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WO1992013511A1 - Systemes stables a trois phases - Google Patents

Systemes stables a trois phases Download PDF

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Publication number
WO1992013511A1
WO1992013511A1 PCT/EP1992/000180 EP9200180W WO9213511A1 WO 1992013511 A1 WO1992013511 A1 WO 1992013511A1 EP 9200180 W EP9200180 W EP 9200180W WO 9213511 A1 WO9213511 A1 WO 9213511A1
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WO
WIPO (PCT)
Prior art keywords
group
water
phase
phase systems
oil
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/EP1992/000180
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German (de)
English (en)
Inventor
Fred Schambil
Fritz Lange
Claudia Klink
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 WO1992013511A1 publication Critical patent/WO1992013511A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C09K23/16—Amines or polyamines
    • 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
    • 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
    • A61K8/03—Liquid compositions with two or more distinct layers
    • 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
    • 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
    • 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
    • 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
    • C09K23/42—Ethers, e.g. polyglycol ethers of alcohols or phenols

Definitions

  • the invention relates to stable three-phase systems consisting of three mutually immiscible liquid phases separated by phase interfaces with a wide three-phase range in terms of temperature and emulsifier concentration containing a water insoluble oil body at normal temperature (25 ° C), a special emulsifier as well as water.
  • Water and a water-immiscible organic phase usually form a metastable emulsion in the presence of a surface-active substance, henceforth called an emulsifier.
  • Ma differentiates between oil-in-water emulsions (O / W emulsions) in which the oil is finely distributed in the water and water-in-oil emulsions (W / O emulsions) in which the water is finely distributed in the oil is.
  • double emulsions by emulsifying a W / O emulsion in water or an O / W emulsion in oil (W / 0) W or (0 / W) 0 emulsions, so-called double emulsions, can be produced.
  • double emulsions consisting of three liquid phases, however, only result in two superimposed liquid phases after the separation of the phases, since they only consist of two immiscible liquids.
  • Such emulsions are described, for example, in Ull ann Encyklopedia of industrial chemistry, Volume 10, Weinheim 1975, p.449ff. They represent macroemulsions of milky appearance because of the particle size of the finely divided droplets.
  • phase behavior of such systems was e.g. by M. ahlweit and R.Strey in Angew. Chem. 1985 (87) 655-669.
  • Microemulsions have found increasing interest in recent years.
  • DE 3009 763 AI describes liquid cosmetic compositions which consist of three immiscible liquid phases.
  • JGMartinez, JMMorega and J.Pereda describe the use of microemulsions for the extraction of copper from solutions of several metals, cf. 2nd World Surfactant Congress, Paris 1988, p. 316: Kahlweit and Strey mentioned in the article cited above as important areas of application of Microemulsions, the tertiary oil production and concentrated solutions of pharmaceuticals, herbicides or insecticides.
  • the separation into three immiscible phases also depends on the temperature.
  • Type I mixtures consist of water, nonionic emulsifiers such as alkyl polyglycol ethers and an oil, e.g. an n-alkane.
  • Type II mixtures consist of water, an ionic emulsifier, a coemulsifier, usually a short-chain linear alcohol, and an oil.
  • Emulsifiers whose Al yl chain consists of at least 8 carbon atoms are particularly suitable for industrial applications.
  • For mixtures from Type I based on such emulsifiers have found Kahlweit and Strey that the corresponding areas of existence of the three-phase microemulsions are either very narrow or at temperatures far above room temperature, see Figure 21, p. 664, the above publication.
  • the alkyl polyglycol ethers used by the authors as emulsifiers also have the disadvantage that they are homologous substances.
  • emulsifiers which are addition products of ethylene oxide with alcohols can be used in the commercially available form, ie as mixtures of different homologs.
  • Kahlweit and Strey have based their studies on aliphatic and / or aromatic hydrocarbon oils.
