Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
This invention relates to an improved, substantially
non-flammable, non-~luorocarbon containing propellant system
and two antiperspirant compositions util~zing the same. More
particularly, this invention relates to a carbon dioxide, hy-
drocarbon propellant, chloroethane propellant system for use
in dispensing antiperspirant compositions having aluminum
chlorhydroxide mixed with emollients, bulking agent and per
fume.
Recent events have caused concern among a number o~ -
manu~acturers o~ antiperspirant compositions. Most antiper-
spirant compositions currently sold today are similar to those
disclosed in Spitzer British Patent 1,167,173. These composi~
tions are ~luorocarbon type propellants as solvent and propel-
lant ~or the active ingredients in the composition. These
compositions typically include ~rom 0.2-10~ aluminum chlorhy-
droxidej from 2-50~ of an emollienk material, ~rom 0.05-1~ o~
a bulking agent, and f'rom 50-98~ o~ a ~luorinated propellant
or mixtures of fluorinated propellants.
Antiperspirant composit~ons of the type disclosed in
the above Britlsh patent have ~ound widespread acceptance as
the same are both cosmetically acceptable and perceived as e~-
~ectîve. HoweverJ since the fluorocarbon propellants act both
as the solvent and propellant in these systems, the formulation
or preparation o~ a non-fluorina~ed~ hydrocarbon propellant
system ~or these type compositions has been most difficult be-
cause the hydrocarbon propellants have different density and
solubility characteristiçs than the fluorocarbons.
There are currentl~ two general types of formulations
sold embodying the disclosure o~ the above British patent: the
regular type and the dry powder type. The prime di~ference
between these compositions is the dry powder type has a sig~
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nificantly higher percentage of powder components, i.e., the
bulking agent, astringent salt, and powder) than the oils in
the system. This gives the compositions a dryer or more pow-
dery feel on application. The regular type are somewhat wet
and oily on application. The propellant systems of the pres-
ent invention are ef~ective with either the dry powder type or
the regular type antiperspirants.
There have been numerous attempts to formulate pro-
pellant systems using l,l,l-trichloroethane or dichloromethane.
Most of these propellant systems have included fluorinated hy-
drocarbons and/or non-condensable gases such as nitrous oxide
or carbon dioxide. Examples of such disclosures are U.S.
Patent 3,342,672, an article in SOAP ~ CHEMICAL ENGINEERI~G,
February 1957 issue at page 99 entitled "Chlorothene in
Aerosols1', and an article in AEROSOL AGE, June 1963, page 29,
entitled "Blend of Nitrous Oxide and Fluorocarbons". None of
the above'articles or patents disclose the concept of utiliz-
ing l,l,l-trichloroethane or dichloromethane in combination
with a carbon dioxide and a hydrocar'bon propellant to produce
a ~ubstantially non-~lammable aerosol spray and more particu-
larly to produce a substantially non-flammable antiperspirant
composition of the type similar to that disclosed in the above
British patent.
Unexpectedly, it has been found that a substantially
non-~lammable fluorocarbon-free propellant syctem can be pro-
duced comprising from about 65-85~ by weight of a compound se-
lected from l,1,1-trichloroethane, dichloromethane, and mix-
kures thereof, from about 14-32% by weight of a hydrocarbon
propellant, and from about 0.5-3~3% by weight carbon dioxideO
Also, it has been unexpectedly found that an effective and
cosmetically acceptable antiperspirant composition can be pre
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pared by mixing the above propellant with an antiperspirantintermediate comprising rrom about 20-60% by ~eight based on
antiperspirant intermediate astrlngent salt, from about 20-79
by weight based on antiperspirant intermediate emollients,
~rom about 0-10~ by weight o~ a powder selected ~rom talc~
starch, baking soda and mixtures thereo~, and from about 1-10%
by weight based on antiperspirant intermediate bulking agent
in a ratio of propellant to antiperspirant intermediate o~
~rom 33 1 to 2:1.
It is, therefore, the primary ob~ect of the present
invention to provide a substantially non-~lammable, ~luoro-
carbon-free propellant system.
It is a ~urther object of the present invention to
provide a substantially non-flammable, fluorocarbon~free anti-
perspirant composition.
It is a still further object o~ the present inven-
tion to provide a substantially non-~lammable, fluorocarbon-
~ree propellant system utilizing conventional antiperspirant
intermediate compositions.
It is a ~urther obJect o~ the present`invention to
provide a substantlally non-flammable propellant system includ-
ing hydrocarbon and carbon dioxide.
Stlll further objects and advantages of the propel-
; lant system and antiperspirant composition o~ the invention
will become more apparent ~rom the ~ollowing more detailed de-
scription.
