MX2008008136A - Antiperspirant compositions - Google Patents

Abstract

An antiperspirant composition comprising a carrier substance and a water-soluble or water-dispersible thiolated polymer.

Description

COMPOSITIONS ANTITRANSPI RANTES FIELD OF THE INVENTION This invention relates to the field of antiperspirant compositions and to methods for reducing perspiration. In particular, this invention concerns reducing transpiration on the surface of the human body through the use of water-dispersible or water-soluble thiomers.

BACKGROUND Conventional antiperspirant actives are astringent metal salts, such as aluminum and / or zirconium salts. Such materials can work extremely effectively, however, they can cause some problems, including the possibility of skin irritation. Water soluble thiomers or Water dispersible have not been previously recognized for their antiperspirant property, but are well known in the field of drug delivery. They have been used, for example, in non-invasive delivery of polypeptides and have been found to have mucoadhesive properties (Leitner et al. J Pharm Sci, 93 (7), 1682, 2004) A wide range of such materials has been synthesized, including thiolated polyacrylic acid using cysteine (Bernkop-Schnurch et al, Drug Dev I nd Pharm, 30 (1), 1 , 2004) Such materials are also described in WO 00/25823 (Bernkop-Schnurch) BRIEF DESCRIPTION OF THE INVENTION We have discovered that water-soluble or water-dispersible thiomers can be used as antiperspirant actives and can be formulated into effective antiperspirant compositions. In a first aspect of the invention, there is provided an antiperspirant composition comprising a carrier substance and a water-soluble or water-dispersible thiomer. In a second aspect of the invention, there is provided a method for manufacturing an antiperspirant composition, comprising dispersing a thimer in a carrier substance. In a third aspect of the invention, there is provided a method for reducing perspiration comprising the delivery to the surface of the human body of a composition comprising a water-soluble or water-dispersible thiomer. In a fourth aspect of the invention, there is provided the use of a water-soluble or water-dispersible thiomer as an antiperspirant active.

DETAILED DESCRIPTION The compositions of the invention can take any of the product forms known in the art. In this way, they can be bars, soft solids, gels, aerosols or liquids (for roll-on application or other means of application). All compositions of the invention comprise a carrier substance and a water-soluble or water-dispersible thiomer; in general, they comprise a continuous phase Anhydrous with the water-soluble thimer dispersed in it. It is preferred that the compositions according to the invention be anhydrous. Throughout this specification, the term "anhydrous" should be understood as meaning that it has less than 10% by weight of water, in particular less than 5% by weight of water, and especially less than 1% by weight of water . The compositions of the invention can be applied to the surface of the human body to deliver an anti-transpiration benefit. They are particularly suitable for application to the armpit regions of the human body.

