TECHNICAL FIELD

The present invention relates to a hair spray composition for styling and refreshing the hair.

BACKGROUND OF THE INVENTION

Compositions on the market usually fall into two market segments. Rinse off products that are primarily for cleaning and/or conditioning the hair and leave-in products that are primarily for styling and/or conditioning hair.

WO 03/047541 (Unilever) discloses rinse off hair treatment compositions comprising particles of clay and charged organic molecules. The advantage of such compositions is that they leave the hair feeling smooth and moisturised.

JP05/246,824 (Shiseido Co Ltd) discloses a hair cosmetic which is a water-in-oil emulsion containing an organically modified clay mineral (prepared by treating a water swelling clay with a nonionic surfactant and a cationic surfactant), a water-soluble high molecular weight substance and a high molecular weight silicone. The benefits claimed are smooth feel, lustre, firmness and flexibility to hair.

The present invention recognises a need for a leave in product that can be used to both refresh and style the hair. To this effect, it has been found that a hair spray composition can be formulated that effectively styles the hair and leaves the hair feeling clean and smelling fresh. The product has the additional advantage that it can be used on wet or dry hair.

DEFINITION OF THE INVENTION

According to a first aspect of the invention, there is provided a hair spray composition characterised in that it comprises a dispersion of

i) an anionic clay with a net negative surface charge; and

ii) a cationic styling polymer

According to a second aspect of the invention, there is provided a method for styling hair and for modifying the odour of hair by applying to the hair the composition described above.

According to a third aspect of the invention, there is provided the use of a hair treatment composition as described above for styling hair and to freshen the hair.

DETAILED DESCRIPTION OF THE INVENTION

The Clay

The term clay refers to a composition comprising fine particles which in this instance have a net negative electrostatic charge on at least one surface. Preferably, the clay has a layered structure comprising sheets of coordinated cations, wherein the cations form tetrahedra or octahedra with close packed oxygens and hydroxyl groups. The surface charge is usually balanced by the presence of charge balancing ions (sometimes called exchangeable ions) which are usually present between the layers of the clay and at the edges of the layers.

The term anionic clays and related terms, as used herein, refer to clays which are negatively charged at their layer surface. In this embodiment, the composite particles are formed with a cationic charged organic molecule, which is in addition to and separate from any charge balancing cations which may be present.

The clay may be a natural, synthetic or chemically modified clay. Preferably, the layers of the clay comprise hydrous sheets of octahedrally coordinated aluminium, magnesium or iron, or of tetrahedrally coordinated silicon. The arrangement of octahedrally coordinated cations to coordinating anions in the clay sheets may be dioctahedral or trioctahedral. The charge balancing ions are cations at the layer surfaces and anions at the edges and may be those occurring naturally in the clay or by exchange using ion exchange techniques. The charge balancing cations of the anionic clays employed in the composite particles of the invention will contain cationic counterions such as protons, sodium ions, potassium ions, calcium ions, magnesium ions, and the like.

Preferred anionic clays are 2:1 phyllosilicates, in which the clay layers comprise two tetrahedral sheets to one octahedral sheet. Preferred 2:1 phyllosilicates are smectite clays.

Other suitable clays have a 1:1 phyllosilicate structure, with an assemblage of one tetrahedral to one octahedral coordinated sheet in the clay layers.

Smectite clays, used in laundry compositions are, for example, disclosed in U.S. Pat. Nos. 3,862,058, 3,948,790, 3,954,632 and 4,062,647 and in EP-A-299,575 and EP-A-313,146, all in the name of Procter & Gamble Company.

The term smectite clays herein includes both the clays in which aluminium oxide is present in a silicate lattice and the clays in which magnesium oxide is present in a silicate lattice. Typical smectite clay compounds include the compounds having the general formula Al₂(Si₂O₅)₂(OH)₂.nH₂O and the compounds having the general formula Mg₃(Si₂O₅)₂(OH)₂.nH₂O, and derivatives thereof, for example in which a proportion of the aluminium ions are replaced with magnesium ions or a proportion of the magnesium ions are replaced with lithium ions and/or some of the hydroxyl ions are replaced by fluoride ions; the derivatives may comprise a further metal ion to balance the overall charge.

