FQAMABLE COLORING COMPOSITIONS COMPRISING A

THERMO-SENSITIVE POLYMER Technical field of the invention

The present invention relates to a foamable ready-to-use composition for coloring human hair which after application to the head transforms into a transparent drip-free gel.

Background of the invention

Throughout the years, there has been a desire to alter the color of synthetic and natural fibers. In particular, coloring of human hair has been sought in view of changing styles and fashion.

The coloring of hair is currently subject to the most varied trends. Whereas in the past hair was colored primarily to cover gray hair, today there is an increasing demand for integrating the hair color into current fashion as an expression of personality.

Now as before, two established methods of hair coloring are broadly applied. One is the semi-permanent system which consists of the possibility of coloring hair with colorants containing non-oxidative, direct dyes (often referred to as toners). Although the dyes used for this purpose are optimized for dyeing performance as well as for remaining on the hair as long as possible, the color shade gradually weakens with every hair washing. Thus, depending on the type of hair and the used product, such colorants as a rule do not last more than a maximum of 10 hair washings. Although designed for direct dyeing, some of these dyes can also be applied in presence of hydrogen peroxide in order to intensify the color result and to obtain better root-to-tip evenness.

Besides the semi-permanent system, oxidation dyes have attained substantial cosmetic significance in the field of conventional hair dyeing. The color is created by reaction of certain primary intermediates and couplers in the presence of an oxidant. In addition to the creation of color effects, very high requirements are placed on oxidation dyes that are intended for the treatment of human hair. On the one hand, the dyes must be safe from a toxicological and dermatological point of view. Moreover, it must be possible, by a combination of suitable primary intermediates and couplers, to produce a wide range of different color nuances. Furthermore, the hair colorations produced are required to have good wash fastness, light fastness, perspiration resistance, resistance to permanent wave treatments, acid resistance, base resistance and abrasion resistance. At any rate, such hair colorations must remain stable for at least four to six weeks under normal everyday conditions.

The oxidative system is based on the reaction of so called primary intermediates with couplers; both molecule types are practically colorless. In presence of air or oxidants such as hydrogen peroxide primary aromatic amines with an additional hydroxy group, amino group, mono- or di- substituted amino group in the para or ortho position react with couplers which are of the resorcinol, m-aminophenol, m-phenylenediamine or 1-naphthol type. Some years ago, a new primary intermediate, a substituted 4,5-diaminopyrazole, was introduced to provide intense red shades with most of the commonly used couplers.

As the size of the dye molecules formed in the hair is larger than the size of the highly diffusible starting primary intermediates and couplers, no significant fading normally occurs after dyeing. Therefore the oxidative hair coloring which produces a very durable coloring result is also called "permanent" system.

The base used for pH adjustment has preferably been ammonium hydroxide. The advantage of using ammonium hydroxide is that the combination with hydrogen peroxide provides slight enlightening of the hair. During processing, enlightening occurs in parallel with coloring the hair. In this connection the lightening effect is essential for providing even color results.

Instead of ammonium hydroxide which has a characteristic pungent odor numerous primary hydroxyalkylamines which are widely odorless can be used instead. As alkanolamines are not volatile under hair coloring conditions the hair has to be well rinsed after processing.

Over the years chasses for hair colorants have been established. Very common in European countries are hair colorants based on cream or gel compositions. In numerous American countries liquid formulations are preferred which, when mixed with aqueous hydrogen peroxide compositions, form a gel. The colorants can either be prepared and applied by the traditional way; in particular hairdressers prepare the ready-to-use mixtures in a bowl and apply it by a brush; or compositions are shakable and are therefore preferentially mixed with the developer composition in a vessel. Then the colorants are applied from the vessel via a nozzle or a system of nozzles which have the design of a comb. The latter is especially suitable for applications at home.

In all these cases it is ensured that the hair colorants remain exactly where applied and do not drip from the head.

Examples for coloring compositions are disclosed in the standard literature, e.g. K. Schrader, "Grundlagen und Rezepturen der Kosmetika", 2 ^nd edition (1989, Huthig Buchverlag), pp. 784-804.

In recent years a new application method has been developed in the field of hair colorants. EP 1470812A1 for instance claims a hair cosmetic product in form of a foam. The hair treatment method comprises discharging a mixed liquid of dye and developer preparations from a foamer vessel. After the application to the hair, the mixture is allowed to act for 3 to 60 minutes to bleach and/or color the hair.

Despite considerable advantages in terms of application of the colorant the claimed composition can also have significant inconveniences. Depending on the individual condition of the hair which can be from non-damaged to damaged, from dry to greasy, from thin to thick, from short to long, the composition on the head may not always have the required stability over the whole processing time. Especially at extended processing times compositions have the tendency of running down from the head and produce stains on the skin. This becomes especially critical if, for example caused by the individual hair quality, the foam breaks down and an important amount of liquid is reformed which cannot be retained by the hair.

The authors of this patent application claimed for the ready-to-use composition a broad viscosity range from 1 to 300 mPa-s measured at 25°C before foaming. Compositions having viscosities in the lower range may be easily foamable; but when the foam is braking down the risk of dripping is given. Compositions having viscosities in the higher viscosity range may have improved on-head stability; however, efforts to produce foam with liquids of increased viscosities via pump or squeeze foamer may be considerable as frequent pushing or squeezing a foamer device cannot be fatigue-free in use.

