CA2106566A1 - Stable multiple emulsions - Google Patents
Stable multiple emulsionsInfo
- Publication number
- CA2106566A1 CA2106566A1 CA002106566A CA2106566A CA2106566A1 CA 2106566 A1 CA2106566 A1 CA 2106566A1 CA 002106566 A CA002106566 A CA 002106566A CA 2106566 A CA2106566 A CA 2106566A CA 2106566 A1 CA2106566 A1 CA 2106566A1
- Authority
- CA
- Canada
- Prior art keywords
- emulsifier
- multiple emulsions
- oil
- emulsions according
- esters
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/066—Multiple emulsions, e.g. water-in-oil-in-water
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/017—Mixtures of compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/017—Mixtures of compounds
- C09K23/018—Mixtures of two or more different organic oxygen-containing compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/005—Preparations for sensitive skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/007—Preparations for dry skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q3/00—Manicure or pedicure preparations
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Dispersion Chemistry (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Dermatology (AREA)
- Cosmetics (AREA)
- Medicinal Preparation (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Colloid Chemistry (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
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.
- 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.
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 :~
~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 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 O
H2~
,' I .
H~C~O-X-C-R~
H2C-o-X-C-R4 ~diglyceryl ester), , :
.
~, , ':
~;
i~ ~
.~. :
..;:
:
: .
,,: :
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 :
, 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, :-:
.:, ~ ' " ' ~ ' ' . ' . ' , . !;
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. `;
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
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 %
.. ~ . . . . - ... ..... . .. . .
,' , , ' . '" ' " ,' ' `,' . ' ,' ' ' ' " ' . ', ' " " . ' ' ' ",' ' ' '.' ' ~ ' " ' . ' , ' ' " , 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 ~
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 , . . . .. ..
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 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 O
H2~
,' I .
H~C~O-X-C-R~
H2C-o-X-C-R4 ~diglyceryl ester), , :
.
~, , ':
~;
i~ ~
.~. :
..;:
:
: .
,,: :
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 :
, 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, :-:
.:, ~ ' " ' ~ ' ' . ' . ' , . !;
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. `;
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
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 %
.. ~ . . . . - ... ..... . .. . .
,' , , ' . '" ' " ,' ' `,' . ' ,' ' ' ' " ' . ', ' " " . ' ' ' ",' ' ' '.' ' ~ ' " ' . ' , ' ' " , 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 ~
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 , . . . .. ..
Claims (15)
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.
- 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.
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 (emulsifier A), in which R1 = C10-30-alkyl, Q = methylene or carbonyl, X = H or methyl, Y = H or methyl, 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 (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 (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.
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 (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 (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 (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.
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.
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, 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.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4112127.9 | 1991-04-13 | ||
| DE4112127 | 1991-04-13 | ||
| DE4131678A DE4131678A1 (en) | 1991-04-13 | 1991-09-24 | STABLE MULTIPLE EMULSIONS |
| DEP4131678.9 | 1991-09-24 | ||
| PCT/DE1992/000231 WO1992018227A2 (en) | 1991-04-13 | 1992-03-19 | Stable multiple emulsions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2106566A1 true CA2106566A1 (en) | 1992-10-14 |
Family
ID=25902815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002106566A Abandoned CA2106566A1 (en) | 1991-04-13 | 1992-03-19 | Stable multiple emulsions |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0580620B1 (en) |
| JP (1) | JPH06506392A (en) |
| AT (1) | ATE196999T1 (en) |
| AU (1) | AU1442392A (en) |
| CA (1) | CA2106566A1 (en) |
| CZ (1) | CZ215593A3 (en) |
| DE (2) | DE4131678A1 (en) |
| ES (1) | ES2152226T3 (en) |
| FI (1) | FI934503A (en) |
| HU (1) | HUT65296A (en) |
| MX (1) | MX9201632A (en) |
| PT (1) | PT100374A (en) |
| WO (1) | WO1992018227A2 (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4309390C2 (en) * | 1993-03-23 | 2003-06-18 | Goldschmidt Ag Th | Method for regulating the viscosity of emulsions |
| DE4311445C1 (en) * | 1993-04-07 | 1994-10-06 | Henkel Kgaa | Multiple W / O / W emulsions, process for their preparation and their use |
| GB9319112D0 (en) * | 1993-09-15 | 1993-11-03 | Allied Colloids Ltd | Stabilisation and use of heterogeneous liquid composition |
| DE4341113B4 (en) | 1993-12-02 | 2006-04-13 | IFAC Institut für angewandte Colloidtechnologie GmbH & Co. KG | Stable multiple X / O / Y emulsion |
| DE4343833A1 (en) * | 1993-12-22 | 1995-06-29 | Beiersdorf Ag | W / O / W emulsions |
| US5589177A (en) * | 1994-12-06 | 1996-12-31 | Helene Curtis, Inc. | Rinse-off water-in-oil-in-water compositions |
| US5656280A (en) * | 1994-12-06 | 1997-08-12 | Helene Curtis, Inc. | Water-in-oil-in-water compositions |
| DE19501288A1 (en) * | 1995-01-18 | 1996-07-25 | Beiersdorf Ag | Lotions containing fatty acid derivatives |
| DE19509301A1 (en) * | 1995-03-15 | 1996-09-19 | Henkel Kgaa | Multiple W / O / W emulsions |
| DE19548013A1 (en) * | 1995-12-21 | 1997-06-26 | Beiersdorf Ag | Process for the preparation of O / W or O / W / O emulsions and O / W and O / W / O emulsions obtainable by such processes |
| SE0000774D0 (en) | 2000-03-08 | 2000-03-08 | Astrazeneca Ab | New formulation |
| SE0102993D0 (en) | 2001-09-07 | 2001-09-07 | Astrazeneca Ab | New self emulsifying drug delivery system |
| EP2172263A4 (en) * | 2007-07-02 | 2015-08-05 | Nisshin Oillio Group Ltd | W/o/w emulsion composition |
| HU227970B1 (en) | 2007-07-10 | 2012-07-30 | Egis Gyogyszergyar Nyrt | Pharmaceutical compositions containing silicones of high volatility |
| DE102010034389B4 (en) | 2010-08-13 | 2018-03-22 | Beiersdorf Ag | Stabilized W / O emulsions |
| DE202010011395U1 (en) | 2010-08-13 | 2010-11-11 | Beiersdorf Ag | Stabilized W / O emulsions |
| US11154535B2 (en) | 2012-07-31 | 2021-10-26 | Egis Pharmaceuticals Plc | Transdermal formulation containing COX inhibitors |
| US10045935B2 (en) | 2012-07-31 | 2018-08-14 | Egis Pharmaceuticals Plc | Transdermal formulation containing COX inhibitors |
| DE102013222164A1 (en) | 2013-10-31 | 2015-04-30 | Deb Ip Limited | Stabilized multiple emulsions as a skin protection product |
| CN113181082B (en) * | 2021-04-30 | 2023-04-07 | 广州市奥源贸易有限公司 | Double-layer milk-cap essence liquid matrix and preparation method thereof |
| CA3228281A1 (en) * | 2021-08-19 | 2023-02-23 | Morse Laboratories L.P. | Anhydrous topical delivery system for lipid, aqueous, and alcohol solubilized actives |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1541463A (en) * | 1975-10-11 | 1979-02-28 | Lion Dentifrice Co Ltd | Process for prparing a multiple emulsion having a dispersing form of water-phase/oil-phase/water-phase |
| ATA207181A (en) * | 1981-05-08 | 1983-09-15 | Schering Wien | COSMETIC AGENT AND METHOD FOR THE PRODUCTION THEREOF |
| JPS60166604A (en) * | 1984-02-09 | 1985-08-29 | Kobayashi Kooc:Kk | Preparation of weakly acidic w/o/w-type emulsion cosmetic |
| JPS60199833A (en) * | 1984-03-26 | 1985-10-09 | Meiji Milk Prod Co Ltd | Preparation of w/o/w-type composite emulsion for pharmaceutical, cosmetic, etc. |
| DE69020211T2 (en) * | 1989-04-05 | 1995-11-02 | Kao Corp | Cosmetic double emulsion composition. |
-
1991
- 1991-09-24 DE DE4131678A patent/DE4131678A1/en not_active Ceased
-
1992
- 1992-03-19 EP EP92907091A patent/EP0580620B1/en not_active Expired - Lifetime
- 1992-03-19 DE DE59209873T patent/DE59209873D1/en not_active Expired - Fee Related
- 1992-03-19 WO PCT/DE1992/000231 patent/WO1992018227A2/en active IP Right Grant
- 1992-03-19 JP JP4506703A patent/JPH06506392A/en active Pending
- 1992-03-19 AU AU14423/92A patent/AU1442392A/en not_active Abandoned
- 1992-03-19 CZ CS932155A patent/CZ215593A3/en unknown
- 1992-03-19 AT AT92907091T patent/ATE196999T1/en not_active IP Right Cessation
- 1992-03-19 CA CA002106566A patent/CA2106566A1/en not_active Abandoned
- 1992-03-19 HU HU9302884A patent/HUT65296A/en unknown
- 1992-03-19 ES ES92907091T patent/ES2152226T3/en not_active Expired - Lifetime
- 1992-04-09 MX MX9201632A patent/MX9201632A/en unknown
- 1992-04-10 PT PT100374A patent/PT100374A/en not_active Application Discontinuation
-
1993
- 1993-10-12 FI FI934503A patent/FI934503A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| FI934503A0 (en) | 1993-10-12 |
| CZ215593A3 (en) | 1994-04-13 |
| WO1992018227A3 (en) | 1993-05-27 |
| PT100374A (en) | 1993-07-30 |
| HU9302884D0 (en) | 1994-01-28 |
| JPH06506392A (en) | 1994-07-21 |
| EP0580620B1 (en) | 2000-10-18 |
| MX9201632A (en) | 1992-10-01 |
| HUT65296A (en) | 1994-05-02 |
| EP0580620A1 (en) | 1994-02-02 |
| ATE196999T1 (en) | 2000-11-15 |
| WO1992018227A2 (en) | 1992-10-29 |
| FI934503A (en) | 1993-10-12 |
| DE4131678A1 (en) | 1992-10-15 |
| ES2152226T3 (en) | 2001-02-01 |
| DE59209873D1 (en) | 2000-11-23 |
| AU1442392A (en) | 1992-11-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |