WO2004073663A1

WO2004073663A1 - Hair treatment compositions

Info

Publication number: WO2004073663A1
Application number: PCT/EP2003/002261
Authority: WO
Inventors: Viviana Ines Claus; Arun Nandagiri
Original assignee: Unilever Plc; Unilever Nv; Hindustan Lever Limited
Priority date: 2003-02-18
Filing date: 2003-03-05
Publication date: 2004-09-02
Also published as: GB0303733D0; BR0318123A; MXPA05008731A; AU2003215633A1; AR038925A1

Abstract

Hair treatment compositions comprise a ceramide, a fatty acid ester of retinol and a water-insoluble oil. Methods for preparing the compositions and their use for treating the hair are also disclosed.

Description

HAIR TREATMENT COMPOSITIONS COMPRISING A CERAMIDE, A FATTY ESTER OF RETINOL AND AN OIL

The invention relates to hair treatment compositions, particularly hair conditioning compositions which repair damaged hair and which provide improved colour retention for dyed hair by reducing colour loss when the hair is washed.

Conventional grooming habits such as shampooing, combing, brushing and hot-air drying can lead to damage to the hair known as hair dryness. Environmental exposure to sunlight can also damage the hair. In addition, treatments to the hair such as dyeing or colouring, styling, waving or relaxing can cause damage and dryness. This also may lead to other problems such as frizziness, split ends, lack of manageability and hair breakage.

In particular, damaged or dry hair is particularly poor at retaining hair colourants or dyes. These are leached out from damaged hair more readily than from undamaged hair during subsequent washes after dyeing or colouring.

Hence it is highly desirable to provide hair treatment compositions which repair the damage to already damaged hair in order to overcome the problems of damage. In particular, it is desirable to provide hair treatment compositions which improve the retention of hair dyes and colourants for coloured hair when it is subsequently washed. It is also desirable to provide compositions which act upon the hair to protect or prevent the hair from damage during subsequent treatments. Hair conditioning compositions and rinse creams are typically applied to wet hair, after washing and rinsing, in order to improve ease of combing and manageability. Such compositions often comprise silicone-based polymers such as disclosed in US 4,220,167.

Ceramides are members of a class of lipids known as sphingolipids . They are found within the cell membrane complex of hair cuticle cells. It is thought that it is necessary to maintain the ceramide content of the hair in order to prevent damage. To this end, hair treatment compositions comprising ceramides are known.

EP 647617, describes new synthetic ceramide compounds which are useful in cosmetic and dermatological compositions.

FR 2718961 describes a composition containing ceramide and a cationic polymer for washing hair and treating hair. FR 2718960 describes a hair treatment and protecting composition containing ceramide and specific cationic polymers used in a non washing process with synergistic effect. EP 680743 describes compositions for hair and eyelash styling containing ceramide and vinylpyrrolidone polymer.

Retinol (known also as vitamin A) is known commercially for use in the treatment of ageing skin. The palmitate derivative, retinyl palmitate, is used as an ingredient in pharmaceutical and cosmetic skin treatment compositions. EP 0 742 005 discloses skin conditioning compositions comprising retinol or a retinyl ester and a fatty acid amide. US 6,013,250 discloses a hair treatment composition for treating hair against chemical and photo-induced damage.

Summary of the Invention

It has now surprisingly been found that hair treatment compositions comprising both a ceramide and retinyl palmitate, combined with a water-insoluble oil, can provide damage prevention and damage repair to hair. It has also been found that the combination can improve the retention of hair dyes and colourants when the hair is washed after it has been dyed or coloured.

Hence, in a first aspect, the invention is concerned with a hair treatment composition comprising a ceramide, a fatty acid ester of retinol and a water-insoluble oil.

Detailed Description

By water-insoluble is meant that the solubility in water at 25 °C is 0.1% or less by weight of water, preferably 0.01% or less, more preferably 0.001% or less.

It is preferred if the ceramide and the fatty acid ester of retinol are dissolved in a liquid phase which comprises the water-insoluble oil. The solubility of the ceramide in the water-insoluble oil may not be sufficient for all the ceramide in the composition to be solubilised in the oil. In this case, it is preferred if the composition further comprises a solubilising solvent to aid the solubilisation of the ceramide into the water insoluble oil . It is particularly preferred if the ceramide and the fatty acid ester of retinol are dissolved in a liquid which consists essentially of the water-insoluble oil and any solubilising solvent .

Preferably, compositions according to the invention comprise 1% by weight or more of the water-insoluble oil, preferably 2% or more, more preferably 5% or more and most preferably 10% or more .

Suitably there is 0.0005% by weight or more of ceramide by weight of the water-insoluble oil, preferably .0.001% or more, more preferably 0.002% or more.

Suitably there is 0.0005% by weight or more of fatty acid ester of retinol by weight of the water-insoluble oil, preferably .0.001% or more, more preferably 0.002% or more.

Suitably, the ratio of fatty acid ester of retinol to ceramide in compositions of the invention is from 1:1 to

500:1, preferably from 1.5:1 to 100:1, more preferably from 2:1 to 10:1.

