CA2135386C - Antiperspirant gel stick composition - Google Patents

Antiperspirant gel stick composition

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Publication number
CA2135386C
CA2135386C CA002135386A CA2135386A CA2135386C CA 2135386 C CA2135386 C CA 2135386C CA 002135386 A CA002135386 A CA 002135386A CA 2135386 A CA2135386 A CA 2135386A CA 2135386 C CA2135386 C CA 2135386C
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Prior art keywords
composition according
gel stick
antiperspirant
stick composition
antiperspirant gel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
CA002135386A
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French (fr)
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CA2135386A1 (en
Inventor
Brian D. Hofrichter
John M. Gardlik
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Procter and Gamble Co
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Procter and Gamble Co
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Publication of CA2135386A1 publication Critical patent/CA2135386A1/en
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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q15/00Anti-perspirants or body deodorants
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0216Solid or semisolid forms
    • A61K8/0229Sticks
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/042Gels
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S424/00Drug, bio-affecting and body treating compositions
    • Y10S424/05Stick

Abstract

The present invention discloses antiperspirant gel stick compositions made from a n-acyl amino acid amides, a liquid base material, and an antiperspirant active. The above combination provides gel stick antiperspirant compositions having excellent efficacy, stability, low residue, low skin irritation and aesthetic advantages over compositions disclosed in the art. These compositions are easily prepared by conventional techniques.

Description

21 353~6 AN~IPERSPIRAN~ GEL STICK CO~POSI~ION

FIELD OF T~E INVENTION
The presen~ invention are antiperspirant ~el stick compositions to prevent perspiration and body odors having superior stab;lity, low residue on the skin, low skin irritation, and excellent aesthetic characteristics. Furthermore, these compositions can be easily prepared by conventional techniques.
BACKGROUN~ OF TH' INVFNTION
Personal hygienic habtts typically include a means for reducing of human body odors. These habits include routine bathing or washing the body, particularly the axilla, and treating said areas w~th a compositions to retard odor formation. Among such compos~tions are deodorants and antiperspirants.
Deodorants are generally regarded as odor masking compositions which inhlbit odors by retarding the growth of bacteria. Absent ~acteria, the sweat produced by the body is not subjected to breakdown to odoriferous fatty acids. Antiperspirants also prevent formation of odoriferous fatty acids by retarding the growth of bacteria. However, unlike deodorants, antiperspirants prevent the formation of sweat which could be attacked by bacteria.
Antiperspirants are well known in the art, and typically comprise an astringent material in a suitable carrier. Astringent materials typically used in antiperspirants are metal salts, particularly aluminum and zinc metal complexes. Said metal salts is disclosed in Plechner, AntiPersDirants and Deodorants, 2 Cosmetics, Science and Technology, Balsam and Sagarin, 374-4G0, 1972.
In addition to these above disclosure, Plechner also discloses that antiperspirants can take a number of different forms~ eacn dependent on the ingredients used in addition to the above mentioned astrinaent metallic salts. The forms disclosed tnerelr include liquids. solids, and semi-solids. ExamDles of tnese rorm;

~ .

include lotions. solid sticks, and creams; the most popular Deing solid sticks.
Antiperspirant sticks are well known in the art. For example antiperspirant sticks are disclosed in U.S. Patent 2.890.g87.
S Hilfer, issued June 16, 195Q; and U.S. Patent 3,25~,082, Barton et al, issued June 7, lg66.
There are three main types of such stick formulations. These are compressed powder sticks, gel sticks , and wax sticks. While each may have advantages in certain use situations, each also has disadvantages.
Antiperspirant compressed powder sticks mainly comprise powdery materials such as talc, powdered antiperspirant actives, and a binder which allows the stick to be formed using compressive forces. Although these sticks are generally stable, application to the skin is difficult since they are brittle and hard.
Furthermore, since they are white, and opaque, they leave a cosmetically undesirable dusty residue after application.
Wax sticks are disclosed in U.S. Patents 4,822,603, Farris et al, issued April 18, 1989; 4,919,934, Deckner, issued April 24, 1990; and 4,944,937, McCall, issued July 31.1990 - Wax sticks comprise liquid materials generally selected based on the desired physical properties thev impart to the stick. Generally these liquid materials include silicones, hydrocarbon oils, esters, propoxylated and/or ethoxylated alcohols, and mixtures thereof. In addition to the liquid material, solidifying agents are added to impart stable physical structure to the stick. Typical solidifyin~ agents used in wax sticks include fatty alcohols. fatty acids, fatty esters.
triglycerides, and waxes having melting points from about 65~C to about 110~C. These waxes and fatty materials, however. can - Dromote cosmetically unacceptable products due to such factor such as hardness, greasiness, stickiness, and difficul;
application. Furthermore. the crystalline nature of these wa~
rormulations contributes to ooacity and Produces an undeslrablL
resiaue durinq use.

