WO2004045567A1

WO2004045567A1 - Use of ascorbic acid derivatives in hair care products

Info

Publication number: WO2004045567A1
Application number: PCT/EP2003/010472
Authority: WO
Inventors: Philippe Emmanuel Maillan; Horst Westenfelder; Michael Weller
Original assignee: DSM IP Assets BV
Current assignee: DSM IP Assets BV
Priority date: 2002-11-19
Filing date: 2003-09-19
Publication date: 2004-06-03
Anticipated expiration: 2005-05-19
Also published as: AU2003270228A1

Abstract

The invention relates to the use of an ascorbic acid derivative in the manufacture of hair care products for stabilizing the colour of artificially coloured hair, particularly against the impact of actinic radiation.

Description

Use of ascorbic acid derivatives in hair care products

The present invention relates to a novel use of ascorbic acid derivatives in hair care products. In accordance with the present invention it has been found that the treatment of artificially coloured hair with hair care products containing an ascorbic acid derivative results in protection and stabilisation of the colour of the hair. Thus, the present invention, in one aspect, relates to the use of ascorbic acid derivatives in the manufacture of hair care products for protecting and stabilizing artificially coloured hair, particularly against the impact of actinic radiation. In another aspect the invention relates to a method of protecting and stabilizing the colour of artificially coloured hair, particularly against the impact of actinic radiation, by treatment of such hair with a hair care product containing an ascorbic acid derivative.

The term "artificially coloured hair" as used herein denotes hair that has been coloured by any method of dyeing hair, e.g.by oxidative dyeing or by semi-permanent dyeing.

The term " hair care product" as used herein denotes any conventional hair care product,such as shampoos, conditioners, tonics, styling gels, mousses, hair sprays, pomades, setting lotions, colouring and permanent waving compositions. Of particular interest for the purpose of the present invention are shampoos, tonics and conditioners.

The term ascorbic acid derivative as used in accordance with the present invention may by any non-toxic, non skin-irritating water-soluble or oil-soluble ascorbic acid derivative. Example of such oil soluble derivatives are ascorbic acid esters of long-chain fatty acids such as ascorbyl palmitate, ascorbyl tetraisopalmitate, ascorbyl linoleate, ascorbyl octanoate, Preferred are water soluble ascorbyl derivatives such as sodium ascorbyl phosphate, magnesium ascorbyl phosphate and ascorbyl glycoside. Most preferred is sodium ascorbyl phosphate.

The amount of ascorbic acid derivative in the hair care product for use in accordance with the present invention is suitably in the range from about 0.0001 wt.-% to about 10 wt.-%, preferably from about 0.01 wt.-% to about 5 wt.-%, and most preferably from about 0.1 wt.-% to about 3 wt.-%. The ascorbic acid derivative may be incorporated in hair care products by adding it to the final formulation or at any appropriate intermediate step in the manufacture of said products.

According to one embodiment of the invention, the ascorbyl phosphate is used in combination with one or more agents selected from UV screening agents, vitamin A or derivatives thereof, vitamin E or derivatives thereof, a vitamin from the B complex, panthenol, phytantriol or derivatives thereof.

