WO2004082646A1

WO2004082646A1 - Method for preventing or reducing colour loss of hair

Info

Publication number: WO2004082646A1
Application number: PCT/GB2004/000813
Authority: WO
Inventors: Stephen Watkins; Heather Eyre
Original assignee: Quest International Services B.V.
Priority date: 2003-03-22
Filing date: 2004-02-27
Publication date: 2004-09-30
Also published as: GB0306635D0

Abstract

Polyphenols, particularly flavonoids e.g. those present in various plant and plant product extracts such as red grape skin extract and purple carrot extract, have been found to have the effect of preventing or reducing colour loss of hair, particularly human hair that has been coloured by oxidation dyeing. The invention thus provides a method of preventing or reducing colour loss of hair; use of polyphenols to prevent or reduce colour loss of hair, by applying to the hair one or more polyphenols.

Description

Title: METHOD FOR PREVENTING OR REDUCING COLOUR LOSS OF HAIR

Field of the Invention

This concerns hair care, particularly hair that has been coloured using oxidative hair colouring compositions.

Background to the Invention

Compositions for colouring or dyeing hair can be categorised into temporary, semi- temporary, semi-permanent, permanent and, more recently, the so-called demi-permanent products. Although these names try to describe the general longevity of the colour in terms of wash-out, there is considerable blurring of the categories depending upon the brand of hair colour purchased, the dyes used and the formulation of the carrier base. However, as a guide:

- Temporary lasts only one wash

- Semi-temporary lasts approximately 5 washes

- Semi-permanent lasts approximately 10 washes

- Demi-permanent last approximately 20 washes

- Permanent is not washed out and lasts until the colour fades or grows out

Other products on the market are sold as post-colour formulations and these claim to extend the life of the hair colour. These can be split into 'colour maintenance' products, normally shampoos, which are formulated to be mild and help reduce colour washout, and 're-tint' products, which possess a low concentration of colour to reinforce the existing colour of the hair. The chemistry of hair dyes differs greatly. Temporary and semi-temporary colours tend to be larger molecules that are unable to penetrate the hair shaft and so reside on the hair surface. This makes them easy to remove with washing. Semi-permanent, demi- permanent and permanent colours are smaller molecules, able to penetrate the hair shaft, making them more resistant to hair washing.

The following list is a guide to the types of dye often found in the particular category of hair product. It should be noted that many commercially available products contain combinations of dye types:

- Temporary hair colours include the food or vegetable dyes or their insoluble lakes (pigments). Here, the colouring formulation normally contains fixatives such as resins to hold the colour onto the hair. These are easily removed with shampoo.

- Semi-temporary dyes are cationic in charge. The cationic charge allows them to bind to the hair surface and makes them more resistant to washing.

- Semi-permanent dyes are normally small, nitro-dyes, able to penetrate the hair shaft. This makes them less readily removed with washing.

- Permanent dyes (and couplers) are themselves colourless precursors called oxidation dyes. These precursors, in the presence of peroxide, undergo a chemical reaction to produce coloured compounds of varying degrees of polymerisation. Penetration of the colourless precursors into the hair fibre can be 'encouraged' by the use of an alkali, such as ammonia, which causes the hair shaft to swell and become more porous. Once within the hair fibre, the small colourless precursors polymerize to form the larger coloured compounds. These are then trapped within the hair fibre by their physical size.

- Demi-permanent colours use the similar, colourless, precursors to the permanent colours. However, the use of different coupling agents restricts polymerization to the formation of smaller coloured molecules. These smaller compounds are more easily washed out of the hair. Also, the reduction or elimination of ammonia from the formulation helps to limit the penetration of the precursors. Many products contain a combination of different dye types. For example, some semi- temporary dyes are mixed with the semi-permanent dyes to produce more natural looking shades. The demi-permanent and permanent products can provide a wide variety of colours even on dark hair because the natural hair colour is bleached during the process. The use of the temporary, semi-temporary and semi-permanent colours are dependent upon the individual's natural hair colour; a dark haired person cannot become blond.

One problem arising with permanent (oxidative) hair colour is that the hair colour has a tendency to fade. The initial rich colours achieved with oxidation dyeing tend to be rapidly lost as a result of washing and also exposure to light, particularly sunlight, that acts to cause light-induced oxidation of the colour. This can leave the hair looking and feeling faded, dry, brittle and damaged, and is a source of constant frustration to consumers and the cosmetic industry. Attempts have been made to reduce colour fading by use of sunscreens on hair, which block high energy ultraviolet (UV) light and so reduce light induced oxidation of the colour.

Summary of the Invention

It has surprisingly been found that polyphenols, particularly flavonoids, e.g. as found in various plant and plant product extracts, have the effect of preventing or reducing such colour loss of hair, particularly human hair that has been coloured by oxidation dyeing, but also human hair generally including non-coloured hair and hair dyed or coloured by non-oxidative methods.

In one aspect the present invention provides a method of preventing or reducing colour loss of hair, particularly human hair that has been coloured by oxidation dyeing, comprising applying to the hair one or more polyphenols.

The invention also provides use of one or more polyphenols to prevent or reduce colour loss of hair, particularly human hair that has been coloured by oxidation dyeing. Also within the scope of the invention is use of one or more polyphenols in a hair care composition for the purpose of preventing or reducing colour loss of hair, particularly human hair that has been coloured by oxidation dyeing.

A further aspect of the invention resides in a hair care composition, including one or more polyphenols.

The composition may be in the form of a preparation such as a shampoo, rinse-off conditioner, leave-on conditioner, styling formulation, protecting formulation. Preferably the composition is in the form of a post-colour treatment formulation intended to be applied to the hair immediately after the oxidative colouring process. The composition is desirably a leave-on product, intended to be applied to and left on the hair.

The composition suitably includes one or more polyphenols in an amount in the range 0.001 % to 5% by weight, preferably 0.01 % to 1 % by weight, typically 0.05% to 0.5% by weight of the total weight of the composition.

The composition can otherwise be of generally conventional formulation. The polyphenol, e.g. a plant or plant product extract as discussed below may be incorporated directly into the hair care composition, or pre-mixed with other ingredients prior to incorporation.

The term "polyphenol" is used to mean compounds with more than one phenolic group. This includes low molecular weight compounds and high molecular weight polymeric compounds such as vegetable tannins that are capable of precipitating proteins from solution. Polyphenols, particularly coloured polyphenols, occur naturally in many plants and plant products such as many fruits and vegetables, and plant extracts provide a rich and valuable source of polyphenols. Particularly suitable extracts include purple carrot extract (which contains anthocyanins and which is also an effective UV absorber), grape skin (red or white) extracts (which contain anthocyanins, particularly diglucosides, monoglucosides and acylated diglucosides of the anthocyanidins cyanidin, peonidin, malvidin, delphinidin and petunidin), tea (black, green or white) extracts and cocoa extracts.

Further details of useful polyphenols and commercial suppliers are as follows:

Tea Polyphenols: Suppliers include Maruzen Pharmaceuticals, Dragoco, Inocosm, Indena, Active Organics, Quest International, Grau, Alban Muller, Solabia, Ennagram, Collaborative Labs, Greentech, Bio-Botanica, Kobo, Arch Chemicals, Bioland, Plantech, Provital, Euromed, Crodarom, Lucas Meyer, Ichimaru Pharcos, Bertin, Gattefosse, Prod'Hyg, Taiyo Kagaku.

Mate Tea (Ilex Paraguariensis/ Paraguay Tea/ Yerba Tea): Suppliers include Wella, Active Organics, Alban Muller, Indena, Phytochim, Centerchem, Vege-Tech.

Quercetin from apples, onions and berries: Suppliers include Jan Dekker, Lipo.

Olive Extract - contains cleurpoein: Suppliers include Active Organics, Ennagram, Vevy, Cosmetochem, Vege-Tech, Bertin, Maruzen Pharmaceuticals, Provital, Ichimaru Pharcos, Sederma, Alban Muller, Fanning, Arch Chemicals.

Grape Seed Extract, Grape Extracts, Wine Extracts, resveratrol: Supplier include A & E Connock, Phytochim, Active Organics, Quest International, Ennagram, Coletica, Alban Muller, Greentech, Dragoco, Grau, Vevy, Indena, Provital, Gattefosse, Ichimaru Pharcos, Crodarom, MU, Cosmetochem, Sederma, Solabia, Prod'Hyg, Vege-Tech, Interhealth Nutraceuticals, Euromed, Premier Specialities, Berkem, Kobo, Collaborative Labs, Biochemicals International, Mibelle, Lalilab.

Anthocyanins - found in red fruits, including grapes; also Purple Carrot, cherries, strawberries, plums: Suppliers include Quest International. Tetrahydrocurcumin from turmeric: Suppliers include Sabinsa, Maruzen, Heidelberger, Grau, Cosmetochem, Chemyunion, Ichimaru Pharcos, Vege-Tech, Logona, Vevy.

Rosmarinic acid from rosemary: Suppliers include Provital, Flavex, Vevy, Naturex, Indena, Phytochim, Robertet, Kansai Koso, Active Organics, MU, Ennagram, Ichimaru Pharcos, Bio-Botanica, Alban Muller, Arch Chemicals, Haarman & Reimer, Croda, Dragoco, Plantextrakt, Crodarom, Cosmetochem, Vevy, Bertin, AGI Dermatics, Indena, Bio-Botanica, Fabriquimica, Naturex, Universal Flavors, Prod'Hyg, Maruzen Pharmaceuticals, Grau, Ichimaru Pharcos, Sederma, Rahn, Solabia, Vege-Tech, Gattefosse, Lipo, LCW.

