Note: Descriptions are shown in the official language in which they were submitted.
1 ~ ~654 9
60SI-330
~OLATILE SILICONE~WATER EMULSIONS AND METHODS
OF PREPARATION AND USE
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Background of the _nventlon
The present invention discloses compositions
of matter and methods for producing stable silicone-
water emulsions of volatile cyclic polysiloxanes
without the need for milling or homogenization and
which are particularly useful in cosmetic and
medicinal applications.
The silicone-water emulsion composition of
` the present invention is particularly well-suited for
~, ; serving as a vehicle for the application of epidermal
enhancing agents. The expression "epidermal enhancing
agen-ts" refers to those compositions having properties
generally considered as being beneficial when applied
to portions of the body. For example, such agents
'include a wide range of cosmetics and medical and
15 ~pharmaceutical compounds.
In the cosmetic category 'there are many
; types of~products which can be beneficially applied
to the skin in a silicone emulsion form. For
examp~le, such cosmetics would include cream eye
shadows, foundations~, blushes, lip gloss, mascara
and eyeliner, cover-up-type compositions and wrinkle
creams t; moisturizers, acne cover-up! depila-tories
and cuticle~removers, etc.
Such emulsions can also be used for cleansing
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60SI-330
purposes and may take the form of shampoos, soaps,
conditioners and moisturizers. Additionally, hair
dyes may be applied in a silicone-water emulsion
vehicle.
Additional cosmetic uses include the
application of perfumes, colognes and sachets to
the body. Among the particularly useful applications
would be deodorants and antiperspiran-ts.
Among the many medical uses of such an
emulsion vehicle would be firs-t aid uses such as
burn ointments and the application o~ antiseptics.
Furthermore, corn, wart and callous removing agents,
for example, can be successfully applied to the skin
in such a silicone-water emulsion vehicle.
Of course, the consistency of the silicone-
water emulsion of the present invention can be
varied through many degrees from a lotion-like
consistency through cold cream-like pastes up to
gel-type ointments or salves on the order of a
petroleum jelly.
Silicones are synthetic polymers ordinarily
commercially prepared from chlorosilane monomers
and available in the form of fluids, resins and
rubber gums. Of particular interest to the cosmetic
industxy are those polymers formulated into emulsions,
~reases, pastes, etc. In these formulations a wide
variety of materials may be used in conjunction with
the silicones.
Monomeric chlorosilanes are very reactive
volatile materials which readily react with mois~ure
to form silicones and byproduct hydrochloric ae~s.
Thus, in the presence of moisture they are considered
corrosive materials and may have hazardous properties
~ and must be handled with care. However, after
;~ 35 processing into silicone polymers these materials
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60SI-330
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become bland and inert substances. Silicones may
be further formulated with other materials to produce
various end use compositions and often the physiological
effect of the fïnished composition is determined by
the nature of the non-silicone component.
The toxocological properties of silicones
have been widely studied and, as a group, polymeric
silicone fluids and resins ordinarily have a very low
order of toxicity. Considered ~rom a practical
viewpoint, the hazards they present are exceedingly
minor. Silicone fluid polymers have been the subject
of skin irritation and sensitization patch test
stuides and are typically shown to be safe. The low
level of toxici-ty of silicone materials has even led
to the acceptance and successful use of silicone
fluids in medical and dental applications.
Silicone fluids generally provide excellent
protection against water-borne irritants such as
harsh deteryents and other household cleaning
specialties. The chemical inertness and excellent
water-repellency of silicone fluids are the major
reasons for their effectiveness in preventing
dermatitis. Silicones may also function as emollients,
and provide a pleasant non~stick "feel". Superior
suntan lotions and creams can be prepared using
silicones, since the silicone fluid is a carrier for
the sunscreening agent and resists wash-off by either
bathing or perspira-tion.
Emulsions containing volatile silicone
cyclic polysiloxanes have been previously formulated
by utilizing emulsifying agents such as dodecyl
benzene sulfonic ac~d, however, these systems require
~; milling or homogenization in order to emulsify the
immiscible phases. It is possible to emulsify
preparations of this type having only up to about 55
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concentration oE volatile cyclics and emulsions of
this type are fre~uently utilized to carry out
emulsion-type polymerization of cyclic such as
octamethyltetrasiloxane.
The present invention provides a method
which makes it possible to emulsify larger concentrations
of cyclic polysiloxanes ~hile at the same time
eliminating the necessity of milling or homogenization.
