WO2010006957A1 - Coloring means comprising natural dye - Google Patents

Abstract

The object of the invention are means for modifying the color of keratin fibers, said means comprising at least one natural dye, at least one polysaccharide containing at least one repeating monomer unit with at least one anionic group, and at least one optional hydrated plant oil, said means being contained in a cosmetically acceptable carrier. The means according to the invention are sufficiently stable and lead to satisfactory colorations, which can also have an intense effect by way of multiple applications, in other words through the build-up of color. The coloring means enable coloring while at the same time maintaining the fibers, which can be made to have an increase in sheen, a pleasing suppleness (surface smoothness) and increased fiber strength.

Description

 COLORING AGENT WITH NATURAL COLOR

The present application relates to color-modifying agents for keratinic fibers containing at least one natural dye, at least one specific polysaccharide and at least one optionally hydrogenated vegetable oil, as well as hair treatment methods using such agents.

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

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

For temporary dyeings usually dyeing or tinting agents are used, which contain as coloring component so-called direct drawers. These are dye molecules that attach directly to the hair and do not require an oxidative process to form the paint. These dyes include, for example, the henna already known from antiquity for coloring body and hair. These dyes are usually sensitive to shampooing, so that a much undesirable nuance shift or even a visible "discoloration" can occur. Finally, recently, a novel dyeing process has received much attention. In this process, precursors of the natural hair dye melanin are applied to the hair; These then form naturally-analogous dyes in the course of oxidative processes in the hair. Such a process with 5,6-dihydroxyindoline as dye precursor was described in EP-B1-530 229. In particular, multiple use of agents with 5,6-dihydroxyindoline, it is possible to reproduce natural hair color to people with graying hair. The coloration can be done with atmospheric oxygen as the sole oxidant, so that no further oxidizing agents must be used. In individuals with originally medium blond to brown hair, the indoline can be used as the sole dye precursor. Nevertheless, this novel method has the disadvantage that, although natural nuances can be achieved well, but fashionable shades, for example, in the red area are not available.

Despite this variety of modern hair dyeing methods, the vegetable dyes based on natural dyes, such as henna, are enjoying growing popularity. This is due, among other things, to the growing need among many consumers to use a hair dyeing product that also meets the requirements of health, ecology and sustainability. However, these colorants often have a poor Aufziehverhalten, little convincing

Fastness properties and a low gray coverage on.

It has now surprisingly been found in the context of the work underlying this application that hair color-changing agents based on natural dyes, the at least one special

Polysaccharide and an optionally hydrogenated vegetable oil, are sufficiently stable and result in satisfactory colorations which can be achieved by multiple application, i. due to color structure, can also be intense. The dyes allow dyeing while maintaining the fibers, which are characterized by an increased gloss, a pleasant

Smoothness (surface smoothing) and strengthening the fibers can be noticeable.

A first subject of the present application are therefore agents for color change keratinischer

Fibers containing in a cosmetically acceptable carrier at least one natural dye, at least one polysaccharide having at least one repeating monomer unit bearing at least one anionic group and at least one optionally hydrogenated vegetable oil.

According to the invention, "keratinic" fibers are understood to mean furs, wool, feathers and, in particular, human hair.

As the first essential ingredient, the colorants of the invention contain at least one natural dye.

According to the invention, the term "natural dyes" refers to the naturally occurring organic dyes which are contained in plants, animals, insects, algae, fungi, lichens and bacteria and / or can be obtained therefrom contained species are included.

Particularly preferred natural dyes within the meaning of the invention are dyes which are obtained from parts of plants. For this purpose, preferably different parts of plants, depending on the desired dye. It is understood, however, that a dye can be obtained from more than one plant part.

The preferred plant parts for obtaining natural dyes are included in the group formed from root, stems, bark, heartwood, resin, flower, leaf, fruit and sap. The following classes of natural dyes are preferred in the compositions according to the invention:

a) Diaryloylmethane dyestuffs, as for example contained in turmeric (Cl. Natural Yellow 3) - Curcuma domestica with the coloring constituents curcumin (Cl.75300), demethoxycurcumin and bisdemethoxycurcumin.

Curcumin (R = R '= OMe) Demethoxycurcumin (R = H; R' = OMe) Bisdemethoxycurcumin (R = R '= H)

b) Naphthoquinone dyes, such as in henna, red (CI Natural Orange 6) from the leaves of the henna ■ Lawsonia inermis L. with the coloring ingredient Lawson (Cl.75480):

in fruit peel and leaves (Cl. Natural Brown 7) of the walnut tree - Juglus regia L with the coloring ingredient Juglon (Cl.

in alkana root or shikonin root (Cl.Natural Red 20) - Alkanna tinctoria or Lithospermum erythrorhizon with the coloring ingredients alkannane (Cl.75520) and alkannine (Cl.75530) or shikonin (Cl.75535):

in Lapacho wood from Tecoma ipe, Tecoma lapacho, Tecoma leucoxylon or Tecoma achracea (Cl., Natural Yellow 16) with the coloring ingredient lapachol (Cl.75490), as well as subordinate desoxylapachol, α-lapachone, β-lapachone, melchinone I, lapachonone and dehydro- α-lapachone:

α-lapachone dehydro-α-lapachone β-lapachone c) anthraquinone dyes, as for example in madder roots (Cl.Red Red 8) - Rubia peregrina and Rubia tinctorum with the coloring ingredients purpurin (Cl.75410), pseudopurpurin (Cl.75420, Cl.58220- synthetic), alizarin (Cl.75330), Rubiadin (Cl.75350) and Munjistine (Cl.75370): Purpurin (R = H, R '= R "= OH)

Pseudopurpurin (R = CO ₂ H; R '= R "= OH) Alizarin (R = OH, R = R" = H) Rubiadine (R = CH ₃ ; R = OH; R "= H) Munijistine (R = CO ₂ H; R = OH; R "= H)

in the roots and stems of the Indian madder (Cl.Natural Red 16) - Rubia cordifolia and Rubia sikkimensis with the coloring ingredients purpurin (Cl.75410), pseudopurpurine (cl.75420, Cl.58220-snythetic), alizarin (Cl.75330 Munjistin (Cl.75370) as well as Nordamnacanthal, Physcion and Purpuroxanthin (Cl.75340):

in Rharbarber roots - Rheum undulatum L, Rheum palmatum L. and other Rheum species with the coloring constituents Emodin, Chrystophanol (Cl.75400, CI Natural Yellow 23), Aloe-emodin, Physcion, Rhein, the Heterodianthronen Rheidin A, B, C, palmidin A, B, C, D and sennidine C as well as derived anthra- and diglycosides:

Emodin (R = OH, R '= CH ₃ ) Chrysophanol (R = H, R' = CH ₃ ) Aloe-emodin (R = CH ₂ OH, R = H) Rhein (R = CO ₂ H, R '= H )

in the roots of the genus Labiata - Galium verum L, Common labweed - Galium mollugo L, Catchstraw - Galium aparine L, Woodruff - Galium odoratum (Cl. Natural Red 14) with the coloring constituents Purpurin (Cl.75410), Pseudopurpurin (Cl. 75420; Cl 58220-synthetic), alizarin (CI 75330), rubiadin (CI 75350), purpuroxanthin (CI 75340), lucidin, alizarin 1-methyl ether, alizarin 2-methyl ether, 2-hydroxyanthraquinone and 1 Hydroxy-2-methylanthraquinone: Lucidine (R '= CH ₂ OH; R = R "= OH)

Alizarin 1-methyl ether (R = 0 Me, R = OH; R "= H) Alizarin 2-methyl ether (R = OH, R = OMe; R" = H) 2-hydroxyanthraquinone (R '= OH, R = R "= H) 1-hydroxy-2-methylanthraquinone (R = OH; R = CH _3; R" = H)

in Dyer's Master's Root (Cl.Natural Red 13) - Asperula tinctoria with the coloring ingredients purpurin (Cl.75410), pseudopurpurine (Cl.75420, Cl.S 58220-synthetic) and alizarin (Cl.75330), in the bark of the buckthorn tree - Rhamnus fragula L. tinctoria with the coloring constituents Emodin, 4 emodin glucosides: glucofragulin A, glucofrangulin B, frangulin A, frangulin B, physcion and chrysophanol (Cl.75400):

