WO2004071473A1

WO2004071473A1 - Use of phenolic diterpenes for protecting the colour of hair

Info

Publication number: WO2004071473A1
Application number: PCT/EP2003/013860
Authority: WO
Inventors: Thomas Kripp; Christian Springob; Beate Grasser
Original assignee: Wella Aktiengesellschaft
Priority date: 2003-02-14
Filing date: 2003-12-06
Publication date: 2004-08-26
Also published as: DE10306255A1; AU2003288238A1

Abstract

The invention relates to the use of phenolic diterpenes, especially carnosol and the derivatives thereof, in cosmetic hair care products for protecting the colour of hair.

Description

USE OF PHENOLIC DITERPENES FOR COLOR PROTECTION

OF HAIR

The present invention relates to the use of phenolic diterpenes, in particular carnosol and its derivatives, in cosmetic hair treatment compositions for protecting the color of hair.

Human hair is exposed to numerous harmful influences. In addition to structural damage that occurs more in secret, these influences can also have more or less clearly visible effects. So even under normal, that is by no means excessive exposure to sunlight, such severe hair damage can occur that this visibly reduces the attractiveness of the hair. The hair can lose a lot of shine and elasticity due to the influence of light, especially when wet. It becomes rough, brittle and rough.

However, the most visible impairments naturally include all hair damage that goes along with a color change. The natural hair color can fade just like the artificially applied oxidative hair colors or the direct dyes.

In addition to total bleaching, the hair can also lose shine, depth and brilliance. Since such color changes do not normally occur evenly, the result is an unsightly, spotty overall picture of the hair. In the worst case, especially with synthetic hair colors, there is no constant brightening, but a shift in the color tone due to the different light sensitivity of the individual coloring components.

It would therefore be desirable to have a product that can prevent fading from sunlight. Since the influence of a strong dose of sunlight often occurs in connection with water, such as during a beach holiday in the south, it would also be desirable to protect the hair provided, which is retained when bathing, even in chlorine or sea water. In this context, it would be particularly desirable to have a product that can develop its hair-protecting effect even after it has been exposed to sunlight.

There are numerous approaches to suppress light-induced color changes in human hair. Attempts have also been made to protect hair with little success using UV absorbers, such as those used very successfully in skin cosmetics. Despite the ostensible logic of such approaches, this usually fails because only very small layer thicknesses can be applied to the hair without a disruptive effect on the appearance being noticeable. For example, when using conventional UV absorbers, gray hair often appears yellow due to its own color; Light-scattering pigments based on titanium dioxide, on the other hand, are particularly distracting on dark hair. In addition, it is not so easy to create a coherent protective film on the hair without undesirable effects, such as greasy appearance and sticky feel of the hair. Furthermore, unlike sunburn on the skin, the hair color is not only damaged by UV light, but also by the entire wavelength range of the visible spectrum. In order to shield the visible light, dark or strongly light-scattering (i.e. therefore again color-changing) protective substances would have to be applied to the hair.

On the assumption that the bleaching processes are oxidative or radical-induced processes, various reducing agents and radical scavengers have also been used. In some cases it was possible to find light protection effects that could be measured using certain natural or synthetic antioxidants; however, there has been no clearly visible effect so far.

From WO 94/14414 A1 a pharmaceutical or cosmetic product for the protection of the skin and the hair is known which damages by free radicals Treat on skin, hair or mucous membrane and prevent premature aging. It contains a synergistic antioxidant combination of a polyphenol, such as. B. a flavonoid, carnosol or camosolic acid, and a ginko leaf extract obtained using an apolar solvent.

No indication of the possible use of phenolic diterpenes for protecting the color of hair is disclosed from the prior art.

For the reasons mentioned above, there is a need to provide a cosmetic agent for use in protecting hair color that does not have the disadvantages of the agents of the prior art.

The object of the present invention is therefore to show the use of a cosmetic agent for protecting the hair color, by means of which the hair color is not only protected prophylactically, but by which - even after the hair has already been damaged by influences such as, for. B. has been exposed to UV radiation - is able to repair or heal color damage (after-sun repair, after-sun healing, time activated sun protection) and neutralize damaging effects and thus restore the original condition of the hair color receive (stops light or UV light-related color degradation), stabilize or restore (Color Rescue), reactivate and revitalize (Color Vitalizer).

Surprisingly, it was found that, in contrast to commercially available UV absorbers, known reducing agents or free radical scavengers, it is possible to use phenolic diterpenes alone, in particular carnosol and camosol derivatives, e.g. B. camosolic acid, its salts and esters, in a cosmetic agent for protecting the hair color, to protect the hair color from damage caused by light. The protective effect not only extends to reaching optical measurements, but is also clearly visible in the sunlight simulation test. The object was thus achieved according to the invention by using an agent according to claim 1.

Further advantageous embodiments of the present invention are presented in the further claims.

The measured values documented below are therefore only used to quantify the effects that are already visible to the naked eye.

For the tests to prove the protective effect of the phenolic diterpenes according to the invention, two completely different application forms were selected, a pre-sun leave-in hair treatment (comparative test 1) and an after-sun rinse-off hair treatment (comparison test 2).

The results of the two series of measurements (Figures 1 and 2) show a significantly higher protective effect of the diterpene-containing products compared to the comparison products, which also contained free-radical scavengers used in cosmetics. Surprisingly, it was found that the protective effect of camosolic acid and carnosol turned out to be even higher when used in an after-sun hair treatment than in pre-sun hair treatment: during pre-sun leave-in hair treatment after radiation Between 65% and 75% of the original hair color was still present (depending on the concentration of the mixture of camosolic acid and carnosol), between 97% and 100% of the original color was found in the after-sun application. This makes it possible for the first time to protect the hair from bleaching even if it gets wet (and thus "washed") several times during the sun exposure, as is usual for a summer bathing vacation. Even in the case of an unforeseen (and thus unprepared) Exposure to sunlight can protect the color of the hair afterwards. The use according to the invention makes the color resistant to sunlight and UV light, and builds up a self-protection against the sun. color) or helps the hair to protect itself and thus not only counteracts the fading of the hair color but also reactivates (color recall, color energizer) and revitalizes the hair color (color revival, color recharge, color recapture, color recovery) , color memory). Since the aftertreatment of the hair is the more effective protection method anyway, it is not absolutely necessary to apply the product to the hair beforehand (if necessary waterproof).

Preference is given to using the agent containing phenolic diterpenes to protect a synthetic hair color which was largely produced only on the hair surface using direct organic dyes or using oxidative dyes, it also being located inside the hair. The use for protecting an oxidatively generated hair color is particularly preferred.

The oxidative dye with which the hair color to be protected was produced is preferably selected from the group 4,5-diamino-1- (2-hydroxyethyl) -1 H-pyrazole, 4,5-diamino-1 - (1-methylethyl) - 1 H-pyrazole, 4,5-diamino-1 - [(4-methylphenyl) methyl] -1 H-pyrazole, 4,5-diamino-1 - [(4-chlorophenyl) methyl] -1 H-pyrazole, 4 , 5-diamino-1-methyl-pyrazole, 2-amino-6-methylphenol, 2-amino-5-methylphenol, 4-amino-3-methylphenol, 4-methylamino-phenol, 4-amino -2- (aminomethyl) phenol, 4-amino-2 - [(2-hydroxyethyl) amino] methyl-phenol and 4-amino-2- (methoxymethyl) -phenol, with the 4,5-diamino-pyrazole derivatives particularly are preferred. The oxidation dye precursor can also be selected from 1,4-diaminobenzene, 1,4-diamino-2-methylbenzene, 1,4-diamino-2,6-dimethylbenzene, 1,4-diamino-2,5-dimethylbenzene , 1,4-diamino-2,3-dimethyl-benzene, 1,4-diamino-2-chloro-benzene, 4-di [(2-hydroxyethyl) amino] aniline, 4 - [(2-methoxyethyl) amino ] -aniline, 1,4-diamino-2- (2-hydroxyethyl) benzene, 1,3-bis- [N (2-hydroxyethyl) -N- (4-aminophenyl) amino-2-propanol and 2, '2- [1,2-ethanediyl-bis (oxy-2,1-ethanediyloxy)] bis-1,4-diamino-benzene.

Preferred is the oxidative coupler with which the hair color to be protected was produced, selected from the group 1,3-diamino-benzene, 2-amino-4 - [(2- hydroxyethyl) amino] anisole, 2,4-diamino-1-fluoro-5-methyl-benzene, 2,4-diamino-1-methoxy-5-methyl-benzene, 2,4-diamino-1-ethoxy-5 -methylbenzene, 2,4-diamino-1- (2-hydroxyethoxy) -5-methylbenzene, 2,4-di [(2-hydroxyethyl) amino] -1,5-dimethoxybenzene, 2nd , 4-diamino-1 - (2-hydroxyethoxy) benzene, 3-di [(2-hydroxyethyl) amino] aniline, 4-amino-1-ethoxy-2-di [(2-hydroxyethyl) amino] benzene , 3 - [(2-hydroxyethyl) amino] aniline, 3 - [(2-aminoethyl) amino] aniline, 1, 3-di (2,4-diaminophenoxy) propane, 2,4-dimethoxy- 1,3-diamino-benzene, 2,6-bis (2-hydroxyethyl) aminotoluene, 3-dimethylamino-phenol, 5-amino-2-methyl-phenol, 5-amino-4-fluoro-2-methyl- phenol, 5-amino-4-methoxy-2-methylphenol, 5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichlorophenol, 3-diethylamino-phenol, 3- Amino-2-chloro-6-methylphenol, 3-aminophenol, 3 - [(amidomethyl) amino] phenol, 5 - [(2-hydroxyethyl) amino] -2-methylphenol, 3 - [(2- Hydroxyethyl) amino] phenol, 5-amino-2-ethylphenol, 5 - [(3-hydroxypropyl) amino] -2-methylphenol, 3 - [(2,3-Dih ydroxypropyl) amino] -2-methylphenol, 3 - [(2-hydroxyethyl) amino] -2-methylphenol, 5-amino-4-chloro-2-methylphenol, methylenedioxyphenol, resorcinol, meth- thylresorcinol and 4-chlororesorcinol.

The hair color can also have been produced with direct dyes, which are selected from the following groups:

Nitro dyes (blue)

4-N-ethyl-N- (2'-hydroxyethyl) amino-1- (2 "-hydroxyethyl) amino-2-nitro-benzene, 1-amino-3-methyl-4- (2'-hydroxyethyl) amino- 6-nitro-benzene, 1 - (2'-hydroxyethyl) amino-2-nitro-4-bis (2 "-hydroxyethyl) amino-benzene, 4-bis (2'-hydroxyethyl) amino- 1- (2 "-methoxyethyl) amino-nitrobenzene, 1- (2 ', 3'-dihydroxypropyl) aminor 2-nitro-4- [ethyl- (2" -hydroxyethyl) aminol-benzene, 1 - [(2', 3'-dihydroxypropyl) amino] -2-nitro-4- [ethyl-2 "- (hydroxyethyl) amino] benzene, 1- (3'-hydroxypropylamino) -2-nitro-4- bis (2" -hydroxyethylamino )-benzene.

Nitro dyes (red)

1-amino-4- (2'-hydroxyethyl) amino-nitrobenzene, 1-hydroxy-2-amino-4,6-dinitro-benzene, 1-amino-2-nitro-4-bis- (2'-hydroxyethyl ) amino-benzene, 1-amino-2-nitro-4- (2'- hydroxyethyl) amino-5-chlorobenzene, 1- (2-hydroxyethyl) amino-2-nitro-4-amino-benzene, 1-hydroxy-3-nitro-4-aminobenzene, 1 - (2'-aminoethyl) amino-2-nitro -4- (2 "- hydroxyethyl) oxybenzene, 3-nitro-4- (2'-hydroxyethyl) aminophenylglycerol ether, 1-amino-5-chloro-4- (2 ', 3'-dihydroxypropyl) amino-2 -nitro-benzene, 1,4-bis - [(2 ', 3'-dihydroxypropyl) amino-5-chloro-2-nitro-benzene, 1-hydroxy-2 (2'hydroxyethyl) amino-4,6-dinitro -benzene, 2-amino-6-chloro-4-nitrophenol, 1 -hydroxy-3-nitro-4- (3'-hydroxypropylamino) -benzene, 3-nitro-4-ethylamino-benzoic acid, 4-amino-2- nitro-diphenylamino-2-carboxylic acid, 2-chloro-6-ethylamino-4-nitrophenol, 2,5-diamino-6-nitropyridine, 1, 2,3,4-tetrahydro-6-nitroquinoxaline.

Nitro dyes (yellow)

4- (2'-hydroxyethyl) amino-3-nitro-benzonitrile, 4- (2'-hydroxyethyl) amino-3-nitro-benzamide, 1-amino-2- (2'-hydroxyethyl) amino-5-nitro- benzoI, 1-methoxy-2- (2'-hydroxyethyl) amino-5-nitro-benzene, 1-hydroxy-3-nitro-4- (2'-hydroxyethyl) amino-benzene, 1-hydroxy-2-amino- 3-nitro-benzene, 1-amino-2-methyl-6-nitro-benzene, 1 - (2'-hydroxyethyl) -oxy-3-methylamino-4-nitrobenzoi, 1-methylamino-2-nitro-5- ( 2 ', 3'-dihydroxypropyl) oxybenzene, 1- (2'-hydroxyethyl) amino-2-hydroxy-4-nitrobenzene, 1-methoxy-3- (2'-aminoethyl) amino-4-nitro- benzene, 1- (2'-ureidoethyl) amino-4-nitro-benzene, 1- (2'-hydroxyethyl) amino-2-nitro-benzene, 4- (2'-hydroxyethyl) amino-3-nitrotrifluoromethyl-benzene, 2,4-bis- [N- (2'-hydroxyethyl) amino] -5-chloro-nitrobenzene, 4- (2 ', 3'-dihydroxypropyl) amino-3-nitro-trifluoromethyl-benzene, 4- {2' Hydroxymethyl) amino-3-nitro-methylbenzene, 4- (2'-hydroxyethyl) amino-3-nitro-chlorobenzene,

azo dyes

1 - (4'-nitrophenylazo) -2-methyl-4-bis (2 "-hydroxyethyl) amino-benzene, 1 - (3'-nitro-4-amino) -phenylazo-2-hydroxy-7-trimethyl- ammonium chloride-naphthalene, 1- (2'-hydroxy-4'-sulfo-6'-nitro) -naphthylazo-2-hydroxynaphthalene, 1- (4'-aminophenylazo) - 2-methyl-4-bis - [(2 ' -hydroxyethyl) amino] -benzene, 5- (4'-dimethylaminophenylazo) - 1, 4-dimethyl-triazonium chloride, 1- (2'-methoxyphenylazo) -2-hydroxy-7-trimethylammonium-naphthalene chloride, 1- (4 ' Aminophenylazo) -2-hydroxy-7-trimethylammonium-naphthalene, 4- (3'-trimethylammoniumphenylazo) -N-phenyl-3- methyl-pyrazolone (5), 4-hydroxy-3 - [(4'-sulfo-l'-naphthyl) azo] -1 -naphthalenesulfonic acid, 1 - (4'-sulfophenylazo) -2-hydroxy-naphthalene, 1 - (4'-Sulfophenylazo) -2-hydroxy-6-sulfonaphthalene, 4-amino- [4'-bis- (2 "-hydroxyethyl) amino-azobenzene, 4-amino- [4'-bis- (2nd "-hydroxyethyl) amino] -2'-methyl-azobenzene, 3- (2 ', 6'-diaminopyridyl-3'-azo) pyridine, 7-phenylazo-l-amino-3,6-disulfo-8-hydroxy -naphthalene, 5-acetylamino-4-hydroxy-3 - [(2'-methylphenyl) azo] -2,7-naphthalenedisulfonic acid, 2- (2 ', 4'-dimethylphenylazo) -6- (4 "-sulfophenylazo ) -1,3-dihydroxybenzene.

Quinone dyes 1,4-bis- (2 ', 3'-dihydroxypropyl) amino-anthraquinone, 1-methylamino-4- (2'-hydroxyethyl) amino-anthraquinone, 2- (2'-aminoethyl) amino-anthraquinone, 2-bromo-4,8-diamino-6- (3'-trimethylammonium) phenylamino-1, 5-naphthoquinone, 1- (2'-sulfo-4'-methylphenyl) amino-4-hydroxyanthraquinone , 1,4-diamino-anthraquinone, 1-amino-2-sulfo-4-cyclo-hexylamino-anthraquinone, 1-methylamino-4-aminopropylamino-anthraquinone, 1-aminopropylamino-anthraquinone.

triphenylmethane

4 ', 4 ", 4'" - triamino-3-methyl-triphenylcarbonium chloride, bis- (4,4-diethylaminophenyl) -4'-ethylanlino-naphthyl-carbonium chloride, bis- (4,4-dimethylaminophen) -4 '- phenyl-amino-naphthyl-carbonium chloride and 4,4-bis (N-ethyl-3-sulfobenzyl) - amino-2 "-sulfofuchsonium.

Natural hair dyes such as henna, indigo or yuglon are also suitable.

The preferred phenolic diterpenes carnosol and camosolic acid

are natural components of rosemary oil (Rosmarinus officinalis) and are enriched from it. These substances are also contained in Salvia carnosa and other salvia species (sage). In food technology, fats are protected from becoming rancid without giving the food in question a too strong rosemary note, which would otherwise be the case if the native oil were used. The experiments described here were carried out with such an enriched, commercially available, powdered rosemary oil fraction. The active component of 9% by weight contained 90% by weight camosolic acid and 10% by weight carnosol. Of the salts of camosolic acid, the sodium, ammonium and potassium salts are particularly preferred.

The phenolic diterpenes can be used in the hair treatment products together with all customary cosmetics-relevant substances apart from hydrogen peroxide. The active ingredients can be dissolved, emulsified (W / O and O / W), suspended, in the liquid-crystalline phase, as an aerosol, gel, wax, powder or foam.

The phenolic diterpenes can be used in a concentration range from 0.00001% by weight to 20% by weight, preferably from 0.001% by weight to 5% by weight, particularly preferably from 0.01% by weight to 1% by weight, to protect the Hair color, especially used to prevent damage from solar radiation.

Carnosol and / or camosolic acid can preferably be used as the only antioxidants or can also be combined with other antioxidants and / or radical scavengers. The agents used preferably contain no other plant extracts, in particular no ginko extract. The active ingredients can be present as a respective pure substance, slightly enriched, as a crude extract or as a component of natural vegetable oils, in particular from Rosmarinus officinalis. According to the invention, the cosmetic agents are used before, during or preferably after sunbathing outdoors or in the solarium.

The cosmetic agents used to protect the hair color can also contain synthetic UV protective substances such as UV quats and / or UV filters.

All commercially available UV quats which have at least one quaternary ammonium group and at least one UV light-absorbing group can be considered as UV quat. The UV quats absorb in the following range: UV-A 400-320 nm, UV-B 320-280 nm, UV-C 280-200 nm. Suitable UV quats are described, for example, in US-A 4061730 and US-A 5427773 ,

Particularly suitable UV quats are poly (N-hydroxypolyoxypropylethyl) -N- (adipylpolyoxypropyl) -N-methyl-N- (2-hydroxy-3-cinnamidopropyldimethylammonium chloride) methanesulfonate (INCI name: Polyquatemium-59 (and ) Bu tylene glycol) marketed by Croda Inc., Parsippany, NJ 07054, USA, under the trade name Crodasorb ^® UV-HPP, and

Dodecyl- [3-para-dimethylaminobenzamido) propyl] dimethylammonium toluenesulfonate / propane-1,2-diol-1-octadecanoate (INCI name: DimethylPABAmidopropyl Laurdimonium Tosylate (and) Water (and) Propylene Glycol Stearate ), sold by the company ISP Chemicals NJ 07470, USA under the trade name Escalol® ^® HP 610th

In contrast to UV quat, UV filter substance is to be understood below as an inorganic or organic filter substance that can be used in cosmetic products and absorbs UV light without quaternary nitrogen.

Inorganic pigments absorbing UV light are all pigments or micropigments known for this use, in particular metal compounds or semimetal compounds which are sparingly soluble or insoluble in water. Compounds in ionic as well as non-ionic or in oxidized form. The pigments can be present in this form individually or as mixtures or individually or as mixtures of mixed oxides, mixtures of mixed oxides with pure oxides also being included. Examples include titanium oxides (for example TiO ₂ ), zinc oxides (for example ZnO), aluminum oxides (for example Al ₂ O ₃ ), iron oxides (for example Fe ₂ O ₃ ), manganese oxides (for example MnO), silicon oxides (for example SiO ₂ ) , Silicates, cerium oxide, zirconium oxides (for example Zr0 ₂ ), barium sulfate (BaSO ₄ ) or mixtures thereof. Suitable pigments or micro pigments are commercially available, for example, Homburg bitec ^® L5 (INCI name: Titanium Dioxide) from Merck.

The total amount of the UV-light-absorbing inorganic pigments in the agent used according to the invention can be between 0.01 and 20.0% by weight, in particular between 0.05 and 10.0% by weight, preferably between 0.05 and 5.0 % By weight, based on the amount of the composition, may be present.

Of the organic UV filter substances, all known UVA, UVB and UVA / UVB filter substances can be used, individually or in combination with one another, which are usually contained in cosmetic and / or dermatological preparations. The UV filters can be oil-soluble or water-soluble. Since a preferred embodiment of the agent according to the invention is that the pigments are incorporated into the water phase and the organic UV filter substance into the oil phase, oil-soluble UV filter substances are preferred in this case.

For UVA filters, for example, the derivatives of dibenzoylmethane (for example Parsol 1789 from Givaudan / Roure, INCI name: butyl methoxydibenzoylmethane) come into consideration.

The following compounds can be mentioned as examples of UVB filters: benzylidene camphor or derivatives thereof, in particular methylbenzylidene camphor (for example 3-benzylidene camphor, 3- (4-methylenebenzylidene) dl-camphor), derivatives and esters of cinnamic acid, in particular derivatives and ester methoxycinnamic acid (for example octyl 4-methoxycinnamate or isopentyl 4-methoxycinnamate, 2-ethylhexyl 4-methoxycinnamate (INCI: ethylhexyl methoxycinnamate)), derivatives and esters of benzoic acid, especially 4-aminobenzoic acids; 2-Cyano-3,3-diphenyl-acrylic acid 2-ethylhexyl ester (INCI: Octocrylene), polyhydroxybenzoic acids (e.g. methyl polyhydroxybenzoate or polyhydroxybenzoic acid propyl ester), esters of salicylic acid (e.g. salicylic acid (2-ethylhexyl) ester or salicylic acid (4-isopropylbenzyl) ester). Examples of water-soluble UV filter substances are: sulfonic acids, benzophenones and their derivatives, for example the sulfonic acid derivatives of benzophenones (for example 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid) as UVB / UVA filters or the benzimidazoles (for example 2- Phenylbenzimidazole-5-sulfonic acid) and their salts, in particular the sodium and potassium salts.

Other UV filter substances that can be used are: dibenzoylmethanes or suitable polypeptides, in particular oxygen radical scavengers, for example the known Mn, Fe or Zn superoxide dismutases, and tocopherols and vitamins (for example ascorbic acid).

The organic UV filter substances are preferably 2-ethylhexyl 4-methoxycinnamate and 2-ethylhexyl 2-cyano-3,3-diphenyl-acrylate.

The organic UVA, UVB or UVB / UVA filter substances can be present in the agent used according to the invention in a total amount between 0.1 to 30.0% by weight, in particular between 0.5 to 25.0% by weight, preferably between 0 , 3 and 5.0% by weight, based on the amount of the agent.

The weight ratio of UV quat to UV filter should preferably be in the range from 1: 1 to 1:15, particularly preferably from 1: 1 to 1: 5, very particularly preferably from 1: 2 to 1: 3. The agent used according to the invention can advantageously additionally contain at least one synthetic polymer. The synthetic polymers are preferably to be selected from acrylic polymers, in particular from the group of cross-polymers made from acrylates and alkyl acrylates and / or from acrylates and allyl ethers.

For example, Pemulen ^® , Carbopol ^® and Acrisint ^® types are suitable, for example Pemulen TR1 from Goodrich (INCI name: Acrylates / C 10-30 Alkyl Acrylate Crosspolymer), Carbopol 1382 from Goodrich (INCI name: Acrylates / C 10-30 Alkyl Acrylates Crosspolymer), Carbopol 2984 from Goodrich, (INCI name: Carbomer) or Carbopol Ultrez 10 from Goodrich, (INCI name: Carbomer) or Acrisint 400 from 3 V (INCI name: Carbomer), which may be present individually or in combination in the agent according to the invention. The synthetic polymers in question can be incorporated into the oil or lipid phase or into the water phase, preferably into the water phase, of the agent according to the invention and are therein in a total amount between 0.05 and 5.0% by weight, in particular between 0.1 and 3.0% by weight, very particularly between 0.1 and 1.0% by weight, based on the total amount of the composition.