Ellagic Acid from punica granatum (pomegranate): Suppliers include Lion Corp., Active Organics, Greentech, Dragoco, Alban Muller, Vege-Tech.

Hypericin from hypericum perforatum (St John's Wort): Suppliers include Flavex, Indena, Phytochim, Alban Muller, Active Organics, Ennagram, Croda, Dragoco, Solabia, Crodarom, Cosmetochem, Maruzen Pharmaceuticals, Ichimaru Pharcos, Chemisches Laboratorium, Indena, Universal Flavors, Serobiologiques, Provital, Prod'Hyg, Rahn, Sederma, Grau, Cognis Care Chemicals, Vege-Tech, Gattefosse.

Chlorogenic acid from vaccinium vulgaris (blueberry): Suppliers include MMP.

Pycnogenol from pine bark: Suppliers include Preventive Nutrition, Berkem, Euromed, Alban Muller, Ennagram.

The plant extracts are generally water-soluble and non-oil-soluble. Plant extracts are commercially available, e.g. from suppliers as listed above, or can be readily produced by those skilled in the art, e.g. by techniques including water extraction, sulphur dioxide extraction, expression, heat treatment etc, possibly followed by concentration. Polyphenols may also be prepared synthetically. One particular preferred class of polyphenols is known as flavonoids. Flavonoids include the coloured polyphenols found in many fruits and vegetables.

Flavonoids

Flavonoids are divided into five sub-groups according to their chemical structure. These are as follows:

1) Anthocyanidins

2) Flavones and flavonoles

3) Flavanones

4) Catechins and leucoanthocyanidins

5) Proanthocyanidins

All flavonoids are derived from flavan (2 - phenol - benzo - dihydropyran). The general structure (C6-C3-C6) is given below:

General Structural Formulae of Flavonoids

1) Anthocyanidins

Anthocyanidins are found in nature as glycosides called anthocyanins. Anthocyanins are natural colour pigments, which have a colour range varying from rich red to blue. The characteristic colour of most fruits is due to anthocyanins. In the flavylium cation configuration, they posses a red colour, which are dependent of the substituents of B - ring. More OH - groups cause a shift towards blue. Methoxylation of these OH - groups intensifies the red colour.

The general structural formulae of anthocyanidins is given below:

Rl K2 Anthocyanid

H H Pelargonidin

OH H Cyanidin

OH OH Delphinidin

OCH₃ H Peonidin

OCH₃ OH Petunidin

OCH₃ OCH₃ Malvidin

2) Flavones and Flavonols

Flavones and flavonols, which have slight yellow colour, are practically found in all plants. Flavones differ from flavonols in the absence of OH - group at C3 - atom of the centre ring (shown by X below):

Rl R2 Flavonol Flavone X = OH X = H H H Kamferol Apigenin

OH H Quercetin Luteolin

OH . OH Myricetin

OCH₃ H Isorhamnetin

OCH₃ OCH₃ Tricin

OCH₃ H Chrysoeriol

3) Flavonones

Flavonones do not have a double bond at the centre ring. Their glycosides are mainly found in citrus fruits. Chemical structure of naringin is shown below:

4) Catechins and leucoanthocyanidins

Catechins are flavan-3-ol monomers comprising one OH - group at C3 - atom. The leucoanthocyanidins flavan - 3,4 - diols, have one OH - group at C3 - and C4 - atoms. The most frequent catechins are dia - stereoisomer pair (+) - catechin and (-) - epicatechin, as well as (+) - gallocatechin and (-) - epigallocatechin shown below:

R Catechin R Catechin H (+)-Catechin H (-)-Eρicatechin

OH (+)-Gallocatechin OH (-)-Epigallocatechin

5) Proanthocyamdms

Proanthocyanidins are colourless if their chains are short. Yellowish to brown colour are formed with increasing polymerisation. When they are heated up in acidic mediums, they transform into corresponding anthocyanidins getting typical reddish - violet colour.

Polyphenols, particularly the flavonoids, are among the most potent plant antioxidants. Polyphenols can form complexes with reactive metals such as iron, zinc and copper - reducing their absorption and so reducing generation of free radicals and potential for oxidation damage. In addition to their chelating effect on metal cations, polyphenols also function as potent free radical scavengers within the body, where they can neutralise free radicals before they can cause cellular damage.

The invention will be further described, by way of illustration, in the following Examples.

Examples

Example 1

Experiments were carried out to test the effect of purple carrot extract and red grape skin extract on the colour of hair swatches coloured by oxidation dyeing.

Hair Colouration

Five bleached swatches of European hair, each weighing about lOg, were grouped together and coloured using 50g of a commercial permanent hair colourant [L'Oreal's Feria Colour 3D - 66 Ruby Fusion]. The colouring procedure followed the instructions supplied:

- The hair was made wet and dried with a towel

- Colourant was applied, thoroughly massaged into the hair, and left for 30 minutes

- The hair was then rinsed in 45 °C water until the water ran clear

- The hair was dried using a hair dryer

Treatment

Dilute aqueous solutions of purple carrot extract and red grape skin extract were prepared according to the formulations:

%w/w %w/w

Water 69.80 69.98

Ethanol 30.00 30.00

Purple Carrot Extract 0.20

Red Grane Skin Extract 0.02

The red grape skin extract was prepared by water extraction of Mediterranean grape pomace to give a product having a total polyphenol concentration of 70 to 80% by weight consisting mainly of the anthocyanins referred to above. The purple carrot extract was prepared by expression followed by heat treatment and concentration to give a product having a total polyphenol concentration of 3 to 4% by weight. Such extracts are commercially available.

The five coloured hair swatches were ungrouped, labelled A to E, and then treated in the following way:

1) Swatch A was kept untreated to act as a 'colour control' .

2) Swatches B to E were re-combined, washed once using lOg of a simple SLES (sodium lauryl ethyl sulphate)/betaine shampoo formulation, before being dried with a hair dryer. 3) Swatch B was then kept as a 'colour wash-out control' .

4) Swatch C was fixed into a stainless steel tray using wooden stays, ready for light exposure. Swatch C was a 'colour wash-out & light control⁵.

5) Swatch D was treated with lg of the purple carrot extract solution. The solution was sprayed evenly onto/into the hair and combed through before being allowed to air dry for ten minutes. The swatch was then fixed next to swatch C ready for light exposure.

6) Swatch E was treated with lg of the red grape skin extract solution. The solution was sprayed evenly onto/into the hair and combed through before being allowed to air dry for ten minutes. The swatch was then fixed next to swatch C ready for light exposure.

7) Swatches C to E were placed in a solar simulator cabinet and exposed to simulated bright daylight for 3 hours.

8) Swatches C to E were removed from the solar simulator and combined with swatch B.

9) Points (2) to (8) were repeated a further three times. This meant that swatches B to E had a total of four washes and swatches C to E had a total of twelve hours of simulated bright day light.

Care was taken to ensure that the orientation of the swatches was maintained with successive light exposure, so that only one 'side' of the hair swatches were exposed. This exposed side was used for all colour measurements and assessments.

10) All tresses were left to thoroughly air-dry overnight prior to assessment.

Colour Measurement The final hair colour of each swatch (A to E) was measured using the Minolta Chroma CR-300 meter, taking the mean of three readings, and assessed/ranked by untrained volunteers, 'blind'.

Results

Minolta Chromameter

Swatch: A B C D E

L. 27.01 30.79 33.40 32.78 32.25 a*_! 22.55 20.71 20.47 20.08 20.70 b*_! 10.93 12.85 14.51 13.82 14.10

L₂ 27.91 30.43 35.16 31.58 32.15 a*₂ 22.48 20.81 19.77 21.13 20.91 b*₂ 11.07 12.95 14.47 14.01 14.46

L₃ 27.79 29.94 33.98 31.43 32.96 a*₃ 22.62 21.12 20.12 20.72 20.95 b*₃ 10.82 12.96 14.27 14.08 14.13

^■'-'mean 27.57 30.39 34.18 31.93 32.45 a "* mean 22.55 20.88 20.12 20.64 20.85 b "* mean 10.94 12.92 14.41 13.97 14.23

Delta E (ΔE) measures the difference between one colour and another, the larger the ΔE value, the greater the difference [loss] in colour.

Comparing swatches B, C, D and E to swatch A (colour control), gives ΔE values of:

A → B = 3.83 A→ C = 7.85 A→ D = 5.64 A → E = 6.13 Comparing swatches C, D and E to swatch B (colour wash-out control) gives ΔE values of:

B →- C = 4.15 B → D = 1.88 B → E = 2.45

Ranking

Swatches A-E were ranked, blind, for colour intensity by eight untrained volunteers.

Ranked Swatches

Volunteer (Strong Weak)

1 A B D E C

2 A B D E C

3 A B D E C

4 A B D E C

5 A B E D C

6 A B D E C

7 A B D C E

8 A B D E C

These results show that purple carrot extract and red grape skin extract provide consumer- noticeable protection of the permanent hair colour, helping to prevent the fading due to UV light. Both ingredients contain polyphenols, known to protect unsaturated compounds from oxidation, preventing degradation and the formation of destructive radical pathways.

Example 2 - After Sun Shampoo

A shampoo composition has the following ingredients:

Trade Name INCI Name %W/W

Purified water Aqua to 100.00 Empicol ESB3 Sodium Laureth Sulfate (28%) 40.00 Empigen BB Lauryl Betaine 6.60 Euperlan PK771 BENZ Glycol Distearate & Sodium Laureth 5.00 Sulfate & Cocamide MEA & Laureth- 10

Plantaren 2000 Decyl Polyglucose 2.00

Sodium Chloride 1.60

Ascorbic acid 0.50

Naturein Rice Peptide Hydrolyzed Rice Protein 0.50

Green Tea Extract Alcohol & Camellia Sinensis Leaf Extract 0.10

Nervanaid BA2 Disodium EDTA 0.10

Caroquest P CI75130 and Beta carotene and 0.10 Zea mays (corn) starch

Preservative q.s.

