CA1132908A - High internal phase emulsions - Google Patents
High internal phase emulsionsInfo
- Publication number
- CA1132908A CA1132908A CA336,219A CA336219A CA1132908A CA 1132908 A CA1132908 A CA 1132908A CA 336219 A CA336219 A CA 336219A CA 1132908 A CA1132908 A CA 1132908A
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- phase
- internal
- emulsion
- improved high
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Abstract
ABSTRACT OF THE DISCLOSURE
An improved high-internal-phase emulsion having increased stability under conditions of long term storage at elevated temperatures and freeze-thaw conditions, methods for preparing and stabilizing said emulsions and cosmetic preparations based thereon are disclosed. The improvement comprises incorporating into said emulsion an amount sufficient to increase the stability of said emulsion of an electrolyte contained in the aqueous phase of the emulsion.
An improved high-internal-phase emulsion having increased stability under conditions of long term storage at elevated temperatures and freeze-thaw conditions, methods for preparing and stabilizing said emulsions and cosmetic preparations based thereon are disclosed. The improvement comprises incorporating into said emulsion an amount sufficient to increase the stability of said emulsion of an electrolyte contained in the aqueous phase of the emulsion.
Description
~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 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).
- , ' . -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 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).
S. C. I. Monograph ~o. 21 (1966).
4. J. ~ixon, A. Beerbower, Am. Chem. Soc. Petrochem.
Preprints 14, 49-59 (1969).
Preprints 14, 49-59 (1969).
5. A. Beerbower, J. Nixon, Am. Chem. Soc.
Petrochem. Preprints 14, 62-71 (1969).
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).
Eng., 90 27-~3 (1968).
9. I. Rusgnak, B. G. Bercsenyi, Mag~. Kem. ~abja., 25 (9), 452-7 (1970).
i -^";` ~ J . 354
i -^";` ~ J . 354
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,
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.
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- . . . . ~ .. -~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.
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 .
': ,' . . ! , - :
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16. K. J. Lissant (Petrolite Corp ~ ), U . S . 3700 . .
- 594, 24.10 ~ 72.
, . ,
- 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.
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 _ ~. .. . .
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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.
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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.
.
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.
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1, ' , ~9~, ~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:
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'~ 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.
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' . 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
, . . .
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.
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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.
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~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.
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; 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.
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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, :, ~-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.
.. . . . ~ ..................... .
. . . .
. . , ~ . ~
~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 .
.
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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
- 2408663, 7.8.75.
_ 5 _ ~. .. . .
jl ~
.
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.
- .
.
' .
- : - . . . .
.
. .
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.
.
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~, ~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
, . . .
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.
.
- ~ ~ . - . . ~ .
~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, :, ~-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.
.. . . . ~ ..................... .
. . . .
. . , ~ . ~
~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 .
.
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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&~-'' , ~ .
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 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.
` ~
-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 ' . . , - . . ..
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, -. ~
~ 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.
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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.
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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~
-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 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
- ~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:
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Parleam 8 -. Mineral oil (ESSO) 8 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 `--Example 17: This example also illustrates thè formla~ion of a cream for topical application to the skin:
% w/w 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. .
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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&~-'' , ~ .
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 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.
` ~
-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 ' . . , - . . ..
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, -. ~
~ 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
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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~
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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.
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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.
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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~
-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 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
- ~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 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 `--Example 17: This example also illustrates thè formla~ion of a cream for topical application to the skin:
% w/w 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. .
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Claims (43)
The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows
1. 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 chosen from potassium sulphate and magnesium sulphate contained in said aqueous phase thereby providing for increased stability of said emulsion.
an amount sufficient to increase the stability of said emulsion of an electrolyte chosen from potassium sulphate and magnesium sulphate contained in said aqueous phase thereby providing for increased stability of said emulsion.
2. An improved high-internal-phase emulsion according to claim 1, wherein the internal phase of said emulsion is said aqueous phase.
3. An improved high-internal-phase emulsion according to claim 2, wherein said emulsifier is present at a level of about 5 to about 30 percent by weight of the external phase of said emulsion.