Glucofangulin A (R = O-3-β-L-rhamnc-1-β-D glucofangulin B (R = OL-rhamno-D-glucosii frangulin A (R = O-3-β-L-rhamnoside) frangulin B ( R = O-3-α-L-rhamnoside)

d) Indigoid dyes, such as, for example, in the leaves and partial stems of Indian Indigo Indigo Farmera (Indigofera argentea), Fawnwort lsatis tinctoria, Dyeing Colanders - Wrightia tinctoria and Wild Indigo - Baptisia tinctoria (CI Natural Blue 1) with the dye precursors lsatan B and Indican, which are oxidatively converted by a fermentation process into the actual dye indigo (Cl.75780, Cl.73000) and subordinated indirubin (Cl.75790, Cl.73200) and isatin:

^ OH

indirubin isatin, inter alia, under the names Indigofera folium or Henna, black as a commercial product, usually in combination with extracts of Lawsonia Inermis, available, e) Flavonoidfarbstoffe, such as in the flower heads of Roman chamomile - Chamaemelum nobile (Cl. Natural Yellow 1) and German Chamomile - Chamomilla recutica with the coloring ingredients Apigenin (Cl.75580, Cl. Natural Yellow 1, 2), Rutin (Cl.75730, Natural Yellow 10), and subordinated Luteolin (Cl.75590), camphor oil (Cl. Cl., Natural Yellow 13, 10) and quercetin (Cl.75670, CI Natural Yellow 10, 13; Cl, Natural Red 1) and glucosides derived therefrom:

Apigenin (R = R '= H) Luteolin (R = OH, R' = H) Camphor Oil (R = H, R '= OH) Quercetin (R = R' = OH)

in the leaves and stems of sage - Salvia tribola L with the coloring ingredients luteolin (Cl. 75590) and salvigenin:

in the leaves and stems of rosemary - Rosmarinus Officinalis with the coloring ingredients luteolin (Cl.75590) and apigenin (Cl.75580, CI Natural Yellow 1, 2) and other flavonoids, f) Neoflavanoidfarbstoffe, such as in blue wood (Cl. Natural Black 1), heartwood of Haematoxylum campechianum L. with the coloring flavinoid quercetin and the dye precursor hematoxylin, which is oxidatively converted into the dye hematin (Cl.75290, CI Natural Black 1 and 2):

in sappan wood - Caesalpinia sappan L, brazil wood - Caesalpinia brasiliensis L, Nicaraguan wood - Caesalpinia echinata, pernambunk wood - Caesalpinia crista L, braziliette wood - Haematoxylum braziletto, each as heartwood (Cl. Natural Red 24), with the dye precursor Brasilin, oxidative in the Dye Braziline (Cl.75280, Cl. Natural Red 24) is converted:

g) insoluble redwood dyes, such as in red sandalwood, heartwood of Pterocarpus santalinus L, Narrawood - Pterocarpus indicus L, Barwood - Pterocarpus soyauxii L, Camwood - Bahia nitida (Cl. Natural Red 22) with the coloring ingredients Santalin A, Santalin B, tetra-O-methyl-santarubin, hompterocarpine, pterocarpine, maackiain, the isoflavionidene formononetin and santal, and the chalcone isoliquiritigenin and the flavone liquiritigenin:

Homopterocarpine pterocarpine (R = OMe) Maackiain (R = OH)

Isoliquiritigenin Liquiritigenin h) Betaine dyes such as in beetroot roots - Beta vulgaris with the main coloring ingredients betanidine and prebetanin as well as subordinated further betacyanines, betaxanthines, vulgaxanthines, anthocyanins and iron and copper complexes:

betanidin

i) Gallotannin dyes, for example in the bark of stalk or summer areas - Quercus robur L. with the main coloring constituents from the group of gallotannins and ellagannins (glycosides of gallic acid or ellagic acid, Cl.75270):

Gallic Acid Ellagic Acid j) Dyestuffs of condensed tannins, such as in Catechu (Cl., Natural Brown 3), a mixture of extracts of staining plants, preferably Acacia catechu, Areca catechu and Uncaria gambier, with a high proportion of condensed tannins ('proanthocyanidins') of the catechin type:

(+) - catechin as in the leaves of green and black (= fermented green) tea - Camellia sinensis, with the ingredients gallic acid, m-digallic acid, catechin, glycosides of flavonoids such as, among others, luteolin, apigenin, camphor oil, quercetin, Myriecetin, as well as thearubingenins ('proanthocyanidins'), theaflavin and isotheaflavin: theaflavin

Isotheaflavin

In particular, the cosmetic compositions according to the invention comprise at least one natural dye selected from the group comprising diaryloylmethane dyes, naphthoquinone dyes, flavonoid dyes, anthraquinone dyes, betalain dyes, gallotannin dyes and indigoid dyes.

Particularly preferred natural dyes according to the present invention are those obtained from a plant selected from the group consisting of Indigofera tinctoria, Curcuma longa, Lawsonia inermis, Chamomilla recutita, Quercus robur, Rosmarinus officinalis, Rheum undulatum and Beta vulgaris.

Very particular preference is given to the group which is formed from diaryloylmethane dyes, naphthoquinone dyes and indigoid dyes.

Very particular preference is given in the cosmetic compositions according to the invention to natural dyes of plants selected from the group consisting of Curcuma longa (turmeric, CI Natural Yellow 3), Lawsonia inermis (Henna, red, CI Natural Orange 6) and Indigofera tinctoria (Henna, black, Cl. Natural Blue 1).

According to the invention, those dyes have proved to be preferred which can be obtained from at least one constituent of said species by mechanical comminution and / or separation or by extraction.

Examples of mechanical comminution methods include, for example, cutting, pureeing and crushing.

Mechanical separation methods according to the invention are to be understood as meaning separation methods based on the use of mechanical forces, such as, for example, gravity, centrifugal force, pressure or vacuum. These include, for example, decanting, filtration, sedimentation, ultrafiltration and centrifuging.

Instead of or following the mechanical comminution and / or separation, extraction of the constituents of the species mentioned can be carried out according to the invention for obtaining the natural dyes.

The extractants used to prepare the extracts may include water, alcohols and mixtures thereof. Among the alcohols are lower alcohols such as ethanol and isopropanol, but especially polyhydric alcohols such as ethylene glycol, propylene glycol and butylene glycol both as sole extractant and in admixture with water, are preferred. Extracts based of water / propylene glycol in the ratio 1:10 to 10: 1 have been found to be particularly suitable. The steam distillation according to the invention falls under the preferred extraction method. The extracts can be used according to the invention both in pure and in diluted form. If they are used in diluted form, they usually contain about 2 to 80 wt .-% of active substance and the extractant or extractant mixture used in their extraction as a solvent.

In particular, for anhydrous compositions, it may be preferred according to the invention to first dry the extract and then to take up in an oil or oil-soluble or hydrophobic solvent. Particularly preferred oils for this purpose are isopropyl myristate and isopropyl palmitate. or Guerbet alcohols, in particular hexyldecanol.

Furthermore, it may be preferred according to the invention to subject the extract or extracts to spray drying individually or together, to mix the product with an inert carrier and, if desired, subsequently to granulate it.

According to the invention, substances which are water-soluble at room temperature (25 ° C.) have proved to be advantageous as inert carriers. Particularly preferred carrier substances according to the invention are sucrose, dextrose and maltodextrin.

Furthermore, it may be preferable to use mixtures of several, in particular two, different extracts in the compositions according to the invention.

In the context of the present invention, it has proven to be advantageous if the natural dye is obtained from henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, green tea, buckthorn bark, sage, bluewood, madder root, catechu, seder, alkano root , Walnut shell, indigo, cochineal, elderberry, rhubarb roots, vines, grapes, rosemary, hibiscus, rooibos, oak bark, coffee, turmeric or beetroot. Particularly preferred according to the invention are the plant dyes, in particular henna red, henna neutral, henna black, chamomile flower, elderberry, rhubarb roots, grapevines, grapes, rosemary, hibiscus, rooibos, oak bark or beetroot. Very particularly preferred plant dyes are the natural dyes obtained from elderberries, rhubarb roots, grapevines, grapes, rosemary, hibiscus, rooibos, oak bark or beetroot. The following combinations of two different natural dyes have proven to be particularly advantageous.

Elderberries and rhubarb roots

Elderberries and vines

- Elderberries and grapes elderberries and rosemary elderberries and hibiscus

- Elderberries and rooibos Elderberries and oak barks Elderberries and beetroot

- Rhubarb roots and vines Rhubarb roots and grapes - rhubarb roots and rosemary rhubarb roots and hibiscus

- rhubarb roots and rooibos

- Rhubarb roots and oak bark Rhubarb roots and beetroot

- vines and grapes

- Grape vines and rosemary grape vines and hibiscus

- Grape vines and Rooibos

- Grape vines and oak bark grape vines and beetroot

- Grapes and rosemary

- Grapes and hibiscus grapes and Rooibos vines and oak barks

- Grapes and beetroot rosemary and hibiscus

- rosemary and rooibos

- Rosemary and oak bark rosemary and beetroot

- hibiscus and rooibos

- Hibiscus and oak bark hibiscus and beetroot

- Rooibos and oak barks

- Rooibos and red beds, as well as oak barks and beets.

Furthermore, the following combinations of three different natural dyes have proven to be particularly advantageous:

Elderberries, rhubarb roots and grape vines

- Elderberries, grapes and vines Elderberries, rosemary and vines Elderberries, hibiscus and vines

- elderberries, rooibos and vines

- Elderberries, oak barks and vines, elderberries, beets and vines

- elderberries, rhubarb roots and grapes

- elderberries, rosemary and grapes elderberries, hibiscus and grapes

- elderberries, rooibos and grapes - Elderberries, oak bark and elderberry, red beet and grape grapes

- elderberries, rhubarb roots and rosemary

- Elderberries, hibiscus and rosemary elderberries, rooibos and rosemary

- elderberries, oak bark and rosemary

- Elderberry, beetroot and rosemary elderberries, rhubarb roots and hibiscus

- elderberries, rooibos and hibiscus

- Elderberries, oak bark and hibiscus elderberry, beetroot and hibiscus

- elderberries, rhubarb roots and rooibos

- elderberries, oak bark and rooibos elderberry, beetroot and rooibos elderberries, rhubarb roots and oak bark

- Elderberry, beetroot and oak bark Elderberry, rhubarb root and beetroot

- Rhubarb roots, vines and grapes

- Rhubarb roots, rosemary and grapes Rhubarb roots, hibiscus and grapes

- Rhubarb roots, rooibos and grapes

- Rhubarb roots, oak bark and grapes Rhubarb roots, beetroot and grapes

- Rhubarb roots, vines and rosemary

- Rhubarb roots, grapes and rosemary rhubarb roots, hibiscus and rosemary

- rhubarb roots, rooibos and rosemary

- Rhubarb roots, oak bark and rosemary rhubarb roots, beetroot and rosemary rhubarb roots, vines and hibiscus

- Rhubarb roots, grapes and hibiscus Rhubarb roots, rooibos and hibiscus Rhubarb roots, oak bark and hibiscus

- Rhubarb roots, beets and hibiscus Rhubarb roots, vines and Rooibos rhubarb roots, grapes and rooibos

- Rhubarb roots, oak bark and rooibos rhubarb roots, beetroot and rooibos rhubarb roots, vines and oak bark - Rhubarb roots, grapes and oak bark Rhubarb roots, beetroot and oak bark

- Rhubarb roots, vines and beets

- Rhubarb roots, grapes and beetroot vines, grapes and rosemary

- vines, hibiscus and rosemary

- Grape vines, rooibos and rosemary vines, oak bark and rosemary

- vines, beets and rosemary

- Grape vines, grapes and hibiscus vines, rooibos and hibiscus

- Grape vines, oak bark and hibiscus

- vines, beetroot and hibiscus vines, grapes and rooibos vines, oak barks and rooibos

- vines, beetroot and rooibos vines, grapes and oak barks

- Grapevines, beetroot and oak bark

- Grapes, rosemary and hibiscus grapes, rooibos and hibiscus

- Grape vines, oak bark and hibiscus

- Grapes, beets and hibiscus grapes, rosemary and rooibos

- vines, oak barks and rooibos

- Grapes, beetroot and Rooibos grapes, rosemary and oak bark

- Grapes, beets and oak bark

- rosemary, hibiscus and rooibos rosemary, oak bark and rooibos rosemary, beetroot and rooibos

- Rosemary, hibiscus and oak bark rosemary, beetroot and oak bark hibiscus, rooibos and oak bark

- Hibiscus, beetroot and oak bark, rooibos, oak bark and beetroot.

Without explicitly disclosing the different combinations of four different natural dyes, five different natural dyes and six or more different natural dyes in the context of this application, these are likewise particularly preferred in the context of the present invention. In the context of this embodiment, it has proved to be very particularly preferred

To obtain plant dyes from the respective plant constituents by extraction. With regard to the extraction parameters, reference is explicitly made to the above statements at this point.

The agents used in the process according to the invention contain the natural dyes preferably in an amount of 0.005 to 20 wt .-%, in particular from 0.01 to 10 wt .-% based on the total application preparation.

As a second constituent essential to the invention, the compositions of the present invention contain at least one polysaccharide which has at least one repeating monomer unit which carries at least one anionic group.

Although, in principle, anionically modified polysaccharides are suitable according to the invention, it has proved to be particularly advantageous if the polysaccharide containing at least one recurring

Monomer unit carrying the at least one anionic group, occurs in this form in nature.

As an anionic group, the polysaccharides of the invention may carry one or more groups selected from carboxy groups, sulfonyl groups, sulfate groups, phosphate groups and nitrate groups. Particularly preferred anionic groups according to the invention are the carboxy group and the

Sulfonyl group. Polysaccharides which have at least one recurring monomer unit which carries at least one carboxy group are very particularly preferred according to the invention.

Furthermore, it has proved to be preferred according to the invention if the polysaccharide has at least two different repeating monomer units, of which at least one unit carries at least one anionic group.

Furthermore, according to the invention, polysaccharides are preferred in which the at least one repeating monomer unit has a single anionic group.

In a further embodiment, however, it may also be preferred if the polysaccharide has two different repeating monomer units, one of which is nonionic and the other carries a plurality of anionic groups, preferably carboxy groups. An example of such

Polysaccharides are the xanthans, which are known, for example, under the INCI name xanthan gum. Such a product is commercially available under the trade name Keltrol ^® CG.

According to the invention, the combination of a xanthan and at least one cellulose, in particular a microcrystalline cellulose, has proven to be particularly preferred. An example of a preferred cellulose according to the invention are those sold under the INCI name Microcrystalline Cellulose products, such as those sold under the trade name Avicel ^® (FMC Biopolymer) known raw materials. It has proved to be very particularly preferred according to the invention, if the microcrystalline cellulose still amounts of another polysaccharide, such as a

Alginates were added. Such a particularly preferred microcrystalline cellulose is, for example, a mixture of cellulose with calcium alginate, such as that sold under the trade name Avicel ^® PC 815th

Furthermore, it has proven to be advantageous according to the invention if the polysaccharide has at least one monomer unit which carries only a single anionic group. Very particular preference is given according to the invention polysaccharides, the two different recurring Have monomer units, each having a einizige anionic group, preferably a

Carboxy group, carry. Examples of such polysaccharides are the alginates.

Preferred polysaccharides according to the invention are selected from the alginates, the xanthans, the

Pectins, tragacanth types, gum arabic, karaya gum, anionically modified

Celluloses and the anionically modified starches.

An example of anionic modified celluloses preferred according to the invention are the

Carboxymethyl. For example, the sodium salts of the glycolic acid ether of cellulose fall into this group. This class of compounds is characterized by 2 different recurring

Monomer units, both of which each carry several carboxy groups.

Examples of preferred anionically modified starches according to the invention are anionic ethers and

Ester of strength. Carboxymethyl starch, starch sulfate, starch phosphates and starch citrates fall into this group. The anionically modified starches are generally characterized by a repeating monomer unit, each of which carries a plurality of anionic groups.

Very particularly preferred polysaccharides according to the invention are the alginates. In principle, come as

Counter acid for the anionic polysaccharides all alkali or Erdalkalikationen and

Ammonium ions in question, these are in particular sodium cations, potassium cations, calcium cations and magnesium cations. Examples of alginates which are particularly suitable according to the invention are the sodium alginates which are known under the INCI name algin, as are known, for example, from US Pat

Protanal ^® trade names PC 6850 (FMC polymer) and Hydagen ^® 558P (Cognis) are displaced. The combination of different alginates such as a combination of the raw materials Protanal ^® PC 6850 and Hydagen ^® 558P is inventively preferred.

The polysaccharides which have at least one recurring monomer unit which carry at least one anionic group are present in the compositions according to the invention in amounts of from 0.05 to 5% by weight.

%, in particular from 0.1 to 0.3 wt .-%, based on the ready-to-use agent.

As a third constituent essential to the invention, the hair color-modifying agents of the present application comprise at least one optionally hydrogenated vegetable oil.

Under a vegetable oil, a plant formed by mixture of different fatty acid glycerides is understood according to the invention, whose melting point is below 50 ⁰ C, preferably below 35 ° C, particularly preferably below 20 ^0C.

According to the invention, both oils derived from oilseeds and oils derived from

Oilseeds (oil seeds and oil kernels) are found to be particularly suitable.

Examples of oil fruits suitable according to the invention are the fruits of the olive trees (olives), the oil palm

(Palm oil) as well as the avocado. Examples of oilseeds suitable according to the invention are the seeds and

Kernels of rapeseed, flax, wheat, soybean, cotton, chamomile, macadamia, peach, apricot,

Plum, palm kernel oil, peanut, sunflower, pumpkin, coriander, castor, jojoba, poppy, sesame,

Coconut, cocoa and almonds.

Furthermore, oils are suitable according to the invention, which can be obtained from the shells of fruits, such as citrus fruits (oranges, lemons, tangerines).

According to the invention, the oils obtained from oilseeds have proven to be particularly preferred. A particularly preferred oil according to the invention is palm oil. Further oils preferred according to the invention can be obtained, for example, from Elaeis guinensis or Butyrosperum Parkii. Oils are particularly preferred according to the invention

- sold under the INCI name Elaeis guineensis (palm) OiI known raw material as it is marketed, for example under the tradename Lipex ^® Genova of N R, as well as under the trade designation Akofrite ^® from Aarhus,

- the well-known under the INCI name Butyrospermum Parkii Butter raw material as it is marketed under the tradename Lipex ^® Shea by the company N & R and Lipex ^® Shea Soft by the company Aarhus, the well-known under the INCI name Canola OiI raw materials such as it is marketed under the trade name Akorex ^® from Aarhus, the well-known under the INCI name Vegetable OiI raw material as it is marketed under the tradename Lipex ^® Bassol by the company Aarhus,

- Under the INCI name Theobroma Cacao butter known raw material, as it is marketed, for example, under the trade name Lipex ^® Cocoasoft by the company Aarhus and

- The known under the INCI name Soybean Glycerides raw material, as it is sold in combination with the raw material of the INCI name Butyrospermum parkii butter unsaponifiables example, under the trade name Lipex ^® L'sens of the company Aarhus.

Instead of or in addition to the vegetable oils, it has been found to be preferred according to the invention if the agents of the present invention contain at least one hydrogenated vegetable oil. With regard to the usable oils, reference is explicitly made to the above statements at this point. According to the invention, the vegetable oils have proved to be particularly preferred as the basis for the hydrogenated vegetable oils whose acid fraction is at least 30 wt .-%, preferably at least 50 wt .-% of saturated and / or unsaturated fatty acids, in particular from oleic acid, linoleic acid, stearic acid and Palmitic acid is exemplified according to the invention are preferred hydrogenated vegetable oils

- sold under the INCI name Hydrogenated Vegetable OiI known commodity as it is marketed, for example, by the company Aarhus under the trade name Akofine ^® P, Lipex ^® BC and Akogel ^®,

- the well-known under the INCI Hydrogenated Bezeicnung Cocoglycerides raw material as it is sold for example by the firm Aarhus under the trade name Akosoft ^® and

- the under the INCI Bezeicnung Hydrogenated Coconut OiI known commodity as it is sold for example by the firm Aarhus under the tradename Lipex ^® four hundred and first

The optionally hydrogenated vegetable oil is contained in the hair color-modifying agents according to the invention preferably in an amount of from 0.1 to 10% by weight, in particular from 0.5 to 5% by weight, in each case based on the total ready-to-use agent. The following combinations of at least one polysaccharide having at least one repeating monomer unit bearing at least one anionic group and at least one optionally hydrogenated vegetable oil have been found to be particularly preferred according to the invention:

- Xanthan, Hydrogenated Vegetable OiI,

- Xanthan, Hydrogenated Palm OiI, Xanthan, Hydrogenated Cocoglycerides,

- Xanthan, Hydrogenated Coconut OiI,

Algin, Hydrogenated Vegetable OiI, Algin, Hydrogenated Palm OiI,

- Algin, Hydrogenated Cocoglycerides,

- Algin, Hydrogenated Coconut OiI,

Algin, Xanthan, Hydrogenated Vegetable Oil

- Algin, Xanthan, Hydrogenated Palm OiI

- Algin, Xanthan, Hydrogenated Cocoglycerides Algin, Xanthan, Hydrogenated Coconut OiI

- Xanthan, Hydrogenated Vegetable OiI and Hydrogenated Palm OiI Xanthan, Hydrogenated Cocoglycerides and Hydrogenated Palm OiI Xanthan, Hydrogenated Coconut OiI and Hydrogenated Palm OiI

- Algin, Hydrogenated Vegetable OiI and Hydrogenated Palm OiI

- Algin, Hydrogenated Cocoglycerides and Hydrogenated Palm OiI Algin, Hydrogenated Coconut OiI and Hydrogenated Palm OiI

- Xanthan, Hydrogenated Vegetable OiI and Hydrogenated Coconut OiI

- Xanthan, Hydrogenated Cocoglycerides and Hydrogenated Coconut OiI Algin, Hydrogenated Vegetable OiI and Hydrogenated Coconut OiI

- Algin, Hydrogenated Cocoglycerides and Hydrogenated Coconut OiI

- Xanthan, Hydrogenated Vegetable OiI and Hydrogenated Cocoglycerides as well as Algin, Hydrogenated Vegetable OiI and Hydrogenated Cocoglycerides.

According to the invention, the color-changing agents preferably contain the components essential to the invention in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose of hair coloring such carriers are, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair.

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

According to the invention, a carrier has proved to be advantageous, the water, a C-ι-C ₄ alcohol, especially ethanol, and glycerol. In the context of this embodiment, it has proved to be advantageous if these three components are contained in a weight ratio that come to 1 part of glycerol 1 to 3 parts dC ^ alcohol and 3 to 15 parts of water. Particularly preferred is a weight ratio of 1 part of glycerol to 1, 5 to 2.5 parts of CrC ₄ alcohol to 8 to 1 1 parts of water. Furthermore, it was found in the context of the work carried out that the effects according to the invention can be further increased if the compositions according to the invention contain at least one fatty alcohol.

