Note: Descriptions are shown in the official language in which they were submitted.
~l~ZgO8
BACKGROUND OF THE INVENTION
- , ' . -
Field of the Invention
.
This invention relates to high-internal-phase
.
emulsions. High internal-phase emulsions,hereafter
referred to as HIPE'S t are liquid/liguid immiscible dispersed
systems wherein the volume of the internal or dispersed
phase occupies a volume more than about 74 to 75 percent of
the total volume, i. e. a volume greater than is
geometrlcally possible for close packing of mono-dispersed
spheres.
HIPE'S possess radically different properties
from emulsions of the low or medium internal phase ratio
types. Specifically HIPE'S are non-Newtonian in nature
exhibiting a yield valve phenomenon and a decrease in the
effective viscosity with shear rate. In contrast to gels
which require significant time periods to recover their body
when subject to shear HIPE'S, or as they are also known,
high internal phase ratio emulsions, recover to high viscosities
almost instantaneously. Because of these radically different
properties HIPE'S have been sub~ect to investigation with
- -a- ~ ~
., ~ .
J.364
1132908
respect to applications in such varied disciplines as:
fuels, oil exploration, agricultural sprays, textile printing,
foods, household and industrial cleaning, cosmetics, transport
of solids, fire extinguishers, and crowd control to name just
a few.
HIPE's appear to have attracted very little interest
prior to the mid-nineteen-sixties when workers in the fields
of agricultural sprays, low flammability aircraft fuels and
textile printing pastes, published papers describing their
use properties and preparation. Representative of these
early applications and etc. are set forth in the following
publications:
1. R. E. Ford, C. G. ~. Furmidge, J. Colloid &
Interface Sci., 22, 331-341 (1966).
2. R. E. Ford, C. G. L. Furmidge, J. Sci. ~ood Agric.,
18 (9), 419-28 (1967).
3. J. P. Colthurst, C. G. B. Furmidge, R. ~. ~ord,
J. A. Pearson. ~he Formulation of Pesticides.
S. C. I. Monograph ~o. 21 (1966).
4. J. ~ixon, A. Beerbower, Am. Chem. Soc. Petrochem.
Preprints 14, 49-59 (1969).
5. A. Beerbower, J. Nixon, Am. Chem. Soc.
Petrochem. Preprints 14, 62-71 (1969).
6. A. Beerbower, J. ~ixon, W. Philippoff,
~. J. Wallace, S. A. E. ~ransations,
Section 2, 1446-54 (1968).
7. A. Beerbower, J. ~ixon, ~. J. Wallace, J. Aircra~t,
5 (4), ~67-72 (1968).
8. J. Nixon, A. Beerbower, ~. J. Wallace, Mech.
Eng., 90 27-~3 (1968).
9. I. Rusgnak, B. G. Bercsenyi, Mag~. Kem. ~abja.,
25 (9), 452-7 (1970).
i
-^";` ~ J . 354
113Z908
10. L. G. ~erscenyi, Textilveredlung, 7 (12) 778-780
(1972).
11. ~. G. ~erscen~i, M. I. Ehalil, A. Eantouch,
A. Hebeish, Eolor. ~rtesito, 15, 254-260 (1973).
12. L. G. Berscenyi, A. Hebeish, A. Eantouch,
M. I. Ehalil, Eolor. Ertesito, 16, 73-81 (1974).
13. A. Eantouch, M. I. Ehalil, ~. G. ~erscenyi,
A Hebeish, Kolor, Ertesito, 16, 140-147 (1974).
Recognized, perhaps, as one of the foremost workers in
the areas of HIPE'S is E. J. ~issant of the Petrolite
Corporation, St. ~ouis, Missouri, who has published numerous
papers in the field and who holds numerous patents related
to HIPE technology. lhese publications and patents include
the following:
1. E. J. ~issant, J. Colloid & Interface ~ci.,
22, 462-468 (1966).
2. E. J. ~issant, J. Soc. Cosmetic Chem.,
21, 141-154 (1970).
3. E. J. Lissant, E. G. Mayhan, J. Colloid &
Interface Sci., 42, 201-207 (1973).
4. E. J. ~issant, Emulsions and Emulsion
~echnology. Part 1 (Dekka), 49-66 (1974).
5. E. J. ~issant, ~. W. Peace, S. H. Wu,
E. G. Mayhan, J. Colloid & Interface Sci.,
47, 416-423 (1974).
6. E. J. ~issant, Colloid & Interface Sci.,
Proceedings of 50th Int. Conf., 4 473-485 (1976).
7. K. J. ~issant (Petrolite Corp.), U. S 3343599,
26.9.67.
8. E. J. ~issant (Petrolite Corp.), U. S. 3352109,
14.11.67.
9. E. J. ~issant (Petrolite Corp.), U. S. 3396537,
13.8.68.
~' ' .
~ - 4 -
, . . ` ~
- . . . . ~ .. -
~13Z908-
10. K. J. Lissant (Petrolite Corp. ), U. S. 3490
237, 20.1.70.
11. K. J. Lissant (Petrolite Corp. ), U. S . 3523
826, 11.8.70.
12. K. J. Lissant (Petrolite Corp. ), U. S .
3539 406, 10.11.70.
13. K~ J. Lissant (Petrolite Corp. ), U. S. 3565
817, 23.2~71~ -
14. K. J~ Lissant (Petrolite Corp~ ) U. S . 3613372, 19.10.71.
15~ K. J~ Lissant (Petrolite Corps~), U~ S~ 3617
.
': ,' . . ! , - :
16. K. J. Lissant (Petrolite Corp ~ ), U . S . 3700
. .
- 594, 24.10 ~ 72.
, . ,
17. K. J. Lissant (Petrolite Corp~ ), U~ S~ 3732 - -
' 166, 8.5.73.
18 ~ K. J~ Lissant (Petrolite Corp. ), U. S . 3974
.. . ~ . ~
116. I0.8~76.
- 19. K. J. Lissant (Petrolite~ Corp~), U~ S~ 3983
213, 28.9.76.
20. K. J. Lissant (Petrolite Corp~ ), U~ S . 3988
508, 26 ~ 10 ~ 76.
.
21. R. J. Lissant (Petrolite Corp. ), G. B . 1227
345, 7.4.71.
22. K . J. Lissant ~Petrolite Corp . ), G. B . i227
346, 7.4.71.
23. K. J. Lissant (Petrolite Corp . ), G . B . 1465
528, 23.2.77.
24. R. J. Lissant (Petrolite Corp. ) G. B . 146
529, 23.2.77.
25. K. J. Lissant (Petrolite Corp. ), G. B . 146
530, 23.2. 77.
26. K. J. Lissant (Petrolite Corp . ~, Ger. Offen .
- 2408663, 7.8.75.
_ 5 _
~. .. . .
jl ~
113Z908 -
.
As stated, this invention relates to high-internal- .
phase emulsions. More particularly, the invention relates
. to HIPE'S wherein the liquid/liquid immiscible dispersed
systems are water ànd oil, i. e. having an aqueous.phase and
an oil phase. By oil phase is meant a material, solid or
liquid, but preferably liquid at room temperature that broadly
meets the following requirements:
1. is only sparingly soluble in water;
~ 2. has a low surface tension; and
. 3. possesses a characteristic of a greasy
-. feel to the touch.
.: Uaterials included under this definition include,
for example,-but in no way limited to: straight, branched
- or cyclic parafin compounds, vegetable oils, esters of fatty
. 15 acids, or al.cohols and silicon olls.
Both oil-in-water, hereafter referred to as o/w,
and water-in-oil,.hereafter referred to as w/o, HIPE'S are
,. . . . . . ~
subject to the instant invention. By oil-in-water is meant
that the oil phase is dispersed in the water phase and
conversely, by water-in-oil is meant that the water phase
is dispersed in the oil phase.
