CA2109307A1 - Gel stick antiperspirant compositions containing 2-oxazolidinone derivative and process for making them - Google Patents

Gel stick antiperspirant compositions containing 2-oxazolidinone derivative and process for making them

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Publication number
CA2109307A1
CA2109307A1 CA002109307A CA2109307A CA2109307A1 CA 2109307 A1 CA2109307 A1 CA 2109307A1 CA 002109307 A CA002109307 A CA 002109307A CA 2109307 A CA2109307 A CA 2109307A CA 2109307 A1 CA2109307 A1 CA 2109307A1
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CA
Canada
Prior art keywords
gelling agent
oxazolidinone
solvent
composition according
substituted
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.)
Abandoned
Application number
CA002109307A
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French (fr)
Inventor
John M. Gardlik
Brian D. Hofrichter
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Procter and Gamble Co
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Individual
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Filing date
Publication date
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Publication of CA2109307A1 publication Critical patent/CA2109307A1/en
Abandoned legal-status Critical Current

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Classifications

    • 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
    • A61K8/02Cosmetics 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
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • A61K8/345Alcohols containing more than one hydroxy group
    • 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
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q15/00Anti-perspirants or body deodorants
    • 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

Antiperspirant compositions in the form of gel sticks, having acidic pH, and including an antiperspirant active, a gelling agent which comprises a dibenzylidene alditol, or mixture thereof, a hydroxy solvent for the gelling agent, and a 2-oxazolidinone derivative having a C1-C4 alkyl radical substituted at the 3 position of the heterocyclic ring are disclosed.

Description

~ W O 92/19222210 9 3 ~ ~ PCT/US92/03348 GEL STICK ANTIPERSPIRANT COMPOSI~IONS
CON~AINING 2-0XAZ0LI~INONE DERIVATIVE AND
PROCESS FOR MAKING THEM

~CHNICAL FLL~
The present invention re1ates to antiperspirant compositions in the form of so1id gel sticks~ More particularly, the present invention relates to ant1perspirant gel sticks containing di-benzyl idene alditol gelling agent. ~he present invention further relates to a process ~or making the antiperspirant gel stick compositions.
1~ ~
~ here are three main types of antlperspirant stick formula-tions: compressed powder st1cks, gel sticks, and wax sticks.
~hile each of these formulation typ~s may have advantages in ; : certain usage situations, e~h also has disadvantages. For example, comr essed powder sticks~ ~re often brittle and hard, 1eaving a co~metically-unacceptable powder on the skin upon appl ication. ~ Wax-based formulations can al50 yield cosmetically-unacceptable products due to such :faétors as hardness, greasiness, and:stick~ness.~ ~he opacity of ~such wax sticks and the residue 25 created by their:use may also be aesthetically undesirable.
Gel-based sticks~have~several~advantages over both compressed ~: powder and:~wax ~ticks. For ex~mple. the gel sticks tend to leave little or no residue:or:dust on t he skin~ Gel stiçks also pro~ide a~vehiclle which glides:easily over the skin's surface resulting in :~` 3~ very:easy and:comfortable application of the product.
UnfQrt~n~telyl the formulation of antipers~irant compositions in the form:ol ef~:ective and stable gel sticks is difficult. One critical ingr~iient in :antiperspirant gel stlcks is the gelling : agent. Many :known cosmetic gel:sticks ~comprise 9elled alcoholic :solutions.~:Gel:ling~agents, such as:sodium stearate, are commonly :: : :
2 1 ~
WO 92/1g222 . . lPCr/lJS92/033q uced to form the gel. Such gell;ng agents cannot be used in the presence of acidic antiperspirant active salts, due to interaction between the gelling agent, which is alkaline, and the antiper-spirant active.
S Gell ing agents which are more useful in the preparation of antiperspirant gel sticks are the dibenzylidene alditols. For example, dibenzylidene sorbitol (DBS) is a well-known gelling agent. See7 for exampl e , U ~ S . Patent 4 , 1 54 , 816 , Roehl et al ., issued May 15, 1979; U.S. Patent 4,816,261, Luebbe et alO, issued March 28, 1989; and U.S. Patent 4,743,444, McCall, issued May 19, 1988. Various substituted d~benzyliden~ alditol gelling agents have ~een found to be of benefit in antiperspirant gel sticks since they can exhibit improYed stability in the açidic environ-ment of the ant~perspirant gel stick, and consequently improve shelf life of the product.
Japanese Published Application 64-62377, Kao, pu~lished March 8, 1989, describes fluorinated d~benzylidene polyhydric alcohol derivat1ves which are effectiYe gelling agents for cosmetic compositions containing a wide range of organic solvents.
. 20 U.S. Patent 4?429,1409 Murai et ~1., issued January 31, 1984,discloses a method ~or produc~ng DBS and its derivatives. Dis-closed DBS derivatives include those where the benzene ring is substituted with from 1 to 3 lower alkyl groups, lower alkoxy groups, halogen atoms or nitro gr~ups.
U.~. Patent 4,3717~45, Mahaffey~ issued February l, 1983, describes plastic composit~ons wh~ch inslude D8S derivatives for improved transparency. Th~se D8S derivatives must include a chlorine or brominc substituent in the meta and/or para positions I and may also include lower ialkyl, hydroxy~ ~ethoxy, mono- or : 30 dialkyl a~ino. or fluorine substituents. Di(para-chloro) DBS, : d;(para-fluoro) DBS, and di(para-methoxy) DBS are all specifically disclosed. ~ ;
European Patent Application 0286522, Roquette Freres, pub-: lished December 1, 1988, describes a process for making high purlty alditol diacetals. Para-chloro DBS is disclosed.

:

Wo ~2/19222 2 ~ 3 ~ 7 Pcr/us92/o3348 DBS-type compounds found to be particul ar1y u~eful for antiperspirant gel sticks are disclosed in U.S. Patent Application Serial Number 696,377 . ~Gel Stick Antiperspirant Composi-tions", Oh, Juneja, and Connor~ filed on May 6, 1991, the same f~ling date as the present patent, and its parent application 07/505,807, Oh, Juneja, and Connor, filed April 6, 1990. Dis-closed are substituted dibenzyl1dene aldi~ols that are derivat1zed at the meta position of the benzene rings. Exemplary campounds ~nc1ude di(meta-fluoro) DBS and dl(meta-chloro) D~S. These meta-substituted dibenzyl~dene alditols have improved stability in ac~dic conditions.
During processing and manufackure of ant~perspirant gel sticks containing d~benzyl~dene alditol gell~ng agents, lt is necessary to solubilize the gelling agent 1n a solvent, typically a monohydric or polyhydr~c alcohol. In order to do this~ ~t is necessary to heat the ingred~ents to a temperature which iç high enough to induce solubil~zation and wh~ch is also above the gel po~nt of the gelling agent/solvent solut1~n. Unfortunately, the relat~vely hlgh temperatures required tend to cause even the best dibenzylidene alditol gelling agents to degrade in the presence of :~ the acidic antiperspir~nt act~ve,~ or other ac~d~c mater~al.
Accordlngly, there is a~need to provide antiperspirant gel stiçk co~pos~t10ns contatn~ng benzyl~dene alditol gelling agents that can be made at:;reduced~processlng temperatures. Th1s can prov1de r¢duced decompos1t~on~of the~d~benzylidene alditol gelling agent during processing, and~: provide more efficient ut~lization of gell~ng agent in the final~;~product. The ability to form the gels by processing~at lowered;~;~processing: temperatures also can reduce by-products ~nd improve~stabiltty :and processing of other ingrq-dients typically included :in antiperspirant composit~ons, e.g., : perfumes and~other~ volatile components, as well as improve com-- - patibility with~pi~astic~packagin9~into which heated molten anti-perspirant compositions may~ be~added. There is further a need to provide a process for~ making such antiperspirant gel st~ck compositions.

