Note: Descriptions are shown in the official language in which they were submitted.
Description of the Invention
The use of anhydrous particulate absorbant
materials capable of sorbing water exothermically in
autoheatir,g cos~etic and similar compositions is well
knowrl. Menkart, et al., in Canadian Patent No. 748,049,
disclose liquids, creams, gels and pastes which utilize
materials such as silica gel, activated alumina, and
alkali rnetal alumino silicate molecular sieves (Zeolites)
in non-aqueou~- vehicles which warm automatically on
contact with moisture in or on the skin. Analgesic
preparations containing Zeolite in an anhydrous liquid are
disclosed in r).s. Patent ~Jo. 4,379,143. Cosmetic vehicles
comprising a carboxy vinyl polymer and Zeolites are
disclosed in U.S. Patent No. 4,362.715. A toothpaste
containing Zeolite is disclosed in U;S. Patent No.
4,349,533.
Despite the foregoing cdisclosures, no products
based on such formulations have been successfully marketed
because such formulations are cosmetically inelegant,
i.e., they are very oily, greasy and pasty in consistency;
spread poorly on the skin, and leave the skin with a
greasy feel and appearance. ~hese undesirable
characteristics result from the fact that water or
hydroxylated solvents such as alcohols or glycols must
~6~ S
normally be omitted in order to preserve the exothermic
reactivity of the particulate absorbants.
U.S. Patent No. 4,639,367
issued on January 27 ,1987 describes and claims
novel annydrous aerosol foams which are capable of
suspending up to 50~ by weight of a dispersed solid
without causing malfunction of an aerosol valve. The
novel properties of these aerosol foams make them suitable
for use as delivery systems for a wide range of
therapeutic agents and provide ~n alternative to tablets
or capsules, which are difficult to swallow or bad tasti~g
llquid medications.
It has now been unexpectedly discovered that the
aerosol foam delivery system described and claimed in
U.S. Patent No. 4,639,367 is capable of
functioning to provide a cosmetically elegant delivery
system for formulations containing particulate absorbant
mat~rials capable of sorbing water exothermically alone or
in combination with other therapeutic or cosmetic
2a ingredients. Specifically, it ha~ now been found that a
stable, anhydrouc aerosol fo,am or whip capable of
suspending up to 50% by weight of a dispersed solid can be
prepared from a foamable anhydrous liquid oil; a foaming
agent; and controlled amounts of a propellant which are
sufficient to produce a stable foam rather than a spray.
~he foam, as delivered from an aerosol canister, has the
consistency of whipped cream~ is stable for extended
~z~ p~
periods and i.s hostile to the growth of micro-organisms.
While not wishing to be limited to any
particular theor~, it is presently believed that the
expansion of the formulations caused by the presence of a
propellant causes the product to spread in the form of a
thin Lilm on the skin, thereby giving a soft, silky, and
co~rnetically elegant feel. The observed effect is
analogous to a comparison between whipped cream and
bu~ter. ~Ihile both of these products are produced from
cream, butter is a dense, yreasy water in oil emulsion,
whereas whipped cream is a liyht air in oil emulsion in
which the oil is extended over a ouch yreater volume,
thereby masking its greasy properties to a substantial
extent. In the present invention, by foaming the oils
~Jith a propellant to produce a low density aerated whip or
mousse, the greasy property of the oil in the forrnulation
is eliminated. The invention rnakes it possible to achieve
the foregoing results without valve clogging due to a
novel combination of ingredients that produces a high
viscosity formulation capable of keeping the small solid~
particles dispersed and of lubricating the aerosol valve.
The foamable, anhydrous liquid oils utilized in
the present invention are varied and of no great critical
significance. Typical among the organic oils useful for
the present invention are those such as .soybean oil,
partially hydrogerlated soybean oil, linseed oil, corn oil,
peanut oil, sun10wer oil, cottonseed oil, olive oil,
~Z~ Y~
castor oil, liquid petrolatum, oleic acid, lauric acid,
and mono- and diglyceride oils. As indicated above, the
basic criterion for a liquid oil utilizable in the present
invention is that it is foamable.
