminophenol coupler components are selected from at least one compound from the group which is formed from m-aminophenol, 5-amino-2-methyl phenol, 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-methyl phenol, 2,4-dichloro-3-aminophenol and the physiologically compatible salts of all the compounds mentioned above.

The usable in this invention m-diaminobenzenes or their derivatives are preferably selected from at least one compound of formula (K2) and / or at least one physiologically acceptable salt of a compound of the formula (K2),

wherein

- G 5, G 6, G 7 and G 8 are independently a hydrogen atom, a (Ci to C 4) alkyl group, a (C 3 -C 6) cycloalkyl group, a (C 2 to C 4) alkenyl , a (Ci to C 4) monohydroxyalkyl, a (C 2 to C 4) -polyhydroxyalkyl group, a (Ci to C 4) - alkoxy (Ci -C 4) alkyl group, an aryl (Ci to C 4) alkyl group, a heteroaryl- (Ci to C 4) - alkyl group, a (C 2 to C 4) -Perfluoracylgruppe, or form together with the nitrogen atom form a five-membered or six-membered heterocycle

- G 9 and G 10 are independently a hydrogen atom, a halogen atom, a (C 1 to C 4) alkyl group, an ω- (2,4-diaminophenyl) - (d to C4) alkyl group, a ω- (2,4-Diaminophenyloxy) - (Ci to C 4) alkoxy, (Ci to C 4) alkoxy group, a hydroxy group, a (Ci to C 4) alkoxy (C 2 to C 4) alkoxy, alkoxy polyhydroxyalkyl group, a hydroxy (Ci to C 4) - an aryl group, a heteroaryl group, a (Ci to C 4) monohydroxyalkyl, a (C 2 to C 4).

Particularly preferred m-diaminobenzene coupler components are selected from at least one compound from the group which is formed from m-phenylene diamine, 2- (2,4- diaminophenoxy) ethanol, 1, 3-bis (2,4-diaminophenoxy), 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-ylphenyl) amino] ethanol, 3-amino-4- (2 - methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis- (2'-hydroxyethyl) aminobenzene and the physiologically compatible salts of all the compounds mentioned above.

The invention can be used according o-diaminobenzenes or their derivatives are preferably selected from at least one compound of the formula (K3) and / or at least one physiologically acceptable salt of a compound of the formula (K3), wherein

- G 11, G 12, G 13 and G 14 are independently a hydrogen atom, a (Ci to C 4) alkyl group, a (C 3 -C 6) cycloalkyl group, a (C 2 to C 4) alkenyl , a (Ci to C 4) monohydroxyalkyl, a (C 2 to C 4) -polyhydroxyalkyl group, a (Ci to C 4) - alkoxy (Ci -C 4) alkyl group, an aryl (Ci to C 4) alkyl group, a heteroaryl- (Ci to C 4) - alkyl group, a (C 2 to C 4) -Perfluoracylgruppe, or form together with the nitrogen atom form a five-membered or six-membered heterocycle

- G 15 and G 16 are independently a hydrogen atom, a halogen atom, a carboxyl group, a (Ci to C 4) alkyl group, a (Ci to C4) alkoxy group, a hydroxy group, a (Ci to C 4) - monohydroxyalkyl, a (C 2 to C 4) - polyhydroxyalkyl group, a hydroxy (Ci to C4) alkoxy group.

Particularly preferred o-diaminobenzene coupler components are selected from at least one compound from the group which is formed from 3,4-diaminobenzoic acid and 2,3-diamino-1-methyl benzene, and the physiologically compatible salts of all the compounds mentioned above.

Preferred di- or trihydroxybenzenes and their derivatives are selected from at least one compound which is formed the group of resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1 , 2,4-trihydroxybenzene.

The pyridine derivatives useful in this invention are preferably selected from at least one compound of formula (K4) and / or at least one physiologically acceptable salt of a compound according to Formula (K4),

wherein - G and G independently represent a hydroxy group or a group -NG 21 G 22, wherein G 21 and G 22 are independently a hydrogen atom, a (Ci to C 4) alkyl group, a (C 3 to C 6 ) cycloalkyl group, a (C 2 to C 4) alkenyl group, an aryl group, a (Ci to C 4) monohydroxyalkyl, a (C 2 to C 4) - polyhydroxyalkyl group, a (Ci-C 4) alkoxy- ( Ci to C 4) alkyl group, an aryl (Ci to C 4) - alkyl group, a heteroaryl- (Ci to C4) alkyl group,

- G 19 and G 20 are each independently a hydrogen atom, a halogen atom, a (Ci to C 4) alkyl group or a (Ci to C4) alkoxy group.

It is preferred when the formula (K4) are in ortho-position or meta-position in the radicals G 17 and G 18 each other.

Particularly preferred pyridine derivatives are selected from at least one compound formed from 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine the group, 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, 3,5-diamino-2, 6- dimethoxypyridine, 3,4-diaminopyridine, 2- (2-methoxyethyl) amino-3-amino-6-methoxypyridine, 2- (4'-methoxyphenyl) amino-3-aminopyridine, and the physiologically compatible salts of the abovementioned compounds.

Preferred naphthalene derivatives having at least one hydroxyl group are selected from at least one compound formed from 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol group, 1, 3 -Dihydroxynaphthalin, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene.

The indole derivatives useful in this invention are preferably selected from at least one compound of formula (K5) and / or at least one physiologically acceptable salt of a compound according to formula (K5),

- G 23 represents a hydrogen atom, a (C 1 to C 4) alkyl group, a (C 3 -C 6) - cycloalkyl group, a (C 2 to C 4) alkenyl group, a (Ci to C 4) monohydroxyalkyl , a (C 2 to C 4) alkyl polyhydroxyalkyl group, an aryl (Ci to C 4),

- G 24 represents a hydroxy group or a group -NG 26 G 27, wherein G 26 and G 27 are independently a hydrogen atom, a (C 1 to C 4) alkyl group, a (C 3 -C 6) cycloalkyl group , a (C 2 to C 4) alkenyl group, a (C 1 to C 4) - monohydroxyalkyl, a (C 2 to C 4) polyhydroxyalkyl group,

- G 25 hydrogen atom, a halogen atom or a (C 1 to C 4) alkyl group, with the proviso that G 24 in the meta position or ortho-position to the structural fragment of the formula 23 NG binds.

Particularly preferred indole derivatives are selected from at least one compound formed from 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole and physiologically compatible salts of the abovementioned compounds of the group.

The indoline derivatives usable in this invention are preferably selected from at least one compound of formula (K6) and / or at least one physiologically acceptable salt of a compound according to formula (K6),

wherein

- G 28 represents a hydrogen atom, a (C 1 to C 4) alkyl group, a (C 3 -C 6) - cycloalkyl group, a (C 2 to C 4) alkenyl group, a (C 1 to C 4) - monohydroxyalkyl, a (C 2 to C 4) -polyhydroxyalkyl group, an aryl- (C-ι-C 4) alkyl group,

- G 29 31 G 32 represents a hydroxy group or a group -NG wherein G 31 and G 32 are independently a hydrogen atom, a (C 1 to C 4) alkyl group, a (C 3 -C 6) cycloalkyl group , a (C 2 to C 4) alkenyl group, a (C 1 to C 4) - monohydroxyalkyl, a (C 2 to C 4) polyhydroxyalkyl group,

- G 30 hydrogen atom, a halogen atom or a (C 1 to C 4) alkyl group, with the proviso that G 29 in meta-position or ortho-position to the structural fragment of the formula 28 NG binds. Particularly preferred indoline derivatives are selected from at least one compound formed from 4-hydroxyindoline, 6-hydroxyindoline and 7-hydroxyindoline and physiologically compatible salts of the abovementioned compounds of the group.

Preferred pyrimidine derivatives are selected from at least one compound formed from 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2 amino-4-methylpyrimidine, methylpyrimidine 2-amino-4-hydroxy-6- and 4,6-dihydroxy-2-methylpyrimidine and the physiologically compatible salts of the abovementioned compounds.

According to the invention particularly preferred coupler components are selected from m-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4- aminophenoxyethanol, 5-amino-4-chloro-2-methylphenol , 5- (2'-hydroxyethyl) amino-2-methyl phenol, 2,4-dichloro-3-aminophenol, o-aminophenol, m-phenylenediamine, 2- (2,4- diaminophenoxy) ethanol, 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-methyl benzene, 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, 1-amino-3-bis- (2'-hydroxyethyl) aminobenzene, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 1, 2,4- trihydroxybenzene, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyrid in 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-phenyl-3-methylpyrazole-5-one, 1-naphthol, 1, 5-dihydroxynaphthalene, 2, 7- dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline, or mixtures of these compounds or the physiologically tolerated salts of the aforementioned Links.

The coupler components are preferably used in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the ready for use oxidation colorant.

The primary intermediates and secondary intermediates are generally used in substantially equimolar ratio to one another. When molar use has proved to be expedient, a certain excess of individual oxidation dye precursors is not a disadvantage, so that the developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2 can stand. In the following, examples of the substituents as the compounds of formulas (K1) to be

Said radicals (K6) enumerated:

Examples of (C 1 to C 4) -alkyl radicals are the groups -CH 3, -CH 2 CH 3,

-CH 2 CH 2 CH 3, -CH (CH 3) 2, -CH 2 CH 2 CH 2 CH 3, -CH 2 CH (CH 3) 2, -CH (CH 3) CH 2 CH 3, -C ( CH3 J. 3

Inventive examples of (C 3 -C 6) cycloalkyl groups are the cyclopropyl, the

Cyclopentyl and cyclohexyl.

Inventive examples of (C 1 to C 4) alkoxy groups are -OCH 3, -OCH 2 CH 3,

-OCH 2 CH 2 CH 3, -OCH (CHs) 2, -OCH 2 CH 2 CH 2 CH 3, -OCH 2 CH (CH 3) 2, -OCH (CH 3) CH 2 CH 3, -

OC (CH 3) 3, in particular a methoxy or an ethoxy group.

In addition, preferred examples of a (C 1 to C 4) monohydroxyalkyl group -CH 2 OH,

-CH 2 CH 2 OH, -CH 2 CH 2 CH 2 OH, -CH 2 CH (OH) CH 3, -CH 2 CH 2 CH 2 CH 2 OH are called, the

-CH 2 CH 2 OH being preferred.

A particularly preferred example of (C 2 to C 4) polyhydroxyalkyl group is the 1, 2-

Dihydroxyethyl.

Examples of halogen atoms are F, Cl or Br atoms, chlorine atoms are particularly preferred examples.

Examples of nitrogen-containing groups are especially -NH 2, (C 1 to C 4) -

Monoalkylamino, (C 1 -C 4) -dialkylamino, (C 1 to C 4) -

Trialkylammonium groups, (C 1 to C 4) -Monohydroxyalkylaminogruppen, imidazolinium and -

NH 3 +.

Examples of (C 1 to C 4) monoalkylamino groups are -NHCH 3, -NHCH 2 CH 3, -NHCH 2 CH 2 CH 3, -

NHCH (CH 3). 2

Examples of (C 1 to C 4) dialkylamino group are -N (CH 3) 2, -N (CH 2 CH 3). 2

Examples of (C 1 to C 4) alkoxy alkyl groups are (C-ι-C 4) the groups -CH 2 CH 2 -O-CH 3,

-CH 2 CH 2 CH 2 -O-CH 3, -CH 2 CH 2 -O-CH 2 CH 3, -CH 2 CH 2 CH 2 -O-CH 2 CH 3, -CH 2 CH 2 -O-CH (CH 3) 2,

-CH 2 CH 2 CH 2 -O-CH (CH 3). 2

Examples of (C 1 to C 4) alkoxy (C-ι-C 4) alkoxy groups are the groups -0-CH 2 CH 2 -O-CH 3, -

0-CH 2 CH 2 CH 2 -O-CH 3, -0-CH 2 CH 2 -O-CH 2 CH 3, -0-CH 2 CH 2 CH 2 -O-CH 2 CH 3, -0-CH 2 CH 2 -O-

CH (CH3) 2, -O-CH 2 CH 2 CH 2 -O-CH (CH 3). 2

Examples of hydroxy (C, to C 4) alkoxy groups are -0-CH 2 OH, -0-CH 2 CH 2 OH, -0-CH 2 CH 2 CH 2 OH,

-O-CH 2 CH (OH) CH 3, -O-CH 2 CH 2 CH 2 CH 2 OH.

Examples of (C 1 to C 4) -aminoalkyl are -CH 2 NH 2, -CH 2 CH 2 NH 2, -CH 2 CH 2 CH 2 NH 2,

-CH 2 CH (NH 2) CH S1 -CH 2 CH 2 CH 2 CH 2 NH 2.

An example of the aryl group is the phenyl group which may be substituted.

Examples of aryl- (d to C4), the benzyl and the 2-phenylethyl group are alkyl groups. As the dye precursors of nature-analogous dyes, such indoles and indolines are preferably used, at least two groups selected from hydroxy and / or amino groups or, preferably as a substituent on the six-membered ring. These groups can carry further substituents such. Example in the form of an etherification or esterification of the hydroxy group or alkylation of the amino group. In another embodiment, the colorants contain at least one indole and / or indoline derivative. Compositions of the invention which contain precursors of nature-analogous dyes, are preferably used as air-oxidative colorants. In this embodiment, said compositions are therefore not treated with an additional oxidizing agent.

Particularly suitable as precursors of nature-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of formula (RN1),

in independently

- R 1 represents hydrogen, a dC 4 alkyl group or a Ci-C 4 hydroxyalkyl group,

- R 2 is hydrogen or a -COOH group, where the -COOH group may also be present as salt with a physiologically compatible cation,

- R 3 represents hydrogen or a 4 alkyl dC,

- R 4 represents hydrogen, a dC 4 alkyl group or a group -CO-R 6 in which R 6 represents a Ci-C 4 alkyl group, and

R 5 represents one of the groups mentioned for R 4, and physiologically compatible 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 and 5,6-dihydroxyindoline-2-carboxylic acid.

Of particular note are within the group of N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and, in particular, the 5, 6-Dihydroxyindolin. Precursors of nature-analogous hair dyes are derivatives of 5,6-dihydroxyindole corresponding to formula are excellently suitable to continue (RN2),

in independently

R 1 represents hydrogen, C-ι-C 4 alkyl group or a C-ι-C 4 hydroxyalkyl group,

R 2 is hydrogen or a -COOH group, where the -COOH group may also be present as salt with a physiologically compatible cation,

R 3 represents hydrogen or a 4 alkyl dC,

R 4 is hydrogen, a dC 4 alkyl group or a group -CO-R 6 in which R 6 represents a Ci-C 4 alkyl group, and

R 5 represents one of the groups mentioned for R 4, and physiologically compatible 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.

