U.S. patent number 3,725,540 [Application Number 05/059,691] was granted by the patent office on 1973-04-03 for color and odor stabilized dry aerosol antiperspirant.
This patent grant is currently assigned to The Procter & Gamble Company. Invention is credited to Errol H. Wahl.
United States Patent |
3,725,540 |
Wahl |
April 3, 1973 |
COLOR AND ODOR STABILIZED DRY AEROSOL ANTIPERSPIRANT
Abstract
Dry aerosol antiperspirant compositions containing
hexachlorophene and/or perfumes which are subject to deterioration
and are stabilized by the incorporation of a small amount of citric
acid.
Inventors: |
Wahl; Errol H. (Cincinnati,
OH) |
Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
|
Family
ID: |
22024615 |
Appl.
No.: |
05/059,691 |
Filed: |
July 30, 1970 |
Current U.S.
Class: |
424/46; 424/47;
424/66; 424/68; 514/735; 424/65; 424/67; 424/69 |
Current CPC
Class: |
A61K
8/365 (20130101); A61K 8/26 (20130101); A61K
8/37 (20130101); A61Q 15/00 (20130101) |
Current International
Class: |
A61k 007/00 () |
Field of
Search: |
;424/47,45,68,69,46 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
Lester et al., Handbook of Cosmetic Materials, 1954, pp. 96. .
Sagarin, Cosmetics Science and Technology, 1957, pp. 1,035, 1,053
and 1,067. .
Winter, Handbuch Der Gesamten Parfumerie Und Kosmetik, 1952, pp.
156 and 675..
|
Primary Examiner: Meyers; Albert T.
Assistant Examiner: Clarke; Vera C.
Claims
What is claimed is:
1. A dry aerosol antiperspirant composition consisting essentially
of:
A. from about 2.5 percent to about 6 percent by weight of finely
divided aluminum hydroxychloride;
B. from about 0.3 percent to about 0.75 percent by weight of a
reaction product of Bentonite and dimethyldistearylammonium
chloride;
C. from about 0.1 percent to about 0.5 percent by weight of
hexachlorophene;
D. from about 0.01 percent to about 0.04 percent by weight of
citric acid;
E. from about 0.25 percent to about 2 percent by weight of a
solvent for the citric acid selected from the group consisting of
methanol, ethanol, propanol and isopropanol;
F. from about 6 percent to about 10 percent by weight of a carrier
liquid of low volatility selected from the group consisting of
isopropyl myristate, isopropyl palmitate, di-n-butyl phthalate,
diethyl sebacate, disopropyl adipate, and ethyl ethylcarbomethyl
phthalate; and
G. the balance, an anhydrous, liquefiable propellant selected from
the group consisting of trichlorofluoromethane,
dichlorodifluoromethane, dichlorotetrafluoroethane, isobutane, and
mixtures thereof in an amount of from about 70.7 percent to about
93.9 percent.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to aerosol antiperspirant compositions of
the type which are essentially anhydrous, i.e., containing only a
small amount of water. Specifically, this invention relates to such
compositions containing materials such as hexachlorophene and
perfumes which tend to deteriorate during storage.
2. Prior Art
Combinations of hexachlorophene and citric acid in solid detergent
compositions are disclosed in British Pat. No. 786,285. It is also
known that dicarboxylic acids such as oxalic, sebacic, adipic and
malonic acids are useful in preventing the color degradation of bar
soaps containing hexachlorophene upon exposure to light; see, e.g.,
U.S. Pat. No. 3,085,066. Salts of citric acid have also been
disclosed for this same purpose; see e.g., U.S. Pat. No. 2,970,917
which discloses dihydrazinium and monohydrazinium citrates in soap
bars containing hexachlorophene. Antiperspirant compositions have
been disclosed containing astringent salts, hexachlorophene, a
perfume, and tartaric acid; see, e.g., U.S. Pat. No. 3,509,253.