This invention relates to a substantially non-flam-
mable, non-fluorocarbon propellant system comprising from
about 55-85% by weight of a compound selected from the group
consisting of 1~13 l-trichloroethane, dichloromethane, and mixW
tures thereof, ~rom about 14 32~ by weight o~ a hydrocarbon
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propellant selected from normal butane, isobutane, propane,
and mixtures thereof, and ~rom about 0.5-3.3~ by weight of
carbon dioxide.
The invention further resides in a substantially
non-flammable antiperspirant composition comprising a propel-
lant intermediate comprising from about 65-85~ by weight based
on propellant intermediate of a compound selected from the
group consisting of l,l,l-trichloroethane, dichloromethane,
and mixtures thereof, from about 14-32% by weight based on
; 10 propellant intermediate of a hydrocarbon propellant selected
: from the group consisting of normal butane, isobutane, propane,
and mixtures thereof, from about 0.~5-3.3~ by weight based on
propellant intermediate of carbon dioxide, and an antiper-
spirant intermediate )comprising from about 20-60% by weight
based on antiperspirant intermediate astringent salt, from
about 20-79% by weight based on antiperspirant intermediate
emollient, up to about 10~ of a powder selected ~rom talc~
starch3 sodium bicarbonate, and mixtures thereof, and from
~ about 1-10% by weight based on antiperspirant intermediate of
a bulking agent, wherein the ratio of propellant intermediate
to antiperspirant intermediate is within the.range of from .
.
about 3~:1 to 2:1. :
The propellant compositlons o~ the present invention
~: comprises a first ingredient from about 65-85~ by weight of a .
compound selected ~rom the group consisting o~ l,l,l-trichloro-
ethane, dichloromethane, and mixtures thereof, pre~erably from
about 70-80% by weight the compound,~ and most preferably from
about 74-76.5% by weight the compound... The preferred compound - .
is l,l,l-trichloroethane. The compounds are most important ln
the composltion o~ the present invention since they have a
solubilizing e~fect on the carbon dioxide which enables the
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carbon dioxide to be used without high loss of vapor pressureduring the use of the aerosol product. Also the propellant
compositions can be used in con;junction with a vapor tap
valve. This is not possible with normal carbon dioxide sys-
tems. Furthermore~ the above compounds have a density and
physical properties similar to those of the fluorinated hydro-
carbon propellants previously widely used in antiperspirant
type compositions. E'or this reason the above compounds de-
press the effective vapor pressure o~ the composition and sol-
ubilizes the propellants in the active ingredient oils.
The hydrocarbon propellants used in the present in-
vention are the conventional~hydrocarbon propellant materials
such as normal butane, isobutane~ and propane. Mixtures o~
these materials also may be used and are advantageously used
to obtain the desired pressure in combination w~th the carbon
dioxide compressed gas material. The hydrocarbon propellants
are present in the propellant system in an amount o~ ~rom about
14-32% by weight and pre~erably from about 14-26~ by weight and
most pre~erably from ~rom 21-24% by weight. The pre~erred hy~
drocarbon propellant is a blend ~rom 70-90% isobutane and 10-
30% propane which gives a vapor pressure ln the range o~ 40-52
psig and the most preferred is a blend of 80% isobutane and 20%
propane which glves a vapor pressure o~ 46 psig.
The third ingredient in the propellant composition of
the present invention is carbon dioxide. Carbon dioxide is
present in an amount of from about 0.5-3.3% and preferably
from about 1.0-2.5~ and most pre~erably ~rom about 1.5-2.5~ by
weight. The carbon dioxide adds a vapor pressure to the compo-
sitions o~ the present invention while at the same time not
appreciably adding to the ~lammability o~ the same.
The compositions utilizing the propellant system o~
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the present invention are substantially non-rlammableO To be
classed as "substantially non flammable" as these words are
used in the instant speci~ication or claims, the composition
must be non-flammable when tested by either the flame exten-
sion test or the c105 ed drum test as published in the Test
Proceedings of the Chemical Specialties Manu~acturing Associa-
tion. To be considered non-~lammable in the flame extension
test, a spray of the antiperspirant across an open flame of a
plumber's candle should not extend the flame more than 18
inches. With regard to the closed drum test~ the aerosol can
should be able to be sprayed into a closed drum ~or a period
of greater than 60 seconds before the candle contained in the
drum causes an explosion. Some of the compositions included
within the claims of the present invention may be classed as
flammable by one or the other o~ the~e"~s~. However, the
pre~erred compositions are not Plammable when tested by both
o~ these methods.