:

,: ~ ' 3 ~ ~1 WO 92/19222 PCI/US92/033' Various attempts have been made in the past to meet these objects. For example, in U.S. Patent 4,719,102~ Randhawa et al., issued January 12, 1988, it is disclosed to prepare an antiper-spirant gel stick containing an acidic antiperspirant active, a dibenzylidene monosorbitol acetal gelling agent, alcohol solvent, and an organic compatible solvent of not greater than about five carbon atoms which is a good hydrogen ~ond donor or acceptor .
Cyclic esters, amides, am~nes, ketones, ureas, carbamates, sulf-oxides, and sulfones are d~scussed. More particularly, such 10 materials as lactones, lactams, cycl k ketones, urea, cyclic carbamates, cyclic sulfoxi~es, cyclic sulfones, ~nd their open chain analogs ha-ling no more than five carbon atoms are discussed.
Specific examples ar~ morpholine, pyrid~ne, acetic acid, ethylene carbonate, propylene carbonate, N-methyl pyrrol1done, pyrrolldone, butyrolactone, dimethylsulfoxide, d~methyl formamide, 2-ethyl-ethanol, ~nd caprolaetam. In U.S. Patent 4,722t~35~ Schamper et al., issued February 2, 1988, it ~s proposed to incorporate into an antipersp~rant st1ck a small, polar :organic compound in com-bination with the dibenzylidene monosorbitol ac0tal gelling agent, antiperspirant active, a basic metallic salt, and an alcohol co-solvent. The small, polar organic compound i5 morpholine, py-ridine, acetic acid, ethylene: carbonate, propylene carbonate, N-methyl pyrrol.idone, pyrrolidone, butyrolactone, dimethylsulf-oxide, dimethyl:~ormamtde, ~ 2-ethoxyethanol~ and ~prolactam.
: 25 ~hereas the compositions of these patents are sa1d to be able to be processed at~:reduced temperaturest the exemplified solvents added ta reduce processing temperature unfortunately tend to either ca~se of~-odors in :the final product~ are not stable under ac;dic conditions, or~present: skln~ compatibility issues, such as (but not limlted to~:skin irr~tation. Thus it remains desirable, and lt is an obJect of this invention, to provide compositions and method of mlking them, which exhibit a combination of signifi-: ~
: cantly reduce~ :processing temp~rature requirements without in-curring the disadvantages associated with prior known ~ 3s cDmpositions~ ~

wo 92t19222 2 1 Q 9 3 ~ ~ Pcr/us92/o3348 It is also an object of this invention to provide composi-tions and a method for making them, as desoribed above, which provide effe~ive gels for use in antiperspirant applications, and which can provide both good antiperspirant effieacy and cosmetic S characteristlcs.
The present invention provides antiperspirant compositions containing particular cosolvents ~sed in combinatton with hydroxy solvents (such as mono- and polyhydric alcohols) in benzylidene alditol-containing antiperspirant gel st~ck compositions which enable the compositions to be made at reduced temperatures.
Specifically, the 2-oxazolidinone compounds have a lower alkyl (e.g., C1-C4) substituent located at the 3 position of the hetero-cyclic ring. The present invention also provides a method of making such compositions, by which processing temperature can be reduced relative to processes not ircluding the selected 2-oxa-zol idi none cosol vent .
The use of 2-oxazo1idinone oompounds as cosolvents in di-benzyl~den~ ald~tol-containing gel stick composit~ons can lower the processiny temperature required, and consequently can reduce gelling agent degradation during process~ng. They can also improve the gelling agent efficiency and the gel characteristi~s in the final product.
2-oxazclidinone compounds are disclosed for use in various applicat~ons, such as electro-chemical applicat~ons,~e.g., U.S.
Pat~nt 3,951,685, and Japanese Pat~nt JP 61 55,196 ~1985). They atso have been~disclosed, ~for ex~mple, as being useful as anti-wear/antiox1dant compounds for lubricants in eleotronic devices, e.g., JP 615519$ ;(1986),~ and~ as a topical mosquito repellent, e.g., ~Topical Mosquito Repel:lents X: 2-Oxazolidones~, A. Skinner, ` 30 H. T. Craw~ord, D. Skidmore, and I. Maibach, J. Pharmaceutjcal Sciences, Vol~.: 66,~::No.~ 4, Aprll 1977, pp 587-589. 2-Oxazolidi-nones are also:described~, ~for example, in "Liquid 2-Oxazolidones.
` 1. Dielectric Constants,~Y:iscositie:s, and Other Physical Proper-ties of Several~Liquid 2-Qx:azolidon~esn, H. L. Huffman, Jr. and P.
3~ G. Sears, J. ~o1ution Chemistry, Vol. 1, No. 2,:1972, pp 187-196, 23 ~'~3~7 WO 92/19222 Pcr/us92/o33~

and as solvents, detergents, pigments, dye compositions, polymers, and chemical intermediates. Whereas patents to Schamper ek al.
and Randhawa et al., referenced above, very generally mention cyclic carbamates, i.e., 2-u~azolidinones, ~hey do not disclose the 3-(a1kyl)-substituted 2-oxazolidinones hereof nor suggest the necessity of the alkyl substituent at the 3 position o~ the hete~ocyolic ring for fulfilling the objects here for a stable, efficacious, and sk1n con~patible antiperspirant gel stick.
SUMMARY OF THE INY~IQ~
The present invention pravides for sol~d antiperspirant compositians in gel st~ck form, havin9 ~cidic pHs, comprising:
(a) from about 0.5% to abo~t 35% of an ant1perspirant active;
(b) from about 0.5% to about 10% of a gelling agent selected from the group consisting of substituted and unsubstituted dibenzylidene alditols (such as sorbitols, xylitols, and ribitols), and mixtures thereof;
(c) from about 5% to about:98% of a hydroxy solvent ~or said gelling agent, satd solvent selected from the group consist-ing of monohydric and polyhydric alcoholsi and (d) from about 0.5%:to absut 40% of a 2-oxazolidinone cosolvent having a Cl~-C~ alkyl radical substituted at the 3 position of the heterocyclic ring, or a mixture thereof.
The present invention also relates to an improve~ process for making an antiperspirant gel stick compo~ition, havin~ acidic pH, containing hydroxy solvent, substituted or unsubstituted diben-zylidene alditol gelling agent,~and antiperspirant active, said :~ process comprising solubilizing ~said gellin~ agent in a heated solvent s~stem to form~;a solution and subsequentty cooling said solution to form a gel, wher2ln the improvement comprises incor-porating into said solvent sys~em a su:fficient amount of 2-oxazo-: ~ lidinone substituted at the 3 position of the heterocyclic ring with C~-C~ alkyl to significantly redùce the g011ation temperature . of the solution.
35 : ~ :
;

I

wo ~2/,g222 2 1 ~ ~ 3 ~ 7 P~/US92/03348 ~E~AILED D~S~RIPTION OF THE XNVENTI~N
The solid antiperspirant compositions encompassed by the present invention are in the form of gel sticks. ~hese sticks have a suitable hardness such that they deposit an effective 5 amount of antip~rspirant material on the skin during normal use, while maintaining dimensional stability upon use and storage.
Hardness of sticks can be determined by ~ variety of methods, in-cluding American Societ~ far Testing and Materials (ASTM) Method D^5. This method involves the use of a needle or pol~shed cone of 10 particular weight and dimension~ which is allowed to travel dswnward through the st1ck material for a pr~determined period of time. The distance travelled by the needle or cnne is a relative measure of stick hardness. Using Method D-5, with an AS~M-D1321 arrowhead-type penetration needle (Model 13-401-10, sold by Fischer Scientific Co~), weighing 50 grams, and a Model 13-395-10 Penetrometer (sold by Fischer Scientific Co.), the stick composi-tions of the pr~sent invention;preferably have an average pene-tration value of ~rom about 60 to about 200, measured ~n units of tanths of a ~illimeter, more preferably from about 100 to about 20 160, over a period of S seconds at ambient temperature. These values represent in average penetration for sticks w1thin a given production bat~h, since such penetratlon values may vary from stick to stick within the batch.
The st1ck compositions of the present invention, by virtue of their incorporation of antipersp~rant actives, are acidic in nature. Spe~ifically, they have an apparent pH of from about 1.S
to about 4. The term "apparent pH~ is used herein since the compositions are generally non-aqueous and, therefore, the pH of the comp~sition is being measurad in a non-aqueous system.
! Specifica~ly~ he pH is determined by melting the stick and measuring its pH at 25-C using a standard pH meter. If the stick is melted at a relatively high te~p~rature (for example, about 120-C for about 1 hour), it will not resolidify upon cooling and the pH at 25-C can be easily measured~ Under these conditions, the apparent pH of the compositions of the present invention : should be from about 1.5 to~about 4.