Additionally, the present invention provides stable
emulsions of cyclic polysiloxanes such that these
emulsions do not ordinarily "break" under normal
storage and use conditions even when the concentration
of volatile cyclic polysiloxane is 80~ or more. This
is a particularly useful property for consumer
; 15 oriented products since these emulsions can therefore,
ideally be utilized as vehicles for conveying epidermal
enhancing agents onto the skin of a user in a beneficial
manner.
Furthermore, the present invention offers
a system for emulsifying volatile cyclic polysiloxanes
which yield opaque to transparent materials, which
~; can be readily formulated into many consumer products
and particularly antiperspirants and deodorants, etc.
Other potential uses for water based cyclic emulsions
are skin care products such as hand lotions, skin
fresheners, hair preparàtions and other grooming aids.
As noted above, the method of the present invention
provides a means for selectively varying the
consistency of these emulsions depending upon the
ultimate purposes of the product.
An additional advantage resides in the fact
that these silicone-water emulsions are comprised o~
relatively volatile cyclic polysiloxane constituents
such that an emulsion vehicle base will eventually
evaporate from the skin and only the beneficial
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-- 5
epidermal enhancing ayent will be left thereon.
It is therefore an object of the present
invention to provide a stable silicone-waker emulsion
formed from volatile cyclic polysiloxanes which is
suitable for cosmetic and medicinal applications.
It is another object of the present invention
to provide methods of preparing such silicone-water
emulsions and methods for applying epidermal enhancing
agents.
Summary of ~he Invention
The present invention provides a silicone-
water emulsion and methods of preparation and uses
wherein said emulsion comprises:
(a) 100 parts by weight of a cyclic
polysiloxane or a combination of cyclic polysiloxanes
selected from those having the general formula,
: - C~3 ~
~i - O
_ ~
~ n
wherein n is an integer from 3 to 10, R is selected
from the group consisting of -CH3, -(C~2)zCH3,
: -CH2CH2CF3, -CH2-CH~, and -C6H5 and combinations thereof
and z is an integer from 1 to 10;
(b) from 0.7 to 666 parts by weight of
an emulsifier; and
(c) from 5.0 to 960 parts by weight of
water; and stirring with moderate heat unti.l an
emulsion having a desired consistency is produced.
~ ~; 30 escription of the Invention
;~ The present inVention provides a silicone-
water emulsion, which is comprised of 100 parts by
weight of a cyclic polysiloxane or a combination of
cyclic polysiloxanes having a general formula,
~ ~ .
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60SI-330
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~ Cl 3 ~
wherein n is an inteyer from 3 to 10, R is -CH3,
-(CH2)2CH3~ -CH2cH2cF3~ CH2 CH2, 6 5
combinations thereof and z ls an integer from 1 to 10.
The polysiloxanes designated by this formula are
known as volatile silicone cyclics and this property
of volatility imparts advantageous properties to
the emulsion composition. Particularly useful
volatile silicone cyclic are octamethyltetrasiloxane
and decamethylpentasiloxane.
The volatile cyclic polysiloxane is
combined with an emulsifying agent and water to form
a silicone-water emulsion. The order of mixing the
ingredients is not critical, however, particularly
satisfactory results can be obtained when the emulsifying
agents and the water are mixed together in a preblend
to which the volatile cyclics are added.
Preferably, the cyclic polysiloxane is
added to a preblend consisting of approximatley, 50 to
200 parts by weight of water, which is mixed with 100
parts by weight of one or more emulsifying agents
and heated until a uniform blend is achieved.
This preblend is suitable for producing
a paste-like silicone-water emulsion, however, if a
more liquidous or lotion-like consistency is desired,
there may range up to 2,000 or more parts water per 100
~30 parts of the emulsifying agents. The emulsifying
agents may be nonionic, anionic, cationic or amphoteric
but of particular importance are those classes of
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nonionic emulsifiers ~hich are highly ethoxylated.
The ethoxylated fatty acids, ethoxylated and
non-ethoxylated sorbitan esters, ethoxylated alkyl
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phenols, and ethoxylated ethers provide the best
results.
Examples of emulsifiers which may be used
to formulate the silicone-water emulsions of the
present invention are .included in but not limited by
the following list:
1) ethoxylated fatty acids like:
polyoxyethylene 8 stearate, polyoxyethylene 40 stearate,
polyoxyethylene 50 stearate;
s~ sorbitan esters like:
sorbitan monolaurate, sorbitan monopalmitate,
sorbitan monostearate, sorbitan tristearate,
sorbitan monooleate, sorbitan -trioleate;
3) ethoxylated sorbitan esters:
polyoxyethylene (20) sorbitan monolaurate,
polyoxyethylene (4) sorbitan monolaurate,
polyoxyethylene (20 sorbitan monopalmitate,
polyoxyethylene (20) sorbitan monostearate,
polyoxyethylene 20 sorbitan tristearate,
polyoxyethylene 20 sorbitan monooleate,
polyoxyethylene 5 sorbitan monooleate,
polyoxyethylene 20 sorbitan trioleate;
. 4) ethoxylated ethers like:
. polyoxyethylene 4 lauryl ether, polyoxyethylene 23
:25 lauryl ether, polyoxyethylene 20 cetyl ether,
polyoxyethylene 10 stearyl ether, polyoxyethylene 20
oleyl ether; and
5) ethoxylated alkyl phenols like:
(alkyl phenoxy polyoxyethylene glycol),
8 17C6H4)l (OCH2CH2)nOH~ CAS #9036-19 5
(CgHlgC6H4) (OCH2CH2)nOH,, CAS #26-27-38-3
Approximately, 15 to 50 parts hy weight of
this e~ulsi~ier-water pxeblend is added per 100 parts
by weight of the cyclic polysiloxane ~hen a paste-like
silicone-water emulsion is desiredO
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60SI-330
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Up to approximately, lO00 parts of this
preblend can be added per lO0 parts of the volatile
cyclic polysiloxane in order to provide a low
viscosity, lotion-like product.
B~ adjustin~ the various process parameters
such as content of the volatile cyclic polysiloxane,
emulsifying agent, and water as well as the degree
of mixing, it is po~sible to influence the consistency
of the product. The silicone-~ater emulsion can be
made in the form of a lotion as well as a paste or
cream-like consistency and can be made further viscous
inthe form of an ointment, salve or a gel. Each of
these consistencies is, of course, chosen with regard
to the desired end use of the product.
The silicone-water emulsions useful as a
vehicle for applying from 0.1 to 20,000 parts by
weight of one or more epidermal enhancing agents p~r
100 parts of the emulsion.
This broad range is intended to encompass
those products consisting of nearly pure silicone-
water emulsion having a small amount of epidermal
enhancing agent contained therein, as well as other
products which have but a small amount of silicone-
water emulsion cGntained therein. Epidermal enhancing
agent refers to an additive of a cosmetic or medicinal
nature which is generally regarded as providing
beneficial results when applied externally to the
skin of a user. The silicone-water emulsion of the
present invention is particularly well-suited to serve
as a vehicle for applying deodorant or antiperspirant
agents to the body.
The preblended water-emulsifier mixture is
provided by stirring with moderate heat until a
;uniform blend is obta~ned whereupon the cyclic
~35 polysiloxane i5 added and mixed slowly without the
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~OSI-330
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need for milling or homogenization. Of course,
milling and homogenization may be utilized if desired
and it is intended that the term "mixing" encompasses
these methods as ~ell as mere ayitation. Thus,
the expression "mixing" is meant to encompass a
continuous process utilizing, for example, a Wener-
Pfleiderer wherein individual streams o~ the
components can be metered into a twin screw processor.
Likewise, a Henschel high speed mixer, a sonolator
homogenizer with a vibrating reed and a plain vessel
equipped with a mechanical agitator turbine blade will
all produce satisfactory results. The silicone-water-
emulsifier mixture is then vigorously stirred at
20 to ~0C until an emulsion having a desired
consistency is achieved. An anti-bacteria agent
such as Formalin may be added if desiredO
To a 2 liter stainless steel beaker
equipped with a hot plate, mechanical air stirrer and
thermometer, the water and emulsifier are preblended
by adding together and heating to approximately 20 to
80C and preferably 65 to 75C and stirred to achieve
a uniform mixture when all the solids have melted.
Then the volatile cyclic polysiloxanes, which may be
octamethyltetrasiloxane or decamethylpentasiloxane
or a combination of these or others are slowly added
to the aqueous preblend and stirred vigorously at,
approximately, 30 to 80C and preferably, 50 to 60C
until a uniform, grease-like emulsion is formed.