. While HIPE'S are defined as emulsions whose
internal phase comprises more than about 74 to 75 of the
emulsi`on by yolume, usually,.the volume fraction o~ the
internal phase in such emulsions is greater than sn percent
and frequently is about 95 percent with some being reported
as high as 98 pRrcent
. Both o/w and w/o HIPE'S have several properties
which make them potentially useful in a variety of
30 applications. These emulsions are viscous fluids and have
appreciable yiçld values. Because of their high viscosity
and lower flammability compared to the separate internal oil
phase, these emulsions have been proposed as rocket and jet
fuels. Water-in-oil emulsions which are 90-96 percent
! - c
. . . .
.. ...
113Z9~j8
aqueous phase can be prepared in forms ranging from a
pourable fluid to a stiff gel. These emulsions can find
- application in several areas such as:
1. in cosmetics and drugs as an inexpensive
- vehicle or suspending medium for other
ingredients such as sunscreens, emollients,
- humectants, etc,;
2. in foods such as in dietary products,
dressings, and sauces.
Although these emulsions are attractive in terms of cost
versus performance (since they are mainly water), the
problem until now, has concerned the-type of emulsifier
required to produce emulsions of adequate stability.
~ Because HIPE'S are so concentrated, there is
great stress applied to the films separating the water
droplets in the emulsion. Such stress is quite demanding
on the emulsifier and up until now r rather uni~ue and in
~ ' '` ' - ' .
many cases, rather complicated or sophisticated and expensive
- emulsifiers wère required to obtain reasonably stable
HIPE'S. Such emulsifiers have not been readily available -
and must be specially synthesized. Moreover, since it is
generally recognized that an emulsifier which works well
with one emulsion composition may not work well with another
emulsion compositionj the synthesis of a wide range of
expensive exotic emulsifiers is currently required in order
to stabilize the various types of compositions for which one
may to employ HIPE'S.
- .
.
'
.
- : - . . . .
.
113Z908
. .
The State of the Art
.
As stated previously, previous work on stabilizing
emulsions has been confined to rather complicated emulsifiers. .
The instant invèntion is directed to an improved
high-internal-phase emu.lsion of the.type comprising an
.
. aqueous phase, an oil phase, and an emulsifier. The
. improvement comprises incorporating into said emulsion an
amount sufflcient to increase.the stability of said emulsion
of an electrolyte con~ained in said aqueous phase.
. 10 The relationship between electrolyte and emulsions-
~ of the low and medium ;nternal phase types is well known, and -
it.is generally recognized that electrolytes are incompatible
with emuIsions generally. causing the dispersed and
continuous phases to separate.into distinct liquids. In fact,
.
15 a signifi~ant amount of work-has.been done to devise systems
. . that will allow the incorporation of electrolytic materials
so that the specific property of the electrolyte may be .-
employed. -
. In ~rown, U! S. Patent No. 2,322,822 an emulsion
.
. 20 comprising an oil phase, a water phase and an electrolyte
is disclosed as being stabilized by the inclusion of an
emulsifier consisting of a mixture of hexide mono ester of
a fatty acid having at least six carbon ato~s and the other
este~s produced in the reaction of a polyhydroxylic
Z5 material selected from the group consisting of hexitols,
hexitans, hexides, and the said fatty acid with at least six
carbon atoms, said mixture having a ratio of fatty acid
equivalents to.carbon atoms of polyhydroxylic residue of
about 0.15 to 0.25 and the ratio of hydroxyl value to
. ester value of said mixture being about 0.5 to 2Ø As can
be seen, the stabilization of an emulsion, which without the
inclusion of an electrolyte could have been accomplished simply,.
. when containing an electrolyte, required a specific and
complex emulsifier system.
113Z908
.
In ~oZey, et a~., U. S. Patent No. 3,2~4,638
there is disclosed an emulsion composition of the water-in-
oil type which is claimed to remain stable at high temperatures
and in the presence of electrolytes. The key to the stability
5. is stated to be the emulsifier composition which consists of:
1. about 1 to about ~ parts by weight of the
condensation product of an amine, selected
from the group consisting of mono-and dialkyl,
. mono-and dialkanol amines, said alkyl and
alkanol amines having from 1 to 8 carbon .
. atoms in the alkyl and alkanol chains, alkyl
polyamines selected from the group consisting
of ethylene diamine, diethylene triamine,
: triethylene tetramine and tetraethylene
pentamine, and mixtures thereof, with about
..
. an equal molar amount of a fatty acid chosen
from the group consisting of aliphatic mono- -
~ . -,~ ~ .. - , . .
carboxylic acids having from 8 to 22 carbon
- atoms in the aliphatic-chain and reactive
. 20 esters and halides thereof;
¦ - ` 2. about 1~3 to about 2 parts by weight of a long
chain aliphatic monohydric alcohol having from
; 8 to 22 carban atoms in the aliphatic chain; and
. 3. about 0 to about 5 parts by weight o~ a
~5 : coupling agent selected from the group
consisting of aliphatic monohydric alcohols
having from about 3 to about 5 carbon atoms
: in thè aliphatic chain, water immiscible
. liquid chlorinated hydrocarbons, and low
boiling liquid aliphatic and àromatic
hydrocarbons having fat solubilizing
properties and mixtures thereof.
.
1, ' , ~9~,
1132908
~v _
Again as can be seen, the destabilizing action of the
elec~rolyte required a specific and complex emulsifier
. system.
In L~ssant, U. S. Patent No. 3,352,109 there
5 ' is disclosed the use of HIPE'S in rocket and jet fuels
having the characteristics of bôth liquid and solid fuels.
In Lis sant, U. S . Patent No. 3, 892,881 there is
disclosed non-Newtonian cosmetic, nutritive and pharmaceutical
compositions using ~IPE'S.
In L~ssant, U . S . Patent N~ 3,490,237 there is
disclosed a thixotropic hydrocarbon-in-water emulsion fuel..
In ~issan~, U. S. Patent No. 3,396,537'-there is
. disclosed emulsions of hydrazine and hydrazine derivative
.
. useful for rocket~fuel. ~ . -
'' 15 . :~'- In.'each of the above cases specific, complicated
emulsion systems.must be employed and.in many cases be
specifically tailored for their particular use. - . `
Thus, while the art of HIPE'S has developed along
. the dlrection of various applications of the emulsions to
different dlsciplines wherein their radical properties may
. : . be employed the stabilization of such emulsions still
r`equire~ the use of specific sophisticated emulsions.
'. It is, therefore, an object of this invention. to
.
'' provide a means for obtaining a stable.HIPE without the
.
.25 need for specialized emulsifiers.
. It is a further object of this invention to provide . .
- ~ a means for obtaining stable HIPE'S using conventional
emulsifier compounds.
- These and other objects of the instant invention :
are fulfilled in an improved high-internal-phase emulsion
of the t~pe comprising an aqueous phase, an oil phase, and
an emulsifler; wherein the improvement comprises the '.
inclusion of an amount sufficient to increase the stability
of said emulsion of an electrolyte contained in said aqueous
35 phase.
.. . . .. .
l \ .
" 1~3Z908
THE DlSCLO5URE
Applicants have discovered that an improved high-
internal-phase emulsion, i. e. , having increased stability,
can be obtained by the inclusion of an electrolyte in
said emulsion. Specifically, ~he inclusion of an amount
sufficient to increase the stability of said emulsion
contained in the aqueous phase of a HIPE of the type
. ": . , .
comprising an aqueous phase, an oil phase, and an emulsifier
will~provide an increased stability of said emulsion
especially when said emulsion is èxposed to elevated
temperature and freeze-thaw cycles.
e improved high-internal-phase emulsions of
the instant invention include both water-in-oil and oil-in-
water HIPE'S. That is, high-internal-phase emulsions
having water or oil as the dispersed phase.
. - :. .
The Emulsifier
- , . . , , - .
- The emulsifiers of the instant invention are
conventional emulsifiers applicable for use in low and mid- -
internal-phase emulsions. GeneraLly, these are nonionic
materials~ Generally, such emulsifiers have an HLB value
. .
of about 1 ~o about 7 and preferably from about 2 to about 6.
Examples of typical emulsifiers subject to the instant -
invention include, but are in no way lïmited to:
.
"''" "' ' , .
- :
.
. , . ' ' ' . ' , .
- ' -11-
- :
, ~ - .
