COSMETIC PRODUCT

Abstract: A substantially anhydrous antiperspirant product, in solid or liquid form, which is suitable for applying to the skin comprises an antiperspirant agent in the form of a finely divided powder, an anhydrous liquid or solidified liquid medium comprising an anhydrous alcohol chosen from ethanol, isopropanol or a mixture thereof, a perfume and a perfume-stabilising agent chosen from compounds having a basic nitrogen function, compounds having a basic oxygen function or mixtures thereof.

Description: FIELD OF INVENTION The invention relates to antiperspirant products, and more particularly to perfumed products comprising a finely divided antiperspirant agent suspended in a non-aqueous liquid, which when in the form of a liquid is especially suitable for dispensing from a roll-on dispenser, or from an aerosol can, and which when in the form of a solid is conveniently used in the form of a stick housed in a suitable holder or container. BACKGROUND & PRIOR ART It is normally considered desirable to provide antiperspirant products for topical application to human skin which are pleasantly perfumed, so as to enhance the benefit of the antiperspirant agent in not only reducing or eliminating perspiration, but also in reducing body malodour usually associated with perspiration. To meet this need, there is, for example, a proposal in US-A-2 955 983 (Colgate-Palmolive Co) to provide an antiperspirant lotion containing aluminium chlorohydroxide, urea, ethanol, perfume and water, the water constituting about half of the formulation. In this lotion, however, the aluminium chlorohydroxide is dissolved in the water and perfuming of this type of product generally presents no problem. It is however apparent that the solution type of antiperspirant is not particularly effective in combating perspiration, owing to the impossibility of delivering to the skin surface from solution an effective amount of the antiperspirant agent to combat profuse perspiration. EP-A-175,074 (American Cyanamid) discloses a method for producing solid gel antiperspirant compositions at a lower processing temperature, the compositions an acidic metal antiperspirant active, dibenzyl monosorbitol acetal as a gelling agent, and at least one solvent. DE-A-2,503,963 (Thomae GMBH) discloses deodorant spray compositions containing at least 10% of one or more solvents with a boiling point of at least 37°C which evaporate on the skin, a powdered material suspended in the liquid phase, and known base, active and additive materials. The suspended powdered material is said to fix the perfume to the skin. Attempts have been made to improve the efficacy of such solution products by providing the antiperspirant agent in a finely divided form suspended in the liquid carrier in which it is virtually insoluble, but whereas such suspension products have proved to be successful in enhancing the efficacy so far as antiperspirancy is concerned, we have noted that there is a difficulty in maintaining an adequate level of perfume stability after the product has been stored, particularly when the product contains ethanol. It is accordingly apparent that perfumes can be unstable in suspension-type alcoholic lotion antiperspirant products to such an extent that unless freshly prepared, little or no fragrance may remain detectable in such products after storage in the factory, shop or home under normal ambient temperature conditions, for more than about one month. In our attempts to discover why this may be so and to establish conditions whereby the fragrance of perfumed anhydrous alcoholic antiperspirant products might be preserved until the product is used, we have found that the addition of one or more special perfume stabilising agents to such formulations mitigates the deterioration of the perfume, such that the product remains fragrant for many months with little or no noticeable decrease in the intensity of the fragrance present when the product is first manufactured. We have also discovered that these same perfume stablising agents inhibit the dissolution of the antiperspirant agent in the anhydrous alcohol which forms at least part of the product, with the consequent benefit that the antiperspirant efficacy particularly in liquid lotions for use in roll-on dispensers is enhanced, since a greater quantity of the antiperspirant-agent in solid form will then be deposited on the skin. It is also apparent that perfume deterioration is mitigated and dissolution of antiperspirant agent in anhydrous alcohol is reduced in the corresponding aerosol and stick products. DEFINITION OF INVENTION According to the invention, there is provided an anhydrous antiperspirant product suitable for applying to the skin which comprises: i) from 1 to 60% by weight of a finely-divided powder antiperspirant agent; ii) from 10 to 90% by weight of an anhydrous liquid or solidified liquid medium, comprising an