Of course, the agent used in accordance with the invention can contain all additives known and customary for such agents, e.g. B. thickeners such as clays, bentonite, cellulose derivatives or alginates, fatty acids, starch, polyacrylic acid and their derivatives, petroleum jelly, paraffin oils, wetting agents or emulsifiers from the classes of anionic, cationic, amphoteric or non-ionic surface-active substances, for example fatty alcohol sulfates , Fatty alcohol ether sulfates, alkyl sulfonates, alkyl benzene sulfates, quaternary ammonium salts, alkyl betaines, ethoxylated alkylphenols, fatty acid alkanolamides or ethoxylated fatty acid esters, also opacifiers, such as. B. polyethylene glycol ester, alcohols, such as. B. Example ethanol, propanol, isopropanol, polyols such as ethylene glycol, 1, 2- or 1, 3-propanediol, 1, 2-, 1, 3- or 1, 4-butanediol, 1, 2-, 1, 3rd -, 1, 4- or 1,5-pentanediol and glycerol. As a suitable aroma Matic ether alcohol is an ethylene glycol ether, in particular an ethylene glycol monophenyl ether, for example phenoxetol from Nipa (INCI name: phenoxyethanol). Other suitable additives are sugars such as B. D-glucose, solubilizers, stabilizers, anti-fatty substances, inorganic or organic acids such as lactic acid, citric acid, glycolic acid and phosphoric acid; Buffer substances, preservatives, antioxidants such as tocopherol and its esters, perfume oils, dyes and hair conditioning and hair care ingredients, such as. B. cationic polymers, lanolin derivatives, vitamins or provitamins, in particular biotin, vitamin C or D-panthenol; Cholesterol, proteins, pantothenic acid and betaine.

The ingredients mentioned are used in the agent in the usual amounts for such purposes, e.g. B. the wetting agents and emulsifiers in concentrations of a total of 0.2 to 30 wt .-%, the alcohols in an amount of 0.5 to 30 wt.%, In particular from 1 to 25 wt.%, Preferably from 2 to 20 wt %, very preferably from 3 to 15% by weight, based on the total amount of the agent; the opacifiers, perfume oils and dyes in an amount of 0.01 to 1% by weight; the acids and buffer substances in a total amount of 0.1 to 10% by weight; Sugar, solubilizers, vitamins, antioxidants, stabilizers, and hair conditioning and hair care ingredients in an amount of 0.1 to 10% by weight each, while the thickeners and solubilizers in a total amount of 0.5 to 20% by weight. % can be included in this average. Aromatic ether alcohols can be present on average in an amount between 0.1 and 10% by weight, in particular between 0.2 and 5% by weight, preferably between 0.5 and 2% by weight.

Of course, the composition used according to the invention can contain all further additives, auxiliaries and carriers customary and known for hair cosmetics. In principle, the person skilled in the art knows which additives, auxiliaries and carriers are used in hair cosmetics, so that the above substances are only of an exemplary nature and are only intended to further illustrate the present invention. The agents used according to the invention can be present in all dosage forms as are known for cosmetic hair treatment agents. For example in the form of shampoos, rinses, gels, cures, cream gels, creams, lotions, shake mixes, sprays or foams.

EXAMPLES

Example 1 Color protection leave-in spray cure

Stearyl alcohol 0.13000 g

Glyceryl stearate 0.16000 g

Cetylstearyl alcohol with 20 EO 0.10000 g

(INCI: Ceteareth-20)

Camosolic acid 0.00001 g

PHB methyl ester 0.10000 g

Perfume 0.20000 g

Ethanol 5.00000 g

Water ad 100.00000 g

Example 2 Color protection hair milk

Cetyl alcohol 0.50 g

Glycerin 0.30 g

Cetyltrimethylammonium chloride 0.25 g

Styrene / vinyl pyrrolidone copolymer 0.20 g

Carnosol / Camosolic acid 1:10 0.10 g

Perfume 0.20 g

Ethanol 4.80 g

Water ad 100.00 g Example 3 Color protection balm rinse-off

Cetylstearyl alcohol 1.40 g

Glyceryl stearate 0.70 g

Cetylstearyl alcohol with 20 EO 0.10 g (INCI: Ceteareth-20)

Cetyltrimethylammonium chloride 0.60 g

Carnosol 1.00 g

Perfume 0.40 g water, fully desalinated ad 100.00 g

Example 4 Color protection rinse

Cetylstearyl alcohol 4.30 g

Cetyl lactate 0.40 g

Vaseline 0.50 g

Cetyltrimethylammonium chloride 1, 20 g

Polyvinyl pyrrolidone 0.45 g

Rosemary oil 2.00 g water ad 100.00 g

Example 5 Color protection cure

Cetylstearyl alcohol (Lanette O ^® ) 5.5 g

Vaseline 1, 2 g

Paraffinum Liquidum 1.0 g

Dimethylpolysiloxane (Belsil DM 500 ^® ) 0.5 g

Lanolin alcohol 0.3 g Lanolin 0.2 g

Carnosol 0.3 g

Camosolic acid 0.2 g

Cetyltrimethylammonium chloride 1, 2 g

Citric acid 0.3 g

Perfume 0.4 g water ad 100.0 g

Example 6 Color protection intensive hair treatment

Cetylstearyl alcohol 6.0 g

Glycerin 1.7 g

Cetyltrimethylammonium chloride 1.0 g

Vegetable oil 1.0 g

Carnosol 5.0 g

Camosolic acid 5.0 g

Silicone oil (dimethylpolysiloxane) 0.5 g

Perfume 0.2 g water ad 100.0 g

Measurement of the color protection effect of the phenolic diterpenes

In order to determine the color protection effect of carnosol and camosolic acid on the color stability of human hair, radiation tests were carried out on human hair strands in a sunlight simulator, the hair strands being treated with various hair care agents known to be antioxidative before and after the radiation. The influence of the plant extracts sunflower seed extract and olive leaf extract as well as a tocopherol / ascorbic acid mixture commercially available as radical scavenger (consisting of 24% tocopherol, 1% ascorbic acid, 5% ascorbic acid palmitate, 1% citric acid in polyethylene glycol; Trade name: Oxynex K liquid, from Merck) on the color stability of the hair in comparison to untreated hair and in comparison to strands of hair, which were only treated with the active ingredient-free hair care product.

