Note: Descriptions are shown in the official language in which they were submitted.
~153313
ANTIPERSPIRANT COMPOSITION CONTAINING ALUMINUM
CHLOROHYDRATE, ALUMINUM CHLORIDE AND AN ALUMIN~M ZIRCONIUM
POLYCHLOR~HYDR~TE-CO~ EX AND METH~D OF USE
. . _
This invention relates to antiperspirant compositions.
More particularly, it concerns antiperspirant compositions
having incorporated therein aluminum chlorohydrate, aluminum
chloride, an aluminum zirconium polychlorohydrate complex
and a buffering agent e.g. glycine.
Aluminum chlorhydrate (ACH) has been known for many
years to be an effective and safe antiperspirant. Never-
theless, there is room for improvement and the search to
find more effective antiperspirant materials is constantly
going on. It has also been known in the art for sometime
that aluminum chloride and zirconium salts provide exceptionally
effective antiperspirants. However, solutions of aluminum
chloride hexahydrate and zirconium oxy- or hydroxychloride
are very acidic and therefore, they are not widely used
alone because of their irritation potential and
high fabric damage. Therefore, various efforts have been
centered on raising the pH to 3 to 4 by using less acidic
aluminum salts and incorporating organic nitrogen containing
compounds.
Daley (U.S. Patents 2,814,584 and 2,814,585) and
Grad (U.S. Patent 2,854,382) showed that when zirconium
oxy- or zirconium hydroxychloride are buffered with ACH
and glycine, the antiperspirant efficacy is greater than
an ACH system alone. Since then, the combination of aluminum
chlorohydrate, zirconium hydroxychloride and glycine has
been used widely as a most effective antiperspirant active
system.
Luedders et al in U.S. Patent 3,792,068 suggest a
process for preparing an antiperspirant which comprises
spray drying a solution containing, for example, ACH,
zirconyl hydroxychloride and glycine. It is claimed that
~153313
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this combination has superior characteristics not possessed
when the components are dried separately and combined by
simple physical mixing.
The British patent to Shin et al 1,347,950 discloses
the use of a combination of ACH and aluminum chloride as an
effective antiperspirant material. This combination was
found to be particularly useful in an aerosol composition.
However, as in the case with other antiperspirant materials
known in the prior art, it still left room for improvement.
Other antiperspirant systems containing aluminum and
zirconium salts have been reported, for example, ~eekman
(U.S. Patent 2,906,668), Rubino (U.S. Patents 3,97g,510;
3,981,896 and 4,017,599), Siegel et al (U.S. Patent 3,407,254),
Mecca (U.S. Patent 3,g70,748), Shelton (U.S. Patent 4,202,879),
etc. The antiperspirant activity of all these salts in these
patents has not been clearly claimed as having superiority
over systems containing æirconium hydroxychloride, ACH and
glycine.
Although aluminum chloride, aluminum chlorohydrate,
zirconyl hydroxychloride and certain aluminum zirconium chloro-
hydrate complexes, individually have been suggested for use as
antiperspirant materials in the prior art and the combination
of aluminum chloride and aluminum chlorohydrate on the one
hand, and the combination of aluminum chlorohydrate and
zirconyl hydroxychloride on the other hand, have also been
suggested for use as an active antiperspirant, it has been
unexpectedly found that combination of aluminum chloride,
aluminum chlorohydrate, an aluminum zirconium polychloro-
hydrate complex as defined more particularly below act
synergistically and at the same level of concentration of
actives show a higher degree of antiperspirant activity
than would be expected from the level of activity of the
individual ingredients or certain combination of ingredients
which are shown in the prior art. In combination with a buff-
ering agent e.g. glycine, these materials provide a high
~ 53313
performance antiperspirant having a low potential for skin
irritation and/or fabric damage.
It is accordingly an object of the present invention
to provide highly effective antiperspirant compositions.
It is also an object of this invention to provide a
process for inhibiting perspiration on the skin of individuals
by application to the skin area the aforesaid antiperspirant
compositions.
Other and more detailed objects of this invention will
be apparent from the following description and claims.
In the following description, unless otherwise
specified, the percentages are expressed as percentages by
weight based on the total weight of the composition.
The aluminum chloride that is incorporated in the compo-
sitions of the present invention may be aluminum chloride
hydrated to various degrees. However, aluminum chloride
hexahydrate (AlC13. 6H20) has been found to be most effect-
ive and is therefore preferred for the purposes of the
present invention.
The quantity of aluminum chloride that may be incor-
porated in the present composition may vary somewhat.
Generally, the aluminum chloride will be incorporated in
these compositions at a level of between about 0.5~ and about
6% by weight on an anhydrous basis based on the total weight
of the composition. As the hexahydrate (AlC13. 6H20) it
will be incorporated at a concentration of from about 0.9%
to about 11% by weight based on the total weight of the
composition with the preferred range being from about 2%
to about 6% on the same basis.
The aluminum chloride hexahydrate will usually be
incorporated in the present composition as a 50% a~ueous
solution. When employed in this form, from about 1.8% to
about 22% by weight of this composition based on the total
~;3313
-- 4 --
weight of the composition will be used.
The aluminum chlorohydrate (sometimes referred to as
aluminum chlorhydroxide) may also be incorporated in the
composition of this invention in varying amounts. Usually,
this will be used at a level in the range of from about 1%
to about 15~ by weight on an anhydrous basis based on the
total weight of the composition with the preferred level
falling in the range of from about 2% to about 10% by weight
on the same weight basis. Aluminum chlorohydrate is also
supplied as a 50% aqueous solution. When employed in this
form, it will be used at a concentration of from 2.6~ to about
38% by weight based on the total weight of the com~osition.
to thls composition
The ACH and aluminum chloride may be added~in whole
or in part as a powdered mixture as described in the British
patent to Shin et al 1,347,950. This may be prepared by
drying an aqueous solution of aluminum chloride hexahydrate
and ACH using conventional drying techniques such as oven drying,
vacuum oven drying, spray drying or freeze drying. These
compositions are characterized by the fact that the molar
ratio of aluminum to chloride will fall within the range of
from about 0.78:1 to about 1.95:1 with the preferred range being
about 1.2:1 to about 1.5:1. When the molar ratio of aluminum
to chloride is less than 1, the addition of larger amounts
of buffering agent e.g. glycine may be necessary to reduce
irritation potential and fabric damage.
The aluminum zirconium polychlorohydrate complexes
that may be incorporated in the composition of the present
invention may be described by the general formula:
(I) Alxzr(oH)yclz . nCH2COOH . mH2O
NH2
30wherein:
(a) x is a number from 2 to 10;
(b) Z is a number from 3 to 8;
.;
~53313
-- 5 --
(c) y equals (3x + 4) - Z;
(d) the sum of y ~ Z is a number from 10 to 34;
(e) m is a number from 0 to 12;
(f) n is a number from 0 to 3
y ordinarily will have a value of from about 5 to about 29.
As will be clear from Formula I, the glycine may be bound in
the complex or it may be absent. The presence or absence of
the glycine in the complex will determine the amount of unbound
glycine or other buffer that may be incorporated in the composi-
tion to increase the pH to a le~el of from about 2.5 to about
4~5 or the preferred pH of fr~m about 2.8 to about 3.8.
A number of aluminum zirconium polychlorohydrate com-
plexes are known i~ the prior art which are useful for the
present purposes. By way of example, the following may be
mentioned along with their empirical formulas: aluminum
zirconium tetrachlorohydrate (A14Zr(OH)12C14); aluminum
zirconium tetrachlorohydrate glycine (Wickenol #E-369)
~A14Zr(OH)12C14 . NH2CH2COOH); aluminum zirconium trichloro-
hydrate (A14Zr(OH)13C13; aluminum zirconium trichlorohydrate
glycine (A14Zr(OH)13C13 . NH2CH2COOH); aluminum zirconium
pentachlorohydrate (A110Zr(OH)29C15); aluminum zirconium
pentachlorohydrate glycine (A110Zr(OH)29C15 . NH2CH2COOH);
aluminum zirconium octachlorohydrate (A16Zr(OH)14C18);
aluminum zirconium octachlorohydrate glycine (A16Zr(OH)14C18 .
NH2CH2COOH). The aluminum zirconium polychlorohydrate
complex can be mixed individually with the ACH and
AlC13 . 6H20 in solution or powder form or in various
combinations thereof.
The OTC Panel on antiperspirants of the Food and
3~ Drug Administration has adopted certain nomenclature and
specifications for various aluminum zirconium polychloro-
hydrates that are useful in the present invention. These
are set out in Table A below:
B * Trademark
~53313
-- 6 --
Table A
Panel Adopted Metal-Halide Al/Zr
Nomenclature Ratio Range Ratio Range
Aluminum zirconium 2.1 down to but not 2.0 up to but not
5trichlorohydrate inc~udin~ 1.5:1 including 6.0:1
Aluminum zirconium 1.5 down to and 2.0 up to but not
tetrachlorohydrate including 0.9:1 including 6.0:1
Aluminum zirconium 2.1 down to but not 6.0 up to and
pentachlorohydrate including 1.5:1 including 10.0:1
10Aluminum zirconium 1.5 down to and 6 . o up to and
octachlorohydrate including 0.9:1 including 10.0:1
A number of the aluminum zirconium polychlorohydrate
complexes that are useful in the present invention are avail-
able commerically~ Reheis Chemical Company promotes a series
of materials under the general trademark REZALTM. The follow-
ing Table describes a number of these products together with
their specifications:
Table I
1 REZAL 36G Aluminum zirconium tetrachlorohydrex Gly (soln.)
2 REZAL 36 Aluminum zirconium trichlorohydrate (pdr.)
3 REZAL 67 Aluminum zirconium pentachlorohydrate (soln.)
4 REZAL 67 Aluminum zirconium pentachlorohydrate (pdr.)
1 2 3 4
.
Approx.
