CA2191112C - Gel stick compositions comprising optically enriched gellants - Google Patents

Abstract

The subject invention relates to antiperspirant gel stick compositions comprising: (a) an antiperspirant active; (b) a gelling agent comprising: (i) an optically enriched primary gellant selected from the group consisting of 12-hydroxystearic acid, esters of 12-hydroxystearic acid, amides of 12-hydroxystearic acid, and mixtures thereof, and (ii) a secondary gellant selected from the group consisting of n-acyl amino grams of force or more.

Description

WO 95131961 PCTlUS95/06104 GEL STICK COMPOSITIONS COMPRISING
OPTICALLY ENRICHED GELLANTS
FIELD OF THE INVENTION
The subject invention relates to gel stick compositions useful in preventing perspiration and body odors. Specifically, the subject invention relates to low-aqueous antiperspirant and/or deodorant compositions in the form of a gel stick.
BACKGROUND OF THE INVENTION
Personal hygiene habits typically include a means for reducing human body odors. These habits include routine bathing or washing of the body, particularly the axilIa, and treating the axilla with compositions, such as antiperspirant or deodorant compositions, to retard odor formation.
Antiperspirants and deodorants generally include an astringent material in a suitable carrier. Astringent materials typically used are metal salts, particularly aluminum and zirconium metal complexes. Exemplary metal salts are disclosed in Plechner, Antipersyirants and Deodorants, 2 Cosmetics, Science and Technology, Balsam and Sagarin, 374-400, 1972 , Antiperspirant and deodorant compositions cari be formulated in a variety of ways, each dependent on the particular ingredients involved. Such formulations include lotions, solid sticks, and creams. Solid stick formulations include gel sticks, which contain a liquid material and gelling agents.
One significant disadvantage of typical gel stick compositions is a tendency of the liquid material to escape or leak from the gel network. This leaking of the liquid material can result in reduced e~cacy of the actives, poor gel formation and lower gel stability over time of any gei which is formed. The leaking may also cause processing diff collies at the temperatures and holding times typically encountered during manufacture. Gel stick compositions may have additional disadvantages such as a wet, cold and sticky feel on the skin, skin irritation, and shrinkage and containment problems due to high volatility.
It is an object of the subject invention to provide harder low-aqueous gel stick compositions.
It is a further object of the subject invention to provide low-aqueous gel stick compositions with superior gel formation.

WO 95131961 PCTlUS95106104 SUMMARX OF THE INVHNTION
The subject invention involves low-aqueous gel stick compositions comprising:
(a) an antiperspirant active;
(b) a gelling agent comprising:
(i) an optically enriched primary gellant selected from the group consisting of 12-hydroxystearic acid, esters of 12-hydroxystearic acid and amides of 12-hydroxystearic acid; and (ii) a secondary gellant selected from the group consisting of n-acyl amino acid amide derivatives; and (c) a liquid base material;
wherein the gel stick has a hardness of 75 grams of force or above.
DET.~ED DESCIZ1~'TION OF THE INVENTION
As used herein, the term "alkyl" means carbon-containing chains which may be straight, branched or cyclic; substituted or unsubstituted; saturated, monounsaturated (i.e., one double or triple bond in the carbon chain), or polyunsaturated (i.e., two or more double bonds in the carbon chain, two or more triple bonds in the carbon chain, one or more double and one or more triple bonds in the carbon chain). Unless otherwise indicated, preferred alkyl are as follows.
Preferred alkyl are straight or branched chain, more preferably straight chain.
Preferred alkyl are mono-, di-, or tri- substituted, more preferably monosubstituted or unsubstituted, most preferably unsubstituted. Preferred alkyl are CI to C26~
more preferably C6 to C22, more preferably still C 12 to C 1 g.
As used herein, "substituted", in reference to alkyl groups, means such groups that can be mono- or polysubstituted. Preferred substituents are selected from the group consisting of halogen, hydroxy, amino, vitro, carboxy, thio, aryl, alkyl, alkoxy, and aryloxy. More preferred substituents include alkyl, alkoxy and aryl.
As used herein, the term "aryl" means aromatic rings which may be unsubstituted or substituted. Preferred aryl are phenyl or naphthyl, especially phenyl. Preferred aryl are mono-, di- or tri- substituted, or unsubstituted;
more preferred aryl are monosubstituted or unsubstituted. Preferred aryl substitutents include alkyl, halo, amino, hydroxy, alkoxy, cyano, vitro and trifluoromethyl.
As used herein, the term "alkoxy" means O-alkyl.
As used herein, the term "aryloxy" means O-aryl.