Typically, the oils utilized in the present
invention are present in the formulation in a percentage
of 40 to 95~ by weight of the total composition. A
pre~erred range is 50 to 70% by weight of the total
composition. The amount of oil may be varied based upon
the nature and arnount of the other ingredients in the
formulation, such as the amount of dispersed solids.
Ordinarily, the percentaye amount of each other ingredient
in the formulation is first selected and the oil is the
ingredient added to bring the formulation to 100~.
Foaming agents utilizable in the prescnt
invention are selected from the yroup consisting of
lecithin, various polyol fatty acid esters and mixtures
thereof, or solid silicone copolymers as disclosed in U.S.
Patent No. 3,770,648. Lecithin is the commercial name for
a clas of naturally occurring cornpounds derived from
soybeans. These compounds are phosphatides and
phospholipids. The principal components of lecithin are a
naturally occurring mixture of phosphatidyl choline,
phosphatidyl ethanolamine, inositol phosphatides and
related phosphorous containing lipids. Chemically,
lecithin is described as phosphatidyl choline and is a
mixture of the diglyceride~ of stearic, palmitic and oleic
3~
acids lirlked to the choline ester of phosphoric acid. It
is available commercially as a 60% solution in soybean oil
or as a granular powder essentially free of soybean oil.
A hydroxylated lecithin, modified to increase the
hydrophilic properties is also commercially available.
This hydroxylated lecithin is commonly supplied as a 60%
solution in soybean oil.
The polyol fatty acid esters utilizable in the
pre.~ent invention are commercial products and are
comprised of three types:
l. Glycerol esters of fatty acids.
2. Polyglycerol esters of fatty acids.
3. Sorbitan esters of fatty acids.
The glycerol esters which have been found to be
advantageous in generating a suitable anhydrous aerosol
foam are prepared by standard esterification mettlods and
have a HLB of bet~leen 2.5 and ~.5. Among the preferable
glycerol fatty ester~ utilizable in the present invention
are those ~uch a glycerol monostearate (HLB 3.2) and
glycerol monooleate (HLB 3.4).
The polyglycerol esters utilizable itl the
present invention are cornmercial products prepared by
first polymerizing glycerine under alkaline conditions.
The polymerization is controlled to yield the particular
desired average rnolecular weight. Investigations indicate
that the polymerization of glycerol proyresses
predominateJy in a straight-chairl marlrler, The ester~ are
prepared by reactiny the polyglycerols with a specific
fatty acid or by the alcoholysis of a triglyceride. By
this method, it is possible to prepare esters ranging
anywhere from hydrophilic monoesters such as decaglycerol
monolaurate to a lipophilic decaglycerol decaoleate.
The polyglycerol esters preferably used in the
present invention have an HLB value of between 4.0 and
13Ø Tnese have been iound to be most advantayeous in
yeneratirly a suitable anhydrous aerosol foam. Among the
preferable polyyly-erol esters utilizatle in the present
invention are those such as: hexaylycerol distearate ( HLB
4.0), lecaylycerol tetraoleate (~LB 6.0), triylycerol
morlostearate (Ill.B 7.0), triglycerol monooleate (HLB 7.0),
octaylycerol monostearate (~ILB 12.0) and octaglycerol
monooleate ( HLB 13 . O ) .
Ttle sorbitan fatty acid esters which have been
found to be advantageous in generatin~ a suitable
anhydrous aerosol foam are cormmercial pro~ucts prepared by
standard esterification methods and have an ~ILB of bet
3.0 and 7.0 Amony the preferable sorbitan esters
utilizable in the present inventiorl are tho;e suctl as
sorbitan rnonostearate (IILB 4.7), sorbitan monooleate (HLB
4.3), and sorbitan rnono palmitate (HLB 6.7).
Additionally, a combination of any of the polyol
fatty acid esters may be utilized in the present invention.
The polyol fatty acid esters are somewhat more
hydrophilic than lecithin ;o that tneir use allows ttle
~2~
foamable, anhydrous liquid oil to be more easily dispersed
when contacted with an aqueous medium. Additionally, they
may be used in conjunction with lecithin in the same
system which causes the lecithin to become more
hydrophilic and therefore more water miscible than the
lecithin alone.
qhe solid silicone copolymers which are useful
as foaming agents in this invention are fully disclosed in
U.S. Patent No. 3,770,648.