Two different hair care formulations were selected for the tests, one formulation was applied as a leave-in pre-sun product before the irradiation, the other product as a rinse-off after sun product after each irradiation cycle. This should check whether the rosemary extract has an effect on color stability in both pre and after-sun hair care products.

irradiation apparatus

The strands of hair were irradiated by means of a table exposure device from Atlas (model Suntest XLS +, with UV special glass shell with limitation of the radiation at approx. 290 nm for the simulation of solar radiation outdoors; the IR radiation> 800 nm is also filtered out by a filter bowl ). The air temperature during the radiation in the sun tester was approx. 40 ° C, the black standard temperature approx. 55 ° C; The floor on which the strands of hair were located could be cooled with water and the relative humidity was about 50 + 5%. The irradiance was 765 W / m ² , the irradiation time was 48 h (the strands were re-treated after 12 h each time and turned over and thus irradiated from both the top and the bottom), so that an irradiation dose of approximately 13.2 kJ / cm ² resulted.

hair material

Human hair tresses, color blond, length 17 cm, width 2.5 cm, average diameter 65.4 μm, cysteic acid value 25.3 μmol / g hair. Carnosol / Camosolic acid

Trade name: Stabiloton WS, company Raps, Kulmbach;

Active content 9% diterpenes, including 90% camosolic acid and 10% carnosol.

Pretreatment of the hair

Each 2 g of hair was washed twice with 0.5 ml of standard shampoo (9.8% lauryl ether sulfate, 2% NaCl) for 1 minute and rinsed out for 1 minute (water, 35 ° C.).

color measurement

The color measurements were carried out according to the CIE-L * a * b * system, which is based on a color system adapted to the subjective perception of color (see, among others, DIN 6174). The L value of the strands or the change in the L value due to the irradiation was measured, since the L value indicates the brightness of a color. The Spectrolino colorimeter from Gretag Macbeth was used to determine the L values. The spectral reflection is measured in the range from 380 to 730 nm with a resolution of 10 nm. At the beginning of each measurement series, a calibration was carried out using a bright white surface as the reference standard (PTB-calibrated BaSO standard). The larger the L number, the lighter the color (L = 0 means ideal black and L = 100 ideal white). Lightening the hair due to the radiation is thus manifested in an increase in the L value. The difference between the L values after irradiation and those before irradiation is therefore a measure of the color loss or the brightening; a positive value for this difference indicates a loss of color. To visualize the influence of the tested active ingredients on the color stability, this L-value difference is converted into percentage color protection values, normalized to the color loss value of the only irradiated, otherwise untreated pattern (0% color stability: only irradiated, untreated) Pattern; 100%: no color loss). Comparative test 1 Pre-Sun application:

The tresses were placed in water (35 ° C) for 15 minutes and then blotted. 0.5 ml of hair treatment was applied per section (three sections of hair were treated with the treatment at the same time) and massaged in evenly for 1 minute. The strands were irradiated for 12 hours in the Suntest XLS + from Atlas (filter B: coated quartz glass + UV special glass). The tresses were then shampooed with 0.5 ml of standard shampoo per tress for 1 minute and rinsed with water (35 ° C.) for 1 minute. The tresses were then treated again as described above and irradiated. This process was carried out a total of 4 times, taking care that the strands were turned before each irradiation interval, so that the front and the back were irradiated twice. After the last radiation interval, the strands were washed once with standard shampoo and dried in a climatic room (20 ° C / 65% humidity) with the exclusion of light.

The following hair treatments were used: 1. Pre-sun leave-in hair treatment without active ingredient 2. Pre-sun leave-in hair treatment with 0.045% by weight of a mixture of 90% by weight of camosolic acid and 10% by weight of carnosol

3. Pre-sun leave-in hair treatment with 0.09% by weight of a mixture of 90% by weight of camosolic acid and 10% by weight of carnosol

4. Pre-Sun leave-in hair treatment with 0.2% by weight of Oxynex K liquid 5. Pre-Sun leave-in hair treatment with 0.5% by weight of Oxynex K liquid

6. Pre-sun leave-in hair treatment with 0.2% by weight sunflower seed extract

7. Pre-sun leave-in hair treatment with 0.5% by weight sunflower seed extract

8. Pre-sun leave-in hair treatment with 0.5% by weight olive leaf extract

9. Pre-sun leave-in hair treatment with 1% by weight olive leaf extract Result:

In Figure 1, the color protection effect of the agent used according to the invention for application before UV irradiation with 0.045% by weight or 0.09% by weight of the mixture of 90% camosolic acid and 10% carnosol can be clearly seen, since the color stability values are very high here are much higher than with the carnosol-free basic recipe (pattern "without active ingredients"). The other hair treatments examined showed no color protection effect regardless of the concentration tested.

Comparative experiment 2 after-sun application

The dry strands were irradiated for 12 hours in the Suntest XLS + from Atlas (filter B: coated quartz glass + UV special glass). Immediately after the end of the irradiation period, the strands and only the irradiated and untreated hair were placed in water (35 ° C.) for 15 minutes, dabbed, then 0.5 ml of hair treatment applied per section and massaged in for 1 minute (simultaneous treatment of three strands). After an exposure time of 10 minutes, the strands were rinsed out with water (35 ° C.) for 1 minute and then dried in a climatic room (20 ° C./65% atmospheric humidity) for approx. 5 hours with the exclusion of light. Thereafter it was irradiated again for 12 hours. This process was carried out a total of 4 times, taking care that the strands were turned before each irradiation interval, so that the front side and the back side were irradiated twice. The L value of all hair samples was then determined.

The following hair treatments were used 10. After-sun rinse-off hair treatment without active ingredients 11. After-sun rinse-off hair treatment with 0.045% by weight of a mixture of 90% camosolic acid and 10% carnosol 12. After-sun rinse-off hair treatment with 0.09% by weight of a mixture of 90% camosolic acid and 10% carnosol

13. After-sun rinse-off hair treatment with 0.2% by weight of Oxynex K liquid

14. After-sun rinse-off hair treatment with 0.5% by weight of Oxynex K liquid. 15. After-sun rinse-off hair treatment with 0.2% by weight of sunflower seed extract

16. After-sun rinse-off hair treatment with 0.5% by weight sunflower seed extract

17. After-sun rinse-off hair treatment with 0.5% by weight olive leaf extract

18. After-sun rinse-off hair treatment with 1.0% by weight olive leaf extract

Result:

As Figure 2 shows, the hair treatment without active ingredients (basic formulation) already offers a low level of color protection, but the Carnosol leads to an even more pronounced improvement in color stability when applied in after-sun leave-in hair care products than with the corresponding formulation in Pre-Sun leave-in hair care products. In the formulation in the after-sun products, practically no color loss due to the irradiation process can be measured (almost 100% color stability) at an application concentration of 0.045% by weight of the mixture of 90% camosolic acid and 10% carnosol, while the other active ingredients (everything otherwise highly effective antioxidants) have no color protection effect (no difference compared to the basic recipe without active ingredients).

As a result of the use according to the invention, in addition to preventive protection of the color of the natural or colored hair, there is also a questionable repair or healing of color damage (after sun repair), a rescue of the hair color of irradiated hair (color apres healing, color apres rescue) ) or a refresh of the color (color recall, color energizer).

Claims

1. Use of phenolic diterpenes, their salts or their esters in cosmetic hair treatment compositions for protecting the color of hair.

2. Use according to claim 1, characterized in that the phenolic diterpene is selected from carnosol, camosolic acid, carnosolic acid salt or carnosolic acid ester.

3. Use according to claim 2, characterized in that the carnosolic acid ester is the alkyl ester having 1 to 6 carbon atoms.

4. Use according to one of claims 1 to 3, characterized in that the phenolic diterpene is used in an amount of 0.001 to 1 wt.%.

5. Use according to one of claims 1 to 4, characterized in that the hair color to be protected is a synthetic

Hair color is.

6. Use according to claim 5, characterized in that the hair color is an oxidative hair color.

7. Use according to one of claims 1 to 6, characterized in that the agent additionally contains a UV filter.

8. Use according to claim 7, characterized in that the UV filter is selected from 2-ethylhexyl 4-methoxycinnamate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylic acid.

9. Use according to one of claims 1 to 8, characterized in that the agent additionally contains a UV quat.

10. Use according to claim 9, characterized in that the UV quat is selected from poly (N-hydroxypolyoxypropylethyl) -N- (adipylpolyoxypropyl) -N-methyl-N- (2-hydroxy-3-cinnamidopropyl-dimethylammonium chloride) methanesulfonate and dodecyl- [3-para-dimethylaminobenzamido) propyl] dimethylammonium toluenesulfonate / propane-1,2-diol-1-octadecanoate.

11. Use according to one of claims 1 to 10, characterized in that the weight ratio of UV quat to UV filter is in the range of 1: 2 to 1: 3 on average.

12. Use according to one of claims 1 to 11, characterized in that the hair treatment agent is an agent to be rinsed out after use (rinse-off product).

13. Use according to one of claims 1 to 12, characterized in that the hair treatment agent is used after sunbathing.

14. Use according to claim 11, characterized in that the aftertreatment agent is a color protection shampoo, a color protection rinse or a color protection cure.

15. Use of phenolic diterpenes, their salts or their esters in cosmetic hair treatment compositions for maintaining the color of hair.

16. Use of phenolic diterpenes, their salts and / or their esters in cosmetic hair treatment compositions for repairing or restoring the color of hair.

17. Use of phenolic diterpenes, their salts and / or their esters in cosmetic hair treatment agents for neutralizing light-induced damage to the color of the hair, for reactivating the hair color, for proactive or time-activated protection of the color of the hair, for revitalizing the hair color, for stopping the light-related color degradation , to prevent the

Fading the color of the hair, repairing and / or curing the color of the hair after damage from sunlight, saving the hair color, building up a self-protection of the hair color and improving the resistance of the color of the hair to damage by UV and sunlight.