12-hydroxy stearic acid esters, compositions based upon same and methods of using and making such compositions

The present invention relates to a synthetic, branched chain, oil soluble, fatty acid esters which, when preferably partially neutralized in situ, is revealed as a new water-in-oil emulsifier. Formulations are presented which demonstrate a method for using the disclosed emulsifier to prepare stable water-in-oil emulsions of varying polarity and viscosity for use in a variety of dermatological applications, and/or wherever emulsions according to the present invention may be used.

FIELD OF THE INVENTION 
The present invention relates to synthetic, branched chain, oil soluble, 
fatty acid esters which, when preferably partially neutralized in situ, is 
revealed as a new water-in-oil emulsfier. Formulations are presented which 
demonstrate a method for using the disclosed emulsifier to prepare stable 
water-in-oil emulsions of varying polarity and viscosity for use in a 
variety of dermatological applications, and/or wherever this type of 
emulsion may be useful. 
BACKGROUND OF THE INVENTION 
Since 1957 for the inventor, and much earlier for the art, the use of a 
beeswax-borax system to prepare a water-in-oil emulsion has been available 
in the art. This is a classical method for preparing water-in-oil 
emulsions, i.e, which generally comprise at least about 2/3 by weight of 
an oil phase and no more than about 1/3 by weight of a water phase. 
Typically, prior art emulsions of this type comprise about 9-10% by weight 
of beeswax in the oil phase and about 1% Borax NF in the water phase. The 
oils used to produce the oil phase include mineral oil and petrolatum and 
viscosity was built with paraffin and other waxes such ozokerite in minor 
amounts. 
According to the Merck index, beeswax is comprised of approximately 22-25% 
by weight of a 36 carbon acid. In addition, beeswax generally comprises 
approximately 25% by weight C.sub.35 -C.sub.36 alkanes and approximately 
50% by weight of C.sub.35 -C.sub.36 esters. Using beeswax, in the 
traditional water-in-oil emulsion, the acid and borax together form a 
"soap" emulsifier in situ which facilitates formation of the water-in-oil 
emulsion. Although the system functions reasonably well, problems emerge 
as beeswax may vary in componentry from batch to batch and produce quality 
control problems. In addition, compositions which utilize beeswax often 
require strenuous mixing or homogenization to facilitate the production of 
a stable final formulation. 
Since 1982, the present inventor worked with 12-hydroxystearic acid to 
prepare solid di-fatty esters such as 12-stearoyl, stearyl and stearate. 
One of the first products synthesized in this series was a "tri fatty" 
solid emollient which is still sold under the tradename Hetester SSS. 
After almost 40 years of research, the present inventor tried to make a 
C.sub.36 then a C.sub.40 acid to mimic beeswax in the latter's ability to 
form water-in-oil emulsion compositions, but without the other "solids" 
present in beeswax, which he identified as possibly being responsible for 
certain non-optimal characteristics of these compositions. In addition, it 
was surmised that the synthesis of a synthetic beeswax fatty acid would be 
more controllable and therefore would result in more accurate quality 
control ("QC") during processing. 
OBJECTS OF THE INVENTION 
It is an object of the invention to provide 12-hydroxy stearic acid esters 
which function as emulsifiers to provide storage stable water-in-oil 
emulsions. 
It is an additional object of the invention to provide a method of making 
water-in-oil emulsions which are easy to formulate, are self-homogenizing 
and provide for accurate quality control. 
It is yet another object of the invention to provide water-in-oil emulsions 
which can be used to readily manufacture personal care products including 
cosmetic products such as lipsticks as well as a myriad of types of creams 
and lotions. 
It is still another object of the invention to provide water-in-oil 
emulsion compositions which exhibit significantly greater storage 
stability than those compositions of the prior art which include beeswax. 
These and other objects of the invention may be readily gleaned from the 
detailed description of the invention which follows. 
BRIEF DESCRIPTION OF THE PRESENT INVENTION 
The present invention relates to 12-hydroxystearic acid ester compounds of 
the structure: 
##STR1## 
Where R is a linear or branch chained saturated or unsaturated C.sub.6 
-C.sub.35 hydrocarbon group, more preferably a C.sub.11 -C.sub.23 
hydrocarbon group. Most preferably, R is a C.sub.21 -H.sub.43 group (such 
that the emulsifier is the behenoyl ester of 1 2-hydroxystearic acid or 
behenoyl stearic acid, "BSA"). 
The present 12-hydroxystearic acid esters may be utilized to produce 
water-in-oil emulsions for use as personal care products, such as creams 
and lotions, including pigmented formulations and as substitutes for 
beeswax in water-in-oil emulsions. The present compounds find particular 
use in emulsions, such as pigmented emulsions or moisturizing emulsions, 
among numerous others. These compounds provide excellent emulsification 
and, quite unexpectedly, are also excellent emollients. In many instances, 
the present compounds also plasticize the oils which are present in 
water-in-oil emulsion compositions to leave a dry, waxy feel rather than a 
predominantly oily, greasy feel. This unique feel is an unexpectedly 
favorable characteristic of water-in-oil emulsions according to the 
present invention. 
