Note: Descriptions are shown in the official language in which they were submitted.
`~ 2~82~1~
wo 91/18587 PCr/US91/026~,
-- 1 --
LIQUID ANTIPERSPIRANT COMPOSITIONS
~ L ~ u
S The present invention relates to unique clear, sprayable,
liquiu an.,.e,,~l.ant cvm?os,~ ons having viscosities of less than
about !i cQntistokes and ~ihich provide excellent intiperspirancy
an~ r~ r~
.~n~ i sa nt c 'i~ pOs !;i on ~ hâve oecome part of many people's
pers~nal ca,e arb g ^cming regimen. ~he formulation of such
comDositions~ ho~ever, yeneraliy is an exercise in efficacy and
aesthetic .rade-offs~ with the resulting composition being
acceptable overall, but not outstanding~ For example, the
15 formulation of a composition to give it good usage aesthetic
properties (e.g., minimized residue on the skin, and/or a clean,
dry and non-sticky feel) often compromises antiperspirant
efficacy. It is particularly difficult to maximize usage
aesthetics and efficacy, when creating a low-viscosity liquid
20 product, such as a spray-on antiperspirant composition, and
maintain good physical properties (e.g., stability o~er time and a
broad range of physical conditions, esDecially stability over a
broad temperature range).
Nonaerosol pump spray antiperspirant compositions, in
25 general, are known, having been disclosed in, for example, U.S.
Patent 4,053,581, Pader et al., issued October 11, 1977; U.S.
Patent 4,06i,564, Miles, Jr.~ issued December 27, 1977; U.S.
Patent 4,073,880, Pader et al., issued February 14, 1978; and
Great Britain Application 1,536,222, published December 20, 1978.
Generally, such compositions comprise high levels of an alcohol
solYent. Formulation in such a way generally results in products
with poor in-use characteristics, i.e., residue on skin, sticky,
cold feel, and stinging upon application.
Hence, it is an object of the present invention to provide a
low viscosity, clear, sprayable, liquid antiperspirant composition
W O 91/18587 ~ V ~ 2 X 1 ~ PCT/~S91/026<
which exhibits excellent antiperspirancy and cosmetic in-use
properties.
It is also an object of the present invention tO prOYi(~e l
low viscosity, clear, spray2ble, liqui~ an~iperspinal~ co:,~pos. :o,.
which is physically and chemically stable over time and a broad
range of physical conditions.
These and other objects ~ill become readily ~pparen- r~om `'-e
deta;led description ~hich follows.
SU~.~1A~ 0~ T~
The present invention rela~es ~o c ie~?~ i?U~ o a~
antiperspirant solutions, ha~/ing a visoosity o,^ less ~na, a~vu; l~
centistokes, comprising:
a. from about 10% to about 25% of a monohvdric alcnho1-co1
uble antiperspirant salt;
b. from about 3% to about 1~% of a non-volatile silicone
emollient having a viscosity of from about l centistoke to
about 50 centistokes and a solubility parameter of from about
4 to about 9;
c. from about 5X to about 25% of a volatile silicone
emollient having a viscosity of from about 0.65 centistokes
to about I0 centistokes and a solubility parameter of from
about 4 to about 9;
d. from about 5% to about 20~ of a non-volatile emollient
ester having a solubility parameter of from about 7 to about
10;
e. from about 1% to about 12~ of a solubilizer comprising
an agent selected fro~ the group consisting of ethoxylated
and propoxylated nonionic surfactants having an HLB of from
about 5 to about 18, and mixtures thereof;
such that the average HLB of the solubilizer is from about 8
to about l4; and
f. from about 30X to about 5070 of a monohydric alcohol
solvent;
wherein the antiperspirant composition comprises no more than
about 5% water.
W o 91/18~87 2 0 ~ 2 ~ }~CT/~S91/026X-
A preferred composition of the present invention comprises a
clear, sprayable, liquid antiperspirant solution, having a
viscosity of less than about lS centistokes, comprising:
a. from about 14X to about 16`~o of an ethanol-solubie
sesquichlorohydrate antiperspirant salt;
b. from about 3~ ~o about lC~ of a non-volat,l~ ~iliev,,a
emollient selected from the group consisting of phenyl
dimethicone, phenyl trimethicone, dimethicon~ ~luids hav,.
viscosities of from about 1 centis~oke ~o abou. i~
centistokes, and mixtures thereof;
c. from about lCX to about 15~ of a volatile silicone
emollient selected from the group consisting Qt O~-~S
cyclomethicones, phenethyl pentamethyl disiloxane~
dimethicone fluids having viscosities of less than
centistoke, and mixtures thereof;
d. from about gX to about 11% of a non-volatile emollient
selected from the group consisting of Cl2-C~s alcohols
benzoate, isopropyl myristate, isopropyl palmitate, and
mixtures thereof;
e. from about lX to about 2% of a solubilizer which
is selected from the group consising of:
A. ethoxylated nonionic surfactant materials selected
from the group consisting of compounds of the formula:
CH3(CH2)x(OCH2cH2)noH
wherein x is 12, 14, 16, or 18, and n is 10, and
mixtures thereof;
B. ethoxylated nonionic surfactant materials selected
from the group consisting of compounds of the formula:
CH3(CH2)x(OCH2cH2)noH
wherein x is 12, 14, 16, or 18, and n is 20, and
mixtures thereof;
and mixtures of A and Bi such that the average HLB of
the solubilizer is from about 8 to about 14, and wherein
if A and B are both present, they are at a ratio of A to
B of from about 2:1 to about 1:2;
w o 91/l8587 PCT/US91/026~
f. from about 5Xo to about 8X. of a co-solubilizer which
is selected rrom the group consisting of propylene glycol (n)
stearyl ether, ~nere n is on the average from 10-16, and
pnop~ 97~col ~n) ;~ riity1 ether, ~here n is on the
aver~ne t`rom 2-10, and mixtures thereofi and
.. ,,~v", ~vu~ c~ ~7~. of ath~nol;
~herain the antiperspirant composition comprises no more than
r.
v~T~ ;V~C'\'~ '~,Y vF T!~ Q~
iO ~ n;i~ eli ~ oQ~io,lal components of the present
co."pcsi io"s arY d~sc,i^ea belcl~.
4n.ioers~inant Mat~rial
~ critical comoonent c- the present compositions is an
antiperspirant material that i, soluble and which remains soluble
in ethanol or another suitable monohydric alcohol solvent.
Solubilization of the antiperspirant material allows for the
formulation of the present clear antiperspirant solutions.
A variety of publications disclose antiperspirant actives
which are soluble in non-aqueous solvents, typically monohydric
alcohols (e.g., ethanol). U.S. Patent 3,873,686, Beekman, issued
March 25, 1975, (incorporated herein by reference) provides a
useful summary of work in this area. The following publications
relate to antiperspirant actives soluble in non-aqueous solvents
and/or processes for making such actives: U.S. Patent 3,359,169,
Slater et al., issued December 19, 1967; U.S. Patent 3,420,932,
Jones et al., issued January 7~ 196g; U.S. Patent 3,507,896t
Jones et al., issued April 21, !.970; U.S. Patent 3,523,130, Jones
et al., issued August 4, 1970i U.S. Patent 3,555,146, Jones et
al., issued January 12, 1971; U.S. Patent 3,876,758, Beekman,
issued April 8, 1975i Great Britain Patent Speciflcations
1,159?685 and 1,159,686, both oublished July 30, 1969, Armour
Pharmaceutical Company; and European Published Patent Application,
7,191, published January 23, 1980, Unilever Limited.
U.S. Patent 2,890,987, Hilfer, issued June 16, 1959,
describes the preDaration of relatively dilute solutlons of
W O 91/18587 2 ~ ~ 2 ~ 1 ~ PC~r/~'S91/02687
astringent aluminum compounds in propy)ene glycol having
rela~ively h,gh water con-ent. U.S. Pa~ent 4,13~,306, Rubino et
al~ sued Oanuary 30, 1379~ d~scribes anhydrous propylene glycol
solu~l~n, . ~ conol io~ub7e a~ gen, ba~7c aluminum compounds.
Any alu~inum astringent antiperspirant salt or aluminum
and,!on _~r!~n~.um 1st-ingant complr-.Y ~hat is soluble, and which
remains snlubl~ in the present alcohol solvent can be used herein.
S~l '.S ~ s ~;~gen~ lntlpers~i,ant salts or as components
a.~ as~n ;~ - ~m~pl~x~ ncll~d~ a7u~inum halides, aluminum
iO ;~ in~ u~ `'nai 'I(iei~ C~nyl hydroxyhalides, and
m i x ~ `a ~ ~ t. i~s~ a~
A1~imlilU,~ sai ~S or cnis ~ype include aiuminum chloride and the
aluminum n~droxyhalides haYing the general formula Al2(0H)XQy-XH20
where Q is chloride, bromide, or iodide (preferably chloride); x
is from about 2 to about 5, and x + y = abôut 6, and x and y do
not need to be integers; and where x is from about 1 to about 6.
Aluminum salts of this type can be prepared in the manner
described more fully in U.S. Patent 3,887,692, Gilman, issued ~une
3, 1975, and U.S. Patent 3,904,741, Jones and Rubino, issued
September 9, 1975, incorporated herein by reference.
The zirconium compounds which may be used in the present
invention include both zirconium oxy salts and zirconium hydroxy
salts, also referred to as the zirconyl salts and zirconyl hydroxy
salts. These compounds may be represented by the following
general empirical formùla:
ZrO(OH~ 2 -~28Z
wherein z may Yary from about 0.9 to about 2 and need not be an
integer; n is the Yalence of B; 2-nz is greater than or equal to
O; and B may be selected from the group consisting of halides
(preferably chloride), nitrate, sulfamate, sulfate, and mixtures
thereof. Although only zirconium compounds are exemplified in
this specification, it will be understood that other Group IVB
metal compounds, including hafnium, could be used in the present
invention.
wo gl/18587 ~ D ~ w ~ t ~J PCT/~S91/026~
As with the basic aluminum compounds, it will be understood
that the above formula is greatly simplified and is i.,te"d d ~o
represent and include compounds having coordinated and/or bound
water in various quantities, as well as poly;"~a.As, ,.,l~;..e~
complexes of the above. As will be seen from the above tormula.
the zirconium hydroxy salt~ actually represent a ^~n~e !~
compounds having various amounts of the hydroxy group~ var~ing
from about 1.1 to only slightly great~r thail ~ g~ou~
molecule.
Several types o' an~i~er~3iran. ccm~lex^à u'~ H`~
antiperspirant salts are '~nown in the ar~ O`~A examp ia~ b.J.
Patent 3!;32,06~, Luedders e. al~, issueu Febtuary i ~ ii,;.
discloses complexes of aluminum, zirconium, and amino acidâ àuch
as glycines~ Complexes such as those disclosed in the Luedders e~
al. patent and other similar complexes are commonly known as ZAG~
ZAG complexes are chemically analyzable for the presence of
aluminum, zirconium, and chlorine. ZAG complexes useful herein
are identified by the specification of both the molar ratio of
aluminum to zirconium (hereinafter ~Al:Zr~ ratio) and the molar
ratio of total metal to chlorine (hereinafter "Metal:Cl n ratio).
ZAG complexes useful herein have an Al:Zr ratio of from about 1.67
to about 12.5 and a Metal:Cl ratio of from about 0.~3 to about
1.93.
Preferred ZAG complexes are formed by
(A) co-dissolving in water
(1) one part Al2(0H)6 mQm, wherein Q is an anion
selected from the group consisting of chloride, bromide,
and iodide; and m is from about 0.8 to about 2.0;
(2) x parts Zr0(0H)2 aQa-nH20, where q is chloride,
bromide, or iodide; a is from about 1 to about 2; n is
from about 1 to about 8; and x is from about 0.16 to
about 1.2;
(3) p parts neutral amino acid selected from the group
consisting of glycine, dl-tryptophane, dl-~-phenyl-
alanine, dl-valine, dl-methionine, and ~-alanine, and
` w o 91~18587 2 ~ ~ 2 ~ ~ ~ PCT/~S91/026~~
where p is from about 0.06 to about 0.53;
(B) codrying the resultant mlxture to a friable solid; and
(C) reducing the resultant dried inorganic-organic antiper-
spirant complex to a particulate ,orm.
A preferred aluminum compound for preparation of such ZAG
type complexes is aluminum chlorhydroxide of the empirical fo~ula
Al2(0H)sCl-2H20. Preferred zlrconium compounds for preoaration of
such ZAG-type complexes are zirconyl hydroxychloride h3~in~ t~
empirical formula ~rO(OH)Cl~3H20 and the ~,rconyl hyd a~yhal~das
of the empirical formula ZrO(OH)2 aCl2-l-;i20 wherein a is l~o
about 1.5 to about 1.87, and n is from abou. 1 to about ~. ~he
preferred amino acid for preparing suci~ LAG-type comDlexes is
glycine of the formula CH2(HN2)COOH~ Salts of sùch amino acids
can also be employed in the antiperspirant complexes~ See U.S.
Patent 4,017,599, Rubino, issued April 12, 1977, incorporated
herein by reference.
A wide variety of other types of antiperspirant complexes are
also known in the art. For example, U.S. Patent 3,903,258,
Siegal, issued September 2, 1975, discloses a zirconium aluminum
co~plex 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
3,981,8S6, issued September 21, 1976, discloses an antiperspirant
complex prepared from an aluminum polyol compound, a ~irconium
compound and an organic buffer. U.S. Patent 3,9~0,748, ~ecca,
issued July 20, 1976, discloses an aluminum chlorhydroxy glycinate
complex of the appropriate general formula ~Al2(0H)~Cl][H2CNH2-
COOH]. All of these patents are incorporated by reference herein.
Of all of the above types of antiperspirant act;ves,
preferred compounds include the 5/6 basic aluminum salts of the
empirical formula Al2(0H)sC1-2H20; mixtures of AlCl3-6H20 and
Al2(0H)sC1-2H20 with aluminum chloride to aluminum hydroxychloride
weight ratios of up to about 0.5; ZAG type complexes wherein the
W o 91/18587 2 ~ PCT/~S91/026
zirconium salt is Zr0t0H)Cl-3H20, the aluminum salt is Al2(0H)5Cl-
~H20 or Lhe arorementioned mixtures of AlCl3-6H20 and Al2(0H)sCl-
ZH20 wherein the total metal to chloride molar ratio in the
co~npieV is ~ n ai`~ou~ i.^i and he ~:2r molar ratio is about
3.3. and the amino acid is glycine; and the ZAG-type complexes
.Yhe in ~h z~. n.u;, alt is ,'(n.Y)2.aCla nH20 ~her~in a is from
abollt l~ to abollt l.37 and n is from about 1 to about ~, the
~lui,n:m a i~ ~7.(~ Cl !l 0, and `he amino acid is glycine.
~ r;^^ ~ d ~ t ~ s use~ul i~ ~h~
c;~ ?~ n1C o~ u~ntioll are antiperspirant actives
wi~n ~nl2no~ errica y due 'o ~mproYed rclecular distribution.
~luminum calorilyarovide sal;~ zlrconyl hydroxychloride salts, and
mixtures thereof naving i~,oved molecular distributions are
known, having b~en disclosea, for example, in the following
documents, all incorporated by reference herein: U.S. Patent
4,359,456, Gosling et al., issued November 16, 1982; European
Published Patent Application 6,739, Unilever Ltd., published
~anuary 9, 1980; European Published Patent Application, 183,171,
Armour Pharmaceutical Company, published June 4, 1986; British
Patent Specification 2,048,229, The Gillette Company, published
December 10, 1980; European Published Patent Appl kation 191,628,
Unilever PLC, published August 20~ 1986; and British Patent
Specification 2,144,992, The Gillette Company, pùblished March 20,
1985.
The improved molecular distribution is determined by the
known analysis method called gel permeation chromatography. This
analysis method is described, for example, in several of the
above-incorporated patent specifications as well as in European
Published Patent Application 7,191, Unilever Ltd., published
January 23, 1980, the disclosures of wh kh are incorporated
herein. It is preferred for purposes of the present invention
that the antiperspirant actives utilized have enhanced efficacy
due to improved molecular distribution with a ratio of peak 4 to
peak, 3 greater than about 0.1:1 as dPtermined by gel permeatlon
chromatography. This ratio, as is recognized by one skilled in
w o 91/18587 2 o ~ ~? ~ 1 ~ PCT/~'S91/0268/
the art, relates to the relative area under those two peaks as
measured by ~"e yel ~elme2~ion chromatography analysis method.
,~iynly desiraDle an~ip~rspirant salts for use herein are
selec;ed ~ s`!m ;ii~ ~jl 011~ cùn~ rlg ùr aiuminum chlorohydrex (sold
under the name ~Phydrol9, by Reheis Chemical Company), aluminum
chlo,on~_ra~ '~^, alu~inum chloroh,ydre~ PG, aluminum sesqui-
chlorohvdrate~ aluminum se~quichlorohydrex PEG, aluminum
ses pm C.` I ore"~dr~ `i'.. tni ~ t~lrs~ thereof. All of these
mat 'r 1 al . a;`a ,a a;`: '. ^" '' ` :~, ` S a ~'_ .'a .' `Jic ~ a ~ r r ay-on compositions.
T;l`~ i i"~ n~ ja~ use ner~in is aluminum
sesquich70roilJIra'~.
U.S. ~acen; ~,ù53~ aaer e~ al., issued October 11, 1977;
U.S. Pat~nt l1~065~o~ iles Jr. et al.. issued December 27, 1977;
and U~S. Patent ~,û73,380, ?ader et al., issued February 14, 1978;
all disclose formulations for pump-spray or roll-on antiperspir-
ants comprising alcohol-soluble aluminum chlorohydroxide antiper-
spirant salts, an alcohol vehicle, and silicone materials.
The antiperspirant salt is present in the liquid
antiperspirant compositions of the present invention at a level of
from about 1~X to about 25X, preferably from about 14% to about
16%. These weight percentages are calculated on an anhydrous
metal salt basis (exclusive of glycine, the salts of glycine, or
other complexing agents).
Solvent for the Anti~ersDirant Salt
The antiperspirant salts of the present invention are
solubilized in a solvent. Suitable solvents include monohydric
alcohols, especially C2-C, monohydric alcohols. The preferred
solvent for use herein is ethanol. A small amount of water is
also necessary in the present compositions to solubilize the
antiperspirant material. However, the present compositions will
comprise no more than about 5%, preferably no more than about
2.5X, water.
The solvent is present in the compositions of the present
invention at a level at leasl sufficient to solubilize the
antiperspirant salt. It is desirable to keep the level of
2 ~ 8 ~ Q,~
WO 91/18587 PCr/- S91/02
- 10 -
monohydric alcohol solvent in the present compositions low to
allow for the incorporation of as much emollient materials as
possible. This results in a product with improved in-use cha~
teristics. Generally, the solvent is prPs~nt in ~he co~ a;
at a level of from about 30% to about 50%, preferably from about
43~O to about 47~.
Em~llients
The~present antiperspirant composition also c3m~i^ i .S e I .n~ ~ .?
amounts of non-volatile ~ollient esters and uel~' l^ ^n~
10 non-vola~ile silicone .~mollien~s. It ,s ~hes~ ;umlpùllc~
primarily responsible for the desirable produc~ aes~,let~c~. ai,o.
in-use characteristics of the ~rese,n. co,mpos~,~ions. Eù, ~am~ia.
these components provide the smooth, clean, dry, non^s~ic'<y -,eel
upon application to the s~in. These components are present in the
15 antiperspirant compositions at relatively high levels to maximize
these benefits. Generally, these components are present at a
total level of from about 20% to about 35%, preferably from about
24X to about 33X. These emollient materials must have a viscosity
in the range of from about 0.65 centistokes to about 50
20 centistokes as measured by a Brookfield~ cone and plate
viscometer, at ambient temperature (or other suitable methods).
These emollient materials must also be of a certain polarlty to
remain stable in the present compositions. i.e., they must have a
solubility parameter (units equal (cal/cm3)l/2) in the range of
from about 4 to about 10, preferably from about 5 to about 9.
The solub;lity parameter is defined in the Po~ymer Hdndbook
3rd Ed. (John ~iley and Sons, New York), J Brandrup and E.H.
Immergut, Chapter VII, PP. 519-559, as the square root of the
cohesive energy density and describes the attractive strength
between molecules of the material. Solubility parameters may be
determined by measurement, correlations with other physical
properties, or indirect measurement. The solubility parameters
for the present emollient materials were determined by surface
tension measurement as outlined in Vaughan, C.D., J. Soc. Cosmet.
Chem., 36, 319-333, 1985.
2~82~
W O 91/18587 PCT/~S9t/0268/
Part of the emollient ~aterial of the present compositions
comprises a non-volatile emollient ester. This material may
comprise Cl2-Cls alcohol benzoates; esters, diesters, or tetra-
esters of C2-C2~ alcohols and C6-C,6 fatty acids (e.g. diiiopropy~
sebacate, diisopropyl adipate, lauryl lactate, myristyl myristate,
and pentaerythrityl tetrapelargonate); and ~ixtures ther~cf, ~h.ch
meet the solubility parameter requirement described abo~e. The
preferred of these non-volatile emollient materials are esters,
diesLers, and tetraes~ers of C~-82o alcohols and C6-~ ;tt
acids. Especially preferre~ are isopropyl myristate, i~ODro~y,
palmitate, C~2-Cls alcohols ben20ate, and mixtures thereot. Ine
most preterred of tnese emollient esters for use herein are
C,2-Cls alcohols benzoate.
Generally, from about 5% to about 20/~o, preferably from abôut
9~0 to about 11%, of the present compositions comprise these
non-volatile emollient ester materials. The non-~olatiie
emollient ester component of the present compositions has a
solubility parameter of from about 7 to about 10.
The emollient material of the antiperspirant compositions of
the present invention also comprises silicone emollient materials.
Of course the silicone emollient materials used herein must also
meet the particular emollient viscosity and solubility parameter
requirements as outlined above.
Various types of silicone materials have been disclosed for
use in ~arious forms of antiperspirant compositions. For example,
U.S. Patent 4,784,844, Thimineur et al., issued November 15, 1988;
U.S. Patent 4,499,069, Krafton, issued February 12, 1985; U.S.
Patent 4,268,499, Keil, issued May 19, 1981; U.S. Patent
4,264,586, Callingham et al., issued April 28, 1981; U.S. Patent
4,053,581, Pader et al., issued October 11, 1977; U.S. Patent
4,065,564, Miles, ~r. et al., issued December 27, 1977; U.S.
Patent 4,073,880, Pader et al., issued February 14, 1978; U.S.
Patent 4,673,570, Soldati, issued June 16, 1987; U.S. Patent
4,559,226, Fogel, issued December 17, 1985; U.S. Patent 4,435,382,
Shin et al., issued March 6, 1984; European Patent Office
~ i~ 3 ;~
W O 91/18587 PCT/~IS91/026~
Application 343,843, published November 29, 1989; Great Britain
Patent iiipplica~ion 1,535,~22, published December 20, 1978i Great
itaill ~d~ pplica~ion 2,0i3,590, published October 24, 1979;
and O;-pallai~ 'ub`i~ an~ ~ppii.a~ion 53-15~,318, published
August 31, 1984.
.h s.l~aona ~molliein mîterials cf the prosont compositions
ccmoriso ~ Yola~ilo silicone emollient~ having a viscosity of from
:~bO~ , `?~ ; t,o ~brllt 10 contisto!~es, and a solubility
r~ " ~ silicon~
O ~ Vi 5 '~ I ~)X~ cont~ i n i n~J l^roln
aboul ~ o ~bou~ i ii i on a~o-~, meet tlese reyùirements and are
use;ui ileroin. ~ ciejcrip~ion o, voiatiie silicones is ;ound in
Todd and Bvers~ "Yolatile Silicone Fluids for Cosmeticsn,
Cosmetics and Toi1etries, 91:27-32 (1976), incorporated herein by
reference. Other volatile silicones useful herein are taught in
U.S. Patent 4,874,868, Bolich, Jr., issued October 17, 1989,
incorporated by reference herein. A preferred volatile silicone
for use in the present compositions, which is covered in that
patent, is phenethyl pentamethyl disiloxane.
The present compositions comprise from about 5% to about 25%,
preferably from about lOX to about 15%, of these volatile silicone
materials. The preferred volati,e silicone emollient materials of
the present invention are D4-G5 cyclomethicones, phenethyl penta-
methyl disiloxane, and mixtures thereof.
Additionally, the present compositions may comprise a
volatile dimethicone fluid emollient material, having a viscosity
of less than 1 centistoke, preferably 0.65 centistoke, at a level
of from about 2X to about 5~ of the composition.
The silicone emolllent materials of the present compositions
also comprise non-volatile silicone emollient materials. Such
materials have a viscosity of from about 1 to about 50 centi-
stokes, and a solubility parameter of from about 4 to about 9.
The present compositions compnise from about 3X to about 10%,
preferably from about 3% to about 5~, of such materials.
Preferably, such materials comprise phenyl dimethicone, phenyl
W 0 91/18587 2~ Q 1 ~ PCT/US91/026g7
- 13 -
trimethicone, non-volatile dimethicone fluids having a viscosity
of trom abou~ 1 centisto~e to about 10 centistokes, and mixtures
thereof.
Because the leYel of emollients is relatively high in the
presen~ ,ui~l ant,pers?li^,r' compositions~ formulation of the
compositions so that they remain physically and chemically stable
o~er ~ e ~ d a b,oa(1 ranga of oby~ical conditions (especially
ia`'`i'.'.``~ i~` -~m.bie?t tem e~ e~ -ecui-es incorporation of
Ihieie i~lu~ . S a. 2 rim.~. ily respcnsible for providing
produo~ ab "i~y. l`,le iui`~C~aii; io1u iliz~ors of the present
invention must be so~uble in ;he antiperspirant solvent, must have
a low s~in irritation pot~ntial, must be able to solubilize large
amounts of oil phase at temperatures ranging from about -20-C to
about 60'C, must have an average HLB in the range of from about 8
to about 1q, and must, of course, haYe a low base odor. HLB is
fully described, and HLB values for various materials are provided
in the publication rhe HL~ System, A Time-SaYing Guide to
Emu1sifier Se7ection (published by ICI Americas Inc., Wilmington,
DE; 1984~, the disclosure of this publication being incorporated
by reference herein.
Silicone-in-water emulsions stabilized by nonionic surfactant
emulsifiers having certain HLB values are known, having been
disclosed in such references as U.S. Patent 4,874,547, Narula,
issued October 1~, 1989; U.S. Patent 4,788,001, Narula, issued
NoYember 29, 198~3; and Great Britain Patent Publication 2,155,337,
published September 25, 1985.
The present antiperspirant compositions comprise from about
lX to about 12%, preferably from about 1% to about 2%, of a
surfactant solubilizer.
The solubilizer of the present invention comprises, as a
critical component, ethoxylated or propoxylated nonionic
surfactant materials, and mixtur=; thereof. More specifically,
the solubilizer comprises an agent selected from the group
2 0 ~) h (~
w o 91/18587 PC~/~S9l/026~
consisting of ethoxylated and propoxylated nonionic surfactants
having an HLB in the range of from about 5 to abo~t 18, or
mixtures thereof; such that the averagP HLB of the solubi',2e, i,
from about 8 to about 14. Hence, a single solui~iil i2'`^ .~
may be used which itself has an HLB in the range of from about 8
to about 14. Alternatively, a mixture of materials "ay b~ used
the solubilizer herein, each having an ~LB in the range ol 'ro~
about 5 to about 18, such that the average HL3 of Lhe rlii`'~Ura ',~
from about 8 to about 14. Surfactant material~, Qr miYt~:r~
surfactant materials, with n HL~ in this ranget ^r^v~
across a broad temperature range. Most pr~f~r ~/y. h~ e
solubili.er materials a.i~ s.~l~ct~d from ~he group coni~i; n~ v
ethoxylated or propoxylated fatty acid ethers, ana mixtures
thereof, so that the average HLB of the solubilizer is from about
8 to about 14.
Examples of solubilizer materials which meet these
requirements and, hence, are useful in the present invention
include Oleth-5, Oleth-10, Oleth-20, Laureth-4, Laureth-7,
Laureth-10, Laureth-12, Laureth-23, Steareth-2, Steareth-10,
Steareth-20, Steareth-21, Ceteareth-10, Ceteareth-20, Ceteth-10,
Ceteth-20, and mixtures thereof.
Ethoxylated or propoxylated fatty acid ethers, and mixtures
thereof, have been disclosed for use as emulsifiers in
antiperspirant compositions. U.S. Patent 4,784,844, ~himineur et
al., issued November 15, 1988, discloses silicone-in-~ater
emulsions containing highly ethoxylated nonionic emulsifiers such
as Ceteth-20. U.S. Patent 4,499,069, Krafton, issued February 12,
1985; U.S. Patent 4,268,499, Keil, issued May 19, 1981; and U.S.
Patent 4,264,586, Callingham et al., issued April 28, 1981; also
disclose the use of such materials in antiperspirant compositions.
Highly preferred surfactant solubilizers of the present
invention comprise from about 1% to about 2X of materials selected
from the group consisting of compounds of the formula:
CH3(CH2)x(OCH2CH2)nOH (A)
wherein x is 12, 14, 16, or 18, and n is 10, and mixtures thereor;
2 0 ~
w o gl/18587 PCT/~S91/026
and compounds of the formula:
CH3(cH2)x(ocH2cH2)noH (B)
wherein x is 12, 14, 16, or 18, and n is 20, and mixtures thereof;
and mixtures of A and B; such that the average HLB o~ ~he
solubilizer is from about 8 to about 14, and wherein if A and B
are both present, they are at a ratio of A to 8 of from a~ou~
to about 1:2.
Especially preferred solubilizérs for use in the present
inventi~ll comprise, Steareth-20 alon~, at a level of from ~bout
to about 2~; or a combination of Ceteth-10 and Ceteth 2', a~
ratio of about 1:1, and at a totat level of from about 1~ ~o ~bou~
2%.
The compositions of the present invention can also comprise
from about 5% to about 8% of other co-solubilizer surfactants.
For example, polypropylene glycol (`'PPG~) ethers of C~-C22
(preferably C1o-C20) fatty alcohols may be included in the present
compositions~ Examples of such materials include PPG-2 myristyl
ether, PPG-4 lauryl ether, PPG-10 cetyl ether, PPG-3 myristyl
ether, PPG-11 stearyl ether, PPG-15 stearyl ether and mixtures
thereof. Additional examples are found in C~FA Cosmetic
In~redient Dict~onary, Third Edition (Extrin et al., Editors; The
Cosmetic, Toiletry and Fragrance Association, Inc., 1982)~ pages
252-260 and 494-500, the disclosures of which are incorporated by
reference herein. Preferred co-solubilizers of the present
compositions are selected from the group consisting of propylene
glycol (n) stearyl ether, where n is on the average from 10-16i
and propylene glycol (n) myristyl ether, where n is on the average
from 2-10; and mixtures thereof. Most preferred in the present
compositions is PPG-3 myristyl ether (HLB about 9.8).
ODtional components
The compositions of the present composition may also comprise
a number of optional components to provide cosmetic or aesthetic
benefits. For example, preservatives, deodorant actives, such as
anti-microbials or bacteriocides, perfumes, coloring agents and
dyes may be used.
2 ~ ~, 2 (' '~ t, .
W o 91/18587 PCT/~S91/026~
These optional components must be chosen so as not to
inter,^ere .~i~h the antip~,spi.ant efficacy and the composition
stabili.y. Thase optional components are generally present in the
composi ~;Oilà Ol- ~he ~rasen~ inven~ion at a l"v21 0~ frcm about
0.O1~O to about lO~o.
Produc~.j
The prosent compositions are proferably in the form of a
o~y-yjcC,~c;~ ~On'l?~'OiO~ plimla S)rlY. ~lo~ever. the present
j "~,~Q~ " ~ ?;~ ^s~ir~nt ~roduct
~y~ y~e~. ~roduc.â
formula~ed as aeiojolj ~,11 a~jo COIlnpi`lâe a ?ropellant material.
Any or ~h~ c~ nonlv ùi~u L`rO~ an-~à ml he an~toerspirancy art
are sui~able~ Produc~s i^ormulated as roll-ons ~ill also comprise
a thickening agent to raise the viscosity of the composition.
Suitable thickening agents include carboxymethyl cellulose, clay
thickeners, colloidal sil ka, and Microthene~ beads, manufactured
by U.S.I. Chemicals, having a mean particle diameter of less than
about 20 microns.
Methods of Manufactu.~e
The antiperspirant compositions of the present invention may
be manufactured using methods known in the art. In making the
compositions, the antip~rspirant salt is first solubilized in the
monohydric alcohol solvent, and a small amount of water (no more
than 5X water, by weight of the antiperspirant composition) to
form a clear solution. The remaining components are then added to
the composition using conventional formulation methods.
~ethod for Preventing P~erspiration and Malodor
The present invention also provides methods for treating or
preventing perspiration and malodor associated with human underarm
perspiration. These methods comprise applying a safe and
effective amount of the liquid antiperspirant compositions of the
present invention to the skin in the axillary area of a human.
The term a "safe and effective amount" as used herein, is an
amount wnich is erfective in eliminating or substantially reducing
the production of perspiration ~hich ultimately generates the
W O 91/18587 2 Q 8 2 ~ ~ ~ PCT/~S91/02687
- 17 -
malodors detected throuqh formatton of pungent fatty acids, while
being sa;e '~or human uie a~ a reasonable risk/benefit ratio.
Tne iiquid antiperspirant compositions of the present
inven~ioll pro~ide exc-l,en; cosme~ic ~,tributes both on
application and throughout use. They are non-sticky, non-greasy,
anci qu~,c:~ dr;mn~. Th comp~si~lons s~ai.q clothing less than other
liquid spr~y-on antiperspir~nt compositions. In addition, the
pr ~nt c~osi~?on~ 7 e ~`!" no Wi~it~! c~a~ V res;due on skin upon
~i^J~
Th~ ?X~'1i1p~ ' `n~ w esent invention. It
wi71 be ~pprecla~;ei sha- other modirica~ions of the present
inven~ion w~ in ;he skili or tnose in the antiperspirant
formulation art can be underta~en without departing from the
spirit and scope of this invention.
All parts, percentages, and ratios herein are by weight
unless otherwise specified.
ExamDle I
The following is a clear, liquid, spray-on antlperspirant
composition representative of the present invention.
Component Weiqht %
Aluminum Sesquichlorohydrate 15.00
SD Alcohol 40 46.00
D4 Cyclomethicone lO.00
C 12 - C 1 ~ A~cohols Benzoate1 I0.00
PPG-3 Myristyl Ether 6.50
Phenyl Dimethicone 4.00
Dimethicone Fluid (5 ctsk) 3.50
DR0 ~ater 2.50
Steareth-20 2.00
Perfume 0.50
Total=100.00
Available under the trade name Finsolv TN~ from Finetex,
Inc.
The composition is prepared as follows. An aluminum
sesquichlorohydrate (ASQCH) premix is prepared by combining the
W O 91/18587 2 ~ ~ 2 ~ ~ ~ PCT/~S91/026~,
ASQCH, about 2/3 of the ethanol and the DR0 water. The main mix
is then prepared by adding to the ASQCH premix the remainiils
ethanol, the D4 cyclomethicone, the C12-C1s alcohols benzoate, ~ha
PPG-3 myristyl ether, the phenyl dimethicone, ~he ~Jimë-~,iico"e
S fluid, the Steareth-20, and the perfume, in that order.
The resulting antiperspirant co~position proYides exc~t 'n
antiperspirancy efficacy with good product aesthetics and in-use
characteristics. The compositton also remains stable oYer ~ ?
and broad ranges of physical ccnditions. especiall~ amb.e.,
~emperatures.
Examol ê I I
Thê following is a clear liquid spray-on dn t i perso i ran
composition representative of the present invention.
Component `~eiqht ~l,
Aluminum Sesquichlorohydrate Premix 50.00
Ethanol 14.00
Ceteth-10 0.92
Ceteth-20 1.08
PPG-15 Stearyl Ether 4.00
Isopropyl Myristate 10.00
Phenethyl Pentamethyl Disiloxane 6.00
D4 Cyclomethicone 14.00
Total~100.00
Aluminum Sesquichlorohydrate Premix
Component ~eight ~,
Aluminum Sesquichlorohydrate 30.0
Ethanol 65.0
DR0 Water 5.0
Total-100.0
This composition is prepared as follows. The aluminum
sesq,uichlorohydrate (ASQCH) premix is prepared by combining the
ASQCH, ethanol and water. The main mix is then prepared by adding
to the ASQCH premix the remaining ethanol, the Ceteth-10, the
Ceteth-20, the PPG-lS stearyl ether, the isopropyl myristate, the
3;
` W O 91/18587 2 Q .~ 2 ~ 1 ~ Pcr/~lS91/02687
- 19 -
phenethyl pentamethyl disiloxane, and the D4 cyclomethicone, in
that order.
The resulting antiperspirant composition provides excellent
antiperspirancy efficacy with good product aesthetics and in-use
characteristics. The composition also remains stable over time
and broad ranses of physical conditions, especially ambient
temperatures.
Example IIl
The follo~ing is a clear liquid spray-on antiperspira,t
10 compositio,~ ,epresentativ~ of the prPsent i~venticn.
Component ~eiqht ,c
Aluminum Sesquichlorohydrate Premix 50.00
Ethanol 13 50
Ceteth-10 0.92
Ceteth-20 1.08
PPG-3 Myristyl Ether 6.50
C12-C1s Alcohols Benzoate1 10.00
Perfume 0.40
Phenyl Dimethicone 4.00
Dimethicone Fluid (5 cstk) 3.50
D4 Cyclomethicone 10.10
Total-100.00
Available under the trade name Finsolv TN from Finetex,
Inc.
Aluminum Sesquichlorohydrate Premix
Compo~n~ ~eiqht %
Aluminum Sesquichlorohydrate 30.0
Ethanol 65.0
DR0 Water 5.0
Total-100.0
This composition is prepared as follows. The aluminum
sesquichlorohydrate (ASQCH) premix is prepared by combining the
ASQCH, ethanol and water. The main mix is then prepared by adding
to the ASQCH premix the remaining ethanol, the Ceteth-10, the
Ceteth-20, the PPG-3 myristyl ether, the C,2-C1s alcohols
W 0 91/18587 2 ~ CT/US91tO26
- 20 -
benzoate, the perfume, the phenyl dimethicone, the dimethicone
fluid, and th~ D4 cyclomet.hicor.e, in that cr~er.
The resulti.lg antip~rspira,l~ composition provides excellent
anti~:~r, mrailey a.^~!c~c~ c~' pn^l~c` ~ s~het,cs and in-us~
characteristics. The composition also re~ains stable over time
and ~roa~i ranaes of n~-s,~ l cond,tiols~ especially ambient
temperatures~
T~ -C~ ?~ 9 is - ~ . d `~ p '`." ~ i ?^ ~ ~ t composition
Comncn~n~ l~eiaht
Alu,~ u~ "~ ",~ 50 00
Ethanol 13.50
Steareth-20 1.00
PPG-3 Myristyl Ether 6.50
C12-C~5 Alcohols Benzoate 10.00
Perfume 0.40
Phenyl Dimethicone 4.00
Dimethicone Fluid (5 cstk) 3.50
D4 Cyclomethicone 11.10
Total=100.00
Aluminum Sesquichlorohydrat2 Premix
ComDonent Weiqht ,0
Aluminum Sesquichlorohydrate 30.0
thanol 65.0
DRO Water S.O
Total-100.0
This composition is prepared as follows. The aluminum
sesquichlorohydrate (ASQCH) premix is prepared by combining the
ASQCH, ethanol and water. The main mix is then prepared by adding
to the ASQCH premix the remaining ethanol, the Steareth-20, the
PPG-3 myristyl ether, the Cl2-Cls alcohols benzoate, the perfume,
the phenyl dimethicone, the dimethicone fluid, and the D4
cyclomethicone, in that order.
WO 91/18587 2 0 3 2 3 ~ 3 PCl`/US91/0268/
- 21 -
The resulting antiperspirant composition provides excellent
antiperspirancy ef,~icacy with gcod product aesthetics and in-use
characteri~tics. Tne co",posi.ivn also remains stable over time
and broad .~an~ei ~ n~i;.aa oo,l~.'.vns, especially ambient
temperatur~s.
The ,~ollowing is a liquid antiperspirant composition
represen~ti~e o~ ~h~ i^?~ne ,n~ien~ion.
Cc~ponent '~ ht 7
Aluminu"l svu`,e;ll~n~ d^s~ m.; 50.00
Ethanol 13.00
Ceteth-10 0.9L
Ceteth-20 1.08
Benzalkonium Chloride1 0.25
PPG-3 Myristyl Ether 6.50
C 12 -C 1 s Alcohols Benzoate 10.00
Phenethyl Pentamethyl Disiloxane 6.00
D4 Cyclomethicone 12.25
Total-100.00
1Antimicrobial, available from Lonza, Inc., under the trade
name - Barquat MB-802
Aluminum Sesquichlorohydr2te Premix
Component Weiqht X
Aluminum Sesquichlorohydrate 30.0
Ethanol 65.0
DR0 ~ater 5 0
Total~100.0
This composition is prepared as follows. The aluminum
sesquichlorohydrate (ASQCH) premix is prepared by combining the
ASQCH, ethanol and water. The main mix is then prepared by adding
to the ASQCH premix the remaining ethanol, the Ceteth-10, the
Ceteth-20, the Barquat MB-80~, the PPG-3 myristyl ether, the
C12-C1s alcohols ben~oate, the phenethyl pentamethyl disiloxane,
and the D4 cyclomethicone, in that order.
W O 91/18587 2 ~ ~ 2 o 1 3 PCT/~ISgl/02fi.
- 22 -
The resulting antiperspirant composition provides excellent
antiperspirancy efficacy with good product aesthetics and in-use
characteristics. The composition also remains stable over ti~"e
and broad ranges of physical conditions, especially a;.`~
S temperatures.
~xamcle Yt
The following is a liquid antiperspirant composition
represen~ative of the present invention.
Component ~e;qh,
Aluminum SesquichlorohydratP Premix S~.~0
Ethanol 1~ 50
Stear~th-20 2.C0
PPG-3 Myristyl Ether 6.~0
C, 2 -Cl 5 Alcohols Benzoate 11. 00
Fragrance - 0-50
Dimethicone Fluid (5 centistokes) 5.00
D4 Cyclomethicone 10.50
Total-100.00
Aluminum Sesquichlorohydrate Premix
ComDonent Weiqht X
Aluminum Sesquichlorohydrate 30.0
Ethanol 65.0
DR0 Water 5 0
Total-100.0
This composition is prepared as follows. The ASQCH premix is
prepared by combining the ASQCH, ethanol and water. The main mix
is then prepared by adding to the ASQCH premix the remaining
ethanol, the Steareth-20, the PPG-3 myristyl ether, the C,2-Cls
alcohols benzoate, the fragrance, dimethicone fluid, and the D4
cyclomethicone, in that order.
The resulting antiperspirant composition provides excellent
antiperspirancy efficacy with good product aesthetics and in-use
characteristics. The composition also remains stable over time
and broad ranges of physical conditions, especially ambient
temperatures.
` ~ w O 91/18587 ~ ~ 8 ~ PCT/US91/02687
- 23 -
ExamDle VII
The following is a liquid antiperspirant composition
representative of the present invention.
Component '~eiaht
Aluminum Sesquichlorohydrate Premix 50.00
Ethanol 13.50
Steareth-20 2.00
PPG-3 Myristyl Ether ~ 50
C12-C15 Alcohols Benzoate 11.00
Fragrance il jO
Dimethicone Fluid (S centistokes) 4.00
D4 Cyclomethicone 12.S0
Total~100.0
Aluminum Sesquichlorohydrate Premix
ComDonent Weiqht ~O
Aluminum Sesquichlorohydrate 30.0
Ethanol 65.0
DR0 Water 5.0
Total~100.0
Th;s composition is prepared as follows. The ASQCH premix is
prepared by combining the ASQCH, ethanol and water. The main mix
is then prepared by adding to the ASQCH premi~ the remaining
ethanol, the Steareth-20, the PPG-3 myristyl ether, the C~2-C~s
alcohols benzoate, the fragrance, the dimethicone fluid, and the
D4 cyclomethicone, in that order.
The resulting antiperspirant composition provides excellent
antiperspirancy efficacy with good product aesthetics and in-use
characteristics. The composition also remains stable over time
and broad ranges of physical conditions, especially ambient
temperatures.
WHAT IS CLAIMED IS:
