GB1598567A - Hair preparation - Google Patents

Description

(54) HAIR PREPARATION (71) We, UNILEVER LIMITED, a company organised under the laws of Great Britain, of Unilever House, Blackfriars, London E/C 4, England, do hereby declare the invention for which we pray that a patent may be granted to us and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to hair conditioner preparations and more especially to hair conditioner preparations having antigrease properties.

Hair conditioner preparations are normally applied to the wet hair immediately following shampooing. Only single application is made, and after massaging in for about one minute, the hair is thoroughly rinsed before being dried. This procedure will be referred to hereinafter as the conventional rinse-off method.

Another method of use is that in which the hair conditioner preparation after application is not rinsed off, but left on the hair. This procedure will be referred to hereinafter as the "leave-on" method.

Hair conditioners are functional products used by the consumer to improve the appearance, feel, and manageability of the hair. To be specific, their main functionality lies in their ability to make wet hair, and to a less extent, dry hair easier to comb, reduce the fly away or static, and to enhance the soft, smooth feel of the hair. Of these attributes the most important, and major reason given for conditioner usage is "ease of wet combing".

Conventional hair conditioner products are usually based on long chain quaternary ammonium compounds e.g. cetyl trimethyl ammonium bromide, combined with fatty materials such as fatty alcohols, fatty acid esters, and mineral oil. However, although such products do improve the combability of hair, due to the development of a hydrophobic coating on the hair, they also render the hair oleophilic. As a result these compositions are perceived by the consumer as making their hair greasy. Since greasy hair is a major hair care problem, the deposition of such materials on the hair aggravates this probem, either by appearance or feel of the hair or more specifically, by leaving the hair with a coating over which sebum, the naturally oily secretion of the scalp, can spread more easily.

It should be possible to use a volatile hydrophobing agent in order to provide the necessary combing benefits on wet hair without the development of an oleophilic surface.

An application of such a preparation to the hair, and after providing the combining benefits, the hydrophobing agent would volatilise from the hair and thereby avoid the disadvantage of the substantive deposits derived from conventional products.

However, although the use of a volatile hydrophobing agent would indeed overcome the problem of substantive fatty deposits and faster re-greasing of the hair, it will not help to solve the specific problem of greasy hair.

We have now discovered how to formulate a hair conditioner preparation which will not only provide the wet combining benefits and leave no fatty residues, but which will also modify the hair surface to make it oleophobic and hence grease-repellant. This oleophobic action will inhibit the normal rate of regreasing of the hair.

Accordingly, the invention provides a hair conditioner comprising a volatile silicone having a boiling point within the range 99 to 2650C and a water-soluble or water-dispersible fluoresurfactant having the general formula:

Wherein: Rf is a straight or branched C6 to 2 wholly or partially fluorine substituted alkyl or alkenyl group, R is hydrogen or a C1 to C7 alkyl group, Rl is a C1 to C alkylene group, Ar is a mono or dinuclear aromatic residue, X is a carboxylic, phosphoric or sulphonic acid group, in free acid, in amide, ester or in salt form, or hydroxyl group, Y is an organic or inorganic anion, e.g. a halogen, sulphate, phosphate, citrate, tartrate or acetate.

Without wishing to be bound to any theory it is believed that by rendering the hair oleophobic, the hair conditioner composition of the invention would retard or prevent the spontaneous spread of sebum, and would constitute an effective antigrease treatment.

The ability to modify the hair surface rendering it oleophobic is determined by a test involving measuring the contact angle to a-bromonaphthalene of hair treated with the hair conditioner composition. The test is based on that described by A.K. Kuzilenka and L.B.

Aleksandrova in Khimicheskie Volkna (1965), 3, 65-67, and is performed as follows: A switch of virgin Italian blue string hair is degreased with ether, washed with a shampoo and treated with a hair conditioner, which is either rinsed-off or left-on the hair, and dried.

A single hair is then removed, using rubber gloves, from this switch and sandwiched between two microscope slides which are held together by screw clamps at either end. A drop of a-bromonaphthalene is placed at one end of the slides and is spread between them by capillary attraction. A liquid film is formed between the slides which contacts the hair to give two contact angles. The angle which is required is the so-called "advancing" contact angle and this can be determined by screwing in the screw clamps so that the film is "squeezed" along the hair shaft. The advancing contact angle of the hair can then be measured under the microscope. The larger the contact angle the more oleophobic is the hair surface and hence the antigrease effect is shown by an increase of the contact angle.

The volatile silicone oil which can be used in the present invention will have a boiling point within the range of 99"C to 265"C and may be low molecular weight linear polydimethyl siloxane but is preferably a cyclic material containing four or five (CH3)2 SiO-units arranged in a cyclic structure. Other dimethyl polysiloxanes which can be used in the present invention are described in Specification No. 1,158,139. Suitable materials are those available from Union Carbide Corporation under the designations VS 7207 and VS 7158, respectively, and from Dow Corning under the designation 200 fluid series having viscosity within the range of 0.65 to about 5.0 centistokes. Up to 5% or more by weight of the volatile silicone may be present in the composition. Generally a range of 0.1 to 5% by weight, and preferably of between 0.5 to 3.0%, will be suitable.

The amount of fluorosurfactant present in the composition according to the invention may be as low as 0.01% by weight and up to about 5% or more by weight, preferably from 0.05 to 3.0% by weight, though in practice a range of from 0.1 to 2% by weight will generally be sufficient.

The hair conditioner composition according to the invention can be formulated in any suitable form, e.g. as lotions or emulsions, which may be presented as such or as aerosols or in pump sprays. A thickening agent may be incorporated for thickening the aqueous medium of the product. Suitable thickeners are the well known high molecular weight carboxyvinyl polymers available from the BF Goodrich Company under the trade mark Carbopol (e.g. Carbopol 934; 940 and 941) and the hydroxyalkyl ether cellulose derivatives, e.g. the hydroxyethyl ether cellulose derivative. Amounts of thickener present will, of course, depend on the particular thickener employed and the viscosity required. The carboxy polymers will usually be employed in amounts up to about 1%, such as in the range 0.05 to 0.5%, and these will be employed in the pH range of 3 to 8, particularly 5 to 7, with addition, if necessary, of an inorganic or organic base. The hydroxyalkyl ether cellulose derivatives will normally be used in greater amounts, say 0.2 to 3% by weight and in the pH range of 3 to 8.

An essential feature of the hair conditioner product of the invention is that not only is it substantially free of fatty materials as used in known hair conditioner products, particularly the cationic long chain quaternary ammonium compounds and the long chain fatty alcohols and like materials, but also it inhibits the spread of grease on the hair and so provides an effective anti-grease treatment.

Optional ingredients which may be included in the compositions of the invention include a lower aliphatic alcohol, for example ethanol or isopropanol, perfume, colour, preservative, and other functional additives.

In summary the aqueous compositions according to the invention comprise: 0.1 to 5% preferably 0.5 to 3% by weight of a polydimethyl siloxane 0.01 to 5% preferably 0.05 to 3.0% by weight of a fluorosurfactant 0 to 5% by weight of a thickening agent, and 0 to 90% by weight of ethanol or isopropanol.

Examples of hair conditioner rinse compositions in accordance with the invention will now be described. Percentages are by weight.

Component Example I Example II Volatile silicone VS 7158 2.50 2.50 Fluorosurfactant Zonyl FSP 0.16 0.33 (Compound of Formula 4; X being a phosphoric acid group) Hydroxyethyl ether cellulose 1.50 (Natrosol 250HR) Carboxyvinyl polymer - 0.30 (Carbopol 941 Triethanolamine (to give q.s. q.s. pH 7.0) Water to 100.0 to 100.0 Silicone VS 7158 is a cyclic polydimethyl siloxane having a viscosity at 200C of 4.2 centipoises and a boiling range (ASTM) at 760 mm Hg of 190 to 2100C.

"Zonyl" and "Natrasol" are trade marks.

Example III The effect of a florosurfactant Zonyl FSP on the ease of wet combing was examined.

Aqueous alcoholic solutions containing the following substances were used and the results obtained, using a rinse-off procedure were as follows: % reduction in wet combing resistance 2.5% volatile silicone VS 7158 55

2.5% volatile silicone VS 7158 +) 0.5% Zonyl FSP ) 52 The presence of Zonyl FSP fluorosurfactant does not detract from the volatile silicone's functionality as regards ease of wet combing.

Example IV The following contact angles were achieved with solutions containing volatile silicone and Zonyl FSP at different levels. All treatments were employed in a leave-on manner, and contact angles were recorded after 24 hours. The solvent used was aqueous alcohol 10:90.

Concentration of volatile silicone MS 200/ICS (%) 0 1 5 Conc. of Zonyl FSP 0 42" - 38 (% actives) 0.15 55" 62" 0.50 65" 67" Measurements of the contact angle on dry hair show that the fluorosurfactant Zonyl FSP causes a significant increase in contact angle relative to untreated hair (42"). The above results further show that the volatile silicone itself does not increase the contact angle nor does it reduce the effectiveness of the fluorosurfactant. Thus only compositions combining a volatile hydrophobing agent and a fluorosurfactant result in increased contact angle and a reduction in combing resistance.

Example V Whilst some consumers leave the conditioner on the hair, the majority use such products in a rinse-off mode. The following results were obtained using a rinse-off protocol.

Concentration of volatile silicone VS7158 (%) 0 2.5 Conc. of Zonyl FSP 0 38 37 (% actives) 0.16 42" 46" 0.33 64" 53" 0.66 63" 53" The above results again show that the composition increases the contact angle after treatment and that the volatile silicone itself neither increases the contact angle, nor does it inhibit the effectiveness of the fluoro surfactant.

Examples VI-VIII Three systems have been examined for contact angles and wet-combing resistance.

(1) Thickened aqueous emulsion for "rinse-off" use Composition (%) VI VIa VIb Volatile silicone VS 7158 2.50 2.50 Fluorosurfactant Zonyl FSP 0.66 - 0.66 Thickening agent Carbopol 940 0.15 0.15 0.15 Thickening agent Natrosol 250 HR 0.60 0.60 0.60 Water up to - 100% % Reduction in wet combing resistance + 59 + 60 - 38 Contact angle 64" 36 66" (2) Thickened aqueous emulsion for "leave-on" use Composition (%) VII VIIa VIIb VS 7158 1.0 1.0 Zonyl FSP 0.5 - 0.5 Carbopol 940 0.2 0.2 0.2 Water up to - 100% % Reduction wet combing resistance + 47 + 57 - 7 Contact angle 82" 33 90" (3) Aqueous alcoholic solution, predominantly for "leave-on" use Composition (%) VIII VIIIa VIIIb Volatile silicone 1.0 1.0 (Dow Corning Grade 200/1 centistoke) Fluorosurfactant Zonyl FSP 0.5 - 0.5 Mixture of isopropylalcohol 55% and 98.5 99.0 99.8 H2O 45% % Reduction in wet combing resistance 46 43 nil Contact angle 74" 37 78" WHAT WE CLAIM IS: 1. Hair conditioner preparation containing a volatile silicone having a boiling point within the range of 99" to 2650C and a water-soluble or water-dispersible fluorosurfactant having the general formula: 1. RfX 2. RfRlX 3. RfArX 4. RfRl(C2H4O)nX n = 0 to 6

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (8)

**WARNING** start of CLMS field may overlap end of DESC **. (2) Thickened aqueous emulsion for "leave-on" use Composition (%) VII VIIa VIIb VS 7158 1.0 1.0 Zonyl FSP 0.5 - 0.5 Carbopol 940 0.2 0.2 0.2 Water up to - 100% % Reduction wet combing resistance + 47 + 57 - 7 Contact angle 82" 33 90" (3) Aqueous alcoholic solution, predominantly for "leave-on" use Composition (%) VIII VIIIa VIIIb Volatile silicone 1.0 1.0 (Dow Corning Grade 200/1 centistoke) Fluorosurfactant Zonyl FSP 0.5 - 0.5 Mixture of isopropylalcohol 55% and 98.5 99.0 99.8 H2O 45% % Reduction in wet combing resistance 46 43 nil Contact angle 74" 37 78" WHAT WE CLAIM IS: 1. Hair conditioner preparation containing a volatile silicone having a boiling point within the range of 99" to 2650C and a water-soluble or water-dispersible fluorosurfactant having the general formula:

1. RfX

2. RfRlX

3. RfArX

4. RfRl(C2H4O)nX n = 0 to 6

wherein: Rf is a straight or branched C6 to C22 wholly or partially fluorine substituted alkyl of alkenyl group, R is hydrogen or a C1 to C7 alkyl group, Rl is a C1 to C7 alkylene group, Ar is a mono or dinuclear aromatic residue, X is a carboxylic, phosphoric or sulphonic acid group, in free acid, in amide, ester or in salt form, or hydroxyl group, Y is an organic or inorganic anion, e.g. a halogen, sulphate, phosphate, citrate, tartrate or acetate.

2. A preparation according to claim 1 wherein the fluorosurfactant is a compound having the general formula RfR1 (C7H4O)X as defined in Claim 1.

3. A preparation according to claim 1 or claim 2 wherein the volatile silicone is a cyclic polydimethyl siloxane having a viscosity at 20"C of 4.2 centipoises and a boiling range (ASTM) at 760 Hg of 190 to 210 C.

4. A preparation as claimed in any one of the preceding claims containing the fluorosurfactant in an amount of from 0.01 to 5% by weight of the composition.

5. A preparation as claimed in any one of claims 1, 2 or 3 containing the fluorosurfactant in an amount of from 0.05 to 3% by weight of the composition.

6. A preparation as claimed in any one of the preceding claims containing the volatile silicone in an amount of from 0.10 to 5% by weight of the composition.

7. A preparation as claimed in claim 6, containing the volatile silicone in an amount of from 0.5 to 3% by weight of the composition.

8. A hair conditioner preparation containing a volatile silicone and a water-soluble or water-dispersible fluorosurfactant substantially as hereinbefore described in any of the Examples.