  • a universally employable emulsifier must, however, be required to be applicable to mixtures containing polar oils such as ethers and esters.
  • the invention had for its object to develop mixtures of water, oil and emulsifiers which form stable three-phase systems in a wide range of temperatures and concentrations from three immiscible liquid phases separated from one another by phase interfaces.
  • the object was achieved according to the invention by three-phase systems consisting of three liquid phases which are immiscible with one another and separated by phase interfaces and having a wide three-phase range in terms of temperature and emulsifier concentration, characterized in that they contain
  • the Rl radical is an alkyl or 2-hydroxyalkyl group with 8 to 18 carbon atoms
  • X is a group OR 2 or a group R3R4
  • R 2 a group CH2-CH (0H) -CH20H, a group CH2-C (C2Hs) - (CH 2 0H) 2 , a group C (CH 2 0H) 3
  • One of the radicals R3 or R 4 is a group CH2-CH2-OH and the other is hydrogen, an alkyl group with 1 to 4 carbon atoms or a group CH2-CH2-OH
  • - n is the number 0 or 1 or an adduct of 1 to 4 moles of ethylene oxide with a compound of the formula I (C) 40 to 90% by weight of water
  • oil body (A) it is possible to use all liquid, water-insoluble, branched or linear, aliphatic or aromatic hydrocarbons, ethers or esters at normal temperature (25 ° C.).
  • solid or higher-melting paraffins, esters, waxes or fats can also be used, provided that their mixtures with other oil bodies from the above-mentioned group are liquid at normal temperature.
  • Well suited as oil bodies from the group of aliphatic hydrocarbons are e.g. Squalane, squalene, paraffinum perliquidum and paraffinum subliquidum, isohexadecane (hydrogenated polybutylene), paraffin delta and dialkylcyclohexanes with 6 to 14 carbon atoms in the alkyl group, e.g. Dioctylcyclohexane.
  • Esters of trihydric and polyhydric alcohols in particular vegetable triglycerides, e.g. Olive oil, almond oil, peanut oil, sunflower oil or the esters of pentaerythritol with e.g. Pelargonic acid or oleic acid.
  • vegetable triglycerides e.g. Olive oil, almond oil, peanut oil, sunflower oil or the esters of pentaerythritol with e.g. Pelargonic acid or oleic acid.
  • Mono- and diesters of the general formulas II, III and IV are also particularly suitable as oil bodies (II) Ri-COOR 2
  • R1C00-R3-00CR 1 in which R 1 is an alkyl group with 8 to 22 C atoms and R 2 is an alkyl group with 3 to 22 C atoms and R 3 is alkylene groups with 2 to 16 C atoms and which is at least 11 and at most 40 Contain carbon atoms.
  • Oil bodies of the type of the mono- and diesters of the formulas (II), (III) and (I) are known as cosmetic and pharmaceutical oil components and as lubricants and lubricant components.
  • the products which are liquid at normal temperature are the most important
  • solid products can also be used, as long as they result in liquid mixtures in combination with other oil components.
  • suitable monoesters (II) are the isopropyl esters v fatty acids with 12-22 C atoms, such as isopropyl myristate, isopropyl palmitate,
  • Other suitable monoesters are, for example, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl steara, isononyl palmitate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethyl hexyl laurate, 2-hexyldecyl, 2-hexyldec PaImitat, Oleylolea Oleylerucat, erucyl oleate and esters obtained from technical aliphatic alcohol mixtures and technical aliphatic carboxylic acids ind, for example esters of saturated and unsaturated fatty alcohols with 12 22 C atoms and saturated and unsaturated fatty acids with 12
  • Suitable dicarboxylic acid esters (III) are e.g. Di-n-butyl adipate, di-n-butyl sebacate, di- (2-ethylhexyl) adipate, di- (2-hexyldecyl) succinate and di isotridecylfugate.
  • Suitable diol esters (IV) are e.g.
  • the oil bodies are used in the O / W emulsions according to the invention in a quantity of 0.2 to 20% by weight, in particular 5 to 10% by weight.
  • a preferred group of emulsifiers for the purposes of the present invention are compounds of the general formula (I) in which the radical R * is an alkyl group having 8 to 18 carbon atoms and X is a group NR 3 R 4 .
  • emulsifiers are compounds of the general formula (I) in which X is a group OR 2 and R 2 is a group CH2-CH (0H) -CH20H or a group CH2-C (C2H5) (CH 2 0H) ) 2 and n means the number 0.