Thiomers Thiomers are thiolated polymers. Preferred thiomers are polymers having from 0.5% to 20% of their repeating units comprising a thiol group. These thiol groups can be introduced by copolymerization or by thiolation of a pre-formed base polymer (vide infra). Throughout this specification, the term "polymer" should be understood as including co-polymers comprising more than one type of repeating unit. Without wishing to be bound by theory, it is believed that thiol thiol groups allow or enhance the ability of the polymer to act as a mucoadhesive and that this ability allows or enhances the antiperspirant activity of the thimer. "Mucoadhesives" are materials that can bind to mucin in a biological surface. It is believed that the Antiperspirant activity results, at least in part, from the ability of the thiomers to act as pore blockers. The thiomers, when swollen by water, are believed to serve as plugs that can, at least in part, block the saliva of sweat from the eccrine sweat glands. It is essential that the thiomer be soluble in water or dispersible in water in order to dissolve or disperse in eccrine sweat. Water-dispersible thiomers should be understood as thiomers that are dispersible in water to a sufficient degree that they function as mucoadhesives, self-gelling polymers in the manner described herein. Preferred thiomers are soluble in water, having a solubility in water of at least 1 g.drrf3, in particular at least 0 g. Dm "3, and especially at least 1 00 g .dm" 3. Once the thimer has dissolved or dispersed in eccrine sweat, it is able to begin acting as an antiperspirant active. In order to do this with the best advantage, it is highly desirable that the thiomer be self-gelling when dissolved in water at 37 ° C. When dissolved or dispersed in water, such self-gelling thiomer causes the viscosity of the solution of which a part is to increase with time. The most effective thiomers, when dissolved or dispersed in water at a concentration of 100 g.dm "3, will increase the viscosity of the water by at least 1 00% within 30 minutes of being dissolved at 37 ° C. More than one thimer can be used in compositions of the invention The total amount of thimer incorporated in the Compositions of the invention is preferably from 0.01% to 50%, more preferably from 0.1% to 25%, and most preferably from 1% to 25% by weight of the total composition. In one embodiment of the invention, the thiomer is present in the form of a particulate dispersion within the carrier substance (vide infra), the carrier substance usually comprising an anhydrous continuous phase, as defined above. For reasons of stability and / or compositional efficiency, the thiomer particulate dispersion preferably has at least 90% of the particulates having a particle size of from 1 to 1000 microns. In a second embodiment of the invention, the thiomer is dissolved in one or more of the components of the carrier substance. This modality offers benefits of stability and / or compositional efficiency, benefits that can be further intensified when the composition is homogeneous. The carrier substance usually comprises an anhydrous continuous phase with the thiomer dissolved in it or in a liquid phase dispersed therein. When the thiomer is dissolved in a liquid phase dispersed in an anhydrous continuous phase, the emulsion is preferably anhydrous, the liquid dispersed phase preferably comprises a mono- or polyhydric alcohol of C? -C6. Preferred water-soluble or water-dispersible thiomers have as their non-thiolated base polymer a polymer which is itself soluble in water or dispersible in water. The non-thiolated base polymer of a thimer should be considered as the thimer minus the monomer units possessing thiol groups, if such groups were introduced by copolymerization, and as the polymer before thiolation, if the thiolation of a pre-formed polymer was employed. Preferably, the non-thiolated base polymer is soluble in water, having a solubility in water of at least 1 gm / dm3, in particular at least 1.0 gm / dm3, and especially at least 1000 gm. dm "3. It is highly preferred that the base polymer be mucoadhesive, for example, a vinylpyrrolidone polymer.For optimal performance, the molecular weight of the thimer is preferably from 1 Da to 5,000 kDa, more preferably from 5 kDa up to 2,000 kDa, and most preferably from 20 kDa to 1,000 kDa The introduction of the thiol groups of the thimer can be by any means known in the art.; Co-polymerization with a source of a thiol group is one such means. This can be done by co-polymerization of free radicals. The non-thiolated monomers may include acrylates and methacrylate (including the acids themselves), vinylbenzoic acid and acrylamide. The source of the thiol groups can be N, N'-bisacryloylcystamine, the disulfide bonds are subsequently cleaved to free thiol groups, or an N, N-dialkyldithiocarbamate (eg, vinylbenzyl-N, N-diethyldithiocarbamate, being hydrolyzed subsequently the thiocarbamate to liberate the free thiol groups The co-polymerization with a source of a thiol group can be done by a polyaddition reaction.The preferred thiomers produced by this route are thiolated polyamidoamines. thiomers include those produced from the polyaddition in the form of steps of a primary or secondary amine to a bis (acrylamide), the primary or secondary amine including a proportion (usually up to 25 mol%) of a thiolated amine, such as cysteine, the thiol group of the amine being protected normally during the polyaddition stage.

