STABLE MULTIPLE EMULSIONS

EMULSIONS MULTIPLES STABLES

English Abstract

Abstract
Stable multiple emulsions, containing an emul-
sifier mixture comprising
- a first, hydrophobic emulsifier (emulsifier A),
or a mixture of several such emulsifiers, having
the following properties:
- it must be very readily soluble in the oil
phase of the emulsion at the preparation
temperature of the emulsion
- it must not be soluble in water to give an
isotropic solution below approximately 50°
- it must be soluble in water to give an
isotropic solution in the temperature range
between approximately 50° to the preparation
temperature of the emulsion and
- it must act primarily as a w/o emulsifier in
the temperature range between approximately
50° to the preparation temperature of the
emulsion
- and a second, hydrophilic emulsifier
(emulsifier B), or a mixture of several such
emulsifiers, having the following properties:
- it must be soluble in water to give an
isotropic solution
- its solubility in the temperature range
between approximately 50° to the preparation
temperature of the emulsion must be essen-
tially stable.

Claims

- 27 -
Patent Claims
1. Stable multiple emulsions, containing an emul-
sifier mixture comprising
- a first, hydrophobic emulsifier (emulsifier A),
or a mixture of several such emulsifiers, having
the following properties:
- it must be very readily soluble in the oil
phase of the emulsion at the preparation
temperature of the emulsion
- it must not be soluble in waker to give an
isotropic solution below approximately 50°
- it must be soluble in water to give an
isotropic solution in the temperature range
between approximately 50° to the preparation
temperature of the emulsion and
- it must act primarily as a w/o emulsifier in
the temperature range between approximately
50° to the preparation temperature of the
emulsion
- and a second, hydrophilic emulsifier
(emulsifier B), or a mixture of several such
emulsifiers, having the following properties:
- it must be soluble in water to give an
isotropic solution
- its solubility in the temperature range
between approximately 50° to the preparation
temperature of the emulsion must be essen-
tially stable.
2. Stable multiple emulsions according to Claim 1,
in which the emulsifier(s) A are soluble in an unpolar
oil to an extent of more than 0.01 % by weight, in
particular more than 5.0 % by weight, if an unpolar oil
is used, or in which the emulsifier(s) A are soluble in
a polar oil to an extent of more than 0.02 % by weight,
advantageously more than 20.0 % by weight, if a polar oil
is used.

- 28 -
3. Stable multiple emulsions according to Claim 1 in
which the hydrophobic emulsifier(s) A are selected from
the group comprising the glycerol ethers, polyglycerol
ethers, polyglycerol esters, methyl glucosides, sucrose
esters, alkyl polyglycosides, sorbitan esters, sorbitol
esters and isosorbide esters.
4. Stable multiple emulsions according to Claim 1 in
which the hydrophilic emulsifier(s) B are selected from
the group comprising glycerol ethers, polyglycerol
ethers, polyglycerol esters, methyl glucosides, sucrose
esters, alkyl polyglycosides, sorbitan esters, sorbitol
esters and isosorbide esters.
5. Stable multiple emulsions according to Claim 1,
in which the hydrophobic emulsifier(s) A are selected
from the group comprising
sorbitan oleate, sorbitan monostearate, Steareth-2,
glycerol monostearate, glyceryl oleate,
polyglycerol-4-isostearate, PEG-7-hydrogenated
castor oil, PEG-40-sorbitan monostearate, Laureth-4,
and the hydrophilic emulsifiers B from the group
comprising
Oleth-20, PEG-40-stearate, sucrose cocoate,
Trilaureth-4-phosphat, Gluceth-20, PPG-20-methyl glucose
ether, polyglycerol-3-stearate, polysorbate-120, sucrose
laurate, Ceteareth 20.
6. Stable multiple emulsions according to Claim 1,
containing
(a) at least one hydrophobic emulsifier of the general
formula
<IMG> (emulsifier A),
in which
R1 = C10-30-alkyl,
Q = methylene or carbonyl,
X = H or methyl,
Y = H or methyl,

- 29 -
Z = methylene or a single bond and
m = a number from 1 to 40,
and
(b) at least one hydrophilic emulsifier of the general
formula
<IMG> (emulsifier B)
in which
R2 = C10-30-alkyl
Q = methylene or carbonyl,
X = H or methyl,
Y = H or methyl,
Z = methylene or a single bond and
n = a number from 10 to 400,
with the proviso that the quotient n/m must be at
least 1.5,
and
(c) if appropriate, further emulsifiers,
is therefore according to the invention.
7. Stable multiple emulsions according to Claim 1,
characterised in that the emulsifier(s) A are selected
from the group comprising the polyoxyethylene fatty
alcohol ethers, in particular those of the general
formula
<IMG> (emulsifier A)
in which
R1 = C15-25-alkyl,
Q = methylene,
X = H,
Y = H,
Z = a single bond and
m = a number from 1 to 10.

- 30 -
8. Stable multiple emulsions according to Claim 1,
characterised in that the emulsifier(s) B are selected
from the group comprising the polyoxyethylene fatty
alcohol ethers, in particular those of the general
formula
<IMG> (emulsifier B)
in which
R2 = C15-25-alkyl,
Q = methylene,
X = H,
Y = H,
Z = a single bond and
n = a number from 10 to 400.
9. Stable multiple emulsions according to Claim 1,
characterised in that the emulsifier(s) A are selected
from the group comprising the polyoxyethylene fatty acid
esters, in particular those of the general formula
<IMG> (emulsifier A)
in which
R1 = C15-25-alkyl,
Q = carbonyl,
X = H,
Y = H,
Z = a single bond and
n = a number from 1 to 10.
10. Stable multiple emulsions according to Claim 1,
characterised in that the emulsifier(s) B are selected
from the group comprising the polyoxyethylene fatty acid
esters, in particular those of the general formula
<IMG> (emulsifier B)

