LIQUID ANTIPERSPIRANT COMPOSITIONS
TECHNICAL FIELD The present invention relates to unique clear, sprayable, liquid antiperspirant compositions having viscosities of less than about 15 centistokes which are stable and which provide excellent antiperspirancy and cosmetic in-use properties.
BACKGROUND OF THE INVENTION Antiperspirant compositions have become part of many people's personal care and grooming regimen. A highly desirable antiperspirant composition will provide a number of benefits at the same time. First and foremost of these is, of course, antiperspirancy efficacy. Good usage aesthetics are also highly desirable. A composition that goes onto the skin easily without dripping or running off is important. It is also desirable that the composition goes onto the skin with a clean, dry, non-irrita- ting, non-sticky feel. Upon dry-down preferred compositions will leave minimized residue on the skin and clothing. Finally, it is important that an antiperspirant composition remain both chemically and physically stable over time and a broad range of physical conditions, especially changes in temperature. The formulation of antiperspirant compositions generally is an exercise in efficacy and aesthetic trade-offs, with the resulting composition being acceptable overall, but not outstanding. For example, the formulation of a omposition to give it good usage aesthetic properties (e.g., minimized irritation to skin, minimized residue on the skin, and/or a clean, dry and non-sticky feel) often compromises antiperspirant efficacy.
It is particularly difficult to formulate an antiperspirant composition which provides maximum usage aesthetics and efficacy, when it is in the form of a low-viscosity liquid product, such as
a spray-on antiperspirant composition, and at the same time maintain good physical properties (e.g., stability over time and a broad range of physical conditions, especially changes in temperature). Non-aerosol pump spray antiperspirant compositions have increased in popularity recently over aerosol antiperspirant forms. Such antiperspirant forms, in general, have been disclosed in, for example, U.S. Patent 4,053,581, Pader et al., issued October 11, 1977; U.S. Patent 4,065,564, Miles, Jr., issued December 27, 1977; U.S. Patent 4,073,880, Pader et al., issued February 14, 1978; and Great Britain Application 1,536,222, published December 20, 1978.
Pump spray antiperspirant compositions generally comprise high levels of an alcohol solvent and little or no emollient materials. Formulation in such a way generally results in products with poor in-use characteristics. That is, such compo¬ sitions result in a sticky, cold, stinging feel upon application. Often such compositions are too thin in consistency and tend to run off of the skin after application. Generally, such composi- tions will leave a residue on skin upon dry down.
Hence, it is an object of the present invention to provide a low viscosity, clear, sprayable, liquid antiperspirant composition which exhibits excellent antiperspirancy properties.
It is also an object of the present invention to provide a low viscosity, clear, sprayable, liquid antiperspirant composition which exhibits excellent cosmetic in-use properties.
It is a further object of the present invention to provide a low viscosity, clear, sprayable, liquid antiperspirant composition which is physically and chemically stable over time and a broad range of physical conditions.
These and other objects will become readily apparent from the detailed description which follows.
SUMMARY OF THE INVENTION The present invention relates to clear, sprayable, liquid antiperspirant solutions, having a viscosity of less than about 15 centistokes, comprising: a. from about 10% to about 25% of a monohydric alcohol-sol¬ uble antiperspirant salt; b. from about 0.5% to about 20% of a non-volatile emollient ester selected from the group consisting of esters of C2-C20 alcohols and benzoic acid, esters of C2-C20 alcohols and C6-C16 fatty acids, and mixtures thereof, having a solubility parameter of from about 7 to about 10; c. from 0% to about 15% of a propylene glycol ether of a C -C22 fatty alcohol ; d. from 0% to about 20% of a volatile silicone emollient; e. from 0% to about 3% of a pH buffer; f. from 0% to about 4% of a mixture of a dimethicone copolyol in a suitable solvent therefor; f. from about 2% to about 10% of water; g. from about 45% to about 65% of a monohydric alcohol solvent; and i. from 0% to about 2% of a non-volatile dimethicone fluid having a viscosity of less than about 20 centistokes; and j. from 0% to about 6% of a C12-C20 branched chain alcohol emollient.
Preferred compositions of the present invention are as follows:
A clear, sprayable, liquid antiperspirant composition, having a viscosity of less than about 15 centistokes, comprising: a. from about 10% to about 25% of a monohydric alcohol-sol¬ uble antiperspirant salt; b. from about 3% to about 20% of a non-volatile emollient ester selected from the group consisting of esters of C2-C20 alcohols and benzoic acid, esters of C2-C20 alcohols and C6-C16 fatty acids, and mixtures thereof,
having a solubility parameter of from about 7 to about 10; c. from 0% to about 8% of a propylene glycol ether of a C4-C22 fatty alcohol; d. from 0% to about 20% of a volatile silicone emollient; e. from 0% to about 3% of a pH buffer; f. from 0% to about 4% of a mixture of a dimethicone copolyol in a suitable solvent therefor; g. from about 2% to about 10% of water; and h. from about 50% to about 65% of a monohydric alcohol solvent. More specific embodiments of such compositions are as follows:
A clear, sprayable, liquid antiperspirant solution, having a viscosity of less than about 15 centistokes, comprising: a. from about 14% to about 16% of a monohydric alcohol-soluble antiperspirant salt, which is preferably an ethanol-soluble aluminum sesquichlorohydrate antiperspirant salt; b. from about 3% to about 7% of a non-volatile emollient ester selected from the group consisting of esters of C2-C20 alcohols and benzoic acid, esters of C2-C20 alcohols and C6-C16 fatty acids, and mixtures thereof, having a solubility parameter of from about 7 to about 10, which is preferably C12-C15 alcohols benzoate; c. from about 3% to about 6% of a propylene glycol ether of a C4-C22 fatty alcohol, which is preferably PPG-3 myristyl ether; d. from about 2% to about 3% of a pH buffer, which is preferably urea; e. from about 2% to about 4% of a mixture of a dimethicone copolyol and a suitable solvent therefor, which is preferably a mixture of D4 cyclomethicone and dimethicone copolyol at a ratio of about 88:12; f. from about 7% to about 10% of water; and
g. from about 50% to about 65% of a monohydric alcohol solvent, which is preferably ethanol.
A clear, sprayable, liquid antiperspirant composition, having a viscosity of less than about 15 centistokes, comprising: a. from about 14% to about 16% of a monohydric alcohol-soluble antiperspirant salt which is preferably an ethanol-soluble sesquichlorohydrate antiperspirant salt; b. from about 3% to about 8% of a non-volatile emollient ester selected from the group consisting of esters of C2-C20 alcohols and benzoic acid, esters of C2-C20 alcohols and C6-C16 fatty acids, and mixtures thereof, having a solubility parameter of from about 7 to about 10, which is preferably C12-C15 alcohols benzoate; c. from about 3% to about 6% of a propylene glycol ether of a C -C22 fatty alcohol, which is preferably PPG-3 myristyl ether; d. from about 2% to about 3% of a pH buffer, which is preferably urea; e. from about 7% to about 10% of water; and f. from about 50% to about 65% of a monohydric alcohol soluble solvent, which is preferably ethanol. A clear, sprayable, liquid antiperspirant solution, having a viscosity of less than about 15 centistokes, comprising: a. from about 18% to about 24% of a monohydric alcohol-soluble antiperspirant salt, which is preferably an ethanol-soluble aluminum chlorohydrex antiperspirant salt; b. from about 10% to about 20% of a non-volatile emollient ester selected from the group consisting of esters of C2-C20 alcohols and benzoic acid, esters of C2-C20 alcohols and C6-C16 fatty acids, and mixtures thereof, having a solubility parameter of from about 7 to about 10, which is preferably selected from the group consisting of C12-C15 alcohols benzoate, isopropyl myristate, and mixtures thereof; c. from about 5% to about 15% of a volatile silicone
emollient, which is preferably selected from the group consisting of D4-D5 cyclomethicone, phenethyl pentamethyl disiloxane, dimethicone fluids having viscosities of less than about 1 centistoke, and mixtures thereof; d. from about 2% to about 3% of water; and e. from about 50% to about 60% of a monohydric alcohol solvent, which is preferably ethanol.
A clear, sprayable, liquid antiperspirant composition, having a viscosity of less than about 15 centistokes, comprising: a. from about 14% to about 16% of a monohydric alcohol soluble antiperspirant salt, which is preferably an ethanol-soluble sesquichlorohydrate antiperspirant salt; b. from about 8% to about 14% of a non-volatile emollient ester selected from the group consisting of esters of C2-C20 alcohols and benzoic acid, esters of C2-C20 alcohols and C6-C16 fatty acids, and mixtures thereof, having a solubility parameter of from about 7 to about 10, which is preferably selected from the group consisting of Clz-C15 alcohols benzoate, isopropyl myristate, and mixtures thereof; c. from about 3% to about 6% of a propylene glycol ether of a C4-C22 fatty alcohol, which is preferably PPG-3 myristyl ether; d. from about 2% to about 3% of a pH buffer, which is preferably urea; e. from about 4% to about 8% of a volatile silicone emollient, which is preferably selected from the group consisting of D4-D5 cyclomethicone, phenethyl pentamethyl disiloxane, dimethicone fluids having viscosities of less than about 1 centistoke, and mixtures thereof; f. from about 2% to about 3% of water; and g. from about 50% to about 65% of a monohydric alcohol solvent, which is preferably ethanol.
Another preferred execution hereof is as follows:
A clear, sprayable, liquid antiperspirant composition, having a viscosity of less than about 15 centistokes, comprising:
a. from about 14% to about 16% of a monohydric alcohol-sol¬ uble antiperspirant salt; b. from about 0.5% to about 6% of a non-volatile emollient ester selected from the group consisting of esters of C2-Cj,0 alcohols and C6-C16 fatty acids, and mixtures thereof, having a solubility parameter of from about 7 to about 10; c. from about 10% to about 15% of a propylene glycol ether of a C4-C22 fatty alcohol; d. from about 12% to about 16% of a volatile silicone emollient; e. from about 2% to about 6% of a C12-C20 branched chain alcohol emollient; f. from about 0.25% to about 1% of a non-volatile dimethicone fluid having a viscosity of about 2 to about
20 centistokes; g. from about 2% to about 3% water; and h. from about 45% to about 55% of a monohydric alcohol solvent. An especially preferred embodiment of a composition as described immediately above is provided when: a. the monohydric alcohol-soluble antiperspirant salt comprises an ethanol-soluble sesquichlorohydrate anti¬ perspirant salt; b. the non-volatile emollient ester is selected from the group consisting of ethyl myristate, isopropyl yris- tate, and mixtures thereof; c. the propylene glycol ether is PPG-3 myristyl ether; d. the volatile silicone emollient is selected from the group consisting of cyclomethicone, phenethyl penta¬ methyl disiloxane, and dimethicone fluids having vis¬ cosities of less than about 1 centistoke, and mixtures thereof; e. the C12-C20 branched chain alcohol emollient comprises from about 2% to about 6% isocetyl alcohol;
f. the non-volatile dimethicone fluid has a viscosity of about 2 to about 10 centistokes; and g. the monohydric alcohol solvent is ethanol.