4. An improved high-internal-phase emulsion according to claim 3, wherein said emulsifier is present at a level of about 7 to about 30 percent by weight of the external phase of said emulsion.
5. An improved high-internal-phase emulsion according to claim 4, wherein said emulsifier is present at a level of about 10 to about 20 percent by weight of the external phase of said emulsion.
6. An improved high-internal-phase emulsion according to claim 2, wherein said electrolyte is present at a level of about 0.001 to about 10 percent by weight of said aqueous phase.
- 59 - J.364 CA
- 59 - J.364 CA
7. An improved high-internal-phase emulsion according to claim 6, wherein said electrolyte is present at a level of about 0.01 to about 10 percent by weight of said aqueous phase.
8. An improved high-internal-phase emulsion according to claim 7, wherein said electrolyte is present at a level of about 1 to about 6 percent by weight of said aqueous phase.
9. An improved high-internal-phase emulsion according to claim 8, wherein said electrolyte is present at a level of about 2 to about 4 percent by weight of said aqueous phase.
10. An improved high-internal-phase emulsion according to claim 1, wherein the internal phase of said emulsion is said oil phase.
11. An improved high-internal-phase emulsion according to claim 10, wherein said emulsifier is present at a level of about 5 to about 30 percent by weight of the external phase of said emulsion.
12. An improved high-internal-phase emulsion according to claim 11, wherein said emulsifier is present at a level of about 7 to about 30 percent by weight of the external phase of said emulsion.
13. An improved high-internal-phase emulsion according to claim 12, wherein said emulsifier is present at a level of about 10 to about 20 percent by weight of the external phase of said emulsion.
14. An improved high-internal-phase emulsion according to claim 11, wherein said electrolyte is present at a level of about 0.001 to about 10 percent by weight of said aqueous phase.
- 60 - J.364 CA
- 60 - J.364 CA
15. An improved high-internal-phase emulsion according to claim 14, wherein said electrolyte is present at a level of about 0.01 to about 10 percent by weight of said aqueous phase.
16. An improved high-internal-phase emulsion according to claim 15, wherein said electrolyte is present at a level of about 1 to about 6 percent by weight of said aqueous phase.
17. An improved high-internal-phase emulsion according to claim 16, wherein said electrolyte is present at a level of about 2 to 4 percent by weight of said aqueous phase.
18. An improved high-internal-phase emulsion according to claim 2, further comprising an amount sufficient to provide a moisturizing effect to the skin when said emulsion is contacted to said emulsion is contacted to said skin of a skin moisturizer.
19. An improved high-internal-phase emulsion according to claim 10, further comprising an amount sufficient to provide a moisturizing effect to the skin when said emulsion is contacted to said skin, of a skin moisturizer.
20. An improved high-internal-phase emulsion according to claim 2, further comprising an amount sufficient to provide a sunscreening effect when said emulsion is contacted to the skin or hair, of a sunscreen agent.
21. An improved high-internal-phase emulsion according to claim 10, further comprising an amount sufficient to provide a sunscreening effect when said emulsion is contacted to the skin or hair, of a sunscreen agent.
22. An improved high-internal-phase emulsion according to claim 2, further comprising an amount sufficient to provide - 61 - J.364 CA
antibacterial activity of an antibacterial agent.
antibacterial activity of an antibacterial agent.
23. An improved high-internal-phase emulsion according to claim 10, further comprising an amount sufficient to provide antibacterial activity of an antibacterial agent.
24. An improved high-internal-phase emulsion according to claim 2, further comprising an amount sufficient to provide deodorant activity when said emulsion is applied to the skin of a deodorant.
25. An improved high-internal-phase emulsion according to claim 10, further comprising an amount sufficient to provide deodorant activity when said emulsion is applied to the skin of a deodorant.
26. An improved high-internal-phase emulsion according to claim 2, further comprising an amount sufficient to provide antiperspirant active material.
27. An improved high-internal-phase emulsion according to claim 10, further comprising an amount sufficient to provide antiperspirant activity when said emulsion is applied to the skin of an antiperspirant active material.
