AU721094B2 - Gelling compositions comprising optically enriched gellants - Google Patents

Description

I,

rILKU ;M I 2&SdVl Regutalaon 3.2(2)

AUSTRALIA

Patents Act 1990

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT a. a a a.

a. a a.

a Application Number: Lodged: Invention Title: GELLING COMPOSITIONS COMPRISING OPTICALLY ENRICHED

GELLANTS

a The following statement Is a full description of this Invention, Including the best method of performing It known to us GELLING COMPOSITIONS

COMPRISING

OPTICALLY EN.RICHED GELLANTS FIELD OF THE rNVENTION The subject invention relates to low-aqueous gelling compositions.

BACKGROUND OF THE INVENTION Organic cosmetic products with different hardness and rheological properties can be achieved by varying the ratio of waxy and/or pasty oils to liquid organic oils in a given composition. In general, these cosmetic products provide s1 good skin feel. but are limited in the amount of liquid oil that can be formulated.

These products can also leave visible residue on the skin.

Gels have the ability to retain increased amounts of liquid in a cosmetic composition while significantly reducing or eliminating the visible residue on the skin as compared to a waxy cosmetic of equal hardness. However, one significant 20 disadvantage of typical gel 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 poor gel formation and lower gel stability of any gel which is formed. The leaking may also cause processing difficulties at the temperatures and holding times typically encountered during manufacture.

It is an object of the subject invention to provide low-aqueous gelling compositions with superior gel formation.

SUMMARY OF THE INVENTION The subject invention involves gelling compositions comprising optically enriched, asymmetric, di-chiral, di-hydroxy fatty acid gellants having adjacent chiral centers.

DETAILED DESCRIPTION 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 one double or triple bond in the carbon chain), or polyunsaturated 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 unsubstituted, or mono-, di-, or tri-substituted, more preferably monosubstituted or unsubstituted, most preferably unsubstituted.

Preferred alkyl are C6 to C30, more preferably C10 to C28, more preferably still C14 to C24, and most preferably 022.

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, nitro, 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 substituents include alkyl, halo, amino, hydroxy, cyano, nitro and trifluoromethyl.

*As used herein, the term "alkoxy" means O-alkyl.

As used herein, the term "aryloxy" means O-aryl.

As used herein, the terms "comprise", "comprises", "comprised" and "comprising" when used in this specification are taken to specify the presence of stated features, integers, steps or components but does not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.

Gelling Agent The subject compositions comprise optically enriched gelling agents.

The subject gelling agents are asymmetric, linear, branched or cyclic, substituted or unsubstituted, di-chiral, di-hydroxy fatty acids having the structure: O OH OH

HO-C-A-C-C-B-CH

3

(I)

wherein A and B each represent linear, branched or cyclic, saturated or unsaturated, substituted or unsubstituted alkyl having from about 1 to about 13 carbon atoms, preferably from about 3 to about 12 carbon atoms, more 2a preferably from about 5 to about 10 carbon atoms; such that structure (I) represents a di-hydroxy fatty acid having from about 6 to about 30 carbon atoms, more preferably from about 10 to about 24, more preferably still from about 14 to about 22, most preferably about 18 carbon atoms. The two chiral centres in the subject gellants lie in the carbon atoms substituted by the hydroxyl moieties.

Preferred gellants include 9,10-dihydroxystearic acid, 13,14dihydroxystearic acid, 13,14-dihydroxydocosanoic acid, and 11,12dihydroxystearic acid. The most preferred gellant is 13,14-dihydroxydocosanoic S 10 acid.

As used herein, the term "optically enriched" means that the gelling agent contains about 90% or more, preferably about 95% or more, more preferably 98% 9 or more, most preferably about 100% of a given stereoisomer intramolecularly. both chiral centers are R or both chiral centers are Thus, the gelling agent contains less than about 10%. preferably less than about more preferably less than about most preferably 0% of the racemic form S or S.

R stereochemistry within the same molecule). It has been unexpectedly found that when an optically enriched sample of gellant is used in the subject invention, superior gelling results. While not limited to any particular mechanism of action, it is believed that the optically enriched gellant is thermodynamically favored to form fibrils that are aligned and bundle, thereby contributing to a more ordered 1o macrostructure in which the liquid base is trapped. The racemic mixture, on the other hand, is thermodynamically favored to form large crystals.