- 31 -
in which
R2 = C15-25-alkyl,
Q = methylene,
X = H,
Y = H,
Z = a single bond and
n = a number from 10 to 400.
11. Stable multiple emulsions according to Claim 1,
characterised in that the concentration of the total of
emulsifiers A and B is between 0.5 and 15.0 %, relative
to the entire cosmetic or medicinal composition, and the
molar ratios of emulsifier A : emulsifier B are from
10 : 1 to 1 : 10, particularly advantageously 5 : 1 to
1 : 5, in particular 2 : 1 to 1 : 2, particularly
favourably 1.2 : 1 to 1 : 1.2.
12. Stable multiple emulsions according to Claim 1,
characterised in that Steareth 2 is selected as emul-
sifier A and Steareth 21 as emulsifier B, where a ratio
of emulsifier A : emulsifier B of 5 : 1 to 1 : 5 is
chosen and the total amount of this emulsifier system
relative to the total composition is between 1 and 10 %.
13. Stable multiple emulsions according to Claim 1,
characterised in that they contain vegetable oils con-
taining large amounts of linoleic acid glyceride, in
particular wheat germ oil, grape-pip oil, kukui oil,
safflower oil, and other oils which contain at least 5 %
by weight of linoleic acid glycerides, where the emul-
sions preferably contain 0.1 - 50 % by weight of such
oils or mixtures thereof relative to the total weight of
the composition.
14. Stable multiple emulsions according to Claim 1,
characterised in that they contain stearic acid and/or
hydroxyoctacosanyl hydroxystearate to an extent of 0.1 -
10 % by weight, in particular when the ratios by weight
of stearic acid and/or hydroxyoctacosanyl hydroxystearate
to each other are 10 : 1 to 1 : 10.
15. Process for the preparation of table multiple
emulsions according to one of Claims 1 - 14,

- 32 -
characterised in that the hydrophilic emulsifier(s)
(emulsifier B) are incorporated into the aqueous phase
and the hydrophobic emulsifier(s) (emulsifier A) are
incorporated into the oil phase, and the two phases are
then combined with each other.

Description

.~,.; ~f~r~
~eiersdorf Aktiengesellschaft . .
''..' ' '
Description ~.
Stable multiple emulsion~
The present invention relates to stable multiple
emulsions, to processe6 for their preparation, and to : :
their use for cosmetic and medical purpose~ :
Cosmetic skincare is mainly understood as meaning
the enhancement or re~toration of the natural function of
10 the ~kin as a barrier against impacts from the environ- ;
ment (for example pollution, chemicalR, microorganisms)
and against the 108~ 0~ the body~s own sub~tances (for
example~water, natural fats, electrolytes).
The disturbance o f this function may result in 15 increased resorption of toxia or allergenic substànces or
invasion of microorgani ms and,~as a consequence, toxic
:: or~allergic skin~reactions.
~ Another~aim~of skincare~is~to:~compensate for the
loss of fats and water, by the skin, caused~by daily
washlng.~This~is particularIy~important when~the natural
regeneration~capacity ~g insu~ficient. Skincare products
are~furthermore intended to protect again t impacts ~rom
:the~environment, in particular sun and wind,:~ànd~to delay
ageing of the~sXin. :~
;:25~ Mediaal topical~compositions~ generally contain I :
one ~or:~ mo~e pharmaceu~icals in an~ e~feGtive concen-
tration~To~differentiate~ clearly:~between~cosmetic~and
medic l~us;e and~the~corresponding~products,~mention~will
be~-~madq,~ or~simpliaity~ ~ake,~o~ the~legal~situation o~ : :
30~ th~ Féderal~`Republic~:of~Ger~any~;(;for~:example Kosmetik~
~e~roxd ~ ~ osmetics~ Act~]~ Leben mit el~ und~
A~rsnéimittelgesetz~ Foodstu~fs and Pharmaceutical Act]~ :
It~:is~ known ~that~:~mul~iple~èmulcion~ ca~ be
d~lstinguished,~; in~er :alia,~i~by a~par~i~cularly~delicate ;~
.~ThLn~property maken thom~outntandingly~nuitablc :~

- 2 ~
as a basis for both cosmetic and medical topical prepar-
ations. Wherea~ cosmetics are only applied externally,
all customary mean~ of administration, for exampl~ oral
formulations, are conceivable wh~n emulsions are used for
medical purposes~
A simple emulsion compri~es, in the one phase,
finely-disperse droplets of the second phase which are
surrounded by a layer of emulsifier (water droplets in
w/o emulsions, or lipid ve~icles in o/w emulsions). In
contrast, a multiple emulsion (second order) contains
more finely dispersed droplets of the first phase emul-
sified in said droplets. In these droplets, in turn,
there may exist even more finely dispersed droplets
tmultipl~ emulsion of the third order~, and so on.
In the case of the simple emulsions, the techni- -
cal terms used are w/o-emulsions or o/w-emulsions (water- -
in-oil or oil-in-water), and, in the case o~ the multiple
emulsions, w/o/w-, o/w/o-, o/w/o/w-, w/o/w/o-emul~ions,
and so on.
Multiple emulsions in which the particular
internal and external aqueous phases and internal and
external oil phase~ are of a different nature (for
example w/o/w~- and o/w/o~-emulsions) can be prepared by
two-pot pxocesses. Those emulsion~ in which the internal
and external water or oil phases are not of a di~ferent
nature can be obtained by both one- and two-pot
proces~e~.
The multiple emulsions of the~second order are
occa~ionally termed ~bimultiple systems", those of the
third~ order a3 "trimultiple systems", and so on
~W.Seifriz, "Studie~ in Emul~ions", J Phys.Chem , 29
(19~25) 7~38 ~- 749j.
Proces~es for the preparation of multiple
~emul~ions, are known per se to a per~on skilled in the
35 ~ art. For example~ there are two-pot proce8se~ in which a
simple~emulsion ~or example a w/o-emul~ion) i8 intro-
duaed and converted in~o a multiple emul8ion ( in this
case a w/o/w-emulsion~ by adding a further phase (in this
~` ~ . . ~,
;~
: 1.,, :.. ,.".

