MXPA99005848A - Methods of making low residue antiperspirant gel-solid stick compositions - Google Patents

Abstract

Disclosed are methods of making anhydrous antiperspirant gel-solid stick compositions comprising 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 made in accordance with the methods herein provide improved low residue performance, efficacy and aesthetics.

Description

METHODS FOR ELABORATING ANTITRANSPIRANT COMPOSITIONS IN SOLID GEL BARS THAT LEAVE LITTLE WASTE TECHNICAL FIELD The present invention relates to methods for the preparation of antiperspirant compositions in the form of gel-solid bars. In particular, the present invention relates to methods for the preparation of gel-solid antiperspirant sticks having a selected product hardness, a selected visible residue index and a selected rheology profile, and preferably having a gel matrix. crystalline containing small and / or elongated crystalline particles. Antiperspirant gel-solid stick compositions made according to the methods herein provide poor performance appearance of residue, efficacy and improved 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 sprays by pump or as aerosols, spraying liquids, creams, emulsions, gels, gel- P845 solids or other type of solid bar formulations, and comprise an astringent material, such as zirconium or aluminum salts or combinations thereof, incorporated in 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. 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 the bars P845 antiperspirants 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 which also provide improved efficacy and consistent performance of little residue during and after application to the skin, or which 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 are, however, expensive in their processing due to the cost of using raw materials that have 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 can result in a lower efficacy of the active ingredient, by gel deformation and low gel stability for extended periods during shipping 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. Furthermore, although the visible residue is reduced in these compositions, there is still 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 remains with the antiperspirant bars containing the antiperspirant active ingredient in 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 the fused gellant is soluble in the solvent, and then the composition is cooled to form the gel composition. desired solid. 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 methods for making low residual solids gels can be used without relying on the use of the select combination of gelling agents described by Hofrichter et al. The new methods that relate to the formulation of an anhydrous system comprise 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 organic polymeric gelling agents, inorganic thickening agents, dibenzylidene alditol or of 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 / cm3) ° ') 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 at about 5,000 grams-force, a ratio of elastic modulus (G ') to viscous modulus (G ") of between about 0.1 to about 100 The method described here does not require to match the refractive indexes of the particulate antiperspirant active agent, the solid non-persistent gelling agent polymer and anhydrous liquid carrier in order to obtain the performance of little appearance of waste. The methods, preferably, result in compositions comprising crystalline gelling particles having an average particle size of less than about 1 μm and / or an elongated particle morphology defined by a dimensional ratio greater than about 2. Thus an object of the present invention is to provide a method for making a gel-solid antiperspirant, anhydrous bar 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, provide this method for the composition without being based on specific gelling agents such as dibenzylidene alditols or as dual gelling systems containing n-acyl amino acid derivatives. A further object of the present invention is to provide this method wherein the crystalline size and the morphology of the gellant are controlled to achieve a performance of little appearance of residue, efficiency and improved aesthetics. a 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 a method for the preparation of an anhydrous antiperspirant gel-solid stick composition, comprising the steps of: (A) combining the following components: (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 gelling agent that is essentially free of organic polymeric gelling agents, inorganic thickening agents, dibenzilidene to alditol, N-acyl amino acid derivatives or combinations thereof; (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 3] 0.5 and (B) liquefying the gelling agent per solid and non-polymeric and then (C) solidifying the liquefied gellant in the presence of an anhydrous liquid carrier and a particulate antiperspirant active agent to form a gel-solid antiperspirant composition having a visible residue ratio of between about 11 about 30 L, a product hardness of P845 between about 500 grams force at about 5,000 grams force and a modulus of elastic modulus to viscosity modulus of between about 0.1 to about 100. where the refractive indexes of the particulate antiperspirant active agent, the solid non-polymeric gellant and the carrier Anhydrous liquid are not coincident. It has been found that anti-perspirant gel-solid stick compositions, when made according to the methods of the present invention, can provide a performance of leaving little residue, without the need to use a solubilized antiperspirant active agent and without relying on a selection of gelling agents that leave little residue, such as alditides should be selected or in selecting combinations of gelling agents containing n-acyl amino acid derivatives. This is achieved by formulating an anhydrous gel-solid stick composition having the selected hardness and rheology profile and preferably provided by a three-dimensional, non-polymeric crystal gel network made up of small, elongated crystalline particles having 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.

P845 DETAILED DESCRIPTION OF THE INVENTION The methods of the present invention are directed to the formulation of 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 matrix, non-polymeric, gel-solid. The term "anhydrous" as used herein refers to gel-solid stick compositions made in accordance with the methods of the present invention and also refers to the essential or optional components of said compositions other than the particulate antiperspirant active ingredient, which are essentially free of added water or free water. From a formulation point of view, this means that the gel-solid antiperspirant compositions preferably contain less than about 5%, preferably less than about 3%, more preferably less than about 1%, still more preferably zero percent by weight of free or added water, other than water of hydration typically associated with the particulate active antiperspirant ingredient, prior to formulation. The term "low residue or leaving little residue" in the sense used here generally refers to the P845 visible residue remaining on the areas of skin on which the product is applied, during and immediately after application, and more specifically refers to the visible residue index of the composition as defined by the methodology described then. The term "environmental conditions" as used herein refers to the surrounding conditions that are approximately one atmosphere of pressure, at approximately 50% relative humidity and approximately 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 combinations thereof, resulting in the composition. The term "essentially free" refers to that the compositions herein preferably contain 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 pertain only to those gelling agents and P845 thickeners that are also solid under ambient conditions and that 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 personal care compositions, which are used to provide gelling or thickening, or other physical or aesthetic benefits. to the composition; Specific examples of these include copolymers of hydrogenated butylene / ethylene / styrene, polyethylene, oxidized polyethylene, polyamides, acrylic acid polymers, ethylene-acrylate copolymers and other agents P845 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, Substi tuent Constants for Correlation Analysis in Chemistry and Biology (1979), whose listing and description are incorporated herein by reference. Examples of these substituents include, but are not limited to, alkyl, alkenyl, alkoxy, hydroxy, oxo, nitro, amino, aminoalkyl. (for example aminomethyl, etc.), cyano, halo (for example chlorine, fluorine, bromine, iodine), carboxy, alkoxyaceil (for example carboethoxy, etc.), thiol, aryl, cycloalkyl, 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 P845 prepared from glutamic acid, lysine, glutamine, aspartic acid and combinations thereof, and which are especially 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 pressure. of non-measurable vapor or having a vapor pressure of less than about 0.2 mm Hg under ambient conditions. The solid non-polymeric gelling agent, the antiperspirant active ingredient and the anhydrous liquid carrier which are components of the gel-solid stick compositions herein, preferably do not coincide in their refractive indices and, more preferably, at minus two of these components have refractive indices (? D) which differ by at least about 0.02, more preferably by at least about 0.04.

P845 The methods 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 herein. 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 gel-solid stick antiperspirant compositions made according to the methods 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 module. Each of these characteristics is defined according to the methodologies and other limitations described below.

P845 a) Hardness Antiperspirant gel-solid stick compositions made in accordance with the methods 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, more preferably from 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-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 P845 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 cone surface of approximately 15.5 mm. The cone is a smooth stainless steel construction and weighs approximately 17.8 grams.

Residue The gel-solid antiperspirant bar composition made according to the methods 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 approximately 20 L value. The term "visible residue index" as used herein refers to. in general to the extent to which the gel-solid antiperspirant stick compositions herein are clearly visible as a thin topical film after application to the skin and, more specifically, refer to visible residue values (expressed as L on the scale of 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 about 500 grams-force at approximately 5,000 grams-force.

P845 A piece of black felt, 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 piece of suitable 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 Series No. A-14934 manufactured by Testing Machines, Inc., Amityville, New York, USA, or a Vel System ex Unislide Positioning System, 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 The product extends out of the package or package and is oriented towards the felt piece 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 gel-solid stick composition of P845 antiperspirant then moves slowly towards the piece of black felt and allows it to come into contact with it gently. A 1,000-gram weight is applied to 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 size 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 cm2 of the surface of the template. The template is placed on P845 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 herein and the average particle size of the crystalline gelling particles in the antiperspirant gel-solid stick composition made according to the methods 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 L-value scale correlates with a crystalline, gelling particle size, average of less than about μm and / or particle morphology. gelling, crystalline, characterized by a dimensional crystalline growth in a way that results P845 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 residue index greater than the L value of 30. In view of this correlation between the values of the visible residue index and the average crystalline particle size or the morphology of elongated particle, the measurement of the visible residue index 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) Rhysis The antiperspirant stick compositions made according to the methods of the present invention are gel-solid type having the selected rheology profile defined herein. The rheology profile is defined herein in terms of the relationship between the elastic modulus (G1) and the viscous modulus (G ") (G '/ G") of the gel-solid stick composition. To provide the P845 rheology required, the gel-solid stick compositions should 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 with 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 refers to 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 "for the purpose of defining the composition of the present invention are determined according to environmental conditions using 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 configuration and P845 cone (approximately Io). 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 G1 and G. "It has been found that the gel-solid stick compositions made in accordance with The methods of the present invention exhibit improved development of little appearance of residue when formulated as described herein, wherein the composition has the select ratio G AG "which has already been described, especially when the defined rheology is associated with a matrix of crystalline gel 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 gel-solid stick compositions made in accordance with the methods of the present invention have rheological characteristics that result in better performance, especially performance in terms of the little residue left. These selected gel-solid compositions that are defined here behave as solids before being applied while remaining within a P845 canister and other type of container, but behave like 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.

Active Antiperspirant Antiperspirant gel-solid stick compositions made in accordance with the methods 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 concentration of the particulate active in the composition should be sufficient to provide the desired control in odor and P845 humidity by transpiration with the selected gel-solid antiperspirant bar formulation. The antiperspirant gel-solid stick compositions made according to the methods of 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 complexing 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 the particles of the antiperspirant active within the preferred range of particle size provide a performance P845 of less visible residue of the gel-solid compositions of the present than other preferred smaller ranges of particle size. The antiperspirant active which is used in the antiperspirant gel-solid stick compositions herein include any compound, composition or material having 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. The preferred aluminum salts used in the present include those conforming to the formula: Al2 (OH) aClb • x H20 wherein a is from about 2 to about 5; the sum of a and b is approximately 6; x is from about 1 to about 6 and where a, b and x can be non-integer values. Particular preference is given to aluminum chlorhydroxides referred to as "basic 5/6 chlorohydroxide" where a = 5 and "chlorohydroxide" P845 2/3 basic "where a = 4. Processes for preparing aluminum salts are set forth in US Patent No. 3,887,692 to Gilman issued June 3, 1975; United States Patent No. 3,904,741 to Jones et al, issued September 9, 1975, United States Patent No. 4,359,456 to Gosling et al., issued November 16, 1982, and British Patent Specification No. 2,048,229 to Fitzgerald et al., published December 10, 1975. 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. of zirconium that are used in the present include those that conform to the formula: ZrO (OH) 2.aCla • x H20 where a is from about 1.5 to about 1.87, x is from about 1 to approximately 7 and where a and x can be the two values not integers. These zirconium salts are described in Belgian Patent 825,146 of Schmitz issued August 4, 1975, which is incorporated herein by reference. Particularly preferred zirconium salts are those complexes that additionally contain aluminum and glycine, commonly known as P845 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 Number 3679,068 by 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 made according to the methods of the present invention may also be formulated to comprise other dispersed solids or other matter, in addition to or in place of the particulate antiperspirant active ingredient. These other dispersed solids and other materials include any known or suitable material 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.