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

Furthermore, the compositions can comprise at least one direct dye instead of or in addition to the dye precursors. Here are dyes that attach directly to the hair and require no oxidative process to develop the color. Direct dyes are usually nitrophenylendiamines, Nitroaminophenole, azo dyes, anthraquinones or Indophenole.

The direct dyes are each preferably used in an amount of 0.001 to 20% by weight, based on the total preparation. The total amount of direct dyes is preferably at most 20 wt .-%. Direct dyes can be divided into anionic, cationic and nonionic direct dyes.

Anionic direct dyes:

, 2,4-dinitro-1 -2-naphthalinsulfonsäuredinatriumsalz (FD & C Yellow No. 6;; Food Yellow No. 3 Cl 15,985.) [(4-sulfophenyl) azo] - Suitable anionic direct dyes, in particular, 6-hydroxy-5 are naphthol-7-sulfonic acid disodium salt (Cl 10,316;. Acid Yellow 1; Food Yellow No. 1), 2- (indan-1, 3-dione-2-yl) quinoline-x, x-sulfonic acid (mixture of mono - and disulfonic acid) (CI 47,005; D & C Yellow No. 10; Food Yellow No. 13;. Acid Yellow 3, Yellow 10), 4 - ((4-amino-3-sulfophenyl) azo) benzenesulfonic acid disodium salt (Cl 13.015. (acid Yellow 9), 5-hydroxy-1- 4-sulfophenyl) -4 - [(4-sulfophenyl) azo] pyrazole-3-carboxylic acid trisodium salt (Cl.

19,140; Food Yellow No. 4; Acid Yellow 23), 3 - [(4-

Phenylamino) phenyl] azobezolsulfonsäuresäure-natriunnsalz (Cl 13.065;. Ki406; Acid Yellow 36), 9- (2-carboxyphenyl) -6-hydroxy-3H-xanthen-3-one (CI 45,350;. Acid Yellow 73; D & C Yellow No . 8), 5 - [(2,4-dinitrophenyl) amino] -2-phenylaminobenzolsulfonsäure sodium salt (CI 10,385;. Acid Orange 3), 4 - [(2,4-dihydroxyphenyl) azo] benzenesulfonic acid sodium salt (Cl 14,270; Acid Orange 6), 4 - [(2-hydroxynaphth-1-yl) azo] -benzenesulfonic acid sodium salt (CI 15,510;.. Acid Orange 7), 4 - [(2,4-dihydroxy-3 - [( 2,4-dimethylphenyl) azo] phenyl) azo] benzenesulfonic acid sodium salt (Cl 20.170; Acid Orange 24), 4-hydroxy-3 - [(2-methoxyphenyl) azo] -1-naphthalenesulfonic acid sodium salt (Cl.. 14.710; Acid Red 4), 4-hydroxy-3 - [(4-sulphonaphth-1-yl) azo] -1-naphthalene-sulfonic acid disodium salt (Cl 14.720; Acid Red No.14), 6-hydroxy-fifth - [(4-sulphonaphth-1-yl) azo] -2,4-naphthalene-disulfonic acid trisodium salt (CI 16,255; Ponceau 4R; Acid Red. 18), 3-hydroxy-4 - [(4-sulphonaphth-1 yl) azo] -2,7-naphthalene-disulfonic acid trinatri umsalz (Cl. 16.185; Acid Red 27), 8-amino-1-hydroxy-2- (phenylazo) -3,6-naphthalene-disulphonic acid disodium salt (Cl 17,200;. Acid Red 33, Red 33), 5- (acetylamino) -4-hydroxy -3 - [(2-methylphenyl) azo] -2,7-naphthalene-disulfonic acid disodium salt (Cl 18.065; Acid Red. 35), 2- (3-hydroxy-2,4,5,7-tetraiodo-dibenzopyran- 6-on-9-yl) benzoic acid disodium salt (CI 45,430; Acid Red 51), N- [6- (diethylamino) -9- (2,4-disulfophenyl) -3H-xanthen-3-ylidene] -. N-ethylethanannnnoniunn- hydroxide, inner salt, sodium salt (CI 45,100;. Acid Red 52), 8 - [(4- (phenylazo) phenyl) azo] -7-naphthol-1, 3-disulfonic acid disodium salt (CI 27,290;. Acid Red 73), 2 ', 4', 5 ', 7'-tetrabromo-3', 6'-dihydroxyspiro [isobenzofuran-1 (3H), 9 '- xanthen [9H]] -3-one disodium salt (Cl . 45,380; Acid Red 87), 2 ', 4', 5 ', 7'-tetrabromo-4,5,6,7-tetrachloro-3', 6'-dihydroxyspiro [isobenzofuran

1 (3H), 9 '[9H] xanthene] -3-one disodium salt (CI 45,410;. Acid Red 92), 3', 6'-dihydroxy-4 ', 5'-diiodospiro [isobenzofuran-1 (3H) , 9 '(9H) - xanthen] -3-one disodium salt (CI 45425; Acid Red 95th), 2-hydroxy-3 - ((2-hydroxynaphth-1-yl) azo) -5-nitrobenzenesulfonic acid sodium salt ( Cl 15.685;. Acid Red 184), 3-hydroxy-4- (3-methyl-5-oxo-1-phenyl-4,5-dihydro-1 H-pyrazol-4-ylazo) naphthalene-1-sulfonic acid sodium salt, chromium complex (Acid Red 195), 3-hydroxy-4 - [(4-methyl-2-sulfonic pheny ^ azo ^ -naphthalincarbonsäure acid calcium salt (CI 15,850: 1; pigment Red 57: 1); 3. - [(2,4-dimethyl-5-sulfophenyl) azo] -4-hydroxy-1-naphthalene-sulfonic acid disodium salt (Cl 14,700; Food Red No. 1; Ponceau SX; FD & C Red No. 4)., 1, 4- bis [(2-sulfo-4-methylphenyl) amino] -9,10-anthraquinone disodium salt (CI 61, 570; Acid Green. 25), bis [4- (dimethylamino) phenyl] - (3,7- disulfo-2-hydroxynaphth-1-yl) carbenium inner salt, sodium salt (Cl 44.090;. Food Green No. 4; Acid Green 50), bis [4- (diethylamino) phenyl] (2,4-disulfophenyl) carbenium HEART salt, sodium salt (2: 1) (Cl. 42.045; Food Blue No. 3; Acid Blue 1), bis [4- (diethylamino) phenyl] (5-hydroxy-2,4-disulfophenyl) -carbenium inner salt, calcium salt (2: 1) (Cl 42,051; Acid Blue 3), N- [. 4 - [(2,4-disulfophenyl) [4- [ethyl (phenylmethyl) amino) phenyl] methylene] -2,5-cyclohexadien-1- ylidene] -N-ethylbenzolmethanaminium hydroxide, inner salt, sodium salt (Cl 42.080. ; Acid Blue 7), (2-sulfophenyl) di [4- (ethyl ((4-sulfophenyl) methyl) amino) phenyl] -carbenium disodium salt

Betaine (Cl 42,090;. Acid Blue 9; FD & C Blue No. 1), 1-amino-4- (phenylamino) -9,10-anthraquinone-2-sulfonic acid (Cl 62.055;. Acid Blue 25), 1-amino 4- (cyclohexylamino) -9,10-anthraquinone-2-sulfonic acid sodium salt (Cl 62045;. Acid Blue 62), 2- (1, 3-dihydro-3-oxo-5-sulfo-2H-indol-2- ylidene) -2,3-dihydro-3-oxo-1 H-indole-5-sulfonic acid disodium salt (CI 73,015; Acid Blue 74), 9- (2-carboxyphenyl) -3 - [(2-methylphenyl) amino. ] -6 - [(2-methyl-4-sulfophenyl) amino] xanthylium inner salt, sodium salt (Cl 45.190;. Acid Violet 9), 1-hydroxy-4 - [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone sodium salt (Cl 60,730; D & C Violet No. 2; Acid Violet. 43), bis [3-nitro-4 - [(4- phenylamino) -3-sulfo-phenylamino] phenyl] sulfone (Cl 10.410; Acid Brown. 13), 5-amino-4-hydroxy-6 - [(4-nitrophenyl) azo] -3- (phenylazo) -2,7-naphthalene-disulfonic acid disodium salt (CI 20,470;. Acid Black 1), 3-hydroxy-4 - [(2-hydroxynaphth-1-yl) azo] -7-nitro-1-naphthalene-sulfonic acid chromium complex (3: 2) (Cl 15.711; Acid Black 52). (4- Acetylamino) -5-hydroxy-6 - [(7-sulfo-4 - [(4-sulfophenyl) azo] naphth-1-yl) azo] -1, 7-naphthalene disulfonic acid tetrasodium salt (Cl. 28.440; Food Black No. 1), 3 ', 3 ", 5', 5" -Tetrabromphenolsulfonphthalein (bromophenol blue).

Preferred anionic direct dyes are known under the International names or trade names Acid Yellow 1, Yellow 10, Acid Yellow 23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52, Pigment Red 57: 1, Acid Blue 7 Acid Green 50, Acid Violet 43, Acid Black 1 and Acid Black 52 known compounds.

Cationic direct dyes:

, Di [4- (diethylamino) phenyl] [4- (ethylamino (Basic Blue 6175 Cl 51,.) Benzo [a] phenoxazin-7-ium chloride - as cationic direct dyes are in particular 9- (dimethylamino) ) naphthyl] carbenium chloride (. Cl 42.595; Basic Blue 7), di- (4- (dimethylamino) phenyl) - (4- (methyl-phenylamino) -naphthalen-1-yl) carbenium-chloride (Cl 42.563;. Basic Blue 8), 3,7-di (dimethylamino) phenothiazin-5-ium-chloride (Cl. 52,015 Basic Blue 9), di [4- (dimethylamino) phenyl] [4- (phenylamino) naphthyl] carbenium-chloride ( Cl 44,045; Basic Blue 26), 2 - [(4- (ethyl (2-hydroxyethyl) amino) phenyl) azo] -6-nnethoxy-3-nnethyl-benzothiazoliunn-nnethylsulfat (CI 11, 154;. Basic Blue 41st ), 8-amino-2-bromo-5-hydroxy-4-imino-6 - [(3-

(Trinnethylannnnonio) phenyl) Annino] -1 (4H) -naphthalenone chloride (Cl 56.059;. Basic Blue No. 99), bis [4- (dimethylannino) phenyl] - [4- (nnethylannino) phenyl] carbeniunn chloride ( Cl 42.535;. Basic Violet 1), tri (4-amino-3-methylphenyl) carbenium-chloride (Cl 42.520;. Basic Violet 2), tri [4- (dimethylamino) phenyl] carbenium-chloride (Cl 42,555. Basic Violet 3), 2- [3,6- (diethylamino) dibenzopyraniunn-9-yl] - benzoic acid chloride (CI 45,170;. Basic Violet 10), di (4-aminophenyl) (4-Annino-3- methylphenyl) carbeniunnchlorid ( . Cl 42.510 Basic Violet 14), 1, 3- bis [(2,4-diamino-5-methylphenyl) azo] -3-methylbenzene (Cl 21, 010; Basic Brown 4), 1 - [(4-aminophenyl. ) azo] -7- (trimethylammonio) - 2-naphtholchlorid (Cl 12,250;. Basic Brown 16), 1 - [(4-amino-2-nitrophenyl) azo] -7- (trinnethylannnnonio) -2-naphtholchlorid, 1 - [azo (4-amino-3-nitrophenyl)] -7- (trimethylannnnonio) -2-naphthol chloride; 3 - [(4-amino-2,5-dimethoxyphenyl) (Cl 12,251 Basic Brown 17). azo] -N, N, N-trinnethylbenzolanniniunnchlorid (Cl. 12.605, Ba sic Orange 69), 3,7-diamino-2,8-dinnethyl- 5-phenylphenazinium chloride (Cl. 50.240; Basic Red 2), 1, 4-dimethyl-5 - [(4- (dinnethylannino) phenyl) azo] -1, 2,4-triazoliunn chloride (11 Cl, 055; Basic Red 22), 2-hydroxy. 1 - [(2-methoxyphenyl) azo] -7- (trinnethylannnnonio) naphthalene chloride (. Cl 12,245; Basic Red 76), di [4- (dimethylamino) phenyl] iminomethan hydrochloride (41 Cl, 000; Basic. Yellow 2), 2- [2 - ((2,4-dimethoxyphenyl) amino) ethenyl] -1, 3,3-trimethyl-3H-indol-1-ium-chloride (Cl 48.055; Basic Yellow 11); 3. -methyl-1-phenyl-4 - [(3- (trimethylannnnonio) phenyl) azo] -pyrazol-5-one hydrochloride (. Cl 12,719; Basic Yellow 57), bis [4- (diethylamino) phenyl] Phenylcarbenium hydrogen sulfate (1: 1) (. Cl 42,040; Basic Green 1) (Cl 42,000; Basic Green 4.), di (4- (dimethylamino) phenyl) -phenylmethanol, 1- (2- Morpholiniumpropylannino) -4-hydroxy-9, 10-anthraquinone-nnethylsulfat, 1 - [(3- (dimethyl-propylaminium propyOaminol ^ ^ methylamino ^ θ.iO-anthraquinone chloride and direct dyes which contain a heterocycle which has at least one quaternary nitrogen atom.

Preferred cationic direct dyes are

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

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

(C) direct dyes which contain a heterocycle which has at least one quaternary nitrogen atom, as it is taken for example in EP-A2-998 908 on which at this point explicit reference, are mentioned in claims 6 to. 11

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

CH 3 SO 4 "

cl "

(DZ4)

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

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

Nonionic direct dyes:

As nonionic direct dyes, in particular, non-ionic nitro and quinone dyes and neutral azo dyes are suitable.

