MXPA05008731A - Methods and devices for determining a correction value for a measured segment time. - Google Patents

Abstract

The invention relates to methods and devices for determining a correction value for a measured segment time which the shaft of an internal combustion engine, especially a crankshaft, requires for rotating about a defined angular degree. The aim of the invention is to provide a method and a device which allow for the determination of such a correction value for individual cylinders. For this purpose, the following correlation is evaluated: AZn=[(TGn-TG0)-(n/z)*(TG0'-TG0)] / [TG0+(n/z)*(TG0'-TG0)], whereby z is the number of cylinders of the internal combustion engine, n is the number of the cylinder presently observed, TGn is the measured segment time of the cylinder having the number n, TG0 is the measured segment time of a reference segment of a reference cylinder, TG0' is the segment time of the reference segment of the reference cylinder measured two crankshaft rotations after the segment time TG0, and AZn is a correction value for the segment time of the cylinder having the number n. The invention allows the determination of correction values irrespective of the availability of possible speed gradients.

Description

COMPOSITION IS OF TRATAM I ENTO FOR HAIR The invention relates to hair treatment compositions, in particular hair conditioning compositions which repair damaged hair and which provide improved color retention for dyed hair by reducing color loss when the hair is washed. Conventional grooming habits such as shampooing, combing, brushing and drying with hot air can lead to damage to hair known as dry hair. Environmental exposure to sunlight can also damage the hair. In addition, hair treatments such as dyeing or coloring, styling, curling or straightening can cause damage and dryness. This can also lead to other problems such as curling, ursuela, lack of manageability and hair breakage. In particular, damaged or dry hair is particularly poor in retaining dyes or hair dyes. These are leached from damaged hair more easily than from undamaged hair during subsequent washes after dyeing or coloring. From there, it is highly desirable to provide hair treatment compositions, which repair the damage to already damaged hair in order to overcome damage problems. In particular, it is desirable to provide hair treatment compositions, which improve the retention of dyes and hair colorants for colored hair when subsequently washed. It is also desirable to provide compositions that act on the hair to protect or prevent hair from being damaged during subsequent treatments. The hair conditioning compositions and rinsing creams are usually applied to wet hair, after washing and rinsing, in order to improve the combability and manageability. Such compositions often comprise silicone-based polymers, such as those described 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. For this purpose, 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 271 8960 describes a hair treatment and protective composition containing ceramide and specific cationic polymers used in a non-washing process with synergistic effect. EP 680743 describes compositions for hair and stylized eyelashes containing ceramide and vinylpyrrolidone polymer.

Retinol (also known as vitamin A) is commercially known for use in the treatment of aged 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.

BRIEF DESCRIPTION OF THE INVENTION Surprisingly, it has now been discovered that hair treatment compositions comprising both a ceramide and retinyl palmitate, combined with a water-insoluble oil, can provide damage prevention and repair of hair damage. It has also been found that the combination can improve the retention of dyes and dyes for hair when the hair is washed after it has been dyed or colored. Hence, in a first aspect, the invention concerns a treatment composition for hair comprising a ceramide, a fatty acid ester of retinol and a water-insoluble oil.

Detailed description By insoluble in water it 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 retinol fatty acid ester 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 of the ceramide in the composition to be solubilized in the oil. In this case, it is preferred if the composition additionally comprises a solubilizing solvent to assist in the solubilization of the ceramide in the water insoluble oil. It is particularly preferred if the ceramide and the retinol fatty acid ester are dissolved in a liquid consisting essentially of the oil insoluble in water and any solubilizing solvent. Preferably, the 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 oil insoluble in water, preferably 0.001% or more, more preferably 0.002% or more. Suitably, there is 0.0005% by weight or more of a retinol fatty acid ester 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 mixture comprising the oil insoluble in water, ceramide and retinyl fatty acid ester and; ii) dispersing the mixture with the rest of the composition. Preferably, the ceramide and retinol fatty acid are dissolved in the water-insoluble oil in step (i) above. In a preferred form of the invention suitable for preparing emulsion compositions, the mixture of water insoluble oil, ceramide and retinol fatty acid ester further comprises an emulsifying surfactant to facilitate the preparation of oil-in-water emulsions, water emulsions, in-oil or multiple emulsions. Such emulsifiers are well known to those skilled in the art or can be selected from the surfactants described hereinafter.