Compositions based upon the present compounds exhibit consistent 
manufacture, thus obviating the quality control problems which occur when 
beeswax is used in traditional formulations. In addition, many of the 
compositions which are produced using the present compound are 
self-homogenizing, i.e., they are relatively easy to mix into a consistent 
formulation, without reliance on high speed sheer forces or other 
strenuous methods of mixing. Moreover, the water-in-oil emulsions 
according to the present invention exhibit unexpectedly favorable storage 
stability even at high temperatures (50.degree. C.). This is a 
particularly advantageous feature compared to water-in-oil emulsions which 
have shown storage instability (i.e., separation into phases upon storage) 
leading to limited commercial application. 
Emulsion compositions according to the present invention remain 
significantly more stable without separation at high temperatures 
(50.degree. C.) compared to prior art compositions which utilize beeswax 
in the formulation. 
Water-in-oil emulsion compositions according to the present invention 
comprise an oil phase and a water phase, with the oil phase generally 
ranging from about 10% to about 90% by weight of the water-in-oil emulsion 
composition and the water phase ranging from about 10% to about 90% by 
weight of the water-in-oil emulsion composition. More preferably, the oil 
phase in the composition ranges from about 25% to about 80% by weight of 
said composition, even more preferably about 40% to about 75% by weight of 
said composition, even more preferably about 50-60% to about 75% by 
weight, still more preferably about 65 to 70% by weight, and most 
preferably about 66-67% (about 2/3) by weight of said composition. The 
water phase (such phase including the borax-containing compound or related 
compound which reacts with the 12-hydroxystearic acid ester in the oil 
phase to produce an oil soluble salt upon mixing the water and oil phases) 
in the water-in-oil emulsion compositions according to the present 
invention comprises about 10% to about 90% by weight, preferably about 20% 
to about 75% by weight, more preferably about 25 to about 60% by weight, 
even more preferably, about 25% to about 40-50% by weight, still more 
preferably about 30 to about 35% by weight, most preferably about 33-34% 
(about 1/3) by weight of the emulsion composition. 
In the present invention, the oil phase comprises an oil in a major amount 
(i.e., greater than about 50% by weight, more preferably at least about 
70% and even more preferably about 75 to about 99.75% by weight of the oil 
phase) and as a minor component a hydroxystearic acid ester compound 
according to the chemical structure: 
##STR2## 
Where R is a linear or branch chained saturated or unsaturated C.sub.6 
-C.sub.35 more preferably, a C.sub.11 -C.sub.24 hydrocarbon group, even 
more preferably, a C.sub.21 H.sub.43 group, as a minor component (i.e., 
less than about 50% by weight). Thus, in the present invention the 
hydroxystearic acid ester preferably comprises about 0.25% to about 30% by 
weight of the oil phase, more preferably, about 0.5% to about 20% by 
weight of the oil phase, even more preferably about 1.0% to about 10% by 
weight of the oil phase, and even more preferably about 1% to about 7.5% 
by weight of the oil phase. The amount of oil in the oil phase preferably 
ranges from about 70% to about 99.75% by weight, more preferably, about 
80% to about 99.5% by weight, even more preferably about 92.5% to about 
99% by weight. It is noted here that the amount of the hydroxystearic acid 
ester compound and oil to be included within the oil phase will vary 
depending upon the amount of water to be included in the water-in-oil 
emulsion composition. As the amount of water increases in the emulsion 
composition, the amount of the hydroxystearic acid ester which is included 
in the emulsion composition also generally increases and the amount of oil 
decreases, as does the inversion temperature. 
In addition to water, the water phase may also include an amount of a 
"neutralizing agent or compound" effective to produce an emulsion when the 
water phase and oil phases are combined. Examples of such compounds 
include, for example, boron-containing compounds such as sodium 
tetraborate decahydrate (Borax NF), sodium tetraborate tetrahydrate, 
Ca(OH).sub.2, Mg(OH).sub.2, Al(OH).sub.3, disodium monohydrogen phosphate 
or dipotassium monohydrogen phosphate (i.e., Na.sub.2 HPO.sub.4 or K.sub.2 
HPO.sub.4), trisodium phsophate or tripotassium phosphate (Na.sub.3 
PO.sub.4 or K.sub.3 PO.sub.4), NaHCO.sub.3, KHCO.sub.3, Na.sub.2 CO.sub.3, 
K.sub.2 CO.sub.3, NaOH and KOH (preferably, buffered NaOH and KOH) and 
fatty amine compounds (i.e., primary, secondary and tertiary amine 
compounds containing at least one C.sub.10 to C.sub.22 alkyl, alkene or 
substituted alkyl or alkene group). 
Emulsion compositions according to the present invention may also include 
optional additives, for example, fragrances, preservatives, anti-oxidants, 
vitamins, pigments, conditioning agents, among numerous other standard 
cosmetic additives. These additives may be included in emulsion 
compositions according to the present invention in amounts up to about 25% 
by weight, preferably, in amounts ranging from about 0.01% to about 10% by 
weight, most preferably less than about 5% by weight within this range. 