Citric acid has been disclosed as a metal scavenger to protect
vitamins and other oxygen-sensitive materials.
SUMMARY OF THE INVENTION
This invention relates to dry aerosol antiperspirant compositions
consisting essentially of:
A. from about 1 percent to about 12 percent by weight of a finely
divided astringent comprising an acidic, metallic salt that is
insoluble in the composition;
B. from about 0.1 percent to about 5 percent by weight of a
suspending agent for the astringent;
C. from about 1 percent to about 15 percent by weight of a carrier
liquid of low volatility;
D. from about 0.1 percent to about 1.5 percent by weight of
hexachlorophene;
E. from about 0.005 percent to about 0.5 percent by weight of
citric acid;
F. a solvent for the citric acid in an amount sufficient to
dissolve at least a portion of the citric acid; and
G. the balance, an anhydrous liquefiable propellant in an amount
sufficient to produce an aerosol spray.
THE ASTRINGENT SALT
Suitable antiperspirant compounds for use in this invention can be
any of those well known in the art that are insoluble in the
aerosol composition as a whole. Generally, these are acidic,
metallic salts, often of aluminum, zirconium or zinc. Most
preferably, aluminum chlorhydroxide (ACH) is used, although other
astringent salts are also suitable. Examples of other salts are
aluminum chloride, aluminum sulfate, aluminum oxychloride, aluminum
oxysulfate, zirconyl chloride, zirconyl hydroxychloride, zirconium
oxychloride, zinc sulfate and zinc sulfocarbolate. Many
inorganic-organic mixtures and complexes are also known in addition
to the simple antiperspirant salts. Examples of these are zirconium
salt/ amine/ and amino acid complexes as taught by Siegal in U.S.
Pat. No. 3,407,254 (Oct. 22, 1968); zirconium salt/aluminum
chlorhydroxide/glycol complexes as taught by Jones et al. in U.S.
Pat. No. 3,405,153 (Oct. 8, 1968); and aluminum chlorhydroxide/
glycol complexes as taught by Jones et al. in U.S. Pat No.
3,402,932 (Jan. 7, 1969). Other complexes which can be used include
those aluminum chlorhydroxide/zirconyl hydroxychloride complexes
disclosed in the co-pending application of Raymond E. Bolich, Jr.,
Ser. No. 59,690, and the aluminum hydroxide/zirconyl
hydroxychloride/amino acid complexes disclosed in the co-pending
application of Wilmer L. Luedders, Ser. No. 59,693, said
applications being filed concurrently herewith. The latter
application is now abandoned. These applications and patents are
incorporated herein by reference.
Commercial availability of the above astringent salts is
widespread, and the choice of the desired antiperspirant compound
is limited only by factors well known to those skilled in the art.
As heretofore discussed, the above-mentioned aluminum salts are
preferred, and for the purposes of the present invention, aluminum
chlorhydroxide and the complexes described in the applications of
Bolich and Luedders filed concurrently herewith, are especially
preferred,
In dry aerosol antiperspirant compositions, the antiperspirant
active is dispersed as a finely divided powder. The powder must be
in the form of a uniform size particle and must be small enough to
remain suspended in the composition within the aerosol container
and to pass through the valve without clogging. The particle size
must also be such that the antiperspirant is adequately dispersed
on the skin and reacts rapidly enough with the moisture of the skin
and air to convert the antiperspirant compound in dry powder form
into the ionic state which is needed for effectiveness in
suppressing perspiration. In this connection, the emollient-carrier
of the present invention which will be discussed in more detail
hereinafter is also a very important part of this mechanism.
Particle sizes smaller than about 100 microns have been found to be
suitable for the practice of the present invention. Preferably,
particles averaging from about 10 microns to about 26 microns are
desirable. Normally, from about 1 percent to about 12 percent by
weight of the composition is a desirable amount for perspiration
control. Below about 2 percent, the antiperspirant effectiveness
drops off, while above about 12 percent is not practical because
the antiperspirant effectiveness does not increase commensurate
with the additional quantities used, and in addition, the viscosity
of the product increases so that handling is more difficult and
atomization is less satisfactory. The most preferred range is from
about 2.5 percent to about 6 percent.
