AU713391B2 - Antiperspirant actives and compositions - Google Patents

Description

N

AUSTRALIA

PATENTS ACT 1990

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT TITLE OF INVENTION ANTIPERSPIRANT ACTIVES AND COMPOSITIONS Name and Address of Applicant: UNILEVER AUSTRALIA LIMITED of 20-22 CAMBRIDGE STREET, EPPING NSW 2121 The following statement is a full description of this invention, including the best method of performing it known to me:-

I

1 J7045 ANTIPERSPIRANT ACTIVES AND COMPOSITIONS This invention relates to antiperspirant active materials, and antiperspirant compositions for topical application to 5 the human skin.

The antiperspirant market is dominated by products based on aluminium and/or zirconium-salts, which are intended to reduce or preyent perspiration at the skin surface, 10 particularly the underarm.

*I

However, doubts as to the safety in use of aluminium salts have stimulated research into alternative antiperspirant actives. From this research, it is known that other metal salts may exhibit an antiperspirant effect. One of these metals is titanium.

For example, US-A-3,090,728 t;o Carter Products describes the use of certain titanium salts of hydroxy aliphatic carboxylic acids as antiperspirant actives. Salts disclosed in this reference include the mono- and di-acid salts of citrate, gluconate, glycolate and lactate.

However; it is noticeable from this reference that it teaches towards antiperspirant compositions which have a .2relatively low pH, i n the region of pH 2.5 to 5. Above this pH, so the reference says, the composition will not be effective. It is also apparent that compositions according to this teachinlg,* because of the fairly low pH of the may have a tendency to cause skin irritation, particularly in people with delicate skin. Such compositions having such a low pH are also most likely-to cause damage to fabrics and clothing.

We have surprisingly found that antiperspirant having good efficacy can be made from ~6 titanium salts of hydroxY aliphatic carboxylic adids having a chain length of from C2 to C1O, which have a pH greater than Thus, according to the inventi .on, there is provided an anti.perspiranlt composition for topical application to the hun~n skin, comprising an effective amount of a titanium salt of a hydroxy aliphatic carboxy'lic acid having from 2 to 10 carbon atoms in its aliphatic chain, a cosmetically 2 20 acceptable ingredient other than water and optionally water, .0 the composition having a pH of greater than The present invention, and in particular preferred features and embodiments thereof, will now be described in detail.

In the accompanying drawings: Figure 1 is a schematic diagram of the apparatus used to conduct the in vitro test procedure for compositions according to the invention, as described in the Exampfles hereinbelow;

F

3 J7045 Figure 2 is a graph showing flow rate in the apparatus as a function of applied pressure, with the cell detached, which is used as a correction curve in the in vitro test procedure.

Preferably the titanium salt is present in the compositions of the invention at a concentration of from about 0.1 to about 50% by weight of the composition.

The amount of the salt required for an effective antiperspirant activity may depend on the product form in which the composition is provided for use.

o For example, typical preferred concentrations of the salt in the case of solid sticks, lotions, creams and the like are from about 5 to about 50% by weight of the composition, more preferably from about 10 to about by weight of the composition, most preferably from about to about 25% by weight of the composition. In the case of propellant driven aerosol compositions, for example, the concentration of the salt may typically be lower than the above figures, e.g. preferably in the range of from about 0.1 to about 20% by weight of the total composition, more preferably from about 0.5 to about 15% by weight of the total composition, most preferably from about 1 to about 10% by weight of the -total composition.

Preferably, the pH of the composition in aqueous solution is greater than about 5.1, especially greater than about 5.5, particularly from about 5 or 5.5 to about 10.5, preferably from about 6 to about 10, more preferably from about 6 to about 7.