28. An improved high-internal-phase emulsion according to claim 2, further comprising an amount sufficient to provide a therapeutic effect of a therapeutic agent.
29. An improved high-internal-phase emulsion according to claim 10, further comprising an amount sufficient to provide a therapeutic effect of a therapeutic agent.
30. An improved high-internal-phase emulsion according to claim 2, further comprising solid particulate matter suspended in said emulsion.
- 62 - J.364 CA
- 62 - J.364 CA
31. An improved high-internal-phase emulsion according to claim 30, wherein said solid particulate matter is selected from the group consisting of:
i) abrasives;
ii) pigments;
iii) opacifiers; and iv) mixtures thereof.
i) abrasives;
ii) pigments;
iii) opacifiers; and iv) mixtures thereof.
32. An improved high-internal phase emulsion according to claim 10, further comprising solid particulate matter suspended in said emulsion.
33. An improved high-internal-phase emulsion according to claim 32, wherein said particulate matter is selected from the group consisting of:
i) abrasives;
ii) pigments;
iii) opacifiers; and iv) mixtures thereof.
i) abrasives;
ii) pigments;
iii) opacifiers; and iv) mixtures thereof.
34. An improved high-internal-phase emulsion according to claim 2, further comprising a cleansing agent selected from the group consisting of:
i) anionic surface active agents;
ii) nonanionic surface active agents;
iii) cationic surface active agents;
iv) zwitterionic surface active agents;
v) soap; and vi) mixtures thereof.
i) anionic surface active agents;
ii) nonanionic surface active agents;
iii) cationic surface active agents;
iv) zwitterionic surface active agents;
v) soap; and vi) mixtures thereof.
35. An improved high-internal-phase emulsion according to claim 10, further comprising a cleansing agent selected from the group consisting of:
i) anionic surface active agents;
ii) nonanionic surface active agents;
iii) cationic surface active agents;
- 63 - J.364 CA
iv) zwitterionic surface active agents;
v) soap; and vi) mixtures thereof.
i) anionic surface active agents;
ii) nonanionic surface active agents;
iii) cationic surface active agents;
- 63 - J.364 CA
iv) zwitterionic surface active agents;
v) soap; and vi) mixtures thereof.
36. An improved high-internal-phase emulsion according to claim 2, further comprising water soluble polymeric materials.
37. An improved high-internal-phase emulsion according to claim 36, wherein said water soluble polymeric material is selected from the group consisting of:
i) facial mask polymeric materials; and ii) hair spray polymeric materials.
i) facial mask polymeric materials; and ii) hair spray polymeric materials.
38. An improved high-internal-phase emulsion according to claim 2, further comprising at least one ingredient selected from the group consisting of:
i) perfume; and ii) coloring agents.
i) perfume; and ii) coloring agents.
39. An improved high-internal-phase emulsion according to claim 10, further comprising at least one ingredient selected from the group consisting of:
i) perfume; and ii) coloring agents.
i) perfume; and ii) coloring agents.
40. An improved process for preparing a high-internal-phase emulsion of the type defined in claim 1, comprising an aqueous phase, an oil phase and an emulsifier and prepared by the steps comprising:
i) dissolving said emulsifier in oil to provide said oil phase; and ii) homogenizing said oil phase with said aqueous phase to provide said high-internal-phase emulsion;
the improvement comprising:
- 64 - J.364 CA
i) dissolving an amount sufficient to increase the stability of said emulsion of an electrolyte chosen from potassium sulphate and magnesium sulphate in said aqueous phase thereby providing for increased stability of said emulsion.
i) dissolving said emulsifier in oil to provide said oil phase; and ii) homogenizing said oil phase with said aqueous phase to provide said high-internal-phase emulsion;
the improvement comprising:
- 64 - J.364 CA
i) dissolving an amount sufficient to increase the stability of said emulsion of an electrolyte chosen from potassium sulphate and magnesium sulphate in said aqueous phase thereby providing for increased stability of said emulsion.