Citric Acid q.s.

Perfume q.s.

Empicol ESB3, Empigen BB, Euperlan PK771 BENZ, Plantaren 2000, Naturein, Nervanaid BA2 and Caroquest P are Trade Marks. The Green Tea Extract contains polyphenols

The shampoo was prepared by adding the EDTA to water, stirring to dissolve fully, then adding the Caroquest P with stirring. The Naturein Rice Peptide was then added, and the mixture stirred to dissolve. The Empicol, Plantaren, Euperlan, Kathon, salt, ascorbic acid and Empigen were added, with stirring until homogeneous between additions. pH was adjusted using citric acid, then the Green Tea Extract and the Perfume were added.

This results in a rich and creamy shampoo designed for use after a day in the sun. It contains a rice peptide, which includes essential arnino acids to repair the hair, and green tea extract to counteract the effects of free radicals triggered by sunlight. It is coloured with carotene, a natural colour and protector from UV damage.

Example 3 - Mild Antioxidant Shampoo

A shampoo composition has the following ingredients: Trade Name INCI Name % W/W

Deionised water to 100.00

Empicol AL30/T Ammonium Lauryl Sulfate 16.00

Texapon NS/IOS Sodium Laureth Sulfate (28%) 10.00

Tego Betain L7 Cocamidopropyl Betaine 5.00

Merquat Plus 3330 Poly quaternium-39 3.00

Plantacare PS10 NP Sodium Laureth Sulfate & 3.00 Lauryl Glucoside

Salt 2.00

Citric Acid (20% soF) 1.80

Antil 171 PEG- 18 Glyceryl Glycol dioleococoate 0.50

Purple Carrot Extract Daucus Carota 0.05

White Grapeskin Extract Vitis Vinifera Fruit Extract 0.1

Nervanaid BA2 Disodium EDTA 0.10

Kathon CG Methylchloroisothiazolinone & 0.05 Methylisothiazolinone

Uvinul MS40 Benzophenone-4 0.04

Perfume q.s.

Empicol AL30/T, Texapon NS/IOS, Tego Betain L7, Merquat Plus 3330, Plantacare PS10 NP, Antil 171, Nervanaid BA2, Kathon CG and Uvinul MS40 are Trade Marks.

The shampoo was prepared by mixing the Uvinul and Nervanaid into the water, warming gently for easier incorporation. The surfactants were added and then the citric acid, with stirring between additions. The rest of the ingredients were added, with stirring to ensure the batch is uniform between each addition. The perfume, salt and Antil were added last.

This results in a gentle yet effective shampoo.

Example 4 -Conditioner for Dry Hair A conditioner for dry hair has the following ingredients:

Trade Name INCI Name %w/w

Deionised water to 100.00 Cetyl Alcohol 4.00 Schercomid CME Cocamide MEA 2.00 Lexamine S13 Stearamidopropyl Dimethylamine 2.00 Dehyquart A Cetrimonium Chloride 1.50 Lactic Acid 1.00 Sodium Stearate 0.90 D-Panthenol 75L Panthenol 0.75 Naturein Wheat Peptide Hydrolyzed Wheat Protein 0.50 Ceramide II Ceramide 2 0.10

White Grapeskin Extract Vitis Vinifera Fruit Extract 0.10 Preservative q.s. Perfume q.s.

Schercomid CME, Lexamine S13, Dehyquart A, D-Panthenol 75L, Naturein and Ceramide II are Trade Marks.

The conditioner was prepared by combining the water, wheat peptide, Dehyquart and lactic acid, and heating to 80 °C. The cetyl alcohol, Schercomid, Lexamine, sodium stearate and Ceramide II were separately combined, and heated to 80 °C. This mixture was then added to the water phase, and homogenised until smooth. The mixture was cooled to room temperature, and the remaining ingredients added.

This result in a product in the form of a light emulsion that develops pearlescence over time. The formulation contains ceramide and wheat protein for added strength and shine.

Example 5 - Hair Colour, Protecting and Sheen Mousse A hair mousse composition has the following ingredients:

Trade Name INCI Name %w/w

Deionised water 81.00

Ethanol 10.00

Nature's Green CI 75810 6.00

Volpo NIO Oleth-10 1.00

Gafquat 734 Polyquaternium-11 0.80

Naturein Rice Peptide Hydrolyzed Rice Protein 0.50

Red Grapeskin Extract Vitis Vinifera Skin Extract 0.10

Dow Corning 929 Amodimethicone, Tallowtrimonium 0.50 Chloride & Nonoxynol-10

Preservative q.s.

Perfume q.s.

Nature's Green, Volpo N10, Gafquat 734, Naturein and Dow Corning 929 are Trade

Marks.

The mouse was prepared by dissolving the Gafquat in the ethanol. The water was added, then the remaining ingredients, with stirring between additions.

This results in a light, moisturising mousse, to bring shine and condition to the hair. The product also contains a temporary colouring agent to provide a hint of colour until the next wash.

Example 6 - Temporary Colour, Conditioning And Styling Mousse A hair mousse composition has the following ingredients:

Trade Name INCI Name %w/w D-Panthenol 1.00

Schercomid AME-100 Acetamide MEA 5.00

PVP K300 Polyvinyl pyrrolidone 1.00

Empigen BS Cocamidopropyl Betaine 5.00

Kathon CG Methylchloroisothiazolinone & 0.05 Methylisothiazolinone

Caroquest P CI75130 and Beta carotene and 3.50 Zea mays (corn) starch

Red Grapeskin Extract Vitis Vinifera (Grape) Skin Extract 0.3

Deionised Water to 100.00

Schercomid AME-100, PVP K300, Empigen BS, Kathon CG and Caroquest P are Trade Marks.

The mousse was prepared by dissolving all the materials of the concentrate into water, one at a time and mixing until homogeneous. The mixture was combined with aerosol propellant in the ratio shown below.

Concentrate 80.0%

Butane CAP 30 20.0% Example 7 - Leave on Conditioner A hair conditioner product has the following ingredients:

Trade Name INCI Name %w/w

Purified Water to 100.00 Witch Hazel Distillate Hamamelis Virginiana (Witch Hazel) 7.00

Distillate

Rosewater Rosa Centifolia Flower Water 5.00 Eumulgin L PPG-l-PEG-9 Lauryl Glycol Ether 4.00 Propylene Glycol 3.00 Questice Liquid Menthyl PCA 2.00 Glycerine 1.00

Apricot Extract Alcohol & Water & Prunus Armeniaca 0.50

(Apricot) Fruit Extract

Liquorice Concentrate Alcohol & Water & Glycyrrhiza Glabra 0.50

(Licorice) Extract

Green Tea Polyphenols Alcohol & Camellia Sinensis Leaf Extract 0.50

Germaben li-E Propylene Glycol & Diazolidinyl Urea & 0.50

Methylparaben & Propylparaben

Citric Acid q.s.

Eumulgin L, Questice and Germaben U-E are Trade Marks.

The conditioner was prepared by combining the Eumulgin and Questice, with stirring until uniform. In a main vessel, the other ingredients were mixed together one by one, stirring until clear after each addition. Citric acid was used to balance to pH 5-6. The Questice mixture was added, and stir until clear and uniform.

This results in a light, non-greasy lotion that will gently condition the hair, leaving it refreshed and soft. The gentle coolant and moisturiser gives a pleasant refreshing sensation to the scalp without the need for alcohol, while astringent rosewater and witch hazel will help to close pores, helping to reduce greasiness.

Example 8 - Aerosol Hair Hold & Protection Spray

A hairspray has the following ingredients:

Trade Name INCI Name % w/w

Amphomer Octylacrylarmde/acrylates/butylamino 3.000 ethyl methacrylate polymer

Fragrance 0.200

2-Amino-2-Methyl-l-Propanol (AMP) 0.492 Ethanol to 100.000 d,l- Alpha Tocopherol 0.020

Red Grapeskin Extract Vitis Vinifera (Grape) Skin Extract 0.10

Amphomer is a Trade Mark.

The spray was prepared by dissolving the AMP in the ethanol. The Amphomer was slowly added with constant sthring. The fragrance and alpha tocopherol were added and mixed until clear.

The base was filled into epoxyphenolic lacquered tinplate or aluminium aerosol cans and filled with hydrocarbon propellant as follows:

% w/w Base 55.00

Hydrocarbon Propellant 65.00

Example 9 - Firm Hold Pump Hairsprav (80% VOC)

A hairspray product has the following ingredients:

Trade Name INCI Name % w/w

Luvimer 100 P Aery late Copolymer. 6.00

AMP 2-Amino-2-methyl-l-propanol 1.39

Deionised Water 12.61

White Grapeskin Extract Vitis Vinifera (Grape) Fruit Extract 0.10

Ethanol to 100.00

Fragrance as required

Luvimer 100 P is a Trade Mark. The spray was prepared by mixing the ethanol, AMP, water & fragrance. The Luvimer was slowly added and mixed well until clear.

The resulting product contains water to allow the formulation of a firm hold hairspray, with good performance attributes, whilst containing a reduced level of volatile organic compounds. It contains a natural antioxidant to protect hair colour from fading.