B

Gel sticks are also well known in the art. These sticks contain a liquid material and solidifying agents. The liquid materials typically are water, lower monohydric alcohols, polyhydric alcohols, and mixtures thereof. The solidifying agents most often used include fatty acid soaps, and dibenzylidine monosorbitol acetals (hereinafter OBS). See the following patents for soap gels: U.S. Pat. 2,900,306, Slater, issued Aug. 18. 1959;
U.S. Pat. 3,255,082, Barton, issued June 7, 1966; U.S. Pat.
4,1~7,306, Rubino, Issued Jan. 30, 1979; U.S. Pat. 4,226,889, Yuhas, issued Oct. 7, 1980; U.S. Pat. 4,944,937, McCall, issued July 31, 1990. - See the following patents for DBS gels: U.S. Patents 4,154,816, Roehl et al, issued May 15, 1979; 4,371,645, Mahaffey, issued Feb.
1, 1983; 4,518,582, Schamper et al, issued May 21, 1985;
4,719,102, Randhawa et al, issued Jan. 12, 1988; 4,722,835, Schamper et al, issued Feb. 2, 1988; and 4,725,430, Schamper et al, issued Feb. 16, 1988; 4,781,917, Luebbe et al, November 1, 1988; 4,816,261, Luebbe et al, March 28, 1989; 4,822,602, Sabetelli, issued April 18, 1989.
DBS gel sticks are generally regarded as more stable;
see Japanese Application 64-62377, Kao, published March 8, 1989, which discloses that certain monosorbitol acetals, particularly fluroinated DBS have good stability than other antiperspirant stick gelling agents known in the art. U.S. Patent 4,429,140, Murai et al, issued Jan. 31, 1984, and European Patent Application 0286522, Salome et al, published January 123, 1988, disclose methods for making fluorinated DBS. U.S. Patent 5,106,999, Gardlik et al, issued April 21, 1992, ~ - discloses methods for preparing DBS compounds, particularly meta-substituted halogenated derivatives. The product of the claimed process are- purer and have superior gelling properties in antiperspirant stick compositions.
Gel sticks avoid the use of waxy solidifying agents and, therefore, don't suffer from the aesthetic disadvantages PCTi'~,~93/a3887 ~.
associated with wax sticks such as difficult application and high residue. Antiperspirant gel sticks made using soaps however do experience problems associated ~ith interaction between the basic soap solidif~ing agents and the acidic antiperspirant actives.
~his interaction can result in poor gel formation reduced efficacy of the actives and lower stability over time of any gel formed. The interaction may also cause processing difficulties at high temperatures and extended holding times typically encountered during manufacturing. Even the gel sticks made using DBS instead of a basic soap are subject to instability since the acetal portion of the OBS is relatively unstable. In fact improving the stability of OBS gels has been the object of many patents; see above DBS patents. In addition to the stability issue DBS must be dissolved in a polar solvent. Polar solvents can contribute to undesirable stick characteristics such as wet cold and sticky feel on the skin shrinkage and containment problems due to high volatility and skin irritation.
~he art contains other clear stick compositions that avoid using conventional gellants such as soap or DBS to cure the poor stability created by the interaction of such gellants and conventional antiperspirant actives. European Patent Application (EPO) O U 8 278 published September 29 1991, to Colgate-Palmolive discloses antiperspirant gel sticks comprising an aqueous aluminum active complexing agent and hardening agent.
EPO O 373 499 published June 20 1988 to Colgate-Palmolive discloses clear antiperspirant stick compositions comprising an aluminum salt active water insoluble volatile emollients volatile siloxanes water soluble emollients. coupling agents and a solublizer. EPO O 396 137 published Hovember 7 1990 to Gillette discloses clear anhydrous antiperspirant compositions comprising an anhydrous vehicle such that no significant dissolution of the active antiperspirant in the vehicle.
Furthermore the refractive indicies of the active antiperspirant component and the vehicle are matched. U.S. Patent 4 948 578 Burger et al issued August 14 1990 discloses antiperspirant r~Ji ~

CA 0213~386 1998-04-06 -~-~ 93/~30~ PCT/~'S93/038g, sticks comprising an antiperspirant active, nonionic surfactant, oil, and water. The surfactants are at levels from about 10-40%, and the active no greater that 20%.
While these references disclose sticks which avoid the above mentioned problems associated with soap and DBS sticks, they do have some negatives. For example, using the disclosed reactive materials and surfactants disclosed above typically reduces the effectiveness of the antiperspirant compositions. Additionally, some of the disclosed compositions require processes steps which involve mixing several viscous phases at specific times, and at specific temperatures. Furthermore, the gels formed from the disclosed polymers and emulsions do not maintain the desirable aesthetics of the typical soap or DBS gel sticks disclosed above.
Gels of non-polar liquids and n-acyl amino acids and derivatives thereof used as gelling agents is disclosed in U.S.
Pat. 3,969,087, issued July 13, 1976 .
This patent discloses gelling non-polar materials such as fuels, motor oils, paints, edible oils, and cosmetics.
Cosmetic stick compositions utilizing n-acyl amino acids as gelling agents is disclosed in Japanese Patent Application 1-207223, published August 21, 1989, (hereinafter'223), and Japanese Patent Application 2-180805, published July 13, 1988 (hereinafter '805). In '223, the n-acylamino acid amide is combined with a starch fatty acid ester to form a cosmetic gel compositions. The n-acylamino acid amide must be highly soluble in certain oils which are typically used in the cosmetic arts. In '805, the cosmetic gel compositions disclosed therein have improved transparency. The gel comprises methylphenyl polysiloxanes and n-lauroyl-L-glutamic acid dibutylamide. Gels absent the methylphenyl polysiloxanes have poor transparency as compared with those claimed therein. None of the above Japanese references teach using the presently disclosed gel compositions to overcome the stability problems noted above since the cosmetic gel compositions taught therein do not contain antiperspirant actives.