Suitable blue nitro dyes are in particular:

1, 4-bis [(2-hydroxyethyl) amino] -2-nitrobenzene, 1- (2-hydroxyethyl) amino-2-nitro-4- [di (2-hydroxyethyl) amino] benzene (HC Blue 2), 1-methylamino-4- [methyl- (2,3-dihydroxypropyl) amino] - 2-nitrobenzene (HC Blue 6), 1 - [(2,3-dihydroxypropyl) amino] -4- [ethyl- (2- hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue 9), 1 - [(2,3-dihydroxypropyl) amino] -4- [(2-hydroxyethyl) amino] -2-methyl-nitrobenzene (HC Blue 10) , 4- [di (2-hydroxyethyl) amino] -1 - [(2-methoxyethyl) amino] -2-nitrobenzene (HC Blue 11), 4- [ethyl- (2-hydroxyethyl) amino] -1- [ (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue 12), 2 - ((4-amino-2-nitrophenyl) amino) - 5-dimethylamino-benzoic acid (HC Blue 13), 1-amino-3 -methyl-4 - [(2-hydroxyethyl) amino] -6-nitrobenzene (HC Violet 1), 1- (3-hydroxypropylamino) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzene (HC Violet 2 ), 1- (2-aminoethylamino) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzene, 4- (di (2-hydroxyethyl) amino) -2-nitro-1-phenylamino-benzene.

Suitable red nitro dyes are in particular:

1-amino-4 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red 7), 2-amino-4,6-dinitrophenol (picramic acid) and salts thereof, 1, 4-diamino-2-nitrobenzene ( Cl. 76.070), 4-amino-2-nit.ro- diphenylamine (HC Red 1), 1-amino-4- [di (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Red 13), 1 amino-4 - [(2-hydroxyethyl) amino] -5-chloro-2-nitrobenzene, 4-amino-1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red 3), 4- [ (2-hydroxyethyl) methylamino] -1- (methylamino) - 2-nitrobenzene, 1-amino-4 - [(2,3-dihydroxypropyl) amino] -5-methyl-2-nitrobenzene, 1-amino-4- ( methylamino) -2-nitrobenzene, 4-amino-2-nitro-1 - [(prop-2-en-1-yl) -amino] -benzene, 4-amino-3-nitrophenol, 4 - [(2-hydroxyethyl ) amino] -3-nitrophenol, 4 - [(2-nitrophenyl) amino] phenol (HC Orange 1), 1 - [(2-aminoethyl) amino] -4- (2-hydroxyethoxy) -2-nitrobenzene (HC orange 2), 4- (2,3-dihydroxypropoxy) -1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC orange 3), 1-amino-5-chloro-4- [(2,3- dihydroxypropyl) amino] -2-nitrobenzene (HC Red 10), 5-chloro-1, 4- [di (2,3-dihydroxypropyl) on ino] -2-nitrobenzene (HC Red 1 1), 2 - [(2-hydroxyethyl) amino] -4,6-dinitrophenol, 4-ethylamino-3-nitrobenzoic acid, 2 - [(4-amino-2-nitrophenyl) Annino] -benzoic acid, 2-chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 4 - [(3-hydroxypropyl) amino] -3-nitrophenol (HC Red BN), 2 , 5-diamino-6-nitropyridine, 6-amino-3 - [(2-hydroxyethyl) Annino] -2-nitropyridine, 3-amino-6 - [(2-hydroxyethyl) Annino] -2-nitropyridine, 3-amino -6- (ethylannino) -2-nitropyridine, 3 - [(2-hydroxyethyl) amino] -6- (methylamino) -2-nitropyridine, 3-amino-6- (nnethylannino) - 2-nitropyridine, 6- (ethylamino ) -3 - [(2-hydroxyethyl) Annino] -2-nitropyridine, 1, 2,3,4-tetrahydro-6-nitroquinoxaline, 7-amino-3,4-dihydro-6-nitro-2H-1, 4 benzoxazine (HC Red 14).

Suitable yellow nitro dyes are in particular:

1, 2-diamino-4-nitrobenzene (76.020 Cl.), 1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Yellow 2), 1- (2-hydroxyethoxy) -2 - [(2-hydroxyethyl ) amino] -5-nitrobenzene (HC Yellow 4), 1-amino-2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 5), 4 - [(2,3-dihydroxypropyl) amino] -3-nitro-1- trifluoromethyl-benzene (HC Yellow 6), 2- [di (2-hydroxyethyl) amino] -5-nitrophenol, 2 - [(2-hydroxyethyl) amino] -1-nnethoxy-5-nitrobenzene , 2-amino-3-nitrophenol, 2-amino-4-nitrophenol, 1-amino-2-methyl-6-nitrobenzene, 1- (2-hydroxyethoxy) -3-methylannino-4-nitrobenzene, 2,3- ( dihydroxy-propoxy) -3-methylannino-4-nitrobenzene, 3 - [(2-aminoethyl) amino] -1-methoxy-4-nitrobenzene hydrochloride (HC Yellow 9), 1-chloro-2,4-bis [( 2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 10), 2 - [(2-hydroxyethyl) amino] -5-nitrophenol (HC Yellow 11), 1 - [(2'-ureidoethyl) amino] -4 nitrobenzene, 1-amino-4 - [(2-aminoethyl) Annino] -5-nnethyl-2-nitrobenzene, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-chloro-4- [(2-hydroxyethyl) amino] -3-nitrobenzene (HC Yellow 12), 4 - [(2-hydroxyethyl) amino] -3-nitro-1-trifluornnethyl-benzene (HC Yellow 13), 4 - [(2-hydroxyethyl) amino] -3-nitro-benzonitrile (HC Yellow 14) 4 - [(2-hydroxyethyl) amino] -3-nitro-benzamide (HC Yellow 15) 3- [(2-hydroxyethyl) amino] -4-nnethyl-1-nitrobenzene, 4-chloro-3- [ (2-hydroxyethyl) amino] -1-nitrobenzene.

Suitable quinone dyes are in particular:

1, 4-di [(2,3-dihydroxypropyl) amino] -9,10-anthraquinone, 1, 4-di [(2-hydroxyethyl) amino] -9,10-anthraquinone (Cl. 61, 545, Disperse Blue 23) 1 - [(2-hydroxyethyl) amino] -4-methylamino-9,10-anthraquinone (Cl 61, 505, Disperse Blue 3). 2 - [(2-aminoethyl) amino] -9,10 anthraquinone (HC Orange 5), 1-amino-4-hydroxy-9,10-anthraquinone (Cl. 60.710, Disperse Red 15), 1-hydroxy-4- [(4-methyl-2-sulfophenyl) amino] -9 , 10-anthraquinone, 7-beta-D-glucopyranosyl-9,10-dihydro-1-methyl-9,10-dioxo-3,5,6,8-tetrahydroxy-2-anthracenecarboxylic acid (Cl. 75.470, Natural Red 4 ), 1- [(3-aminopropyl) amino] -4-methylamino-9,10-anthraquinone (HC Blue 8), 1 - [(3-aminopropyl) - amino] -9,10-anthraquinone (HC Red 8) , 1, 4-diamino-2-methoxy-9,10-anthraquinone (Cl. 62.015, Disperse Red 11, Solvent Violet No. 26), 1, 4-dihydroxy-5,8-bis [(2-hydroxyethyl) amino ] -9,10-anthraquinone (Cl. 62,500, Disperse Blue 7, Solvent Blue No. 69), 1, 4-diamino-9,10-anthraquinone (Cl. 61, 100, Disperse Violet 1), 1-amino 4- (methylamino) -9,10-anthraquinone (Cl. 61, 105, Disperse Violet 4, Solvent Violet No. 12) 2-hydroxy-3-methoxy-1, 4-naphthoquinone, 2,5-dihydroxy-1, 4-naphthoquinone, 2-hydroxy-3-methyl-1, 4-naphthoquinone, N- {6 - [( 3-chloro-4- (methylamino) phenyl) imino] -4-methyl-3-oxo-1, 4-cyclohexadiene-1-yl} urea (HC Red 9), 2 - {{4- [di (2- hydroxyethyl) amino] phenyl} Annino} -5 - [(2-hydroxyethyl) Annino] -2,5-cyclohexadiene-1, 4-dione (HC Green 1), 5-hydroxy-1, 4-naphthoquinone (Cl 75,500. , Natural Brown 7), 2-hydroxy-1, 4- naphthoquinone (Cl. 75.480, Natural Orange 6), 1, 2-dihydro-2- (1, 3-dihydro-3-oxo-2H-indol-2- ylidene) -3H-indol-3-one (Cl 73,000), 4 -. {{5 - [(2-hydroxyethyl) amino] -1-methyl-1 H- pyrazol-4-yl} imino} -4.5 dihydro-5 - [(2-hydroxyethyl) -innino] -1-nnethyl-1 H-pyrazole sulphate (1: 1), hydrate (1: 1).

Suitable neutral azo dyes are in particular:

1- [di (2-hydroxyethyl) amino] -3-nnethyl-4 - [(4-nitrophenyl) azo] benzene (. 1 Cl 1, 210, Disperse Red 17), 1- [di (2-hydroxyethyl) amino] -4 - [(4-nitrophenyl) azo] benzene (Disperse Black 9), 4 - [(4-aminophenyl) azo] -1- [di (2-hydroxyethyl) Annino] -3-nnethylbenzol (HC Yellow 7), 2,6-diamino-3- [(pyridin-3-yl) azo] pyridine, 2 - {[4- (acetylamino) phenyl] azo} -4-nnethylphenol (Cl 11855; Disperse Yellow 3). , 4 - [(4-nitrophenyl) azo] aniline (CI 11, 005; Disperse Orange 3.).

Preferred nonionic direct dyes are known under the International names or commercial names of HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 known compounds, and 1, 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1, 4-bis (2-hydroxyethyl) -amino-2-nitrobenzene, 3-nitro-4- (2-hydroxyethyl) - aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-amino-4- (2-hydroxyethyl) amino-5- chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 2 - benzoic acid [(4-amino-2-nitrophenyl) Annino], 6-nitro-1 , 2,3,4-tetrahydroquinoxaline, 2-hydroxy-1, 4-naphthoquinone, picramic acid and salts thereof, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoesä acid and 2-chloro-6-ethylamino-4-nitrophenol.

It is not necessary that the direct dyes to be single compounds. Rather, may be conditionally included the preparation processes for the individual dyes, in minor amounts of other components, as far as they do not adversely affect the coloring result or toxicological for other reasons, for example, must be excluded. Furthermore occurring dyes Henna Chamomile, sandalwood, black tea, buckthorn bark, sage, logwood, madder root, catechu, cedar and alkanet can be used as direct dyes in nature are used as red for example, henna, henna neutral, black, are included.

The compositions of the invention contain the direct dyes preferably in an amount of 0.01 to 20 wt .-%, based on the total preparation.

It is not necessary that the oxidation dye precursors or the substantive dyes to be single compounds. Rather, may be caused by containing the manufacturing processes for the individual dyes, in minor amounts of other components in the inventive hair dyes, insofar as they do not adversely affect the coloring result or eg toxicological, must be ruled out for other reasons.

Regarding the useable in the inventive hair coloring and dyes -tönungsmitteln continues expressly to the monograph Ch Zviak, The Science of Hair Care, Chapter 7 (pages 248-250; direct dyes). And Chapter 8, pages 264-267; Oxidation dye precursors), published as Volume 7 of the Series "Dermatology" (Ed .: Ch. Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, and the "European Inventory of Cosmetic Raw Materials" published by the European Community, available in diskette form by the Federal Association of German industrial and trading Firms for pharmaceuticals, health products and personal care products, Mannheim, reference is made.

In a second embodiment of the present invention, the agents contain as active ingredient at least one color-changing peroxo compound. These agents are typically called bleaching.

For the bleaching of human hair - especially for the tress application -Be usually solid or pasty preparations containing solid peroxo compounds mixed with a dilute hydrogen peroxide solution immediately before use. This mixture is then applied to the hair and rinsed out again after a certain contact time.

The solid peroxo compounds are as a rule no adducts of hydrogen peroxide onto other components is the selection of these peroxo not subject to any restrictions. bonds usual, known to those skilled Peroxover- example, ammonium peroxydisulfate, potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, potassium, sodium,

Kaliumperoxidiphosphat, percarbonates such Magnesiumpercarbonat and peroxides such as barium peroxide. Among these peroxo compounds, which can also be used in combination, the inorganic compounds are preferred in the invention. Particularly preferably, the peroxodisulfates, in particular ammonium peroxydisulfate are.

The peroxy compounds are preferably contained in the inventive compositions in amounts of 5-30 wt .-%, especially in amounts of 8-20 wt .-%.

Another important component contain a bleaching alkalizing agent to adjust the alkaline pH of the application mixture. According to the invention the skilled person can also known for bleaching, conventional alkalizing agent such as ammonium, alkali metal and alkaline earth metal hydroxides, carbonates, bicarbonates, - hydroxycarbonates, silicates, in particular metasilicates, as well as alkali metal phosphates are used. In a preferred embodiment, bleaching according to the invention contain at least two different alkalizing agents. Mixtures for example, a metasilicate and a hydroxycarbonate may be preferred.

Bleaching contain alkalizing agents preferably in amounts of 5-25 wt .-%, in particular 10-20 wt .-%.

Bleaching usually contain as a further essential component, hydrogen peroxide or a solid addition compound of hydrogen peroxide with inorganic or organic compounds, such as sodium perborate, sodium percarbonate, percarbamide, polyvinylpyrrolidone, urea and melamine.

The concentration of this hydrogen peroxide solution is determined on the one hand by the legal requirements and on the other hand by the desired effect; are usually used 6- to 12-percent solutions in water. The proportions of the component containing the peroxygen compound to the hydrogen peroxide solution is typically in the range 1: 1 to 1: 2, with an excess of hydrogen peroxide solution is particularly selected when no to pronounced bleaching effect is desired.

In a further preferred embodiment, the inventive means to permanently shape-modifying agents. These means usually consist of two or three preparations which are applied successively to the fibers. In addition, the following terms are used:

"Waving agent" for the aqueous preparation of the keratin-reducing substance

"Intermediate rinse" for the first rinse and

"Fixer" for the aqueous preparation of the oxidizing agent.

Although the combination of active ingredients according to the invention can in principle be used in any of the aforementioned preparations, it has become more preferably proved according to the invention, when the combination of active ingredients contained in the waving composition.

The waving agent according to the invention necessarily contain at least one keratin-reducing substance, preferably mercaptans. Such compounds are for example thioglycolic acid, thiolactic acid, thiomalic acid, mercaptoethane sulfonic acid and salts and esters thereof, cysteamine, cysteine, Bunte salts and salts of sulfurous acid. Particularly suitable are the alkali metal or ammonium salts of thioglycolic acid and / or thiolactic acid and the free acids. These are inserted into the waving compositions preferably in concentrations of 0.5 to 1, 0 mol / kg at a pH value of from 5 to 12, especially from 7 to 9.5. Well compositions of the invention for adjusting this pH usually contain alkalizing agent such as ammonia, alkali metal and ammonium carbonates and hydrogencarbonates, or organic amines such as monoethanolamine.