Example 10 - Protective Fixative Gel

A gel product has the following ingredients:

Trade Name INCI Name % w/w

Phase A: Purified Water 50.00 Carbopol 980 Carbomer 0.50

Phase B: Purified Water To 100.00 Gafquat HS-100 Polyquaternium-28 10.00 Panthequat Steardimonium Panthenol 1.25 Vitamin E Acetate Alpha-Tocopherol Acetate. 0.10 Uvinul P25 Peg-25 PABA 0.50 Purple Carrot Extract Daucus Carota 0.20 Preservative as required

Phase C: Purified Water 5.00 Triethanolamine 0.35

Phase D: Eumulgin L PPG-Ceteareth-9 2.50 Fragrance as required

Carbopol 980, Gafquat HS-100, Panthequat, Uvinul P25 and Eumulgin L are Trade Marks.

The product was prepared by dispersing the Carbopol in the water of phase A, with rapid stirring. The ingredients of phase B were combined and added to phase A. Phase C was added slowly, avoiding excessive air entrainment. Phase D was premixed and slowly added to the gel, with stirring until clear.

This produces a clear gel that is designed to protect the hair, whilst aiding styling.

Example 11 - Styling Gel With Ipa

A gel product has the following ingredients:

Trade Name INCI Name %w/w

Phase A: Carbopol 980 Carbomer 0.75 Purified Water To 100.00

Phase B:

Purified Water 30.00

Triemanolamine 0.75

Dc 193 Surfactant Dimethicone Copolyol 0.30

PVP K30 PVP 2.50

Panthequat Steardimonium Panthenol 0.50

Red Grapeskin Extract Vitis λ^inifera (Grape) Skin Extract 0.05

Preservative as required

Isopropanol (Ipa) 20.00 Phase C: Eumulgin L PPG-2-Ceteareth-9 2.00 Fragrance as required

Carbopol 980, DC 193, Panethequat and Eumulgin L are Trade Marks.

The gel was prepared by dispersing the Carbopol in the water of phase a with rapid agitation. The ingredients of Phase B were mixed together and stirred until a clear solution is produced. Phase B was added to Phase A, with gentle stirring until a smooth, clear gel is formed. The eumulgin was premixed with the fragrance and added to the gel. The materials were mixed well.

This produces a clear, gel product that is designed to be applied to wet or dry hair before styling. It will aid styling, and "hold" the hair in the desired style.

Example 12 - Hair Pomade/Plaiting Aid

A Hair Pomade/Plaiting Aid has the following ingredients:

Trade Name INCI Name %w/w

White Petroleum Jelly to 100.00

Microcrystalline Wax 15.00

Light Mineral Oil 50.00

BHT Butylated Hydroxytoluene 0.05

Volpo N3 Oleth-3 3.00

Green Tea Polyphenols Alcohol & Camellia Sinensis Leaf Extract 0.50

Colour as required

Fragrance as required

Volpo N3 is a Trade Mark. Heat all the ingredients, except the fragrance and purple carrot extract, until melted. Mix well. Cool until just above the setting point, add the perfume and purple carrot extract, mix well and pack. The ratio of petroleum jelly/ wax may be varied to give a product of suitable consistency i tropical countries.

This product is a mineral oil/wax blend pomade to give good hair control and gloss. With tightly curled hair, the adhesive properties of the pomade gives sufficient control to allow easy plaiting and styling.

Example 13 - Oil Free Aerosol Hair Gloss

A Hair Gloss product contains the following ingredients:

Fragrance as required

Dow Corning 1401 Cyclomethicone And Dimethiconol. 3.00

Dow Corning 344 Cyclomethicone 70.00

Crodamol DA Diisopropyl Adipate 10.00

Crodamol OSU Di-2-Ethyl Hexyl Succinate 3.00

Finsolv TN Cj2 " Cχ5 Alkyl Benzoate 10.00

Escalol 507 Octyl Dimethyl Paba 2.00

Chamomile Oil 1.50

Vitamin Extract VC, Isopropyl Myristate & Soybean Oil &

Oil Soluble Retinyl Palmitate & Safflower Oil &

Linoleic Acid (And) Tocopherol 0.50

Purple Carrot Extract Daucus Carota 0.20

Dow Corning 1401, Dow Corning 344, Crodamol DA, Crodamol OSU, Finsolv TN and Escalol 507 are Trade Marks.

Sequentially mix all materials with moderate stirring to ensure good mixing. Fill the base into suitable epoxyphenolic lacquered aerosol cans, vacuum crimp on suitable aerosol valves and fill with hydrocarbon propellant as below:

AEROSOL FILL: % w/w

BASE: 65.00 CAP 30 35.00

This non-oil formulation is designed to be sprayed onto the hair to give a slick, shiny effect. It contains a sunscreen to protect the hah plus chamomile oil and a complex of vitamins.

Example 14 - Clear, Colourless Leave-In Hair Conditioner Spray

A conditioner spray contains the following ingredients:

Trade Name INCI Name %w/w

Purified Water to 100.00

Preservative as required

White Grapeskin Extract Vitis Vinifera (Grape) Fruit Extract 0.10

D-Panthenol 751 Panthenol 1.50

Merquat Plus 3331 Polyquaternium-39 3.50

Fragrance as required

D-Panthenol 751 and Merquat Plus 3351 are Trade Marks.