The term "UV screening agent" means a compound or composition that absorbs UV radiation in the range of about 320 nm to about 400 nm (UV-A) or in the range of about 280 nm to about 320 nm (UV-B). Such UV filters include, for example, dibenzoylmethane derivatives such as butyl methoxydibenzoylmethane (PARSOL 1789), benzylidene- cyanoacetates such as 4-methoxy-benzylidene-cyanoacetic acid n-hexyl ester, triazine derivatives such as 4,4'-(6-(bis(2-ethyl-hexyl)-amino)-s-triazine-2,4-diyl)-diresorcinol, anilinomethylene derivatives such as 2-(4-ethoxy-anilinomethylene)-propanedioic acid diethyl ester, camphor derivatives sich as 4-methyl benzylidene camphor (PARSOL 5000) and terephtalylidene-3,3'-dicamphor-10,10'-disulfonic acid, benzimidazol derivatives such as 2,2'-(l,4-phenylen)-bis-lH-benzimidazol-4,6-disulfonic acid Na salt; cinnamates such as octyl methoxycinnamate (PARSOL MCX); salicylic acid derivatives such as octyl salicylate and homomenthyl salicylate; p-aminobenzoic acid derivatives such as p- dimethylaminobenzoic acid 2-ethylhexyl ester; benzophenone derivatives such as 2- hydroxy-4-methoxy-benzophenone, and 4-phenyl-benzophenone-2~carboxylic acid 2- ethylhexyl ester; anthranilates such as homomenthyl-N-acetylanthranilate and menthylanthranilate; acrylates such as 2-ethylhexyl-2-cyano-3,3-diphenylacrylate (PARSOL 340); benzimidazole derivatives such 2-phenylbenzimidazole-5-sulphonic acid (PARSOL HS); benzoxazole derivatives such as 2-phenyl-5-methyl-benzoxazole, malonate derivatives such as dimethico diethylbenzalmalonate (PARSOL SLX); triazine derivatives such as 2,4-Bis((4-(ethyl-hexylox)-2-hydroxy)-phenyl)-6-(4-methoxyphenyl)-l,3,5- triazine (Tinosorb S - Ciba); benzotriazol derivatives such as 2,2'-Mefhylene-bis-(6(2H- benzotriazol-2-yl)-4-(l,l,3,3,-tetramethylbutyl)phenol) (Tinosorb M - Ciba), Uvinul T- 150 (BASF), UVASORB HEB (3V-Sigma). In preferred compositions the UV-A filter is selected from the group consisting of PARSOL 1789, 4,4'-(6-(bis(2-ethyl-hexyl)-amino)-s- triazine-2,4-diyl)-diresorcinol (Triazin), 2-(4-ethoxy-anilinomethylene)-propanedioic acid diethyl ester, and mixtures thereof, PARSOL MCX or PARSOL SLX. Further examples of UV filters for use in the present invention are :

Compounds as disclosed in European patent application No. 02015849.9 filed 16.7.2002 the contents of which are incorporated herein for reference, and which are characterized by the presence of one each of the structural elements (H^C^-Si- (I) and -O-Si(CH₃)₃ (II), and 2-200 elements in arbitrary order selected from -O-Si(CH₃)[CH(CH₃)R¹]- (Ilia), -O- Si(CH₃)(CH₂-CH₂-R¹)- (Illb), -O-Si(CH₃)[C(=CH₂)R¹]- (IIIc), and -O- Si(CH₃)(CH=CH-R¹)- (Hid) wherein R¹ is a UV light absorbing group; and 2-200 elements in arbitrary order selected from Ilia, Illb, IIIc and Hid wherein R¹ is hydrogen or a lipophilic group; and, optionally, 1-100 elements in arbitrary order selected from Ilia, Illb, IIIc and Hid wherein R¹ is a group which is able to form ionogenic or hydrogen bonds, and, further optionally, 1 - 20 elements in arbitrary order of formula -O- SiH(CH₃)-;

Compounds as disclosed in European patent application No. 02008419.0 filed 12.4.2002 the contents of which are incorporated herein for reference, which comprise a unit of the formula

Z-Si-0_(3.a)/2

wherein

a is 0, 1 or 2,

R¹ is hydrogen, a saturated or unsaturated CrC₃₀hydrocarbon group or a trimethylsilyloxy group; and

Z is an amino substituted hydroxybenzophenone of the formula

wherein

R and R independently are hydrogen, Cr nalkyl, C -C₂oalkenyl, C₃-Cιocycloalkyl or Cs- ocycloalkenyl or R and R , together with the nitrogen atom they are bound to, form a 5 to 6 membered ring;

X is -O- or -NR⁵- wherein R⁵ is hydrogen, C₁-C₂₀alkyl, C₂-C₂oalkenyl, C₃-Cιocycloalkyl or C₃-Cιocycloalkenyl; and

Y is a divalent C₃-C₁₂alkylene or alkenylene chain;

and, optionally, a unit of the formula

R b

Si-0 ( -b)/2 wherein

b is 0, 1, 2, 3; and

R is hydrogen, a saturated or unsaturated -C₃ohydrocarbon group or a trimethylsilyloxy group;