Generally, it is most desirable that the initial
pressure in pounds per square inch gauge at 70F. be within
the range of 25-75 psi. Within this pressure range, the com-
positions will be adequately dispensed ~rom the container
while insuring a margin oP saPety against expLosion in the
vent the containers are subjected to extreme temperature.
Also, an important ~actor in the ~lammabillty char-
acteristics oP antiperspirant and aerosol compositions is the
discharge rate o~ the composition. The discharge rate can be
varied greatly depending on the particular valve orifices used
in the aerosol valve. However, for most conventional aerosol
valves of the type commonly used in antiperspirant compositions
having a vapor tap orifice of from 0.010-0.050 -in.~ a stem
ori~ice oP from 0.10-0.50 in., a button ori~ice o~ from 0.010-
0.050 in., and any conventional dip tube, the compositionswithin the range of the present invention will be considered
substantially non-~lammable. The pre~erred valve has a vapor
tap o~ 0.135 in., a stem orifice o~ 0.020 in.~ a button ori~ice
of 0.018 in. J and uses a capillary type dip tube having a di-
ameter of 0.040 in. Generally, these compositions have an
initial discharge rate o~ from 0.55 gram per second ko 1.0
grams per second.
The propellant composition of the present invention
can be used with substantially any a;erosol intermediate in a
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ratio of propellant to intermediate o~ from 33:1 to 1-:~, al-
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- ~ though a non-aqueous intermediate is pre~erred. The propellant
composition is speci~ically adapted to be used with antiper-
spirant type compositions wherein the ratio of propellant to
antiperspirant intermediate which comprises astringent, emol-
lient, and bulking agent in a ratio of propellant to antiper-
spirant intermediate of from 33:1 to 2:1 and preferably ~rom
20:I~to 4:1, and most pre~erably 15:1 to 7:1 and optimally
~rom about 10:1 to 8:1.
These antiperspirant compositions, as described in
the above-noted ~ritish patent, include an astringent salt
selected from ~inc chloride, zinc su1fate, zinc sul~ocarbo1ate,
aluminum sul~ate,~aluminum chloride, aluminum sul~ocarbo1ate,
aluminum chlorhydrate~ zirconium chloride~ zirconium tetra
chloride, and ~irConium sulfate. These astringent salts are
generally found in the ankiperspirant intermediate of the corn-
position o~ the present invention in an amount ~rom about 20~
60~ by ~Aeight based on antiperspirant intermediate, and pre~er-
ably from about 25-40% by weight based on an antiperspirant
intermediate and most preferably from about 30-35% by weight
based on antiperspirant intermediate.
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The compositions also include an amolli.ent type
material which is generally non-volatile, non-hydroscopic
liquid. These materials may be selected from a wide range of
materials such as organic esters including isopropyl myristate,
isopropyl palmitate, 2-ethylhexyl laurate, the various esters
as disclosed in U.S. Patent 3,833,720, including Cl-C4 alkyl
lactate, diCl-C4 alkyl succinate, diethyl malate, diethyl
maleate, diC2-C4 alkyl tartarate, diCl-C4 alkyl glutarate,
dimethyl adipate, and diethyl adipate; certain polyalkylene
glycols such as the Ucon fluids supplied by Union Carbide and
disclosed in U.S. Patent 2,425,755, such as the monohydro~y . .
o~yethylene, oxy 1,2-propylene aliphatic monoethers wherein
the aliphatic monoether group has from 1 to lO carbon atoms,
the ratio of oxy-1,2-propylene to o~yethylene being at least
0.33:1 and having a molecular weight of at least 500, alcohols
such as lauryl alcohol, carboxylic acids such as maleic acids,
and silicone oils such as dimethyl polysiloxanes and various
volatile silicone oils. These emol.lient materials may be
present in the antiperspirant intermediate of the compositions
of the present invention from about 20~79% by weight based on -
: antiperspirant intermediate, preferably from about 56-72.5% by
: weight based on antiperspirant intermediate, and most prefer-
ably from about 61.5-67.5% by weight based on antiperspirant
intermediate. ~ .
A maior optional component is a powder added to the
dry powder type to enhance the cosmetic properties of the com-
position. These powders are present in amounts of up to about
lO~ by weight of the antlperspirant intermediate, and prefer~
ably from about l-5~ by weight. Suitable powders include talc,
starch, including starch derivatives, baking soda or sodium
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bicarbonate) and mixtures of these materials.
Lastly, it is desirable to include a small amount of
a bulking agent in the compositions of the present invention.