Foaming of more viscous liquids require foamer types which are able to produce foams having a higher air-to-liquid ratio. This is unfavorable in so far as active ingredients dissolved in the liquid phase of the foam can hardly be in contact with the hair fibers because of the high foam volume. For this reason high air-to-liquid ratios combined with high foam stability is unfavorable to produce intense colors.

The authors also pointed out that the foam stability plays an important role in providing a drip-free composition; their focus was therefore on a superior foam quality which should have been obtained by appropriate surfactants and, for further improving the stability, the use of higher alcohols.

In the patent application EP2324811A2 the authors also shared that high foam stability is crucial for preventing the colorant from dripping off the head.

However, technically it is indispensable that the foam breaks down to ensure that sufficient amounts of active ingredients have quickly contact to the hair fibers. In this connection, a negative point resulting from high foam stability is that in the course of processing important amounts of active ingredients remain physically separated from the hair and can therefore not interact with the fibers. To a large extent dye formation reactions occur outside the fibers which leads to considerable performance issues, predominantly in terms of color intensity and gray coverage. The claimed compositions are therefore not satisfying. Furthermore, colorants for short processing times, especially drip-free colorants which should provide dark shades, have not been feasible.

There was therefore the need to provide a foamable composition for carrying out oxidative coloration, particularly suitable for human hair, which should not show the afore-indicated drawbacks.

The composition should be easily applicable and be drop-free once applied to the head.

An object of the present invention was therefore to find a color composition which allows easy foaming by means of a non-aerosol device.

Another object of the present invention was that once the foam was applied to the head most of the foam should break down quickly to obtain strong colorations.

Furthermore, the composition should remain localized over the whole processing times which are usually between 10 to 60 minutes.

Summary of the invention

The present invention relates to a foamable ready-to-use composition for coloring hair in the form of aqueous solution comprising:

at least one thermo-sensitive polymer,

at least one tenside,

one or more oxidation dyes and optionally one or more direct dyes, at least one alkaline reacting agent,

hydrogen peroxide or alternatively a hydrogen peroxide adduct.

Detailed description of the invention

Surprisingly, it has been found that this goal can be reached by applying a ready-to-use foamable composition in the form of aqueous solution comprising:

at least one thermo-sensitive polymer,

at least one tenside,

one or more oxidation dyes and optionally one or more direct dyes, at least one alkaline reacting agent,

hydrogen peroxide or alternatively a hydrogen peroxide adduct.

The composition may optionally comprise auxiliary agents and/or additives, as needed.

The composition may be used for simultaneous lightening and coloring hair, especially human hair.

Thermo-sensitive polymers are able to change their physical state upon a change in temperature; this change preferably occurs in the temperature range between 20 to 80°C.

Useful for the current compositions are such polymers which are distinctly soluble in water.

Particularly useful for the current invention are polymers comprising hydrophobic blocks of polypropylene oxide (PPO), hydrophilic blocks of polyethylene oxide (PEO) or both. Such polymers are for instance described in US7339013, which makes explicit reference to this. Especially useful thermo- sensitive polymers may be obtained from PolymerExpert SA, France, and have the trade name ExpertGel ^® .

Preferably the thermo- sensitive polymer is bis-methoxy PEG- 13 PEG-438/PPG- 1 10 SMDI copolymer (ExpertGel ^® EG 56), bis-methoxy PEG- 13 PEG-502/PPG-57/SMDI copolymer (ExpertGel ^® EG 230) or a mixture thereof.

The thermo-sensitive polymers may be used in an amount from 0. 1 to 10 percent by weight of the composition, preferably the concentrations vary from 0.25 to 4% by weight, more preferably from 0.5 to 2.5% by weight.

The tenside may be selected from anionic, neutral, amphoteric or cationic surface -active compounds.

Anionic tensides may be selected from the group consisting of alkylsulfate, alky lether sulfate, alkylsulfonate, alkylarylsulfonate, alkylsuccinate, alkylsulfosuccinate, N-alkoylsarkosinate, acyltaurate, acylisethionate, alkylphosphate, alkyletherphosphate, alkylethercarboxylate, alpha-olefinsulfonate, especially selected from their alkali, such as sodium, ammonium and triethanolamine salts.

The alkylethersulfate, alkyletherphosphate and alkylethercarboxylate may comprise between 1 to 10 ethylenoxide or propylenoxide units, preferably 1 to 3 ethylenoxide -units per molecule.

Preferred tensides are sodium lauryl sulfate, ammonium lauryl sulfate, sodium laurylethersulfate, ammonium laurylethersulfate, sodium lauroylsarkonisate, sodiumoleylsuccinate, ammonium laurylsulfosuccinate, sodium dodecylbenzolsulfonate, triethanolamidodecylbenzolsulfonate.

Suitable amphoteric tensides may be alkylbetaine, alkylamidopropylbetaine, alkylsulfobetaine, alkylglycinate, alkylcarboxyglycmate, alkylamphoacetate or propionate, alkylamphodiacetate or dipropionate, such as for example cocodimethyl sulfopropylbetain, laurylbetain, cocamidopropylbetain or sodium cocamphopropionate.

