MXPA99005854A - Antiperspirant gel-solid stick compositions substantially free of select polar solvents - Google Patents

Abstract

Disclosed are anhydrous antiperspirant gel-solid sticks which comprise particulate antiperspirant active;a solid non-polymeric gellant that is substantially free of dibenzylidene alditol, inorganic thickening agents, organic polymeric gellants, n-acyl amino acid derivatives, or combinations thereof;an anhydrous liquid carrier that is substantially free of polar, water-immiscible, organic solvents, wherein the composition has a visible residue index of from about 11 to about 30 L-value, a product hardness of from about 500 to about 5,000 gram-force, a rheology profile defined by a ratio of an elastic modulus (G') to a viscous modulus (G'') of from about 0.1 to about 100. The refractive indices of the particulate antiperspirant active, the solid non-polymeric gellant, and the anhydrous liquid carrier are not matched. The compositions preferably comprise crystalline gellant particles having an average particle size of less than about 1&mgr;m and/or a particle morphology having an aspect ratio of greater than about 2. These compositions provide improved low residue performance, efficacy and aesthetics.

Description

COMPOSITIONS OF AN I RANSPIRANT BAR IN GE - SOLID SUBSTANTIALLY FREE OF SELECTED POLAR SOLVENTS TECHNICAL FIELD The present invention relates to antiperspirant compositions in the form of gel-solid sticks. In particular, the present invention relates to select compositions in the form of gel-solid sticks that provide improved performance properties of appearance, residue and aesthetics, improved - and that are substantially free of polar immiscible organic solvents in water or liquid carriers.

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 spray or pump sprays, roll-on liquids, creams, emulsions, gels, solid-gels or other solid-bar formulations, and comprise an astringent material, such as, for example, zirconium salts 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 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 topically. However, these gel bars are expensive to 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. Nevertheless, these gelling agents, similar to many other gelling agents known in the art, are not stable acids and therefore tend to interact with the antiperspirant active due to the acid nature of the active ingredient. 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 improving lower performance of 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 which is 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 by 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-hydroxyl tertiary 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 solid gels 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 gelling agent which is substantially free of dibenzylidene alditol, inorganic thickening agents, organic polymeric thickening agents, n-acyl amino acid derivatives and combinations thereof; from about 10% to about 80% by weight of an anhydrous liquid carrier that is substantially free of poisonous, water immiscible, organic liquid carriers or solvents; 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 (C) to a viscous modulus (G ") from about 0.1 to about 100. The UNC composition requires comparable refractive index of the active antiperspirant particulate, solid non-polymeric gelling agent and anhydrous liquid carrier to achieve 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 lower residue appearance, efficacy and aesthetics, and furthermore provide a composition without relying on specific gelling agents such as dibenzylidene alditols or double gelling systems containing n-acyl amino acid derivatives. It is a further object of the present invention to provide this composition without relying 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 comprising an anhydrous liquid carrier that is substantially free of organic, water miscible, polar solvents.

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 that is substantially free of dibenzylidene alditol, inorganic thickeners, organic polymeric gelling agents, n-acyl amino acid derivatives, or combinations thereof; from about 10% to about 80% by weight of an anhydrous liquid carrier that is substantially free of polar miscible, water miscible organic solvents, wherein the composition has a visible residue index of L value from about 11 to about 30, product hardness of approximately 500 grams - strength at approximately 5000 grams - force, a rheology profile defined by a ratio of an elastic modulus (G ') to a viscous modulus (G ") of approximately 0.1 to approximately 100. The refraction of the particulate antiperspirant active, the solid non-polymeric gelling agent and the anhydrous liquid carrier are not comparable, Preferably, the compositions comprise crystalline gelling particles having an average particle size of less than about 1 μm and / or a morphology of particle having a dimensional ratio greater than about 2. Preferably, the compositions also comprise from about 0.1% to about 50% by weight of the modified silicone liquid carrier, and most preferably in combination with a volatile silicone. - 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 solubilized antiperspirant active, and without relying on select low residue gelling agents, such as, for example, dibenzylidene alditols or combinations of selected gelling agents containing n-acyl amino acid derivatives. This is accomplished by formulating an anhydrous gel-solid stick composition having the preferred hardness and rheology profile provided by a three-dimensional non-polymer crystal gel network consisting of small elongated crystalline particles having an average particle size. less than about 1 μm and / or a particle morphology defined by a dimensional ratio of at least about 2. It has been found that the gel-solid antiperspirant stick compositions of the present achieve improved antiperspirant and deodorant efficacy when the anhydrous liquid carrier is substantially free of organic solvents, miscible in water, polar.

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 a 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 formulation. The term "low residue" as used herein, refers generally 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 as defined by the methodology described hereinafter. 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 amount or concentration of inorganic thickening agents, agents organic polymeric thickeners, dibenzylidene alditol 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-hydroxy-threo 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, fumed silicas, and silicates, including montmorillonite clays and hydrophobically treated montmorillonites, such as, for example, bentonites, hectorites and silicates of colloidal magnesium. 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 butylene / ethylene / is hydrogenated tirene, 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 Dekker, 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, Subsitu t um t Cons tan ts for Correl a ti on Ana lysi s in Chemi st and Biolo gy (1979), whose list and description are incorporated herein by reference. Examples of these substituents include, for example, alkyl, alkenyl, alkoxy, hydroxy, oxo, nitro, amino, aminoalkyl (for example aminometyl), etc.), cyano, halo (for example chlorine, fluorine, bromine, iodine) , carboxy, alkoxyacetyl (eg, carboethoxy, etc.), thiol, aryl, cycloalkyl, heteroaryl, heterocycloalkyl (eg, 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 I gelifiers selected from the group consisting of n-acyl amino acid amides, n-acyl amino acid esters, glutamic acid, lysine, glutamine, aspartic acid preparations 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 more preferably, have at least 2 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 about 800 grams-strength at 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. The larger values represent the harder product, and the smaller values represent the softer 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, U.S.A. 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 diameter of angled surface of the cone of approximately 15.5 mm. The cone is a smooth 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 the 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 antiperspirant stick compositions having a product hardness of approximately 500 grams-force at approximately 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 Adhesion and Release Tester Serial No. A-14934, 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 then moves slowly to the piece of bonded black felt and is 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, delivered by the heavy products, to approximately 1.75 grams. of the antiperspirant stick composition is optionally applied over an area of 5 cm x 20 cm of 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 gelling 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 gelifier particle morphology characterized by a dimensional relationship of growth in such a way as to result 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, preferably greater than 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 to elongate, the measurement of the visible residue index 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 module proportion (G '/ G ") viscous elastic (G') _ (G") of the gel-solid stick composition. To provide the necessary rheology, gel-solid stick compositions must 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 gel-solid stick 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-solid stick compositions herein 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 art. of the formulation. For example, a Bohlin St res s-Strain Rheometer, available from Bohlin Reology, Cranberry, New Jersey, can be used using a cone (approximately Io) and plate configuration. Approximately 1.0 mg of the product is carefully removed from the composition with minimal application of shear stress and then placed between the cone and the plate fixings for the measurement of G 'and G ". It has been found that gel-stick compositions solid of the present invention exhibit lower residue appearance performance when formulated as described herein, wherein the composition has the selected G '/ G "ratio described above, especially when the defined rheology is associated with a matrix of crystalline gel having a preferred small particle size and / or particle morphology as described herein. These gel-solid stick formulations are gently sprayed onto the skin and cut quickly and melt during the spray to form a thin, thin 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 residue appearance performance. These selected gel-solid compositions, as defined herein, behave as solids prior to their application while remaining within a can, or other container, but behave more like liquids or fluids during application to the skin or immediately after it. 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 antiperspirant 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 active agents as 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, even more preferably, from about 20 μm to about 100 μm. 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 are also preferred. It has been found that 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 for use in the gel-solid antiperspirant stick compositions 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 Cli 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, 975, 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-aCli 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 Schmitz, 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 material known or otherwise suitable for topical application to human skin. Gel-solid antiperspirant stick compositions may also be formulated as solid-gel stick compositions that do not contain antiperspirant or other active, or otherwise particulate, material.

GELIFICANT The gel-solid antiperspirant stick compositions of the present invention comprise a solid non-polymeric gellant suitable for topical application to human skin, other than inorganic thickeners, organic polymeric gelling agents or other gelling agents such as dibenzylidene alditol and nitrile derivatives. -Acyl amino acid. These solid non-polymeric gelling agents must form within the composition a crystalline matrix within which an anhydrous liquid carrier or other liquid component of the composition is entrapped or contained. Preferably, these solid non-polymeric gelling agents form crystalline particles having an average particle diameter and particle morphology as described hereinafter. The gel-solid antiperspirant stick compositions are substantially free of inorganic thickening agents, organic polymeric thickening agents and gelling agents selected from the group consisting of dibenzylidene alditols and n-acyl amino acid derivatives. In this context"substantially free" means that the compositions contain less than an effective amount of these agents that when used alone could provide any thickening or measurable viscosity increase 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. The gel-solid antiperspirant stick compositions are preferably substantially free of fatty alcohols which are solid under ambient conditions and which contain from 12 to 40 carbon atoms. More specifically, the compositions herein preferably do not contain more than about 5%, preferably from zero to about 2%, by weight of these fatty alcohol materials. However, minimal concentrations of these materials in the composition can be used as a nucleating agent as described hereinafter. The concentration of the gelling agents in the compositions may vary with each selected gel-solid antiperspirant stick formulation, especially with each anhydrous liquid carrier selected from the formulation, but these concentrations will generally be in the range of 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 non-polymeric gelling agents must be solid under ambient conditions. The solid non-polymeric gelling agents for use in solid gel antiperspirant stick compositions are those that can be melted and form 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 processing temperature of 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 non-polymeric gelling agent 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. By selecting a combination of solid non-polymeric gelling agent and a liquid carrier for use in the solid gel antiperspirant stick compositions, the selected 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, less than about 0.4 μm, even more preferably, less than about 0.2 μm, more preferably, less than about 0.001 μm to about 0.2 μm, and / or where 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 microscopy or electronics. Gel-solid stick compositions can be prepared by methods well known in the art of the formulation to produce the gels-solids having a minimum crystalline particle size or the preferred elongated particle morphology. The gel-solid stick compositions are preferably prepared by the selected methods described hereinafter intended to minimize the crystalline particle size and / or establish the preferred crystalline particle morphology. Solid non-polymeric gelling agents suitable for use in the gel-solid antiperspirant stick compositions of the present invention include fatty acid gelling agents, esters and amides of fatty acid gelling agents, hydroxy acids, hydroxy fatty acids, cholesterol materials, lanolinol materials and other amide gelling agents known to be used as gelling agents or which are otherwise described in detail hereinafter. Other crystalline gelling agents can be used in the gel-solid stick compositions of the present invention with the proviso that these various gelling agents can be formulated to provide the required crystal gel matrix and the product and rheology characteristics defined herein. Other solid non-polymeric gelling agents suitable for use in the solid gel antiperspirant stick compositions herein include fatty acid gelling agents that include, but are not limited to, fatty acid and hydroxy or alpha hydroxy fatty acids, having from about 10 to about 40 atoms. of carbon, examples of which include 12-hydroxy tearic acid, 12-hydroxy lauric acid, 16-hydroxyhexadecanoic acid, behenic acid, euricic acid, stearic acid, caprylic acid, lauric acid, isostearic acid and combinations of the same. Preferred fatty acid gelling agents are those having the dimer to acid monomer ratio as described hereinafter. Preferred solid non-polymeric gelling agents suitable for use in solid gel antiperspirant stick compositions include 12-hydroxyl tertiary acid, 12-hydroxystearic acid esters, 12-hydroxyl-tertiary acid amides and combinations thereof. These preferred gelling agents include those corresponding to the following formula: wherein Ri is 0R 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. Among these preferred gelling agents are those selected from the group consisting of 12-hydroxystearic acid, 12-hydroxystearic acid methyl ester, 12-hydroxystearic acid ethyl ester, 12-hydroxystearic acid stearyl ester, 12-hydroxystearic acid benzyl ester, 12-hydroxystearic acid amide Theoretical hydroxies, isopropyl acid 12-hydroxystearic acid, 12-hydroxystearic acid, 12-hydroxystearic acid benzylamide, 12-hydroxystearic acid phenylamide, 12-hydroxystearic acid t-butyl amide, 12-hydroxystearic acid cyclohexylamide -hydroxystearic, 1-adamantylamide of 12-hydroxystearic acid, 2-adamantylamide of 12-hydroxystearic acid, diisopropylamide of 12-hydroxystearic acid, and mixtures thereof; even more preferred, 12-hydroxy-aroic acid, 12-hydroxyl-isopropylamide, and combinations thereof. The most preferred is 12-hydroxyl tertiary acid. Suitable amide gelling agents include disubstituted or branched monoamide gelling agents, monosubstituted or branched diamide gelling agents, triamide gelling agents and combinations thereof, excluding n-acyl amino acid derivatives selected from the group consisting of n-acyl amino acid amides, n-acyl amino acid esters, prepared from glutamic acid, lysine, glutamine, aspartic acid and combinations thereof and specifically described in U.S. Patent No. 5,429,813. Preferred amide gelling agents used herein include di- and / or tribasic anhydride alkylamides or carboxylic acids, the concentrations of which are preferably between about 0.1% and about 25%, preferably, between about 1% and about 15%, more preferably between about 1% and about 10% by weight of the composition. Suitable alkylamides that are used in the gel-solid antiperspirant stick compositions of this invention include those corresponding to the formula: Rg O RS R, C -C -N -R2 1 R R X -Y - Z - R8 I ° R - c "-C_N -R4 I R 10 wherein a is a structure formed from the bonding of C ', C "and X, and wherein: a) Ri is zero, hydroxy, hydrogen, aryl, siloxane or aryl substituted with C? -C22 alkyl or ethers C 1 -C 22 alkyl, C 1 -C 22 alkylesters, C 1 -C 22 alkoxy, C 1 -C 22 alkenyl, C 1 -C 22 alkyl, straight chain, cyclic or branched, substituted or unsubstituted, saturated or unsaturated preferably C4-C18 alkyl, C4-C8 alkenyl, C4-C8 alkoxy, C4-C8 alkyl esters, C4-C8 alkyl ethers or C4-C18 alkyl substituted aryl , more preferably, C? 2-C? alkyl, C? 2 -C 8 alkenyl, C? 2-C? 8 alkoxy, C alqu-C? alqu alkylesters / C? 2-C alkyl ethers 8 or aryl substituted with C 2 -C 8 alkyl, b) R 2, R 4, R 5 and Re together or independently are hydrogen, hydroxy, aryl, siloxane or aryl substituted with C 1 -C 22 alkyl or C 1 alkyl ethers C22 Alkyl esters of C? -C22 / - C? -C22 alkoxy / - C? -C22 alkenyl, straight chain C? -C22 alkyl, branched each or cyclic, substituted or unsubstituted, saturated or unsaturated; preferably, C4-C? alkyl, C4-C10 alkenyl, C4-C alco alkoxy, C alqu-C? alkylesters, C alqu-C10 alqu alkylethers or C4-C10 alquilo alkyl substituted aryl? more preferably, C4-C8 alkyl, C4-C8 alkenyl, C4-C8 alkoxy, C-C8 alkyl esters, C4-C8 alkyl ether or C4-C8 alkyl substituted aryl; c) R3 is null, hydroxy, hydrogen, C1-C4 alkylethers or C1-C4 alkylesters, C?-C4 alkoxy, C?-C4 alkenyl, straight chain, branched C alquilo-C alquilo alkyl or cyclic, substituted or unsubstituted, saturated or unsaturated; preferably, C 1 -C 4 alkoxy, hydroxy or hydrogen, more preferably, a hydroxy or hydrogen; d) R and R8 independently or together are, null, hydrogen, hydroxy, aryl, siloxane or aryl substituted with C? -C22 alkyl or C? -C22 alkyl ethers C? -C22 alkylesters, C? - C22 alkoxy, C? -C22 alkenyl-straight, branched or cyclic C? -C22 alkyl, substituted or unsubstituted, saturated or unsaturated; preferably C4-C10 alkyl, C -C? alkenyl, C4-C? alkoxy, C4-C10 alkyl esters, C4-C? alkyl alkylethers or aryl substituted with C4-C10 alkyl, more preferably , C4-C8 alkyl, C4-C8 alkenyl, C-C8 alkoxy, C4-Cs alkylesters, C4-C8 alkyl ethers or C4-C8 alkyl substituted aryl; e) Rg is zero or hydrogen; f) R? 0 and Rxx independently or together are, null, hydrogen, hydroxy, aryl, siloxane or aryl substituted with C? -C6 alkyl or C? -C6 alkyl ethers, C? -C6 alkyl esters, C alkoxy? -C6, C? -Ce alkenyl, straight chain, branched or cyclic C6 alkyl, substituted or unsubstituted, saturated or unsaturated; preferably, C1-C4 alkyl, C? -C alkenyl, C? -C4 alkoxy, C-C4 alkyl esters, C-C4 alkyl ethers, aryl substituted with C1-C4 alkyl or hydrogen, more preferably, a hydrogen; g) X is zero, nitrogen, aryl or + CH2 ní where n is an integer from 1 to 6, preferably, -fCH2 -) - n / 'where n is an integer from 1 to 3; h) Y is zero, acyl or carbonyl; i) Z is zero, hydrogen, hydroxy, aryl, siloxane, nitrogen or aryl substituted with C 1 -C 22 alkyl ethers, or C 1 -C 22 alkylesters, C 1 -C 22 alkoxy, C 1 -C 22 alkenyl, C? -C22, C? -C22 straight-chain, branched or cyclic alkyl, substituted or unsubstituted, saturated or unsaturated; preferably, C4-C ?alkyl, C4-C? alkenyl, C4-C10alkoxy, C4-C10alkyl esters, C4-C10 alkyl ethers or C4-C alquiloalkyl-substituted aryl, with greater preferably, C4-C8 alkyl, C4-C8 alkenyl, C4-C8 alkoxy, C4-C8 alkyl esters, C4-C8 alkyl ethers or C4-C8 alkyl substituted aryl; j) "a" is a double or single bond as long as: (i) when X is zero, Y, Z, R3, R7 and R8 are zero, C1 is directly linked to C "and Rx is not a hydrogen; ii) when X and Z are not null and Y is zero, X is directly linked to Z, (iii) when Z is zero, a hydrogen or a hydroxy, R7 and R8 are zero, and (iv) "a" is a double bonds, R3 and R9 are null The alkylamides or di and tribasic carboxylic acids or anhydrides suitable for use in the gel-solid antiperspirant stick composition include cyclic acid alkylamides, ticarbicarbal acid, aconitic acid, nitrilotriacetic acid, succinic acid and itaconic acid, for example 1, 2, 3-propane tributylamide, 2-hydroxy-1,2,3-propane tributylamide, l-propene-1,2,3-trioctylamide, N, N'N "-tri (acetodecylamide) amine, 2-dodecyl-N, N'-dihexylsuccinamide and 2-dodecyl-N, N'-dibutyl-succinnamide. Preferred are alkylamides of di-carboxylic acids, such as, for example, di-amides of alkylsuccinic acids, alkenylsuccinic acids, alkylsuccinic anhydrides and alkenylsuccinic anhydrides, more preferably 2-dodecyl-N, N'-dibutylsuccinamide. The alkylamide gelling agents, preferably, have opposite and essentially parallel end chains that extend outwardly from the structure of the gelling agent. It is considered that this spatial arrangement or structural configuration of "tuning trench" facilitates the formation of networks essential for the formulation of gel-stick or solid-gel compositions. By the phrase "tuning fork configuration", which is used herein, reference is made to any configuration that resembles an article or implement having a handle portion that extends longitudinally toward one end to form two fingers. It is also preferred that end chains are attached to the structure of the gelling agent by means of acyl-amide linkages wherein the acyl portion of the acyl-amide linkage is attached directly to the main structure of the gelling agent. The alkylamide gelling agents can be synthesized using any of the following one or two step reaction procedures. The one-step procedure involves direct amidation of the di or tribasic anhydride or organic acid with the appropriate alkylamine under the reaction temperatures typically at or near the boiling point of the alkylamine, preferably, between about -30 ° C and about 200 ° C, followed by removal of the excess amine. Certain reactions, due to their exothermic nature, may not require external heating. The alkylamide gelling agents can also be synthesized using a two step process involving the esterification of the di or tribasic organic acid or anhydride with methanol using a boron trifluoride or other Lewis acid catalyst at a temperature between about 30 ° C to about 100 ° C, followed by removal of excess methanol and catalyst. The resulting trimethyl ester is then amidated as described in the previous step process, using the appropriate alkylamine followed by removal of excess amine. The alkylamides are preferably non-polymeric. These solid non-polymeric gelling agents described herein are especially effective when used in combination with selected anhydride carriers, for example volatile silicones, especially volatile cyclomethicone. These gelling agents are most preferably used in combination with a liquid carrier comprising a volatile silicone and a non-volatile silicone (for example, non-volatile dimethicones or other organofunctional siloxanes well known in the art) and / or a non-volatile organic carrier.

Preferred enantiomeric gelifers Preferred solid and non-polymeric gelling agents that are used herein include those enantiomeric compounds or enantiomeric materials that contain at least one asymmetric (chiral) carbon atom. Non-limiting examples of these preferred enantiomeric gelling agents include 12-hydroxystearic acid, other hydroxy acids such as for example alpha hydroxy acid, ternary cabbages, lanolin and derivatives thereof. It has been found that these preferred enantiomeric gelling agents, when used in the gel-solid antiperspirant compositions of the anhydrous type herein, provide the composition with the required hardness of the product, the required values of visible residue index and the properties Required Rheological (G '/ G ") It is believed that these enantiomeric gelling agents are especially effective to form one-dimensional elongated particles in the form of filaments, fibrils or strands that simply twist or twist to form a three-dimensional, stable, crystalline matrix in the composition These elongated particles have a dimensional ratio of greater than about 2, preferably greater than about 6. These gelling agents are considered to form elongated crystalline particles which result in a stable crystalline matrix which, in part due to the small size and the elongated morphology of these parts These cells cause less diffusion of light when they are applied to the skin in the antiperspirant composition, resulting in less visible residue after application.

Preferred Morphology of the Particles The solid and non-polymeric gelling agents used herein include the crystalline gelling agents which inherently form or can be formulated or are made to form elongated crystalline particles having a dimensional ratio greater than about 2, preferably, greater than 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, still 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 elongated crystalline 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 give the gel-solid antiperspirant stick compositions a structure three-dimensional crystalline which can provide the composition with the characteristic of leaving little residue, a ratio of elastic modulus to viscous required and the required hardness of the product, as defined herein. This crystalline morphology is considered to be especially effective in providing a crystalline matrix within the composition that provides a strong intertrawn gel-solid matrix network., but that also includes crystalline particles that are small enough to contribute minimally to the visible residue when they are 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 antiperspirant particle or any other component of the composition. 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, more 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 fusion profile provide improved cosmetic or aesthetic properties when applied topically to the skin, and in particular provide a lower perception of moisture, tackiness or softness of the product during and immediately after application. The selected melting profile also helps to further reduce the visible residue index of the composition, also improving the performance of less waste appearance.

Preferred ratio of dimer to monomer The solid and non-polymeric gellant of the gel-solid antiperspirant stick composition herein preferably comprises a fatty acid gellant having a selected ratio of dimer to monomer. The fatty acid gelling agents having the required ratio of dimer to monomer can be used alone or in combination with an additional or secondary gellant of the composition. The dimer-to-monomer ratio selected helps to provide the gel-solid stick compositions herein with improved performance of little appearance of residue, efficacy and aesthetics and in particular provides a lower performance of little appearance of residue and better hardness of the product. The fatty acid gelling agents of the gel-solid antiperspirant stick composition, when used in combination with additional or secondary gelling agents, have a selected ratio of dimer to monomer of between about 1: 1 to about 25: 1, preferably, from about 1.5: 1 to about 25: 1, more preferably, from about 2.5: 1 to about 20: 1, still more preferably, between about 3: 1 to about 10: 1. The higher dimer to monomer ratios are preferred. The dimer to monomer ratio of the fatty acid gellant can be determined by methods or techniques well known in the field of formulations, including infrared methods such as Fourier Transform Infrared Spectroscopy (FTIR). These methods are discussed in The Infared Spectra of Complex Molecules, L.J. Bellamy, 2nd. Edition, 1958, Introduction to Infared and Raman Spectroscopy, N.B. Colthup, et al., 3a. Edition, and Fourier Transf orm Infared Spectroscopy, P.R.

Griffiths, et al., 1986, which are incorporated herein by reference. According to these methods or techniques, fatty acids are typically characterized by their carbonyl elongation frequencies, which are measured as absorption bands between 1740 cm "1 and 1680 cm -1. The fatty acid gellant of the antiperspirant compositions of The present invention comprises fatty acid monomers and fatty acid dimers which are components of the carbonyl absorption band, However, due to the formation of hydrogen-bonded dimers, the fatty acid dimer component can be displaced up to the frequencies of the fatty acid dimer. 30 cm-1 lower than the frequency of the fatty acid monomer With the use of infrared spectral data, the ratio of dimer to monomer is determined by calculating the ratio of the peak area of the band derived from the second dimer bound to hydrogen near 1696 cm-1 with respect to the peak area of the band derived from the second fatty acid monomer about 1712 cm "1. According to the following methodology, an infrared spectrum is recorded using an Attenuated Total Reflectance ("ATR") crystal of 45 ° ZnSe and a horizontal ATR apparatus (obtained from Spectra Tech. Inc., Shelton, Connecticut, USA). ) attached to a Nicolet 20scx FTIR Spectrometer. The Nicolet 20scx FTIR Spectrometer is obtained from Nicolet Instrument Corporation, Madison, Wisconsin, U.S.A. The Nicolet 205scx FTIR Spectrometer is equipped with a narrowband cadmium and mercury telluride detector with which an average of 256 scans are co-added to generate the infrared spectra. The infrared spectra are then imported into the software program of the computer, for example GRAMS / 386 (obtained from Galactic Industries Corporation, Salem, New Hampshire, USA) to calculate the ratio of dimer to monomer using a second derivative algorithm. 5 points, which is a mathematical procedure defined by Savis ts ky-Golay. The required dimer to monomer ratio can be established with the fatty acid gelling agents described herein, which include alpha-hydroxy fatty acids and fatty acids having from about 10 to about 40 carbon atoms, examples of which include 12- hydroxystearic, 12-hydroxylauric acid, 16-hydroxyhexadecanoic acid, behenic acid, euricic acid, stearic acid, caprylic acid, lauric acid, isostearic acid and combinations thereof. Examples of some of the suitable fatty acid gelling agents are described in U.S. Patent No. 5,429,816, issued to Hofrichter et al. on July 4, 1995; and in U.S. Patent No. 5,552,136 issued to Motley on September 3, 1996, which are incorporated herein by reference. 12-Hydroxystearic acid is most preferred. The required ratio of dimer to monomer can also be established with the fatty acid gelling agents described herein, in combination with an additional or secondary gelling agent, wherein the molar ratio of the fatty acid gelling agent to the additional or secondary gelling agent is between about 1. : 2 and about 20: 1, preferably, between about 1: 1 and about 10: 1, more preferably, between about 2: 1 and about 7: 1, still more preferably, between about 3: 2 and about 5 :1. Anyone with average skill in the chemical or formulation technique can formulate these fatty acid gelling systems to control or obtain the ratio described. Additional or secondary gelling agents suitable for use in the formulation of the required dimer-to-monomer ratio include the solid, non-polymeric gelling agents, which are described herein.

ANCHID LIQUID CARRIERS The anhydrous gel-solid antiperspirant stick compositions of the present invention comprise an anhydrous carrier that is liquid under ambient conditions and that is substantially free of polar, water immiscible, organic liquid carriers or solvents. The compositions preferably comprise a modified silicone carrier selected from the group consisting of polyalkyl siloxanes, polyalkylaryl siloxanes, polyester tersiloxanes, polyethersiloxanes, in the form of copolymers, polyfluoros, siloxanes, polyaminosiloxanes and combinations thereof. The concentrations of the anhydrous liquid carrier in the gel-solid stick composition 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 concentrations of the preferred modified silicone carrier components of the anhydrous liquid carrier can vary from about 0.1% to about 80%, preferably, from about 0.1% to about 50%, most preferably, from about 1% to about 20%, and even more preferably, from about 15 to about 10%, by weight of the gel-solid antiperspirant stick composition.

The anhydrous liquid carrier of the gel-solid antiperspirant stick composition is substantially free of organic, liquid immiscible or liquid carriers or solvents. It has been found that the antiperspirant and deodorant efficacy of the gel-solid stick compositions are improved to minimize or eliminate the concentration amount of these 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 about 3%, still more preferably zero percent by weight of the liquid carriers polar, immiscible in water, organic which are liquid under ambient conditions and which are monohydric and polyhydric alcohols, fatty acids, esters of mono and dibasic carboxylic acids with monohydric and polyhydric alcohols, polyoxyethylenes, polyoxypropylenes, polyalkoxylate ethers of alcohols and combinations of the same. Examples of some organic, polar, water immiscible solvents or liquid carriers are described in Cosmetics, Science, and Technology, vol. 1, 27-104, edited by Balsam and Sagarin (1972); in U.S. Patent No. 4,202,879 issued to Shelton on 13, 1980 and in U.S. Patent No. 4,816,261 issued to Luebbe et al. on March 28, 1989, which are incorporated herein by reference. The anhydrous liquid carrier of the gel-solid antiperspirant stick composition comprises one or more carrier liquids suitable for topical application to human skin and include liquid, polar or non-polar solvents or carriers, volatile or non-volatile, containing silicone or containing fluorine, organic, with the proviso that the resulting liquid carrier forms a solution or other homogeneous liquid or liquid dispersion with the non-polymeric gelling agent 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. The anhydrous liquid carrier has a solubility parameter of between about 3 and about 13 (cal / cm3) 0"5, preferably, between about 5 and about 11 (cal / cm3) 0.5, more preferably, between about 5 and about 9 (cal / cm3) 0"5. The solubility parameters for liquid carriers or for other materials and media to determine these parameters are well known in the chemical field A description of the solubility parameters and the means to determine them is described in CD 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, 3333, September / October 1988, which are incorporated herein by reference. These modified silicone carriers for use in the selected embodiments of the gel-solid antiperspirant stick composition of the present invention should also be liquid at ambient conditions and have a viscosity less than about 100,000 centistokes, preferably less than about 500 centistokes, more preferably, from about 1 and 50 centistokes, and still more preferably, between about 1 and 20 centistokes. These modified silicone carriers are generally known in the chemical field, some examples of which are described in Cosm e t i cs r Sci en ce an d Technolgy 27-104 M. Balsam and E. Sagarin ed. 1972); U.S. Patent No. 4,202,879, issued to Shelton on May 13, 1980; U.S. Patent No. 5,069,897, issued to Orr on December 3, 1991; which are incorporated here as a reference. Modified silicone carriers suitable for use in gel-solid antiperspirant stick compositions include, but are not limited to, compounds or materials as defined above and which are generally characterized in the following manner: silicone polyethers or silicone glycols (for example dimethicone copolyol); alkyl-linked polyethers (for example, Goldschmidt EM-90 or EM-97); siloxane surfactants of a hanging / rake / comb configuration, silicone surfactants of a trisiloxane configuration and silicone surfactants of ABA / alpha-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 copolymers with other functional groups including: hydrogen, alkyl, methyl, amino, trifluoropropyl, vinyl, alkoxy, arylalkyl, aryl, phenyl, styryl, polyethers, esters, carboxylic compounds; alkylmethylsiloxanes or silicone waxes (for example, hexyl, octyl, lauryl, cetyl, stearyl); nonionic 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; tetrametoxisi laño; hexametoxy ilicone; oximetoxitrisiloxane; silicone emulsifiers; siloxane or silicone resins; alkyl silicone resins; polyoxyalkylene silicone resins; MQ resins such as those of Shiseido / Shin-etsu, for example Japanese Patent Publication JP86143760 or of Walker Chem. 6MBH (described in EP722970); alkoxysiloxanes; alkoxysilanes; methicones (polimet ilalqui lsiloxanos); 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 (phenyl trimethicone); DC-704 Diffusion Pump Fluid (Tetramet il-Tetraphenyl-Trisiloxane); DC-705 Diffusion Pump Fluid; DC-1784 Emulsion; DC-AF Emulsion; DC-1520-US Emulsion; DC-593 Fluid (Dimethicone [y] Trimethylsiloxysilicate); 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 Laurylmeticone); 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 (Estearoxit rimet ilsilano [y] Alcohol Stearyl); DC-I-3563 (Dimet iconal); DC-X2-1286 (Dimeticonol); DC-X2-1146A (Cyclomethicone [y] Dimethiconol); DC-8820 Fluid (with functional group Not me); DC Q5-0158A wax (e stearoxitrimet ils ilano); DC-Q2-8220 (Trimet ils ililamodimet icone); DC-7224 (Trimet ilsilylamodimetone icone); DC-X2-1318 Fluid (Cyclomethicone [y] Vinylimetone icone); DC-QF1-3593A fluid (Trimet ilsiloxysilicate) and combinations thereof. 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 (Dimethyl-Diphenyl-Siloxane); 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 (Silicone and polyether copolymer); GE SF-1288 (silicone-polyether copolymer, dimethyl-methyl-3-hydroxypropyl ethoxylate); GE SF-1318 (Methyl Siloxane); GE SF-1328 (silicone surfactant, ethoxylated-propoxylated dimethyl-methyl-3-hydroxypropyl); GE SF-1550 (methylphenyl siloxane, hexamethyl-3-phenyl-3- [[trimethylsilyl] oxy] trisiloxane); GE SF-1632 (silicone wax); GE SS-4267 (Dimethicone [y] Trimethylsiloxysilicate) and combinations thereof.

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 the gel-solid antiperspirant stick compositions include the following: Masil 756 from PPG Industries (Tet Rabutoxypropyl Trisiloxane); bis-phenylhexamet icone (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 (Tri s [ributoxyloxy] methylsilane); F-754 silicone copolymer (dimethicone copolyol from SWS Silicones), and combinations thereof The anhydrous liquid carrier preferably comprises a volatile silicone carrier, preferably in combination with a modified silicone carrier described herein. 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 constituents 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 used herein 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 CH3? H3 CH, H CH, I I CH, -s¡- oj-s > ? i-- or -s 3¡- CH3 CH3- Si- O- Si- O- -Si- CH-, I 1 I I CH3 CH3 CH3 CH, CH, CH. 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 which are used in antiperspirant compositions include, but are not limited to, Dow Corning 200, hexamethyldisiloxane, Rhodorsil Oiis 70047 which is obtained from Rhone-Poulenc, Fluid Masil SF 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 also comprise liquid, organic, polar, water miscible, anhydrous carrier or solvent, preferably in combination a modified silicone carrier, a volatile silicone carrier, a non-volatile silicone carrier, or combinations thereof . An example of this solvent, organic, polar, miscible in water, includes short chain alcohols such as ethanol. These and other polar organic solvents or carriers 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 polar water miscible organic solvents, classified 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 obtained 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 fluorochemicals in addition to or instead of the modified silicone carrier. These fluorochemicals include fluorosurfactants, fluorotelémeros and per fluoropoliéteres, some examples of which are described in Cosmetics &; Toiletries, Using Fluorinated Compounds in Topical Preparations, Vol. 111, p. 47-62, (October 1996) which is incorporated herein by reference. Some specific examples of these liquid carriers include, but are not limited to, perfluoropolyimethyl iso-propyl ethers, perfluoropolypropyl ethers, fluorinated telomer of acrylamide, fluorinated amide surfactants, perfluorinated thiol surfactants. Other more specific examples include, but are not limited to, polyperf luoroisopropyl ethers available from Dupont Performance Chemicals under the tradename Fluortress® oils PFPE, and the series of fluorosurfactants from Dupont Performance Chemicals under the trade name Fluorosurfactants Zonyl®.

OPTIONAL NUCLEATING AGENT The gel-solid antiperspirant stick compositions of the present invention preferably further comprise a 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 gelling agent is not Psyllid, 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 inorganic, micronized nucleating agents) and then 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 anhydrous liquid carrier.

The nucleating agent used in the antiperspirant compositions includes fatty alcohols, fatty alcohol esters, ethoxylated fatty alcohols, esters or fatty acid ethers including waxes and triglycerides, silica, titanium dioxide, solid polyol and carboxylic acid polyesters and mixtures thereof. Suitable fatty alcohols which 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, but are not limited to, Unithox 325, Unithox 400 and Unithox 450, Unithox 480, Unithox 520, Unithox 550, Unithox 720, Unithox 750, all of which are available from Petrolite. Non-limiting examples of suitable fatty alcohol esters include t-isostearyl citrate, di-12-hydroxies tearat or ethylene glycol, tristearyl citrate, stearyl octanoate, stearyl heptanoate, and trilauryl citrate.

Suitable fatty acid esters which are used as nucleating agents include esters waxes, monoglycerides, diglycerides, triglycerides and mixtures thereof. Glyceride esters are preferred. Non-limiting examples of suitable ester waxes include stearyl stearate, stearyl behenate, palmityl 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, tristearin, 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 glycends 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 solid polyol and carboxylic acid polyesters 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 long chain unsaturated carboxylic acid 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 to 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 of from about 7 to about 8 of the hydroxyl groups of the polyol, they 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%. Preferred polyols of polyol carboxylic acid esters, solids, are sugars, including monosaccharides and disaccharides and t-lactaccharides, containing from about 4 to about 11 hydroxyl groups. The most preferred sugars are those containing from about four to 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 preferred polyol is sucrose. Examples of long chain unsaturated carboxylic acid entities include, but are not limited to, lauroleate, myristolate, palmitoleate, oleate, elaidate, erucate, linoleate, linolenate, arachidonate, eicosapentaentoate and docosahexaenoate. For oxidative stability, mono and dis 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 cerotate. 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, C20 and higher acids, or their derivatives, for example methyl or other lower alkyl esters, 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 sucrose is virtually 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 unsaturated C18 radicals to higher saturated acid radicals C20 of 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 that are used in the antiperspirant compositions herein include, without limitation, the octaester of raffinose, wherein the esterifying carboxylic acid entity is linoleate and behenate in a molar ratio of 1: 3, the maltose heptaester wherein the esterifying carboxylic acid entities are fatty acids of sunflower seed oil and lignocerate in a molar ratio of 3: 4; the octaester of sucrose wherein the carboxylic acid entities are tertiary 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 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-solubilized, 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 bacterial and fungistatic bacteria, and "non-active" components such as dyes, perfumes, emulsifiers, chelators, distributing agents, preservatives, waste masking agents, process aids as modifiers of viscosity and washing elimination aids. 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 particles solid. 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 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. Appropriate techniques to decrease 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 crystallization rates including controlling the formulation, the flow regime of the process and the processing temperatures and other methods described herein. 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 is preferably 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 7 1 - . 1 - Dow Corning 245 Fluid; General Electric SF-1202 2 - EM-97 of Goldschmidt 3 - DC-3225 of Dow Corning 4 - SF-1023 of G.E. Silicones 5 - SF-1188a from G.E. Silicones 6 - Sucrose octa ester predominantly esterified with behenic acid entities

Claims (10)

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 gelling agent that is substantially free of organic polymeric gelling agents, dibenzylidene alditol, inorganic thickening agents, n-acyl amino acid derivatives, or combinations thereof; and (c) from 10% to 80% by weight of an anhydrous liquid carrier having a solubility parameter of 3 to 13 (cal / cm3) 0.5 which is substantially free of polar, water immiscible, organic carrier liquids; wherein the composition has a visible residue index of value L of 11 to 30, a product hardness of 500 grams-force to 5000 grams-force, preferably, of 350 grams-force to 2,000 grams-force, and a proportion from a viscous elastic modulus of 0.1 to 100, preferably from 0.1 to 50, and wherein the composition is preferably substantially free of fatty alcohols having from 12 to 40 carbon atoms.
2. 2. The composition, according to claim 1, characterized in that the anhydrous liquid carrier is substantially free of polar, water immiscible, organic carrier liquids selected from the groups consisting of monohydric alcohol, polyhydric alcohol, fatty acids, mono carboxylic acid esters and dibasic with mono- and polyhydric alcohol, polyoxyethylenes, polyoxypropylenes, ethers of polyalkoxylate alcohols, and combinations thereof.
3. 3. The composition, according to any of the preceding claims, characterized in that the composition contains less than 3%, preferably zero percent, by weight of the carrier liquid, organic, immiscible in water, polar.
4. 4. The composition, according to any of the preceding claims, characterized in that the solid non-polymeric gellant is selected from the group consisting of fatty acid gelling agents, fatty acid gelling gels and esters, hydroxy fatty acids, spherical materials, lanolinol materials and combinations thereof, preferably selected from the group consisting of 12-hydroxyl tertiary acid, 12-hydroxyl-tertiary acid esters, 12-hydroxystearic acid amides, and combinations thereof, most preferably selected from the group consisting of -hydroxystearic, 12-hydroxystearic acid methyl ester, acid ethyl ester 12 -. 12 -hydroxystearic, 12-hydroxystearic acid stearyl ester, 12-hydroxystearic acid benzyl ester, acid amide 12-hydroxystearic, isopropyl acid amide 12-hydroxystearic, 12-hydroxystearic acid butyl amide, 12-hydroxystearic acid benzylamide, 12-hydroxystearic acid phenylamide, 12-hydroxystearic acid t-butyl amide, cyclohexyl lamide 1-hydroxystearic acid, 1-adamantyl amide 1-Hydroxystearic acid, 2-adamantyl ilamide of 1-12-hydroxystearic acid, diisopropylamide of 1-12-hydroxyl-tertiary acid, and combinations thereof, most preferably, 12-hydroxyl-tertiary acid.
5. 5. The composition according to claims 1, 2 or 3, characterized in that the solid non-polymeric gelling agent comprises a gelling agent according to the formula: c '-c -N - wherein a) Ri is zero, hydroxy, hydrogen, aryl, siloxane or aryl substituted with C 1 -C 22 alkyl or C 1 -C 22 alkyl ethers, C 1 -C 22 alkylesters, C 1 -C 22 alkoxy, alkenyl C? -C22, C1-C22 alkyl? straight chain, cyclic or branched, substituted or unsubstituted, saturated or unsaturated; preferably, C4-C18 alkyl, C4-C18 alkenyl, C4-C18 alkoxy, C4-C18 alkyl esters, C4-C8 alkyl ethers, or C4-C18 alkyl substituted aryl, more preferably C12 alkyl -C 18, C 2 -C 8 alkenyl, C 2 -CI 8 alkoxy, C 2 -C 8 alkylesters, C 2 -C 8 alkylethers or C 2 -alkyl substituted aryl C? 8; b) R2, R4, R5 and Re together or independently are hydrogen, hydroxy, aryl, siloxane or aryl substituted with C? -C22 alkyl or C? ~ 22 alkyl ethers, C? alkyl esters? C22 r C 1 -C 22 alkoxy, C 1 -C 22 alkenyl, straight, branched or cyclic C 1 -C 22 alkyl, substituted or unsubstituted, saturated or unsaturated; preferably, C4-C10 alkyl, C4-C10 alkenyl, C4-C10 alkoxy, C4-C10 alkylester, C4-C10 alkyl ether or C4-C6 alkyl substituted aryl, or, more preferably, C4-C10 alkyl; C4-C8, C4-C8 alkenyl, C-C8 alkoxy, C4-C8 alkyl esters, C4-C8 alkyl ethers or C4-C8 alkyl substituted aryl; c) R3, is null, hydroxy, hydrogen, C1-C4 alkyl ethers or C1-C4 alkylesters, C1-C4 alkoxy, C1-C4 alkenyl, straight chain, branched or cyclic C1-C4 alkyl, substituted or unsubstituted, saturated or unsaturated; preferably, C1-C4 alkoxy, hydroxy or hydrogen, more preferably, a hydroxy or hydrogen; d) R7 and Rs independently or together are, null, hydrogen, hydroxy, aryl, siloxane or aryl substituted with C1-C22 alkyl or C1-C22 alkylethers C1-C22 alkylesters C?-C22 alkoxy, alkenyl of CI-C22 straight-chain, branched or cyclic C1-C22 alkyl, substituted or unsubstituted, saturated or unsaturated; preferably, C4-C10 alkyl, C4-C10 alkenyl, C4-C10 alkoxy, C4-C10 alkyl esters, C4-C10 alkyl ethers or C4-C10 alkyl substituted aryl, more preferably C4-alkyl C8, alkenyl of C -Cs, C-C8 alkoxy, C4-C8 alkylesters, C4-C8 alkyl ethers or aryl substituted with C4-C8 alkyl; e) R9 is zero or hydrogen; f) Rio and R11 independently or together are, null, hydrogen, hydroxy, aryl, siloxane or aryl substituted with CI-CT alkyl or Ci-Cβ alkyl ethers, C-alkyl esters? - C ß r CI-CT alkoxy, C? -C6 alkenyl, straight chain, branched or cyclic C? -C6 alkyl, substituted or unsubstituted, saturated or unsaturated; preferably C 1 -C 4 alkyl, C 1 -C 4 alkenyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylester, C 1 -C 4 alkylethers, aryl substituted with C 1 -C 4 alkyl or hydrogen, more preferably a hydrogen; g) X is zero, nitrogen, aryl or -CH2 -) - n ^ wherein n is an integer from 1 to 6, preferably, -CH2 ní wherein n is an integer from 1 to 3; h) Y is zero, acyl or carbonyl; i) Z is zero, hydrogen, hydroxy, aryl, siloxane, nitrogen or aryl substituted with C1-C22A alkyl ethers or alkyl esters of G? - C22 r C? -C22 alkoxy, C? -C22 alkenyl, alkyl of CI-C22A straight-chain, branched or cyclic C1-C22 alkyl, substituted or unsubstituted, saturated or unsaturated; preferably, C 4 -C 0 alkyl, C 4 -C 10 alkenyl, C 4 -C 10 alkoxy, C 4 -C 10 alkylester, C 4 -C 10 alkyl ether or C 4 -C 10 alkyl substituted aryl, more preferably alkyl from C4-Cs, C4-C8 alkenyl, C-C8 alkoxy, C-C8 alkyl esters, C-C8 alkyl ethers or C4-C8-alkyl substituted aryl; j) "a" is a double or single bond, provided that: (i) when X is zero, Y, Z, R3, R7 and R8 are zero, C 'is directly attached to C "and Ri is not a hydrogen (ii) when X and Z are not null and Y is zero, X is directly linked to Z, (iii) when Z is zero, a hydrogen or a hydroxy, R7 and R8 are zero, and (iv) "a" it is a double bond, R3 and R9 are null.
6. 6. The composition according to any of the preceding claims, characterized in that the solid non-polymeric gellant is in the form of elongated crystalline particles, having a dimensional ratio of at least 2, preferably at least 6.
7. 7. 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.
8. 8. 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.
9. 9. The composition, according to any of the preceding claims, characterized in that the anhydrous carrier liquid comprises a volatile silicone according to the formula: where n is 3
10. 10. 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, according to any of the preceding claims to the desired area of the skin. SUMMARY OF THE INVENTION Anhydrous gel-solid antiperspirant sticks are described, which comprise active particulate antiperspirant; a solid non-polymeric gelling agent, which is substantially free of dibenzylidene alditol, inorganic thickening agents, organic polymeric gelling agents, n-acyl amino acid derivatives, or combinations thereof; an anhydrous liquid carrier that is substantially free of polar immiscible organic solvents in water, wherein the composition has a visible residue index of L value of about 11 about 30, a product hardness of 500 to about 5000 grams-strength, a rheological profile defined by a ratio of an elastic modulus (G ') to a viscous modulus (G ") of from approximately 0.1 to approximately 100. The refractive indexes of the particulate antiperspirant active, the solid non-polymeric gelling agent and the anhydrous liquid carrier not preferably, the compositions comprise crystalline 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. These compositions provide lower performance characteristics of appearance of waste, efficiency and aesthetics.