  • the emulsifiers of the general formula (I) can be obtained by processes known from the literature: compounds in which X is a group NR 3 R 4 and n is the number 0, for example according to EP 102140 AI, by reacting alkyl sulfates with excess primary or secondary amines; Compounds in which X is a group NR 3 R 4 and n is the number 1, according to DE 3504242 AI by reacting tertiary amines with sulfuric acid half-ester salts; Compounds in which X is a group OR 2 and R 2 is a group CH2-CH (0H) -CH2 ⁇ H or a group CH2-C (C2Hs) (CH20H) 2 and n is the number 0, for example by reacting trimethylolpropane with long-chain 1,2-epoxyalkanes in the presence of a basic catalyst or by reacting alkyl sulfates with glycerol.
  • the emulsifiers according to the invention also include substances which can be obtained by adding 1 to 4 mol of ethylene oxide to a compound of the general formula (I).
  • the conditions of the ethoxylation are known in the literature. Alcohols or polyols are usually used at temperatures from 100 to 200 ° C., preferably 150 to 180 ° C., at 2 to 10 bar with the exclusion of water in the presence of a basic catalyst with the desired molar excess of ethylene oxide. Hardness-free water is generally used to produce the three-phase systems according to the invention. This procedure is advantageous if ma wants to use the three-phase systems for cosmetic or pharmaceutical formulations.
  • the three-phase systems according to the invention are accessible by mixing Olkör by (A), emulsifier (B) and water at normal temperature: after shaking or stirring the ternary mixtures, three liquid phases which are immiscible with one another by phase boundaries are separated from one another by standing. If desired, the process of phase separation can be accelerated by centrifugation.
  • the three-phase systems according to the invention are suitable, for example, for use in the field of tertiary oil production and for the production of cosmetic and pharmaceutical formulations.
  • Cetiol V oleic acid decyl ester, from Henkel, Düsseldorf
  • Cetiol S dioctylcyclohexane, from Henkel, Düsseldorf
  • Paraffin del. DAB8 low viscosity, from Rhenania E. Wasserbow, Bonn Corav 22: Spindel ⁇ lraffinat, from Esso, Hamburg Mineralöl: Motoröl, Multigrade Oil HD SAE50W50, from Eurotex n-Decan: Merck-Schuchardt
  • (B2) n-octyl-mono- (2-hydroxyethyl) amine, n-C8Hi7-NH-CH 2 -CH 2 0H
  • (B4) adduct of 2 moles of ethylene oxide with 1 mole of glycerol mono- (Ci2 / i4) ether
  • (B5) trimethylolpropane mono- (2-hydroxydodecyl) ether
  • (B6) trimethylolpropane mono- (2-hydroxytetradecyl) ether
  • (B7 ) Adduct of 2 moles of ethylene oxide with trimethylolpropane mono- (2-hydroxydodecyl) ether
  • (B8) adduct of 2 moles of ethylene oxide with trimethylolpropane mono- (2-hydroxytetradecyl) ether
  • (B9) adduct of 4 moles of ethylene oxide with trimethylolpropane mono- (2-hydroxydodecyl) ether
  • (BIO) adduct of 4 moles of ethylene oxide with trimethylolpropane mono- (2-hydroxytetradecyl) ether
  • glycerol mono- (Ci2 / 14) ether was prepared by using decyl / tetradecyl sulfate, Na salt (70% Ci2, 30% C14) instead of octyl sulfate, Na salt. Subsequently, 600 g of glycerol mono- (Ci2 / 14) ether and 3.9 g of a 30% by weight solution of sodium methylate in methanol were introduced into an autoclave under a nitrogen atmosphere. The methanol was removed in vacuo by heating at 100 ° C for 30 minutes.
  • the emulsifiers (B7) to (BIO) were prepared by reaction with 2 or 4 mol of ethylene oxide with 1 mol (B5) or (B6).
  • the ethoxylation conditions were analogous to those described for (B4).
  • phase behavior of ternary mixtures of oil body (A), emulsifier (B) and water the three components were combined in the desired proportions at normal temperature (25 ° C.), shaken or stirred for a few minutes and then heated to the respective measurement temperature .
  • the phases were allowed to stand for 1 to 2 hours.
  • the number of phases was determined visually in the temperature range from 25 to 90 ° C.
  • the mixtures were used to accelerate the Phase separation in a laboratory centrifuge centrifuged for 1 to 40 hours at 4000 U / mi.
  • compositions of the ternary mixtures are always given in the following examples:
  • the components water and oil are characterized by their weight ratio, the concentration of the emulsifier is to be understood in% by weight based on the mixture as a whole.
  • Example 4 was repeated at 80 ° C. The results are summarized in the table. As in Example 4, the ethoxylated derivatives can be used more widely under these conditions than the non-ethoxylated ones.
  • Example 6