41. An improved process according to claim 40, wherein the internal phase of said emulsion is said aqueous phase.
42. An improved process according to claim 41, wherein i) said emulsifier is present at a level of about 30 percent by weight of the external phase of said emulsion; and ii) said electrolyte is present at a level of about 0.001 to about 10 percent by weight of said aqueous phase.
43. An improved process according to claim 40, wherein:
i) the internal phase of said emulsion is said oil phase;
ii) said emulsifier is present at a level of about 5 to about 30 percent by weight of external phase of said emulsion; and iii) said electrolyte is present at a level of about 0.001 to about 10 percent by weight of said aqueous phase.
i) the internal phase of said emulsion is said oil phase;
ii) said emulsifier is present at a level of about 5 to about 30 percent by weight of external phase of said emulsion; and iii) said electrolyte is present at a level of about 0.001 to about 10 percent by weight of said aqueous phase.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US94575278A | 1978-09-25 | 1978-09-25 | |
| US945,752 | 1978-09-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1132908A true CA1132908A (en) | 1982-10-05 |
Family
ID=25483510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA336,219A Expired CA1132908A (en) | 1978-09-25 | 1979-09-24 | High internal phase emulsions |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1132908A (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1985003646A1 (en) * | 1984-02-18 | 1985-08-29 | The British Petroleum Company P.L.C. | Preparation of emulsions |
| US4746460A (en) * | 1984-12-07 | 1988-05-24 | The British Petroleum Company P.L.C. | Preparation of emulsions |
| JPH0397788A (en) * | 1989-09-12 | 1991-04-23 | Kao Corp | Super-heavy oil emulsion fuel |
| US5641433A (en) * | 1985-01-25 | 1997-06-24 | Intevep, S.A. | Preparation of HIPR emulsions |
| US5670087A (en) * | 1985-04-24 | 1997-09-23 | Intevep, S.A. | Method of preparing HIPR bituminous emulsions |
| US5753596A (en) * | 1995-11-09 | 1998-05-19 | Baker Hughes Incorporated | Methods and emulsions for inhibition of oil well corrosion |
| US5756112A (en) * | 1995-04-27 | 1998-05-26 | The Procter & Gamble Company | Carrier substrate treated with high internal water phase inverse emulsion made with an organopolysiloxane-polyoxyalkylene emulsifier |
| US5763332A (en) * | 1996-04-30 | 1998-06-09 | The Procter & Gamble Company | Cleaning articles comprising a polarphobic region and a high internal phase inverse emulsion |
| US5863663A (en) * | 1994-11-09 | 1999-01-26 | The Procter & Gamble Company | Wet-like cleaning wipes and like articles comprising a carrier treated with an emulsion having a continuous lipid phase |
| US5908707A (en) * | 1996-12-05 | 1999-06-01 | The Procter & Gamble Company | Cleaning articles comprising a high internal phase inverse emulsion and a carrier with controlled absorbency |
| US5948540A (en) * | 1995-04-27 | 1999-09-07 | The Procter & Gamble Company | Carrier substrate treated with high internal phase inverse emulsions made with an organopolysiloxane-polyoxyalkylene emulsifier |
| US5980922A (en) * | 1996-04-30 | 1999-11-09 | Procter & Gamble Company | Cleaning articles treated with a high internal phase inverse emulsion |
| US6121165A (en) * | 1997-07-31 | 2000-09-19 | The Procter & Gamble Company | Wet-like cleaning articles |
| US6133166A (en) * | 1997-07-01 | 2000-10-17 | The Procter & Gamble Company | Cleaning articles comprising a cellulosic fibrous structure having discrete basis weight regions treated with a high internal phase inverse emulsion |
| EP2249773B2 (en) † | 2008-03-07 | 2018-03-21 | Kimberly-Clark Worldwide, Inc. | Moisturizing hand sanitizer |