Compounds as disclosed in European patent application No. 02002093.9 filed 12.2.2002 the contents of which are incorporated herein for reference, and which are of the general formulas

wherein m is 1 or 2; R and R are identical or different electron-withdrawing groups, or one of R and R is hydrogen and the other of R¹ and R² is an electron-withdrawing group; R³, R⁴, R⁵, are R⁶ are, independently, hydrogen, alkyl or aryl; R³ and R⁵ and/ or R⁴, and R⁶ taken together with the carbon atoms to which they are attached, may form a 5 or 6 membered ring which optionally is substituted with one to four alkyl or alkoxy groups; X is a moiety R⁷ , when m is 1; and is alkylene or poly(oxyalkylene) when m is 2; and R⁷ is hydrogen, alkyl, alkoxyalkyl or aryl; and

Compounds as disclosed in European patent application No. 02014158.6 filed 25.6.2002 the contents of which are incorporated herein for reference, and which are of the general formula I

wherein R¹ and R² are, independently from each other, hydrogen; halogen; hydroxy; ( - o)- alkyl; (C₂-C₂o)-alkenyl; or (Cι-C₂o)-alkoxy; X is oxygen or an imino group, optionally substituted with R¹; R³ and R⁴ are, independently from each other, cyano; -COOR⁵; -COR⁶; -CONH₂; -CONHR⁷; or -CONR⁸R⁹; R⁵, R⁶, R⁷, R⁸ and R⁹ are, independently from each other, hydrogen; (C₁-C₂o)-alkyl, wherein one or more methylene groups are optionally replaced by one or more oxygens; ( -C^-haloalkyl; (C₂-C₂o)-alkenyl, optionally substituted by tri-(Ci-C₅)-alkylsilyl, triphenylsilyl or a group -Si [CH₃]_n[OSi(CH₃)₃]₃-_n> wherein n is 0, 1, 2 or 3.

Prefered UV filters are PARSOL SLX and PARSOL 1789.

The sunscreens agents may be present in the hair care products in an amount from about 0.01 wt.-% to about 5.0 wt.-%.

A vitamin A derivative for use in the present invention is, e.g. a fatty acid ester such as vitamin A acetate or palmitate which may be present in the hair care products in an amount from about 0.01 wt.-% to about 1.00 wt.-%. A vitamin E derivative for use in the present invention is, e.g. tocopheryl acetate. Tocopheryl acetate may be present in the hair care products in an amount from about 0.05 wt.-% to about 5 wt.-%. Examples of vitamins from the B complex for use in the present invention are vitamin B₂, B₆ and biotin. Vitamin B₂ may be present in the hair care products in an amount from about 0.01 wt.-% to about 1.00 wt.-%. Vitamin B₆ may be present in the hair care products in an amount from about 0.01 wt-% to about 1.00 wt.-%. Biotin may be present in the hair care products in an amount from about 0.001wt.-% to about 0.5 wt.-%. Panthenol may be present in the hair care products in an amount from about 0.05 wt.-% to about 5.00 wt- %. Phytantriol may be present in the hair care products in an amount from about 0.01 wt- % to about 2.5 wt.-%.

For the purpose of the present invention, the hair care products comprising an ascorbic acid derivative may be, otherwise, of conventional composition such as disclosed in general terms in Ullmann's Encyclopedia of Industrial Chemistry (1989), Vol A 12, Hair Preparations, and more specifically, e.g., in International Patent Application No. WO 00/06094, WO 00/07550 and WO 01/06994, the contents of which are incorporated herein for reference.

Thus, a hair shampoo is any composition that contains at least one surfactant suitable for cleaning hair, such as for example, the shampoo compositions set forth in the examples below. The base ingredient of a shampoo composition is a water/anionic surfactant system that emulsifies the accumulated surface oils and removes them during the rinsing process. Suitable anionic surfactants are Cio-₁₈ -alkyl ether sulfates, C₁₀-ι₈ -alkyl sulfates, sulfuric acid fatty alcohol esters and salts thereof like e.g. ammonium, sodium, potassium or mono-, di-or triethanolamine salts. Examples of o-is -alkyl ether sulfates are sodium lauryl ether sulfate, potassium lauryl ether sulfate, ammonium lauryl ether sulfate. Examples of o-is -alkyl sulfates are sodium lauryl sulfate (Sodium Laureth Sulfate), potassium lauryl sulfate and ammonium lauryl sulfate. Sodium Laureth Sulfate is available from Henkel under the tradenames TEXAPON N25 and TEXAPON N28. Still further suitable anionic surfactants include α-olefin sulfonates, alkyl monoglyceride sulfonates, alkyl benzene sulfonates, alkyl sarcosinates, alkyl monoglyceride sulfates, monoalkylether sulfosuccinates, alkyl ether carboxylates and the like. The anionic surfactant can be employed at concentrations within the range from about 5 to about 40 wt%, preferably about 15 wt%.

In the present invention, a "hair conditioner" is any composition that is used to restore the original condition of hair. Such conditioners include, for example, silicones, cationic surfactants and quaternary ammonium compounds, and synthetic cationic polymers. Other components for use in hair care compositions in accordance with the present invention include moisturizing agents, thickeners or viscosity modifying agents for enhancing hand application, lathering agents for increasing foaming, foam stabilizers, and pearlizing agents. Examples of yet other components which are commonly included in hair care compositions are perfumes, pH control agents, colorants, preservatives, and antimicrobials. In a preferred embodiment of the invention, the ascorbic acid derivative is used in combination with a cationic conditioning agents, e.g. those disclosed in International Patent Application WO 00/07550, particularly those referred to collectively as Polyquaternium, see Pharm Ind. 44, Nr. 6, 576-580 (1982) and Cosmetic, Toiletry, and Fragrance Association, CTFA, as well as International Patent Application WO 00/06094, WO 01/06994 e.g Polyquaternium 6, Polyquaternium 7, Polyquaternium 10, Polyquaternium 11, and Polyquaternium 16. The Polyquaternium compounds maybe used, in addition to the ascorbic acid derivative, in amounts of about 0.01 to about 5.0 wt%.

The following Examples illustrate the invention further.

Example 1

Two groups of three medium brown European hair swatches (Kerling International Haarfabrik GmbH, Backnang-Waldrems, cut up with a width of 2 cm) were bleached using BLONDOR CREAM SPECIAL™ (Wella AG, Darmstadt) to medium blonde and dyed to a red shade with an oxidative hair dye (KOLESTON PERFECT™ Extra Red 1+1 (7/64), Grenadine, Wella AG, Darmstadt).

Afterwards the hair swatches were submitted to a standard shampooing. Group 1 of hair swatches was treated with a placebo hair tonic (formulation without Sodium Ascorbyl Phosphate) and group 2 of hair swatches was treated with a hair tonic containing 0.50%

Sodium Ascorbyl Phosphate (STAY-C 50™, Roche Vitamins AG, Basel). All six hair swatches were kept under standard climatic conditions for 1 week. The colour of the hair tresses was measured and specified according to the CIELAB system. The swatches were irradiated with artificial light with the help of a Weather- O meter 12 hours on each side. After totalizing 24h of irradiation, the swatches were removed from the irradiation chamber and the colour of the swatches was measured with the help of a colorimeter.

The effects of Sodium Ascorbyl Phosphate (SAP) were evaluated from the colour changes of the untreated with respect to the treated swatches. The use of SAP in the formulation provided significant protection of the artificial colour of the hair against simulated solar radiation. The composition of the hair tonic was as shown in Table 1 below

Table 1

Ingredients % (w/w)

Water 59.00

Sodium Ascorbyl 0.50

Phosphate

Ethanol 30.00

Isopropanol 10.00

Citric acid 10 % 0.50

100.00

Bleaching

The initial depth of shade of the hair tress was: 4/0. At first, the hair were bleached with BLONDOR CREAM SPECIAL which was mixed in a ratio of 1:2 with a commercially available hydrogen peroxide formulation (with 6 % hydrogen peroxide). The bleaching was performed for 30 min at room temperature. Afterwards a standard hair washing with lauryl ether sulfate was performed. The hair swatches were dried under a hair drier for 30 min. A depth of shade of 6/0 was achieved for the bleached hair swatches.

Dyeing

In the second step, the hair swatches were dyed with KOLESTON PERFECT 1+1 (7/64) which was mixed according to the recommendations of the manufacturer in a ratio 1 : 1 with a commercially available hydrogen peroxide formulation (9 % H₂0₂). The dyeing was performed for 30 min at room temperature. Afterwards, the hair swatches were subjected to a standard hair washing with lauryl ether sulfate. The hair swatches were dried under a hair drier for 30 min. Conditioning of hair swatches

The six dyed hair swatches were stored for 7 days in the dark at standard atmosphere (20 + 2 °C, 65 ± 2 % r. h.).

Treatment with hair tonic with Sodium Ascorbyl Phosphate or placebo

After storage in standard atmosphere, three of the hair swatches (No. 4-6) were treated at room temperature with the hair tonic containing Sodium Ascorbyl Phosphate. For this, the hair tonic was brought onto the hair swatches in a ratio 1:1 (v/w, based on dry hair) with the help of a brush for 2 min. The hair swatches were combed and dried with a hair drier for 30 min.

In parallel, three further hair swatches (No. 1-3) were treated with a placebo formulation, which contained the same ingredients as described above for the hair tonic except Sodium Ascorbyl Phosphate. Then, the hair swatches were stored for 16 h in the dark at standard atmosphere.

Colour measurement

The colour of the hair swatches was measured by means of a Datacolor colorimeter 3890 (Datacolor GmbH, Marl) using the 10° observer and illuminant D65. For the colour measurement of the hair swatches a special sample holder was used. The hair swatches were put on the sample holder after thorough parallelisation and combing. In each case six measurements were performed for each swatch, three measurements on each side of the swatch. The colour values of the hair swatches were calculated with the Datacolor formula which are based on^'the CIELAB system. The colour value; were subjected to statistical evaluation (confidence coefficient: 95 %). The colour of the hair swatches was measured before the irradiation and after 24h of irradiation (12 h on each side of the hair swatch).

Irradiation

The irradiation was performed by means of an Atlas Weather- Ometer ES25 (Atlas, Chicago/USA) which is equipped with a water-cooled high-pressure xenon burner using the filter system inner filter: borosilicate, outer filter: soda lime. The hair swatches were put into a special sample holder for irradiation. They were turned after 12 h of irradiation in order to obtain an even irradiation of the hair swatches. After 24 h of irradiation, the hair swatches were taken out of the irradiation chamber, stored for 2h in the dark at standard atmosphere and the colour of the hair swatches was measured as described above.

During irradiation, the irradiance was kept constant at 0.30 W/m²/nm (recorded at 340 nm with the help of a light monitor system). A mean black standard temperature of 59.6 °C and an average relative humidity of 58.5 % were recorded.

Results

The hair swatches underwent discoloration during exposure to simulated sunlight. After the irradiation time, less pronounced colour changes were analysed for hair swatches treated with the Sodium Ascorbyl Phosphate containing formulation than for hair which was treated with the placebo formulation. Most pronounced are the differences in the Δa and Δb values after the irradiation for placebo- and SAP-treated hair swatches.

ΔE : Change in color (CIE L*a*b measurements)

ΔL : Change in lightness (CIE L*a*b measurements)

Δa : Change in the a value (CIE L*a*b measurements)

Δb : Change in the b value (CIE L*a*b measurements)

s : standard deviation

Figure 1 shows the mean Colour differences (ΔE, CIE L*a*b system) of bleached and dyed hair swatches which were treated with a hair tonic with STAY-C 50 or with a placebo during irradiation (in each case the mean colour values of three hair swatches are given).

Change in color

ΔE

□ Placebo Hair Tonic

M Hair Tonic with 0 5% SAP

Figure 1. Colour changes (as ΔE) of human hair swatches (in each case the mean colour values of three hair swatches is given) which were treated with a Placebo or with a Hair Tonic with SAP after irradiation.

As is apparent from Table 1 und Figure 1 the application of a hair tonic with Sodium Ascorbyl Phosphate onto bleached and oxidatively dyed human hair swatches leads to a significant stabilisation of the hair colour during short irradiation periods (12 hours on each side of the hair swatches).