Al/Zr ratio 3.6:1 3.6:1 6.7:1 6.7:1
Approx.
metal/Cl ratio1.4:1 1.6:1 1.7:1 1.7:1
Concentration
of solids ~ 35% 100% - 40% 100%
Aluminum(Al)5.0%-5.7%16.3%-17.7% 7.6%-8.4% 19.0%-21.0%
Zirconium(Zr)4.4%-5.7%13.8%-15.2%3.7%-4.3% 9.2%-10.8%
Glycine 3.6~-4.7~ --- --- ---
Chloride(Cl)5.9%-6.7%16.0%-19.0% 6.5%-7.2% 16.2%-18.0%
Iron(Fe) NMT 50ppm NMT lOOppm NMT 50ppm NMT lOOppm
Heavy metals
(as Pb) NMT lOppm NMT 20ppm NMT lOppm NMT 20ppm
Particle size
(thru 325! mesh) --- ~ 97% min. --- ~97% min.
-' ~1533~3
- 7 -
Similar products are marketed by Wickhen Products, Inc. and
the Comet Chemical Corporation.
The quantity of any aluminum zirconi~m polychlorohydrate
comp~ex that will be incorporated in the composition of the
present invention may also vary somewhat. Usually, it will
be used at a concentration level in the range of from about
5% to about 16% by weight on an anhydrous basis based on
the total weight of the composition. In the preferred forms
of this invention, the levels will be in the range of from
about 8% to about 14% by weight on an anhydrous basis based
on the total weight of the composition.
The aluminum zirconium polychlorohydrate complex of
choice in the present invention is aluminum zirconium tetra-
chlorohydrate glycine complex. This is usually used at a
level of from about 5% to about 16% by weight on an anhydrous
basis based on the total weight of the composition with the
preferred level being in the range of from about 8% to about
14~ based on the same weight basis. The aluminum zirconium
tetrachlorohydrate glycine complex is supplied as a 35%
aqueous solution. When employed in this form, it is usually
incorporated in the present composition at a level in the
range of from about 18% to about 60% by weight based on the
total weight of the composition.
Glycine, the preferred buffering agent, is an important
component of the present composition. This may be incorporated
as free glycine or as part of the aluminum zirconium polychloro-
hydrate complex or as a combination of the both. In general,
the total ~lycine incorporated in these compositions (i.e.
as free glycine, complexed glycine or a combination of both)
will fall in the range of from about 0.5% to about 5~ by
weight based on the total weight of the composition. The
preferred range of total glycine, however, is from about 1.5%
to about 3~ on the same weight basis.
Other buffering or complexing agents besides glycine
can also be used in this invention. For example, other amino
~153313
-- 8 --
acids or their salts (e.g. sodium glycinate, dihydroxy
aluminum glycinate), urea, organic base containing
nitrogen, metal hydroxide, carbonate, and oxide including
alkaline and alkaline earth metal (Mg(OH)2, Na2C~3,ZnO,
etc.). These buffering agents can be used alone or in
combination with glycine to giYe the composition a pH
in the range of from 2.5 to 4.5 (preferably 2.8 to 3.8).
These complexing and bufferiny agents serve to
reduce irritation potential and fabric damage. They also
function to stabilize the antiperspirant system.
~ he compositions of the present invention may take
a variety of dosage forms. Thus, they might be emulsion
roll-on products or a clear hydro-alcoholic or aqueous roll-on
products. Aqueous solutions of the aluminum chloride,
ACH, aluminum zirconium polychlorohydrate complex and
buffering agent e.g. glycine may be spray dried into an
impalpable powder. This can be used as such or incorporated
into sticks, suspensions, powders or roll-on products.
~ ~,
33i3
g _
Although the compositions of the present invention may
take a variety of forms, they appear very effective in system
that contain a relatively high water content. These may take
the form of solution or emulsion ~n which the active ingredients
(i.e. the aluminum chloride, ACH, aluminum zirconium polychloro-
hydrate complex and buffer) are contained in the aqueous phase.
The aqueous emulsion systems are preferred since they give
more organoleptically elegant compositions. ~hese emulsion
systems will usually be of the oil-in-water type in which the
active ingredients will be contained in the continuous
aqueous phase.
The quantity of water that may be contained in these
compositions may vary somewhat. Usually, it will comprise
from about 40% to about 80% by weisht based on the total
weight of the composition, the preferred range being from
about 60% to about 75% on the same weight basis.
The emulsion type products of the present invention ~ -
may also contain other ingredients that are commonly found
in roll-on antiperspirant of the lotion or emulsion type.
These will include such things as emollients, surfactants,
sequestering agents, perfumes, coloring agents, etc.