The pH of the composition may readily be measured where the composition is aqueous. However, where the composition is anhydrous-, or contains insufficient water to allow a pH reading to be meaningful, the pH for the 4 j704 purposes of this ivnonmay be determined by taking an aqueous solution of the titanium salt in an aqueous composition at the same concentration as it 4s found in the anhydrous composition, along with any other components of the composition that would affect the pH, such as buffers. Tn these circumstances, the pH of the composition in the aqueous solution should be greater than about 5, e.g. greater than about 5.5, preferably in the region of ~about 6 to Compositions according to the invention have improved mildness to the skin compared with the compositions of US-A- 3,090,728, and provide less risk of fabric damage or skin ~.:irritation. However, and contrary to the teaching of US-A- 3,090,728, we have surprisingly found that such compositions having a pH greater than 5 do in fact exhibit a remarkably good efficacy as antiperspirant compositions.

Preferred hydroxy aliphatic carboxylic acids for use in the invention are those which have a C2 to C10 aliphatic carbon chain carrying from 1 to 6 hydroxyl. groups.

:Preferred titanium hydroxy aliphatic carboxylic acid salts according to the inven~ion are the mono- and di-acid salts of citrate-, gluconate, glycolate, and lactate, especially lactat-e.

The pH of the compositions according to the invention may conveniently be adjusted with acids or bases, such as hydrogen chloride or ammnonia. A particular advantage of systems comprising titanium lactate is that such a system may additionally comprise itsonbfesytm wherein the lactate/lactic acid equilibrium in the system adjusts itself as the amount of acid in the composition is varied.

Such a buffer system may typically retain the composition at a pH in the range 5.5-8. However it is thought that other zreferred salts, suchn as citrate, may also be capable of generating their own buffer system in the comnoosit:ion.

"I

5 J7045 Thus, a particularly preferred embodiment of the invention involves a composition which has as ics antiperspirant active predominantly an ammonium titanium lactate salt. Such a compound is commercially available.

Other Ingredients The antiperspirant composition according to the invention may comprise other ingredients, depending on the nature 10 and form of the finished product.

Examples of other ingredients which can optionally be present in a composition according to the invention include: cosmetically acceptable vehicles, such as straight-chain and branched chain alcohols, for example ethanol, isopropanol, or isobutanol; volatile and.non-volatile silicones, such as dimethyl 20 cyclosiloxanes, such as DOW CORNING fluids DC 344 and DC 345,- or polydimethylsiloxane, having a viscosity in excess of 5 mmns', for example from 50 to 100 mmns-', such as DOW CORNING 200 Fluids (standard viscosities 50-1000 mms'-) deodorants; deoperfumes, and deodorant compounds which can also act as antimicrobial agents, such as unsaturated fatty acids, and monoglycerides, for example glycerol monolaurate; hydrophobic oils, such as liquid paraffin oils; inorganic electrolytes, such as .sodium chloride and sodium sulphate cationic polymers, such as ABILQUAT 3272 and ABILQUAT 3270, both ex.TH Goldschmidt AG; 6 J7045 thickeners, such as clays, for example Bentone 38 (trade mark), silicas, for example Aerosol 200 (trade mark), and hydroxypropyl celluloses such Klucel (trade mark); skin feel improvers, such as talc and finely divided polyethylene, an example of which is ACUMIST B18; gelling agents, such as stearyl alcohol or waxes, for example castor wax; emulsifiers, in particular in stick compositions; humectants, such as polyols, for example glycerol; 10 emollients; perfumes; preservatives and antioxidants; skin benefit agents, such as allantoin; colours; other cosmetic adjuncts conventionally employed in stick, roll-on lotion, liquid spray, cream, and propellant-driven aerosol antiperspirant products.

The ingredients other than the antiperspirant active can 20 conveniently form the balance of the composition, and accordingly may form up to 95% by weight of the total composition, preferably from 60 to 90% by weight of the total composition, most preferably 75-85% by weight of the composition.

Product Form The composition according to the inventionmay take the form of a liquid or solid product, each of which is suited to, or adapted for, topical application to human skin. One convenient form of the composition according to the invention is a solid stick, usually contained in a suitable holder or dispenser to enable it to be applied to the area of the skin, particularly the underarm, where -7 J7045 control of perspiration and deodorancy is required.