1~
The foaming agent utilized in the present
invention i8 present in an amount of from 2 to 40~ by
weigh~. The amount of foaming agent utilized depends upon
the particular foaming agent being utilized, the
particular foamable, anhydrous liquid oil being utilized
and the propellant ~y~tem. A preferred range of foaming
agent i~ from about 3 tO 15% by weight of the composition,
with 4 to 6S being especially prefer~ed. It i8 a
particularly desirable additional feature of the foaming
agent~ that they pos~ess surfactant properties and,
therefore, affect the rate ~t which the insoluble solid
active ingredient of the foam is released. Accordingly,
some variations in the amount of foaming agent in a
particular formulation may be purposely chosen based on
the nature of the solid active ingredient in order to
control the rate of release.
The propellant can be selected from the class of
,, , --..
hydrocarbons that are gaseous under atmospheric pressures
and liquefy when compressed, or certain fluorocarbons such
as ~REON 115; monochloropentafluorethane; FREON 12,
dichlorodifluoromethane; Dymel 22; chlorodifluoromethane;
Dymel 152; 1, 1, difluoroethaane; and dirnethylether.
Propellants other than the liquefied hydrocarbon or
fluorocarbon gases can be used including compressed gases
like nitrogen, nitrous oxide and carbon dioxide, but they
do not produce the most desirable foams over the life of
the product in use. The most commorlly used propellants
are propane, butane and isobutane. Since these liquefied
yases are soluble in the oil vehicle oE the composition,
there is a resulting reduction in their vapor pressure.
There~ore, it is most advantageous to use propane since it
has the hi~hest pressure of the three hydrocarbon
propellants and, everl when dissolved in the low
concentrations normally employed in this invention,
produces a product with a pressure of 30-40 pounds per
~quare inch over atrnospheric pressure. This pressure is
required to eject the foam frorn the container and produce
a stable, dense foam. ~lowever, since propane is soluble
in the oil base, there is very little pressure drop from
the first to the last actuation of the aerosol valve and a
satisfactory foam is produced when each dose is expelled.
The amount of propellant used is critical since
too much will produce an undesirable spray rather than the
desired stable "neasurable foam. Arnourlts of propellant in
~Z~
the range of from l-10 wt. % are operative, but 4-6 wt. %
is the preferred concentration based upon the total weight
of the contents of the aerosol container. The amount of
propellant used may vary somewhat, depending upon the
nature and amount of the other ingredients in the
composition but, in all cases, the lowest amount
sufficient to forrn a stable, measurable foam without
forrning an unmeasurable spray will be selected.
The anhydrous solid particulate matter capable
of sorbiny water exothermally whicil can constitute between
lU ana 5~% by weight of the basic composition, includes
any materials irl this class which are physiologically
compatible with hair and skin and which are further
compatible with any pharmaceutically active agents to be
added to ~aid basic composition In this general category
may be included calcillm chloride, silica gel, activated
alumina and alkali metal alumino silicate molecular
BieVes. The latter generally beiny know as Zeolites. Of
particular interest, are the 7,eolites, especially those of
the general formula Mx/n[~L2)x(SiO2)yJ, wherein X
and Y are integers greater than ~, the molecular ratio of
X to Y is 0.1 to l.l and M is a metal with a valence of
n. These Zeolites are preferably in the activated foam
which effectively means that they have been pretreated in
25 SUCtl a manner that they contain not in excess of 5~ by
weight of water.
~he anhydrous aerosol ioam oi the present
~ Z~ ~} .3 ~
invention may be used as a vehicle for any of a large
variety of active pharmaceutical materials or cosmetic
inyredients in addition to the exothermic material.
The foam itself may be used as a carrier for a
large variety of additional hair or skin modifying
agents. Such modifying agents may be cosmetics or
pharmaceuticals and may include both prescription and
non-prescription agents. Thus, there may be incorporated
hair dyes and hair conditioning agents, shampoos, shaving
~oaps, skin emollients, anti-darldruff agents,
anti-seborrheic agents, anti-inflammatory agents, muscle
relaxants, and any other generally accepted agents for
modifyill~ the condition of hair, the surface of the skin
and subdermal areas generally treated by topical
application of physiologically active materials. As
eY.amples of conditioning agents, there may be mentioned
the quaternary salts of fatty acids having a carbon
content of 12 to 18 carbon atoms, yenerally accepted
conditioniny oils such as i~opropyl myristat~, isopropyl
palmitate, isopropyl sebacate and the like may be used; as
anti-dandru~f ayents, there may be utili~ed ~inc
pyrithione or selenium 5ulfide; as anti-seborrheic or
anti-inflarnmatory agents there may be mentioned
hydrocortisone; as hair dyes any of the conventionally
used hair dyes may be employed. This list is to be
considered as merely illustrative and in no way lirniting.