These latter compositions are particularly advantageous in that they can provide good product aesthetics and in-use charac¬ teristics, including antiperspirant efficacy and minimal skin irritation, without the necessity for a pH buffer.
DETAILED DESCRIPTION OF THE INVENTION The essential as well as optional components of the present compositions are described below. Antiperspirant Material
A critical component of the present compositions is an antiperspirant material that is soluble and which remains soluble in ethanol or another suitable monohydric alcohol solvent. Solubilization of the antiperspirant material allows for the formulation of the present clear antiperspirant solutions.
A variety of publications disclose antiperspirant actives which are soluble in non-aqueous solvents, typically monohydric alcohols (e.g., ethanol). U.S. Patent 3,873,686, Beek an, issued March 25, 1975, (incorporated herein by reference) provides a useful summary of work in this area. The following publications relate to antiperspirant actives soluble in non-aqueous solvents and/or processes for making such actives: U.S. Patent 3,359,169, Slater et al., issued December 19, 1967; U.S. Patent 3,420,932, Jones et al., issued January 7, 1969; U.S. Patent 3,507,896, Jones et al., issued April 21, 1970; U.S. Patent 3,523,130, Jones et al., issued August 4, 1970; U.S. Patent 3,555,146, Jones et al., issued January 12, 1971; U.S. Patent 3,876,758, Beekman, issued April 8, 1975; Great Britain Patent Specifications 1,159,685 and 1,159,686, both published July 30, 1969, Armour Pharmaceutical Company; and European Published Patent Application, 7,191, published January 23, 1980, Unilever Limited.
U.S. Patent 2,890,987, Hilfer, issued June 16, 1959, describes the preparation of relatively dilute solutions of astringent aluminum compounds in propylene glycol having
relatively high water content. U.S. Patent 4,137,306, Rubino et al., issued January 30, 1979, describes anhydrous propylene glycol solutions of alcohol soluble astringent basic aluminum compounds. Any aluminum astringent antiperspirant salt or aluminum and/or zirconium astringent complex that is soluble, and which remains soluble in the present alcohol solvent can be used herein. Salts useful as astringent antiperspirant salts or as components of astringent complexes include aluminum halides, aluminum hydroxyhalides, zirconyl oxyhalides, zirconyl hydroxyhalides, and mixtures of these salt materials.
Aluminum salts of this type include aluminum chloride and the aluminum hydroxyhalides having the general formula Al2(0H)xQyXH20 where Q is chloride, bromide, or iodide (preferably chloride); x is from about 2 to about 5, and x + y = about 6, and x and y do not need to be integers; and where x is from about 1 to about 6. Aluminum salts of this type can be prepared in the manner described more fully in U.S. Patent 3,887,692, Gil an, issued June 3, 1975, and U.S. Patent 3,904,741, Jones and Rubino, issued September 9, 1975, incorporated herein by reference. The zirconium compounds which may be used in the present invention include both zirconium oxy salts and zirconium hydroxy salts, also referred to as the zirconyl salts and zirconyl hydroxy salts. These compounds may be represented by the following general empirical formula: Zr0(0H)2-nzBz wherein z may vary from about 0.9 to about 2 and need not be an integer; n is the valence of B; 2-nz is greater than or equal to 0; and B may be selected from the group consisting' of halides (preferably chloride), nitrate, sulfamate, sulfate, and mixtures thereof. Although only zirconium compounds are exemplified in this specification, it will be understood that other Group IVB metal compounds, including hafnium, could be used in the present invention.
As with the basic aluminum compounds, it will be understood that the above formula is greatly simplified and is intended to
represent and include compounds having coordinated and/or bound water in various quantities, as well as polymers, mixtures and complexes of the above. As will be seen from the above formula, the zirconium hydroxy salts actually represent a range of compounds having various amounts of the hydroxy group, varying from about 1.1 to only slightly greater than 0 groups per molecule.
Several types of antiperspirant complexes utilizing the above antiperspirant salts are known in the art. For example, U.S. Patent 3,792,068, Luedders et al., issued February 12, 1974, discloses complexes of aluminum, zirconium, and amino acids such as glycines. Complexes such as those disclosed in the Luedders et al . patent and other similar complexes are commonly known as ZAG. ZAG complexes are chemically analyzable for the presence of aluminum, zirconium, and chlorine. ZAG complexes useful herein are identified by the specification of both the molar ratio of aluminum to zirconium (hereinafter "Al:Zrπ ratio) and the molar ratio of total metal to chlorine (hereinafter "Metal :C1H ratio). ZAG complexes useful herein have an Al'Zr ratio of from about 1.67 to about 12.5 and a Metal :C1 ratio of from about 0.73 to about 1.93.
Preferred ZAG complexes are formed by (A) co-dissolving in water
(1) one part Al2(0H)6.mQ , wherein Q is an anion selected from the group consisting of chloride, bromide, and iodide; and m is from about 0.8 to about 2.0;
(2) x parts Zr0(0H)2.aQa-nH20, where q is chloride, bromide, or iodide; a is from about 1 to about 2; n is from about 1 to about 8; and x is from about 0.16 to about 1.2;
(3) p parts neutral amino acid selected from the group consisting of glycine, dl-tryptophane, dl-0-phenyl- alanine, dl-valine, dl-methionine, and 0-alanine, and where p is from about 0.06 to about 0.53; (B) codrying the resultant mixture to a friable solid; and
(C) reducing the resultant dried inorganic-organic antiper¬ spirant complex to a particulate form.
