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EP0692957A1 - Procede de preparation d'emulsions multiples eau/huile/eau - Google Patents

Procede de preparation d'emulsions multiples eau/huile/eau

Info

Publication number
EP0692957A1
EP0692957A1 EP94913085A EP94913085A EP0692957A1 EP 0692957 A1 EP0692957 A1 EP 0692957A1 EP 94913085 A EP94913085 A EP 94913085A EP 94913085 A EP94913085 A EP 94913085A EP 0692957 A1 EP0692957 A1 EP 0692957A1
Authority
EP
European Patent Office
Prior art keywords
emulsion
emulsifier
weight
fatty alcohols
emulsions
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.)
Withdrawn
Application number
EP94913085A
Other languages
German (de)
English (en)
Inventor
Catherine Le Hen-Ferrenbach
Isabelle Terrisse
Armelle Magnet
Monique Seiller
Francis Puisieux
Jean-Louis Grossiord
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0692957A1 publication Critical patent/EP0692957A1/fr
Withdrawn legal-status Critical Current

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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/10—Dispersions; Emulsions
    • A61K9/107—Emulsions ; Emulsion preconcentrates; Micelles
    • A61K9/113—Multiple emulsions, e.g. oil-in-water-in-oil
    • 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
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair

Definitions

  • the invention relates to a process for the preparation of multiple W / O / W emulsions, in which a W / O pre-emulsion is first prepared from water, an oil body and an emulsifier I under strong shear, and these are then washed under black cher shear treated with an aqueous emulsifier II, multiple W / O / W emulsions obtainable by this process and the use of these multiple W / O / W emulsions for the production of cosmetic and pharmaceutical products.
  • emulsions are emulsions of emulsions.
  • W / O / W water / oil / water
  • oil / water / oil (0 / W / O) emulsions The most important application of multiple emulsions is to process active ingredients that are otherwise not miscible or ready for assembly in a recipe. Another advantage is that the active ingredients can be released in a controlled manner over a longer period of time. Multiple emul Sions are therefore particularly important for the production of cosmetic and pharmaceutical products rCosm.Toil.105. 65 (1990)].
  • W / O / W emulsions are also known from Yakugaku Zasshi 112, 73 (1992), which contain glycerol trifatty acid esters as oil bodies and hydrophilic polymers, such as gelatin, as stabilizing agents.
  • the use of albumin and polyacrylates as stabilizers for the water phase and nonionic surfactants for the oil phase is known from J. Controlled Release. 3, 279 (1986).
  • Such formulations have proven to be insufficiently stable in storage, in particular in the case of temperature fluctuations.
  • a particular problem in the production of multiple emulsions is therefore the selection of suitable pairs of emulsifiers, which ensure adequate thermal stability even after prolonged storage.
  • Another disadvantage is that mineral oils are usually used as oil bodies, which show an unfavorable biodegradability.
  • the object of the invention was therefore to develop a new method for producing multiple W / O / W emulsions which is free from the disadvantages described.
  • the invention relates to a method for producing multiple W / O / W emulsions, in which
  • aqueous emulsifier II from the group consisting of the adducts of ethylene oxide with fatty alcohols and / or sterol and, if appropriate, fatty alcohols.
  • the multiple W / O / W emulsions obtainable by the process according to the invention ions are stable in storage for a long time even when the temperature fluctuates significantly.
  • the invention includes the finding that by selecting the specified oil bodies and dispensing with polymeric stabilizers, multiple emulsions of a biodegradability which is significantly improved compared to the prior art can be provided.