Furthermore, suitable cationic tensides may be for example quaternized ammonium compounds such as cetyltrimethylammonium chloride (INCI: cetrimonium chloride), hydroxyethylcetyldimonium phosphate (INCI: Quaternium-44), Luviquat® Mono LS (INCI: cocotrimoniummethosulfate), poly(oxy- 1,2-ethandiyl), (octadecylnitrilio)tri-2, l-ethandiyl)tris-(hydroxy)- phosphate (INCI Quaternium-52).

The tensides, useful as foaming agents, may be used from 0.1 to 20 percent by weight of the composition.

Preferred are amounts from 1 to 10 percent by weight calculated in form of the pure compounds.

As dye forming components can be used common primary intermediates and couplers as well as known dye intermediates.

The primary intermediates may be p-phenylenediamine type, p-amino- phenol type, 4,5-diaminopyrazole type primary intermediates.

Examples of precursors suitable for use according to the present invention and which may function as primary intermediates are: 1,4-diamino- benzene (p-phenylenediamine); l,4-diamino-2-methyl-benzene

(p-toluylenediamine); l,4-diamino-2,6-dimethyl-benzene; l,4-diamino-3,5- diethyl-benzene; l,4-diamino-2,5-dimethyl-benzene; l,4-diamino-2,3- dimethylbenzene; 2-chloro-l,4-diaminobenzene; l,4-diamino-2-(thiophen-2- yl)benzene; l,4-diamino-2-(thiophen-3-yl)benzene; l,4-diamino-2-(pyridin-3- yl)benzene; 2,5-diaminobiphenyl; l,4-diamino-2-methoxymethyl-benzene; l,4-diamino-2-aminomethylbenzene; l,4-diamino-2-hydroxymethyl-benzene; l,4-diamino-2-(2-hydroxyethoxy)benzene; 2-(2-(acetylamino)ethoxy)- 1,4- diaminobenzene; 4-phenylamino-aniline; 4-dimethylamino-aniline; 4-diethylamino-aniline; 4-dipropylamino-aniline; 4-[ethyl(2- hydroxyethyl)amino]-aniline; 4-[di(2-hydroxyethyl)amino]-aniline; 4-[di(2- hydroxyethyl)amino]-2-methyl-aniline; 4-[(2-methoxyethyl)amino]-aniline; 4- [(3 -hydroxypropyl)amino] -aniline; 4-[(2,3-dihydroxypropyl)amino-aniline; l,4-diamino-2-(2-hydroxyethyl)-benzene; l,4-diamino-2-(l-methylethyl)- benzene; l,3-bis[(4-aminophenyl)(2-hydroxyethyl)amino]-2-propanol;

1.4- bis[(4-aminophenyl)amino]-butane; l,8-bis(2,5-diaminophenoxy)-3,6- dioxaoctane; 4-amino-phenol; 4-amino-3 -methyl-phenol; 4-amino-3- (hydroxymethyl)-phenol; 4-amino-3-f uoro-phenol; 4-methylamino-phenol; 4-amino-2-(aminomethyl)-phenol; 4-amino-2-(hydroxymethyl)-phenol; 4-amino-2-f uorophenol; 4-amino-2-[(2-hydroxyethyl)-amino]methylphenol; 4-amino-2-methyl-phenol; 4-amino-2-(methoxymethyl)-phenol; 4-amino-2-(2- hydroxyethyl)-phenol; 5 -amino- salicylic acid; 2,5-diamino-pyridine; 2,4,5,6- tetramine-pyrimidine; 4,5-diamino-l-(2-hydroxyethyl)- lH-pyrazole;

4.5- diamino- l-(l-methylethyl)-lH-pyrazole; 4,5-diamino- l-[(4- methylphenyl)methyl]-lH-pyrazole; l-[(4-chlorophenyl)methyl]-4,5-diamino- lH-pyrazole; 4,5-diamino-l-methyl- lH-pyrazole; 2-aminophenol; 2-amino-6- methylphenol; and 2-amino-5-methylphenol.

The couplers may be m-dihydroxybenzene type, m-aminophenol type, m-phenylenediamine type or the o-aminophenol type couplers.

Examples of couplers suitable for use according to the present invention are 2,6-diamino-pyridine; 2-amino-4-[(2-hydroxyethyl)amino]anisole; 2,4-diamino- l-fluoro-5-methylbenzene; 2,4-diamino-l-methoxy-5- methylbenzene 2,4-diamino-l-ethoxy-5-methyl-benzene; 2,4-diamino-l-(2- hydroxyethoxy)-5-methylbenzene; 2,4-di[(2-hydroxyethyl)amino]- l,5- dimethoxybenzene; 2,3-diamino-6-methoxy-pyridine; 3-amino-6-methoxy-2- (methylamino)pyridine; 2,6-diamino-3,5-dimethoxypyridine; 3,5-diamino-2,6- dimethoxy-pyridine; 1,3-diaminobenzene; 2,4-diamino-l-(2- hy droxyethoxy)benzene ; 1 , 3 -diamino-4-(2, 3 -hy droxypropoxy)benzene ;

2,4-diamino- l,5-di(2-hydroxyethoxy)-benzene; l-(2-aminoethoxy)-2,4- diaminobenzene; 2-amino-l-(2-hydroxyethoxy)-4-methylaminobenzene;

2.4- diaminophenoxyacetic acid ester; 3 -[di(2-hydroxyethyl)amino] aniline;