A preferred aluminum compound for preparation of such ZAG type complexes is aluminum chlorhydroxide of the empirical formula A12(0H)5C1 -2H20. Preferred zirconium compounds for preparation of such ZAG-type complexes are zirconyl hydroxychloride having the empirical formula Zr0(0H)Cl -3HZ0 and the zirconyl hydroxyhalides of the empirical formula Zr0(0H)2-aCl2-nH20 wherein a is from about 1.5 to about 1.87, and n is from about 1 to about 7. The preferred amino acid for preparing such ZAG-type complexes is glycine of the formula CH2(HN2)C00H. Salts of such amino acids can also be employed in the antiperspirant complexes. See U.S. Patent 4,017,599, Rubino, issued April 12, 1977, incorporated herein by reference. A wide variety of other types of antiperspirant complexes are also known in the art. For example, U.S. Patent 3,903,258, Siegal, issued September 2, 1975, discloses a zirconium aluminum complex prepared by reacting zirconyl chloride with aluminum hydroxide and aluminum chlorhydroxide. U.S. Patent 3,979,510, Rubino, issued September 7, 1976, discloses an antiperspirant complex formed from certain aluminum compounds, certain zirconium compounds, and certain complex aluminum buffers. U.S. Patent 3,981,896, issued September 21, 1976, discloses an antiperspirant complex prepared from an aluminum polyol compound, a zirconium compound and an organic buffer. U.S. Patent 3,970,748, Mecca, issued July 20, 1976, discloses an aluminum chlorhydroxy glycinate complex of the appropriate general formula [A12(0H)4C1][H2CNH2-
C00H]. All of these patents are incorporated by reference herein.
Of all of the above types of antiperspirant actives, preferred compounds include the 5/6 basic aluminum salts of the empirical formula A12(0H)5C1 •ΣHjO; mixtures of A1C13-6H20 and A12(0H)5C1 -2H20 with aluminum chloride to aluminum hydroxychloride weight ratios of up to about 0.5; ZAG type complexes wherein the zirconium salt is Zr0(0H)Cl -3H20, the aluminum salt is A12(0H)5C1- 2H20 or the aforementioned mixtures of A1C13-6H20 and A12(0H)5C1-
2H20 wherein the total metal to chloride molar ratio in the complex is less than about 1.25 and the Al:Zr molar ratio is about 3.3, and the amino acid is glycine; and the ZAG-type complexes wherein the zirconium salt is Zr0(0H)2-aCla*nH20 wherein a is from about 1.5 to about 1.87 and n is from about 1 to about 7, the aluminum salt is A12(0H)5C1 -2H20, and the amino acid is glycine.
The most preferred antiperspirant actives useful in the compositions of the present invention are antiperspirant actives with enhanced efficacy due to improved molecular distribution. Aluminum chlorhydroxide salts, zirconyl hydroxychloride salts, and mixtures thereof having improved molecular distributions are known, having been disclosed, for example, in the following documents, all incorporated by reference herein: U.S. Patent 4,359,456, Gosling et al . , issued November 16, 1982; European Published Patent Application 6,739, Unilever Ltd., published January 9, 1980; European Published Patent Application, 183,171, Armour Pharmaceutical Company, published June 4, 1986; British Patent Specification 2,048,229, The Gillette Company, published December 10, 1980; European Published Patent Application 191,628, Unilever PLC, published August 20, 1986; and British Patent Specification 2,144,992, The Gillette Company, published March 20, 1985.
The improved molecular distribution is determined by the known analysis method called gel permeation chromatography. This analysis method is described, for example, in several of the above-incorporated patent specifications as well as in European Published Patent Application 7,191, Unilever Ltd., published January 23, 1980, the disclosures of which are incorporated herein. It is preferred for purposes of the present invention that the antiperspirant actives utilized have enhanced efficacy due to improved molecular distribution with a ratio of peak 4 to peak 3 greater than about 0.1:1 as determined by gel permeation chromatography. This ratio, as is recognized by one skilled in the art, relates to the relative area under those two peaks as measured by the gel permeation chromatography analysis method.
Highly desirable antiperspirant salts for use herein are selected from the group consisting of aluminum sesquichloro¬ hydrate, aluminum sesquichlorohydrex PEG (a coordination complex of aluminum sesquichlorohydrate and PEG-4, in which some of the water molecules normally coordinated to the metal have been displaced by the PEG-4), aluminum sesquichlorohydrex PG (a coordination complex of aluminum sesquichlorohydrate and propylene glycol in which some of the water molecules normally coordinated to the metal have been displaced by the propylene glycol), alumi- num chlorohydrex, in the form of aluminum chlorohydrex PEG (a coordination complex of aluminum chlorohydrate and PEG-4 in which some of the water molecules normally coordinated to the metal have been displaced by the PEG-4), and most preferably aluminum chloro¬ hydrex PG, sold under the names Rehydrol II® or Activated Rehydrol II*, by Reheis Chemical Company (coordination complex of aluminum chlorohydrate and propylene glycol in which some of the water molecules normally coordinated to the metal have been displaced by propylene glycol so that about 25% of the complex comprises propylene glycol). Mixtures of these antiperspirant materials may also be utilized. The coordination complex antiperspirant mate¬ rials tend to have a higher pH, and are therefore less irritating to skin.