_ 3 _
case an aqueous phase) with a ~uitable emulsifier (in
this case an o/w-emulsifier).
A second process comprises the conversion of
emulsifier mixtures with an oil phas~ and an aqueous
phase into a multiple w/o/w emulsion by a one-pot
process. The emulsifiers are dissolved in ths oil phase
and combined with the a~ueous phase. The prerequisite for
such a process is that the HLB values (HLB = Hydrophilic-
Lipophilic Balance) of the individual emulsifiers used
differ substantially from each other.
The formula
HLB = 20 ' ( 1 - S/A)
provides the definition of the HLB value of polyol fatty
acid esters.
The formula
HLB = E/5
in which S = ~aponification number of the e~ter,
A = acid number of the acid recovered~
E = ethylene oxide in the total molecule (%)
applies to a group of emulsifieræ whose hydrophilic
- moiety i~ composed of ethylene oxide units only.
~ Literature: "Kosmetik - Entwicklung~ Herstellung und
Anwendung ko metischer Mittel~ [Co metics -
Development, Preparation and Use of cosmetic
preparation ]; W.Umbach (editor), Georg
Thieme Verlag 1988.
Hydrophilic emulsifiers (thosa having high HLB
values) are generally o/w-emulsifiers. Accordingly, -~
hydrophobic or lipophilic emulsifiers (those haviny low
30 HLB values) are generally w/o-emul ifiers~ -
~ ; Patent Specification US-A-4,931,210 describes a
; proce s for the preparation of a w/olw-emulsion, in which
;~ polyglycerol polyricino1éates are used as emulsifiers.
~ .
~: '
~ '', -' ' . ' - ' : ' .,' . ' ; ` " ~ ' ', ' ' . ' ~ ' ` ' ' ' '' , " ' . : ' '
- ,

~2 .~
Even though this show~ that multiple emulsions
are known per ~e and that simple processes ~or ,their
prepar,~tion certainly exist, there has therefore ~een to
date a lack of those systems which are microscopically
stable. This i5 to be under~tood a~ meaning that the
multiple emulsions uf the prior art gradually undergo
change~ and result in a simple emulsion, that is to say
that ~heir storage sta~ility with respect to multiplicity
is poor~ This is particularly disadvantageou~ since the
droplet size distribution of these conversion products is
extremely inhomogeneous.
Such conversion products are, at their best,
aesthetically unsatisfactory or inelegant from ~he
cosmetic point of view. ~owever, inhomogeneous size
distribution of the droplets is frequently also combined
with insufficient macroscopic stability, that is to say
the ~tability to decomposition into separate phases.
From thi~ point of view, the conventional mul-
tiple emulsions have also always left something to be
desired.
Unles3 otherwise indicated, the term "stability"
in this Paten~ Application i~ therefore ~o be understood
as meaning microscopic and macroscopic ~tability with
equal importance.
- 25 It was therefore an object of the pre ent inven-
tion to provide stable multiple emulsions and to
eliminate the shortcomin~s of the preparations of the
prior art.
It wa~ furthermore an object of the invention to
develop processes which allow multiple emulsion having
the de~ired advantageou~ proper~ies to be prepared in a
simple and targeted manner.
Surprisingly~ it has now been show~, and this is
the achievement of the object, that stable multiple
emulsions are obtained when an emul~ifiex mixtura is
u~ed,j comprising
- a first, hydrophobia emulsi~ier (emulsifier A),
or mixture of everal 3uch emulsifiers, having
.
.:
I j.', .

- s
the following properties:
- it must be very readily soluble in the oil
pha~e of the emul~ion at the preparation
temperature of khe emulsion
- it must not be solu~le in water to give an
isotropic solution below approximately 50
- it must be soluble in water to give an
isotropic solution in the temperature range
between approximataly 50 to the preparation
temperature of the emulsion and
- it must act primarily as a w/o emulsifier in
the temperature range between approximately
~- 50 to the preparation temperature of the
emulsion
- ~and a second, hydrophilic emulsifier
(emulsifier B~, or a mixture of several such
emulsifiers, having the following properties:
- it must be solubIe in water to give an
isotropic 801ution
its solubility in the temperature range
between approximately 50 to the preparation
temperature of the emulsion must be e sen-
tially~stable.
Such an emul~ifier mixture can be used, in par-
- 25 ticular, for preparing:advantageous w/o/w-emulsion~.
: The emulsi~iers a~e advantageously chosen in such
a way that the hydrophilic emulsifier uses the hydro-
phobic emulsifier at~the phase inversion point, that is
to~say so that it act~ as a wetting agent for the oily : -
phase and make~ the formation of an in-~itu multiple
emul3ion in a vne-~t~ep proces~ po~sible in the:`first
plac~
::It is furthexmors~advantageou~ if em~lsi~ier: A
and;~emulsifier B: can form:~ a~ joint liquid-cry talline
35~ phasQ~whiah forms the inter~ace of the emuIsion drop1ets.
Particularly advantageou~ emulsIfier mixtures are
those~;in which the: hydrophobic emulsi~ier~s~ A are
lUb~ n an UnPlaF:oil:nt th~ prGce 9ing temp
:: ~ : ~ : : : I . .