By way of illustrating the emollients that may be employed
herein, mention may be made of fatty acid esters (isopropyl
myristate , isopropyl palmitate);diesters of dicarboxylic
acids (diisopropyl adipate), polyoxyalkylene glycol esters
(polypropylene glycol 2000 monooleate); propylene glycol
diesters of short chain fatty acids*(C8-C10)* (Neobee M-20);
polyoxypropylene fatty ethers (Procetyl, Arlamol E, Witconol
APS, Witconol APM, etc.), propoxylated monohydric alcohol
M.W. 880-930 (Fluid AP), fatty alcohol (hexadecyl alcohol),
silicone oils (dimethyl po~siloxane, 10-2000 centistokes),
cyclomethicones (volatile silicone 7207 and 7158-Unin
Carbide), polyoxyethylene polyoxypropylene fatty ether
(Procetyl AWS Modified, Witconol APES). Alone or mixtures
of the above non-polar liquids are equally suitable for the
purposes of this invention. Generally, the above emollients
are organic oily liquids which are non-polar in character
~Trademarks
~S
313
-- 10 --
and have ~a) a boiling point under atmospheric pressure
not lower than about 120C; (b) a specific gravity between
about 0.7 and 1.6, preferably between 0.7 and 1.2.
The quantity of emollient employed will vary somewhat,
the level usually being within the range of from about 1
to about 30% by weight based on the total weight of the
composition. Preferably, this will fall in the range of
from about 2% to about 15% on the same weight basis.
A variety of surfactants and combinations of surfactants
are also useful in preparing the present lotion or emulsion
type products. These include such materials as generally
nonionic, cationic and amphoteric surfactants which can
be used in antiperspirant emulsion systems. Examples are
as follows:
I. Nonionic Surfactants
* *
1. Polyoxyethylene fatty ethers - Brij 30, Brij 35,
* *
Brij 72, Brij 78, etc.
2. Polyoxypropylene polyoxyethylene fatty ethers -
Procetyl AWS, Witconol APEM, Witconol APES, etc.
3. Polyoxyethylene alkyl phenyl ethers - Igepal*
CO 530, etc.
4. Polyoxyethylene sorbitan fatty acid esters -
Tween*20, Tween*80, etc.
5. Sorbitan fatty acid esters - Span 60, Span 85, etc.
6. Lanolin ethers - Laneto 50, Solulan 98, etc.
7. Fatty alcohols a~d polyoxyethylene fatty
ethers - Pro~ulgen G, Polawax, etc.
II. Cationic Surfactants
N(Lauryl colamino formyl methyl)pyridinium chloride
(Emcol*E607L)
III. Amphoteric Surfactants
Coconut imidazoline (Monateric CA-35%)
IV. Auxiliary Surfactants
1. Glyceryl fatty acid esters - Glyceryl monostearate
* Trademarks
B
-- ~lS3313
2. Fatty acid amides - Witcamide 70 (Witco Chem. Co.)
3. Fatty alcohols - Stearyl alcohol
As in the case with the emollients, the quantity
employed can vary sQmewhat. For the most part, this will be
in the range of from about 1% to about 10% by weight on an
anhydrous basis based on the total weight of the composition
with the preferred range being from about 2% to about 6% on
the same weight basis.
As indicated above, one of the popular antiperspirant
systems employed in the prior art is an aluminum zirconium
trichlorohydrate glycine compleg . ~he present system has
the following advantages over said popular system:
1. Low cost of goods. The above popular system is
much more expensive than either AlC13 . 6H2O or ACH.
2. Better emulsion stability and more ease to manu-
facture. Straight Al/Zr ~olychlorohydrate glyeine systems
are difficult to stabilize and to manufacture as emulsions.
3. Low fabric staining potential. Generally~ straight
Al/Zr polychlorohydrate glycine salts stain more than
aluminum salts.
The following Examples are given to further illustrate
the present invention. It is to be understood, however,
that the invention is not limited thereto.
EXAMPLE 1
Formula 1908
Ingredients % by Wt.
PPG-ll stearyl ether 2.25
Polyoxyethylene(2)stearyl
ether 1.65
30 Polyoxyethylene(20)stearyl
ether 0.60
Perfume 0.30
Disodium edetate, dihydrate 0.10
Water, deionized 35.40
Aluminum chlorhydroxide, 50% 18.00
. "
.
.
~ ~1533~3
- 12 -
Aluminum chloride hexahydrate
solution, 50% 6.00
Aminoacetic acid (Glycine Crystal
USP)-- 0.50
Aluminum zirconium tetrachloro-
hydrex-glycine solution, 35% 35.00
Color FD&C Blue ~1 (0.1% Aq. Sol.) 0.20
100.00
Appearance: Smooth, opaque lotiQn
Color: Pale blue
p~: 3.3 + 0.3
Viscosity: #3 spindle at 20 RPM 15 seconds
Overnight viscosity: 500-1500 cps
. . . .
-
Procedure:
1. In a suitable stainless steel kettle, melt together
polyoxypropylene fatty alcohol ethers, polyoxyethylene(2)stearyl
ether and polyoxyethylene(20)stearyl ether by heating to 140F.
Add the perfume and mix together just prior to Step 3.
2. In a separate stainless steel kettle, dissolve
the disodium edetate in the water and heat to 140F.
3. Slowly add the oil phase to the water phase
(both at 140F) using a Lightnin' mixer at slow agitation.