The introduction of the thiol groups of the thimer can be done by thiolation of a pre-formed base polymer. A variety of techniques can be employed to do this: i) Polymers comprising carboxylic acid groups can be linked to cysteine using known amidation procedures; ii) Polymers comprising amine groups (eg, chitosan) can be: a) linked to a thiol containing acid, such as cysteine or thioglycolic acid; or b) thiolates through the use of a heterobifunctional reagent, such as, N-succinimidyl-3- (pyridyldithio) propionate; or c) thiolates using 2-iminothiolane (Traut's reagent); iii) Polymers comprising hydroxyl groups can be: a) derivatives with 2-i-minothiolane (Traut's reagent); or b) activated by reaction with an active chloroformate ester (eg, 4-nitrophenylformate) and then reacted with a bi-functional thiol, such as 2-aminothioethanol. Thiomers which are the thiolation product of a preformed base polymer are preferred, in particular thiomers which are produced via thiolation using cysteine. Thiomers which are thiolation products of a preformed base polymer comprising carboxylic acid groups or amine groups are preferred, in particular, thiomers which are cysteine derivatives of such polymers. Examples of thiomers of this type are thiolation products (in particular, cysteine derivatives) of the following pre-formed base polymers: i) Acrylic acid polymers; ii) Methacrylic acid polymers; ii) Polymers of maleic acid; iv) Itaconic acid polymers; v) carboxylated polysaccharides (e.g. carboxymethylcellulose sodium or carboxylated dextran); vi) Alginates; vii) Chitosan; viii) Polyethylenimine, ethoxylated polyethylenimine, or partially quaternized derivatives of any of these polymers; or ix) Pectin, pectin acid, or derivatives of any of these materials. Particularly preferred thiomers which are thiolation products of a preformed base polymer are derivatives of an acrylic acid polymer or chitosan. The repeating units that can be advantageously incorporated in the thiomers used in the present invention are ethoxylated repeating units, such repeating units enhance the solubility in water, and / or repeating units that are cationic or become cationic in use, such repeating units enhance muco-adhesion. It is preferred that the thiomer comprises repeating units. which are cationic or become cationic in use Repetition units that are cationic or can become cationic include those derived from polymerization of N-metacployl-N'-alkylpiperazine or N-acployl-N'-alkylpiperazine, for example, N-acployl-N'-methylpiperazine The thiol groups of such polymers are preferably introduced by thiolation of a pre-formed base polymer, in particular, a base polymer comprising carboxylic acid groups, such as can be introduced by polimeptation with acrylic acid Repetition units that are cationic or can become cationic also include those that are Polymerization of N, Nd? met? lam? noet? lmetacr? lato or N, Nd? met? lam? noet? partially quaternized limetac? er The thiomers that are derived from polysaccharides capable of binding hydrogen to themselves and / or mucins are also useful due to their good mucoadhesive properties Such thiomers include those which are derivatives of dextran, gelana, guar gum and xanthan gum. Preferred thiomers of this type are polysaccharides which are cationic or can become cationic. Normally, such polysaccharides comprise groups amine or quaternary ammonium groups, examples include N, N-diethylamidoethyldextran and partial ethers of guar gum 2-hydroxy-3- (N, N, N-trimethylammonium) propyl, such as Jaguar C13S. Particularly suitable thiomers can be (poly) acrylic acid derivatives. Especially preferred thiomers are those having the formula: - (CHX-CH2) a- (CHY-CH2) b- where X = CO2H, Y = CO.NH-CH (C02H) CH2SH and a and b vary according to the polymer molecular weight and the degree of thiolation. The degree of thiolation of such polymers is preferably from 1 to 20%, more preferably from 1 to 10% and most preferably from 1.5 to 7.5%, expressed as a percentage of the carboxylic acid groups in the base polymer. Other particularly suitable thiomers are co-polymerization derivatives of acrylic and / or methacrylic acid and an amine functionality containing monomer (e.g., N-acryloyl-N'-alipiperazine), followed by conversion of a proportion of the carboxylic acid groups of the co-polymer in thiol containing amide groups (e.g., -CO.NH (CH2) nSH groups, where n is from 2 to 6, preferably from 2 to 4, and most preferably 2). In such thiomers, the molar ratio of acrylic and methacrylic acid residues to residues derived from the amine-containing monomer is preferably from 2: 1 to 1:10, more preferably from 1: 1 to 1: 5, and most preferably from 1: 2 to 1: 4. The proportion of carboxylic acid groups converted to thiol containing amide groups is preferably 1% or more, more preferably 2% or more, and most preferably 5% or more. Normally, a proportion (preferably from 25 to 99%, more preferably from 50 to 98%, and most preferably from 75 to 95%) of the carboxylic groups is released. The carboxylic acid groups are preferably derivatives of acrylic acid. Particularly suitable thiomers can also be polyethylene imine derivatives. Especially preferred thiomers of this type have at least some of the primary PEI amine groups converted to thiolated amide groups of formula: R-NH-CO. (CH2) n-SH where R represents the remainder of the polymer and n is from 2 to 5, preferably from 3 to 4, and most preferably 3. The degree of conversion is such that preferably from 1 to 50%, more preferably from 5 to 50%, and most preferably from 25-50% of the primary amine groups are converted.