'~ J.364
~3Z908
~ype Representative Trademarked Product
sorbitan triolates ARLACEL 85 (Atlas Chemical Industries)
mono-, di-, and HOS~APHA~ KO~OON (Hoechst)
triphosphoric esters
of oleic acid
polyoxyethylene ATLAS G-1050 (Atlas Chemical
sorbitol hexastearates Industries)
ethylene glycol EMCOL EL-5 (Witco Chemical Co.)
fatty acid esters
glycerol mono-180 IMWITOR 780~ (Witco ~hemical Co.)
stearates
sorbitan monooleates AR~ACE~ 80 (Atlas Chemical Industries)
polyoxyethylene (2) BRIJ92 (Atlas Chemical Industries)
oleyl ethers
ether of glycerol and CREMOPHOR WO/A
fatty alcohols
sorbitan isostearates ARLACEL 987 (Atlas Chemical Industries)
esters of polyalcohols EMUL~EX WS (~a ~essilchimica)
polyethoxylated (2) SIMUSO~ 92 (Produits Chimiques de la
oleyl alcohols Montagne ~oire)
synthetic primary SY~PERO~IC A2 (ICI)
alcohol ethylene oxide
~ondensates
mono and diglycerides A~MOS ~00 (ICI)
of fat forming fatty
acids
The above listing is representative of the various
conventional emulsifying agents subject to the instant
invention and should in no way be considered limiting. In
fact, any emulsifier whose ability to stabilize a XIPE is
improved by the inclusion of an eleGtrolyte in the aqueous
phase of said emulsion is within the contemplated invention.
Generally, the emulsifier can be present in said
emulsion at a level of about 5 to about 30 percent by weight
~5 of the external phase of the XIPE. Usually, however, said
e~ulsifier will be present at a level of about 7 to
about ~0 percent and preferably from about 10 to about 20
percent. Based upon percent by weight of the total
emulsion, the quantity of emulsifier in the HIPE is
generally about 0.5 to about 5, usually, about 0.5 to about
X _ J,2 -
T ~ ' .
ll;~Z908
_/3
4 percent by weigh~ of said emulsion and preferably about
0~5 to about 3 percent by weiqht of said emulsion.
,
The Oil
' 5. 'As stated, the invention particularly relates to
, ,HIPE'S wherein the'liquid/liquid immiscible dispersed
systems are water and oil, i. e. , the HIPE having an
aqueous phase and an oil phase. By oil is mèant a material,
'solid or liquid,'but'preerably liquid at room temperature
. 10 ,that broadly meets the following requirements:
- 1.. is only sparingly soluble in water;
- .
. : 2. has a low surface tension; and ' '
' 3. possesses a characteristic greasy feel to
, the touch.
.
' . 15 Additionally, since application of the emulsion may
.. . . .
ultimately involve a drug or cosmetic use, the oil should
.. . .
~'~ be cosmetically and pharmaceutLcally acceptable.
' Mate.ri,als contemplated under, the instant invention
' . incl~de, for example, but are in no way limited to:
' zo - straight, branched or cyclic parafine compounds; vegetable
.- ~ils, esters:of fatty acids or.alcohols and silicon oils~ '
:, 'Preferably the oil should be non-polor and should contain
.
., . branch chain alkyl groups.' Very desirable are hi~hly
branched chain mineral oils.
, 25 Examples of preferred-oils include, but are in no
.~ way limited to such oils as:- '
a) C10 to C12 isoparafines such as ISOPAR L
b)-Squalane such as COSBIOL
c) Branched chain parafin oil such as'VASELINE OIL
d) Petrolatum such as VASELINE
e) Ethyl hexylpalmitate such as ~ickenol 155
' d) C16 to Clg fatty alcohol di-isooctanoate such as
CETIOL SN
. fj-Mineral oil such as that manufactured by ESSo
~) Polyisobutene such as PARLEAM
, . . .
113Z908
With respect to the quantity of oil~in these
emulsions, the actual amount of oil is less material ~han
the quantity of the oil phase which phase comprises the oil,
which a.re soluble in oil and any other additional components
of the emulsion is generally less than about 24 to 25 percent
by volume. Usually, the oil ph~se is present at a level of
about 2 to about 24 percent by volume and preferably at a
levèl of about 3 to about 20 percent by volume of said emulsion.
On the other hand, in o/w HIPE'S the level of the oil phase
l0 `- in said emulsion will be generally greater than about 74 to
75 percent by volume of said emulsion. Thus, if the emulsion
contains a level of oil phase between about 25 and about 74
percent by volume of the emulsion, the emulsion ceases to
. be of the high internal phase type~and will not exhib1t the
15 . spec1al properties and çharacteristics attributa~le to
HIPE'S.
''"'`'' `'' ` '','. " '
The Aqueous Phase
The aqueous phase comprises water, the elec.trolyte,
. 20 . and any other components of the emulsion which are.so1uble
in water. As with respect to the quantity of oil i.n the
emulsion,. the actual amount of water.is less material than
: the quantity of the aqueous phase. With respect to w/o
.
HIPE'S, the quantity of the aqueous phase present in the
çmulsion is generally greater than about 74 to 75 percent-
by volume. Usually, the aqueous phase is present at a
. . level of about 76 to about 98 percent by volume and
preferably at a level of about 80 to about 97 percent by
volume of said emulsion. On the other hand, in o/w HIPE'S,
. 30 the level of the aqueous phase in said emulsion is. generally
less than about 24 to 25 percent by volume. In such
emulsions the aqueous phase will usually be present at a
level of about 2 to about 24 percent by volume and preferably
at a level of about 3 to about 20 percent by volume of said
emulsion.
~' '`, ~. - ,'' , :
1~3Z908
The Non- mulsion Phase
As previously stated, the HIPE'S of the instant
invention'comprise an oil phase, an aqueous phase, an
emulsifier, and an amount sufficient to increase the
stability of said-emulsion of an electrolyte contained in
said aqueous phase. The two'phases, i. e. , the oil phase
and the aqueous phase themselves comprise respectively oil
and water and those other ingredients of the emulsion or
emuIsion product which are soluble in the respective phases.-
' For example, since by definition the electrolytes of the
' ~ instant lnvention must be water soluble, said electrolytes
will be part of the aqueous phase. Thu's, the aqueous phase
will comprise water, said electrolyte and any other desired'
components which are soluble in the aqueous phase. These
. .
additional components will be set forth in detail in the
secti'on dealing with additives which will follow.
.. .. .
With respect to the emulsifier, the emulsifier
' ' ' may be present as-a component of either the oil phase or the ' -
aqueous phase. Generally, the'emulsifier will be soluble in
' the external phase of the particular emulsion, however, in
; some instances the emulsifier may be mutually soluble in both
' ' the external and internal phases. In such specific cases of
' mutual solubility, however, the relative solubility will
favor the external phase and as such it can generally be
.
''25 expected that the greatest distribution o~ the emulsifier
will be found in the external phase. Accordingly, for w/o
HIPE'S the oil phase can generally be presumed to comprise
the oil, the emulsifier and any other desired components
~ which are soluble in the oil phase. Again as with the
the aqueous phase, these additional components will be set
forth in detail in the section dealing wlth additives which
will follow.
.
-15-
- ~ ~ . - . . ~ .
~132908- :
_ ~ 6 -
While the oil and aqueous phase comprisè those
other components of the emulsion which are soluble in the
respective phases, still other materials may be incorporated
into the emulsion or emulsion product which ingredients are
neither soluble in the oil nor oil phase. These materials
will be referred to, hereafter, as components of the non-
emulsion phase.
As stated previously, HIPE'S possess radically
.
different properties from emulsions of the low-, or medium-
internal phase ratio types. In addition to those properties
previously discussed, HIPE'S have the ability to suspend -
insoluble particulate matter a superior to other known
systems. Because of this ability, HIPE'S are adaptable and
- . . . .:
desirable for use in products where an insoiuble solid
particulate material is to be incorporated in a liquid or
~semiliquid form. Exa~ples of such products, but in no way
limited there,-are such things as cosmetics such as lipstick
and pancake make~p rocket fueL containing finely divided
combustible solids; salad dressings containi~g suspended whole
food particles and seasonings; dentifrices containing
abrasive polishing agents; and solid transport mediums for
piping finely divided solids such as coal ores, grains, and
.