Mixtures of optically enriched gelling agents are also effective in the subject invention.

The subject compositions preferably comprise from about 0.1% to about 15 25%, more preferably from about 1% to about 15%, more preferably still from about 3% to about 12%, most preferably from about 4% to about 10% of the gellant.

Liquid Base Material The subject compositions also comprise a liquid base material. A liquid 20 base matrix is formed by combining the gelling agent with a liquid base material.

As 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 term "non-polar" typically means that the solution has a solubility parameter below about 6.5. The term "volatile" as used herein refers to materials which exhibit a vapor pressure of more than about 2mm Hg at 25 0 C at one atmosphere and/or to materials which have a boiling point at one atmosphere of at less than about 3000C. The non-polar, volatile oil tends to impart highly desirable aesthetic properties to the gel and is preferably used at levels from about 10% to about 70% of the composition; more preferably, from about 25% to about more preferably from about 40% to about 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, incorporated herein by reference. 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 C 7

-C

8 through C 1 2-C 1 5 isoparaffins (such as the Isopar@ Series available from Exxon Chemicals).

Non-polar, volatile silicone oils are highly preferred because they provide the gel 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); both incorporated herein by reference. Particularly preferred volatile silicone oils include cyclic volatile silicones corresponding to the formula: Sf

CH-

o S. CH3 Se n wherein n is from about 3 to about 7; and linear volatile silicones corresponding to the formula:

(CH

3 3 Si-O-[Si(CH 3 2 0]m-Si(CH 3 3 wherein m is from about 1 to about 7. Linear volatile silicones generally have a viscosity of less than about 5 centistokes at 250C, whereas the cyclic silicones have viscosities of less than about 10 centistokes at 250C. Highly preferred examples of volatile silicone oils include cyclomethicones of varying viscosities, Dow Coming 200®, Dow Corning 244®, Dow Coming 245®, Dow Coming 344®, and Dow Coming 345®, (commercially available from Dow Coming Corp.); SF-1204® and SF-1202® Silicone Fluids (commercially available from G.E. Silicones), GE 7207® and 7158® (commercially available from General Electric and SWS-03314® (commercially available from SWS Silicones Corp.).

The phrase "relatively polar" as used herein means more polar than another material in terms of solubility parameter; the higher the solubility parameter the more polar the liquid. 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 has a higher solubility parameter) than at least one of the non-polar, volatile oils. The relatively polar co-solvent of the subject invention aids in the utilization of reduced processing temperatures by solubilizing the gellant 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 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 2% to about 60% of the composition; more preferably from about 5% to about 25%; and 1o most preferably from about to about Relatively polar, non-volatile liquids useful as the co-solvent in the subject invention are disclosed, for example, in Cosmetics, Science, and Technology, Vol.

S 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 15 March 28, 1989; all incorporated herein by reference. Relatively polar, nonvolatile 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; polyoxypropylenes; mixtures of polyoxyethylene and polyoxypropylene ethers of fatty alcohols; and 20 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 S 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 8 fatty alcohols having a degree of propoxylation below about 50, esters of C 2

-C

8 alcohols and C 12

-C

2 6 carboxylic acids ethyl myristate, isopropyl palmitate), esters of C 12

-C

2 6 alcohols and benzoic acid (e.g.

Finsolv TN supplied by Finetex), diesters of C2-C 8 alcohols and adipic, sebacic.

and phthalic acids diisopropyl sebacate, diisopropyl adipate, di-n-butyl phthalate), polyhydric alcohol esters of C 6

-C

26 carboxylic acids propylene glycol dicaprateidicaprylate. propylene glycol isostearate): and mixtures thereof.

Even more preferred relatively polar, ion-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; all incorporated 15 herein by reference. 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 polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, polyethersiloxane copolymers, and mixtures thereof. .Examples of these include polydimethyl 20 siloxanes having viscosities of from about 5 to about 100,000 centistokes at Among the preferred non-volatile silicone emollients useful in the subject compositions are the polydimethyl siloxanes having viscosities from about 2 to S* about 400 centistokes at 250C. Such polyalkylsiloxanes include the Viscasil® series (sold by General Electric Company) and the Dow Coming 200® series (sold by Dow Coring Corp.). Polyalkylarylsiloxanes include polymethylphenyl siloxanes 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 25 0

C.