THE SUSPENDING AGENT
The suspending agent can be any of those which have been disclosed
in the prior art. Suitable examples include: a colloidal silica
such as Cab-O-Sil, a pyrogenic silica having a particle diameter
between about 0.001 and 0.03 microns as disclosed in British Pat.
No. 987,301, and British Pat. No. 1,167,173; finely divided
hydrophobic clays such as a reaction product of a clay such as
Bentonite and dimethyldistearyl ammonium chloride (Bentone 34 or
Bentone 38) as disclosed in British Pat. No. 1,167,173; those
nonionic suspending agents disclosed in U.S. Pat. No. 3,014,844;
those suspending agents disclosed in U.S. Pat. No. 3,218,262; those
aliphatic monoalkylol amides (C.sub.12 - C.sub.20 acyl; C.sub.2 -
C.sub.3 alkylol) disclosed in the co-pending application of Douglas
L. Dannemann and Jerry J. Yetter, Ser. No. 888,958, filed Dec. 29,
1969, now abandoned; and those primary aliphatic amines (C.sub.12 -
C.sub.20) disclosed in the co-pending application of Charles L.
Scripps and Jerry J. Yetter, Ser. No. 888,959, now abandoned filed
Dec. 29, 1969. All of the above patents and applications are
specifically incorporated herein by reference. The preferred
suspending agent is Bentone in an amount from about 0.1 percent to
about 1.5 percent, preferably in an amount from about 0.3 percent
to about 0.75 percent, and most preferably from about 0.4 percent
to about 0.6 percent.
THE CARRIER LIQUID
A carrier liquid of low volatility is used in the instant invention
so that the stream issuing from the aerosol container is a moist
spray rather than a gritty, dusty cloud. This imparts a cosmetic
feeling to the skin when applied thereto an reduces the likelihood
of breathing the otherwise dry powder. The carrier liquid also aids
efficacy be keeping the antiperspirant compound in contact with the
skin so that it does not flake off or wash off. Thus, the carrier
liquid is needed for practical use of the instant invention though
it is not required per se for purposes of preparing a dry powder
antiperspirant composition in stable form. The carrier liquid also
decreases the vapor pressure of the propellant mixture which is
desirable.
Any of the carrier liquids that are known in the art are suitable
for the compositions of the instant invention. Examples are
carboxylic esters like isopropyl myristate and isopropyl palmitate;
hydrocarbons like mineral oil and tetradecane; alcohols such as
lauryl alcohol, hexadecyl alcohol, and oleyl alcohol; carboxylic
acids such as lauric and oleic acid; lanolin and its derivatives
such as acetylated lanolin; and silicone oils such as
dimethylpolysiloxane. Other operable carrier liquids are more
hydrophilic than the above-mentioned compounds, for example,
organic compounds containing multiple ester groups. This includes,
but is not limited to, diesters of dibasic organic acids. Examples
of compounds containing multiple ester groups that are suitable for
the instant invention are di-n-octyl-n-decyl phthalate, di-n-octyl
phthalate, di-n-hexyl phthalate, di-n-butyl phthalate, diethyl
sebacate, diisopropyl adipate, and ethyl ethylcarbomethyl phthalate
[ortho C.sub.2 H.sub.5 OOC-.phi.-COOCH.sub.2 COOC.sub.2 H.sub.5
].
Still other operable carrier liquids are even more hydrophilic than
these esters. Among them are polyethylene glycol monolaurate and
butoxy-polyoxyethylene oxypropylene glycols [the Ucon 50 HB series;
Trade Mark -- Union Carbide].