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Medicinal Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Birds (AREA)
  • Dermatology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Cosmetics (AREA)

Abstract

Des systèmes à trois phases composés de trois phases liquides non miscibles, mutuellement séparées par des interphases, contiennent un corps huileux insoluble dans l'eau, liquide à la température normale (25 °C), un émulsifiant spécial et de l'eau. Ces systèmes sont stables dans une large plage de températures et de concentration en émulsifiants. Ces systèmes à trois phases sont utiles dans des compositions cosmétiques et pharmaceutiques, ainsi que pour la récupération tertiaire de pétrole.
PCT/EP1992/000180 1991-02-06 1992-01-28 Systemes stables a trois phases Ceased WO1992013511A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4103488A DE4103488A1 (de) 1991-02-06 1991-02-06 Stabile dreiphasensysteme
DEP4103488.0 1991-02-06

Publications (1)

Publication Number Publication Date
WO1992013511A1 true WO1992013511A1 (fr) 1992-08-20

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Application Number Title Priority Date Filing Date
PCT/EP1992/000180 Ceased WO1992013511A1 (fr) 1991-02-06 1992-01-28 Systemes stables a trois phases

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DE (1) DE4103488A1 (fr)
WO (1) WO1992013511A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10302190A1 (de) * 2003-01-20 2004-07-29 Hans Schwarzkopf & Henkel Gmbh & Co. Kg 3-Phasen-Stylingmittel
DE202009008612U1 (de) 2009-06-21 2009-09-24 Dötterl, Matthias Flüssige Mehrphasensysteme zur Verwendung in Dekorationsartikeln

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4335103A (en) * 1977-03-28 1982-06-15 Almay, Inc. Multiphase cosmetic composition
EP0190708A1 (fr) * 1985-02-08 1986-08-13 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation d'étheramines tertiaires
EP0217250A2 (fr) * 1985-09-28 1987-04-08 Henkel Kommanditgesellschaft auf Aktien Préparations moussantes tensio-actives ayant des composants huileux insolubles dans l'eau, solubilisés clairement
EP0345586A1 (fr) * 1988-06-06 1989-12-13 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation d'une émulsion stable et peu visqueuse d'huile dans de l'eau avec des huiles polaires
WO1990007976A2 (fr) * 1989-01-12 1990-07-26 Henkel Kommanditgesellschaft Auf Aktien Dispersion de graisse non-ionique fluide
EP0412865B1 (fr) * 1989-07-12 1993-09-29 L'oreal Gel aqueux contenant en suspension des sphéroides d'une substance lipidique solide non hydrophile

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4335103A (en) * 1977-03-28 1982-06-15 Almay, Inc. Multiphase cosmetic composition
EP0190708A1 (fr) * 1985-02-08 1986-08-13 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation d'étheramines tertiaires
EP0217250A2 (fr) * 1985-09-28 1987-04-08 Henkel Kommanditgesellschaft auf Aktien Préparations moussantes tensio-actives ayant des composants huileux insolubles dans l'eau, solubilisés clairement
EP0345586A1 (fr) * 1988-06-06 1989-12-13 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation d'une émulsion stable et peu visqueuse d'huile dans de l'eau avec des huiles polaires
WO1990007976A2 (fr) * 1989-01-12 1990-07-26 Henkel Kommanditgesellschaft Auf Aktien Dispersion de graisse non-ionique fluide
EP0412865B1 (fr) * 1989-07-12 1993-09-29 L'oreal Gel aqueux contenant en suspension des sphéroides d'une substance lipidique solide non hydrophile

Also Published As

Publication number Publication date
DE4103488A1 (de) 1992-08-13

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