MXPA99005847A - Antiperspirant gel-solid stick compositions - Google Patents

Abstract

Disclosed are anhydrous antiperspirant gel-solid stick compositions which comprise a particulate antiperspirant active;a solid non-polymeric gellant that is substantially free of dibenzylidene alditol, n-acyl amino acid derivatives, organic polymeric gellants, and inorganic thickening agents;and an anhydrous liquid carrier having an average solubility parameter of from about 3 to about 13 (cal/cm3)0.5, wherein the composition has a visible residue index of from about 11 to about 30 L-value, a product hardness of from about 500 gram.force to about 5,000 gram.force, a ratio of an elastic to viscous moduli of from about 0.1 to about 100. The refractive indices of the particulate antiperspirant active, solid non-polymeric gellant, and anhydrous liquid carrier are not matched. The solid non-polymeric gellant is preferably a crystalline material having an average particle size of less than about 1&mgr;m, and/or has an elongated particle morphology having an aspect ratio of greater than about 2. These antiperspirant gel-solid stick compositions provide improved low residue performance, antiperspirant and aesthetics.

Description

ANTITRANSPIRANT COMPOSITIONS IN SOLID GEL BAR TECHNICAL FIELD The present invention relates to antiperspirant compositions in the form of gel-solid sticks. In particular, the present invention relates to selected compositions in the form of gel-solid sticks that provide better performance by leaving little residue and improving efficiency and aesthetics.

BACKGROUND OF THE INVENTION There are many types of topical antiperspirant products that are commercially available or are known in the antiperspirant art. Most of these products are formulated as spray cans or as aerosols, ball application liquids, creams, emulsions, gels, gel solids or other solid bar formulations, and comprise an astringent material, such as salts of zirconium or aluminum or combinations thereof, incorporated into a suitable carrier. These products are designed to provide effective control of perspiration and odor while also being cosmetically acceptable during and after application on the axillary area or other areas of the skin.

P844 Within this group of products, solid antiperspirant bars have become especially popular with consumers. These antiperspirant bars comprise a solid matrix within which the active antiperspirant material is contained. The active component can be solubilized in a liquid carrier comprising water, glycols and / or other types of alcohols, or it can be stored within a solid matrix as a dispersible solid in an anhydrous system. Solid bars containing the dissolved active component usually provide some low residue performance, but tend to be wet or sticky during and immediately after application to the skin and, more importantly, are usually not effective in providing an antiperspirant and deodorant performance as solid bars containing the dispersed particulate active component. Although antiperspirant sticks containing particulate actives are more effective, they also tend to leave a fairly visible residue on the skin. Many attempts have been made to produce anhydrous antiperspirant sticks containing the particulate antiperspirant active in dispersed form and also provide improved efficacy and consistent performance of low residue during and after P844 application to the skin, or that either provide clarity to the product before application (in the form of a packed product) or after application (such as a clear film or leaving little residue on the skin). One of these attempts involves the combination of particulate antiperspirant active agents, gelling agents and liquid carriers in a gel bar, where all the components of the combination have matching refractive indices. The coincident refractive index allows greater passage of light through the gel bar with less scattering of light, resulting in products that have a lighter or translucent appearance when they are as a packaged composition or when they are initially applied topically to the skin. These gel bars, however, are expensive in their processing due to the cost of using raw materials having only selected matching refractive indices. These compositions are also very difficult to formulate since matching the refractive indices in a three-component system (particulate active ingredient, solvent and gelling agent) is extremely difficult and greatly limits the materials that can be used to prepare this type of formulation. Another attempt to make antiperspirant sticks that leave little residue involves the use of gelling agents such as dibenzylidene alditols. These gelling agents, like many other gelling agents known in the art, are not stable to acid and therefore tend to interact with the antiperspirant active agent due to the acidic nature of the active ingredient. This interaction may result in a lower efficacy of the active ingredient, by deformation of the gel and low stability of the gel for prolonged periods during shipment or storage. This interaction can also cause processing difficulties at the temperatures and retention times that are normally used during the formulation and manufacturing process. These gelling agents are also commonly used in combination with glycol carriers or with other solvents that tend to moisten and taint the product as well as to irritate the skin. Yet another attempt to make antiperspirant sticks that leave little residue involves the use of residue masking agents, 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 with other waxes that leave little residue, which are commonly used in solid antiperspirant sticks. These agents help to reduce the visible residue during and immediately after the application of the solid stick to the skin, but also tend to associate with a sticky or oily perception on the skin, during application. In addition, although the visible residue is reduced in these compositions, there is still a visible residue on the skin when used in combinations with high residue waxes for example stearyl alcohol, and this reduced residue is still more visible or evident than the topical residue which it remains with the antiperspirant bars that contain the antiperspirant active ingredient in a solubilized form. Another attempt to improve the performance of little residue on the skin in an antiperspirant composition has focused on the use of anhydrous antiperspirant creams. These creams can be applied to the skin by conventional means or by a cream applicator device and result in very low residue during and immediately after application to the skin. These compositions comprise an active ingredient in particles dispersed through an anhydrous carrier and content either within the matrix that is in solid form or thickened with an inorganic or polymeric gelling agent or with a thickening agent. However, many consumers find it convenient to use a solid antiperspirant stick, even if the solid stick tends to leave a high amount of visible residue on the skin. A recent method for making antiperspirant sticks that leave little residue is described in U.S. Patent 5,429,816, issued to Hofrichter et al. on July 4, 1995, the description of which is incorporated herein by reference. Antiperspirant sticks provide little residue during and immediately after application to the skin and are physically and chemically stable for prolonged periods of time. The improved antiperspirant sticks comprise a dual gelling system having a primary gelling agent such as for example 12-hydroxystearic acid or esters or amides thereof and a secondary gelling agent such as for example n-acyl amino acid derivatives. The formation of this antiperspirant stick with this dual gelling system has been characterized by a "gel-solid" antiperspirant stick. An antiperspirant gel-solid, as described by Hofrichter et al. It is an antiperspirant bar that has a three-dimensional and non-polymeric gel network where the solvent is contained or trapped. This gel-solid is typically formed by the solubilization of the gellant in the solvent at temperatures above the melting point of the gellant and at temperatures at which P844 The fused gellant is soluble in the solvent, and then the composition is cooled to form the desired gel-solid composition. The gels-solids of little appearance of residue described by Hofrichter et al. they are markedly stable, both physically and chemically, and retain the desired hardness of the product for extended periods of time. The solid gels described by Hofrichter et al. they are limited to selected dual gelling systems and do not include or describe any method for making the gel-solid antiperspirant bars that leave little residue, which contains some other gel or gelling system. It has now been found that other low residue solids gels can be formulated without relying on the select combination of gelling agents described by Hofrichter et al. The new low residue appearance gels-solids are anhydrous systems comprising from about 0.5% to about 60% by weight of a particulate antiperspirant active, from about 1% to about 15% by weight of a solid non-polymeric gellant which is essentially free of dibenzylidene alditol or n-acyl amino acid derivatives, from about 10% to about 80% by weight of an anhydrous liquid carrier for the solid non-polymeric gellant having an average solubility parameter ((cal / cm ) ') of between about 3 and 13 and wherein the composition has a visible residue index of between about 11 to about 30 of the L value, a product hardness of between about 500 grams-force to about 5,000 grams-force, a ratio of elastic modulus (G ") to viscous modulus (G") of between about 0.1 to about 100. The composition must be essentially It is free of gelling agents or inorganic or polymeric thickeners and does not require to match the refractive indexes of the particulate antiperspirant active agent, the non-polymeric solid gelling agent and the anhydrous liquid carrier in order to obtain low residue performance. The compositions preferably 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 of greater than about 2. It is therefore an object of the present invention to provide an antiperspirant, anhydrous gel-solid stick containing the active ingredient antiperspirant particulate, and which provides a better performance of little appearance of residue and a better antiperspirant efficacy, and in addition to provide this composition without being based on specific gelling agents like dibenziliden alditols or as gelling systems duals containing n-acyl amino acid derivatives. A further object of the present invention is to provide this composition without relying on matching the refractive indices of the component materials or the use of a solubilized antiperspirant active ingredient in order to obtain clarity in the product or a performance of little appearance of residue. . Still the object of the present invention is to provide this composition which is physically and chemically stable over extended periods of time and which furthermore provides this stability in an anhydrous system without relying on the use of gelling agents or inorganic or polymeric thickeners.