anhydrous alcohol chosen from ethanol, isopropanol and mixtures thereof; iii) from 0.001 to 10% by weight of a perfume; and iv) from 0.1 to 25% by weight, expressed in terms of the anhydrous alcohol present, of a perfume-stabilising agent chosen from compounds having a basic nitrogen function and compounds having a basic oxygen function, and drying agents and mixtures thereof. DISCLOSURE OF THE INVENTION The Antiperspirant Agent The antiperspirant product according to the invention comprises an antiperspirant agent in the form of a finely divided powder so as to enable it to be suspended when desired in the liquid medium. Preferably the antiperspirant agent powder has a maximum particle diameter of no greater than 100µm preferably no greater than 70µm and preferably about 45µm. Examples of suitable antiperspirant agents include aluminium chloride, aluminium sulphate, aluminium chlorohydrate, basic aluminium bromide, zirconyl chloride; zirconyl hydroxide; zirconyl chlorohydrate complexes of aluminium hydroxide, zirconyl chloride and aluminium chlorohydrate; complexes of aluminium hydroxide, zirconyl chlorohydrate, and aluminium chlorohydrate; complexes of dihydroxyaluminium glycinate, zirconyl chloride and/or zirconyl chlorohydrate and aluminium chlorohydrate; complexes of zirconyl chloride and/or zirconyl clhorohydrate and aluminium chlorohydrate; complexes of zirconyl chloride and/or zirconyl chlorohydrate with aluminium chlorohydrate and an amino acid, such as glycine; and mixtures of two or more of the above. Most preferred materials are those which have a high antiperspirant efficacy. One class of such materials are the aluminium zirconium chlorohydrate complexes. Examples are aluminium zirconium trichlorohydrate, aluminium zirconium tetrachlorohydrate and aluminium zirconium pentachlorohydrate (these are CTFA generic names). These compounds may be combined with glycine to give for example the compounds known under the CTFA generic names aluminium zirconium trichlorohydrex-GLY and aluminium zirconium tetrachlorohydrex-GLY. Suitable aluminium zirconium chlorhydrate powders for use in the antiperspirant compositions of this invention are available from the Reheis Chemical Company under the trade names REZAL 36GP and REZAL 67P (REZAL is trade mark) and from Wickhen Products, Incorporated under the trade names WICKENOL 369 and WICKENOL 379 and WICKENOL 373 (WICKENOL is a trade mark). Other preferred antiperspirant active materials of high efficacy are the special active forms of basic aluminium chloride which have a particular distribution of polymeric species in aqueous solution and obtainable by procedures described in US Patent No. 4 359 456 (Gosling et al). Similar processes for making highly active forms of aluminium chlorohydrate involving the ageing of aluminium chlorohydrate in an aqueous medium are described in British Patent Specification No 2 048 229 (Gillette). Other suitable materials are described in British Patent Specification No. 2 144 992 (Gillette). The antiperspirant agent may also be a urea or glycine complex of aluminium chlorohydrate prepared as described in European Patent No. 6738 (Unilever) and British Patent No. 1 597 497 (Unilever), respectively. A further example of activated aluminium chlorohydrate which can be employed as the antiperspirant agent is REACH available from Reheis. The amount of the antiperspirant agent present in the product according to the invention will depend on the form of the product and in general will be within the range of from 1 to 60%, preferably from 5 to 50% by weight. When the product is a propellant-based aerosol, these amounts refer to the aerosol concentrate without the propellant. The anhydrous liquid or solidified liquid medium The antiperspirant product according to the invention also comprises an anhydrous medium comprising an alcohol chosen from anhydrous ethanol, anhydrous isopropanol and mixtures thereof. By "anhydrous" is meant that the ethanol and/or the isopropanol contains no more than 1% by weight of water. The anhydrous liquid or solidified liquid medium preferably comprises the anhydrous alcohol. It is, however, possible for other anhydrous liquids to form part of the anhydrous medium of the antiperspirant product of the invention. Such additional liquids can be incorporated to give emollient cosmetic benefits and can be either hydrophilic or hydrophobic liquids. Examples of the emollient liquids than can optionally be employed include a polar liquid such as water-miscible polyoxyalkylene glycol or a water-miscible partial butyl either thereof; hexylene glycol; a C₁-C₄ alkyl monoether or a simple or condensed C₂-C₄ alkylene glycol for example dipropylene glycol monomethyl ether; or 2-ethyl-1,3-hexane diol. Other commercially available hydrophilic materials which are suitable are Pluronics (eg. Poloxamer 101, Poloxamer 105, Poloxamer 181, Poloxamer 182), Carbowaxes (eg. PEG-4, PEG-8, PEG-12), Witconol APEM (PPG-3 Myreth-3), Witconol APES (PPG-9 Steareth-3), Standamul OXL (PPG-10 Cetearth-20), Procetyl AWS Modified (PPG-8 Ceteth-2). Glycols and their citrate, lactate and tartrate esters as taught in Canadian Patents 1 121 728; 1 121 729 and 1 121 730 can also be used. Hydrophilic materials which are the dimethicone copolyols that is polymers of dimethylsiloxane with polyoxyethylene and/or polyoxypropylene side chains. Examples of these are SILWET L-270, L-7600 and L-7610 from Union Carbide, Silicone 190 and 193 surfactants both from Dow Corning and ABIL B 8842, 8843 and 8851 from Goldschmidt. These dimethicone copolyols are also referred to in the literature as polyalkylene oxide modified dimethylpolysiloxanes, as silicone glycol copolymers and as polysilicone polyether copolymers. Dimethyl isosorbide is a further example of a suitable hydrophilic liquid. Examples of non-polar water-immiscible liquids are the linear volatile silicones having 2 to 9 silicon atoms such as hexamethyl disiloxane, the cyclic volatile silicones having 3 to 6 silicon atoms such as tetramer and pentamer, linear non-volatile silicones, paraffin oils, fatty acid esters such as isopropyl myristate and dibutyl phthalate, and polyoxypropylene fatty ethers such as Fluid AP, and mixtures thereof. When the product according to the invention is solid, for example in the form of cosmetic stick, then the solidfied liquid medium can comprise a gelling agent. Examples of gelling agents include low melting point waxes, having a melting point of from about 40°C to 70°C, such as fatty acids and fatty alcohols containing from 8 to 22 carbon atoms, silicone waxes and glycerol monostearate. Preferred examples of such waxes include lauric acid, stearic acid, palmitic acid, cetyl alcohol, stearyl alcohol, myristyl alcohol and behenyl alcohol. The amount of the low melting point wax when employed will normally be from 8 to 35%, preferably 12 to 25% by weight of the product. A quantity of water-insoluble high melting wax may also be incorporated in the antiperspirant stick composition to help provide the basic structure of the stick. Suitable waxes for this purpose are water-insoluble waxes, having a melting point of from about 70°C to about 100°C. Examples of suitable waxes include; Castorwax MP80, Synchrowax HRC, carnaubau, beezwax spermaceti, ozokerite and paraffin wax. These may constitute from 0 to 10%, preferably from 2 to 8% by weight of the product. The normally solid higher fatty acid amides of alkylolamines are also useful as gelling agents in the antiperspirant stick compositions of the invention. Such amides can be derived by the usual condensation, at elevated temperatures of from 150 to 175°C of normally solid higher fatty acids such as palmitic acid, stearic acid, myristic acid and lauric acid, with primary or secondary alkylolamines or hydroxyalkyl amines such as, monoethanoloamine, diethanolamine, n-propanolamine, hydroxyethyl ethylenediamine, glycerolamine, 1-amino-2, 3-propanediol and 2-amino-1,3-propanediol. The condensation products of myristic acid, palmitic acid or stearic acid with monoethanolamine are preferred. The alkylolamides when employed should constitute from 15 to 35% preferably from 20 to 30% by weight of the product. The gelling agent may also be dibenzyl monosorbitol acetal (DBS), desirably together with a co-solvent such as dihydric and polyhydric alcohols and stabilising agents to prevent acid decomposition of the acetal and subsequent gel breakdown. When employed, DBS should be present in an amount of from 0.5 to 10% preferably 1 to 5% by weight of the product. Specific examples of co-solvents for DBS include 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol, diethylene glycol, diethylene glycol monomethylether, 1,2-propylene glycol, 1,3-butylene glycol, dipropylene glycol, hexylene glycol, 2,4-dihydroxy-2-methylpentane, polyetherlene glycols and mixtures thereof. These should be present in amounts of from 10 to 60%, preferably from 15 to 45% by weight of the product. Agents suitable for stabilising products according to the invention containing dibenzyl monosorbitol acetal include amines such as methenamine (hexamethylene tetramine), amides such as acetamide monoethanolamide and cocofatty acid monoethanolamide and basic metallic salts such as zinc oxide, zinc acetate, calcium acetate, zinc carbonate, potassium carbonate, magnesium carbonate and calcium hydroxide. Mixtures of the above organic and inorganic gel stabilising agents are also effective. Ordinarily, the stabilisers will be used in an amount ranging from 0.02 to 10%, preferably from 0.1 to 5% by weight of the product. The amount of the anhydrous liquid or solidified liquid medium present in the product according to the invention will usually form from 10 to 90%, preferably from 30 to 80% by weight, the anhydrous alcohol forming at least 10% by weight