All of these materials are particularly safe for use in spray-on compositions. The most preferred antiperspirant salts for use herein are aluminum sesquichlorohydrate and Rehydrol II® or Activated Rehydrol II®.
U.S. Patent 4,053,581, Pader et al., issued October 11, 1977 U.S. Patent 4,065,564, Miles Jr. et al., issued December 27, 1977 and U.S. Patent 4,073,880, Pader et al., issued February 14, 1978 all disclose formulations for pump-spray or roll-on antiperspir- ants comprising alcohol-soluble aluminum chlorohydroxide antiper¬ spirant complexes, an alcohol vehicle, and volatile and/or non¬ volatile silicone materials.
The antiperspirant salt is present in the liquid antiper- spirant compositions of the present invention at a level of from
about 10% to about 25%. If an aluminum sesquichlorohydrate antiperspirant salt is used in the present compositions, it is preferably present at from about 14% to about 16%. This weight percentage is calculated on an anhydrous metal salt basis (ex- elusive of co plexing agents). If one of the Rehydrol* anti¬ perspirant salts is used in the present compositions, it is preferably present at from about 18% to about 24% of the compo¬ sition. This higher level of material is necessary since this antiperspirant material contains not only the antiperspirant active but a complexing agent (propylene glycol) as well. Solvent for the Antiperspirant Salt
The antiperspirant salts of the present invention are solu- bilized in a solvent. Suitable solvents include monohydric alcohols, especially C2-C monohydric alcohols. The preferred solvent for use herein is ethanol. A small amount of water is also necessary in the present compositions to solubilize the antiperspirant material. The present compositions will comprise from about 2% to about 10% of water.
The solvent is present in the compositions of the present invention at a level at least sufficient- to solubilize the antiperspirant salt. It is desirable to keep the level of monohydric alcohol solvent in the present compositions as low as possible to allow for the incorporation of as much emollient materials as possible. This results in a product with improved in-use characteristics. Generally, the alcohol solvent is present in the compositions at a level of from about 45% to about 65%, preferably from about 45% to about 60%, more preferably from about 45% to about 55%. Emollients The present antiperspirant composition also comprise non¬ volatile emollient esters, and optionally, propylene glycol ethers of C -C22 fatty alcohols, C12-C20 branched chain alcohols, and volatile silicone emollients. It is these components that are primarily responsible for the desirable product aesthetics and in-use characteristics of the present compositions. For example, these components provide the smooth, clean, dry, non-sticky feel
upon application to the skin. The non-volatile emollient mate¬ rials are also responsible for lessening the amount of residue on skin after dry down. These emollient components are present in the antiperspirant compositions at maximized levels to provide these benefits.
Part of the emollient material of the present compositions comprises a non-volatile emollient ester. This material may comprise C2-C20 alcohol esters of benzoic acid, e.g., C12-C15 alcohol benzoates; esters, diesters, or tetraesters of C2-C20 alcohols and C6-C16 fatty acids (e.g. diisopropyl sebacate, diisopropyl adipate, lauryl lactate, ethyl myristate, isopropyl yristate, myristyl myristate, and pentaerythrityl tetrapelargo- nate); and mixtures thereof. The preferred of these non-volatile emollient materials are ethyl myristate, isopropyl myristate, C12-C15 alcohols benzoate, and mixtures thereof.
In order to maintain the clear stable solution of the present antiperspirant compositions, the non-volatile emollient ester must be of a certain polarity, i.e., it must have a solubility parameter (units equal (cal/cm3)1/2) in the range of from about 7 to about 10.
The solubility parameter is defined in the Polymer Handbook 3rd Ed. (John Wiley and Sons, New York), J. Brandrup and E.H. I mergut, Chapter VII, PP. 519-559, as the square root of the cohesive energy density and describes the attractive strength between molecules of the material. Solubility parameters may be determined by measurement, correlations with other physical properties, or indirect measurement. The solubility parameters for the present emollient materials were determined by surface tension measurement as outlined in Vaughan, CD., J. Soc. Cosmet . Chem. , 36, 319-333, 1985.
Generally, these compositions comprise from about 0.5% to about 20% of the non-volatile emollient ester materials.
The antiperspirant compositions of the present invention also preferably comprises volatile silicone emollient materials. These materials have solubility parameters of from about 5.5 to about 8.
Various types of silicone materials have been disclosed for use in various forms of antiperspirant compositions. For example, U.S. Patent 4,784,844, Thimineur et al., issued November 15, 1988; U.S. Patent 4,499,069, Krafton, issued February 12, 1985; U.S. Patent 4,268,499, Keil, issued May 19, 1981; U.S. Patent 4,264,586, Callingham et al., issued April 28, 1981; U.S. Patent 4,053,581, Pader et al., issued October 11, 1977; U.S. Patent 4,065,564, Miles, Jr. et al . , issued December 27, 1977; U.S. Patent 4,073,880, Pader et al., issued February 14, 1978; U.S. Patent 4,673,570, Soldati, issued June 16, 1987; U.S. Patent 4,559,226, Fogel , issued December 17, 1985; U.S. Patent 4,435,382, Shin et al., issued March 6, 1984; European Patent Office Application 343,843, published November 29, 1989; Great Britain Patent Application 1,536,222, published December 20, 1978; Great Britain Patent Application 2,018,590, published October 24, 1979; and Japanese Published Patent Application 59-152,318, published August 31, 1984.