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 paraffinic 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, incorporated herein by reference. Preferred mineral oils have the following properties: viscosity from about 5 centistokes to about 70 centistokes at 40 0

C;

density between about 0.82 and 0.89 g/cm3 at 25 0 C; flash point between about 1380C and about 2160C; and carbon chain length between about 14 and about carbon atoms.

Preferred branched chain hydrocarbon oils have the following properties; density between about 0.79 and about 0.89 g/cm 3 at 200C; boiling point greater than about 2500C; and flash point between about 1100C and about 2000C.

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; Permethyl 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.

o. 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 a solubility parameter in the range of from about 5 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 art of antiperspirant stick formulation and the means to determine them are disclosed 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, Sept/Oct, 1985; both incorporated herein by reference.

The liquid base material preferably 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 solubilise the gelling agent when heated, to permit substantially uniform mixing. 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 minimised visible residue, without significant interference with other components of the formulation. The particular liquid base material should be safe for application to human skin.

0* 9 .9 9 9• 0* •oe As used herein, the term "gel" means a non free flowing solid after the gellant has been melted and allowed to cool to ambient temperature.

As used herein, the term "low-aqueous gel composition" means a gel composition comprising less than 50% water, preferably less than 30%. more preferably less than 20% water, even more preferably less than 10% water, also preferably less than 5% water. The most preferred gel 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.

Optional Ingredients Gel 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 15 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 S. 20 which published on August 29, 1984; and Geria, "Formulation of Stick Antiperspirants and Deodorants", Cosmetics and Toiletries. 99:55-60 (1984); all incorporated herein by reference.

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 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; incorporated herein by reference.

Thickeners are also useful in the subject invention. Typically, thickeners comprise, less than about 5% 6f 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; incorporated herein by reference. 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 thickeners, such as clay and silica, are also useful.

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 Such materials are disclosed in U.S. Pat. 5.019,375. Tanner et al., issued May 28. 1991: incorporated herein by reference. 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; incorporated herein by reference. 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 15 be washed off. The wash-off agent is preferably a non-liquid. The wash-off agent is typically in the gel in an amount from about 0.1% to about 10% of the composition.

"o Typical wash-off agents are non-liquids selected from the group consisting of polyoxyethylene ethers having the formula RI(OCH2CH 2 )nOH; 20 polyoxyethylene esters having the formula RICO(OCH2CH 2 )nOH; polyoxyethylene glyceryl esters having the formula (R 1COO)CH2CH(OH)CH 2

(OCH

2

CH

2 )nOH or having the formula HOCH2CH(OOCR I)CH 2 (OCH2CH 2 )nOH; and polyoxyethylene glyceryl diesters having the formula RICOOCH 2 CH(OOCR2)CH 2

(OCH

2

CH

2 )nOH, preferably, the polyoxyethylene ethers, wherein R 1 and R 2 are, independently, alkyl, alkenyl, S" or aromatic hydrocarbon which may be substituted or unsubstituted, preferably an alkyi radical, having from about 4 to about 22 carbon atoms; and n is from about 2 to about 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 glyceryl stearate; more preferably, ceteareth-20, steareth-21, 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®.

Antiperspirants The subject gels are particularly useful for antiperspirant and/or deodorant compositions. Such compositions contain an astringent antiperspirant active.

Antiperspirant actives useful in the subject invention are well known in the art.

See e.g. "Antiperspirants and Deodorants". Cosmetic Science and Technology Series, K. Laden C. Felger.. eds., Vol. pp. 42-56 (1988): incorporated herein by reference. 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 hydroxv-halides, and mixtures of these materials.

Aluminum salts of this type include aluminum chloride and the aluminum hydroxyhalides having the general formula A2(OH)xQy.XH20 wherein: Q is chlorine, bromine or iodine; x is from about 2 to about 5, and x+y about 6, and x and y do not need to be integers; and X is from about 1 to about 6.

20 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; both incorporated herein by reference.

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: ZrO(OH) 2 -nzBz wherein: z may vary from about 0.9 to about 2 and need not be an integer; n is the valence of B; 2-nz is greater than or equal to 0: 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 IVB metal compounds, including hafnium, can be used in the subject 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 1.1 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, U.S. Patent 3,792,068 issued to Luedders et al. on February 12, 1974 discloses complexes of aluminum, zirconium and to 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 "AJ:Zr" ratio) and the molar 15 ratio of total metal to chlorine (hereinafter "Metal:Cl" ratio). ZAG complexes useful herein have an AJ:Zr ratio of from about 1.67 to about 12.5 and a Metal:CI ratio of from about 0.73 to about 1.93.

Preferred ZAG complexes are formed by co-dissolving in water- 20 one part Al2(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 x parts ZrO(OH)2.aQa.nH 2 0, 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; p parts neutral amino acid selected from the group consisting of glycine, dl-tryptophane, dl-b-phenylalanine, dlvaline, dl-methionine and b-alanine, and where p has a value of from about 0.06 to about 0.53; co-drying the resultant mixture to a friable solid; and 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 A1 2

(OH)

5 C1.2H 2 0. Preferred zirconium compounds for preparation of such ZAG-type complexes are zirconyl hydroxychloride having the empirical formula ZrO(OH)C1.3H 2 0 and the zirconyl hydroxyhalides of the empirical formula ZrO(OH)2_aCI.nH20O wherein a is from about 1.5 to about 1.87. and n is from about I to about 7. The preferred amino acid for preparing such ZAG-type complexes is glycine of the formula CH 2

(NH

2 )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; incorporated herein by reference.

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 aluminum 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 Pauling 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

[A

2

(OH)

4 Cl][H 2

CNH

2

COOH].

Of all the above types of antiperspirant actives, preferred compounds include the 5/6 basic aluminum salts of the empirical formula A 2

(OH)

5 C1.2H 2 0; mixtures of AICI 3 .6H 2 0 and A 2

(OH)

5 C1.2H 2 0 with aluminum chloride to aluminum hydroxychloride weight ratios of up to about 0.5; ZAG type complexes wherein the zirconium salt is ZrO(OH)C1.3H 2 0, the aluminum salt is

A

2

(OH)

5 C1.2H 2 0 or the aforementioned mixtures of AIC1 3 .6H20 and A 2

(OH)

CI.2H 2 0 wherein the total metal to chloride molar ratio in the complex is less than about 1.25 and the Al:Zr molar ratio is about 3.3, and the amino acid is glycine; and ZAG-type complexes wherein the zirconium salt is ZrO(OH)2-aCla.nH20 wherein a is from about 1.5 to about 1.87 and n is from about I to about 7, the aluminum salt is A 2

(OH)

5 C1.2H 2 0, 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 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/cm 3 and an average particle 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 1o and preferably less than 15% of the composition. Examples of such actives are *o *taught, for example, in U.S. Patent 4,137.306 issued to Rubino on January 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; all S. incorporated herein by reference.

METHODS OF MANUFACTURE The subject compositions may be manufactured by typical methods known to those skilled in the art. See, Gels and Sticks Formulary, 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 800C and about 140°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 0 C and about 1200C. 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.

In case of antiperspirants, 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.

EXAMPLES

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 scope thereof.

The levels of the components in the examples below are expressed by total weight of the composition.

Iniziedient EXAIMIPLE NO.

I 2 3 4 5 6 7 8 11. 12 di-hydroxystearic acid (S.S isomer) 2 1 5 7 6 11I, 12 di-hydroxystearic acid isomer) 2 3 4 1 3 1 Cyclomethicone D-5 1 q. s. q. s. q. s. q. s. q. s. q. s. q. s. q. s.

Polyphenvimethyl- *10 siloxane 2 3 5 Light mineral oil 3 2 Panalane-L- 14E®& 4 15 10 11 Isopropyl Myristate 15 15 16 1 *:Isopropyl Alcohol 18 Captex 200g5 15 C C 12 -C 15 Alcohols Benzoate 6 8 PPG-3 Myristyl Ether 26 *Diisopropyl Sebacate 7 43 Aluminum Zirconium Trichiorhydrex Gly® 8 25 20 40 25 Aluminum *Chlorohydrate 9 30 EDTA 0.2 0.1 0.5 1 5 10 7 0.01 Talc 3 2 1) Dow Corning 245 Fluid®&-cycfic polydimethylsiloxane 2) Dow Corning 556 fluid® 3) Benol White Mneral Oil supplied by Witco Chemnical Corp.

4) polyisobutene supplied by Amoco Chemical Company propylene glycol dicaprate/dicaprylate supplied by Capital City Products 6) Finsolv TN® supplied by Finetex 7) Schercemol DIS®V supplied by Scher Chemicals Inc.

8) Supplied by Westwood Chemical Co.

9) Westchlor DM200® supplied by Westwood Chemical Co.

Ln red ie nt EXAMPLE NO.

9 10 1 1 12 13 14 15 16 17 18 cid 13. l4-dihydroxcydocosanojc a e a. a (S.S isomer) Cyclomethicone D-41 Cyclomethicone D-5 2 PPG-3-myristyl ether ether PPG- I 0-cetyl ether Isocetyl alcohol Isostearyl alcohol Octyldodecanol Polydecene 3 Citric Acid Ceteareth-20 Dipropyleneglycol

C

20 4 0 alcohols 4 6 6 q. s.

a. s. 6 6 6 6 q. s. q. s, q. s. q.s.

[2 q. s. q. s.

10.5 12.5 7 8 6 6 13 0.1 2 0.2 0.5 0.01 0.05 2.5 0.25 0.5 *a a.

1) Dow Corning 245 Fluid®& cyclic polydimethylsiloxane 2) Dow Corning 244 Fluid 9- cyclic polydimethylsiloxane 3) Ethylflo 364® supplied by Ethyl Corp.

4) Unilin 4250 supplied by Petrolite Octyldodecanol 6,7 dihydroxystearic acid (S,S isomer) Unithox 480®D Unithox 425S® Aluminum Zirconium Trichiorohydrex Glyy® 1 Cyclomnethicone D-5 2 1 uple by Westwood Chemical Co.

2 Dow Corning 245 Fluid®& cyclic polydimethylsiloxane EXAMPLE 19 14 7 1.25 26 q. s.

In~redient .EXAMPLE 20 C 1 2-C 15 Alcohols Benzoate (Finsolv 30 Cyclomethicone D-5 q.s.

11, 12 dihvdroxvstearic acid S isomer) 10 Aluminum Zirconium Trichiorohydrex Gly® 26 EXAJAPLE 21 q. s.

S. S S S Ineredient 13. 14-dihydroxvdocosanoic acid R isomer) Triclosan 10 Perfume Cyclomethicone D-5 C 12 -C 15 Alcohols Benizoate (Finsolv TN®) Ingredient 11, 12-dihydroxystearic acid R isomer) 9, 1 0-dihydroxystearic acid R isomer) Triclosan Perfume Cyclomethicone D-5 C 12 -C 15 Alcohols Benzoate (Finsolv TN®D) EXAMIPLE 22 0.3 0.1 q.s.

33.1 EXAMPLE 23 4 0.3 0.1 q.s.

33.1 S. US

S

S

SSSSSS

S

Claims (27)

1. A low-aqueous gel composition including: a) an optically enriched gellant having the structure: O OH OH 11 I I HO-C-A-C-C-B-CH 3 wherein A and B independently represent linear, branched or cyclic, saturated or unsaturated, substituted or unsubstituted alkyl groups wherein the gellant is an asymmetric, di-chiral, di-hydroxy fatty acid whose content of a given stereoisomer is 90% or more in the R, R or S, S form and has from 6 to carbon atoms; and b) a liquid base material.

2. The composition of claim 1 wherein the liquid base material includes a volatile, non-polar oil.

3. The composition of claim wherein the liquid base material includes a non-polar, volatile oil selected from the group consisting of cyclic volatile silicones have the structure: CH3 L- n wherein n is from 3 to 7; and linear volatile silicones corresponding to the structure: (CH 3 3 Si-O-[Si(CH 3 2 0]m-Si(CH 3 3 wherein m is from 1 to 7; and mixtures thereof.

4. The composition of any one of claims 1 to 3 wherein the liquid base material includes a relatively polar co-solvent. i 18 The composition of any one of claims 1 to 4 wherein A and. B independently represent linear or branched alkyl.