of the product. The alcohol can alternatively comprise from 10 to 80%, preferably from 15 to 75% by weight expressed in terms of the antiperspirant product. The perfume The antiperspirant product according to the invention also comprises a perfume, the function of which is primarily to enhance the benefits of the product when applied topically to skin to reduce or eliminate perspiration. The fragrance derived from the product can thus assist in masking body malodour frequently associated with perspiration. Although the nature and formulation of the perfume is not critical, it is preferred to employ a perfume having distinct deodorant properties which functions not only as an odour maskant, but also in the elimination of materials accummulating at the skin surface which contribute to body malodour. Deodorant perfumes of this type are described, for example, in US patent 4 278 658 (Lever Brothers Company). The amount of perfume present in the product according to the invention will usually form from 0.001 to 10%, preferably from 0.1 to 5% and ideally from 0.2 to 2% by weight. The perfume stabilising agent The antiperspirant product according to the invention also comprises a perfume stabilising agent. As has been stated earlier, the perfume normally included in suspension-type lotion antiperspirant products can deteriorate rapidly during storage prior to use. The reasons for this are not fully understood, particularly since solution type antiperspirant compositions apparently do not suffer from the same problem. It does appear, however, that the loss of fragrance and, where applicable, the deodorant properties of a perfume in the suspension type products such as the antiperspirant compositions according to the invention can be mitigated by including in the product an effective amount of a perfume stabilising agent chosen from compounds having a basic nitrogen function, compounds having a basic oxygen function and drying agents, or mixtures thereof. Examples of compounds having a basic nitrogen function are urea; natural amino acids for example glycine, alanine, taurine, serine, sarcosine, arginine valine, leucine, proline, methionine, threonine, ornithine, histidine, lysine monohydrochloride, glutamic acid monomethyl ester (which amino acids include the neutral amino acids and basic amino acids); and organic amines, such as C₁ to C₂₀ alkylamines and hydroxylamines, for example triethylamine, mixed C₁₃/C₁₅ alkylamine and 2-amino-2-methyl-propan-1-ol. Examples of compounds having a basic oxygen function are inorganic bases such as the hydroxides of the alkali metal and the alkaline-earth metals and ammonium hydroxide, including sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide and magnesium hydroxide, as well as the basic metallic oxides, for example aluminium oxide, zinc oxide and lanthanum oxide; and the alkali metal salts of inorganic acids, such as sodium carbonate, sodium thiosulphate, anhydrous sodium sulphate, dipotassium hydrogen orthophosphate, zinc carbonate and C₁ to C₂₀ organic carboxylic acids for example trisodium citrate, sodium acetate sodium n-octanoate and sodium stearate. Drying agents such as molecular sieve Type 3A can also be used as a perfume stabilising agent. The amount of the perfume stabilising agent present in the product according to the invention is that which is effective in stabilising the perfume in the composition for at least one month at a storage temperature of 37°C. The actual amount required will depend on the particular perfume stabiliser employed, and is conveniently related to the amount of the anhydrous alcohol present in the product. In general, a sufficient amount will be from about 0.1 to about 25% by weight of the anhydrous alcohol present in the liquid medium of the product. The amount of urea or amino acid will generally be in the range of from 0.5 to 25% preferably from 1 to 10% and ideally from 1 to 5% by weight of the alcohol, although in practice any amount can be included which is consistent with an acceptable product. The organic amines can be used in an amount of from 0.5 to 4% by weight of the alcohol. The alkali metal inorganic bases and ammonium hydroxide are suitably used in amounts of about 0.1 to about 2% by weight of the alcohol, and other inorganic bases, basic oxides and inorganic acid salts in amounts of about 0.5 to 10% by weight of the alcohol. The salts of the C₁-C₂₀ carboxylic acids and the drying agent molecular sieve type 3A can be used in an amount of from 0.5 to 20% by weight of the alcohol. OPTIONAL INGREDIENTS The product according to the invention can also comprise optional ingredients further to improve and modify its performance and acceptability as judged by the consumer. Examples of such optional ingredients include suspending agents and colourants. Optional suspending agent The antiperspirant product according to the invention can also optionally comprise a