  • Dialkylcyclohexanes and dialkyl ethers are suitable as oil bodies for the preparation of the multiple W / O / W emulsions according to the invention.
  • dialkylcyclohexanes are known substances that can be obtained by relevant processes in preparative organic chemistry.
  • An example of their preparation is, for example, subjecting dialkyl aromatics (ortho / meta / para-xylene) from the BTX fraction of the petroleum to a catalytic hydrogenation.
  • R 1 and R 2 independently of one another are alkyl radicals having 1 to 12 carbon atoms and C is a cyclohexyl radical.
  • Typical examples are dimethylcyclohexane, diethylcyclohexane, methylethylcyclohexane, dipropylcyclohexane, Di-n-butylcyclohexane, di-tert-butylcyclohexane, di-2-ethylhexylcyclohexane and in particular di-n-octylcylohexane.
  • Dialkyl ethers are to be understood as meaning compounds of the formula (II)
  • R ⁇ and R 4 are independently alkyl radicals having 6 to 22 carbon atoms.
  • the particularly preferred dialkyl ethers for the purposes of the invention are thus di-n-octyl ether and di-2-ethylhexyl ether.
  • the oil bodies can be used in amounts of 10 to 30, preferably 15 to 25,% by weight, based on the pre-emulsion A.
  • Suitable emulsifiers I are glycerol and / or oligo- or polyglycerol esters. Typical examples are technical mono- and / or diesters of glycerol with fatty acids having 12 to 22 carbon atoms, such as, for example, glycerol monolaurate, glycerol monopalmitate, glycerol onostearate, glycerol mono isostearate, glycerol monooleate and glycerol mono-henate.
  • oligo- or polyglycerol mixtures degree of self-condensation 2 to 20, preferably 2 to 10
  • polyglycerol -di-isostearate polyglycerol-di-oleate
  • mixtures of glycerol and oligo- or polyglycerol esters for example consisting of glycerol monooleate and triglycerol di-isostearate (mixing ratio, for example 80:20 parts by weight).
  • the emulsifiers I can be used in amounts of 1 to 10, preferably 1 to 4,% by weight, based on the pre-emulsion A.
  • Adducts of an average of 20 to 50, preferably 20 to 30, mol of ethylene oxide with fatty alcohols having 16 to 22, preferably 16 to 13, carbon atoms are suitable as emulsifier II.
  • Typical examples are adducts of an average of 25 to 30 mol of ethylene oxide with stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, arachyl alcohol, Gadoleyl alcohol, behenyl alcohol and erucyl alcohol as well as their technical mixtures, such as are obtained, for example, in the high-pressure hydrogenation of native fatty acid methyl esters or aldehydes from Roelen's oxosynthesis.
  • Addition products of an average of 25 to 30 moles of ethylene oxide with technical grade cetylstearyl alcohols are preferably used.
  • sterols here is understood to mean steroids with 27 to 30 carbon atoms which only carry a hydroxyl group at C-3, but otherwise have no functional groups and are often incorrectly referred to as sterols [ROEMPP Chemie Lexikon, Vol. 5 , 1992, p.4302].
  • Typical examples are addition products of on average 10 to 40, preferably 25 to 30, moles of ethylene oxide with zoosterols, such as cholesterol, lanosterol, spongosterol or stellasterin or phystosterols, such as ergosterol, stigmasterol and sitosterol. Adducts of on average 25 to 30 moles of ethylene oxide with soyasterol are particularly preferred.
  • mixtures of addition products of an average of 20 to 50 moles of ethylene oxide with fatty alcohols with 16 to 22 carbon atoms and sterols of vegetable and / or animal origin are used.
  • a typical example is a mixture of an adduct of an average of 30 moles of ethylene oxide with cetylstearyl alcohol and a adduct of an average of 25 moles of ethylene oxide with soybean sterol in a weight ratio of 1: 5 to 5: 1, preferably 2 : 1.