Among these various carrier liquids, carboxylic esters having from
about 12 to about 26 carbon atoms are preferred. As described
supra, they can be either aliphatic or aromatic and can contain
either one ester group or multiple ester groups. Especially
preferred are di-n-butyl phthalate, diethyl sebacate, diisopropyl
adipate, and ethyl ethylcarbomethyl phthalate.
Any of the carrier liquids described supra can be used in amounts
from about 1 percent to about 15 percent. Below about 2 percent,
the carrier liquid is insufficient to form a moist spray and the
spray is, therefore, undesirably dusty and gritty and does not
adhere well to the skin. Above about 15 percent, the composition
deposited upon the skin feels undesirably oily and greasy. Amounts
of carrier liquid from about 6 percent to about 10 percent are
preferred.
THE HEXACHLOROPHENE
2,2'-dihydroxy-3,5,6,3'-,5', 6'-hexachlorodiphenylmethane
(hexachlorophene) is a well-known antibacterial agent. Recently,
hexachlorophene has been incorporated in small amounts in dry
aerosol antiperspirant compositions of the type disclosed herein.
When it is incorporated in such antiperspirant compositions, it
forms a pink color upon aging. The reason for this result is
unobvious in view of the fact that previous discoloration problems
with hexachlorophene took place in light; and these aerosol
compositions are not exposed to light. It is, of course,
undesirable to have an antiperspirant composition colored pink,
since it tends to discolor clothing and skin. It is not known what
causes this pink color, but is is theorized that some kind of
complex is forming between the hexachlorophene and ferric ions.
Preferably, the amount of hexachlorophene is at least about 0.05
percent and most preferably, from about 0.1 percent to about 0.5
percent.
PERFUME
Perfumes are common ingredients of aerosol compositions; and many
common perfume ingredients such as aldehydes, cyclic materials,
ketones, etc., tend to undergo reactions in the presence of, e.g.,
metal ions, such as ferric and copper ions. This is undesirable
since small amounts of perfume ingredients can cause a very large
change in the overall odor impact of the perfume. It is believed
that the citric acid also stabilizes the perfume. The amount of
perfume is preferably at least about 0.1 percent and is most
preferably from about 0.2 'percent to about 0.9 percent.
THE CITRIC ACID
The hexachlorophene and the perfume are stabilized in dry aerosol
compositions by the inclusion of a very small amount of citric acid
as described hereinbefore. Preferably, there is from 0.01 percent
to about 0.5 percent citric acid present. A preferred range is from
about 0.01 percent to about 0.04 percent. This range is preferred
since excessive amounts of citric acid can actually cause a worse
odor grade than the smaller amounts from about 0.01 percent to
about 0.04 percent, although the odor grade is still better than if
no citric acid were present.
It is surprising that the citric acid is effective in an
essentially anhydrous system and in such small amounts despite the
presence of large amounts of the astringent, etc. It is believed
that citric acid is unique in this respect.
Citric acid monohydrate is preferred, since it dissolves more
readily.
The solvent for the citric acid is preferably ethanol in an amount
from about 0.25 percent to about 2.0 percent. Other solvents such
as methanol, isopropanol, propanol, etc., can be substituted in
substantially equivalent amounts. The solvent is used to
predissolve the citric acid before it is mixed into the
composition.
THE PROPELLANT
Any liquefiable propellant can be used in the compositions of this
invention. Examples of materials that are suitable for use as
propellants are trichlorofluoromethane, dichlorodifluoromethane,
dichlorotetrafluoroethane, monochlorodifluoromethane,
trichlorotrifluoroethane, propane, butane, and isobutane, used
singly or admixed. Trichlorofluoromethane, dichlorodifluoromethane,
dichlorotetrafluoroethane, and isobutane, used singly or admixed,
are preferred.
The amount of the propellant gas is governed by normal factors as
well known in the aerosol art. It is satisfactory to consider the
propellant as constituting the balance of the composition of the
instant invention that is not accounted by the other components as
detailed herein. The preferred limits of propellant are therefore
from about 70.7 percent to about 93.9 percent. Especially preferred
limits are from about 80 percent to about 92 percent.
