Patent Description:
Consumers desire hair treatments, such as shampoos and conditioners, that provide conditioning benefits, for example smoothness, ease of comb and softness to their hair.

The most widely used conditioning agents used in hair treatments products are silicones. They are widely recognised for their lubricating properties and the characteristically soft smooth feel they help create. Conditioning is achieved by the silicone being deposited onto the hair resulting in the formation of a film. The silicone film gives excellent conditioning and has been attributed to a wide range of benefits, for example, softness, smoothness and ease of comb.

The effectiveness of silicone as a conditioning agent can be largely attributed to its high lubricity, which in turn, confers a low coefficient of friction to treated hair.

So effective are silicones at delivering such benefits, that they have been the conditioning agent of choice, by formulators in the field, for over half a century. However, demand from the modern consumer for hair treatment compositions that are free from silicone has arisen over recent years.

Conditioning benefits are desired and perceived by the consumer both during and after the wash process. Thus, conditioning is evaluated both when the hair is wet and when it is dry. As such, it is desirable that rinse-off haircare products such as conditioners provide multiple benefits at different stages of use. Wet conditioning and dry conditioning are different benefits and are typically delivered in different ways.

The impact of the gel phase component of a conditioning product is most apparent when wet or damp hair is evaluated, as well as during application and distribution through the hair. At the post drying stages, conditioning benefits are primarily provided by silicones.

In silicone-free conditioner formulations alternative approaches are required to provide such benefits. However, the lubrication properties of silicone are unmatched in the field and suitable alternatives have proved a difficult need to fulfil.

Starches have been used in hair conditioning compositions:
<CIT> - uses a composition comprising, a cationic surfactant, a starch which is preferably modified, a non-silicone cationic polymer with a cationic charge density of greater than or equal to <NUM> meq/g, and a nonionic non-polymeric solid compound with a melting point of greater than or equal to <NUM> degrees C and/or with a viscosity, at a temperature of <NUM> degrees C and at a shear rate of <NUM>-<NUM>, of greater than or equal to <NUM> Pa. s, to provide an improved conditioning effect to hair, especially smoothing of the ends.

<CIT> - discloses a cosmetic composition comprising a combination of pumice particles (i); one or more starches (ii); one or more solid fatty alcohols (iii); and one or more fatty esters (iv) to provide durable treatment of keratin fibers that are damaged on the surface. A use for smoothing hair is disclosed. Distarch phosphate of pregelatinized hydroxypropyl maize is exemplified.

<CIT> discloses a cosmetic composition, comprising, at least one starch, at least one carboxylic ester, water and up to <NUM> wt % of fatty phase relative to the total weight of composition. The use of these compositions, based on a specific ester and a starch allegedly provides hair that is easy to disentangle and is smooth from root to tip, with an improvement in the hold of the style. A pregelatinized corn distarch phosphate or Potato fecula modified with <NUM>-chloro-ethylamidodipropionic acid neutralized with sodium hydroxide are utilised in the examples on wet hair to provide wet hair that is not heavy and hair shaping is easy.

<CIT> dislcoses a cosmetic composition comprising: water; an ingredient selected from detergents and non-detersive conditioning agents; a cationic starch characterized by: a) an amylopectin/amylose weight ratio of greater than or equal to <NUM>/<NUM>; b) an apparent cationic molecular weight of greater than or equal to <NUM> million daltons; and c) a cationic degree of substitution of from <NUM> meq/g to <NUM> meq/g to provide improved conditioning properties to personal care compositions. The personal care formulations can be used with or without silicone. Shampoos comprising cationic substituted starches allegedly give conditioning benefits in the wet stage.

<CIT> discloses aqueous compositions for keratin fibres comprising an oil and/or wax, a natural starch, an emulsifier and a film forming polymer.

Despite the prior art, there remains a need for hair treatment compositions which are free from silicone yet are equally effective at conditioning the hair.

We have now surprisingly found that dry conditioning at parity with that achieved with silicone, as evidenced by delivery of low coefficient of friction, can be delivered from a conditioner by the use of a particulate boiling resistant starch, blended with an oil.

In a first aspect, the invention provides a hair conditioner composition comprising.

In a second aspect, there is provided a method of treating hair, comprising the step of applying to hair a composition of the first aspect. Preferably, the method comprises the step of rinsing the composition from the hair. More preferably, the composition comprises the step of leaving the composition on the hair for from <NUM> seconds to <NUM> minutes, for example for <NUM> seconds to <NUM> minutes, and then rinsing from the hair.