Specific examples of suitable smectite clays include those selected from the classes of the montmorillonites, hectorites, volchonskoites, nontronites, saponites, beidelites and sauconites, particularly those having an alkali or alkaline earth metal ion within the crystal lattice structure. Particularly preferred are hectorites, montmorillonites, nontronites, saponites, beidelites, sauconites and mixtures thereof. More preferably the clay is a synthetic hectorite.

The cation exchange capacity (CEC) of a clay is a well known parameter and may be determined by well established analytical techniques, including by electrodialysis, by exchange with ammonium ion followed by titration or by a methylene blue procedure, all as fully described in Grimshaw, â€œThe Chemistry and Physics of Claysâ€ , pp. 264-265, Interscience (1971). It is customary to measure the cation exchange capacity of a clay in terms of milliequivalents per 100 g of dry clay (meq/100 g).

Preferred anionic clays for use in the present invention have a cation exchange capacity of from 0.7 meq/100 g to 150 meq/100 g. Particularly preferred are clays having a cation exchange capacity of from 30 meq/100 g to 100 meq/100 g.

The clays preferably have a volume-based median particle diameter (D_0.5) from 0.001 Î¼m to 80 Î¼m, more preferably from 0.01 Î¼m to 50 Î¼m and most preferably 0.02 Î¼m to 20 Î¼m. Particle diameters can be determined using a Malvern Mastersizer (Malvern Instruments, UK).

Examples of synthetic hectorites useful in the present invention include those products sold under the trade names Laponite RD, Laponite RDS, Laponite XLG, Laponite XLS, Laponite D, Laponite DF, Laponite DS, Laponite S and Laponite JS (all from Southern Clay products, Texas, USA, a subsidiary of Rockwood).

Examples of montmorillonites (also known as bentonites), which are suitable for use in the present invention include: Gelwhite GP, Gelwhite H, Gelwhite L, Mineral Colloid BP, Mineral Colloid MO, Gelwhite MAS 100 (sc), Gelwhite MAS 101, Gelwhite MAS 102, Gelwhite MAS 103, Bentolite WH, Bentolite L10, Bentolite H, Bentolite L, Permont SX10A, Permont SC20, and Permont HN24 (Southern Clay Products, Texas, USA); Bentone EW and Bentone MA (Dow Corning); Bentonite USP BL 670 and Bentolite H4430 (Whitaker, Clarke & Daniels); Clarit 100 G1 and Clarit 1100 G1 (calcium bentonites from SÃ¼d Chemie AG); and Volclay 2 (sodium bentonite from SÃ¼d Chemie AG).

Clays may be used as obtained from the supplier and may contain conventional additives such as, for example, disintegrating agents (also known as peptisers) and water of hydration. The clays may be used in their natural state or in a purified or semi-purified form, for example with the removal of mineral impurities.

The level of the clay in the total composition is preferably from 0.01 to 10 wt % of the total composition, more preferably from 0.02 to 5 wt %, most preferably from 0.05 to 2 wt %.

In the compositions of the invention, the clay is advantageously present in the form of a dispersion (for example a sol or gel) or as a suspension.

Cationic Styling Polymer

These compositions of the invention comprise at least one hair styling polymer.

Hair styling polymers are well known articles of commerce and many such polymers are available commercially which contain moieties which render the polymers cationic in nature. The polymers may be synthetic or naturally derived.

The amount of the polymer may range from 0.01 to 10%, more preferably 0.05 to 6%, most preferably from 0.1 to 4% by weight of the total composition.

Examples of cationic hair styling polymers are copolymers of amino-functional acrylate monomers such as lower alkyl aminoalkyl acrylate, or methacrylate monomers such as dimethylaminoethyl methacrylate, with compatible monomers such as N-vinylpyrrolidone, vinyl caprolactam, alkyl methacrylates (such as methyl methacrylate and ethyl methacrylate) and alkyl acrylates (such as ethyl acrylate and n-butyl acrylate).