~ the li~e.
.
; With respect to emulsions and emulsion products
containing such non-emulsion phases, the proportions of
ingredients contained in the emuLsion are exclusive of
-components of the non-emulsion phase. Thus, while an -
emulsion product, eg. , an abrasive containing dentifrice,
may contain non-emulsion phase components, and while said
product would appear as a homogenious mixture, the
calculation of the percentages of ingredients in said
,
emulsion and the percent volume of the respective phases
would exclude for calculation purposes the presence of non-
emulsion phase ingredients. Accordingly, an emulsion product
- 35 containing non-emulsion phase ingredients, should be vièwed
il32908
as a HIPE in combination with a non-emulsion constituent,
wherein said constituent is suspended by said emulsion.
.
The Electrolyte
' The improved stability of the HIPE'S of the
. 5 . instant invention is the result~of the incorporation into
- the aqueous phase of sald emulsion an.amount sufficient to
increa.se the stabllity of said emulsion of an electrolyte.
By increased stability is meant that the resulting emulsion
will be less likely to break into the two distinct immiscible
10 liquid phas.es under adverse storage conditions and for .
extended periods of time. ~ '
' Much work with previously indicated "stable"
' ' HIPE'S have'proven disappointing.when those emulsions were
subjected.to test conditions approximating conditions that
would be expected to be encountered by commercial products.
' . Previously, stability at room temperature for 30 to 45 days
' ' was held to be an indication'''of"HIPE stability.
" - ' Unfortunately, these conditions are far too mild to approxi-
.matè what a commercial product might be subjected to. When
20. such products were subjected to harsher storage conditlons,
i. e. ,
1. accelçrated room temperature aging ~ -
. ' via periodic centrifugation;
2. storage at 125 F; and
3. freeze--thaw (0 to 70') cyclic storage,
' most, if not all, showed signs of deterioration of the ~ -
emulsion.
. The improved stability that is the result of the
instant invention results from the incorporation of an
amount sufficient to increase the stability of said
emulsion of an electrolyte in the aqueous phase of the emulsion.
The amount of electrolyte required to stabilize a
.particular emulsion varies with respect to the composition
~ 7_
.~` ~
ll;~Z908
. . . ~ .
of the emulsion, its intended use, the degree`of stability
required, and the electrolyte being used. Unfortunately,
applicants have not been able to devise a means for predicting
electrolyte effect. Some general observation within, for
example, classes of electrolytes can be made. However, a
worker in the art will have to perform some simple
experimentation with the particular system with which he is
involved to optimize both electrolyte species and quantity
thereof for his particular application. This experimentation
is rather simple, and within the scope of someone with
ordinary skill in the art.
,
While any amount of electrolyte sufficient to
increase the stability of the HIPE will suffice, generally, a
level of about 0.001 to about lO percent by weight of said
electrolyte should be present in said aqueous phase. Moire
.
desirably, the levèl of said electrolyte should be about
0.01 to about 10 percent by weight of said aqueous phase.
Preferably, said electrolyte should be ~resent at a level of
.
about 1 to about 6 percent and most preferably at a level of
about 2 to about 4 percent by weight of said aqueous phase.
.
- While any electrolyte, which incorporated in an
amount sufficient to stabilize a HIPE, provides improved
stability, is contemplated by the instant invention
it has been generally found that the preferred electrolytes
of the instant invention are selected from the group consisting
of:
1. inorganic electrolytes;
2. organic electrolytes;
3. complex polyelectrolytesi and
4. mixtures thereof.
Generally, it has been found that inorganic
electrolytes are preferable based upon their ability to
stabilize various emulsions, however, it should be remembered
that this is a generality and that simple experimentation
should be performed 'o determine the best system for a
specific need.
- ~ :
`~` `
1~32908
While any inorganic electrolyte, which when
incorporated in an amount sufficient to stabilize a HIPE,
provides improved stability, is contemplated by the instant
invention it has generally been found that the preferred
S inorganic electrolytes of the instant invention include those
selected from the group consisting of:
water soluble:
l. monovalent inorganic salts;
2. divalent inorganic salts;
3. trivalent inorganic salts and
4. mixtures thereof.
With respect to the inorganic water soluble salts, it has
been found that generally the trivalent salts are preferable
to the divalent salts which in turn are preferable to the
monovalent salts. It should be remembered, however, that
some simple experimentation will be required to chose the
optimum inorganic water soluble salt for a particular
application.
Of * e water soluble monovalent inorganic salts,
preferred salts include: alkali metal halides, alkali metal
sulfates, alkali metal carbonates, alkàli metal phosphates,
and mixtures thereof. Of even more particular preference are
potassium chloride and sulfate as well as sodium chloridè
and sulfates and lithium chloride.
Of the water soluble divalent inorganic sal~s,
prqferred salts include: alkaline earth halides, alkaline
earth sulates, alkaline earth carbonates, alkaline earth
- phosphates, heavy metal halides, heavy metal sulfates,
heavy metal carbonates, heavy metal phosphates, and mixtures
thereof. Particularly preferred salts include: magnesium
chloride, calcium chloride, and magnesium sulfate.
Of the water soluble trivalent inorganic salts,
preferred salts include: heavy metal halides, heavy metal
carbonates, heavy metal phosphates, and mixtures thereof.
A part~_ularly preferred salt is alumuminum chloride.
1~32908
_ 20--
While any or~anic electrolyte -that when incorporated
in an amount sufficient to stabilize a HIPE, provides improved
stability is contemplated by the instant invention it has
gènerally been found that the preferred organic electrolytes
of the instant invention include those selected from the
group consisting of:
water soluble:
1. salts of carboxylic acids;
2. salts of amino acids;
10 3. salts of organic phosphoric acids;
4. salts of organic phosphonic acids;
5. quaternary ammonium halides; - - .
6. quaternary ammonium acetates; and
7. mixtures thereof.
Of the water soluble salts of carboxylic acids,
preferred salts include: alkali metal carboxylic acids,
preferred salts incl~ude: alkali metal carboxylates,-
alkaline eartk carboxylates, heavy metal carboxylates,
. ammonium carboxylates, substituted ammonium carboxylates,
.
and mixtures thereof. With respect to alkali metal, ammonium,
and substituted ammonium carboxylates, preferred carboxylates
. include- acetates, citrates, butyrates, lactates. Cyclic
. . aromatic carboxylate9 such as: benzoates, cyclic aliphatic
.. carboxylates, and mixtures thereof. With respect to
alkaline earth carboxylates, preferred carboxylates include:
acetates, lactates, glycolates, and mixtures thereof. With
respect to heavy metal carboxylates, preferred carboxylates
include acetates.
Of,the water soluble salts of amino acids, preferred
salts include: alkali metal salts of amino acids, alkaline
earth salts of amino acids, heavy metal salts of amino .
acids, ammonium salts of amino acids, substituted salts of
amlno acids, and mixtures thereof. Preferred amino acids
include: glutamic acid, aspartic acid, glycine, ~-alanine,
:,
113Z908
~-alanine, serine, arginine hydrochloride, histidine
hydrochloride, lysine hydrochloride, and mixtures thereof. -
Preferred salts include: sodium glutamate, potassium
glutamate, sodium aspartate, and mixtures thereof.
5~ Of the water soluble salts of organic phosphoric
and phosphonic acids, preferred salts include: alkali metal
salts, alkaline.earth salts, heavy metal salts, ammonium
salts, substituted ammonium salts, and mixtures thereof.
Of the water soluble quaternary ammonium.halides
or acetates, preferred quaternaries are of the general
formula: . .
. .. 2
. . ' ' , ' I '- . ' ., .
~ +
., I" '
. ~ 3
Wherein,~Rl, and R2, and R3 are each selec~ed
from the group consisting of methyl, ethyl, isopropyl,
.hydroxymethyl, and hydroxyethyl, R4 is an alkyl or alkenyl
radical having.l to about 22 carbon atoms; and M is a
.. . .
halide or acetate.