WO 95/31961 . PC'T/US95/0610~i AIItIDerSDlrant ACtiye The compositions of the subject invention contain an astringent antiperspirant active. Antiperspirant actives useful in the subject invention are well known in the an. See e.g. "Antiperspirants and Deodorants", Cosmetic Science and TechnoloQV Series, K. Laden & C. Felger, eds., Vol. 7., pp. 42-56 ( 1988).
These actives are used at levels from about 0.5% to about 60% of the composition, preferably from about 5% to about 35%, of the gel stick composition. These weight percentages are calculated on an anhydrous metal salt basis (exclusive of complexing agents).
Any aluminum astringent antiperspirant salt or aluminum and/or zirconium astringent complex can be employed herein. Salts useful as astringent antiperspirant salts or as components of astringent complexes include aluminum halides, aluminum hydroxy-halides, zirconyl oxyhalides, zirconyl hydroxy-halides.
and mixtures of these materials.
Aluminum salts of this type include aluminum chloride and the aluminum hydroxyhalides having the general formula A12(O)~xQy.XH2p wherein:
(a) Q is chlorine, bromine or iodine;
(b) x is from about 2 to about 5, and x+y = about 6, and x and y do not need to be integers; and (c) X is from about 1 to about 6.
Aluminum salts of this type can be prepared in the manner described more fully in U.S. Patent 3,887,692 issued to Gilman on June 3, 1975, and U.S.
Patent 3,904,741 issued to Jones and Rubino on September 9, 1975.
The zirconium compounds which are useful in the present invention include both the zirconium oxy salts and zirconium hydroxy salts, also referred to as the zirconyl salts and zirconyl hydroxy salts. These compounds may be represented by the following general empirical formula:
Zr0(OI-~2-~Bz wherein:
(a) z may vary from about 0.9 to about 2 and need not be an integer;
(b) n is the valence of B;
(c) 2-nz is greater than or equal to 0:
(d) B is selected from the group consisting of halides, nitrate, sulfamate, sulfate, and mixtures thereof.
Although only zirconium compounds are exemplified in this specification.
other Group NB metal compounds, including hafnium, can be used in the subject W095/31961 Q ~ ~ PCT/US95/06104 invention.
As with the basic aluminum compounds, the above formula is greatly simplified and is intended to represent and include compounds having coordinated and/or bound water in various quantities, as well as polymers, mixtures and complexes of the above. As will be seen from the above formula, the zirconium hydroxy salts actually represent a range of compounds having various amounts of the hydroxy group, varying from about I.1 to only slightly greater than zero groups per molecule.
Several types of antiperspirant complexes utilizing the above antiperspirant salts are known in the art. For example, LLS. Patent 3,792,068 issued to Luedders et al. on February 12, 1974 discloses complexes of aluminum, zirconium and amino acids, such as glycine. Complexes such as those disclosed in the Luedders et al. patent and other similar complexes are commonly known as ZAG. ZAG
complexes are chemically analyzable for the presence of aluminum, zirconium and chlorine. ZAG complexes useful herein are identified by the specification of both the molar ratio of aluminum to zirconium (hereinafter "AI:Zr" ratio) and the molar ratio of total metal to chlorine (hereinafter "Metal:Cl" ratio). ZAG complexes usefitl herein have an AI:Zr ratio of from about 1.67 to about 12.5 and a Metal:Cl ratio of from about 0.73 to about 1.93.
Preferred ZAG complexes are formed by (A) co-dissolving in water (I) one part A12(OH)6_mQm, wherein Q is an anion selected from the group consisting of chloride, bromide and iodide, and m is a number from about 0.8 to about 2.0;
(2) x parts Zr0(OH)2_aQa nH20, where Q is chloride, bromide or iodide; where a is from about 1 to about 2; where n is from about 1 to about 8; and where x has a value of from about 0.16 to about 1.2;
(3) p parts neutral amino acid selected from the group consisting of glycine, dl-tryptophane, dl-b-phenylalanine, dl-valine, dl-methionine and b-alanine, and where p has a value of from about 0.06 to about 0.53;
(B) co-drying the resultant mixture to a friable solid; and (C) reducing the resultant dried inorganic-organic antiperspirant complex to particulate form.
A preferred aluminum compound for preparation of such ZAG type complexes is aluminum chlorhydroxide ~of the empirical formula . : CA 02191112 1999-OS-25 WO 95131961 ~~ PC'T/US95/06103 A12(OH)SC1.2H20. Preferred zirconium compounds for preparation of such ZAG-type complexes are zirconyl hydroxychloride having the empirical formula Zr0(OH)C1.3H20 and the zirconyl hydroxyhalides of the empirical formula Zr0(OH)2_aCh.nH20 wherein a is from about l.~ to about 1.87, and n is from about 1 to about 7. The preferred amino acid for preparing such ZAG-type complexes is glycine of the formula CH2(IV'H2)COOH. Salts of such amino acids can also be employed in the antiperspirant complexes. See U.S. Patent 4,017,599 issued April 12, 1977, to Rubino.
A wide variety of other types of antiperspirant complexes are also known in the art. For example, U.S. Patent 3,903,258 issued to Siegal on September 2, 1975 discloses a zirconium aluminum complex prepared by reacting zirconyl chloride with aiuminum hydroxide and aluminum chlorhydroxide. U.S. Patent 3,979,510 issued to Rubino on September 7, 1976 discloses an antiperspirant complex formed from certain aluminum compounds, certain zirconium compounds, and certain complex aluminum buffers. U.S. Patent 3,981,896 issued to Paining on September 21, ~ 1976 discloses an antiperspirant complex prepared from an aluminum polyol compound, a zirconium compound and an organic buffer.
U.S. Patent 3,970,748 issued to Mecca on July 20, 1976 discloses an aluminum chlorhydroxy glycinate complex of the approximate general formula ~~2(0~4C1J~2C~2COOHJ.