4- amino-2-di[(2-hydroxyethyl)amino]- l-ethoxy-benzene; 5-methyl-2-(l- methylethyl)phenol; N-(3-dimethylamino-phenyl)-urea; 3-[(2- hy droxyethyl)amino] aniline ; 3 - [(2-aminoethyl)amino] aniline ; 1 , 3 -di(2,4- diaminophenoxy)propane; di(2,4-diaminophenoxy)methane; l,3-diamino-2,4- dimethoxybenzene; 2,6-bis(2-hydroxyethyl)aminotoluene; 4-hydroxyindole; 3-dimethylaminophenol; 3-diethylaminophenol; 5-amino-2-methylphenol; 3-amino-2,6-dimethylphenol; 5-amino-4-f uoro-2-methyl-phenol; 5-amino-4- methoxy-2-methylphenol; 5-amino-4-ethoxy-2-methylphenol; 3-amino-2,4- dichlorophenol; 5-amino-2,4-dichlorophenol; 3-amino-2-methyl-phenol; 3-amino-2-chloro-6-methylphenol; 3-aminophenol; 2-[(3-hydroxyphenyl)- amino]acetamide; 5-[(2-hydroxyethyl)amino]-4-methoxy-2-methylphenol;

5- [(2-hydroxyethyl)amino]-2-methylphenol; 3-[(2-hydroxyethyl)amino]- phenol; 3-[(2-methoxyethyl)amino]-phenol; 5-amino-2-ethyl-phenol; 5-amino-

2- methoxyphenol; 2-(4-amino-2-hydroxyphenoxy)ethanol; 5-[(3- hydroxypropyl)amino]-2-methylphenol; 3-[(2,3-dihydroxypropyl)amino]-2- methylphenol; 3-[(2-hydroxyethyl)amino]-2-methylphenol; 2-amino-3- hydroxypyridine; 5-amino-4-chloro-2-methylphenol; 1-naphthol; 2-methyl- 1- naphthol; 1,5-dihydroxynaphthalene; 1,7-dihydroxy-naphthalene;

2.3- dihydroxynaphthalene, 2,7-dihydroxy-naphthalene; 2-methyl- 1-naphthol- acetate; 1,3-dihydroxybenzene; l-chloro-2,4-dihydroxy-benzene; 2-chloro- 1 , 3 -dihydroxybenzene ; 1 ,2-dichloro-2,4-dihydroxy-4-methylbenzene ;

1.5- dichloro-2,4-dihydroxy-benzene; l,3-dihydroxy-2-methyl-benzene;

3.4- methylenedioxy-phenol; 3,4-methylenedioxy-aniline; 6-bromo- 1-hy droxy- 3,4-methylenedioxybenzene; 3,4-diaminobenzoic acid; 3,4-dihydroxy-6- hydroxy-l,4(2H)benzoxazine; 6-amino-3,4-dihydro- l,4(2H)-benzoxazine;

3 - methyl- l-phenyl-5 -pyrazolone; 5,6-dihydroxyindole; 5,6-dihydroxyindoline; 5-hydroxyindole; and 6-hydroxyindole.

The primary intermediates and couplers can be employed both as free bases and also in form of their physiologically compatible salts with inorganic or organic acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, lactic acid or citric acid.

The composition according to the invention can also contain at a further dye intermediate, such as for example 6-amino-2-methylphenol and 2-amino- 5-ethylphenol.

Even though a broad shade palette can be achieved by combinations of primary intermediates and couplers it might be necessary to add direct dyes to the oxidative colorants in order to obtain brilliant reflexes on the dyed hair. Some of these dyes are also called "booster dyes". The direct dyes that may be used according to the invention are preferably chosen from neutral, acidic or cationic nitrobenzene direct dyes; neutral, acidic or cationic azo direct dyes; neutral, acidic or cationic quinone and in particular anthraquinone direct dyes, azine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.

Such direct-dyeing compounds can be for instance:

- aromatic nitro dye compounds (neutral dyes), such as:

2-amino-3-nitrophenol; 2-[(2-hydroxyethyl)amino]- l-methoxy-5- nitrobenzene; l-(2-hydroxyethoxy)-3-methylamino-4-nitrobenzene; 2,3-(dihydroxypropoxy)-3-methylamino-4-nitrobenzene; l-[(2- ureidoethyl)amino]-4-nitrobenzene; 4-[(2-hydroxyethyl)amino]-3-nitro-l- methylbenzene; l-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Yellow No. 2); l-(2-hydroxyethoxy)-2-[(2-hydroxyethyl)amino]-5-nitrobenzene (HC Yellow No. 4); l-amino-2-[(2-hydroxyethyl)amino]-5-nitrobenzene (HC Yellow No. 5); 4-[(2,3-dihydroxypropyl)amino]-3-nitro-l- trifluoromethylbenzene (HC Yellow No. 6); 3-[(2-aminoethyl)amino]- l- methoxy-4-nitrobenzene hydrochloride (HC Yellow No.9); l-chloro-2,4-bis- [(2-hydroxyethyl)amino]-5-nitrobenzene (HC Yellow No. 10); 2-[(2- hydroxyethyl)amino]-5-nitrophenol (HC Yellow No. 1 1); l-chloro-4-[(2- hydroxyethyl)amino]-3-nitrobenzene (HC Yellow No. 12); 4-[(2- hydroxyethyl)amino]-3-nitro- l-trifluoromethyl-benzene (HC Yellow No. 13); 4-[(2-hydroxyethyl)amino]-3-nitro-benzonitrile (HC Yellow No. 14); 4-[(2- hydroxyethyl)amino]-3-nitro-benzamide (HC Yellow No. 15); l,4-diamino-2- nitrobenzene; l,4-bis[(2-hydroxyethyl)amino]-2-nitrobenzene; 2-amino-4,6- dinitro-phenol; 4-amino-3-nitrophenol; l-amino-5-chloro-4-[(2- hydroxyethyl)amino]-2-nitrobenzene; 4-[(2-hydroxyethyl)amino]-3- nitrophenol; l-[(2-aminoethyl)amino]-4-(2-hydroxyethoxy)-2-nitrobenzene (HC Orange No. 2); 4-(2,3-dihydroxypropoxy)- l-[(2-hydroxyethyl)amino]-2- nitrobenzene (HC Orange No. 3); 2-[(2-hydroxyethyl)amino]-4,6-dinitro- phenol; 4-ethylamino-3-nitrobenzoic acid; 2-[(4-amino-2-nitrophenyl)amino]- benzoic acid; 2-chloro-6-ethylamino-4-nitrophenol; 2-amino-6-chloro-4- nitrophenol ; 4- [(3 -hy droxypropyl)amino] -3 -nitrophenol ; 2, 5 -diamino-6- nitropyridine; l,2,3,4-tetrahydro-6-nitroquinoxaline; 4-amino-2-nitro- diphenylamine (HC Red No. 1); 4-amino- l-[(2-hydroxyethyl)amino]-2- nitrobenzene (HC Red No. 3); l-amino-4-[(2-hydroxyethyl)amino]-2- nitrobenzene (HC Red No. 7); l-amino-5-chloro-4-[(2,3- dihydroxypropyl)amino]-2-nitrobenzene (HC Red No. 10); 5-chloro- l,4- [di(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC Red No. 1 1); l-amino-4- [di(2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride (HC Red No. 13); 7-amino-3,4-dihydro-6-nitro-2H- l,4-benzoxazine (HC Red No. 14); 4-[(3- hydroxypropyl)amino] -3 -nitrophenol (HC Red BN); l-amino-3-methyl-4-[(2- hydroxyethyl)amino]-6-nitrobenzene (HC Violet No. 1); l-(3- hydroxypropylamino)-4-[di(2-hydroxyethyl)amino]-2-nitrobenze ne (HC Violet No. 2); l-(2-hydroxyethyl)amino-2-nitro-4-[di(2-hydroxyethyl)amino]- benzene (HC Blue No. 2); l-methylamino-4-[methyl-(2,3- dihydroxypropyl)amino]-2-nitrobenzene (HC Blue No. 6); l-[(2,3- dihydroxypropyl)amino]-4-[ethyl-(2-hydroxyethyl)amino]-2-nit robenzene hydrochloride (HC Blue No. 9); l-[(2,3-dihydroxypropyl)amino]-4-[methyl- (2-hydroxyethyl)amino]-2-nitrobenzene (HC Blue No. 10); 4-[di(2- hydroxyethyl)amino]- l-[(2-methoxyethyl)amino]-2-nitrobenzene (HC Blue No. 11); 4-[ethyl-(2-hydroxyethyl)amino]-l-[(2-hydroxyethyl)amino]-2- nitrobenzene hydrochloride (HC Blue No. 12); 2-((4-amino-2- nitrophenyl)amino)-5-dimethylaminobenzoic acid (HC Blue No. 13); N,N- dimethyl-3 - { [4-(methylamino)-9, 10-dioxo-9, 10-dihydro- 1 - anthracenyl]amino}-N-propyl-l-propanaminium bromide (HC Blue No. 16);

basic dyes (cationic dyes), such as:

2-[2-((2,4-dimethoxyphenyl)amino)ethenyl]-l,3,3-trimethyl-3H -indol- 1-ium-chloride (C.I. 48055; Basic Yellow 1 1); 3-methyl-l-phenyl-4-[(3- (trimethylammonio)phenyl)azo]-pyrazol-5-on-chloride (C.I. 12719; Basic Yellow 57); l-methyl-4-((methylphenylhydrazono)methyl)-pyridinium methylsulfate (Basic Yellow 87); 2-[(4-aminophenyl)azo]- 1,3 -dimethyl- 1H- imidazolium chloride (Basic Orange 31); 3,7-diamino-2,8-dimethyl-5- phenylphenazinium-chloride (C.I. 50240; Basic Red 2); l,4-dimethyl-5-[(4- (dimethylamino)phenyl)azo]- l,2,4-triazolium-chloride (C.I. 1 1055; Basic Red 22); 2-[((4-Dimethylamino)phenyl)azo]- l,3-dimethyl-lH-imidazolium chloride (Basic Red 51); 2-hydroxy-l-[(2-methoxyphenyl)azo]-7- (trimethylammonio)-naphthalin-chloride (C.I. 12245; Basic Red 76); bis [4- (dimethylamino)phenyl][4-(methylamino)phenyl]carbenium-chlor ide (C.I. 42535; Basic Violet 1); tris[4-(dimethylamino)phenyl]carbenium-chloride (C.I. 42555; Basic Violet 3); 2-[3,6-(diethylamino)dibenzopyranium-9-yl]- benzoesaure-chloride (C.I. 45170; Basic Violet 10); di(4-aminophenyl)(4- amino-3-methylphenyl)carbenium-chloride (C.I. 42510; Basic Violet 14); 9-(dimethylamino)-benzo[a]phenoxazin-7-ium-chloride (C.I. 51175; Basic Blue 6); di[4-(diethylamino)phenyl] [4-(ethylamino)naphthyl]carbenium- chloride (C.I. 42595; Basic Blue 7); 3,7-di(dimethylamino)phenothiazin-5- ium-chloride (C.I. 52015; Basic Blue 9); l-methylamino-4-(amino-N- propyltrimethylammonium)anthraquinone methyl sulf at. (C.I. 61512; Basic Blue 22); di[4-(dimethylamino)phenyl] [4-(phenylamino)naphthyl]carbenium- chloride (C.I. 44045; Basic Blue 26); 2-[(4-(ethyl(2- hydroxyethyl)amino)phenyl)azo]-6-methoxy-3-methyl-benzothiaz olium- methylsulfate (C.I. 1 1154; Basic Blue 41); 4-[(2,6-dichlorophenyl) (4-imino- 3,5-dimethyl-2,5-cyclohexadien-l-ylidene) methyl]-2,6-dimethylaniline phosphate(l : l) (C.I. Basic Blue 77); 3-[(4-amino-6-bromo-5,8-dihydro-l- hydroxy-8-imino-5-oxo-2-naphthalenyl)amino]-N,N,N- trimethylbenzenaminium chloride (C.I. 56059; Basic Blue 99); bis[4- (diethylamino)phenyl]phenylcarbenium-hydrogenosulfate(l : 1) (C.I. 42040; Basic Green 1); l,3-bis[(2,4-diamino-5-methylphenyl)azo]-3-methylbenzene (C.I. 21010;Basic Brown 4); l-[(4-aminophenyl)azo]-7-(trimethylammonio)- 2-naphthol-chloride (C.I. 12250; Basic Brown 16); l-[(4-amino-2- nitrophenyl)azo]-7-(trimethylammonio)-2-naphthol-chloride (C.I. 12251 ; Basic Brown 17);

and also 2-((4-(acetylamino)phenyl)azo)-4-methylphenol (C.I. 1 1855;

Disperse Yellow 3); l-(4'-aminophenylazo)-4-nitrobenzene (C.I. 11005; Disperse Orange 3); l-[di(2-hydroxyethyl)amino]-3-methyl-4-[(4- nitrophenyl)azo] -benzene (C.I. 1 1210, Disperse Red 17) and 4-((4-(di(2- hydroxyethyl)amino)phenyl)azo)-aniline (Disperse Black 9).

Among the azo direct dyes that may also be included are the following dyes described in the Colour Index International, 3rd edition:

Acid Yellow 1 ; Acid Yellow 9; Acid Yellow 23; Acid Yellow 36; Acid Orange 7; Acid Orange 24; Acid Red 33 ; Acid Red 35; Acid Red 92; Acid Violet 43 ; Acid Violet 49; Acid Blue 1; Acid Blue 3 ; Acid Blue 9; Acid Blue 62; Acid Black 1.

These dye compounds may be contained in the dye composition of the invention in amounts from about 0.01 to 4.0 percent by weight of the composition.

Among the natural direct dyes that may be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin and apigenidin. Extracts or decoctions containing these natural dyes may also be used and, especially, henna-based poultices or extracts.

The total amount of dyes can range from 0.01 to 10 percent by weight of the composition, preferably from 0.01 to 8% by weight.

Suitable alkaline reacting agents may be selected from ammonium carbonate, ammonium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate as well as ammonium hydroxide, monoethanolamine (MEA), l-amino-2-propanol, 2-amino-2-methyl-propanol (AMP), 2-amino-2- methyl- 1,3 -propanediol, 2-amino-2-ethyl-l,3-propanediol and tris(hydroxymethyl)-aminomethane (Tromethamine, Tris).

Ready-to-use composition may also contain a combination of at least one inorganic alkaline reacting salt with at least one alkanolamine.

The total amount of alkaline reacting agent can vary from 0.5 to 10 percent by weight of the composition.

Auxiliary agents may be for instance ammonium chloride, ammonium citrate, triammonium phosphate or amino acids, such as glycine or arginine, and salts thereof.

The composition according to the invention may also contain one or more additive. The additives may be used in lower amounts, such as stabilizers and complexing agents, and are preferably selected from: salicylic acid, 8-hydroxyquinoline, 1 -hydroxy ethane- 1, 1 -diphosphonic acid, ethylenediamine tetraacetic acid (EDTA), ethylenediamine-N,N'-disuccinic acid (EDDS), iminodisuccinic acid and the corresponding sodium or ammonium salts thereof.

A perfume may also be added optionally.

Auxiliary agents may be used in variable amounts from 1 to 10% by weight of the composition, whereas the additives may be used in much lower amounts, e.g. in amounts form 0.1 to 1.0% by weight each of the composition.