; 20 . Of the water soluble salts of complex polyelectrolytes,
preferred salts include: salts of polyacrylic acids,.
quaternary nitrogen substituted cellulose ethers, vinyl
pyrrolidine/dimethyl amino ethyl methacrylate copolymers,
salts of poly (methyl vinyl ether/mallic acid), alkyl
substituted carboxy-cellulosics, and mixtures thereof. Of
. the water soluble salts of polyacrylic acids, preferred
. salts include: polyacrylic acid, polyethyl acrylic acid,
.polymethyl acrylic acid, and mixtures thereof.
-21-
.. . . . ~ ..................... .
. . . .
. . , ~ . ~
~132908
The Additives
The emulsion, according to the instant invention, can
be employed as a vehicle for a wide variety of products and
uses. These include, but are in no way limited to such
5~ areas as summarized in Table 1. This listing is-, of course,
exemplary and by no means exhau~tive; nor is the list of
~additives for any particuIar use exhaustive.
In particular, these improved HIPE'S are
... . .
particularly attractive as vehicles for a wide variety of
cosmetically or pharmaceutically active ingredients,
~ partic~larly in~redients which have some beneficial effect
~ . . .
when applied to the skin.
~ m e emulslon thus provides a means whereby such
active ingredients can be diluted, preserved, conveyed to
15 ~ and distributed on the skin surface at an appropriate
.:: ~ - .
concentration.
a) Moisturizers
. ~ . - .
A preferred use of HIPE'S is as a vehicle for a
s~in lsturizing product. Skin moisturizing actives as
~20 well as their appropriate required use levels are well known
in~the cosmetics art. The$e actives include, for example,
but are in no way limited to such materials as:
1. sodium pyrollidone carboxylate
2. sodium lactate
3. lactic acid ~
4. triethanolamine lactate
- 5. orotic acid
6. inositol
7. sodium chloride
8. -hydroxy C6 to C10 carboxylic acids
-22-
.
.
J. 364
1~32908
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113Z908
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~13Z908
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3Z908
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~13Z908 -
Accordingly, a preferred aspect o~ the instant invention is
a skin molsturizing product comprising an improved high
internal phase emulsion; of the type comprising an aqueous
phase, an oil phase, and an emulsifier. The improvement
comprises: an amount sufficient to increase the stability
of said emulsion of an electrolyte contained in said aqueous
phase; in combination with an amount sufficient to provide
a moisturizing effect to the skin when said emulsion is
contacted to said skin of a skin moisturizing agent. The
moisturizing agents, contemplated by this preferred aspect
.
of the invention, include `all cosmetically and physiologically
.
acceptable moisturizing agents known in the art as well as
compounds that will be found to exhibit such properties. It
. .
should be noted that where such actives exhibit electrolytic
activity, said active may serve a dual purpose as-providing
the active basis for the product as well as the basis for
sta~ilizing the product.
b) Sunscreens -
~ -- Ano~her preferred use of-HIPE'S is as a vehicle
for a sunscreen agent. Sunscreen agents and their use
levels are well known in the cosmetics art. These agents
.
provide a means of protecting both skin and hair from the
harmful effects of solar radiation. Typical of these
, . ., , . . - .
~5 actives lnclude, but are in no way limited to, such
materials as:
. . . .
- - 1. p-amino benzoic acid
2. propoxylated (2)ethyl p-amino benzoate
3. 2-hydroxy-4-n-octoxybenzophenone
4. dipropylene glycol salicylate
5. 2, 2', 4, 4'-tetrahydroxybenzophenone
6. 2-hydroxy-4-methoxy benzophone-5-sulphonic
acid
7. ethylexyl-2-cyano-3, 3-diphenyl acrylate
-27-
- 1~32908-
Accordingly, a preferred aspect of the instant invention
is a sunscreen product comprising an improved high-
internal-phase emulsion; of the type comprising an
aqueous phase, an oil phase, and an emulsifier. The improve-
ment comprising:an amount sufficient to increase the
stability of said emulsion of an electrolyte contained in
said aqueous phase in combination with an amount sufficient
to provide a sunscreening effect when said emulsion is
contacted to the skin or hair of a sunscreen agent. The
sunscreen agents comtemplated by this preferred aspect of
the inventlon include all known cosmetically and
physiologically acceptable sunscreen agents known to the
art as well as compounds that will be found to possess such
- activity. Again, it should be noted that whjere such
actives exhibit sufficient electrolytic activity, said
.
active may serve a dual function providing both the basis
for product stability and actlvity.
c) Antibacterial agents
Another preferred use of HIPE'S is as a vehicle
for an antibacterial agent. ~ntibacterial agents including
germicides, fungicides, and other such agents are well
known in both the cosmetic and pharmaceutical arts; and
their use levels are well understood. These agents provide
an effective means of providing antibacterial action on
body surfaces as well as other surfaces~ Typical of these
actives include,but are in no way limited to such
materials as:
1. 2-bromo-2-nitro propan-l, 3-diol
2. cetyl pyridinium chloride
3. 3, 4, 4'- trichlorocarbanilide
; 4. 2, 4, 4' -trichloro-2'-hydroxydiphenyl ether
5. benzalkonium chloride
6. para hydroxy benzoic acid
7. dehydroacetic acid
~ Z&~-
'' , ~ .
1132908
Accordingly, a preferred aspect of the instant
invention is an antibacterial product comprising an improved
high-internal-phase emulsion; of the type comprising: an
aqueous phase, an oil phase, and an emulsifier, the improve-
ment comprising an amount sufficient to increase the stability
of said emulsion of an electrolyte contained in saia
aqueous phase; in combination with an amount sufficient
to provide antibacterial activity of an antibacterial
agent. The antibacterial agents contemplated by this
preferred aspect of the invention include all known
cosmetically and physiologically acceptable antibacterial
agents known in the art as well as compounds that will be
found to possess such activity. Again, it should be noted
that were such actives possess sufficient electrolytic
activity, said actives may provide a dual function in providing
both the basis for product stabiiity and activity.
d) Deodorants
Another preferred use of HIPE'S is as a vehicle
for deolorants. Deodorant agents and their use levels are
welI known in the cosmetic art.
mese agents provide an effective means of
providing odor supresssion and/or odor masking. Typical
of these deodorants include, but are in no way limited to
such materials as.
1. 2-ethyl-1, 3- hexane diol
2. 2, 4, 4' trichloro-2'-hydroxydiphenyl ether
3. zinc oxide
4. zinc phenylsulfonate
Accordingly, a preferred aspect of the instant
invention is a deodorant product comprising an improved
high-internal-phase emulsion; of the type comprising an
aqueous phase, an oil phase and an emulsifier, the
improvement comprising an amount sufficient to increase the
stability of said emulsion of an electrolyte contained in
said aqueous phase; in combination with an amount sufficient
~13Z90-8
~o _ . .
to provide a deodorant effect when said prodùct is applied
to the skin of a deodorant agent. The deodorant a~ents
contemplated by this preferred aspect o~ the invention
include all known cosmetically and physiolo~ically acceptable
antibacterial agents known in the art as well as compounds
that will be found to possess such activity. ~gai~ it should
be noted that where such actives possess sufficient
eLectrolyte activity,said actives may provide a dual
function in providing both the basis for product stability
.
and activity.
e) Antiperspirants
Another preferred use of HIPE'S is as a
vehicle for antiperspirant compositions. Antiperspirant
agents are well known in the cosmetic art and the use
levele of said agents are also well understood. These
,
agents provide an effective means for perspiration reduction.
Typical o these agents include, but are in no way li-mited
... . ~ .
to, such materials as:
1. aluminium chlorhydrate
2. aluminium chloride
3. sodium aluminium chlorhydroxy lactate
complex
4. zirconyl chlorhydrate
Accordingly, a preferred aspect of the instant
invention is an antiperspirant product comprising an improved
high i~ternal phase emulsion of the type comprising an
aqueous phase, an oil phase, and an emulsifier~ the improve-
ment comprising an amount sufflcient to increase the
stability of said emulsion of an electrolyte contained in
said aqueous phase;jin combination with an amount sufficient
to provide a deodorant effect when said product is appLied
to the skin of an antiperspirant agent. The antiperspirant
agent contemplated by this preferred aspect of the invention
include all known cosmetically and physiologically
accepta~le antiperpsirant a~ents known in the art as wcl
113Z908
as compounds that will be found.to possess such activity.
