CA2275571C - Antiperspirant gel-solid stick compositions containing select nucleating agents - Google Patents

Abstract

Disclosed are anhydrous antiperspirant compositions comprising from about 0.5 % to about 60 % by weight of particulate antiperspirant active; from about 1 %
to about 15 % by weight of a solid non-polymeric gellant; from about 10 % to about 80 % by weight of an anhydrous liquid carrier having an average solubility parameter of from about 3 to about 13 (cal/cm3)0.5; and from about 0.0001 % to about 5.0 % by weight of a solid nucleating agent wherein the molar ratio of the solid non-polymeric gellant to the nucleating agent is from about 10:1 to about 1000:1. These antiperspirant compositions provide improved low residue performance and improved antiperspirant efficacy.

Description

JUN-17-1999 02:29 P&G PRTENT ITC CINN S13 627 6333 P.~89i127 wo 9srz~ Pcrius97rz4uo ANTIPERSPIRANT GEL-SOLID STICK COMPOSITIONS
CONTAINING SELECT NUCLEATING AGENTS
FIELD OF THE INVENTION
The present invention relates to antipexspirant compositions having Improved low residue and effcacy performance, and which contain select nucleating agents in combination with a crystalline gallant.
BACKGROUND OF THE INVENTION
There are many types of topical atttipessprtant products, that are eomtnereially available or otherwise known in the antiperspirant art. Most of these products are formulated as aerosol or pump sprays, roll-oft liquids. cps, emulsions, gels, gel-solids, or other solid stick formulations, astd comprise an astringent material, e.g. rircextium or aluminum salts or combinations theraoE incorporated into a suitable carrier. These products are designed to provide effective perspiration and oetor control while also being cosmetically acceptable during and after application auto the axiliary area or other areas of the skin.
Within this product group, solid antiperspirant sticks have become especially popular amnttg consumers. These atrtiperspirant sticks comprise a solid matrix wit6ia which the antiperspirant active material is contained- The active can be solubilized in a liquid catrid~
comprising water. glycois aod/o~
other alcoholq, or maintained within a solid matrix as disposed solids is an anhydrous systan. The solid sticks which contain dissolved etctive ofttn provide some !ow residue pa~fa<mance, but tend to be wet ar sticky during and itnmediaGeiy aflec spplicatmn to the skin, and more importantly. are often not as effexrive in providirtg antipestspirattt and deodocaat pctfotiaance as solid sticks containing dispersed patriculade active. Although the atttipetspirsat sticks which ex>tdaia particulate actives are more effective.
they also tend to leave a higher visible rrsidue on the skin.
There have been many attempts at p~toducin6 snitydrous antiperspirant sticks which contain dispersed paracatiate a~ipaspirant active, and which also provide improved e»cacy end lour residue perfomsanex during and at~er appiicaaon to the skier, or which otherwise provide product clarity prior to (as a packaged prod!) ar aRes such application (as a clear or low-residue film on the skin).
One such a~mpt mvohKS the coatbiaaZiod of perrdculate antipospiraat active, gellenes and liquid cattier in a gel stick, wbenin ttU such components is the cotabioation have matching reeve indices.
R.efraaive index g allows for tttara of tight tbrouglt the gd stick with less seutaering of the light, thus resuhyag in products which appear mote clear or translucent as a packagod eorapositioa opt when initially applied topically to the skin. These get sticks, however, are expeasiva to make due to the cost of using raw materiaL~ having only select matehiag refractive indices.
These: compositiorts are also very difficult to formulate given that refractive index matching for a thtxe eompe>nont system (parciwlace active, solvent and gallant) is exttsmety ditFuvlt; and greatly limits the materials that can be used to prep:re such a fotmuission.

_2_ Another attempt at making low residue antiperspirant sticks involves the use of eellants such as dibenrylidene alditols. These gellants, however, like many other gellants known in the art, are not acid stable and therefore tend to interact with the antiperspirant active due to the acidic nature of the active.
This interaction can result in reduced efficacy of the active, poor gel formation, and lower gel stability over extended periods during shipping or storage. This interaction may also cause processing difficulties at the temperatures and holding times often used during the formulation and manufacturing process.
These gellants are also commonly used in combination with glycol carriers or other solvents which tend to be wet and sticky and irritating to the skin.
Yet another attempt at making low residue antiperspirant sticks involves the use of residue masking agents such as non-volatile paraffinic hydrocarbon fluids, phenyl trimethicone, low melting point waxes and combinations thereof. These agents are used in combination with stearyl alcohol or other high residue waxes commonly used in solid antiperspirant sticks. These agents help reduce visible residue during and immediately after application of the solid stick to the skin, but also tend to be associated with an oily or sticky skin feeling during application. Moreover, although the visible residue is reduced in such compositions, there remains a visible residue on the skin when used in combination with high residue waxes such as stearyl alcohol, and this reduced residue is still more visible or apparent than the topical residue left by antiperspirant sticks which contain solubilized antiperspirant active.
Other attempts at improving low residue performance from an antiperspirant composition has focused on the use of anhydrous antiperspirant creams. These creams can be applied to the skin by conventional means, or by a cream applicator device, and results in very low residue during and immediately after application to the skin. These compositions comprise particulate active dispersed throughout an anhydrous carrier, and either contained within a solid-like matrix or thickened with an inorganic or polymeric gellant or thickening agent. Many consumers, however, still prefer the convenience of using a solid antiperspirant stick, even if the solid stick tends to leave a higher visible residue on the skin.
A recent method of making low residue antiperspirant sticks is described in U.S. Patent 5,429,816, issued to Hofrichter et al. on July 4, 1995;
The antiperspirant sticks provide low visible residue during and immediately after application to the skin, and are physically and chemically stable over extended periods of time. The improved antiperspirant sticks comprise a dual gellant system having a primary geliant such as 12-hydroxystearic acid or esters or amides thereof and a secondary gellant such as n-acyl amino acid amides.
Formation of such an antiperspirant stick with such a dual geilant system has been characterized as a "gel-solid" antiperspirant stick.
An antiperspirant gel-solid, such as that described by Hofrichter et. al., is an antiperspirant stick having a three-dimensional, non-polymeric, gel network in which solvent is contained or trapped. These gel-solids are typically formed by solubilizing the gellant in the solvent at temperatures above the melt JuN-1r-i'~7'~ vJG~.Sd rtSU rr-i~CW W ~ LWN J1.5 b~'f b.S5.5 r.d~Wl~~
WO 98/27939 PCTlUS9'1~

point of the gallant and at temperatures at which the melted gallant is soluble in the solvent, and then cooling the composition to form the desired gel-solid composition. ~lte low residue gel-solids described by HoFrichter et al. are remarkably stable, both physically and chemically, and will maintain the desired product hardness over an extended period of time. The gel-solids described by Hofrichter et al., however.
are limited to select dual gallant systems and do not include or otherwise describe any method of making a low-residue antiperspirant gel-solid stick containing any other gallant or gellaitt system.
It has now been found that improved antiperspirant compositions can be fotnsulateA using a single crystalline gallant or a combittatioa of crystalline gallants in combination with select nucleating agents to help tnittimizc gallant crystalline particle size. The smaller gallant crystalline particle sizes made possible by such combinations result in antiperspirant compositions haviteg lower visible residue when applied topically to the skin. It has been found that the txysrapine matrix of such compositions Causes less scattering of light, thus providing the appearance of reduced residue when such a composition is applied to the shin. Moroover, the small crystalline particles from the composition more easily matt when applied to tile skin, thus forming a topical fluid or liquid layer on the applied surface that further provides the appeacettu of reduced residue. 'Ihe select nucleating agents as defined herein are especially useful whoa ustad in combuuttion with solid non-polymeric crysuliiae getlants.
These compositions may be formulsted as liquids, soft-gets, a~r harder ge!-solids.
It is therefore an object of the p~e~e5erlt iaventioa to provide as anhydrous antipet3pitaat composition having unproved hand low visible t~idue, and furt6ee to provide such a composition which contains crystalline gallants io combination with a nucleating agent. It is a further object of the ptssettt invention to provide such a composition that comsins a single cxystallitte gcliant or a combinatiott of ciyStauine gehanes in contbn with a nucleating agent It is yet anodta objtet of the present invention to provide sue6 a cdttposition that is pltysicauy and chemically stable over extended periods of time. and fu>~r to provide as anhydrous gel stick composition cattaiaiag a gellotg agent which is stable in the ptsx~.aoe of a particulate rantiperspirattt sarvc.
SU'MM~Y OF THE INVENTION
Tlx present iav~n is dire~d to an anhydrous anapersp~ct coatpositioa ccHttprising from about 0.3% to about 60'y6 by weight of pa>nicttlatt atuipt~spirant native:
frota a6oui 194 to about 1596 by weigiu of a solid non-polymaie geUapt: from about t 0'/, to about 8096 by weight of an anhydrous liquid cattier for the solid naQ-polymeric gellapt having an average solubility paameter of from about 3 to atxxrc l3 (cal/cm3~.s; and frnaa about 0.000191 to about 596 by weight of select nucleating agars wherein the molar ratio of the solid aoa-polymeric gellam to the nucleating agent i' from 10:1 to about 1000: ! . The nucleating agent fly tans a melt point near the malt poiru of the solid non-pvlytneric ,gCllani, a solubility is the npaaquteous liquid tsarier which is kss than the solubility of the solid non-polymeric getlaat in the noitaqueous liquid cattier, or is in the form of inorganic, mitaonized particles.

It has now been found that this combination of solid non-polymeric gellant and the select nucleating agents helps minimize gellant particle size in the composition, which then results in an antiperspirant composition having lower visible residue when applied topically to the skin.. it has been found that the crystalline matrix arising from such compositions causes less scattering of lisht due to the smaller geliant particle size, thus providing the appearance of reduced residue when the composition is applied to the skin. Moreover, the small crystalline particles from the composition more easily melt when applied to the skin, thus forming a topical fluid or liquid layer on the applied surface that further provides the appearance of reduced residue. The select nucleating agents as defined herein are especially useful when used in combination with the solid non-polymeric crystalline gellants.
DETAILED DESCRIPTION OF THE INVENTION
The antiperspirant get-solid stick compositions of the present invention are anhydrous systems which are dispersions of particulate antiperspirant active held or contained within a non-polymeric crystalline gel-solid matrix.
The tetrn "anhydrous" as used herein means that the antiperspirant gel-solid stick composition of the present invention, and the essential or optional components thereof other than the particulate antiperspirant active, are substantially free of added or free water. From a formulation standpoint, this means that the antiperspirant gel-solid stick compositions of the present invention preferably contain less than about 5%, preferably less than about 3%, more preferably less than about I%, most preferably zero percent, by weight of free or added water, other than the water of hydration typically associated with the particulate antiperspirant active prior to formulation.
The term "low residue" as used herein refers generally to the visible residue left an the applied areas of the skin during or immediately after application, and more specifically refers to the visible residue index of the composition as defined by the methodology described het'einafter.
The term "ambient conditions" as used herein refers to surrounding conditions under about one atmosphere of pressure, at about 50% relative humidity, and at about 25°C, unless otherwise specified.
The term "substituted" as used herein, unless otherwise specified, refers to chemical moieties or substituents known or otherwise suitable for attachment to the compounds or other chemical materials described or referred to herein. These substituents include, but are not limited to, those listed and described in C. Hansch and A. Leo, Substituenr Constants for Correlation Analysis in Chemistry and Biolog~ ( 1979), ~ Examples of such substituents include, but are not limited to, alkyl, alkenyl, alkoxy, hydroxy, oxo, nitro, amino, aminoalkyl (e.g., aminomethyl, etc.), cyano, halo (e.g., chlorine, fluorine, bromine, iodine), carboxy, alkoxyaceyl (e.g., carboethoxy, etc.), thiol, aryl, cycloalkyl, heteroaryl, heterocycloalkyl (e.g., piperidinyl, morpholinyl, pyrrolidinyl, etc.), imino, thioxo, hydroxyalkyl, aryloxy, arylalkyl, amides, esters, ethers, combinations thereof, and the tike.