Of all the above types of antiperspirant actives, preferred compounds include the 5/6 basic aluminum salts of the empirical formula AI2(OH)SC1.2H20;
mixtures of A1CI3.6H20 and A12(OH)SCL2H20 with aluminum chloride to aluminum hydroxychloride weight ratios of up to about 0.5; ZAG type complexes wherein the zirconium salt is Zr0(OH)CL3H20, the aluminum salt is AI2(OH)SCL2H20 or the aforementioned mixtures of AICI3.6H20 and Al2(OH)5 CL2H20 wherein the total metal to chloride molar ratio in the complex is less than about 1.25 and the AI:Zr molar ratio is about 3.3, and the amino acid is glycine;
and ZAG-type complexes wherein the zirconium salt is Zr0(OH)2_aCla.nH20 wherein a is from about 1.5 to about 1.87 and n is from about 1 to about 7, the aluminum salt is A12(OH)SC1.2H20, and the amino acid is glycine.
The active may be incorporated either in solubilized or particulate form.
Reduction in the amount of interaction between the antiperspirant active and the gelling agent results in better gel stick compositions. This interaction can be reduced by decreasing the surface area of the antiperspirant active; thereby reducing the interaction sites. The antiperspirant active is preferably in particulate form wherein the surface area of the active is relatively low. The surface area of ' CA 02191112 1999-OS-25 WO 95/31961 - p~/US95106104 the antiperspirant active can be reduced by increasing the size and density of the active particles. The particulate antiperspirant active preferably has a density which is greater than about 0.7 g/cm3 and an average panicle size (as measured by a Coulter Multisizer 11 manufactured by Coulter Corporation, Haleah, Florida) greater than about 10 microns; more preferably, greater than about 30 microns:
and most preferably, greater than about 40 microns. Such preferred materials can be purchased from Westwood Chemical Company, Middletown, N.Y. under the trade name Westchlor ZR. Suitable antiperspirant actives are disclosed, for example, in U.S. Patent 4,147,766 which issued on April 3, 1979 to Kozischek.
Solubilized antiperspirant actives which may be utilized in the subject invention are also well known in the art. These materials utilize monohydric or polyhydric alcohols or water to solublize the antiperspirant active before it~
is incorporated into the product. The levels of these polar solvents is less than 25%, and preferably less than 1 S% of the composition. Examples of such actives are taught, for example, in U.S. Patent 4,137,306 issued to Rubino on January 30, 1979; U.S. Patent Application Serial No. 370,559, Smith and Ward, filed June 23, 1989; and European Patent Application 0295070 published December 14, 1988 .
Gelling Ascent The subject compositions also comprise a gelling agent. The level of the gelling agent is typically fmm about 1 ~ to about 15 ~ of the composition;
preferably, from about 3 ~ to about 12 °~ ; more preferably, from about 5 °,& to about 10 ~ . As used herein, the term "gelling agent" means a mixture of a primary gellant and a secondary gellant.
As used herein, the term "primary gellant" means a compound with one chiral carbon selected from the group consisting of 12-hydroxystearic acid, esters of 12-hydroxystearic acid, amides of 12-hydroxystearic acid and mixtures thereof, having the structure:
O H
R~ C-f CI-I~~--C~CI-I~~--CFi3 OH
wherein:
(a) R1 is OR2 or NR2R3; and (b) R2 and R3 are, independently, hydrogen, alkyl, or aryl. At least VJO 95131961 PCTlU595/06104 one of R2 or R3 is preferably a hydrogen atom.
The primary gellant is preferably selected from the group consisting of 12 hydroxystearic acid, 12-hydroxystearic acid methyl ester, 12-hydroxystearic acid V
ethyl ester, 12-hydroxystearic acid stearyl ester, 12-hydroxystearic acid benzyl ester, 12-hydroxystearic acid amide, isopropyl amide of 12-hydroxystearnc acid, ' butylamide of 12-hydroxystearic acid, benzylamide of 12-hydroxystearic acid, phenylamide of 12-hydroxystearic acid, t-butylamide of 12-hydroxystearic acid, cyclohexylamide of 12-hydroxystearic acid, 1-adamantylamide of 12-hydroxystearic acid, 2-adamantylamide of 12-hydroxystearic acid, diisopropylamide of 12-hydroxystearic acid, and mixtures thereof; even more preferably, 12-hydroxystearic acid, isopropyl amide of 12-hydroxystearic acid, and mixtures thereof. 12-hydroxystearic acid is the most preferred primary gellant.
In the subject invention, the primary gellant is used in an optically enriched form. As used herein "optically enriched" means a primary gellant sample wherein the ratio of R isomer : S isomer or S isomer : R isomer is from about 0% :
100%
to about 45% : 55%; preferably 0% : 100% to about 30% : 70%; more preferably from about 0% : 100% to about 15% : 85%; more preferably still from about 0%
100% to about 5% : 95%; most preferably 0% :100%.
It has been unexpectedly found that when an optically enriched sample of primary gellant is used in the subject invention, superior gelling results.
Wtule not limited to any particular mechanism of action, it is believed that the optically enriched primary gellant, in the presence of the secondary gellant, is thermodynamically favored to form to form twisted fibrils that are aligned and bundle, thereby contributing to a more ordered macro structure in which the liquid base is trapped. The racemic mixture (which comprises a 50:50 ratio of R:S), on the other hand, is thermodynamically favored to form crystals.
As used herein, the term "secondary gellant" means an n-acyl amino acid derivative. Preferred secondary gellants include n-acyl amino acid amides and n-aryl amino acid esters. Preferred secondary gellants are prepared from glutamic - acid, alanine, lysine, glutamine, aspartic acid and mixtures thereof Both d and 1 amino acids are effective in the subject invention; however, natural amino acids (I
isomers) are preferred. Preferred secondary gellants include n-acyl glutamic acid amides and n-acyl glutamic acid esters having the structure:

W095/31961 ~ ~ g 1 i 12 POT~S95/06104 II I I II

H NH ~R~
C
II
O
wherein:
(a) RI is alkyl, or aryl;
(b) R2 and R3 are, independently, alkyl, or aryl ester or amide; R2 and R3 are preferably the same.
Preferred secondary gallants include N-lauroylglutamic acid diethylamide, N-lauroylglutamic acid dibutylamide, N-lauroylglutamic acid dihexyiamide, N-lauroyiglutamic acid dioctylamide, N-Iauroylglutamic acid didecylamide, N-Iauroytglutamic acid didodecylamide, N-lauroylglutamic acid ditetradecylamide, N-lauroylglutamic acid dihexadecylamide, N-lauroylglutamic acid distearylamide, N-stearoylglutamic acid dibutylamide, N-stearoylglutamic acid dihexylamide, N-stearoyiglutamic acid diheptylamide, N-stearoylglutamic acid dioctyiamide, N-stearoylglutamic acid didecylamide, N-stearoylglutamic acid didodecylamide, N-stearoylglutamic acid ditetradecylamide, N-stearoylglutamic acid dihexadecylamide, N-stearoylglutamic acid distearylamide and mixtures thereof More preferred secondary gallants include n-lauroylglutamic acid dibutylamide, n-stearylglutamic acid dihexylamide, and mixtures thereof The primary gallant : secondary gallant ratio is typically between about 1:2 and about 20:1; preferably, from about 1:1 to about 10:1; more preferably, from about 2:1 to about 7:1; and even more preferably, from about 3:1 to about 5:1.
The presence of a secondary gallant offers significant benefits when used in an antiperspirant gel stick, such as decreased residue upon application to the skin, increased hardness and better aesthetics, relative to a similar composition having either of the two gallants alone. The primary and secondary gallants are, in combination, more effective than either alone so that the overall level of gelling agent within the composition can be reduced while maintaining such desirable stick characteristics.
Liauid Base Material A liquid base matrix of antiperspirant stick compositions of the subject invention is formed by combining the gelling agent with a liquid base material. As w0 95/31961 ~ PCTlUS95/06104 used herein, the term "liquid" refers to materials which are liquids at ambient conditions and the term "liquid base material" includes all liquids within the composition.
The liquid base material of the subject invention is preferably used at levels from about 10% to about 95% of the subject compositions; and more preferably from about 45% to about 80%. The liquid base material preferably includes a volatile, non-polar, oil and a non-volatile, relatively polar co-solvent.
The non-polar, volatile oil tends to impart highly desirable aesthetic properties to the gel stick and is preferably used at levels from about 10% to about 70% of the composition; more preferably, from about 25% to about 60%; more preferably from about 40% to about 60%. The term "non-polar" typically means that the emollient has a solubility parameter below about 6.5.
Particularly useful non-polar, volatile oils include silicone oils, hydrocarbons, and mixtures thereof. Such non-polar, volatile oils are disclosed, for example, in Cosmetics, Science, and Technology, Vol. 1, 27-104 edited by Balsam and Sagarin, 1972, The non-polar, volatile oils useful in the present invention may be saturated or unsaturated, straight or branched chained, aliphatic or aromatic. Preferred non-polar, volatile hydrocarbons include isodecane (such as Permethyl-99A~, available from Presperse Inc.) and the C7-Cg through C 12-C 15 isoparaffins (such as the Isopar~
Series available from Exxon Chemicals).
Non-polar, volatile silicone oils are highly preferred because they provide the gel stick composition with highly desirable aesthetics. Non-polar, volatile liquid silicone oils are disclosed in U.S. Pat. 4,781,917 issued to Luebbe et al., on November 1; 1988; and in Todd et al., "Volatile Silicone Fluids for Cosmetics", Cosmetics and Toiletries, 91:27-32 (1976) Particularly preferred volatile silicone oils include cyclic volatile silicones corresponding to the formula:
r.
I
I I
1 ~ I
_ ___S~_o-_ _ I

n wherein n is from about 3 to about 7; and linear volatile silicones corresponding to the formula:
(CH3)3Si-D-[Si(CH3)20]m-Si(CH3)3 wherein m is from about 1 to about 7. Linear volatile silicones generally have a . CA 02191112 1999-OS-25 WO 95!31961 . ' pCTlUS95/06104 viscosity of less than about ~ centistokes at 25oC, whereas the cyclic silicones have viscosities of less than about 10 centistokes at 25oC. Highly preferred examples of volatile silicone oils include cyclomethicones of varying viscosities.
e.g., Dow Corning 200~, Dow Corning 244~, Dow Corning 245~, Dow Corning 344~, and Dow Corning 345~, (commercially available from Dow Cornins Corp.); SF-1204~ and SF-1202~ Silicone Fluids (commercially available from G.E. Silicones), GE 7207~ and 7158~ (commercially available from General Electric Co.); and SWS-03314~ (commercially available from SWS Silicones Corp.).
The term "non-volatile" as used herein refers to materials which exhibit a vapor pressure of no more than about 2mm Hg at 25oC at one atmosphere and/or to materials which have a boiling point at one atmosphere of at least about 300o~C.
The phrase "relatively polar" as used herein means more polar than another material in terms of solubility parameter; i.e., the higher the solubility parameter the more polar the liquid. The relatively polar co-solvent of the subject invention aids in the utilization of reduced processing temperatures by solubilizing at least one of the gellants and being soluble in the non-polar, volatile oil when subjected to reduced processing temperatures. In addition to enabling reduced processing temperatures, the co-solvent enables the inclusion of greater amounts of the non-polar, volatile oil. This is advantageous because, as discussed above, the non-polar, volatile oil provides significant cosmetic benefits. The non-volatile co-solvent is "relatively polar" as compared to the non-polar, volatile oil discussed above. Therefore, the non-volatile co-solvent is more polar (i.e., has a higher solubility parameter) than at least one of the non-polar, volatile oils.
The quantity of relatively polar, non-volatile co-solvent is preferably kept to a minimum because it tends to adversely affect product cosmetics. The relatively polar, non-volatile co-solvent is preferably included at levels from about 5%
to about 60% of the composition; more preferably from about 5% to about 25%; and most preferably from about 7% to about 20%.
Relatively polar, non-volatile liquids useful as the co-solvent in the subject invention are disclosed, for example, in Cosmetics, Science, and Technology, Vol.
1, 27-104 edited by Balsam and Sagarin, 1972; U.S. Pat. 4,202,879 issued to Shelton on May 13, 1980; and U.S. Pat. 4,816,261 issued to Luebbe et al. on March 28, 1989. ~ Relatively polar, non-volatile co-solvents useful in the subject invention preferably include silicone oils;
hydrocarbon oils; fatty alcohols; fatty acids; esters of mono and dibasic carboxylic acids with mono and polyhydric alcohols; polyoxyethylenes; poiyoxypropylenes;

. . CA 02191112 1999-OS-25 WO 95/31961 PCT/US95/0610a mixtures of polyoxyethylene and polyoxypropylene ethers of fatty alcohols; and mixtures thereof. The relatively polar, non-volatile co-solvents useful in the subject invention may be either 'saturated or unsaturated, have an aliphatic character and be straight or branched chained or contain aliphatic rings or aromatic rings.
More preferably, the relatively polar, non-volatile liquid co-solvents include fatty alcohols having from about 12-26 carbon atoms; fatty acids having from about 12-26 carbon atoms; esters of monobasic carboxylic acids and alcohols having from about 14-30 carbon atoms; esters of dibasic carboxylic acids and alcohols having from about 10-30 carbon atoms; esters of polyhydric alcohols and carboxylic acids having from about 5-26 carbon atoms; ethoxylated, propoxylated, and mixtures of ethoxylated and propoxylated ethers of fatty alcohols with from about 12-26 carbon atoms and a degree of ethoxylation and propoxylation of -below about 50; and mixtures thereof.
More preferred relatively polar, non-volatile liquid co-solvents include propoxylated ethers of C 14-C 1 g fatty alcohols having a degree of propoxyiation below about 50, esters of C2-C8 alcohols and C 12-C26 carboxylic acids (e.g.
ethyl myristate, isopropyl palmitate), esters of C12-C26 alcohols and benzoic acid (e.g.
Finsolv TN supplied by Finetex), diesters of C2 Cg alcohols and adipic, sebacic, and phthalic acids (e.g., diisopropyl sebacate, diisopropyl adipate, di-n-butyl phthalate), polyhydric alcohol esters of C6-C26 carboxylic acids (e.g., propylene glycol dicaprate/dicaprylate, propylene glycol isostearate); and mixtures thereof.
Even more preferred relatively polar, non-volatile liquid co-solvents include branched-chain aliphatic fatty alcohols having from about 12-26 carbon atoms, such as isocetyl alcohol, octyldecanol, octyldodecanol and undecylpentadecanol.
Octyldodecanol is most preferred. Such preferred aliphatic fatty alcohols are particularly useful in combination with the volatile liquid silicone oils discussed herein to adjust the average solubility of the liquid base material.
In addition to the liquids discussed above, the liquid base material may optionally include non-volatile, non-polar emollients which tend to improve product cosmetics. Typical non-volatile, non-polar emollients are disclosed, for example, in Cosmetics, Science, and Technology, Vol. 1, 27-104 edited by Balsam and Sagarin, 1972; U.S. Pat. 4,202,879 issued to Shelton on May 13, 1980; and U.S. Pat. 4,816,261 issued to Luebbe et al. on March 28, 1989.
The non-volatile silicone oils useful in the present invention are essentially non-volatile polysiloxanes, paraffinic hydrocarbon oils, and mixtures thereof. The polysiloxanes useful in the subject invention include WO 95/31961 ~ PCT/US95/06104 polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, polyethersiloxane copolymers, and mixtures thereof. Examples of these include polydimethyl siloxanes having viscosities of from about ~ to about 100,000 centistokes at 25°C.
Among the preferred non-volatile silicone emollients useful in the subject compositions are the polydimethyl siloxanes having viscosities from about 2 to about 400 centistokes at 25oC. Such polyalkylsiloxanes include the Viscasil~
series (sold by General Electric Company) and the Dow Corning 200~ series (sold by Dow Corning Corp.). Polyalkylarylsiloxanes include polymethylphenyl silox-anes having viscosities of from about 15 to about 65 centistokes at 25°C. These are available, for example, as SF 1075 methyl-phenyl fluid~ (sold by General Electric Company) and 556 Cosmetic Grade Fluid~ (sold by Dow Corning Corp.).
Useful poly-ethersiloxane copolymers include, for example, a polyoxyalkylene ether copolymer having a viscosity of about 1200 to 1500 centistokes at 25oC.
Such a fluid is available as SF1066~ organosilicone surfactant (sold by General Electric Company). Polysiloxane ethylene glycol ether copolymers are preferred copolymers for use in the subject compositions.
Non-volatile paraffnic hydrocarbon oils useful in the subject invention include mineral oils and certain branched-chain hydrocarbons. Examples of these fluids are disclosed in U.S. Pat. 5,019,375 issued to Tanner et al. on May 28, 1991. Preferred mineral oils have the following properties: viscosity from about 5 centistokes to about 70 centistokes at 40°C;
density between about 0.82 and 0.89 g/cm3 at 25°C; flash point between about 138°C and about 216°C; and carbon chain length between about 14 and about 40 carbon atoms.
- Preferred branched chain hydrocarbon oils have the following properties:
density between about 0.79 and about 0.89 g/cm3 at 20°C; boiling point greater than about 250°C; and flash point between about 1 I O°C and about 200°C.
Particularly preferred branched-chain hydrocarbons include Permethyl 103A~, which contains an average of about 24 carbon atoms; Permethyl 104A~, which contains an average of about 68 carbon atoms; Pcrmethyl 102A~, which contains an average of about 20 carbon atoms; all of which may be purchased from Permethyl Corporation; and Ethylflo 364~ which contains a mixture of 30 carbon atoms and 40 carbon atoms and may be purchased from Ethyl Corp.
The liquid base materials include emollients which have a solubility parameter from about 5 to about 9. It is preferable that, in aggregate, the average solubility parameter of the liquid base material be from about 6 to about 9.
Hence, a mixture of emollients may be used as the liquid base material herein, each having '" CA 02191112 1999-OS-25 a solubility parameter in the range of from about ~ to about 9, such that the average solubility parameter of the mixture is from about 6 to about 9.
Solubility parameters are common to the an of antiperspirant stick formulation and the means to determine them are disclosed by C.D. Vaughan, "Solubility EtFects in Product, Package, Penetration and Preservation" 103 Cosmetics and Toiletries 69, October, 1988; and C.D. Vaughan, " Using Solubility Parameters in Cosmetics Formulation", 36 J Soc. Cosmetic Chemists 319-333, Sept/Oct, 1985.
The liquid base material comprises at least two solvents. One solvent is preferably a silicone oil. The second solvent is preferably an organic solvent with a solubility parameter of less than 9.
It is important that the liquid base material be of a type, and used at a level sufficient to solubilize the gelling agent when heated, to permit substantially uniform mixing of the antiperspirant active into the heated solution at the mixing temperature, and form a stick when cooled to ambient temperature. The liquid base material must be compatible with the gelling agent so that the mixture of the two remains homogeneous and does not phase separate during manufacturing and so that the finished product remains homogeneous and does not phase separate at ambient conditions over the normal shelf life which may be upwards of one year. Furthermore, the liquid base materials are typically selected to provide aesthetic benefits, such as emolliency, low tack and/or minimized visible residue, without significant interference with the effectiveness of the antiperspirant active component. The particular liquid base material should be safe for application to human skin.
Gel Sticks As used herein, the term "stick" means a non free flowing solid with a hardness of at least 75 grams of force, more preferably at least 100 grams of force, more preferably still at least 150 grams of force, as measured by using a Steven's-LFRA Texture analyzer with a 2mm x 64mm steel cylinder blunt tip probe at 2mm/sec to a constant depth. The depth of measurement is typically l5mm for samples of approximately 10 grams. For samples of approximately 3 grams, the depth is lOmm. Three readings are taken per sample and averaged. The typical _ standard deviation is approximately 10 grams.
As used herein, the term "low-aqueous gel stick composition" means a gel stick composition comprising less than 50% water, preferably less than 30%, more preferably less than 20% water, even more preferably less than 10% water, also ' CA 02191112 1999-OS-25 WO 95131961 ~ - " " p~'/US95/06104 preferably less than ~% water. The most preferred gel stick compositions are substantially water free. As used herein, the term "substantially water free"
means that the only water content in the formulation comes from the degrees of hydration associated with the raw materials used in the formulation.
Ooty'onal Ingredients Antiperspirant and/or deodorant gel stick compositions of the subject invention may contain optional components which act as additional actives or modify the physical characteristics of the composition or the components making up the compositions. Such components are well known in the art. A non-limiting group of these optional components include colorants, perfumes, thickeners, distributing agents, emulsifiers, bacteriostats, fungistats, and mixtures thereof.
Optional components useful herein are described in the following references:
U. S.
Patent 4,049,792 issued to Elsnau on September 20, 1977; Canadian Patent 1,164,347 which. issued to Beckmeyer et al. on March 27, 1984; European Patent Application 117,070 which published on August 29, 1984; and Geria, "Formulation of Stick Antiperspirants and Deodorants", Cosmetics and Toiletries 99:55-60 ( 1984), Emulsifiers are particularly useful in the subject invention. The level of emulsifiers used in the subject invention is typically less than about 10% of the composition, preferably less than about 5%. These emulsifiers include non-ionic surfactants useful for forming water-in-oil emulsions. Examples of these emulsifiers include polyoxyethylene ethers of fatty alcohols, and polyoxyethylene-polysiloxane copolymers. Such emulsifiers are disclosed by EPO
Application 373,424 Raleigh et al., and United States Serial Number 530,671, Cedeno et al., filed July 2, 1991, Thickeners are also useful in the subject invention. Typically thickeners comprise less than about 5% of the composition. Examples of thickeners useful in the subject compositions are disclosed in U.S. Pat. 4,985,238, Tanner et al., issued Jan. 15, 1991. These thickeners include wax-like materials such as beeswax, cerasin, hydrogenated castor oil, synthetic waxes such as Fisher Tropsch~ waxes, microcrystalline waxes, polyethylene waxes, and mixtures thereof.
Particulate and filler materials may also be included in the subject compositions. These materials are typically used at levels from about 0.5% to about 5% of the composition, preferably not more than 3%. Such materials are disclosed in U.S. Pat. 5,019,375, Tanner et al., issued May 28, 1991.