Specific examples of suitable cationic polymers are:

copolymers of N-vinylpyrrolidone and dimethylaminoethyl methacrylate, available from ISP Corporation as Copolymer 845, Copolymer 937 and Copolymer 958;

copolymers of N-vinylpyrrolidone and dimethylaminopropylacrylamide or methacrylamide, available from ISP Corporation as StylezeÂ® CC10;

copolymers of N-vinylpyrrolidine and dimethylaminoethyl methacrylate;

copolymers of vinylcaprolactam, N-vinylpyrrolidone and dimethylaminoethylmethacrylate;

Polyquaternium-4 (a copolymer of diallyldimonium chloride and hydroxyethylcellulose);

Polyquaternium-11 (formed by the reaction of diethyl sulphate and a copolymer of vinyl pyrrolidone and dimethyl aminoethylmethacrylate), available from ISP as GafquatÂ® 734, 755 and 755N, and from BASF as LuviquatÂ® PQ11;

Polyquaternium-16 (formed from methylvinylimidazolium chloride and vinylpyrrolidone), available from BASF as LuviquatÂ®FC 370, FC 550, FC 905 and HM-552;

Polyquaternium-46 (prepared by the reaction of vinylcaprolactam and vinylpyrrolidone with methylvinylimidazolium methosulphate), available from BASF as LuviquatÂ®Hold.

Examples of suitable naturally derived polymers include shellac, alginates, gelatins, pectins, starch, cellulose derivatives and chitosan or salts and derivatives thereof. Commercially available examples include KytamerÂ® (ex Amerchol) and AmazeÂ® (ex National Starch).

The weight ratio of the clay to the cationic styling polymer is preferably from 1:5 to to 5:1, more preferably 1:3 to 3:1, most preferably from 1:1 to 3:1.

Silicone Conditioning Agents

The compositions of the invention preferably contain silicone conditioning agents selected from volatile and non-volatile silicone fluids.

Silicones may be added as a pre-formed emulsion. Viscosities of the pre-emulsified silicones range up to 10 McP at 25Â° C.

Volatile silicone fluids are preferably oils chosen from cyclic or linear polydimethyl siloxanes containing from 3 to 9, preferably from 4 to 5 silicon atoms.

Cyclomethicone is the most preferred cyclic volatile silicone. Linear volatile silicone oils generally have viscosities less than about 5 centistokes at 25Â° C. while cyclic fluids typically have viscosities of less than about 10 centistokes.

Non-volatile silicone oils useful for the present invention include polyalkyl siloxanes, polyalkylaryl siloxanes and polyether siloxane copolymers. Non-volatile polyalkyl siloxanes useful herein include, for example, polydimethyl siloxanes with viscosities of from 5 to 100,000 centistokes at 25Â° C. Among the preferred non-volatile silicones are the polydimethyl siloxanes having viscosities from 10 to 400 centistokes at 25Â° C. These siloxanes are available, for example, from the General Electric Company as SF 1075 methyl phenyl fluid or from Dow Corning as 556 Cosmetic Grade Fluid.

The non-volatile polyalkylaryl siloxane fluids that may be used include, for example, polymethylphenylsiloxanes having viscosities of about 15 to 30,000 centistokes at 25Â° C.

Further Components

The aqueous hair styling aids of the invention can contain a variety of nonessential, optional components suitable for rendering the compositions more aesthetically acceptable or to aid use, including discharge from the container, of the product. Such conventional optional ingredients are well known to those skilled in the art, e.g. surfactants, particularly preferred are non-ionic surfactants, preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidazolidinyl urea, fatty alcohols such as cetearyl alcohol, cetyl alcohol and stearyl alcohol, pH adjusting agents such as citric acid, succinic acid, sodium hydroxide and triethanolamine, colouring agents such as any of the FD&C or D&C dyes, perfume oils, chelating agents such as ethylenediamine tetraacetic acid, polymer plasticising agents such as glycerin and propylene glycol.

Hair Treatment Compositions

Compositions in accordance with the invention are preferably formulated as leave on products for the treatment of hair without subsequent rinsing.

It is preferred if the compositions are delivered in the form of a spray, particularly preferred is an aqueous/ethanolic spray. The preferred level of ethanol in the composition is from 3 to 50 wt % of the total composition, more preferably from 5 to 20 wt %.

Examples

The invention will now be further illustrated by the following, non-limiting Examples. Examples of the invention are illustrated with a number, comparative Example with a letter.