hydrophobic clay as an agent for suspending the particles of the antiperspirant in the anhydrous liquid or solidified liquid medium. Particularly suitable clays are the hydrophobically treated smectite clays. Smectite clays are those characterised by having an expanding lattice. Examples of these clays include the montmorillonites, hectorites, and colloidal magnesium aluminium silicates. Montmorillonite is colloidal, hydrated aluminium silicate obtained from bentonite of which it is the predominant constituent. A detailed discussion of bentonites can be found in the Kirk-Othmer Encyclopedia of Chemical Technology, 2nd Edition, Vol. 3 (1964) pp. 339-360, published by Interscience Publishers. Hectorite, also a smectite clay, differs from montmorillonite in that there is almost a complete substitution of aluminium in the lattice structure of montmorillonite by magnesium and in addition, it contains lithium and fluorine. The magnesium aluminium silicates are complexes of colloidal magnesium aluminium silicate richer in magnesium than aluminium. The hydrophobically treated magnesium aluminium silicates are commercially available under the name VEEGUM PRO from the R T Vanderbilt Co. Preferred suspending agents for optional use in the invention are hydrophobic clays available under the trade name of BENTONE. BENTONES are prepared by reacting a suitable clay in a cation exchange system with an amine. Different amines are reacted to obtain a variety of BENTONES, which may also differ in proportions of Si, MgO and Al₂O₃. Examples of useful BENTONE suspending agents are BENTONE-27, which is a stearaluminium hectorite; BENTONE-34, which is quaternium 18 bentonite; BENTONE-38, which is quaternium 18 hectorite; and BENTONE-14 which is a clay-extended quaternium 18 hectorite, all of which have a particle size of below 5 microns and are commercially available in USA from NL Industries Inc. Other suitable BENTONE clays are BENTONE SD1 and Bentone SD2. Yet further suitable clays are those hydrophobically treated smectite clays available under the trade names PERCHEM and TIXOGEL. Specific examples are PERCHEM clays 44, 97 and 108 and TIXOGEL VZ. A further class of hydrophobically treated clays comprises hormite clays, an example of which is hydrophobically modified attapulgite clay available under the name PERCHEM DMA. PERCHEM clays are sold by Perchem Limited of Harlow, Essex, Great Britain and TIXOGEL clays by Production Chemicals Limited of Stockport, Cheshire, Great Britain. Other useful suspending agents are fine silica powders especially the fumed silicas available commercially under the names AEROSIL and CAB-O-SIL, and hydroxypropyl cellulose (KLUCEL). Mixtures of suspending agent can also be employed. The amount of the suspending agent which is optionally present in the product according to the invention will in general be within the range of from 0.5 to 15% by weight. PROCESS FOR MANUFACTURE OF ANTIPERSPIRANT COMPOSITION The invention also provides a process for the manufacture of the antiperspirant product according to the invention, which process comprises the step of mixing together the antiperspirant agent, the anhydrous liquid, the perfume and the perfume stabilising agent. It is preferable to add the perfume-stabilising agent to the anhydrous alcohol either before or simultaneously with the perfume, but not after it. The product so obtained is then filled into a convenient dispenser such as a roll-on dispenser, an aerosol can, or a mould, when the product is to be solidified. According to a preferred process, a thickening agent is also incorporated into the product so as to suspend the antiperspirant agent in the form of fine particles. METHOD OF USE The invention also relates to a method for the control of perspiration which comprises the step of applying the product according to the invention in the form of a lotion from a roll-on dispenser a spray from an aerosol can or a solidified stick to the skin, particularly to the underarm, in order to prevent or reduce perspiration. EVIDENCE TO CONFIRM PERFUME STABILITY The stability during storage of perfume in the suspension type antiperspirant product according to the invention is assessed by a standard test in which antiperspirant products, either with or without a perfume-stabilising agent, are compared using a subjective olfactory method by two or more expert assessors. In order to perform this test, a lotion containing an antiperspirant agent, together with anhydrous ethanol and/or anhydrous isopropanol and a perfume, as well as other materials as desired with the exception of perfume-stabilising agents is prepared. A perfume-stabilising agent under test is then introduced into a part of the lotion so prepared to provide the test sample, the remaining part of the lotion containing no perfume-stabilising agent serving as the control. Portions of the test and control lotion samples so prepared are