  • Emulsifiers II can be used in amounts of 1 to 10, preferably 2.3 to 6.5,% by weight, based on the multiple W / O / W emulsion.
  • fatty alcohols having 12 to 22, preferably 16 to 18 carbon atoms can be added to the emulsifier II as co-emulsifiers, which form a liquid-crystalline network in the emulsifier phase and to further improve the stability of the resulting W / O / W emulsions.
  • Suitable fatty alcohols are, for example, technical cetyl / stearyl alcohols.
  • the weight ratio between emulsifier II and co-emulsifier can be 1: 1 to 1: 2, preferably 1: 1.5 to 1: 1.8.
  • the oil body is placed in a stirring device and the lipophilic emulsifier I is added.
  • the components are homogenized under strong shear, ie at a stirrer speed of 1000 to 2000, preferably 1200 to 1700 rpm. Centripetal turbines or, in particular, colloid mills can be considered as stirring devices. It has proven to be particularly advantageous to carry out the preparation of the pre-emulsion A at elevated temperature, ie at 50 to 90, preferably 70 to 80 ° C.
  • the homogenization time is usually in the range from 5 to 40, preferably 10 to 30, minutes.
  • the pre-emulsion salt preferably add magnesium sulfate in amounts of 0.5 to 2% by weight, based on the pre-emulsion.
  • composition of the pre-emulsion A is therefore typically:
  • the water content of the pre-emulsion A is usually 58 to 88.5, preferably 70 to 83% by weight.
  • the pre-emulsion A is placed in a stirrer and mixed with the aqueous emulsifier II.
  • the pre-emulsion A can be used in amounts of 50 to 90, preferably 65 to 80,% by weight, based on the multiple W / O / W emulsion.
  • the components are homogenized under low shear, ie at a stirrer speed of 10 to 500, preferably 150 to 250 rpm. Zen tripetal turbines or, in particular, colloid mills are again suitable as stirring devices. It has proven particularly advantageous to carry out the preparation of pre-emulsion A at 20 to 60 and in particular 20 to 25 ° C.
  • the homogenization time is usually in the range from 5 to 50, preferably 10 to 30, minutes.
  • the composition of the multiple W / O / W emulsion is thus typically:
  • bl 50 to 90 (preferably 65 to 80)% by weight of pre-emulsion b2) 1 to 10 (preferably 2 to 7)% by weight of emulsifier II b3) 0 to 5 (preferably 1 to 4)% by weight Co-emulsifier b4) ad 100 wt .-% water.
  • the water content of the multiple W / O / W emulsion - including the water content of the pre-emulsion A - is 57 to 93, preferably 74 to 89% by weight.
  • Another object of the invention relates to particularly stable multi-W / O / W emulsions containing
  • Glycerol monooleate (4: 1 parts by weight) 0.5 to 2% by weight magnesium sulfate
  • the multi-plen W / O / W emulsions obtainable by the process according to the invention prove to be stable even after prolonged storage and are readily biodegradable. They are suitable for picking up and controlled, time-delayed delivery of active substances that cannot otherwise be assembled.
  • Another object of the invention therefore relates to the use of the multiple W / O / W emulsions obtainable by the process according to the invention for the production of cosmetic and pharmaceutical products, in particular agents for hair and body cleaning and care, in which the multiple emulsions can be contained in amounts of 1 to 99, preferably 10 to 50% by weight, based on the composition.
  • 60 g of pre-emulsion A were introduced and within 40 s with a solution of 1.4 g Mergital ( R ) E 1471, 0.7 g Generol ( R) 122 E 25 and 3.52 g cetyl / stearyl alcohol added to 34.4 g of water and homogenized at 60 ° C. over a period of 30 min at a speed of 200 rpm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Dispersion Chemistry (AREA)
  • Epidemiology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Birds (AREA)
  • Dermatology (AREA)
  • Medicinal Preparation (AREA)
  • Colloid Chemistry (AREA)
  • Cosmetics (AREA)