A preferred process for making compositions according to the invention comprises the steps of :

i) forming a first blend comprising the water-insoluble oil, ceramide and fatty acid ester of retinol and;

ii) dispersing the blend with the rest of the composition. Preferably, the ceramide and fatty acid of retinol are dissolved in the water- insoluble oil in step (i) above.

In a preferred form of the invention suitable for preparing emulsion compositions, the blend of water-insoluble oil, ceramide and fatty acid ester of retinol further comprises an emulsifying surfactant to facilitate the preparation of oil-in-water emulsions, water-in oil emulsions or multiple emulsions, such emulsifiers are well known to those skilled in the art or may be selected from the surfactants disclosed hereinbelow.

Ceramide

Ceramides are a form of lipid which occurs naturally in hair and skin, specifically they are sphingolipids . Although any suitable ceramide may be used in compositions according to the invention, it is preferred if the ceramide is selected from the group consisting of the ceramides with the INCI nomenclature Ceramide 1 and Ceramide 2, and mixtures thereof .

Retinyl Fatty Acid Ester

Fatty acid esters of retinol (vitamin A) are present in compositions according to the invention. Although any suitable fatty acid aster may me employed, if is preferred if the fatty acid used in preparing the ester has a carbon chain length (including the carbon of the carboxylate group) from 2 to 22. The fatty chain may be saturated or unsaturated, straight or branched. Particularly preferred for compositions of the invention are the esters retinyl palmitate, retinyl acetate and retinyl propionate. Mixtures of these esters are also particularly suitable.

Water-Insoluble Oil

It is preferred if the water-insoluble oil used in compositions according to the invention is a non-silicone oil

Preferred oils are selected from hydrocarbon oils, ester oils and mixtures thereof.

Hydrocarbon oils

Suitable hydrocarbon oils include cyclic hydrocarbons, straight chain aliphatic hydrocarbons (saturated or unsaturated) , and branched chain aliphatic hydrocarbons (saturated or unsaturated) . Straight chain (linear) hydrocarbon oils will typically contain from about 6 to about 16 carbon atoms, preferably from about 8 up to about 14 carbon atoms. Branched chain hydrocarbon oils can and typically may contain higher numbers of carbon atoms, e.g. from about 6 up to about 40 carbon atoms, preferably from about 8 up to about 18 carbon atoms.

Suitable hydrocarbon oils of the invention will generally have a viscosity at 25°C and 21 sec-1 of from 0.0001 to 0.5 Pa.s, preferably from 0.001 to 0.05 Pa.s, more preferably from 0.001 to 0.02 Pa.s as measured by a Carri-Med CSL2 100 controlled stress rheometer, from TA Instruments Inc., New Castle, Delaware (USA) . A preferred hydrocarbon oil is light mineral oil. Mineral oils are clear oily liquids obtained from petroleum oil, from which waxes have been removed, and the more volatile fractions removed by distillation. The fraction distilling between 250 °C to 300 °C is termed mineral oil, and it consists of a mixture of hydrocarbons, in which the number of carbon atoms per hydrocarbon molecule generally ranges from Cio to

C₄₀. Mineral oil may be characterised in terms of its viscosity, where light mineral oil is relatively less viscous than heavy mineral oil, and these terms are defined more specifically in the U.S. Pharmacopoeia, 22nd revision, p. 899 (1990) . A commercially available example of a suitable light mineral oil for use in the invention is Sirius M40

(carbon chain length C₁0-C₂8/ mainly C₁2- ₂0/ viscosity 4.3 x 10-3 Pa.s at 25°C), available from Silkolene.

Other hydrocarbon oils that may be used in the invention include relatively lower molecular weight hydrocarbons including linear saturated hydrocarbons such a tetradecane,hexadecane, and octadecane, cyclic hydrocarbons such as dioctylcyclohexane (e.g. CETIOL S from Henkel) , branched chain hydrocarbons (e.g. ISOPAR L and ISOPAR V from Exxon Corp . ) .

The oil may be volatile or non-volatile. An example of a suitable volatile mineral oil is Permethyl 101A.

The hydrocarbon oil may be present in compositions of the invention as a single material or as a blend with oils. Ester Oils

By ester oils is meant the esters formed between alcohols and long chain carboxylic acids such as C₆-C₃0 carboxylic acids. The carboxylic acids may be linear or branched, saturated or unsaturated or contain hydrophilic groups such as hydroxyl .

Suitable alcohols forming the ester oils include, but are not limited to, ethylene glycol, propylene glycol, glycerol, sorbitol, pentaerithrytol and the various sugars such as sucrose, glucose, fructose and dipentaerythritol . There may be only one long-chain acid bonded to the alcohol by an ester link, or several.

Preferred ester oils are mono-, di- and tri- esters of glycerol. Particularly preferred are tri-esters of glycerol, also known as triglycerides .

Preferred glyceride fatty esters are derived from carboxylic acids of carbon chain length ranging from CQ to C₂₄, preferably C₁₀ to C₂₂ most preferably C₁₂ to Cis.

Suitable glyceride fatty esters for use in hair oils of the invention will generally have a viscosity at 25°C and a

-1 shear rate of 21 sec from 0.01 to 0.8 Pa.s , preferably from 0.015 to 0.6 Pa.s, more preferably from 0.02 to 0.065 Pa.s as measured by a Carri-Med CSL2 100 controlled stress rheometer, from TA Instruments Inc., New Castle, Delaware (USA) . A variety of these types of materials are present in vegetable and animal fats and oils, such as camellia oil, coconut oil, castor oil, safflower oil, sunflower oil, peanut oil, cottonseed oil, corn oil, olive oil, cod liver oil, almond oil, avocado oil, palm oil, sesame oil, lanolin and soybean oil . These have various ranges of carbon chain lengths depending on the source, typically between about 12 to about 18 carbon atoms. Synthetic oils include trimyristin, triolein, tristearin and glyceryl dilaurate. Vegetable derived glyceride fatty esters are particularly preferred, and specific examples of preferred materials for inclusion in hair oils of the invention as sources of glyceride fatty esters include almond oil, castor oil, coconut oil, jojoba oil, sesame oil, sunflower oil and soya bean oil. Coconut oil, soya bean oil, jojoba oil and mixtures thereof are particularly preferred.

The water-insoluble oil may be present in compositions of the invention as a single material or as a blend.

Solubilising Solvent

The solubility of the ceramide in the water-insoluble oil may not be sufficient for all the ceramide in the composition to be solubilised in the oil. In this case, it is preferred if the composition further comprises a solubilising solvent to aid the solubilisation of the ceramide into the water insoluble oil .

The solubilising solvent is selected to improve the solubility of the ceramide in the mineral oil . Straight or branched chain alkyl benzoates and mixtures thereof are preferred solubilising agents. Preferably, the alkyl chain of the alkyl benzoate comprises from 4 to 22 carbon atoms, more preferably from 8 to 18, most preferably from 12 to 16.

Suitably, the solubilising solvent is present from 1 to 20% by weight of the weight of water-insoluble oil, preferably from 4 to 16%, more preferably from 6 to 10%.

A suitable solubilising solvent is a C₁₂-C₁₅ alkyl benzoate

TM available commercially as Finsolv

Hair Treatment Composition

Hair treatment compositions according to the invention may suitably take the form of shampoos, conditioners, sprays, mousses, oils, styling products, hair colouring products or lotions and pre-treatment products for application to the hair prior to colouring or dyeing. Compositions according to the invention may be applied to the hair and left on the hair for hours or days (as leave-on products) or they may be rinsed off the hair soon after application (as rinse-off products) .

Shampoo Compositions

A particularly preferred hair conditioning composition in accordance with the invention is a shampoo composition. Such a shampoo composition will comprise one or more cleansing surfactants which are cosmetically acceptable and suitable for topical application to the hair.

Suitable cleansing surfactants, which may be used singularly or in combination, are selected from anionic, nonionic amphoteric and zwitterionic surfactants, and mixtures thereof .

Anionic Cleansing Surfactant

Shampoo compositions according to the invention will typically comprise one or more anionic cleansing surfactants which are cosmetically acceptable and suitable for topical application to the hair.

Examples of suitable anionic cleansing surfactants are the alkyl sulphates, alkyl ether sulphates, alkaryl sulphonates, alkanoyl isethionates, alkyl succinates, alkyl sulphosuccinates, N-alkyl sarcosinates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, and alpha- olefin sulphonates, especially their sodium, magnesium, ammonium and mono-, di- and triethanolamine salts. The alkyl and acyl groups generally contain from 8 to 18 carbon atoms and may be unsaturated. The alkyl ether sulphates, alkyl ether phosphates and alkyl ether carboxylates may contain from 1 to 10 ethylene oxide or propylene oxide units per molecule.

Typical anionic cleansing surfactants for use in shampoo compositions of the invention include sodium oleyl succinate, ammonium lauryl sulphosuccinate, ammonium lauryl sulphate, sodium dodecylbenzene sulphonate, triethanolamine dodecylbenzene sulphonate, sodium cocoyl isethionate, sodium lauryl isethionate and sodium N-lauryl sarcosinate. The most preferred anionic surfactants are sodium lauryl sulphate, sodium lauryl ether sulphate (n) EO, (where n ranges from 1 to 3) , ammonium lauryl sulphate and ammonium lauryl ether sulphate (n) EO, (where n ranges from 1 to 3) .

Mixtures of any of the foregoing anionic cleansing surfactants may also be suitable.

The total amount of anionic cleansing surfactant in shampoo compositions of the invention is generally from 5 to 30, preferably from 6 to 20, more preferably from 8 to 16 percent by weight of the composition.

Co-surfactant

The shampoo composition can optionally include co- surfactants, to help impart aesthetic, physical or cleansing properties to the composition.