The composition according to the invention may also contain cationic polymers with the INCI name Polyquaternium, such as for example copolymers of vinylpyrrolidone/N-vinylimidazolium salts (products commercially available under the name "Luviquat®"), copolymers of N-vinylpyrrolidone/dimethylaminoethyl methacrylate, quaternized with diethylsulfate, copolymers of N-vinylcaprolactam/N-vinylpyrrolidone/N- vilylimidazolium salts; cationic cellulose derivatives (Polyquaternium-4 and - 10), acrylamide/diallyldimethylammonium chloride copolymers (Polyquaternium-7). A particularly preferred cationic polymer is the, if desired crosslinked, poly(methacryloyloxyethyltrimethylammonium chloride) with the INCI name Polyquaternium-37.

The preferred on-head amount of such polymers may vary from 0.01 to 1% by weight, more preferably from 0.01 to 0.5% by weight of the composition.

Hydrogen peroxide solutions suitable for the current invention are preferably clear aqueous solutions which can be stabilized as usually. The concentration of hydrogen peroxide may vary in a wide range, preferred are commercially available qualities such as aqueous solutions of 3%, 6%, 9%, or 12% strength.

Preferentially the solutions having the above standard strength are mixed with the dye solutions in a 1 : 1, 1 : 1.5 or 1 :2 ratio, whereby the hydrogen peroxide concentration in the ready-to-use composition normally does not exceed 8% by weight of the composition, preferably it does not exceed 6% by weight of the composition and more preferably it ranges from 1 to 6% by weight of the composition or the amount of the hydrogen peroxide adduct ranges from 2.5% to 17% by weight of the composition.

Besides hydrogen peroxide, it is also possible to use a hydrogen peroxide adduct from which hydrogen peroxide is split off, for example a urea-hydrogen peroxide adduct (urea peroxide, carbamide peroxide), a melamine-hydrogen peroxide adduct (melamine peroxide), an amino acid-hydrogen peroxide adduct typified by a histidine-hydrogen peroxide adduct (histidine peroxide).

Preferably, urea peroxide is used.

The amount of released hydrogen peroxide normally does not exceed 8% by weight referred to the ready-to-use composition, preferably it does not exceed 6%. More preferably, the hydrogen peroxide adduct provides a one- head concentration of 1 to 6% by weight of the composition.

The pH of the ready-to-use composition may vary between 7.5 and 11.5, preferably from 8.5 to 10.5.

The composition according to the invention is a solution having a viscosity that may vary from 10 to 40 cP at 22°C.

The ready-to-use compositions free of any insoluble materials are ideal for being applied to the dry hair by a foamer device which can either be a squeeze foamer, a pump foamer or a squeeze foamer for upside-down usage.

Besides the above-mentioned sophisticated foamers, the foam of the composition can also be produced by means of a hair color shaker bowl of 300-500 ml volume which gives a useful foam quality after intense shaking of the composition for approximately 10 to 20 seconds.

The composition produces a foam quality which is widely independent from the used foamer device; especially it is independent from mesh coarsenesses of all tested foamer heads.

Once the foam is applied, hair is massaged best in a circular motion until it is completely saturated in foam. After a few minutes the drip-free foam transforms into a gel which does not drip from the head either. The massage can be continued occasionally.

The advantage of this composition is to start from an easily applicable mousse which transforms into a viscous gel which in consideration of its consistency would have normally been applicable by brush and bowl technique only.

The foamable composition may be used for coloring human hair and after application to the head transforms into a drip-free gel in the course of its application and the period of processing.

By the gel formation it is ensured that a maximum of active ingredients are in contact with the hair after a short transition time and can diffuse to the fibers either to form dyes in case of an oxidative coloration or to deposit dyes in case direct dyes are used.

The processing time is predominantly depending from the design of the colorants and the target shades and is usually between 10 minutes up to 1 hour. Shorter processing times are chosen for fast developing colorants which normally require a somewhat higher dye load compared to colorants which require a standard processing time of 30 minutes.

Completely unexpected was that by the presence of a thermo-sensitive polymer all desired properties were obtained. Namely, the foamable hair colorant composition is easy foamable and applicable, a drip-free foam and finally a drip-free and very compact gel on the head. All these factors ensure easy and fast application combined with outstanding performance.

An aqueous system as chassis, which is free of commonly used higher alcohols, waxes and emulsifiers, is used. Consequently, the viscosity of the solution is low. The addition of a thermo- sensitive polymer does not significantly change the viscosity of this system.

Once the foam is applied to the head the consistency of the foam changes very quickly. Upon contacting the hair, the foam becomes very creamy and transforms progressively into a drip-free coloring gel whereby the transformation of important amounts of the foam occurs within a few minutes, which is accompanied by a strong increase in viscosity. In the course of the transition from the starting liquid to the gel on the head, neither in the status of the mousse, nor in the form of the gel, nor in the transition phase, any dripping off the head is observed. Surprisingly, the compositions have not exhibited any inconveniences in terms of delayed gelation although the tested compositions were highly salt-loaded.

Neither the thermo- sensitive polymer nor the high load with various color ingredients has any significant impact in the excellent foaming and gelation properties of the composition once applied to the head. The foam exhibits excellent adhesion properties on the head. As important amounts of foam are already transformed into a gel within minutes the composition has the appropriate physical consistency that the active ingredients of the colorant can efficiently interact with hair fibers and provide the desired color.

With the current invention easily applicable hair colorants can be prepared which require standard processing times of 30 minutes and, beyond that, also fast developing colorants which require not more than 10 minutes processing time. The latter demonstrates the outstanding properties of the current invention as fast developing color foams have been unknown so far.