Example 2

Colour Protective and Styling Hair Mousse

Ingredients INCI Nomenclature % w / w

A) Water Aqua 82.90

STAY-C 50 Sodium Ascorbyl Phosphate 0.50

Celquat L-200 Polyquaternium-4 2.00

Aminoxid WS 35 Cocamidopropylamine Oxide 0.40

Silicone DC 193 PEG- 12 Dimethicone 0.20

Germaben II Propylene Glycol & Diazolidinyl 1.00

PARSOL SLX Dimethico Diethylbenzalmalonate 3.00

B) Propane / Butane 10.00

100.00

Example 3

Shampoo for Hair Colour Protection

Ingredients INCI Nomenclature % w / w

A ) Texapon NSO Sodium Laureth Sulfate 50.00

Carbopol Aqua SF-1 Acrylates Copolymer 7.00

PARSOL SLX Polysilicone 15 1.00

Kathon CG Methylchloroisothiazolinone and 0.10

D-Panthenol 75 L Panthenol 1.00

STAY-C 50 Sodium Ascorbyl Phosphate 0.50

Deionized Water Aqua 29.50

B) NaOH 30% Sodium Hydroxide 1.20

C) Cetiol HE PEG-7 Glyceryl Cocoate 1.00

Tego Betaine F 50 Cocamidopropyl Betaine 5.00

Euperlan PK-3000 Glycol Distearate and Laureth-4 and 3.00

EDETA BD Disodium EDTA 0.20

Sodium Chloride Sodium Chloride 0.50

100.00

Example 4

Clear Multi vitamin Shampoo

Ingredients INCI Nomenclature % w / w

A ) Texapon NSO Sodium Laureth Sulfate 50.00

Cetiol HE PEG-7 Glyceryl Cocoate 3.00

Tego Betain L7 Cocamidopropyl Betaine 5.00

Kathon CG Methylchloroisothiazolinone & 0.10

Deionized Water Aqua 30.85

Panthenol 75L Panthenol 1.00

Sodium Chloride Sodium Chloride 2.00

EDETA BD Disodium EDTA 0.20

STAY C 50 Sodium Ascorbyl Phosphate 0.50

B) Vitamin E acetate Tocopheryl Acetate 0.20

Phytantriol Phytantriol 0.10

Cremophor RH PEG-40 Hydrogenated Castor Oil 2.00

Perfume Parfum q.s.

BHT BHT 0.05

C) Crothix LVR PEG-150 Pentaerythrityl Tetrastearate & 3.00

D) KOH 10% Potassium Hydroxide 2.00

100.00

Example 5

Vitaminized Hair Tonic

Ingredients INCI Nomenclature % w / w

A ) Water deionized Aqua 57.18

STAY-C 50 Sodium Ascorbyl Phosphate 0.20

Ethanol Alcohol 30.00

Isopropanol Isopropyl Alcohol 10.00

Panthenol 75 L Panthenol 0.50

EDETA BD Disodium EDETA 0.20

Silicon DC 193 Dimethicone Copolyol 0.20

B) Cremophor RH 410 PEG-40 Hydrogenated Castor 1.00

Phytantriol Phytantriol 0.10

Vitamin E Acetate Tocopheryl Acetate 0.20

C) Citric Acid 10% Citric Acid 0.42

0.42.00

Example 6

Vitaminized Styling Gel

Ingredients INCI Nomenclature % w / w

A ) Carbopol etd 2020 Acrylates/C10-30 Alkyl Acrylate 1.50

Deionized Water Aqua 50.00

Ethanol Alcohol 20.00

B) STAY C 50 Sodium Ascorbyl Phosphate 0.50

Deionized Water Aqua 9.24

Panthenol 75 L Panthenol 1.33

EDETA BD Disodium EDTA 0.10

Uvinul MS 40 Benzophenone-4 0.03

C) Triethanolamine Triethanolamine 2.00

D) Luviskol VA 64 PVP/VA Copolymer 3.00

Ethanol Alcohol 10.00

F) Vitamin E Acetate Tocopheryl Acetate 0.20

Phytantriol Phytantriol 0.10

Cremophor RH 410 PEG-40 Hydrogenated Castor 2.00

100.00

Example 7

Vitaminized Hair Conditioner

Ingredients INCI Nomenclature % w / w

A ) Deionized Water Aqua 58.20

Panthenol Panthenol 1.00

EDETA BD Disodium EDTA 0.20

Kathon CG Methylchloroisothiazolinone 8. 0.10

SILICONE DC Q2-5220 Dimethicone Copolyol 1.00

B) Deionized Water Aqua 38.00

Polymer JR 400 Polyquaternium- 10 0.5

STAY-C 50 Sodium Ascorbyl Phosphate 1.0

C) Citric Acic 10% Citric Acid q.s.