The volatile silicone emollient materials of the present compositions generally have a viscosity of from about 0.65 centistokes to about 10 centistokes. Certain volatile silicone materials, such as cyclic polydimethylsiloxanes containing from about 3 to about 7 silicon atoms are useful herein. A description of volatile silicones is found in Todd and Byers, 'Volatile Silicone Fluids for Cosmetics", Cosmetics and Toi letries, 91:27-32 (1976), incorporated herein by reference. Other volatile silicones useful herein are taught in U.S. Patent 4,874,868, Bolich, Jr., issued October 17, 1989, incorporated by reference herein. A volatile silicone that may be used in the present compositions, which is covered in that patent, is phenethyl pentamethyl disiloxane.
The present compositions comprise up to about 20% of such volatile silicone emollient materials. The preferred volatile silicone emollient materials of the present invention are D4-D5 cyclomethicones, phenethyl penta methyl disiloxane, dimethicone fluids having viscosities of less than about 1 centistoke, and mixtures thereof.
The compositions also may comprise C12-C20 branched chain alcohols as preferred emollients hereof, and mixtures thereof. These C12-C20 branched chain alcohols must be liquid at room temperature, and are preferably liquid at 0*C, and should have solubility parameters of from about 7 to about 10, and viscosities of from about 15 to about 50 centistokes at 25*C. The preferred alcohol is the C16 branched chain alcohol, isocetyl alcohol ; Other C12-C20 branched chain alcohols include isododecanol, isostearyl alcohol, etc. The degree of branching can vary widely, so long as the above viscosity and solubility parameters are met. The branched chain alcohol component hereof can be conveniently made by condensation of straight chain alcohols in alkaline medium according to the reaction referred to in the art as the Guerbet isomerization reaction (alternately, Guerbet condensation) the branched chain alcohols in the reaction product thereof being referred to as Guerbet reaction branched alcohols. This reaction which will typically produce a mixture of branched chain isomer alcohols in the reaction product is well known in the art and is described by Edman and Lowden, in Drug Cos et. Ind. , Vol. 93, p 631, Nov. 1963, by Pruett, Young, Duncan, and Mozeleski in European Patent Application 88-306359, July 12, 1988, and by Veibel and Nielsen in "Mechanism of the Guerbet Reaction", Tetra¬ hedron, 23 (4), pp 1723-33. Suitable C12-C20 branched chain alcohols, including isocetyl alcohol, are also widely commercially available, e.g., Henkel, Inc. (Teaneck, NJ).
The compositions of the present invention also comprise up to about 15%, preferably from about 3% to about 8%, more preferably from about 3% to about 6%, of polypropylene glycol ("PPG") ethers of C -C22 (preferably C10-C20) fatty alcohols as emollients. Examples of such materials include PPG-2 myristyl ether, PPG-4 lauryl ether, PPG-10 cetyl ether, PPG-3 myristyl ether, PPG- 1 stearyl ether, PPG-15 stearyl ether and mixtures thereof. Addi¬ tional examples are found in CTFA Cosmetic Ingredient Di ctionary, Third Edition (Extrin et al., Editors; The Cosmetic, Toiletry and Fragrance Association, Inc., 1982), pages 252-260 and 494-500, the
disclosures of which are incorporated by reference herein. The preferred of such emollients for use in the present compositions is PPG-3 myristyl ether. Buffer The compositions of the present invention may also comprise a pH buffer to raise the low pH inherent in antiperspirant composi¬ tions. Such a buffer may comprise urea or the buffering agents described in U.S. Patent 4,154,816, Roehl et al., issed May 15, 1975; U.S. Patent 4,346,079, Roehl et al., issued August 24, 1982; and U.S. 4,518,582, Schamper et al., issued May 21, 1985, e.g., diethanolamine, triethanola ine, glycine, and ditallowmethyla ine, all of which are incorporated herein be reference.
The buffer, if used in the present compositions, is present at up to about 3%, preferably from about 2% to about 3%. The preferred buffer for use herein is urea. Detackifier
The present compositions may also comprise a detackifying agent to further improve the cosmetic in-use benefits of the present compositions. The detackifier may comprise a mixture of a dimethicone copolyol in a suitable volatile solvent therefor. Useful solvent materials comprise the volatile silicone materials described supra. A preferred material that can be used for this purpose in the present compositions is a material sold under the trade name Q2-3225C Formulation Aid® by Dow Corning. It comprises a mixture of D4 cylcomethicone and dimethicone copolyol (polymer of dimethyl siloxane with polyoxyethylene and/or polyoxypropylene side chains) at a ratio of about 88:12. If this material is included in the compositions of the present invention it is at a level of up to about 4%, preferably from about 2% to about 4%. Other preferred materials that can be included and which can be used as detackifiers include non-volatile dimethicone fluids, preferably with viscosities less than about 20 centistokes and also preferably at least about 2 centistokes, more preferably from about 2 to about 10 centistokes, most preferably from about 5 to about 10 centistokes. Mixtures of such fluids can be used.
Non-volatile dimethicone will preferably be present in the compo¬ sitions hereof at a level of from 0% to about 2% by weight. Typically, when utilized as a detackifier, the compositions will comprise from about 0.1% to about 2%, preferably from about 0.25% to about 1% of the non-volatile dimethicone. Optional components
The compositions of the present composition may also comprise a number of optional components to provide cosmetic or aesthetic benefits. For example, preservatives, deodorant actives, such as anti-microbials or bactericides, perfumes, coloring agents and dyes may be used.