The composition of the invention is particularly well suited for using in cosmetic hair treatments, especially for simultaneous lightening and coloring human hair, in particular, for the treatment of dyed hair which shows naturally pigmented regrow at the root parts.

Due to its excellent overall properties the foam composition containing a thermo-sensitive polymer is not only suitable for full-head applications but also for creative stand techniques.

Examples

Example 1: Hydrogen peroxide solutions

The recipes of the developer compositions given in Table 1 represent widely used standard compositions (not inventive). The pH of the compositions is 3.0.

Table 1

Formulation

Ingredient Example la Example lb

Water 82.30 g 65.29 g

Hydrogen peroxide 35% 17.14 g 25.71 g

Disodium pyrophosphate 0.05 g 0.05 g

Sodium stannate 0.10 g 0.10 g

Etidronic acid 0.04 g 0.04 g

Pentasodium pentetate 0.07 g 0.07 g

Phosphoric acid 85% 0.16 g 0.16 g

100.00 g 100.00 g

Developer concentration 6% by weight 9% by weight

Examples 2-5: Color Mousse 30 min, compositions and shades

The following compositions were prepared, mixed 1 : 1 (w/w) with a standard developer according to Example 1. Viscosities of the compositions were all in the range from 15 to 30 cP measured at 22°C (viscosity measurements were performed with a Brookfield DV-II Viscometer D 220).

The ready-to-use compositions were applied to the head by means of a pump foamer. After processing for 30 minutes the hair was rinsed out, washed with a shampoo and dried. Compositions and color results are given in Table 2. Table 2

Formulation

Ingredient Example 2 Example 3 Example 4 Example 5

Bis-Methoxy PEG- 13 PEG-438/

PPG-110 SMDI copolymer 2.00 g 1.80 g 2.000 g

Bis-Methoxy PEG- 13 PEG-502/

PPG-57/SMDI copolymer 1.50 g

Tego betain L7 30% 18.00 g 10.00 g 20.000 £

Plantacare 818 UP 12.00 g 5.00 g

EDTA 0.30 g 0.30 g 0.30 g 0.300 g

Sodium sulfite 0.40 g 0.40 g 0.40 g 0.400 g

Erythorbic acid 0.40 g 0.40 g 0.40 g 0.400 g

Glycine 8.00 g

Toluene-2,5-diamine sulfate 0.20 g 0.240 g

2-Methoxymethyl-p-phenylenediamine 2.97 g

Resorcinol 1.10 g 0.60 g 0.070 g

2-Methylresorcinol 0.10 g 0.080 g m-Aminophenol 0.70 g 0.010 g

2,4-Diaminophenoxyethanol HC1 0.56 g 0.002 g

4-Amino-2-hydroxytoluene 1.20 g

1 -Hydroxy ethyl-4, 5- diaminopyrazole sulfate 0.08 g 2.00 g

p-Aminophenol 1.00 g 0.030 g

3-Amino-2,6-dimethylphenol 0.55 g

2-Amino-6-chloro-4-nitrophenol 0.20 g

Basic Red 51 0.12 g

Ethanolamine 2.74 g 3.13 g 0.41 g 4.170 g

Aminomethyl propanol (AMP) 2.50 g

Ammonium hydroxide 28% 5.20 g 3.80 g 6.000 g

Poly quaternium-37 0.20 g 0.10 g 0.020 g

Polyquaternium-22 0.50 g

Perfume 0.30 g 0.40 g 0.50 g 0.600 g

Water ad 100.00 g 100.00 g 100.00 g 100.000 ;

Hydrogen peroxide 1 : 1,

concentration * ⁾ 6% 9% 6% 9% pH 8.9 9.9 9.9 10.2

Shade black intense red golden red light blon

* according to Example la or lb, respectively

Examples 6-7: Color Mousse 10 min, compositions and shades

The following compositions were prepared, mixed 1 : 1 (w/w) with a standard developer according to Example 1. Viscosities of both compositions were in the range from 15 to 30 cP measured at 22°C.

The ready-to-use compositions were applied to the head by means of a squeeze foamer. After processing for 10 minutes the hair was rinsed out, washed with a shampoo and dried. Compositions and color results are given in Table 3.

Table 3

Formulation

Ingredient Example 6 Example 7

ExpertGel EG 56 2.00 g 1.50 g

ExpertGel EG 230 0.50 g

Tego betain L7 30% 20.00 g 15.00 g

EDTA 0.30 g 0.30 g

Sodium sulfite 0.40 g 0.40 g

Erythorbic acid 0.40 g 0.40 g

Ammonium chloride 4.00 g 6.00 g

Toluene-2,5-diamine sulfate - 1.30 g

Toluene-2,5-diamine 3.50 g -

Resorcinol 2.20 g 0.30 g

2-Methylresorcinol 0.50 g 0.50 g m-Aminophenol 1.30 g 0.07 g

2,4-Diaminophenoxyethanol HC1 0.70 g -

4-Amino-2-hydroxytoluene - 0.01 g

Ethanolamine 4.41 g 5.86 g

Polyquaternium-22 0.10 g 0.05 g

Perfume 0.20 g 0.20 g

Water ad 100.00 g 100.00 g

Hydrogen peroxide 1 : 1, concentration * ^} 6% 9% pH 9.0 9.2

Shade blue-black mid-blond

* according to Example la or lb,

respectively