JUN-17-1999 82:31 P&G PATENT ITC CINN S13 627 6333 P.e93i127 WO 98n7939 PGT/[1$99 -S-fhe terms "alkyl" end "alkenyl" as used herein, unless otherwise specified.
refer to substituted or unsubstimted, branched, cyclic or linear. hydrocarbons having from 1 to about 22 carbon atoms.
The term "n-acyl amino acid derivatives" as used herein refers to gallants selected from the group consisting of n-acyi amino acid amides, n-acyl amino acid esters prepartd from glutamie acid, lysine, glutamine, apatuc acid, and combinations thereof, and which are specifically disclosed in U.S_ Patent 5.429,816.
The term "volatile" as used herein refers to materials which have a vapor pnyssttre under ambient conditions of at least about 0.2 mm of Hg. Conversely, the term "non-volatile"
as used herein refers to matrrials which have no measurable vapor ptssswe or which have a vapor of less tttart about 0.2 mm of Hg under ambisnt conditions.
The solid non-polymeric gallant, antiptrspirant active and anhydrous liquid carrier components of the gtl-solid stick composition herein are preferably not refractive index matehtd and mote preferably have at (east two of such components with refractive indices (n~ that differ by at least about 0.02. more preferably by at least about 0.04. The tenor "non~polymeric" as used herein does not mean polytrtetic derivatives of 12-hydrox~earic acid, and combinations thereof:
The antipetspiraat gal-solid stick compositions of the present iuventivtt calf comprise, consist of, or consist essentially of the elements mfd limitations of the invention described herein, as well as any of the additional or optional ingredients, compomena, or Iimirations described herein.
As percentages, parts and ratios are by weight of the total Composition, unless otherwise specified. All such weights as they pertain to listed ingredietm are based on the specific ingredient level and, thetrfo~, do not inchide solves, casrieta, by-ptodttcm, filler or other minor ingredients that may be included in commacisily available macaials, wtkas ot6erwix specified Product C6g_rseteristles The aaciperspiraat gel-solid stick compositions of the ptzsent invention are peefaably charactai~ed ~ terms of pmodnct hardness, visible residtts index, mad s~
theology profile defined by a ratio of as elastic to viseous maduli, l:.acb of the'e characteristics is defined in a~dance with the methodoiogix and other limitations described hereipaftes.
a) The at>siperspinuu get-sotid stick compositions of the t iovattion prefietably have a product hardness of flan about 300 gram-foere to tb0itt 5.000 grrtn-force, tttore pKferabty from about 750 grant.
force to about 2,000 gram-fotne, even mate preferably from about 800 gt'am~force to about 1,400 gtam-force.
T6e term "product hard~s" as used herein is a rettectiort of how touch force is t~eqttited to move a lion cone a distance atld at a controlled rate into a4 antiperspirant gel-solid stick composition under the following test conditions. Higher values reprrshu hardest product, and Iower vahus represent soRtr product. These values ase messur~ed at Z7°C.
15~/e relative humidity. using a TA-JUN-17-1999 82:31 P&G PATENT ITC CINN 513 627 6333 P.a94i127 WO 98127939 PCTlUS97I24250 ~6-xn Texture Analyzer, available from Texture Technology Corp., Scarsdale, New York, U.S.A. The product hardness value as used herein represenu the amount of force required to move a standard 45°
angle penetration cone through the composition for a distance of lOmm at a rate of 2mm/sccond. The standard cone is available from Texwre Technology Corp., as part number TA-l5, and has a total cone length of about 24.7 mm. angled cone length of about l8_3 mm, a maximum diameter of the angled surface of the cone of about 13.5 mm. Tltt cone is a smooth, stainless steel construction and weighs about 17.8 grams.
b) Res' ne The antiperspirant get-solid stick compositions of the present invention preferably have a visible residue index of from 11 to vbout 30 L-value, more preferably from about 11 to about 25 L-value, even more preferably from 11 to about 20 L-vahte. The term "visible residue index"
as used herein refers generally to the extent to which the composition of the present invention is visibly apparent as a thin topical film after application to the skin, and snore speci6eally refers to measured visible residue values (expressed as an L-value an the L. a. b color stain) in ac.~ordaoce with the following methodology, performed at 27°C. under atmospheric ~sst~, and at 1396 relative humidity on antiperspirant stick compositions having a hardasms of from about S00 grs<n~force to about 5,000 gram~fatce.
A piece of black felt, approximaoely 10 cm x 30 an, is attached to a movable haimtttal slide which is movably attached or fixes to a larger md~ttleal unit. M example of s suitable piece of black felt for use herein is Supreme Robe Velour, FN-6354, Color 4040., Style 31854, available from So-Fro Fabrit~, Evendaie, Ohio, U.S.A. M example of s suitsbb mahanical assanbiy far use herein is the Release and Adhesion Tester, Secisl No. A~14934, mamrfa~md by Testing Machines, InG., Amityville, New Yori~ U.S_A_, or a Veimex Unis~lide Pasitiwtiog System, Unislide assembly series (MH6000~, available from Velmex, Irte., Bkiomfteld, New York U.SA An antipecspaanc stick composition contained within and patually rxbatdias out about 0.5 cm from s coaveationai package or corttai<ter is positioned pGpendicuJa to and above the enschcd piece of fch, sack that the product extending our of the package or cantairur is facnng the piece of fort and the surrrntrtding package is positioned sway from the piece of felt. 'The surrottndcng prcnge is posrooaed in place using s mechanical arm or other device suitable for applying the requisiac mov~t to the product ss described herein.
The antipasp~artt stick composition is dtert slowly moved toward sod allowed to gently contact the attuhed piece of biacir feh. A 1,000 gram weight is placed on the prod<tct sample so drat the product contissuously contacts the piece of black fete dmittg testing. The weightod sample is then moved repeanedly back snd fords acaoss the piece of feh at a fixed speed (about 3 ctn/aecond). and with a fixed amount of applied prrsstne provided by the weighted product, until about 1.75 grams of the antiperspirant stick composition is evenly applied over a S cm x 20 Cnt aroa of the piece of black feh. The piece of felt is~ then careFully tnmoved from the apparatus, JUN-1'7-1'~'~'~ d~~.~l NisV NHftNT ITC UINN 51-5 627 633-1 r.d~5il~'7 WO 9812?939 PCTIUS9~2d?.'~0 _7_ A calibrated Minolta CR-300 chromameter (available from Minolta Corp., Ramsey, New Jersey.
U.S_A.) is then used to measure the i.-value (on the L,a.b color xale) of the applied surface area. First, a template is placed on top of the piece of felt to facitirate the Minolta readings. Template dimensions are 5 cm x 20 cm. The template has twelve circular openings (2.2 cm diameter) positioned within the template, each opening positioned centrally within adjacent 6.5 cmz areas of the template surface. The template is positioned over the applied sutfaee area of die piece of felt such that each of the twelve circular openings covers a non-overlapping area of the applied surface. The chromameter's view port is fitted into each of the circular openings and L-value measttrtunents taken. Alt average L-value is then determined for the twelve tneasttraszents (standard deviation of less than about Q.B) which then corresponds to the visible residue index as described bercin.
It has been found that there is a correlation between the visible residue index range defined herein and the average particle sine of the crystalline gallant particles is the antiperspirant gel-solid stick composition of the prdetu invention. Generally, as the average particle sire of crystalline gallant particles in the composition de~sa, low residue performance intptoves. In particular, it has been found that a visible residue index of fr~nm about 1 ! to about 30 L-value cornelates with an average crystalline gelhutt particle sin of less thaw about 1 Nm, and/or a crystalline gallant particle morphology characterizdd by one dimensional crystalline growth such as that rrstthing in crystalline filaments, fibers, strings on other elongated particles, whert:in the aspect ratio as defused by the major and minor axis of the crystalline particle is gtt~et titan about 2, lmeferably grcatar than about 6.
Conversely, solid compositions containing crystalline gallant particles greater thaw 1 pin (average patticie diameter) have a visible residue index of gremu than 30 L-value, In view of this cocrslation between visible residue index values and average cryst~lliae particle size or elongated particle tttocphology, the visible residue index measurtmsent can now be treed as an aloanative mesas for establishing average crystalline gellans particle size or crystalline gellartt marp):oliog)r, at least to the extent that such average particle size is less than about 1 pin.
a) C
The atatipaspiraot stick tbmpositiaas of the present invention ane gel-solids having the select theology profile defined 6aein. This rheolog~r pro~k is defused herein in terms of the elastic (G~ to viscous (G'7 tssoduli ratio ( G' I G" ) of the gef-solid stick composition. To provide rise tWtlisite Theology.
the geLsolid stick oompositioes must have a G' / G" ratio of fiom about 0.1 to about 100, pteferabty from about 0.1 to about 50, more preferably from about 1 to about 20, even more prefc:abty from about 5 to about 20. Tbia ratio represents the extent to which the gel-solid stick compositions herein exhibit solid cdars~r and the cxoau oo which the compositions exhibit liquid x thud character atsd specifically refers to the numerical ratio G' I G" as desermined by the following methodology.
The elastic mpdulus is a meaeuteatent which correlates wide the solid character of the gel-solid stick compositions hsxrip, arid the viscous modular is a measurement which correlates with the fluid or JUN-1?-1999 82:32 P&G PRTENT ITC CINN S13 62? 6333 P.096i127 WO 9827939 PCT/US9'7fZ4?50 -g_ liquid character of the gel-solid stick compositions herein. Measurements for G' and G" for purposes of defining the composition of the present invention are determined under ambient conditions using conventional techniques well known in the formulation arts. For exampis, a Bohlin Sarss-Strain ftheometer, available from Bohlirt Reologi. Cranberry, New Jersey. can be used using a cone (about 1 °) and plate configuration. About 1.0 mg of the product is carefully removed for the composition with minimal application of shear force and is then placed between the cone and plate fixtures foe measurement of G' and G".
(t has beer found that the gel-solid stick compositions of the present invention exhibit itnproved low residue performance where formulated as described herein, wherein the composition has the select G'/G" ratio described hereinabove, especially when the defined theology is associated with a crystalline gel matrix having a preferred small pttsticle size aadJor particle morphology as described herein. These gel-solid stick formulations spread smoothly ova the skin, and shear quickly and molt during such sproadiutg to form a thin, low residue film ova the applied surface.
In particuh, it has been found that the geI-solid stick compositions of the present invention have theology characteristics that result in unproved performance, especially lour residue performance. These select gel-solid compositions as defused herein behave as solids prig to application while maintained within a canister or other package, but behave more as liquids or fluids during or immediately aftc application to the skip. In other words, the solid compositions shear thin during application to the skin, melt or almost melt (except for particulate active which remains umtteitt:d) during the shear thinning application, thus resulting in a thus, low residue, liquid or fluid film on the skin during or immediately after topical application to !hc skin. The applied film is clear or has very low visible residue. and remains suissoaretially as such over extended periods of time after application.
AntJ~s~lt~ttnt Activ The metipuapirafu gel-solid stick compositions of the pinventiott comprise particulate antipezspiraat active suitable for appiicatiap to htunan skid. 'Ibese particulate actives must eetnain stiaUy utesobebiliaoed as dispersed or precipitated solids itt the aobydtous or subsmnrially anhydrous systems as described haieio. The copcentratioo of paaticttlata active in the composition should be suffecient to provide the d~ petspitation wetness and odor control from the antiperspirant get-solid stick formulation selecxed The antiperspirant gal-solid stick' eotxtpositions of the pteseat invention preferably comprise particulate antiperspirant active err concetiaations of front about 0.5'36 to about 60°6, rstae preferably from about 59G to about 3S%, by weight of the coatposition. These weight percentages are calculated on an anhydrous metal salt basis exclusive of water and any complexing agents such as glycine. S1Y~~ salts. or other complexing agents. The particulate aatipetspirant active as fornnuiatcd in the composition are in the forth of disperseid solid psrticks having a preferred avcsage particle size or diseneta of less than about 100 pm, more preferably from about 15 pm to about l00 pm, even more preferably from about 20 pm to about 100 pm. Also preferred are dispersed solid particulates having an average particle size or diameter of less than about 2 pm, even more preferably from less than about 0.4 pm. !t has been found that antiperspirant active particles within the preferred panicle size ranges provide lower visible residue performance from the gel-solid compositions herein than other less preferred particle size ranges.
The antiperspirant active for use in the antiperspirant gel-solid stick compositions of the present invention include any compound, composition or other material having antiperspirant activity. Preferred antiperspirant actives include the astringent metallic salts, especially the inorganic and organic salts of aluminum, zirconium and zinc, as well as mixtures thereof. Particularly preferred are the aluminum and zirconium salts, such as aluminum halides, aluminum chlorohydrate, aluminum hydroxyhalides, zirconyl oxyhalides, zirconyl hydroxyhalides, and mixtures thereof.
Preferred aluminum salts for use in the antiperspirant gel-solid stick compositions include those which conform to the formula:
A12(OH)a Cl b ~ x H20 wherein a is from about 2 to about 5; the sum of a and b is about 6; x is from about 1 to about 6; and wherein a, b, and x may have non-integer values. Particularly preferred arc the aluminum chlorhydroxides referred to as "SIG basic chlorhydroxide", wherein a = 5, and "2/3 basic chlorhydroxide", wherein a = 4. Processes for preparing aluminum salts are disclosed in U.S.
Patent 3,887.692, Gilman, issued June 3, 1975; U.S. Patent 3,904,741, Jones et al., issued September 9, 1975; U.S. Patent 4,359,456, Gosling et al., issued November l~, 1982; and British Patent Specification

