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WO1996025137A1 - Emulsions multiples eau/huile eau/eau - Google Patents

Emulsions multiples eau/huile eau/eau Download PDF

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Publication number
WO1996025137A1
WO1996025137A1 PCT/EP1996/000474 EP9600474W WO9625137A1 WO 1996025137 A1 WO1996025137 A1 WO 1996025137A1 EP 9600474 W EP9600474 W EP 9600474W WO 9625137 A1 WO9625137 A1 WO 9625137A1
Authority
WO
WIPO (PCT)
Prior art keywords
emulsions
emulsifiers
emulsion
weight
water phase
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.)
Ceased
Application number
PCT/EP1996/000474
Other languages
German (de)
English (en)
Inventor
Achim Ansmann
Rolf Kawa
Helga Gondek
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 WO1996025137A1 publication Critical patent/WO1996025137A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/39—Derivatives containing from 2 to 10 oxyalkylene groups
    • 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
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • B01F23/41—Emulsifying
    • B01F23/414—Emulsifying characterised by the internal structure of the emulsion
    • B01F23/4144—Multiple emulsions, in particular double emulsions, e.g. water in oil in water; Three-phase emulsions

Definitions

  • the invention relates to multiple W / O / W emulsions containing polyol polyhydroxystearates as emulsifiers, a process for their preparation and the use of polyolpolyhydroxystearates as emulsifiers for the production of multiple W / O / W emulsions.
  • 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 emulsions are therefore particularly important for the production of cosmetic and pharmaceutical products [Cosm.Toil. 105, 65 (1990) and 106, 97 (1991)].
  • W / O / W emulsions 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.
  • polyglycerol polyricinoleates as emulsifiers for the production of multiple emulsions is also known from European patent application EP-AI 0174377 (Meji Milk Products). Also however, these emulsions have not proven to be sufficiently stable, particularly in the case of temperature fluctuations.
  • the object of the invention was therefore to provide stable multiple W / O / W emulsions which are also resistant to temperature fluctuations and which, from an application point of view, have a lipophilic emulsifier which is at least equivalent to cetyl dimethicone copolyols, but with contain improved skin cosmetic properties. Furthermore, the emulsions should be as free as possible of hydrophilic, co-emulsifiers containing ethylene oxide. Description of the invention
  • the invention relates to multiple W / O / W emulsions which are obtained by first preparing a primary W / O emulsion I from an oil phase and a water phase in the presence of polyol polyhydroxystearates as emulsifiers, and then producing this emulsified with a water phase II.
  • polyol polyhydroxystearates in general and polyglycerol polyhydroxy stearates in particular are suitable as effective lipophilic emulsifiers for the preparation of multiple W / O / W emulsions and thus represent an at least equivalent substitute for cetyl dimethicone copolyols from an application point of view; at the same time, the ethylene oxide-free polyol polyhydroxy stearates have better skin cosmetic properties.
  • the invention also includes the knowledge that the use of hydrophilic ionic or nonionic emulsifiers for stabilizing the phases is no longer absolutely necessary.
  • the polyglycerol polyhydroxystearates have been shown to be significantly improved over polyglycerol polyricinoleates with regard to the temperature dependence of the emulsifying action.
  • polyol polyhydroxystearates which are suitable as emulsifiers for the production of multiple W / O / W emulsions in the sense of the invention are known substances which are prepared by the relevant methods of preparative organic African chemistry can get.
  • polyhydroxystearic acid with a degree of self-condensation in the range from 2 to 20, preferably 2 to 10
  • polyols in a manner known per se.
  • the polyol polyhydroxystearates can be derived from polyols which have at least two, preferably 3 to 12 and in particular 3 to 8 hydroxyl groups and 2 to 12 carbon atoms.
  • Typical examples are glycerol, alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol; Polyglycerin; Methyl compounds, such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol; Alkyl glucosides with 1 to 22, preferably 1 to 8 and in particular 1 to 4 carbons in the alkyl radical, such as, for example, methyl and butyl glucoside; Sugar alcohols with 5 to 12 carbon atoms such as, for example, sorbitol or mannitol, sugars with 5 to 12 carbon atoms such as, for example, glucose or sucrose; or aminosugars such as gluc
  • the emulsifiers used are polyglycerol polyhydroxystearates which are obtained by polyhydroxystearic acid having a degree of self-condensation in the range from 2 to 20, preferably 2 to 10, with a polyglycerol mixture of the composition (GC method)
  • Glycerin 5 to 35 (15 to 30) wt% diglycerols 15 to 40 (20 to 32) wt% triglycerols 10 to 35 (15 to 25) wt% tetraglycerols 5 to 20 (8 to 15) wt. % Pentaglycerols 2 to 10 (3 to 8)% by weight (Oligoglycerols ad 100 wt .-%) esterified in a conventional manner; the preferred areas are given in brackets.
  • the polyol polyhydroxystearates can be prepared in a manner known per se.
  • the polyglycerol polyhydroxystearates the polyglycerol is preferably first produced and then the polyhydroxystearic acid, and finally both are esterified.
  • a polyglycerol of the abovementioned composition can be prepared by self-condensation of glycerol in the presence of suitable catalysts such as, for example, potassium carbonate, silicates according to DE-Al 4029323 (Henkel) or borates according to DE-Al 4117033 (Henkel) at temperatures in the range of 200 to 260 ° C are carried out.
  • suitable catalysts such as, for example, potassium carbonate, silicates according to DE-Al 4029323 (Henkel) or borates according to DE-Al 4117033 (Henkel) at temperatures in the range of 200 to 260 ° C are carried out.
  • the polyhydroxystearic acid is prepared, for example, by alkaline-catalyzed polycondensation of hydroxystearic acid, preferably 12-hydroxystearic acid, which is obtained by curing ricinoleic acid or technical castor oil fatty acid. Linear esterification products having 2 to 10 and in particular 2 to 8 fatty acid units are preferably formed.
  • the following distribution (GPC method) is typically achieved:
  • mixtures of hydroxystearic acid and ricinoleic acid or technical castor oil fatty acid which consists of approximately 90% by weight of ricinoleic acid, in a weight ratio of 90:10 to 50:50 and preferably 75:25 to 60: 40 used.
  • polystyrene resin for example the polyglycerol with the polyhydroxystearic acid or the mixtures with polyricinoleic acid
  • a complex mixture of homologous polyesters is formed.
  • the proportions of mono-, di-, tri- and oligoesters in the polyol polyhydroxystearates according to the invention and preferably polyglycerol polyhydroxy stearates depend on the conditions of use of the starting compounds.
  • an emulsifier with particularly advantageous performance properties is used, which is obtained by subjecting about 1000 kg of 12-hydroxystearic acid to self-condensation until a product with an acid number in the range from 50 to 55 results and this is then further esterified with about 150 kg of polyglycerol of the composition given above until the acid number has decreased to a value of less than 2.
  • oil phase A is obtained by subjecting about 1000 kg of 12-hydroxystearic acid to self-condensation until a product with an acid number in the range from 50 to 55 results and this is then further esterified with about 150 kg of polyglycerol of the composition given above until the acid number has decreased to a value of less than 2.
  • oil phase can also contain fats, waxes, stabilizers and superfatting agents.
  • esters of linear C -C20 fatty acids with linear C6-C20 fats oil / h ° l ⁇ n / esters of branched C ⁇ come as oil bodies, for example -Ci3- carboxylic acids with linear Cß-Ci8- fatty acids, esters of linear Cg-C ⁇ g fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of linear and / or branched fatty acids with polyhydric alcohols and / or Guerbet alcohols, triglycerides based on C5-C ⁇ o ⁇ Fe ⁇ t t acids, vegetable oils, branched primary alcohols, substituted cyclohexanes, Guerbet carbonates and / or dialkyl ethers into consideration.
  • Both known W / O and O / W emulsifiers such as, for example, polyglycerol fatty acid esters or glycerol fatty acid esters can be used as co-emulsifiers.
  • Typical examples of fats are glycerides, waxes, etc. Beeswax, paraffin wax or micro waxes optionally in combination with hydrophilic waxes, e.g. Cetyl stearyl alcohol in question.
  • Metal salts of fatty acids such as magnesium, aluminum and / or zinc stearate can be used as stabilizers.
  • Substances such as, for example, polyethoxylated lanolin derivatives, lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used as superfatting agents, the latter optionally serving at the same time as foam stabilizers.
  • the water phase B which is processed with the oil phase A to form the primary W / O emulsion I, can, in addition to water - the main constituent of which is approximately 50 to 85% by weight, based on the primary W / O emulsion - also polyols such as preferably contain glycerol and electrolyte salts such as table salt, ammonium chloride or magnesium sulfate.
  • the water phase II which results in the multiple W / O / W emulsion with the primary W / O emulsion I, can in principle have the same ingredients.
  • the main constituent water which in turn usually makes up 50 to 85% by weight, based on the multiple W / O / W emulsion, it may in particular contain polymers or thickening agents.
  • Typical examples of this are polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, furthermore higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinyl pyrrolidone.
  • preservatives such as, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid can also be present.
  • Another object of the invention is a process for producing multiple W / O / W emulsions, in which a primary W / O emulsion I is prepared from an oil and a water phase in the presence of polyol polyhydroxy stearates as emulsifiers, and this then emulsified with a water phase II.
  • the oil phase is preferably heated to temperatures in the range from 50 to 90 ° C. together with the emulsifier - that is to say the polyol polyhydroxystearate and preferably the polyglycerol polyhydroxy stearate - and then the likewise preheated water phase is stirred in .
  • the emulsifiers are preferably used in amounts of 1 to 10 and in particular 2 to 4% by weight, based on the primary W / O emulsion I.
  • the weight ratio between oil phase A and water phase B can be in the range from 50:50 to 10:90 and preferably 30:70 to 40:60.
  • the primary W / O emulsion After the primary W / O emulsion has been prepared, it is preferably reacted at room temperature with vigorous stirring with the water phase II to form a multiple W / O / W emulsion, the weight ratio of the two components W / O emulsion to water phase II 15: 85 to 70:30 and preferably 30:70 to 60:40 may be.
  • the emulsions can also be produced by cold, hot, hot-hot / cold or PIT emulsification. This is a purely mechanical process, there is no chemical reaction.
  • the multiple W / O / W emulsions according to the invention are notable for particular stability, in particular even at fluctuating temperatures.
  • Another object of the invention therefore relates to the use of polyol polyhydroxystearates in general and polyglycerol polyhydroxy stearates in particular as emulsifiers for the preparation of multiple W / O / W emulsions in which they are used in amounts of 0.1 to 10, preferably 0, 2 to 4% by weight, based on the multiple emulsions, can be present.
  • the multiple W / O / W emulsions in turn can be used to produce cosmetic and pharmaceutical preparations such as creams, ointments and lotions.
  • An oil phase A consists of
  • cetearyl isononanoate (Cetiol ( R ) SN)

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Chemical & Material Sciences (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Emergency Medicine (AREA)
  • Dermatology (AREA)
  • Cosmetics (AREA)
  • Medicinal Preparation (AREA)

Abstract

Selon l'invention, on obtient des émulsions multiples eau/huile/eau stables en constituant une émulsion primaire eau/huile I à partir d'une phase huile et d'une phase eau, en présence de polyhydroxystéréates de polyol en tant qu'émulsifiants, puis en émulsifiant cette émulsion primaire avec une phase eau II.
PCT/EP1996/000474 1995-02-15 1996-02-06 Emulsions multiples eau/huile eau/eau Ceased WO1996025137A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19505004.5 1995-02-15
DE19505004A DE19505004C1 (de) 1995-02-15 1995-02-15 Multiple W/O/W-Emulsionen und Verfahren zu deren Herstellung

Publications (1)

Publication Number Publication Date
WO1996025137A1 true WO1996025137A1 (fr) 1996-08-22

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/000474 Ceased WO1996025137A1 (fr) 1995-02-15 1996-02-06 Emulsions multiples eau/huile eau/eau

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DE (1) DE19505004C1 (fr)
WO (1) WO1996025137A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999004749A3 (fr) * 1997-07-25 1999-04-15 Henkel Kgaa Emulsions eau dans l'huile dans l'eau multiples a forte teneur en polyols
DE19826750A1 (de) * 1998-06-16 1999-12-23 Beiersdorf Ag Zubereitungen vom Emulsionstyp W/O mit erhöhtem Wassergehalt, enthaltend ferner ein oder mehrere Alkylmethiconcopolyole und/oder Alkyl-Dimethiconcopolyole

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100233221A1 (en) * 2007-06-29 2010-09-16 Nestec S.A. Stable double emulsions

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5715829A (en) * 1980-07-02 1982-01-27 Shiseido Co Ltd Preparation of multiphase type emulsion
EP0174377A1 (fr) * 1984-03-26 1986-03-19 Meiji Milk Products Company Limited Emulsion du type multiple eau/huile/eau pour usage cosmetique ou medical
JPH0678671A (ja) * 1992-09-03 1994-03-22 Dai Ichi Kogyo Seiyaku Co Ltd 油中水型乳化物
WO1994022414A1 (fr) * 1993-04-07 1994-10-13 Henkel Kommanditgesellschaft Auf Aktien Procede de preparation d'emulsions multiples eau/huile/eau

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5715829A (en) * 1980-07-02 1982-01-27 Shiseido Co Ltd Preparation of multiphase type emulsion
EP0174377A1 (fr) * 1984-03-26 1986-03-19 Meiji Milk Products Company Limited Emulsion du type multiple eau/huile/eau pour usage cosmetique ou medical
JPH0678671A (ja) * 1992-09-03 1994-03-22 Dai Ichi Kogyo Seiyaku Co Ltd 油中水型乳化物
WO1994022414A1 (fr) * 1993-04-07 1994-10-13 Henkel Kommanditgesellschaft Auf Aktien Procede de preparation d'emulsions multiples eau/huile/eau

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE CAPLUS [online] "TRIPLE PHASE EMULSION", XP002003802, accession no. STN Database accession no. 1982:444145 *
DATABASE CAPLUS [online] XP002003803, accession no. STN Database accession no. 1994:456245 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999004749A3 (fr) * 1997-07-25 1999-04-15 Henkel Kgaa Emulsions eau dans l'huile dans l'eau multiples a forte teneur en polyols
DE19826750A1 (de) * 1998-06-16 1999-12-23 Beiersdorf Ag Zubereitungen vom Emulsionstyp W/O mit erhöhtem Wassergehalt, enthaltend ferner ein oder mehrere Alkylmethiconcopolyole und/oder Alkyl-Dimethiconcopolyole

Also Published As

Publication number Publication date
DE19505004C1 (de) 1996-09-12

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