Ceramide Ceramides are a form of lipid that occurs naturally in hair and skin, specifically sphingolipids. Although any suitable ceramide can 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 nomenclature INCI 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 fatty acid ester can be employed, it is preferred if the fatty acid used to prepare the ester has a carbon chain length (including the carbon of the carboxylate group) from 2 to 22. The fatty chain can be saturated or unsaturated, linear or branched. In particular, for compositions of the invention, the esters of retinyl palmitate, retinyl acetate and retinyl propionate are preferred. Mixtures of these esters are also particularly suitable.

Water-insoluble oil It is preferred if the water-insoluble oil used in the 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). Linear chain hydrocarbon oils typically contain from about 6 to about 16 carbon atoms, preferably from about 8 to about 14 carbon atoms. The branched chain hydrocarbon oils can and usually can contain higher numbers of carbon atoms, for example, from about 6 to about 40 carbon atoms, preferably from about 8 to about 18 carbon atoms. Suitable hydrocarbon oils of the invention generally have a viscosity at 25 ° C and 21 s-1 from about 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 tension controlled rheometer Carri-Med CSL2 100, from TA Instruments Inc., New Castle, Delaware (US). A preferred hydrocarbon oil is light mineral oil. Mineral oils are transparent oily liquids obtained from petroleum oil, from which the waxes have been removed and the more volatile fractions removed by distillation. The fraction that distills between 250 ° C to 300 ° C is called mineral oil and consists of a mixture of hydrocarbons in which the number of carbon atoms per hydrocarbon molecule generally varies from C10 to C40. The mineral oil can be characterized in terms of its viscosity, where the light mineral oil is relatively less viscous than the heavy mineral oil, and these terms are defined more specifically in the U.S. Pharmacopoeia (American Pharmacopoeia), 22nd revision, p. 899 (1990). A commercially available example of a light mineral oil suitable for use in the invention is Sirius M40 (carbon chain length C10-C28, mainly C12-C2o, viscosity 4.3 x 10-3 Pa.s at 25 ° C), available from Silkolene . Other hydrocarbon oils which may be used in the invention include relatively low molecular weight hydrocarbons including linear saturated hydrocarbons, such as tetradecane, hexadecane and octadecane, cyclic hydrocarbons such as dioctylcycoubane (e.g., CETIOL S from Henkel), branched chain hydrocarbons (For example, I SOPAR L and I SOPAR V of Exxon Corp.). The oil can be volatile or non-volatile. An example of a suitable volatile mineral oil is Permethyl 1 01 A. The hydrocarbon oil may be present in compositions of the invention as a material alone or as a mixture with oils.

Ester oils Ester oils are the esters formed between alcohols and long chain carboxylic acids, such as C6-C3o carboxylic acids. The carboxylic acids can be linear or branched, saturated or unsaturated or contain hydrophilic groups such as hydroxyl. Suitable alcohols which form the ester oils include, but are not limited to, ethylene glycol, propylene glycol, glycerol, sorbitol, pentaerythritol and the various sugars, such as sucrose, glucose, fructose and dipentaerythritol. There may be only one long chain acid linked to the alcohol by one or more ester linkages. The preferred ester oils are glycerol mono-, di-, and tri-esters. Particularly preferred are glycerol tri-esters, also known as triglycerides. The preferred glyceride fatty esters are carboxylic acid derivatives of carbon chain lh ranging from C5 to C24, preferably C0 to C22, m and preferably C12 to Ci8. Glyceride ester esters suitable for use in hair oils of the invention will generally have a viscosity at 25 ° C and a cutting speed of 21 s "1 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 tension-controlled rheometer Carri-Med CSL2 1 00, from TA I nstruments Inc., New Castle, Delaware (US) A variety of these types of materials it is present in animal and vegetable 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 different ranges of carbon chain lhs depending on the source, normally between approximately 12 to approximately amente 18 carbon atoms. Synthetic oils include trimyristin, triolein, tristearin, and glyceryl dilaurate. Fatty esters of vegetable derived glycerides are particularly preferred and specific examples of preferred materials for inclusion in hair oils of the invention as sources of fatty esters of glycerides include almond oil, castor oil, coconut oil, jojoba oil, sesame oil, sunflower oil and soybean oil. Coconut oil, soybean oil, jojoba oil and mixtures thereof are particularly preferred. The water insoluble oil may be present in compositions of the invention as a simple material or as a mixture.

Solubilizing Solvent The sol ubility of the ceramide in the water-insoluble oil may not be sufficient for all the ceramide in the composition to be used in the oil. In this case, it is preferred if the composition additionally comprises a solubilizing solvent to aid in the solubilization of the ceramide in the oil insoluble in water. The solubilizing solvent is selected to improve the solubility of the ceramide in the mineral oil. Alkyl benzoates of straight or branched chain and mixtures thereof are preferred solubilizing 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 1 to 16. Suitably, the solvent is present from 1 to 20% by weight. weight of water insoluble oil weight, preferably from 4 to 16%, more preferably from 6 to 10%. A suitable solubilizing solvent is a Ci2-C5 alkyl benzoate commercially available as Finsolv ™.

Treatment composition for hair The hair treatment compositions according to the invention can conveniently take the form of shampoos, conditioners, sprays, mousses, oils, styling products, hair coloring products or lotions and pre-treatment products. for application to the hair before coloring or dyeing. The compositions according to the invention can be applied to the hair and left in the hair for hours or days (as products that are left on) or can be rinsed from the hair shortly after application (as rinsing products).

Shampoo compositions A particularly preferred hair conditioning composition according to 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 hair. Suitable cleaning surfactants, which may be used alone or in combination, are selected from anionic, nonionic, amphoteric and zwitterionic surfactants and mixtures thereof.

Anionic cleaning surfactant The shampoo compositions according to the invention will usually comprise one or more anionic cleaning surfactants, which are cosmetically acceptable and suitable for topical application to hair. Examples of suitable anionic cleaning surfactants are alkyl sulphates, alkyl ether sufates, alkaryl sulfonates, alkanoyl isethionates, alkyl succinates, alkyl sulfosuccinates, N-alkyl sarcosinates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates and alpha-olefin sulfonates, especially their salts of sodium, magnesium, ammonium and mono-, di- and triethanolamine. The alkyl and acyl groups generally contain from 8 to 18 carbon atoms and can be unsaturated. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates may contain from 1 to 10 units of ethylene oxide or propylene oxide per molecule. Normal anionic cleaning surfactants for use in shampoo compositions of the invention include sodium oleyl succinate, ammonium lauryl sulfosuccinate, ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, triethanolamine dodecylbenzene sulfonate, sodium cocoyl isethionate, sodium lauryl isethionate and N-lauryl sarcosinate sodium. The most preferred anionic surfactants are sodium lauryl sulfate, sodium lauryl ether sulfate (n) EO, (where n varies from 1 to 3), ammonium lauryl sulfate and lauryl ether sulfate (n) EO ammonium, (where n varies from 1 to 3). Mixtures of any of the above anionic cleaning 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 weight percent of the composition.

Co-surfactant The shampoo composition may 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 sulfobetaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl ampropropionates, alkylalanoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, wherein the groups alkyl and acyl have from 8 to 19 carbon atoms. Normal amphoteric and zwitterionic surfactants for use in shampoos of the invention include lauryl amine oxide, cocodimethyl suifopropii betaine and preferably lauryl betaine, cocamidopropyl betaine and sodium cocacanopropionate. Another preferred example is a nonionic surfactant, which may be included in an amount from 0 to 8, preferably from 2 to 5 weight percent of the composition. For example, representative nonionic surfactants that may be included in shampoo compositions of the invention include condensation products of aliphatic (C8-C18), primary or secondary, linear or branched alcohols or phenols with alkylene oxides, usually ethylene oxide and they generally have from 6 to 30 ethylene oxide groups. Other representative nonionic surfactants include mono- or dialkyl alkanolamides. Examples include coconut mono- or di-ethanolamide and coconut mono-isopropanolamide. Additional nonionic surfactants which may be included in shampoo compositions of the invention are the alkyl polyglycosides (APGs). Usually, APG is one comprising an alkyl group connected (optionally via a bridging group) to a block of one or more glycosyl groups. The preferred APGs are defined by the following formula: RO - (G) n wherein R is a straight or branched chain alkyl group, which may be saturated or unsaturated and G is a saccharide group. R may represent an average alkyl chain length from about C5 to about C2o- Preferably, R represents an average alkyl chain length from about C8 to about C12. Most preferably, the value of R falls between about 9.5 and about 10.5. G may be selected from monosaccharide residues of C5 or C6, and preferably is a glucoside. G can be selected from the group comprising glucose, xylose, lactose, fructose, mannose and derivatives thereof. Preferably, G is glucose. The degree of polymerization, n can have a value from about 1 to about 10 or more. Preferably, the value of n falls in the range from about 1.1 to about 2. Most preferably, the value of n falls in the range from about 1.3 to about 1.5. The alkyl polyglucosides suitable for use in the invention are commercially available and include, for example, those materials identified as: Oramix NS10 eg Seppic; Plantaren 1200 and Plantaren 200 ej Henkel. Other nonionic surfactants derived from sugar, which may be included in shampoo compositions of the invention, include the amides of C 10 -C 8 N-alkyl (C 4 -Ce) polyhydroxy fatty acids, such as C 12 -C 18 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 Ci0-C18 N- (3-methoxypropyl) glucamide. The shampoo composition may 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% by weight. Useful cationic surfactants are described hereinafter in relation to hair conditioning 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 weight percent of the composition.

Cationic polymer A cationic polymer is a preferred ingredient in shampoo compositions of the invention, to enhance the conditioning performance of the shampoo. The cationic polymer can be a homopolymer or be formed of two or more types of monomers. The molecular weight of the polymer will generally be between 5,000 and 10,000,000, usually at least 1,000 and preferably in the range 1,000,000 to approximately 2,000,000 units of unified mass. The polymers will have groups containing cationic nitrogen, such as protonated or quaternary ammonium groups, or a mixture thereof. The group containing cationic nitrogen will generally be present as a substituent in a fraction of the total monomer units of the cationic polymer. Thus, when the polymer is not a homopolymer, it may contain units of non-cationic monomer separators. Such polymers are described in the CTFA Cosmetic Ingredient Directory (CTFA Cosmetic Ingredients Directory), 3rd edition. The ratio of the cationic monomer 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 functionalities of quaternary ammonium or cationic amine with separate water-soluble 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 C 1 -C 7 alkyl groups, more preferably C 1-3 alkyl groups. Other suitable separators include vinyl esters, vinyl alcohol, maleic anhydride, propylene glycol and ethylene glycol. The cationic amines can be primary, secondary or tertiary amines, depending on the particular species and the pH of the composition.

In general, secondary and tertiary amines, especially tertiary, are preferred. The vinyl monomers substituted with amines 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 monomer substituted with quaternary ammonium and / or amine and / or compatible spacer monomers. Suitable cationic conditioning polymers include, for example: - copolymers of 1-vinyl-2-pyrrolidine and 1-vinyl-3-methyl-imidazolium salt (for example, chloride salt), referred to in the industry by Cosmetic, Toiletry, and Fragrance Association (CTFA) (Association of Cosmetics, Toiletries and Fragrances), such as Polyquaternium-16.

This material is available from BASF Wyandotte Corp.

(Parsippany, NJ, US) under the trade name LUVIQUAT (for example, LUVIQUAT FC 370); copolymers of 1-vinyl-2-pyrrolidine and dimethylaminoethyl methacrylate, referred to in the industry (CTFA) as Polyquaternium-1 1. This material is commercially available from Gaf Corporation (Wayne, NJ, US) under the trade name GAFQUAT (for example, GAFQUAT 755N); - cationic diallyl quaternary ammonium containing polymers including, for example, dimethyldiallylammonium 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 co-polymers of unsaturated carboxylic acids having from 3 to 5 carbon atoms, (as described in US Pat. No. 4,009,256); - cationic polyacrylamides (as described in WO 95/2231 1). Other cationic conditioning polymers which may be used include polymers of cationic polysaccharides, such as cationic cellulose derivatives, cationic starch derivatives and cationic guar gum derivatives. Suitably, such polymers of cationic polysaccharides have a charge density in the range from 0.1 to 4 meq / g. Polymers of cationic polysaccharides suitable for use in compositions of the invention include those of the formula: A-0- [R-N + (R1) (2) (R3) X "], wherein: A is a residual group of anhydroglucose, such as an anhydroglucose residue of starch or cellulose. R is an alkylene, oxyalkylene, polyoxyalkylene or hydroxyalkylene group or combination thereof. R1, R2 and R3 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 cationic portion (i.e., the sum of carbon atoms in R, R2 and R3) is preferably about 20 or less, and X is an anionic counterion. Cationic cellulose is available from Amerchol Corp. (Edison, NJ, US) in its polymer series Polymer JR (trademark) and LR (trademark), as salts of hydroxyethyl cellulose reacted with epoxide substituted with trimethyl ammonium, referenced in US Pat. Industry (CTFA) as Polyquaternium 10. Another type of cationic cellulose includes the polymeric salts of quaternary ammonium of hydroxyethyl cellulose reacted with epoxide substituted with lauryl dimethyl ammonium, referred to in industry (CTFA) as Polyquaternium 24. These materials are available from Amerchol Corp (Edison, NJ, US) under the trade name Polymer LM-200. Other suitable cationic polysaccharide polymers include quaternary nitrogen containing cellulose ethers (e.g., as described in U.S. Patent 3,962.41 8) and etherified cellulose and starch copolymers (e.g., as described in U.S. Patent 3,995,581). ). 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 its trademark series JAGUAR). Examples are JAGUAR C 1 3S, 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 C1 6, which is a hydroxypropylated cationic guar derivative containing a low level of substituent groups as well as groups of cationic quaternary ammonium and JAGUAR 162, which is guar of high transparency, medium viscosity having a low degree of substitution. Preferably, the cationic conditioning polymer is selected from cationic guar and cationic cellulose derivatives. Particularly preferred cationic polymers are JAGUAR C13S, JAGUAR C15, JAGUAR C17, JAGUAR C16 and JAGUAR C162. The cationic conditioning polymer will generally be present in compositions of the invention at levels 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.

Conditioning compositions for hair The compositions according to the invention can also be formulated as conditioners for the treatment of hair (usually after shampooing) and subsequent rinsing.

Surfactant conditioner Such a conditioner will comprise one or more conditioning surfactants, which are cosmetically acceptable and suitable for topical application to hair. Suitable conditioning surfactants are selected from cationic surfactants, used alone or as a mixture. Cationic surfactants useful in compositions of the invention contain hydrophilic portions of amino or quaternary ammonium, 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 (R1) (R2) (R3) (R4)] + (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 aikarylaryl group having up to 22 carbon atoms; and X is a salt-forming anion, such as those selected from halogen radicals, (e.g., chloride, bromide), acetate, citrate, lactate, glycolate, phosphate nitrate, sulfate and alkyl sulfate. The aliphatic groups may contain, in addition to carbon and hydrogen atoms, ether linkages and other groups such as amino groups. Longer chain aliphatic groups, for example, those of about 12 carbons, or more, can be saturated or unsaturated. The most preferred cationic surfactants for conditioning 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, sebotrylammonium chloride, cocotrimethylammonium chloride, PEG-2 oleylammonium chloride and salts thereof, where the chloride is replaced by halogen (eg, bromide), acetate, citrate, lactate, glycolate, phosphate nitrate, sulfate or alkyl sulfate. Additional suitable cationic surfactants include those materials having the CTFA designations Quaternium-5, Quaternium-31 and Quaternium-18. Mixtures of any of the above materials may also be suitable. A cationic surfactant particularly useful for use in hair conditioners of the invention is cetyltrimethylammonium chloride, commercially available, for example, as GENAMIN CTAC, eg Hoechst Celanese. Salts of primary, secondary and tertiary fatty amines are also suitable cationic surfactants. Alkyl groups of such amines preferably have from about 12 to about 22 carbon atoms and can be substituted or unsubstituted. The amido substituted tertiary fatty amines are particularly useful. Such amines, useful herein, include stearamidopropyldimethylamine, stearamidopropyldiethylamine, stearamidoethyldiethylamine estearamidoetild i meti lamina palmitamidopropyldimethylamine, palmitamidopropyldiethylamine, pal mitamidoetildieti palmitamidoetildimeti lamina lamina, lamin to be enamidopropildi meti behenamidoetildietilamina behenamidopropildietilamina, behenamidoetildimeti lamina araquidamidopropildimeti lamina, araquidamidopropildietilamina, arachidamidoethyldiethylamine araquidamidoetildimeti dietilaminoetilestearamida lamina. Dimethyl stearamine is also useful, dimethylsoyamine, soyamine, myristylamine, tridecylamine, ethylstearylamine, N-sebopropane diamine, ethoxylated stearylamine (with 5 moles of ethylene oxide), dihydroxyethyltearylamine and arachidi! behenylamine. These amines are normally used in combination with an acid to provide the cationic species. The preferred acid useful herein include 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 described in U.S. Patent 4,275,055 to Nachtigal, et al. , issued on June 23, 1981. The molar ratio of protonatable amines for H + from the acid is preferably from about 1: 03 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 1.0, more preferably 0.05 to 5, most preferably 0.1 to 2% of the total composition.

Fatty materials The conditioning compositions of the invention preferably additionally comprise fatty materials. It is believed that the combined use of fatty materials and cationic surfactants in conditioning compositions is 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 completely 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 as they contribute to the overall conditioning properties of compositions of the invention. Alkoxylated fatty alcohols (eg, ethoxylated or propoxylated), having from about 12 to about 18 carbon atoms in the alkyl chain, may 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 conveniently from 0.01 to 15, preferably from 0.1 to 10, and more preferably from 0.1 to 5% by weight. The weight ratio of cationic surfactant to fatty alcohol is conveniently from 10: 1 to 1: 10, preferably from 4: 1 to 1: 8, optimally from 1: 1 to 1: 7, for example, 1: 3 . The conditioner compositions of the invention may also contain a cationic polymer. Suitable cationic polymers are described hereinbefore in relation to shampoo compositions.

Suspension Agents In a preferred embodiment, the hair conditioning composition, especially if it is a shampoo composition, additionally comprises from 0.1 to 5% by weight of a suspending agent. The role of this material is to stabilize the composition against the physical separation of the aqueous and insoluble phases in water when both phases are present in compositions of the invention. Suitable suspending agents are selected from polyacrylic acids, crosslinked polymers of acrylic acid, copolymers of acrylic acid with a hydrophobic monomer, copolymers of monomers containing carboxylic acid and acrylic esters, crosslinked copolymers of acrylic acid and acrylate esters, gums of heteropolysaccharides and crystalline long chain acyl derivatives. The long chain acyl derivative is desirably selected from ethylene glycol stearate, fatty acid alkanolamides 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 commercially available as Carbopol 420, Carbopol 488 or Carbopol 493. Acrylic acid polymers crosslinked with a polyfunctional agent can also be used, they are commercially available 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 esters of acrylic acid is Carbopol 1342. All Carbopol (trademark) materials are available from Goodrich. Suitable crosslinked 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.

Ousses The hair treatment compositions according to the invention can also take the form of aerosol foams (mousses), in which case a propeller must be included in the composition. This agent is responsible for expelling the other materials from the container and forming the character of hair mousse. The propellant gas may be any liquefiable gas conventionally used for aerosol containers. Examples of suitable propellants include dimethyl ether, propane, n-butane and isobutane, used alone or as a mixture. 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 weight percent of the total composition. Small amounts of surfactant varying anywhere from 0.1 to 10, preferably from 0.1 to about 1 weight percent of the composition, for example, 0.3 weight percent 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. The hair oils comprise predominantly water insoluble oily materials as described herein. The lotions are aqueous emulsions comprising oil-insoluble water-conditioning materials. Suitable surfactants and suspending agents as described herein may also be included in lotions to improve their phase separation stability. It is preferred if these compositions according to the invention are applied to the hair as a pre-treatment before dyeing or coloring 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 colorants Hair colorants or dyes are another composition that can be prepared in a form according to the invention. In addition to the essential components of the invention, such products additionally comprise permanent, semi-permanent or temporary dyes.

Uses The compositions according to the invention are used particularly for repairing damaged hair, for improving the color 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 before applying a dye to the hair. In another aspect, the invention concerns the application of compositions according to the invention to hair. Particularly suitable compositions are shampoos comprising a cleansing surfactant, hair oils and rinse conditioners comprising a conditioning surfactant. Another particularly suitable composition is a pre-treatment composition to be applied to the hair within 1 hour before applying a dye to the hair. The compositions according to the invention can also be used as conditioners for hair to be worn, which are applied to the hair after washing and remain in the hair until the next wash. The invention is further illustrated with reference to the following examples: EXAMPLES The following experiment was performed showing the color protection benefits of the invention. A combination of 1 part of ceramides to 2.5 parts of retinyl palmitate was used in three separate formulations called Prototype 1, Prototype 2 and Prototype 3. Prototype 1 is a normal standard conditioner, which contains (in addition to the ceramide and palmitate of retinyl) as its ingredients, water, cetearyl alcohol, dimethiconol & TEA dodecylbenzenesulfonate, ceterimonium chloride, hydroxyethylcellulose, fragrance, octyl methoxycinnamate, methyl paraben, formaldehyde, citric acid, tocopheryl acetate and extracts of lemon, grape and apple. Prototype 2 is a normal pre-treatment conditioner, which contains (in addition to ceramide and retinyl palmitate) its ingredients, water, propylene glycol, polysorbate 20, hydroxyethylcellulose, Polyquaternium-6, hydroxyethyl hydroxyethyl collagen hydrolyzate, polymethacrylamidopropyltrimonium chloride , essential oils containing fragrance, D DM hydantoin, disodium EDTA, citric 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 samples was bleached and then treated with a color for normal permanent hair, Sedal 6RRMR, which is a red shade. These samples were then divided into five groups. Group 1 was used as untreated control. Group 2 was treated with Prototype 2 formula and then shampoo / conditioner was applied with a normal shampoo conditioner. Group 3 was treated with Prototype 3 formula and then shampoo / conditioned with a normal shampoo conditioner. Group 4 was treated with Prototype 1 formula and then shampoo / conditioned with a normal shampoo conditioner. Group 5 was not treated with any formula before applying shampoo and conditioner with a normal shampoo and conditioner. Each group of samples was then evaluated for color retention using L values. The results are as follows (Tukey test for statistical significance).