Another form of the composition of the invention is a lotion suitable for inclusion in a roll-on dispenser, fitted with a ball valve, to enable the product to be rolled on to the skin in a manner which is conventional in the art. A further example of a composition according to the invention is the liquid composition for dispensing via .a finger-operated pump spray or a hand-operated squeeze 10 spray to provide for delivery to the skin of a finely divided spray or aerosol, without the use of propellant gases to deliver it.

Alternatively, a composition according to the invention can take the form of liquid, containing suspended particulate solids, which is suited to, or adapted for, topical application to human skin from an aerosol container by use of a suitable propellant, examples of which are well known in the art. The aerosol container can then be used to dispense the composition as a spray to enable it to be applied to the area of the skin, particularly the underarm, where control of perspiration and deodorancy is required.

The composition according to the invention can also take the form of a cream, suited to, or adapted for, topical application to the human skin.

In a preferred embodiment of the invention, the antiperspirant active is present in the composition as a finely divided powder suspended in a substantially anhydrous medium in which the antiperspirant active is highly insoluble. By "substantially anhydrous medium" in this context is meant-one that contains less than 1% by weight water. The anhydrcus medium is conveniently a 8 J7045 liquid medium, and is preferably a substantially anhydrous alcohol comprising ethanol, isopropanoi, or mixtures thereof. In a lotion type formulation, the anhydrous medium will conveniently make up from 50-80% by weight of the composition.

composition.

Use of the composition The invention provides for the use of an antiperspirant 10 composition in accordance with the invention in perspiration control, following topical application to the 0 9 human skin.

A particularly preferred composition according to the invention is an antiperspirant composition containing an antiperspirant active according to the invention, and a hydrophobic clay, especially a Bentone (trade mark) clay, most-especially Bentone 38. It has been found that formulations containing Bentone clays have superior 20 properties to similar compositions not containing Bentone in terms of improved efficacy. The Bentone clay may be present in the formulation at a concentration of from more preferably 8-15% by weight of the total composition.

A further preferred composition according to the invention is one which comprises a surfactant which strongly interacts with the skin, thereby causing improved adhesion of the antiperspirant active to the skin. Such surfactants may comprise, for example, cationic surfactants, or alphahydroxy acids. Preferably, such additives may be present in the composition at a concentration of from 0.1 to 2% by weight of the total composition.

9 J7045 Examples The invention will now be further described by way of example only. The following compositions were prepared, using standard techniques known in the art. For the formulations not containing Bentone, it was sufficient simply to mix together the components of the mixture, and make the composition to the appropriate amount with a solvent such as ethanol. However, for the formulations 10 containing Bentone, it was necessary to shear the Bentone into an aliquot of the ethanol, at a high rate of shear at approximately 75% of the maximum speed of an "Ultraturrax" mixer for at least 5 minutes at a temperature of at least 45'C, before cooling the mixture and adding the remainder of the components of the composition.

Example 1 Composition 1 w/w) 0* Component 1 Tyzor LA 20 Hydrogen chloride (as aqueous hydrochloric acid) 0.6% Perfume Klucel M 0.8% R R Ethanol 51.6% Distilled water to 100 Tyzor LA is ammonium titanium lactate, ex. Du Pont, supplied as a 50 w/w aqueous solution.

Included to reduce the pH from around 10 to 7.8.

(HD400, ex Quest).

ex Aqualon.

10 J7045 Composition 1 was formulated as a roll-on lotion.

For comparison, an in vivo test procedure used to evaluate the efficacy of Composition 1 was also used on Composition 2, the commonly available "Sure" (trade mark) roll-on antiperspirant.

This composition is available in the UK and is considered to be the most efficacious aqueous ethanolic zirconium aluminium chlorohydrate product commercially available, and contains 15% by weight of the zirconium/aluminium 10 active.

