U.S. patent number 3,585,982 [Application Number 04/836,314] was granted by the patent office on 1971-06-22 for self-heating composition.
This patent grant is currently assigned to The Gillette Company. Invention is credited to James A. Hollinshead.
United States Patent |
3,585,982 |
Hollinshead |
June 22, 1971 |
SELF-HEATING COMPOSITION
Abstract
The present invention is concerned with self-heating
compositions and more specifically with self-heating cosmetic
compositions such as aqueous shaving creams. In the compositions
disclosed herein, at least one of the components of a
heat-generating combination are encapsulated in rupturable capsules
and dispersed in the composition. In especially useful embodiments,
the capsules have melting points at or below the temperatures which
will be generated in the composition.
Inventors: |
Hollinshead; James A.
(Winchester, MA) |
Assignee: |
The Gillette Company (Gillette
Park, Boston, MA)
|
Family
ID: |
25271699 |
Appl.
No.: |
04/836,314 |
Filed: |
June 25, 1969 |
Current U.S.
Class: |
126/263.1;
D9/415 |
Current CPC
Class: |
A45D
27/02 (20130101); A61K 8/02 (20130101); A61Q
9/02 (20130101); B65D 75/5811 (20130101); A61K
2800/242 (20130101) |
Current International
Class: |
A45D
27/00 (20060101); A45D 27/02 (20060101); A61Q
9/02 (20060101); F24j 001/00 () |
Field of
Search: |
;126/263 ;44/3 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Myhre; Charles J.
Claims
Having thus described the invention, what I claim is:
1. An aqueous self-heating composition comprising a combination of
at least first and second heat-generating components which when in
contact with one another effect an exothermic reaction; at least
one of said components which is nonaqueous being encapsulated into
a plurality of frangible capsules which are dispersed in said
aqueous composition, the encapsulating material for said capsules
being both inert and impermeable with respect to the aqueous
composition and the heat-generating components.
2. A self-heating composition as defined in claim 1 wherein the
encapsulating material has a melting point which is at or below the
temperature which is generated in the composition when said
heat-generating components effect the exothermic reaction.
3. A self-heating composition as defined in claim 2 which includes
a foam-generating material, said foam-generating material being a
liquid at room temperature and having a boiling point which is
below the temperature which is generated in the composition when
said heat-generating components effect the exothermic reaction.
4. A self-heating composition as defined in claim 1 which includes
a foam-generating material, said foam-generating material being a
liquid at room temperature and having a boiling point which is
below the temperature which is generated in the composition when
said heat-generating components effect the exothermic reaction.
5. A self-heating composition as defined in claim 1 in which said
composition is a shaving cream.
6. A self-heating composition as defined in claim 4 wherein said
composition is a shaving cream.
7. A self-heating composition as defined in claim 4 wherein said
foam-generating material is encapsulated into a plurality of
frangible capsules which are dispersed in said composition, the
encapsulating material for said capsules being both inert and
impermeable with respect to said composition and said
foam-generating material.
8. A single-use packet containing a self-heating composition, said
packet comprising an enclosed chamber in which said composition is
disposed, said chamber being bound by at least one resilient wall
and having a dispensing opening which is closed off by a removable
closure, said composition comprising a combination of at least
first and second heat-generating components which when in contact
with one another effect an exothermic reaction; at least one of
said components being encapsulated in at least one frangible
capsule which is positioned in the packet contiguous with the
composition, the wall material of said capsule being both inert and
impermeable with respect to said composition and said
heat-generating components.
9. A packet as defined in claim 8 wherein said composition also
comprises a foam-generating material, said foam-generating material
being a liquid at room temperature and having a boiling point below
the temperature which is generated in the composition when said
heat-generating components effect the exothermic reaction.
10. A packet as defined in claim 9 in which said composition is a
shaving cream.
11. A packet as defined in claim 9 wherein said foam-generating
material is encapsulated in at least one frangible capsule which is
positioned within the packet contiguous said composition, the
encapsulating material for said capsule being both inert and
impermeable with respect to said composition and said
heat-generating composition.
12. A packet as defined in claim 11 in which said composition is a
shaving cream.
13. A packet as defined in claim 8 in which said composition is a
shaving cream.
14. An aqueous self-heating composition which is capable of
evolving heat over a prolonged period, said composition comprising
a combination of at least first and second heat-generating
components which in contact with one another effect an exothermic
reaction said combination of heat-generating components being
present in amounts in excess of that which is required to bring the
composition to a desired specified temperature, at least one of
said components which is nonaqueous being encapsulated into a
plurality of frangible capsules which are dispersed in said
composition, the encapsulating material for said capsules being
both inert and impermeable with respect to the aqueous composition
and the heat-generating components and having a melting point at or
below said specified temperature whereby upon rupturing at least
that portion of the capsules which will bring at least a portion of
the composition above said melting point, the unruptured capsules
will gradually melt over a prolonged period and continuously
release additional quantities of the heat-generating component.
