MXPA99005846A - Low residue antiperspirant gel-solid stick compositions containing select gellants - Google Patents

Abstract

Disclosed are anhydrous antiperspirant gel-solid stick compositions which comprise a particulate antiperspirant active;a solid non-polymeric gellant selected from the group consisting of 12-hydroxystearic acid, esters of 12-hydroxystearic acid, amides of 12-hydroxystearic acid, and combinations thereof, and an anhydrous liquid carrier having an average solubility parameter of from about 3 to about 13 (cal/cm3)0.5, wherein the composition has a visible residue index of from about 11 to about 30 L-value, a product hardness of from about 500 gram.force to about 5,000 gram.force, a ratio of an elastic to viscous moduli of from about 0,1 to about 100. The refractive indices of the particulate antiperspirant active, solid non-polymeric gellant, and anhydrous liquid carrier are not matched. The solid non-polymeric gellant is preferably a crystalline material having an average particle size of less than about 1&mgr;m, and/or having an elongated particle morphology having an aspect ratio of greater than about 2. These antiperspirant gel-solid stick compositions provide improved low residue performance, efficacy and aesthetics.

Description

ANTI-RANSPIRANT BAR COMPOSITIONS IN LOW RESIDUE GEL-SOLID CONTAINING SELECTED GELIFIERS TECHNICAL FIELD The present invention relates to antiperspirant compositions in the form of gel-solid sticks. In particular, the present invention relates to antiperspirant compositions in the form of 'gel-solid' bars that provide improved performance properties of appearance, residue and aesthetics, improved and containing selected gelling agents.

BACKGROUND OF THE INVENTION There are many types of topical antiperspirant products that are commercially available or that are otherwise known in the antiperspirant art. Most of these products are formulated as an aerosol or pump spray, roll-on liquids, creams, emulsions, gels, solid gels or other solid-bar formulations, and comprise an astringent material, such as salts of zirconium or aluminum or combinations thereof, incorporated in a suitable carrier. These products are designed to provide effective transpiration properties and odor control as they are cosmetically acceptable during application and after application in the axillary area or other areas of the skin. Within this group of products, solid antiperspirant sticks have become especially popular with consumers. These antiperspirant bars comprise a solid matrix within which the antiperspirant active material is contained. The active can be solubilized in a liquid carrier comprising water, glycols and / or other alcohols, or it can be maintained within a solid matrix as dispersed solids in an anhydrous system. The solid stick containing the dissolved active often provides some minor performance of residue appearance, but tends to be damp or sticky during application to the skin and immediately after it, and most importantly, often is not so effective to provide antiperspirant and deodorant performance as the solid bars containing dispersed particulate active material. Although antiperspirant sticks containing the particulate active materials are more effective, they also tend to leave a visible residue higher in the skin. There have been many attempts to produce anhydrous antiperspirant sticks containing the dispersed, particulate antiperspirant active, and which also provide improved efficacy and low residue appearance performance during application to and after the skin, or which otherwise provide clarity of the product before application (as a packaged product) or after application (such as a transparent or low residue film on the skin). One of these attempts involves the combination of the active antiperspirant particulate, gelling agents and liquid carrier in a gel bar; wherein all the components in combination have comparable refractive indices. The comparable refractive index allows more light to pass through the gel bar with less dispersion of the same, resulting in products that appear more transparent or translucent as a packaged composition or when initially applied to the skin in a topical manner. However, these gel bars are expensive in their manufacture due to the cost of using raw materials that only have comparable refractive indices. These compositions are also very difficult to formulate since the comparable refractive index for a three component system (active particulate, solvent and gelling agent) is extremely difficult, greatly limiting the materials that can be used to prepare a formulation. Another attempt to manufacture low residue antiperspirant sticks involves the use of gelling agents such as, for example, dibenzylidene alditols. However, these gelling agents, similar to many other gelling agents known in the art, they are not stable acids and therefore tend to interact with the antiperspirant active due to the acid nature of the active. This interaction can result in reduced efficacy of the active, poor gel formation and inferior gel stability for long periods of time during shipment or storage. This interaction can also cause processing difficulties at the temperatures and waiting times frequently used during the formulation and manufacturing process. These gelling agents are also commonly used in combination with carriers of glycol or other solvents that tend to be moist and sticky and irritate the skin. Yet another attempt to manufacture low residue antiperspirant sticks involves the use of residue masking agents such as for example 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 to reduce the visible residue during the application of the solid stick to the skin and immediately after it, although they also tend to be associated with an oily or sticky skin sensation during application. In addition, although the visible residue is reduced in these compositions, there remains a visible residue on the skin when used in combination with high residue waxes such as, for example, stearyl alcohol, and this reduced residue is even more visible or evident than the residue topical left by antiperspirant sticks containing the solubilized antiperspirant active.

Other attempts at the improvement of lower performance appearance of residue of an antiperspirant composition have focused on the use of anhydrous antiperspirant creams. These creams can be applied to the skin by conventional means, or by means of a cream applicator device and result in a very low residue during application to and immediately after the skin. These compositions comprise the particulate active dispersed through an anhydrous carrier, and either contained within an almost solid matrix or thickened with a polymeric or inorganic thickening or gelling agent. However, many consumers still prefer the convenience of using a solid antiperspirant stick, although the solid stick tends to leave a high visible residue on the skin. A recent method for manufacturing low residue antiperspirant sticks is described in U.S. Patent 5,429,816, issued to Hofrichter et al., On July 4, 1995, the disclosure of which is incorporated herein. as reference. The antiperspirant sticks provide low visible residue during application to the skin and immediately after it, and are physically and chemically stable for long periods of time. The improved antiperspirant sticks comprise a double gelling system having a primary gelling agent such as, for example, 12-hydroxystearic acid or esters or amides thereof, and a secondary gelling agent such as, for example, n-acyl amino acid derivatives. The formation of an antiperspirant stick with this double gelling system has been characterized as a "gel-solid" antiperspirant stick. A gel-solid antiperspirant, such as, for example, the one described by Hofrichter et. al., is an antiperspirant bar that has a three-dimensional, non-polymer gel network in which the solvent is contained or trapped. These solid gels are typically formed by solubilizing the gellant in the solvent at temperatures above the melting point of the gellant and at temperatures at which the molten gellant is soluble in the solvent, and then cooling the composition to form the gel composition. -Solid desired. The low residue solids gels described by Hofrichter et al., Are remarkably stable, both physically and chemically, and will maintain the hardness of the desired product over a long period of time.

However, the gels - solids described by Hofrichter et al., Are limited to selecting double gelling systems and do not include or otherwise describe any method for manufacturing a low residue antiperspirant gel-solid stick containing any gelling agent distinct or gelling system. It has now been found that other low residue solids gels can be formulated without depending on the select combination of gelling agents described by Hofrichter et al. The novel low residue gels-solids are anhydrous systems comprising from about 0.5% to about 60% by weight of the particulate antiperspirant active; from about 1% to about 15% by weight of solid non-polymeric gellant selected from the group consisting of 12-hydroxyl-tertiary acid, 12-hydroxyl-tertiary acid esters, 12-hydroxyl-tertiary acid amides, and combinations thereof; from about 10% to about 80% by weight of the anhydrous liquid carrier for the solid non-polymeric gellant having a parameter of average solubility ((cal / cmJ) U-D) from about 3 to about 13; wherein the composition has a visible residue index of L value from about 11 to about 30, a product hardness of about 500 grams-force to about 5000 grams-force, a ratio of an elastic modulus (G ') to a module viscous (G ") from about 0.1 to about 100. The composition does not require comparable refractive index of the particulate antiperspirant active, solid non-polymeric gelling agent and anhydrous liquid carrier to obtain the lowest residue appearance performance. Preferably, the compositions comprise crystalline gelling particles having an average particle size of less than about 1 μm and / or an elongated particle morphology defined by a dimensional ratio greater than about 2. Therefore, it is an object of the present invention. invention provide an anhydrous antiperspirant gel-solid stick containing particulate antiperspirant active material that provides characteristics of reduced residue appearance and improved antiperspirant efficacy, and furthermore provide a composition without relying on specific gelling agents such as for example lead dibenz alditols or gelling systems doubles containing n-acyl amino acid derivatives.

It is a further object of the present invention to provide this composition without depending on the comparable refractive index of component materials or the use of solubilized antiperspirant active, to obtain product clarity or lower residue appearance performance. It is still another object of the present invention to provide a composition using only gelling agents selected from the group consisting of 12-hydroxyl-tertiary acid, 12-hydroxyl-tertiary acid esters, 12-hydroxystearic acid amides and combinations thereof.