SUB~ 111 ~JTE SHEEr 3~C~887 It is, therefore, the object of the present invention to provide antiperspirants gel sticks having excellent efficacy, and reduced residue on the skin, which are stable. It is also the object of the present invention to provide antiperspirant gel S sticks which can be made by conventional techniques known in the art. Lastly, the object of the present invention is to provide antiperspirant sticks having excellent aesthetics and minimal skin irritation.
SUMMARY OF THE INVENTION
The present invention are antiperspirant gel stick compositions comprising:
a. a gelling agent;
b. a liquid base material; and c. an antiperspirant active.
wherein the gelling agent is selected from the group consisting of n-acyl amino acid amides, and mixtures of n-acyl amino acid amides and 12-hydroxystearic acid.
~hese antiperspirant gel sticks have superior stability, low residue on the skin, low skin irritation, and excellent aesthetic characteristics. Furthermore, these compositions can be easily prepared by conventional techniques known in the art.
DETAILED DESCRIPTION OF THE INVENTION
The present invention comprises the ingredients disclosed below.
A. Gelling Agents:
The gelling agents of the present invention are n-acyl amino acid amides, or mixtures of n-acyl amino acid amides and 12-hydroxystearic acid. The level of the gelling agent is from about 1% to about 15%, preferably from 3% to about 12X, most preferably from about SX to about 10% total weight of the gel composition. ~hen the mixture of a n-acyl amino acid amide and 12-hydroxystearic acid is the gelling agent, the ratio of n-acyl amino acid amide to 12-hydroxystearic acid is from 1:20 to about
2:1, preferably from about 1:10 to about 1:1, and most preferably A~EN~E~ SHEET

from about 1:5 to about 1:2, wherein the level of n-acyl amino acid amide is at least about O.lZ total weight of the gel composition.
N-acyl amino acid amides are disclosed in U.S. Pat. 3,969,087, Saito et al, issued July 13, 1976.
The preferred n-acyl amino acid amides are prepared from glutamic acid, lysine, glutamine, aspartic acid and mixtures thereof. Particularly preferred are n-acyl glutamic acid amides corresponding to the following formula:
O O
R2-N-~-CH2-CH2-CH-C-N-R2 H NH H
C=O
Rl wherein Rl is an aliphatic hydrocarbon radical having from about 12 to about 22 carbon atoms, and R2 is an aliphatic hydrocarbon radical having from about 4 to about 12 carbon atoms.
Non-limiting examples of these include n-lauroyl-L-glutamic acid dibutyl amide, n-stearoyl-L-glutamic acid diheptyl amide, and mixtures thereof. Most preferred is n-lauroyl-L-glutamic acid dibutyl amide.
Although the presently disclosed antiperspirant gel sticks can be made solely with the n-acyl amino acid amide as the gelling agent, it has been found that incorporating 12-hydroxystearic acid into the gelling agent is advantageous. When 12-hydroxystearic acid is used in combination with the n-acyl amino acid amide, the level of said gellant can be reduced while maintaining desirable stick characteristics such as hardness, low residue, and easy application qualities. Furthermore, the 12-hydroxystearic acid is suprisingly an excellent solvent for the n-acyl amino acid amide.
~herefore, the processing temperatures used to make the gel stick can be reduced. Lower processing temperatures reduces the
3~ tendency of the antiperspirant active and the perfumes used ~:~

e i 3 ~ ~ 3 therein to degrade during processing. Also the lower processing temperatures improves the compatibility of the above components with other gel stick components having lower boiling points, and packaging materials used to contain the stick.
The 12-hydroxystearic acid useful in the present invention is known in the art. Japanese Patent Application 2-180805, cited supra, and Japanese Patent Application 2-264707, published October 31, 1990, disclose using 12-hydroxystearic acid in making cosmetic gel compositions. In fact, 2-180805 discloses cosmetic gel compositions comprising phenylmethylsiloxanes and n-lauroyl-L-glutamic acid dibutyl amide in an amount necessary to achieve transparency and a gel consistency to facilitate easy spreading of the gel over the skin's surface.
B. Liquid Base Material The base matrix of gel stick compositions of the present invention is formed by combining the above gelling agent with the liquid base material. As used herein, the term liquid is defined as materials which are liquids at ambient conditions. It is important that the liquid base material selected is of a type, and at such a level to sufficiently solubilize the gelling agent when heated, and form a gel when cooled to ambient temperature. The liquid base material must be compatible with the gelling agent so that the mixture of the two does not phase separate during processing. Furthermore, the liquid base materials are selected in order to provide aesthetic benefits, such as as emolliency, low tack or minimized visible residue, without substantial interference with the effectiveness of the antiperspirant active component. Lastly, the particular liquid base material should be safe for human application.
The liquid base materials of the present invention are preferably used at levels from about 10% to about 95%, more preferably from about 30% to about 80% of the composition. These liquid base materials generally comprise non-polar emollient oils having solubility parameters from about 5 to about 11, or mixtures thereof such that the average solubility parameter of the ~ Ç5 SHEE~

~1 35386 g liquid base material is from about 6 to about 10. Hence, a single non-polar emollient oil comprising the liquid base material may be used which itself has a solubility parameter in the range of from about 6 to about 10. Alternatively, a mixture of non-polar emollients may be used as the liquid base material herein, each having a solubility parameter in the range of from about 5 to 11, such that the average solubility parameter of the mixture is from about 6 to about 10. Solubility parameters and the means to determine them are disclosed by C.D. Vaughan, "Solubility Effects in Product, Package, Penetration and Preservation~ 103 Cosmetics and Toiletries 47-6g, October, 1988; and C.D. Vaughan, u Using Solubility Parameters in Cosmetics Formulationn, 36 J Soc.
Cosmetic Chemists 319-~3, Sept/Oct, 1985-l; Non-polar emollients useful in the present invention are disclosed in Cosmetics, Science, and Technology, Vol. 1, 27-104 edited by Balsam and Sagarin, 1972; U.S. Pat. 4,202,879, Shetton, issued May 13, 1980; and U.S. Pat. 4,816,261, issued March 28, 1989. Non-polar emollient oils particularly useful in the present invention are selected from the group consisting of silicone oils; hydrocarbon oils; fatty alcohols; fatty acids; esters of mono and dibasic carboxylic acids and mono and polyhydric alcohols;
polyoxyethylene, polyoxypropylene, mixtures of polyoxyethylene and polyoxypropylene ethers of fatty alcohols; and mixtures thereof.
The emollients useful in the present invention may be either saturated or unsaturated, have an aliphatic character and be straight or branched chained or contain alicyclic or aromatic rings.
Silicone oils, as disclosed above, include both volatile and non-volatile silicone oils. Volatile silicone oils are particularly useful as the non-polar emollients in the liquid base material since they endow the gel stick with highly desirable aesthetics. Volatile silicone oils preferably comprise at least 3, about 50Y., more preferably about 60X, and most preferably about 70X of the liquid base material.

B

- 1 o -Volatile silicone oils are disclosed in U.S. Pat. 4,781,917, Luebbe et al, issued Nov. 1, 1988.
A description of various volatile silicones materials is found in Todd et al., "Volatile Silicone Fluids for Cosmetics".
Cosmetics and Toi1etries, ~1:27-32 (lg76), As previously disclosed, non-polar emollients having solubility parameters below 6 may be used in the present invention. Therefore, volatile silicone oils having a solubility lo parameter from about S to about 6 may be useful in the present invention. These volatile silicone oils are selected from the group consisting of cyclic volatile silicones corresponding to the formula , , CH3 -- -- --S i -- O------CH
-- ~n wherein n is from about 3 to about 7i and linear volatile silicones corresponding to the formula (CH3)3Si-O-[Si(CH3)2O]m-si(CH3)3 ~, wherein m is from about 1 to about 7. Linear volatile silicones generally have viscosities of less than about S centistokes at 25-C, whereas the cyclic silicones have viscosities of less than about 10 centistokes. Examples of volatile silicones useful in the present invention include: Dow Corning 344, Dow Corning 345, and Dow Corning 200 (commercially available from Dow Corning - Corp.); GE 7207 and 7158 (commercially available from General Electric Co.); and SWS-03314 (commercially available from SWS
Silicones Corp.).
Volatile silicone oits having solubility parameters below 6 3, are combined with additional non-polar emollient oils having solubility parameters preferably from about 7 to about 11 B~' P 8 '7 to bring the average solubility parameter of the liquid base material to from about 6 to about 10. Additional non-polar emollient oils preferred for use in combination with volatile silicone oils having solubility parameters below 6 are selected S from the group consisting fatty alcohols having from about 12-22 carbon atomsi fatty acids having from about 12-22 carbon atoms;
esters of monobasic carboxylic acids and alcohols having from about 14-30 carbon atomsi esters of dibasic carboxylic acids and alcohols having from about 10-30 carbon atoms; esters of polyhydric alcohols and carboxylic acids having from about S to 22 carbon atoms; ethoxylated, propoxylated, and mixtures of ethoxylated and propoxylated ethers of fatty alcohols with from about 12 to 22 carbon atoms and a degree of ethoxylation and propoxylation of below about 50; and mixtures thereof. Preferred are propoxylated ethers of C~,-C~ fatty alcohols having a degree of propoxylation below about 50, esters of C2-Cg alcohols and C12-C22 carboxylic acids (e.g. ethyl myristate, isopropyl palmitate), esters of C12-C22 alcohols and benzoic acid (e.g.
Finsolv TN supplied by Finetex), diesters of C2-C8 alcohols and adipic, sebacic, and phthalic acids (eg., diisopropyl sebacate, diisopropyl adipate, di-n-butyl phthalate), polyhydric alcohol esters of C6-C22 carboxylic acids (e.g., propylene glycol dicaprate/dicaprylate, propylene glycol isostearate); and mixtures thereof.
The non-vol~tile silicone oils useful in the present invention are essentially non-volatile polyalkyl siloxanes selected from the group consisting of polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, polyethersiloxane copolymers, and mixtures thereof. ~xamples of these include polydimethyl siloxanes having viscosities of from about 5 to about 100,000 centistokes at 25-C.
Among the preferred non-volatile silicone emollients useful in the present compositions are the polydimethyl siloxanes having ~fiENDED SHEET

viscosities from about 2 to about 400 centistokes at 25-C. S~h polyalkyl siloxanes include the Viscasil series (sold by General Electric Company) and the Dow Corning 200 series (sold by Go~
Corning Corp.). Polyalkylaryl siloxanes include polymethylphen~l siloxanes having viscosities of from about 15 to about 65 centi-stokes at 25-C. ~hese are available, for example, as SF 107~
methylphenyl fluid (sold by General Electric Company) and 556 Cosmetic Grade Fluid (sold by Dow Corning Corp.). Useful polyether siloxane copolymers include, for example~ a polyoxyalkylene ether copolymer having a viscosity of about 1~3 to 1500 centistokes at 25-C. Such a fluid is available as SF106 organosilicone surfactant (sold by General Electric Company).
Polysiloxane ethylene glycol ether copolymers are preferred copolymers for use in the present compositions.
Non-volatile paraffinic hydrocarbon oils or fluids useful in the present invention include mineral oils and certain branched-chain hydrocarbons. Examples of these fluids are disclosed is U.S. 5,019,375, Tanner et al, issued May 28, 1991.