15. A self-heating composition as defined in claim 14 which
includes a foam-generating material which is encapsulated into a
plurality of frangible capsules which are dispersed in said
composition, the encapsulating material for said capsules being
both inert and impermeable with respect to said composition and
having a melting point at or below said specified temperature
whereby said capsules will be melted over a prolonged period and
continuously release additional quantities of said foam-generating
material.
16. An aqueous self-heating composition which rises gradually to a
specified temperature over a prolonged period said composition
comprising a combination of at least first and second
heat-generating components which in contact with one another effect
an exothermic reaction, at least one of said heat-generating
components which is nonaqueous being encapsulated in a plurality of
encapsulating materials, said plurality of encapsulating materials
being inert and impermeable with respect to said composition and
said heat-generating components and having sequentially higher
melting points which are above the temperature at which the aqueous
composition is normally stored and at or below said specified
temperature.
17. A self-heating composition as defined in claim 16 which evolves
heat over a prolonged period when said composition reaches the
specified temperature said composition comprising said
heat-generating components in amounts in excess of that required to
elevate the composition to said specified temperature, the excess
of heat-generating components being encapsulated in the
encapsulating material which has the highest melting point in said
plurality of encapsulating materials.
Description
One object of the present invention is to provide self-heating
compositions.
Another object of the present invention is to provide self-heating
compositions which provide heat over a prolonged period.
Still another object of the present invention is to provide
self-heating compositions which are also self-foaming.
A further object of the present invention is to provide
compositions such as set forth above which can be packaged in
low-pressure containers or single-use packets.
Other objects should be clear from the following detailed
description, claims and drawing, wherein:
FIG. 1 is a perspective front view showing a single-use packet
containing a composition within the scope of the present invention,
and
FIG. 2 is a perspective front view of another single-use packet
containing a composition within the scope of the present
invention.
Self-heating compositions such as shaving creams are presently
available in aerosol containers. Generally such compositions
involve the use of a combination of heat-generating components
which effect an exothermic reaction when in contact with one
another. The aerosol containers which are used for such
compositions generally comprise at least two separate compartments
wherein the heat-generating components can be stored separately,
along with the other ingredients, until time of use. Upon use, the
heat-generating components are dispensed from the separate
compartments through concurrently operated valves into a common
discharge passageway where they come together to effect the
exothermic reaction and thereby elevate the temperature of the
composition. Although such aerosol-dispensed, self-heating
compositions have met with considerable success, they require
multicompartment containers and close tolerance valving systems in
order to store the heat-generating components separately and to
dispense said components in the proper stoichiometric amounts under
a myriad of operating modes and conditions. The compositions of the
present invention eliminate the need for such multicompartment
containers and close tolerance valving systems.
In the self-heating compositions of the present invention the need
for multicompartment containers and close tolerance valving systems
is eliminated by encapsulating at least one of the heat-generating
components in frangible capsules and dispersing the capsules in the
composition. The second heat-generating component may be added
directly to the composition or it may also be encapsulated and
dispersed in the composition. During use, the capsules are ruptured
by mechanical force, e.g. by rubbing the composition in one's hands
to release the heat-generating components and bring them together
to effect the exothermic reaction. Generally, the present invention
is broadly applicable to a wide range of hydrophilic and
hydrophobic compositions. It is particularly useful in
aqueous-based pharmaceutical and cosmetic compositions such as
shaving creams wherein heat is desired to increase the
effectiveness of the composition.
Processes for encapsulating the heat-generating components are
known. As examples of such processes, mention may be made of
chemical methods such as disclosed in U.S. Pat. Nos. 2,800,457,
2,800,458, and 3,155,590 mechanical methods such as disclosed in
U.S. Pat. Nos. 3,015,128, and 3,423,489 and electrostatic processes
such as disclosed in U.S. Pat. No. 3,159,874. Generally, such
processes comprise forming a continuous wall of the encapsulating
material around the material to be encapsulated and thereafter
solidifying the encapsulating material. A wide variety of
substances have been found useful as encapsulating materials. Such
materials, in addition to being capable of being deposited around
the material to be encapsulated, also have to be inert and
impermeable with respect to both the compositions in which they are
to be dispersed as well as the encapsulated material. Generally, if
the encapsulated material and the composition in which it is to be
dispersed are hydrophilic, the encapsulating material will be of a
hydrophobic nature and if the encapsulated material and the
composition in which it is to be dispersed are hydrophobic, the
encapsulating material will be of a hydrophilic nature. As examples
of typical encapsulating materials, mention may be made of gelatin,
ethyl cellulose, polymethylmethacrylate, wax, gum arabic, starch,
paraffin, polyethylene, polyvinyl alcohol, and polystyrene.