2,048,229, Fitzgerald et al., published December 10, 1980, . Mixtures of aluminum salts are described in British Patent Specification 1,347,950, Shin et al., published February 27, 1974, Preferred zirconium salts for use in the antiperspirant gel-solid stick compositions include those which conform to the formula:
Zr0(OH~_aCla ~ x H20 wherein a is from about 1.5 to about 1.87; x is from about 1 to about 7; and wherein a and x may both have non-integer values. These zirconium salts are described in Belgian Patent 825,146, Schmitz, issued August 4, 1975, which description is incorporated herein by reference.
Particularly preferred zirconium salts arc those complexes which additionally contain aluminum and glycine, commonly known as ZAG
complexes. These ZAG complexes contain aluminum chlorhydmxide and zirconyl hydroxy chloride conforming to the above described formulas. Such ZAG complexes are described in U.S. Patent

3,679,068, Luedders et al., issued February l2, 1974; Great Britain Patent Application 2,144,992, Callaghan et al., published March 20, 1985; and U.S. Patent 4,120,948, Shelton, issued October 17, 1978, JUN-1 r-1'~'~'~ t'~ ~ .S~ r'>SU NH TtN ~ 1 i L C. t NN 513 627 6333 I-'.

4~'31~i12 T
WO 98/Z7~39 pCTIU5971Z41S0 The arttiperspirsat gel-solid stick compositions of the present invention can also be formulated to comprise other dispersed solids or other materials in addition to or in place of the particulate antiperspirant active. Such other dispersed solids or other materials include arty material known or otherwise suitable for topical application to human skin. The antiperspirant gel-solid stick compositions can also be formulated as gel-solid stick compositions which contain no antiperspirant or other active material, particulate or otherwise.
Gellset The antipetspirarrt compositions of the present invention comprise a solid non-polymeric gallant suitable for topical application to human skin. These solid non-potymcric geUants must form within the composition a orystalline matrix within which an anhydrous liquid carrier or othtr liquid compvncnt of the compositi4tt is trapped or contained. These solid non-polymeric gallants preferably form crystalline particles having an average particle diameter and particle morphology as described hereinafter.
T'he antiperspirant coalpositions may comprise, but art preferably substantially free of, gallants such as dibentylidene alditols and fatty alcohol gallants or nucleating agents (described hereinafter) having from about 1Z to 40 carbon atoms including stearyl alcohol. tn this context, "subs:antially free"
means that the compositions prcfaably contain less than :o effective amount of such agents that whtn used alone would provide any thickening or measurable viscosity iltcrasse to the composition under ambient conditions. Generally, the compositions preferably contain less than

5'/~, more preferably less than t'/~, mom preferably Its then 0.5%, most preferably zero percent, of such agents by weight of the composition.
The cortcenttxtion of the solid tton-polymethc gellanb in the compositions may vary wieh each selected antiperspirmo~t fortrtulatioa, especially with each selecttd anhydrous liquid carrier of the formulation, but such conectarations will gentrafly range from about 0.1% to about 20%, preferably from about 1% to about 15%, tpooe prtferably fmm about 3% to about 1294, by weight of the, composition.
The r>ott-polymeric gdLosa trust be solids under ambient conditions.
The solid non-Qolyrturic gellaoss far use in the antiperspirant compositions are those which can matt and foertt a solution or other hoatogsnous liquid or liquid dispes9ian with the xketed anhydrous liquid carrier. attd at the sekcxed gallant and liquid carrier cocrcerraatioru, at a proc~ing temperature of from about 28°C m about 250°C, preferably from abotu ZS°C
to about 100°C, more preferably from about 28°C to about 7$°C. T'he melted nop-polymeric gallant is typically dissolved by or dispersed throughout the selected liquid canna to thta form a solution or other homogeaotts liquid. The solution or odter homogartous liquid, nerd other esse~ist and optiartal ingrrdi~, are proferably combined in accordmux with rite rrtaaufacnuatg method dexn'bed herein or other conventional or otherwise known technique, and then pieced is s suitable package as a flowabk Solution err homogenous liquid, and then allowed to solidify (for non-liquid embodiments of the preseart invention) and form rate desired crystalline JUN-1?-19'9 t32~33 P8G PRTENT ITC: CINN 513 627 6333 P.~99i127 WO 98127939 PCT/US97lZ4Z50 ael matrix within the composition as the temperature returns to ambient temperature and drops to below the solidification point of the selected non-polymeric gallant.
In selecting a combination of solid non-polymeric gallant and liquid carrier for use in the antiperspirant gel-solid stick compositions, the selected combination should allow for the development of a crystalline gallant matrix within the cmapositioa wherein the component crystalline particles preferably have an average particle siu of less than about 1 pat, more preferably less than about 0.4 pm, even more preferably less than about 0.2 pm, most preferably from about 0.001 lun to about OZ um, and/or wherein the crystalline particles have the requisite elongated morphology described herein, wherein particle size is measured yr determined by the methods described herein or by methods well-known oo dtose skilled en the art such as tight or electron microscopy. The ge!-solid stick compositions can be prepared by methods well known is the formulation art for malting gel-solids having minimal crystalline particle size or the preferred elongated particle morphology. The gel-solid stick compositions are preferably prepared by the select medtods described hercinaRer directed to matimizing crystalline particle size and/or establishing the preferred crystalline particle morphology.
5oiid nonpoiymeric gallants suitable fat use in the antiperspirant compositions of the present invention include fatty acid gallants, esters and amides of fatty acid gallants, hydroxy acids, hydroxy fatty acids, choiesterolic materials, tanolinolic naaedrials, and other amide gallants known for use as gelling agents of which aro otherwise described in detail hereinafter. The solid non-polymeric gallants can be used as a single gallant or as a combirtatiatt of geihtnts in canbination with the select nucleating agent.
Other crystehine gellattts can also be used in the atttiperspirattt compositions of the prrsertt invention provided Heat such other gallants tan be formulated with the selected outlasting agent to provide the requisine crystalline gel tttatroc.
Suitable smide gellatto include di~tuted or branched monoamide gallants, monosubstiWted or branched diamide geltaots, tt7amide galleons, n-scyt amitfo acid derivatives, and combinations thereof.
Noa-limiting exaatpks of suitable saoodety amide gallants include select alkyl aatides of a di-andlor tri-basic carboxylic acids wbicb aottfona to ehe frntntale:
R p R
9 II I s R1 C '-,-C -N ~RZ
a ~ R
I~
R 3 X -Y -Z -Rg O
Rte C -C-N'R4 I l R

wherein a backbone is formed from the linkage of C', C" and X and wherein al Rl is nil, hydcnxy, hydrogen, aryl, siloxane as sanua:ed or unsaatrated, substituted or unaubstituted, s~aight, branched or cyclic chain Cl-C~ alkyl, C1_ JUN-17-1999 02:33 P&G PRTENT ITC CINN S13 627 6333 P.100i127 wo ~erzrW 9 PcrrUS~ru2so ~ 12-C~ alkenyl, C 1-C== alkoxy, C 1-C22 alkyl esters, C 1-C22 alkyl ethers, oc C 1-C~2 alkyl substituted aryl, preferably C4-C 1 g alkyl, C4-C 1 g alkenyl, C4-C

alkoxy, C4-C 1 g alkyl esters. C4.C 18 alkyl ethers, or C4-C l g alkyl substituted aryl, more preferably C I Z'~ 18 ~'l. C 12'C 18 a~rnyl. C 1 Z-C 18 alkoxy, C I

C 1 g alkyl esters, C I 2fi 1 g alkyl ethers, « C 12-C 1 g alkyl substituted aryl;
b) R2, R4, RS arid R6 are independently or together. hydrogen, hydroxy, aryl, siloxane or saturated or unsaturated, substituted or unsubstituted, straight.
branched or cyclic chain Cl-CZ2 aUryl, C1-C~ aikenyi, CI-C~ atiwxy, C1-C~
alkyl ester's, C1-C~ alkyl tthers, or C1-C~ alkyl substituted aryl, preferably C4~
C 10 atkyb C4-C 10 alkenYt, C4-C 10 Y. C4-C 10 ~Y) tasters, C4-C 10 alkY1 ethers, « C4-C 10 alkyl substituted aryl, more preferably C4-C8 alkyl, C4-CS
alkenyl, C4-Cg alkaxy, Ca-Cg allryl esters, C4-Cg alkyl ethers, or C4-Cg alkyl sttbstituicd aryl:
c) R3 is nil, hydt~oxy, hydrogen, saturated or uasarirtased, substituted or unsubstiWted, straight, branched or cyclic chain C LC4 alkyl, C 1-Cd allcenYt, C 1 _ C4 alkaaty. CI-C4 alkyl tasters or C1-C4 alkyl ettsers, preferably a C!-C4 alkoxy.
hydroxy ar hydrogen, nr«e preferably ahy~Oxy or hydt~ogett:
d) R~ and Rg ere qtly or coge~r, ail, hyd<oge3t, hydroocy. ~'Yl. siloxane « sannated or uasatueaKd" subst>atted or uasubsddsted. straight, branched or cyclic cdain Cl-C~ alkyl. Cl-C~ alkenyt, CI.C~ alkoxy. C1-C22 ~Yl ~.
C 1'C22 ~Yl mss. a C 1-C22 a11tY1 subsoituted aryl, PreferabtY C4~ l0 C4~ 10 alketryl. C4-C 10 a~1'. C4'C 10 ~ C4-C l 0 ~'1 edtars. «
C4-Clp alkyl substi;~ed aryl, moer pnefaably C4-CS alkyl, C4.C~ siitatrl. C4.
Ce altoxy, C4~g alkyl esters. e4-cg alkyl edters, « C4~a alkyl sttbsantted FYI:
e) Rg is ail « hydrogen;
R10 and Ri 1 are is>dependently or cogetlux, nil, 6ydrogrn, hydroxY. arY~
siloxsae « satttra>ted « tro:mrrated, red « uasub:tinr~d, straight, «
cyclic chain c!-C6 alkyl, C!'C6 ~Yl. C!-C6 alkoxy, Cl~b alltyl esters, c!~
C6 alkyl e0s~s, yr C I-C6 alkyl subst~ed aryl. preferably C !'C4 FYI. C 1-C4 ~alkeayl, C1~4 alkoxy, C1-C4 alkyl esters, C!'C4 ~kYl ~. C1-~d ~
subsbiamed aryl « hydco~nt, morn: pKfa'ably a hydrogesr g) X is aitr'ogat. aryl or ~f;l~n where a is an imeger ftrnn 1 to 6, preferably ~~~n wlrar n is an integer from 1 to 3: .
- h) Y iS ttil, aryl « Carbonyl;