2n C. Antiperspirant Active The compositions of the present invention also contain an astringent antiperspirant active. These actives are used at levels from about about 1% to about 60X, preferably from about 5X
to about ~5%, of the antiperspirant gel composition. This active may be incorporated either in solubilized or particulate form.
These weight percentages are calculated on an anhydrous metal salt basis (exclusive of glycine, the salts of glycine, or other complexing agents). If used in particulate form, the material preferably has a particle size of from about 1 to about 100 3n microns, preferably from about 1 to about 50 microns, and have a high bulk density (e.g., qreater than about 0.7 g/cm3). Such materials include, for example, many aluminum or zirconium astringent salts or complexes and are well known in the antiperspirant art.

B~

Any aluminum astringent antiperspirant salt or aluminum and/or zirconium astringent complex can be employed herein. Salts useful as astringent antiperspirant salts or as components of astringent complexes include aluminum halides, aluminum hydroxyhalides, s zirconyl oxyhalides, zirconyl hydroxyhalides, and mixtures of these materials.
Aluminum salts of this type include aluminum chloride and the aluminum hydroxyhalides having the general formula Al2(0~)xQy.XH20 where Q is chlorine, bromine or iodine; where x is from about 2 to about 5, and x+y ~ about 6, tnd x and y do not need to be inte-gers; 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, Gilman, issued June 3, 1975, and U.S.
Patent 3,904,741, Jones and Rubino, issued September 9, 1975.
The zirconium compounds which are useful in the present invention include both the 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 follow-ing general empirical formula:
ZrO(OH) 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, nitrate, sulfamate, sulfate, and mixtures thereof. Although on1y zirconium compounds are exemplified in this specificat~ion, it will be understood that other Group IYB metal compounds, including hafnium, can 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, mi~xtures and complexes of the above. As will be seen from the above formula, the zirconium hydroxy salts actually represent a range of com-3, pounds having various amounts of the hydroxy group, varying from ri . ~3iO388 7 2135381i 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,~92,068, Luedders et al., issued February 12, 1974, S discloses complexes of aluminum, zirconium and amino acids, such as glycine. 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 alumi-num to zirconium (hereinafter ~Al:Zr~ ratio) and the molar ratio of total metal to chlorine (hereinafter ~Metal:Cl~ ratio). ZAG
complexes useful herein have an Al:Zr ratio of from about 1.6~ to about 12.5 and a Metal:Cl ratio of from about 0.73 to about 1.93.
Preferred ZAG complexes are formed by (A) co-dissolving in water (1) one part A12(0H)6 mQm, wherein Q is an anion selected from the group consisting of chloride, bromide and iodide, and m is a number from about 0.8 to about 2.0;
(2) x parts zro(oH)2-aQa.nH2o~ where Q is chloride, bromide or iodide; where a is from about 1 to about 2; where n is from about 1 to about 8; and where x has a value of from about 0.16 to about 1.2i ~3) p parts neutral amino acid selected from the group consisting of glycine, dl-tryptophane, dl-~-phenyl-alanine, dl-valine, dl-methionine and ~-alanine, and where p has a value of from about 0.06 to about 0.53;
(B) co-drying the resultant mixture to a fryable solid; and (C) reducing the resultant dried inorganic-organic anti-perspirant complex to particulate form.
A preferred aluminum compound for preparation of such ZAG type complexes is aluminum chlorhydroxide of the empirical formula A12(0H)5Cl.2H20. Preferred zirconium compounds for preparation of AMENDED SHEET

such ZAG-type ~complexes are zirconyl hydroxychloride having the empirical formula ZrO(OH)Cl.3H20 and the zirconyl hydroxyhalides of the empirical formula ZrO(OH)2 aCl2.nH20 wherein a is from about l.S to about 1.8~, 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(NH2)COOH. 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.

lo 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 approximate general formula [Al 2 (OH)4ClJ[H2CNH2-COOH].
Of all the above types of antiperspirant actives, preferred compounds include the 5/6 basic aluminum salts of the empirical formula Al2(0H)sCl.2H20; mixtures of AlCl3.6H20 and Al2(0H)sCl.
2H20 with aluminum chloride to aluminum hydroxychloride weight ratios of up to about 0.5; ZAG type complexes wherein the zir-conium salt is ZrO(OH)Cl.3H20, the a~uminum salt is Al2(0H)5Cl.
2H20 or the aforementioned mixtures of AlCl 3 .6H20 and Al 2 (OH)s Cl.2H20 wherein the total metal to chloride molar ra~io 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 ZAG-type complexes wherein the zirconium salt is ZrO(OH)2 aCla.nH20 wherein a is from about 3;