DETAILED DESCRIPTION OF THE INVENTION 
The terms "emulsion" and "water-in-oil emulsion" are used synonymously 
throughout the specification to describe compositions according to the 
present invention. An "emulsion" according to the present invention is a 
cream or lotion which is generally formed by the suspension of a very 
finely divided liquid, in this case water, in another liquid, in this 
case, an oil. In the present invention, an emulsion is formed when the 
water phase is compatibilized in the oil phase, such that the water phase 
becomes "hidden" within the oil phase. While not being limited by way of 
theory, it is believed that in the water-in-oil emulsion compositions 
according to the present invention, the oil phase produces a liposome- or 
encapsulation-like structure or a related structure surrounding water 
and/or the water phase, with the reaction product of the 12-hydroxy 
stearic acid ester and neutralizing compound serving to enhance the 
formation of the liposome-like structure and consequently, the emulsion 
composition. The term emulsion is used to distinguish the present 
compositions from compositions which contain at least two distinct phases, 
i.e., an oil phase and a water phase. 
The term "hydrocarbon" is used throughout the specification to describe R 
groups according to the present invention. R may be a linear or branch 
chained saturated or unsaturated C.sub.6 -C.sub.35 hydrocarbon group, more 
preferably, a C.sub.11 -C.sub.24 hydrocarbon group, even more preferably, 
a C.sub.21 -H.sub.43 group. The term hydrocarbon embraces, but is not 
limited to, for example, alkyl, alkene groups (including those groups 
containg more than one unsaturated double bond), alkyne groups, aryl 
groups, aralkyl groups and related groups which are comprised of carbon 
and hydrogen atoms. Groups which may be found on fatty amines according to 
the present invention also may be described as hydrocarbons, although the 
number of carbon atoms which are found in hydrocarbon groups in the fatty 
amine according to the present invention falls within a more narrow range 
than do the hydrocarbon groups which may be used as R groups in stearic 
acid esters or emulsifiers according to the present invention. 
The term "inversion temperature" is used throughout the specification to 
describe a temperature at which emulsion formation occurs with stability. 
Emulsion compositions according to the present invention generally have 
inversion temperatures of at least about 40.degree. C., more preferably 
about 50.degree. C. or higher. 
The term "oil" is used throughout the specification to describe any of 
various lubricious, hydrophobic and combustible substances obtained from 
animal, vegetable and mineral matter. Oils for use in the present 
invention may include petroleum-based oil derivatives such as purified 
petrolatum and mineral oil. Petroleum-derived oils include aliphatic or 
wax-based oils, aromatic or asphalt-based oils and mixed base oils and may 
include relatively polar and non-polar oils. "Non-polar" oils are 
generally oils such as petrolatum or mineral oil or its derivatives which 
are hydrocarbons and are more hydrophobic and lipophilic compared to 
synthetic oils, such as esters, which may be referred to as "polar" oils. 
It is understood that within the class of oils, that the use of the terms 
"non-polar" and "polar" are relative within this very hydrophobic and 
lipophilic class, and all of the oils tend to be much more hydrophobic and 
lipophilic than the water phase which is used in the present invention. 
In addition to the above-described oils, certain essential oils derived 
from plants such as volatile liquids derived from flowers, stems and 
leaves and other parts of the plant which may include terpenoids and other 
natural products including triglycerides may also be considered oils for 
purposes of the present invention. 
Petrolatum (mineral fat, petroleum jelly or mineral jelly) and mineral oil 
products for use in the present invention may be obtained from a variety 
of suppliers. These products may range widely in viscosity and other 
physical and chemical characteristics such as molecular weight and purity. 
Preferred petrolatum and mineral oil for use in the present invention are 
those which exhibit significant utility in cosmetic and pharmacuetical 
products. Cosmetic grade oils are preferred oils for use in the present 
invention. 
Additional oils for use in the present invention may include, for example, 
mono-, di- and tri-glycerides which may be natural or synthetic (derived 
from esterification of glycerol and at least one organic acid, saturated 
or unsaturated, such as for example, such as butyric, caproic, palmitic, 
stearic, oleic, linoleic or linolenic acids, among numerous others, 
preferably a fatty organic acid, comprising between 8 and 26 carbon 
atoms). Glyceride esters for use in the present invention include 
vegetable oils derived chiefly from seeds or nuts and include drying oils, 
for example, linseed, iticica and tung, among others; semi-drying oils, 
for example, soybean, sunflower, safflower and cottonseed oil; non-drying 
oils, for example castor and coconut oil; and other oils, such as those 
used in soap, for example palm oil. Hydrogenated vegetable oils also may 
be used in the present invention. Animal oils are also contemplated for 
use as glyceride esters and include, for example, fats such as tallow, 
lard and stearin and liquid fats, such as fish oils, fish-liver oils and 
other animal oils, including sperm oil, among numerous others. In 
addition, a number of other oils may be used, including C.sub.12 to 
C.sub.30 (or higher) fatty esters (other than the glyceride esters, which 
are described above) or any other acceptable cosmetic emollient. 