Example 2 In vivo test procedure Each of the compositions was tested in a standard hot-room assessment procedure. In this, human volunteers are subjected to thermal stress and gravimetric determination of the perspi'ration produced under the thermal stress, and this is summarised as follows: Subjects: Panels of around 66 women who use no antiperspirants for the 14 days before the test.

Hot room: Temperatures 40 0 C 2 0 C; relative humidity 40% Test Design: Subjects attended daily for 3 consecutive days. They received one treatment with the products on each of the three days. After product application on the third day, the panellist was subjected to a hot-room sitting in which sweat was collected.

11 J7045 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.

Product Application: The operator conducting the test applies the test product in a standard manner, so as to 0 deposit an appropriate quantity of product on each axilla.

For a stick or roll-on product this will be on average about 300 mg of product to each axilla, whereas for an aerosol product approximately 1-1.5 grams of product is dispensed.

Sweat Collection: Absorbent "Raytex" cotton pads are used to collect the sweat. On entering the hot room, each panellist has the test product applied to the axilla, and then is subje6ted to a 40-minute 'warm-up' period, during which no sweat is collected. After this, sweat is then collected for a 20-minate period and the sweat weight determined.

Analysis of Data: The statistical treatment includes an analysis of variance which allows for effects due to the different degree of sweating from the different axillae of a given panellist. The efficacy is calculated from the geometric mean weight of sweat collected from the axillae treated with each product using the formula:

(C-T)

sweat reduction -12 J7045 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.

Results Composition sweat reduction 1 2 32 In vitro test crocedure Compositions according to the invention were also subjected to an in vitro test method to investigate their efficacy as antiperspirant actives. The formulation of the compositions used for this test are given in Table 1 below.

The following describes the apparatus and test protocol used. The apparatus and test protocol are based on the apparatus and method described by H.H. Reller W.L.

Luedders, "Pharmacologic and toxicological effects of topically applied agents on the eccrine sweat glands", Mod. Toxicol. 4: 1-54 (1977).

Apparatus Desian The apparatus used to approximate the degree of pore blocking that would be provided by antiperspirant -13 J7045 compositions on the skin surface is shown schematically in Figure 1 of the accompanying drawings. The apparatus comprises four major elements, namely: the pressure control unit, the sweat reservoir, the cell, and the detection and measurement system.

10 Pressure Control Unit (10-32) A white spot nitrogen cylinder 10 and gas regulator 12 are connected to an on/off isolation valve 14 and pressure release safety valve 16. Stainless tubing and 15 Swagelock couplings are used for subsequent connections.

The primary pressure source is followed by a parallel arrangement of needle 20 and on/off 22 valves, a gas ballast reservoir 24 and a 0.5 micron particle filter 26. The'unit is terminated via a 0 to 3 Bar pressure transducer 30, with accompanying three and a half digit meter 32.

The pressure unit delivers a controlled pressure, which may be stepped or ramped as a function of time.

In these experiments, which were to evaluate flow rates, the stepped mode of the apparatus was used.

The in-line particle filter 26 eliminates contamination of the sweat reservoir "Sweat" Reservoir This is a laboratory-grade glass reservoir of one litre capacity. Connection to the preceding pressure 14 J7045 unit is via a glass to metal seal and Swagelock coupling. Connection to the subsequent cell 46 is via a rapid action on/of valve 42 and Tygon tubing, terminated in the male portion of a Luer-Lok fitting. The reservoir is easily removed for cleaning. For experiments evaluating flow rates with lipid test substances, the "sweat" may be distilled water.

However, when this test method is used to evaluate ionic antiperspirant actives, the "sweat" should be a 10 0.2-0.3% saline solution.

Both the pressure control and reservoir units are enclosed in an aluminium box, for safety reasons.

Normal operation involves a maximum pressure of less 15 than one atmosphere above ambient.