B' 2 1 3~386 1.5 to about 1.87 and n is from about 1 to about 7, the aluminum salt is Al2(0H)sCl.2H20, and the amino acid is glycine.
Solubilized antiperspirant actives which may be utilized in the present invention are also well known in the art. These materials utilize monohydric or polyhydric alcohols or water to solubilize the antiperspirant active before it is incorporated into the product. The levels of these polar solvents is less than 25%, and preferably less than 15% of the composition. Examples of such actives are taught, for example, in U.S. Patent ~.137,306, Rubino, issued January 30, 1979, U.S. Patent Application Serial No. 370,559, Smith and Ward, filed June 23, 1989, and European Published Application 0295070, published December 14, 1988. :
. . .
D. Optional Ingredients:
The compositions of the present invention may also contain optional components which act as additional active or modify the physical characteristics of the composition or the components making up said compositions. Such components are well known in the art. A non-limiting group of these optional components include colorants, perfumes, thickeners, emulsifiers, bacteriostats, fungistats, and mixtures thereof.
Emulsifiers are particularly useful in the present invention.
These emulsifiers include non-ionic surfactants useful for forming water-in~oil emulsions. The leve~ of emulsifiers used in the present invention is typically less than about 10%, preferably less than about 5%. Examples of these emulsifiers include polyoxyethylene ethers of fatty alcohols, and polyoxyethylene -polysiloxane copolymers. Such emulsifiers are disclosed by EPO
Application 373,424 Raleigh et al., and United States Serial Number 530,671, Cedeno et al., filed July 2, 1991 , Thickeners are also useful in the presently invention. Their selection and the level they are used at should be so as not to significantly affect the aesthetics of the gel composition.
Typical levels of thickners are at levels of less than about 5%.
Examples of said thickeners are disclosed in U.S. Pat. 4,g85,238, Tanner et al., issued Jan.15, 1991.
These thickeners include wax-like materials such as beeswax, cerasin, hydrogenated castor oil, synthetic waxes such as Fisher Tropsch waxes, microcrystalline waxes, polyethylene waxes, lo and mixtures thereof.
Particulate and filler materials may also be included in the present compositions. These materials are typically used at levels from about 0.5% to about 5Y., preferably not more than 3%.
Such materials are disclosed in U.S. Pat. 5,019,375, Tanner et al., issued May 28, 1991. Suitable filler materials include collodial silica (such as Cab-O-Sil, sold by Cabot Corp~, clays (such as bentonite), hydrophobic (quaternized) clays, silica/alumina thickeners, silicate powders such as talc, alumina silicate, and magnesium silicate, modified corn starches, metallic 70 stearates, and mixtures thereof. The use of such fillers as stabilizing agents in cosmetic sticks is disclosed in U.S. Pat.
4,126,679, Davy et al., issued November 21, 1987.
Examples of other particulate materials include particulate hydrophilic polymers such as cellulose ether polymers, ~, modified starches, polyamides, and polypeptides.
METHOOS Of MANUFACTURE
The present invention may be made by using any of the typical methods known to those skilled in the art, and disclosed in Gels and Sticks FormularY, 99 Cosmetics & Toiletries 77-84, lg84.
~ Methods found particularly - useful follow below:
Combine the gelling agent and the liquid base material into a vessel equipped with a heat source. Heat the mixture to about 130~C to about 150-C with stirring, until the mixture forms a 3; homogeneous solution. Add the antiperspirant active and other B

3 i 0 3 8 8 7 ingredients, such as fragrances and colors, into the above vessel with stirring. Pour the mixture into containers allowing them to cool. Alternatively, the antiperspirant active may be added along with the gelling agent and the liquid base material in the first S step.
~ hen using the combination of n-acyl ~mino acid amide ~nd 12-hydroxystearic acid, the above method may be used, except the temperature of the mixture is lowered to about 80~C to about 130~C.
METHODS fOR USE
The present invention provides methods for preventing perspiration and malodor associated with human perspiration.
These methods comprise applying to the skin of a human a safe and effective amount of the antiperspirant gel of the present lS invention. ~he term ~a safe and effective amount~ as used herein, is an amount which is effective in eliminating or substantially reducing malodor associated with humin underarm perspiration while being safe for human use at a reasonable risk/benefit ratio.
EYAMPLES
~he following examples further describe and demonstrate embodiments within the scope of the present invention. These examples are solely for the purpose of illustration and are not to be construed as limitations of the present invention as many variations are possible without departing from the spirit or scope thereof.
~he levels of the components in the examples below are expressed by total weight of the composition.

EXAMPLES

N-Lauroyl-L-glutamic acid-di-n-butyl amide~ 8 4 10 6 8 13 9 C~clomethicone D-52 28 40 49 47 42 SO
Polyphenylmethylsiloxane 3 1 0 Light mineral oil' 15 5 Panalane-L-14E' 10 Isopropyl Myristate 28 10 20 13 PPG-3 Myristyl Ether 30 3 AMENDED SHEET

p~-l, J~ ~ ~ / U 7 ~ o r - ~135386 C12-15 Alcohols Benzoate' 62 Diisopropyl Sebacate' 10 Aluminum Zirconium ~richlorhydrex Gly~ 15 40 20 25 25 20 Aluminum Chlorohydrate9 25 1 GP-l supplied by Ajinomoto Inc.
2 Dow Corning 245 Fluid - cyclic polydimethylsiloxane 3 Dow Corning 556 Fluid 4 Benol ~hite Mineral Oil supplied by ~itco Chemical Corp.
S polyisobutene supplied by Amoco Chemical Company 6 Finsolv TN supplied by Finetex 7 Schercemol DIS supplied by Sher Chemicals Inc.
8 supplied by ~estwood Chemical Co.
9; ~estchlor DM200 supplied by ~estwood Chemical Co.
The antiperspirant gel stick compositions were prepared by combining the N-lauroyl glutamic acid amide and liquid base components. ~hose components ~ere heated to about 130-150~C to form a clear solution. Once clear the solution is cooled and held at approximately 115-140~C at which time the antiperspirant active is added. The active is mixed thoroughly into the composition and the mixture is poured into containers. Upon cooling a stable antiperspirant gel stick is obtained. Similar results ~ere obtained when using N-stearoyl-L-glutamic acid diheptyl amide for 1) above.
VIII IX X XI XII XIII XIV XV
N-Lauroyl-L-glutamic acid-di-n-butyl amide 1 4 5 1 3 2 2 2 12-hydroxystearic acid 2 S S 6 ~ 3 6 12 Cyclomethicone D-52 40 49 39 43 40 43 46 Polyphenylmethylsiloxane3 3 S
Light mineral oil' 23 Panalane-L-14E5 15 10 11 Isopropyl Myristate 15 15 16 11 Isopropyl Alcohol 18 Captex 200' 15 C12-C15 Alcohols Benzoate' 8 PPG-3 Myristyl Ether 26 Diisopropyl Sebacatet 43 Aluminum Zirconium Trichlorhydrex Gly' 25 20 20 20 40 25 Aluminum Chlorohydrate10 30 10 Talc 3 2 5 A'~iE~DED SHEET

