Note: Descriptions are shown in the official language in which they were submitted.
STICK ANTIPERSPIRANTS
John Paul Luebbe
BACKGF<OUND OF THE INVENTION
The present invention relates to antiperspirant compositions
in solid stick form. More particularly, it relates to antiperspirant
sticks with improved cosmetic characteristics.
Many solid antiperspirant compositions are described in the
chemical and cosmetic literature. In ~eneral, there are three
types of such antiperspirant stick formulations: compressed
powder sticks, gel sticks and wax sticks. While each of these
formulation types may have advantages in certain situations, each
also has disadvantages. For example, compressed powder sticks
are often brittle and hard, and leave a cosmetically-unacceptable
dust upon application. Gels may be unstable due to evaporation
of alcohol and ~more importantly) due to interaction of astringent
metal salts with the soaps used in the sticks. Wax-based formu-
lations can also yield cosmetically-unacceptable products due to
such factors as hardness, greasiness and stickir,ess.
Nevertheless, the increased stability and antiperspirant efficacy
afforded by wax-based formulations has resulted in such sticks
being generally preferred for antiperspirant stick products.
The use of a wide variety of materials is described in the
literature in order to optimize the cosmetic characteristics of
antiperspirant wax-based sticks . For example, U . S. Patent
4,126,S79, Davy, et al., issued November 21, 1978, describes
antiperspirant sticks containing volatile silicone oils, long-chain
fatty alcohols, and a powdered material (such as an antiperspirant
active, fumed silica, talc or sodium bicarbonate~ for stable sticks
with good glide properties. U.S. Patent 4,280,994, Turney,
issued July 28, 1981, claims antiperspirant sticks containing
volatile silicone, a waxy material and polyethylene glycol, in order
to ease application of the composition. British Patent Application
2,139,496, Geria, published November 14, 1984, describes the use
of a water-soluble emollient in order to avoid the waxy feel of a
wax-based antiperspirant stick. European Patent Publication
117,070, May, published August 29, 1984, describes wax-based
antiperspirant sticks containing certain fatty alcohols in order to
increase produc~ stability.
While many stick formulations described in the literature may
have certain desirable characteristics, such as acceptable product
5 hardness and stability, or pleasing aesthetics or application
characteristics, or good in-use characteristics, these formulations
~o npt provide optimal overall performance. Thus, sticks that
have good "glide" or other good application characteristics may,
however, have poor stability and may be too s~ft. Conversely,
10 sticks which are dimensionally stable and of adequate hardness
may impart a waxy feel and have poor application cosmetics.
Furthermore, tt e wax-based sticks described in the literature
typically produce high levels of visible residue which is
aesthetically unappealing and may leave visible soil on clothin~.
It is now been discovered that wax-based antiperspirant
sticks contair~ing selected emollients, fillers, and waxes have ~ood
compositional stability as well as good application and in-use
cosmetic characteristics. In partic~lar, the compositions of the
present invention leave lower levels o~ visible residue, and have
20 improved "glide" and other application cosmetics, while main-
taining good product stability and hardness.
SUMlvIARY OF THE INVENTION
. .
The present invention provides antiperspirant stick
25 compositions comprising: (a) from about 35% to about 60%
of a volatile silicone oil; (b) from about 1% to about
10% of a non-volatile emollient selected from the group
consisting of water-insoluble ethers, polyoranosiloxanes,
and mixtures thereof; (c) from about 3~ to about 5% of a
high melting point wax; (d) from about 10% to about 18% of
a low melting point wax selected from the group consisting
of stearyl alcohol, cetyl alcohol, and mixtures thereof;
(e) from about ~.3~ to about 1.5% of a fumed colloidal
silica material; and (f) from about 15~ to about 50% of a
particulate antiperspirant active; wherein said compo-
sition is essentially free of particulate materials other
than said fumed colloidal silica material and said
particulate antiperspirant material.
6~
DESCRIPTION OF THE iNVENTlON
The antiperspirant sticks of this invention contain five
essential ingredients: a volatile silicone oil, a non-volatile
emollient, a high melting point wax, a low melting point wax, a
colloidal silica material, and an antiperspirant active. These
compositions (herein "antiperspirant sticks") encompass any solid
~or semi-solid) composition intended for human use in order to
deposit an~iperspirant material on human ~issue. The essential
and optional components to be included in the present
10 antiperspirant sticks must be "cosmetically-acceptable", i.e., safe
for human use and aesthetically acceptable as the levels at which
such materials are used in the present compositions, at a reason-
able ri~k/benefit ratio.
Specifically, the antiperspirant sticks of the present
15 invention comprise:
(a) from about 359~ to about 60% of a volatile silicone oil;
(b) from about 1~ to about 10% of a non-volatile emollient;
lc) from about 3~ to about 5~ of a hi~h melting point wax;
(d) from about 10% to about lS% of a low melting point wax;
(e) from about 0.3~ to about 3.û% of a colloidal silica
material: and
(f) from about 15g6 to about 50% of a particulate antiper-
spirant material;
wherein said composition contains no more than about 2~ of
25 particulate materials other than said colloidal silica material and
said particulate antiperspirant material. ~AII percentages herein
are by weight of total composition. )
Preferably, the present antiperspirant sticks contain from
about 40% to about 55~ of the volatile silicone oils. The
- 30 non-volatile emollients are preferably present at a level of from
about 1 . 54 to about 8%, more preferably from about 2 . 5~ to about
6.5~. The high melting point wax is preferably present at a level
of about 4%, and the low melting point wax preferably present at
a level of from about 11~ to about 15~. Preferably, the colloidal
35 silica material is present at a level of from about 0. 4~ to about
1.0%, more preferably from about 0.4~ to about 0.8~. The
antiperspirant material is preferably incorporated a~ a level of
from about 15~ to about 40%, more preferably from about 20~ to
about 40%. Also preferably, the present compositions ere
substantially anhycirous, i.e., containing less than about 2~ of
free lchemically unboundl water.
The compositions of this invention are made by
well-established methods that are known in the art. Care should
be taken in the processes of making these compositions so as to
maintain uniform distribution of particulate materials throughout
the antiperspirant sticks. Specific essential and non-essential
materials to be included, and their levels, are selected in order
to produce a stick of desired hardness, so as to maintain
dimensional stability while depositing a suitable amount of
antiperspirant material on ~he skin during normal use. Hardness
of sticks can be determineci by a variety of methods, including
American Society for T~sting and Materials (ASTM) Method D-5.
This method involves the use of a needle or polished cone of
particular weight and dimension, which is allowed to travel
downward through the stick material for a pre-determined period
of time. The distance traveled by the needle or cone is a rela-
tive measure of the stick hardness. Utilizing Method D-5, with a
#1554 penetration needle (manufactured by Sergeant-Welch
Scientific Company) weighing 50 grams, and a Precision Model
73515 Penetrometer (manufactureci by Precision Scientific,
subsidiary of GCA Corporation), the antiperspirant sticks of the
present invention preferably yleld a penetration of from about 60
to about 150 niilimeters, more preferably from about 80 to about
150 millimeters, over a period of 5 seconds.
Essential Components
Volatile Silicone Oil:
The antiperspirant sticks of this invention contain a volatile
polyorganosiloxane, which mày function as a liquid emollient. lAs
used herein, "volatile" refers to those materials which have a
measuralle vapor pressure at ambient conditions. ~ The volatile
polyorganosiloxanes useful herein may be cyclic or linear. A
description of various volatile silicones is found in Todd, et ai.,
"Volatile Silicone Fluids for Cosmetics", Cosmetics and Toiletries,
~6~
91, 27 - 32 (1976), Preferred
cyclic silicones include polydimethylsiloxanes containing from about
3 to about 9 silicon atoms, preferably containing from about 4 to
about 5 silicon atoms. Preferred linear silicone oils include the
5 polydimethylsiloxanes containing from about 3 to about 9 silicon
atoms. The linear volatile silicones generally have viscosities of
less than about 5 centistokes at 25C., while the cyclic materials
have viscosities of less than about l O centistokes . Examples of
silicone oils useful in the present invention include: Dow Corning
l O 344, Dow Corning 345, and Dow Cornin~ 200 (manufactured by
the Dow Corning Corporation); Silicone 7207 and Silicone 7158
(manufactured by the Union Carbide Corporatlon); SF1202
(manufactured by General Electric); and SWS-03314 (manufactured
by Stouffer Chemicat).
15 Non-voiati le Emol I ient:
The present antiperspirant sticks contain one or more non-
volatile emollients. Such materials include fatty acid and fatty
alcohol esters, water-insoluble ethers and alcohols, polyorgano-
siloxanes, and mixtures thereof. Water-insoluble ethers are
20 particularly preferred non-volatile emollient materials, including
polypropylene glycol and the eondensation products of an alkylene
oxide with an alcohol. A particularly preferred water-insoluble
ether is the condensation product of about 14 moles of propylene
oxide with one mole of butyi alcohol, sold as Fluid APR by Union
25 Carbide C:orporation. Emollients among those useful herein are
described in 1 Cosmetics, Science and Techno!ogy 27-104 ~M.
Balsam and E. Sagarin ed. 1972~, and U.S. Patent 4,202,879,
Shelton, issued May 13, 1980,
The present compositions also preferably contain a non-
30 volatile slticone oil as an emollient material. Such silicone oils
include polyalkysiloxanes, polyalkyarylsiloxanes, and polyether-
siloxane copolymers. The essentially non-volatile polyalkyl
siloxanes useful herein include, for example, polydimethyl
siloxanes with viscosities of from about 5 to about 100, 000
35 centistokes at 25C. Among the preferred non-volatile emollients
useful in the present composition are the polydimethyl siloxanes
;~
-- 6 --
having viscosities from about 10 to about 400 centistokes at 25C.
Such polyalkyl siloxanes include the Vicasil series (sold by
General Electric Company) and the Dow Corning 200 series (sold
by Dow Corning Corporation ) . Polyalkylaryl siloxanes include
poly methylphenyl siloxanes having viscosities of from about 15 to
about 65 centistokes at 25C. These are available, for example,
as SF 1075 methylphenyl fluid (sold by General Electric Company)
and 556 Cosmetic Grade Fluid (sold by Dow Corning Corporation).
Useful polyether siloxane copolymers include, for example, a
l O polyoxyalkylene ether copolymer having a viscosity of about 1200
to 1500 centistokes at 25C. Such a fluid is available as SF-1066
organosilicone surfactant (sold by General Electric Companyl.
Polysiloxane ethylene glycol ether copolymers are preferred
copolymers for use in the present compositions.
Hiclh Meltin~ Point Wax:
The antiperspirant sticks of the present invention contain
one or more materials having wax-like characteristics and having
a melting point of from about 65C to about 1 02C . Such waxes
include beeswax, spermaceti, carnauba, baysberry, candelilla,
montan, ozokerite, ceresin, paraffin, hydrogenated castor oil
(castor wax), synthetic ~axes such as Fisher-Tropsch waxes,
microcrystalline wax, and mixtures thereof. Castor wax is a
preferred high-melting point wax useful herein. Such high-
melting point waxes among those useful herein are disclosed in
U.S. Pa~ent 4,049,792, Elsnau, issued Sep~ember 20, 1977
Low Meltina Point Wax:
The present antiperspirant sticks contain ~ax-like materials
having a low melting point, i.e., having a melting point of from
about 37C to about 75C. Such materials include fatty acids,
fatty alcohols, fatty acid esters and fatty acid amides, having
fatty chains of from about 8 to about 30 carbon atoms, preferably
from about 12 to about 18 carbon atoms, and mixtures thereof.
Preferred low melting point waxes include cetyl alcohol, palmitic
acid, myristyl a/cohol, stearyl alcohol, paraffin, and mixtures
,~ ,
~3
-- 7 --
thereof. Stearyl alcohol, cetyl alcohol, and mixtures thereof are
particularly preferred.
Colloidal Silica Material:
.
The present antiperspirant sticks contain a finely divided
5 silica material. Preferably, the silica material used in the present
cornpositions is a fumed silica, present at a level of from about
0.3~ to about 1.5~. Fumed silicas can generally be described as
fluffy, white, superfine powders of extremely low bulk density
but having high surface areas. These fumed silicas are typically
10 made by a vapor phase process that produces colloidal silica by
the hydrolysis of silicon tetrachloride at a very high temperature.
These materials consist of about 99. 8~ silicon dioxide by weight
(on a moisture free basis), existing in three dimensional branched
chain aggregates, with a surface that is hydrophilic and capable
15 of hydrogen bonding. Such siilcas have surface areas ranging
from about 2.5 to about 1,200 square meters per gram. Colloidal
silica materials are described in Hardy, et al., "The Use of
Fumed Silica in Cosmetics", 2 Cosmetic Technolo~y 35 ( 1980)
_ _
and R. Iler, The ~f
20 Siiica (1979).
Colloidal silica materials useful herein are available from a
variety of sources, including Syloid silicas (manufactured by
Davison Chemical Division of W. F~o Grace), Cab-O-Sil (manufac-
tured by Cabot Corporation), and Aerosil (manufactured by
25 Degussa A.G. ) . Cab-O-Sil is a particularly preferred
commercially available colloidal silica useful herein, with surface
areas ranging from about 200 to about 400 square meters per
gram.
P iculate AntieersE~rant Materia!:
The particulate antiperspirant materials of this invention
comprise any compound or compositlon having antiperspirant
actlvity. Astringent metallic salts are preferrPd antiperspirant
materials for use herein, particularly including the inorganic and
organic salts of aluminum, zirconium and ~inc, and mixtures
35 thereof. Particularly preferred are the aluminum and zirconium
salts such as aluminum halides, aluminum hydroxide halides,
.~ ' .
~_ - R -
zirconyl oxide halides, zirconyl hydroxy halides, and mixtures
thereof .
Preferred aluminum salts include those of the formula
A12 ( OH )aCIb Xt~2
s wherein a is from about 2 to about 5; a~b = 6; x is from about 1
to about 6; and wherein a, b, and x may have non-integer
values. Particularly preferred are aluminum chlorhydroxides
referred to as "5/6 basic chlorhydroxide", wherein a = 5, and
"2/3 basic chlorhydroxide, " wherein a = 4. Processes for prepar-
10 ing aluminum salts are disclosed in the following documents:
U . S . Patent 3, 887, 692,
Gilman, issued June 3, 1975; U.S. Patent 3,904,741, Jones et al.,
issued September 9, 1975; U.S. Patent 4,359,456, Cosling, et al.,
issued November 16, 1982; and British Patent Specification
2,048,229, Fitzgerald, et al., published December 10, 1980.
Mlxtures of aluminum salts are described in British Pa~ent
Specification 1,347,950, Shin, et al., published February 27, 1974
Zirconium salts are also preferred for use in antiperspirant
sticks of the present invention. Such salts are of the general
20 formula
ZrO(OH )2_aCla xH2O
wherein a is from about 1. 5 to about 1 . 87; x is frorr, about 1 to
about 7; and wherein a and n may have non-inte~er values.
These zirconium salts are disclosed in Belgium Patent 825,146,
25 Schmitz, issued August 4, 1975.
Particularly preferred zirconium salts are those
complexes also containing aluminum and glycine, commonly known
as "ZAG complexes". Such ZAG complexes contain aluminum
chlorhydroxide and zirconyl hydroxychloride of the formulae
d~tailed above. These compounds in ZAC complexes are disclosed
in U.S. Pa~ent 3,679,068, Luedders, et al., issued February 12,
1974, and U.S. Patent 4,120,948, Shelton, issued
October 17, 1978.
;
i
)3
g
Partic~1ar1y preferred antiperspirant materia1s are
described in concurrently f iled Canadian Patent Application
Seria1 No. 505,640. Such particulate antiperspirant
actives, yièlding lower levels of visible residue, contain
at least 80% of the particles with a diameter ~reater than
about 10 microns, and at least about 75%
of the antlperspIrant materlal partlcles wlth a dlameter yreater
than abou. 16 microns. Preferably, at least about 80~, more
preferably at least about g0% of the antiperspirant particles, have
a diameter greater than about 16 microns.
~e~
The compositions of the present invention may also contain
optional components which modify the physical characteristics of
the vehicles or serve as "active" components when deposited on
the sk~n in additlon ~o the particulate antiperspirant material.
Additional active components include bacteriostats and fungistats.
Optional components useful herein are described in thP following
documents: U.S. Patent 4,049,792, Elsnau, issued
September 20, 1~77; Canadian Patent 1,164,347, Beckmeyer,
et al., issued March 27, 1984; European Patent
SpeciEication 117,070, May, published August 29, 1985;
Canadian Patent Application Serial Number 497,958, McCall,
filed December 18, 1985; and Geria, "Formulatic,n of Stick
Antiperspirants and Deodorants, " 99 Cosmet1cs & To11etrles
55-60 (1984) .
The particuIar non-active components that may be useful will
depend upon the form of application that is desired. 5uch com-
ponents include, for example, emollients, colorants, perfumes,
and emulsifiers. Althou~h the present compositions may also
contain fillers and other particulate materials other than the
particulate active and colloidal silica materials described above,
such particulates may adversely affect the perceived residue
benefits of the present Invention. (As used herein, "particulate
materials" are those materials that neither dissolve in the
composition components, nor melt during manufacture of the
stick. ) Preferably, then, the present compositions contain a total
6~
- 1D -
level of particulate materials, other than the particulate
antiperspirant materials and the colioidal silica materials, less than
about 2~. More preferably, the present compositions are
essentially free from particulate materials other than the
5 particulate antiperspirant active and the colloidal silica material.
The following non-limitiny examples illustrate the composi-
tions, processes and uses of the present invention.
EXAMPLE I
A stick antiperspirant composition, accordiny to the present
10 invention, was made with the following components:
Components % by weight
cyclomethicone 45. 75
MacrosphericalTM - RE5011 30,50
stearyl alcohol 12 . ûO
15 Fluid Ap2 5.00
dimethicone (350 cs viscosity) 1.50
castor wax 4.00
Cab-O-Sil H S-53 û . 75
PEG-8 distearate 0.50
1: 5/5 basic aluminum chlorhydroxide particulate antiperspirant
material, sold by Reheis Chemical Company, with approximately
~7.5% of the particles having a diameter of greater than 10
microns and approximately 92~ greater than 16 microns
water insoluble ether, condensation product of about 14
moles propylene oxide with one mole butyl alcohol, sold by Union
Carbide Corporation
3: colloidal silica material, sold by Cabot Corporation, having a
surface area of approximately 325 m per gram, and a nominal
particle size of 0.008 microns.
The cyclomethicone, dimethicone and Fluid AP were mixed
and heated to about 82C. The stearyl alcohol, castor wax and
PEG-8 distearate were then added, and the temperature main-
tained at about 82C until the waxes dissolved. The Cab-O-Sil
was then added ancl the mixture heated to about 93C and the
35 antiperspirant active was added. Stirring was continued and the
~2~ 3
batch cooled to approximately 56C and poured into stick forms.
Solid antiperspirant sticks were obtained upon cooling below 48C.
An antiperspirant stick, as formulated above, was applied to
the underarm of a human subject reducing the perspiration in the
5 applied area~ In the above example, cetyl alcohol is substituted
for stearyl alcohol, with substantially similar results. Also, in
the above example, dimethicone (100 cs viscosity) is substituted
for dimethicone (350 cs viscosity), with substantially similar
results .
EXAMPLE I !
A stick antiperspirant composition, according to the present
invention, is made with the following components:
Component_ %_by wei~
cyclomethicone 49 . 80
Rezal 36GP active* 26.70
stearyl alcohol 12 . 00
Fluid AP 6 . 50
castor wax 4.00
PEG-8 distearate 0. 50
Cab-O-Sil 0.50
*: zirconium-aluminum-glycine hydroxychloride complex
antiperspirant active, sold by Reheis Chemical Company
An antiperspirant stick is made in a manner similar to that
described in Example 1. The product, when applied to the
25 underarm of a human subject, is effective as an antiperspirant.
EXAMPLE l l l
A stick antiperspirant composition, according to the present
invention, is made with the following components:
(::omponents ~ by weight
cyclomethicone 44.30
MacrosphericalTM-95l 30 50
cetyl alcohol 6. 00
stearyl alcohol ~, oo
Fluid AP 4.00
dimethicone (350 cs ~ 2 . 50
~2~ 3
-- 12 --
castor wax 4.20
Syloid 722 2 . 50
1 S/6 basic aluminum chlorhydrate par~iculate antiperspirant
material, sold by Reheis Chemical Company, with approximately
5 98~ of the particles having a diameter greater than 10 microns
and approximately 96~ greater than 16 microns
~: colloidal silica material, sold by Davison Chemical l)ivision of
W. R. Grace, having a surface area of approximately 340 m2 per
gram and a nominal particle size of 4 microns.
An antiperspirant stick is made in a manner similar to that
described in Example i. The product, when applied to the
underarm of a human subject, is effective as an antiperspirant.