Maintain the temperature of 140F for 15 minutes.
4. At 140F, slowly add to the batch, using slow
agitation, a solution consisting of the aluminum chlorhydroxide,
aluminum chloride hexahydrate, glycine and aluminum zirconium
tetrachlorohydrex-glycine solution which has been preheated
to 120F. Continue agitation and cool the batch to 125F.
Mix for 15 minutes, maintaining the batch temperature at
120F-125F.
5. Cool the batch to 105F, add the dye solution and
continue agitation and cooling.
6. When the batch temperature reaches 80-85F,
stop agitation and adjust for water loss, if necessary.
, ,
5l333~3
EXAMPLE 2
The composition and procedure of Example 1 is followed
except that in place o the PPG-ll stearyl ether, Arlamol ESP
(PPG-15 stearyl ether~ is employed.
EX~MPLE 3
Formula 1956
Following the procedure of Example 1, the following
composition is prepared:
_ngredients % by Wt.
PPG-ll stearyl ether 2.25
Polyoxyethylene(2)stearyl
ether 1.65
Polyoxyethylene(20)stearyl
ether 0.60
Perfume 0.32
Disodium edetate, dihydrate 0.10
Water, deionized 35.13
Butylated hydroxytoluene ~ 0.05
Aluminum chlorhydroxide, 50% 18.00
Aluminum chloride hexahydrate
solution, 50% 6.00
Aminoacetic acid (Glycine Crystal
USP) 0.50
Aluminum zirconium tetrachlorohydrex-
glycine solution, 35% 35.00
D&C Red #19 (0.1% Aq. Sol.) 0.08
D&C Yellow #10 (0.1% Aq. Sol.) 0.32
100. 00
Appearance: Smooth, opaque lotion
Color: Pink
pH: 3.3 + 0.3
Viscosity: #3 spindle at 20 RPM 15 seconds
Overnight viscosity: 500-1500 cps
1~3313
- 14 -
EXAMPLE 4
The composition and procedure of Example 3 is followed
excepting that in place of the PPG-11 stear~l eth~r, Arlamol ESP
(PPG-15 Stearyl Ether) is used.
E ~MPLE 5
The procedure of Example 1 is followed and the following
composition is prepared:
Ingredients ~ by Wt.
PPG-ll stearyl ether 2.25
Polyoxyethylene(2)stearyl
ether 1.65
Polyoxyethylene(20)stearyl
ether 0.60
Perfume 0.30
Disodium edetate, dihydrate 0.10
Water, deionized 31.40
Aluminum chlorhydroxide, 50%12.00
Aluminum chloride hexahydrate solution,
50% 6.00
Aminoacetic acid (Glycine Crystal
USP) 0.50
Aluminum zirconium tetrachlorohydrex-
glycine solution, 35%
45.00
FD&C Blue #1 (0.1% Aq. Sol.) 0.20
100.00
Appearance: Smooth, opaque lotion
Color: Pale blue
pH: 3.3 ~ 0.3
Viscosity: #3 spindle at 20 RPM 15 seconds
Overnight viscosity: 500-1500 cps
EXAMPLE 6
The procedure and composition of Example 5 is followed
excepting that in place of the PPG-ll stearyl ether, ~lamol ESP
(PPG-15 Stearyl Ether) is employed.
L153313
- 15 -
EXAMPLE 7
Formula 1979
The procedure of Example 1 is followed and the following
composition is prepared:
Ingredients % by Wt.
PPG-ll stearyl ether 2.25
Polyoxyethylene(2)stearyl ether 1.65
Polyoxyethylene(20~stearyl ether 0.60
Perfume 0.30
Disodium edetate, dihydrate 0.10
Water, deionized 35.40
Aluminum chlorhydroxide, 50% 15.50
Aluminum chloride hexahydrate solution,
50% 8.00
Aminoacetic acid (Glycine Crystal
USP) ' 1 . 00
Aluminum zirconium tetrachlorohydrex-
glycine solution, 35%
35.00
FD&C Blue #1 (0.1% Aq. Sol.) 0.20
100.00
Appearance: Smooth, opaque lotion
Color: Pale blue
pH: 3.3 + 0.3
Viscosity: #3 spindle at 20 RPM 15 seconds
Overnight viscosity: 500-2000 cps
EXAMPLE 8
The composition and procedure of Example 7 is followed
excepting that in place of the PPG-lI stearyl ether, Arlamol ESP
(PPG-15 Stearyl Alcohol) is employed.
~, ,,
-~ ~L153313
- 16 -
EXAMPLE 9
Formula 1991
The procedure of Example 1 is followed and the following
composition is prepared:
Ingredients % by Wt.
PPG-ll stearyl ether 2.25
Polyoxyethylene(2)stearyl ether 1.65
Polyoxyethylene(20)stearyl ether 0.60
Perfume 0.30
Disodium edetate, dihydrate 0.10
Water, deionized 31.40
Aluminum chlorhydroxide, 50% 10.00
Aluminum chloride hexahydrate
solution, 50% 8.00
Aminoacetic acid (Glycine Crystal
USP) 0.50
Aluminum zirconium tetrachlorohydrex-
~lycine solution, 35%
45.00
FD&C Blue #1 (0.1% Aq. Sol.) 0.20
100. 00
Appearance: Smooth, opaque lotion
Color: Pale blue
pH: 3.3 + 0.3
Viscosity: ~3 spindle at 20 RPM 15 seconds
Overnight %iscosity: 500-1500 cps
EXAMPLE 10
The composition and procedure of Example 9 is followed
excepting that in place of the PPG~ll stearyl ether, Arlamol ESP
(PPG-15 Stearyl Ether) is employed.
~.~ .~
, :
~ 3313
- 17 -
EXAMPLE 11
Formula 1955
The procedure of Example 1 is followed and the following
co~position is prepared:
Ingredients % by Wt.
PPG-ll stearyl ether 2.25
Polyoxyethylene(2)stearyl ether1.65
Polyoxyethylene(20)stearyl ether0.60
Perfume 0.30
Disodium edetate, dihydrate 0.10
Water, deionized 35.60
Aluminum chlorhydroxide, 50% 18.00
Aluminum chloride hexahydrate
solution, 50% 6.00
Aminoacetic acid (Glycine Crystal
USP) 0.50
Aluminum zirconium tetrachlorohydrex-
glycine solution, 35~ 35.00
100 . 00
Appearance: Smooth, opaque lotion
Color: White
pH: 3.3 + 0.3
Viscosity: #3 spindle at 20 RPM 15 seconds
Overnight viscosity: 500-1500 cps
EXAMPLE 12
The composition and procedure of Example 11 is followed
excepting that in place of the PPG-ll stearyl ether, Arlamol ESP
(PPG-15 Stearyl Ether) is employed.
i3313
-- 18 --
EXAMPLE 13
Formula BA 1810-64
Aluminum zirconium trichlorohydrate 31 powder was
employed. The number following the term "trichlorohydrate"
in this and other Examples designates the Al/Zr molar
ratio in the compound. Thus, for example, 31 designates
an Al/Zr molar ratio of 3/1.
Primary Emulsion A % by Wt.
PPG-ll stearyl ether ~ 5.56
Polyoxyethylene(2)stearyl
eth~r 4.07
Polyoxyethylene(20)stearyl
ether 1.48
Perfume 0.74
Disodium edetate, dihydrate 0.25
FD&C Blue #1 (0.1% Aq. Sol.) 0.49
Water, deionized 87.41
100. 00
Ingredients % by Wt.
Al/Zr trichlorohydrate 31 powder10.00
ACH 50% solution 18.00
AlC13 . 6H20, 50% solution 6.00
Glycine 1.50
'~Jater, deionized 24.00
Primary Emulsion A q.s. to 100.00
pH: 3.4 + 0.3
Overnight viscosity: 500-1500 cps
-` ~153313
-- 19 --
EXAMPLE 14
Formula BA 18~0-65
Aluminum zirconium trichlorohydrate 21 powder
(Al/Zr molar ratio = 2/1) was used:
Ingredients % by Wt.
Al/Zr trichlorohydrate 21 powder10.00
ACH 50~ solution 18.00
AlC13 . 6H2O ,50% solution 6.00
Glycine 1.50
Water, deionized 24.00
Primary Emulsion A q.s.-to 100.00
pH: 3.5 + 0.3
Overnight viscosity: 500-1500 cps
EXAMPLE 15
Formula BA 1810-56
Aluminum zirconium octachlorohydrex-glycine powder 81
(Al/Zr molar ratio = 8/1) was used:
Ingredients% by Wt.
Al/Zr octachlorohydrex-glycine
powder 81 15.00
ACH 50% solution10.00
AlC13 . 6H2O solution 8.00
Glycine 0.50
Water, deionized26.00
Primary Emulsion A q.s. to 100.00
pH: 3.2 + 0.3
Overnight viscosity: 500-1500 cps
- ~153313
- 20 -
EXAMPLE 16
Formula BA 1810-57
Aluminum zirconium pentachlorohydrate solution
(Al/Zr molar ratio = 10/1) was used:
Ingredients % by Wt.
Al/Zr pentachlorohydrate solution, 30~ 35.00
ACH 50% solution 10.00
AlC13 . 6H2O 50% solution 8.00
Glycine 2.00
Water, deionized 4.50
Primary Emulsion A q.s. to 100.00
pH: 3.4 + 0.3
Overnight viscosity: 450-1500 cps
EXAMPLE 17
Formula BQ 1856-83
Different buffering agent such as sodium carbonate is
used as an additional buffering agent in this Example.
Primary Emulsion B % by Wt.
PPG-ll stearyl ether 6.43
Polyoxyethylene(2)stearyl
ether 4.71
Polyoxyethylene(20)stearyl
ether 1.71
Perfume 0.86
Disodium edetate, dihydrate 0.29
FD&C Blue #1 (0.1~ aq. sol.) 0.57
Water, deionized 85.43
100.00
~ 53313
- 21 -
Ingredients % by Wt.