A preferred example is an amphoteric or zwitterionic surfactant, which can be included in an amount from 0 to about 8, preferably from 1 to 4 percent by weight of the composition.

Examples of amphoteric and zwitterionic surfactants include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulphobetaines (sultaines) , alkyl glycinates, alkyl carboxyglycinates, alkyl amphopropionates, alkylamphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, wherein the alkyl and acyl groups have from 8 to 19 carbon atoms. Typical amphoteric and zwitterionic surfactants for use in shampoos of the invention include lauryl amine oxide, cocodimethyl sulphopropyl betaine and preferably lauryl betaine, cocamidopropyl betaine and sodium cocamphopropionate .

Another preferred example is a nonionic surfactant, which can be included in an amount from 0 to 8, preferably from 2 to 5 percent by weight of the composition.

For example, representative nonionic surfactants that can be included in shampoo compositions of the invention include condensation products of aliphatic (Cs - Ciβ) primary or secondary linear or branched chain alcohols or phenols with alkylene oxides, usually ethylene oxide and generally having from 6 to 30 ethylene oxide groups.

Other representative nonionic surfactants include mono- or di-alkyl alkanolamides . Examples include coco mono- or di- ethanolamide and coco mono-isopropanolamide.

Further nonionic surfactants which can be included in shampoo compositions of the invention are the alkyl polyglycosides (APGs) . Typically, the APG is one which comprises an alkyl group connected (optionally via a bridging group) to a block of one or more glycosyl groups . Preferred APGs are defined by the following formula: RO - (G) _n

wherein R is a branched or straight chain alkyl group which may be saturated or unsaturated and G is a saccharide group. R may represent a mean alkyl chain length of from about C₅ to about C₂0 • Preferably R represents a mean alkyl chain length of from about Cs to about C₁₂. Most preferably the value of R lies between about 9.5 and about 10.5. G may be selected from C₅ or Cζ monosaccharide residues, and is preferably a glucoside. G may be selected from the group comprising glucose, xylose, lactose, fructose, mannose and derivatives thereof. Preferably G is glucose.

The degree of polymerisation, n, may have a value of from about 1 to about 10 or more. Preferably, the value of n lies in the range of from about 1.1 to about 2. Most preferably the value of n lies in the range of from about 1.3 to about 1.5.

Suitable alkyl polyglycosides for use in the invention are commercially available and include for example those materials identified as: Oramix NS10 ex Seppic; Plantaren 1200 and Plantaren 2000 ex Henkel .

Other sugar-derived nonionic surfactants which can be included in shampoo compositions of the invention include the

Cιo-Ci8 N-alkyl (Ci-Cg) polyhydroxy fatty acid amides, such as the C₁₂-C₁₈ N-methyl glucamides, as described for example in WO 92 06154 and US 5 194 639, and the N-alkoxy polyhydroxy fatty acid amides, such as Cio-Ciβ N- (3-methoxypropyl) glucamide .

The shampoo composition can also optionally include one or more cationic co-surfactants included in an amount ranging from 0.01 to 10, more preferably from 0.05 to 5, most preferably from 0.05 to 2 wt%. Useful cationic surfactants are described hereinbelow in relation to hair conditioner compositions .

The total amount of surfactant (including any co-surfactant , and/or any emulsifier) in shampoo compositions of the invention is generally from 5 to 50, preferably from 5 to 30, more preferably from 10 to 25 percent by weight of the composition.

Cationic Polymer

A cationic polymer is a preferred ingredient in shampoo compositions of the invention, for enhancing conditioning performance of the shampoo.

The cationic polymer may be a homopolymer or be formed from two or more types of monomers . The molecular weight of the polymer will generally be between 5 000 and 10 000 000, typically at least 10 000 and preferably in the range 100 000 to about 2 000 000 unified mass units. The polymers will have cationic nitrogen containing groups such as quaternary ammonium or protonated amino groups, or a mixture thereof . The cationic nitrogen-containing group will generally be present as a substituent on a fraction of the total monomer units of the cationic polymer. Thus when the polymer is not a homopolymer it can contain spacer non-cationic monomer units . Such polymers are described in the CTFA Cosmetic Ingredient Directory, 3rd edition. The ratio of the cationic to non-cationic monomer units is selected to give a polymer having a cationic charge density in the required range.

Suitable cationic conditioning polymers include, for example, copolymers of vinyl monomers having cationic amine or quaternary ammonium functionalities with water soluble spacer monomers such as (meth) acrylamide, alkyl and dialkyl (meth) acrylamides, alkyl (meth) acrylate, vinyl caprolactone and vinyl pyrrolidine. The alkyl and dialkyl substituted monomers preferably have C1-C7 alkyl groups, more preferably Cl-3 alkyl groups. Other suitable spacers include vinyl esters, vinyl alcohol, maleic anhydride, propylene glycol and ethylene glycol .

The cationic amines can be primary, secondary or tertiary amines, depending upon the particular species and the pH of the composition. In general secondary and tertiary amines, especially tertiary, are preferred.

Amine substituted vinyl monomers and amines can be polymerized in the amine form and then converted to ammonium by quaternization.

The cationic conditioning polymers can comprise mixtures of monomer units derived from amine- and/or quaternary ammonium-substituted monomer and/or compatible spacer monomers .

Suitable cationic conditioning polymers include, for example : copolymers of 1-vinyl-2-pyrrolidine and l-vinyl-3- methyl-imidazolium salt (e.g. chloride salt), referred to in the industry by the Cosmetic, Toiletry, and Fragrance Association, (CTFA) as Polyquaternium-16. This material is commercially available from BASF Wyandotte Corp. (Parsippany, NJ, USA) under the LUVIQUAT tradename (e.g. LUVIQUAT FC 370) ;

copolymers of 1-vinyl-2-pyrrolidine and dimethylaminoethyl methacrylate, referred to in the industry (CTFA) as Polyquaternium-11. This material is available commercially from Gaf Corporation (Wayne, NJ, USA) under the GAFQUAT tradename (e.g., GAFQUAT 755N) ;

cationic diallyl quaternary ammonium-containing polymers including, for example, dimethyldiallyammonium chloride homopolymer and copolymers of acrylamide and dimethyldiallylammonium chloride, referred to in the industry (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively;

mineral acid salts of amino-alkyl esters of homo-and copolymers of unsaturated carboxylic acids having from 3 to 5 carbon atoms, (as described in U.S. Patent 4,009,256) ; cationic polyacrylamides (as described in W095/22311) .

Other cationic conditioning polymers that can be used include cationic polysaccharide polymers, such as cationic cellulose derivatives, cationic starch derivatives, and cationic guar gum derivatives. Suitably, such cationic polysaccharide polymers have a charge density in the range from 0.1 to 4 meq/g.

Cationic polysaccharide polymers suitable for use in compositions of the invention include those of the formula:

A-0-[R-N⁺(R¹) (R²) (R³)X^"] ,

wherein: A is an anhydroglucose residual group, such as a starch or cellulose anhydroglucose residual. R is an alkylene, oxyalkylene, polyoxyalkylene, or hydroxyalkylene

1 2 3 group, or combination thereof. R , R and R independently represent alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18 carbon atoms . The total number of carbon atoms for each

1 2 cationic moiety (i.e., the sum of carbon atoms in R , R and

₃ R ) is preferably about 20 or less, and X is an anionic counterion.

Cationic cellulose is available from Amerchol Corp. (Edison, NJ, USA) in their Polymer JR (trade mark) and LR (trade mark) series of polymers, as salts of hydroxyethyl cellulose reacted with trimethyl ammonium substituted epoxide, referred to in the industry (CTFA) as Polyquaternium 10. Another type of cationic cellulose includes the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium-substituted epoxide, referred to in the industry (CTFA) as Polyquaternium 24. These materials are available from Amerchol Corp. (Edison, NJ, USA) under the tradename Polymer LM-200.

Other suitable cationic polysaccharide polymers include quaternary nitrogen-containing cellulose ethers (e.g. as described in U.S. Patent 3,962,418), and copolymers of etherified cellulose and starch (e.g. as described in U.S. Patent 3,958,581).

A particularly suitable type of cationic polysaccharide polymer that can be used is a cationic guar gum derivative, such as guar hydroxypropyltrimonium chloride (commercially available from Rhone-Poulenc in their JAGUAR trademark series) .

Examples are JAGUAR C13S, which has a low degree of substitution of the cationic groups and high viscosity. JAGUAR C15, having a moderate degree of substitution and a low viscosity, JAGUAR C17 (high degree of substitution, high viscosity) , JAGUAR C16, which is a hydroxypropylated cationic guar derivative containing a low level of substituent groups as well as cationic quaternary ammonium groups, and JAGUAR 162 which is a high transparency, medium viscosity guar having a low degree of substitution. Preferably the cationic conditioning polymer is selected from cationic cellulose and cationic guar derivatives. Particularly preferred cationic polymers are JAGUAR C13S, JAGUAR C15, JAGUAR C17 and JAGUAR C16 and JAGUAR C162.

The cationic conditioning polymer will generally be present in compositions of the invention at levels of from 0.01 to 5, preferably from 0.05 to 1, more preferably from 0.08 to 0.5 percent by weight of the composition.

Hair Conditioner Compositions

Compositions in accordance with the invention may also be formulated as conditioners for the treatment of hair (typically after shampooing) and subsequent rinsing.

Conditioning Surfactant

Such a conditioner will comprise one or more conditioning surfactants which are cosmetically acceptable and suitable for topical application to the hair.

Suitable conditioning surfactants are selected from cationic surfactants, used singly or in admixture.

Cationic surfactants useful in compositions of the invention contain amino or quaternary ammonium hydrophilic moieties which are positively charged when dissolved in the aqueous composition of the present invention. Examples of suitable cationic surfactants are those corresponding to the general formula:

[N(Rι) (R₂) (R₃) ( 4)] (X)

in which Ri, R₂, R₃ , and R₄ are independently selected from

(a) an aliphatic group of from 1 to 22 carbon atoms, or (b) an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to 22 carbon atoms; and X is a salt-forming anion such as those selected from halogen, (e.g. chloride, bromide), acetate, citrate, lactate, glycolate, phosphate nitrate, sulphate, and alkylsulphate radicals.

The aliphatic groups can contain, in addition to carbon and hydrogen atoms, ether linkages, and other groups such as amino groups. The longer chain aliphatic groups, e.g., those of about 12 carbons, or higher, can be saturated or unsaturated.

The most preferred cationic surfactants for conditioner compositions of the present invention are monoalkyl quaternary ammonium compounds in which the alkyl chain length is C16 to C22.

Examples of suitable cationic surfactants include: cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, cetylpyridinium chloride, tetramethylammonium chloride, tetraethylammonium chloride, octyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octyldimethylbenzylammonium chloride, decyldimethylbenzylammonium chloride, stearyldimethylbenzylammonium chloride, didodecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, tallowtrimethylammonium chloride, cocotrimethylammonium chloride, PEG-2 oleylammonium chloride and salts of these where the chloride is replaced by halogen, (e.g. , bromide) , acetate, citrate, lactate, glycolate, phosphate nitrate, sulphate, or alkylsulphate.

Further suitable cationic surfactants include those materials having the CTFA designations Quaternium-5, Quaternium-31 and Quaternium-18. Mixtures of any of the foregoing materials may also be suitable. A particularly useful cationic surfactant for use in hair conditioners of the invention is cetyltrimethylammonium chloride, available commercially, for example as GENAMIN CTAC, ex Hoechst Celanese.

Salts of primary, secondary, and tertiary fatty amines are also suitable cationic surfactants. The alkyl groups of such amines preferably have from about 12 to about 22 carbon atoms, and can be substituted or unsubstituted.

Particularly useful are amido substituted tertiary fatty amines. Such amines, useful herein, include stearamidopropyldimethylamine, stearamidopropyidiethylamine, stearamidoethyldiethylamine, stearamidoethyldimethylamine, palmitamidopropyld imethylamine, palmitamidopropyldiethylamine, palmitamidoethyldiethylamine, palmitamidoethyldimethylamine, behenamidopropyldimethylamine, behenamidopropyldiethylamine, behenamidoethyldiethylamine, behenamidoethyldimethylamine, arachidamidopropyldimethylamine, arachid amidopropyldiethylamine, arachidamidoethyldiethylamine, arachidamidoethyldimethylamine, diethylaminoethylstearamide . Also useful are dimethylstearamine, dimethylsoyamine, soyamine, myristylamine, tridecylamine, ethylstearylamine, N- tallowpropane diamine, ethoxylated (with 5 moles of ethylene oxide) stearylamine, dihydroxyethylstearylamine, and arachidyl behenylamine . These amines are typically used in combination with an acid to provide the cationic species. The preferred acid useful herein includes L- glutamic acid, lactic acid, hydrochloric acid, malic acid, succinic acid, acetic acid, fumaric acid, tartaric acid, citric acid, L- glutamic hydrochloride, and mixtures thereof; more preferably L-glutamic acid, lactic acid, citric acid. Cationic amine surfactants included among those useful in the present invention are disclosed in U.S. Patent 4,275,055 to Nachtigal, et al . , issued June 23, 1981.

The molar ratio of protonatable amines to H from the acid is preferably from about 1:0.3 to 1:1.2, and more preferably from about 1:0.5 to about 1:1.1.

In the conditioners of the invention, the level of cationic surfactant is preferably from 0.01 to 10, more preferably 0.05 to 5, most preferably 0.1 to 2 wt% of the total composition. Fatty Materials

Conditioner compositions of the invention preferably additionally comprise fatty materials. The combined use of fatty materials and cationic surfactants in conditioning compositions is believed to be especially advantageous, because this leads to the formation of a lamellar phase, in which the cationic surfactant is dispersed.

By "fatty material" is meant a fatty alcohol, an alkoxylated fatty alcohol, a fatty acid or a mixture thereof.

Preferably, the alkyl chain of the fatty material is full saturated.

Representative fatty materials comprise from 8 to 22 carbon atoms, more preferably 16 to 22. Examples of suitable fatty alcohols include cetyl alcohol, stearyl alcohol and mixtures thereof. The use of these materials is also advantageous in that they contribute to the overall conditioning properties of compositions of the invention.

Alkoxylated, (e.g. ethoxylated or propoxylated) fatty alcohols having from about 12 to about 18 carbon atoms in the alkyl chain can be used in place of, or in addition to, the fatty alcohols themselves. Suitable examples include ethylene glycol cetyl ether, polyoxyethylene (2) stearyl ether, polyoxyethylene (4) cetyl ether, and mixtures thereof . The level of fatty alcohol material in conditioners of the invention is suitably from 0.01 to 15, preferably from 0.1 to 10, and more preferably from 0.1 to 5 wt%. The weight ratio of cationic surfactant to fatty alcohol is suitably from 10:1 to 1:10, preferably from 4:1 to 1:8, optimally from 1:1 to 1:7, for example 1:3.