6. The composition of claim 1 wherein A and B independently represent straight chain alkyl.

7. The composition of any one of claims 1 to 6 wherein A and B independently represent alkyl having from 3 to 12 carbon atoms.

8. The composition of claim 7 wherein A and B independently represent alkyl having from 5 to 10 carbon atoms.

9. The composition of any one claims 1 to 8 wherein A and B each are unsaturated alkyl groups. The composition of any one of claims 1 to 9 wherein A and B are independently unsubstituted alkyl or substituted alkyl and the substituents are selected from the group consisting of halogen, hydroxyl, amino, nitro, carboxy, thio, aryl, alkyl, alkoxy, aryloxy groups and mixtures thereof.

11. The composition of claim 10 wherein the substituents are selected from alkyl, alkoxy and aryl.

12. The composition of claim 10 wherein A and B are unsubstituted alkyl.

13. The composition of any one of claims 1 to 12 wherein the gellant is or more in the R, R or S, S form.

14. The composition of claim 13 wherein the gellant is 98% or more in the R, R or S, S form. i I 19 The composition of any one of claims 1 to 14 wherein the gellant contains from 14 to 24 carbon atoms.

16. The composition of claim 15 wherein the gellant contains 22 carbon atoms.

17. The composition any one of claims 2 to 16 wherein the non-polar volatile oil is cyclomethicone

18. The composition of any one of claims 1 to 17 wherein the liquid base material includes at least two solvents.

19. The composition of any one of claims 1 to 18 wherein the composition is substantially water free and the gellant is 100% in the R, R or S, S form. 9* The composition of selected from the group dihydroxystearic acid, dihydroxystearic acid.

21. The composition dihydroxydocosanoic acid. any one of claims 1 to 19 wherein the gellant is consisting of 9,10-dihydroxystearic acid, 13,14- 13,14-dihydroxydocosanoic acid, and 11,12- of claim 20 wherein the gellant is 13,14-

22. A low-aqueous antiperspirant gel composition including: a) an antiperspirant active; b) an optically enriched gellant having the structure: 0 OH OH HO-C- -C-II I I HO-C-A-C-C -B-CH 3 A It wherein A and B independently represent linear, branched or cyclic, saturated or unsaturated, substituted or unsubstituted alkyl groups wherein the gellant is an asymmetric, di-chiral, di-hydroxy fatty acid that is 90% or more in the R, R or S, S form and has from 6 to 30 carbon atoms; and c) a liquid base material.

23. The composition of claim 22 wherein A and B are independently unsubstituted or substituted alkyl and the substituents are selected from the group consisting of halogen, hydroxyl, amino, nitro, carboxy, thio, aryl, alkyl, alkoxy, aryloxy groups and mixtures thereof. oo

24. The composition of claim 23 wherein A and B each represent linear, saturated alkyl which are unsubstituted or substituted, any substituent being selected from the group consisting of alkyl, alkoxy and aryl. 0 The composition of any one of claims 22 to 24 wherein the liquid base material selected from the group consisting of volatile and non-polar oils, non- volatile and relatively polar co-solvents and mixtures thereof.

26. The composition of any one of claims 22 to 25 wherein: a) A and B independently represent linear or branched alkyl having from 3 to 12 carbon atoms; b) the gellant has from 10 to 28 carbon atoms and is 95% or more in the R, R or S, S form; and c) the active is a complex of aluminum, zirconia and amino acids.

27. The composition of claim 26 wherein A and B independently represent linear saturated alkyl.

28. The composition of any one of claims 22 to 27 wherein the gellant is 98% or more in the R, R or S, S form. S* I 21

29. The composition of claim 28 wherein the composition is substantially water free. The composition of any one of claims 22 to 29 wherein the liquid base material includes at least two solvents.

31. The composition of any one of claims 22 to 30 wherein the gellant has 22 carbon atoms, and is 100% in the R, R or S, S form.

32. The composition of claim 1 substantially as hereinbefore described with reference to the examples.

33. The composition of claim 22 substantially as hereinbefore described with o reference to the examples. DATED this 10th day of May 1999 THE PROCTER AND GAMBLE GROUP WATERMARK PATENT TRADEMARK ATTORNEYS 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA LCG:JGC:VRH