Al/Zr tetrachlorohydrex-glycine
solution, 35% 45.00
ACH, 50% solution 10.00
AlC13 . 6H2O, 50% solution 8.00
Glycine 1.20
Sodium carbonate monohydrate 0.50
Water, deionized 0.30
Primary Emulsion B q.s. to 100.00
pH: 3.4 + 0.3
Overnight viscosity: 500-1500 cps
EXAMPLE 18
Formula BQ 1856-83
Magnesium hydroxide was used as an additional buffering
agent.
Ingredients % by Wt.
Al/Zr tetrachlorohydrex-glycine
solution, 35~ 45.00
ACH, 50% solution 10.00
AlC13 . 6H2O, 50% solution 8.00
Glycine 0.50
Magnesium hydroxide 0.50
~later, deionized 1.00
Primary Emulsion B q.s. to 100.00
pH: 3.4 + 0.3
Overnight viscosity: 500-1500 cps
.,~,...
:
. .
-' ~lS33~3
- 22 -
EXAMPLE 19
Formula 1509-61
Ingredients % by Wt.
PPG-ll stearyl ether 2.25
5 Polyoxyethylene(2)stearyl
ether 1.65
Polyoxyethylene(20)stearyl
ether 0.60
Perfume 0.30
Water, deionized 41.20
Disodium edetate, dihydrate 0.10
DC Antifoam AF, 25% 0.10
Al/Zr tetrachlorohydrex-glycine
solution, 35~ 35.00
15 ACH, 50% solution 15.00
AlC13 . 6H20, 50~ solution 3 . 00
Glycine 0.60
FD&C Blue #1 (0.1% aq. sol.) 0.20
100.00
pH: 3.4 + 0.3
overn~ght-vi~cosity; 400-1200 cps
To demonstrate that the combination of aluminum chloride,
ACH, aluminum zirconium polychlorohydrate and glycine act
synergistically, a number of formulas identified in Table II
below were prepared. Formula ~ 1908 is representative of
the present invention.
~ ' ~
.
~1~3313
-- 23 --
~ d ~ C~ H
O O Pl ~ 0 0 ~ 1~ ~
0 1- bn 1~ v~ m
P ~ 0~ ~ ~ I t~ ~ oP I~ pJ ~ It
1~ o ~D O ~ (I
3 ~ ~ P X ~ X
- n ~ ~ 3
~n ~ ~ 1- ~ 1--~ ~ ~ ~ ~ O~
m ~:
I~ ~ P t ~ ~ ~ ~n
~ ~ ~ O ~ S~ O O ~S
(D u~ O 1~ O
O P
o ~ ^ ~ tn O
o
o ~
~S tn
CO 1~ #
o o . . . I I I . I_
~ (- ~O O ~ Ul
CO O O 1-- ~ ~ CO I I #
. . . . . . . . I I i-
CO ~ I_ ~ ~n o co ~ a~
a~
o~
p~ ~
I_ ~ ~ H
1~ O O i~ 1 :~-
.. . . . . .. . . #
~n ~ 9 W ~I Ul I_ 1'- v~
ul ~n ~9 ~ pl
O
CO r~
O
_ 1--
CO O ~ ~ ~ ~ ~ ~ #
. - . . . . I 1-
o ~ I~ ~ w n o I o ~ ~
H ~1 ~ _ DI O O
~_~ O ~ (D C~ ~ I_
~D~v 1'- P I ~ ~P W I ~
. 1~ t I I O It
~S O tD Pl I ~ I I
_ p~
v~ ~ W Y
P P~ p p C~ ~ ~ P
G~ P l'~ ~n ~
p ~ < --O'
~ t
tD Ul o ~ ~
~C
-' ~1533~3
- 24 -
As will be noted, each of these formulas is similar
excepting for the active ingredients that are employed.
Further, each contains the total active ingredients at
essentially the same concentration i.e. about 18% on an
anhydrous basis.
Each of these compositions was tested for antiper-
spirant activity. The general procedure employed was
as described in Federal Register, Vol. 43, Number 196,
October 10, 1978. It is called the gravimetric axillary
antiperspirant test. Paired comparison (treated vs.
treated) studies of the antiperspirant effectiveness of
antiperspirant emulsion.
The details of the test procedure are given below.
Test Procedure
A random test pattern supplied by Statistical Services
is employed, e.g. if one test material is evaluated, half of
the panelists receives the test material under the left
axilla while the remaining half receives it under the right.
The opposite axilla serves as a control. If two test
materials are evaluated, half the panel has product A
applied to the left axilla and product B to the right while
the remaining panelists have the reverse product/axilla
allocations.
The test is conducted during a five-day period
(~onday through Friday). Sweating is induced under environ-
mental conditions of 100F ~ 2 and 40% relative humidity
+ 2%.