- 6 ~ $ ~
typically approximately 70C, to an extent of more than
0.01 % by weight, advantageously more than 5.0 % by
weight, if an unpolar oil i5 used, or in which the
emulsifier(s) A are soluble in a polar oil to an extent
of more than 0.02 % by weight, advantageously more than
20.0 % by weight, if a polar oil is used.
The advantageous concentrations of emulsifier A
in an lnpolar oil may deviate from 5.0 % by weight in
individual c~ses if the critical micelle formation
concentration (CMC) in this oil deviate~ markedly from
the 5.0 % by weight which have been assumed a~ a guide
value. ~ critical micelle formation concentration is not
( observed in polar oil~.
Examples of unpolar oil~ are mineral oils, that
i~ to say tho~e which are di~tinguished by a low content
of components having polar molecule groups.
Examples of polar oil~ are vegetable oil~ (for
example maiæe germ oil and wheat germ oil) or their
synthetic and part-~ynthetic equivalents, and similar
~il , that i~ to say those which are distinguished by a
higher content of component~ having polar molecule
groups, for example ester or ether groups.
This Patent Application distinquishes between
isotropic solubility and anisotropic solubility, since
the conventional terms of solubility can only be applied
with difficulty to surfactant~l A substance i~ iso-
tropically soluble in another substance if it forms a
true solution in thi~ substance without the formation o~
micelles or other formation of aggregates which can be
detected by means o~ light-microscopic methods- A
substance i~ ani-qotropically soluble in another substance
if it is soluble in this sub3tance, for example ccl-
loidally soluble, with the foxmation o~ micelles or the
~ormation o~ other a~gregates which can be detected by
means of light-micro~copic methods~
The hydrophobic emulsifier~ A can be ~elected
advantageously from the group compri ing the glycerol
ether~, for example
! ~
. . .. . .,, . . . . .. - , .. . , ~. , . ' .. ... - ., -. ..... - . .... .

7 ~ 2 ~ ~ ~ r3 ~ ~
H2~C-O-R 1
H-C-û-R2
H2-C-O-R
and polyglycerol ethers, where tha radicals Rl-s represent
H or a saturated or unsaturated or~anic radical,
polyglycerol esters, for example
H2~0~X~C-R 1
H~C-O~X-C R2
H2C
O
H2~
,' I .
H~C~O-X-C-R~
H2C-o-X-C-R4 ~diglyceryl ester),
,
:
.
~, ,
':
~;
i~ ~
.~. :
..;:
:
: .
,,: :

- 8
H2C-O~X-C~R 1
H'C -O-X-C-R~
.
H;2C
o
~2~
I
~-c~o-X c R3
., .
H2 I ~:
O
. .
H2~
:
H-C-o-X-C-R4
~2C~O-X-C-RS (triglyceryl ester),
where R~-5, as i6 known to a person ~killed in the art,
independently of one another can represent H or a satur-
ated or unsaturated organic radical, and X can repre~ent
S a ingle bond or a carbonyl radical,
as well a~ methyl gluco~ides, sucrose esters, alkyl
polyglycosides, sorbitan ester~, sorbitol esters j iso-
sorbide esters. For the abovementioned classes of emul-
~i~iers, ~ee "Lexikon der ~ilf~stof~e fur Pharmaziet
Ko~metik und angrenzende Gebiete" tDictionary of
Au~iliaries in Pharmacology, Cosmetics and Related
Field ]: ~.P.Fiedler, Editio C~ntor Aulandorf, Third
Edition, 1989~ for the cor~e~ponding entrie~, and, if
appropriat~, parallel references a~d cross-refer~ce~.
: 15 Wh t~is dis~losed under these entrie~ in t~i~ dictionary
inalud~d in th~ di~closure~ of the present Patent ~:
Application~ ~
It i~ advantageous to s~lect repre~enta~ives of - :
the::abovemsntioned classes of emulsifiers which, i~ they `~
~' ~: ' : . ;"

- 9 - 2~ ,r~
are in ester form, contain mainly saturated fatty acid
radicals or which, if they are in ether form, are derived
from saturated fatty alcohols, that i8 to sa, for
example, this means for the glycerol ethers and poly-
glycerol ethers which have been listed above ~y way ofex~mple that, if Rl-s do not represent a hydrogen radical,
they ~hould represent saturated hydrocarbon radicals. The
same applies to the other abovementioned classes of
emulsifiers.
Particularly advantageous i~ the use of those
hydrophobic emulsifiers which are solid at room
temperature
The hydrophobic emulsifiers are particularly
advantageously selected from the group comprising
sorbitan oleate, sorbitan monostearate, St0areth-2,
glycerol monostearate, glyceryl oleate,
polygly~erol-4-isostearate, PEG-7-hydrogenated
castor oil, PEG-40-sorbitan monostearate, Laureth-4.
Emulsifier(s) B ca~ also expediently be s01ected
from the e substances, but it must be ensured that
emulsifier(~) B have the solubility propertie~ demanded
ak the outset.
The hydrophilic emul~ifiers B are particularly
advantageously selected from the group compriqing
Oleth-20, PEG-40-~tearate, ~ucro~e cocoate,
Trilaureth-4-pho~phate, Gluceth-20, PPG-20-methyl gluco~e
ether, polyglycerol-3-stearate, polysorbate-120, su~rose
lauxate, Ceteareth 20.
Stable multiple emulsions are also obtained
according to the invention, and this i a further ad-
vantageous embodiment of the present invention, when an
emulsifier mixture i~ u~ed in which the hydrophobic
emulsifier A and the hydrophilic emul~ifier B represent
ethoxylated products. An emulsifier mixture compri~ing
(a) at~least one emulsifier of the general formula
H H
R1-~-0-(C-C-~-O-)m-H
X Y ~emul3ifier Al~
:
,
!i
~ . ; .. . ,~ ;, ", . ;, . ..