Preferred oils for use in the present invention include petrolatum, mineral 
oil or mixtures of petrolatum and mineral oil where the amount of 
petrolatum to mineral oil (on a weight/weight basis) ranges from about 
1:20 to about 10:1, preferably about 1:5 to about 5:1, more preferably 
about 1:3 to about 1:1, depending upon the end use of the emulsion 
composition. The inclusion of petrolatum and/or mineral oil and/or the 
ratio of petrolatum to mineral oil in the present compositions will 
greatly influence the final viscosity of the water-in-oil compositions 
according to the present invention. 
The term "storage stability" is used throughout the specification to 
describe an unexpected characteristic of emulsion compositions according 
to the present invention which relates to the fact that the present 
emulsions are generally storage stable at 50.degree. C. for a period of at 
least about three months, and often longer than six months, a year or even 
longer. This is a particularly advantageous feature of emulsion 
compositions according to the present invention in comparison to prior art 
compositions, especially those which utilize beeswax to form the emulsion. 
Those prior art compositions tend to separate into at least two separate 
phases, generally a water phase and an oil phase within a relatively short 
period at a temperature at or above about 50.degree. C. 
The term "carboxylic acid reactive neutralizing agent or compound" or 
"neutralizing compound" is used throughout the specification to describe a 
compound which is reactive with the carboxylic acid group of the stearic 
acid ester to produce a salt or complex of the carboxylic acid in an 
amount effective to produce a stable emulsion when the water phase and oil 
phases are combined. In the present invention, the neutralizing agent or 
compound reacts or complexes with the carboxylic acid moiety of the 
12-hydroxy stearic acid ester compound. A neutralizing compound for use in 
the present invention may be any alkaline compound which forms a 
hydrophobic/lipophilic soap (salt) with the 12-hydroxy stearic acid ester 
compound. In certain embodiments according to the present invention, 
preferred neutralizing compounds include any alkaline salt whose 5% 
aqueous solution gives a pH ranging from about 8 to about 12, preferably 
about 9-11. Preferred alkaline salts include, for example, Na.sub.2 
HPO.sub.4 or K.sub.2 HPO.sub.4 Na.sub.3 PO.sub.4, K.sub.3 PO.sub.4, 
NaHCO.sub.3, KHCO.sub.3, Na.sub.2 CO.sub.3, K.sub.2 CO.sub.3, and mixtures 
thereof, among others. In the present invention, the amount of 
neutralizing compound to 12-hydroxy stearic acid ester compound used in 
the final emulsion composition ranges from about 1 part (weight/weight) to 
10 to about 2 parts to 1, more preferably about 1:4 to about 1:1, more 
preferably about 1:2. The amount of neutralizing compound to 12-hydroxy 
stearic acid ester compound used in the present compositions is not 
necessarily a stoichiometric amount. It is noted that this amount should 
serve as a guide, but not to limit, the understanding as to the amount of 
neutralizing compound to be used in the present invention. Examples of 
preferred neutralizing compounds include, for example, boron-containing 
compounds such as sodium tetraborate decahydrate (Borax NF), sodium 
tetraborate tetrahydrate, tetrahydroxy boron, boron monoxide (which 
converts to tetrahydroxy boron on reactions with water), Ca(OH).sub.2, 
Mg(OH).sub.2, Al(OH).sub.2, Na.sub.2 HPO.sub.4 or K.sub.2 HPO.sub.4 
Na.sub.3 PO.sub.4, K.sub.3 PO.sub.4, NaHCO.sub.3, KHCO.sub.3, Na.sub.2 
CO.sub.3, K.sub.2 CO.sub.3, NaOH, KOH and fatty amine compounds (i.e., 
primary, secondary and tertiary amine compounds containing at least one 
C.sub.10 to C.sub.22 alkyl group) and mixtures thereof, especially 
mixtures of the previously described phosphate and carbonate salts. 
Preferred neutralizing compounds which are used in the present invention 
include, for example, sodium tetraborate decahydrate (Borax NF) and sodium 
tetraborate tetrahydrate, with sodium tetraborate decahydrate (Borax NF) 
being the preferred compatibilizing agent for use in the present 
invention. 
The term "self-emulsifier" or "self-emulsification" is used to describe 
compounds according to the present invention which are the reaction 
products of a 12-hydroxy stearic acid ester compound and a neutralizing 
compound according to the present invention and may be used to create 
emulsion compositions according to the present invention by simple mixing, 
i.e., without relying on shear forces or high speed mixing action. These 
emulsifiers may be created in situ by mixing the 12-hydroxy stearic acid 
ester with the neutralizng compound during formation of the emulsion, or 
alternatively, may be prepared separately, by neutralizing the 12-hydroxy 
stearic acid ester with the neutralizing compound and then adding the 
pre-formed emulsifier to other components to form the emulsion 
composition. 
The term "secondary emulsifier" or "helper emulsifer" is used throughout 
the specification to describe compounds which are added to the emulsifier 
compositions according to the present invention to provide a more stable 
and in some embodiments consistent emulsion composition. Secondary or 
helper emulsifiers may be particularly advantageous when formulating 
emulsions compositions which utilize one or more salts such as phosphate 
salts or carbonate salts to neutralize the srtearic acid ester. 
Emulsifiers as used generally are considered surfactants which exhibit 
good surface activity and produce a low interfacial tension in the system 
in which it is used. Secondary emulsifiers preferably used in the present 
invention exhibit a tendency to migrate to the interface, rather than 
remain dissolved in either one of the water or emollient oil phase. 
Mixtures of secondary emulsifiers actually may be preferred in certain 
embodiments, where the need is to provide better interaction between the 
oil and water phases. Secondary emulsifiers have been advantageously used 
in the present invention where the neutralizing agent is or contains at 
least one phosphate or carbonate salt, or where the oil is a synthetic 
ester or more polar oil. One of ordinary skill in the art may readily 
determine the type of emulsifier or emulsifying system (group of 
emulsifiers) which may be used in the water-in-oil emulsions according to 
the present invention. A secondary emulsifier is used in the present 
invention in an amount effective to aid or promote emulsification of the 
water phase and oil phase ("emulsification effective amount"). As a 
general rule, the amount of secondary emulsifer which is included in 
compositions according to the present invention ranges from about 0.01% to 
about 10% by weight, more preferably about 0.1% to about 5.0% by weight of 
the final emulsion composition. In emulsion compositions according to the 
present invention, where secondary emulsifiers are optionally included, 
the weight ratio of 12-hydroxystearic acid esters to secondary emulsifier 
ranges from about 20:1 to about 1:20, more preferably about 10:1 to about 
1:1. 
Exemplary secondary emulsifiers for use in the present invention may be any 
cosmetically acceptable oil soluble non-ionic or anionic (and in rare 
instances quaternary or amphoteric) surfactant which has a hydrophilic 
group ("tail") at one end of the molecule, of which polyethylene glycol 
1500 dihydroxystearate (Arlacel P135.RTM., available from ICI Americas, 
Inc) and diethanolamine cetyl phosphate (Amphisol.RTM., available from 
Givaudin-Roure, division of Roche, Inc.) are particularly preferred, 
although a large number of other secondary emulsifiers may be used in the 
present invention. One of ordinary skill will understand to include one or 
more secondary emulsifiers in emulsion compositions according to the 
present invention in order to facilitate and enhance interaction of the 
water and oil phases. 
In addition to 12-hydroxy stearic acid ester compounds, an oil, water and 
neutralizng compound, the emulsion compositions may also comprise, in 
amounts totalling up to about 25% by weight of the total emulsion 
composition, preferably comprising about 0.001% to about 10% by weight, 
even more preferably no more than about 5% by weight within this range, of 
one or more optional additive selected from one or more secondary 
emulsifier, fragrances, preservatives, anti-oxidants, vitamins, pigments, 
conditioning agents, among numerous other standard cosmetic additives. 
12-Hydroxy stearic acid ester compounds according to the present invention 
are generally made by reacting 12-hydroxy stearic acid with another 
carboxylic acid (depending upon the length and degree of unsaturation of 
the carboxylic acid which is reacted to form the ester group at the 12 
hydroxyl position) in the presence of an effective amount of a catalyst 
(the amount can range from 0.005% to 1% or more by weight of the 
12-hydroxy stearic acid and other carboxylic acid reactant used) such as 
dibutyl tin oxide or tin oxalate, among numerous others. In a preferred 
method, stoichiometric amounts (i.e., a 1:1 molar ratio) of the reactants 
are combined with the catalyst in a reaction chamber which will allow 
ample heat to be added to the mixture (the temperature of the reaction may 
vary depending upon the rate of reaction desired, but will preferably be 
above about 200.degree. C.) and water to be removed (as the esterification 
reaction proceeds). The reaction mixture is heated until a desired 
saponification value is obtained evidencing completeness of the reaction. 
Upon cooling the reaction mixture, the stearic acid ester compound is 
readily separated from impurities, by extraction, fractionation (under 
reduced pressure), simple crystrallization or related techniques which are 
all well known in the art. Preferably, the stearic acid ester is obtained 
in quantitative or near quantitative yields. 
Emulsion compositions according to the present invention may be made by 
mixing the individual components in any order at elevated temperature, but 
are preferably made by first preparing the oil phase and water phase at 
elevated temperature (preferably, above about 70-75.degree. C., more 
preferably above about 85.degree. C.) separately, then combining the oil 
phase with the water phase also at an elevated temperature (preferably, by 
adding the water phase to the oil phase) such that the oil phase remains 
soluble within itself during mixing. Generally, the temperature at which 
mixing is effected is preferably at least about 50.degree. C., more 
preferably at least about 65 to 75.degree. C., even more preferably at 
least about 75 to 85.degree. C., and most preferably at least about 
85.degree. C. These are temperatures which are generally effective to 
allow the oil phase to remain soluble within itself (at a temperature 
wherein the oil phase remains clear and in a solution) during mixing. 
After mixing for at least about 10-15 minutes, more preferably at least 30 
minutes or more (depending upon batch size) at elevated temperatures, the 
mixture is then cooled before use and/or packaging. Mixing is generally 
performed in a simple propeller mixer with vortex formation without the 
application of high shear force. Although one could use higher mixing 
speeds, the self-emulsifiers which are used make mixing the compositions 
relatively easy. All components may be mixed together in a one pot 
preparation, or one or more components (such as the oil phase, water phase 
or emulsifier) may be prepared separately and then combined. In preferred 
embodiments, after the separate water and oil phases are prepared, the 
water phase is added to the oil phase and the combined phases are mixed 
thoroughly for maximum result. It is noted that the preferred method for 
making the present composition comprises first making the water and oil 
phases separately, preferably adding the water phase to the oil phase, 
followed by mixing the phases together, all at elevated temperature. 