JUN-17-1999 02:33 P8.G PRTENT ITC CINN 513 627 6333 P.101i127 WO 9SJ2'1939 7PCTIUS97I1A250 -l3-i) Z is nil. hydrogen, hydtoxy, aryl, siloxane, nitrogen or saturated or unsaturated.
substituted or unsttbstituted, straight, branched or cyclic chain Cl-C2~
alkyl, Cl-Cz~ alkenyl, C!-C~ alkoxy, C1-C» alkyl esters, Ct-C~ alkyl ethers, or Cl-C~ alkyl substituted aryl, preferabty C4-C 1 p allryl, C4-C l p alkettyl, C4-G

sikoxy, C4-C ! p alkyl esters, C4-C ! p alkyl ethers, or C4-C t p alkyl substituted aryl, more Preferably C4~g alkyl. C4-Cg alkenyl, C4-Cg aikoxy, C4..Cg alkyl esters, C4-Cg alkyl ethers, or C4-Cg alkyl subsdtutcd aryl; and J) -a" is a double or single bond provided:
(i) when X and Z are not nil atsd Y is nil, X is directly bonded oo Z;
(its when Z is nil, a hydrogen ar ahydroxy, R~ and Rg are nil: and (iii) when -a" is a double bond, R~ and R9 alit nil.
Some specific examples of suitable alkyl amides of di- and tri-basic carboxylic xids include. but are not limited to. alkyl autides of citric acid, tricarballyiic acid, acooitic acid, nieriloaiacetie acid utfd itaconic acid such as 1;2,3-propane ttibueyhunide, 2-hydroxy-1,2,3-propane tributylamide. 1-pr~opene-1.2.3-trioctylamide, N,N',N"-tri(mtthyidetylamide)atnine, 2 docecyl-N,N-dibutyisueeinimide, and combinations t!>eteof. Preferred tire alkyl amides di-carboxylic acids, more preferably 2 docecyl-N,N'.
dibutylsuccinamide.
Suitable o-acyl amino acid derivatives include, but are sot limited to, N-lamroyl-glutatnit: acid diethyl air,ide, N-latuoyl-ghnemic acid dibpryl ataide, N-hturoyl-glutamic acid di4exyl amidt:, N-latu~oyl-glutamic acid dioetyl amide, N-larrrnyl-gluttuaic pCid didecyi amide, N-iaurpyl-gtutanric acid didoduyl amide, N-Isuroyl-glte:z~ic acid dioetradecy) amide, N-lauroyl-glutarnie acid dihexadecyl amide, N-lattcnyl-gltrtamic acid disteatyl annide, N-stearoyl-gJtttantic acid dibutyl amide, N-stearoyl-glutamic acid dihexyl amide, N-stearoyl-gluttsmic acid dl>tep<yl notide, N-stearoyl-glutatnic acid dioctyl amide. N~
staaroyl-g6~miC arid didexyi amide, N-stearoyl.glutamic acid didod~yl amide, N.s<eaeoyl-glutamic acid d»ttdecyi amide N~~soditoyl-ghrtamic acid dihdcadecyl amide, and N-stearoybgluttrmic acid di~ryl atoids. Prafa't~ed atz n-lauroyl-glutamic acid dibutyl amide, erst~estyl-glutamic acid dihexy) amide, erred cnatbittations thereof.
'1110 select alkyl ~pide gellt~tta are preferably sytnltesized by direct amiduion of the coenspondireg di- or tri-basic organic acid with the appropriate alkyl amine under suitable reaction temperaterne~r, followed by removal of excess amine from the resulting mixture corrtaiaing the aikylaced atttide gcllactti.
The select alkyl amide gallants tray also be synthesized by esoerif>cuion of the corr~oetding di-or tri-basic organic acid with methanol using a borat trilluoride catolyst followed by removal of the excess methanol and cablyst 'The resstlti:rg trimethyl ester is then amidated using the appropriate _ 14_ alkylamine followed by removal of excess amine. The resulting alkyl amides for use in the composition should be non-polymeric.
Suitable fatty acid gellants include, but are not limited to, hydroxy fatty acids including alpha-hydroxy acids and 12-hydroxystearic acid and derivatives thereof (including amides and esters thereof), fatty acids having from about 10 to about 40 carbon atoms (e.g., behenic acid, eurcic acid, stearic acid) and related gellants, some preferred examples of which are disclosed in U.S.
Patent 5,429,816, issued to Hofrichter et al. on July 4, 1995; and U.S. Patem 5,552,336, issued to Motley on September 3, 1996, ' Preferred are 12-hydroxystearic acid and derivatives thereof.
These solid non-polymeric gellants described herein are especially effective when used in combination with select anhydrous carriers such as volatile silicones, especially volatile cyciomethicone.
These gellants are most preferably used in combination with a liquid carrier comprising a volatile silicone and a non-volatile silicone (e.g., non-volatile dimethicones or other organofunctional siloxanes well known in the art) and/or a non-volatile organic carrier.
Preferred enantomeric eellants Preferred solid 'non-polymeric gellants for use herein include those enantomeric compounds or materials containing at least one asymmetric (chiral) carbon atom. Non-limiting examples of these preferred enantomeric gellants include 12-hydroxystearic acid, other hydroxy acids such as alpha hydroxy acids, cholesterols, lanolin, and derivatives thereof.
It has been found that these preferred enantomeric gellants, when used in the anhydrous antiperspirant gel-solid stick compositions herein, provide the composition with the requisite product hardness, visible residue index values and Theological properties (G' / G").
It is believed that these enantomeric gellants are especially effective in forming one-dimensional elongated particles in the form of filaments, fibrils or strings which are intertwined or twisted to form a stable, three-dimensional crystalline matrix in the gel-solid composition. Those elongated particles have an aspect ratio of greater than about 2.
preferably greater than about G. It is believed that these gellants form elongated crystalline particles that result in a stable crystalline matrix that, in part because of the small size and elongated morphology of these particles, cause less scattering of light when applied to the skin in the antiperspirant composition, which then results in low visible residue after such application.
_Preferred particle moroholoev The solid non-polymeric gellants for use herein preferably include those crystalline gellants that inherently form, or can be formulated or otherwise made to form, elongated crystalline particles having an aspect ratio greater than about 2, preferably greater than about 6. These elongated crystals preferably have an average particle size as measured along a minor axis of the elongated crystal of less than I pm, more preferably less than about 0.4 Vim, even more preferably less than about 0.2 ~zm, most preferably from about 0.2 pm to about 0.002 um.

JUN-1'T-1'~'~'~ d~~34 rx.U h='F-ITENf 1 fC. L1NN 513 627 b333 t-'.14~3i1~'T
w0 9g!!?939 PC'rWSSn~