10 ~ 3
in which
:E~ = Cl0 30-alkyl,
Q 3 methylene or carbonyl,
X - H or methyl,
Y = ~ or methyl,
Z = methylene or a ~ingle bond and
n = a number from 10 to 40,
and
(b) at least one emul~ifier of the general formula
H H
R~-Q-O~tC-C-z-o-~ -H
n (emul~ifier B)
in which
R2 - C10 30-alkyl
Q = methylene or carbonyl,
X = H or methyl,
Y - ~ or methyl,
Z Y methylene or a -~ingle bond and
m = a number from 1 to 400,
with the proviso that the quotient n/m must be at
least 1.5,
and
(c) if appropriatet further emulsifiers,
(, i8 there~ore according to the invention.
It is advantageous to select the emulsi~ier(s)
from the group comprising the polyoxyethylene fatty
25 alcohol ether~; in thi~ case, these emulsifierc .-
preferably have the general formula - -
.
.
~ R~ 0~[C-C~-Z~ 'H (emulsifier A)
~X Y
; in which
- C~030-alkyl, .
:3~0~ Q = methylene,
. .

Z = a single bond and
m - a n~mber from 1 to 20.
In this case, particularly preferred emulsi-
fiers A are those in which
Rl = C~s2s-alkyl,
Q = methylene,
X = H,
y a H,
Z = a single bond and
m = a number from 1 to 10.
~owever~ emulsifier(s) A can also advant~geously
be selected from the group comprising the polyoxyethylene
( fatty acid esters; in this case, th~se emulsifiers
preferably have the general formula
H H
Rl-Q-0-(C-C-Z~0-)m-H (emulsi~ier A)
X Y ' ,' '`
in which
R1 = C1030-alkyl,
Q = carbonyl,
X - H,
Y = Hl
Z - a sin~le bond and `
m a a number from 1 to 20.
In this case, parti~ularly preferred emulsi-
f;ers ~ are those in which . :~
Rl - Cls2s-alkyl,
Q = carbonyl,
X ~ H~
Y = H,
: Z = a;singl~ bond and
3a :~ ~ m - a number ~rom ~1 to 10
E~ul ifier(s) B are preferably selected from the ~ :
; group~ comprising the :pQlyoxyethylens fatty alcobol
ethors, in:this case, th~ e emul ifiers preferably have
the;general ~ormula
:
,

- - 12
H H
R2-Q-O-(C-C-2-O~n~H (emulsifier B)
X Y
in which
R2 = Cl0 30-alkyl,
Q = methylenP ~
. X = ~I, -
!i! = H ~
Z = a single bond and
n - a number from lO to 400.
In this case, particularly preferred ~mul~i-
fiers B are those in which
~2 - C15-25-alkYl ~ .
Q - methylene,
X = IEI, :
Y = ~,
Z - a single bond and
n - a number from 10 to 400.
Elowever, emulsifier(s) ~ can also advantageously
be ~elected from the group comprising the polyoxyethylsne
fatty acid ester~; in this ca~e, these emulsifier~
preferably have the general formula
( 2 H H .;
R -Q-O- (C-C-Z~O~) -H (emulsifier B)
in which
~2 = C~0 30-alky~
Q a carbonyl,
2 5 X = H ~ ~ ~
Y = ~ . ~. - ''. .
Z = a single bond and
m = a number frolll 10 to 400.
In thi case,, partic:ularly preferred emulsi-
30 ~iers B: are those in which
:
= C~5 25 al~y~
Q = carbonyl,
:-
:
.:, ~ ' " ' ~ ' ' . ' . ' , . !;

- 13 -
X = H,
Y = ~,
Z = a single bond and
n = a number from 10 to 400.
However, it-may also be advantageous to mix tho~e
above~escribed emulsi~iers A which do not represent
ethoxylated products with those emulsifiers B which
represent ethoxylated product~, if the physical proper-
~ies of the emul~ifiers meet the requirements.
Furthermore, it may also be advantageous to mix
those abovedescribed emulsifiers B which do not represent
ethoxylated products with thosie emul~ifiers A which
- represient e~hoxylated products if the physical properties
of the emulsifiers meet the requirement~.
Multiple emulsions in which the emulsifiers A
and/or B are emulsifier~ of the Steareth type are re-
garded as advantageous composition according to the
present invantion. Steareth emulsifiers are hvailable,
for example, under the tradename Brij~ (Atlas-Chemie).
The emulsifier ~ystem Steareth-2 (emulsifier A)
and Steareth-21 (emulsifier ~) has proved to be par-
ticularly advantageous.
Steareth-2 i9 POE-(2)-stearyl alcohol, that is to
say, a stearyl alcohol which is ethoxylated with two
ethylene oxide units.
Steareth-21 is POE-(21)-stearyl alcohol, that is
to ~ay, a ~tearyl alcohol which is ethoxylated with
21 ethylene oxide unit~.
Stable multiple emulsions comprising the above-
designated emulsi~iers which are described in greaterdetail in the claims and the cu~tomary ~cosmetic or
medici~al components and, if appropriate, ~ur her emulsi-
~iers and~or auxiliarie and/or additives are~therefore ;
~accordi~g to the invention. ~ ~
; ~ 35; ~ The concentration of the total of emulsifiers Aand B ~i~ preferably b~tween 0.5 and 15.0 %, relative to
th~entire co~metic or medicinal compo~ition.
:: .
.
i
. . ~ .