BRIEF DESCRIPTION OF THE INVENTION The present invention is directed to anhydrous gel-solid antiperspirant stick compositions comprising from about 0.5% to about 60% by weight of the particulate antiperspirant active; from about 1% to about 15% by weight of a solid non-polymeric gellant selected from the group consisting of 12-hydroxyl-tertiary acid, 12-hydroxystearic acid esters, 12-hydroxystearic acid amides, and combinations thereof; from about 10% to about 80% by weight of an anhydrous liquid carrier for the solid non-polymeric gellant having an average solubility parameter from about 3 to about 13 ((cal / cm3) 0.5); where the composition has a visible residue index of L value of. about 11 to about 30, a product hardness of about 500 grams-force at about 5000 grams-force, a rheology profile defined by a ratio of an elastic modulus (G ') to a viscous modulus (G ") of about 0.1 to about 100. The refractive indices of the particulate antiperspirant active, the solid non-polymeric gelling agent and the anhydrous liquid carrier are not comparable, Preferably, the compositions comprise christitalino gelling particles having an average particle size of less than about 1. μm and / or a particle morphology having a dimensional ratio greater than about 2. It has been found that the "gel-solid" antiperspirant stick compositions of the present invention can provide lower residue appearance performance without the need to use active solubilized antiperspirant, and without relying on low residue gelling agents chosen, for example, dibenzylidene-alditols, combinations of gelling agents containing n-acyl amino acid derivatives or other gelling agents other than those select gelling agents described herein. This is accomplished by formulating an anhydrous gel-solid stick composition having the preferred hardness and rheology profile preferably provided by a three-dimensional non-polymer crystal gel network consisting of small elongated crystalline particles having a size- of average particle of less than about 1 μm and / or a particle morphology defined by a dimensional ratio of at least about 2, wherein the solid non-polymeric gelling agent used to provide these gelling or composition characteristics is selected from the group consisting of of 12-hydroxyl-tearic acid, 12-hydroxyl-tertiary acid esters, 12-hydroxyl-tertiary acid amides, and combinations thereof.

DETAILED DESCRIPTION OF THE INVENTION The gel-solid antiperspirant stick compositions of the present invention are anhydrous systems which are dispersions of sustained particulate antiperspirant active or contained within a non-polymeric crystalline gel-solid matrix. The term "anhydrous" as used herein, means that the gel-solid antiperspirant stick composition of the present invention, and the essential or optional components thereof, other than the particulate antiperspirant active, are substantially free of aggregates or free of water. From the formulation point of view, this means that the gel-solid antiperspirant stick compositions of the present invention preferably contain less than about 5%, preferably less than about 3%, more preferably less than about 1%, 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 the formulation. The term "low residue" as used herein, generally refers to the visible residue left over the areas of the applied skin, during or immediately after the application, and more specifically refers to the visible residue index of the composition according to it is defined by the methodology described hereafter. The term "ambient conditions" as used herein, refers to surrounding conditions under about one atmosphere of pressure, about 50% relative humidity, and about 25 ° C, unless otherwise specified. The term "substantially free" as used herein, unless otherwise specified, refers to preferred negative limitations of the compositions of the present invention, and is directed to the preferred amount or concentration of inorganic thickeners, organic polymeric thickening agents, lead alditol dibenz gelling agents, n-acyl amino acid derivatives, or combinations thereof in the composition. The term "substantially free" preferably means that the compositions contain less than an effective amount of these agents when used alone to provide any increase in thickening or measurement for the composition. In this context, the negative limitations pertain only to those thickeners or gelling agents which are also solid under ambient conditions, and which do not contain silicone materials or polymeric derivatives of 12-hydroxystearic acid. In general, preferably, the compositions contain less than 5%, preferably less than 2%, more preferably less than 1%, even more preferably less than 0.5%, most preferably zero percent by weight of these agents of the composition. Examples of organic thickening agents to which the negative limitations described above belong include finely divided or colloidal silicas, fuming silicas, and silicates, including montmorillonite clays and montmori 1 hydrophobically treated leaves, such as, for example, bentonites, hectorites and colloidal magnesium silicates. Examples of organic polymeric gelling agents to which the negative limitations described above belong include organic polymers well known in the antiperspirant or personal care art for use in providing gelation or thickening or other physical or aesthetic benefits to a composition, specific examples of which include copolymer of hydrogenated butylene / ethane / ethylene oxide, polyethylene, oxidized polyethylene, polyamides, acrylic acid polymers, ethylene-acrylate copolymers and other organic polymeric gelling agents described in Rheological Properties of Cosmetics and Toiletries , edited by Dennis Laba, published by Marcel De er, In. ,. New York (1993), whose description is incorporated herein by reference. The term "substituted" as used herein, unless otherwise specified, refers to chemical entities or substituents known or otherwise suitable for the binding of the compounds or other chemical materials described or referenced herein . These substituents include, but are not limited to, those listed and described in C, Hansch and A. Leo, Substituent Constants for Correlation Analysis in Chemistry and Bio lo gy (1979), the list and description of which are incorporated herein by reference. Examples of these substituents include, but are not limited to, alkyl, alkenyl, alkoxy, hydroxy, oxo, nitro, amino, aminoalkyl (for example aminomethyl), etc.), cyano, halo (for example chlorine, fluorine, bromine, iodine), carboxy, 1-coxalkyl (eg, 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 like. The term "n-acyl amino acid derivatives" refers to gelling agents selected from the group consisting of n-acyl amino acid amides, n-acyl amino acid esters, glutamic acid preparations, lysine, glutamine, aspartic acid and combinations thereof , and which are specifically described in U.S. Patent 5,429,816. The terms "alkyl" and "alkenyl" as used herein, unless otherwise specified, refer to linear or cyclic, branched, substituted or unsubstituted hydrocarbons having from 1 to about 22 carbon atoms. The term "volatile" as used herein, refers to materials having a vapor pressure under ambient conditions of less than about 0.2 mm Hg. Conversely, the term "non-volatile" as used herein, refers to materials that do not have vapor pressure measurement or that have a vapor pressure of less than about 0.2 mm Hg under ambient conditions. The solid non-polymeric gelling agent, the antiperspirant active and the anhydrous liquid carrier components of the gel-solid stick compositions herein preferably do not have comparable refractive index, and most preferably, have at least 2 of the components with refractive indices (? D) that differ by at least about 0.02, more preferably by at least about 0.04. The gel-solid antiperspirant stick compositions of the present invention may comprise, consist of, or consist substantially of essential elements and limitations of the invention described herein, as well as any additional or optional ingredients, components or limitations described in the present. Unless otherwise specified, the percentages, parts and relationships are represented by weight of the total composition. All weights belong to the listed ingredients, are based on the specific ingredient level and, therefore, do not include solvents, carriers, by-products, fillers or other minor ingredients that may be included in commercially available materials, unless Specify otherwise.

PRODUCT CHARACTERISTICS The gel-solid antiperspirant stick compositions of the present invention are characterized in terms of product hardness, visible residue index and a rheology profile defined by a ratio of an elastic or viscous modulus. Each of these characteristics is defined according to the methodologies and other limitations described hereinafter. a) Hardness The gel-solid antiperspirant stick compositions of the present invention have a product hardness of about 500 grams-force at about 5,000 grams-force, preferably about 750 grams-strength at approximately 2,000 grams-force , more preferably of about 800 grams -for approximately 1,400 grams- force.

The term "product hardness" as used herein, is a reflection of how much force is required to move a penetration cone at a specific distance and at a controlled rate within a gel-solid antiperspirant stick composition under the following test conditions. Larger values "represent the harder product, and lower values represent the softest product." These values are measured at 27 ° C, 15% relative humidity, using a Texture Analyzer TA-XT2, available from Texture Technology Corp. , Scarsdale, New York, USA The hardness value of the product as used herein, represents the amount of force required to move a cone of penetration at a standard 45 ° angle through the composition at a distance of 10 mm. at a speed of 2 mm / second, the standard cone is available from Texture Technology Corp., as part number TA-15, and has a total cone length of approximately 24.7 mm, an angled cone length of approximately 18.3 mm, a maximum cone angled surface diameter of approximately 15.5 m The cone is a mild stainless steel construction and weighs approximately 17.8 grams. b) Residue The gel-solid antiperspirant stick compositions of the present invention have a visible residue index of L value from about 11 to about 30, preferably, an L value from about 11 to about 25, most preferably, a L value from 11 to about 20. The term "visible residue index" as used herein, refers generally to the extent to which the composition of the present invention is visibly evident as a thin topical film after application to a the skin, and more specifically refers to visible residue values (expressed as an L value on the color scale L, a, b) as measured according to the following methodology, performed at 27 ° C, under atmospheric pressure , and at 15% relative humidity in the stick antiperspirant compositions having a product hardness of about 500 grams-force to about 5,000 grams-force. A piece of black felt of approximately 10 cm x 30 cm is attached to a movable horizontal slider, which is movably or fixedly attached to a larger mechanical unit. An example of a suitable piece of black felt for use herein is Supreme Robe Velor, FN-6554, Color 404L, Style 31854, available from So-Fro Fabrics, Evendale, Ohio, U.S.A. An example of a suitable mechanical unit for use herein is the No. A-14934 Release and Adhesion Tester, manufactured by Testing Machines, Inc. Amityville, New York, USA, or a Velmex non-slip positioning system, Unwrapping unit series (MB6000), available from Velmex, Inc., Bloomfield, New York, USA A stick antiperspirant composition contained within a conventional container or container extending partially outward approximately 0.5 cm thereof is placed perpendicular to the piece of felt bonded or above it, such that the product extends outwardly. of the container or container that is oriented towards the piece of felt and the surrounding container is placed out of the piece of felt. The surrounding container is placed in place using a mechanical arm or other suitable device to apply the required movement to the product as described herein.