Again, it should be noted that where such actives possess
sufficient electrolyte activity, said actives may provide
a dual function in providing the basis for product stahility
5 . ,and activity.
f) Theraputic agents
- , . 'Another preferred use of HIPE'S is a vehicle for
theraputic compositions. Theraputic compositions of the
instant invention are essentially intended for typical
application to the body surfaces. Theraputic compositions
can.serve various functions and may contain antibiotics such
as neomycin, tetracycline, penicillin, and other such ' ' ,
. agents; steroids, for example, cortisone and prednisolone;
. ' rubefacients such as mustara oil and methyl salicylate;
:15 antifungal agents.such as undecylenic acid and antiparasitic
agents such,as gamma benzene hexachloride as well.as heallng
' . ' promoters such as magnesium or zinc sulphate. This list is,
' by no means exhaustive and should serve only to point out the
various types of theraputic agents that may he combined with
the HIPE'S of the instant invention. Accordingly', a preferred
aspect of the instant invention is an antiperspirant
.. , product comprising an improved high internal phase emulsion
of'the type comprising an aqueous phase, an oil phase and an
, .. . ............................... - -
emulsifier, the improvement comprising an amount sufficient
25. to:increase the;stability of said emulsion of an electrolyte
, contained in said aqueous phase;in combination with an
amount'suficient to'provide a theraputic effect,when ' :
said product is applied to the skin of a theraputic agent
' The theraputi'c agents comtemplated by this preferred aspect
o the invention include ,well-known theraputic agents as
well as compounds that will be found to possess such
activity. Again, where such actives possess sufficient
electrolytic activity, said active may provide a dual
function in providing both the basis for product efficiency
and stability.
` ~
113Z908
-3~
g) Particulate'ingredients
As previously stated, HIPE'S have the ability
to suspend particulate material. As such, another preferred
aspect of the'invention are compositions in which there are
'sus~ended particulate matter. Any solid particulate
matter insoluble in either of the phases and that will
be suspended by one of the improved HIPE'S are contemplated
by the invention. ~ -
.
The examples of such products would be pancake-
makeups, lipsticks, abrasive cleaning products, as well as
previously mentioned jet fuels and foods such as salad
.
dressings that contain suspended bits of food matter,
.
` condiments,and seasonings. This l'ist is by no`means
' .
e~haustive and only points out the broad types of products for
15 ~ which this application can be made- Accordingly, a preferred
aspect of the instant lnvention is antiperspirant product
comprising an improved high-internal-phase emulsion of the
type comprising an aqueous phàse, an oil phase, and an
emulsifier, the improvement comprising an amoun't sufficient
to inc'rease the stability of saidemulsion of electrolyte - -
contained in said aqueous phase;in combination with
.,
' particulate ingredients. In particular, preferred particulate'
.
ingredients 'are g'elected from the group consisting of abrasives
pigments, opasifiers, and mixtures thereaf. -
h) Cl'eansing agents
.
' Another preferred use of HIPE'S is a vehicle
for cleansing compositions. Cleansing compositions of the
instant invention are essentially intended for use on the-
skin. However, the application can include cleansing agents
for hard surfaces. Cleansing agents provide an effective
means for removing dirt and grease from either of these
surfaces. Typical of cleansing agents are, but in no way
limited to, such materials as: soaps, anionic, nonionic,
cationic, zwitterionic, surfaces active agents, and mixtures
'
. . , - . . ..
32908
thereof. These a~ents are well known in the detergent and
cosmetic art
and their use levels for various applications are also
well understood.
Accordingly, preferred aspect of the instant
invention is a cleansin~ product comprising an
improved high-internal-phase emulsion of the type
comprising an aqueous phase, an^oil phase, and an
emulsifier. The improvement comprises an amount
- sufficient to increase the stability of said emulsion of
an electrolyte contained in said aqueous phase in combina-
tion with an amount sufficient to provide a cleansing
effect of a cleansing agent~ The cleansing agents contem-
plated by this preferred aspect of the invention include
aLl non-cleansing agents that are cosmetically and physiolog-
ically acceptable and that are aIso compatible with said
lS HIPE emulsion. Additionally, contemplated within the scope
of the invention are those compounds that will be found to
exhibit similar properties Again, ~here such actives
possess sufficient electrolytic activi~y, said actives may
provide a dual function in pLoviding both the basis for a
product activity and stability.
i) P ymeric materials
An ~dditional preferred us~ Gl HIPE ~ 9 ~ in
"~
particular water-in-oll HIPE'9, is as a vehicle for water
soluble polymeric materials. Water soluble polymeric
materials are used in the;cosmetic arts for facial masks
and hair sprays. These materials,presènted in a aqueous
medium such as water-in-oil high-internal-phase emulsion,
can be applied to the skin or hai~ and upon the evaporation
of the water, forms a stiff film or coating on those
surfaces. These agents are well known in the cosmetic art
and the use levels of said agents are well understood.
These polymeric materials provide an effective means of
holding hair set as well as the removal of unwanted
contaminants on the skin via a facial mask.
~ 3~ _
:- : . . `
` ~i32908
Accordingly, preferred aspect of the instant
invention is a high-internal-phase emulsion of the type
comprising an aqueous phase, an oil phase, and an emulsifier.
The improvement comprising an amount sufficient to increase
the stability of said emulsion of electrolyte contained in
said aqueous phase in combination with water soluble polymeric
material as selected ~rom the group consisting of facial
mas~ polymeric materials and hair spray polymeric materials.
The polymeric materials contemplated by this preferred aspect
o-f the invention include all non-cosmetically and physiolog-
icaliy acceptable polymeric agents known in this art as
well as those compounds that will be found to possess such
activity;
i) h r~tic ~d~g~t ~ t~ri~ls
15 - Still another preferred use of HIPE'S is a
vel~icle for cosmetic ingredients that will be applied to
the skin. By cosmetic adjunct ingredient is meant materials
. . , . ~ . .
which either perfume or color the skin. Perfumes and
: colorants are well known in the cosmetic art and have been
incorporated in emulsions of low and medium internal-phase
ratios. The use levels in emulsions are also well understood.
Accordingly, preferred aspect of the instant
invention is anitperspirant product comprising an improved
high-internal-phase emulsion as set forth above in combination
with ingredients selected from the group conslsting of -
perfume and coloring agents.
Additional materials, as well as combinations of
the above materials in a single produc~ are contemplated
within the scope of the invention. These additional
materials include such functional adjuncts as antioxidants,
: such as, but in no ~lay limited to: tocopherol, ascorbyl
palmitate, propyl gallate, butylated hydroxy toluene,
butylated hydroxyanisole, and mixtures thereof; propellants,
such as, but in no way limited to: trichlorofluoro methane,
-
-34- -
. ~
~ 1132908
dichlorodifluoro methane, dichlorotetrafluoro ethane,
monoahlorodifluoro methane, trichlorotrifluoro ethane,
propane, butàne, isobutane, dimethyl ether, carbon dioxide,
and mixtures thereo~; solvents, sùch as, but in no way
limited to: ethyl alcohol, 2-ethylhexanol, ethylene . -
carbonate, propylene carbonate,'methylene chloride, iso-
propyl alcohol, castor oil, linear ethoxylated.polymer of ..
methanol, ethylene glycol monoethyl ether, diethylene
: glycol monobutyl ether, diethylene glycol monoethyl et~er,
,
lp - propoxylated butanol, propoxylated oleyl alcohol, butyl
.stearate, butyl myristate, and mixtures thereof; humectants,
: such as, but in no way limited to: glycerin, sorbitol,
.. , : . .
: ' sodium 2-pyrollidone-5-carboxylate, soluble collagen,
.dibutyl phthalate, gelatin,-polyglycerogen, ethoxyLated
::15 ''(10-20 moles) glucose, propoxylated (10-20 moles glucose,
. '. . and mixtures thereof;thickiners for the oily phase, such . . ''
as, but in no way limited to tetra alkyl and/or trialkyl
. 'aryl ammonium smectites, chemically modified magnesium
~: ' aluminium silicate, organically modified montmorillonite
.
~ elay, fumed silica, hydroxyethyl stearate amide, and
:. mixtures thereof; emollients, such as, but in no'way . . .
limited to: stearyl alcohol, glyceryl monoricinoleate',
glyceryl monostea~ate, sulphated tallow, propylene glycol,
.mink oil, cetyl alcohol, stearyl stearate, isopropyl
. isostearate/ dimethyl brassylate, stearic acid, isobutyl
,
palmitate, isocetyl stearate oleyl alcohol, myristyl
stearate, isopropyl lanolate, isopropyl laurate, hexyl'
laurate, decyl oleate, di-isopropyl adipate, 2-octadecanol,. .
' iso-cetyl alcohol, myristyl ethoxymyrista~te, cetyl palmitate,
30 dimethylpolysiloxane, di-n-butyl sebacate, di-isopropyl
sebacate, di-2-ethyl hexyl sebacate, 2-ethyl hexyl palmitate .
isononyl isononanoate, isodecyl isononanoate, isotridecyl
isononanoate, 2-ethyl hexyl palmitate, 2-ethyl hexyl stearate,
di-(2-ethyl hexyl) adipate, di-(2-ethyl hexyl) succinate,
``` ~13Z908
isopropyl myristate, isopropyl palmitate, isopropyl stearate,
butyl stearate,'glyceryl monostearate, polyethylene glycols,
propylene glycol, triethylene glycol, lanolin, castor oil,
acetylated lanolin alcohols, acetylated lanolin, petrolatum,
isopropyl ester of lanolin fatty acids, mineral oils,'
butyl my~istate, isostearic acid, palmitic acid, isopropyl
linoleate, cetyl lactate, laury lactate, myristyl lactate,
quaternised hydroxy alkyl aminogluconate, decyl oleate,
isodecyl oleate, di-isopropyl-adipate, 2-ethyl hexyl
palmit'ate, 1sostearyl neopentanoate, myristyl myristate,
di-isopropyl adipate,' oleyl ethoxy myristate, di-glycol
' stearate, ethylene glycol monostearate, and mixtures thereof.
: , ' ' ' ' : ' ~ . -
- Preparation of the Emulsion '
15 ' The emulsions and emulsion products of the
instant invention may be'prepared'via a batch or continuous
.
' process. In-fact, any processing techniques already
~, .. ... .
available to the HIPE art, may be employed with the singular
' ~ modification of the step of adding an electrolyte to the
'~ '20 aqueous phase of said emulsion.
~ With respect to batch processing, the emulsifier
is dissolved or dispersed in the oil to form the basic
' oil phase;'and the electrolyte is added to' the water to ; '
' form the basic aqueous phase. The oil phase is'then
25 ' transferred to a mixing vessel and the aqueous phase is -'
continuously addèd thereto in small aliguots under constant
mixing.
For the purposes of viscosity control, it has
been found desirable to first prepare a rathèr coarse and
fluid emulsion of the desired composition by slo~ mixing
during the incorporation of the aqueous phase. Once the
desired amount of aqueous phase has been incorporated,
the speed of mixing is increased and the period extended
until the desired consistency of the emulsion is obtained.
i13Z9Q8
.
In instances where the emulsion contains ingredi-
ents that will be part of either the aqueous or oil phases,
these ingredients should be incorporated into the basic
phases prior to bringing the phases together. In instances
where the emulsion will have ingredients in a non-emulsion
phases, these ingredients may be dispersed in one of the two
phases prior to making the emulsion; or they may be blended
and mixed into the emulsion once it is formed.
'' ~ ~ ', - ' ' ,' ,:
- Stabiiity of the Emulsions
As stated previously, previous assessments of
stability, i. e. 30 to 45 days standing at room temperature,
are insufficiently rigorous to evaluate products intended for
commercial use. Because of this, several accelerated tests
-15 were designed to subject the emulsions of the-instant
.
invention to greater strain. These tests are as follows:
.
a) Accelerated room temperature aging via periodic
centrifugation.
To study stability towards ~epeated
centrifugatio~ a known portion of emulsion or
. .
- emulsion product is placed in a graduated centrifuge
tube and centrifuged periodically (i. e. every 2
to 5 days) at 2,000 r.p.m. for 5 minutes. The
volume of aqueous phase which separated was
then recorded.
- .
b) Righ temperature stability.
High temperature stability is assessed by
storing sealed samples of the emulsion or emulsion
product at 125 F. These samples are then examined
for-phase separation with respect to length of
s~orage.
- 3~~
~13Z908
c) Room temperature stability.
Room temperature stability is accomplished in
' the same manner as the high temperature stability
with the exception that samples are stored at 70 F.
.
5 ' d) Freeze-thaw stability.
To assess free~e-thaw stability, sealed
samples of emulsion or emulsion product are
subjected to cycled temperatures between about
0 F and 70Q F. One such cycle, i. e. 0 F to
10 ' 70 F to Q F, being about 48 hours. At the
end of the cycles, samples are examined for'phase -
.
' 'separation.
EXAMPLES
`The following examples will illustrate further the
' - present invention without, however, limiting the same thereto.
All percentages in the examples will follow the conventions
.. ..
15 ' previously set forth unless otherwi'se indicated. In
particular, all electrolyte levels are based on the aqueous
phase. ' "
Several abbreviations will be used during the'
examples, and such abbreviations are generally trade mark
names for chemical compounds. The following is a listing of
the names of emulsifiers and identification of their
chemical composition and manufactureF.
Emulsifier 'Composition Supplier '
,~
~25 Igepal Ca 420 Ethoxylated octyl phenol GAF
~ri'j 92 Ethoxylated (2) oleyl etherICI
,~1; , .
Span 80 Sorbitan monooleate ICI
Span~85 Sorbitan trioleate- ICI
Atmos 300 Mono and di glycerides of fat ICI
30 - forming fatty acids ICI
-38- cont'd
no~eS tr~de M~
~i3Z9O~
Emulsifier Composition Supplier
.
Drewmulse GMO Glycerol monooleate PVO
Kessco Ester Glycerol monooleate ARMAK
Drewpole 10-4-0 Decaglycerol tetraoleate PVO
Liposorb SQO Sorbitan Sesquioleate Lipo
Chemicals
,
Magnesium oleate
. . ,~ , .
Volpo~3 Ethoxylated (3) oleyl ether Croda
Chemicals
Hodag GMR Glycerol mono ricinoleate Hodag
Example l: Stability of Several Water-in-Oil
HIPE'S (91~-Internal Phase) Towards
Periodic Centrifugation at Room
Temperature ~ -
" . . '
Several water-in-oil HIPE'S were prepared using
,
mineral oil or kerosene as the oil component of the oil phase.
The emulsions were prepared by dissolving or dlspersing the
emulsifier in the oil phase and dissolving the electrolyte,
if any, in the water of the aqueous phase. The aqueous
phase was then added in the aliquots to the oil phase under
constant mixing. Samples-o the resulting emulsions were
then transferred to centrifuge tubes to be stored at room
temperature.~ Periodically (i. e. every 2 to 5 days) the
samples were centri~uged at about 2,000 r.p.m. for about
5 minutes. Percent separation of the aqueous phase was
recorded with respect to time. The results of this experiment
2~ are shown~in Table 2.
The table system refers to the emulsi~ier oil
mixture. It is clear from Table 2 that the emulsifying
ability of all the quite different emulsifiers tested
(ranging in HLB from 1.8-6.6) is greatly enhanced by
electrolyte. It appears from Table 2, that divalent salts,
- -3~
~ olenD~ r~ , ,
`` 1132908
such as K2SO4 and MgSO4/ are more effective than monovalen-t
salts sùch as KCl or KSCN. It is also seen in Table 2 that
the relative stabilizing effect of the salts depends on the
particular emulsifier used.
The room temperature shelf stability of these
emulsions paralleled the behavi~r recorded in Table 2. In
some cases, the effect of electrolyte was even more dramatic.
For example, water-in-mineral oil HIPE'S prepared from
glycerol monooleate ~PVO) coarsened badly after 1 month and
broke after ca. 2 months. Identical emulsions containing
0.S molar M,gSO4 or 0.5 molar K2SO4 showed no change in
appearance or texture and showed no water separation after
10 months!
.
,
Example 2: Influence of Electrolyte on High
Temperature (125 F) Stability of
Water-in-Mineral Oil HIPE'S
- , ~. -
Several water-in-oil HIPE'S were prepared
similarly as in Example 1. The HIPE'S were then subjected
to storage at 125 F for up to 200 days. Phase separation -
as percent water separated was recorded versus time. The
results of this experiment are given in Table 3. The phase
- ratio of these emulsions was 91 percent aqueous phase. ~gain,
the enhanced stabillty in the presence of electrolyte ~s
evident regardless of the HLB of the emulsifier (2.8-6.0).
,
It is clear from Table 3 that certain electrolytes such as
MgSO4, sodium polyacrylate, and sodium lactate are capable
of greatly increasing the high temperature stabilizing
ability of the emulsifiers. Certain electrolytes such as
~lC13 and LiC1 were not particularly effective in
enhancing high temperature stability. However, it will be
shown that these electrolytes were quite effective in
in¢reasing freeze-thaw stability.
4
- . . :
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~13Z908
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Example 3: Influence o~ Electrolyte on Freeze~Thaw
Stability of Several Water-in~Oil HIPE'S'
.
Several water-in-oil HIPE'S were prepared similarly
as in Examples 1 and 2. These HIPE'S were then sub~ected
to 48 hour freeze-thaw cycles (i. e. one cycle is 70 F to
0 F to 70 F). Percent separation of water was recorded
versus time.
The influence of electrolyte on the freeze-thaw stability
of several water-in-mineral oil ~Marcol-52, Exxon) HIPE'S
(91% aqueous phase by volume) is recorded in Table 4. Here
again, the influence of electrolyte is quite dramatic. In
fact, all emulsions prepared with the emulsifiers listed in
Table J broke down completely after one freeze-thaw cycle in,
the,absence of the electrolyte. With certain electrolytes'
such as LiCl, AlC13, MgSO4 or sodium polyacrylate, over
100 cycles could be tolerate'd without deterioration of the
emulsions. It should be not:ed that the concentrations of
electrolyte used in all the freeze-thaw experiments were
much less than that required to supress the,freezing point
of the aqueous phase below 0 F. Thus, the influence of '~
electrolyte on freeze-thaw sta,bility is not produced by
lowering of the freezing point.
.
, Example 4: Influence of Electrolyte on the Freeze-Thaw
2S Stability of Complex Water-in-Oil HIPE'S-
Example 3 was repeated, this time employing
complex mixtures of materials in the oil phase. The stability
results are shown in Table 5. Table 5 shows that electrolytes
are capable of improving the stability of such complex
' emulsions.
,
- -44-
~132908
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~132908
Example 5: Water-in-Oil HIPE'S
The following HIPE'S were prepared in a similar
manner as in the previous examples. The oil employed was
, mineral,oiL and the emulsifier was Span 80. The emulsifier
was present at a level~of abou~ 10 percent of the oil phase.
In each case the HIPE'S c~ntaining electrolyte exhibited very,,
much superior stahility to those without electrolytes.
INTERNAL PHASE VOLUME ELECTROLYTE
95% by volume 1~5 KCl
95% by volume 1% K2SO4 ,
95% by volume none
97% by volume 1% KCl
97% by volume 1~ K2S4
97~ by volume none
lS , Example 6: Oil-in-Water Emulslon
The following HIPE'S were prepared using the oil
phase as the internal phase.' Mineral oil was employed with
an equal part mixture of Span 80, Tween 80, and Tween 20 as
the emulsifier. The emulsifier was present at a level of
10 percent by volume of the oil phase. The oil phase
comprised 91 percent by volume of the emulsion. HIPE'S
containing electrolytes were more stable than those without
electrolytes.
INTERNAL PHASE (91%) ELECTROLYTE-
Mineral oil; and 0.01 M KCl , '
10 % mixture of Span 80, 1.0 M CaC12
Tween'80 and Tween 20, none
1. 0 M CaCI2
" " none
~7letlo~e5 f,~ tnar~
--50--
-
1~3Z908
Example 7: An oil-in-water HIPE, accordiny to Example 6,
was made this time by employing 4 to 6 M CaC12
as the electrolyte. The resulting emulsions
were virtually transparent.
Examples 8 and 9: These examples~ illustrate emulsions
according to the invention in the form
o~ gels for topical application to the
skin as moisturizing products.
Components
- Percent by Wei~ht
8 - 9
HOSTAPHAT KO300N 3
IMWITOR 780X - 3
ISOPAR L 15 15
Sodium glutamate 2.5 2.5
Triethanolamine lactate - 50%:pH 5.5
(moisturizing agent) 6 6
Para p(l) 0.1 0.1
1, 3-butylene glycol 3 - 3
Water 70.4 70-4
(1) propyl p-hydroxybenzoate
:
The oil was mixed with the emulsifier, the Para P
added and dissolved at a temperature of 60-70C. The aqueous
phase containing the amino acid, the lactate and the glycol
were heated gently at 45-50 C. Finally, the emulsion was
prepared after cooling by emulsifying the aqueous phase with
the oily phase to provide a water-in-oil emulsion at a
temperature no higher than 50 C.
~132908
xamples 10 1~ ~mul.sions llavjn~ -tllQ. fol~o~;.n~l for~ulation
as further examples of skin moisturizin~
products for topical application, were
prepared by the method described for Examples
5 ` 8 and 9.
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` ~32908
Example 13: This example illustrates the formulation of a
cream for topical application to the skin:
- ~ w/w
CREMOPHOR W O~A 3
. Mineral oiI (ESSO) 13
Glycine 3
Triethanolamine lactate ~pH 5.5) 3
1, 3-butylene glycol 3
. Para M(l) 0.2
- 10 Para P . Ø1
Perfume - 0.2
. .-
Water 74.5
. ~ methyl p-hydroxybenzoate
'
. Example 14: This example also illustrates the formulation
. of a cream for topical application to the skin:
, -: ~ w/w
CREMOPHOR W O/A . 2.5
LYTOL (i) 8.65
I MODULA~ (ii) 1
¦ 20 CEREWAX L 0.25
¦ Trie~hanolamine lactate. (pH 5.5) 6
. Sodium glutamate . 2.5
. ~ 1, 3-butylene glycol 3
. Para P . 0.1
25 . Water 76
I (i)Light branched chain
¦ polycyclic mineral oil
¦ supplied by WITCO CHEMICALS
(ii)
Acetylated lanolin supplied
by A~ERCHOL
-54-
- ~i32908
Example 15: This example illustrates the formùlation of a
lotion for topical application to the skin:
--O w/w
ARLACEL 987 3.5
ISOPAR L ^ . 7
Parleam -- 8
Sodium pyrollidone carboxylate (50% solution) 4
l, 3-butylene glycol 3
Sodium glutamate 3
! lo Para p 0.1
¦ Para M - 0.2
I . Perfume . 0.2
¦ Water 71
Example 16: This example also illustrates the formulation
. of a lotion for topical application to the skin:
. . ' ' ~ % W!W
Parleam 8 -
. Mineral oil (ESSO) 8
BRIJ 92 3
l, 3-butylene glycol 3
Collagen hydrolysate 3
Zinc sulphate 0.5
. Para P 0.1
. . Para M 0.2
Perfume . 0.2
Water 74
-55-
`--
113Z908
Example 17: This example also illustrates thè formla~ion
of a cream for topical application to the skin:
% w/w
HOSTAPHAT K0300N 3
Parleam ` ' 5
I Mineral oil (ESSO) 5
¦ l, 3-butylene glycol 3
i Collagen hydrolysate 3
Sodium chloride 3
lO . Para P 0.1
Para M 0.2
.Perfume 0.2
Water . . 77,5
., '
. .Examples 18 - 29: In the following Examples the various
commercial application of HIPE'S are .
illustrated. .
'' ' ' . /
.
. . . _
-56-
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~13Z908
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