Small amounts of Formalin may be added once the
product is uniform in order -to prevent bacterial
activity. Unli~e many conventional silicone emulsions,
neither colloid milling nor homogenization is
required in order to prepare these emulsions, but
these means may be utilized if desired.
The consistency of the emulsion can be
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60SI-330
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controlled by the amount of water added. At a 15 to
20~ water le~el, the emulsion has a grease like
consistency, but additional ~ater will lower the
viscosity of the system to a lotion-like consistency
and even more water can be utilized in order to
prepa~e a low viscosity emulsion. The silicone-
water emulsions o~ the present invention are fully
dispersible in water.
Additionally~ the consistency of the
ormulation can be further modified by the quantity
o~ the cyclic polysiloxanes added. In other words,
the more cyclics - the thicker the emulsion and more
grease-like it will be. A lower ratio of cyclic
polysiloxanes will provide a thinner emulsion.
The emulsifiers themselves influence the
consistency of the product. A solid emulsifier like
polyoxyethylene 40 stearate will make the emulsion
thicker and more grease-like while a more liquidous
emulsifier will provide a lotion-like product.
As can be seen, a wide range of emulsion
formulations can be achieved by varying any one of
~ these process parameters: concentration o~ water,
- cyclic polysiloxane, or emulsifiers, and the type of
emulsifiers, whether solid or liquid.
Example 1
To a 2 liter stainless steel beaker was
added 200 grams water, 82 grams polyoxyethylene 40
stearate, and 67 grams sorbitan monostearate which
are heated at 65 to 75C with stirring until a
uniform mixture was achieved when all the solids had
melted. Whereupon, 900 grams decamethylpentasiloxane
was slowly added to the aqueous system and stirred
vigorously at, approximately, 50 to 60C in order
to form a uniform grease-like emulsion. ~wo grams
3~ o~ Formalin ~as added orce the product had achieved
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uniformity, in order to prevent bacterial activity.
~he emulsion was formed without colloid milling nor
homogenization and a stablel stiff, paste-like
emulsion was forme~ ~hich was suitable for serving as
a vehicle for applying an epidermal enhancing agent
such as a deodorant or antiperspirant for application
directly to the skin.
Example 2
The pxocedure of Example 1 was followed
but was modified by the further addition of 11% b~T
weight of polyoxyethylene 20 sorbitan monooleate
whereupon an emulsion having the consistency of a
lotion containingt approximately, 64~ by weight of
the pentasiloxane was obtained as was sui-table for
use in cosmetic products.
Example 3
Following the example of method 1, a
water-emulsifier preblend consisting of 135 grams of
polyoxyethylene 40 stearate and 100 grams sorbitan
monostearate along with 300 grams of water was
prepared. To this was added 1300 grams of
decamethylpentasiloxane, which formed a grease-like
emulsion~ Formalin was added as an anti-bacterial
agent.
Example 4
An emulsifier preblend
consistin~ of 255 grams of water, 82 grams polyoxyethylene
40 stearate and 67 grams sorbitan monostearate was
prepared in accordance with the method in Example 1, ~ ~ 30 whereupon thi~ preblend was added to 900 grams of
octamethyltetrasiloxane in order to form a paste-
like emulsion.
Example 5
An e~lulsion was formed from a 50-50
cyclic silicone mixture consisting of 450 grams
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60SI-330
- 12 -
octamethyltetrasiloxane and 450 grams
decamethylpentasiloxane, which was formulated with an
emulsifier-water preblend consistin~ of 82 grams
polyoxyethylene 40 stearate and 57 grams sorbitin
monostearate and 280 grams water~ A silicone-
water emulsion having a grease-like consistency was
formed~
To 900 grams of decamethylpentasiloxane
was added a preblend consisting of 60 grams sorbitan
monostearate and 200 grams of 70% octylphenoxypolyethoxy
39 ethanol and 200 grams water. Following the method
described in Example 1 a silicone-water emulsion
having soft paste-like consistency was formed.
~
An antiperspirant was formed by combining
100 grams of the silicone-water emulsion paste of
Example 4 with 20 grams aluminum chlorhydrate in the
; form of Micr-Dry Ultrafine (Trademark of Releis Co.).
Example 8
skin freshener was formed by combining
100 grams o~ the silicone-water emulsion paste of
Example 6 with 0.25% perfume.
Example 9
A suntan lotion was formed by combining
lO0 grams of the silicone-water emulsion lotin of
Example 2 with 3.0% homosalate and 0.25% perfume.
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