Gelifying The antiperspirant stick compositions in P845 gel-solids prepared in accordance with the methods of this invention comprise a solid non-polymeric gelling agent suitable for topically applying to human skin, other than inorganic thickeners, organic polymeric gelling agents or other gelling agents such as dibenzylidene alditol and derivatives thereof. 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. In general, the compositions contain less than 5%, with P845 greater preference 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. Non-polymeric gelling agents must be solid under ambient conditions.

P845 The solid and non-polymeric gelling agents that are used in gel-solid antiperspirant stick compositions are those that 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 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 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 gel-solid matrix within the composition, as the temperature returns to room temperature and falls below the solidification point of the composition. When selecting a combination of gelling agent P845 non-polymeric solid and liquid carrier for use in 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 component preferably have a size of average particle 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 in 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 electron 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 preferred morphology of the crystalline particle.

P845 Suitable non-polymeric solid gelling agents which are used in gel-solid antiperspirant stick compositions include fatty acid gelling agents, fatty acid gelling gels and esters, hydroxy acids, hydroxy fatty acids, cholesteric materials, lanolinol materials and other gelling agents. amide which is 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 which are included have been 12-hydroxystearic, 12-hydroxylauric acid, 16-hydroxyhexadecanoic acid, behenic acid, euric acid, stearic acid, caprylic acid, lauric acid, isostearic acid and combinations of the P845 themselves. 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 R3 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 acid, methyl ester of 12- Hydroxystearic P845, 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, 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. hydroxystearic 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, n-acyl amino acid esters, prepared from glutamic acid, lysine, glutamine, aspartic acid and combinations thereof and especially disclosed P845 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: # II R-C '- -c • - N-R 2 to 1 -X -? 'R 3 ~ - y - Z R 1 0 II R - c - -c -? - .4 R 10 R 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 C1 alkyl -C22 or C 1 -C 2 alkyl ethers, C 1 -C 22 alkylesters, C 1 -C 22 alkoxy, CJ-CJJ alkenyl, C 1 -C 22 alkyl, straight chain, cyclic or branched, substituted or unsubstituted, saturated or unsaturated; Preference, C4-C18 alkyl, C4-C18 alkenyl, C4-C18 alkoxy, C4-C18 alkyl esters, C4-C18 alkyl ethers or substituted aryl P845 with C4-C18 alkyl, more preferably, C12-C18 alkyl, C12-C18 alkenyl, C12-C18 alkoxy, C12-C13 alkyl esters, C12-C18 alkyl ether or C12-C18 alkyl substituted aryl; 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 6 alkyl or C 1 -C 4 alkyl ethers, C 1 -C 22 alkyl esters, C 1 -C 22 alkoxy, C 1 alkenyl ^ C ^, Cx-C22 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; . c) R3, is zero, hydroxy, hydrogen, alkyl ethers C ^ C ,. or C1-C4 alkylesters, C1-C4 alkoxy, C1-C1 alkenyl, straight-chain, branched or cyclic C1-C4 alkylamino, substituted or unsubstituted, saturated or unsaturated; preferably, C1-C4 alkoxy, hydroxy or hydrogen, more preferably, a hydroxy or hydrogen; d) R7 and Rs independently or together are, null, hydrogen, hydroxy, aryl, siloxane or aryl substituted with C 1 -C 12 alkyl or C 1 -C 22 alkyl ethers, C 1 C alkylesters, 1, C 1 -C 22 alkoxy, C 1 alkenyl -C22, straight chain, branched or cyclic Cx-C22 alkyl, substituted or unsubstituted, P845 saturated or unsaturated; preferably, C4-C10 alcjuyl, C4-C10 alkenyl, C4-C10 alkoxy, C4-C10 alkylester, C4-C10 alkyl ether or C4-C10 substituted alkyl, 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) R 10 and Ru independently or together are, null, hydrogen, hydroxy, aryl, siloxane or aryl substituted with C 1 -C 3 alkyl or C 1 -C 6 alkyl ethers, C 1 Cg alkylesters, C 1 -C 6 alkoxy, C 1 -C 3 alkenyl, C alkyl ^ Cj of straight, branched or cyclic chain, substituted or unsubstituted, saturated or unsaturated; preferably C 1 -C 4 alkyl, C 1 -C 4 alkenyl, C 1 -C 4 alkoxy, C 1 Cj 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 alkoyl or C 1 -C 4 alkylethers, C 1 -C 4 alkylesters, C 1 -C 22 alkoxy, C 1 C 4 alkenyl, alkyl C1-C22 straight chain, branched or cyclic, substituted or unsubstituted, saturated or P845 unsaturated; preferably, C4-C10 alkyl, C4-C10 alkenyl, C4-C10 alkoxy, C4-C10 alkylester, C4-C10 alkyl ether or C4-C10 substituted alkyl, more preferably C4-C8 alkyl, C4-C8 alkenyl, C4-C8 alkoxy, C4-Ca alkylesters, C4-C8 alkyl ethers or C4-J alkyl substituted aryl) "a" is a double or single bond provided that: (i) when X is zero, Y, Z, R3, R7 and R8 are null, C1 is directly attached to C "and R? Is not a hydrogen; (ii) when X and Z are not null and Y is null, 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 R9 are null. The alkylamides or di and tribasic carboxylic acids or anhydrides suitable for use in the gel-solid antiperspirant stick composition include alkylamides of cyclic acid, tricarballylic acid, aconitic acid, nitrilotriacetic acid, succinic acid and itaconic acid, for example 1,2 , 3-propane tributylamide, 2-hydroxy-1,2,3-propane tributylamide, 1-propene-1, 2, 3-trioctylamide, N, N'N "- P845 tri (acetodecylamide) amine, 2-dodecyl-N, N '-dihexyl succinamide and 2 dodecyl-N, N' -dibutyl succinamide. Preference is given to alkylamides of dicarboxylic acids, such as, for example, alkylsuccinic acid di-amides, alkenylsuccinic acids, alkylsuccinic anhydrides and alkenyl succinic anhydrides, more preferably 2-dodecyl-N, N'-dibutylsuccinamide. The alkylamide gelling agents, preferably, have opposite and essentially parallel end chains that extend outwardly from the structure of the gelling agent. It is considered that this spatial arrangement or structural configuration of "tuning trench" facilitates the formation of networks essential for the formulation of gel stick or solid gel compositions. By the phrase "tuning fork configuration", which is used herein, reference is made to any configuration that resembles an article or implement having a handle portion that extends longitudinally toward one end to form two fingers. It is also preferred that the end chains be attached to the structure of the gelling agent by means of acyl-amide linkages wherein the acyl portion of the acyl-amide linkage is attached directly to the main structure of the gelling agent. Alkylamide gelling agents can P845 is 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 described herein are especially effective when used in combination with anhydride carriers P845 selected 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 that are used herein include those enantiomeric compounds or enantiomeric materials that contain at least one asymmetric (chiral) carbon atom. Non-limiting examples of these preferred enantiomeric gelling agents include 12-hydroxystearic acid, other hydroxy acids such as for example alpha hydroxy acid, 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 for forming elongated one-dimensional filament particles, fibrils or strands that twist or twist simply to form a crystalline, three-dimensional, stable matrix in the gel-solid composition. These elongated particles have a dimensional ratio of greater than about 2, preferably greater than about 6. These gelling agents are considered to form elongated crystalline particles resulting 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 I application.

Preferred Morphology of the Particles The solid and non-polymeric gelling agents used herein include the crystalline gelling agents which inherently form or can be formulated or are made to form elongated crystalline particles having a dimensional ratio greater than about 2, preferably, greater than about 6. These elongated crystals preferably have an average particle size, measured along a minor axis of the P845 elongated crystal, 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. The "dimensional relationship" as used herein to define the preferred embodiments of the gel-solid stick compositions herein can be determined by measuring or otherwise determining the ratio between the length of the major axis of the crystalline particles and the length of the minor axis of the crystalline particles. This ratio of lengths between the major axis and the minor axis is characterized by the dimensional relationship referred to herein. The dimensional relationship can be determined by conventional methods or by known methods of electron microscopy or light, where the crystalline particles are measured in the dimensions of the major axis and the minor axis, or by these methods it is observed that they clearly have a structure elongated crystalline with a dimensional ratio substantially greater than about 2, preferably, greater than about 6. It has been found that these crystalline gelling agents having the selected dimensional ratios that are defined herein provide the gel-solid antiperspirant stick compositions with a structure three-dimensional crystalline which can provide the composition with the characteristic of leaving little residue, a ratio of elastic modulus to viscous required and the required hardness of the product, as defined herein. This crystalline morphology is considered to be especially effective in providing a crystalline matrix within the composition that provides a 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 preferred melting profile refers to the temperature at which the gel-solid antiperspirant stick composition begins to melt and the temperature range within which the composition melts completely, except for any dispersed antiperspirant particle or any other component of the composition. high melting point. The temperature at which the composition begins to melt is determined by the measurement of a start temperature in Calorimetry of P845 Differential Exploration (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 melting profile also helps to further reduce the visible residue index of the composition, also improving the performance of less waste appearance.

P845 Preferred Dimer to Monomer Ratio The solid, non-polymeric gellant of the gel-solid antiperspirant stick composition herein, made in accordance with the methods herein preferably comprises a fatty acid gellant having a selected dimer-to-dimer ratio. monomer The fatty acid gelling agents having the required ratio of dimer to monomer can be used alone or in combination with an additional or secondary gellant of the composition. The dimer-to-monomer ratio selected helps to provide the gel-solid stick compositions 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 about 20: 1, still more preferably, between about 3: 1 to about 10: 1. The higher dimer to monomer ratios are preferred.