'. ' CA 02191112 1999-OS-25 WO 95/31961 -' ~ PCT/US95/06104 IS
Suitable filler materials include collodial silica (such as Cab-O-Sil~, sold by Cabot Corp.), clays (such as bentonite), hydrophobic (quaternized) clays, silica/alumina thickeners, silicate powders such as talc, alumina silicate, and magnesium silicate, modified corn starches, metallic stearates, and mixtures thereof. The use of such fillers as stabilizing agents in cosmetic sticks is disclosed in U.S. Pat. 4,126,679, Davy et al., issued November 21, 1987.
Examples of other particulate materials include particulate hydrophilic polymers such as cellulose ether polymers, modified starches, polyamides, and polypeptides.
A wash-off agent may be utilized to improve the ease with which the ingredients, particularly the gelling agent and the non-polar, non-volatile oils, may be washed off. The wash-off agent is preferably a non-liquid. The wash-off went is typically in the gel stick composition in an amount from about 0.1% to about 10% of the composition.
Typical wash-off agents are non-liquids selected from the group consisting of polyoxyethylene ethers having the formula R1(OCH2CH2)nOH;
polyoxyethylene esters having the formula R1C0(OCH2CH2)nOH;
polyoxyethylene glyceryl esters having the formula (R1C00)CH2CH(OH)CHZ(OCH2CH~nOH or having the formula HOCH2CH(OOCR1)CH2(OCH2CH2)nOH; and polyoxyethylene glyceryl diesters having the formula R1COOCH2CH(OOCR2)CH2(OCH2CH2)nOH, preferably, the polyoxyethylene ethers, wherein R I and R2 are, independently, alkyl, alkenyl, or aromatic hydrocarbon which may be substituted or unsubstituted, preferably an alkyl radical, having from about 4 to about 22 carbon atoms; and n is from about 2 to about 80.
Preferred examples of such wash-off agents include: ceteth-2 through ceteth-30, steareth-2 through steareth-30, ceteareth-2 through ceteareth-30, PEG-2 stearate through PEG-30 stearate, PEG-12 isostearate, PEG-16 hydrogenated castor oil, PEG-40 hydrogenated castor oil, Unithox-480~, Unithox-425~, and PEG-20 glyceryl stearate; more preferably, ceteareth-20, steareth-21, PEG-20 stearate, Unithox-480~, Unithox-425~, and PEG-16 hydrogenated castor oil;
more preferably still, ceteareth-20, Unithox-480~ and Unithox-425~; also preferably Unithox-480~ and Unithox-425~.
METHODS OF 1~ZAMJFACTURE
The subject compositions may be manufactured by typical methods known to those skilled in the art. See, e.g., Gels and Sticks Formularv_, 99 Cosmetics &