Additional ayents not listed hereirl would be apparent to
~L2~
those skilled in the art.
rrhe amount of these added agents will depend
upon the required effective concentration and whether they
are solid or liquid. If they are liquid, they may
constitute up to 95% of the total composition by weight,
although 20 to 65~ is to be preferred. If they are
solids, they may constitute up to 40~ of the total
conlposition, provided that the combined proportion of the
anhydrous solid particulate material and said solid agent
rJoes not excee~ 50% of the entire composition.
A particularly important and surprising feature
of the foams o~ this invention is their ability to suspend
high concentrations, i.e., up to 50~ by weight, of
solids. Preferably, the suspended particles are ground to
a very fine particle size since this facilitates the
formation and maintenance of a uniforrn dispersion and
prevents clocJging. Particle sizes less than 100 microns,
preferably in the range of 50 to 100 microns in diameter,
~re empioyed.
rrhe foam of the present invention can contain up
to 50 wt. % of suspended solid particles without any
appreciable valve malfunctiorlirlc3, and will usually contain
in excess of 15 wt. % of such solid particles since a
primary purpose of the foam system is to deliver a high
concentration of the active ingredient in the solid
particles in a relatively small dose. This ability to
suspend higtl percentayes of solids WittlOUt valve
s
malfunctioning enables the aerosol foam system of the
present invention to be utilized for a wide variety of
formulations. The reasons for the unique ability of the
foams to suspend such a high concentration of solids
without valve clogging are not fully understood, but it is
believed to result from a combination of the small
particle size, the high viscosity of the foam formulation
due tv its low propellant content which aids in keeping
the particles dispersed and reduces agylomeration and
settling, and the lubricating effect of the oil on the
valve.
The foarns of the present invention are prepared
by conventional formulating techniques. Thus, typically,
the foamable anhydrous liquid oil and the foaming agent
are mixed together alony with any other soluble
ingredients of the composition. The solid to be dispersed
is then added and the resultant mixture passed through an
appropriate mill to ensure uniform particle size. The
batch is then submitted for aerosol filling to an aerosol
can. An aerosol valve is placed on the can and the can is
crimped. The propellant is;then added by pressure filling.
In addition to the active solid to be dispersed
in the foam and the essential ingredients of the foam,
there may also be incorporated in the foams of the present
invention any of a variety of additives or a combination
thereof, commonly added to aerosol compositions or to
toiletries, cosmetics, or pharmaceuticals. Typically,
~ 2~ ~t~.S
14
such additives are those such as emollients, lubricants,
humectants, abrasives, perfumes and colorants.
It will be apparent to those skilled in the art
that many modifications, both of materials and methods,
may be practiced without departing from the purpose and
intent of the disclosure.
EXAMPLE 1
Hot Oil Hair Mousse Foa~l
1. *Valfor 950, anhydrous sod.
1~ aluminosilicate (P.Q. Corp.) 35.00%
*
2~ Cabosil M-5, Fumed Silica .50
3. Decaglycerol Tetra Oleate 6.00
4. Polyethylene glycol 400 dioleate 2.00
5. Soybean Oil, partially
hydrogenated 51.20
6. Propane 5.00
7. Fragrance 0.30
100. 0096
Procedure-
The items #3, 4, 5,and 7 are mixed at ambient
temperature until uniform. The powders #1 and #2 are
added and mixed until uniform. The batch is passed though
a colloid mill and then submitted for aerosol filling
during which the propane is added.
Use
When used as a hot oil hair mousse foam, it is
* Trade-mark
~L2~
preferred, but not essential, that the hair be washed and
touch dried with a towel so as to leave the hair moist but
not dripping. A sufficent amount of mousse is applied to
the hair to cover the entire area and worked into the
hair. The contact with moist hair will cause the mousse
to heat up giving rise to the desired heat conditioning.