Furthermore, waving lotions according to the invention waving power enhancing components may include, for example,

• heterocyclic compounds such as imidazole, pyrrolidine, piperidine, dioxolane, dioxane, morpholine and piperazine, and derivatives of these compounds such as the C- |.4 alkyl derivatives, d- 4 -hydroxyalkyl derivatives and C-ι- 4 -Anninoalkyl derivatives. Preferred substituents which may be positioned both on carbon atoms and on nitrogen atoms of the heterocyclic ring systems are methyl, ethyl, ß-hydroxyethyl and .beta.-aminoethyl-groups. According to the invention, preferred derivatives of heterocyclic compounds are, for example, 1-methylimidazole, 2-methylimidazole, 4 (5) -methylimidazole, 1, 2- dimethylimidazole, 2-ethylimidazole, 2-lsopropylimidazol, N-methylpyrrolidone, 1-methylpiperidine, 4-methylpiperidine, 2- ethylpiperidine, 4-methylmorpholine, 4- (2-hydroxyethyl) morpholine, 1- ethylpiperazine, 1- (2-hydroxyethyl) piperazine, 1- (2-aminoethyl) piperazine. Further inventively preferred imidazole derivatives are biotin, hydantoin and benzimidazole. Most preferably, the imidazole.

• amino acids such as arginine, in particular, citrulline, histidine, ornithine, and lysine. The amino acids can be used as free amino acid and as salts, for example. For example, be used as hydrochlorides. Furthermore, also oligopeptides from 2-3 amino acids on average, a high proportion (> 50%, in particular> 70%) have, have proven to be used according to the invention to said amino acids. According to the invention, particularly preferred are arginine and its salts and arginine-rich oligopeptides.

• diols such as 2-ethyl-1, 3-hexanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 2-propanediol, 1, 3-propanediol, neopentyl glycol and ethylene glycol. 1, 3-diols, particularly 2-ethyl-1, 3-hexanediol and 1, 3-butanediol, have proved to be particularly suitable.

With regard to further information on such waving power amplifying components, reference is made to the publications DE-OS 44 36 065 and EP-B1-363 057, the contents of which reference is expressly made.

The waving power enhancing compounds can be used in the inventive well lotions in amounts of from 0.5 to 5 wt .-%, based on the total lotion well be included. Amounts of from 1 to 4 wt .-%, in the case of the diols of 0.5 to 3 wt .-%, have proved to be sufficient, therefore, these amounts are particularly preferred.

Mandatory part of the fixing invention are oxidizing agents, for example. B. Na- triumbromat, potassium bromate, hydrogen peroxide, and the usual order to stabilize aqueous hydrogen peroxide preparations stabilizers. The pH of such aqueous H 2 O 2 - preparations containing usually about 0.5 to 15 wt .-%, ready for use is usually about 0.5 to 3 wt .-%, H 2 O 2, is attached preferably 2 to 6, especially from 2 to 4; it is adjusted by inorganic acids, preferably phosphoric acid. Fixative bromate base containing bromates usually in concentrations of 1 to 10 wt .-% is used and the pH of the solutions is adjusted to 4 to 7th Also suitable are fixing enzyme-based (eg. As peroxidases), which contain no or only small amounts of oxidizing agents, in particular H 2 O 2.

The wave agent or a fixing agent according to the invention are usually formulated single phase, enclosed by this term are systems comprising a continuous phase, such as pure oil-in-water or water-in-oil emulsions.

It has been shown that the invention also two- and multiphase systems are preferred. These are systems in which there are at least two separate continuous phases. Examples of such systems are preparations which comprise the following phases:

• an aqueous phase and a non-aqueous phase which separately exist • an aqueous phase and two non-aqueous immiscible phases present separately

• an oil-in-water emulsion and, separately from this non-aqueous phase

• a water-in-oil emulsion and, separately from this aqueous phase.

It has been found according to the invention to be advantageous if the means of the present invention in addition to the inventive active ingredient combination of one other active substance which has care, anti-inflammatory, anti-irritant and / or soothing properties.

As part of a first preferred embodiment, color changing means according to the invention contains as a care substance at least one cationic surfactant.

According to the invention cationic surfactants of the quaternary ammonium compounds, esterquats and the amidoamines are. Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkyl methyl ammonium chlorides, for. B. cetyl trimethylammonium chloride, Stearyltrimethylammonium- chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryl dimethylbenzylammonium chloride and tricetyl methyl ammonium chloride, as well as those known under the INCI names Quaternium-27 and Quaternium-83 imidazolium compounds. The long alkyl chains of the above surfactants preferably have 10 to 18 carbon atoms.

Ester quats are known substances which contain both at least one Esterfunktion and at least one quaternary ammonium group as structural element. Preferred esterquats are quaternized Estersalze of fatty acids with triethanolamine, quaternized Estersalze of fatty acids with diethanol alkylamines and quaternized Estersalzen of fatty acids with 1, 2-dihydroxypropyl. 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, Dehyquart ® C-4046, Dehyquart ® L80 and Dehyquart ® AU-35 are examples of such esterquats.

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

Further according to the invention suitable cationic surfactants are known under the INCI names Linoleamidopropyl PG-Dimonium Chloride Phosphate, Cocamidopropyl PG-Dimonium Chloride Phosphate Stearamidopropyl PG-Dimonium Chloride and Phosphate substances. These are phospholipid EFA ®, Phospholipid PTC ® and Phospholipid SV ® for example sold by the company Mona under the trade names.

The cationic surfactants are contained in the used in the invention preferably in amounts from 0.05 to 10 wt .-%, based on the total preparation. Amounts of 0.1 to 5 wt .-% are particularly preferred.

As part of a second preferred embodiment of the present invention, the color-modifying agents contain as maintaining at least a nurturing polymer.

A first group of conditioning polymers are the cationic polymers. Cationic polymers are polymers according to the invention to be understood which have, "temporarily" in the main and / or side chain a group or may be "permanently" cationic. As will be "permanently cationic" according to the invention denotes those polymers which independently of the pH value of the agent is a cationic group. These are generally polymers that contain a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic groups are quaternary ammonium groups . in particular, those polymers in which the quaternary ammonium group via a C- |. 4 - are attached to a hydrocarbon group made up of acrylic acid, methacrylic acid or derivatives thereof, polymer backbone have been found to be particularly suitable.

Homopolymers of the general formula (G1-I), R 1

- [CH 2 -CJ n X "(G 1-1)

CO-O- (CH 2) m -N + R 2 R 3 R 4

R 2, R 3, and R is wherein R 1 = -H or -CH 3, 4 are independently selected from C- |.4 - alkyl, -alkenyl or -hydroxyalkyl groups, m = 1, 2, 3 or 4, n is a natural number and X "is a physiologically compatible organic or inorganic anion, and copolymers consisting essentially of (in the formula G1 monomer units, and -I) nonionogenic monomer units are particularly preferred cationic polymers. In

These polymers, are those preferred in the invention, for which at least one of the following conditions applies:

R 1 represents a methyl group

R 2, R 3 and R 4 are methyl groups m has the value of 2.

'Suitable physiologically acceptable counter ions X, for example, halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions. Halide ions, especially chloride are preferred.

A particularly suitable homopolymer is the optionally crosslinked, poly (methacryloyloxyethyltrimethylammonium chloride) with the INCI name Polyquaternium 37. The crosslinking can, if desired, with the aid of olefinically polyunsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, Polyallylpolyglycerylether, or allyl ethers of sugars or carried sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose or glucose. Methylenebisacrylamide is a preferred crosslinking agent.

The homopolymer is preferably used in the form of a non-aqueous polymer dispersion, which should not have less than 30 wt .-% a polymer content. Such polymer dispersions are (under the names Salcare ® SC 95 about 50% polymer content, additional components: mineral oil (INCI name: Mineral Oil) and tridecyl-polyoxypropylene-polyoxyethylene-ether (INCI name: PPG-1 trideceth-6) ) and Salcare ® SC 96 (about 50% polymer content, additional components: mixture of diesters of propylene glycol with a mixture of caprylic and capric acid (INCI name: propylene glycol Dicaprylate / Dicaprate) and tridecyl polyoxypropylene-polyoxyethylene-ether (INCI lots: PPG-1 trideceth-6)) are commercially available.

Copolymers contain monomer units having the formula (G1-I) as a non-ionic monomer, preferably acrylamide, methacrylamide, acrylic acid-C- |.4 alkyl ester and methacrylic acid-C-ι- 4 -alkyl. Among these, non-ionic monomers, acrylamide is particularly preferred. These copolymers can also be cross-linked as in the case of the homopolymers described above. An inventively preferred copolymer is the crosslinked acrylamide-methacryloyloxyethyltrimethylammonium chloride copolymer. Such copolymers in which the monomers are present in a weight ratio of about 20:80, are commercially available as approximately 50% non-aqueous polymer dispersion 92 under the name Salcare ® SC.

Other preferred cationic polymers are for example quaternised CeIIu lose-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, cationic alkyl polyglycosides according to DE-PS 44 13 686, cationized honey, for example the commercial product Honeyquat ® 50, cationic guar derivatives, such as in particular the products sold under the trade names Cosmedia® ® guar and Jaguar ® products,

Polysiloxanes with quaternary groups, such as the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), 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 polydimethyl siloxanes, Quaternium-80), polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers,

Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate, such as, for example, quaternized with diethyl sulfate, vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers. Such compounds are sold under the names Gafquat ® 734 and Gafquat ® 755 commercially,

Vinylpyrrolidone-vinyl imidazolium copolymers, such as those offered under the names Luviquat ® FC 370, FC 550, FC 905 and HM 552, quaternized polyvinyl alcohol, as well as by the names of Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27, having quaternary nitrogen atoms in the polymer main chain.

Can be used as cationic polymers are sold under the names Polyquaternium-24 (commercial product z. B. Quatrisoft ® LM 200), known polymers. , Gaffix ® VC 713 (manufactured by ISP): Also according to the invention can be used the copolymers of vinylpyrrolidone, such as the commercial products Copolymer 845 (ISP manufacturer) are Gafquat ® ASCP 1011, Gafquat ® HS 110, Luviquat ® 8155 and Luviquat ® MS 370 available are.

Other cationic polymers of the invention are the "temporarily cationic" polymers. These polymers usually contain an amino group present at certain pH values ​​as a quaternary ammonium group and hence cationic. For example, chitosan and its derivatives are preferred as Hydagen CMF ®, Hydagen HCMF ®, Kytamer ® PC and Chitolam ® NB / 101 are freely available commercially, for example under the trade names.

According to the invention preferred cationic polymers are cationic cellulose derivatives and chitosan and its derivatives, in particular the commercial products Polymer ® JR 400, Hydagen ® HCMF and Kytamer ® PC, cationic guar derivatives, cationic honey derivatives, in particular the commercial product Honeyquat ® 50, cationic Alkylpolyglycodside according to DE-PS 44 13 686, and polymers of the type Polyquaternium-37.

Furthermore, cationized protein to the cationic polymers are to be counted, the protein hydrolyzate can originate from animals, for example from collagen, milk or keratin, from plants, such as wheat, corn, rice, potatoes, soy or almonds, from marine life forms, for example, may be selected from fish collagen or algae, or biotechnologically obtained protein hydrolyzates. The protein hydrolysates the cationic derivatives according to the invention are based may be obtained from both types of hydrolysis of the corresponding proteins by a chemical, in particular alkaline or acidic hydrolysis, by enzymatic hydrolysis and / or a combination thereof. The hydrolysis of proteins usually yields a protein hydrolyzate with a molecular weight distribution of from about 100 daltons up to several thousand daltons. Those cationic protein whose underlying protein fraction has a molecular weight of 100 to 25,000 Daltons are preferred, preferably from 250 to 5000 daltons. Quaternized amino acids and mixtures thereof are to be understood as cationic protein. Quaternization of protein hydrolysates or amino acids is often by means of quaternary ammonium salts such as N, N-dimethyl-N- (n-alkyl) -N- performed (2-hydroxy-3-chloro-n-propyl) -ammoniumhalogeniden. The cationic protein hydrolysates can also be further derivatized. Names in the "International Cosmetic Ingredient Dictionary and Handbook" (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1101 17 th Street, NW, Suite 300 - as typical examples of the inventive cationic protein hydrolysates and derivatives are under the INCI are , above and commercially available products Washington DC 20036-4702) mentioned: Cocodimonium hydroxypropyl Hydrolyzed collagen, Cocodimopnium hydroxypropyl hydrolyzed casein, Cocodimonium hydroxypropyl Hydrolyzed collagen, Cocodimonium hydroxypropyl Hydrolyzed Hair keratin, Cocodimonium hydroxypropyl Hydrolyzed keratin, Hydrolyzed Rice protein Cocodimonium hydroxypropyl, hydroxypropyl Cocodimonium 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 lin protein 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, Lauryidimonium hydroxypropyl hydrolyzed casein, Lauryidimonium hydroxypropyl hydrolyzed collagen, Lauryidimonium hydroxypropyl hydrolyzed keratin, Lauryidimonium 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, Hydrolyzed Vegetable protein steardimonium hydroxypropyl, Steardim onium 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.

Most preferably, the cationic protein hydrolysates and derivatives based on plants.

Further according to the invention can be used care polymers are the amphoteric compounds mentioned in the British Laid-Open Patent 2,104,091, European Patent Publication 47,714, European Patent Publication 217274, European Patent Publication 283,817 and German Offenlegungsschrift 28 17 369th

Preferably used amphoteric polymers are those polymers which consist essentially of

(a) monomers with quaternary ammonium groups of general formula (II), R 1 -CH = CR 2 -CO-Z- R 4 R 5 A () (II) (C n H 2n) -N (+) R 3 in R 1 and R 2 independently of one another represent hydrogen or a methyl group and R 3,

R 4 and R 5 are independently alkyl of 1 to 4 carbon atoms, Z is an NH

(-) group or an oxygen atom, n is an integer from 2 to 5 and A is the anion of an organic or inorganic acid, and

(B) monomeric carboxylic acids of the general formula (III),

R R where 6 and R 7 are independently hydrogen or methyl groups 6 -CH = CR 7 -COOH (IM).