Cell (46) A 5 pm Millipore SM filter was held in a stainless steel Millipore holder with a Luer-Lok fitting. This particular filter'has a simple well-defined structure, and is appropriate for the materials tested.

Detection System (48) Liquid was collected in a measuring cylinder in the flow studies, with the rate of fluid collection being measured.

Experimental Millipore filters are immersed in double-distilled water, at 600C, for several hours. Occasional agitation and

IM

15 J7045 several water changes ensure chorough cleaning. The container is covered to keep particulate contamination to a minimum.

The "sweat" reservoir is filled to a predetermined mark with filtered, double-distilled water and pressurised to 0.2 atmospheres above atmospheric pressure via the pressure unit.

0 The filter is transferred to the cell, flooded with :distilled water and attached to the reservoir, ensuring that all air bubbles have been expelled. A flow experiment is commenced by opening the rapid action valve between the cell and reservoir.

The average of three ten-second collections gives the unblocked filter flow rate. The filter is then impregnated with a test solution of antiperspirant active by immersion for three minutes.

The filter is removed,'gently shaken, or blotted with a *.i solution-impregnated filter paper, and introduced into a "sweat" solution to gel the entrapped test solution.

The average of three further flow experiments gives the blocked filter flow rate.

The fractional increase in filter blockage equals the fractional flow rate reduction (FFRR), where FFRR 1 Blocked flow rate (Ifhb)/Unblocked flow rate (Ifu), for a constant pressure drop(PD) across the filter.

16 J7045 However, it is the total applied pressure that is fixed in the present experiments and allowance must be made for the pressure drop in the apparatus preceding the cell; this pressure drop varies with flow rate.

The corrected formula is FFRR 1 (Pfu/Pfb).(Ifb/Ifu) 0 where Pfb is the pressure drop in the apparatus preceding the filter with the filter blocked; Pfu is the pressure drop in the apparatus preceding the filter with the filter unblocked; Ifb is the flow rate through the blocked filter; and 15 Ifu is the flow rate through the unblocked filter.

The portion of the calculation which contains Pfu and Pfb represents a correction factor for the pressure drop which occurs in the'apparatus before the filter, which is dependent on flow rate.

S. Figure 2 of the accompanying drawings shows the Sapparatus flow rate as a function of applied pressure, with the cell detached. Pfu and Pfb are read from curve, at the unblocked and blocked experimental flow rates, respectively.

a a a a a a a *aa a a aa a a a a a. a a..

a a a a a a a a *aa a. a a a a a. a a a a a a a a a a a a a a .0 a.a a a ITABLE 1 composition Component 3 4 151617_ 8 9 Tyzor LA 1.5 3.0 6.0 6.0 6.0 6.0 10.0 Hydrogen Chloride (as aqueous HCI) 0.4 0.27 0.54 0. 54 Tilcom Ti. NaOff Chroracel ACH Aqueous ethanol to 100% S S 0 a S 55 S S S S S S S

S

S. S. S S S S S S 0 5 5 5* S S S S S 5 S *Se SOS 555 5 5 T13LE 1 (Cont Component 10 1 12 j137 14 Th',zor LA Hydrogen Chloride (as aqueous HCl) Tilcom TI, 0.3 0.3 11,1011 2.2 Chlorace] 1.5 ACH. Aqueous ethanol 1) (2) (3) (4) Arrinnium titanium, dilactate, supplied as a Dilactic acid chelated titanium hydroxide.

Added as a 0.1.M. solution.

Sodium Aluminium Chiorohydroxy lactate (ex Ethanol: distilled water ratio 2:1.

50% w/w aqueous solution, ex Dui PunL Reheis).

I 19 J7045

RESULTS

Formulation in vitro pore blocking 3 13 2 4 10 4 10 4 6 10 4 10 7 12 4 8 8 2 9 10 2 10 12 2 S11 11 2 12 10 2 S13 2.0 0.2 S14 2.0 0.2

C

The results clearly show that at pH's characteristic of these compositions of the invention tested, compositions containing Tyzor LA and Tilcom TL are superior in their pore blocking ability over Chloracel, a conventional aluminium-based antiperspirant active.