100.00

Beispiel 8

Vitaminized Snampoo

Ingredients INCI Nomenclature % w / w

A ) Texapon NSO-BZ Sodium Laureth Sulfate 50.00

Cetiol HE PEG-7 Glyceryl Cocoate 3.00

Tego Betain L7 Cocamidopropyl Betaine 5.00

Kathon CG Methylchloroisothiazolinone & 0.10

B) Deionized Water Aqua 38.00

Polymer JR 400 Polyquaternium- 10 0.2

STAY-C 50 Sodium Ascorbyl Phosphate 0.5

C) Sodium Chloride Sodium Chloride 2.00 EDETA BD Disodium EDTA 0.20

D) KOH 10% Potassium Hydroxide 1.00

100.00

Claims

1. The use of an ascorbic acid derivative in the manufacture of hair care products for stabilizing the colour of artificially coloured hair, particularly against the impact of actinic radiation.

2. The use as in claim 1 wherein ascorbic acid derivative is used in combination with one or more agents selected from UV screening agents, vitamin A or derivatives thereof, vitamin E or derivatives thereof, a vitamin from the B complex, panthenol, phytantriol or derivatives thereof.

3. The use as in claim 1 or 2 wherein the ascorbic acid derivative is an ascorbic acid ester, or glycoside or salt thereof.

4. The use as in claim 1 or 2 wherein the ascorbic acid derivative is sodium ascorbyl phosphate.

5. The use as in claim 2 wherein the UV screening agent is PARSOL 1789 and/or PARSOL SLX.

6. The use as in any one of claims 1-5 wherein the hair care product is a shampoo, a conditioner, a tonic, a styling gel, a styling mousse, a spray, a pomade, a setting lotion, a colouring or permanent waving composition.

7. The use as in any one of claims 1-6 wherein the hair care product is to protect oxidatively dyed hair.

8. The use as in any one of claims 1-6 wherein the hair care product is to protect non- oxidatively dyed hair.

9. The use as in any one of claims 1-8 wherein the hair care product contains from about 0.0001 wt.-% to about 10 wt.-% of ascorbic acid derivative.

10. The use as in any one of claims 1-8 wherein the hair care product contains from about 0.01 wt.-% to about 5 wt.-% of ascorbic acid derivative.

11. The use as in any one of claims 1-8 wherein the hair care product contains from about 0.1 wt.-% to about 3 wt.-% of ascorbic acid derivative.

12. A method of stabilizing the colour of artificially coloured hair, particularly against the impact of actinic radiation, which comprises treating such hair with a hair care-product- containing an ascorbic acid derivative.

13. The method as in claim 12 wherein the hair care product further contains one or more agents selected from UV screening agents, vitamin A or derivatives thereof, vitamin E or derivatives thereof, a vitamin from the B complex, panthenol, phytantriol or derivatives thereof.

14. The method as in claim 12 or 13 wherein the ascorbic acid derivative is an ascorbic acid ester, or glycoside or salt thereof.

15. The method as in claim 12 orl3 wherein the ascorbic acid derivative is sodium ascorbyl phosphate.

16. The method as in claim 13 wherein the UV screening agent is PARSOL 1789 and/or PARSOL SLX.

17. The method as in any one of claims 12-16 wherein the hair care product is a shampoo, a conditioner, a tonic, a styling gel, a styling mousse, a spray, a pomade, a setting lotion, a colouring or permanent waving composition.

18 The method as in any one of claims 12-17 wherein the hair care product is to protect oxidatively dyed hair.

19. The method as in any one of claims 12-17 wherein the hair care product is to protect non- oxidatively dyed hair.

20. The method as in any one of claims 12-19 wherein the hair care product contains from about 0.0001 wt.-% to about 10 wt.-% of ascorbic acid derivative.

21. The method as in any one of claims 12-19 wherein the hair care product contains from about 0.01 wt.-% to about 5 wt.-% of ascorbic acid derivative.

22. The method as in any one of claims 12-19 wherein the hair care product contains from about 0.1 wt.-% to about 3 wt.-% of ascorbic acid derivative.

23. The invention as described hereinbefore especiall with reference to th Examples.