Generally, encapsulation processes such as set forth above are
capable of producing capsules having diameters varying from about a
few microns up to about 4000 microns and even larger. In the
compositions of the present invention, the size of the capsules may
be chosen to fit the particular need. In embodiments wherein the
capsules are intended to be ruptured by hand, the rupturing can be
facilitated by using the larger diameter capsules, e.g. 2000
microns and above.
The heat-generating components for use in the compositions of the
present invention may be broadly selected from the various
combinations of materials which effect an exothermic reaction when
in contact with one another. As can be appreciated, when the
composition is to be topically applied, the heat-generating
components and the byproducts of the exothermic reaction should be
nontoxic and nonirritating. As examples of types of heat-generating
combinations, mention may be made of the combination of an acid and
base and the combination of a solvent and a solute having an
appreciable heat of solution or dilution in the solvent, e.g. the
combination of water and ethylene glycol and the combination of
water and salts such as aluminum sulfate, calcium chloride, copper
sulfate, ferric chloride, magnesium chloride, magnesium sulfate,
etc. The latter combinations may be conveniently used in
aqueous-based composition by merely encapsulating the salt in a
water-insoluble, water-impermeable encapsulating material and
dispersing the capsules in the composition.
In preferred embodiments of the present invention, the combination
of an oxidizing reagent and a reducing reagent are used as the
heat-generating components. Such oxidizing and reducing reagents
may be selected broadly from the various compounds of this nature
available. As examples of oxidizing agents, mention may be made of
chlorates, perchlorates, permanganates, persulfates, peroxides,
nitrates, metal oxides, such as copper oxide, lead oxide, and iron
oxide, and perborates. The preferred oxidizing agents include
hydrogen peroxide, urea peroxide, sodium peroxide, sodium
perborate, sodium persulfate, ammonium persulfate, potassium
persulfate, and mixtures of any of two or more of the foregoing. As
examples of reducing reagents mention may be made of metals such as
magnesium, zinc, aluminum and iron; sulfites, thio-sulfates,
thioureas, imidazolinethiones, thiotriazoles, thiopyridines,
thio-pyrimidines, thiols, thio-acids, sulfoxides, xanthates, ortho-
and para-polyhydroxy benzenes, aldehydes, and glycols. A preferred
class of reductants for use in compositions which are to be
topically applied is disclosed in U.S. Pat. No. 3,341,418. Such
compounds may be represented by the structure: ##SPC1##
in which R.sub.1 may be hydrogen, lower alkyl, lower hydroxyalkyl,
lower alkoxy, or lower alkanoyl, and R.sub.2 may be any of the
foregoing except hydrogen and may in addition be phenyl. Among such
compounds, are 1-phenyl-2-thio-barbituric acid,
1-phenyl-5-ethyl-2-thio-barbituric acid, 1-methyl-2-thiobarbituric
acid, 1-methyl-5-methyl-2-thio-barbituric acid,
1-methyl-5-ethyl-2-thiobarbituric acid,
1-ethyl-5-ethyl-2-thiobarbituric acid,
1-phenyl-5-methyl-2-thiobarbituric acid, and the like.
Generally, the amounts of heat-generating components employed in
the compositions will vary depending upon factors such as the heat
of reaction of the components; the specific heat of the composition
and the ultimate temperature desired. Usually, the heat-generating
components will be used in amounts which will provide a sensible
temperature rise to the composition (e.g. a rise of 25.degree. F.
from room temperature in a minute). As can be appreciated, the
amounts which will produce such a rise will vary from system to
system but can be readily calculated or empirically determined. In
aqueous systems, such as shaving creams, when employing the
heat-generating components disclosed in U.S. Pat. No. 3,342,418 as
little as 0.8 percent by weight of oxidant based on the total
weight of the aqueous composition will suffice to produce a
sensible temperature rise when a stoichiometrically equivalent
amount of reductant is used. In preferred embodiments of such
aqueous compositions, at least 1 percent by weight of the oxidant,
with a stoichiometrically equivalent amount of the reductant, is
employed.