210~3~7 WC) 92~19222 PCl'/US92/033 ~3 -All parts, percentages ~nd ratios specified herein are by weight, unless otherwise specified The required, as well as ~he optional, components of the present invention are described in detail below.
G~ n9LQ9~Q~
The compositions of the present invention include from about 0.5X to about 10%, preferably from about 2% to about 5%, most preferably from about 2% to about 3.5%, of a specifically defined gelling agent component~ This g~lling ayent component is a dibenzylidene alditol ~or example, a sorb~tol, xylitol or ribi-tol) which can be substituted or unsubstituted. Preferred are dibenzylidene sorbitol (DBS~ and DBS d~rivatives.
~ o aid in understanding the present invention~ the following are diagrams of dibenzylidene sorbitolt and dibenzylidene xylitol 15 with the ortho, meta and para positions indicated.
fH20H
CHOH

meta ortho ~ /o-para ~ ~ ),'~ fH-o~
0-CH2 dibenzyl idene sorbitoS
..
: CH OH
2~ 1 2 ~ ~ Cll-O
meta ~ortho; `

para ~ CH-O
~ ~ 0-CH2 dibenzylidene xylitol Dibenzyl:idene ribitol~is:~:structurally: similar to dibenzyli-: dene xylitol~, except~lt~is~based~on~ribitol, rather than xylitol.
Other uns:ubstituted:dibenzylidene~alditols include dibenzyli-dene xylitol:(DBX3 and dlbenzyl;dene ribitol ~DBR).
: 35 ::

~ 21~3~'l , 1~ W092/1g222 PCI/US92/03348 The preferred substituted dibenzylidene alditols are sub-stituted with one or more electron withdrawing groups. It is especially preferred for the substituents that are electron withdrawing groups to be 10cated at the meta position, although substituents c~n a1so be located ~t the para or ortho posittons.
Likewise, substituents can be located at a combination of the meta and para, meta and ortho, or para and ortho positions. The preferred electron withdrawing substltuents include -CH2F, -CH2Cl, -f, -Cl, -Br, -I, and -CH~CHNO2. Preferably, at least one of the electron withdrawing subst~tuents is loçated at the meta position of the benzene ring. Multiple substituents (including those not on the list3 may be ut~lized in these preferred gelling agents as long as at least one from the list is located at the meta position. Most preferably, the alditol is sorbitol.
In other preferred 9elling a~ents, at least one of certain substituents are 10cated at the meta or para position of the benzene ring. On~ce again, more than one of these substituents (or even substituents not on the list) may b~ included in a pa~ticular molecule, as long as at l~ast one from the list 1s position~d at the meta or para position. These substituents include:
+
-N~2, -NH3, -NR3, -PR3, -PH3, -SR2j~-CF3, -CCl3, -CHF2, -CHCl 2 ~ - CHClF, -CCl2F, -CF2C1, -SO3H, -SO3R, -CO2H, -CO~R, -CONH2, -CHO~ OR, and~-C~N,~where~in R is C,-C4 a1kyl.
2~ Especially preferred~substituted gelling agents for use in the present~ nvention includè~ the fol1~owing substituents at the meta position~ CH2F,~ CH2Cl, -F,~ -Cl, -Br, -I, and -CH~CHNOz;
particularly~preferred are the~ -F and -Cl substituents. It is preferred that this meta substitution be the only substitution on 3b the benzene ring. The~s~ubstituents described herein will gene-rally be found on both~ benzené rings of the compound. Particu-larly pre~erred are ~idi~meta-fluorobenzylidene) sorbitol and di(meta-çhlorobenzylidenej sorbitol. ~
The substltuents 11~sted a;bove;~p~rovide selling agents whiçh ` 3~ exh~ibit good~stability in~the~aci~d~environment of an antiperspi-rant composition. A preferred sub-group of these substituents are :: : : ~ :: : ~ ~

2 ~ 3 ~ 7 WO ~2/1~22~ P~/U~i92/033~

those which have smaller molecular sizes since they tend to generally provide stronger gels. Thus, for example, the gel provided by a fluorine or chlorine substituted compound tends to be stronger than one provided by a trifluoromethyl substituted compound. It is also preferred that the gelling agents utilized in the compositions of the present invention ha~e a high purity.
For example, they should be substantially free of para-toluene sulfonic acid or any other catalyst used in their synthesis as well as any salt forms (e.g., sodium) of these gelling agents.
The presence of such impurSt~es may tend to weaken the gel formed.
Mixtures of the gelling agents specified here~n may be used in the compositions of the present inv~ntion.
Gelling agents that can be used herein are generally disc1Osed in British Patent 1,291,B19, published October 4, 1972, U.S. Patent 4,518,582, Schamper et al., issued May 28, 1985, U.S.
Patent 41154,816, Roehl et al., issued Ma~ 15, 1979; U.S. Patent 4,816,261, Luebbe et al., issued March 28, 1989; U.S. Patent 4,743,444, McCall, issued May 10, 1988, and U.S. Patent 4,429,140, Mura~ et al., issued January 31~ 1984, all of which are incorporated by reference herein. The preferred unsubstituted DBS
is commereially available, ~or example, as GELL-ALL-D
(manufactured by New Japan Chemical: Co., Ltd.~ and MILLITHIX 925 (manufactured by Millik~n ~hemical, Division of Milliken Csmpany). ~ ~
7he preferred meta-substltu~ed gelling agents are generally formed by converting a~ meta-s~bstituted benzaldehyde to the corresponding meta-substituted DBS:using a reaction such as that taught in European Patent Appli~catio~ 0286522, Roquette Freres~
published December 1, 1988, incorpor~ated herein by referenee. As specific examplès, the synthesis of meta-fluoro DBS and meta-ohloro DBS is described below.:
A solution of D-sorbit:ol (1006 9t 5.52 mol) in 3000 mL of distilled water, m-fluorobenzaldehyde (1240 9; 9.99 mol ) t and p-toluenes~lfonic acid monohydrate (I310 ~; 6.87 mol3 is stirred at 30-C for ZI~h. The resultlng suspension is neutralized to a pH

: ' ,,. 2lG~3a7 3~ W o 92/l9222 PcT/uss2/03348 of 7.0-7.5 with an a~ueous 10X NaOH solution, and the white precipitate is collected by filtration. The solid is then suspended and stirred, in succession, in rQagent grade acetone (3 x 10.0 L), and hot (60-C) distilled water (3 x 10.0 L), collected, and dried in vacuo at 50'C to give 11}3 9 (47~) of purified di(meta-fluoro) DBS.
Di(met~-chloro) DBS is synthesized using a similar procedure, except th~t meta chloro benzyaldehyde is used in place of meta-fluoro benzaldehyde.
Para-subst1tuted compounds used in the pr~sent ~nvention are synthesized using a s~milar procedure, except that para-substi-tuted benzyaldehyde is utilized as ~he starting material. The general method for synthesizin~ substituted dibenzylidene xylitols and substituted dibenzylidene ribitols is taught in Japanese Published Application 64-62377, Kao, published March 8, 1989, and U.S. Patent 4,429,14Q, Murai et al., issued January 31, 1984, both incorporated here~n by reference. Ortho-subst~tuted compounds can be made in a s~milar manner~
Anti~er~Dirant Active The compositions of the present invention also csntain from about 0.5% to about 35%~ preferably from about 5% to about 35%, more preferably from about 5% to about 25%7 of an antiperspirant actiYe. The ?ntiperspirant actives hereof are antiperspirant active astringent metal:salts and astringent complexes of such salts. The actiYe may be incorporated either in solubilized or particulate form. If a clear or translucent stick composition is desired, the composition must comprise an antiperspirant active which can exist in solubilized form in the solvent system. This solvent system can essentially be the same hydr~xy solvent and !" ~ 30 cosolvenlt used to form the base matrix with the gelling agent.
: Alternately, other:solvents can be used as the antiperspirant : active solvent. 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 :~
~:

2 1 ~3 9 3 0 7 w o 92/19222 PCT/US92/033~

to about 100 micronst preferably ~rom about 1 to about 50 microns.
~hey may bs impalpable or microspherical in form and, preferably, have a high bulk density (e.g., greater 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 anti-perspirant art.
Any aluminum astringent antiperspirant salt or aluminum and/or zirçonium astringent complex can be employed herein. Salts useful as astringent antiperspirant salts ar as components of astringent complexes include aluminum hal ides, aluminum hydroxy-halides, zirconyl oxyhalides, zirconyl hydroxyhalid~s1 and mix-tures o~ these materials.
Aluminum salts of this type include aluminum shloride and the aluminum hydroxyha1ides having the general ~ormula Al2(0H)xQy.XH20 where Q is chlorine, bromine or 10dine; where x is from about 2 to about 5, and x~y - about 6, and x and y do not need to be inte-gers; and where X is from about 1 to about ~. Aluminum salts of ~this type can be prepared in the manner described more fully in U.S. Patent 3~887,692, G11~an, ~ssued June 3:, l975, and U.S.
Patent 3,904,741, Jones and Rub1no,~ issued September 9, 1975, incorporated herein by ref~rence.
: Zirconium compounds wh~ch are useful in the present invention includ~ both~ the zirconium oxy salts and zirconium hydroxy salts, also referred to as th~ zircsnyl salts and zirconyl hydroxy salts.
~5 These compounds may be represented by the fol 1 5Wi ng general emp~irical~formula~
: Zro(~H) 2 -nzBz whereîn 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 ! O, and B may be selected from the group consisting of halides, nitrate, sulfamate, sulfate,~and mixtures thereof. Although only : zirconium compounds are exempl:ified in this specification, it will : be:understood that other Group lVB metal compounds, including ~: hafnium, can be used ln:the~present invention.

:

;~ WO ~2/192~2 ~ 9 3 ~ ? P~/US~2/03348 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 we11 as polymers, mixtures and S compl ex~s of the above . As wi 11 be seen from the above formul a, the zircon~um hydroxy salts actually re~resent a range of com-pounds having ~arious amounts of the hydroxy group, varying from about 1.1 to only slightly greater than 0 groups per molecule.
Several types of antiperspirant complexes utiliz~ng the above antiperspirant salts are known in the art. For example, U.S.
Patent 3,792,068, Luedders et al~, ~ssued February 12, 1974, discloses complexes of aluminum, zirconium and amino acids, such as glycine. Complexes su~h as those disclosed 1n 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 co~plexes usef~l herein are identified by the specif~cation of both the molar ratio of alumi-num to z1rconium (hereina~ter "Al:Zrq ratio) and the molar ratio of total metal to chlorin~ ~here`inafter ~Metal:Cl~ ratio). ZAG
complexes useful here~n have an Al:Zr ratio of from about 1.67 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-disso1virg in water (1) ~one part Al2(0~)6 m~m, wherein Q is an anion :~sele~ted:~from the ~roup consisting of chloride, bromide and::iodide, and m is a number from about 0.8 to about Z.0;
(2)~: x parts: Zr0(0H)2 aQa.nH20, 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 (3J~ :p parts neutral amino acîd selected from the gro~p consisting:of:~glycine, dl-tryptophane, dl-~-phenyl-al:anine, dl-valine,~ dl;-methionine and ~-alanine, ~093Q'~
WO 92/19222 . P~/US92/033~

- lq -and where p has a value of from about 0006 to about 0.53;
~B) co-drying the resultant mixture to a friable solid; and (C) reducing the resultant dried inorganic-organic anti-p~rspirant complex to particul~te form.
A preferred aluminum co~pound ~or preparat~on of such ZAG
type comple~es is aluminum chlorhydrox~de sf the empirical formula A12(0H)5C1.2~20. Preferred zirconium compounds f~r preparation of such ZAG-type complexes are zircnnyl hydroxychtoride having the empirical fsrmula ZrO(OH)C1.3H20 and the zirconyl hydroxyhalides of the empirical formula ZrO(OH)2 aCl2.nH20 wher~in 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 C~12(NH2)COOH. Salts of such amino acids can also be employed in the antiperspirant complexes. See U.S.
Patent 4,017,559, Rubino, iss~ed April 12, 1977, incorporated herein by reference.
A wide variety of other types of antiperspirant co~plexes are al so known i n the art . For exampl e 7 U.S. Patent 3~903,258, : 20 Siegal, issued September Z, 1975, discloses a z~rconium alum1num comple% prepa~ed by re~ct~ng zirconyl chloride with aluminum hydroxide and aluminum chlorhydrox~de. U.S. Patent 3,979,510, Rubino, issued September 7, ~1976, discl~ses an antipersp~r~nt complex form~d ~rom cert~in aluminum compounds, cert~in z~rconium compounds, ~and certain complex aluminu~ buffers. U.S. Patent 3,981,896, issued September 21, l9J6~ disclsses an antiperspirant complex prepared~ from an :alumihu~ polyol compound, a zirconium compound and~an organic buffer. U.S. Patent 3,970,748, Mecca, issued J~ly~20, lY76, discloses an aluminum chlorhydroxy glycinate complex of the approximate general~ormula [A12(0H34Cl~H2CNH2-COOH]. All of these patents~are incorporated herein by reference.
: : ~Of all the:above types of antiperspirant actives, preferred compounds include~ the 5/6: basic aluminum salts of the empirical formula Al2(0H)5Cl.2H~:O~ such compounds: being commonly referred to as aluminum chl:orohydrates (~ACHn); mixtures of AlCl3.6H20 and :

: :

: wo 92/19222 210 3 3 ~ 7 P ~ /US92/03348 Al2(aH)5Cl. 2H20 with aluminum chloride to aluminum hydroxy-chloride weight ratios of up to about 0.5; ZAG type complexes wherein the zirconium salt is ZrO(OH)C1.3H20, the aluminum salt is Al2(0H)sCl~ 2H20 or the aforem~ntioned mixtures of AlCl3.6H20 and Al2(0H)s Cl,2H20 wherein the total metal to chloride molar ratio in the complex is 1ess than about 1.25 and the Al:Zr molar ratio is about 3~3t and the amino acid is glycine; and ZAG-type com-plexes wherein the zirconium salt is ZrO(OH)2 ~Cl~.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 Al2(0H)5Cl.~HzO. and the amino acid is glycine.
Solubilized antiperspirant actives which may be utilized in the present invention are also well known in the art, and include the actives described abov~. Compositions conta~ning solubilized antiperspirant active ut~lize solvents, such as monahydric or polyhydric alcohols or water, to solub~lize the antiperspirant act~ve before ~t is incorporated into the product. Examples of actives for such ~se are taught, for examp1e, in U.S. Patent 4,137,306, Rubino, issued January 3Q, 197g, U.S. Patent Appl~c~-tion Serial No. 370,559, Smith ind Ward, fil~d June 231 1989, and European Published Application 0295070, publish~d December 14, 19881 all of which are incorporated by reference herein. ACH is the preferred typ~ of active for compositions containing solu~i-lized antiperspirant active~.
Examples of especially :preferred actives inelude improved efficacy ACH ~IACH) and improved efficacy ZAG (I7AG). The en-hanced efficacy is due to improved molecular distribution. Such materials are described in U.S~ Patent 4,359,456, Gosling et al., issucd November 16, 198~; European Patent Applic~tion Publication No. 6,739, to UnileYer Limlted, published January 9, 1980;
European Patent Appl;cation Publication No. 183,171, to Armour Pharmaceutical Company, published June 4, 1986i British Patent Specification No. 2,048~2Z9, The Gillette Company, published December 10, 1980; European P~tent Application Publication No.
191,~28, to Unilever PLC, published August 20, 1985; British 21 U93~7 WO 92/192~2 PCI/US92/033~' j Patent Specification No. 2,144,992 to The Gillette Company, published M~rch 20, 1985; European Patent Application Publication No. 7,191, to Unilever Limit~d, published January 23, 1980; all incorporated by reference herein in its entirety; as well as previously incorporated U.S. Serial No. 370,559, filed June 23, l9B9 and Europ~an Patent Ho. 0295070.
HYdroxY-~olv~n~
The compositions of the present invention include from about 5~ to about 98%, preferably from about 7% to abo~t 90%, most preferably from about 60~ to about 85X, of a hydroxy solvent ~or the gelling a~ent. This solvent, in combinat~on with the 2 oxazolidinone cosolYent, forms the base matrix of the solid stick when combined with the gelling agent. As will be appre-ciated by those skilled in the art, the selection of a particular hydroxy solvent will depend upon the ~haracteristics of the stick desired. For example, the hydrox~ solvent can also solubilize the antiperspirant activ@ compon~nt in fonmu1ations having solubilized antiperspirant active material. ~For another example, the hydroxy solvent may be selected to provide such cosmetic benefits as emolliency when applied to the skin. Hy~roxy solYents useful ;: herein include monohydric alcohols (particularl j~ lower monohydric alcohols), polyhydric alcohols, and mixtures thereof. ~ater may act as a solv~nt and may also be included in the compositio~s.
~` Water is generally present at le~els of no greater than about 5%, by weight, of the ~inal composition.
Examples~: of hydroxy solvents which may be utilized in ~he presen~ inventi:on include l i~id polyethylene glycols (e.g., diethylene: glycol, trlethylene glycol), 7iquid polypropylene glycols (e.g., dipropylene::~glycol, tripropylene glycol), liquid polypropylene polyethylene glycol copolymers, water, éthano1, : ~ n-propanol, n-butanol, t-butanol, 2-metho%yethanol, 2-ethoxy-: ethanol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glyccl, 1,4-:butylene glycol:, 1,2-butylene glycol, isopropanol, isobutanol, d~ie~thylene gl~ycol monomethylether, diethylene glycol : 35 monoethylether, i,3-butylene glycol, 2,3-butylene glycol, 2,4-:
:
;: ~

2~L0~3~7 dihydroxy-2-methylpentane, trimethylene glycol, glycerine, 1,3-butane diol, 1,4-butane diol, and the like, and mixtures thereof.
As used herein, polyethylene glycols, polypropylene glycols, and polypropylene polyethylene glycol copolymers include the alkyl ether derivatives of these compounds (e.g., ethyl, propyl, and b~tyl ether deri~atives). Examples of such compounds are butyl ~ther derivatives of polypropylene polyethylene glycol copolymers, such as PPG-5-buteth-7.
These solvents ar~ fully described, for example, in U.S.
Patent 4,51~,582, Schamper et al., issued May 21, 1985, and European Published Application 107,330, Luebbe et al~, published May 2, 1984, both incorporated herein by reference. The preferred solvents for use herein include liquid polyethylene glycols, liquid polypropylene glycols, l~quid polypropylene ~olyethylene glycol copolymers, propylene glycol, 1~3-butylene glycol, and 2,4-dihydroxy-2-methylpentan~ ~sometimes referred to as hexylene glycol ), and mixtures thereof. Parti~ularly preferred solvents include propylene glycol, d1propylene glycol, tripropylene glycol, triethylene glycol, hexylene glycol, and mixtures thereof.
20 Cosol vent ~ he compositions hereof include, as an essential ingredient, a specific cosolvent for the gelling agent. The cosolvent is a 2-oxa~otidinone compound having a Cl-C4 alkyl radical substituted at the 3 pos1tion of the heterocyclic ring, or a mixt-ure of such compounds. This cosolvsnt should also ~e misc~ble with the hydroxy solvent.~ The gelling agent must be more soluble in the cosolvent than in;the hydroxy~sol~ent, in ordsr for the cosolvent to depress :thei gellation temperature of the composition and, accordingly, reduce the temperature at which the compositions hereof can be processed. For purposes hereof, the gelling agent should be sufficiently;soluble in the solvents to form a substan tially clear, isotropic solution.
The 3-alkyl~substituted, 2-oxazolidinone cosolvent will be generally present ~in thè composi~ion at a level of about 0.5% to : 3~
: ` :

2109f3 ~ 7 wo ~2/lg222 PCT/US92/033i ;j~

ab~ut 4~%t by weight, of the composition, preferably from about 1%
to about 2~, more preferably from about 5% to about 15%.
The composltions hereof should contain a sufficient amount of the 2-oxazolidinone cosolvent to significantly reduce the gella-s tion temperature of the solution of the solvent system (said system containing the hydroxy solvent and the 2-oxazolidinone cosolvent) and the gell~ng agent. This ts determ~ned relative to the gellation temper~ture of a solutlon containing the gell ing agent and hydroxy solvent, but not the 2-oxazolidinone cosolvent.
Gellation temperature determination methods are well known in the art. The particular method by whlch gellat~on temperature is determined is not critical, although the sam~ method m~st be used throughout any gellation temperature comparison~ ~he total level of solvent should be consistent ~n the comparison. A proportional decrease of hydroxy solvent(s) to compensate for the addition of cosolvent will account for thisO Proportions af hydroxy s~lvents, relative to one another, used in hydroxy sol~ent mixtures should also be the same. As will be appreciated by those skilled in the art, the gell1ng agent must be mor~ soluble in the cosolvent than : 20 in the hydroxy solvent ~or a:reduction in gellation temperature to : occur. As used:herein, by a sufficient amount of the cosolvent to significantly reduce the gellation t~mperature is meant that a sufficient amoynt~of the 2-oxazolid~none cosolvent is used such that:the gellation temperature is at least about 2 C~ lower than . 2s for:a corr~spooding system wit~hout the 2-ox~zolidinone cosolvent, prefe~ably~at~least about:3 ;C^, ~ven more preferably at least about S:C~. In: the most preferred cases, the temperature d~ffer-ent1al;is ~rom;about lO C- to:abo~t 30 C-.
The weight;~rat~o of the hydroxy solvent to the 2-oxa~nlidi-none coso1vent~is preferably from about 1:l to about 50.1, more preferably from:~about 3:1~to:about~20:1, and the weight ratio of : gelling agent to the 2-oxazol;dinone:cosolvent is preferably from ; about .05:1 to;abou~ 2:1, more~preferably from about .1:1 to about , ~ ~ Preferred ;;3-a1ky1-substituted 2-oxazolidinone compounds hereof have the formul;a:

~. WO 92/1~22Z 21 U ~ 3 ~ 7 PCI`/US92/03348 O

, R

~ J

wherein the radical R at the 3 pvsition is a Cl-C" alkyl, prefer-ably a Cl-C2 alkyl~ more prcferably Cl (i.e., methyl).
The preferred cosolvents are 3-(Cs-CI alkyl)-2-oxazolidi-10 nones, preferably 3-(Cl-C2 alkyl)-2-oxazol~dinones. Most pre-ferred is 3-me~hyl-2-oxazolidinon~.
The 3-al kyl -substituted 2-oxazol idinone may al 50 have sub-stituents located at the 4 and 5 positions of the heterooycl ic ring insSead of hydrogen. Preferably, if used, such substituents are lower alkyls, e.g., Cl-C~ alkyl, preferably Cl-C2 alkyl, more preferably methyl. Other subst~tuents can be présent which do not cause the compound to be immiscibl~ with the hydroxy solv~nt or reduce solubility of the gelling a~ent in it to less than the hydroxy solvent. Also, the compound should remain stable aga~nst dec~mposition in the processing of~ and undcr the typi~al storage and use conditions of, the gel stick co~positions.
The 3-alkyl subst~tut~d, 2 oxazolidinone cosolvents hereof can be mad~ accord~ng to processes known in the art. Exemplary processes are disclosed in U.S. Patent 2,755~286, Belt et al., issued July ]7, 1956, U.S. Paten~- 2,399~118, Hofmeyer, issued April 23, 1946, and prewiously re~ferenced "L~quid 2-Oxazolidones.
1. Dielectric Constants, Viscosities~, and Other Physical proper-ties of Several Liquid 2-Oxazolidones", by Huffman and Sears, J.
of 501ution Chemistry, Vol. 1, No. 2, 1972, pp l~t-196. 3 Methyl-30 ' 2-oxazol,idinone i con~tercially available, for example, from Raylo Chemicals, a division of Terochem Laboratories, Ltd (Edmonton, Alb~rta, Canada), and from Aldrich Chemical Co. ~Milwaukee, Wi scons i n USA) .
O~tional Com~onents ~ ~
~; The compositions of the pres~nt invention may also contain op~ional components whlch modify the physical characteristics of the compositicns or serve as "active' components when deposited on ~9~2~ 7 PCT/US92/0334~ ;

the skin in addition to the antiperspirant material. Optional components useful herein are described in the following documents, all incorporated by reference herein: U.S. Patent 45049,792, Elsnau, iss~ed September 20, 1977; Canadian Patent 1,164,347, S Beckmeyer et al., issu~d March 27, 1984; European Patent Appli-cation 117,070, May, published August 29, 1984; and Geria, ~Formu-lation of Stick Antip~rsplrants and Deodorants", Cosmetics &
ToiletriesJ 99:$5-60 (1984).
The specific non-active components that may be useful will depend upon the characteristics desired ~or the parttc~lar stick composition. Such components ~nclude, for example, emollients, humectants, hardeners (e.g, wax), fillers and particulate mate-rials, colorants, perfumes, and emulsifiers. As used herein, Uparticulate materials~ are those materials, ~ncluding colloidal dispersions, that neither dissolve in the composition components nor melt during the manufactur2 of the st~ck.
The compositions of the present invention may contain from about 1% to about 49X of one or more emoll~ents. These emollients may have an ~ntermediate polarity, such as the ethyl, isopropyl and n-butyl diesters of adipic,~ phthalic and sebacic acids.
Preferred examples of such emollients include ~i-n-butyl phtha-late, d~ethyl sebacate, dt~sopropyl adipate and ekhyl carbomethyl phthalate, all of which are d~sclosed in ~.S. Patent 4,045,54~, ~ Luedders et al., ~ssued August 30~ 1977, wh~ch is incorporate~ by: :25 re~erence her~.in.: Other useful ~moll~ents include Cl2-C,5 alcohol benzoates (commercially~availab1e~ as Fins~l~ from Finetex, lnc.).
Useful emollients also include fatty alcohols, such as cetyl and stearyl alcohols,~which~ (:if used):~will preferably be present at a level of from about 1% to about lOX, more preferably from about 1%
to about ~5%. The compositions af the present invention may also include non-polar emollients, such as volatile silicone oils, non-polar non-volatile emollients,~ and mixtures thereof. The term "volatile", as used herein,~refers~to thos~ materials which have a measurable vapor pressure at:ambient temperature.
Vol~tile sil ico~ne oils ose~ul in the cosmetic stick com-positions of the present:invention are preferably cyclic or linear :

:: :

WO 92/19222 21 ~J ~ ~ Q 7 PCI'/USg:;!/03348 polydimethylsiloxanes containing from about 3 to about 9, pref-erahly from about 4 to about 5, silicon atoms. The fo11Owing ~ormula illustrates cyolic volatile polydimethylsiloxanes useful in the antiperspirant stick compositions disclosed herein:
~I CH3 L~ O]~n wherein n e~ua1s about 3 to abnut 7~ Linear po1ydimethylsiloxanes contain from dbout 3 to about 9 silicon atoms per molecule and have the following general fsrmula:
(CH3) 35i -O- [Si (CH3~ 2 -~n-Si (C~3 ) 3 wherein n equals about 1 to about 7. Linear volatile sil k one materials generally haYe viscosities of less than about 5 centi-stokes at 25-C, while cyclic materials typically have viscosities of less than about 10 centistokes. A description of various volatile silicone oils is fo~nd ~n Todd et al., ~Volatile Silicone Fluids for Cosmeticsn, Cosmetic & Toi1etries, 91, pages 27-32 (1976), the disclosu~es of which are incorporated by reference herein.
: Examples of preferred volatile silicone oils us~ful herein include: Dow Corning 344~ Dow Corning 345, and Dow Corning 200 (manufactured by Dow C~rning Corp.); Silicone 7207 and Silicone 7158~(manufactured by Union Ca~btde Carp.); SF 1202 (~anufactured : ~5 by Gen~ral Electric), and SWS-03314 (manu~actured by SWS Sili-cones, Inc.)~
Non~vol:~tile silicone ~oils::useful as~ emollient materials : include polya~lkylsiloxanes, polyarylsiloxanes and polyethersilox-ane copolymers.~; The essentially non-volatile polyalkyl siloxanes ` 30 useful hersin include, for example, p~lydimethyl siloxanes with~ viscosities of from about; 5~to about 100,000 centistokes at 25-C.
: ~ : Among the preferred non-volatile emollients useful in the present :
~: ~ compositions~are the polydimethyl sIIoxanes having viscosities from about 2 ~to about 400 centistokes at 25-C. Such polyalkyl si~loxanes Include~the Viscasil series (so1d by General Electric :~ Company) and~ the Dow Corning 200 series (sold by Dow Corning 2~.0~3~ ~
WO 92~19222 PCl /US92/0334f.' Corp.). Polyal~ylaryl siloxanes include polymethylphenyl silox-anes having viscosities af from about 15 to about 65 centistokes at 25-C. These are available, for example, as SF 1075 methyl-phenyl fluid (sold by General Electric Company) and 556 Cosmetic Grade Fluid (sold by Dow Corning Corp.). Usefu1 polyether silox-ane copolymers include, for example, a polyoxyalkylene ether copolymer having a viscosity of about 1200 to 1500 centistokes at 25-C. Such a fluid is available as SF1066 organosilicone sur-factant (sold by General Electric Company). Polysiloxane ethylene glycol ether copolymers are preferred copolymsrs for use in the present composit~ons.
The compositions of the pr~sent invention may include a stabilizing agent which acts to stabilize the compositîon (espe-cially the gel1ing agent~ during the high temper~ture steps of the manufacturing process, during st4rage of the product, or both.
These m~erials are generally used at levels of about 0.05X to about 5% of the composition. Exa~ples of these material include zinc acetate, m~then~mine, magnesium acetate, calcium acetate, triethanolamine, diethanolamine,Oand mixtures thereof. Preferre~
stabilizing ag~nts are salts of C4 -C6 (saturated) dicarboxylic, C6-C~ (saturated) monocarboxylic, and substituted and unsubsti-tu~ed benzoic ~acids. These will be added as salts which are at least partially soluble tn She solY~nt system. Suitable salt-forming cat~ons include sodium, potassium, lith~um, -magnesium, calcium, and zinc. Preferred~ salt-forming cations are sodium, potassium, magnesium, and calciu~, especially sodium. Especbally preferred stabilizing agents include the benzoates, succinate, and octanoate salts such as disodium succinate, sodium benzoate, and sodium octanoate.
!.', ' 30 The compositions of the present invention may also contain from about 0.5YO to about 10% of an inert filler material. Suit-able;filler materials include~colloldal silica (such as Cab-0-Sil, sold by Cabot Corp.), clays~:(s~ch as bentonite), hydrophobic : (quaternized) ~clays, silica/alumina thickeners, silicate powders such as talc, alumina sil~icate, and magnesium silicate, modified corn starches, metallic stearates,~and mixtures thereof. The use .

WO 92/19222 210 9 3 ~ 7 PCI`/US92/03348 cf such ~illers as stabilizing agents in cosmetic sticks is disclosed in U.S. Patent 4,126,679, Davy et al., issued November 21, 1987, incorporated h rein by reference. The compositions of the present invention may also include perfumes, emulsifiers and coloring agents well known in the art, at levels of from about 0.1% to about 5%.
In addition to the an~iperspirant actives, discussed above, the antiperspirant sticks of the present invention may also contain a safe and effective amount of one or more ~dditional components which are meant to be deposited upon human tissue.
Such active component~ incl~de astringents, bacteriostats, fungi-stats, pigments, dyes, colorants, perfumes, emollients, ultra-violet absorbers, and mixtures thereof. These components must be stable in the formulation of the instant invent~on. A ~safe and ef~eetive" amount of such active compon~nts is that amount which yields the desired benefit at a reasonable b~nefit/risk ratio f~r human usage. ~arious active components among those useful in the present invention are described in U.S. Patent 4,226~889, Yuhas, issued October 7~ 1980, incorporated by reference herein.
The present invention further relates to a process for making an antiperspirant gel stick composition utiliziDg a dibenzylidene alditol gelling agent, 2-oxazolidinone subst~tuted at the 3 position with a C~-C~ alkyl as~a cosolvent along with a hydroxy solvent and the antiperspirant act1Ye.
The process ut;ilizes ~a su~ficient a~ount of the 2-oxa~olidlnone :cosolvent~ to s~gni~icantly reduce the gellation temperature:of the:solution.: This is determined relative to the gellation te~perature of a solutinn containing the gelling agent and hydroxy :solvent, ~b~t not the 2-oxazoltdinone cosolvent, as '` 30 described above.
` ~ The preferred: components:and ;levels are described in more detail above.~ ~ Thus, ~the invention~ also relates to an improved ~; process for:mak~;ng an antiperspirant g~l stick, having acidic pH, : composition containing:hydroxy ~solvent, substituted or unsubsti-tuted dibenzylidene ~lditol:gelling agent~ and antiperspirant active, said p~ocess comprising solubilizing said gelling agent in a heated solvent to:form a solution and subsequently cooling said :

2~93~ ~
w o 92/19222 Pc~/uss solution to form a gel 7 wherein the improvement comprises incor-porating into said solvent system a sufficient amount of 2-oxazo-lidinone substituted at the 3 position of the heterocyclic ring with Cl-C~ alkyl to significantly reduce the ~ellation temperature of the solution.
In a preferred process, the ant~p~rspirant gel stick composi-tions are made according to the steps of:
(a) preparing a solution containing a hydroxy solvent9 a substituted or unsubstituted dibenzylidene alditol gelling agent, and a Z-oxazo~dinone having a C~-C~ alkyl radical, or mixture thereof, su~st~tuted at the 3 pos~tion of the heterocyclic ring, wheretn said gelling agent is soluble in said 2-oxazolidinone and said composition preferably has a weight ratio of said hydroxy solvent to said 2-oxazolidinone of from about 1:1 to about 50:1, and a weight ratio of said gelling agent to said 2-nxazul~dinone of from abou~ 0.05:I to about O.1:1;
(b) mixing an antiperspirant active into said sol~tion; and (c) cooling said solut~on to amblsnt temperature;
wherein said composition haç an avera9e penetration v~lue of from about 60 to about 200 tenths o~ a mil}i~eter at ambient temperature.
The preferred 1 evel s of the hydroxy sol vent, cosol vent, gell ~ng agent, and ant~pe~spirank active in the final composition are as described above.
Consistent with the aboYe, th~ compositions of this invention may be made~b~ msthods known to tho5e skilled in the art. Such methods are described in "Gels~and Sticks Formulary~ Cosmetics &
To71etries, 99, J7-84 (1984],~incarporated by reference herein.
After the antiperspirant act~ve~ and optional components are added, the solution is poured:into st1:ck molds. A solid gel forms upon cooling. As the: stick composition may solidify rapidly upon cooling, care should be taken so as to maintain an elevated ` temperature while mixing and prucessing the composition.
The gel form antiperspirant stick compositions of the present invention are used in~a conventional manner. Specifically, the : ~:
, :

f ~ WO 92/19222 2 :10 9 3 ~ 7 PCl`/US92/03348 - ~5 -compositions ~ay be used to prevent and/or control perspiration wetness by topically applying, one or more times a day, an effec-tive amount of the composition to 2reas of the body particularly prone to perspiration (e.g., the underarm or axillary area).
The ~ollowing non-limiting examples illustrate the composi-tions~ methods of makin~, and methods of use described in the present application.
EXAMPLES I-III
Opaque an~iperspirant gel stick compositions are exemplified in these exa~ples. The compositions are made according to the fol l owi ng procedure .
Phase A - If applicable, weigh the water into a beakert add the sodium benzoate, and agitate at room temperature until the sodium benzoate ts dissolved, to form a sodium benzoate solution.
Add the sudium benzoate solution (if any), the Phase A
portion of the hydroxy solvent, and 3-methyl-2 oxazolidinone (3M20) into a 3-neck round bottom flask equipped with a reflux condenser, thermometer, and magnetic st~r bar. Place the flask in a heating mantle connected to a rheostat.
Weigh the gelling agent and add it to the flask. Heat the flask while stirring until the gelling agent is completely dis-solved at about 110^C to about 132~C for Example I, absut 100-C to about 1~2C for Ex~mple Il, and about 90-C to about 110-C for Example III. Hold within`the t~mperat~re range with st~rring.
Phas0 B - W~igh the Phase B portion of the dipropylene glycol and the ethanol (1~f applicable)~ into a round bottom flask ~quipped w~th a reflux condenser,~thermometer, and mechanical stirrer. Add : ::the ~antiperspirant :active and mix until well dispersed. Mixing can alternately be performed with a high shear mixer. Add the fumed silicai and,` if applicable, the fumed aluminum oxide or diethyl sebacate, to~the~:~lask, place the flask in a heating mantle connected to a rheostat, and heat the flask to about 65-C
: ~to about 90-C while stlrring. ~:Hold at about 65~C to about 90~C
for Example I, at about~55-C to~about 80-C for Example II, and : 35 about 45'C to about 70-C for Example III, with stirring , 'J ~
wo 92/1s222 PC~/US92/0334~
.
!

Add Phase B to Phase A flask and mix until homogenous. Cool to near, but above, gellation temperature, to aYoid premature gelling, e g., about 5 to about 10 C- above gellation temperature, determined at the point that the gelling agent visibly (with the naked eye) begins to come out of solution, i.e., begins to gel.
For Example I, gellation temperature will typically be about 12-15 C- below that which would be expected in a simi1ar composi~
tion wlthout the 3M20 (based upon a proportional increase in the hydroxy solvent(s~ to replace the 3M20). For Exa~ple II, gella-tton temperature wlll typical1y be about 18-21 C- lower than without 3M20. For Example III, gellat1On temperature will typic-ally be about 7-10 C' lower than without 3M20. ~hus, the compo-sitions can be processed:and held during pro~essing prior to gellation at reduced temperatures to thereby reduce decomposition of the gelling agent and improve gel stick properties. A prac-t1cal benefit of th~s, for example, is that reduced gelling agent decomposition can be obtained while the pre-gelled product is be~ng held in bulk during packaging ~e.g., sequent1al pouring o~
the product into cannist~rs for subsequent cooling belaw gellation temperature).
: In~redients : ExamDl~ (wt. X!
Phase A : I II III
Sodium Benzoate~ ~ 1.00 - 1.b0 ~ater ~ : 2.QO - 2.00 2S Hydroxy So~vent Dlpropylene~Glyc4l : ~ 15.00 - 4~.50 Propylene &lycol ~ ~ 15.00 31.00 ~:: : 3-Methyl-2-Oxazolidinone (3M20) 10.00 15.00 5.00 Di (m-fluorobenzylidene~ Sorbitol 3.00 3.00 Dibenzy1idene Sorbitol (unsubsti~tutedj - - 3.50 Phase ~ B ~ :
`~ Hydroxy:Sol~ent~
Dipropylene Glycol~ 27.00 30.00 20.00 Ethanol ~ :10.00 - 10.00 Zirconium Alumlnum sr~? W 0 92/19222 2 ~L ~ 9 3 Q 7 PCI/US92/03348 Trichlorohydrex Gly (ZAG)* 15.00 15.00 15.00 Fumed Silica** 1.67 1.00 1.00 Fumed Aluminum Oxide*** 0.30 - -Diethyl Sebacate - 5,0 * Available as WESTCHLOR ~R 30B ~M Powder from Westwood Chemical Corp. (Middletown, NY, USA).
** Available as CABOSIL from Cabot Corp; (Tuscola, I~, USA).
*** Available as Aluminum Oxide C from Deyussa~ Inc. (~eterboro, NJ, USA).
The opaque gel sticks exhibit excellent gel properties and can provide excellent antiperspirant eff~cacy when applied to the axîllary area.
EXAMPLES IV-VI
Clear ant~perspirant gel stick compositions are exemplified in these examples. The compositions are made according to the follow~ng procedure.
ihase A - If appl1cable, weigh the Phase A portion of the water into i beaker. Add the sodium benzoate and agitate at ro~m temperature until the sod~um benzoate ~ dissolved, to form a sod~um benzoate solution. Add the sodium benzoate solution (if applicable), ~he Phase A port~on o~ hydro~y solvent, diethyl sebacate, and the 3-methyl-2-oxazo1id~none into a 3-neck round bottom flask equipped with a reflux condenser, thermometer, and magnetic st~r bar. Place the flask 1n a heat~ng mantl~ connected to a rheostat.
We~gh the gelling agent and;~add it to the flask. Heat the flask while st~rring until the gelling agent is completely dis-solved at about ;llO~C to about 132-C for Exa~ple IV, at about lOO-C to about 122~C for Example V, and at about 90-C to about i 110-C for Example~VI. Hold within this range with stirring.
Phase B - Weigh the propylene~ glycol into a flask. Add the anti:perspirant active and~mix until homo~enous. Add the Phase B
portion of the water.: Mix: with a hi~h energy mixer and heat to :~ about 45-C to about 85q~ wh11e :mixing until the active is ~ 35 solubilized. ~eaerate. ~ ~ ~

: ::::

2 ~ 1 3 13 7 W o g2/19222 PCT/VS92/033 Add solubilized active and, if applicable, the ethanol and silica into a round bottom flask equipped with a reflux condenser, thermometer, and m~gnetic stir bar. Place the flask in a heating mantle connected to a rheostat, and heat the flask to about 65~C
S to about 90-C for Example IV, to about 55'C to about 80'C for Ex~mple I, and to about 45~C to about 70C for Example VI, wh~le stirring. Hald within the applicab1e range w1th st1rring.
Add Phase B to Phase A flask and mix until homogenous~ Cool to near, but above, gellation te~perature, to aYo~d premature gell~ng, e.g., about 5 to about 10 C- above 9ellation temperatur~, determined at the point that the gelling agent v~sibly (with the nakad eye) begins to come out of solut~onl i.e., ge1. For Example IV, gellation temperature will typically be about 12-15 C' be10w that which would be expected in a s1~i1ar composition without the 3M20 (based upon a proportional increase in the hydroxy solvent(s) to replaee the 3M20). For Example V, gellat10n temperature will typically be about 12-15 C- lower than without 3M20. For Example VI, gellation temperature will typ~cally be about 7-lQ C- lower than w~thout 3M20. ~hus, the compositlons can be processed and held dur~ng process~ng pr~or to gellation at reduced temperatures to thereby reduce decompos~tton of the gelllng agent and improve gel st1ck properties. A practical benefit of this, for example, is that reduced gelling agent deco~position ean b~ obtained wh~;e the pre-gell~ed product ~s b0~ng he1d in b~lk during packaging : 25 (e.g., sequenti~al pou~ing of the product into cannisters for s~bsequ~nt cool~ing below gellation temperature).
D9rÇ51ÇD~ xam~1es ~We1qht %) ~: ` Phase A : : IY V VI
Sodium Benzoste ~ 1.00 - 1.00 ~' ` ` 30 Water I 2.00 - 2.00 Hydroxy Solvent ~
Di:propylene Glycol 43.00 - 47.50 : Prop~lene G!yco~ 47.00 -3-Mèthyl-2-Oxazolidone (3M20) 10.00 15.00 5.00 Diethyl Sebacate ~ : - 5.00 : ~ :

i W~ 92/19222 2 1 0 ~ 3 û 7 PCI/US92/03348 - 2g -Di(m-fluorobenzylidene) Sorbitol 3.~0 3.00 Dibenzylidene Sorbitol ~unsubstituted) - - 3.50 Phase B
Hydroxy Solvenk Ethanol 10.00 - 10.00 Propylene ~lycol 15.00 15.00 15.00 Aluminum Chlorohydrate* 13.50 13.50 13.50 Fumed S1lica** 1.00 - 1,00 Water 1.50 1.50 1.50 * Available as WESTCHLOQ DM ZOO Powder from Westwood Chemical Corp. (Middletown, NY, USA).
** Availab1e as CABOSIL from Cabot Corp. (Tuscola, IL, USA~.
The sticks have excellent gel properties and can provide 15 excellent antiperspirant efficacy when applied to the axillary area~ The composition will be clear or translucent.
~HAT IS CLAIMED IS:

.

:
:

:
, .
` 30 3~

::

Claims (22)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A solid antiperspirant composition in gel stick form, having an acidic pH, comprising:
(a) from about 0.5% to about 35% of an antiperspirant active;
(b) from about 0.5% to about 10% of a gelling agent selected from the group consisting of substituted and unsubsti-tuted dibenzylidene alditols, and mixtures thereof;
(c) from about 5% to about 98% of a hydroxy solvent for said gelling agent selected from the group consisting of monohydric and polyhydric alcohols; and (d) from about 0.5% to about 40% of a 2-oxazolidinone having a C1-C4 alkyl radical substituted at the 3 position of the heterocyclic ring, or a mixture thereof, wherein said gelling agent is more soluble in said 2-oxazoli-dinone than in said hydroxy solvent.
2. A solid antiperspirant composition according to Claim 1 wherein said composition has a weight ratio of said hydroxy solvent to said 2-oxazolidinone of from about 1:1 to about 50:1, and a weight ratio of said gelling agent to said 2-oxazolidinone of from about 0.05:1 to about 2:1.
3. A solid antiperspirant composition according to Claim 2, wherein said 2-oxazolidinone compound is a 3-(C1-C4 alkyl)-2-oxazolidinone, or a mixture thereof.
4. A solid antiperspirant composition according to Claim 3, wherein said 2-oxazolidinone compound is 3-methyl-2-oxazolidinone.
5. A solid antiperspirant composition according to Claim 3, wherein the weight ratio of said hydroxy solvent to said 2-oxa-zolidinone is from about 3:1 to about 20:1 and the weight ratio of said gelling agent to said 2-oxazolidinone is from about 0.1:1 to about 1:1.
6. A solid antiperspirant composition according to Claim 5 comprising from about 7% to about 90% of said hydroxy solvent, from about 1% to about 25% of said 2-oxazolidinone, and from about 2% to about 5% of said gelling agent.
7. A solid antiperspirant composition according to Claim 4, wherein the weight ratio of said hydroxy solvent to said 2-oxa-zolidinone is from about 3:1 to about 20:1 and the weight ratio of said gelling agent to said oxazolidinone is from about 0.1:1 to about 1:1.
8. A solid antiperspirant composition according to Claim 7 comprising from about 7% to about 90% of said hydroxy solvent, from about 1% to about 25% of said 2-oxazolidinone, and from about 2% to about 5% of said gelling agent.
9. A solid antiperspirant composition according to Claim 8, comprising from about 60% to about 85% of said hydroxy solvent and from about 5% to about 15% of said 2-oxazolidinone.
10. A solid antiperspirant composition according to Claim 1 wherein substituted and unsubstituted dibenzylidene alditol, is selected from the group consisting of substituted or unsubstituted dibenzylidene sorbitols, substituted or unsubstituted dibenzyli-dene xylitols, substituted or unsubstituted dibenzylidene ribi-tols, and mixtures thereof.
11. A solid antiperspirant composition according to Claim 4 wherein the gelling agent is a substituted or unsubstituted dibenzylidene sorbitol, or a mixture thereof.
12. A solid antiperspirant composition according to Claim 11 wherein the gelling agent is di(meta-fluorobenzylidene) sorbitol, di(meta-chlorobenzylidene) sorbitol, unsubstituted dibenzylidene sorbitol, or a mixture thereof.
13. A solid antiperspirant composition according to Claim 1 wherein the hydroxy solvent is selected from the group consisting of liquid polyethylene glycols, liquid polypropylene glycols, liquid polyethylene polypropylene glycol copolymers, ethanol, n-propanol, n-butanol, t-butanol, 2-methoxyethanol, 2-ethoxy-ethanol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,2-butylene glycol, isopropanol, isobutanol, diethylene glycol monomethylether, diethylene glycol monoethylether, 1,3-butylene glycol, 2,3-butylene glycol, 2,4-dihydroxy-2-methylpentane, trimethylene glycol, triethylene glycol, glycerine, 1,3-butane diol, 1,4-butane diol, and mixtures thereof.
14. A solid antiperspirant composition according to Claim 13 wherein the solvent is selected from the group consisting of triethylene glycol, propylene glycol, dipropylene glycol, tri-propylene glycol, hexylene glycol, and mixtures thereof.
15. A solid antiperspirant composition according to Claim 1 wherein the antiperspirant active is in solubilized form.
16. A solid antiperspirant composition according to Claim 1 wherein the antiperspirant active is in particulate form.
17. A solid antiperspirant composition in gel stick form, having an acidic pH, comprising:
(a) from about 5% to about 35% of an antiperspirant active;
(b) from about 2% to about 5% of a gelling agent selected from the group consisting of substituted and unsubstituted dibenzylidene sorbitols;
(c) from about 60% to about 85% of a hydroxy solvent selected from the group consisting of monohydric and polyhydric alcohols, and mixtures; thereof; and (d) from about 5% to about 15% of a cosolvent selected from the group consisting of 3-(C1-C4) methyl-2-oxazolidi-nones;
wherein said gelling agent is more soluble in said cosolvent than in said hydroxy solvent.
18. A method for preventing and controlling perspiration wetness in humans comprising the application to the underarm area of an effective amount of the solid antiperspirant composition according to Claim 1.
19. A process for making an antiperspirant gel stick compo-sition, having acidic pH, containing hydroxy solvent, substituted or unsubstituted dibenzylidene alditol gelling agent, and antiper-spirant active, said process including the steps of solubilizing said gelling agent in a heated solvent and subsequently cooling said solution to form a gel, wherein the improvement comprises incorporating into said solvent system a sufficient amount of 2-oxazolidinone substituted at the 3 position of the heterocyclic ring with C1-C4 alkyl to significantly reduce the gellation temperature of the solution.
20. A process for making an antiperspirant gel stick compo-sition, said composition having acidic pH, comprising:
(a) preparing a solution containing an alcoholic solvent, a substituted or unsubstituted dibenzylidene alditol gelling agent and a 2-oxazolidinone having a C1-C4 alkyl radical substituted at the 3 position of the hetero-cyclic ring, or a mixture thereof, wherein said gelling agent is more soluble in said 2-oxazolidinone than in said hydroxy solvent, and said composition has a weight ratio of said alcoholic solvent to said 2-oxazolidinone of from about 1:1 to about 50:1, and a weight ratio of said gelling agent to said 2-oxazolidinone of from about 0.05:1 to about 2:1;

(b) mixing an astringent antiperspirant active into said solution; and (c) cooling said solution to ambient temperature;
wherein said composition has an average penetration value of from about 60 to about 200 tenths of a millimeter at ambient temperature.
21. The product made according to the process of Claim 19.
22. The product made according to the process of Claim 20.
CA002109307A 1991-05-06 1992-04-24 Gel stick antiperspirant compositions containing 2-oxazolidinone derivative and process for making them Abandoned CA2109307A1 (en)

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US07/696,375 US5200174A (en) 1991-05-06 1991-05-06 Gel stick antiperspirant composition containing 2-oxazolidinone derivative and process for making them

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CN1067373A (en) 1992-12-30
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TW213417B (en) 1993-09-21
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US5200174A (en) 1993-04-06
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