Conditioner compositions of the invention may also contain a cationic polymer. Suitable cationic polymers are described hereinabove in relation to shampoo compositions.

Suspending Agents

In a preferred embodiment, the hair conditioning composition, especially if it is a shampoo composition, further comprises from 0.1 to 5 wt% of a suspending agent. The role of this material is to stabilise the composition against physical separation of the aqueous and water- insoluble phases when both such phases are present in compositions of the invention. Suitable suspending agents are selected from polyacrylic acids, cross-linked polymers of acrylic acid, copolymers of acrylic acid with a hydrophobic monomer, copolymers of carboxylic acid- containing monomers and acrylic esters, cross-linked copolymers of acrylic acid and acrylate esters, heteropolysaccharide gums and crystalline long chain acyl derivatives. The long chain acyl derivative is desirably selected from ethylene glycol stearate, alkanolamides of fatty acids having from 16 to 22 carbon atoms and mixtures thereof. Ethylene glycol distearate and polyethylene glycol

3 distearate are preferred long chain acyl derivatives. Polyacrylic acid is available commercially as Carbopol 420, Carbopol 488 or Carbopol 493. Polymers of acrylic acid cross-linked with a polyfunctional agent may also be used, they are available commercially as Carbopol 910, Carbopol 934, Carbopol 940, Carbopol 941 and Carbopol 980. An example of a suitable copolymer of a carboxylic acid containing a monomer and acrylic acid esters is Carbopol 1342. All Carbopol (trade mark) materials are available from Goodrich.

Suitable cross-linked polymers of acrylic acid and acrylate esters are Pemulen TR1 or Pemulen TR2. A suitable heteropolysaccharide gum is xanthan gum, for example that available as Kelzan mu.

The suspending agent is preferably a polymeric suspending agent

Mousses

Hair treatment compositions in accordance with the invention may also take the form of aerosol foams (mousses) in which case a propellant must be included in the composition. This agent is responsible for expelling the other materials from the container and forming the hair mousse character.

The propellant gas can be any liquefiable gas conventionally used for aerosol containers. Examples of suitable propellants include dimethyl ether, propane, n-butane and isobutane, used singly or in admixture. The amount of the propellant gases is governed by normal factors well known in the aerosol art. For hair mousses, the level of propellant is generally from 3 to 30, preferably from 5 to 15 percent by weight of the total composition.

Small quantities of surfactant ranging anywhere from 0.1 to 10, preferably from 0.1 to about 1 percent by weight of the composition, for example 0.3 percent by weight of the composition may be present in the hair mousse compositions of the invention. The surfactant may be an anionic, nonionic or cationic emulsifier. Particularly preferred are nonionic emulsifiers which are formed from alkoxylation of hydrophobes such as fatty alcohols, fatty acids and phenols.

Hair Oils and Lotions

Hair oils are also suitable hair treatment compositions according to the invention. Hair oils predominantly comprise water-insoluble oily materials as described herein. Lotions are aqueous emulsions comprising water-insoluble oily conditioning materials. Suitable surfactants and suspending agents as described herein can also be included in lotions to improve their stability to phase separation. It is preferred if these compositions according to the invention are applied to the hair as a pre-treatment prior to dyeing or colouring the hair. Another preferred form of composition according to the invention is a conditioning composition which is applied to the hair and left on the hair until the next wash. Hair colourants

Hair colourants or dyes are another composition which can be prepared in a form according to the invention. In addition to the essential components of the invention, such products further comprise permanent, semi-permanent or temporary colourants .

Uses

Compositions according to the invention are particularly used for the repair of damaged hair, for improving the colour fastness of dyed hair and for preventing damage to hair. A preferred use is as a pre-treatment composition applied to the hair within one hour prior to applying a colourant to the hair.

In another aspect, the invention is concerned with the application of compositions according to the invention to the hair. Particularly suitable compositions are shampoos comprising a cleansing surfactant, hair oils and rinse-off conditioners comprising a conditioning surfactant. Another particularly suitable composition is a pre-treatment composition to be applied to the hair within 1 hour prior to applying a colourant to the hair.

Compositions according to the invention may also be used as leave-on hair conditioners, which are applied to the hair after washing and remain on the hair until the next wash. The invention is further illustrated with reference to the following examples:

Examples

The following experiment was carried out showing the colour protection benefits of the invention. A combination of 1 part of Ceramides to 2.5 parts of Retinyl Palmitate was employed in three separate formulations called Prototype 1, Prototype 2 and Prototype 3.

Protoype 1 is a typical standard conditioner which contains (in addition to the ceramide and retinyl palmitate) as its ingredients, Water, Cetearyl Alcohol, Dimethiconol & TEA Dodecylbenzenesulfonate, Ceterimonium Chloride,

Hydroxyethylcellulose, Fragrance, Octyl Methoxycinnamate, Methyl Paraben, Formaldehyde, Citric Acid, Tocophyeryl Acetate and extracts of Lemon, Uve, and Apple.