The antiperspirant stick composition is then moved slowly to the piece of bonded black felt and allowed to gently contact it. A weight of 1,000 grams is placed on the product sample in such a way that the product continuously contacts the piece of black felt during the test. The heavy sample is then repeatedly moved back and forth through the felt piece at a fixed speed (approximately 3 cm / second), and with a fixed amount of applied pressure, provided by the heavy products, up to approximately 1.75 grams. of the antiperspirant stick composition is optionally applied over an area of 5 cm * 20 cm from the piece of black felt. The piece of felt is carefully removed from the apparatus. A calibrated Minolta CR-300 chromameter (available from Minolta Corp. Ramsey, New Jersey, U.S.A.) is then used to measure the L value (on the color scale L, a, b) of the applied surface area. First, a temper is placed on the top of the piece of felt to facilitate Minolta readings. The temperate dimensions are 5 cm x 20 cm. The tempering has 12 circular openings (2.2 cm in diameter) placed inside the tempering, each of the openings placed centrally within the adjacent areas of 6.5 cm2 of the tempered surface. The tempering is placed on the applied surface area of the felt piece in such a way that each of the twelve circular openings covers a non-overlapping area of the applied surface. The inspection port of the chromimeter is fixed within each of the circular openings and the measurements of value L are taken. An average L value is determined for the twelve measurements (standard deviations of less than approximately 0.8) which corresponds to the index of visible residue as described herein. It has been found that there is a correlation between the range of visible residue index defined herein and the average particle size of the crystalline gel particles in the gel-solid antiperspirant stick composition of the present invention. In general, as the average particle size of the crystalline gelling particles in the composition decreases, the lower residue appearance performance is improved. In particular, it has been found that an L value of visible residue index of about 11 to about 30 correlates with an average crystalline gelifier particle size of less than about 1 μm and / or a crystalline gelling particle morphology characterized by a dimensional relationship of growth such that it results in crystalline filaments, fibers, strands or other elongated particles, wherein the dimensional relationship as defined by the major and minor axis of the crystalline particle is greater than about 2, greater preference of about 6. Conversely, solid compositions containing crystalline gelling particles greater than 1 μm (average particle diameter) have an L value of visible residue index greater than 30. In view of this correlation between the index values of visible residue and average crystalline particle size or particle morphology the elongated, visible residue index measurement can now be used as an alternative means to establish the average crystalline gelling particle size or the crystalline gelling morphology, at least to such an extent that the average particle size is smaller than about 1 μm. c) Rheology The antiperspirant stick compositions of the present invention are solid gels having the selected rheology profile defined herein. This rheology profile is defined herein in the terms of modulus (G '/ G ") elastic modulus (G') to viscous (G") of the gel-solid stick composition. To provide the necessary rheology, gel-solid stick compositions should have a G '/ G ratio of from about 0.1 to about 100, preferably from about 0.1 to about 50, more preferably from about 1 to about 20, even more preferably from about 5 to about 20. This ratio represents the degree to which the solid-gel bar compositions of the present exhibit solid character and the degree to which the compositions exhibit liquid or fluid character, and specifically refers to the numerical proportion G '/ G "as determined by the following methodology. The elastic modulus is a measurement that correlates with the solid character of the gel-solid stick compositions herein, and the viscous modulus is a measurement that correlates with the fluid or liquid character of the gel stick compositions -solid of the present. The measurements for G 'and G "for the purposes of defining the composition of the present invention are determined under ambient conditions using conventional techniques well known in the formulation arts For example, a Bohlin St res s-St Rheometer can be used. rain, available from Bohlin Reology, Cranberry, New Jersey, using a cone (approximately 1 °) and plate configuration Approximately 1.0 mg of the product is carefully removed from the composition with minimal shear application and then placed between the cone and the plate fixings for the measurement of G 'and G ". It has been found that the gel-solid stick compositions of the present invention exhibit lower residue appearance performance when formulated as described herein, wherein the composition has the selected G '/ G "ratio described in the foregoing. , especially when the defined rheology is associated with a crystalline gel matrix having a preferred small particle size and / or particle morphology as described herein.These gel-solid stick formulations are sprayed gently on the skin and they are quickly cut and melted during the spray to form a thin, low residue film on the applied surface In particular, it has been found that the gel-solid stick compositions of the present invention have rheological characteristics that result in lower improved performance, especially lower waste appearance performance These select gel-solid compositions, as defined in the present, they behave as solids before they are applied while kept inside a jar, or other container, but behave more like liquids or fluids during application to or immediately after the skin. In other words, the thin-cut solid compositions during application to the skin, melt or nearly melt (except for the particulate active that remains unmelted) during the application of the thinning cut, resulting in a liquid or film of fluid, low residue, thin, on the skin during topical application to the skin or immediately after it. The applied film is clear or has very little visible residue, and remains substantially for long periods of time after application.

ANTITRANSPIRANT ACTIVE The solid gel antiperspirant stick compositions of the present invention comprise a particulate antiperspirant active for application to human skin. These particulate actives must remain substantially unsolubilized as dispersed or precipitated solids in the anhydrous or substantially anhydrous systems as described herein. The concentration of the particulate active in the composition should be sufficient to provide the moisture control and desired perspiration odor from the selected gel-solid antiperspirant stick formulation. The gel-solid antiperspirant stick compositions of the present invention preferably comprise a particulate anti-perspirant active at concentrations from about 0.5% to about 60%, more preferably, from about 5% to about 35% by weight of the composition. These percentages by weight are calculated on an anhydrous metal salt base exclusive of water and any complexing agents such as, for example, glycine, glycine salts, or other complexing agents. Antiperspirant actives such as those formulated in the composition are in the form of dispersed solid particles having a preferred average particle size or diameter of less than about 100 μm, more preferably, from about 15 μm to about 100 μm, yet more preferably, from about 20 μm to about 100 μm Also preferred are dispersed solid particulates having an average particle size or diameter of less than about 2 μm, even more preferably less than about 0.4 μm. found that the antiperspirant active particles within the preferred particle size ranges provide lower visible residue appearance performance from the solid gel compositions herein than other less preferred particle size ranges The antiperspirant active agent to be used in the compositions of anti bar gel-solid perspirants of the present invention include any compound, composition or other material having antiperspirant activity. Preferred antiperspirant actives include the astringent metal salts, especially the inorganic and organic salts of aluminum, zirconium and zinc, as well as mixtures thereof. Particularly preferred salts are the aluminum and zirconium salts, such as, for example, aluminum halides, aluminum chlorohydrate, aluminum hydroxyhalides, zirconyl oxyalurides, zirconyl hydroxyhalides and mixtures thereof. Preferred aluminum salts for use in gel-solid antiperspirant stick compositions include those corresponding to the formula: Al2 (OH) to Clb «x H20 wherein a is from about 2 to about 5; the sum of a and b is approximately 6; x is from about 1 to about 6; and where a, b, and x may not have integer values. Aluminum chlorohydroxides are particularly preferred, referred to as "5/6 basic hydrochloride", where a = 5 and as "2/3 basic hydrochloride", where a = 4. The processes for preparing the aluminum salts are described in United States Patent No. 3,887,692 to Gilman, issued June 3, 1975; U.S. Patent No. 3,904,741 to Jones et al., issued September 9, 1975, U.S. Patent No. 4,359,456 to Gosling et al., issued November 16, 1982; and British Patent Specification No. 2,048,229 to Fitzgerald et al., published December 10, 1980, all of which are incorporated herein by reference. Mixtures of aluminum salts are described in British Patent Specification No. 1,347,950 to Shin et al., Published February 27, 1974, the disclosure of which is also incorporated herein by reference. Preferred zirconium salts for use in gel-solid antiperspirant stick compositions include those corresponding to the formula: ZrO (OH) 2_aCla »x H20 wherein a is from about 1.5 to about 1.87; x is from about 1 to about 7; and where a and x can both not have integer values. These zirconium salts are described in Belgian Patent No. 825,146 of Sch itz, issued August 4, 1975, the disclosure of which is incorporated herein by reference. Particularly preferred zirconium salts are those complexes which additionally contain aluminum and glycine, commonly known as ZAG complexes. These ZAG complexes contain aluminum chlorhydroxide and zirconyl hydroxy chloride corresponding to the formulas described in the above. These ZAG complexes are described in U.S. Patent No. 3,679,068 to Luedders et al., Issued February 12, 1974; British Patent Application No. 2,144,992 to Callaghan et al., published March 20, 1985; and U.S. Patent No. 4,120,948 to Shelton, issued October 17, 1978, all of which are incorporated herein by reference. The gel-solid antiperspirant stick compositions of the present invention may also be formulated to comprise other dispersed solids or other materials in addition to or in place of the particulate antiperspirant active. These other dispersed solids or other materials include any known or otherwise suitable material for topical application to human skin. Gel-solid antiperspirant stick compositions may also be formulated as gel-solid stick compositions that do not contain antiperspirant or other active, or otherwise particulate, material.