These compounds may be used according to the invention both directly and in salt form, which is, for example, with an alkali hydroxide, obtained by neutralization of the polymers. Regarding the details of the preparation of these polymers, reference is explicitly 39 29 973 made to the content of the German patent application. Very particularly preferred polymers are in which monomers of type (a) are used in which R 3, R 4 and R 5 are methyl groups, Z is an NH group and A () is a halide, methoxysulfate or ethoxysulfate ion is; Acrylamidopropyl trimethyl ammonium chloride is a particularly preferred monomer (a). As monomer (b) for the polymers mentioned acrylic acid is preferably used.

The color-changing compositions of the invention contain the cationic polymers preferably in an amount of 0.01 to 5 wt .-%, in particular in an amount of 0.1 to 2 wt .-%, each based on the total preparation.

As part of a third preferred embodiment color-changing compositions of the invention contain at least one UV filter. The inventively suitable UV filters are not generally limited in terms of their structure and their physical properties. Instead, all used in the cosmetic field UV filters whose absorption maximum in the UVA (315-400 nm) -, in the UVB (280-315) - or in the UVC (<280 nm) - range. UV filters having an absorption maximum in the UVB region, in particular in the range of about 280 to about 300 nm, are particularly preferred.

The inventively preferred UV filters can for example be selected from substituted benzophenones, p-aminobenzoic acid esters, diphenylacrylates, cinnamates, salicylates, benzimidazoles and o-aminobenzoic acid esters. Examples of the present invention suitable UV filters are 4-amino-benzoic acid, N, N, N-trimethyl-4- (2-oxoborn-3-ylidennnethyl) aniline nnethylsulfat, SSδ-Trinnethyl-cyclohexyl salicylate (homosalate), 2-hydroxy 4-methoxy-benzophenone (benzophenone-3; Uvinul ® M 40, Uvasorb MET ®, ® Neo Heliopan BB, Eusolex ® 4360), 2-phenylbenzimidazole-5-sulfonic acid and potassium, sodium and triethanolamine salts (phenylbenzimidazole sulfonic Acid; Parsol ® HS; Neo Heliopan Hydro ®), 3,3 '- (1, 4-phenylenedimethylene) bis (7,7-dimethyl-2-oxo-bicyclo [2.2.1] hept-1-yl-methane sulfonic acid) and salts thereof, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1, 3- dione Methoxydibenzoylmethane (butyl; Parsol ® 1789 Eusolex ® 9020) α- (2- oxoborn-3-ylidene) - toluene-4-sulfonic acid and salts thereof, ethoxylated 4-aminobenzoic acid ethyl ester (PEG-25 PABA; Uvinul ® P 25), 4-dimethylaminobenzoic acid 2-ethylhexyl (octyl dimethyl PABA; Uvasorb ® DMO Escalol ® 507, Eusolex ® 6007), salicylic acid 2 -ethylhexylester (octyl salicylate; Escalol ® 587, Neo Heliopan OS ®, Uvinul ® O18), 4-methoxycinnamic acid isopentyl (isoamyl p-methoxycinnamate; Neo Heliopan E 1000 ®), 4-methoxycinnamic acid 2-ethylhexyl ester (Octyl Methoxycinnamate; Parsol ® MCX, Escalol ® 557, Neo Heliopan AV ®), 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt (Benzophenone-4; Uvinul ® MS 40; Uvasorb S 5 ®), 3- (4'-methylbenzylidene) -D, L-camphor (4-methylbenzylidene camphor; Parsol ® 5000, Eusolex ® 6300), 3-benzylidene camphor (3-benzylidene camphor), 4-lsopro- pylbenzylsalicylat, 2,4,6-trianilino- (p-carbo-2 '-ethylhexyl-1' -oxi) -1, 3,5-triazine, 3-imidazol-4-yl- acrylic acid and their ethyl esters, polymers of N - {(2 and 4) - [2-oxoborn-3-ylidenemethyl ] benzyl} - acrylamide, 2,4-dihydroxy (benzophenone-1; Uvasorb ® 20 H, Uvinul ® 400) 1, 1 '- Diphenylacrylonitrilsäure-2-ethylhexyl ester (Octocrylene; Eusolex ® OCR, Neo Heliopan ® Type 303 , Uvinul ® N 539 SG), o-aminobenzoic acid menthyl ester (menthyl Anthrani late; Neo Heliopan MA ®), 2,2 ', 4,4'-tetrahydroxy benzophenone (benzophenone-2; Uvinul ® D-50), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (Benzophenone-6), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5-sodium sulfonate, and 2-cyano- 3,3-diphenylacrylate 2'-ethylhexyl. 4-amino-benzoic acid, N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) aniline methyl sulfate, 3,3,5-trimethyl-cyclohexyl salicylate, are preferably 2-hydroxy-4-methoxy-benzophenone , sulfonic acid, 2-phenylbenzimidazole-5 and its potassium, sodium and triethanolamine salts, 3,3 '- (1, 4- phenylenedimethylene) bis (7,7-dimethyl-2-oxo-bicyclo [2.2.1] hept-1-yl-methane-sulfonic acid) and salts thereof, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1, 3-dione, α- (2-oxoborn-3- ylidene) toluene-4-sulfonic acid and salts thereof, ethoxylated 4-aminobenzoic acid ethyl ester, A- dimethylaminobenzoic acid 2-ethylhexyl ester, salicylic acid 2-ethylhexyl ester, A-

Methoxycinnamic acid isopentyl ester, 4-methoxycinnamic acid 2-ethylhexyl ester, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt, 3- (4'-methylbenzylidene) -D, L-camphor, 3-benzylidene camphor, 4-isopropylbenzyl salicylate, 2,4,6-trianilino- (p-carbo-2' 'ethylhexyl-1 -oxi) -1, 3,5-triazine, 3-imidazol-4-yl-acrylic acid and its ethyl ester, polymers of N- {(2 and 4) - [2-oxoborn-3-ylidenemethyl] benzyl} acrylamide. According to the invention are very particularly preferably 2-hydroxy-4-methoxybenzophenone, 2-phenylbenzimidazole-5-sulfonic acid and potassium, sodium and triethanolamine salts thereof, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) - propan-1, 3-dione, 4-methoxycinnamic acid 2-ethylhexyl ester and 3- (4'-methylbenzylidene) -D, L-camphor.

those UV filters whose molar extinction coefficient of 15, 000 above, in particular above 20000, at the absorption maximum are preferred.

Furthermore, it was found that with structurally similar UV filters, in many cases, the water-insoluble compound having the higher activity against such water-soluble compounds in the context of the teaching according to the invention, which differ from it by one or more additional ionic groups. As water-insoluble are understood to those UV filters in the context of the invention, at 20 0 C to not more than 1 wt .-%, in particular not more than 0.1 wt .-%, dissolves in water. Furthermore, these compounds should be wt .-% soluble in conventional cosmetic oil components at room temperature to at least 0.1, in particular at least 1). The use of water-insoluble UV filters can therefore be preferred in the invention.

According to another embodiment of the invention, UV filters are preferred which have a cationic group, in particular a quaternary ammonium group.

These UV filters have the general structure U - Q.

The structural moiety U stands for a UV absorbing group. This group can in principle from the prior art, used in the cosmetic field, derived above-mentioned UV filters, in which a group, generally a hydrogen atom, of the UV filter by a cationic group Q, in particular with a quaternary amino function, ,

Compounds from which the structural moiety U may be derived are for example substituted benzophenones, p-aminobenzoic acid esters, diphenylacrylic esters, cinnamic acid esters, salicylic esters, benzimidazoles and o-aminobenzoic acid esters. Structural parts U derived from cinnamic acid amide or from N, N-dimethylaminobenzoic acid amide are preferred in the invention.

The structural parts U can in principle be chosen such that the absorption maximum of the UV filters in both the UVA (315-400 nm) -, and in the UVB (280-315) - or in the UVC (<280 nm) - can range. UV filters having an absorption maximum in the UVB region, in particular in the range of about 280 to about 300 nm, are particularly preferred.

Furthermore, the structural moiety U, as a function of structural element Q is preferably chosen so that the molar extinction coefficient of the UV filter higher than 15,000, in particular above 20000, at the absorption maximum.

The structural element Q contains as cationic group is preferably a quaternary ammonium group. This quaternary ammonium group may be directly connected to the structural moiety U, in principle, so that the structural moiety U represents one of the four substituents of the positively charged nitrogen atom. Preferably, however, one of the four substituents at the positively charged nitrogen atom is a group, especially an alkylene group having 2 to 6 carbon atoms, which acts as a link between the structural moiety U and the positively charged nitrogen atom.

Advantageously, the group Q has the general structure - (CH2) χ-N + R 1 R 2 R 3 X ", where x is an integer from 1 to 4, R 1 and R 2 are independently C |. 4 alkyl groups, R 3 stands for a C |. 22 alkyl group or a benzyl group and X "is a physiologically acceptable anion. Within this general structure, x is preferably the number 3, R 1 and R 2 each represent a methyl group and R 3 is either a methyl group or a saturated or unsaturated, linear or branched hydrocarbon chain having from 8 to 22, in particular 10 to 18 , carbon atoms.

Physiologically compatible anions are, for example, inorganic anions such as halides, particularly chloride, bromide and fluoride, sulfate ions and phosphate ions, and organic anions such as lactate, citrate, acetate, tartrate, methosulfate and tosylate.

Two preferred UV filters with cationic groups are the commercially available compounds cinnamic acid-trimethylammonium chloride (lncroquat ® UV-283) and dodecyl tosylate (Escalol ® HP 610). Of course, the teaching of the invention also includes the use of a combination of several UV-filters. Within this embodiment, the combination of at least one water-insoluble UV filter is preferably at least one UV filter having a cationic group.

The UV filters are in the inventive compositions typically in amounts of 0.01-5 wt .-%, based on the entire application preparation. Amounts of 0.1-2.5 wt .-% being preferred.

As part of a fourth preferred embodiment color-changing compositions of the invention contain as a conditioning substance at least one vitamin, provitamin, vitamin precursor and one of their derivatives.

In this case, such vitamins, pro-vitamins and vitamin precursors are preferred in the invention, which are commonly assigned to the groups A, B, C, E, F and H.

The group of substances designated as vitamin A include retinol (vitamin A 1) and 3,4-didehydroretinol (vitamin A 2). The beta-carotene is a provitamin of retinol. As vitamin A component according to the invention are for example vitamin A acid and its esters, vitamin A aldehyde, and Vitamin A alcohol and its esters such as the palmitate and the acetate. The formulations used in the invention include vitamin A component preferably used in amounts of 0.05-1 wt .-%, based on the total preparation.

The vitamin B group or the vitamin B complex vitamins include vitamin B 1 (thiamine), B 2 (riboflavin)

Vitamin B3. Under this designation, the compounds nicotinic acid and nicotinamide (niacinamide) are often performed. According to the invention the nicotinamide, which is in accordance with the invention preferably in amounts from 0.05 to 1% by weight based on the total preparation, is.

Vitamin B 5 (pantothenic acid, panthenol and pantolactone). Within this group, panthenol and / or pantolactone is preferably used. According to the invention usable derivatives of panthenol are the esters and ethers of panthenol and cationically derivatized panthenols. Individual representatives are, for example, panthenol, panthenol and its monoacetate, and those disclosed in WO 92/13829 the cationic panthenol. The compounds of the vitamin B 5 type are present in the agents preferably in amounts of 0.05 - 10 wt .-% contain, based on the total preparation. Amounts of 0.1 to 5 wt .-% are particularly preferred.

Vitamin B 6 (pyridoxine and pyridoxamine and pyridoxal). The compounds of vitamin B 6 -type are mentioned in the present invention preferably in amounts from 0.01 to 5 wt .-%, based on the entire application preparation. Amounts of 0.05 to 1 wt .-% are particularly preferred.

Vitamin C (ascorbic acid). Vitamin C is used in the used in the invention preferably in amounts from 0.1 to 3 wt .-%, based on the total preparation. Use in the form of palmitic acid ester, the glucosides or phosphates may be preferred. Use in combination with tocopherols can likewise be preferred.

Vitamin E (tocopherols, in particular α-tocopherol). Tocopherol and its derivatives, including in particular the esters such as the acetate, nicotinate, phosphate and succinate, are in the present invention preferably in amounts of 0.05-1 wt .-%, based on the entire application preparation.

Vitamin F. The term "vitamin F" is usually essential fatty acids, especially linoleic acid, linolenic acid and arachidonic acid.

Vitamin H., the compound (3aS, 4S, 6aR) -2-Oxohexahydrothienol [3,4-c /] Vitamin H - referred imidazole-4-valeric acid, for which, however in the meantime the trivial name biotin has. Biotin in the inventive compositions preferably in amounts of 0.0001 to 1, 0 wt .-%, in particular in amounts of from 0.001 to 0.01 wt .-%, each based on the total preparation.

Preferably color-changing means vitamins according to the invention, pro-vitamins and vitamin precursors from the groups A, B, C, E and H.

Panthenol, pantolactone, pyridoxine and its derivatives as well as nicotinamide and biotin are particularly preferred.

As part of a fifth embodiment of color-changing agents of the invention contain as a conditioning substance at least one carboxylic acid. Advantageous for the purposes of the invention, short-chain carboxylic acids may be particular. Short-chain carboxylic acids and their derivatives according to the invention carboxylic acids are meant, which may be saturated or unsaturated and / or straight-chain or branched or cyclic and / or aromatic and / or heterocyclic and having a molecular weight of less than 750th Preferred according to the invention, saturated or unsaturated geradkettigte or branched carboxylic acids having a chain length of 1 up to 16 carbon atoms in the chain may be very particularly preferred are those having a chain length of 1 up to 12 carbon - atoms in the chain.

The short-chain carboxylic acids in the meaning of the invention, one, two, three or more carboxy groups. Preferred according to the invention are carboxylic acids having more carboxyl groups, especially di- and tricarboxylic acids. The carboxyl groups may be completely or partially as an ester, acid anhydride, lactone, amide, imidic, lactam, lactim, dicarboximide, carbohydrazide, hydrazone, hydroxamic, hydroxime, amidine, amidoxime, nitrile, phosphonic or Phosphatester. The carboxylic acids according to the invention can of course be substituted along the carbon chain or the ring structure. The substituents of the carboxylic acids according to the invention are, for example, to include C-ι-C 8 alkyl, C 2 -C 8 alkenyl, aryl, aralkyl and aralkenyl, hydroxymethyl, C 2 -C 8 hydroxyalkyl, C 2 -C 8 -Hydroxyalkenyl-, aminomethyl, C 2 -C 8 aminoalkyl, cyano, formyl, oxo, thioxo, hydroxy, mercapto, amino, carboxy or imino groups. Preferred substituents are dC 8 alkyl, hydroxymethyl, hydroxy, amino and carboxy groups. Particularly preferred substituents are in α- position. Very particularly preferred substituents are hydroxy, alkoxy and amino groups, the amino function may be optionally further substituted by alkyl, aryl, aralkyl and / or alkenyl radicals. Furthermore, preferred carboxylic acid derivatives are also the phosphonic and Phosphatester.