Protoype 2 is a typical pre-treatment conditioner which contains (in addition to the ceramide and retinyl palmitate) as its ingredients.

Water, Propylene Glycol, Polysorbate 20, Hydroxyethylcellulose, Polyquaternium-6, Stertrimonium Hydroxyethyl Hydrolyzed Collagen,

Polymethacrylamidopropyltrimonium Chloride, Fragrance containing Essential oils, DMDM Hydantoin, Disodium EDTA, Citirc Acid, Sodium Hydroxide, Isoleucine and Glucose.

Prototype 3 is a pre-treatment hair oil which contains (in addition to ceramide and retinyl palmitate) as its ingredients: 100% pure, edible coconut oil. A set of hair swatches was bleached and then treated with a typical

TM permanent hair colour, Sedal 6RR which is a red shade. These swatches were then divided into five groups.

Group 1 was used as untreated control

Group 2 was treated with Prototype formula 2 and then shampooed/conditioned with a typical shampoo conditioner. Group 3 was treated with Prototype formula 3 and then shampooed/conditioned with a typical shampoo conditioner. Group 4 was treated with Prototype formula 1 and then shampooed/conditioned with a typical shampoo conditioner. Group 5 was not treated with any formula prior to shampoo and conditioner with a typical shampoo and conditioner.

Each group of swatches was then evaluated for colour retention.using L values. Results are as follows (Tukey test for statistical significance) .

Consumers were then shown a pair of swatches and then asked which swatch in the pair lost more colour. Results are in agreement with the instrumental measurements of L value, but the consumers are further able to determine that the group 4 lost more colour than Group 3 or 2.

Group 4 vs. Group 2 (conventional conditioner vs. pre treatment containing oils)

Group 4 vs. Group 3 (conventional conditioner vs. pre treatment containing oils)

These results indicate that when there is no pretreatment to protect the hair from colour loss, the swatches lose a significant amount of colour compared to those swatches that have been pre-treated with compositions according to the invention (Comparison of Group 5 with Groups 2, 3 and 4) . A second conclusion is that among the swatches that ceramide and retinyl palmitate as part of the treatment, Group 2 and Group 3, which also had water-insoluble oil, present better performance than a conventional conditioner formula without water-insoluble oil. Note that this conclusion is from consumers' evaluation of these swatches along with the L values shown above. Pre-Shampoo treatment hair oil.

Coconut oil q.s. to lOOparts

Retinyl Palmitate 0.0025parts Ceramides 0. OOlOparts

Pre-Shampoo treatment hair conditioner

Soyabean oil, Jojoba oil & Coconut oil...0.5 parts Propylene Glycol 4.0 parts

Polysobate 20 1.0 parts

Hydroxyethyl cellulose q.s. to obtain viscosity

CETAC 1.0 parts

RetinyPalmitate 0.0025 parts Ceramides 0.0010 parts

WATER q.s. to 100

Claims

1. A hair treatment composition comprising a ceramide, a fatty acid ester of retinol and a water-insoluble oil.

2. A composition according to claim 1 wherein the ceramide and fatty acid ester of retinol are dissolved in a liquid phase comprising the water insoluble oil.

3. A composition according to any preceding claim comprising 1% or more by weight of the water-insoluble oil.

4. A composition according to any preceding claim comprising 0.0005% or more of ceramide and 0.0005% or more of fatty acid ester of retinol by weight of water- insoluble oil .

5. A composition according to any preceding claim wherein the weight ratio of fatty acid ester of retinol to ceramide is from 1:1 to 500:1

6. A composition according to any preceding claim wherein the ceramide is selected from the group consisting of ceramide I, ceramide II and mixtures thereof.

7. A composition according to any preceding claim wherein the fatty acid ester of retinol is selected from the group consisting of retinyl palmitate, retinyl acetate, retinyl propionate and mixtures thereof.

8. A composition according to any preceding claim wherein the water-insoluble oil is selected from the group consisting of mineral oils, ester oils and mixtures thereof.

9. A composition according to any preceding claim wherein the water-insoluble oil is selected from the group consisting of coconut oil, jojoba oil, soya bean oil and mixtures thereof .

10. A composition according to any preceding claim which is a shampoo composition comprising a cleansing surfactant.

11. A composition according to any preceding claim which is a leave-on conditioning composition.

12. A composition according to any preceding claim which is a rinse-off conditioning composition comprising a conditioning surfactant.

13. A method of preparing a composition according to any preceding claim comprising the steps of :

ii) dispersing the first blend with the rest of the composition.

14. A method of treating the hair comprising applying to the hair a composition according to any of claims 1 to 12.

15. The use of a composition according to claims 1 to 12 for the repair of damaged hair.

16. The use of a composition according to claims 1 to 12 for improving the colour-fastness of dyed hair.

17. The use of a composition according to claims 1 to 12 for preventing damage to hair.