- 14 - f~
The molar ratio~ of emulsifier A : emulsifier B
can advantageously be from 10 : 1 to l : 10, particularly
advantageously 5 : 1 to 1 : 5, in particular 2 : 1 to
1 2, preferably 3 : 2 to 2 : 3, very particularly
5preferably 1.2 : 1 to 1 : 1.2.
I~ perc~ntages are mentioned in this Patent
Application, these are always to be understood as meaning
percentages by weight unless specifically mentioned
otherwi.se.
10It is advantageous to employ a mixture of
Steareth-2 : Steareth-21 in a ratio of 5 ~ 1 to 1 : 5.
The most favourable total amount of this emul~ifier
~ystem relative to the total composition i3 between 1 and
10 % in this embodiment.
15Very particularly advantageous are compositions
which contain, in addition to the compositions according -: :
to the invention, linoleic acid glycerides (trivial name :-
for glycerol linoleates).
It is also advantageou~ to u8e vegetable oils ~-
which contain large amounts of linoleic acid glycerides.
Surpri~ingly, the effect of the veg~table oils,
or of the l~noleic acid glycerides~ consists in par- :
ticular in the fact that they influence the microscopic
structure of the multiple emulsion~ according to the ~ .-
invention in an advantageou~ manner, they lead to a
reduction in size of the droplet~ of the multiple emul-
sion and to an increased multiplicity of the ~ystems.
The linoleic acid glycerides, reprPsented herein-
after in their Fischer projectio~, are to be under~tood
as meaning the following:
The glycerol monolinoleate~ (glycerol 1-mono- :
linoleate has two optical isomers):
~,:
.. ..
:
.
:-.
1: . :

` - 15 - 2 ~6
H2C O~H
,
H-C-O-L
. ' .
H2c-o-H
H2~-o L H2C-O-L
H-C-O-H and H-Q-C-H
H2C O-H ~2C-O-H
The qlycerol dilinoleate~ (the glycerol 1,2-
dilinoleate ha~ two optical isomers):
H2C o-L
H-C-O~H
H2C-O-L ...
H2C O-L H2C-O_L -
I
H^C-O-I. and L-O-C~H
2C-O-Il H2C-O~H
The glycerol trilinoIeate
H~C-O-L
H-C~O-L
In ~his context r~pre~ent~ the ~Li8~Ci~-9, LZ-oot~dec~-
S~ dLenoyl radical~
Wheth*r oils ~re used in which the linoleic acid
glyc~eride~ of variou toichiomet~ic and i~omeric ~orms
ex~t~as individual sub~tances or in any desired mixture
with~oach cther is not~of prime impor ance. `;

- - 16 -
The vegetable oils can preferably be selected
from the group comprising
wheat germ oil, grape~pip oil, kukui oil, safflower oil
and other oils which contain at least 5 % by weight of
linoleic acid glycerides.
~ here tha diameter of the multiple emulsions
without an addition of these oils is, typically, 20 l~m,
the diameter of the droplets can ~e reduced to 5 ~ 10 ~m
with such an addition.
At the same time, the vegetable oils, or the
linoleic acid glycerides, increase the yield of multiple
emulsion droplets.
According to the invention, the multiple emul-
sions can contain 0.5 - 50 % by wei~ht of vegetable oils,
it is advantageous to use contents of 1.0 ~ 10.0 % by
weight of these oil8.
The compositions according to the invention can
furthermore contain stearic aeid and/or
hydroxyoctacosanyl hydroxystearate, if this is desired.
Surprisingly, an addition of this substance increases the
stability of the multiple emulsions according to the
invention to high temperatures. It is preferred to use
contents of 0.1 - 10 % by weight of stearic acid and/or
hydroxyoctaeosanyl hydroxystearate in the compositions
according to the invention. Particularly advantageou~ are
ratios by weight o~ stearic acid and/or hydroxy-
o~tacosanyl hydroxystearate of 10 : 1 to 1 : 10. - -
The simultaneous use of vegetable oils and
~tearic acid and/ox hydroxyoctacosanyl hydroxystearate in
the compositions according to the invention is particu-
larly advantageous.
The multiple emulsions according to the invention
can be prepared from the starting material~ by proCesse~ :
known per se, i.e. both by one-pot and by two-pot pro- -
cesse~. However, it has been damonstrated, and this i9
regarded a~ a further advantageous embodiment of the
present invention, that particularly finely-textured and
highly stable multiple emulsions are obtained, if not/ a9 ~
: .

r, 17 ~
was hitherto customary, the total amount of emulsifiers
is added to the fatty phase and the mixture is then
combined with the aqueo~s phase. ~nstead, the hydrophilic
emulsifier(s) (emulsifier B) are incorporated into the
aqueous phase and the hydropho~ic emulsifier(s)
(emulsifier A) are incorporated into the oil phase. Both
phases are then combined with each other, advantageously
at a temperature at which the fatty phase is decidedly in
liquid form. This proces~ ;s a one-pot proce~s.
A process for the preparation of stable multiple
emulsions, characterised in that the hydrophilic emul-
sifier is incorporated into the aqueous phase and the
- hydrophobic emulsifier i8 incorporated into the oil phase
and both phases are then combined with each other,
advantageously at a temperature at whiah the fatty pha~e
is decidedly in liquid form, iq therefore according to
the invention.
Advantageou auxiliaries and additives are, for
example, consistency~imparting agents, fillers, perfume,
coIorants, emul3ifiers, additional active substances such
as vitamins or proteins, light stabilisers, stabilisers,
antioxidants, preservatives, insect repellants, alcohol,
water, salts, proteolytically or keratolytically active
substance~, etc.
The multiple emulsion~ according to the invention
can advantageou~ly be used in bodycare product~ ~uch a~,
~or example, creams or lotion3 for the face, hand creams,
hand lotions, body creams or hody lotions, ~un protection
formulations, moisturisers, massage creams, nailcare
products and the like.
The examples which follow are intended to
illustrate the present invention in greater detail
without intending to restri~t the invention to these
examples. Rather, a person ~killed in the art is capable
o~ varying the invention on the ba~is of his expert
knowledge~ without departing from the ba~is of the
invention.
-
,` . . :: ::: . ::: . ,. . :. . : : : ! . . ' :

- 18 - 2~
Example 1
Massage cream I
Steareth-2 3~00 %
Steareth 21 3.00
Petrolatum DAB [German
Pharmacopoeia] 9 4O20
Paraffin oil DAB [~erman
Pharmacopoeia~ 9 3.00 %
Squalane 3.00 %
10 Isopropyl palmitate 1.80 %
Acrylamide/sodium acrylate
copolymer 0.18 %
Demineralised water to 100.00 %
Example 2
Massage cream II
Steareth-2 5-00 %
Steareth-21 3.00 %
Petrolatum DAB [German
Pharmacopoeia] 9 1.50 %
Paraf~in oil DA~ ~German
~Pharmacopoeia~ 9 6.00 %
Isopropyl palmitata 3.00 ~ -
Cl2ls-alcohol benzoate 1.50 %
Cetcaryl alcohol 1.00 %
Hydroxyoctacosanyl
hydroxystearate 0.40 % :.
MgSO4 0.60 %
Cyclomethicone 2.50 ~ ;
Preservative 0~50 %
30 Demineralised water to lOO.Oa $
- .:
.
: , : , - :: . . , . : . : . ~ : . . . .
- :: : : ,..... ..
. .

Example 3
Hand cream
Steareth-2 4.50 %
Steareth-21 1.50 %
5 Petrolatum DA~ [German
Pharmacopoeia] 9 4.20 %
Paraffin oil DAB f~erman
Pharmacopoeia] 9 3.00
Squalane 3.00 %
10 Isopropyl palmitate 1.80
Acrylamide/sodium acrylate
copolymer 0.18 %
Demineralised water to 100.00 %
Example 4
Sun cream
Steareth-2 4.50 %
Steareth-21 1.50 %
Petrolatum DAB [German
Pharmacopoeia] 9 4.20 %
20 Paraffin oil DAB [German
Pharmacopoeia] 9 3~00 % .~:
Squalane 3.00 %
Isopropyl palmitate 1.80 %
Acrylamide/sodium acrylate
25 copolymer 0,18 %
~usolex 6300 2.00 %
Demineralised water to 100.00 %
'-
'
.
.: , .
~`'' ' '.
. .
.. : .. :,-. . ,: : - : . :. . ... :.,:: . :: :; :. : : : . ,

~.
~xample 5
Moisturising cream I
Sorbitan oleate 5.00 %
Oleth-20 3.00
5 Petrolatum DAB [German
Pharmacopoeia3 9 4.20 %
Paraf f in oil DA~ [German -
Pharmacopoeia] 9 6.00 %
Isopropyl palmitate 2.50 %
10 Cetearyl alcohol 1.00 %
Hydroxyoctacosanyl
hydroxystearate 0. ao %
MgSO4 0.60 %
Cyclomethicone 2.50 %
Demineralised water to 100.00 %
i;, .
Example 6 :
Moisturising cream II
Sorbitan monostearate 5.00 %
PEG-~0-stearate 3.00 %
20 Petrolatum DAB ~German :
Pharmacopoeia] 9 4.20 %
Para~fin oil DAB ~German .
Pharmacopoeia] 9 6.00 % .
I~opropyl palmitate 2.50 %
25 Cetearyl alcohol 1.00 %
~ydroxyoctacosanyl ~:
hydroxystearate 0.80 % ~: -
NgSO4 0.60 %
Cy~lomethicone 2.50
30:- Safflower oil 4-00 %
Demineralised water to 100.00 %
.

2 ~ J
- 21 -
Example 7
Moi turising cream III
Steareth-2 5-00 %
Sucrose cocoate 3.00
5 Petrolatum DAB [German
Pharmacopoeia] 9 4.20 %
Paraffin oil DAB [~erman
Pharmacopoeia] 9 6.00 %
Isopropyl palmitate 2.50 %
10 Cetearyl alcohol 1.00 %
Hydroxyoctacosanyl
hydroxystearate 0.80 %
MgSO4 0.60 %
Cyclomethicone 2.50
15 Grape-pip oil 4.50 %
Demineralised waterto 100.00
Example 8
Moisturising cream IV
, . .
Glycerol monostearate 5.00 %
(20 Sucrose cocoate 3.00
Petrolatum DAB [~erman
Pharmacopoeia] 9 4.20 %
Paraf~in oil DAB ~German
Pharmacopoeia] 9 6.00 % . .
25 Isopropyl palmitate 2~50 %
Cetearyl alcohol 1.00 % : ; :
Hydroxyoctaco,~,anyl
: hydroxystearata 0.80
Mg~O~ 0~60 %
~30 Cyclomekhicone 2.50 %
~ukui oil ~ : 6.00 %
Demineralised water to 100.00
.

~2 ~ 2
Example 9
Moisturising cream V
Glyceryl oleate 5.00 %
Trilaureth-4-phosphate 3.00 %
5 Petrolatum DAB CGerman
Pharmacopoeia] 9 4.20 %
Paraffin oil DAB [German
Pharmacopoeia] 9 6.00 %
Isopropyl palmitate 2.50 ~ -
10 Cetearyl alcohol 1.00 %
~ydroxyoctacosanyl
hydroxystearate 0.80 ~ .
MgS04 0.60
Cyclomethicone 2.50 %
15 ~heat germ oil 7.00 % i
Demineralised water to 100.00 %
Example 10 .-.
' ' ''
Moisturising cream VI
'
Polyglycerol-Iv-isostearate 5.00
Gluceth-20 3.00
Petrolatum DA~ [German
Pharmacopoeia] 9 4.20 %
Paraffin oil DA~ [German
Pharmacopoeia] 9 6~00 %
25. Isopropyl palmitate2.50 %
Cetearyl alcohol1.00 %
~ydroxyoctacosanyl
hydroxy~tearate0.80 ~
~gS04 0.60 %
30 Cyclomethicone 2.50 %
Wheat yerm oil 4,50 %
Stearic acid 3.00 %
Demineralised waterup to 100.00 %
.
: : : :, ~ . ~. . :, . . . :: :: :
:: . :; :: . . ..
, i , ~ . .
.

, ~ ~3 - 2~ v
Example 11
Moisturi~ing cream VII
PEG-7-hydrogenated castor oil 5.00 %
PPG-20-methyl glucose ether 3.00 %
5 Petrolatum DAB [German
Pharmacopoeia] 9 4.20
Paraffin oil DAB ~German
Pharmacopoeia] 9 6.00 %
Isopropyl palmitate 2.50 ~
10 Cetearyl alcohol 1.00 %
Hydroxyoctacosanyl
hydroxy~tearate 0.80 %
MgSOi 0.60 ~
Cyclomethicone 2.50 %
15 Kukui oil 5.30 %
Stearic acid 3-00 %
Demineralised water up to 100.00 %
Example 12
' - ' .
Moisturising cream IX
PEG-40-sorbitan-monostearate 5.00 %
Polyglycerol-3 ætearate3000 %
Retrolatum DAB [German
Pharmacopoeia~ 9 4.20 %
Paraf~in oil DAB [German
25 Pharmacopoeia] 9 6.00 ~
Isopropyl palmitate 2.50 %
Cetearyl alcohol 1.00 %
Hydroxyoctaco~anyl
hydroxy~tearate 0.80 %
MgS0~ 006Q %
Cyclomethicone 2.50 %
Grape-pip::oil 4.80 %
St;earic acid 3~80 ~
Demineralised waterto:100000 % ::
~: ' ' ' "'
"
: . :

Example 13
Hand protection cream
Laureth~4 5.00 %
Poly~orbate-120 3.00 %
5 PEG-40 stearate 2.00 %
Petrolatum DA~ [German
Pharmacopoeia] 9 1.50
Paraffin oil DAB [German
Pharmacopoeia] 9 6.00 ~
10 Isopropyl palmitate 3.00 %
Cl2ls-alcohol benzoate 1.50 %
Cetearyl alcohol 1.00
Hydroxyoctacosanyl
hydroxystearate 0.40 %
MgSO4 0.60 ~
Cyclomethicone 2.50 %
Demineralised water to 100.00 %
Example 14
Body lotion
20 Glyceryl oleate 2.50 %
Sucrose laurate 1.00 %
PEG-40 stearate 0.75 %
Petrolatum DAB tGerman
Pharmacopoeia] 9 l.S0 %
25 Paraffin oil DAB tGerma~
Pharmacopoeia] 9 6.00 %
: ~Isopropyl palmitate3 7 00 %
C~2~s-alcohol benzoate 1.50 %
Cetearyl alcohol 1.00 %
30 Hydroxyoctaaosanyl
: : hydroxystearate 0.40 %
~gS~, ~ 0.60 %
Cyclomethico~e 2.50 %
`Demineralised waterto 100.00 %
.. ~ . . . . - ... ..... . .. . .
,' , , ' . '" ' " ,' ' `,' . ' ,' ' ' ' " ' . ', ' " " . ' ' ' ",' ' ' '.' ' ~ ' " ' . ' , ' ' " ,

- 25 -
Example 15
Hand and nailcare emulsion
Laureth-4 5.00 %
Ceteareth 20 3.00 %
5 Petrolatum DAB [German
Pharmacopoeia] 94.20 %
Paraf f in oil DAB [German
Pharmacopoeia~ 96.90 %
PPG-15 stearyl ethex4.00 ~
10 Cy~lomethicone 2.50 %
Preservative 0.50 ~
Deminerali~ed waterup to 100.00 %
Example 16
Moisturising lotion
15 Laureth-4 5.00 %
Ceteareth 20 3.00 %
Petrolatum DAB [German
Pharmacopoeia] 92.20 %
Squalane . 4.00 %
20 Isopropyl palmitate2.50 %
Ethylhexyl cocoate4.00 %
Cetearyl alcohol1.00 %
Hydroxyoctacosanyl
hydroxystearate0.80 %
25 MgSO4 0O60 %
Cyclomethicone 2.50 %
Preservative 0.50 %
Demlnerall~ed waterto 100.00 %
:
. .
' ',' ~.
- .
,

2 ~
- 26 -
Example 17
Eyecare cream
Steareth-2 3-75 %
Steareth-21 2.25 %
Petrolatum DAB ~German
Pharmacopoeia] 9 1~20 %
Squalane 4.00 %
Ethylhexyl cocoate4.00 %
Cetearyl alcohol 0.50 %
~ydroxyoctacosanyl
hydroxy~tearate 0.80 %
MgS04 0.60 %
Cyclomethicone 2.50 %
Preservative 0.50 %
Demineralised waterto 100.00 %
Example 18
Moisturising lotion
Steareth-2 3-75 ~
Steareth-21 2.25 %
Petrolatum DAB [German
Pharmacopoeia] 9 1.20 %
Squalane 4.00 %
Ethylhexyl cocoate4.00 %
. Cetearyl alcohol 0.50
25 Shea butter 4.00
Hydroxyoctacosanyl
hydroxy~tearate 0 80 ~
MgS04 0 60 %
~ Cyclomethicone 2.5b %
30 Preservative 0.50 ~
D~minerali3ed water to 100~00 %
: .:: : ,- . ., .- . - i , . . . .. ..