As examples of the invention carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, glyceric acid, glyoxylic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, propiolic acid, crotonic acid, isocrotonic , elaidic acid, maleic acid, fumaric acid, muconic acid, citraconic acid, mesaconic acid, camphoric acid, benzoic acid, o, m, p-phthalic acid, naphthoic acid, Toluoylsäure, hydratropic acid, atropic acid, cinnamic acid, isonicotinic acid, nicotinic acid, Bicarbaminsäure, 4,4 '- dicyano-6, 6 '-binicotinsäure, 8-Carbamoyloctansäure, 1, 2,4-pentanetricarboxylic acid, 2-pyrrolecarboxylic acid, 1, 2,4,6,7-Napthalinpentaessigsäure, malonaldehydic, 4-hydroxy-phthalamic acid, 1-pyrazolecarboxylic acid, gallic acid or propanetricarboxylic acid, a dicarboxylic acid selected from the group formed by Verbi inventions of the general formula (NI),

(NI)

in which Z denotes a linear or branched alkyl or alkenyl group having 4 to 12 carbon atoms, n is a number from 4 to 12 and one of the two groups X and Y is a COOH group and the other is hydrogen or a methyl or ethyl radical, dicarboxylic acids of the general formula (NI) which additionally carry 1 to 3 methyl or ethyl substituents on the cyclohexene ring and dicarboxylic acids arising from the dicarboxylic acids of the formula (NI) formally by addition of one molecule of water onto the double bond in the cyclohexene ring.

Dicarboxylic acids of formula (NI) are known in the literature. For example, to remove a fabrication method of the US Patent 3,753,968.

The dicarboxylic acids of the formula (NI) can be prepared, for example, cyclization by reaction of polyunsaturated dicarboxylic acids with unsaturated monocarboxylic acids in the form of a Diels-Alder. Usually, one will start with a polyunsaturated fatty acid as a dicarboxylic acid component. accessible from natural fats and oils, linoleic acid is preferred. As monocarboxylic acid component are in particular acrylic acid, as well as methacrylic acid and crotonic acid are preferred. Typically, in reactions according to Diels-Alder isomer mixtures, in which one component is present in excess. These isomer mixtures can be used according to the invention as well as the pure compounds.

According to the invention addition to the preferred dicarboxylic acids of the formula (NI) are those dicarboxylic acids which differ from the compounds according to formula (NI) are different, or by 1 to 3 methyl or ethyl substituents on the cyclohexyl ring of these compounds formally by addition of one molecule of water are formed across the double bond of the cyclohexene ring. As according to the invention is particularly effective, the dicarboxylic acid (mixture) has been found that arises by reacting linoleic acid with acrylic acid. This is a mixture of 5- and 6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid. Such compounds are commercially available under the designations Westvaco Diacid 1550 Westvaco Diacid ® ® 1595 (manufacturer: Westvaco).

Besides the above-exemplified inventive short-chain carboxylic acids themselves, their physiologically acceptable salts can be used according to the invention. Examples of such salts are the alkali metal, zinc salts and ammonium salts, which for the purposes of the present application, the mono-, di- and trimethylamine, ethyl and - are understood hydroxyethyl-ammonium salts. Very particularly preferably, however, neutralized acids can be used in the invention with alkaline amino acids such as arginine, lysine, ornithine and histidine. Furthermore, it may be preferred for formulation reasons to select the carboxylic acid from the water-soluble representatives, in particular the water-soluble salts.

Furthermore, it is preferable in the invention 2-pyrrolidinone-5-carboxylic acid and their derivatives to use as the carboxylic acid. Contributes to C 4 alkyl groups - particularly preferably the sodium, potassium, calcium, magnesium or ammonium salts in which the ammonium ion addition to hydrogen, one to three C 1 are. The sodium salt is most preferred. The amounts used in the inventive compositions are from 0.05 to 10 wt.%, Based on the total preparation, more preferably 0.1 to 5, and especially 0.1 to 3 wt.%.

Furthermore, it is preferred according hydroxycarboxylic acids and here in turn in particular the dihydroxy-, trihydroxy and polyhydroxy and dihydroxy, trihydroxy and polyhydroxy di-, tri- and polycarboxylic use. It has been shown that, in addition to hydroxycarboxylic acids, the hydroxycarboxylic acid esters and the mixtures of hydroxycarboxylic acids and their esters and polymeric hydroxycarboxylic acids and their esters can be very particularly preferred. Preferred hydroxycarboxylic acid esters are, for example, Vollester of glycolic acid, lactic acid, malic acid, tartaric acid or citric acid. More fundamentally suitable hydroxycarboxylic are esters of .beta.-hydroxypropionic acid, tartronic acid, D-gluconic acid, sugar acid, mucic acid or glucuronic acid. The alcohol component of these esters are primary, linear or branched aliphatic alcohols having 8-22 C-atoms, eg fatty alcohols or synthetic fatty alcohols. The esters of C 12 -C 5 fatty alcohols are particularly preferred. Esters of this type are commercially available, eg under the trademark Cosmacol® ® EniChem, Augusta Industriale. Particularly preferred polyhydroxypolycarboxylic are polylactic acid and polytartaric and their esters.

As part of a sixth preferred embodiment color-changing compositions of the invention contain as a conditioning substance at least one protein hydrolyzate and one of its derivatives.

Protein hydrolysates are product mixtures obtained by acid-, base- or enzyme-catalyzed degradation of proteins (proteins) are obtained. The term protein also total hydrolysates as well as individual amino acids and their derivatives as well as mixtures of different amino acids are understood according to the invention. Furthermore, composed of amino acids and amino acid derivatives polymers are understood under the term protein hydrolysates according to the invention. The latter, for example, polyalanine, polyaspartic, Polyserin etc. to count. Further examples of useful compounds according to the invention are L-alanyl-L-proline, polyglycine, glycyl-L-glutamine, or D / L-methionine-S- Methylsulfoniumchlorid. Of course, .beta.-amino acids and their derivatives such as beta-alanine, anthranilic acid or hippuric acid can also be used according to the invention. The molecular weight of the protein hydrolysates according to the invention can be used is between 75, the molar mass for glycine, and 200,000, preferably the molecular weight is 75 to 50,000, and particularly preferably 75 to 20,000 Daltons.

According to the invention protein hydrolysates of both plant and animal or marine or synthetic origin can be used.

Animal protein hydrolysates are for example elastin, collagen, keratin, silk and may also be in the form of salts milk protein hydrolyzates. Such products are, for example, under the trademarks Dehylan ® (Cognis), Promois® ® (Interorgana) Collapuron ® (Cognis), Nutrilan® ® (Cognis), Gelita-Sol ® (German Gelatinefabriken Stoess & Co), Lexein ® (Inolex) sericin (Pentapharm) and kerasol tm ® (Croda) sold.

According to the invention the use of protein hydrolysates of plant origin, is z. B. soy, almond, pea, potato and wheat. Such products are, for example, under the trademarks Gluadin ® (Cognis), diamine ® (Diamalt) ® (Inolex), Hydrosoy ® (Croda), hydro Lupine ® (Croda), hydro Sesame ® (Croda), Hydro tritium ® (Croda) and Crotein ® (Croda) available. Although the use of protein hydrolysates as such is preferred, amino acid mixtures obtained in other ways may be used in its place if necessary. Also possible is the use of derivatives of protein hydrolysates, for example in the form of fatty acid condensation products. Such products are marketed for example under the names Lamepon ® (Cognis), Lexein ® (Inolex), Crolastin ® (Croda), Crosilk ® (Croda) or Crotein ® (Croda).

Of course includes the teaching of all isomeric forms, such as cis invention - trans - isomers, diastereomers and chiral isomers.

According to the invention, it is also possible to use a mixture of several protein hydrolysates.

The protein hydrolyzates are contained in the color-changing means according to the invention in concentrations of from 0.01.% To 20 wt.%, Preferably from 0.05.% To 15 wt.% And very particularly preferably in amounts of 0.05. % up to 5 wt.%, each based on the entire application preparation.

As part of a seventh preferred embodiment, the preparations of the invention contain as a care substance ectoin or ectoin derivatives containing allantoin, bisabolol, and taurine.

According to the invention, the term "ectoine and ectoin derivatives" Compounds of formula (IV)

and / or stereoisomeric their physiologically acceptable salt and / or an isomeric or

Understood form wherein

R 10 represents a hydrogen atom, a branched or unbranched C 1 - C 4 alkyl group or a C 2 - C 4 hydroxyalkyl radical,

R 11 represents a hydrogen atom, a group -COOR 14 or a group -

CO (NH) R 14, wherein R 14 represents a hydrogen atom, a C 1 - C 4 alkyl group may stand, an amino acid residue, a dipeptide or a tripeptide radical,

R 12 and R 13 independently represent a hydrogen atom, a C 1 - C 4 alkyl group or one of the two radicals is a hydroxy group and n is an integer of 1 to 3

Suitable physiologically acceptable salts of the compounds according to formula (IVa) or (IVb) include the alkali metal, alkaline earth metal, ammonium, triethylamine or tris- (2-hydroxyethyl) amine salts, as well as those derived from the reaction of compounds according to the formula (IVa) or (IVb) with organic and inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, branched or unbranched, substituted or unsubstituted (for example, by one or more hydroxy) C 1 - C 4 - mono- or dicarboxylic acids, aromatic carboxylic acids yield and sulfonic acids such as acetic acid, citric acid, benzoic acid, maleic acid, fumaric acid, tartaric acid and p-toluenesulfonic acid. Examples of particularly preferred physiologically acceptable salts are the Na, K, Mg and Ca, and ammonium salts of the compounds according to formula (IVa) or (IVb), as well as the salts derived (by reaction of compounds of the formula IVa ) or (IVb) yield with hydrochloric acid, acetic acid, citric acid and benzoic acid.

Isomeric or stereoisomeric forms of the compounds according to formula (IVa) or (IVb) according to the invention are understood all occurring optical isomers, diastereomers, racemates, zwitterions, cations or mixtures thereof. The term amino acid represents the stereoisomeric forms, including D and L forms of the following compounds:

Asparagine, arginine, aspartic acid, glutamine, glutamic acid, beta-alanine, γ-aminobutyrate, N ε - acetyllysine, N 8 -Acetylornitin, N γ -Acetyldiaminobutyrat, N α -Acetyldiaminobutyrat, histidine, isoleucine, leucine, methionine, phenylalanine, serine, threonine and tyrosine.

L-amino acids are preferred. Amino acid residues are derived from the corresponding amino acids. The following amino acid residues are preferred:

Gly, Ala, Ser, Thr, Val, .beta.-Ala, γ-aminobutyrate, Asp, Glu, Asn, AIn, N ε -Acetyllysin, N δ -Acetylornithin, N γ -Acetyldiaminobutyrat, N α -Acetyldiaminobutyrat.

The short form of the amino acids was carried out according to the generally accepted spelling. The di- or tripeptide are in their chemical nature amides and decompose on hydrolysis in 2 or 3 amino acids. The amino acids in the di- or tripeptide are linked by amide bonds.

Regarding the preparation of di- and tripeptide is expressly made to EP 0671161 A1 of the Marbert company. Examples of di- and tripeptide are shown 0,671,161 A1 the disclosure of EP.

Examples of Ci - C 4 alkyl groups in the compounds of this invention are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. Preferred alkyl groups are methyl and ethyl, methyl is a particularly preferred alkyl group. Preferred C 2 - C 4 - hydroxyalkyl groups are the 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl; 2-hydroxyethyl is an especially preferred hydroxyalkyl group.

The color-changing compositions of the invention containing these active ingredients preferably in amounts of from 0.001 to 2, particularly from 0.01 to 0.5 wt .-%, each based on the total preparation.

In the context of an eighth preferred embodiment color-changing compositions of the invention contain as a conditioning substance at least one mono- or oligosaccharide.

It can be used both monosaccharides and oligosaccharides such as cane sugar, lactose and raffinose. The use of monosaccharides is preferred according to. Among the monosaccharides, such compounds are again preferred which contain 5 or 6 carbon atoms. Suitable pentoses and hexoses, for example, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, fucose, and fructose. Arabinose, glucose, galactose and fructose carbohydrates are preferably used; is very particularly preferably glucose, both in the D - is suitable configuration or as a racemate - (+) - or L - (-).

Furthermore, derivatives of these pentoses and hexoses, such as the corresponding onic and uronic acids (sugar acids), sugar alcohols and glycosides, are used according to the invention. Preferred sugar acids are gluconic acid, glucuronic acid, saccharic acid, mannosaccharic acid and mucic acid. Preferred sugar alcohols are sorbitol, mannitol and dulcitol. Preferred glycosides are the methyl glucosides.

As the mono- or oligosaccharides used are usually obtained from natural raw materials such as starch, they have the corresponding configurations on these raw materials (for example, D-glucose, D-fructose and D-galactose) in the rule.

The mono- or oligosaccharides are present in the inventive hair treatment compositions preferably in an amount of 0.1 to 8 wt .-%, particularly 1 to 5 wt .-%, based on the entire application preparation.

As part of a ninth embodiment, the preparation of the invention (B) as the hair-care component at least one silicone oil and / or one silicone gum.

According to the invention suitable silicones or silicone gums are particularly dialkyl and alkylaryl siloxanes such as dimethylpolysiloxane and methylphenyl polysiloxane, as well as alkoxylated, quaternized or anionic derivatives.

Examples of such silicones are:

Oligomers polydimethylcyclosiloxanes (INCI name: Cyclomethicone), in particular the tetrameric and pentameric compound, which are sold as commercial products DC 344 and DC 345 from Dow Corning,

Hexamethyldisiloxane (INCI name: Hexamethyldisiloxane) z. As the sold under the name Abil ® K 520,

Polydimethylsiloxanes polymers (INCI name: dimethicone), for example. As the sold under the name DC 200 of Dow Corning products, polyphenylmethylsiloxanes (INCI name: Phenyl Trimethicone) z. As the commercially available 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 ® (INCI name: dimethicone copolyol Meadowfoamate) are distributed,

Dimethylsiloxanes having hydroxyl end groups (INCI name: Dimethiconol) z. , The commercial products DC 1401 and Q2-1403 from Dow Corning amino functional polydimethylsiloxanes and hydroxylaminomodifizierte silicones (INCI name: eg amodimethicone and quaternium-80) (such as the commercial products XF42-B1989 (manufacturer GE Toshiba Silicones) Q2-7224 Manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning ® 939 emulsion (containing a hydroxylamino-modified silicone which is also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and abif-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 of the invention comprise a combination of a volatile and a nonvolatile silicone. Volatile in the meaning of the invention are those silicones which have a volatility, which is equal to or greater than the volatility of the cyclic dimethylsiloxane pentamer. Such combinations are also available as commercial products (eg., Dow Corning ® 1401 Dow Corning ® 1403 and Dow Corning ® 1501 each mixtures of a cyclomethicone and dimethiconol).