Abstract

Afin de préparer des émulsions multiples eau/huile/eau, on transforme en une pré-émulsion A d'eau dans l'huile un mélange d'un corps huileux facilement biodégradable et d'un émulsifiant aqueux (I) du groupe des esters de glycérine et/ou des esters d'acides gras d'oligo- ou polyglycérine, sous un fort cisaillement, puis on traite la pré-émulsion A sous un faible cisaillement avec un émulsifiant aqueux du groupe des produits d'addition d'oxyde d'éthylène sur des alcools gras et/ou stérols, et le cas échéant, avec des alcools gras. Ces produits sont utiles pour préparer des produits cosmétiques et pharmaceutiques.
EP94913085A 1993-04-07 1994-03-30 Procede de preparation d'emulsions multiples eau/huile/eau Withdrawn EP0692957A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4311445A DE4311445C1 (de) 1993-04-07 1993-04-07 Multiple W/O/W-Emulsionen, Verfahren zu deren Herstellung und ihre Verwendung
DE4311445 1993-04-07
PCT/EP1994/000996 WO1994022414A1 (fr) 1993-04-07 1994-03-30 Procede de preparation d'emulsions multiples eau/huile/eau

Publications (1)

Publication Number Publication Date
EP0692957A1 true EP0692957A1 (fr) 1996-01-24

Family

ID=6484971

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94913085A Withdrawn EP0692957A1 (fr) 1993-04-07 1994-03-30 Procede de preparation d'emulsions multiples eau/huile/eau

Country Status (5)

Country Link
US (1) US5714154A (fr)
EP (1) EP0692957A1 (fr)
JP (1) JPH08508202A (fr)
DE (1) DE4311445C1 (fr)
WO (1) WO1994022414A1 (fr)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19505004C1 (de) * 1995-02-15 1996-09-12 Henkel Kgaa Multiple W/O/W-Emulsionen und Verfahren zu deren Herstellung
DE19630176C2 (de) * 1996-07-26 2000-11-02 Babor Gmbh & Co Dr Kosmetische und pharmazeutische Mittel, gebildet durch eine nach dem Phaseninversionsverfahren erzeugte W/O/W-Emulsion
US5853740A (en) * 1996-08-07 1998-12-29 Abbott Laboratories Delivery system for pharmaceutical agents encapsulated with oils
DE19732013A1 (de) * 1997-07-25 1999-01-28 Henkel Kgaa Multiple W/O/W-Emulsionen mit hohem Polyolgehalt
EP0937495A3 (fr) * 1998-02-23 2002-07-10 Unilever Plc Mélanger de liquides immiscibles
CO5150202A1 (es) 1998-12-31 2002-04-29 Kimberly Clark Co Composicion de tisu facial y metodo para usarla para el secuestro de irritantes de la piel de la secrecion nasal
US6190720B1 (en) * 1999-06-15 2001-02-20 Opta Food Ingredients, Inc. Dispersible sterol compositions
DE19947550A1 (de) * 1999-10-02 2001-04-05 Beiersdorf Ag W/O/W-Emulsionen mit hohem Wassergehalt
US6777450B1 (en) * 2000-05-26 2004-08-17 Color Access, Inc. Water-thin emulsions with low emulsifier levels
US6515031B2 (en) * 2001-02-13 2003-02-04 Platte Chemical Company Technique for emulsifying highly saturated hydroisomerized fluids
DE10136483A1 (de) * 2001-07-27 2003-02-13 Cognis Deutschland Gmbh Emulgator Gemisch
FR2833184B1 (fr) * 2001-12-11 2004-01-23 Rhodia Chimie Sa Procede de preparation d'une emulsion multiple de type eau/huile/eau
US8207236B2 (en) * 2006-05-23 2012-06-26 Ferro Corporation Method for the production of porous particles
US8778669B2 (en) 2009-07-22 2014-07-15 Corning Incorporated Multilayer tissue culture vessel
JP2015196663A (ja) * 2014-04-01 2015-11-09 ロレアル ナノ又はマイクロエマルションの形態の組成物

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE8004580L (sv) * 1980-06-19 1981-12-20 Draco Ab Farmaceutisk beredning
JPS602903B2 (ja) * 1980-07-02 1985-01-24 株式会社資生堂 多相型エマルションの調製方法
JPS60166604A (ja) * 1984-02-09 1985-08-29 Kobayashi Kooc:Kk 弱酸性ｗ／ｏ／ｗ型乳化化粧料の製造方法
DE4010393A1 (de) * 1990-03-30 1991-10-02 Henkel Kgaa Verfahren zur herstellung von oel-in-wasser-cremes
DE4039950A1 (de) * 1990-12-14 1992-06-17 Hoechst Ag Verfahren zur herstellung von ungesaettigten ethern
DE4103489A1 (de) * 1991-02-06 1992-08-13 Henkel Kgaa Verfahren zur herstellung von verzweigten dialkylethern
DE4131678A1 (de) * 1991-04-13 1992-10-15 Beiersdorf Ag Stabile multiple emulsionen
DE4122033A1 (de) * 1991-07-03 1993-01-07 Henkel Kgaa Konservierungsmittelfreie wasser-in-oel-emulsionen
JPH088737B2 (ja) * 1993-06-18 1996-01-29 基孝 梁 電気接続用ボックス

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9422414A1 *

Also Published As

Publication number Publication date
US5714154A (en) 1998-02-03
DE4311445C1 (de) 1994-10-06
JPH08508202A (ja) 1996-09-03
WO1994022414A1 (fr) 1994-10-13

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