Toiletries 77-84, 1984; incorporated herein by reference. The following method is particularly preferred.
The gelling agent and the liquid base material are combined in a vessel equipped with a heat source. The mixture is heated to between about 80°C and about 130°C with stirring, until a homogeneous, molten solution is formed.
Preferably, the homogeneous, molten solution is allowed to cool to a mixing temperature, typically between about 65~C and about 120oC, Alternatively, the mixture is heated to the mixing temperature until the mixture forms a homogeneous, molten solution. This alternative method, however, typically takes longer than overheating and cooling.
The active and optional ingredients, such as fragrances and colors, are added into the homogeneous molten solution in the above vessel with stirring.
The mixture is cooled until thickening occurs and poured into containers.
!y1'ETI-IODS FOR USE
The subject invention provides methods for preventing perspiration and malodor associated with human perspiration. These methods comprise applying to the skin of a human a safe and effective amount of the gel of the subject invention.
The term "a safe and effective amount" as used herein, is an amount which is effective in eliminating or substantially reducing malodor associated with human underarm perspiration while being safe for human use at a reasonable risk/benefit ratio. Typically, the safe and effective amount used is from about 0.1 gram per axilla to about 1.0 gram per axilla.
EXP~PLES
The following examples further describe and demonstrate embodiments within the scope of the subject invention. These examples are solely for the purpose of illustration and are not to be construed as limitations of the present invention as many variations are possible without departing from the spirit or scopethereof The levels of the components in the examples below are expressed by total , weight of the composition.
In i EXAMPLE N0. _ . . .._ _ ....
N-Lauroyl-L-glutamic acid-di-n-butyl amidel 4 5 1 3 2 2 2 I

12-hydroxystearic acid (100% R isomer) 2 5 S 6 7 3 6 1 Cyclomethicone D-52 q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s.
Polyphenylmethyl-siloxane3 _ _ _ 3 _ _ ' Light mineral oil4 2 - - _ _ _ - -Panalane-L-14E~5 - 15 10 11 - - _ _ Isopropyl Myristate - IS 15 16 - - 11 -Isopropyl Alcohol - - _ _ lg _ _ -Captex 200~6 - - - - - 15 - -C 12-C I5 Alcohols Benzoate - _ _ _ _ _ g -PPG-3 Myristyl Ether - - _ _ _ _ - 26 Diisopropyl Sebacate8 43 - - _ _ _ _ _ VVO 95131961 219 ~ 1 l 2 PCT~S95106104 Aluminum Zirconium Trichlorhydrex Gly~9 25 20 20 20 - 40 25 -Aluminum Chlorohydratel0 - - - - 30 - - 10 EDTA 0.2 0.1 0.5 1 5 10 7 0.01 Talc 3 - - 2 - - - 5 1) GP-1~ supplied by Ajinomoto, Inc.
2) Dow Corning 245 Fluid~-cyclic polydimethylsiloxane 3) Dow Corning 556 Fluid~
4) Benol White Mineral Oil supplied by Witco Chemical Corp.
5) polyisobutene supplied by Amoco Chemical Company 6) propylene glycol dicaprate/dicaprylate supplied by Capital City Products 7) Finsolv TN~ supplied by Finetex 8) Schercemol DIS~ supplied by Scher Chemicals Inc.

9) Supplied by Westwood Chemical Co.

10) Westchlor DM200~ supplied by Westwood Chemical Co.
IagI~dI~Bi E3 fA11rIPLE O.
N

N-Lauroyl-L-glutamic acid-di-n-butyl 2 2 2 2 2 2 2 2 2 2 amidel 12-hydroxystearic acid (85% S isomer, 15% R isomer) 6 6 6 6 6 6 6 6 6 6 -Cyclomethicone q.s.- q.s.- q.s.q.s.q.s.q.s.- -Cyclomethicone - q.s.- q.s.- - - - q.s.q.s.

PPG-3-myristyl - - - - - 12 - - - -ether PPG-5-butyl ether- - - - - - 10.5- - -PPG-10-cetyl ether- - - - - - - 12.5- --Isocetyl alcohol 7 8 13 - - - - - - -Isostearyl alcohol- - - 13 - - - - - -Octyldodecanol - - - - 8.5 - - - 14 14 Polydecene4 - - 26 - - - - - - -Citric Acid 4 1 10 0.1 2 5 0.2 0.5 0.010.05 Ceteareth-20 - - - - - - - - 2.52.5 Dipropyleneglycol- - - - - - - 0.25 WO 95!31961 PCTlUS9~3/D61D4 020-40 alcohols5 - - - - - - - - 0.5 0.5 040-60 alcohols6 0.5 0.5 0.5 OS.. . 0.5 0.5 ..
0.5 0.5 -Aluminum Zirconium Trichlorhydrex Gly~7 26 26 26 26 26 26 26 26 26 1) GP-I~ supplied by Ajinomoto, Inc.

2) Dow Corning 245 Fluid~ - cyclic polydimethylsiloxane 3) Dow Corning 244 Fluid ~- cyclic polydimethylsiloxane 4) Ethylflo 364~ supplied by Ethyl Corp.

5) Unilin 425~ supplied by Petrolite 6) Unilin 700~ supplied by Petrolite 7) Supplied by Westwood Chemical Co.

In_ edient .. E

N-Stearyl-L-glutamic acid-di-n-hexyl amide! 2 2 - - - - -N-Lauroyl-L-glutamic acid-di-n-octyl amide! - - 2 2 - - -N-Lauroyl-L-glutamic acid-di-n-decyl amide! - - - - 2 - -N-Stearyl-L-glutamic acid-di-n-decyl amide! - - - - - 2 -N-Lauroyl-L-glutamic acid-di-n-stearyl amide! - - - - - - 2 12-hydroxystearic acid (30% R isomer, 70% S isomer) - - 6 6 6 6 6 Isopropyl amide of I2-hydroxystearic acid!

(30% R isomer, 70% S isomer 6 6 - - - - -Cyclomethicone D-52 q.s. q.s. q.s. q.s.q.s.q.s. q.s.

Salicylic Acid 0.01 1 10 5 0.2 0.5 3 012-15 Alcohols Benzoate3 25 - 25 - 25 25 25 Octyldodecanol - 14 - 14 - - -Ceteareth-20 - 2.5 - - 2.5 - - --C40-60 alcohols4 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Aluminum Zirconium Trichlorhydrex Gly~5 26 26 26 26 26 26 26 W095131961 21911 12 PCT~S95/06104 1) Supplied by Starks Chemical Co.
2) Dow Corning 245~ Fluid - cyclic polydimethylsiloxane 3) Finsolv TN~ supplied by Finetex 4) Unilin 700~ supplied by Petrolite 5) Supplied by Westwood Chemical Co.
r ~neredient EXAMPLE 26 Octyldodecanol 14 12-Hydroxystearic acid (100% S isomer) 7 N-Lauroyl Glutamate Dibutylamidel 2 Unithox 480~ 1.25 Unithox 425~ 0.5 Aluminum Zirconium Trichlorohydrex Gly~ 26 Cyclomethicone D-53 q.s.

1 Supplied by Starks Chemical Co 2Supplied by Westwood Chemical Co.

3Dow Corning 245 Fluid~ - cyclic polydimethylsiloxane Although particular examples of gel stick of the subject compositions invention have been described, modifications departing may be made without from the spirit and scope of the subject invention.
Accordingly, the subject invention comprises all embodiments within the scope .
of the appended claims

Claims (19)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Antiperspirant gel composition comprising:
a. an effective amount of an antiperspirant active b. an effective amount of a gelling agent, comprising:
(i) an optically enriched primary gellant selected from the group consisting of 12-hydroxystearic acid, esters of 12-hydroxystearic acid, amides of 12-hydroxystearic acid corresponding to the formula:

wherein R4 is OR5 or NR5 R6; and R4 and R5 are, independently selected from the group consisting of hydrogen, alkyl moieties, aryl moieties and mixture thereof, wherein said moieties have from 1 to about 26 carbon atoms, wherein said primary gellant is the S isomer and combinations of the S isomer and R isomer of said primary gellant, wherein the ratio of S to R or R to S isomers is not less than 45%:55%;
(ii) a secondary gellant selected from the group consisting of d or 1 n-aryl amino acid amide derivatives corresponding to the formula:

wherein R1 is an alkyl moiety, aryl moiety and mixtures thereof having from about 6 to about 22 carbon atoms; and R2 and R3 are independently selected from the group consisting of alkyl ester, aryl ester, alkyl amide, aryl amide and mixtures -22-~

thereof having from about 1 to about 26 carbon atoms;
and c. an effective amount of a liquid base material having a solubility parameter of 9 or below wherein the gel stick has a hardness of 75 g of force or more.

2. The composition of claim 1 wherein the composition comprises less than 30% water.

3. The composition of claim 2 wherein the liquid base material comprises a volatile, non-polar, oil, a non-volatile, relatively polar co-solvent, and mixtures thereof.

4. The composition of claim 1 wherein the liquid base material comprises a non-polar, volatile oil selected from the group consisting of cyclic volatile silicones having the structure:

wherein n is from about 3 to about 7; and linear volatile silicones corresponding to the formula:

(CH3)3Si--O--[S1(CH3)2 O]m --S1(CH3)3 wherein m is from about 1 to about 7; and mixtures thereof.

5. The composition of claim 4 wherein the composition has a hardness of 100 g of force or more and comprises less than 20% water.

6. The composition of claim 5 wherein:
a) the primary gelling agent is 12-hydroxystearic acid;
and b) the secondary gelling agent is in 1 form.

7. The composition of claim 6 wherein the secondary gelling agent is selected from the group consisting of N-lauroylglutamic acid diethylamide, N-lauroylglutamic acid dibutylamide, N-lauroylglutamic acid dihexylamide, N-lauroylglutamic acid dioctylamide, N-lauroylglutamic acid didecylamide, N-lauroylglutamic acid didodecylamide, N-lauroylglutamic acid ditetradecylamide, N-lauroylglutamic acid dihexadecylamide, N-lauroylglutamic acid distearylamide, N-stearoyl-glutamic acid dibutylamide, N-stearoylglutamic acid dihexylamide, N-stearoylglutamic acid diheptylamide, N-stearoylglutamic acid dioctylamide, N-stearoylglutamic acid didecylamide, N-stearoylglutamic acid didodecylamide, N-stearoylglutamic acid ditetradecylamide, N-stearoylglutamic acid dihexadecylamide, N-stearoylglutamic acid distearylamide and mixtures thereof.

8. The composition of claim 7 wherein the secondary gelling is selected from the group consisting of N-lauroylglutamic acid dibutylamide, N-stearylglutamic acid dihexylamide, and mixtures thereof.

9. The composition of claim 7 wherein the composition has a hardness of 150g of force or more and comprises less than 5% water.

10. The composition of claim 9 wherein the 12-hydroxystearic acid has an (R
isomer): (S isomer) or an (S isomer): (R isomer) ratio ranging from about 0%:100% to about 30%:70%.

11. The composition of claim 10 wherein:
(a) the composition comprises from about 3% to about 12% of the gelling agent;
and (b) the primary gellant: secondary gellant ratio is from about 1:1 to about 10:1.

12. The composition of claim 11 wherein the active is an aluminum, zirconium and amino acid complex having an Al:Zr ratio from about 1.67 to about 12.5 and a Metal:C1 ratio of from about 0.73 to about 1.93.

13. The composition of claim 12 wherein the active has an average particle size greater than about 30 microns and a density greater than about 0.7 grams per cubic centimeter.

14. The composition of claim 13 wherein the 12-hydroxystearic acid has an (R
isomer:S isomer) or an (S isomer:R isomer) ratio ranging from about 0%:100% to about 15%:85%.

15. The composition of claim 14 wherein the 12-hydroxystearic acid has an (R
isomer:S isomer) or an (S isomer:R isomer) ratio ranging from about 0%:100% to about 5%:95%.

16. The composition of claim 15 wherein the secondary gelling agent is selected from the group consisting of N-lauroylglutamic acid dibutylamide, n-stearylglutamic acid, dihexylamide and mixtures thereof.

17. The composition of claim 16 wherein the non-polar volatile silicone oil is cyclomethicone D-5.

18. The composition of claim 17 wherein the composition is substantially water free.

19. The composition of claim 18 wherein the primary gellant comprises either 100% R or 100% S 12-hydroxystearic acid.