As fatty alcohols it is possible to use saturated, mono- or polyunsaturated, branched or unbranched fatty alcohols with C ₆ -C ₃₀ -, preferably C ₁ -C _{22 -and} very particularly preferably C _{12 -C 22} -carbon atoms. For the purposes of the invention, for example, decanol, octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, decadienol, octyldodecanol, oleyl alcohol, erucalcohol, ricinoleic alcohol, stearyl alcohol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, myristyl alcohol, arachidyl alcohol, capryl alcohol, capric alcohol, linoleyl alcohol, linolenyl alcohol and behenyl alcohol, and their Guerbet alcohols, this list should have exemplary and non-limiting character. However, the fatty alcohols are derived from preferably natural fatty acids, which can usually be based on recovery from the esters of fatty acids by reduction. Also usable according to the invention are those fatty alcohol cuts which are produced by reducing naturally occurring triglycerides such as beef tallow, palm oil, peanut oil, rapeseed oil, cottonseed oil, soybean oil, sunflower oil and linseed oil or fatty acid esters formed from their transesterification products with corresponding alcohols, and thus represent a mixture of different fatty alcohols. Such substances are, for example, under the names Stenol ^® such as Stenol ^® 1618 or Lanette ^® such as Lanette ^® O or Lorol ^®, for example, Lorol ^® C8, Lorol C14 ^®, Lorol C18 ^{®, ®} Lorol C8-18, HD-Ocenol ^®, Crodacol ^® such as Crodacol ^® CS, Novol ^®, Eutanol ^® G, Guerbitol ^® 16, Guerbitol ^® 18, Guerbitol ^® 20, Isofol ^® 12, Isofol ^® 16, Isofol ^® 24, Isofol ^® 36, Isocarb ^® 12, Isocarb ^® 16 or acquire Isocarb® ^® 24 for sale. Of course, wool wax alcohols, as are commercially available, for example under the names of Corona ^®, White Swan ^®, Coronet ^® or Fluilan ^® can be used according to the invention.

Very particularly preferred fatty alcohols according to the invention are products which contain such a fatty alcohol cut as is produced by reduction of naturally occurring triglycerides. Further preferred fatty alcohols according to the invention are cetyl alcohol, stearyl alcohol, lauryl alcohol and octyldodecanol. Lauryl alcohol is a particularly preferred unbranched fatty alcohol according to the invention. Very particularly preferred according to the invention is a mixture of at least one straight-chain fatty alcohol, in particular cetyl alcohol, stearyl alcohol and / or lauryl alcohol, and a branched fatty alcohol, in particular octyldodecanol. In this case, it is preferred according to the invention if the branched fatty alcohol has more carbon atoms than the unbranched fatty alcohol. It has proved to be advantageous according to the invention if the color-changing agent contains the at least one branched and the at least one unbranched fatty alcohol in a ratio of from 1: 5 to 5: 1, in particular from 1: 2 to 2: 1, very particularly preferably from 1 : 1, 1 to 1: 0.7. The fatty alcohols are used in amounts of from 0.1 to 20% by weight, based on the total preparation, preferably in amounts of from 0.05 to 10% by weight.

Compositions according to the invention which contain xanthan and / or algin in combination with an optionally hydrogenated vegetable oil and lauryl alcohol are particularly preferred. Compositions according to the invention which contain xanthan and / or algin in combination with an optionally hydrogenated vegetable oil and also octyldodecanol are particularly preferred. Compositions according to the invention which contain xanthan and / or algin in combination with an optionally hydrogenated vegetable oil and also lauryl alcohol and octyldodecanol are very particularly preferred.

Within the scope of a further embodiment of the present invention, it has proven to be advantageous to further increase the effects according to the invention if the agents according to the invention also contain at least one nonionic surfactant.

In the field of color-changing agents, non-ionic surfactants which comprise polyethylene glycol and / or polypropylene glycol units are frequently used. Although these may in principle be contained in the agents according to the invention, it has proven to be extremely advantageous with respect to the objects according to the invention if the color-changing agents are formulated free of compounds which comprise polyethylene glycol or polypropylene glycol units. In this context, the term "free of" is understood to mean a content of less than 2% by weight, preferably less than 0.5% by weight, in particular less than 0.05% by weight in view of the object of the present invention, the use of alkyl polyglycosides has been found.

By "alkylpolyglycosides are meant according to the invention compounds of the general formula RO- (Z) _x , where R is alkyl, Z is sugar and x is the number of sugar units. The alkylpolyglycosides according to the invention can only contain one particular alkyl radical R. Usually, however, these compounds are prepared starting from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the particular work-up of these compounds. Particularly preferred alkyl polyglycosides are those in which R consists essentially of C ₈ - and d _o alkyl groups, mainly of C ₁₂ - and C ₁₄ alkyl groups, mainly of C ₈ - to C ₁₆ alkyl groups, mainly of C ₁₂ - To C ₁₆ -alkyl groups or consists essentially of C ₁₆ to C ₁₈ alkyl groups.

As sugar building block Z it is possible to use any desired mono- or oligosaccharides. Usually, sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred. The alkylpolyglycosides according to the invention contain on average 1, 1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 2.0 are preferred. Very particular preference is given to alkyl polyglycosides in which x is 1, 1 to 1, 8.

Compositions according to the invention which contain xanthan and / or algin in combination with an optionally hydrogenated vegetable oil and an alkylpolyglucoside are particularly preferred. Compositions according to the invention which contain xanthan and / or algin in combination with an optionally hydrogenated vegetable oil and also alkylpolyglucoside and at least one fatty alcohol are particularly preferred. Compositions according to the invention which contain xanthan and / or algin in combination with an optionally hydrogenated vegetable oil, lauryl alcohol and octyldodecanol and an alkylpolyglucoside are very particularly preferred.

Another group of inventively preferred nonionic surfactants are the Zuckerfettsäureester.

The term stands for esters of sugar alcohols with organic acids, in particular with fatty acids. A preferred group of substances are the sucrose polyesters of fatty acids. Technically most important sugar esters are still the mono- and diesters of sugars, especially sucrose, with higher fatty acids such as lauric, myristic, palmitic, stearic, oleic or with tallow. Such raw materials are for example under the INCI name: Available Cordesta ^®, GRILLOTEN ^®, Marlosan ^{®, ®} Emulgade® Sucro (Sucrosepolystearate) commercially: sucrose (di) stearate and among the brands. Another group of particularly preferred nonionic surfactants according to the invention are the polyglycerol fatty acid esters. The term "polyglycerol fatty acid ester according to the invention preferably comprises compounds having a polyglycerol core, which preferably contains up to 10 glycerol units, which are esterified with 1-10 acid residues of saturated or unsaturated carboxylic acids having an 8-20 carbon atom number.

The acid radical of a saturated carboxylic acid having an 8-20 carbon atom number which esterifies the polyglycerol backbone is preferably straight-chained with 12, 14, 16 and 18 carbon atoms, e.g. n-dodecanoyl, n-tetradecanoyl, n-hexadecanoyl or n-octadecanoyl.

The acid residue of an unsaturated carboxylic acid having an 8-20 carbon atom number which esterifies the polyglycerol backbone is preferably straight-chained with 12, 14, 16 and 18 carbon atoms and has 1 double bond, e.g. 9-cis-dodecenoyl, 9-cis-tetradecenoyl, 9-cis-hexadecenoyl or 9-cis-octadecenoyl.

The acid residues mentioned are also known under the following designations: dodecenoyl (lauroleoyl), 9-cis-tetradecenoyl (myristoleoyl), 9-cis-hexadecenoyl (palmitoleoyl), 6-cis-octadecenoyl (petroseloyl), 6-trans-octadecenoyl (petroselaidoyl ), 9-cis-octadecenoyl (oleoyl), 9-trans-octadecenoyl (elaidoyl), 1-cis-octadecenoyl (vaccenoyl), 9-cis-losenoyl (gadoleoyl), n-dodecanoyl (lauroyl), n-tetradecanoyl ( Myristoyl), n-hexadecanoyl (palmitoyl), n-octadecanoyl (stearoyl), n-lcosanoyl (arachidoyl).