_ r ~i3 ~ 1~3 ~8 7 1 GP-1 supplied by Ajinomoto Inc.
2 Dow Corning 245 ~luid-cyclic polydimethylsiloxane 3 Dow Corning 556 Fluid 4 Benol ~hite Mineral Oil supplied by ~itco Chemical Corp.
S polyisobutene supplied by Amoco Chemical Company 6 propylene glycol dicaprate/dicaprylate supplied by Capital City 5Products 7 Finsolv ~N supplied by Finetex 8 Schercemol DIS supplied by Scher Chemicals Inc.
9 supplied by ~estwood Chemical Co.
~estchlor DM200 supplied by ~estwood Chemical Co.
~ he antiperspirant gel stick compositions were prepared similarly to Examples l-VII described above except the processing temper-atures are decreased by the addition of the 12-hydroxystearic acid. In the present examples the antiperspirant gel stick compositions were prepared by combining the N-lauroyl-L-glutamic acid amide 12-hydroxystearic acid ~nd liquid b-se components.
These components were heated to approximately 80-130 C to form a clear solution. Once clear the solution is cooled and held at approximately 65-120~C at which time the antiperspirant active (and other optional components such as filler powders or perfumes) is added. ~he active is mixed thoroughly into the composition and the mixture is poured into containers. Upon cooling a stable antiperspirant gel stick is obtained. Similar results were obtained when using N-stearoyl-L-glutamic acid diheptyl amide for 1) above.

i F' 3~ ~HEEr

Claims (29)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An antiperspirant gel stick composition comprising:
a. from about 1% to about 15% of a gelling agent;
b. from about 10% to about 95% of a liquid base material; and c. from about 1% to about 60% of an antiperspirant active;
wherein the gelling agent is a mixture of a n-acyl amino acid amide and 12-hydroxystearic acid having a ratio of the said amide to 12-hydroxystearic acid from about 1:20 to about 2:1; and the level of n-acylamino acid amide is at least about 0.1% total weight of the composition.
2. An antiperspirant gel stick composition according to Claim 1 wherein the liquid base material comprises non-polar emollient oils having a solubility parameter from about 5 to 11, and mixtures thereof such that the average solubility parameter of the liquid base material is from about 6 to about 10.
3. An antiperspirant gel stick composition according to Claim 2 wherein liquid base material comprises non-polar emollient oils selected from the group consisting of silicone oils; hydrocarbon oils; fatty alcohols; fatty acids; esters of mono and dibasic carboxylic acids and mono and polyhydric alcohols; polyoxyethylene, polyoxypropylene, mixtures of polyoxyethylene and polyoxypropylene ethers of fatty alcohols; having a solubility parameter from about to about 11; and mixtures thereof such that the average solubility parameter of liquid base material is from about 6 to about 10.
4. An antiperspirant gel stick composition according to Claim 1 wherein the antiperspiant actives comprise inorganic and organic salts of aluminum, zirconium and zinc, and mixtures thereof.
5. An antiperspirant gel stick composition according to Claim 4 wherein the antiperspirant active is in particulate form, and is selected from the group consisting of ZAG complexes and actives having the formula Al2(OH)xQy.XH2O

where Q is chlorine, bromine or iodine; where 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, and mixtures thereof.
6. An antiperspirant gel stick composition according to Claim 1 wherein the gelling agent is a n-acyl glutamic acid amide corresponding to the formula wherein R1 is an aliphatic hydrocarbon radical having from about 12 to about 22 carbon atoms, and R2 is an alphatic hydrocarbon radical having from about 4 to about 12 carbon atoms.
7. An antiperspirant gel stick composition according to Claim 6 wherein the n-acyl glutamic acid amide is selected from the group consisting of n-lauroyl-L-glutamic acid dibutyl amide, n-stearoyl-L-glutamic acid diheptyl amide, and mixtures thereof.
8. An antiperspirant gel stick composition according to Claim 7 wherein the gelling agent is from about 5% to about 10%.
9. An antiperspirant gel stick composition according to Claim 8 wherein the liquid base material contains at least about 50%
volatile silicone oil.
10. An antiperspirant gel stick composition according to Claim 9 wherein the liquid base material comprises:
a. volatile silicone oils having a solubility parameter of less than about 6, selected from the group consisting of cyclic and linear polydimethyl siloxanes corresponding to the formulas II. (CH3)3Si-O-[Si(CH3)2O]m-si(CH3)3 wherein n is from about 3 to about 7, and m is from about 1 to about 7; and b. an additional non-polar emollient oil having a solubility parameter from about 7 to about 11;
wherein the average solubility parameter of the liquid base material is from about 6 to about 10.
11. An antiperspirant gel stick composition according to Claim 10 wherein the additional non-polar emollient is selected from the group consisting of fatty alcohols having from about 12-22 carbon atoms, fatty acids having from about 12-22 carbon atoms, esters of monobasic carboxylic acids and alcohols having from about 14-30 carbon atoms; esters of dibasic carboxylic acids and alcohols having from about 10-30 carbon atoms; esters of polyhydric alcohols and carboxylic acids having from about 5 to 22 carbon atoms; ethoxylated, propoxylated, or mixtures of ethoxylated and propoxylated ethers of fatty alcohols with from about 12 to 22 carbon atoms, and a degree of ethoxylation and propoxylation below about 50; and mixtures thereof.
12. An antiperspirant gel stick composition according to Claim 11 wherein the additional non-polar emollient oil is selected from the group consisting of propoxylated ethers of C14-C18 fatty alcohols having a degree of propoxylation below about 50, esters of C2-C8 alcohols and C12-C22 carboxylic acid, esters of C12-C22 alcohols and benzoic acid, diesters of C2-C8 alcohols and adipic, sebacic, and phthalic acids, polyhydric alcohol esters of C6-C22 carboxylic acids, and mixtures thereof.
13. An antiperspirant gel stick composition according to Claim 12 wherein the antiperspirant active is in particulate form, and is selected from the group consisting of ZAG complexes and actives having the formula Al2(OH)xQy.XH2O