Use is also provided, of a boiling resistant starch in a silicone free composition of the first aspect to provide conditioning benefits to hair. Use is also provided of a blend of boiling resistant starch particle and non-silicone oil in a silicone free composition of the first aspect to provide conditioning benefits to hair.

In the uses of the invention, the conditioning benefit is preferably a coefficient of friction that is equal to that conferred to hair treated with the same composition comprising silicone and that is free from boiling resistant starch.

The hair conditioner composition of the invention comprises:.

The blend of starch and oil is present in an amount of from <NUM> to <NUM> wt %, preferably from <NUM> to <NUM> wt %, more preferably from <NUM> to <NUM> wt %, most preferably from <NUM> to <NUM> wt %.

The weight ratio of starch to oil in the blend, is from <NUM>:<NUM> to <NUM>: <NUM>, preferably <NUM>:<NUM>.

The compositions of the invention comprise a starch, which is a particulate boiling resistant starch. Such starches are also known as "cook stable" or "Amylum Non Mucinaginosum" (ANM) starches. The starch remains particulate in the composition.

The starch for use in the invention has a Dv(<NUM>) particle size of from <NUM> to <NUM> microns, preferably from <NUM> to <NUM> microns, most preferably from <NUM> to <NUM> microns.

Any suitable particle size analyser, such as a Malvern Mastersizer <NUM> may be used to characterize starch particles. A suitable refractive index (RI) of starch is <NUM> (as given in <NPL>).

A laser diffraction technique may be employed. The sample is dispersed in water (which has a RI of <NUM>) and passed into a sample window using a recirculating cell, where any particles present scatter the light. The refractive indices for both the particles and the suspending media are used for particle size determination. The following method may suitably be used:
Starch powder (<NUM>) is suspended in <NUM> of deionised water and pipetted into a Mastersizer <NUM> Hydro Medium Volume cell until a <NUM> % obscuration limit is reached. This process is preferably repeated three times for each starch sample at a stirrer speed of <NUM> rpm. Results are reported here as 'particle size (µm) against volume (%)' for Dv (<NUM>), Dv (<NUM>) and Dv (<NUM>) indicating that <NUM>%, <NUM>% and <NUM>% respectively, of particles are smaller than the quoted size.

The starches for use in the compositions of the invention are in the form of discrete particles. The starches for use in the present invention remain in particulate form in the compositions of the invention.

The starch is not a gelatinised or "swelling" starch. Gelatinised, or gelatinisable starches do not remain as particles when incorporated in a formulation such as a hair treatment composition. Gelatinisation depends on the hydrophilic nature of the starch. In one study, Senanayake et al (<NPL>), starches substituted with hydroxypropyl groups showed significantly higher levels of swelling power and water-soluble index compared to the unmodified native starch. According to the authors, the presence of hydroxypropyl groups, which are hydrophilic, enhances the attraction of water molecules into the granular structure that causes early swelling in the granule.

A suitable type of boiling resistant starch is crosslinked. A preferred crosslinked boiling resistant starch is a di-starch phosphate. Most preferably, the boiling resistant starch is a crosslinked rice starch. Highly preferred boiling resistant rice starches may be selected from crosslinked di-phosphate starches (for example Rice PO4 Natural from Agrana Starch).

Preferably, the crosslinked boiling resistant starch is selected from crosslinked rice starch, crosslinked quinoa starch, crosslinked amaranth starch and mixtures thereof. More preferably, the starch is selected from crosslinked rice starch, crosslinked quinoa starch and mixtures thereof, most preferably the boiling resistant starch is crosslinked rice starch.

The starch is blended with a hydrophobic non-silicone oil. The starch particle is thus within a continuous oil phase.

The oils for use in the compositions of the invention are hydrophobic non-silicone oils.

Suitable hydrophobic non-silicone oils are selected from hydrocarbon oils, fatty ester oils and mixtures thereof.

The hydrocarbon oils can be natural or synthetic.

Straight chain hydrocarbon oils will preferably contain from about <NUM> to about <NUM> carbon atoms. Also suitable are branched chain hydrocarbon oils, which preferably contain from about <NUM> to about <NUM> carbon atoms. Also suitable are polymeric hydrocarbons of alkenyl monomers, such as C2 to C6 alkenyl monomers.

Specific examples of suitable hydrocarbon oils include paraffin oil, mineral oil, polyalphaolefin, squalane, saturated and unsaturated dodecane, saturated and unsaturated tridecane, saturated and unsaturated tetradecane, saturated and unsaturated pentadecane, saturated and unsaturated hexadecane, and mixtures thereof. Branched-chain isomers of these compounds, as well as of higher chain length hydrocarbons, can also be used. Another suitable material is polyisobutylene.

A preferred polyalphaolefin is commercially available as Silkflo <NUM> ™ (dec-<NUM>-ene) ex Ineos.

Suitable fatty esters are characterised by having at least <NUM> carbon atoms and include esters with hydrocarbyl chains derived from fatty acids or alcohols. Monocarboxylic acid esters include esters of alcohols and/or acids of the formula R'COOR in which R' and R independently denote alkyl or alkenyl radicals and the sum of carbon atoms in R' and R is at least <NUM>, preferably at least <NUM>. Di- and trialkyl and alkenyl esters of carboxylic acids can also be used.

Particularly preferred fatty esters are mono-, di- and triglycerides, more specifically the mono-, di-, and tri-esters of glycerol and long chain carboxylic acids such as C1-C22 carboxylic acids. Preferred materials include cocoa butter, palm stearin, sunflower oil, soyabean oil and coconut oil.

The hydrophobic non-silicone oil is preferably selected from hydrocarbon oils selected from paraffin oil, mineral oil, polyalphaolefin oil, esters with hydrocarbyl chains derived from fatty acids or alcohols and mixtures thereof.

Preferably, the oil is not a wax, particularly petrolatum and ozokerite.

The compositions of the invention comprise an emulsified non-silicone oil. The oil is preferably described as above, for the hydrophobic non-silicone oil for use in the blend with the starch. The oil for use in the blend with the starch and the emulsified oil can be the same or different.

The emulsified non-silicone may be made by any suitable process and a skilled person in the art will know how to prepare such emulsified oils. In a preferred process the emulsified non-silicone oil may be produced via a catastrophic inversion process using a high shear homogeniser (for example, an Ultra Turrax T25 Basic S2 with a S25N-<NUM> dispersing tool, from IKA, Germany). The emulsion may be formed by dropwise addition of water to a mixture of oil and surfactant under shear at a rate of, for example, <NUM> per minute prior to the inversion point.

The emulsifying surfactant(s) may be nonionic, cationic, or a mixture of nonionic and cationic and the inclusion level of the total surfactant amount may typically range from <NUM>% to <NUM>% by weight of the emulsion. Suitable nonionic surfactants will be known to those skilled in the art and may include for example Lutensol XP-<NUM> (ex BASF). Suitable cationic surfactants will be known to a person skilled in the art and may include for example cetrimmonium chloride.

The compositions of the invention are free from silicone. In the context of the invention, by free from is meant having less than <NUM> weight %, more preferably less than <NUM> weight %, even more preferably less than <NUM> weight %, still more preferably less than <NUM> weight %, yet preferably less than <NUM> weight %, and most preferably <NUM> weight % of silicone by weight of the total composition.

Preferably, the compositions of the invention are also free from silanes.

The conditioning base comprises a cationic conditioning surfactant and a fatty alcohol.

The composition according to the invention comprises 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. Examples include quaternary ammonium cationic surfactants corresponding to the following general formula:.

[N(R<NUM>)(R<NUM>)(R<NUM>)(R<NUM>)]+     (X)-.

in which R<NUM>, R<NUM>, R<NUM>, and R<NUM> are each independently selected from (a) an aliphatic group of from <NUM> to <NUM> carbon atoms, or (b) an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to <NUM> carbon atoms; and X is a salt-forming anion such as those selected from halide, (e.g. chloride, bromide), acetate, citrate, lactate, glycolate, phosphate nitrate, sulphate, and alkylsulphate, for example methosulphate, radicals. The aliphatic groups can contain, in addition to carbon and hydrogen atoms, ether linkages, and other groups such as amino groups. The aliphatic groups, e.g., those of about <NUM> carbons, or higher, can be saturated or unsaturated.

Specific examples of such quaternary ammonium cationic surfactants of the above general formula are cetyltrimethylammonium chloride, behenyltrimethylammonium chloride (BTAC), 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, dipalmitoylethyldimethylammonium chloride, PEG-<NUM> oleylammonium chloride and salts of these, where the chloride is replaced by other halide (e.g., bromide), acetate, citrate, lactate, glycolate, phosphate nitrate, sulphate, or alkylsulphate.

In a preferred class of cationic surfactant of the above general formula, R<NUM> is a C16 to C22 saturated or unsaturated, preferably saturated, alkyl chain and R<NUM>, R<NUM> and R<NUM> are each independently selected from CH3 and CH<NUM>CH<NUM>OH, preferably CH3.