3xamples of such materials are hydrophoblc treated clays which
swell in organic solvents such as hydrophobic bentonite includ-
ing the reaction products of bentonite and dimethyldistearyl
ammonium chloride, colloidal silicas~ montmorillonite clays,
and grease-forming soaps such as aluminum stearates. General-
ly these materials are present in small amounts in the compo-
sition of the present invention from about l-lO~ and preferably
from about 2.5-4~ and most preferably about 2.5-3.5~ by weight
based on antiperspirant intermediate.
~ he antlperspirant compositions also may include a
variety of other optional ingredients including perfume in an
amount from 0.1-2.0~ by weight based on the weight of the pro- '~
pellant and antiperspirant intermediate as well as small
amounts of preservatlves and other conventional additives.
The compositlons o~ the present invention will now
be lllustrated by way'of the following examples wherein all
the part~ and percentages are by weight and all temper~tures
in degrees F~hrenheit.
EXAMPL~ A
An antiperspirant intermediate ls prepared~having
khe ~ollowing composition: '
Aluminum chlorhydroxide33.00
Isopropyl myristate 62.00
,I Pumed silica (Cabosil M-5)3.00
Perfume r 2.00
100. 00
This intermediate is prepared by blending the ingre-,
dients together at ~oom temperature to ~orm Antiperspirant
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Clen~es ILr~de ~nAI`fC~
Intermediate A.
EXAMPLES 1-4 and GOMPARATIVE EXAMPLE 1
A series of antiperspirant aerosol compositions are
filled into 3-piece tinplate containers to a ~ill weight of
200 grams. The containers are fitted with a valve including a
vapor tap valve. The compositions are shown in Table I.
TABLE I
1,1)1- 20~ Initial Flammability
tri- Propane Discharge '
CO chloro- 80~ Rate Flame Closed
Ex. Int. A. ~ 2 ethane' Isobutane g_sec. Ext. ~rum
CE 1 10.0 -~ 67 23.00 0.50 No No
1 10.0 5 67 22.~0 o.65 No No
2 1Ø01.00 67 22.00 0.70 No
3 10.02.00 67 21.00 o.86 No No
4 10.03. do 67 20.00 0.95 No Yes
The above examples show the effect of,increas,ing the
C2 level. At abov~ 3.0% C02, the can pressure becomes exces-
sive. With no C02, the discharge ra,te is too low to be e~fec-
tive.
EXAMPLES 5-8 and COMPARATIVE EXAMPLE 2
A series o~ antiperspirant compositions as shown in
Table II are prepared keeping the C02 constant.
As shown in Table II, as the hydrocarbon propellant
ls increased, the flammability increases. HoweverJ composi-
tions within the limits of the present invention are substan-
tlally non-flammable. Further, the application properties of
the above compositions are excellent
~3~ '
A series of antiperspirant compositions is prepared
with the hydrocarbon propellant constant. The compositions
are shown in Table II.
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TABLE II
1,1,1- 20S~ Initial Flammability
tri- Propane Di~charge
C0 chloro- 80~ Rate Flame Closed
~x. Int. 2 ethane Isobutane g/sec. Ext. Drum
CE 2 10 2. 0 55. 0 33 0. 82 No Yes
lo 2.0 60.0 28.0 o.80 No Yes
6 10 2.0 65.o 23.0 o.84 No Yes
7 10 2. 0 70. 0 18. 0 0.90 No l!~o
8 10 2. 0 75. 0 13. 0 0. 84 No No
g 10 5 69. 5 20. o 0. 60 No No
o lo l.o 6g.o 20. 0 0. 72 No No
11 10 2.0 68.o 20.0 0.87 No No
EXAMP~E 12
A series of antiperspirant compositions was prepared
with the following hydrocarbon propellants substituted for the
20~ propane~ 80~ isobutane:
A Normal butane
B Isobutane
C 45% n-butane, 55~ propane ' ,
D Propane
ach o~ the above were tested for flammability. A
and B were non-flammable by both methods, while C and D were
non-flammable by the ~lame extension test but were considered
f'lammable by the closed drum.
~ : :
Examples 2 to ~ were repeated except,that methylene
chloride was substituted for the l~ trichloroethane. The
compositions and results o~ the flammability tests are shown
in Table III.
. .
11
TABLE III
ao~ Flammability
Pro~ane
C0 Methylene ~0% Flame Closed
xt. Int. A. _ 2 Chloride Isobutane Ext. Drum
13 10.0 1.0 67.o 22.0 No No
14 10.0 2.0 67~o 21.0 No No
10.0 3.0 67.o 20.0 No No
The above shows the substantial equivalence between
l,l,l-trichloroethane and methylene chloride.
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