Example A

Chemical NameTrade Name% activePolyoxyl 40 hydrogenatedCremophore RH40⁽¹⁾1.00%Castor oilDimethicone/cyclomethiconeDC1787⁽²⁾â€‚0.5%Ethanol10.0%Polyquaternium 16Luviquat FC550⁽³⁾â€‚0.3%Preservatives, water & minorsto 100%

Preparation

The main vessel is charged with 40.3% of the water. In a side mixer the fragrance and Cremophore are blended before adding into the main vessel, additional water is used to flush the side vessel. The main vessel is stirred at moderate speed until homogeneous. In the side vessel a solution of the styling polymer in water (20%) is prepared, the preservatives are added. This premix is stirred until homogeneous and is then dispelled into the main vessel, followed by an additional flushing with water. The main vessel is again stirred under moderate shear until homogeneous. In the side vessel the silicone emulsion is diluted with water and this mixture is added to the main vessel. The main vessel is then stirred until homogeneous and the pH adjusted before discharging.

Example 1

Chemical NameTrade Name% ActivePolyoxyl 40 hydrogenatedCremophor RH401.00%â€‚Castor oilDimethicone/cyclomethiconeDC1787⁽¹⁾0.5%Ethanol10.0%â€‚Polyquaternium 16Luviquat FC550⁽²⁾0.3%Synthetic silicateLaponite XLS⁽³⁾0.3%Preservatives, water & minorsto 100%

Preparation

The main vessel is charged with 40% of the water. The Laponite is added slowly with agitation to the main vessel, stirring is continued until the clay is fully dispersed in the water. In a side mixer the fragrance and Cremophore are blended before adding into the main vessel, additional water is used to flush the side vessel. The main vessel is stirred at moderate speed until homogeneous. In the side vessel a solution of the styling polymer in water (20%) is prepared, the preservatives are added. This premix is stirred until homogeneous and is then dispelled into the main vessel, followed by an additional flushing with water. The main vessel is again stirred under moderate shear until homogeneous. In the side vessel the silicone emulsion is diluted with water and this mixture is added to the main vessel. The main vessel is then stirred until homogeneous and the pH adjusted before discharging.

Example 2

Chemical NameTrade Name% ActivePolyoxyl 40 HydrogenatedCremophor RH401.00%Castor oilDimethicone/cyclomethiconeDC1787⁽¹⁾â€‚0.5%Ethanol10.0%Polyquaternium 16Luviquat FC550⁽²⁾â€‚0.3%Synthetic silicateLaponite XLS⁽³⁾0.45%Preservatives, water & minorsto 100%Example 2 is prepared in the same manner as example 1, the only difference is that the clay level is increased to 0.45%⁽¹⁾supplied by Dow Corning⁽²⁾supplied by BASF⁽³⁾supplied by Rockwood

Evaluation 1

Methodology

36 women with normal and normal to greasy hair were selected for this test. The respondents washed their hair with a control shampoo 24 hours prior to application of the product. The respondents were treated with both the comparative Example A and example 1 in a random half head design. Four sprays of both products were applied to each half of the respondent's head by a trained stylist.

The respondent assessed the product during application and then they are allowed to style their own hair using whatever tools they prefer. The respondent and stylist assessed each half of the respondent's head in order to determine which product performed better on which attribute.

Results

The results for the evaluation are shown below, only significant differences (student t-test) are illustrated, with the level of significance highlighted in brackets

Normal to greasyStylist N = 36Total respondent n = 36respondents n = 19Hold (99%)Ease of Style (90%)Scalp freshness (90%)Flyaway (90%)Shininess (95%)Ease of Style (95%)Best hair style (90%)Shininess (90%)Pleasant smell (90%)

Evaluation 2

Methodology

The Examples were tested as described above.

Results

The results are illustrated below. The results demonstrate the performance of the invention when applied to either damp or dry hair.

Example A vs Example 1Example 1 vs Example 2Example 1 preferred (Sig)Example 2 preferred (Sig)Applied on wetApplied on dryApplied on wetApplied on dryLess frizz (90%)Ease of combingMoisturisation @(90%)application (95%)Less coatingSoft feel (95%)Soft @(95%)application (95%)Clean feel (90%)Smooth @application (95%)Shine (95%)Less Greasy/oily(95%)Less drynessFresh feel (95%)(95%)Fresh Next dayFresh look (95%)(95%)Shine (95%)

It will be seen that feel attributes are significantly increased on hair treated with compositions according to the invention, compared to hair treated with Comparative Example A.