GELIFICANT The gel-solid antranspirant bar compositions of the present invention comprise select non-polymeric gelling agents. These select gelling agents form within the composition a crystalline matrix within which an anhydrous liquid carrier or other liquid component of the composition is entrapped or contained. These select gelling agents are solids under ambient conditions, and preferably form crystalline particles having an average particle diameter and particle morphology as described hereinafter. The select gelling agents for use in the gel-solid antiperspirant stick composition of the present invention are selected from the group consisting of 12-hydroxyl tea acid, 12-hydroxyl-tertiary acid esters, 12-hydroxyl-tertiary acid amides, and combinations thereof. These select gelling agents include those corresponding to the following formula: wherein Ri is OR2 or NR2R3; and R2 and R3 are hydrogen, or an alkyl, aryl or arylalkyl radical that is branched, linear or cyclic and has from about 1 to about 22 carbon atoms; preferably, from about 1 to about 18 carbon atoms. R2 and R3 may be either the same or different; however, preferably, at least one is a hydrogen atom. The select gelling agent is preferably selected from the group consisting of 12-hydroxystearic acid, 12-hydroxyestaric acid methyl ester, 12-hydroxystearic acid ethyl ester, 12-hydroxystearic acid ester, 12-hydroxystearic acid benzyl ester. , 12-hydroxystearic acid amide, 12-hydroxystaric acid isopropyl amide, 12-hydroxyl-tertiary butylamide, 12-hydroxyl-tertiary-benzylamide, 12-hydroxyl-tertiary-phenylamide, 12-hydroxy-t-butylamide is tearoic, cyclohexylamide of 12-hydroxy acid is tea, 1-adamant ilamide of 12-hydroxyl acid, 2-adamant ilamide of 12-hydroxyl acid, diisopropylamide of 12-hydroxystearic acid, and mixtures thereof; even more preferred, 12-hydroxyl tetraric acid, 12-hydroxyl tetraric isopropylamide, and combinations thereof. Preferred is 12-hydroxy stearic acid. The concentration of the selected gelling agents in the compositions may vary with each gel-solid antiperspirant stick formulation, especially with each anhydrous liquid carrier selected from the formulation, but the concentrations will generally vary from about 0.1% to about 20%, preferably , from about 1% to about 15%, more preferably, from about 3% to about 12% by weight of the composition.

The gel-solid antiperspirant stick composition is substantially free of inorganic thickening agents (which do not contain silicone), organic polymeric thickening agents and organic gelling agents other than the select gelling agents described in the foregoing. In this context, "substantially free" means that the compositions contain less than an effective amount of these agents or other organic gelling agents that when used alone could provide any increase in thickening or measurable viscosity to the composition under ambient conditions. In general, the compositions preferably contain less than 5%, more preferably, less than 1%, even more preferably, less than 0.5%, most preferably, zero percent, of these agents by weight of the composition. However, the term "substantially free" does not pertain to the use of preferred nucleating agents (described hereafter). Select gelling agents for use in the gel-solid antiperspirant stick compositions must be melted and formed into a solution or other homogeneous liquid or liquid dispersion with the selected anhydrous liquid carrier, and in the selected gellant and liquid carrier concentrations, at a temperature of processing from about 28 ° C to about 250 ° C, preferably, from about 28 ° C to about 100 ° C, more preferably, from about 28 ° C to about 78 ° C. The molten gellant typically dissolves or disperses throughout the selected liquid carrier to thereby form a solution or other homogeneous liquid. The solution or other homogeneous liquid, and other essential and optional ingredients, are preferably combined according to the manufacturing method described herein or another conventional technique or in another known manner, and then placed in a suitable container as a solution. flowable or homogeneous liquid, and then allowed to solidify and form the desired solid gel matrix within the composition as the temperature returns to room temperature and falls below the solidification point of the composition. In selecting a combination of solid non-polymeric gelling agent and a liquid carrier for use in solid gel antiperspirant stick compositions, the combination should allow the development of a crystalline gelling matrix within the composition wherein the crystalline particles of the component, preferably they have an average particle size of less than about 1 μm, more preferably, of less than about 0.4 μm, even more preferably, of less than about 0.2 μm, still more preferably, of less than about 0.001 μm to about 0.2 μm, and / or wherein the crystalline particles have the required elongated morphology described herein, wherein the particle size is measured or determined by the methods described herein or by methods well known to those skilled in the art as for example light or electronic microscopy. Gel-solid stick compositions can be prepared by methods well known in the art of the formulation to produce the gels-solids having minimal crystalline particle size or the preferred elongated particle morphology. The gel-solid stick compositions are preferably prepared by the selected methods described hereinafter directed to minimizing the crystalline particle size and / or establishing the preferred crystal particle morphology.

These select gelling agents are especially effective when used in combination with anhydrous carrier liquids such as volatile silicones, especially volatile cyclomethicone. These gelling agents are most preferably used in combination with a liquid carrier comprising a volatile silicone and / or a non-volatile silicone (for example, non-volatile dimethicone or other organo-functional siloxanes) and / or a non-volatile organic carrier.

Preferred morphology of the particles The select gelling agents to be used herein, preferably, include those crystalline gelling agents which inherently form or can be formulated or are made to form elongated crystalline particles having a dimensional ratio of greater than about 2, preferably, greater of about 6. These elongated crystals preferably have an average particle size, measured along a minor axis of the elongated crystal, of less than 1 μm, more preferably, less than about 0.4 μm, still more preferably, less than about 0.2 μm, and even more preferably between about 0.2 μm and about 0.001 μm. Gel-solid stick compositions containing these preferred elongated crystals can be prepared by the methods described herein or by methods otherwise known in the art of formulating to formulate gel matrices comprising these elongated crystalline particles. The "dimensional relationship" as used herein to define the preferred embodiments of the gel-solid stick compositions herein can be determined by measuring or otherwise determining the ratio between the length of the major axis of the crystalline particles and- the length of the minor axis of the crystalline particles. This ratio of lengths between the major axis and the minor axis is characterized by the dimensional relationship referred to herein. The dimensional relationship can be determined by conventional methods or by known methods of electron microscopy or light, where the crystalline particles are measured in the dimensions of the major axis and the minor axis, or by these methods it is observed that they clearly have a structure crystalline elongate with a dimensional ratio substantially greater than about 2, 'preferably, greater than about 6. It has been found that these crystalline gelling agents having the selected dimensional ratios that are defined herein provide the gel-solid antiperspirant stick compositions with a three-dimensional crystalline structure which can provide the composition with the characteristic of leaving little residue, a ratio of elastic to viscous modulus required and the required hardness of the product, as defined herein. It is considered that this crystalline morphology is especially effective to provide a crystalline matrix within the composition that provides a network of gel-solid matrix of. strongly intertrabado, but also includes crystalline particles that are small enough to contribute minimally to the visible residue when applied topically to the skin. It has also been found that the preferred crystalline matrix helps to provide the gel-solid stick compositions with a melting profile that contributes to a lesser appearance of residues. This preferred melting profile refers to the temperature at which the gel-solid antiperspirant stick composition begins to melt and the temperature range within which the composition melts completely, except for any dispersed anti-perspirant particles or any other component of high melting point. The temperature at which the composition begins to melt is determined by the measurement of a start temperature in the Differential Scanning Calorimeter (DSC). The temperature range within which the composition is completely melted is determined by non-additional thermal infusion. Preferred embodiments of the gel-solid stick compositions herein have a DSC start temperature of between about 25 ° C to about 85 ° C, preferably, between about 27 ° C to about 65 ° C, with higher preferably, between about 30 ° C and about 60 ° C, even more preferably, between about 35 ° C to about 50 °. These preferred compositions having the selected melting profile provide improved cosmetic or aesthetic properties when applied topically to the skin, and in particular they provide a lower perception of moisture, stickiness or softness of the product during and immediately after application. The selected fusion profile also helps. to further reduce the visible residue index of the composition, also improving the performance of less appearance of waste.

ANCHID LIQUID CARRIERS The anhydrous gel-solid antiperspirant stick compositions of the present invention comprise an anhydrous liquid carrier for the crystalline gellant described hereinafter. The anhydrous liquid carrier is liquid under ambient conditions and preferably has low viscosity to provide improved dispersion on the skin. The concentrations of the anhydrous liquid carrier in the gel-solid stick compositions will vary mainly with the type and amount of anhydrous liquid carrier, the solid, non-polymeric gellant and the solubility of the solid and non-polymeric gellant in the anhydrous liquid carrier. Preferred concentrations of the anhydrous liquid carrier are between about 10% and about 80%, preferably, between about 30% and about 70%, more preferably, between about 45% and 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 can be organic, they can contain silicone or fluorine, they can be volatile or non-volatile, they can be polar or non-polar, as long as the liquid carrier forms a solution or another type of homogeneous liquid or liquid dispersion with the non-polymeric gelling agent selected at the selected gelling concentration, at a temperature between about 28 ° C to about 250 ° C, preferably, between about 28 ° C and about 100 ° C, more preferably, about 28 ° C and about 78 ° C C. The anhydrous liquid carrier has a solubility parameter of between about 3 and about 13 (cal / cm 3) ° 5, preferably between about 5 and about 11 (cal / cm 3) ° 5, more preferably between about 5 and about 9 (cal / cm3) ° '5. The solubility parameters for liquid carriers or for other materials and the means for determining these parameters are well known in the chemical field. A description of the solubility parameters and the means to determine them is described in 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 descriptions of which are incorporated herein by reference. The anhydrous liquid carrier preferably comprises an organofunctional or modified silicone carrier selected from the group consisting of polyalkylsiloxanes, polyalkylarylsiloxanes, polyestersiloxanes, polyethersiloxanes, in the form of copolymers, polyfluoros and loxanes, polylamines and loxanes and combinations thereof. These modified silicone carriers should be liquid at ambient conditions and have a viscosity of less than about 100,000 centistokes, preferably less than about 500 centistokes, more preferably, from about 1 and about 50 centistokes, and still more preferably, between approximately 1 and approximately 20 centistokes. These modified silicone carriers are generally known in the chemical field, some examples of which are described in 1 Cosm e t i cs, Sci in ce a n d Te ch n o lgy y 27-104 M. Balsam and E. Sagarin ed. 1972); U.S. Patent No. 4,202,879, issued to Shelt.on on May 13, 1980; U.S. Patent No. 5,069,897, issued to "Orr on December 3, 1991, which are incorporated herein by reference." Modified silicone carriers suitable for use in gel-solid antiperspirant stick compositions include, but are not limited to, , compounds or materials as defined in the foregoing and which are generally characterized as follows: silicone polyethers or silicone glycols (for example dimethicone copolyol); alkyl-linked polyethers (for example, Goldschmidt EM-90 or EM-97); siloxane surfactants of a pendant / rake / comb configuration, silicone surfactants of a trisiloxane configuration and silicone surfactants of ABA / fa-omega block copolymers (such as, for example, polyoxyalkylenes, polyoxyethylene or ethoxylated , polyoxyethylene / polyoxypropylene or ethoxylated / propoxylated); silicone emollients substituted with aromatic groups (for example, phenyl, alpha-methyl styryl, styryl, methylphenyl, alkylphenyl); silicone copolymer (s) with other functional groups including: hydrogen, alkyl, methyl, amino, t-fluoropropyl, vinyl, alkoxy, arylalkyl, aryl, phenyl, styryl, polyethers, esters, carboxylic compounds; alkymethyl siloxanes or silicone waxes (for example, hexyl, octyl, lauryl, cetyl, stearyl); non-ionic functional siloxane copolymers with silanol or trimethylsilyloxy end groups; nonionic functional siloxanes with main structure groups which are linked with trisiloxane or methicone; nonionic silicone surfactants; tetraethoxysilane; tetramethoxysilane; hexametoxisyl icone; oximetoxit risiloxane; silicone emulsifiers; siloxane or silicone resins; alkyl silicone resins; polyoxyalkylene silicone resins; MQ resins such as those of Shi seido / Shin-etsu, for example Japanese Patent Publication JP86143760 b of Walker Chem. 6MBH (described in EP722970); alkoxysiloxanes; alkoxysilanes; met iconas (polime t ilalqui ls iloxanos); and combinations thereof. Non-limiting examples of suitable modified silicone carriers that are used in the gel-solid antiperspirant stick compositions herein include the following modified silicones available from Dow Corning: DC-556, Cosmetic Grade Fluid (phenyltrimetone); DC-704 Diffusion Pump Fluid (Te trame til-Te trafeni 1 -Tris iloxane); DC-705 Diffusion Pump Fluid; DC-1784 Emulsion; DC-AF Emulsion; DC-1520-US Emulsion; DC-593 Fluid (Dimethicone [y] Trimet ils iloxy s ilicato); 'DC-3225C Fluid (Cyclomethicone [and] Dimethicone Copolyol); DC-190 Fluid (Dimethicone Copolyol); DC-193 Fluid (Dimethicone Copolyol); DC-1401 (Cyclomethicone [and] Dimethiconol); DC-5200 Fluid (Copolyol from Laurylmethicone); DC-6603 Polymer Powder; DC-5640 Powder; DC-Q2-5220 (Dimethicone Copolyol); DC Q2-5324 (Dimethicone Copolyol); DC-2501 Cosmetic Wax (Dimethicone Copolyol); DC-2502 Fluid (Cetil Dimethicone); DC-2503 Wax (Stearyl Dimethicone); DC-1731 Volatile Fluid (Caproil Trimethicone); DC-580 Wax (Es tearoxi trimet ils ilano [y] Stearyl Alcohol); DC-I-3563 (Dimet iconal); DC-X2-1286"(Dimeticonol), DC-X2-1146A (Cyclomethicone [y] Dimethiconol), DC-8820 Fluid (with Amino functional group), DC Q5-0158A wax (is tearoxi trimet il si tin); Q2-8220 (Trimet ils ili lamodimetone icone), DC-7224 (Trimethylsilylamodimethicon), DC-X2-1318 Fluid (Cyclomethicone [y] Vini ldimetone icone), DC-QF1-3593A fluid (Trimet ilsi loxysilicato) and combinations of Other non-limiting examples of suitable modified silicone carriers that are used in the gel-solid antiperspirant stick compositions herein include the following modified silicones available from General Electric: GE SF-1023 (Dimet i I-Di feni 1 -S i loxane), GE CF-1142 (Methylphenyl Siloxane Fluid), GE SF-1153 (Dimethyl-Diphenyl-Siloxane), GE SF-1265 (Diphenyl-Dimethyl-Siloxane), GE SF-1328, GE SF-1188 ( Dimethicone Copolyol); GE SF-1188A (Polyether and Silicone Copolymer); GE SF-1288 (Silicone and Polyether Copolymer, Dimet I-methyl-3-Hydroxypropyl) i 1 ethoxylated); GE SF-1318 (Methyl Siloxane); GE SF-1328 (silicone surfactant, dimethyl-methyl 1 3-hydroxypropyl 1 and oxidized-propoxy side); GE SF-1550 (methylphenyl siloxane, hexa e t i 1-3-phenyl-1 - 3 - [[trimethyl silyl] oxy] tris il oxa o); GE SF-1632 (silicone wax); GE SS-4267 (Dimethicone [y] Trimet ilsiloxis ilicato) and combinations of the same.

Other non-limiting examples of suitable modified silicone carriers that are used in the gel-solid antiperspirant stick compositions herein include the following modified silicones that are obtained from Goldschmidt; Abil EM-90 (silicone emulsifier); Abil EM-97 (polyether siloxane); Abil Cera 9810 (silicone wax or methicone C24-28); Abil Cera 2434 (Stearoxi Dimethicone); Abil Cera 9800D (Stearil Dimethicone); Tegomer H-Si 2111, H-Si 2311, A-Si 2120, A-Si 2320, C-Si-2141, C-Si 2341, E-Si 2130, E-Si 2330, V-Si 2150, V-Si 2550, H-Si 6420, H-Si 6440, H-Si 6460 (Copolymers of Dimethicone Alpha-Omega) and combinations thereof. Other non-limiting examples of suitable modified silicone carriers that are used in gel-solid antiperspirant stick compositions include the following: Masyl 756 from PPG Industries (Tetrabutoxypropyl Trisiloxane); bis-phenylhexamethicone (from Silbione Oiis 70633 V30 from Rhone-Poulenc); Silbione Oiis 70646 (dimethicone copolyols from Rhone-Poulenc); silicone L-711, L-720, L-721 and L722 (dimethicone copolyols from Union Carbide); Silicone L-7000, L-7001, L-7002, L-7004, L-7500, L-7600, L-7602, L-7604, L-7605 and L-7610 (dimethicone copolyols from • Union Carbide); Unisil SF-R (UPI dimethiconol); Olin Silicate Clod (Tris [t ibutoxis iloxi] met ils i laño); silicone copolymer F-754 (dimethicone copolyol from SWS Silicones); and combinations thereof. The anhydrous liquid carriers preferably comprise a volatile silicone carrier. These volatile silicone carriers can be cyclic, linear or branched chain silicones having the required volatility as defined herein. Non-limiting examples of suitable volatile silicones are described in Todd et al., "Volatile Silicone Fluids for Cosmetics", Cosmetics and Toiletries, 91: 27-32 (1976), which is incorporated herein by reference. Preferred volatile silicones are cyclic silicones having from about 3 to about 7, more preferably, from about 4 to 5 silicon atoms. Those that correspond to the general formula are preferred: wherein n is from about 3 to about 7, preferably from about 4 to about 5, more preferably is 5. Volatile cyclic silicones in general have a viscosity value of less than about 10 centistokes. All viscosity values described herein are measured or determined at ambient conditions unless otherwise specified. Suitable volatile silicones that are used - here include, but are not limited to, cyclomethicone D-5 (commercially available from G. E. Silicones); Dow Corning 344 and Dow Corning 345 (obtained from Dow Corning Corp.); GE 7207; GE 7158 and Silicone Fluids SF-1202 and SF-1173 (obtained from General Electric Co.); SWS-03314, SWS-03400, F-222, F-223, F-250, F-251 (available from SWS Silicones Corp.); Volatile Silicones 7158, 7207, 7349 (available from Union Carbide); Masil SF-V (available from Mazer) and combinations thereof. The anhydrous liquid carrier may also comprise a non-volatile silicone carrier other than or in addition to the preferred silicone modifier carriers described herein. The non-volatile silicone carriers are preferably linear silicones which include, but are not limited to, those corresponding to any of the following formulas: CH3 - wherein n is greater than or equal to 1. These linear silicone materials in general will have viscosity values of up to about 100,000 centistokes, preferably less than about 500 centistokes, more preferably, between about 1 and 200 centistokes, still with greater preference, between approximately 1 and 50 centistokes, measured at ambient conditions. Examples of suitable linear and non-volatile silicones that are used in antiperspirant compositions include, but are not limited to, Dow Corning 200, hexamethyldisiloxane, Rhodorsil Oiis 70047 which is comprised of Rhone-Poulenc, SF Masil Fluid which is obtained from Mazer, Dow Corning 225, Dow Corning 1732, Dow Corning 5732, Dow Corning 5750 (obtained from Dow Corning Corp.); SF-96, SF-1066 and SF18 (350) as Silicone Fluids (from G.E. Silicones); Velvasil and Viscasil (available from General Electric Co.) and Silicone L-45, Silicone L-530, Silicone L-531 (from Union Carbide) and Siloxane F-221 and Slicone Fluid SWS-101 (from SWS Silicones). The anhydrous liquid carrier may further comprise, but is preferably free of polar, water immiscible, organic liquid carriers or solvents. It has been found that the antiperspirant and deodorant efficacy of gel-solid stick compositions are improved to minimize or eliminate the amount of polar, water-immiscible, organic 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 3%, even more preferably zero percent, by weight of a carrier or polar liquid solvent, immiscible in water, organic. These polar solvents are liquid under ambient conditions and include mono- and polyhydric alcohols, fatty acids, mono- and di-basic carboxylic acid esters with mono- and polyhydric alcohols, polyoxyethylenes, polyoxypropyl alcohols, ethers of polyacrylate alcohols and combinations of the same, as long as these solvents are also liquid immiscible in water under ambient conditions. Examples of anhydrous liquid, carriers or liquid, organic, polar, water immiscible solvents are described in Cosmetics, Science, and Technology, vol. 1, 27-104, edited by Balsam and Sagarin (1972); U.S. Patent No. 4,202,879, issued to Shelton on May 13, 1980; and U.S. Patent No. 4,816,261 issued to Luebbe et al, on March 28, 1989, the disclosures of which are incorporated herein by reference. The anhydrous liquid carrier may comprise solvents or liquid carriers, polar, miscible in water, organic, anhydrous, examples of which include short chain alcohols such as ethanol. These and other organic, polar carriers or solvents can be used as cosolvents for the solid, non-polymeric gelling component of the gel-solid antiperspirant stick compositions herein. Non-limiting examples of the suitable polar co-solvents that are used herein are described in U.S. Patent No. 5,429,816. Other suitable polar co-solvents include those described above which are preferably water immiscible organic solvents and other cosolvents such as phthalate co-solvents, benzoate co-solvents, cinnamate esters, secondary alcohols, benzyl acetate , phenyl alkane and combinations thereof. The anhydrous liquid carrier may comprise other non-polar carriers such as, for example, mineral oil, petrolatum, isohexadecane, isododecane, various hydrocarbon oils such as those of the Isopar or Norpar series obtained from Exxon Corp. or those of the Permethyl series which are they obtain from Persperse, and any other organic carrier liquid, miscible in water, polar or non-polar, known or safe and effective for topical application to human skin. The anhydrous liquid carrier may also comprise f luorochemicals such as for example fluorosurfactants, f luorot emersons and perforopolyrets, some examples of which are described in Cosmetics & amp;; Toiletries, Using Fluorinated Compounds in Topical Preparations, Vol. 111, pgs. 47-62, (October 1996) which is incorporated herein by reference. Some specific examples of these liquid carriers include, but are not limited to, fluoropolymers, isopropyl ethers, perfluoropolypropyl ethers, fluorinated telomer of acrylamide, fluorinated amide surfactants, perfluorinated thiol surfactants. Other more specific examples include, but are not limited to, polyperfluoroisopropylethers available from Dupont Performance Chemicals under the tradename Fluortress® PFPE oils, and the fluorosurfactant series from Dupont Performance Chemicals under the tradename Zonyl® Fluorosurfactants.

OPTIONAL NUCLEATING AGENT The gel-solid antiperspirant stick compositions of the present invention preferably further comprise an nucleating agent. The nucleating agent is used to decrease the particle size of the gellant and / or to obtain the preferred morphology of the gelling agent particle described herein. The nucleating agent that is used in the antiperspirant composition of this invention must be a solid material at ambient conditions and have 1) a melting point close to the melting point of the selected gellant; 2) a solubility in the anhydrous liquid carrier less than the solubility of the solid non-polymeric gellant in the anhydrous liquid carrier; or 3) be in the form of a micronized, insoluble, organic particulate. Examples of suitable nucleating agents are described below. The concentration of the nucleating agent in the composition is typical between about 0.0001% to about 5%, preferably between about 0.001% to about 2%, more preferably between about 0.01% to about 1%, wherein the molar ratio of the gelling agent non-polymeric solid relative to the nucleating agent is between about 10: 1 and about 1000: 1, preferably between about 10: 1 and about 100: 1. Preferred nucleating agents are those having a melting point of between about 40 ° C and about 200 ° C, more preferably between about 20 ° C as the lower limit and 100 ° C as the upper limit, the melting point of the gelificante not polymeric, solid, selected. Antiperspirant compositions containing the nucleating agent are preferably prepared by the following: 1) combining the solid and non-polymeric gelling agent, the anhydrous liquid carrier and a nucleating agent as described herein; 2) heating the components or the combination of components to form a solution or another type of liquid dispersion or homogeneous liquid; and 3) solidifying the combination of components by cooling it below the solidification point of the solid non-polymeric gellant to form the antiperspirant composition of the present invention. During this process, the solid and non-polymeric gelling agent is preferably fused or liquefied, and then allowed to solidify in the presence of the anhydrous liquid carrier and the nucleating agent. Also, during this process, the nucleating agent typically melts or liquefies (except for the inorganic, micronized nucleating agents) and de-spues in the presence of the anhydrous liquid carrier and the liquefied or fused gellant, the liquefied nucleating agent crystallizes , gels or solidifies and acts as a seed or core to promote the formation of small gelling nuclei during the crystallization of the gelling agent in the carrier, anhydrous liquid. The nucleating agent used in the antiperspirant compositions includes fatty alcohols, esters of fatty alcohols, ethoxylated fatty alcohols, esters or ethers of fatty acids including waxes and triglycerides, silica, titanium dioxide, solid polyesters of polyol and carboxylic acid and mixtures thereof. . Suitable fatty alcohols that are used as nucleating agents include monohydric alcohols, ethoxylated fatty alcohols and fatty alcohol esters. Specific examples of the commercially available fatty alcohol nucleating agents include, but are not limited to, Unilin 550, Unilin 700, Unilin 425, Unilin 400, Unilin 350 and Unilin 325, all supplied by Petrolite, suitable ethoxylated fatty alcohols include, Examples include Unithox 325, Unithox 400 and Unithox 450, Unithox 480, Unithox 520, Unithox 550, Unithox 720, Unithox 750, all of which are available from Petrolite, and non-limiting examples of suitable fatty alcohol esters include citrate tri-isoes tear ilo, di-12-hydroxies, ethylene glycol, ethylene glycol, tetraaryl ether, stearyl octanoate, stearyl heptanoate, trihaluryl citrate, and suitable fatty acid esters used as nucleating agents include waxes of esters, monoglycerides, diglycerides, triglycerides and mixtures thereof Glyceride esters are preferred Non-limiting examples of ester waxes These include stearyl stearate, stearyl behenate, palmitoyl stearate, stearyl octyldodecanol, cetyl esters, cetearyl behenate, behenyl behenate, ethylene glycol distearate, ethylene glycol dipalmitate, and beeswax. Examples of the commercial ester waxes include Kester waxes from Koster Keunen, Crodamol SS from Croda and Demalcare SPS from Rhone Poulenc. Preferred triglyceride nucleating agents include, but are not limited to, tearin, tribehenate, behenyl palmityl behenyl triglyceride, palmityl stearyl palmityl triglyceride, hydrogenated vegetable oil, hydrogenated rapeseed oil, castor wax, fish oils, tripalmiten, Syncrowax HRC and Syncrowax HGL-C (Syncrowax is obtained from Croda, Inc.). Other suitable glycerides include, but are not limited to, glyceryl stearate and glyceryl distearate. Preferably, the nucleating agent is a solid polyester of polyol and carboxylic acid. Suitable polyesters * solids of polyol and carboxylic acid include those which are polyol esters or polyesters wherein the carboxylic acid ester groups of the polyester comprise a combination of: (a) unsaturated long chain carboxylic acid entities or a mixture of entities of unsaturated long chain carboxylic acids and short chain saturated carboxylic acid entities; and (b) long chain saturated carboxylic acid entities, the ratio between (a) and (b) is about 1 to 15 to about 2 to 1. At least about 15%, preferably at least about 30% , more preferably at least about 50% and still more preferably at least about 60% by weight of the total carboxylic acid entities of the polyesters are C20 or higher saturated carboxylic acid entities. The long chain unsaturated carboxylic acid entities are typically straight chain and contain at least about 12, preferably about 12 to about 26, more preferably about 18 to about 22 carbon atoms. The most preferred unsaturated carboxylic acids are C18 mono- and / or di-unsaturated carboxylic acids. The short chain saturated carboxylic acids are typically unbranched and contain from about 2 to about 12 carbon atoms, preferably from about 6 to about 12 and more preferably from about 8 to about 12 carbon atoms. The long chain saturated carboxylic acids are typically straight chain and contain at least about 20, preferably about 20 to about 26 carbon atoms and more preferably about 22 carbon atoms. The molar ratio of Group (a) of carboxylic acid entities to Group (b) of carboxylic acid entities in the polyester molecule is between about 1:15 and about 2: 1, preferably between about 1: 7 a. about 5: 3, and more preferably between about 1: 7 and about 3: 5. The average degree of esterification of these carboxylic acid esters is such that at least about 2 of the hydroxyl groups of the polyol are esterified. In the case of sucrose polyesters from about 7 to about 8 of the groups Hydroxyl of the polyol are preferably esterified. Typically, practically all hydroxyl groups of the polyol are esterified, for example, at least about 85% and preferably at least about 95%. The preferred polyols of the polyol carboxylic acid esters, solids, are sugars, including monosaccharides and disaccharides and trisaccharides, containing from about 4 to about 11 hydroxyl groups. The most preferred sugars are those containing from about four s about 8, more preferably from about 6 to about 8 hydroxyl groups. Examples of those containing four hydroxyl groups are the monosaccharides of xylose, arabinose and combinations thereof. Suitable polyols containing five hydroxyl groups are monosaccharides of galactose, fructose, mannose, glucose and combinations thereof. Examples of disaccharide polyols that can be used include maltose, lactose, sucrose and combinations thereof, all of which contain eight hydroxyl groups. The polyol preterred is sucrose. Examples of long chain, unsaturated, carboxylic acid entities include, but are not limited to, lauroleate, myolate, palmitoleate, oleate, elaidate, erucate, linoleate, linolenate, arachidonate, eicosapent aenthoate and docosahexaenoate. For oxidative stability, mono- and di-unsaturated fatty acid entities are preferred. Examples of suitable short chain saturated carboxylic acid entities include, without limitation, acetate, caproate, caprylate, caprate and laurate. Examples of suitable saturated, long chain carboxylic acid entities include, without limitation, arachididate, behenate, lignocerate and cerota t o. Of course,. the long chain unsaturated carboxylic acid entities can be used alone or in mixtures with each other or in mixtures with saturated and short chain carboxylic acid entities, in all proportions. Similarly, the long chain saturated carboxylic acid entities can be used in combination with each other, in all proportions. Caboxylic acid entities mixed from source oils containing substantial amounts of the desired saturated or unsaturated acids can be used as the acid entities to prepare the compounds that are used as nucleating agents herein. The mixed carboxylic acids of the oils should contain at least about 30%, preferably at least about 50% and, more preferably, at least about 80% of the desired, saturated or unsaturated acids. For example, rapeseed oil fatty acids or soybean oil fatty acids can be used in place of pure C12 to C16 unsaturated fatty acids. The fatty acids of rapeseed oil, higher, euricic, hydrogenated, can be used in place of the pure saturated acids of C20 to C26. Preferably, the C20 and higher acids, or their derivatives, for example methyl or other lower alkyl, are concentrated, for example, by distillation. Fatty acids from palm kernel oil or coconut oil can be used as a source of C8 to C12 acids. An example of the use of source oils to make solid polyol polyesters which are used in the antiperspirant compositions herein is the preparation of solid sucrose polyester, which employs fatty acids of the higher oleic sunflower oil and rapeseed oil, euricic, superior, substantially hydrogenated in its entirety. When the sucrose is practically completely esterified with a 1: 3 weight mixture of methyl esters of the fatty acids of these two oils, the resulting sucrose polyester will have a molar ratio of Cld unsaturated acid radicals to saturated acid radicals. C20 higher than about 1: 1 and about 28.6 weight percent of the total fatty acids in the polyester will be C22 fatty acids. The higher the proportions of unsaturated and saturated acids desired in the carboxylic acid raw materials that are used to make the solid polyester polyols, the more efficient will be the ability of the ester to function as a nucleating agent. Examples of solid polyol carboxylic acid polyester nucleating agents, which are used in the antiperspirant compositions herein, include, but are not limited to, the octaester of raffinose, wherein the carboxylic acid entity is a tertiary, is linoleate and behenate in a molar ratio of 1: 3, the maltose heptaester wherein the esterifying carboxylic acid entities are fatty acids from sunflower seed oil and lignocerate in a molar ratio of 3: 4; the octaester of sucrose wherein the esterifying carboxylic acid entities are oleate and behenate in a molar ratio of 2: 6, and the octaester of sucrose wherein the esterifying carboxylic acid entities are laurate, linoleate and behenate in a molar ratio of 1 : 3: 4 A preferred material is the sucrose polyester wherein the degree of esterification is 7-8 and wherein the fatty acid entities are mono and / or di-unsaturated, C18 and behenic, in a molar ratio of unsaturated: behenic from 1: 7 to 3: 5. The particularly preferred nucleating agent of polyol ester is the octaester of sucrose wherein there are approximately 7 behenic fatty acid entities and about 1 oleic entity in the molecule. The solid carboxylic acid polyesters herein can be made according to prior art methods to prepare polyol polyesters. 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 on 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, 1995 and U.S. Patent No. 4,517,360 Volpenhein, granted on May 21, 1985, all of which are incorporated as a reference. The non-soluble, micronized, inorganic nucleating agents suitable for the antiperspirant compositions of the present invention include materials such as silica, titanium dioxide, and combinations thereof. These materials contain submicron particles (average particle size, generally less than about 1 μm) that help the production of small crystals or gelling particles. Preferred nucleating agents and preferred concentrations of nucleating agents that are used in antiperspirant compositions include C18 succinic acid (0.1%) 1,9-nonaniodic acid (0.1%), Teflon (0.1%), silica (0.1%), copolymer of polysiloxane (2%), sucrose octabehenate (0.5%, 0.75%, 1.0%), Unilin 350 (0.1%), Unilin 550 (0.1%), Unilin 700 (0.1%), tearin trihydroxies (0.1%) and combinations thereof.