According to a particularly preferred embodiment, component (A) a dialkylpolysiloxane, or one of its derivatives is used. the alkyl groups are methyl, ethyl, i-propyl and n-propyl are preferred. Dimethylpolysiloxane or a derivative thereof is particularly preferably used. Preferred are the derivatives of Dimethylplysiloxans which are aminofunctional. A particularly preferred derivative is available under the INCI name amodimethicone commercially.

The formulations of the invention include the silicones preferably in amounts from 0.01 to 10 wt .-%, in particular 0.1 to 5 wt .-%, based on the total preparation. As part of a tenth embodiment of color-changing agents of the invention comprise at least one lipid as a conditioner.

According to the invention, suitable lipids are phospholipids, for example soya lecithin, egg lecithin and cephalins, and those known under the INCI names Linoleamidopropyl PG-Dimonium Chloride Phosphate, Cocamidopropyl PG-Dimonium Chloride Phosphate Stearamidopropyl PG-Dimonium Chloride and Phosphate substances. These are phospholipid EFA ®, Phospholipid PTC ® and Phospholipid SV ® for example sold by the company Mona under the trade names.

The preparations of the invention contain lipids preferably in amounts from 0.01 to 10 wt .-%, in particular 0.1 to 5 wt .-%, based on the total preparation.

In the context of an eleventh embodiment of color-changing agents of the invention contain at least one further oil body as a conditioner.

Other natural and synthetic cosmetic oil bodies are, for example, to include: liquid paraffin oils, isoparaffin oils and synthetic hydrocarbons and di-n-alkyl ethers containing a total of 12 to 36 carbon atoms, especially 12 to 24 carbon atoms, such as di-n- octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n-undecyl ether, di-n- dodecyl ether, n-hexyl-n-octyl ether, n-octyl-n-decyl ether, n-decyl, n-undecyl ether, n-undecyl-n-dodecyl ether and n-hexyl-n-undecyl ether and di-tert-butyl ether, di-iso-pentyl ether, di-3- ethyldecylether, tert-butyl-n-octyl ether, isopentyl-n-octyl ether and 2-methyl-pentyl-n-octyl ether. The compounds are available as commercial products 1, 3-di- (2-ethyl-hexyl) - cyclohexane (Cetiol ® S), and di-n-octyl ether (Cetiol ® OE) may be preferred. Esteröle. Under Esterölen are to understand the esters of C 6 - C 30 - fatty acids with C 2 - C 30 - fatty alcohols. Monoester of the fatty acids with alcohols having from 2 to 24 carbon atoms are preferred. Examples of fatty acid moieties in the esters are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, apply behenic acid and erucic acid and technical mixtures thereof, for example, in the pressure hydrolysis of natural fats and oils, in the oxidation of aldehydes from Roelen's oxosynthesis or in the dimerization of unsaturated fatty acids. Examples of the fatty alcohol fractions in the Esterölen are isopropyl alcohol, caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, ristylalkohol myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl incurred behenyl alcohol, erucyl alcohol and brassidyl and technical mixtures thereof, for example, in the high-pressure hydrogenation of technical Methylestern based on fats and oils or aldehydes from Roelen's oxo synthesis and as monomer fraction in the dimerization of unsaturated fatty alcohols. According to the invention, particularly preferred are isopropyl myristate (IPM Rilanit ®), isononanoic acid C16-18 alkyl ester (Cetiol ® SN), 2-ethylhexyl palmitate (Cegesoft ® 24), stearic acid-2-ethylhexyl ester (Cetiol ® 868), cetyl oleate, glycerol tricaprylate, Kokosfettalkohol- caprate / caprylate (Cetiol ® LC), n-butyl stearate, oleyl erucate (Cetiol ® J 600), isopropyl palmitate (IPP Rilanit ®), oleyl Oleate (Cetiol ®), hexyl laurate (Cetiol ® A), di-n-butyl adipate (Cetiol ® B), myristyl myristate (Cetiol ® MM), Cetearyl Isononanoate (Cetiol ® SN), decyl oleate (Cetiol ® V).

Dicarboxylic acid ester such as di-n-butyl, di (2-ethylhexyl) adipate, di (2-ethylhexyl) succinate and di-isotridecylacelaat and diol esters such as ethylene glycol dioleate, ethylene glycol di isotridecanoat, propylene glycol di (2- ethylhexanoate), propylene glycol diisostearate,

Propylene glycol di-pelargonate, butanediol diisostearate, neopentyl glycol dicaprylate, symmetrical, asymmetrical or cyclic esters of carbonic acid with fatty alcohols, for example described in DE-OS 197 56 454, glycerol carbonate or dicaprylyl carbonate (Cetiol ® CC),

Trifatty acid esters of saturated and / or unsaturated linear and / or branched fatty acids with glycerol,

Fatty acid, which are monoglycerides, diglycerides and technical mixtures thereof. When using technical products may contain small amounts also be present due to manufacturing triglycerides. The partial glycerides preferably correspond to formula (D4-I),

CH 2 O (CH 2 CH 2 O) m R 1 CHO (CH 2 CH 2 O) n R 2 (D4-I)

CH 2 O (CH 2 CH 2 O) q R 3 in which R 1, R 2 and R 3 independently represent hydrogen or a linear or branched, saturated and / or unsaturated acyl group containing 6 to 22, preferably 12 to 18, carbon atoms, with the proviso that at least one of these groups is an acyl group and at least one of these groups is hydrogen. The sum (m + n + q) is 0 or a number from 1 to 100, preferably 0 or 5 to 25. Preferably, R 1 is an acyl radical and R 2 and R 3 is hydrogen and the sum (m + n + q) is 0. Typical examples are mono- and / or diglycerides based on caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid , arachidic acid, Gadoleinsäure, behenic acid and erucic acid and technical mixtures. Preferably, oleic acid monoglycerides can be used.

The amount of natural and synthetic cosmetic oil bodies in the inventions to the invention color-changing means is usually 0.1 -. 30% by weight, based on the total preparation, preferably 0.1 - 20 wt .-% and especially from 0.1 to 15 wt .-%.

As part of a twelfth embodiment of the invention comprise Zubereitungenein enzyme as a conditioner. According to the invention, particularly preferred enzymes are selected from a group which is formed from proteases, lipases, transglutaminase, oxidases and peroxidases.

Although each of the above in the various embodiments of care substances already gives a satisfactory result by itself, in the context of the present invention also includes all embodiments in which the color-changing means comprise a plurality of care substances from various groups.

Particularly preferred skin care ingredients in the present invention are particularly Ubiquinone, panthenol and its derivatives, ectoine, chamomile extract, bisabolol, olive oil, Royal jelly, mung bean extract and Moringa Olifeira extract.

The color-changing compositions of the invention may also contain any known for such preparations active ingredients, additives and auxiliaries in addition to the inventively essential components.

In many cases, the color-changing means comprise at least one surfactant, both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases it has proved advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants. With regard to the cationic surfactants, reference is made at this point to the above statements. Anionic surfactants suitable for use on the human body anionic surfactants are present in inventive preparations. These are characterized by a water solubilizing anionic group such. B. men, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group containing around 10 to 22 C-Ato. In addition polyglycol ether groups, ester, ether and amide groups and also hydroxyl groups may be contained in the molecule or glycol. Examples of suitable anionic surfactants, each in the form of sodium, potassium and ammonium salts and the mono-, di- and trialkanolammonium salts containing 2 or 3 carbon atoms in the alkanol group: linear fatty acids having 10 to 22 carbon atoms (Soap),

Ether carboxylic acids of formula RO- (CH 2 -CH 2 O) x -CH 2 COOH, = in which R is a linear alkyl group having 10 to 22 carbon atoms and x is 0 or 1 to 16, acyl sarcosides having 10 to 18 carbon atoms in the acyl group, acyl taurides having 10 to 18 carbon atoms in the acyl group, acyl isethionates containing 10 to 18 carbon atoms in the acyl group,

Sulfosuccinic acid mono- and dialkyl esters containing 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters containing 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates having 12 to 18 C atoms, linear alpha-olefin sulfonates having 12 to 18 carbon atoms, alpha-sulfofatty acid methyl esters of fatty acids having 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 carbon atoms and x = 0 or mixtures 1 to 12, 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,

Represent ester of tartaric acid and citric acid with alcohols which are addition products of approximately 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 especially unsaturated C 8 -C 22 - carboxylic acids such as oleic acid, stearic acid, isostearic acid and palmitic acid , Non-ionic surfactants contain as hydrophilic group, for. B. a polyol group, a polyalkylene glycol ether or a combination of polyol and polyglycol ether. Such compounds are for example

Addition products of 2 to 30 mol ethylene oxide and / or 0 to 5 mol propylene oxide onto linear fatty alcohols having 8 to 22 carbon atoms, onto fatty acids having 12 to 22 carbon atoms and

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

C 2 -C 22 fatty acid monoesters and diesters of addition products of 1 to 30 mol

Ethylene oxide onto glycerol,

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

Addition products of 5 to 60 mol ethylene oxide onto 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 contains from 6 to 22 carbon atoms and may be both linear and branched. primary linear and methyl-branched in the 2-position, aliphatic radicals are preferred. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Especially preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. Where so-called "oxo-alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain.

The alkyl polyglycosides used according to the invention may contain only one particular alkyl group R 1, for example. Typically, these compounds are produced from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or to the particular working of these compounds.

Particularly preferred alkyl polyglycosides are those in which R 1 consists essentially of C 8 - and C 10 alkyl groups, mainly of C 2 - 4 alkyl groups and d, consisting essentially of C 8 - to d 6 alkyl groups or substantially of C 2 - to C 6 alkyl groups is.

Sugar building blocks Z Any mono- or oligosaccharides can be used. Usually, 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 units are glucose, fructose, galactose, arabinose and sucrose; Glucose is especially preferred.

The usable in this invention include alkyl polyglycosides in section 1, 1 to 5 sugar units. Alkyl polyglycosides with x values ​​of 1, 1 to 1, 6 are preferred. Very particular preference is given to alkyl glycosides in which x 1, 1 to 1, 4.

The alkyl glycosides can also serve to improve the fixing of fragrance components to the hair in addition to their surfactant. The skilled artisan will therefore in the event that an excess of the duration of the hair treatment effect of the perfume oil is desired on the hair, preferably to fall back to this class of substances as an additional ingredient of the preparations according to the invention.

The alkoxylated homologs of the specified 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.

Furthermore, zwitterionic surfactants can be, in particular as co-surfactants can be used. Zwitterionic surfactants are those surface active compounds which contain in the molecule at least one quaternary ammonium group and at least one -COO () - Wear group Particularly suitable zwitterionic surfactants are the betaines such as N-alkyl-N - or -SO 3 '' '. , N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyl dimethyl ammonium, and 2-alkyl-3-carboxylmethyl-3-hydroxy-ethyl- imidazolines acylaminoethylhydroxyethylcarboxymethylglycinat each having 8 to 18 carbon atoms in the alkyl or acyl group as well as coconut oil. A preferred zwitterionic surfactant is known under the CTFA name of Cocamidopropyl Betaine fatty acid amide derivative.

Likewise particularly suitable as cosurfactants are ampholytic surfactants. Under rule ampholytic surfactants are surface-active compounds which, apart from a C 8 - containing COOH or -SO 3 H group and of forming inner salts - C-is-alkyl or acyl group, contain at least one free amino group and at least one are capable. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkylamino butyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyl- taurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids containing around 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C 12 - 18 - sarcosine.

When used as surfactants, compounds having alkyl groups may be single compounds. However, it is generally preferred to proceed in the preparation of these substances from native vegetable or animal raw materials so that mixtures of substances with different alkyl chain lengths dependent upon the particular raw material.

The surfactants which are addition products of ethylene and / or propylene oxide with fatty alcohols or derivatives of these addition products, both products having a "normal" homologue distribution or those may be used with a narrow homolog distribution. "Normal" homologue distribution are mixtures of homologues are understood to be obtained as catalysts in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali. Narrowed homolog distributions are obtained, however, if hydrotalcite, alkaline earth salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or - alcoholates are used as catalysts. The use of products with a narrow homolog distribution may be preferred.

Furthermore, color-changing compositions of the invention may further active materials and

Additives, such as for example, nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyl trimethyl ammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate ^ -Hydroxypropylmethacrylat 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 Pastes, locust bean flour, linseed, dextrans, cellulose derivatives, eg. Methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives, such as amylose, amylopectin and dextrins, clays such as. For example, bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol, structurants, such as maleic acid and lactic acid, hair-conditioning compounds, such as phospholipids, for example soya lecithin, egg lecithin and cephalins,

Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein, their condensation products with fatty acids and quaternized protein hydrolysates,

Perfume oils, dimethyl isosorbide and cyclodextrins,

Solvent and rin solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, fiber-structure-improving agents, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, fruit sugar and lactose, amines quaternized such as methyl-1-alkylamidoethyl -2-alkylimidazolinium methosulfate defoamers such as silicones, dyes for coloring the composition,

Antidandruff active ingredients such as piroctone olamine, zinc omadine and climbazole, light stabilizers, particularly derivatized benzophenones, cinnamic acid derivatives and triazines,

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

Active ingredients such as allantoin, pyrrolidone and salts thereof and bisabolol, cholesterol,

Thickeners like Zuckerester, polyol esters or polyol, fats and waxes, such as spermaceti, beeswax, montan wax and paraffins, fatty acid,

Complexing agents such as EDTA, NTA, .beta.-alanine diacetic acid and phosphonic acids, swelling and penetration substances, such as glycerin, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates, opacifiers, such as latex, styrene / PVP and styrene / acrylamide copolymers pearlizing agents such as ethylene glycol mono- and distearate and PEG-3 distearate, preservatives,

Stabilizer for Wassserstoffperoxid and other oxidizing agents, propellants such as propane-butane mixtures, N 2 O, dimethyl ether, CO 2 and air, antioxidants.

With regard to further optional components and the amounts of these components is made expressly to the relevant handbooks known to the expert, for. B. Kh. Schrader, bases and Formulations of Cosmetics, 2nd edition, Hüthig Verlag, Heidelberg, 1989, directed.

The color-changing agent to the invention contain the essential components according to the invention preferably in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For coloring hair, such carriers are, for example, creams, emulsions, gels or even surfactant, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair.

Aqueous-alcoholic solutions are aqueous solutions containing 3 to 70 wt .-% of a Ci-C4 alcohol, in particular ethanol or isopropanol, to be understood within the meaning of the present invention. The compositions of the invention may additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1, 2- propylene glycol. All water-soluble organic solvents are preferred.

Furthermore, color-changing compositions of the invention may contain a reducing agent. Examples of the present invention preferred reducing agents are sodium sulfite, ascorbic acid, thioglycolic acid and derivatives thereof, Natriumthionit, Alkalimetallcitratsalze and N-acetyl-L-cysteine ​​The most preferred reducing agents are Alkalimetallcitratsalze, in particular sodium citrate, and N-acetyl-L-cysteine. N-acetyl-L-cysteine ​​is a particularly preferred reducing agent.

Further, agents of the invention alkalizing agent, typically alkali or alkaline earth metal hydroxides, ammonia or organic amines. Preferred alkalizing agents are 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 and alkali and alkaline earth metal. In particular, monoethanolamine, triethanolamine and 2-amino-2-methyl-propanol and 2-amino-2-methyl-1, 3-propanediol preferred for the purposes of this group. The use of ω-amino acids such as ω-aminocaproic acid as alkalizing agents.

Commonly used in dyes pearlescent pigments can be used. According to the invention preferred pearlescent pigments are natural pearlescent pigments such as pearl essence (guanine / hypoxanthine mixed crystals from fish scales), or pearl (from milled mussel shells), monocrystalline pearlescent pigments such as bismuth oxychloride, as well as pearlescent pigments based on mica or mica / metal oxide. The latter pearlescent pigments are provided with a Metalloxidcoating. Through the use of the pearlescent pigments and optionally gloss are obtained in addition color effects in the inventive compositions. However, the color scheme for those used in the means pearlescent does not affect the color result of the coloration of the keratin fibers.

Pearlescent mica-based and mica / metal oxide base are according to the invention are also preferred. Mica are among the layer silicates. The main representatives of these silicates are muscovite, phlogopite, Paragonite, biotite, lepidolite and Margarit. For the preparation of the pearlescent pigments in combination with metal oxides, the mica, muscovite or phlogopite primarily coated with a metal oxide. Suitable metal oxides include TiO 2, Cr 2 O 3 and Fe 2 O 3. By appropriate coating pigments, and interference color luster pigments according to the invention are obtained as pearlescent pigments. These pearlescent pigments have not only a glittering optical effect in addition to color effects. Furthermore, the pearlescent pigments useful in this invention may further contain a pigment which is not derived from a metal oxide.

The particle size of the pearlescent pigments are preferably used is preferably between 1.0 and 100 microns, more preferably between 5.0 and 60.0 microns.

Particularly preferred pearlescent pigments are marketed by Merck under the trade names Colorona ®, wherein the pigments wt Colorona ® red-brown (47-57.% Muscovite mica (KH 2 (AISi0 4) 3), 43-50 wt .% Fe 2 O 3 (INCI: Iran oxide Cl 77491), <3 weight% TiO 2 (INCI: Titanium Dioxide CI 77891)., Colorona ® Blue Black Star (39-47% by weight of muscovite mica (KH 2 (AISi0. 4 ) 3), 53-61 wt% of Fe 3 O 4 (INCI:. Iran oxide CI 77499)), Colorona ® Fine Siena (35-45% by weight of muscovite mica (KH 2 (AISi0 4) 3), 55-65. .% by weight of Fe 2 O 3 (INCI: Iran oxide Cl 77491).), Colorona ® Aborigine Amber (. 50-62% by weight of muscovite mica (KH 2 (AISi0 4) 3), 36-44 wt% of Fe 3 O 4 (INCI: Iran oxide Cl 77499), 2-6 wt% TiO 2 (INCI: Titanium Dioxide CI 77891). (wt 42-54% muscovite mica (KH 2 (AISi0 4) 3.)), Colorona ® Patagonian Purple, 26-32 wt% Fe 2 O 3 (INCI: Iran oxide Cl 77491). wt 18-22% TiO 2 (INCI: Titanium Dioxide CI 77891)., wt% 2-4 Prussian blue (INCI:. Ferric ferrocyanide Cl 77510)), Colorona ® Chameleon (40-50% by weight of muscovite mica (KH 2 (AISi0. 4) 3), weight 50-60% Fe 2 O 3 (INCI:. Iran oxide Cl 77491)), and Silk Mica ® ( > 98 wt.% muscovite mica (KH 2 (AISi0 4) 3)).

Regarding the usable in the agents pearlescent continues explicitly to the monographs Inorganic Pigments, Chemical technology review no. 166, 1980, pp 161-173 (ISBN 0-8155-0811-5) and Industrial inorganic pigment, 2nd edition, Weinheim , VCH, 1998, pages 211-231, reference is made. If the formation of the actual dyeing under an oxidative process, as usual oxidizing agent such as in particular hydrogen peroxide or its addition products may be used with urea, melamine or sodium borate. However, the oxidation with atmospheric oxygen as sole oxidizing agent may be preferred. However, a chemical oxidizing agent is preferably used, especially when a lightening effect is desired on human hair besides the color. Suitable oxidizing agents are persulfates, chlorites and, in particular hydrogen peroxide or its addition products onto urea, melamine and sodium borate in question. According to the invention however, the oxidation can also be applied to the hair together with a catalyst that activates the oxidation of the dye precursors, for example by air oxygen. Such catalysts are for example metal ions, iodides, quinones or specific enzymes.

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

Suitable enzymes are, for example, peroxidases, which can amplify small amounts of hydrogen significantly the effect. Furthermore, such enzymes are useful in this invention, the oxidized using atmospheric oxygen, the oxidation dye precursors directly, such as laccases, or produce hydrogen peroxide in situ small amounts and enable in this way the oxidation of the dye precursors biocatalytically. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, for example,

Pyranose oxidase and as D-glucose or galactose,

Glucose oxidase and D-glucose,

Glycerol oxidase and glycerol,

Pyruvate oxidase and pyruvic acid or salts thereof, - alcohol oxidase and alcohol (MeOH, EtOH),

Lactate oxidase and lactic acid and salts thereof,

Tyrosinase oxidase and tyrosine,

Uricase and uric acid or salts thereof,

Choline and choline,

Amino acid oxidase and amino acids. The actual oxidative colorant is advantageously prepared immediately before use by mixing the preparation of the oxidizing agent with the preparation comprising the dye precursors. The resulting ready-to-use hair coloring preparation should preferably have a pH in the range of 5 to 14, especially from 7 to 12. Particularly preferably, the application of the hair dye in a weakly alkaline milieu. The application temperatures may be in a range between 15 and 40 0 C. After an exposure time of 5 to 45 minutes, the hair colorant is removed by rinsing from the hair to be dyed. The washing with a shampoo is unnecessary when a strong surfactant-containing support, for example a coloring shampoo was used.

Especially with difficult to dye hair preparation containing the dye precursors but can be applied to the hair with the oxidation component without prior mixing. The oxidation component is applied - after a contact time of 20 to 30 minutes is then - optionally after intermediate rinsing. After another contact time of 10 to 20 minutes, is then rinsed and if desired, shampooed. In this embodiment, according to a first variant in which the previous application of the dye precursors is intended to better penetration into the hair, the corresponding agent adjusted to a pH of about 4 to 7th According to a second variant, an air oxidation is first sought, wherein the applied agent preferably has a pH value of 7 to 10 In the subsequent accelerated post-oxidation to use acidified peroxydisulfate solutions may be preferred as the oxidant.

A second object of the present invention is a method for changing the color of keratin fibers in which an agent of the invention with an oxidizing agent preparation is mixed, the application preparation is applied to the fibers and is rinsed off again after a contact time.

A third object of the present invention is a method for changing the color of keratin fibers, in which first, in a step a composition comprising at least at least one plant extract, at least one vegetable oil and at least one unsaponifiable residue of a vegetable oil, is applied to the fibers after a exposure time, a second agent containing at least one color-modifying active ingredient, is applied to the fibers and the agents are rinsed off after a further action time in a third step. It has proved particularly advantageous if the first contact time of 1 to 60 minutes, preferably 1 to 15 minutes, especially 1 to 5 minutes and the second reaction time of 1 to 60 minutes, preferably 30 to 45 minutes, respectively.

A fourth object of the present invention provides a process for changing the color of keratin fibers, in which first, in a step a composition comprising at least one color-modifying active ingredient, is applied to the fibers after a contact time a second composition comprising at least a color changing agent to the fibers after a contact time is applied, a second composition comprising at least one plant extract, at least one vegetable oil and at least one unsaponifiable residue of a vegetable oil, is applied to the fibers and the agents are rinsed off after a further action time in a third step.

In the context of the fourth aspect of the present invention, it has proved to be particularly advantageous if the first contact time of 1 to 60 minutes, preferably 1 to 15 minutes, especially 1 to 5 minutes, and the second exposure time of 1 to 60 minutes, preferably 30 to 45 minutes, respectively.

A fifth object of the present invention is the use of an active substance combination of at least one plant extract, at least one vegetable oil and at least one unsaponifiable residue of a vegetable oil to prevent scalp irritation associated with oxidative colorations of keratin fibers.

A sixth object of the present invention is the use of an active substance combination of at least one plant extract, at least one vegetable oil and at least one unsaponifiable residue of a vegetable oil to improve the care condition associated with oxidative colorations of keratin fibers.

Regarding preferred use concentrations, preferred additional ingredients of the respective agents used and other preferred embodiments of the second to sixth object apply mutatis mutandis to the inventive compositions said.

The following examples are intended to illustrate the present application without limiting it in any way. Examples

The stated amounts are, unless otherwise stated, by weight percent.

It was made the following hair dye.

the following oxidizing agent preparations were also prepared.

1 or 1: immediately prior to application to the hair fibers, the color cream described above in the ratio 1 2 was mixed with one of the oxidant solutions described above (depending on the desired degree of whitening), and the resulting application preparation after an exposure time of 30 - 60 minutes at room temperature again rinsed. The hair treated felt smooth and supple, and was characterized by a comfortable grip

The commercial products used in the examples have the following meanings:

Actysse premiere BG mixture of about 95.5 wt .-% bioactive glass and about 4.5 wt .-% Mica (INCI name: Calcium Sodium phosphosilicates Glass and Mica) (Engelhard).

Cutina ® AGS ethylene glycol (INCI name: Glycol Distearate) (Cognis) Cutina ® GMS-SE INCI name: glyceryl stearate SE (Cognis) Defensil ® INCI name: Octyldodecanol and Cardiospermum Halicacabum Flower / Leaf / Vine Extract and echium Plantagineum Seed OiI and Helianthus annuus (Sunflower) Seed OiI Unsaponifiables; (Rahn)

Eumulgin ® B2 Cetylstearylalkohol with about 20 EO units (INCI name: Ceteareth-20) (Cognis)

Eutanol ® G 2-octyldodecyl alcohol (INCI name: Octyldodecanol) (Cognis) Merquat ® Plus 3330 dimethyldiallylammonium chloride acrylamide, acrylic acid terpolymer (about 9.5% solids in water; INCI name: Polyquaternium-39) (Ondeo-Nalco)

® phospholipid EFA (about 30% solids in water / propylene glycol; INCI name: Linoleamidopropyl PG-Dimonium Chloride Phosphate) (Uniqema) Puricare ® LS 9658 Moringa Pterygosperma extract / glycerol in water (INCI name: Water, Glycerine, Moringa Pterygosperma Seed Extract) (Cognis)

Claims

claims
1. means for color and / or permanent change in shape of keratin fibers, comprising, characterized an active ingredient that changes the color and / or permanently, the shape of keratinous fibers, in a cosmetically acceptable support, at least in that it further
- at least one plant extract,
- at least one vegetable oil,
- contains at least one unsaponifiable residue of another vegetable oil and the like.
2. Composition according to claim 1, characterized in that at least one developer or coupler component is contained as the color-changing agent.
3. Composition according to one of claims 1 or 2, characterized in that at least one indole and / or indoline derivative is contained as the color-changing agent.
4. A composition according to any one of claims 1 to 3, characterized in that it contains at least one substantive dye is contained as the color-changing agent.
5. A composition according to any one of claims 1 to 4, characterized in that it contains as color-modifying active substance contains at least one peroxo compound.
6. A composition according to any one of claims 1 to 5, characterized in that the plant extract is obtained from a climber.
7. The composition according to claim 6, characterized in that the plant extract from the plant Cardiospermum Halicacabum, in particular from the flowers, leaves and vines, is recovered.
8. A composition according to any one of claims 1 to 7, characterized in that the vegetable oil is obtained from flowers of a plant of the genus Echium.
9. A composition according to any one of claims 1 to 8, characterized in that the unsaponifiable residue of a vegetable oil obtained from a plant of the daisy family.
10. A composition according to any one of claims 1 to 9, characterized in that it contains as active ingredient permanently shape-changing one keratin-reducing substance.
11. A method for changing the color of keratin fibers, characterized in that an agent according to any one of claims 1 to 10 mixed with an oxidizing agent preparation, the application preparation is applied to the fibers and is rinsed off again after a contact time.
12. A method for changing the color of keratin fibers, characterized in that in a first step, a composition comprising at least at least one plant extract, at least one vegetable oil and at least one unsaponifiable residue of a vegetable oil, is applied to the fibers after a contact time second means containing at least one color-modifying active ingredient, is applied to the fibers and the agents are rinsed off after a further action time in a third step.
13. A method for changing the color of keratin fibers, characterized in that in a first step, a composition comprising at least one color-modifying active ingredient, is applied to the fibers after a contact time a second composition comprising at least one plant extract, at least one vegetable oil and at least one unsaponifiable residue of a vegetable oil, is applied to the fibers and the agents are rinsed off after a further action time in a third step.
14. Use of an active substance combination of at least one plant extract, at least one vegetable oil and at least one unsaponifiable residue of a vegetable oil to prevent scalp irritation and / or to improve the maintenance state of the fibers in connection with the oxidative dyeing of keratin fibers.
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