Specific examples of such preferred quaternary ammonium cationic surfactants are cetyltrimethylammonium chloride (CTAC), behenyltrimethylammonium chloride (BTAC) and mixtures thereof.

Preferably, the quaternary ammonium cationic surfactant has a cation selected from cetyltrimethylammonium and behenyltrimethylammonium.

Alternatively, primary, secondary or tertiary fatty amines may be used in combination with an acid to provide a cationic surfactant suitable for use in the invention. The acid protonates the amine and forms an amine salt in situ in the hair care composition. The amine is therefore effectively a non-permanent quaternary ammonium or pseudo-quaternary ammonium cationic surfactant.

Suitable fatty amines of this type include amidoamines of the following general formula:.

R<NUM>-C(O)-N(H)-R<NUM>-N(R<NUM>)(R<NUM>).

in which R<NUM> is a fatty acid chain containing from <NUM> to <NUM> carbon atoms, R<NUM> is an alkylene group containing from one to four carbon atoms, and R<NUM> and R<NUM> are each independently, an alkyl group having from one to four carbon atoms.

Specific examples of suitable materials of the above general formula are stearamidopropyldimethylamine, stearamidopropyldiethylamine, stearamidoethyldiethylamine,stearamidoethyldimethylamine, palmitamidopropyldimethylamine, palmitamidopropyldiethylamine, palmitamidoethyldiethylamine, palmitamidoethyldimethylamine, behenamidopropyldimethylamine, behenamidopropyldiethylamine, behenamidoethyldiethylamine, behenamidoethyldimethylamine, arachidamidopropyldimethylamine, arachidamidopropyldiethylamine, arachidamidoethyldiethylamine, arachidamidoethyldimethylamine, and diethylaminoethylstearamide.

Also useful are dimethylstearamine, dimethylsoyamine, oyamine, myristylamine, tridecylamine, ethylstearylamine, N-tallowpropane diamine, ethoxylated (with <NUM> moles of ethylene oxide) stearylamine, dihydroxyethylstearylamine, and arachidyl behenylamine.

Particularly preferred is stearamidopropyldimethylamine.

The conditioning surfactant is present in the composition in a concentration of <NUM> to <NUM>%, preferably at least <NUM>%, more preferably at least <NUM>%, still more preferably at least <NUM>%, even more preferably at least <NUM>% or even at least <NUM>% but typically not more than <NUM>%, preferably not more than <NUM>%, more preferably not more than <NUM>%, still more preferably not more than <NUM>%, even more preferably not more than <NUM>% by weight of the composition.

The compositions of the invention comprise a fatty alcohol having a carbon-carbon chain length of from C<NUM> to C<NUM>.

The combined use of fatty alcohols and cationic surfactants in conditioning compositions is preferred because this leads to the formation of a lamellar phase, in which the cationic surfactant is dispersed.

The fatty alcohol comprises from <NUM> to <NUM> carbon atoms, preferably <NUM> to <NUM>, most preferably C16 to C18. Fatty alcohols are typically compounds containing straight chain alkyl groups. Preferably, the alkyl groups are saturated. Examples of preferred 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 for use in the invention.

The level of fatty alcohol in conditioners for use in the invention will generally range from <NUM> to <NUM>%, preferably from <NUM> to <NUM>%, more preferably from <NUM> to <NUM>%, most preferably from <NUM> to <NUM>% by weight of the composition.

The weight ratio of cationic-surfactant to fatty alcohol is suitably from <NUM>:<NUM> to <NUM>:<NUM>, preferably from <NUM>:<NUM> to <NUM>:<NUM>, optimally from <NUM>:<NUM> to <NUM>:<NUM>. If the weight ratio of cationic surfactant to fatty alcohol is too high, this can lead to eye irritancy from the composition. If it is too low, it can make the hair feel squeaky for some consumers.

A preferred conditioner comprises a conditioning gel phase having little or no vesicle content. Such conditioners and methods for making them are described in <CIT>, <CIT>, <CIT> and <CIT>.

Such a conditioning gel phase comprises, by total weight of the composition,.

and the composition confers a Draw Mass of from <NUM> to <NUM>, preferably <NUM> to <NUM>, more preferably <NUM> to <NUM>, even more preferably <NUM> to <NUM> and most preferably <NUM> to <NUM> to hair treated with the composition.

Draw Mass is the mass required to draw a hair switch through a comb or brush. Thus the more tangled the hair the greater the mass required to pull the switch through the comb or brush, and the greater the level of condition of the hair, the lower the Draw Mass.

The Draw Mass is the mass required to draw a hair switch, for example of weight <NUM> to <NUM>, length <NUM> to <NUM>, and width <NUM> to <NUM> through a comb or brush, as measured by first placing the hair switch onto the comb or brush, such that from <NUM> to <NUM> of hair is left hanging at the glued end of the switch, and then adding weights to the hanging end until the switch falls through the comb or brush.

Preferably, the hair switch is of weight <NUM> to <NUM>, more preferably <NUM> to <NUM>, most preferably from <NUM> to10 g. Preferably, the hair switch has a length of from <NUM> to <NUM>, more preferably from <NUM> to <NUM>, and a width of from <NUM> to <NUM>, more preferably from <NUM> to <NUM>.

Most preferably, the Draw Mass is the mass required to draw a hair switch, for example of weight <NUM>, length <NUM>, and width <NUM> through a comb or brush, as measured by first placing the hair switch onto the comb or brush, such that from <NUM> of hair is left hanging at the glued end of the switch, and then adding weights to the hanging end until the switch falls through the comb or brush.

Unless otherwise indicated, ratios, percentages, parts, and the like, referred to herein, are by weight.

Aspects of the invention will now be illustrated by the following examples.

The following conditioner compositions were prepared:.

In the following table, the oil and starch are present in a blend.

The particle size of the particulate starches were measured using the method described herein.

The emulsified oil was produced via a catastrophic inversion process using an Ultra Turrax T25 Basic S2 high shear homogeniser and dispersing tool. Water was added dropwise to a mixture of oil and surfactant under shear in a <NUM> stainless steel beaker, at a rate of <NUM> per minute, prior to the inversion point. The resulting composition is given in Table <NUM>.

The compositions in Table <NUM> were prepared as follows:.

Further compositions were prepared, using a different conditioner gel base, for use in the ensuing examples:.

The emulsified oil and oil/starch blend were prepared as detailed above.

Compositions <NUM>, according to the invention and comparative A were used to treat hair.

The hair was treated using the following method:
<NUM> <NUM> inch Dark Brown European switches were wetted under a tap. A solution of <NUM> wt % sodium laureth sulfate with one unit of ethoxylation was applied to the switch (at <NUM> per gram of hair). The switch was massaged for <NUM> seconds and then rinsed under the tap for <NUM> seconds. This was repeated. The wet switches were then detangled using a comb. The conditioner composition (<NUM> per gram hair) was then applied to the hair and massaged for <NUM>, before being rinsed for <NUM> under a controlled flow of water. The switches were left to dry at room temperature.

The coefficient of friction of the hair following treatment was then analysed using a device based upon a flat plate attached to multiple force transducers, with appropriate signal processing and data acquisition. Examples of suitable devices and are described in <NPL> and <NPL>, and references therein. The specific device used herein employed a Micro Analog <NUM> signal processing system (Fylde Electronic Laboratories Ltd. , UK), along with Dasylab data acquisition software (National Instruments, USA) and six <NUM> Newton capacity, SMT1 force transducers (Interface Inc. , USA) attached to a glass-balsa panel (Aerospace Composite Products, USA). Data presented herein were collected by an operator running a finger along the surface of a dried, treated hair tress (described above), laid flat upon the device, to allow the recording of friction and load forces and calculation of the resulting friction coefficient.

The results are given in Table <NUM> below:.

The results show that with the composition according to the invention (Example <NUM>), with a boiling resistant particulate starch, a lower coefficient of friction is obtained than for the comparative examples comprising a non-boiling resistant comparative starch.

Compositions <NUM> & <NUM>, according to the invention and comparatives B & C were used to treat hair.

The hair was treated using the method described above and coefficient of friction measured as above.

Claim 1:
A hair conditioner composition comprising
A) <NUM> to <NUM> wt %,by weight of the total composition, of a blend comprising
i) particles of boiling resistant starch, having a Dv(<NUM>) particle size of from <NUM> to <NUM> microns; and
ii) a hydrophobic non-silicone oil;
in a weight ratio of starch to oil of from <NUM>:<NUM> to <NUM>: <NUM>;
B) <NUM> to <NUM> wt % of an emulsified non-silicone oil;
wherein A) and B) are dispersed within:
C) a conditioning gel phase comprising a cationic surfactant and a fatty alcohol and
wherein the conditioner is free from silicone.