N S ubset with alpha = .05 Treatment 1 2 3 4 Group 1 24 1 9630.75 Group 2 24 30281 .54 Group 3 24 21 142.29 31 142.29 Group 4 24 31 662.88 Group 5 24 32988.08 Significance 1 .000 .331 .785 1 .000 Then a couple of samples were shown to the consumers and they were asked which sample in the pair lost more color. The results are in accordance with instrumental L-value measurements, but consumers are additionally able to determine that group 4 lost more color than Group 3 or 2.

Group 4 vs. Group 2 (conventional conditioner vs. pre-treatment containing oils) Group 4 37 88% Group 2 5 12% Total 42 1 00% Group 4 vs. Group 3 (conventional conditioner vs. pre-treatment containing oils) These results indicate that when there is no pre-treatment to protect the hair from color loss, the samples lose a significant amount of color compared to those samples that have been pre-treated with com positions according to the invention (Comparison of Group 5 with Groups 2, 3 and 4). A second conclusion is that between the samples that retinyl ceramide and palm itato as part of the treatment, Group 2 and Group 3, which also had insoluble oil in water, present a better performance than a conventional conditioning formula without Insoluble oil in water. Note that this conclusion is based on the evaluation of the consumers of these samples together with the L values shown above.

Oil for hair treatment pre-shampoo Coconut oil q .s. to 100 parts Retinyl Palmitate, 0.0025 parts Ceramides 0.001 0 parts Pre-shampoo treatment hair conditioner Soybean oil, jojoba oil & coconut oil 0.5 parts Propylene glycol 4.0 parts Polyisobate 20 1.0 parts Hydroxyethylcellulose q.s. to obtain viscosity CETAC 1 .0 parts Retinyl paimitate 0.0025 parts Ceramides 0.001 0 parts Water q.s. to 100

Claims (1)

1. CLAIMS 1 . A hair treatment composition comprising: i) 0.0005% or more by weight water-insoluble oil of a ceramide selected from ceramide I, ceramide I I and mixtures thereof; ii) 0.0005% or more by weight of water-insoluble oil of a retinol fatty acid ester; and iii) an oil insoluble in water. 2. A composition according to claim 1, wherein the ceramide and retinol fatty acid ester are dissolved in a liquid phase comprising the oil insoluble in water. 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, wherein the weight ratio of retinol to ceramide fatty acid ester is from 1: 1 to 500: 1. 5. A composition according to any preceding claim, wherein the retinyl fatty acid ester is selected from the group consisting of retinyl palmitate, retinyl acetate, retinyl propionate and mixtures thereof. 6. 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. 7. A composition according to any preceding claim, wherein the water insoluble oil is selected from the group consisting of coconut oil, jojoba oil, soybean oil and mixtures thereof. 8. A composition according to any preceding claim, which is a shampoo composition comprising a cleansing surfactant. 9. A composition according to any preceding claim, which is a conditioning composition to be left on. 10. A composition according to any preceding claim, which is a rinse conditioner composition comprising a conditioning surfactant. eleven . A method for preparing a composition according to any preceding claim, comprising the steps of: i) forming a first mixture comprising the oil insoluble in water, ceramide and retinyl fatty acid ester and; ii) dispersing the first mixture with the rest of the composition. 12. A method for treating the hair comprising applying to the hair a composition according to any of claims 1 to 10. 13. The use of a composition according to claims 1 to 10 for repairing damaged hair. 14. The use of a composition according to claims 1 to 10 to improve the color fastness of dyed hair. 15. The use of a composition according to claims 1 to 10 to prevent damage to the hair.