stored in sealed containers at 37°C for between one and three months, and another portion of both test and control samples is also stored at 0°C over the same time period. It has been established over many years that perfumes require time to "settle down" in an antiperspirant formulation. Storage at 0°C has the effect of allowing "settling down" to take place yet avoiding further perfume modification. Hence by comparing the same perfumed lotion stored at 0°C and 37°C for the same time, it is possible to establish the extent to which the perfume stored at the higher temperature has been modified over and above the usually small change in note brought about by simply putting the perfume into the formulation. After storage, the extent of perfume modification was estimated using a 0 to 5 hedonic odour scale as follows: 0 : unmodified 1 : v. slight modification 2 : slight modification 3 : moderate modification 4 : severe modification 5 : unacceptable Scores of 2.5 or less were considered to represent an acceptable degree of perfume modification. By way of illustrating the invention, Table 1 shows the effect of adding urea (5.4& w/w of ethanol) to a range of perfumes contained in lotions having ethanol as the liquid medium and aluminium zirconium tetrachlorohydrex -GLY (ZAG) or a special active form of aluminium chloride (AACH) as antiperspirant actives. With all systems, urea has the effect of increasing perfume stability and for most perfumes the degree of modification changes from being unacceptable to being acceptable in presence of urea. A further illustration is given in Table 2 in which it is shown that a number of additives having a basic oxygen or a basic nitrogen functional group can stabilise perfumes via a lotion containing ethanol as the liquid medium and REZAL 36GP as the antiperspirant active. A drying agent, Molecular Sieve Type 3A, is also seen (Table 2) to be effective. Table 3 shows the effect of adding urea (5% w/w of ethanol) to a REZAL 36GP/ethanol lotion to which a range of individual perfume materials have been added rather than complete perfumes. With only one material (methyl cinnamic aldehyde) did urea reduce odour stability. As for the other 15 perfume materials, urea improved the odour stability of 9 of these and had no influence on the remainder. It should be noted that some of the trade names use in this specification, such as Rezal, Wickenol, Reach, Poloxamer, Silwet, Abil, Betone, Tixogel, Perchem, Aerosil, Cab-o-sil, Klucel, and others may be Registered Trade Markes in some of the Contracting States. In a further test to confirm perfume stability, test and control roll-on formulations (with and without added urea) were prepared as follows: After 10 weeks storage, each of the above formulations for each of 5 different perfumes was evaluated by a panel of trained assessors as previously described. The results of this assessment are summarised in Table 4 below: It was concluded from the above results that the presence of urea in all cases stabilised the deodorant perfume, whereas in the absence of urea, moderate or severe modification to the deodorant perfume occured. The deodorant perfume formulations employed in this test were as follows: EVIDENCE TO CONFIRM REDUCTION IN SOLUBILITY OF ANTIPERSPIRANT AGENT IN ETHANOL The following experiments illustrate the ability of the perfume stablising agents to inhibit the dissolution in anhydrous alcohol of antiperspirant agents. Percentages are by weight. Experiment 1 To saturated solutions of urea in anhydrous ethanol (urea concentration about 5.4% w/w) were added various antiperspirant agents in an amount of 25% w/w. The compositions were mixed for 48 hours at 20°C. The concentration of aluminium in the liquid phase was then determined by analysis using atomic absorption spectroscopy. Such concentrations are expressed herein as M which stands for moles of aluminium per litre of ethanolic solution. The anhydrous ethanol was a grade of absolute alcohol containing a maximum amount of water of 0.3% by weight. The results for various antiperspirant agents are given in Table 5. For all the antiperspirant agents, the presence of the urea effected a substantial reduction in the amount of the agent passing into solution in the alcohol. Experiment 2 In this experiment the effect of varying the amount of urea on the extent of dissolution in anhydrous ethanol of two antiperspirant agents is illustrated in Table 6. Experiment 3 In this experiment the effect of additives other than urea in inhibiting the dissolution of aluminium chlorohydrate in anhydrous ethanol was demonstrated, the results being summarised in Table 7. Experiment 4 In this experiment the effect of additives other than urea in inhibiting the dissolution of aluminium zirconium trichlorohydrate in anhydrous ethanol was shown, the results being given in Table 8. Experiment 5 In this experiment, the effect of additives in