The composition can be left on the hair as long as
desired. In one modification of its use, a towel may be
wrapped around the head in order to preserve the heat
factor ~or somewhat longer.
While it i8 not totally necessary to do so, it
is generally preferred to wash the composition out of the
hair with a mild shampoo in the conventional manner.
The essential ingredients are:
1. The heat generating solid (Va;for 950)
which is exothermic upon contact with water on the hair
and scalp. Other heat generating anhydrous solids can be
u ed in placé of the Valfor 950 in the same preparation,
e.g., anhydrous calcium chloride, dried magnesium sulfate.
2Q 2. The foaming agent can be replaced by
lecithin or the sorbitan monp esters or mixtures thereof
or silicone #1252.
3. The foamable oil is any liquid anhydrous
oily material.
The propellant is propane or any high pressure
aerosol propellant.
~,2~
EXAMPLE 2
Hot Oil Anti-dandruff Mousse Foam
-
l. Valfor 950, anhydrous sod.
aluminosilicate (P.~. Corp) 35.00%
2. Cabosil M-5, ~umed Silica .50
~. Sorbitan Mono stearate 4.00
4. Polyethylene glycol 400 dioleate 2.00
5. ~oy~ean Oil, partially
hydrogenated 51.20
~0 6. L'ropane 5.~0
7. ~inc Pyrithione 2.00
. Fragrance 0.30
100 . 00%
Procedure:
The i~em~ #3, 4, 5, 7 and ~ are mixed at 60C.
temperature until uniform. The powders #1 and ~2 are
added and rnixed until uniform. The ~atch is cooled and
passed through a colloid mill and then submitted for
aerosol filliny during which the propane is added.
Use
r
2~ It is preferred, but not essential, that the
hair be washed and touch dried with a towel so as to leave
the hair moist but not dripping. A sufficient arnount of
mousse is applied to the hair to cover the entire area and
worked into the hair. The contact with moist hair will
cause the mousse to heat up givirlg risc to the desired
126~
heat conditioning. The composition can be left on the
hair as long as desired. In one modification of its use,
a towel may be wrapped around the head in order to
preserve the heat factor for somewhat longer.
While it is not totally necessary to do so, it
is generally preferred to wash the composition out of the
hair with a mild shampoo in the conventional manner
EXAMPLE 3
Hot Oil Halr Conditioninq Mousse Foam
1. Valfor ~50, anhydrous sod.
alurninosilicate (P.Q. Corp)35.00%
2~ Cabosil M-5, Fumed Silica .50
3. Lecithin, Powdered 3.00
4. Glycerol Mono Stereate 4.00
15 5. Poiyethylene glycol 400 dioleate2.00
6. Cotton Seed Oil 46.20
7. Propane 5,00
8. Stearyl dimethyl benzyl
ammonium chloride 4,00
29 g. Fragrance 0,30
100 . 00
Procedure:
The items #3, 4, 5, 6 and 8 are mixed at 60 C.
temperature until uniform. The powders #1 and #2 are
added and mixed until uniform. The batch is cooled and
passed throu~h a colloid mill and then submitted for
~L2~3~
18
aerosol filling during which the propane is added.
Use
It is preferred, but not essential, that the
hair be washed and touch dried with a towel so as to leave
the hair moist but not dripping. A sufficient amount of
mousse is applied to the hair to cover the entire area and
worked into the hair. The contact with moist hair will
cause the mousse to heat up giving rise to the desired
heat conditioning. The compositiorl can be left on the
hair as lony as desired. In one modification of its use,
a towel may be wrapped around the head irl order to
preserve the heat factor for somewhat longer.
While it is not totally necessary to do so, it
is generally preferred to wash the composition out of the
hair with a mild shampoo in the conventional manner.
EXAMPLE 4
Hot Oil Anti-Seborrheic Emollient Mo~sse Foam
l. Valfor 950, anhydrous sod.
aluminosilicate (P.Q. Corp) 35.00
2. Cabosil M-5, Fumed Silica .50
3. Dow Corning Silicone #1252
(50~ silicone copolymer,
50% isobutyl isobutyrate) 4.00
4. Polyethylene glycol 400 dioleate 2.00
5. Sunflower Oil 50.00
6. Propane 5.00
19
7. Hydrocor~isone Acetat~ 3.00
8. Fragrance 0.30
10 0 . 00%
Procedure:
The items #3, 4, 5, 7 and 8 are mixed at ambient
temperature until uniform. The powders #l and #2 are
added and mixed until uniform. The batch is passed
through a colloid mill and then submitted for aerosol
filling duriny which the propane is added.
Use
The composition may be used as a skin
emollient. In this use the affected area is washed, the
~urplus water shaken off, and the mousse applied to the
affected area.
This mousse may be used as an anti-seborrheic
hair mousse foam. It is preferred, but not essential,
that the hair be washed and touch dried with a towel so as
to leave the hair moist but not dripping. A sufficient
amount of mousse is applied to the hair to cover the
entire area and worked into the hair. The contact with
29 moist hair will cause the mousse to heat up yiviny rise to
the desired heat conditioning. The composition can be
left on the hair as long as desired. In one modification
of its use, a towel may be wrapped around the head in
order to preserve the heat factor for somewhat longer.
~ZG~ 5
EXAMPLE 5
Hot Oil Hair Dye Mousse Foam
1. Valfor g50, anhydrous sod.
alurninosilicate ~P.Q. Corp) 35.00
2. Cabosil M-5, Fumed Silica .50
3. Dow Corning Silicone #1252
(50% silicone copolymer,
50% isobutyl isobutyrate) 4.00
~. Polyethylene glycol 400 dioleate 2 00
5. Peanut Oil 50.06
6. Propane 5.00
7. Maxilon Blue GRL(500%) 0.3
Deorlene Orange 7GL 1.2
Deorlene Orange 2GL 0.3
Basacryl Red FB 1.0
8. Pragrance 0. 30
100 . 00%
Procedure:
The items #3, 4, 5, 7 and 8 are mixed at ambient
temperature until uniform. ,The powders #1 and #2 are
added and mixed until uniform. The batch is passed
through a colloid mill and then submitted for aerosol
filling during which the propane is added.
Use
When used as a hair dye, it i8 preferred, but
not essential, that the hair be washed and touch dried
5 ~r~
with a towel so as to leave the hair moist but not
dripping. A sufficient amount of mousse is applied to the
hair to cover the entire area and worked into the hair.
The contact wit~ moist hair will cause the mousse to heat
up giviny rise to the desired heat conditioniny. The
composition can be left on the hair as long as desired.
In one modification of its use, a towel may be wrapped
around the head in order to preserve the heat factor for
sornewhat lonyer.
]o WhiLe it is not totally necessary to do so, it
is generally preferred to wash the compositiorl out oE the
hair with a mil~ shampoo in the conventional manner.
~XAMPLE 6
Warm Topical Analqesic Mousse
l. Menthol l0.0%
2. Sodium Alumino Silicate
(Valfor 950) - 35.0
3. Cabosil M-5 1.0
4. Sorbitan Monostearate 4.0
5. Decaglycerol Tetraoleate 6.0
6. Soybean Oil 10.0
7. Isopropyl Myristate 30.0
8. Propane 4.0
100 . U%
Procedure:
Items 4, 5, 6 and 7 are mixed at 60 C.
~L2~ a
temperature until uniform. Items 2 and 3 are ad~ed and
mixed until uniform. The mixture is cooled to 40 C. and
item 1 is added and mixed until uniform. The mixture is
then submitted for aerosol filling during which the
propane is added.
EXAMPLE 7
Warm ToPical Anal~esic Mousse
1. Menthyl Salicylate 15.0%
2. ~odium Alumino Silicate
(Valfor 950) 35.0
3. Cabo~il M-5 1.0
4. Sorbitan Monostearate 4.0
5. Decaglycerol Tetraoleate 6.0
6. Soybean Oil 34,0
7. Propane 5,0
100 . 0%
Procedure:
o
Items 4, 5, and 6 are mixed at 60 C.
temperature until uniform. Items 2 and 3 are added and
mixed until uniform. The mixture is cooled to 40C. and
item 1 is added and mixed until uniform. The mixture is
then submitted for aerosol filling during which the
propane is added.