All parts, percentages, and ratios herein are by weight unless
otherwise specified.
The following examples illustrate the invention.
EXAMPLE I
An aerosol antiperspirant composition is prepared containing 3.5
percent of powdered aluminum hydroxychloride which will pass
through a 325 mesh screen. The composition also contains:
8.00% -- Isopropyl myristate;
0.60% -- Bentone 38;
0.10% -- Hexachlorophene;
0.40% -- Perfume;
0.27% -- Ethanol/H.sub.2 O (95:5);
0.01% -- citric acid monohydrate; and
1.50% -- SDA No. 40 (anhydrous denatured ethanol)
and the balance being a propellant mixture comprising 60 percent
trichlorofluoromethane and 40 percent dichlorodifluoromethane.
The above composition is prepared by dissolving the hexachlorophene
in the isopropyl myristate using a high speed mixer at a
temperature of about 70.degree.F. The aluminum hydroxychloride is
then added to the batch and mixed for about 5 minutes at a
temperature of about 70.degree.F. The Bentone 38 is next added and
mixed. Then the 95 percent ethanol is added and mixed. While the
mixing continues, the temperature is slowly increased at the rate
of 2.degree. to 3.degree.F. per minute, until a temperature of from
about 130.degree. to 150.degree.F. is attained. The mixture is
subsequently cooled to a temperature of about 110.degree.F. while
the mixing continues. The citric acid is dissolved in the SDA No.
40 and then added to the mixture and mixed. The perfume is then
added. The mixing is continued at a temperature of from about
100.degree.F. to about 110.degree.F. until the mixture becomes
homogeneous. The mixture is then allowed to cool to room
temperature and is subsequently charged into an aerosol container.
The propellant mixture is then added to the container, a standard
three-piece tin plated aerosol can, using an under-the-cap
filler.
The result is a highly effective powder aerosol antiperspirant
composition for use on the skin stabilized as to color and odor as
compared with a similar composition which does not contain the
citric acid.
EXAMPLE II
All of the following compositions were prepared by the process of
Example I.
Composition I
Aluminum chloride 7.0% Isopropyl palmitate 10.0 Cab-O-Sil 0.6
Trifluoromethylcarbanilide .2 Perfume .3 Hexachlorophene 0.3%
Citric acid, monohydrate 0.02 SDA No. 40 1.2 Propellant consisting
of: 20% trichlorofluoromethane; 8% dichlorodifluoromethane; 17%
n-butane; and balance the balance dichlorotetrafluoroethane
Composition II
A mixture of aluminum sulfate, 7.0% zinc sulfate, and zirconyl
chloride (1:1:1) A mixture of di-n-butyl phthalate, 14.0 and
diisopropyl adipate (1:1) Octadecyl monoethanol amide 0.75 A
mixture of trichloro- 0.2 carbanilide, trifluoromethyl-
carbanilide, and tribromo- salicylanilide (3:2:1) Perfume 0.8
Hexachlorophene 0.3 Citric acid, anhydrous 0.02 SDA No. 40 1.5 A
mixture of 26% trichloro- balance fluoromethane, 7% dichlorodi-
fluoromethane, 22% n-butane, and the balance dichlorotetra-
fluoroethane
Composition III
A mixture of aluminum oxychloride, 7.0% aluminum oxysulfate, and
zirconium oxychloride (2:1:1) A mixture of dimethylpolysiloxane,
10.0 lauric acid, and oleic acid (1:1:1) A mixture of lauryl amine,
hexa- 1.5 decyl amine, octadecyl amine, and eicosyl amine (1:1:1:1)