SUMMARY OF THE INVENTION The present invention is directed to anhydrous antiperspirant gel-solid stick compositions, comprising from about 0.5% to about 60% by weight of a particulate antiperspirant active ingredient; from about 1% to about 15% by weight of a solid non-polymeric gellant, which is essentially free of debenzilide alditol or n-acyl amino acid derivatives; from about 10% to about 80% by weight of an anhydrous liquid carrier for the solid non-polymeric gellant having an average solubility parameter of between about 3 and about 13 (cal / cm) and wherein the composition has an index of visible residue of between approximately 11 to approximately 30 L value, a product hardness of between about 500 grams-force to about 5,000 grams-force, a rheology profile defined by a ratio of elastic modulus (G1) to viscous modulus (G ") of from about 0.1 to about 100. The composition is essentially free of inorganic or polymeric gelling agents or thickeners.The refractive indexes of the antiperspirant particulate active ingredient, the solid non-polymeric gelling agent and the anhydrous liquid carriers are not coincident.The compositions preferably comprise crystalline gelling particles having a size of average particle less than about 1 μm and / or a particle morphology having a dimensional ratio greater than about 2. It has been found that the antiperspirant gel-solid stick compositions of the present invention can provide a low residue leaving performance without the need to use ingredient and solubilized antiperspirant active and without relying on the selection of low-density gelling agents such as for example dibenzylidene alditols or select combinations of gelling agents containing n-acyl amino acid derivatives.

P844 This is achieved by formulating a gel-solid rod composition of the anhydrous type having selected hardness and rheology profile, and preferably provided by a three-dimensional, non-polymer crystal gel network made from small, elongated, crystalline particles that they have an average particle size of less than about 1 μm and / or a particle morphology defined by a dimensional ratio of at least about 2.

DETAILED DESCRIPTION OF THE INVENTION The antiperspirant gel-solid stick compositions of the present invention are anhydrous systems which are dispersions of particulate antiperspirant agent conserved or contained within a crystalline, non-polymeric, gel-solid matrix. The term "anhydrous" as used herein refers to gel-solid stick compositions of the present invention and, to the essential or optional components thereof other than the particulate antiperspirant active ingredient, which are essentially free of added water or free water. From the formulation point of view, this means that the antiperspirant gel-solid compositions of the present invention preferably contain less than about 5%, preferably P844 less than about 3%, more preferably less than about 1%, still more preferably zero percent by weight of free or added water, other than the water of hydration typically associated with the active particulate antiperspirant ingredient, prior to formulation. The term "low residue or leaving little residue" in the sense used herein generally refers to the visible residue remaining on the areas of skin on which the product is applied, during and immediately after application, and more specifically, it refers to the visible residue index of the composition as defined by the methodology described below. The term "environmental conditions" as used herein refers to the surrounding conditions which are from about one atmosphere of pressure, to about 50% relative humidity and about 25 ° C, unless otherwise specified. The term "essentially free" in the sense 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 thickeners, polymeric thickening agents organic, dibenzylidene alditol gelling agents, n-acyl amino acid derivatives or P844 combinations thereof, in the composition. The term "essentially free" refers to the compositions preferably containing less than an effective amount of these agents, when used alone to provide any measurable increase in viscosity or thickening to the composition. In this context, the negative limitations belong only to those gelling agents and thickeners which are also solid under environmental conditions and which are not silicone-containing materials or polymeric derivatives of 12-hydroxystearic acid. In general, the compositions preferably contain less than 5%, preferably less than 2%, more preferably less than 1%, still more preferably less than 0.5%, most preferably zero percent of these agents, weight of the composition. Examples of inorganic thickening agents to which the negative limitations described above belong include colloidal or finely divided silicas, fumed silicas and silicates including montmorillonite clays and hydrophobically treated montmorilonites, for example bentonites, hectorites and colloidal magnesium silicates. Examples of organic polymeric gelling agents to which the negative limitations described above belong include organic polymers well known in the art of antiperspirants or compositions for the P844 personal care, which are used to provide gelling or thickening, or other physical or aesthetic benefits to the composition; specific examples thereof include copolymers of hydrogenated butylene / ethylene / styrene, polyethylene, oxidized polyethylene, polyamides, polymers of acrylic acid, copolymers of ethylene and acrylate and other organic polymeric gelling agents that are 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 suitable for binding to the compounds or other chemical materials described herein. These substituents include, but are not limited to, those listed and described in C. Hansch and A. Leo, Substituent Constants for Correlation Analysis in Chemistry and Biology (1979), whose listing and description are incorporated herein by reference. Examples of these substituents include, for example, alkyl, alkenyl, alkoxy, hydroxy, oxo, nitro, amino, aminoalkyl (for example aminomethyl, etc.), cyano, halo (for example chlorine, fluorine, bromine, iodine), carboxy, alkoxyaceil (for example carboethoxy, etc.), thiol, aryl, cycloalkyl, P844 heteroaryl, heterocycloalkyl (for example piperidinyl, morpholinyl, pyrrolidinyl, etc.), imino, thioxo, hydroxyalkyl, aryloxy, arylalkyl, amides, esters, ethers, combinations thereof and the like. The term "n-acyl amino acid derivatives" refers to gelling agents selected from the group consisting of n-acyl amino acid, n-acyl amino acid esters prepared from glutamic acid, lysine, glutamine, aspartic acid and combinations thereof, and that in particular are disclosed in U.S. Patent No. 5,429,816. The term "alkyl" and "alkenyl" as used herein, unless otherwise specified, refers to cyclic, linear or 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 at ambient conditions of at least about 0.2 mm Hg. Conversely, the term "non-volatile" as used herein refers to materials having a non-measurable vapor pressure or having a vapor pressure of less than about 0.2 mm Hg under ambient conditions. The solid non-polymeric gelling agent, P844 antiperspirant active ingredient and the anhydrous liquid carrier which are components of the gel-solid stick compositions herein, preferably do not match in their refractive indexes and, more preferably, at least two of these components have refractive indexes (? D) which differ by at least about 0.02, more preferably by at least about 0.04. The antiperspirant gel-solid stick compositions of the present invention may comprise, consist or consist essentially of the essential elements and limitations of the inventions described herein, as well as of any other additional or optional ingredient, component or limitation that is described. here. All percentages, parts and proportions are given by weight of the total composition unless otherwise specified. All weights belong to the listed ingredients based on the specific level of the ingredient and, therefore, do not include the solvents, carriers, by-products, fillers or other minor ingredients that could be included in commercially available materials, unless another thing is specified.

PRODUCT CHARACTERISTICS The antiperspirant gel-solid stick compositions of the present invention are characterized in terms of product hardness, visible residue index and rheology profile defined by a ratio of an elastic modulus to the viscous modulus. Each of these characteristics is defined according to the methodologies and other limitations described below. a) Hardness The antiperspirant gel-solid stick compositions of the present invention have a product hardness of about 500 grams-force at about 5,000 grams-force, preferably from about 750 grams-force to about 2,000 grams-force, with greater Preference of approximately 800 grams-force to approximately 1,400 grams-force. The term "product hardness" as used herein is a reflection of how much force is required to move a cone of penetration at a specified distance and at a controlled rate within the antiperspirant gel-solid stick composition, according to the following test conditions. Higher values represent a harder product and lower values represent a softer product. These values are measured at 27 ° C, 15% relative humidity, using a Texture Analyzer TA- P844 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 standard penetration cone at a 45 ° angle through the composition for a distance of 10 mm at a rate 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 the angled surface of the cone of approximately 15.5 mm. The cone is a smooth stainless steel construction and weighs approximately 17.8 grams.

Residue The antiperspirant gel-solid stick composition of this invention has a visible residue index of between 11 and about 30, L-value, preferably between 11 and about 25 L-value, more preferably between 11 and about 20-L-value The term "visible residue index" as used herein generally refers to the degree to which the composition of this invention is clearly visible as a thin topical film after application to the skin and, more specifically, refers to visible residue values (expressed as L value on the scale of P844 value L, a, b) as measured according to the following methodology, developed at 27 ° C under atmospheric pressure and at 15% relative humidity in the antiperspirant stick composition 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 slide to which it is movably attached or fixed to a larger mechanical unit. An example of a suitable piece of black felt that is used here is Supreme Robe Velor, FN-6554, Color 404L, Style 31854, available from so-Fro Fabrics, Evendale, Ohio, U.S.A. An example of the proper mechanical unit used here is the Adhesion and Release Tester Serial No. A-14934 manufactured by Testing Machines, Inc., Amityvilie, New York, USA, or a Velmex Unislide Positioning System, of the Unislide series (MB6000), available from Velmex, Inc., Bloomfield, New York, USA An antiperspirant stick composition contained within approximately 0.5 cm from a conventional package or packing and extending particularly in this length, is placed perpendicular to the piece attached to the felt and above it, so that the product extends out of the package or package and is oriented towards the piece of P844 felt and the surrounding package is positioned away from the felt piece. The surrounding package 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 towards the black felt piece and is allowed to gently contact it. A weight of 1 is applied, 000 grams on the product mixture so that the product continuously contacts the black felt piece during the test. The sample with the weight is then repeatedly moved back and forth through the piece of felt at a fixed speed (about 3 cm / sec) and with a fixed amount of applied pressure provided by the heavy product, until 1.75. grams of the antiperspirant stick composition are uniformly applied over a 5 cm x 20 cm area of the black felt piece. The piece of felt is carefully removed from the apparatus. Subsequently, a Minolta chromometer is used Calibrated CR-300 (available from Minolta Corp., Ramsey, New Jersey, U.S.A.) to measure the L value (on the color scale L, a, b) of the applied surface area. First, a template is placed on the top of the felt piece to facilitate Minolta readings. The dimension P844 of the template is 5 cm x 20 cm. The template has twelve circular openings (2.2 cm in diameter) placed inside it, each opening is placed centrally within adjacent areas of 6.5 cm from the surface of the template. The template is placed over the applied surface area of the felt piece, so that each of the twelve circular openings covers a non-overlapping area of the applied surface. The observation port of the chromameter is adjusted within each of the circular openings and the measurement of the L value is taken. An average L value is then determined for the twelve measurements (standard deviation of less than approximately 0.8) which then corresponds to the index of visible residue as described here. It has been found that there is a correlation between the range of the visible residue index defined here and the average particle size of the crystalline gelling particles in the antiperspirant gel-solid stick composition of the present invention. in general, as the average particle size of the crystalline gelling particles of the composition decreases, the performance of little residue occurrence is improved. In particular, it has been found that a visible residue index of between about 11 and about 30 on the scale of the L value, is P844 correlates with a gelling, crystalline particle size, average of less than about μm and / or crystalline gelling particle morphology, characterized by dimensional crystal growth so as to result in filaments, fibers, strands or other crystalline elongated particles , wherein the dimensional relationship that is defined by the major and minor axes of the crystalline particle is greater than approximately 2, preferably greater than approximately 6. Conversely, solid compositions containing crystalline gelling particles greater than 1 μm (average particle diameter) have a visible residual index greater than the L value of 30. In view of this correlation between the values of visible residual index and average crystalline particle size or elongated particle morphology, the measurement of the index of visible residue can now be used as an alternative means to establish the average particle size of the crystalline gellant or the morphology thereof, at least insofar as this average particle size is less than about 1 μm. c) Rheology The antiperspirant stick compositions of the present invention are gel-solid type having the P844 selected rheology profile defined here. The rheology profile is defined herein in terms of the relationship between the elastic modulus (G?) And the viscous modulus (G ") (G '/ G") of the gel-solid stick composition. To provide the required rheology, the gel-solid stick compositions must have a G '/ G "ratio of between about 0.1 and about 100, preferably between about 0.1 and about 50, more preferably between about 1 and about 20, still more preferably between about 5 and about 20. This ratio represents the extent to which the gel-solid stick compositions of the present exhibit solid characteristics and the extent to which the compositions exhibit liquid or fluid characteristics, and specifically it refers to the numerical proportion G '/ G "that is determined by the following methodology. The elastic modulus is a measurement that correlates with the solid character of the gel-solid stick compositions of the present and the viscous modulus is a measurement that correlates the liquid or fluid character of the gel-solid stick compositions of the I presented. The measurements for G 'and G "in order to define the composition of the present invention, are determined according to environmental conditions using P844 conventional techniques well known in the art of formulations. For example, Bohlin Stress-Strain Rheometer, available from Bohlin Reologi, Cranberry, New Jersey can be used with a plate and cone configuration (approximately 1 °). Approximately 1.0 mg of the product is carefully removed from the composition with minimal shear application and then placed between the cone and plate abutments to measure G 'and G "The gel-solid stick compositions of this invention have been found to be. exhibit improved development of low residue occurrence when formulated as described herein, wherein the composition has the select G '/ G "ratio already described, especially when the defined rheology is associated with a crystalline gel matrix having a preferred small particle size and / or a particle morphology as described herein. These gel-solid bar formulations are gently smeared onto the skin with low shear and melt rapidly during this operation to form a thin film that leaves little residue on the applied surface. In particular, it has been found that the gel-solid stick compositions of this invention have rheological characteristics that result in better performance, especially performance as to the little P844 residue left. These selected gel-solid compositions that are defined herein behave as solids before being applied while remaining within a basket and other type of container, but behave as liquids or fluids during and immediately after being applied to the skin. In other words, the solid compositions become thin during application to the skin, melt or nearly melt (except for the active compound in particles that remains without melting) during the application of low shear, resulting in a liquid film or fluid, thin and that leaves little residue on the skin, during or immediately after topical application to the skin. The applied film is clear or has a very inconspicuous residue and remains essentially in that form for extended periods of time, after application.

Anti-transpirant Active The antiperspirant gel-solid stick compositions of the present invention comprise the active particulate antiperspirant suitable for application to human skin. These particulate actives must remain essentially insoluble as dispersed or precipitated solids in the anhydrous or essentially anhydrous systems described herein. The P844 concentration of the particulate active in the composition should be sufficient to provide the desired control in odor and moisture by transpiration with the selected gel-solid antiperspirant stick formulation. The antiperspirant gel-solid stick compositions according to the present invention preferably comprise particulate antiperspirant actives at concentrations between about 0.5% and about 60%, more preferably between about 5% and about 35% by weight of the composition. These percentages by weight are calculated based on an anhydrous metal salt, excluding water and any other complexing agent such as glycine, glycine salts and other complexed agents. The particulate antiperspirant active agent, as it is in the composition, is in the form of dispersed solid particles having a preferred average particle size or a diameter less than about 100 μm, more preferably between about 15 μm and 100 μm, still more preferably between about 20 μm and 100 μm. Also preferred are dispersed solid particles having an average particle size or average diameter of less than about 2 μm, even more preferably less than about 0.4 μm. It has been found that P844 antiperspirant active particles within the preferred range of particle size provide less visible residue performance of the gel-solid compositions herein than other preferred smaller particle size ranges. The antiperspirant active that is used in the antiperspirant gel-solid stick compositions of the present invention include any compound, composition or material that has antiperspirant activity. Preferred antiperspirant actives include astringent metal salts, especially organic and inorganic salts of aluminum, zirconium and zinc, as well as mixtures thereof. Particularly preferred are the aluminum and zirconium salts, for example aluminum halides, aluminum chlorohydrate, and aluminum hydroxyhalides, zirconyl oxyhalides, zirconyl hydroxyhalides and mixtures thereof. Preferred aluminum salts that are used in antiperspirant gel-solid stick compositions include those that conform to the formula: Al 2 (OH) aClb • x H 20 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 can be non-integer values. Particularly preferred P844 aluminum chlorhydroxides referred to as "basic 5/6 chlorohydroxide" where a = 5 and "basic 2/3 chlorohydroxide" where a = 4. Processes for preparing aluminum salts are set forth in the United States Patent number 3,887,692 of Gilman granted on June 3, 1975; U.S. Patent No. 3,904,741 to Jones et al. granted on September 9, 1975; U.S. Patent No. 4,359,456 to Gosling et al. granted on November 16, 1982 and British Patent Specification number 2,048,229 of 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 on February 27, 1974, which is incorporated herein by reference. Preferred zirconium salts that are used in gel-solid antiperspirant bar compositions include those that conform to the formula: ZrO (OH) 2_aCla • x H20 wherein a is from about 1.5 to about 1.87; x is from about 1 to about 7 and where a and x can be the two non-integer values. These zirconium salts are described in the Belgian Patent 825,146 of Schmitz granted on August 4, 1975 which is incorporated P844 here by reference. Particularly preferred zirconium salts are those complexes that additionally contain aluminum and glycine, commonly known as ZAG complex. These ZAG complexes contain aluminum chlorhydroxide and zirconyl hydroxy chloride which conform to the formulas described above. These ZAG complexes are described in U.S. Patent No. 3,679,068 to Luedders et al. granted on February 12, 1974, British Patent Application No. 2,144,992 of Callaghan et al. published March 20, 1985 and U.S. Patent No. 4,10,948 to Shelton published on 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 ingredient. These other dispersed solids and other materials include any material known or suitable for topical application to human skin. The gel-solid antiperspirant compositions can also be formulated as gel-solid stick compositions that do not contain antiperspirants or any other active material, in particles or in another form.

P844 Gelifier The gel-solid antiperspirant stick compositions of this invention comprise a solid non-polymeric gelling agent suitable for topically applied to human skin, other than inorganic thickeners, organic polymeric gelling agents or other gelling agents such as dibenzylidene alditol and derivatives of n-acyl amino acid. These solid non-polymeric gelling agents must form within the composition a crystalline matrix within which an anhydrous liquid carrier or any other liquid component of the composition is entrapped or contained. These solid and non-polymeric gelling agents preferably form crystalline particles having an average particle diameter and a particle morphology as described below. The gel-solid antiperspirant stick compositions are essentially free of inorganic thickeners, organic polymeric thickening agents and gelling agents selected from the group consisting of dibenzylidene alditols and n-acyl amino acid derivatives. In this context, "essentially free" refers to the compositions containing less than an effective amount of these agents when used alone to provide a measurable increase or thickening of the viscosity to the composition, under ambient conditions.