Example 3 The following compositions were made up by conventional techniques.

20 J7045 E g.

eLee 0* 0 0* *0 9. 0 5**01

SO

*5 Table 2 Composition w/w) Component 15 16 17 Ammonium titanium dilactate 20 20 Klucel M 0.75 0.75 0.75 Perfume 1.0 1.0 HC1 soln as as as required* required* required* Ethanol/water to to to 100% 100% 100% Supplied as a 50% w/w aqueous solution, ex Du Pont.

Hydroxy propyl cellulose, ex. Hercules.

Added to ensure the final ratio of Ethanol/water in the composition was 3:1, including water in the ammonium titanium dilactate solution.

S.

0R S S S

S.

*The compositions 15 16 and 17 were adjusted using HC1 such their final pH's were 3.5, 6.0 and respectively.

When tested on a hot room panel according to the protocol described in Example 2 above, there was found to be no experimentally significant variation in antiperspirant efficacy between the three compositions.

-21- Example 4 The following compositions, which were prepared by conventional techniques, illustrate further examples of antiperspirant compositions in accordance with the invention.

Composition 18: Alcoholic Roll-On Antiperspirant Ingredient wt.

Titanium Dilactate (50% soln., Tilcom TL ex. Tioxide) 20.00 Hydroxypropylcellulose 0.75 Ethanol 64.25 Ammonia Solution (25% wt.) [to pH 6.0] 4.20 Fragrance 1.00 Distilled Water to 100.0% Composition 19: Alcoholic Roll-On Antiperspirant Ingredient wt.

Titanium Diglycollate (50% soln.) Hydroxyethylcellulose Ethanol Propylene Glycol Sodium Hydroxide Solution (20% wt.) Fragrance Distilled Water 30.00 0.60 35.00 2.00 to pH 1.00 to 100.0% Composition 20: Non-Alcoholic Roll-On Antiperspirant Ingredient Sodium Titanium Citrate (Tilcom STC ex. Tioxide) POE-21 Stearyl Ether POE-2 Stearyl Alcohol Stearyl Alcohol Disodium EDTA

BHT

Fragrance Sodium Hydroxide Solution (20%) Distilled Water Composition 21: Dry Roll-On Antiperspirant Ingredient Diammonium Titanium 2-Hydroxyhexanaoate Decamethylcyclopentasiloxane Dimethicone Modified Hydrophobic Clay (Bentone 38) Ethanol Fragrance wt.

10.00 3.00 1.00 3.00 0.10 0.05 1.00 to pH 5.1 to 100.0% wt.

15.00 75.00 5.00 3.00 1.00 1.00 -22- Composition 22: Non-Greasy Roll-On Antiperspirant Ingredient wt.

Titanium a-Hydroxy Butyrate Isostearyl Benzoate Potassium Hydroxide Solution (50% wt.) Cyclomethicone Fragrance Distilled Water Composition 23: Roll-On Antiperspirant 20.00 10.00 to pH 23.00 1.00 to 100.0% Ingredient wt.

Titanium Glucuronate Magnesium Aluminium Silicate Glycerol Monostearate (acid-stable) Cyclomethicone Triethanolamine Fragrance Distilled Water 18.00 1.00 8.00 2.00 to pH 5.1 '1.25 to 100.0% Composition 24: Emulsion Roll-On Antiperspirant Ingredient wt.

Titanium Lactate Cetostearyl Alcohol Phenoxyethanol

IPM

Glycerol Monostearate (acid-stable) Ammonia Solution (25% wt.) (to pH 6.0) Titanium Dioxide Octyl Methoxycinnamate Fragrance Distilled Water 25.00 6.00 0.20 0.50 7.50 10.50 0.20 0.20 1.00 to 100.0% ComPosition 25: Alcoholic Gel Roll-On Antiperspirant Ingredient wt.