Suitable polyglycerol fatty acid esters having a uniformly defined structure are, for example, diglycerol monocaprate, diglycerol monolaurate, diglycerol diisostearate, diglycerol monoisostearate, diglycerol tetrastearate, triglycerol monooleate, triglycerol monolaurate, triglycerol monostearate, triglycerol monoisostearate, hexaglycerol dioleates, hexaglycerol Distearate, decaglycerol dioleate, decaglycerin Tetraoleate, decaglycerol decaoleate, decaglycerol decastearate. These products are commercially available under the sign Caprol ^® (trademark of Fa.Karlshamns USA Inc., Columbus Ohio). Exact product names: CAPROL 2G4S, 3GO, 3GS, 6G2O, 6G2S, 10G2O, 10G4O, 10G10O, 10G10S. Further products are available under the names DGLC-MC, DGLC-ML, DGLC-DISOS, DGLC-MISOS, TGLC-ML and TGLC-MISOS from Solvay Alkali GmbH, D-3002 Hannover. The mixture of various polyglycerol fatty acid esters is defined under names such as decaglycerol monooleate, decaclycerol di-oleate, polyglycerol ester of mixed fatty acids, polyglycerol esters of fatty acids, polyglycerol caprate, polyglycerol cocoate, polyglycerol laurate, polyglycerol lanolinate, polyglycerol isostearate or polyglycerol rizinolate and commercially available under the word sign Triodan ^® and HOMODAN ^® (trademark of Grindsted Products, Grindsted Denmark.), specific product names: TRIODAN 20, 55, R90 and HOMODAN MO, Radiamuls ^® (. trademark of Petrofina (FINA), Brussels Belgium), the exact product RADIAMULS poly 2253, designation CAPROL PGE 860 or ET, or the word sign Plurol ^® (trademark Gattefosse Etablissements, Saint-Priest, France), the exact product PLUROL Stearique WL 1009 WL or PLUROL Oleique 1173, available. Further products are under the designations PGLC-C 1010 S, PGLC-C 0810, PGLC-C 1010 / S, PGLC-L T 2010, PGLC-LAN 0510 / S, PGLC-CT 2010/90, PGLC-ISOS T UE, PGLC-R UE, PGLC-ISOS 0410 available from Solvay Alkali GmbH, D-3002 Hannover. Another group of preferred nonionic surfactants according to the invention are the sorbitan fatty acid esters. These preferably consist of a substantially pure or mixed sorbitan fatty acid ester in which the sorbitane bulk is esterified with 1-3 acid residues of a saturated or unsaturated straight chain carboxylic acid of 8-20 carbon atoms.

The acid radical of a saturated carboxylic acid of 8-20 carbon atoms which esterifies the sorbitol bulk is preferably straight-chained with 12, 14, 16 and 18 carbon atoms, e.g. n-dodecanoyl, n-tetradecanoyl, n-hexadecanoyl or n-octadecanoyl.

The acid radical of an unsaturated carboxylic acid having a number of 8-20 C atoms is preferably straight-chain with 12, 14, 16 and 18 C atoms, for example oleoyl.

Suitable sorbitan fatty acid esters are in particular sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sorbitan sesquioleate and sorbitan trioleate. These products are commercially available under the mark clamping ^® (trademark of Fa.Atlas, Wilmington USA), specific product names: SPAN 20, 40, 60, 65, 80 and 85, Arlacel ^® (trademark of Fa.Atlas), specific product names: ARLACEL 20, 40, 60, 80, 83, 85 and C, Crill ^® (trademark of Croda Chemicals Ltd., Cowick Hall, Snaith Goole GB.), specific product names: (CRILL 1, 3 and 4, Dehymuls ^® trademark of Exact product names: DEHYMULS SML, SMO, SMS, SSO, Famodan ^® (trademark of Grindsted Products, Grindsted Denmark), exact product names: FAMODAN MS and TS, Capmul ^® (trademark of Karlshamns USA Inc., Columbus Ohio), specific product names: CAPMUL S and O Radiasurf® ^® (trademark of Petrofina (FINA.) Bruxelles Belgium), specific product names: Radiasurf® 7125, 7135, 7145 and 7155, available. While it has been found to be advantageous according to the invention to formulate the color-changing agents free of anionic surfactants, it may be preferred according to the invention to add an anionic surfactant for stabilizing the preparation and / or for increasing the washing activity. Suitable anionic surfactants in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. As a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, ester, ether and amide groups as well as hydroxyl groups can be contained in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group, linear and branched fatty acids having 8 to 30 C atoms (Soap),

Acylsarcosides having 8 to 24 carbon atoms in the acyl group,

Acyltaurides having 8 to 24 carbon atoms in the acyl group,

Acyl isethionates having 8 to 24 carbon atoms in the acyl group,

Sulfosuccinic acid mono- and dialkyl esters having 8 to 24 C atoms in the alkyl group, linear alkanesulfonates having 8 to 24 C atoms, linear α-olefin sulfonates having 8 to 24 C atoms,

Alpha-sulfofatty acid methyl esters of fatty acids having 8 to 30 carbon atoms,

alkyl sulfates,

Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,

Sulfonates of unsaturated fatty acids having 8 to 24 carbon atoms and 1 to 6 double bonds according to

DE-A-39 26 344 and

Esters of tartaric acid and citric acid with monohydric and / or polyhydric alcohols. Preferred anionic surfactants are alkyl sulfates, sulfosuccinic acid mono- and dialkyl esters having 8 to 18 carbon atoms in the alkyl group. The alkyl sulfates are particularly preferred according to the invention. An alkyl sulfate which is very particularly preferred according to the invention is the surfactant known by the INCI name Sodium Cetearyl Sulfate, which is marketed, for example, under the trade name Lanette E by Cognis.

A group of further very particularly preferred anionic surfactants are the esters of a hydroxy-substituted di- or tricarboxylic acid of the general formula (I),

X

HO - C - COOR ¹ (I)

Y - CH - COOR ²

in the

X is H or a -CHzCOOR group, - Y = H or -OH is under the condition that Y = H, when X = -CH ₂ COOR, R, R ¹ and R ^{2 are} independently a hydrogen atom, an alkali or alkaline earth metal cation, an ammonium group, the cation an ammonium-organic base or a radical Z derived from a polyhydroxylated organic compound selected from the group consisting of the etherified (C ₆ -C ₁₈ ) -alkyl polysaccharides having 1 to 6 monomeric saccharide units and / or the N-alkylglucamides and / or of the etherified aliphatic (C ₆ -C ₁₆ ) -hydroxyalkylpolyols having 2 to 16 hydroxyl radicals, with the proviso that at least one of the groups R, R ¹ or R ^{2 is} a radical Z.

In the context of the present invention, R, R ¹ and R ^{2 are} preferably alkali metal cations, in particular the sodium ion, alkaline earth metal cations, in particular the magnesium ion, and the ammonium ion.

The group Z of the compounds of formula (I) is preferably the residue of a (C ₆ -C ₈₎ alkyl-polysaccharide.

As a saccharide, the group Z preferably contains glucose.

As alkyl groups, in particular C ₆ -C ₁₆ -alkyl groups are used, the choice of unbranched saturated groups being preferred. The alkyl groups may also be mixtures obtained from the processing of natural fats and oils. Mixtures consisting essentially of C ₈ -C ₀ -alkyl, C ₂ -C ₁₄ alkyl or C ₈ -C ₁₆ alkyl groups may be preferred in the invention. Very particularly preferred is a mixture of alkyl groups, as obtained in the processing of coconut oil.