Alternatively, it is possible to separately mix the individual components 
in a single pot preparation or prepare the complex of the stearic acid 
ester compound and the neutralizing compound before it is added to the oil 
and/or water phases. 
It is noted that the 12-behenoyl stearic acid (BSA, also known by the names 
12-(behenoyloxy)stearic acid and 12-(decosanoyloxy)octadenaoic acid ) is 
more efficient at producing an emulsion with non-polar oils (such as 
mineral oil or petrolatum) or emollients than it is with polar oils (such 
as fatty esters, etc.) or emollients. In certain instances, when utilizing 
polar oils or emollients, either alone or in combination with a non-polar 
oil, at least one additional secondary or helper emulsifier may be 
advantageously added to produce a superior emulsion composition. In 
certain embodiments, therefore, the inclusion of a secondary emulsifer may 
be advantageously employed. Preferred secondary emulsifiers for inclusion 
in the present emulsion compositions include for example, 
polyethyleneglycol 1500 dihydroxystearate (Arlacel P135.RTM..sup.m, 
available from ICI Americas, Inc.) and diethanolaminecetyl phosphate 
(Amphisol.RTM., available from Givaudin-Roure), in amounts generally 
ranging from about 0.01% to about 10% (up to aobut 20% by weight of the 
final emulsion composition), more preferably about 0.1% to about 5%, by 
weight of the final emulsion composition. 
Emulsion compositions according to the present invention have inversion 
temperatures of at least about 40-45.degree. C., preferably at least about 
50.degree. C., more preferably at least about 60.degree. C. or higher. 
Inversion temperatures of at least about 65 .degree. C. may be 
particularly preferred. The higher the inversion temperature of an 
emulsion composition according to the present invention, generally, the 
more stable is the emulsion composition. 
Having generally described the invention, reference is now made to the 
following examples which are intended to illustrate preferred embodiments 
and comparisons but which are not to be construed as limiting to the scope 
of this invention as is more broadly set forth above and in the appended 
claims.

EXAMPLES 
Example I 
Synthesis of 12-Behenoyl Hydroxystearic Acid (BSA) 
Materials 
1 mole Behenic acid 
1 mole 12-Hydroxy Stearic acid 
0.1% w/w Dibutyl Tin Oxide (Based upon total weight of reactants). 
Procedure 
In a glass vessel, equipped with proper mixing and a water trap to collect 
water, combine all ingredients. Mix and heat at 200.degree. C. until 
desired saponification value, hydroxyl value and acid value are achieved. 
______________________________________ 
Typical Assay for BSA 
sap value = 161.5 
acid value 104.5 
hydroxyl value = 
7.5 
color (melted) = 
gardner 2+ 
melting point = 
68.degree. C. 
______________________________________ 
BSA is the common cosmetic label name. BSA also goes by the names 
12-(behenoyloxy)stearic acid and 12-(decosanoyloxy)octadenaoic acid. 
Example II 
Water-in-Oil Flowing Lotion Based Upon Non-Polar Oils 
The following components were combined in two separate phases, phase A, the 
oil phase and phase B, the water phase. After complete mixing of 
components to produce each sof the individual phases in the amounts as set 
forth below, the two phases are combined under elevated temperature 
(85.degree. C.) and mixing to produce a flowing lotion. 
______________________________________ 
Weight % 
______________________________________ 
Phase A: "BSA" 2.3 
(heat to 85.degree. C. 
White Petrolatum 
10.0 
and mix) 53.2 neral oil 
0.1 
Phase B: 33.3 ed 
1.1 
100.0% 
total 
______________________________________ 
The procedure used was as follows: 
Phase B was added to phase A @85.degree. C.--the combined phases were mixed 
and cooled without aeration to 45-50.degree. C.--package. 
Note: In the case of this emulsion, the "BSA" is the primary and only 
emulsifier used. The use of about a 5:1 ratio of mineral oil to petrolatum 
produced a free-flowing lotion. 
Kaydol- type of mineral oil obtained from Witco, Inc. 
Example III 
Water-in-Oil Cream Based upon Polar and Non-Polar Oils 
The same procedure which was followed for Example II was also followed 
here, except that phase C was added after phases A and B were thoroughly 
mixed. 
______________________________________ 
Weight % 
______________________________________ 
Phase A: "BSA" 2.30 
(heat to 85.degree. C. 
DiBehenyl Fumarate (1) 
8.00 
and mix) White Petrolatum 
10.00 
Mineral Oil (Kaydol) 
33.45 
Di-2-Ethyl Hexyl Fumarate (2) 
10.00 
DEA Cetyl Phosphate (amphisol) (3) 
0.50 
Propyl Paraben 
0.10 
Phase B: Water, deionized 33.30 
(heat to 85.degree. C.) 