The antiperspirant compositions containing these preferred elongated crystals can be prepared by methods described herein, or by methods or techniques otherwise known in the formulation art for establishing gel matrices comprising these preferred elongated crystalline particles.
T'he "aspect ratio" as used herein to define preferred embodiments of the compositions herein can be determined by measuring or othet'wix determining the ratio of the length of the major axis of the crystalline particles to the length of the minor axis of the crystalline particles. This length ratio of the major to minor axis is characterized as the aspect ratio referred to herein.
The aspect ratio can be detet'mined by rnnventional or otherwise known light or electron microscopy methods. wherein the crystalline particles are measured for major and minor axis dimensions, or are otherwise observed by such methods to clearly have an apparent elongated crystalline structure with an aspect ratio substantially greater than about 2, preferably greater than about 6.
1t has been fwutd that these Crystalline gallants having the xlect aspect ratios dei7tted herein.
provide the antiperspirant compositions with a three-dimensional crysmlline structure that can provide the composition with tow residue pafattrlactce, and a preferred elastic oo viscous moduli ratio and product hardness for gel-solid embodiments of the amdpeapiram composition. It is believed that this crystalline morphology is especially e~cAve in pravidipg s crystAlline matrix within the composition that provides fos a strong interlocking gel-solid matrix network, but which also comprises crystalline particles that are sufficiently small in size so as to contn'bute minimally to visible residue when applied topically to the skin.
It ha. also been found that are ptefemd aystallitlt malt of the composition results in an overall melt profile that ~tttributd to low residue performance- ?has prrfeered malt profile refers to the tempettwdttie at which the aatipenpiraat cocupositiop begips to melt, and the ta»petariue range within which the compositiop is completely melL~ except far any dispe~d antiperspirant patticulates or ottttr high melting point componatb. The temperaucre at which the composition begins to melt iS determined by measuring a Dil~ttid Scanning Caloririteter (pSC) onset tempcatu~e. The temperature range withid which the composition is completely melted is dc:ermined by no additional heat infusion.
Prefernad embodiments of the compositions haeia have a DSC onset temperature of from about 25°C to about li3°C. prcfersbly Snm about Z7°C to about 65°C, more prcfaabty front about 30°C to about 60°C.
even more preferably from about 35°C to about 50°C. Thex preferred compositions having the select melt pro&!e provide improved cosmetics of aesthaict when applied topically to the skirt. and especially provide reduced feeling of wa:ttess, stichacess or ptoduct soRness during and immediately attar applic>tdort. The select taelt pt~ofik also helps to funha reduce the visible residue index of the cwnposition, thus furtlcer improving lower residue performance.
LYaeleatine aeeect The antiperspirant compositions of the preSecct inventioct prefetabiy coettprise s nucleating agent for minieaizing gellaat particle size, and/or for obtaining the preferred gallant particle morphology JUN-1?-16~'~ vJ2~34 Ni4U PRTEN~ i i~ C:INN 51~ 6~7 6333 r~.1d4~1~'r WU 98f17939 PCT1U89T>7.42511 described herein. These compositions are also preferably prepared in accordance with the following method involving the use of a nucleating agent.
The nucleating agent for ux in the antiperspirant composition of the present invention must be a solid material under ambient conditions and have a etteiting point near the melting point of the selected gallant, a solubility in the anhydrous liquid carrier that is less than the solubility of the solid non-poiymeric gallant in the anhydrous liquid carrier, or be in the form of an inorganic, insoluble, micronized particulate. The nucleating agent typically crystallizes, gels, solidifies (except when the nucleating agent is a insoluble, mierottized inorganic materials or acts as a nucleus (e_g.
promote formation of stnali gallant nuclei) for the solid non-polymeric gallant just prior to, just about, or at the same time of erysrailization of the gallant in the anhydrous liquid carrier. The molar ratio of the solid non-polymeric gallant to the nucleating agent must be from about t0:1 to about 1000:1, preferably from about 10:1 to about 100:1.
Thex select motet ratios will typically Insult in eucleating agent coneentrtttions of from about 0.00019~f. to about S%, preferably from about 0.0019, to about 2°~6, more preferably from about 0.01% to about 1%.
The nucleating agent preferably has a melting point of from about 40°C
below to about 200°C above.
more preferably from about 20°C below to about 100°C above the melting point of the sekcoed gallant.
The antiperspirant compositiaos containing the nucleating agent are preferably prepared by I) combining the gallant, anhydrous liquid eaeriK and a nuekamg agent as described benein. 2) heating components or the corpblnation of componenn to form a solution or other hottrogeneous liquid or liquid dispersion, and 3) solidify the combirtariott of components by cooling the combiaatioo to below the solidification point of the solid non-polymeric gallant to form the antiperspirant composition of the present invention.
'nte nucleating ~ for tale it the antrpersgirant compositions include faay alcohols, esters of fatty alcohols, ethoxylated fatty alco6oLs, esters or ethers of ferry acids iaehsding waxes, acrd trigiyeaides, silica. titanium dioxide, solid polyol carboxylic skid poiyesucs, and momsr~es dtaeof.
5uimble fatty aleobob for ux as nuckrahtg agents inchrde mono6ydric alcohols, eshoxylated fatty alao6ots, and fatty alex6ol esters. Specifx examples of commercially availtlbie fatty alcohol nucl~g t~ inthrdc, but are not limited o0. Unilin 550, Unilia 700, Uuilin 425, Unilin 400, Unilin 350, and Urtilip 325, all supplied by F~etr~oiite. Suitable ethoxylated fatty akohob include, but are not limited, Unithox 323, Unitifox 400, mud Utti<box 430, Unithox 450, Unitbox 5Z0, Unithox 550, Uaitbox 720, Uttidtttx 750, all of which are available from Petrplite. Non-limiting examples of suitable esters of fatty alcodols include tri-iso~atyl citrate, ethykaegtycol di-l2-hydro~xysoa~te, tristearylcitraoe, straryi octanoace, stat~.l hepeenoate, trilauryicitrace.
Sui4ble faay acid esters for ux as nucleating agents include ester waxes, monogtyca>des, diglycerides, trigiycerides and mocttues thereof. Prefarad are the gly~ide alas. Non-limiting examples of suitable ester waxes iaclttdt stearyl stearate, sttaryl beheaam, palrrtityl stearate, stsaryl octytdodecaetol, cetyl esters, cttearyl b, txhenyl behenate, etbylcne glycol disteerate, ethylene JUN-1?-1999 02:35 P&G PATENT ITC CINN 513 627 6333 P.105i127 wo Qsnr~39 lPrrrcxs~-rriazso -».
glycol dipalmitate, and beeswax. Examples of commercial ester waxes include Kester waxes from Koster Keunen, Crodamol SS from Croda and Demslcare SPS from Rhone Foulrnc.
Preferred triglyceride nucleating agents include, but are not limited to, ttistearin. tribehenate, behenyl palmityl behenyi triglyceride. P~itYl FYI paimityl triglyceride, hydrogenated vegetable oil, hydrogenated nape seed oil, castor wax, fish oils, tripalmiten, Syncrowax HRC
and Syncrowax HGL-C
{Syncrowax is available tmm Croda, Ine.). Other suitable glycerides include, but are not limited to, glyceryl stearate atld glyceryi distearate.
Preferably the nucleating agent is a solid polyol carboxylic acid polyester.
Suitable solid polyol carboxylic acid polyesters include those which are potyol esters or polyesters wherein the carboxylic acid ester groups of the polyester comprise a combination of.- (a) long chant unsautrated carboxylic acid moieties or a mixture of long chain unsattuxted carboxylic acid moitties and short chain saturated carboxylic acid moieties, and (b) long cheat saturated carboxylic acid moieties, the ratio of (a) to (b) being firm about I to I S to about 2 to I . At least about 15~r6, preferably ac least about 309~G, morn preferably at least about SO'f6 and most pr,efa~ably at least about 60'36 by weight of the total carboxylic acid moieties of the polyestd~s are CZO or higher saturate car6mtylic acid moieties. The long chain unsaturated carboxylic acid moieties arc typically s~aight chain and contain at least about lZ, preferably about 12 to about 26, mots prefitrably shout 18 to about 22 cau~bott atoms.
The most preferred unsaturated carboxylic acids am the C 18 mono andlor di uasamrmoed carboxylic acids. The short chain sattnaced carboxylic scida ant typically u>ibtmnched and comain about Z to about 12, preferably about 6 to about 12, and most preferably about 8 to about 12 carbon anorns. The long chain saturated carboxylic acids are typicslly straight chalet and contain at least about 20, preferably about ZO to about 26, and most P~~IY Z2 ca<boet atoms. The molar ratio of Group (a) carboxylic acid rtroieties to Group (b) carboxylic acid moieties in the polyester molecule is from about 1:15 to about 2: I, preferably about I :7 to about 5:3, and more preferably about 1:7 0o about 3:5. The average degree of esterificetion of these carboxylic acid esters is such that at let~t about 2 of the hydroxyl groups of the polyol are esteriSed. tn the case ol< sucrose poiyesora frotp about 7 to about B of the hydroxyl groups of the poiyol ant preferably ~- TYp~Y. substantisily a11, e.g., at hxst about 859t~ P~ne6erablY ac least about 959 of the hydroxyl groups of the pollyol are estsri5ed, Preferred polyols of the solid polyol carboxylic acid esoers are sugars, including monosacsha~ and disttccltarides stud trisacchatidss, containing from about 4 to about t 1 hydroxyl groups. Most prefermd sugars arc those which co<t:;ia about 4 op about 8, more preferably about 6 to abaft 8 hydroocyl groups. Examples of those contaiaiag four hydraacyl groups are tits moaosaccharides xY~. ~inoss, and cotubinations thtroef. Suitable five hydroxyl BmuP-containing polyols are ttte monosaccbarides galaL-tose, frtretos~ maonose, glucose, attd combimhops theroof. Examples of disaccharide poiyola which can be usod include maloose, lactose, sucrose, and cambinatians thereof, all of which cotttara eight hydroxyl groups. The przfen~d polyol is sucrose JUN-17-1999 x2:35 P8G Pf~TENT ITC CINN 513 627 6333 P.le6i127 WO 9~T939 YCTIUS97f14~0 _ !8.
Examples of long chain unsaturated carboxylic acid moieties include, but are not limited to, Jaurolcate, myristoleate, palmitoleate, oleate, elaidate, erucate, linoteate, linolenate, arachidonate, eicosapentaentoate. and docosahexaenoate. For oxidative stability, the mono-anti diunsatutated fatty acid moietits are preferred.
Examples of suitable short chant 58turatsd carboxylic acid moieties include, but are not Iimrced to. acetate. caproate, caprylate, captate, and laurate.
Examples of suitable long chant saturattd carboxylic acid moieties include, but arc not limited to, arachidate, bdtettete, lignocerate, and cerotate.
Of course, the long chain unsaturated carboxylic acid moieties can be used singly or in mixtures with each other or in mixtures with the short chant saturated carboxyiiC acid moieties. in all proportions.
Likewise, the long chain saturated carboxylic acid moietits can be used in combination with each other in all pmpordons. Mixed carboxylic acid moieties from source oils which contain subsdattial amounts of the desired unsaturated or sanuated acids can be used as the acid moieties to prepare compounds for use as nucleating agents herein. Tha raixed carboxylic acids from the oils should contain at least about 30x.
preferably at least about 50°/,, and most prefeeably at least about 8M~G of the desired unsaturated or saturated acids. For exarapIe, rapdeed oil fatty acids or soybean oil fatty acids can be used instead of pure C12-C16 unsadtrated ferry acids. Hardened, i.s. hydrogenated, high crticiu rapeseed oil fatty acids can be used instead of pure C20.C26 sansra~oed acids, Preferably the C20 and higher acids. or their derivatives, e.g. methyl ar other low alkyl ~, are concentre<ed foe example by distillation. The fatty acids Liorn paint kernel oil o~ Coconut oil can be used as a sout~ct of C8 to C l2 acids, Art example of the use of source oils to make solid poiyol polyesters for use in the antipempirant compositions herein is the preparation of solid suero~se polye~. employing the fatty acids of high okio sunflower oil and substantially completally lbydrogeoated high erucic rapeseard nit. When sttaose ~s substantially completely esteritied with a 1:3 by weight blend of the methyl esters of the fatty acids of these two oils, the resulting sucraae pohy~ will htwe a molar ratio of unsautrated C 18 acid radicals to C20 and higher saturated acid rascals of about 1:1 and about Z8.6 weight percent of the total fatty acids in the polyester will be c2a ~ncy a~;ds.
The ltigber the ptoportiooa of the desitrod utcsantcated acrd saturated acids in the carboxylic acid stocks used itt making the solid pofyoi polyester, the more efficient the ester will be in ice ability to funtaon as a nucll~g agept.
1=xatnples of solid polyol carboxylic acid polyester nuci~rtg agents for ,use in the antiparsp;rat,c composi4on herein include, but are trot limited tv. tile octaester of ratf'mose.in which the esceriJrying carboxylic acid moieties ate linokate and behenate in a 1:3 molar ratio; the hepof maltase wherein ~C a~~8 ~~oxYlic acid moieties arc sunflower send oil faayr acids and ligaocerace in a 3:4 molar ~o: ~e octaester of sucrose wherein the esterifying carboxylic acid moieties are oleate and behenate in a 2:6 molar ratio; and the oaaester of suaox wherein the estesfying carboxylic acid rrtoieries are launte.

linoleate and behenate in a 1:3:4 molar ratio. A preferred material is sucrose polyester in which the degree of esterification is 7-8, and in which the fatty acid moieties are C18 mono- and/or di-unsaturated and behenic, in a molar ratio of unsaturates:behenic of 1:7 to 3:5. A
particularly preferred polyol ester nucleating agent is the octaester of sucrose in which there are about 7 behenic fatty acid moieties and about 1 oleic moiety in the molecule.
The solid carboxylic acid polyesters herein can 'be made according to prior art known methods for preparing polyesters of polyols. See, for example U.S. Patent No.
5,306,516, to Letton et al., issued April 26, 1994; U.S. Patent No. 5,306,515, to Letton et al., issued April 26, 1994; U.S. Patent No.
5,305,514, to Letton et al., issued April 26, 1994; U.S. Patent No. 4,797,300, to Jandacek et al., issued January 10, 1989; U.S. Patent No. 3,963,699, to Rizzi et al., issued June 15, 1976; U.S. Patent No.
4,518,772, to Volpenhein, issued May 21, 1985; and U.S. Patent No. 4,517,360, to Volpenhein, issued May 21, 1985.
Suitable inorganic, micronized, non-solubilized nucleating agents for use in the antiperspirant compositions include materials such as silica, titanium dioxide and combinations thereof. These materials contain submicron particles (average particle size generally less than about 1 pm) which aid in the production of small gellant crystals or particles.
Preferred nucleating agents, and preferred concentrations of the nucleating agents, for use in the antiperspirant compositions include C18 succinic acid (0.1%), 1,9-nonanedioc acid (0.1%), Teflon (0.1%), silica (0.1%), polysiloxane copolymer (2%), sucrose octabehenate (0.5%, 0.75%, 1.0%), Unilin 350 (0.1%), Unilin 550 (0.1%), Unilin 700 (0.1%) , trihydroxystearin (0.1%) and combinations thereof.
Anhydrous Li4uid Carrier The anhydrous antiperspirant gel-solid stick compositions of the present invention comprise an anhydrous liquid carrier for the crystalline gellant described hereinbefore.
The anhydrous liquid carrier is liquid under ambient conditions, and preferably has a low viscosity to provide for improved spreading on the skin.
Concentrations of the anhydrous liquid carrier in the gel-solid stick composition will vary primarily with the typo and amount of the anhydrous liquid carrier, the solid non-polymeric gellant, and the solubility of the solid non-polymeric gellant in the anhydrous liquid carrier. Preferred concentrations of the anhydrous liquid carrier arc from about 10% to about 80%, preferably from about 30% to about 70%, more preferably from about 45% to about 70%, by weight of the composition.
The anhydrous liquid carrier comprises one or more liquid carriers suitable for topical application to human skin. These liquid carriers may be organic, silicone-containing or fluorine-containing, volatile or non-volatile, polar or non-polar, provided that the liquid carrier fortes a solution or other homogenous liquid or liquid dispersion with the selected non-polymeric gellant at the selected gellant concentration at a temperature of from about 28°C to about 250°C, preferably from about 28°C to about 100°C, preferably from about 28°C to about 78°C.

.~.0 -The anhydrous liquid carrier has a solubility parameter of from about 3 to about 13 (caU'cm3)o.:.
preferably from about 5 to about 11 (caUcm3)o.5, more preferably from about 5 to about 9 (caUcm3)o.5.
Solubility parameters for the liquid carriers or other materials, and means for determining such parameters, are well known in the chemical arts. A description of solubility parameters and means for determining them are described 'by C.D. Vaughan, "Solubility Effects in Product, Package, Penetration and Preservation" 103 Cosmetics and Toiletries 47-69, October 1988; and C. D.
Vaughan, "Using Solubility Parameters in Cosmetics Formulation", 36 J. Soc. Cosmetic Chemists 319-333, September/October, 1988, The anhydrous liquid carrier preferably comprises a modified or organofunctional silicone carrier selected from the group consisting of polyalkylsiloxanes, polyalkyarylsiloxanes, polyestersiloxanes, polyethersiloxane copolymers, polyfluorosiloxanes, polyaminosiloxanes, and combinations thereof. These modified silicone carriers must be liquid under ambient conditions, and have a viscosity of less than about 100,000 centistokes, preferably less than about 500 centistokes, more preferably from about 1 centistoke to about 50 centistokes, and even more preferably from about 1 centistoke to about 20 centistokes. These modified silicone carriers are generally known in the chemical arts, some examples of which are described in 1 Cosmetics, Science and Technology 27-104 (M. Balsam and E. Sagarin ed. 1972); U.S. Patent 4,202,879, issued to Shelton on May 13, 1980; U.S. Patent 5,069,897, issued to Orr on December 3, 1991:
The modified silicone carriers suitable for use in the antiperspirant gel-solid stick compositions include, but are not limited to, compounds or materials as defined hereinabove and which are generally characterized as follows: silicone polyethers or silicone glycols (such as dimethicone copolyol); silicone alkyl-linked polyethers (such as Goldschmidt EM-90 or EM-97); siloxane surfactants of a pendant/rake/comb configuration, silicone surfactants of a trisiloxane configuration, and silicone surfactants of an ABA/alpha-omega block copolymers (such as polyoxyalkylenes, polyoxyethylene or ethoxylated, polyoxyethylenelpolyoxypropylene or ethoxylated/propoxylated);
aromatic substituted silicone emollients (such as phenyl, alpha-methyl styryl, sryryi, methyiphenyl, alkylphenyl); silicone copolymers with other functional groups include: hydrogen, alkyl, methyl, amino, trifluoropropyl, vinyl, alkoxy, arylalkyl, aryl, phenyl, styryl, polyethers, esters, carboxylics;
alkytmethyl siloxanes or silicone waxes (such as hexyl, octyl, lauryl, ceryl, stearyl); nonionic functional siloxane copolymers with terminal groups being silanol or trimethylsiloxy; nonionic functional siloxanes with backbone groups being trisiloxane or methicone linked; nonionic silicone surfactants;
tetraethoxysilane; tetramethoxysitane;
hexamethoxysilicone; oxmethoxytrisiloxane; silicone emulsifiers; silicone or siloxane resins, alkyl silicone resins, polyoxyalkylene silicone resins; MQ Resins such as Shiseido/Shin-etsu, e.g. Japanese Patent Publication JP86143760 or from Walker Chem. 6MBH (described in EP722970); alkoxysiloxanes;
alkoxysilanes; methicones (polymethylalkyisiloxanes); and combinations thereof.

JUN-17-1999 82~36 P&G Pt~TENT ITC C:INN 513 627 6333 P.109i127 WO 9$127939 PCTIUS97IZ42S0 -zl -Nonlimiting examples of suitable modified silicone carriers for use in the antiperspirant gel-solid stick compositions herein include the following modified silicones available from Dow Corning: OC-556 Cosmetic Gcade Ftuid (phenyl trimethicone); DC-704 Diffusion Pump Fluid (Tetrameihyl-Tetraphenyl-Trisiloxane); !3C-705 Diffusion Pump Fluid; DC-1784 Emulsion; DC-AF Emulsion;

Emulsion: l7C-593 Fluid (Dimethieone [and] Trimerhylsiloxysilieate); DC-32250 Fluid (Cyclomethicone [and] Dimethiconc Copotyol); pC-!90 Fluid (Dimethicone Copolyol); DC-193 Fluid (Dimethicone Copolyol); DC-1401 (Cyclomethicone [and] Dimethiconol); DC-5200 Fluid (Laurylmethicone Copalyol);
DC-6603 Polymer Powder, DC-5640 Powder; DC-Q2-5220 (bimethicone Copolyoi); DC