The group Z contains 1 to 6 monomeric saccharide units. According to a preferred embodiment, the group Z contains 2 to 6 glucose units. However, it may also be preferable to use groups Z with 1, 2 to 3, in particular 1, 3 to 2, glucose units. It should be noted that in the synthesis mixtures always arise and these numerical values are derived from the stoichiometric ratio of the starting materials fatty alcohol and saccharide.

The compounds according to formula (I) are preferably esters of citric acid, tartaric acid or malic acid. Such compounds which are esters of tartaric acid are preferred according to the invention. The commercial product, which is marketed by the company under the names Cesalpinia Eucarol ^® AGE-ET and the INCI name Sodium Coco-Glucoside Tartrate, has proven to be particularly suitable representatives of the compounds of formula (I) were found.

In a further embodiment, to further increase the effects according to the invention, it has proved advantageous if the color-modifying agents according to the invention furthermore comprise a natural and / or synthetic oil body.

As such according to the invention are liquid paraffin oils, isoparaffin oils and synthetic hydrocarbons and di-n-alkyl ethers having a total of 12 to 36 carbon atoms, in particular 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-ethyldecyl ether, tert-butyl n-octyl ether, iso-pentyl-n-octyl ether and 2-methyl-pentyl -n-octyl ether, preferred. 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 particularly preferred.

Other preferred oil bodies are the ester oils. Ester oils are to be understood as meaning the esters of C ₆ - C ₃₀ fatty acids with C ₂ - C ₃₀ fatty alcohols. The monoesters of the fatty acids with alcohols having 2 to 24 carbon atoms are preferred. Examples of fatty acid components used in the esters are caproic, caprylic, 2-ethylhexanoic, capric, lauric, isotridecanoic, myristic, palmitic, palmitoleic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, linolenic Behenic acid and erucic acid and their technical mixtures which are obtained, for example, in the pressure splitting of natural fats and oils, in the oxidation of aldehydes from Roelen's oxo synthesis or the dimerization of unsaturated fatty acids. Examples of the fatty alcohol components in the ester oils are isopropyl alcohol, caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, 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 alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxo synthesis and as a 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), oleic acid decyl ester (Cetiol ^® V).

A third class of natural and / or synthetic oil bodies are the dicarboxylic acid esters such as di-n-butyl adipate, di- (2-ethylhexyl) adipate, di- (2-ethylhexyl) succinate and di-isotridecyl acelate and the diol esters such as ethylene glycol dioleate , Ethylene glycol di-isotridecanoate, propylene glycol di (2-ethylhexanoate), propylene glycol di-isostearate, propylene glycol di-pelargonate, butanediol di-isostearate, neopentyl glycol dicaprylate, and the symmetrical, unsymmetrical 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)

Likewise, as natural and / or synthetic oil body triflic acid esters of saturated and / or unsaturated linear and / or branched fatty acids with glycerol, and fatty acid partial glycerides, which are monoglycerides, diglycerides and their technical mixtures, are used. With the use of technical products production reasons may still contain small amounts of triglycerides. The partial glycerides preferably follow the 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 the R ¹ , R ² and R ^{3 is} independently of one another hydrogen or a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22, preferably 12 to 18, Carbon atoms are provided with the proviso that at least one of these groups is an acyl radical and at least one of these groups is hydrogen. The sum (m + n + q) is 0 or numbers from 1 to 100, preferably 0 or 5 to 25. Preferably, R ^{1 is} an acyl radical and R ² and R ^{3 are} 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, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Preferably, oleic acid monoglycerides are used.

Very particularly preferred cosmetic oil bodies are the di-n-alkyl ethers, in particular the dicaprylyl ethers.

Compositions according to the invention which contain xanthan and / or algin in combination with an optionally hydrogenated vegetable oil and dicaprylyl ethers are particularly preferred. Compositions according to the invention which contain xanthan and / or algin in combination with an optionally hydrogenated vegetable oil, at least one fatty alcohol and dicaprylyl ether are particularly preferred. Compositions according to the invention which contain xanthan and / or algin in combination with an optionally hydrogenated vegetable oil, lauryl alcohol and dicaprylyl ether are particularly preferred. Compositions according to the invention which contain xanthan and / or algin in combination with an optionally hydrogenated vegetable oil, octyldodecanol and dicaprylyl ether are particularly preferred. Compositions according to the invention which contain xanthan and / or algin in combination with an optionally hydrogenated vegetable oil, at least one fatty alcohol, an alkyl polyglucoside and dicaprylyl ether are very particularly preferred. The amount used of the natural and synthetic cosmetic oil bodies in the compositions used according to the invention is usually 0.1 to 30% by weight, based on the total composition, preferably 0.1 to 20% by weight, and in particular 0.1 to 15% by weight. -%.

In a preferred embodiment of the present invention, the effects according to the invention could be achieved to a particular extent if at least 50% by weight, preferably at least 75% by weight, in particular at least 95% by weight, of the ingredients of the color-changing agent are of natural origin.

According to the invention, the term "ingredient of natural origin" is understood to mean that the ingredients are obtained without chemical modifications from the substances occurring in nature.Exclusively excluded from this term are synthetic substances obtained, even if these substances also occur in an identical form in nature , It is particularly preferred according to the invention if at least 50% by weight, preferably at least

75% by weight, in particular at least 95% by weight, of the ingredients of the color-changing agent of plant origin.

The term "ingredient of plant origin" is understood according to the invention that the

Ingredients are obtained without chemical modification of the substances occurring in the plant world.

It is particularly preferred according to the invention if at least 5% by weight, preferably at least

7% by weight, in particular at least 10% by weight, of the ingredients of the organic color-modifying agent.

The term "ingredient from organic farming" is understood according to the invention that the

Ingredients are obtained without chemical modification of the substances occurring in the plant world, the plants according to the issued by the European Union in 1991

Regulation on Organic Farming - Regulation (EEC) No 2092/91 agriculture - must have been grown.

It has been found according to the invention that the color-modifying agents which meet these requirements, in addition to the improved environmental compatibility also have an improved power balance.

In the context of this embodiment, it has therefore proved to be advantageous if the agents according to the invention are free of synthetic thickening polymers, such as, for example, polymers based on acrylic and / or methacrylic acid and derivatives thereof.

Furthermore, it has proved to be advantageous in the context of this embodiment, when the compositions of the invention free from synthetic preservatives, such as

Phenoxyethanol, the parabens, preferably methylparaben, ethylparaben, propylparaben,

Butylparaben and paraben themselves, or 1, 3-dimethylol-5,5-dimethylhydantoin.

Furthermore, it has proven to be particularly preferred in the context of this embodiment if the agents according to the invention are free of substances which have a permanently cationic nitrogen atom.

The term "free from", within the framework of the abovementioned embodiments, stands for a maximum content of

3Gew .-%, preferably of 1Gew .-%, in particular of 0.01 wt .-%.

Furthermore, it has proved to be advantageous according to the invention for the extent of the achievable effects of the invention, when the agents as a preservative sorbic acid and their

Salts, benzoic acid and its salts, salicylic acid and its salts and / or benzyl alcohol.

Likewise, it has proved to be advantageous according to the invention, when the means according to the present

Invention contain at least one pigment.

The term "pigment" is understood according to the invention to mean a substance consisting of particles and virtually insoluble in the application medium, which is used as colorant for the agent and / or the keratinic fibers.

In principle, both pigments of natural and synthetic origin are suitable according to the invention.

The purely inorganic pigments may be e.g. titanium dioxide, zinc oxide, iron oxide,

Silica or silicates, such as mica. But also naturally occurring inorganic pigments such as ocher, umber, green earth, Terra di Siena and graphite are preferred according to the invention.