P844 In general, the compositions contain less than 5%, more preferably less than 1%, still more preferably less than 0.5%, and still more preferably zero percent of these agents, by weight of the composition. The gel-solid antiperspirant compositions are preferably essentially free of fatty alcohols which are solid at ambient conditions and which contain from 12 to 40 carbon atoms. More specifically, the compositions herein preferably contain no more than about 5%, preferably from zero to about 2% by weight of these fatty alcohol materials. The minimum concentrations of these materials can be used in the composition as a nucleating agent, as described below. 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 range from about 0.1% to about 20%, preferably between about 1% and about 15%, more preferably between about 3% and about 12% by weight of the composition. The non-polymeric gelling agents must be P844 solids under environmental conditions. The solid and non-polymeric gelling agents which are used in gel-solid antiperspirant stick compositions are those which can be melted and form a solution and other homogeneous liquid or liquid dispersion with the selected anhydrous liquid carrier, and at the concentrations of the liquid carrier and of the selected gelling agent, at a process temperature of about 28 ° C to about 250 ° C, preferably between about 28 ° C and 100 ° C, more preferably between about 28 ° C and about 78 ° C. The non-polymeric molten gellant is typically dissolved by the selected liquid carrier or dispersed therethrough to thereby form a solution or other homogeneous liquid. The solution or the other homogeneous liquid and other optional and essential ingredients, preferably are combined according to the manufacturing method described herein or to other conventional or otherwise known techniques, and placed in a suitable package as a fluid solution or as a 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.

P844 In selecting a combination of solid non-polymeric gelling agent and liquid carrier for use in the gel-solid antiperspirant stick compositions, the selected combination should allow the development of a crystalline gelling matrix within the composition, wherein the crystalline particles of the preferably have an average particle size of less than about 1 μm, more preferably less than about 0.4 μm, still more preferably less than about 0.2 μm, and still more preferably between about 0.001 μm and about 0.2 μm, and / or wherein the crystalline particles have the required elongated morphology that is 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, such as example electron microscopy or light microscopy. Gel-solid stick compositions can be prepared by methods well known in the art for formulation of gel 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 below, aimed at decreasing the crystalline particle size and / or establishing the morphology.

Preferred P844 of the crystalline particle. Suitable non-polymeric solid gelling agents which are used in the gel-solid antiperspirant stick compositions of the present invention include fatty acid gelling agents, fatty acid gelling gels and esters, hydroxy acids, hydroxy fatty acids, cholesteric materials, lanolinol materials and other amide gelling agents which are known to be used as gelling agents or which are described in other detail in detail below. Other crystalline gelling agents can be used in the gel-solid stick compositions of the present invention as long as these other gelling agents can be formulated to provide the required crystal gel matrix and the defined product and rheology characteristics. Other suitable non-polymeric solid gelling agents that are used in the gel-solid antiperspirant stick compositions herein include fatty acid gelling agents that include, but are not limited to, fatty acids and hydroxy fatty acids or alpha hydroxy fatty acids, having about 10. to approximately 40 carbon atoms. Examples of which are included has been 12-hydroxystearic, 12-hydroxylauric acid, 16-hydroxyhexadecanoic acid, behenic acid, euric acid, stearic acid, caprylic acid, P844 lauric acid, isostearic acid and combinations thereof. Preferred fatty acid gelling agents are those having a dimer to fatty acid monomer ratio as defined below. Preferred solid and non-polymeric gelling agents suitable for use in gel-solid antiperspirant stick compositions include 12-hydroxystearic acid, 12-hydroxystearic acid esters, 12-hydroxystearic acid amides and combinations thereof. Preferred gelling agents include those corresponding to the following formula: wherein Rx is OR2 or NR2R3; and R2 and 3 are hydrogen, or an alkyl, aryl or arylalkyl radical, which is linear, cyclic or branched type and having 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, at least one is preferably a hydrogen atom. Among these gelling agents those selected from the group consisting of 12- Hydroxystearic P844, 12-hydroxystearic acid methyl ester, 12-hydroxystearic acid ethyl ester, 12-hydroxystearic acid stearyl ester, 12-hydroxystearic acid benzyl ester, 12-hydroxystearic acid amide, 12-hydroxystearic acid isopropyl amide, 12-hydroxystearic acid butyl amide, 12-hydroxystearic acid benzyl amide, 12-hydroxystearic acid phenyl amide, 12-hydroxystearic acid t-butyl amide, 12-hydroxystearic acid cyclohexyl amide, 12-hydroxystearic acid 1-adamantyl amide hydroxystearic, 12-hydroxystearic acid 2-adamantyl amide, 12-hydroxystearic acid diisopropyl amide and mixtures thereof, even more preferably 12-hydroxystearic acid, 12-hydroxystearic acid isopropyl amide and combinations thereof. More preferred is 12-hydroxystearic 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 the n-acyl amino acid derivatives selected from the group consisting of n-acyl amino acid amides, esters of n-acyl amino acid, prepared from glutamic acid, lysine, glutamine, aspartic acid and P844 combinations thereof and which are especially disclosed 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 which are used in the gel-solid antiperspirant stick compositions of this invention include those having the formula: R g O R 5 I 'II 15 R, C C N R 2 X -Y - Z R. Or ?? -C -N I I? 10 6 where a is a structure formed from the union of C, C "and X and where: a) Rx is zero, hydroxy, hydrogen, aryl, siloxane or aryl substituted with Ci-C ^ alkyl or alkyl ethers C1- 22, C 1 -C 22 alkylesters C 1 -C 22 alkoxy, C 1 -C 22 alkenyl straight-chain, cyclic or branched alkyl, substituted or unsubstituted, saturated or unsaturated, preferably C 4 -C 18 alkyl, C 4 alkenyl - P844 C18, C4-C18 alkoxy, C4-C18 alkylesters, C4-C18 alkyl ethers or aryl substituted with C4-C18 alkyl, more preferably C12-C18 alkyl, C12-C18 alkenyl, C12-C18 alkoxy, C12-C18 alkyl esters, C12-C18 alkyl ethers or aryl substituted with C12-C18 alkyl; b) R 2, R 4, R 5 and R 6 together or independently are hydrogen, hydroxy, aryl, aryl, siloxane or aryl substituted with C 1 -C 22 alkyl or C, alkyl alkylethers, C 2 -C 22 alkylesters, C 1 -C 22 alkoxy, C 1 alkenyl -C22, C1-C2 alkyl d * 2 straight, branched or cyclic chain, 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-C10 alkyl substituted aryl- more preferably C4-C8 alkyl, C4-alkenyl -C8, C4-C8 alkoxy, C4-C8 alkyl esters, C-C8 alkyl ethers or aryl substituted with C4-C8 alkyl; c) R3, is null, hydroxy, hydrogen, C-C4 alkyl ethers or C ^ -Z ^ alkyl alkylesters, Z ^ -C ^ alkoxy, alkenyl Q.X- < 2, straight chain, branched or cyclic Cx-C4 alkyl, substituted or unsubstituted, saturated or unsaturated; preferably, alkoxy 0, ^ - 0, ^, hydroxy or hydrogen, more preferably, a hydroxy or hydrogen; d) R7 and R8 independently or together are, null, hydrogen, hydroxy, aryl, siloxane or aryl substituted with alkyl ^^ 22 or alkyl ethers Z-222 and alkylesters ^ -022 / P844 C 1 -C 22 alkoxy, C 1 -C 22 alkenyl C 1 -C 22 straight-chain, branched or cyclic 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-C10 substituted aryl, more preferably C4-C8 alkyl, C4-C8 alkenyl, C4-C8 alkoxy, C4-C8 alkyl esters, C4-C8 alkyl ethers or aryl substituted with C4-C8 alkyl; e) R9 is zero or hydrogen; f) R10 and Rlx independently or together are, null, hydrogen, hydroxy, aryl, siloxane or aryl substituted with C? -C6 alkyl or C? -C6 alkyl ethers, Cx-C6 alkyl esters, C? -C6 alkoxy, C? alkenyl? C6, 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 alkyl ether, aryl substituted with C 1 -C 4 alkyl or hydrogen, more preferably hydrogen; g) X is zero, nitrogen, aryl or -CH2 -) - n, wherein n is an integer from 1 to 6, preferably, -CH2 -) - n, 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 C 1 -C 22 alkyl or C 1 -C 22 alkylethers C 1 -C 2 alkylesters, C 1 -C 22 alkoxy, P844 C 1 -C 22 alkenyl, C 1 -C 22 straight-chain, branched or cyclic alkyl, substituted or unsubstituted, saturated or unsaturated; preferably, C4-C10 alkyl, C4-C? alkenyl, C4-C10 alkoxy, C4-C10 alkylester, C4-C10 alkyl ether or C4-C10 substituted alkyl, more preferably C4-C8 alkyl, C4-alkenyl C8, C4-C8 alkoxy, C4-C8 alkyl esters, C4-C8 alkyl ethers or aryl substituted with C4-C8 alkyl; j) "a" is a double or single bond as long as: (i) when X is null, Y, Z, R3, R7 and R8 are null, C is directly attached to C "and Rx is not 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) when "a" is zero. a double bond, 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, tricaxbalyl acid, aconitic acid, nitrilotriacetic acid, acid succinic and itaconic acid, for example 1,2,3- P844 propane tributylamide, 2-hydroxy-1,2,3-propane tributylamide, 1-propene-1, 2, 3-trioctylamide, N, N'N "-tri (acetodecylamide) amine, 2-dodecyl-N, N ' -dihexylsuccinamide and 2-dodecyl-N, N'-dibutylsuccinamide The alkylamides of dicarboxylic acids are preferred, for example, alkylsuccinic acid di-amides, alkenylsuccinic acids, alkylsuccinic anhydrides and alkenylsuccinic anhydrides, more preferably 2-dodecylides. N, N'-Dibutylsuccinamide The alkylamide gelling agents preferably have opposite and essentially parallel end chains extending out of the structure of the gelling agent.This spatial arrangement or structural configuration of "tuning trench" is considered. 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 the terminal chains be attached to the structure of the gelling agent by means of acyl-amide linkages where the acyl portion of the acyl-amide linkage is attached directly to the structure P844 main gelling agent. The alkylamide gelling agents can be synthesized using any of the following one or two step reaction procedures. The one-step process 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 trimethylester is then amidated as described in the process of a previous step, using the appropriate alkylamine followed by removal of excess amine. The alkylamides are preferably non-polymeric. These solid non-polymeric gelling agents P844 described herein are especially effective when used in combination with selected anhydride carriers such as, 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 gelling agents The preferred solid and non-polymeric gelling agents used herein include those enantiomeric compounds or enantiomeric materials that contain at least one asymmetric carbon atom (chiral) Non-limiting examples of these preferred enantiomeric gelling agents include 12-hydroxystearic acid, other hydroxy acids such as for example alpha hydroxy acid, cholesterols, 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 Rheological requirements (G '/ G "). It is believed that these enantiomeric gelling agents are especially effective in forming elongated, one-dimensional filament-shaped particles, "fibrils or strands that twist or twist simply to form a three-dimensional, stable crystalline matrix in the gel-solid composition.These elongated particles have a dimensional ratio greater than about 2, preferably, greater than about 6. that these gelling agents form elongated crystalline particles that result in a stable crystalline matrix which, in part because of the small size and elongated morphology of these particles, cause less diffusion of light when applied to the skin in the antiperspirant composition, which results in a lower visible residue after the 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 P844 preferably elongated crystals, 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, preferably superlative 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 make 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 s determining in some other way the ratio between the length of the largest 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 required elastic to viscous modulus ratio 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 tightly bonded gel-solid matrix network, but also comprises crystalline particles that are small enough to contribute minimally to visible residue when applied topically to the skin. It has also been found that the preferred crystalline matrix helps to provide the gel-solid stick compositions with a melting profile that contributes to a lesser appearance of residues. This fusion profile Preferred P844 refers to the temperature at which the gel-solid antiperspirant stick composition begins to melt and the temperature range within which the composition is completely melted, except for any dispersed antiperspirant particle or any other high-point component. fusion. The temperature at which the composition begins to melt is determined by the measurement of a start temperature in Differential Scanning Calorimetry (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 melting 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 fusion profile also helps reduce P844 additionally the index of visible residues of the composition, improving also the performance of less appearance of waste.

Preferred Dimer to Ptonomer Relationship The solid and non-polymeric gellant of the gel-solid antiperspirant stick composition herein preferably comprises a fatty acid gellant having a selected dimer to monomer ratio. 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 of the present with a low appearance performance of improved residue, efficiency and aesthetics and in particular provides better performance with little residue appearance and better product hardness . 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 P844 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 Spectrsscopy, 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 usually characterized by their carbonyl elongation frequencies, which are measured as absorption bands between 1740 cm "and 1680 cm". 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 absorption band of the carbonyl. However, due to the formation of hydrogen-bonded dimers, the fatty acid dimer component can move to frequencies 30 cm lower than the frequency of the fatty acid monomer.

P844 With the use of infrared spectral data, the dimer to monomer ratio is determined by calculating the ratio of the peak area of the band derived from the second dimer bound to hydrogen about 1696 cm "with respect to the peak area of the band derived from the second fatty acid monomer about 1712 cm 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 (which is obtained from Spectra Tech Inc., Shelton, Connecticut, USA) attached to a Nicolet 20scx FTIR Spectrometer - The Nicolet 20scx FTIR Spectrometer is obtained from the Nicolet Instrument Corporation, Madison, Wisconsin, USA The Nicolet 205scx FTIR Spectrometer is equipped with a cadmium telluride detector and narrow band mercury with which an average of 256 scans are co-added to generate the infrared spectra.The infrared spectra are then impo These are used to calculate the monomer-to-monomer ratio using a second derivative algorithm of 5 points, which is the GRAMS / 386 software (obtained from Galactic Industries Corporation, Salem, New Hampshire, USA). a mathematical procedure defined by Savistsky-Golay. The required ratio of dimer to monomer can P844 set up with the fatty acid gelling agents that are described here, which include alpha-hydroxy fatty acids and fatty acids having from about 10 to about 40 carbon atoms, examples of which include 12-hydroxystearic acid, 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. The 12-hydroxystearic acid is the 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 P844 approximately 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.

Anhydrous Liquid Carrier The anhydrous antiperspirant gel-solid stick compositions of the present invention comprise an anhydrous liquid carrier for the crystalline gelling agent described above. The anhydrous liquid carrier is liquid under ambient conditions and preferably has low viscosity to provide improved dispersion on the skin. The concentrations of the anhydrous liquid carrier in the gel-solid stick compositions will vary mainly with the type and amount of anhydrous liquid carrier, the solid, non-polymeric gellant and the solubility of the solid and non-polymeric gellant in the anhydrous liquid carrier. Preferred concentrations of the anhydrous liquid carrier are between about 10% and about 805, preferably, between P844 about 30% and about 70%, more preferably, between about 45% and about 70% by weight of the composition. The anhydrous liquid carrier comprises one or more liquid carriers suitable for topical application to human skin. The liquid carriers can be organic, they can contain silicone or fluorine, they can be volatile or non-volatile, they can be polar or non-polar, as long as the liquid carrier forms a solution or another type of homogeneous liquid or liquid dispersion with the non-polymeric gelling agent selected at the selected gelling concentration, at a temperature between about 28 ° C to about 250 ° C, preferably, between about 28 ° C and about 100 ° C, more preferably, about 28 ° C and about 78 ° C C. The anhydrous liquid carrier has a solubility parameter of between about 3 and about 13 (cal / cm) ', preferably, between about 5 and about 11 (cal / cm)', more preferably, between about 5 and about 9 ( cal / cm) '. The solubility parameters for liquid carriers or for other materials and the means for determining these parameters are well known in the chemical field. A description of the solubility parameters and the P844 means to determine them is described in C.D. Vaughan, "Solubility Effects in Product, Package, Penetration and Preservation" 103 Cosmetics and Toiletries 47-69, October 1988; and C. D. Vaughan, "Using Solubility Parameters in Cosmetics Formulation", 36 J. Soc. Cosmetic Chemists 319, 3333, September / October 1988, which are incorporated herein by reference. The anhydrous liquid carrier preferably comprises an organofunctional or modified silicone carrier selected from the group consisting of polyalkylsiloxanes, polyalkylarylsiloxanes, polyestersiloxanes, polyethersiloxanes, in the form of polymers, polyfluorosiloxanes, polyaminosiloxanes and combinations thereof. These modified silicone carriers should be liquid at ambient conditions and have a viscosity of less than about 100,000 centistokes, preferably less than about 500 centistokes, more preferably, from about 1 and 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 Cosmetics, Science and Technology 27-104 M. Balsam and E. Sagarin ed. 1972); United States Patent No. 4,202,879, granted to Shelton on 13 P844 May 1980; U.S. Patent No. 5,069,897, granted 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 (eg, hexyl, octyl, lauryl, cetyl, P844 stearyl); nonionic functional siloxane copolymers with silanol or trimethylsiloxy end groups; nonionic functional siloxanes with main structure groups which are linked with trisiloxane or methicone; nonionic silicone surfactants; tetraethoxysilane; tetramethoxysilane; hexametoxy silicone; oximetoxitrisiloxane; silicone emfiers; siloxane or silicone resins; alkyl silicone resins; polyoxyalkylene silicone resins; MQ resins such as those of Shiseido / Shin-etsu, for example Publication of Japanese Patent JP86143760 or from Walker Chem. 6MBH (described in EP722970); alkoxysiloxanes; alkoxysilanes; methicones (polymethylalkysiloxanes); 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 (Tetramethyl-Tetraphenyl-Trisiloxane); DC-705 Diffusion Pump Fluid; DC-1784 Emon; DC-AF Emon; DC-1520-US Emon; DC-593 Fluid (Dimethicone [and] Trimethylsiloxysilicate); DC-3225C Fluid (Cyclomethicone [and] Dimethicone Copolyol); DC-190 Fluid (Dimethicone Copolyol); P844 DC-193 Fluid (Dimethicone Copolyol); DC-1401 (Cyclomethicone [and] Dimethiconol); DC-5200 Fluid (Copolyol from Laurylmethicone); DC-6603 Polymer Powder; DC-5640 Powder; DC-Q2-5220 (Dimethicone Copolyol); DC Q2-5324 (Dimethicone Copolyol); DC-2501 Cosmetic Wax (Dimethicone Copolyol); DC-2502 Fluid (Cetil Dimethicone); DC-2503 Wax (Stearyl Dimethicone); DC-1731 Volatile Fluid (Caproil Trimethicone); DC-580 Wax (Stearoxytrimethylsilane [and] Stearyl Alcohol); DC-1-3563 (Dimethiconal); DC-X2-1286 (Dimeticonol); DC-X2-1146A (Cyclomethicone [and] Dimethiconol); DC-8820 Fluid (with Amino functional group); DC Q5-0158A wax (stearoxitrimethylsilane); DC-Q2-8220 (Trimethylsilyllamodimethicone); DC-7224 (Trimethylsilyllamodimethicone); DC-X2-1318 Fluid (Cyclomethicone [y] Vinyl dimethicone); DC-QF1-3593A fluid (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 available from General Electric: GE SF-1023 (Dimethyl-Diphenyl-Siloxane); GE SF-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 (Silicon copolymer and P844 polyether); 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-4265 (Dimethicone [and] 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 emfier); Abil EM-97 (polyether siloxane); Abil Cera 9810 (silicone wax or methicone C24-28); Abil Cera 2434 (Stearoxi Dimethicone); Abil Cera 9800D (Estearil Dimethicone); Tegomer H-Si 2111, H-Si 2311, A-Si 2120, A-Si 2320, C-Si-2141, C-Si 2341, E-Si 2130, E-Si 2330, V-Si 2150, V-Si 2550, H-Si 6420, H-Si 6440, H-Si 6460 (Copolymers of Dimethicone Alpha-Omega) and combinations thereof. Other non-limiting examples of suitable modified silicone carriers that are used in gel-solid antiperspirant stick compositions include the following: Masil 756 from PPG Industries P844 (Tetrabutoxypropyl Trisiloxane); bis-phenylhexamethicone (from Silbione Oils 70633 V30 from Rhone-Poulenc); Silbione Oils 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); Silicate Clod, from Olin (Tris [tributoxysiloxy] methylsilane); silicone copolymer F-754 (dimethicone copolyol from SWS Silicones); and combinations thereof. Preferred anhydrous liquid carriers comprise a volatile silicone carrier. These volatile silicone carriers can be cyclic, linear or branched chain silicones having the required volatility as defined herein. Non-limiting examples of suitable volatile silicones are described in Todd et al., "Volatile Silicone Fluids for Cosmetics", Cosmetics and Toiletries, 91: 27-32 (1976), which is incorporated herein by reference. Preferred volatile silicones are cyclic silicones having from about 3 to about 7, more preferably, from about 4 to 5 silicon atoms. Preferred are those that conform to the general formula: P844 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 (which is obtained commercially 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. Non-volatile silicone carriers are preferably linear silicones that include, but are not limited to, those that conform to any of the following formulas: wherein n is greater than or equal to 1. These linear silicone materials will generally have viscosity values of up to about 100,000 centistoke, preferably less than about 500 centistoke, more preferably, between about 1 and 200 centistoke, still with higher preference, between approximately 1 and 50 centistoke, measured at environmental conditions. Examples of suitable linear and non-volatile silicones that are used in antiperspirant compositions include, but are not limited to, Dow Corning 200, hexamethyldisiloxane, Rhodorsil Oils 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 carriers can also comprise, but are preferably essentially free, of polar, water-immiscible, organic solvents or liquid carriers. It has been found that the antiperspirant and deodorant efficiency of gel-solid stick compositions improves by decreasing or eliminating the amount of liquid solvents or carriers, immiscible in water, organic, polar in composition. In this context, the term "essentially free" means that gel-solid stick compositions preferably contain less than 7%, more preferably less than about 3%, still more preferably zero percent by weight of a solvent or polar liquid carrier, immiscible in water, organic. These polar solvents are liquids under ambient conditions and include monohydric and polyhydric alcohols, fatty acids, mono and dibasic carboxylic acid esters with mono and polyhydric alcohols, polyoxyethylenes, polyoxypropylenes, polyalkoxylate ethers of alcohols, and combinations thereof, so long as these Solvents are also liquid immiscible in water at ambient conditions. Examples of some organic, polar, water immiscible, liquid and anhydrous liquid carriers are described in Cosmetics, Science, and Technology, vol. 1, 27-104, edited P844 by Balsam and Sagarin (1972); in U.S. Patent No. 4,202,879 issued to Shelton on May 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 can comprise liquid, organic, polar, water miscible, anhydrous carriers or solvents, examples of which include short chain alcohols such as ethanol. These and other polar organic solvents or carriers can be used as co-solvents for the solid, non-polymeric gelling component of the gel-solid antiperspirant stick compositions herein. Non-limiting examples of the suitable polar co-solvents that are used herein are described in U.S. Patent No. 5,429,816. Other suitable polar co-solvents include those described above, preferably organic solvents immiscible in water and other co-solvents such as phthalate co-solvents, benzoate co-solvents, cinnamate esters, secondary alcohols, benzyl acetate, phenyl alkane and combinations thereof. The anhydrous liquid carrier may comprise other non-polar carriers such as, for example, mineral oil, petrolatum, isohexadecane, isododecane, various P844 hydrocarbon oils such as those from the Isopar or Norpar series obtained from Exxon Corp. or from the Permetil series obtained from Persperse, and any other liquid, water-miscible, polar or non-polar organic carrier, known or It is safe and effective for topical application to human skin. The anhydrous liquid carrier may also comprise fluorochemicals such as fluorosurfactants, fluorotelémeros and perfluoropoliéteres, 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, perfluoropolymethyl isopropyl ethers, perfluoropolypropyl ethers, fluorinated telomer of acrylamide, fluorinated amide surfactants, perfluorinated thiol surfactants. Other more specific examples include, but are not limited to, polyperfluoroisopropyl ethers available from Dupont Performance Chemicals under the tradename Fluortress® PFPE oils, and the series of fluorosurfactants from Dupont Performance Chemicals under the tradename Zonyl® Fluorosurfactants.

P844 Optional Nucleating Agents 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 compositions 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 P844 approximately 10: 1 and approximately 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 polymeric, solid, selected. Antiperspirant compositions containing a 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 liquid carrier P844 Anhydrous and the liquefied or fused gelling agent, the liquefied nucleating agent crystallizes, gels or solidifies and acts as a seed or core to promote the formation of small gelling nuclei during 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 esters of P844 suitable fatty alcohols include tri-isostearyl citrate, ethylene glycol di-12-hydroxystearate, 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 glycerides include, but are not limited to, glyceryl stearate and glyceryl distearate.

P844 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 P844 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 the 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, virtually all hydroxyl groups of the polyol are esterified, for example, at least about 85% and preferably at least P844 less approximately 95%. The preferred polyols of the polyol carboxylic acid esters, solids, are sugars, including monosaccharides and disaccharides and trisaccharides, containing from about 4 to about 11 hydroxyl groups. The most preferred sugars are those containing from about four 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, myristoleate, palmitoleate, oleate, elaidate, erucate, linoleate, linolenate, arachidonate, eicosapentaentoate and docosahexaenoate. For oxidative stability, mono and disatured fatty acid entities are preferred. Examples of carboxylic acid entities P844 saturated short chain, suitable, include, but are not limited to, 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, rape seed oil fatty acids or soy oil fatty acids can be used in place of pure fatty acids P844 unsaturated from C12 to C16. 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 used to make the solid polyester polyols, the more efficient 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 from sunflower seed oil and lignocerate in a molar ratio of 3: 4; the octaester of sucrose wherein the esterifying carboxylic acid entities are oleate and behenate in a molar ratio of 2: 6, and the octaester of sucrose wherein the esterifying carboxylic acid entities are laurate, linoleate and behenate in a molar ratio of 1 : 3: 4 A preferred material is sucrose polyester wherein the degree of esterification is 7-8 and wherein the fatty acid entities are mono and / or diunsaturated, C18 and behenic, in a molar ratio of unsaturated behenic of 1. : 7 to 3: 5. The particularly preferred nucleating agent of polyol ester is the octaester of sucrose wherein there is approximately 7 P844 behenic fatty acid entities and approximately 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 of 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 P844 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-nonanodioc 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%), trihydroxystearin (0.1%) and combinations of the same.

Other 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. .

P844 Non-limiting examples of optional materials include active components such as bacteriostats and fungistats, and "non-active" components such as colorants, perfumes, emulsifiers, chelants, distribution agents, preservatives, waste masking agents, process aids such as viscosity modifiers 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 stick compositions in P844 gel-solid that does not contain antiperspirant or any other active material, particulate or otherwise.

Manufacturing Method 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 P844 by techniques well known in the art, including electron or light microscopy of the composition, wherein the composition is formulated for analytical purposes without active particulate antiperspirant or other solid particles. Without this reformulation, it is more difficult to directly determine and directly distinguish the crystalline particle size of the gellant and the morphology from the particle size and morphology with which other non-gelling particles contribute. The reformulated composition is then evaluated by electron or light microscopy or by other similar methods. Techniques for preparing the gel-solid antiperspirant stick compositions of this invention include those methods suitable for formulating compositions containing small gelling crystalline particles. Suitable techniques for decreasing the size of crystalline gelling particle include the use of nucleating agents, the formulation with selected carriers or gelling agents or carrier / gellant combinations, the control of crystallization rates including controlling the formulation, the flow rate of the process and temperatures of the process and other methods that are described here. All these methods should be applied to the formulation to control or minimize the particle size of the gelling crystal and / or P844 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, P844 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 P844 topically to the area of the armpit of the skin, according to the methods of use described here and provides an improved performance of little residue appearance, greater efficiency and aesthetics.

P844 TABLE 1 1 - . 1 - . 1 - . 1 - . 1 - . 1 - Dow Corning 245 Fluid; General Electric SF-1202 2 - . 2 - . 2 - Petrolite Unilin 425 3 - Dow Corning 3225C 4 - Petrolite Unithox 450 5 - Petrolite Unithox 480 6 - Finsolv TN from Finetex TABLE 2 1 - Dow Corning 245 Fluid; General Electric SF-1202 2 - EM-97 of Goldschmidt 3 - DC-3225C 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 P844 TABLE 3 1 - Dow Corning 245 Fluid; General Electric SF-1202 2 - EM-97 of Goldschmidt 3 - DC-3225C 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 7-DC-1401 from Dow Corning 8 - Unilin 425 from Petrolite 9 - Unithox 450 from Petrolite 10 - Unithox 480 from Petrolite TABLE 4 1 - Dow Corning 245 Fluid; General Electric SF-1202 2 - Jarchem Jarcol 1-20 3 - Acme Hardesty 4 - Procter & Gamble 5 - Procter & Gamble 6 - Petrolite Unilin 425 7 - Petrolite Unithox 450 8 - Petrolite Unithox 480 9 - Supplied by Westwood Chemical Corporation -. 10 - Supplied by Ciba-Geigy 11 - Procter & Gamble 12 - Aldrich 13 - Procter & Gamble 14 - Witco P844 TABLE 5 1 - Dow Corning 245 Fluid; General Electric SF-1202 2 - . 2 - . 2 - Jarchem Jarcol 1-20 3 - Acme Hardesty 4 - Procter & Gamble 5 - Procter & Gamble 6 - Petrolite Unilin 425 7 - Petrolite Unithox 450 8 - Petrolite Unithox 480 9 - Supplied by Westwood Chemical Corporation -. 10 -. 10 -. 10 - Supplied by Ciba-Geigy 11 - Procter & Gamble 12 - Aldrich 13 - Procter & Gamble 14 - Witco P844 TABLE 6 P844 TABLE 7 P844 TABLE 8 TABLE 9 TABLE 10 TABLE 11 P844 TABLE 12 P844 TABLE 13 [For Tables 6 to 13] I - Dow Corning 245 Fluid; General Electric SF-1202 2 - Jarchem Jarcol 1-20 3 - Witco White Perfect 4 - Acme Hardesty 5 - Petrolite Unilin 425 6 - Octa ester of sucrose esterified predominantly with behenic acid entities 6 - Petrolite Unilin 425 7 - Petrolite Unithox 450 8 - Petrolite Unithox 480 9 - Witco 10 - Supplied by Westwood Chemical Corporation II - Supplied by Ciba-Geigy 12 - Humphrey Chemicals 13 - Aldrich 14 - Aldrich P844 15 - Cabot 16 - Petrolite Unilin 350 17 - Petrolite Unilin 550 18 - Petrolite Unilin 700 19 - NL Chemicals 20 - Witco 21 - Ajinimoto 22 - Procter & Gamble 23 - Starks Associates 24 - Goldschmidt EM-97 TABLE 14 1 - . 1 - . 1 - Dow Corning 245 Fluid; General Electric SF-1202 2 - Jarchem Jarcol 1-20 3 - Witco White Perfect 4 - Acme Hardesty 5 - Petrolite Unilin 425 6 - Petrolite Unithox 450 7 - Petrolitc Unithox 480 P844 8 - Petrolite Unithox 320 9 - Supplied by Westwood Chemical Corporation - Supplied by Ciba-Geigy 11 - Witco TABLE 15 1 - Dow Corning 245 Fluid; General Electric SF-1202 2 - Jarchem Jarcol 1-20 3 - Witco White Perfect 4 - Acme Hardesty 5 - Petrolite Unilin 425 6 - Petrolite Unithox 450 7 - Petrolite Unithox 480 8 - Petrolite Unithox 320 9 - Supplied by Westwood Chemical Corporation - Supplied by Ciba-Geigy 11 - Witco P844

Claims (2)

CLAIMS: 1. An anhydrous antiperspirant gel-solid stick composition comprising: (i) from about 0.5% to about 60% by weight of a particulate antiperspirant active agent; (ii) from about 1% to about 15% by weight of a solid, non-polymeric gellant that is essentially free of organic polymeric gelling agents, inorganic thickening agents, dibenzylidene alditol, N-acyl amino acid derivatives or combinations thereof; and (iii) from about 10% to about 80% by weight of an anhydrous liquid carrier having an average solubility parameter of between about 3 and about 13 [cal / cm] 'and wherein the composition has a visible residue index from about 11 to about 30 of L value, a product hardness of about 500 grams-force to about 5,000 grams-force, and an elastic modulus to viscous modulus ratio of between about 0.1 to about 100, and wherein of refraction of the particulate antiperspirant active agent, the solid non-polymeric gelling agent and the anhydrous liquid carrier are not coincident. 2. The composition according to claim 1, in P844 wherein the non-polymeric solid gelling agent is selected from the group consisting of fatty acid gelling agents, fatty acid gelling gels and esters, hydroxy fatty acids, cholesteric materials, lanolinol materials and combinations thereof. The composition according to claim 2, wherein the solid, non-polymeric gelling agent is selected from the group consisting of: 12-hydroxystearic acid, esters of 12-hydroxystearic acid, amides of 12-hydroxystearic acid and combinations thereof . The composition according to claim 3, wherein the solid, non-polymeric gellant is selected from the group consisting of 12-hydroxystearic acid, 12-hydroxystearic acid methyl ester, 12-hydroxystearic acid ester, stearyl ester of 12-hydroxystearic acid, 12-hydroxystearic acid benzyl ester, 12-hydroxystearic acid amide, 12-hydroxystearic acid isopropyl amide, 12-hydroxystearic acid butyl amide, 12-hydroxystearic acid benzyl amide, 12- hydroxystearic acid phenyl amide hydroxystearic, t-butyl amide 12-hydroxystearic acid, cyclohexyl amide of 12-hydroxystearic acid, 1-adamantyl amide of 12-hydroxystearic acid, 2-adamantyl amide 12-hydroxystearic acid, diisopropyl amide of 12-hydroxystearic acid and combinations thereof . P844 5. The composition according to claim 4, wherein the solid, non-polymeric gellant is 12-hydroxystearic acid. 6. The composition according to claim 1, wherein the solid, non-polymeric gellant comprises a gellant which is formed with the formula: R, O I II R r c - c - N R 2 a 1 I 'R 3- -X Y - Z - R, i. or R .tc-cll -N-R, 1 R 10 R 6 wherein: a) Rx is null, hydroxy, hydrogen, aryl, siloxane or aryl substituted with C? -C22 alkyl or C? -C22 alkyl ethers, C? -C22 alkylesters, C? -C22 alkoxy, CI-C22 alkynyl C? -C22 alkyl, straight chain, cyclic or branched, substituted or unsubstituted, saturated or unsaturated; preferably, C-C18 alkyl, C4-C18 alkenyl, C4-C18 alkoxy, C4-C18 alkyl esters, C4-C18 alkyl ethers or aryl substituted with C4-C18 alkyl, more preferably C12-C18 alkyl, C12-C18 alkenyl, C12-C18 alkoxy, Ci2-C18 alkyl esters, C12-C18 alkyl ethers or aryl substituted with C ?2-C18 alkyl; b) R2, R4, R5 and R6 together or independently P844 are hydrogen, hydroxy, aryl, aryl, siloxane or aryl substituted with C?-C22 alkyl or C-C2 alkyl ethers, C?-C22 alqu alkylesters, C?-C22 alkoxy, C?-C22 alkenyl, chain Cl-C alquilo alkyl straight, branched or cyclic, substituted or unsubstituted, saturated or unsaturated; preferably, C4-C10 alkyl, C4-C10 alkenyl, C-C10 alkoxy, C4-C10 alkylester, C4-C10 alkyl ether or C4-C10 substituted aryl, more preferably C4-C8 alkyl, C4-C8 alkenyl, C4-C8 alkoxy, C4-C8 alkyl esters, C-C8 alkyl ethers or aryl substituted with C4-C8 alkyl; c) R3, is null, hydroxy, hydrogen, C? -C4 alkyl ethers or Cx-C4 alkylesters, C? -C4 alkoxy, C? -C4 alkenyl, C? -C4 straight chain, branched or cyclic alkyl, substituted or not substituted, saturated or unsaturated; preferably, Cx-C4 alkoxy, hydroxy or hydrogen, more preferably, a hydroxy or hydrogen; d) R7 and R8 independently or together are, null, hydrogen, hydroxy, aryl, siloxane or aryl substituted with C? -C, 2 alkyl or C? -C22 alkyl ethers, C? -C22 alkyl esters, C? -C22 alkoxy, alkenyl C? -C22, C? -C22 straight-chain, branched or cyclic alkyl, substituted or unsubstituted, saturated or unsaturated; preferably, C 4 -C 10 alkyl, C 4 -C 0 alkenyl, C 4 -C 0 alkoxy, C 4 -C 0 alkylester, C 4 -C 10 alkyl ether or aryl substituted with C 4 -C 10 alkyl, more preferably C 4 -C 8 alkyl , C4-C8 alkenyl, P844 C4-C8 alkoxy, C4-C8 alkyl esters, C4-C8 alkyl ethers or aryl substituted with C4-C8 alkyl; e) R9 is zero or hydrogen; f) R10 and Rn independently or together are, null, hydrogen, hydroxy, aryl, siloxane or aryl substituted with C? -C6 alkyl or C? -C6 alkyl ethers, C? -C6 alkylesters, C? -C6 alkoxy, C alkenyl? -C6, C, -C6 alkyl straight chain, branched or cyclic, 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 alkyl ether, aryl substituted with C 1 -C 4 alkyl or hydrogen, more preferably hydrogen; g) X is zero, nitrogen, aryl or -CH2-n, where n is an integer from 1 to 6, preferably, -CH2 -) - n, where n. it 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-C22 alkyl or C? -C22 alkyl ethers, C? -C22 alkyl esters, C? -C22 alkoxy, C? - C22 alkenyl, C? ? -C22 straight chain, branched or cyclic, 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-C10 substituted aryl, more preferably C4-C8 alkyl, C4-C8 alkenyl, C4-C8 alkoxy, alkyl esters P844 C4-C8, C4-C8 alkyl ethers or aryl substituted with C4-C8 alkyl; j) "a" is a double or single bond, provided that: (i) when X is zero, Y, Z, R3, R7 and R8 are null, C is directly attached 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) when "a" is a double bond, R3 and Rg are null 7. The composition according to claim 4, wherein the solid, non-polymeric gelling agent is constituted of elongated crystalline particles having a molar ratio of at least about 2. 8 The composition according to claim 7, wherein the solid non-polymeric gelling agent constitutes elongated crystalline particles having a dimensional ratio of at least about 6. The composition according to claim 7, wherein the solid, non-polymeric gellant, It is made up of crystalline particles that have an average particle size of men about 1 μm. P844 10. The composition according to claim 9, wherein the composition has a start temperature of the Differential Scanning Calorimeter of between about 25 ° C to about 85 ° C. The composition according to claim 10, wherein the composition has a start temperature of the Differential Scanning Calorimeter of between about 30 ° C to about 60 ° C. The composition according to claim 9, wherein the solid, non-polymeric gelling agent is constituted by crystalline particles having an average particle size of less than about 0.2 μm. The composition according to claim 1, wherein the composition has a product hardness of between about 750 grams strength at approximately 2,000 grams strength. The composition according to claim 13, wherein the composition has a modulus of elastic modulus to viscous modulus of from about 0.1 to about 50. The composition according to claim 1, wherein the refractive indexes of the particulate antiperspirant active agent , the solid and non-polymeric gelling agent and the anhydrous liquid carrier differ by more than 0.04. P844 16. The composition according to claim 2, wherein the anhydrous liquid carrier comprises a volatile silicone carrier. The composition according to claim 16, wherein the anhydrous liquid carrier further comprises a non-volatile silicone carrier having a viscosity of less than about 100,000 centistokes. 18. The composition according to claim 2, wherein the anhydrous liquid carrier comprises a fluorochemical selected from the group consisting of fluorosulfactants., fluorotelémeros, perfluoropoliéteres and combinations of the same. 19. The composition according to claim 2, wherein the composition is essentially free of fatty acid alcohols having from 12 to 40 carbon atoms. The composition according to claim 2, wherein the composition further comprises from about 0.001% to about 2% by weight of a solid nucleating agent. The composition according to claim 20, wherein the solid nucleating agent is selected from the group consisting of fatty alcohols, fatty acid esters, fatty acid ethers, polyol polyesters and carboxylic acid solid mixtures thereof. 22. The composition according to claim 21, P844 wherein the nucleating agent is a solid polyester polyol and carboxylic acid having a polyol entity and at least 2 carboxylic acid entities, wherein the polyol entity contains at least 4 hydroxyl groups, wherein the The carboxylic acid consists essentially of (a) higher or C12 unsaturated carboxylic acid entities and (b) higher saturated carboxylic acid or C20 entities, the molar ratio of (a) to (b) is from about 1: 7 to about 3: 5, and wherein at least 2 of the hydroxyl groups of the polyol entity are esterified with the carboxylic acid entities. 23. The composition according to claim 22, wherein the polyol entity of the solid polyol polyesters. and carboxylic acid have from about 4 to about 8 hydroxyl groups and the unsaturated carboxylic acid entities of the solid polyester of polyol and carboxylic acid have from about 12 to about 26 carbon atoms and the saturated carboxylic acid entity of the solid polyol of polyol and The carboxylic acid has from about 20 to about 26 carbon atoms. The composition according to claim 23, wherein the polyol entity of the solid polyester of polyol and carboxylic acid is a sugar. P844 25. The composition according to claim 24, wherein the polyol entity of the solid polyester polyol and carboxylic acid has from about 6 to about 8 hydroxyl groups. 26. The composition according to claim 25, wherein the polyol entity of the solid polyester of polyol and carboxylic acid is sucrose. The composition according to claim 26, wherein the saturated carboxylic acid entity of the solid polyol and carboxylic acid polyester consists essentially of behenic entities. The composition according to claim 27, wherein the solid polyol and carboxylic acid polyester is an octaester of sucrose having approximately one oleoc entity and about 7 behenic entities. 29. The composition according to claim 22, wherein the composition has a molar ratio of solid, non-polymeric gelling agent to solid nucleating agent of between about 10: 1 to about 1000:

1. The composition according to claim 1, wherein the particulate antiperspirant active agent has an average particle size of between about 20 μm to about 100 μm. 31. The composition according to claim 1, wherein the particulate antiperspirant active ingredient P844 has an average particle size of less than about 2 μm. 32. A method for treating or reducing odor and moisture resulting from perspiration, comprising applying from about 0.1 grams to about 20 grams of the composition of claim 1, to the desired area of the skin. 33. A method for treating or reducing malodor and moisture resulting from perspiration, comprising applying from about 0.1 grams to about 20 grams of the composition of claim 22, to the desired area of the skin. 34. A method for treating or reducing odor and moisture resulting from perspiration, comprising applying from about 0.1 grams to about 20 grams of the composition of claim 13, to the desired area of the skin. 35. A method for treating or reducing malodor and moisture resulting from perspiration, which comprises applying from about 0.1 grams to about 20 grams of the composition of claim 16, to the desired area of the skin. P844 SUMMARY OF THE INVENTION Anhydrous antiperspirant gel-solid stick compositions comprising particulate antiperspirant active ingredient are disclosed; a solid non-polymeric gelling agent and which are essentially free of dibenzylidene alditol, n-acyl amino acid derivatives, organic polymeric gelling agents and inorganic thickening agents7 and an anhydrous liquid carrier having an average solubility parameter of between about 3 to about 13 (cal / cm) ', wherein the composition has a visible residue index of between about 11 to about 30, value L, a product hardness of about 500 grams force to about 5,000 grams force, an elastic modulus to viscous modulus ratio, of between about 0.1 to about 100. The refractive indices of the particulate antiperspirant actives, non-polymeric solid gelling agent and the anhydrous liquid carrier are not coincident. The non-polymeric solid gelling agent is preferably a crystalline material having an average particle size of less than about 1 μm and / or having an elongated particle morphology having a dimensional ratio of more than about

2. These gel antiperspirant compositions are solid provide better performance of leaving little residue and better P844 antiperspirant and aesthetic characteristics P844