inhibiting the dissolution of aluminum zirconium trichlorohydrate in anhydrous isopropanol was shown, the results being given in Table 9. Experiment 6 Various other compounds that have been shown to be ineffective for inhibiting the dissolution of aluminum chlorohydrate in anhydrous ethanol are referred to in Table 10. EXAMPLES The following examples illustrate the invention. The products of the Examples are made by shearing the suspending agent in the liquid component or mixture of the liquid components, excluding the perfume, until fully dispersed. The urea, sodium hydroxide and the trisodium citrate were added to the alcohol prior to the addition of the antiperspirant powder. The antiperspirant powder and perfume are then added and dispersed by further high shear mixing. The product is then filled into roll-on dispensers. The products of Examples 1, 2 and 6 were assessed by the following test procedure involving subjecting human volunteers to thermal stress and gravimetric determination of axilla sweat. Subjects: A panel of up to 60 women who use no antiperspirant for the 14 days before the test. Hot Room: Temperatures 40°C± 2°C; relative humidity 40% ± 5%. Products: When testing two products, one being designated the test product and the other the control, the panel is divided into two equal groups. One group receives the test treatment on the left axilla and the control treatment on the right, while the second group receives them the other way round. Alternatively, when comparing two test products against each other and against a control product, then the products are randomly applied to the axillae of the panel subjects, with the proviso that the product applied to the left axilla is different from that applied to the right axilla of each subject. Control Product: This is a placebo deodorant in the form of an aerosol product comprising by weight 25% ethanol, 0.6% isopropyl myristate, 0.3% perfume, and 74.1% propellant (1:1 mixture of Propellants 11 & 12). Product Application: The operator conducting the test applies the test product in the standard manner, so as to deposit an appropriate quantity of product, for example, on average about 300 mg of product on each axilla. Sweat Collection: Absorbent cotton pads are used to collect the sweat. On entering the hot room each panellist is subjected to a 40 minute 'warm-up' period, during which no sweat is collected. Sweat is then collected for a 20 minute period and sweat weight determined. Test Design: Subjects attend daily for 3 consecutive days. They receive one treatment with the products on each of the first three days. Following product application on the third day, the panellist is subjected to a hot room sitting and sweat is collected. Analysis of Data: The statistical treatment includes an analysis of variance which allows for side effects due to the product and the panellist. The efficacy is calculated from the geometric mean weight of sweat collected from the axillae treated with each product using the formula: where C is the geometric mean sweat weight from the axillae treated with the control product and T is the geometric mean sweat weight from the axillae treated with the test product where a correction has been made for the side effect. Significance is calculated by applying Student's t-test to the logarithmically transformed weights. The results of tests conducted with each of the products of Examples 1, 2 and 6 gave sweat reductions as indicated below. The products of all of Examples 1 to 12 are stable antiperspirant lotions which dry quickly to form a structured, tenacious film on the skin. The urea, sodium hydroxide or trisodium citrate present enhance the stability of the perfume, and reduce the solubility of the antiperspirant agent in the ethanol present, thus improving the efficacy of the product. They can each also improve the structure imparted by the Bentone and allow less of the suspending agent to be used. The DPGME present in Examples 8 and 9 results in a less white deposit on the skin. Example 13 The following is the formulation of an antiperspirant aerosol product made according to the invention. The Bentone 27 is sheared in the mixture of the liquid components, excluding the propellant and perfume, until fully dispersed. The urea is pre-dissolved in the alcohol. The aluminium chlorohydrate and perfume are then added. The resulting concentrate is then placed in a can, sealed with a suitable aerosol valve, and pressurised with the propellant. Example 14 The following is the formulation of an antiperspirant stick made according to the invention. The above ingredients, except for the perfume, were heated together with stirring at a temperature of 65°C for 10 minutes and then cooled to 50°C, at which point the perfume was added with continued stirring. The mixture so obtained was poured into stick moulds and allowed to cool and to set to form antiperspirant sticks.

Claims: An anhydrous antiperspirant product suitable for applying to the skin, which comprises: (i) from 1 to 60% by weight of a finely-divided Powder antiperspirant agent; (ii) from 10 to 90% by weight of an anhydrous liquid or solidified liquid medium, comprising an anhydrous alcohol chosen from ethanol, isopropanol or a mixture thereof; (iii) from 0.001 to 10% by weight of a perfume; and (iv) from 0.1 to 25% by weight, expressed in terms of the anhydrous alcohol present, of a perfume-stabilising agent chosen from compounds having a basic nitrogen function compounds having a basic oxygen function, drying agents or mixtures thereof. An antiperspirant product according to Claim 1, in which the antiperspirant agent has a mean particle diameter of not greater than 100µm. An antiperspirant product according to Claim 1 or 2, in which the antiperspirant agent is chosen from aluminium salts, zirconium salts or mixtures thereof. An antiperspirant product according to any of Claims 1, 2 or 3, in which the antiperspirant agent is an aluminium chlorohydrate. An antiperspirant product according to any preceding Claim, in which the antiperspirant agent is chosen from aluminium zirconium trichlorohydrex-GLY, aluminium zirconium tetrachlorohydrex-GLY or mixtures thereof. An antiperspirant product according to any of the preceding claims, in which the perfume stabilizing agent has a basic nitrogen function and is chosen from urea, natural amino acids, organic amines, C₁ to C₂₀ alkylamines and hydroxylamines. An antiperspirant product according to claim 6, in which the stabilizing agent is urea in an amount of from 0.5% to 25% of the alcohol present. An antiperspirant product according to claim 6, wherein the perfume stabilizing agent is an amino acid and is either glycine or leucine, in an amount of from 0.5 to 25% by weight of the alcohol. An antiperspirant product according to claim 6 wherein the perfume stabilizing agent is a C₁ to C₂₀ alkylamine or hydroxyalkyl amine, in an amount of from 0.5% to 4% by weight of the alcohol. An antiperspirant product according to any of claims 1 to 5, in which the perfume stabilizing agent has a basic oxygen function and is chosen from inorganic bases, hydroxides of alkali metal and alkali-earth metals and ammonium hydroxide, basic metallic oxides, alkali metal salts of inorganic acids and C₁ to C₂₀ organic carboxylic acids, and mixtures thereof. An antiperspirant product according to any of Claims 1 to 5, in which the perfume stabilising agent is a particulate alcohol-insoluble inorganic drying agent. An antiperspirant product according to Claim 11, in which the drying agent is a molecular sieve. An antiperspirant product according to any preceding claim, which additionally comprises a suspending agent chosen from hydrophobically-treated clays. An antiperspirant product according to Claim 13, in which the clay is chosen from smectite clays, hormite clays or mixtures thereof. An antiperspirant product according to Claims 13 or 14, in which the hydrophobically-treated clay is quaternium 18 hectorite. A process for the manufacture of an anhydrous antiperspirant product suitable for applying to the skin, which process comprises the step of mixing together ingredients in amounts expressed in terms of the final product, namely:- (i) from 1 to 60% by weight of a finely-divided powder antiperspirant agent; (ii) from 10 to 90% by weight of an anhydrous liquid or solidified liquid medium, comprising an anhydrous alcohol chosen from ethanol, isopropanol or a mixture thereof; (iii) from 0.001 to 10% by height of a perfume; and (iv) from 0.1 to 25% y weight, expressed in terms of the anhydrous alcohol present, of a perfume-stabilising agent chosen from compounds having a basic nitrogen function, compounds having a basic oxygen function, drying agents or mixtures thereof; provided that the perfume stabilising agent is added to the anhydrous alcoholic ingredient either before or simultaneously with the perfume.

Inventors: PARK, ANDREW CAMPBELL
Applicants: UNILEVER N.V., UNILEVER PLC
Application year: 1987
Main classification: A61K7
IPC codes: A61K8, A61Q15