In a preferred embodiment, the pigments are synthetic products, which are constructed according to the same structure principle as beads of several layers with different refractive index (layer-substrate pigments). On a substrate, usually mica, one or more layers of metal oxides are applied (metal oxide mica pigments), wherein the type and thickness of the metal oxide layer determines the effect of the pigments in the respective medium. As metal oxides are preferably titanium dioxide, zinc oxide, tin oxide, iron oxide or silica in question. Instead of or together with the metal oxides, it is possible according to the invention to use colored complexes, such as, for example, Berlin Blue, or organic dyes in the coating. Suitable examples of such film-substrate pigments include the pigments available from Merck under the trade name Timiron ^®, especially Timiron ^® Super Gold, Timiron ^® Sun Gold Sparkle MP-29, Timiron ^® Super SilverThe by the company Eckart under the trade name Prestige ^® marketed pigments, especially Prestige ^® Sun gold, Prestige ^® Bright Mystic Violet, Prestige ^® Sparkling Pure gold, Prestige ^® Fire Red, Prestige ^® Amethyst, Prestige ^® Sparkling Lemon gold,

- marketed by Merck under the trade name Dichrona® ^® pigments, especially Dichrona® ^® RY and

- marketed by Merck under the trade name Colorona® ^® pigments, especially Colorona® ^® Light Blue.

Preference is given to pigments having a particle size distribution in the range from about 2 μm to 150 μm, preferably from 10 μm to 125 μm and from 10 μm to 80 μm.

The pigments are preferably contained in an amount of 0.01-0.2% by weight, particularly preferably 0.05-0.1% by weight.

The naturally occurring pigments, such as, for example, the micatypes, the iron oxides and titanium oxide, are particularly preferred according to the invention.

Compositions according to the invention which contain xanthan and / or algin in combination with an optionally hydrogenated vegetable oil, dicaprylyl ether and an iron oxide pigment are particularly preferred. Compositions according to the invention which contain xanthan and / or algin in combination with an optionally hydrogenated vegetable oil, at least one fatty alcohol, dicaprylyl ether and an iron oxide pigment are particularly preferred. Compositions according to the invention which contain xanthan and / or algin in combination with an optionally hydrogenated vegetable oil, lauryl alcohol, dicaprylyl ether and an iron oxide pigment are particularly preferred. Compositions according to the invention which contain xanthan and / or algin in combination with an optionally hydrogenated vegetable oil, octyldodecanol, dicaprylyl ether and an iron oxide pigment are particularly preferred. Compositions according to the invention which contain xanthan and / or algin in combination with an optionally hydrogenated vegetable oil, at least one fatty alcohol, an alkyl polyglucoside, dicaprylyl ether and an iron oxide pigment are very particularly preferred. A second object of the present invention is a method for changing the color of keratinischer

Fibers in which an agent of the invention is applied to the fibers and after a

Reaction time is rinsed off again.

The exposure time is according to the invention preferably between 5 minutes and 2 hours depending on

Initial hair color, hair texture and desired color loss, an exposure time of 30 minutes to one hour is particularly preferred according to the invention.

The application can be carried out in principle at room temperature or slightly elevated temperature. One

Temperature range of 15 to 45 ° C has been found to be preferred. To achieve higher

Temperatures can, for example, the body heat of the treated person by using a

Plastic hood or a towel can be used. Increased temperatures can also be achieved by technical aids, such as a drying hood.

The pH of the preparation used can be adjusted by suitable ingredients such as Acidifizierungsmittel or alkalizing over a wide pH range. For example, it has proved to be advantageous if the preparation has a pH of from 4 to 8, preferably from 5 to 7.

To adjust the pH alkalizing agents such as alkali or

Alkaline earth hydroxides, ammonia or organic amines. The organic amines are preferably selected from the group consisting of monoethanolamine, monoisopropanolamine, 2-amino

2-methyl-propanol, 2-amino-2-methyl-1, 3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methylbutanol and triethanolamine is formed. In particular monoethanolamine, triethanolamine as well

2-amino-2-methyl-propanol and 2-amino-2-methyl-1,3-propanediol are preferred within this group. The use of amino acids and / or oligopeptides such as the ω-

Aminocaproic acid as the alkalizing agent is preferred in the context of the present invention.

Furthermore, such amino acids and oligopeptides are preferably used, their 2.5 wt .-% pure

Solutions in water have a pH of 9 and greater. Such an amino acid is arginine which is preferably used.

To adjust the pH, preferably at least one organic or inorganic acid is used as the acidifying agent. Particularly preferred inorganic acids are hydrochloric acid,

To name sulfuric acid and phosphoric acid. As organic acids are acetic acid, glycolic acid,

Citric acid, tartaric acid, lactic acid and malic acid are preferred. Citric acid is a particularly preferred acid used.

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

Unless otherwise stated in the examples, the amounts are in each case in percent by weight.

The colorants were applied in a liquor ratio of strand to cream of 1: 4 on natural white strands and left there for 1 hour at 35 ° C. The fibers were then rinsed thoroughly, washed with a commercial shampoo and dried with a hair dryer. The resulting colors are summarized in Table 2: Table 2:

The raw materials incorporated in the dyeing cream have the following meanings:

Akofine ^® P INCI name: Hydrogenated Vegetable OiI (Cognis)

Avicel ^® PC 815 microcrystalline cellulose containing calcium alginate (INCI)

Name: microcrystalline cellulose) (FMC biopolymer)

Cegesoft ^® HF 52 INCI name: Hydrogenated Vegetable OiI (Cognis)

Cetiol ^® LDO mixture of lauryl alcohol and dioctyl ether (INCI name: Lauryl

Alcohol and dicaprylyl ether) (Cognis)

Eutanol ^® G 2-octyldodecyl (INCI name: Octyldodecanol) (Cognis)

Keltrol ^® CG Xanthangum (at least 91% active ingredient content, INCI name

Xanthan Gum) (Kelco)

Plantacare ^® 1200 UP C ₁₂ fatty alcohol -i _{6-1.4-glucoside} (approximately 50-53% active substance content; INCI

Name: Lauryl Glucoside, Aqua (Water)) (Cognis)

Plantacare® ^® 818UP C8-14 polyglucoside (about 51-53% Akticsubstanzgehalt; INCI

Name: Coco-Glucoside, Aqua (Water)) (Cognis)

Protanal ^® PC 6850 Sodium alginate (INCI name: Algin) (FMC Biopolymer)

Texamid ^® 558 P sodium alginate (INCI name: Algin) (Cognis)

Claims

Patent claims

Claims 1. A color change agent for keratinous fibers containing in a cosmetically acceptable carrier

- At least one natural dye, at least one polysaccharide having at least one repeating monomer unit carrying at least one anionic group, and at least one optionally hydrogenated vegetable oil.

2. Composition according to claim 1, characterized in that the natural dye is obtained from at least one component of the plant by mechanical comminution or by extraction.

3. Composition according to one of claims 1 or 2, characterized in that the natural dye of plant constituents of henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre, alkanel Elderberries, rhubarb roots, vines, grapes, rosemary, hibiscus, rooibos, oak bark or beetroot.

4. Composition according to one of claims 1 to 3, characterized in that extracts are used as natural dyes.

5. Composition according to one of claims 1 to 4, characterized in that the anionic group of the polysaccharide is selected from a carboxy group and / or a sulfonyl group.

6. Composition according to one of claims 1 to 5, characterized in that the polysaccharide is selected from the alginates, the xanthanes, the pectins, the Traganthtypen, the gum arabic, the Karayagummi, the anionic modified celluloses and the anionically modified starches.

7. Composition according to one of claims 1 to 6, characterized in that it contains at least one alginate as polysaccharide.

8. Composition according to one of claims 1 to 7, characterized in that the optionally hydrogenated vegetable oil is obtained from almonds, peanuts, palm trees, coconuts, olives, chamomile, jojoba, macadamia, sunflower seeds, soybeans, rape, oranges, wheat germ or peach kernels ,

9. Composition according to one of claims 1 to 8, characterized in that hydrogenated palm oil is used as optionally hydrogenated vegetable oil.

10. Composition according to one of claims 1 to 9, characterized in that the cosmetically acceptable carrier contains water in combination with at least one organic solvent.

11. A process for the color change of keratinous fibers, characterized in that an agent according to any one of claims 1 to 10 is applied to the fibers and rinsed again after a contact time.