(Dimethicone Copolyol); DC-2501 Cosmetic Wax (Dimethicone Copolyol); DC-2502 FIui4 (Cetyl Dimethicone); DC~2503 Wax (Stcaryl Dimethiconc); DC-1731 Volatile Fluid (Caproyl Trimethicvne);
DC-580 Wax (Steatbxytsimethylsilane [aad] Stearyl AICOhoI); OC-1~3563 (Dimetbiconal); DC-X2-1286 (Dimethiconol); DC-XZ-1146A (Cylcomethicotte (and) Dimethiconol); DC-8820 Fluid (Amino functionalized); DC Q5-0i58A wax (sttaroxytrimetbylsilane); DC-Q2-8220 {TrimethylsiiylamodimethiGOne); DC-7224 (Trimethyisilyiacttodimethicone); DC-XZ-1318 Fluid (Cyclomethicone (and] Vinyldimedticone); DC-QFI-3i93A fluid (Trimethylsiloxysilicate); an~i combinatiats thertof.
Other ponlimitarg examples of sttiiable modified siiicotle carriers for use in the antiperspirant gel-solid stick compositions herri4 include the folknving modified silicones available from General Electric: GE SF-1023 (Dtmethyl-Dip6eayl-Siloxane); GE CF-t 142 (Mathylphenyl Siloxane Fluid); GE
SF-1153 (Dimethyl-biphenyl-Siloxme); GE SF-I265 (Diphettyl-Dime:byl-SiIoxane);
GE SF-1328; GE
SF-1 i88 (Dirrtethicone copolyol): GE SF-I 188A (Silicone polyether copolymer); GE SF-1288 (silicone polyetber copolymer, dimethyl-methyl 3-hydtoocypcnpYt etboxylated); GE SF-1318 (Methylester Siloxatrer GE SF-1328 (silicone s~fa~at, dimetbyl-methyl 3-hydsoxypropyl ethoxylated.
pr»poxylated); GE SF-1550 (metbylpheayl siloxatle, hexamethyl-3-phenyl-3-[[trimethybllyl]oxy]trisitaxaoer GE SF-1632 (silicone wax); GE SSrt267 (Dimethieone (atrd]
Trimethylsiloxysilicatek and combinations thmrof.
Other tronli~titierg acamples of suitable modified silicone carriers for ux in dse antiperspirant get-solid stick o4mpo'itions herrin inchrde the following modified siiiavailable; irons Goktxbmidr:
Abil EM~90 (silicoae emubifta~k Abii EM-97 (polyedter siloxaoek Abil Wax 9810 (silicone wax or 024_ 28 raetiticone); Abil Wax 243d (Stearoxy Donctlriooae); Abil Wax 9800D
(Stearyl Dime:lticorac);
Tegomer H-Si 2t 1 l, H-Si 231 i, A-Si 2120, A-Si 2320. C~Si 2141, C-Si Z3al, E-Si 2130, E-Si Z330, V-Si 2150, V-Si 2550, H-$i 6420, H-Si 6440, H-Si 6464 (Alpha-0rttega Ditnetlticone Copolymers): and combia~ions thetmof. .
Other nonlimiting examples of suitable modified silicone ca<riers for use in the ar>:ipetspiraot gel-solid stick compositions herein include the following: Masil 756 from PPG
Industries (Teaabutoxypropyl Trisikxaane); bis-pbenylbexametbicone (available as Siibiorre Oils 70633 V30 from J~JN-17-1999 02:36 P8.G PATENT ITC CINN 513 627 6333 P.110i127 WO 98J2'r939 PCT/US99 Rhone-Poulenc); Silbione Oils 70646 (dimeehicone copolyols from Rhone-Poutenc); Silicone L-711, L-720. L-72i and L722 (dimethicone copolyols froth Union Carbide): Silicone L-7000, L-7001, L-7002, L-7004, L-7500, L-7600, L-7602, L-7604, L-7605, and L-76I0 (dimethicone capolyols from Union Carbide); Unisi! SF-R (dimethiconol from UPI); Silicate Cluster from Olin (Tris[tributoxysiloxy]taeahylsilatte): silicone copolymer F-754 (dimethicone copoly from SWS Silicones);
and combitsations thtteof.
The anhydrous liquid carrier preferably comprises a volatile silicone carrier.
These volatile silicone carriers may be cyclic, linear or branched chain silicones havitf8 the requisite volatility defined herein. Non-limiting examples of suitable volatile silicones are described in Todd eK al., "Volatile Silicone Fluids for Costtfdita", Cosmetics and Toiletries, 91:27-32 (1976), which descriptions ate incorporate hete~ by reference. Preferred among these volatile silicones are the cyclic silicones having from about 3 to about 7, more preferably from about 4 to about 5, silicon atoms. Most preferably are those which rnnfornl to the foratuls Si n whereizt n is from about 3 to about ?, przferably fi~om about 4 to about 5, most preferably 5. Theca volatile cyclic silicones gettes~ally have a viscosity valor: of less than about 10 cer~oites. All viscosity values described herein are measured or detetmitted usidec ambiestt conditions, artless otherwise specified.
Suitable volatile: silicones for use herein include, but are not lintiLod to.
Cyoiomethicone D-5 (commercially available from G. E. Siliexxras); Dow Corning 344, and Dow Corning 3d5 (cvcnatercially available from Dow Cotnotg Corp.); GE 7207, GE 7158 sad Silicone Ftuids SF-1202 and SF-1173 (available from Genaxl Ele~ic Co.~ SWS-03314, SWS-03400. F 7.Z2, F-223, F-250, F-25l (available from SWS Silicones Coop.); Volaaile Silicones 7I58, 7207, 7349 (available front Union Carbide); Masil SF-Y ( svailabte from Maurx and combinations drereo~
The aa6yeh~ous liquid tamer may also comprise s noe..volatile silicone carrier tsthet than or in addition to the taetdified siliextne cartiers described hareirthefore_ These notr-volatile silicone carriers are pttferpbty iitJar silicones which include. but are not limited to, those wbicb cortforat to eithu of the formulas:
CHs H CH3 C~-i ~ S~ i r-CHs CH3~-- ii-Q ii-O Il-.CH3 ~t ~3 ~ CH3 CH3 CH3 ~ or n wherein n is greater than or equal to 1. These linear silicone materials will generally have viscosity values of up to about 100,000 centistoke, preferably less than about 500 centistoke, more preferably from about 1 centistoke to about 200 centistoke, even more preferably from about I
centistoke to about 50 centistoke, as measured under ambient conditions. Examples of non-volatile, linear silicones suitable for use in the antiperspirant compositions include, but are not limited to, Dow Corning 200, hexamethyldisiloxane, Rhodorsil Oils 70047 available from Rhone-Poulenc, Masil SF Fluid available from Mazer, Dow Coming 225, Dow Corning 1732, Dow Corning 5732, Dow Corning 5750 (available from Dow Coming Corp.); SF-96, SF-1066 and SF18(350) Silicone Fluids (available from G.E.
Silicones); Velvasil and Viscasil (available from General Electric Co.); and Silicone L-45, Silicone L530, Silicone L-531 (available from Union Carbide), and Siloxane F-221 and Silicone Fluid SWS-101 (available from SWS Silicones).
The anhydrous liquid carrier may further comprise, but is preferably substantially frtc of, organic, water-immiscibie, polar liquid carriers or solvents. It has been found that the antiperspirant and deodorant efficacy of the gel-solid stick compositions are improved by minimizing or eliminating the amount of polar, organic, water-immiscible, liquid carriers or solvents in the composition. In this context, the term "substantially free" means that the gel-solid stick compositions preferably contain less than 7%, more preferably less than about 3%, even more prcferabiy zero percent, by weight of an organic, water-immiscible, polar liquid carrier or solvent. These polar solvents are liquid under ambient conditions and include mono and polyhydric alcohols, fatty acids, esters of mono and dibasic carboxylic acids with mono and polyhydric alcohols, poiyoxyethylenes, polyoxypropylenes, polyalkoxylates ethers of alcohols, and combinations thereof, provided that such solvents are also water-immiscible liquids under ambient conditions. Examples of some anhydrous liquid, water-immiscible, polar organic liquid carriers or solvents are described in Cosmetics, Science, and Technology, Vol. 1, 27-104, edited by Balsam and Sagarin (1972); U.S. Patent 4,202,879 issued to Shelton on May 13, 1980; and U.S. Patent 4,816,261 issued to Luebbe et al. on March 28, 1989, The anhydrous liquid carrier may comprise anhydrous, water-miscible, polar organic liquid carriers or solvents, examples of which include short chain alcohols such as ethanol. These and other polar organic carriers or solvents can be used as co-solvents for the solid non-polymeric gellant component of the antiperspirant gel-solid stick compositions herein. Non-limiting examples of polar co-solvenu suitable for use herein are described in U.S. Patent 5,429,816. Other suitable polar co-solvents include those described hereinabove, which are preferably water-immiscible organic solvents, and other co-solvents such as phthalate co-solvents, benzoate co-solvents, cinnamate esters, secondary alcohols, benryl acetate, phenyl alkane and combinations thereof.
The anhydrous liquid carrier may comprise other non-polar carriers such as mineral oil, petrolatum, isohexadecane, isododecane, various hydrocarbon oils such as the lsopar or Norpar series available from Exxon Corp. or Permethyl series available from Persperse, and any other polar or non-polar, water-miscible, organic carrier liquid or solvent known or otherwise safe and effective For topical application to human skin.
The anhydrous liquid carrier may also comprise fluorochemicals such as fluarosurfactants, fluorotelemers, and perfluoropolyethers, some examples of which are described in Cosmetics &
Toiletries, Using Fluorinated Compounds in Topical Preparations, Vol. 111, pages 47-6?', (Oct. 1996) which description is incorporated herein by reference. More specific examples of such liquid carriers include, but are not limited to, perfluoropolymethyl isopropyl ethers, perfluoropolypropylethers, acrylamide fluorinated telomer, fluorinated amide surfactants, perfluorinated thiol surfactants. Other more specific examples include, but are not limited to, the polyperfluoroisopropyl ethers available from Dupont Performance Chemicals under the trade name Fluortress ~ PFPE oils, and the series fluorosurfactants from Dupont Performance Chemicals under the trade name Zonyl ~ Fluorosurfactants.
Optional Components The antiperspirant compositions of the present invention may further comprise one or more optional components which may modify the physical, chemical or aesthetic characteristics of the compositions or serve as additional "active" components when deposited on the skin. The compositions may also further comprise optional inert ingredients. Many such optional materials are known in the antiperspirant art and may be used in the antiperspirant compositions herein, provided that such optional materials are compatible with the essential materials described herein, or do not otherwise unduly impair product performance.
Non-limiting examples of optional materials include active components such as bacteriostats and fungiostats, and "non-active" components such as colorants, perfumes, emulsifiers, chelants, distributing agents, preservatives, residue masking agents, process aides such as viscosity modifiers, and wash-off aids. Examples of such optional materials are described in U.S. Patent 4,049,792, Elsnau, issued September 20, 1977; Canadian Patent 1,164,347, Heckmeyer et al., issued March 27, 1984: U.S. Patent 5,019,375, Tanner et al., issued May 28. 1991; and U.S. Patent 5,429,816, Hofrichter et al., issued July 4, 1995. .
The antiperspirant gel-solid stick compositions of the present invention can also be fottrtulated to comprise other dispersed solids or other materials in addition to or in place of the particulate antiperspirant active. Such other dispersed solids or other materials include any material known or otherwise suitable for topical application to human skin. The antiperspirant gel-solid stick compositions can also be formulated as gel-solid stick compositions which contain no antiperspirant or other active material, particulate or otherwise.
The antiperspirant compositions of the present invention can also be formulated as creams, lotions, soft-gels and similar other compositions comprising select nucleating agents, wherein the compositions have a product hardness of less than about 500 gram~force, preferably from about 20 JUN-1 r-lb'~~ d~ ~ ~ ~ ri~U rH i ~N i m m rvN ~m o~ r b.5.5.~ r . 11~~ m r wo 98nT939 ~crrus9~naaso -zs-gam~force to about 300 gram-force. It is understood, however that these softer compositions do not have the preferred theology profile as defined herein.
Method oP Maaatacture The antiperspirant ge!-solid stick compositions of the present invention may be prepared by any known or othetwvise effective technique, suitable for providing an antiperspirant gel-solid stick composition having the reqerisite crystalline matrix nerd other pralua characteristics described herein.
Such methods involve formulation of the essential components of the composition to form a gel-solid having the requisite elastic to viscous moduli ratio, product hardness, and visible residue index, wherein the crystalline matrix within the cotnpositioa comprises elongated non-polymeric gallant crystals having an aspect ratio of greater than about 2, preferably greater than about 6, and an average particle diameter that is minimized (preferably to less than about 1 Vim) through techniques dit~ to minimizing crystalline pazticlt size in a composition.
Crystalline particle size in the preferred embodiments of the prtxettt invention can be determined by teeluiqetes well known in the art, which includes light or ekcnmt microscopy of the composition, wherein the composition is formulated for analysis purposes without particulate araiperspirant active -or other solid patticulates. Without such reformuiacion, it is more diffcult to directly determine and distinguish srystallitte gallant particle size and mosphology froth the particle size and morphology contributed from other non-geilant petricutades. The r~foratulated composition is rhea evaluated by light or eletd~on microscopy or other similar method.
Techniques for prq>ating the atttiperspirattt gtsl-solid stick compositiotu of the present invention include those arethods suinbht for formulating compositions containing small geliant crystalline particles.
Suitable ttclmiques for minimizing Qysealline gallant particle sin include the use of nucleating agents, formulation wim select c:rriers or gallants or earrier/geliattt combinations, controlling rates of crystallimtiott iaehtd>ng ce<ttnolling formulation, controlling process flow rate. and processing tempaaatera, and other aaetbods desan~bed herein. A11 such methods should be applied to the formulation to or miaimia gelhutt crystal particle size, and/or to form the desired elongated crystalline pardclea, to tbus form the desired taysmUine matrix of the compoaition-Met~od of Use Ttte antiptxspiraM gel-solid stick compositions tray be applied topitxtlfy to the axilla or other area of the skin itt an atnotmt effaxive oo teeae or reduce pt~piratioet weoness and malodor. The composition is preferably applied in an amount ranging from about 0. i gram to about 20 grants, more preferably from about 0-1 gram to about l0 grams, even molt preferably from about 0.! gram to about I gram, to the desired area of the skin- the composititms are preferably applied to the axilla or other area of the skin, one or two times daily. preferably arise daily, to achieve effective antiperspirant and malodor control over an extended period.
MPLES

JUN-17-1999 e2~3B P&G PRTENT ITC CINN S13 627 6333 P.114i127 WO 9$I2?939 PGTIU997rZ4230 -z6-The following non-limiting examples illustrate specific embodiments of the antiperspirant gei-solid stick compositions of the present invention, including methods of manufacture and use. _ Each of the exemplified compositions are prepared by combining all of the listed components except the antiperspirant active and other materials such as perfumes. The combined components are heated to about 100°C with agitation to form a hot liquid, after which al! other materials are added to the heated liquid. The heated liquid is allowed to cool with agitation until just before the point of solidification, at which poitlt the cooled. liquid composition is filled into applicator packages and allowed to cool and solidify to the requisite product hardness.
Each of the exemplified compositions fort a crystalline gel mairnc containing crystalline particles having an aspect ratio of grtthan about 6, and an average crystalline gallant particle size of less than about ! pm. Each of the exemplified coetspositiorts also have a visible residue index of between about ! 1 and about 30 L-value, a product hardstess of between about 500 and 3.000 grant~force, and a G'/G" ratio of between about 0.1 and about 100. Each of the exemplified antiperspirant compositions are applied topically to the axilla area of the skin, in accordance with the methods of use described herein. and provide improved low residut performance, efficacy and aesthetics.
~rnooent , Exa mnieosber l~

I ~ II3 IV

Cyciomethicane D51 45.3 45.8I9.7 19.7 ~ylo~ 16.4 16.4-- --- - 44.3 46.3 12-Hydroxysteasic Acids8.0 8.0 B.0 7.0 020.40 alc~holss 0.5 - --. ..

Sucrose Poly~rb 1.0 I.0 l.0 -C20-40 p~-!0~ 1.25 1.25- --020-40 Parxth-40s _ L25 1.25- --Stearyl Alcohols 1.0 l.0 0.1 p.1 -- --AI 7r tri chlorohydt~ Z6.0 Z6.026.0 26.0 glycituteto Disodaunc EDTA t E 0.2 0.2 -- --Residue (L-vahre) 25.0 24.023.0 29.0 Hardness (gram-force) 100 1.2501250 990 Coarponent E samole Nureber V VI ~I,lr Vllt Cyclomethioone DSt 43.3 44.3 43.3 4Z.3 Octyldadecanot2 ! 6.3 16.5 16.5 16.5 12-Nydt~~cyAcids 8.0 9.4 10.0 11.0 JUN-1 I-1'~'~'~ d~ ~ ..iti N2SV Y-'f-1TEN 1 L I C~ 1. l NN 51 .5 b~'7 b.5.5.5 r' . 11» 1~ ~
wo 9a~z~9~ rcr~rsrrrl4~so 020-40 alcoholss 0.5 0.5 0.5 0.5 Sucrose Polyeserb ~ 1.0 I .0 I .0 1.0 020.40 Pareth-10~ 1.25 t.25 1.25 t.25 020-40 Parcttt-4ag 1.25 1 ?5 1.25 I
AI Zr tri chlorohydrex 26.0 26.0 z6.0 .2s glycinatetv 0.2 0.2 0.2 26.0 Disodium EDTA ~ t 0,2 Residue (L-value) 23.0 Z7.0 27.s 28.0 Hardness(gra4y-force) 1170 1450 16b0 1910 Cog,ponenr ~~mole ber Num Cyclo~ssthiaooe Dst 49 9 4 . 4 9.7 49.?
~lo~ .7 14.0 14.0 I d.0 14.0 12-Hydmxysrearic Aaid~

7.0 7.0 7.0 7.0 020-040 Alcoholss o.s o.s 0.s o.s a-~ -la' 1.2s I.zs l.zs t.2s c2o-4o rte,-',o$

I .2s I ~s 1.zs I
AI Zr tri chlorobydrac 26 ss gtyci>aatel0 0 . 26.0 26.0 Z6.0 Disodium F
DTA t 1 . O.Z 0.2 02 0.2 2-Stearylbutmtedipc AcidlZ

0.1 ..

1,9-Nonanedioc Acidt3 -- 0.!

Polytluorocsrboota - o. I
Silicxls -- -- -- o.l Residue (1.-vahu) Z9.0 30.0 29.0 27 Hardness (gzafa.g~) 1200 1200 , t 110 11 s0 C~o, F.xamok Number Cyclometdicon~ bs~

49.3 48.$ 49.03 45.3 14.0 14.0 14.0 16.5 1 Z-Hydroxysseeric Acids 7.0 7.0 7.0 $.99 c2'c'vctiolss os o.s o.s o.s 1.25 l .zs l .zs t Gzo-ao Paned,-4ot .~s l.zs 12s . t.2s i AI Zr tri chloro6ydtcx 2 .2s glyc~l0

6.0 Z6.0 26.0 26.0 DiaodiumEDTAtt 0.2 0.2 01 0.2 sPly~' o.s l.o oas o.l s . 2s.o aa.o X7.0 JUN-1 r-1~~~ J~ ~ ~t~ r~SV rH mN i m ~ mN X15 b~ r b,53~ r. 110 1G ~
w0 98nT939 i'cTnJS97n425o _zs.
Hardness (gram.force) 1480 I I50 1 I00 2700 Comnoaeat ~xamnle Number VII XV11I 7S~X

Cyclomethicone D5~ 49.7 49.7 49.7 Octyldodecanol2 14.0 14.0 I4.0 I2~Hydtoxysteactc Acid47.0 7.0 9.0 CZO-040 Alcoholss 0.5 0.5 0.5 020-40 Pareth-10~ 1.25 I.25 1.25 020-40 Pareth-40a 1 z5 1.25 1.25 A1 Zr tri chlorvhydrex 26.0 26.0 26.0 glycinate~~

Disodium EDTAII 0.2 0.2 Oz 020-040 AlcohoLsl6 0.1 - ...

020-C40Alcoholsi~ _ 0,1 _ 020-040 Alcohoisl= -- - 0.1 Residue (L-value) z8.5 29.0 29.0 H~dlless (gram-force) I ! 40 1~ 140 1050 Component Exampie Number ' Cyclomechicoae D51 49. 49.7 ~7

7 ~Ylo~ 14.0 14.0 14.0 l2.Hydroxystearic Acids7.0 7.0 7.0 CZO-040 Alcoholss 0.5 0.5 0.5 c2o-ao Parah_10~ 1.2.5 1.2s 1zs 1.Z5 1.25 1.25 A1 Zr tri chlorohydrex 26_0 26.0 26.0 glycinaLe Disodiuat EDTAi ~ 0.2 0.2 0.2 Trihydrmcysreilrioi9 0.1 - _ Scearyl Alcoiw~ _ _ 0.1 Cetearyl Alcohol .... _ 0.!

30.0 27.0 27.0 Ha~nar (gram-farce) 1000 990 990 Cl~mpapepy gxam ole t l~Iua~be XIII ~ 7~V ~1~I

Cyclomethicope DSi 45.3 45.$ 19.7 19.7 ~Y~~ 16.4 16.4 --P~'~3 . -- _ 44.3 43.3 N-leuroylglutamic acid 8.0 8.0 8.0 dibutyl amid=

12-Hydroxy~ic Acids .. _ $.0 020-40 alcoholss O.s - ..

Sucrose PotyGStetb I.0 l.0 1.0 c20-40 Pareeh-toy t.25 1.2s - _ 020-40 Pareth~0a 1 z5 125 - ...

Stearyl AlcohON - _ 1.0 1.0 a 0.1 0.1 - .-JVIVii iJJJ YJG'JV ~ OwV !-I-11GIYI W , v.aIVIV ~r.~ uGf OJ-u.~ ~ .ian iGn wo ~~39 >PCTrtJS9"rrztxso Ai Zr n~i chlorohydrrx glycinatela . 26.0 26.0 26.0 26.0 Disodiuaa EDTA ~ 1 0.2 0.2 -_ --Residue (L-value) 25.0 24.5 22.0 19.0 Hardness (gram-force) 1000 1000 1260 1500 Comoooant Eaer ~le ~ber Noa XXVII XXV1I1 C,~1XX

Cyclomethicone DSl 453 45.8 36.360.0 ~Ylp~ 16.4 16.4 16_4-2 dodececyl-N,N-dibutylsuccinamids~8.0 -. _ _.

N-isopropyl-l2hydroxytl~amidl~3- 8.0 -- -12-Hydraxys>xa>ic ACid~ - _- 16.08.0 020-40 alcoholss - 0.5 OS ..

Sucrose Polye~ 1.0 1.0 2.0 ~ 1.0 020-40 Paseet,.lOT 1.25 1.25 125 -C20-40 Paceth.40a 125 1.25 I.Z,S-0.1 0.1 0.1 -A1 Zr tri chlorohydsex z6.0 a6.0 26.026.0 glycinaasl0 ~

Disodiups ~TA~! 02 02 0.2 -Polyether siloat~e~

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S - Cabot l6 - P~uolife Unilis 350 17 - peb~vlile Unitio 330 ! s - Pea~oWr Unilio Tao 14 - M. CIKmInb - Witco JUIV-1 ! 1J~7 C1G' JO r6U rH I CI~I I J I L. L,11V1'1 J1J OG l OUJ,J I . ~iu~

WO 98127939 PCTI~759'7l~ZSO

a ~ . Ajinimoto 22 - Procrcr ~ Gamble 23 - Starlu Associates 2d _ ~t,idt EM-97

Claims (18)

What is claimed is:

1. An anhydrous antiperspirant gel-solid stick composition comprising:
(a) from 0.5% to 60% by weight of particulate antiperspirant active;
(b) from 1% to 15% by weight of a solid non-polymeric gellant;
(c) from 10% to 80% by weight of an anhydrous liquid carrier having an average solubility parameter of from 3 to 13 (cal/cm3)0.5; and (d) from 0.0001% to 5% by weight of a solid nucleating agent;
wherein the composition has a molar ratio of solid non-polymeric gallant to solid nucleating agent of from 10:1 to 1000:1, and wherein the composition has a hardness of from 500 gram-force to 5000 gram-force, a visible residue index of from 11 to L-value, and an elastic to viscous modull ratio of from 0.1 to 100.

2. The composition of Claim 1 comprising from 0.01% to 2%, by weight of the solid nucleating agent.

3. The composition of Claims 1 or 2 wherein the composition has a molar ratio of solid non-polymeric gallant to solid nucleating agent of from 10:1 to 100:1.

4. An anhydrous antiperspirant composition comprising:
(a) from 0.5% to 60% by weight of particulate antiperspirant active;
(b) from 1% to 15% by weight of a solid non-polymeric gellant;
(c) from 10% to 80% by weight of an anhydrous liquid carrier having an average solubility parameter of from 3 to 13 (cal/cm3)0.5; and (d) from 0.0001% to 5% by weight of a solid nucleating agent;
wherein the composition has a hardness of from 20 gram-force to 500 gram-force.

5. The composition of any one of Claims 1 to 4 wherein the solid non-polymeric gellant is selected from the group consisting of 12-hydroxystearic acid, esters of 12-hydroxystearic acid, amides of 12-hydroxystearic acid, C20 to C40 fatty acids, n-acyl amino acid amides and n-acyl amino acid esters of glutamic acid, lysine, glutamine, and aspartic acid, disubstituted and branched monoamides, monosubstituted and branched diamides, triamides, and mixtures thereof.

6. The composition of Claim 5 wherein the solid non-polymeric gellant is 12-hydroxystearic acid.

7. The composition of any one of Claims 1 to 6 wherein the anhydrous liquid carrier is selected from the group consisting of cyclic polydimethylsiloxanes, linear polydimethylsiloxanes, polyalkylsiloxanes, polyalkylarylsiloxanes, polyestersiloxanes, polyethersiloxane copolymers, polyflurosiloxanes, polyaminosiloxanes, isohexadecane, isododecane, mineral oil, petrolatum, and mixtures thereof.

8. The composition of any one of Claims 1 to 7 wherein the solid nucleating agent is selected from the group consisting of fatty alcohols, fatty acid esters, fatty acid ethers, silica, titanium dioxide, solid polyol carboxylic acid polyesters, and mixtures thereof.

9. The composition of any one of Claims 1 to 8 wherein the fatty alcohol is selected from the group consisting of monohydric alcohols, ethoxylated fatty alcohols, fatty alcohol esters, and mixtures thereof.

10. The composition of any one of Claims 1 to 9 wherein the fatty acid ester is selected from the group consisting of stearyl stearate, stearyl behenate, palmityl stearate, stearyl octyldodecanol, cetyl esters, cetearyl behenate, behenyl behenate, ethylene glycol distearate, ethylette glycol dipalmitate, beeswax, tristearin, tribehenate, behenyl palmityl, behenyl triglyceride, palmityl stearyl, palmityl triglyceride, hydrogenated vegetable oil, hydrogenated rape seed oil, castor wax, fish oils, tripalmiten, glyceryl stearate, glyceryl distearate, and mixtures thereof.

11. The composition of any one of Claims 1 to 10 wherein the solid polyol carboxylic acid polyester has a polyol moiety and at least 2 carboxylic acid moieties wherein the polyol moiety is a sugar containing at least 4 hydroxyl groups, wherein the carboxylic acid moiety consists essentially of (a) C12 or higher unsaturated carboxylic acid moieties, and (b) C20 or higher saturated carboxylic acid moieties, the molar ratio of (a) to (b) being from about 1:7 to about 3:5, and wherein at least 2 of the hydroxyl groups of the polyol moiety are esterified with carboxylic acid moieties, and wherein the solid polyol carboxylic acid polyester is a sucrose octaester having about one oleoc moiety and about seven behanic moieties.

12. The composition of Claim 11 wherein the polyol moiety is sucrose.

13. The composition of Claim 11 wherein the polyol moiety is a sugar containing, from 4 to 8 hydroxyl groups.

14. The composition of any one of Claims 11 to 13 wherein the carboxylic acid moiety consists essentially of (a) C20 to C26, unsaturated carboxylic acid moieties.

15. The composition of any one of Claims 11 to 14 wherein the carboxylic acid moiety consists essentially of (b) C20 to C26 saturated carboxylic acid moieties.

16. The composition of any one of Claims 11 to 15 wherein the saturated carboxylic acid moieties are behenic moieties.

17. A method for making an anhydrous antiperspirant gel-solid stick composition, which method comprises the steps of:
(a) combining the following components:
(i) from 0.5% to 60% by weight of particulate antiperspirant active;
(ii) from 1% to 15% by weight of a solid non-polymeric gellant;
(iii) from~l0% to 80% by weight of an anhydrous liquid carrier having an average solubility parameter of from 3 to 13 (cal/cm3)0.5; and (iv) from 0.0001 % to 5.0% by weight of a solid nucleating agent;
(b) liquefying the solid non-polymeric gellant and the solid nucleating agent by heating the composition above the melt point of the solid non-polymeric gellant and the solid nucleating agent; and (c) solidifying the liquefied gellant in the presence of the nucleating agent to form the anhydrous antiperspirant gel-solid stick composition.

18. A method for making an anhydrous antiperspirant gel-solid stick composition, which method comprises the steps of:
(a) combining the following components;
(i) from 0.5% to 50% by weight of particulate antiperspirant active;
(ii) from 1% to 15% by weight of a solid non-polymeric gellant;
(iii) from 10% to 80% by weight of an anhydrous liquid carrier having an average solubility parameter of from 3 to 13 (cal/cm3)0.5; and (iv) from 0.0001%, to to 5.0% by weight of a solid, inorganic, insoluble, micronized nucleating agent;
(b) liquefying the solid non-polymeric gellant by heating the composition above the melt point of the solid non-polymeric gellant; and (c) solidifying the liquefied gallant in the presence of the nucleating agent to form the anhydrous antiperspirant gel-solid stick composition.