Borax 
1.10 
Phase C: Fumed SiO.sub.2 (cabosil) 
1.25 
(add to emul- 100.0% total 
sion at 75- 
80.degree. C.) 
______________________________________ 
(1) obtained by reacting 2 moles behenic alcohol with 1 mole fumaric acid 
using standard ester manufacturing procedures (heated at 160-180.degree. 
C. with 10% by weight of the reactants of a catalyst such as tin oxalate 
or dibutyl tin oxide) in standard manufacturing equipment until an 
appropriate SAP value is reached. 
(2) commercial as Bernel Ester 284 (Bernel Chemical Co., Englewood, New 
Jersey) 
(3) Amphisol available from HoffmannLaRoche, Nutley, New Jersey. 
Procedure 
Add B to A at 85.degree. C. Mix without aeration. Cool and add C at 
75-80.degree. C.; continue to mix until homogeneous and cool to 
approximately 55.degree. C. Package at 55.degree. C. 
Note: the "BSA" from example 1 is the primary emulsifier, however, this 
emulsion uses 2 auxilliary emulsifiers with "BSA". They are amphisol and 
cabosil. The di-behenyl fumarate is a "thickener" in this composition. 
Example IV 
Synthetic Water-in-Oil Cream Based upon Polar Oils 
The same procedure which was followed for Example III was essentially also 
followed here, with minor variation. 
______________________________________ 
Weight % 
______________________________________ 
phase A: 
"BSA" 2.30 
(mix at Di Behenyl Fumarate (1) 
8.00 
85-90.degree. C.) 
Di-C.sub.12-15 Alkyl Fumarate (2) 
10.00 
Di-Decyl Tetra Decyl Fumarate (1) 
28.45 
(Octyl Dodecyl NeoPentanoate) 
ELEFAC I-205 
15.00 
DEA Cetyl Phosphate (Amphisol) (3) 
0.50 
Propyl Paraben 
0.10 
phase B: 
Water, deionized 
33.30 
(mix at Borax N.F. 
1.10 
85-90.degree. C.) 
phase C: 
Fumed SiO.sub.2 (cabosil) 
1.25 
total 100.0% 
______________________________________ 
(1) obtained as per example III; 
(2) commercial as Marrix SF (Bernel Chemical Co., Englewood, New Jersey; 
(3) HoffmannLaRoche 
Procedure 
Add B to A at 85.degree. C. and mix without aeration. Continue mixing while 
slowly adding C. Mix and cool to 50.degree. C. Package. 
Example V 
Comparison of Related Water-in-Oil Emulsion Compositions 
A number of compositions were made to determine the levels of stearic acid 
ester at which stability is affected. The influence of mineral oil and 
petrolatum on stability was also determined. The results appear in Table 
1, below. The compositions were made following the general procedure set 
forth in Example II, above. Essentially, the components of the oil phase, 
the behenyl stearic acid ester (BSA), the mineral oil and where 
applicable, petrolatum were combined in a phase A at elevated temperature 
(phase A also contained 0.1% by weight of propyl paraben dissolved in 
phase A as a preservative). To this phase A was added phase B, which 
included water and the Borax NF, also at elevated temperature 
(approximately 85 .degree. C.). The inversion temperature was determined 
by establishing at which temperature emulsion formation occurred (mixture 
becomes smooth and shiny evidencing the absence of two phases). 
TABLE 1 
__________________________________________________________________________ 
Inversion 
Example 
% BSA 
% Borax NF 
% Water 
% Mineral Oil 
% Petrolatum 
Temp. (.degree. C.) 
__________________________________________________________________________ 
1 2.3 1.1 33.3 40.0 23.3 &gt;68.degree. C. 
2 50.0 
42.5 
56-52.degree. 
3 65.1 
23.1 
46-43.degree. 
4 17 
&gt;68.degree. C. 
__________________________________________________________________________ 
BSA-12-Behenoyl Stearic Acid 
All % are % by weight of the total emulsion composition. 
Inversion Temperaturetemperature at which stable emulsion occurs 
pH's of the compositions are approximately 8.4. 
Conclusion 
1) As the percent by weight of BSA was increased, the amount of water which 
could be included within the composition and still form an emulsion 
increased. Likewise, as the amount of water incrases, the inversion 
temperature tends to decrase significantly. 
2) The highest percent by weight of water which can be included in the 
emulsion compositions is approximately 75%. 
3) The lowest percent by weight of water which can be included in the 
emulsion compositions is approximately 10%. 
Note- In example 2 on the chart of Table 1, all ingredients alternatively 
alternatively were mixed together initially at room temperature 
(20-25.degree. C) in a single pot method. The mixture was heated and mixed 
to 85.degree. C., then with mixing and cooling, we obtained the same 
inversion temperature (56-52.degree. C.) obtained by forming the emulsion 
by mixing two phases together at elevated temperature. This approach 
represents an alternative embodiment of the method of making the emulsions 
according to the present invention. In large production batches, the 
inventor believes that the water phase and oil phase should be prepared 
separately, preferably at a temperaturem of about 85.degree. C. and then 
the water phase should be added to the oil phase at the elevated 
temperature in order to increase the solution of any compounds which might 
be insoluble in one of the phases. 