where Q is chlorine, bromine or iodine; where 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, and mixtures thereof.
14. An antiperspirant gel stick composition according to Claim 13 wherein the level of the antiperspirant active is from about 5% to about 35%.
15. An antiperspirant gel stick composition according to Claim 6 wherein level of the gelling agent is from about 3% to about 12%, and the ratio of the said amide to 12-hydroxystearic acid is from about 1:10 to about 1:1.
6. An antiperspirant gel stick composition according to Claim 6 wherein the level of the gelling agent is from about 5% to about 12%, and the ratio of the said amide to 12-hydroxystearic acid from about 1:5 to about 1:2.
17. An antiperspirant gel stick composition according to Claim 16 wherein the n-acyl glutamic acid amide is selected from the group consisting of n-lauroyl-L-glutamic acid dibutyl amide, n-stearoyl-L-glutamic acid diheptyl amide, and mixtures thereof.
8. An antiperspirant gel stick composition according to Claim 17 wherein the n-acyl amino -acid amide is n-lauroyl-L-glutamic acid dibutyl amide.
19. An antiperspirant gel stick composition according to Claim 18 wherein the level of n-lauroyl-L- glutamic acid dibutyl amide is from about 1% to about 5%.
20. An antiperspirant gel stick composition according to Claim 3, wherein liquid base material is from about 30% to about 80% of the composition.
21. An antiperspirant gel stick composition according to Claim 20 wherein the liquid base material contains at least about 60%
volatile silicone oil.
22. An antiperspirant gel stick composition according to Claim 3 wherein the additional non-polar emollient is selected from the group consisting of fatty alcohols having from about 12-22 carbon atoms; fatty acids having from about 12-22 carbon atoms; esters of monobasic carboxylic acids and alcohols having from about 14-30 carbon atoms; esters of dibasic carboxylic acids and alcohols having from about 10-30 carbon atoms; esters of polyhydric alcohols and carboxylic acids having from about 5 to 22 carbon atoms; ethoxylated, propoxylated, or mixtures of ethoxylated and propoxylated ethers of fatty alcohols with from about 12 to 22 carbon atoms, and a degree of ethoxylation and propoxylation below about 50; and mixtures thereof.
23. An antiperspirant gel stick composition according to Claim 22 wherein the additional non-polar emollient oil is selected from the group consisting of propoxylated ethers of C14-C18 fatty alcohols having a degree of propoxylation below about 50, esters of C2-C8 alcohols and C12-C22 fatty alcohols, esters of C12-C22 alcohols, and benzoic acid, diesters of C2-C8 alcohols and adipic, sebacic, and phthalic acids, polyhydric alcohol esters of C6-C22 alcohols, and mixtures thereof.
24. An antiperspirant gel stick composition according to Claim 23 wherein the liquid base material contains at least about 70%
volatile silicone oil.
25. An antiperspirant gel stick composition according to Claim 24 wherein the antiperspirant active is in particulate form, and is selected from the group consisting of ZAG complexes and actives having the formula Al2(OH)xQy.XH2O

where Q is chlorine, bromine or iodine; where 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, and mixtures thereof.
26. An antiperspirant gel stick composition according to Claim 25 wherein the level of the antiperspirant active is from about 5% to about 35%.
27. An antiperspirant gel stick composition according to Claim 26 additionally comprising colorants, perfumes, thickeners, emulsifiers, bacteriostats, fungistats, and mixtures thereof.
28. A process for making antiperspirant gel stick compositions according to Claim 1 comprising the following steps:
a. combine the gelling agent and liquid base material in vessel equiped with a heat source;
b. stir while heating the mixture to between 130°C and 150°C, obtaining a homogeneous solution;
c. add the antiperspirant active to the heated mixture;
d. stir until uniform;
e. pour the mixture into containers; and f. cool the mixture until a solid gel is formed.
29. A method of preventing formation of perspiration and malodor by applying to the underarm skin a safe and effective amount of the composition according to Claim 1.
CA002135386A 1992-05-12 1993-04-26 Antiperspirant gel stick composition Expired - Lifetime CA2135386C (en)

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