These optional components must be chosen so as not to interfere with the antiperspirant efficacy and the composition stability. These optional components are generally present in the compositions of the present invention at a level of from about 0.01% to about 10%. Products
The present compositions are preferably in the form of a low-viscosity non-aerosol pump spray. However, the present invention is applicable to other liquid antiperspirant product types, such as aerosol or roll-on product types. Products formulated as aerosols will also comprise a propel1ant material. Any of the commonly used propel!ants in the antiperspirancy art are suitable. Products formulated as roll-ons will also comprise a thickening agent to raise the viscosity of the composition. Suitable thickening agents include carboxymethyl cellulose, clay thickeners, colloidal silica, and Microthene® beads, manufactured by U.S.I. Chemicals, having a mean particle diameter of less than about 20 microns. Methods of Manufacture
The antiperspirant compositions of the present invention may be manufactured using methods known in the art. In making the compositions, the antiperspirant salt is first solubilized in the monohydric alcohol solvent, and a small amount of water (no more than 5% water, by weight of the antiperspirant composition) to
form a clear solution. The remaining components are then added to the composition using conventional formulation methods. Method for Preventing Perspiration and Malodor
The present invention also provides methods for treating or preventing perspiration and malodor associated with human underarm perspiration. These methods comprise applying a safe and effec¬ tive amount of the liquid antiperspirant compositions of the present invention to the skin in the axillary area of a human. The term a "safe and effective amount" as used herein, is an amount which is effective in eliminating or substantially reducing the production of perspiration which ultimately generates the malodors detected through formation of pungent fatty acids, while being safe for human use at a reasonable risk/benefit ratio.
The liquid antiperspirant compositions of the present invention provide excellent cosmetic attributes both on application and throughout use. They are non-sticky, non-greasy, and quick drying. In addition, the present compositions leave no white, chalky residue on skin upon dry down.
The following examples illustrate the present invention. It will be appreciated that other modifications of the present invention within the skill of those in the antiperspirant formu¬ lation art can be undertaken without departing from the spirit and scope of this invention.
All parts, percentages, and ratios herein are by weight unless otherwise specified.
Example I The following is a clear, liquid, spray-on antiperspirant composition representative of the present invention. Component Weight % Rehydrol II® Antiperspirant Active1 20.0
Isopropyl Myristate 9.0
C12-C15 Alcohols Benzoate2 9.0
D4 Cyclomethicone 9.5
Water 2.5 Ethanol 50.0
Perfume 0.8
1 Aluminum chlorohydrate and propylene glycol coordination complex available from Reheis Chemical Company
2 Available under the trade name Finsolv TN® from Finetex, Inc.
The composition is prepared as follows. The antiperspirant active is first premixed with at least half of the ethanol. The main mix is then prepared by adding to the premix the remaining ethanol, the isopropyl myristate, the C12-C15 alcohols benzoate, the D4 cyclomethicone, and the perfume.
The resulting antiperspirant composition provides excellent antiperspirancy efficacy with good product aesthetics and in-use characteristics. The composition also remains stable over time and broad ranges of physical conditions, especially ambient temperatures.
Example II The following is a clear liquid spray-on antiperspirant composition representative of the present invention. Component Weight % Rehydrol II® Antiperspirant Active1 20.0
C12-C15 Alcohols Benzoate2 13.75
D4 Cyclomethicone 13.75
Water 2.5
Ethanol 50.0 Perfume 0.8
1 Aluminum chlorohydrate and propylene glycol coordination complex available from Reheis Chemical Company
2 Available under the trade name Finsolv TN® from Finetex, Inc. The composition is prepared as follows. The antiperspirant active is first premixed with at least half of the ethanol. The main mix is then prepared by adding to the premix the remaining ethanol, the C12-C15 alcohols benzoate, the D4 cyclomethicone, and the perfume.
The resulting antiperspirant composition provides excellent antiperspirancy efficacy with good product aesthetics and in-use characteristics. The composition also remains stable over time and broad ranges of physical conditions, especially ambient temperatures.
Example HI The following is a clear liquid spray-on antiperspirant composition representative of the present invention. Component Weight % Aluminum Sesquichlorohydrate 15.0
SD Alcohol 40 60.0
DR0 Water 9.7
CX2-C15 Alcohols Benzoate1 4.0
3225 Formulation Aid2 3.0 Urea 2.5
PPG-3 Myristyl Ether 5.0
Perfume 0.8
1 Available under the trade name Finsolv TN® from Finetex, Inc. 2 A mixture of D4 cyclomethicone and dimethicone copolyol (88:12 ratio) available from Dow Corning This composition is prepared as follows. An aluminum sesquichlorohydrate (ASQCH) premix is prepared by combining the ASQCH, at least half of the ethanol and water. The main mix is then prepared by adding to the ASQCH premix the remaining ethanol, the C12-C15 alcohols benzoate, the 3225 formulation aid, the urea, the PPG-3 myristyl ether, and the perfume.
The resulting antiperspirant composition provides excellent antiperspirancy efficacy with good product aesthetics and in-use characteristics. The composition also remains stable over time and broad ranges of physical conditions, especially ambient temperatures.
Example IV The following is a liquid antiperspirant composition representative of the present invention.
Component
Aluminum Sesquichlorohydrate SD Alcohol 40 DR0 Water C12-C15 Alcohols Benzoate1 3225 Formulation Aid2 Urea
PPG-3 Myristyl Ether Perfume
-1 Available under the trade name Finsolv TN® from Finetex, Inc. 2 A mixture of D4 cyclomethicone and dimethicone copolyol
(88:12 ratio) available from Dow Corning This composition is prepared as follows. An aluminum sesquichlorohydrate (ASQCH) premix is prepared by combining the ASQCH, at least half of the ethanol and water. The main mix is then prepared by adding to the ASQCH premix the remaining ethanol, the C12-C15 alcohols benzoate, the 3225 formulation aid, the urea, the PPG-3 myristyl ether, and the perfume. The resulting antiperspirant composition provides excellent antiperspirancy efficacy with good product aesthetics and in-use characteristics. The composition also remains stable over time and broad ranges of physical conditions, especially ambient temperatures. Example V
The following is a liquid antiperspirant composition representative of the present invention. Component Weight %
Aluminum Sesquichlorohydrate 15.0 SD Alcohol 40 60.0
DR0 Water 3.0
Isopropyl Myristate 10.7
D4 Cyclomethicone 8.0
Urea 2.5 Perfume 0.8
This composition is prepared as follows. An aluminum sesquichlorohydrate (ASQCH) premix is prepared by combining the ASQCH, at least half of the ethanol and water. The main mix is then prepared by adding to the ASQCH premix the remaining ethanol, isopropyl myristate, the D4 cyclomethicone, the urea, and the perfume.
The resulting antiperspirant composition provides excellent
>~ antiperspirancy efficacy with good product aesthetics and in-use characteristics. The composition also remains stable over time and broad ranges of physical conditions, especially ambient temperatures.
Example VI The following is a liquid antiperspirant composition representative of the present invention. Component Weight %
Aluminum Sesquichlorohydrate 15.0
SD Alcohol 40 60.0
DR0 Water 3.0
C12-C15 Alcohols Benzoate1 6.7 D4 Cyclomethicone 8.0
Urea 2.5
PPG-3 Myristyl Ether 4.0
Perfume 0.8
1 Available under the trade name Finsolv TN® from Finetex, Inc.
This composition is prepared as follows. An aluminum sesquichlorohydrate (ASQCH) premix is prepared by combining the ASQCH, at least half of the ethanol and water. The main mix is then prepared by adding to the ASQCH premix the remaining ethanol, the C12-C15 alcohols benzoate, the D4 cyclomethicone, the urea, the PPG-3 myristyl ether, and the perfume.
The resulting antiperspirant composition provides excellent antiperspirancy efficacy with good product aesthetics and in-use characteristics. The composition also remains stable over time
and broad ranges of physical conditions, especially ambient temperatures.
Example VII The following is a liquid antiperspirant composition representative of the present invention.
Component Weight %
Aluminum Sesquichlorohydrate 15.0
SD Alcohol 40 60.0
DR0 Water 9.2 C12-C15 Alcohols Benzoate1 7.0
Urea 2.5
PPG-3 Myristyl Ether 5.5
Perfume 0.8
1 Available under the trade name Finsolv TN® from Finetex, Inc.
This composition is prepared as follows. An aluminum sesquichlorohydrate (ASQCH) premix is prepared by combining the ASQCH, at least half of the ethanol and water. The main mix is then prepared by adding to the ASQCH premix the remaining ethanol, the C12-C15 alcohols benzoate, the urea, the PPG-3 myristyl ether, and the perfume.
The resulting antiperspirant composition provides excellent antiperspirancy efficacy with good product aesthetics and in-use characteristics. The composition also remains stable over time and broad ranges of physical conditions, especially ambient temperatures.
Example VIII The following is a liquid antiperspirant composition representative of the present invention. Component Weight %
Aluminum Sesquichlorohydrate 15.0
SD Alcohol 40 60.0
DR0 Water 2.5
Isopropyl Myristate 9.2 D4 Cyclomethicone 4.0
PPG-3 Myristyl Ether 8.5
Perfume 0.8
This composition is prepared as follows. An aluminum sesquichlorohydrate (ASQCH) premix is prepared by combining the ASQCH, at least half of the ethanol and water. The main mix is then prepared by adding to the ASQCH premix the remaining ethanol, the isopropyl myristate, the D4 cyclomethicone, the PPG-3 myristyl ether, and the perfume.
The resulting antiperspirant composition provides excellent antiperspirancy efficacy with good product aesthetics and in-use characteristics. The composition also remains stable over time and broad ranges of physical conditions, especially ambient temperatures.
Example IX The following is a liquid antiperspirant composition representative of the present invention. Component Weight %
Aluminum Sesquichlorohydrate 15.0
SD Alcohol 40 50.0 D4 Cyclomethicone ~ 13.8
PPG-3 Myristyl Ether 12.0
Isocetyl Alcohol 4.0
Water 2.6
Ethyl Myristate 1.0 Dimethicone fluid (5 centistoke) 0.5
Perfume 1.0
This composition is prepared as follows. An aluminum sesquichlorohydrate (ASQCH) premix is prepared by combining the ASQCH, at lease half of the ethanol and water. The main mix is then prepared by adding to the ASQCH premix the remaining ethanol, the D4 cyclomethicone, the PPG-3 myristyl ether, the isocetyl alcohol, the ethyl myristate, the non-volatile dimethicone fluid, and the perfume.
The resulting antiperspirant composition has relatively low ethanol content and provides excellent antiperspirant efficacy
with good product aesthetics and in-use characteristics without the need for the incorporation of a pH buffer. The composition also remains stable over time and broad ranges of physical conditions, especially temperature. WHAT IS CLAIMED IS: