WO1995026707A1 - Dialkyl ether-containing micro-emulsions - Google Patents
Dialkyl ether-containing micro-emulsions Download PDFInfo
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- WO1995026707A1 WO1995026707A1 PCT/EP1995/001134 EP9501134W WO9526707A1 WO 1995026707 A1 WO1995026707 A1 WO 1995026707A1 EP 9501134 W EP9501134 W EP 9501134W WO 9526707 A1 WO9526707 A1 WO 9526707A1
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- ethylene oxide
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- 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
- A61K8/068—Microemulsions
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- 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
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- 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
- A61K9/1075—Microemulsions or submicron emulsions; Preconcentrates or solids thereof; Micelles, e.g. made of phospholipids or block copolymers
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- 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
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- 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
Definitions
- the invention relates to microemulsions and a process for their preparation, in which dialkyl ethers with a total of 12-24 carbon atoms are used as the oil component.
- Microemulsions are optically isotropic, thermodynamically stable systems which contain a water-insoluble oil component, emulsifiers and water.
- the clear or transparent appearance of the microemulsions is a consequence of the small particle size of the dispersed emulsion droplets, which is essentially below 100 nm, on average below 50 nm.
- the droplet size of macroemulsions is essentially above 100 nm, particularly fine-particle macroemulsions appearing in the range between 100 and 300 nm, which are brown-red in transparency and bluish shimmering in reflected light.
- Microemulsions are frequently described in the literature, but their targeted production is associated with great difficulties, since the areas of existence of the microemulsion in the three-phase diagram formed from oil component, water and emulsifiers are usually very small and the location of these areas of existence is high Dimensions of structural tural characteristics of all components and all other ingredients of such systems is strongly influenced.
- microemulsions are of considerable importance in the formulation of cosmetic and pharmaceutical preparations. There is therefore a need for reliable methods of producing microemulsions.
- the invention relates to a process for the preparation of microemulsions containing oil components, emulsifiers and water, characterized in that a di-alkyl ether having a total of 12-24 carbon atoms in an amount of at least 30% by weight is used as the oil component .-% of the total oil phase used.
- microemulsions are known in principle: mixtures of water, oil component and emulsifiers are prepared and the optically isotropic, thermodynamically stable areas of existence are determined in the three-phase diagram formed from these components.
- dialkyl ethers with 12-24 C atoms as the oil component
- the oil phase of the micro-emulsion can also contain further oil components.
- hydrocarbons for example paraffin oils, isoparaffins, esters, for example natural triglyceride oils, fatty acid esters, silicone oils and other known cosmetic and pharmaceutical oil components.
- suitable oil components are preferably fatty acid esters with a total of 12-26 carbon atoms or hydrocarbons in an amount of at most 70% by weight of the entire oil phase.
- the oil phase is to be understood as the sum of the oil components.
- Suitable fatty acid esters with 12-26 carbon atoms are e.g. Methyl laurate, isopropyl myristate, isopropyl palmitate, n-hexyl laurate and isooctyl stearate.
- Suitable emulsifiers are all emulsifiers which are suitable for emulsifying cosmetic or pharmaceutical oils and are physiologically and dermatologically compatible and soluble in the oil phase. For the production of microemulsions, however, it is necessary to use the emulsifiers in a larger amount than is necessary for the production of macroemulsions.
- the emulsifier is preferably used in an amount of approximately 0.2-2 parts by weight per part by weight of the oil phase (sum of the oil components).
- Emulsifiers of the type of nonionic ethylene oxide adducts with an HLB value of 6-10 are particularly suitable.
- Nonionic ethylene oxide adducts include, for example, the adducts of ethylene oxide with fatty acids with 12-22 carbon atoms, with fatty alcohols with 12- 22 C atoms, on fatty acid monoesters from Ci2-C22 ⁇ fatty acids and polyols with 2-6 C atoms and 2-6 hydroxyl groups, for example on fatty acid monoglycerides and on sorbitan fatty acid esters, on alkyl glycosides, on methyl glucose fatty acid esters, on fatty acid alkanolamides and on other alkoxylatable fat derivatives.
- Suitable emulsifiers are especially e.g. the adducts of 5 moles of ethylene oxide with cetyl and / or oleyl alcohol mixtures (cetyl / 01eyl alcohol + 5 E0) or of 3 moles of ethylene oxide with lauryl and / or myristyl alcohol (lauryl / myristyl alcohol + 3 E0).
- Microemulsions can be obtained particularly easily if, in addition to the lipophilic emulsifier mentioned, a hydrophilic emulsifier is used, e.g. of the type of nonionic ethylene oxide adducts with an HLB value above 11 or of the type of water-soluble ionic surfactants.
- a hydrophilic emulsifier e.g. of the type of nonionic ethylene oxide adducts with an HLB value above 11 or of the type of water-soluble ionic surfactants.
- Another subject of the invention is therefore a process for the production of microemulsions according to the invention, in which the emulsifier is a combination of a lipophilic emulsifier of the nonionic ethylene oxide adduct type with an HLB value of 6-10 and a hydrophilic emulsifier of the type non-ionic ethylene oxide adducts with an HLB value above 11 or the water-soluble ionic surfactants are used.
- ionic surfactants that are at least 1% by weight soluble in water at 20 ° C. are considered water-soluble.
- Anionic, cationic, amphoteric or zwitterionic surfactants can be used as ionic surfactants.
- a large number of such surfactants are known. They are generally characterized by a lipophilic alkyl or acyl group with 12-22 C atoms and an ionic group Water solubility-dependent group, which is preferably attached to one end of the lipophilic group.
- Suitable anionic surfactants are e.g. the water-soluble alkyl (Ci2 ⁇ Ciö) sulfuric acid half-ester salts (alkyl sulfate salts), the alkyl polyglycol ether sulfate salts, the monoalkyl phosphate salts, the soaps, the alkyl polyglycol ether carboxylate salts, the salts of N-acylating ten amino acids, the salts of protein hydrolyzate fatty acid condensates, the acyl isethionate salts, the acyl taurides, the acyl sarcosinate salts, the sulfosuccinic acid monoalkyl (Ci2-Ci8) ester salts and the sulfosuccinic acid dialkyl (C8-Ci6) ester salts and other known water-soluble salts of anionic surfactants.
- Suitable water-soluble cationic, zwitterionic and amphoteric surfactants
- Microemulsions belonging to the water-in-oil type and those belonging to the oil-in-water type can be produced by the process according to the invention.
- certain concentration ranges of the components are preferred:
- component (E) that is to say a diol or polyol having 2-6 carbon atoms.
- Suitable diols or polyols are e.g. Ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, glycerol, erythritol, trimethylolpropane, sorbitol, pentaerythritol, butanediol, diglycerol, diethylene glycol, glycerol monomethyl ether or methyl glucose.
- Microemulsions of the oil-in-water type can preferably be obtained in the following concentration ranges:
- (B) 0-20% by weight, but not more than 70% by weight of the oil phase, a fatty acid ester with a total of 12-26 carbon atoms or a hydrocarbon oil
- microemulsions at 20 ° C The consistency of the microemulsions at 20 ° C is predominantly liquid, but those microemulsions which have a high water content and those which have a proportion of ionic emulsifiers can be quite viscous (example 3) or even solidified in gel form (examples 4-6).
- microemulsions can be produced in a simple manner by mixing the oil components, dissolving the lipophilic emulsifiers and the hydrophilic nonionic emulsifiers therein and mixing this mixture with the mixture of water and optionally polyol and ionic surfactant and - if necessary - homogenizing .
- the mixture of dialkyl ether, fatty acid ester and nonionic ethylene oxide adducts is also suitable as a microemulsion concentrate which can be converted into stable microemulsions by simple mixing with water and, if appropriate, polyols and, if appropriate, hydrophilic nonionic or ionic surfactants.
- Such an emulsion concentrate for the production of microemulsions by the process according to the invention contains e.g.
- part of the oil component is replaced by an essential oil or by a mixture of synthetic fragrance oils.
- the microemulsions produced according to the invention can also contain other auxiliaries and active ingredients which are intended for the particular intended use.
- auxiliaries and active ingredients include skin cosmetic active ingredients, vitamins, humectants, antioxidants, preservatives, antimicrobial and fungicidal active ingredients, dermatological active ingredients and packaging aids such as e.g. Electrolytes, pH buffer substances, complexing agents, water-soluble, polymeric thickeners, foaming agents or foam inhibitors, pearlescent or opacifying substances and dyes.
- Di-n-octyl ether, isopropyl myristate and the nonionic emulsifiers are mixed at 40 ° C. Water and glycerin are also mixed and the mixture is then emulsified into the oil phase with stirring. A homogeneous, optically isotropic microemulsion is formed.
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Abstract
In a process for producing micro-emulsions, the oil component is a dialkyl ether with 12 to 24 C atoms in a proportion of at least 30 wt % of the oil phase. Micro-emulsions of the water-in-oil type preferably contain 20 to 60 wt % of the dialkyl ether, 0 to 40 wt % of a second oil component, preferably a fatty acid ester with 12 to 26 C atoms or a hydrocarbon oil, 20 to 35 wt % of a lipophilic non-ionic emulsifier with an HLB value of 6 to 10, 1 to 10 wt % of a hydrophilic non ionic or a water-soluble ionic tenside, 1 to 10 wt % of a diol or polyol with 2 to 6 C atoms and 1 to 20 wt % of water. Corresponding micro-emulsions of the oil-in-water type contain 3 to 30 wt % of the dialkyl ether , 0 to 20 wt % of a second oil component, 10 to 20 wt % of a lipophilic non-ionic emulsifier with an HLB value of 6 to 10, 1 to 10 wt % of an hydrophilic non-ionic or a water-soluble ionic tenside and 1 to 10 wt % of a diol or polyol. The micro-emulsions of the invention are suitable as supports for cosmetic and pharmaceutical preparations.
Description
Dialkylether enthaltende Mi roemulsionen Micro emulsions containing dialkyl ether
Die Erfindung betrifft Mikroemulsionen und ein Verfahren zu ihrer Herstellung, bei welchem als Olkomponente Dialkylether mit insgesamt 12 - 24 C-Atomen zum Einsatz kommen.The invention relates to microemulsions and a process for their preparation, in which dialkyl ethers with a total of 12-24 carbon atoms are used as the oil component.
Mikroemulsionen sind optisch isotrope, thermodynamisch stabile Sy¬ steme, die eine wasserunlösliche Olkomponente, Emulgatoren und Was¬ ser enthalten. Das klare bzw. transparente Aussehen der Mikroemul¬ sionen ist eine Folge der geringen Teilchengröße der dispergierten Emulsionströpfchen, die im wesentlichen unter 100 nm, im Mittel im¬ mer unter 50 nm, liegt. Die TropfchengröBe von Makroemulsionen liegt im wesentlichen über 100 nm, wobei im Bereich zwischen 100 und 300 nm besonders feinteilige, in der Durchsicht braunrot und im Auflicht bläulich schimmernde Makroemulsionen auftreten.Microemulsions are optically isotropic, thermodynamically stable systems which contain a water-insoluble oil component, emulsifiers and water. The clear or transparent appearance of the microemulsions is a consequence of the small particle size of the dispersed emulsion droplets, which is essentially below 100 nm, on average below 50 nm. The droplet size of macroemulsions is essentially above 100 nm, particularly fine-particle macroemulsions appearing in the range between 100 and 300 nm, which are brown-red in transparency and bluish shimmering in reflected light.
Mikroemulsionen sind in der Literatur häufig beschrieben, ihre ge¬ zielte Herstellung ist aber mit großen Schwierigkeiten verbunden, da die Existenzbereiche der Mikroemulsion in dem aus Olkomponente, Was¬ ser und Emulgatoren gebildeten Dreiphasen-Diagramm meist sehr klein sind und die Lage dieser Existenzbereiche in hohem Maße von struk-
turellen Merkmalen aller Komponenten und aller weiteren Inhaltsstof¬ fe solcher Systeme stark beeinflußt wird.Microemulsions are frequently described in the literature, but their targeted production is associated with great difficulties, since the areas of existence of the microemulsion in the three-phase diagram formed from oil component, water and emulsifiers are usually very small and the location of these areas of existence is high Dimensions of structural tural characteristics of all components and all other ingredients of such systems is strongly influenced.