Titanium Malate Sorbitol (70% soln.) Butane-1, 3-diol PEG 400 Volatile Silicone Fragrance Potassium Hydroxide Solution (25% wt.) Distilled Water 17.00 8.00 10.00 9.00 20.00 1.00 to pH to 100.0% -23- Composition 26: Carbopol Gel Roll-On Antiperspirant Ingredient wt.

Titanium Dilactate (50% soln., Tilcom TL ex. Tioxide) 24.00 Carbopol 1342 1.00 Glycerol 10.20 Fragrance 1.00 Triethanolamine to pH 7.8 Distilled Water to 100.0% Composition 27: Aerosol Antiperspirant Ingredient oooo o oo *eo g oo

O*

o Sodium Titanium Dilactate Bentone 38 PPG-14 Butyl Ether Fragrance Cyclomethicone wt.

16.00 4.00 6.00 4.00 70.00 This base composition was used as 25% by weight of the total formulation with 75% hydrocarbon propellant.

Composition 28: Aerosol Antiperspirant Ingredient Ammonium Titanium Di(a-Hydroxyisobutyrate) Fumed Silica

IPM

Fragrance wt.

45.00 8.00 37.00 10.00 This base composition was used as 23% by weight of the total formulation with 77% hydrocarbon propellant.

Composition 29: High Efficacy Aerosol a.

Ingredient Solid Diammonium Titanium Lactate Bentone 38 (Hydrophobic Clay Derivative) Ethanol Urea Cyclomethicone Pentamer Blend Perfume Pentane Hydrocarbon Propellant (CAP 30) wt.

6.00 2.00 9.50 0.50 1.00 1.00 37.00 43.00 -24- Composition 30: Dry Suspensoid Stick Antiperspirant Ingredient wt.

Sodium Titanium Citrate 20.00 Stearyl Alcohol 23.00 Hydrogenated Castor Oil 4.00 Glycerol Monostearate 1.00 PPG-14 Butyl Ether 2.00 Magnesium Aluminium Silicate 1.00 Perfume 1.00 Cyclomethicone Pentamer Blend 47.00 Composition 31: Dry Suspensoid Stick Antiperspirant Ingredient wt.

Ammonium Titanium Diethyleneglycol Dilactate 30.00 Stearyl Alcohol 20.00 .Hydrogenated Castor Oil 4.00 BHT 0.05 PEG-150 Distearate 1.00 Magnesium Aluminium Silicate 3.20 S Perfume 1.50 Cyclomethicone Pentamer/Tetramer Blend 40.25 Composition 32: Unfragranced Dry Suspensoid Stick Antiperspirant Ingredient %wt.

Potassium Titanium Glucuronate 35.00 Stearyl Alcohol 19.00 Hydrogenated Castor Oil 4.00 Glycerol Tribehenate 2.00 S. PEG-8 Distearate 1.00 Talc 4.00 Cyclomethicone Pentamer/Tetiamer Blend 47.00 Composition 33: Dry Suspensoid Stick Antiperspirant Ingredient wt.

Triethanolammonium Titanium 2-Hydroxy Octanoate 18.00 Stearyl Alcohol 22.00 PPG--2 Myristyl Ether Propionate 45.00 Glycerol Tribehenate 2.00 Stearyl Ether 6.00 Silicone Dioxide 1.00 Oleyl Ether 1.00 C18-C36 Triglycerides 4.00 Perfume 1.00 Composition 34: Moisturising Gel Antiperspirant Ingredient wt.

Diammonium Titanium Lactate (Tyzor LA ex. Du Pont) 20.00 Propylene Glycol 60.00 Sodium Stearoyl Lactylate 15.00 Water 5.00 Composition 35: Stick Ingredient wt.

Monoammonium Titanium (2-Amino-2-methyl-l-propanol) Lactate Diethyleneglycol 10.00 Dibenzylidene Sorbitol 3.00 Ethanol 41.00 Propylene Glycol 30.00 Zinc Acetate 0.50 Stearic Acid 0.50 Cyclomethicone Pentamer Blend 10.00 *POP-15 Stearyl Alcohol 5.00 Composition 36: High Efficacy Stick Ingredient wt.

S Ammonium Titanium Monocitrate 13.00 Bentone 38 6.00 Behenyl Alcohol 13.00 Propylene Glycol 20.00 S Dipropyleneglycol Methyl Ether 7.00 Talc 4.00 Cyclomethicone Tetramer Blend 4.00 Perfume 1.00 Ethanol 22.00 Composition 37: Unfragranced Pump Antiperspirant Ingredient wt Potassium Titanium Dicitrate 15.00 Ethanol 72.00 Hydrogenated Castor Oil 1.00 Isopropyl Myristate 6.00 Propylene Glycol 6.00 Composition 38: Pump Antiperspirant Ingredient wt.

Ammonium Titanium 2-Hydroxy Decanoate 20.00 Ethanol 59.50 Perfume 0.50 Stearyl Alcohol 2.00 Stearic Acid 2.00 Cyclomethicone Tetramer/Pentamer Blend 16.00 -26- Composition 39: Pump Antiperspirant 1-n-gredient I wt.

Ammonium Titanium Lactate 10.00 Ethanol 80.00 Perfume 1.00 Stearic Acid 3.00 Propylene Glycol 5.00 Isopropyl Myristate 1.00 Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

06 0:

Claims (11)

1. An antiperspirant composition suitable for topical application to the human skin, comprising an effective amount of a titanium salt of a hydroxy aliphatic carboxylic acid having a chain length of from C 2 to C 10 a cosmetically acceptable ingredient other than water and optionally water, the composition having a pH in the range 7 to 10, with the proviso that said carrier does not include a polyol having from 3-8 hydroxy groups.

2. An antiperspirant composition according to claim 1, wherein the composition comprises from 0.1-50% by weight of the titanium salt.

3. An antiperspirant composition according to claim 2, wherein the composition

6. comprises from 10 to 40% by weight of the titanium salt. 4. An antiperspirant composition according to claim 2, wherein the composition 1. comprises from 1 to 10% by weight of the titanium salt. An antiperspirant composition according to any preceding claim which is anhydrous 20 and/or comprises as cosmetically acceptable ingredient one or more or a hydrophobic clay, a volatile or a non-volatile silicone, and a surfactant. 6. An antiperspirant composition according to any preceding claim wherein the titanium salt is a mono- or di-acid salt of citrate, gluconate, glycolate or lactate.

7. An antiperspirant composition according to claim 6, wherein the antiperspirant active is an ammonium titanium lactate salt.

8. An antiperspirant composition according to any preceding claim which is substantially anhydrous and additionally comprises ethanol, isopropanol or a mixture thereof. K" V vi~i-r ci: -^A P:\WPDOCS\GRS\746548.doc-06/10/99 -28-

9. An antiperspirant composition according to claim 8, wherein the isopropanol, ethanol or mixture thereof is present in the composition at a level of from 50-80% by weight.

10. An antiperspirant composition according to claim 5, wherein the hydrophobic clay is present in the composition at a level of from 5 to 20% by weight.

11. An antiperspirant composition according to claim 5, comprising from 0.1 to 2% by weight of a surfactant.

12. An antiperspirant composition according to any preceding claim which is in the form of a solid stick, lotion, cream or aerosol spray. .o

13. A method of preventing or limiting perspiration of the human skin, comprising 15 topically applying thereto an antiperspirant composition according to any one of claims 1 to 12. SDATED this 6th day of October, 1999. Unilever PLC By Its Patent Attorneys DAVIES COLLISON CAVE **r