| GB2589961A (en) * | 2019-09-30 | 2021-06-16 | Henkel Ag & Co Kgaa | Deo emulsion for roll-on deodorant with antibacterial action, deodorant comprising the same and use of the deodorant |
-
1979
- 1979-09-24 CA CA336,219A patent/CA1132908A/en not_active Expired
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0156486A2 (en) * | 1984-02-18 | 1985-10-02 | The British Petroleum Company p.l.c. | Preparation of emulsions |
| EP0156486A3 (en) * | 1984-02-18 | 1985-11-21 | The British Petroleum Company P.L.C. | Preparation of emulsions |
| US4934398A (en) * | 1984-02-18 | 1990-06-19 | The British Petroleum Company P.L.C. | Preparaton of HIPR emulsions and transportation thereof |
| WO1985003646A1 (en) * | 1984-02-18 | 1985-08-29 | The British Petroleum Company P.L.C. | Preparation of emulsions |
| US4746460A (en) * | 1984-12-07 | 1988-05-24 | The British Petroleum Company P.L.C. | Preparation of emulsions |
| US5641433A (en) * | 1985-01-25 | 1997-06-24 | Intevep, S.A. | Preparation of HIPR emulsions |
| US5851430A (en) * | 1985-04-24 | 1998-12-22 | Intevep, S.A. | Bituminous emulsions |
| US5670087A (en) * | 1985-04-24 | 1997-09-23 | Intevep, S.A. | Method of preparing HIPR bituminous emulsions |
| JPH0397788A (en) * | 1989-09-12 | 1991-04-23 | Kao Corp | Super-heavy oil emulsion fuel |
| US5952043A (en) * | 1994-11-09 | 1999-09-14 | The Procter & Gamble Company | Process for making wet-like cleaning wipes and like articles comprising an emulsion having a continuous lipid phase |
| US5863663A (en) * | 1994-11-09 | 1999-01-26 | The Procter & Gamble Company | Wet-like cleaning wipes and like articles comprising a carrier treated with an emulsion having a continuous lipid phase |
| US5756112A (en) * | 1995-04-27 | 1998-05-26 | The Procter & Gamble Company | Carrier substrate treated with high internal water phase inverse emulsion made with an organopolysiloxane-polyoxyalkylene emulsifier |
| US5948540A (en) * | 1995-04-27 | 1999-09-07 | The Procter & Gamble Company | Carrier substrate treated with high internal phase inverse emulsions made with an organopolysiloxane-polyoxyalkylene emulsifier |
| US5753596A (en) * | 1995-11-09 | 1998-05-19 | Baker Hughes Incorporated | Methods and emulsions for inhibition of oil well corrosion |
| US6001381A (en) * | 1996-04-30 | 1999-12-14 | The Procter & Gamble Company | Cleaning articles comprising a polarphobic region and a high internal phase inverse emulsion |
| US5763332A (en) * | 1996-04-30 | 1998-06-09 | The Procter & Gamble Company | Cleaning articles comprising a polarphobic region and a high internal phase inverse emulsion |
| US5980922A (en) * | 1996-04-30 | 1999-11-09 | Procter & Gamble Company | Cleaning articles treated with a high internal phase inverse emulsion |
| US5908707A (en) * | 1996-12-05 | 1999-06-01 | The Procter & Gamble Company | Cleaning articles comprising a high internal phase inverse emulsion and a carrier with controlled absorbency |
| US6133166A (en) * | 1997-07-01 | 2000-10-17 | The Procter & Gamble Company | Cleaning articles comprising a cellulosic fibrous structure having discrete basis weight regions treated with a high internal phase inverse emulsion |
| US6121165A (en) * | 1997-07-31 | 2000-09-19 | The Procter & Gamble Company | Wet-like cleaning articles |
| EP2249773B2 (en) † | 2008-03-07 | 2018-03-21 | Kimberly-Clark Worldwide, Inc. | Moisturizing hand sanitizer |
| GB2589961A (en) * | 2019-09-30 | 2021-06-16 | Henkel Ag & Co Kgaa | Deo emulsion for roll-on deodorant with antibacterial action, deodorant comprising the same and use of the deodorant |
| GB2589961B (en) * | 2019-09-30 | 2022-02-09 | Henkel Ag & Co Kgaa | Deo emulsion for roll-on deodorant with antibacterial action, deodorant comprising the same and use of the deodorant |
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