OPTIONAL COMPONENTS The gel-solid antiperspirant stick compositions of this invention may further comprise one or more optional components that may modify the physical, chemical or aesthetic characteristics of the composition or serve as additional "active" components, when deposited on the skin . The compositions may also comprise other optional inert ingredients. Many of these optional materials are already known in the antiperspirant art and can be used in the compositions herein, as long as these optional materials are compatible with the essential materials described herein, or do not unduly diminish the performance of the product. . Non-limiting examples of optional materials include active components such as bacteriostats and fungicides, and "non-active" components such as colorants, perfumes, emulsifiers, chelants, distribution agents, preservatives, waste masking agents, process aids as modifiers of viscosity and elimination aids by washing. Examples of these optional materials are described in U.S. Patent No. 4,049,792 to Elsnau, issued September 20, 1977; Canadian Patent No. 1,164,347 to Beckmeyer et al., issued March 27, 1984; U.S. Patent No. 5,019,375 to Tanner'et al., Issued May 28, 1991; and U.S. Patent No. 5,429,816 to Hofrichter et al., issued July 4, 1995, the disclosures of which are incorporated herein by reference. The gel-solid antiperspirant stick compositions of this invention may also be formulated to comprise other dispersed solids or other materials in addition to or in place of the particulate antiperspirant actives. These other dispersed solids or other materials include any material known or that is suitable for topical application to human skin. The gel-solid antiperspirant stick compositions can also be formulated as gel-solid stick compositions that do not contain antiperspirant or any other active, particulate or otherwise material.

MANUFACTURING METHODS The gel-solid antiperspirant stick compositions of this invention can be prepared by any effective method or technique, suitable for providing a gel-solid antiperspirant stick composition having the required crystalline matrix and other product characteristics described here. These methods involve the formulation of the essential components of the composition to form a gel-solid having the required ratio of elastic modulus to viscous modulus, product hardness and visible residue index, wherein the crystalline matrix within the composition comprises crystals non-polymeric, elongated gelling agents having a dimensional 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 μm) through techniques directed at carrying to the minimum the crystalline particle size in a composition. The crystalline particle size in the preferred embodiments of this invention can be determined by techniques well known in the art, including electron or light microscopy of the composition; wherein the composition is formulated for analytical purposes without active particulate antiperspirant or other solid particles. Without this reformulation, it is more difficult to directly determine and directly distinguish the crystalline particle size of the gellant and the morphology from the particle size and morphology with which other non-gelling particles contribute. The reformulated composition is then evaluated by electron microscopy or light microscopy or by other similar methods. Techniques for preparing the gel-solid antiperspirant stick compositions of this invention include those methods suitable for formulating compositions containing small gelling crystalline particles. Suitable techniques for decreasing the size of crystalline gelling particle include the use of nucleating agents, the formulation with selected carriers or gelling agents or combinations of carrier / gelling agent, the control of the indexes of 'crystallization including controlling the formulation, the flow regime of the process and the processing temperatures and other methods described here. All these methods should be applied to the formulation to control or minimize the particle size of the gelling crystal and / or to form the desired elongated crystalline particles, so as to form the desired crystalline matrix of the composition.

METHOD OF USE The gel-solid antiperspirant stick compositions can be applied topically to the armpit or to any other area of the skin in an amount effective to treat or reduce malodour or moisture by perspiration. The composition preferably is applied in an amount ranging from about 0..1 grams to about 20 grams, more preferably, from about 0.1 grams to about 10 grams, still more preferably, from about 0.1 grams to about 1 gram. of the desired area of the skin. The compositions are preferably applied to the armpit or to another area of the skin once or twice a day, preferably once a day, to achieve effective control of perspiration and odor for a prolonged period of time.

EXAMPLES The following. non-limiting examples illustrate the specific embodiments of the gel-solid antiperspirant stick compositions of this invention, including the methods of manufacture and use. Each of the exemplified compositions is prepared by combining all the listed components, except the antiperspirant active ingredient and other materials such as perfumes. The combined components are heated to about 100 ° C with agitation to form a hot liquid, after which all the materials are added to the hot liquid. The hot liquid is allowed to cool with stirring just before the solidification point, at which point the liquid composition is cooled and poured into the applicator containers and allowed to cool and solidify to the required product hardness. Each of the exemplified compositions comprises a crystalline gel matrix comprising crystalline particles with a dimensional ratio greater than about 6, and an average particle size of crystalline gelling agent of less than about 1 μm. Each of the exemplified compositions also has a visible residue index of between about 11 and about 30 in L value, a product hardness of between about 500 and 5,000 grams-force and a G '/ G "ratio between about 0.1 and about 100. Each of the exemplified antiperspirant compositions are applied topically to the armpit area of the skin, according to the methods of use described herein and an improved performance of less residue, greater efficacy and aesthetics is provided.

EXAMPLES 1 TO 8 1 - . 1 - Dow Cornxng 45 Fluid; General Electric SF-1202 2 - . 2 - Petrolite Unilin 425 3 - Dow Corning 3225C 4 - Petrolite Unithox 450 5 - Petrolite Unithox 480 6 - Finsolv TN from Finetex

Claims (8)

1. CLAIMS 1. An anhydrous gel-solid antiperspirant stick composition, characterized in that it comprises: (a) from 0.5% to 60% by weight of a particulate antiperspirant active; (b) from 1% to 15% by weight of a solid non-polymeric gellant selected from the group consisting of 12-hydroxyl-tertiary acid, esters of 12-hydroxystearic acid, 12-hydroxy-arsenic acid amides, and combinations thereof; and "(c) from 10% to 80% by weight of an anhydrous liquid carrier having a promised solubility parameter of 3 to 13 (cal / cm 3) 0.5 and wherein the composition has a visible value residue index -L from 11 to 30, a product hardness of 500 grams- forces to 5000 grams - force, preferably, of 350 grams-force to 2,000 grams-force, and a ratio of an elastic to viscous modulus of 0.1 to 100, preferably, from 0.1 to 50 and wherein the refractive indices of the particulate antiperspirant active, the solid non-polymeric gellant and the anhydrous liquid carrier are not comparable.
2. 2. The composition, according to claim 1, characterized in that the solid non-polymeric gellant is selected from the group consisting of 12-hydroxystearic acid, 12-hydroxystearic acid methyl ester, 12-hydroxystearic acid ethyl ester, 12-hydroxystearic acid terylester. hydroxies tear, acid benzyl ester 12-hydroxystearic, acid amide 12 -. 12-tearic hydroxies, 12-hydroxystearic acid isopropyl amide, 12-hydroxystearic acid-12-hydroxy stearic acid butylamide, 12-hydroxy stearic acid phenylamide, 12-hydroxystearic acid t-butylamide, cyclohexylamide 1 12-hydroxystearic acid, 1-adamantylamide of 1-12-hydroxy acid is tearoic, 2 -admantyl ilamide of 1-12-hydroxystearic acid, diisopropylamide of 1-12-hydroxyl-tertiary acid, and combinations thereof; preferably, 12-hydroxyl tearic acid.
3. 3. The composition, according to claim 1, characterized in that the solid non-polymeric gelling agent is in the form of elongated crystalline particles having a dimensional ratio of at least 2, preferably at least 6.
4. 4. The composition according to any of the preceding claims, characterized in that the solid non-polymeric gellant is in the form of crystalline particles having a dimensional ratio of less than 1 μm, preferably less than 0.2 μm.
5. 5. The composition according to any of the preceding claims, characterized in that the composition has a starting temperature differential scanning calorimeter of 25 ° C to 85 ° C, preferably, from 30 ° C to 60 ° C.
6. 6. The composition, according to any of the preceding claims, characterized in that the anhydrous liquid carrier comprises a volatile silicone carrier.
7. 7. The composition, according to any of the preceding claims, characterized in that the anhydrous liquid carrier further comprises a non-volatile silicone carrier having a viscosity of less than 100,000 centistokes.
8. 8. A method for treating or reducing moisture and bad odor of perspiration, characterized in that it comprises applying from 0.1 grams to 20 grams of the composition, in accordance with any of the preceding claims to the desired area of the skin. SUMMARY OF THE INVENTION Antiperspirant gel-anhydrous solid bar compositions are disclosed, comprising a particulate antiperspirant active; a solid non-polymeric gelling agent selected from the group consisting of 12-hydroxyl-tertiary acid, 12-hydroxyl-tertiary acid esters, 12-hydroxyl-tertiary acid amides and combinations thereof, and an anhydrous liquid carrier having an average solubility parameter from about 3 to about 13 (cal / cm3) ° ', wherein the composition has a visible residue index of value L from about 11 about 30., a product hardness from about 500 grams-force to about 5000 grams-force, a ratio of an elastic to viscous modulus from about 0.1 to about 100. The refractive indexes of the particulate antiperspirant active, the solid non-polymeric gelling agent and the Anhydrous liquid carrier are not comparable. Preferably, the solid non-polymeric gellant-e is a crystalline material having an average particle size of less than about 1 μm and / or having a particle-like morphology having a dimensional ratio greater than about 2. These compositions of Solid gel antiperspirant bar provide lower performance characteristics of residue appearance, efficiency and aesthetics.