Cab-O-Sil 0.6 Trifluoromethylcarbanilide .2 Perfume .3
Hexachlorophene 0.3 Citric acid monohydrate 0.03 Propyl alcohol 1.2
Propellant consisting of: 20% trichlorofluoromethane; 8%
dichlorodifluoromethane; balance 17% n-butane; and the balance
dichlorotetrafluoroethane
Composition IV
A mixture of zirconyl hydroxy- 10.0 % chloride, aluminum
chlorhydroxide and zinc sulfocarbolate (1:1:1) A mixture of mineral
oil and 15.0 tetradecane (1:1) A mixture of Cab-O-Sil and 0.75
Bentone 38 (1:1) Hexachlorophene 0.3 Citric acid monohydrate 0.08
95% Ethanol 0.17 SDA No. 40 2.0 Perfume 0.9% A mixture of: 10%
dichlorodifluoromethane; 20% isobutane; balance 20%
trichlorofluoromethane; and the balance
dichlorotetrafluoroethane
Composition V
Aluminum chlorhydroxide 8.0 % Isopropyl myristate 10.0 Bentone 0.7
Hexachlorophene 0.1 Citric acid monohydrate 0.1 95% Ethyl alcohol
0.3 Perfume 0.37 Isopropyl alcohol 1.50 A mixture of: 17.15%
trichlorofluoromethane; 8.58% dichlorodifluoromethane; balance
17.15% n-butane; and 42.88% dichlorotetrafluoroethane
Composition VI
A complex prepared by heating 8.0 % and agitating 7.5:4.6 mixture
of aluminum hydroxychloride, and zirconyl hydroxychloride, and
agitating it according to the process of the co-pending application
of Raymond E. Bolich, Jr., Ser. No. 59,690 filed concur- rently
herewith Isopropyl myristate 10.0 Cab-O-Sil 0.7 Hexachlorophene 0.1
Citric acid 0.1 Methanol 0.4 Perfume 0.37 A mixture of: 17.15%
trichlorofluoromethane; 8.58% dichlorodifluoromethane; balance
17.15% n-butane; and 42.88% dichlorotetrafluoroethane
Composition VII
A 1:1 mixture of aluminum hydroxy- 6.0 % chloride and the complex
of Example I of U.S. Pat. No. 3,407,254 The complex of Example I of
the co-pending application of Wilmer L. Luedders, Ser. No. 59,693
filed concurrently herewith Isopropyl myristate 10.0 Bentone 0.7
Hexachlorophene 0.1 Citric acid monohydrate 0.01 SDA No. 40 0.3 95%
Ethyl alcohol 04.% Perfume 0.37 A mixture of: 17.15%
trichlorofluoromethane; 8.58% dichlorodifluoromethane; balance
17.15% n-butane; and 42.88% dichlorotetrafluoroethane
All of the above compositions are desirable, effective
antiperspirant compositions stabilized against odor and color
changes as compared with similar compositions without citric
acid.
EXAMPLE III
All of the following compositions were prepared according to the
process of Example I.
Percent by Weight
Component I II III IV Aluminum hydroxychloride 3.50 3.50 3.50 3.50
Isopropyl myristate 8.00 8.00 8.00 Alon.sup.1 0.6 Bentone 38 0.60
0.60 0.60 EtOH/H.sub.2 O 95/5% wt. 0.27 0.27 0.4 0.27
Trichlorocarbanilide 0.10 Geigy CH 3565.sup.2 0.10 Hexachlorophene
0.2 0.2 0.10 0.10 Citric Acid 0.04 0.02 0.4 0.1 Dibutyl phthalate
8.00 SDA No. 40 1.50 1.00 2.00 0.25 Perfume 0.40 0.40 0.40 0.40
Propellant.sup.3 q.s. 100% 100% 100% 100% 1. Fumed aluminum oxide
Al.sub.2 O.sub.3. 2. 2,4,4',-trichloro-2'-hydroxydiphenyl ether. 3.
CCl.sub.3 F:CCL.sub.2 F.sub.2 (60/40) by weight.
Each of the above compositions is a highly effective dry aerosol
powder antiperspirant for use on the skin, which is stabilized with
respect to color and odor in comparison with similar compositions
without the citric acid.
* * * * *