When desired, catalysts or amounts of one of the heat-generating
components in excess of the stoichiometric amount may be used to
promote or accelerate the heat-generating reaction. When employing
catalysts such materials may be separately encapsulated or they may
be added to the phase of the composition in which they are
inactive. As can be appreciated, the type of catalyst will depend
upon the nature of the heat-generating components. As examples of
catalysts which can be employed in oxidant-reductant systems such
as disclosed in U.S. Pat. No. 3,341,418 mention may be made of the
alkali metal and ammonium salts of molybdates and tungstates.
In especially useful embodiments of the present invention, the
compositions are self-foaming as well as self-heating. This is
accomplished by incorporating into the foamable composition a
foam-generating material which is insoluble or only slightly
soluble in the composition e.g. less than 2 gms. per 100 cc. and
which is a liquid at room temperature, e.g. 25.degree. C. but boils
at the elevated temperature which will result from the reaction of
the heat-generating components. In preferred embodiments of the
present invention, the foam-generating materials will have boiling
points between about 95.degree. F. to about 160.degree. F. As
examples of foam-generating materials mention may be made of
pentane, hexane, dichlorotetrafluoroethane and
trichlorotrifluoroethane. When the compositions are to be marketed
in single use, packets, or in containers which will be open to the
atmosphere, only for short periods of time during the dispensing of
the composition, the foam-generating materials may be added
directly to the compositions. In uses wherein the compositions may
be exposed to the atmosphere for extended periods, the
foam-generating materials may be encapsulated. At time of use, the
capsules containing the foam-generating materials are ruptured
along with those containing the heat-generating components to
provide a self-heating, self-foaming composition.
In preferred embodiments of the present invention, the
heat-generating components are encapsulated in thermoplastic
materials which have melting points at or below the temperature
which will be generated in the compositions. Such embodiments make
it possible to provide compositions which are able to generate heat
over a prolonged period and thus may be called self-sustaining.
Generally, in such self-sustaining compositions the heat-generating
components are present in amounts in excess of that which is
necessary to bring the composition to the desired or specified
temperature. In using such self-sustaining compositions, at least
that portion of the capsules are ruptured which will bring the
composition or a portion of it to the temperature at which the
walls of the unruptured capsules will melt. As the composition or
portions of it reach such temperatures, the walls of unruptured
capsules in the composition or adjacent to the heated portion of it
will gradually melt over a prolonged period and continuously
release additional quantities of the heat-generating components;
thus sustaining the evolution of heat. In compositions which are
self-foaming, as well as self-heating, the foaming action may be
similarly sustained by also incorporating the foam-generating
materials into similar capsules.
In still another preferred embodiment of this invention, the
compositions are compounded so that they may be elevated to the
desired temperature over a prolonged period. This is accomplished
by incorporating the heat-generating components in a plurality of
thermoplastic capsules which have sequentially higher melting
points e.g. a first portion of the heat-generating components are
incapsulated in an encapsulating material which melts at e.g.
120.degree. F., a second portion is encapsulated in a material
which melts at 140.degree. F., and so on. Generally, the melting
points of the encapsulating materials will lie in a range of
temperatures which are above the temperature at which the
composition will normally be stored and at or below the desired
temperature to which the composition is to be heated. When it is
desired that the compositions also be self-sustaining, this is
readily accomplished by using an excess of the heat-generating
components and incorporating the excess components in the highest
melting encapsulating material.
The self-sustaining and/or gradually elevatable compositions
disclosed above are especially useful in heating pads, garments,
etc.
In certain end uses of the compositions of the present invention,
e.g. cosmetics such as shaving creams, the fragments of the
ruptured capsules give the compositions a gritty feel and are
undesirable. Such undesirable characteristics may be substantially
reduced by encapsulating the reagents in thermoplastic materials,
such as taught above, which have melting points at or below the
temperature which will be generated in the compositions by the
reaction of the heat-generating components. In the melted state
such encapsulating materials are usually readily dispersible in the
compositions and thereby provide a convenient mode of eliminating
the undesirable feel of the solid shell fragments. In some
compositions, such as shaving creams, there will be surface active
agents present which will facilitate such dispersion. In
compositions where such surface active agents are not present, it
is preferable, if the formulation will tolerate it, to add such
surface active agents to aid in the dispersion.
Generally, the thermoplastic encapsulating materials for use in
this invention may be selected from the low melting forms of the
encapsulating materials previously mentioned above. A particularly
useful class of thermoplastic materials for use in such embodiments
are the waxes and especially beeswax (solidification point
60.5.degree. to 62.degree. C). Such waxes, in addition to providing
a means of accomplishing the objectives set forth above may also,
in some instances, be a useful ingredient in the composition or
provide it with desirable characteristics such as body.
Thermoplastic capsules for use in the above embodiments may be
readily prepared by known processes. In one such process, the
thermoplastic encapsulating material is dispersed in an external
phase which is a nonsolvent for both the encapsulating material and
the material to be encapsulated. The system is heated to melt the
encapsulating material and the material to be encapsulated is then
added. As the system is cooled, the encapsulating material
solidifies around the material to be encapsulated and thereby forms
the capsules. The capsules, thus produced, are removed from the
system by filtration.
As can be appreciated from the above, the concepts of the present
invention are applicable to a broad range of compositions. Such
compositions may be illustrated by the following shaving cream
formulation which is prepared as set forth below.
An 8.2 percent aqueous hydrogen peroxide solution (the oxidant) is
encapsulated in beeswax by methods such as set forth above, to
provide capsules having an average diameter of at least 2000
microns. The capsules are uniformly dispersed in a shaving cream
formulation having the following composition by weight: ##SPC2##
##SPC3##
The capsules are added to the formulation in amounts such that
there will be about one part by weight of the aqueous peroxide
solution present for each three parts of the shaving cream
formulation.
In using the above composition for shaving, an amount of it,
sufficient for one shave, is applied to the hand and rubbed to
rupture the capsules and release the aqueous peroxide solution.
Upon release, the peroxide reacts with the
1-phenyl-5-ethyl-2-thiobarbituric acid reductant to elevate the
temperature of the composition. The rubbing is continued until the
melted capsule fragments are dispersed in the composition and the
resulting hot shaving cream is then applied to the beard.
If it is desired to make the above shaving formulation self-foaming
as well as self-heating, this can be readily accomplished by adding
a foam-generating material, such as described above, to the
composition. Usually, the use of about 0.75 to about 2.0 gram
molecular weights of the foam-generating material per 1000 gms of
the aqueous composition will provide a useful foam. If it is
desired to sustain the heat-generating action, this is accomplished
by using an excess of the heat-generating components and initially
rupturing that portion of the capsules which will bring the
composition or a portion of it to a temperature which will
gradually melt the remaining unruptured capsules.
In packaging the compositions of the present invention, it is
generally not advisable to use squeeze-type tubes because a certain
portion of the capsules in the unused portion of the composition
will be ruptured during the dispensing operation. If it is desired
to package the compositions in bulk, it is best to use wide-necked
jars which will enable the user to gingerly remove the portion he
wishes to use without rupturing the capsules in the unused portion
of the composition.
When using such bulk packaging, the viscosity of the compositions
should preferrably be such that the capsules will remain uniformly
suspended in the composition until time of use and will not require
stirring. Such suspension of the capsules may be achieved by
employing in the compositions one or more of the many thickening
and suspending reagents which are commercially available.
The compositions of the present invention are particularly useful
in single use packets such as shown in FIGS. 1 and 2. Referring to
FIG. 1, the packet 1 comprises a completely enclosed chamber 3
which is bounded by resilient sidewalls 4 which are sealed to each
other along their peripheries. The chamber opens into a narrow
dispensing channel 7 which is closed off by a tear-off cap 9.
Within the chamber, there is provided a shaving cream composition 5
containing a plurality of first 11 and second 13 capsules. The
first capsules 11 contain a heat-generating material which is
reactive with another heat-generating material which is disposed in
the shaving cream composition and the second capsules 13 contain a
foam-generating material. In use, the sidewalls 4 of the packet 1
are pressed together to rupture the capsules 11 and 13. When the
capsules 11 and 13 are ruptured and the composition becomes hot and
begins to foam, the tear-off cap is removed. Under the pressure of
the foam-generating material, the hot shaving composition is forced
out of the packet 1 for use.
In FIG. 2, there is shown a packet similar to that shown in claim
1, except that it is encased by a rigid protective sheath 15 which
prevents the accidental rupturing of the capsules 11 and 13. The
sheath 15 is provided with an opening 17 in its top through which
the capped dispensing channel 7 protrudes and in its 15 sidewalls
there are positioned openings 21 which provide access to the
resilient sidewalls 4 so that they may be pressed together during
use to rupture the capsules 11 and 13.
It should be appreciated that in single-use packets, such as shown
in FIGS. 1 and 2, the foam-generating material, when desired, may
be disposed directly in the composition. Similarly, the
heat-generating materials and the foam-generating materials may be
disposed in single large frangible capsules which are positioned
contiguous to the composition.
In embodiments of the present invention where the heat-generating
component and the foam-generating material are inert with respect
to each other, it should be understood that they may be
encapsulated in the same capsules.
* * * * *