Day 1: Control measurement followed by product application
Panelists wait one-half hour at room temperature
(approximately 65-80F) after which time they enter the
test room. They then place the untared Webril Pads (which
are folded in half to a size of 4"x2") in their axillae.
Subj~ects sit in the test room for a 40 minute warm-up period.
At the end of this period, the warm-up pads are removed by
the panelists and are discarded.
~53313
- 25 -
The panelists remove the plastic bags containing
the tared collection pads from the manila envelopes. The
subjects insert the pads as directed by a technician.
The pads remain in the axilla for a period of 20 minutes.
After such time, the panelists are instructed to remove the
pads and to place them into the designated plastic bags which
are then returned to the manila envelopes.
The panelists exit the test room, hand in their
envelopes, and then wash their axillae with tepid water with
the aid of gauze pads and towel dry them. Approximately
one to three minutes later, the test material is applied
and the panelists leave. The plastic bags are removed
from the manila envelopes and are weighed by a technician.
Panelists must perspire at least 200 mg/axilla to continue
participation on the panel.
Day 2: Product application only
Panelists wait one-half hour at room temperature,
after which time they wash their axillae with tepid water
with the aid of gauze pads and towel dry them. Approximately
one to three minutes later, the test material is applied
and the panelists leave.
Day 3: Product application and collection
Panelists wait one-half hour at room temperature,
after which time they wash their axillae as described above.
Approximately one to five minutes later the test material
is applied. The panelists then wait one hour at room tempera-
ture. Then they enter the test room for a 40-minute warm-up
and place the untared pads in their axillae. At the end of
this period, the warm-up pads are removed and discarded.
The panelists remove the plastic bags containing the
tared collection pads from the manila envelopes. They
insert the pads as directed by a technician. The pads remain
in the axillae for a period of 20 minutes. Then the panelists
are instructed to remove the pads and to place them into the
.
53313
- 26 -
designated plastic bags which are then returned to the manila
envelopes. The panelists exit the test room, hand in their
envelopes, and leave. The plastic bags are removed from
the manila envelopes and are weighed by a technician.
Day 4: Product application only
Same as Day 2.
Day 5 : Product application and collection
Same as Day 3.
The results of the test are summarized as follows:
I. Formula #1908 vs. Formula #1052
Results:
The data from this study, employing 47 female subjects,
were submitted to the Statistical Services Department for
evaluation.
Briefly, their analysis indicated that Antiperspirant
Roll-on Formula #1908 was significantly more effective than
Formula #1052 at the 0.01 level.
This conclusion is supported by the A/B ratio (amount
ofsweat collected from A treated axilla over B treated axilla)
for thé final treatment-collection day (adjusted by control)
averaging 0.819 which is significantly different from 1.0
equality.
The above data indicates that Formula #1908 is about
18% more effective than Formula #1052.
II. Formula #1908 vs. Formula #1676
Results:
The data from this study, employing 46 female subjects,
were submitted to the Statistical Services Department for
evaluation.
Briefly, their analysis indicated that Formula #1908
was significantly more effective than Formula #1676 at the
0.01 level.
~;33~3
- 27 -
This conclusion ~s supported by the A/B ratio for
the final treatment-collection day (adjusted for control)
averaging 0.883 which is significantly different from 1.0
e~uality.
The above data indicates that Formula #1908 is about
12% more effective than Formula #1676.
III. Formula #1908 vs. Commercial Emulsion Roll-On
Formula # BR 4504 _ _
-
Results~
The data from-this study, employing 48 female subjects,
were submitted to the Statistical Services Department for
evaluation.
Briefly, their analysis indicates that Formula #1908
was significantly more effective than Commercial Emulsion
Roll-On at the 0.01 level.
This conclusion is supported by the A/B ratio for
the final treatment-collection day (adjusted for control)
averaging 0.881 which is significantly different from 1.0
equality.
The above data indicates that Formula #1908 is about 12%
more effective than Formula #BR 4504.
IV. Formula #1341 (see Table II ) which contains as anti-
perspirant actives a combination of ACH and AlC13 . 6H2O
(at a level of about 18.2) in a similar manner was shown
to be on the average 9.6% less effective than the Commercial
Emulsion Roll-on (BR 4504) which contains 19.7% Al/Zr tri-
chlorohydrate as the ~ntiperspirant active (see Table II).
The latter, however, has also been shown to be less effective
than Formula #1908 embodied in the present invention i.e.
Formula #1908 was about 12% more effective than Fo~mula
#BR 4505 (see Paragraph III~.
;33't 3
- 28 -
V. Formula #1991 (See Example 9) in a similar manner was
shown to be 15% more effective than a commercial suspension
roll-on product identified as Formula #BR 4751. The
latter has the following composition:
Formula # BR 4751
Ingredients % by Wt.
Aluminum zirconium tetrachloro-
hydrate (anhydrous basis) 13.8
Glycine 2.0
Bentone 38 3.25
Cyclomethicone and
Perfume q.s. to 100.00
Although the invention has been described with
reference to specific forms thereof, it will be understood
that many changes and modifications may be made without
departing from the spirit of this invention.