Carrier Substances The carrier substance can be any substance in which the thimer can be dissolved or otherwise dispersed. In order to achieve an effective composition, it is highly desirable that the carrier substance be chemically compatible with the thimer.

It is also highly desirable that the carrier substance be cosmetically acceptable, so that the composition can be used in cosmetic application. The carrier substance can comprise more than one component and the term "carrier substance" should be understood to encompass all components of the compositions of the invention except for thimer It is therefore highly desirable that all "non-thimer" components of the composition be chemically compatible with the thimer and that all be cosmetically acceptable, for the reasons stated in the preceding paragraph. The choice of carrier substance it will depend on the form of product and desired properties It is preferred that the carrier substance comprises less than 20% by weight of water and it is more preferred that the carrier substance be anhydrous, as previously defined In soft and sticky solid products, it is generally it requires incorporating a structuring In general, the amount of Structuring will be from 0 1 to 25% and in particular from 1 to 1 5% by weight. Often such structurants are used to thicken or structure a continuous anhydrous phase having the thimer dispersed therein. Structures suitable for the latter purpose are described herein below A suitable structurant may be an organic polymer, which is soluble in the anhydrous continuous phase, although commonly at an elevated temperature above 60 ° C. Such polymers are particularly well suited for producing compositions in the form of soft or firm solids. Such polymers can be selected from polysaccharides esterified with a fatty acid, for example, dextrin palmitate; polyamides, as discussed in US 5, 500,209, for example, Versamid 950M R; copolymer alkylene / arylene block copolymers, for example ethylene / styrene, propylene and / or butylene block copolymers, such as SEBS block copolymers; galactomannan substituted with alkyl, for example, N-HANCEM R; or vinyl (pyrrolidone) copolymers and ethylene containing at least 25 methylene units. The concentration of such polymers in the anhydrous continuous phase is generally from 1 to 20%. A suitable structurant can be a wax. Suitable waxes include beeswax, candelilla wax, carnauba wax and other waxes having similar properties. Such other waxes include hydrocarbon waxes, for example, paraffin wax, mineral wax and microcrystalline wax; synthetic waxes, such as polyethylene of 2000 hasa 1 0000 daltons; waxy derivatives or waxy components of natural waxes, such as ester components, whether extracted or synthesized, derived from solid esters of glycerol or glycol, usually with linear saturated fatty acids, usually containing a significant fraction of C16 acid residues. 22, which can be synthesized or obtained by hydrogenating the corresponding natural oil; petroleum waxes, waxy silicone polymers containing alkyl substituents of chain length of at least C10; and waxy fatty alcohols, which are usually linear and frequently contain from 14 to 24 carbons, such as stearyl alcohol, cetyl alcohol and / or behenyl alcohol. A suitable structurant can be a polymer copolymer of polyamide or amide / silicone soluble in oil; a hydroxystearic acid, for example, 1 2-hydroxystearic acid, or amide or ester derivatives thereof; an N-acylamino acid amide and ester as described in US 3,969,087, such as, in particular, di-n-butylamide of N-lauroyl-L-glutamic acid; an amide derivative as disclosed in WO 98/27954, notably an alkyl N, N'-dialkyl succinamide; similar threitol or amide gelling agents as disclosed in US-A-641 0001; lanosterol, as set forth in US 6,251, 377; a cydohexane amide derivative, as set forth in US 6,41,0,003; a combination of a sterol and a sterol ester, as disclosed in WO 00/61 096, for example, α-oryzanol and β-sitosterol; or a cellobiose fatty acid ester, for example, cellobiose octanonanoate comprising a minor fraction of cellobiose heptanonanoate. In aerosol products, it is usually required to incorporate a volatile propellant or a compressed gas. When a volatile propellant is employed, it is normally present at from 30% to 99% and in particular from 35% to 87% by weight of the total composition. The volatile propellant may be selected from liquefied hydrocarbons or halogenated hydrocarbon gases (in particular fluorinated hydrocarbons, such as 1,1-difluoroethane and / or -trifluoro-2-fluoroethane) having a boiling point below 10 ° C. and especially those with a boiling point below 0 ° C. It is preferred to use volatile, non-chlorinated propellants. It is especially preferred to use gases hydrocarbons, and especially C3 to C6 hydrocarbons, including propane, isopropane, butane, isobutane, pentane and sopentane and mixtures of two or more thereof. The preferred propellants are isobutane, isobutane / isopropane, isobutane / propane and mixtures of isopropane, isobutane and butane. In some embodiments, dimethyl ether can be employed as a volatile propellant. When a compressed gas is employed, it is normally a non-reactive gas, such as air, nitrogen or carbon dioxide. In liquid products, it is required to incorporate a liquid carrier substance. A preferred type of product is a particulate dispersion of the thimer in the liquid carrier substance. The liquid poWder substance can be selected from liquid materials described as sensory modi? Ers and described hereinafter. A preferred liquid carrier substance is a volatile silicone, because such liquid can give a drier sensation to the applied film after the composition is applied to the skin. The carrier substance can contain from 0.1 to 50% and in particular from 10 to 40% by weight of volatile silicone. To classify as "volatile" such material should have a measurable vapor pressure at 20 or 25 ° C. Normally, the vapor pressure of a volatile silicone falls in a range from 1 or 10 Pa to 2 kPa at 25 ° C. A volatile silicone can also be included in a spray, soft solid or bar product. The volatile silicones can be linear, cyclic or mixtures thereof. Preferred cyclic silicones include polydimethylsiloxanes and in particular those containing from 3 to 9 silicon atoms and preferably not more than 7 silicon atoms and most preferably from 4 to 6 silicon atoms, often referred to otherwise as cyclomethicones. Preferred linear loxanes include polydimethylsiloxanes containing from 3 to 9 silicon atoms. Volatile siloxanes normally by themselves exhibit viscosities below 1 0"5 m2 / s (10 centistokes), and particularly above 1 O" 7 m2 / s (0.1 centistokes), linear siloxanes normally exhibit a viscosity below 5 x 1 0"6 m2 / s (5 centistokes) Volatile silicones may also comprise branched linear or cyclic siloxanes, such as linear or cyclic siloxanes mentioned above substituted by one or more -O-Si (CH) groups 3 Examples of commercially available silicate oils include oils having grade designations 344, 345, 244, 245 and 246 from Dow Corning Corporation, Silicone 7207 and Silicone 71 58 from Union Carbide Corporation, and SF 1 202 from General Electric Thickeners are preferred optional components in liquid products.Such materials include particulate inorganic substances, such as clays or finely divided silica.Such materials are also optional components. they are preferred in aerosol products, in which they are frequently referred to as suspending agents. Propylene carbonate can also be used in aerosol products to serve as a suspending agent. In all product forms, it may be desirable to incorporate a conventional antiperspirant active to increase the anti-transpiration of the thimer and to act as an anti-microbial active and deodorant. A conventional antiperspirant active should be understood as an astringent metal salt, such as an aluminum and / or zirconium salt. Examples of suitable conventional antiperspirant salts include aluminum, zirconium and aluminum / zirconium halides and halohydrate salts, such as chlorohydrates. When included, the preferred levels of incorporation are from 0.1% to 50%, in particular from 1% to 25% and especially from 5% to 15% by weight of the composition. Especially preferred aluminum halohydrate salts, known as activated aluminum chlorohydrates, are described in EWP 6, 739 (Unilever PLC and NV). The zirconium aluminum chlorohydrate actives are also preferred materials, as are the so-called ZAG complexes (zirconium aluminum glycine), for example, those described in US Pat. No. 3,792,068 (Procter and Gamble Co.). Zinc phenol sulfonate, preferably up to 3% by weight of the composition can also be used. In all product forms and in particular those comprising a conventional antiperspirant salt, it may be desirable to incorporate a sensory modifier to improve skin feel. Emollients, humectants, volatile oils and non-volatile oils are all suitable classes of sensory modifiers. Examples of such materials include cyclomethicone, dimethicone, dimethiconol, isopropyl mysteret, isopropyl palmitate, C12-C16 alcohol benzoate, PPG-3 myristyl ether, octyl dodecanol, isostearyl alcohol, C7-C14 isoparaffins, di-adipate di- isopropy lo, isosorbide laurate, PPG-14 butyl ether, glycerol, hydrogenated polybutene, polydecene, phenyl tpmeticone, dioctyl adipate and hexamethyl disiloxane When employed, the total amount of sensory modifier is preferably from 0 5% to 50%, more preferably from 1% to 30%, and most preferably from 3% to 20% by weight of the total composition In all product forms and in particular those lacking a conventional antiperspirant salt, it is highly desirable to incorporate an organic anti-microbial agent to act as an anti-microbial agent. conservative and / or as a deodorant when the product is applied to the surface of the human body. Most classes of agents commonly used in the art can be incorporated into compositions of the invention. Incorporation levels are preferably from 0 01% to 3. % and more preferably from 0 03% to 1% by weight of the total composition Preferred compositions of the invention comprise an anti-m agent. icrobiano organic having a minimum inhi bitoria concentration (MIC) of 1 mg mi "1 or less, in particular 200 μg ml "1 or less, and especially 1 00 μg ml or less The MIC of an anti-microbial agent is the minimum concentration of the agent required to significantly inhibit microbial growth. Inhibition is considered" significant "if 80% or greater reduction in the growth of an inoculum of a relevant micro-organism is observed, in relation to a control medium without an anti-microbial agent, over a period of 16 to 24 hours at 37 ° C. - Relevant organism "used for testing should be representative of those associated with the substrate to be treated.When the substrate to be treated is human skin, a relevant micro-organism is Staphylococcus epidermidis Details of suitable methods to determine MICs can be found in" Antimicrobial Agents and Susceptibility Testing ", C. Thornsberry, (in" Manual of Clinical Microbiology ", 5th edition, Ed. A. Balow et al., American Society for Microbiology, Washington DC, 1991) A particularly suitable method is the Macrobroth Dilution Method as described in Chapter 110 of the previous publication (pp. 1101-1111) by DF SAHM and JA Washington II. of an organic anti-microbial suitable for inclusion in the composition of the invention are triclosan: 0.01-10 μg.ml "1 (J. Regos et al., Dermatological (17979), 158: 72-79) and farnesol: ca. 25 μg.ml "1 (K. Sawano, T. Sato and R. Hattori, Proceedings of the 17th IFSCC International Conference, Yokahama (1992) pp. 210-232) In contrast, ethanol and similar albandes have MICs of more than 1 mg.ml "1. Preferred organic antimicrobials are bactericides, for example, quaternary ammonium compounds, such as cetyltrimethylammonium salts; chlorhexidine and salts thereof; and diglycerol monocaprate, diglycerol monolaurate, glycerol monolaurate, and similar materials; as described in "Deodorant Ingredients" (deodorant ingredients), S.A.Makin and M.R.Lowry, in "Antiperspirants and Deodorants", Ed. K. Laden (1999, Marcel Dekker, New York) The most preferred organic antimicrobials for use in the compositions of the invention are polyhexamethylene biguanide salts (also known as polyaminopropyl biguanide salts), an example being Cosmocil CQM R available from Zeneca PLC, preferably used up to 1% and more preferably at 0 03% up to 0 3% by weight, 2 ', 4,4'-tr? chlor, 2-h? drox? -d? phen? l ether (tpclosan), preferably used hasa 1% by weight of the composition and more preferably at 0 05-0 3%, and 3.7, 1 1 -tr? methododeca-2, 6, 10-tr? enol (farnesol), preferably used up to 1% and more preferably up to 0 5% by weight of the composition Organic anti-microbials that are iron chelators (ll l) can be pumped, either alone or in combination with another organic anti-microbial agent. Chelators having a constant of iron binding (lll) of 1026 or more are preferred, with chelators having an iron binding constant (lll) of 1028 or more when or particularly preferred are especially preferred iron chelators (11), N, N'-et? lenb? s [2- (2-hydrox? fen? l) gl? c? na] (EDDHA), tetylenetetraminehexaacetic acid (TTHA), and diethylene-propane-penta-acetic acid (DTPA) Iron chelators (III) are, in general, acidic. They can be used as such in the compositions of the invention, although in compositions having an anhydrous continuous phase are preferably used as a salt or acid salt of a protonated or quaternized amine. Preferred amines for neutralization of the chelator are 2-amino-2-metho-1-propanol, dnsopropanolamine and 2-am? Nobutan-1 - ol, cyclohexylamine. Other anti-microbial agents that can be used in compositions of the invention, in particular those that also comprise an iron chelator (III), are transfer dissociation promoters, such as BHT (butylated hydroxytoluene), as described in US Pat. US 6, 503,490 (Unilever, 2003). In all forms of product, it is highly desirable to incorporate a perfume. Suitable materials include conventional perfumes, such as perfume oils and also include so-called deo-perfumes, as disclosed in EP 545, 556 and other publications. The levels of incorporation are preferably up to 4% by weight, in particular from 0.1% to 2% by weight, and especially from 0.7% to 1.7% by weight. In all product forms, it may be desirable to include one or more washing auxiliaries, often in a proportion of up to about 10% by weight, especially up to about 5% by weight and in particular from 0.5 to 3% by weight. Such washing auxiliaries commonly comprise nonionic surfactants and especially nonionic surfactants, which contain a polyalkylene oxide moiety, the residue of a fatty acid or fatty alcohol, and optionally the reside of an aliphatic polyhydric alcohol linking group. . Although the surfactants may comprise a single fatty residue, they preferably contain two residues. Preferably, the surfactant is an ester surfactant, and especially a diester surfactant. Polyalkylene oxide is often polyethylene oxide or mixed polypropylene oxide or polyethylene oxide / propylene oxide, the polymer containing from 3 to 50 and in particular from 5 to 20 units of alkylene oxide. The fatty residue is often derived from an acid or fatty alcohol containing from 12 to 24 carbons, which in many cases is linear, including examples 16, 18 or 22 linear carbons. Especially preferred washing aids herein include polyethylene oxide diesters of fatty alcohols containing 1 6 to 22 linear carbons, such as PEG-8 distearate.

Manufacturing methods The compositions of the invention can be manufactured by any means that allows the dispersion of a particulate thiomer in an anhydrous continuous phase. In a first embodiment, a particulate thiomer is dispersed in an anhydrous continuous phase. In a second embodiment, a thimer is dissolved in one or more of the components of the carrier substance. This may involve dissolving the thiomer in an anhydrous continuous phase. Alternatively, it could involve dissolving the thiomer in a suitable solvent and then dispersing the thiomer solution thus formed into an anhydrous continuous phase. A suitable solvent is one that is capable of dissolving the thimer.

EJ EMPLOS The following non-limiting examples can be prepared and used according to the invention. The thiomers employed in the formulation examples can be selected from those in the preceding description. The amounts indicated are percentages by weight of the total composition, unless stated otherwise.

Examples 1 to 5: Preparation of thiolated (poly) acrylic acid (PAA) PAA can be thiolated using cysteine by methods known in the art. The Examples indicated in Table 1 were prepared from PAA (eg Sigma) and L-cysteine. HCI (eg Noveon).

Table 1: Thiolated PAAs The given thiolation percentages refer to the degree to which the carboxylic acid groups of the original PAA are converted to thiolated amide groups. The products obtained were of the general formula: - (CHX-CH2) a- (CHY-CH2) b- where X = C02H, Y = CO. NH-CH (C02H) CH2SH and a and b vary according to the molecular weight of PAA and the degree of thiolation as indicated above.

Examples 2 to 5 were compared with their corresponding PAA base polymer in a m vitro muco-adhesion test, using porcine gastric mucin (eg Sigma). Each of the thiolated polymers was found to have significantly greater muco-adhesion than its corresponding PAA base polymer Examples 6 to 17: Preparation of thiolated polyethyleneimine (PEI) Samples of PEI polymer of molecular weight 25, 70-90 and 750 kDa (Lupasol P) were thiolated using β-thiobutyrolactone, using methods known in the art (see, for example). example, T Takagishi et al, Biopolymers, 1972, 1 1, 483) The products indicated in Table 2 were obtained Table 2 Thiolated PEIs The percentages of thiolation given refer to the theoretical degree at which the primary amine groups of the original PEI are converted to thiolated amide groups, based on the amount of β-thiobutyrolactone used in the reaction The structure of the thiolated amide groups can be represented as -N H-CO CH2CH2CH2SH The aqueous solutions of each of Examples 6 to 1 7 were prepared at 10% by weight and pH 7 In contrast to the solutions Analogous to the corresponding PEI base polymers, it was found that these thimer solutions form gels within 5 minutes (in the presence of excess hydrogen peroxide - used to accelerate the oxidation crosslinking of the thiol groups) This is an indication of the expected improvement in self-gelling with thiolated polymers EXAMPLES 1 8-24: Preparation of thiolated co-acid (pol?) Acrylic acid co-(N-acployl-NO-methylpiperazine) A sample of N-acp loyl-N'-methylpiperazine monomer (NANMP) was prepared by reaction of N-methylpiperazm with acylloyl chloride in ice-cold tetrahydrofuran in the presence of tetylamine (used to neutralize the by-product of HCI) Following the removal of salt of t-chylolamine hydrochloride by filtration and rotary evaporation of the solvent, the crude product was purified by distillation under reduced pressure and stabilized by the addition of 0 5% by weight of hydroquinone dimethyl ether NANMP, prepared as described above, and acrylic acid were polimepped at a 3 1 ratio by reaction at 80 ° C in dioxane using azo-bis-isobutyronitide (AI BN) as an initiator. The copolymer produced was isolated and purified using techniques known in the art.

A sample of the co-polymer prepared as described above was dissolved in ethanol and reacted, under a nitrogen atmosphere, with dicyclohexylcarbodiimide (DCC) and cysteamine hydrochloride in the presence of triethylamine. The resulting thiomer was isolated and purified using techniques known in the art. The thiol substituents in the polymer backbone were of the formula: -CO. N H-CH2CH2-SH Using the synthesis described above, the thiomers indicated in Table 3 were produced.

Table 3: PAA-co-NANMP thiolated 1 . Of the polymer before the thiolation. Measured by GPC using PEG as standard. 2. Measure using the Ellman method (G. L. Ellman, Arch Biochem. Biophys., 1 959, 82, 70-77) Table 4 Bar formulations 2 Poly (hexamet? Lenb? Guan? Da) stearate, eg Arch Chemicals 3 Volatile silicone, eg Dow Corning Table 5: Aerosol formulations 1 . Activated aluminum chlorohydrate. 2. Volatile silicone, eg Dow Corning. 3. Quaternium-1 8-hectorite, eg Rheox. 4. Poly (hexamethylenebiguanide) stearate, eg Arch Chemicals. 5. Volatile propellant, proprietary mixture of butane, isobutane and propane, eg Heat.

Claims (3)

1. CLAIMS An antiperspirant composition comprising a carrier substance and a water-soluble or water-dispersible thiomer and having an anhydrous continuous phase with the thimer dispersed therein. An antiperspirant composition according to claim 1, wherein the thiomer is a mucoadhesive 3 An antiperspirant composition according to claim 1 or claim 2, wherein the thimer is self-gelling when dissolved in water at 37 ° C. An antiperspirant composition according to any of the preceding claims, wherein the thiomer is A thiolating product, in particular a cysteine derivative, of an acrylic acid polymer. An antiperspirant composition according to any of the preceding claims, wherein the thiomer is a thiolation product, in particular a cysteine derivative, of chitosan. An anti-capsulin composition according to any of the claims precedents, wherein the thiomer is a thiolation product of a polyethyleneimine 7 U an antiperspirant composition according to any of the preceding claims, wherein the thiomer is soluble in water, having a solubility in water of at least 1 g dm "3 An antiperspirant composition according to any of the preceding claims, comprising an active conventional antiperspirant. 9. An antiperspirant composition according to any of the preceding claims, comprising a sensory modifier. 1 0. An antiperspirant composition according to any of the preceding claims, comprising an organic antimicrobial agent. eleven . A method of making an antiperspirant composition, comprising dispersing a thimer in a carrier substance having an anhydrous continuous phase.
2. 2. A method for reducing perspiration comprising the delivery to the surface of the human body of a composition comprising a water-soluble or water-dispersible thiomer. 1
3. 3. The use of water-soluble or water-dispersible thiomer as an antiperspirant active. SUMMARY An antiperspirant composition comprising a carrier substance and a thiolated polymer soluble in water or dispersible in water.