P845 The dimer to monomer ratio of the fatty acid gellant can be determined by methods or techniques well known in the field of formulations, including infrared methods such as Fourier Transform Infrared Spectroscopy (FTIR). These methods are discussed in The Infared Spectra of Complex Molecules, L.J. Bellamy, 2nd. Edition, 1958, Introduction to Infared and Raman Spectroscopy, N.B. Colthup, et al., 3a. Edition, and Fourier Transform Infared Spectroscopy, P.R. Griffiths, et al., 1986, which are incorporated herein by reference. According to these methods or techniques, fatty acids are normally characterized by their carbonyl elongation frequencies, which are measured as absorption bands between 1740 cm "1 and 1680 cm" 1. The fatty acid gellant of the antiperspirant compositions of the present invention comprises fatty acid monomers and fatty acid dimers which are components of the carbonyl absorption band. However, due to the formation of hydrogen-bonded dimers, the fatty acid dimer component can travel to frequencies of 30 cm "1 lower than the frequency of the fatty acid monomer.With the use of the infrared spectra data, the ratio of dimer to monomer is determined by calculating the ratio of the peak area of the derived band P845 of the second dimer bound to hydrogen about 1696 cm "1 with respect to the peak area of the band derived from the second fatty acid monomer about 1712 cm" 1. According to the following methodology, an infrared spectrum is recorded using an Attenuated Total Reflectance ("ATR") crystal of 45 ° ZnSe and a horizontal ATR apparatus (obtained from Spectra Tech. Inc., Shelton, Connecticut, USA) attached to a Nicolet 20scx FTIR Spectrometer. The Nicolet 20scx FTIR Spectrometer is obtained from Nicolet Instrument Corporation, Madison, Wisconsin, U.S.A. The Nicolet 205scx FTIR Spectrometer is equipped with a narrowband cadmium and mercury telluride detector with which an average of 256 scans are co-added to generate the infrared spectra. The infrared spectra are then imported into the software program of the computer, for example GRAMS / 386 (obtained from Galactic Industries Corporation, Salem, New Hampshire, USA) to calculate the ratio of dimer to monomer using a second derivative algorithm. 5 points, which is a mathematical procedure defined by Savistsky-Golay. The required dimer to monomer ratio can be established with the fatty acid gelling agents described herein, which include alpha-hydroxy fatty acids and fatty acids having from about 10 to P845 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 about 5 :1. Anyone with average skill in the chemical or formulation technique can formulate these fatty acid gelling systems to control either P845 obtain the proportion 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 made in accordance with the methods 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 about 30% and about 70%, more preferably, between about 45% and about P845 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 3) ° "5, preferably, between about 5 and about 11 (cal / cm 3) 0.5, more preferably, between about 5 and approximately 9 (cal / cm3) 0.5 The solubility parameters for liquid carriers or for other materials and the means to determine these parameters are well known in the chemical field A description of the solubility parameters and the means to determine them is described in CD Vaughan, "Solubility Effects in Product, Package, Penetration and P845 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 must 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); U.S. Patent No. 4,202,879, issued to Shelton on May 13, 1980; U.S. Patent No. 5,069,897, issued to Orr on December 3, 1991; that are incorporated P845 here for 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 blog copolymers (such as, for example, polyoxyalkylenes, polyoxyethylene or ethoxylated, polyoxyethylene / polyoxypropylene or ethoxylated / propoxylated); silicone emollients substituted with aromatic groups (for example, phenyl, alpha-methyl styryl, styryl, methylphenyl, alkylphenyl); silicone copolymers with other functional groups including: hydrogen, alkyl, methyl, amino, trifluoropropyl, vinyl, alkoxy, arylalkyl, aryl, phenyl, styryl, polyethers, esters, carboxylic compounds; alkylmethylsiloxanes or silicone waxes (for example, hexyl, octyl, lauryl, cetyl, stearyl); nonionic functional siloxane copolymers with silanol or tri-ethylsiloxy end groups; P845 nonionic functional siloxanes with main structure groups that are linked with trisiloxane or methicone; nonionic silicone surfactants; tetraethoxysilane; tetramethoxysilane; hexametoxy silicone; oximetoxitrisiloxane; silicone emulsifiers; siloxane or silicone resins; alkyl silicone resins; polyoxyalkylene silicone resins; MQ resins such as those of Shiseido / Shin-etsu, for example Japanese Patent Publication JP86143760 or of Walker Chem. 6MBH (described in EP722970); alkoxysiloxanes; alkoxysilanes; methicones (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 Emulsion; DC-AF Emulsion; DC-1520-US Emulsion; DC-593 Fluid (Dimethicone [and] Trimethylsiloxysilicate); DC-3225C Fluid (Cyclomethicone [and] Dimethicone Copolyol); DC-190 Fluid (Dimethicone Copolyol); DC-193 Fluid (Dimethicone Copolyol); DC-1401 (Cyclomethicone [and] Dimethiconol); DC-5200 Fluid (Copolyol from P845 Laurilictone); 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 (Silicone and polyether copolymer); GE SF-1288 (silicone-polyether copolymer, dimethyl-methyl-3-hydroxypropyl ethoxylate); GE SF-1318 P845 (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 [y] Trimethylsiloxysilicate) and combinations thereof. Other non-limiting examples of suitable modified silicone carriers that are used in the gel-solid antiperspirant stick compositions herein include the following modified silicones that are obtained from Goldschmidt; Abil EM-90 (silicone emulsifier); Abil EM-97 (polyether siloxane); Abil Cera 9810 (silicone wax or methicone C24-28); Abil Cera 2434 (Stearoxi Dimethicone); Abil Cera 9800D (Stearil Dimethicone); Tegomer H-Si 2111, H-Si 2311, A-Si 2120, A-Si 2320, C-Si-2141, C-Si 2341, E-Si 2130, E-Si 2330, V-Si 2150, V-Si 2550, H-Si 6420, H-Si 6440, H-Si 6460 (Copolymers of Dimethicone Alpha-Omega) and combinations thereof. Other non-limiting examples of suitable modified silicone carriers that are used in gel-solid antiperspirant stick compositions include the following: Masyl 756 from PPG Industries (Tetrabutoxypropyl Trisiloxane); bis-phenylhexamethicone (from Silbione Oils 70633 V30 from Rhone-Poulenc); Silbione Oils P845 70646 (dimethicone copolyols from Rhone-Poulenc); silicone L-711, L-720, L-721 and L722 (dimethicone copolyols from Union Carbide); Silicone L-7000, L-7001, L-7002, L-7004, L-7500, L-7600, L-7602, L-7604, L-7605 and L-7610 (Dimethicone copolyols from Union Carbide); Unisil SF-R (UPI dimethiconol); Olin Silicate Clod (Tris [tributoxysiloxijmetilsilano]; 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: P845 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. The carriers of P845 non-volatile silicones, preferably linear silicones that include, but are not limited to, those that conform to any of the following formulas: where n is greater than or equal to 1. These linear silicone materials will generally have viscosity values of up to about 100, 100,000 centistoke, preferably less than about 500 centistoke, more preferably, between about 1 and 200 centistoke, still more preferably, between about 1 and 50 centistoke, measured at ambient conditions. Examples of suitable linear and non-volatile silicones that are used in antiperspirant compositions include, but are not limited to, Dow Corning 200, hexamethyldisiloxane, Rhodorsil 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 P845 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, immiscible, organic, polar, water-soluble solvents or carriers in the 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 P845 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 P845 hydrocarbon oils such as those from the Isopar or Norpar series obtained from Exxon Corp. or those from the Permetil series obtained from Persperse, and any other organic carrier liquid, water miscible, polar or non-polar, 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.

P845 Optional Nucleating Agents The gel-solid antiperspirant stick compositions in the present, prepared in accordance with the methods 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 herein must be a solid material at ambient conditions and have 1) a melting point close to the melting point of the selected gelling agent; 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 P845 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 the inorganic, micronized nucleating agents) and then in the presence of the liquid carrier P845 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 Suitable fatty alcohols P845 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.

P845 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 P845 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 P845 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 P845 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 P845 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 the desired unsaturated and saturated acids in the materials P845 carboxylic acid raw materials that are used to make solid polyester polyols, the more efficient the ester's ability 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 the sucrose polyester wherein the degree of esterification is 7-8 and wherein the fatty acid entities are mono and / or di-unsaturated, C18 and behenic, in a molar ratio of unsaturated: behenic from 1: 7 to 3: 5. The particularly preferred nucleating agent of polyol ester is the octaester of sucrose wherein there is approximately 7 P845 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 P845 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 made in accordance with the methods 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 they are 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.

P845 product performance. Non-limiting examples of optional materials include active components such as bacteriostats and fungistats, and "non-active" components such as dyes, perfumes, emulsifiers, chelants, distribution agents, preservatives, waste masking agents, process aids such as viscosity modifiers and auxiliaries. of elimination by washing. Examples of these optional materials are described in U.S. Patent No. 4,049,792 to Elsnau, issued September 20, 1977; Canadian Patent No. 1,164,347 to Beckmeyer et al., issued March 27, 1984; U.S. Patent No. 5,019,375 to Tanner et al., Issued May 28, 1991; and U.S. Patent No. 5,429,816 to Hofrichter et al., issued July 4, 1995, the disclosures of which are incorporated herein by reference. The gel-solid antiperspirant stick compositions made in accordance with the methods of this invention can 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 compositions of P845 gel-solid antiperspirant stick can also be formulated as gel-solid stick compositions that do not contain antiperspirant or any other active, particulate or otherwise material.

Manufacturing Method The gel-solid antiperspirant stick compositions herein are prepared in accordance with the methods of this invention. These methods preferably include any known effective or known techn for making a crystalline matrix containing elongated crystals of non-polymeric gellant having a dimensional ratio greater than about 2, preferably greater than about 6 and / or an average particle diameter that is minimizing (preferably to less than about 1 μm) the techns for minimizing the crystalline particle size in the gel-solid antiperspirant compositions herein include the use of nucleating agents, select formulations of carriers or gelling agents or of carrier / gellant combinations, the control of crystallization rates, which include control of the formulation, control of the process flow rate and processing temperatures and other methods described herein. All these P845 methods should be applied to the formulation to, preferably, control or minimize the crystal particle size of gelling agent and / or to form the desired elongated crystalline particles and thereby form the desired crystalline matrix of the compositions herein. The crystalline particle size in the compositions herein can be determined by techns well known in the art., which include electron or light microscopy of the composition, wherein the composition is formulated for analysis 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.

Method of Use The gel-solid antiperspirant stick compositions made according to the methods of the present invention can be applied topically to the armpit or to any other area of the skin in an effective amount P845 to treat or reduce odor or moisture from perspiration. The composition is preferably applied in an amount ranging from about 0.1 grams to about 20 grams, more preferably, from about 0.1 grams to about 10 grams, still more preferably, from about 0.1 grams to about 1 gram of the desired area of the skin. The compositions are preferably applied to the armpit or to another area of the skin once or twice a day, preferably once a day, to achieve effective control of perspiration and odor for a prolonged period of time.

EXAMPLES The following non-limiting examples illustrate the specific embodiments of the gel-solid antiperspirant stick compositions of this invention, including the methods of manufacture and use. Each of the exemplified compositions is prepared by combining all the listed components, except the antiperspirant active ingredient and other materials such as perfumes. The combined components are heated to about 100 ° C with agitation to form a hot liquid, after which all the materials are added to the hot liquid. The liquid Hot P845 is allowed to cool with stirring just before the solidification point, at which point the liquid composition is cooled and poured into the applicator containers and allowed to cool and solidify to the required product hardness. Each of the exemplified compositions comprises a crystalline gel matrix comprising crystalline particles with a dimensional ratio greater than about 6, and an average particle size of crystalline gelling agent of less than about 1 μm. Each of the exemplified compositions also has a visible residue index of between about 11 and about 30 in L-value, a product hardness of between about 500 and 5,000. grams "force and a G '/ G ratio" between about 0.1 and about 100. Each of the exemplified antiperspirant compositions are applied topically to the skin armpit area, according to the methods of use described herein and It provides improved performance with little residue appearance, greater efficiency and aesthetics.

P845 TABLE 1 1 - . 1 - . 1 - . 1 - . 1 - . 1 - Dow Corning 245 Fluid; General Electric SF-1202 2 - . 2 - . 2 - . 2 - Petrolite Unilin 425 3 - Dow Corning 3225C 4 - Petrolite Unithox 450 5 - Petrolite Unithóx 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 P845 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 P845 TABLE 5 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 -. 10 -. 10 - Supplied by Ciba-Geigy 11 - Procter & Gamble 12 - Aldrich 13 - Procter & Gamble 14 - Witco P845 TABLE 6 P845 TABLE 7 P845 TABLE 8 P845 TABLE 9 P845 TABLE 10 P845 TABLE 11 P845 TABLE 12 P845 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 - Octaester 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 15 - Cabot 16 - Petrolite Unilin 350 17 - Petrolite Unilin 550 18 - Petrolite Unilin 700 P845 19 - NL Chemicals 20 - Witco 21 - Ajinimoto 22 - Procter & Gamble 23 - Starks Associates 24 - Goldschmidt EM-97 TABLE 14 1 - . 1 - Dow Corning 245 Fluid; General Electric SF-1202 2 - . 2 - . 2 - Jarchem Jareo1 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 TABLE 15 P845 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 P845

Claims (22)

1. CLAIMS: 1. A method for the preparation of an anhydrous antiperspirant gel-solid stick composition, wherein the method comprises the steps of: (A) combining the following components: (i) from about 0.5% to about 60% in 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; (iii) from about 10% to about 80% in. weight of an anhydrous liquid carrier having an average solubility parameter of between about 3 and about 13 [cal / cm3] 0"5 and (B) liquefying the gelling agent by solid and non-polymeric and then (C) solidifying the liquefied gellant in the presence of an anhydrous liquid carrier and a particulate antiperspirant active agent to form a gel-solid antiperspirant composition having a visible residue index of between about 11 about 30 L-value, a product hardness of P845 between about 500 grams strength at about 5,000 grams force and an elastic modulus modulus to viscosity modulus of between about 0.1 to about 100. 'where the refractive indexes of the particulate antiperspirant active agent, the solid non-polymeric gelling agent and the Anhydrous liquid carrier are not coincident. The method according to claim 1, wherein the non-polymeric solid gelling agent is selected from the group consisting of fatty acid gelling agents, esters and amides of fatty acid gelling agents, hydroxy fatty acids, cholesteric materials, lanolinol materials and combinations of the same. 3. The method 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 method 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, benzyl ester of 12- Hydroxystearic P845, 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, 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. The method according to claim 4, wherein the solid, non-polymeric gellant is 12-hydroxystearic acid. The method according to claim 1, wherein the solid, non-polymeric gellant comprises a gellant which is formed with the formula: R? O », I 'II I 5 R, C -C -N -R2 wherein: a) R1 is null, hydroxy, hydrogen, aryl, siloxane or aryl substituted with C.sub.2 -C.sub.2 alkyl or C.sub.1 -C.sub.2 alkyl ethers, C.sub.1 -C.sub.2 alkylesters, C.sub.1 -C.sub.22 alkoxy, alkenyl P845 Cj-C., 2, Cj-C., Straight chain, cyclic or branched alkyl, substituted or unsubstituted, saturated or unsaturated; preferably, C4-C18 alkyl, C4-C18 alkenyl, C4-C18 alkoxy, C4-Cla alkylester, C4-Clg alkyl ether or C4-C18 alkyl substituted aryl, 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 1 alkyl alkylethers, C 1 -C 4 alkyl esters, C 2 -C 2 alkoxy; C ^ C ^ alkenyl, C-C22 straight-chain, branched or cyclic alkyl, substituted or unsubstituted, saturated or unsaturated; preferably, C4-C10 alkyl, C4-C10 alkenyl, C4-C10 alkoxy, C4-C10 alkyl esters, C4-Cl0 alkyl ethers or C4-C10 substituted alkyl, 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; c) R3, is null, hydroxy, hydrogen, Cx-C4 alkyl ethers or C1-C4 alkylesters, C1-C4 alkoxy, Cx-C4 alkenyl, straight chain, branched or cyclic Cx-C4 alkyl, substituted or unsubstituted, saturated or unsaturated; preferably, C1-C4 alkoxy, hydroxy or hydrogen, more preferably, a hydroxy or hydrogen; d) R, and R8 independently or together are, null, P845 hydrogen, hydroxy, aryl, siloxane or aryl substituted with C1-C22 alkylalkyl or C1-C22 alkyl ethers, C1-C22 alkylesters, Cx-C22 alkoxy, Cx-C22 alkenyl, straight-chain, branched or cyclic C1-C22 alkyl, substituted or unsubstituted, saturated or unsaturated; preferably, C4-C10 alkyl, C4-C10 alkenyl, C4-C10 alkoxy, C4-C10 alkylester, C4-C10 alkyl ether or C4-C10 substituted aryl, more preferably C4-C8 alkyl, C4-C8 alkenyl, C4-C8 alkoxy, C4-C3 alkyl esters, C4-C8 alkyl ethers or aryl substituted with C4-C3 alkyl; e) Rg is zero or hydrogen; f) R 10 and RX 1 independently or together are, null, hydrogen, hydroxy, aryl, siloxane or aryl substituted with C 1 -C 6 alkyl or C 1 -C 6 alkyl ethers, C 1 Cg alkylesters, C 1 -C 6 alkoxy, C 6 -C 6 alkenyl, Cx-C6 straight-chain, branched or cyclic 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, where n is an integer from 1 to 6, preferably, -CH, where n is an integer from 1 to 3; h) Y is zero, acyl or carbonyl; i) Z is zero, hydrogen, hydroxy, aryl, P845 siloxane, nitrogen or aryl substituted with Cj-C- alkyl. or alkylethers, C, -C, C22 alkylesters, C, -C22 alkoxy, C, C- alkenyl, straight, branched or cyclic, C 1 -C 22 alkyl, substituted or unsubstituted, saturated or unsaturated; preferably, C4-C10 alkyl, C4-C10 alkenyl, C4-C10 alkoxy, C4-C10 alkylester, C4-C10 alkyl ether or C4-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; 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, R, and R are zero, and (iv) "a" is a double bond, R3 and Rg are null 7. The method according to claim 1, wherein the solid, non-polymeric gelling agent is constituted of elongated crystalline particles having a molar ratio of at least about 2. 8. The method according to claim 7, in P845 where the solid, non-polymeric gelling agent is composed of crystalline particles having an average particle size of less than about 1 μm. 9. The method according to claim 8, wherein the composition has a starting temperature of Differential Scanning Calorimeter from approximately 25 ° C to approximately 85 ° C. The method according to claim 9, wherein the composition has a start temperature of the Differential Scanning Calorimeter of between about 30 ° C to about 60 ° C. The method according to claim 8, wherein the solid, non-polymeric gellant is constituted of crystalline particles having an average particle size of less than about 0.2 μm. The method according to claim 1, wherein the composition has a product hardness of between about 750 grams strength at approximately 2,000 grams strength. The method according to claim 12, wherein the composition has a modulus of elastic modulus to viscous modulus of from about 0.1 to about 50. The method according to claim 1, wherein the refractive indexes of the active agent P845 particulate antiperspirant, solid and non-polymeric gelling agent and anhydrous liquid carrier differ by more than 0.04. 15. The method according to claim 2, wherein the anhydrous liquid carrier comprises a volatile silicone carrier. 16. The method according to claim 15, wherein the anhydrous liquid carrier further comprises a non-volatile silicone carrier having a viscosity of less than about 100., 000 centistokes. The method according to claim 2, wherein the anhydrous liquid carrier comprises a fluorochemical selected from the group consisting of fluorosulfactants, fluorotelémeros, perfluoropoliéteres and combinations thereof. 18. The method according to claim 2, wherein the composition is essentially free of fatty acid alcohols having from 12 to 40 carbon atoms. 19. The method according to claim 2, wherein the composition further comprises about 0. 001% to about 2% by weight of a solid nucleating agent. The method according to claim 19, wherein the solid nucleating agent is selected from the group consisting of fatty alcohols, fatty acid esters, P845 fatty acid ethers, polyol polyesters and carboxylic acid solid mixtures thereof. The method according to claim 20, wherein the nucleating agent is a solid polyester of polyol and carboxylic acid having a polyol entity and at least 2 carboxylic acid entities, wherein the polyol entity contains at least 4 carbon atoms. hydroxyl groups, wherein the carboxylic acid entity consists essentially of (a) higher or C 12 unsaturated carboxylic acid entities and (b) higher saturated carboxylic acid or C 20 entities, the molar ratio of (a) to (b) is 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. 22. The method according to claim 21, wherein the polyol entity of the solid polyesters of polyol 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 polyester of polyol and carboxylic acid has from about 20 to about 26 carbon atoms. P845 23. The method according to claim 22, wherein the polyol entity of the solid polyester of polyol and carboxylic acid is a sugar. The method according to claim 23, wherein the polyol entity of the solid polyester polyol and carboxylic acid has from about 6 to about 8 hydroxyl groups. 25. The method according to claim 24, wherein the polyol entity of the solid polyester of polyol and carboxylic acid is sucrose. 26. The method according to claim 25, wherein the saturated carboxylic acid entity of the solid polyester polyol and carboxylic acid consists essentially of behenic entities. . The method according to claim 26, wherein the solid polyester polyol and carboxylic acid is an octaester of sucrose having approximately one oleoc entity and about 7 behenic entities. The method according to claim 27, 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 method according to claim 1, wherein the particulate antiperspirant active agent has an average particle size of between about 20 P845 μm to approximately 100 μm. 30. The method according to claim 1, wherein the particulate antiperspirant active ingredient has an average particle size of less than about 2 μm. P845 SUMMARY OF THE INVENTION Methods for the preparation of anhydrous antiperspirant compositions in gel-solid stick form, comprising a particulate antiperspirant active ingredient, a solid non-polymeric gelling agent that is essentially free of dibenzylidene alditol, n-derivatives are disclosed. acyl animo acids, organic polymeric gelling agents and inorganic thickeners; and an anhydrous liquid carrier having an average solubility parameter of between about 3 and about 13 (cal / cm 3) 0.5, wherein the composition has a visible residue index of between about 11 to about 30, value L, a product hardness of between approximately 500 grams. Strength to approximately 5,000 grams. strength, a ratio of an elastic modulus to a viscous modulus of between -about 0.1 to about 100. The refractive indices of the particulate antiperspirant active agent, the solid and non-polymeric gelling agent and the anhydrous liquid carrier are not coincident. The solid non-polymeric gelling agent is preferably a crystalline material having an average particle size of less than about 1 μm and / or has an elongated particle morphology with a dimensional ratio of more than about 2. These antiperspirant compositions in bar gel-solid P845 prepared according to the methods of the present provide better performance by leaving little residue, be more effective and aesthetic. P845