Mix the ingredients with the water in the order given and stir until homogeneous.

This clear colourless conditioner will remoisturise dry hair leaving it soft and manageable. It is suitable for all types of hah. Example 15 - "Touch" Ultimate Shine Conditioning Spray

A conditioning spray contains the following ingredients:

Trade Name ICNI Name %w/w

Ethanol 35.00

Propylene Glycol 10.00 Crodasone W Hydrolysed Wheat Protein & Polysiloxane Copolymer 2.00

Softigen 767 PEG-6 Caprylic/Capric Glycerides 2.00

Tinopal CBS-X Disodium distyrylbiphenyl disulfonate 1.00

White Grapeskin Extract Vitis Vinifera (Grape) Fruit Extract 0.10

Purified Water to 100.00

Preservative as required

Fragrance as required

Crodasone W, Softigen 767 and Tinopal CBS-X are Trade Marks.

Dissolve the Tinopal in the water with gentle warming. Add the rest of the ingredients with stirring.

This conditioner can be sprayed lightly onto either damp or dry hair to ease combability and leave the hah soft and silky with a beautiful shine, in addition to protecting the colour from sun bleaching.

Example 16 - Non-Conditioning Styling Mousse (Extra Shine)

A styling mousse contains the following ingredients:

Trade Name ICNI Name % w/w

Concentrate: Phase A:

Polawax A31 Emulsifying Wax NF 0.75

Polawax GP200 Self-emulsifying Wax 3.00

PEG 6000 Disteara e PEG-150 Distearate 1.50

Crovol A40 PEG-20 Almond Glycerides 2.00

Phase B:

Methocel F4M "Q" Hydroxypropyl Methyl Cellulose 0.30

Purified Water To 100.00

Saponine 5012 Saponins 0.50

Dow Corning 193 Dimethicone Copolyol 3.00

Purple Carrot Extract Daucus Carota 0.20

Phase C:

Purified Water 5.00

Phase D:

Fragrance as required

Polawax A31, Polawax GP200, Crovol A40, Methocel F4M "Q", Saponine 5012 and Dow Corning 193 are Trade Marks.

Heat Phase A and B separately to 70 - 75°C. Add B to A with efficient stirring. Add phase C below 60°C and Phase D below 30°C. When cool, fill into aerosol containers and crimp with suitable valves.

AEROSOL FILL: % w/w

CONCENTRATE 90.00

HYDROCARBON PROPELLANT, 40 psig 10.00 This product is designed to produce a firm hold so that the hah can be blow-dried into elaborate styles.

Example 17 - Alcohol Free Pump Hairspray

A hairspray product contains the following ingredients:

Trade Name INCI Name % W/W

H20LD EP1 Vinylcaprolactam/Pvp/ Dimethylamino-

Ethyl Methacrylate Copolymer 3.00

D-Panthenol 75L D-Panthenol 0.50 Dow Corning 190 Dimethicone Copolyol 0.10 White Grapeskin Extract Vitis Vinifera (Grape) Fruit Extract 0.10 Euxyl K702 Benzoic Acid & Dehydroacetic Acid &

Phenoxy ethanol. 0.10

Deionised Water To 100.00

H20LD EP1, D-Panthenol 75L, Dow Corning 190 and Euxyl K702 are Trade Marks.

Slowly mix H20LD into the water. Mix without vortexing until full dissolved. Add remaining materials with mixing. Pack into a suitable pump pack.

This formulation is designed to be sprayed from a fine mist, low dosage pump and provide a regular hold hairspray that glosses and conditions the hah whilst styling, in addition to protecting the hah from the bleaching effect of the sun..

Claims

1. A method of preventing or reducing colour loss of hah, comprising applying to the hah one or more polyphenols.

2. Use of one or more polyphenols to prevent or reduce colour loss of hah.

3. Use of one or more polyphenols in a hah care composition for the purpose of preventing or reducing colour loss of hair.

4. The invention according to any one of the preceding claims, wherein the hair is human hair that has been coloured by oxidation dyeing.

5. A hah care composition, comprising one or more polyphenols.

6. A composition according to claim 5, comprising a leave-on product.

7. A composition according to claim 5 or 6, comprising one or more polyphenols in an amount in the range 0.001 % to 5% by weight, preferably 0.01 % to 1 % by weight, more preferably 0.05% to 0.5% by weight of the total weight of the composition.

8. The invention according to any one of the preceding claims, wherein the polyphenol comprises one or more flavonoids.

9. The invention according to claim 7 or 8, wherein the polyphenol comprises one or more polyphenols occurring naturally in plants or plant products.

10. The invention according to claim 9, wherein the polyphenol comprises grape skin extract or purple carrot extract.