Example VI 
Mineral Oil System 
The following components were combined in two separate phases, phase A, the 
oil phase and phase B, the water phase. After complete mixing of 
components to produce each of the individual phases in the amounts as set 
forth below (at 80.degree. C., with mixing), the two phases are combined 
under elevated temperature (80.degree. C.) and mixing to produce a flowing 
lotion. 
______________________________________ 
Weight % 
______________________________________ 
Phase A: "BSA" 5.0 
(heat to 80.degree. C. 
(Kaydol) Mineral oil 
42.5 
and mix) 0.1 
Phase B: 50.0 
2.4 
total0.0% 
______________________________________ 
The procedure used was as follows: 
Phase B was added to phase A @80.degree. C.--the combined phases were mixed 
and cooled without aeration to 40.degree. C.--package. 
Note: In the case of this emulsion which used the non-polar mineral oil, 
the "BSA" is the primary and only emulsifier used. 
Kaydol--type of mineral oil obtained from Witco, Inc. 
Example VII 
Petrolatum Cream 
The following components were combined in two separate phases, phase A, the 
oil phase and phase B, the water phase. After complete mixing of 
components to produce each of the individual phases in the amounts as set 
forth below (at 80.degree. C., with mixing), the two phases are combined 
under elevated temperature (80.degree. C.) and mixing to produce a flowing 
lotion. 
______________________________________ 
Weight % 
______________________________________ 
Phase A: "BSA" 4.5 
(heat to 80.degree. C. 
Petrolatum USP 
47.75 
and mix) 0.1 
Phase B: 45.50 d 
2.10 
total0% 
______________________________________ 
The procedure used was as follows: 
Phase B was added to phase A @80.degree. C.--the combined phases were mixed 
and cooled without aeration to 40.degree. C.--package. 
Note: In the case of this emulsion which used the non-polar mineral oil, 
the "BSA" is the primary and only emulsifier used. 
Example VIII 
Suntan Lotion-SPF 30 Waterproof 
The same procedure which was followed for earlier examples was essentially 
also followed here, with minor variation. 
______________________________________ 
Weight % 
______________________________________ 
phase A: "BSA" 4.0 
(mix at Di Behenyl Fumarate (1) 
3.0 
80.degree. C.) 
Arlacel P135 .RTM. 
2.0 
Capryl isostearate 
21.6 
Beantree .TM. (2) 
ELEFAC I-205 (3) 
10.0 
Octyl Methoxy Cinnamate 
7.5 
Octyl Salicylate 
5.0 
Oxy Benzone 
5.0 
Propyl Paraben 
0.1 
phase B: Water, deionized 
40.0 
(mix at Borax N.F. 
1.8 
80.degree. C.) total 100.0% 
______________________________________ 
(1) obtained as per example III; 
(2) commercial as Beantree from Bernel Chemical Co., , Englewood, New 
Jersey; 
(3) Bernel Chemical Co. 
Procedure 
Add B to A at 80.degree. C. and mix without aeration. Cool to 40.degree. C. 
Package. 
Example IX 
Lotion Base Using Phosphate Salt as Neutralizing Agent 
The same procedure which was followed for the earlier described examples 
was essentially also followed here, with minor variation. 
______________________________________ 
Weight % 
______________________________________ 
phase A: "BSA"(1) 5.0 
(mix at 80.degree. C.) 
Arlacel P-135 
5.0 
Capryl Isostearate (2) 
20.0 
Dibehenyl fumarate (3) 
3.0 
phase B: Water, deionized 
61.9 
(mix at Disodium Acid Phosphate 
5.0 
80.degree. C.) 
(Na.sub.2 HPO.sub.4) 
Phase C: Kathon CG (4) 
0.1 
total100.0% 
______________________________________ 
(1) obtained as per example III; 
(2) commercial as Beantree (Bernel Chemical Co., Englewood, New Jersey); 
(3) commercial as Marrix 222 .RTM. (Bernel Chemical Co., Englewood, New 
Jersey); 
(4) Rohm & Haas. 
Procedure 
Add B to A at 80.degree. C. and mix until uniform. Cool to 70.degree. C. 
and add Phase C. Continue mix and cool to 35-40.degree. C. Package. 
Example X 
Petrolatum Cream Base Using Carbonate Salt as Neutralizing Agent 
The same procedure which was followed for earlier examples was essentially 
also followed here, with minor variation. 
______________________________________ 
Weight % 
______________________________________ 
phase A: "BSA" 4.5 
(mix at 3.0 umarate (1) 
80.degree. C.) 
Arlacel P-135 .RTM. 
2.0 
0.1 
44.3 
phase B: 44.1 
(mix at 1.0 
80.degree. C.) 
NaHCO.sub.3 
1.0 
total00.0% 
______________________________________ 
Procedure 
Add B to A at 80.degree. C. and mix until uniform. Continue mix and cool to 
40.degree. C. Package. 
It is to be understood by those skilled in the art that the foregoing 
description and examples are illustrative of practicing the present 
invention, but are in no way limiting. Variations of the detail presented 
herein may be made without departing from the spirit and scope of the 
present invention as defined by the following claims.