Mikroemulsionen haben wegen ihrer gegenüber Makroemulsionen höheren Stabilität, feineren Verteilung der inneren Phase, der meist höheren Effektivität und der besseren transdermalen Penetration der darin eingearbeiteten Wirkstoffe eine erhebliche Bedeutung bei der Formu¬ lierung kosmetischer und pharmazeutischer Zubereitungen. Es besteht daher ein Bedürfnis an zuverlässigen Verfahren zur Erzeugung von Mikroemulsionen.Because of their greater stability than macroemulsions, finer distribution of the inner phase, mostly higher effectiveness and better transdermal penetration of the active ingredients incorporated therein, microemulsions are of considerable importance in the formulation of cosmetic and pharmaceutical preparations. There is therefore a need for reliable methods of producing microemulsions.
Es wurde nun beobachtet, daß bei Verwendung von Dialkylethern als Olkomponenten sehr leicht Mikroemulsionen gebildet werden, und daß die mit Dialkylethern erhältlichen Mikroemulsionen relativ große Existenzbereiche aufweisen.It has now been observed that when dialkyl ethers are used as oil components, microemulsions are very easily formed and that the microemulsions obtainable with dialkyl ethers have relatively large areas of existence.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Mi¬ kroemulsionen mit einem Gehalt an Olkomponenten, Emulgatoren und Wasser, dadurch gekennzeichnet, daß man als Olkomponente einen Di¬ alkylether mit insgesamt 12 - 24 C-Atomen in einer Menge von we¬ nigstens 30 Gew.-% der gesamten Ölphase verwendet.The invention relates to a process for the preparation of microemulsions containing oil components, emulsifiers and water, characterized in that a di-alkyl ether having a total of 12-24 carbon atoms in an amount of at least 30% by weight is used as the oil component .-% of the total oil phase used.
Die Methoden zur Herstellung von Mikroemulsionen sind im Prinzip bekannt: Man stellt Mischungen aus Wasser, Olkomponente und Emul¬ gatoren her und bestimmt die optisch isotropen, thermodynamisch stabilen Existenzbereiche in dem aus diesen Komponenten gebildeten Dreiphasendiagramm. Bei Verwendung von Dialkylethern mit 12 - 24 C-Atomen als Olkomponente findet man dabei besonders breite Exi¬ stenzbereiche für Mikroemulsionen. Dies gilt in besonders bevor¬ zugter Weise für aliphatische Dialkylether mit jeweils 6 - 10 C- Ato en pro Alkylgruppe.
Neben den Dialkylethern kann die Olphase der Mikroe ulsion noch wei¬ tere Olkomponenten enthalten. Als solche eignen sich Kohlenwasser¬ stoffe, z.B. Paraffinöle, Isoparaffine, Ester, z.B. natürliche Tri- glyceridöle, Fettsäureester, Silikonöle und andere bekannte kosme¬ tische und pharmazeutische Olkomponenten. Bevorzugt geeignete wei¬ tere Olkomponenten sind Fettsäureester mit insgesamt 12 - 26 C-Ato¬ men oder Kohlenwasserstoffe in einer Menge von höchstens 70 Gew.-% der gesamten Olphase. Als Olphase soll in diesem Zusammenhang die Summe der Olkomponenten verstanden werden.The methods for producing microemulsions are known in principle: mixtures of water, oil component and emulsifiers are prepared and the optically isotropic, thermodynamically stable areas of existence are determined in the three-phase diagram formed from these components. When using dialkyl ethers with 12-24 C atoms as the oil component, there are particularly broad ranges of existence for microemulsions. This applies in a particularly preferred manner to aliphatic dialkyl ethers with 6-10 C-ato enes per alkyl group. In addition to the dialkyl ethers, the oil phase of the micro-emulsion can also contain further oil components. Suitable as such are hydrocarbons, for example paraffin oils, isoparaffins, esters, for example natural triglyceride oils, fatty acid esters, silicone oils and other known cosmetic and pharmaceutical oil components. Further suitable oil components are preferably fatty acid esters with a total of 12-26 carbon atoms or hydrocarbons in an amount of at most 70% by weight of the entire oil phase. In this context, the oil phase is to be understood as the sum of the oil components.
Geeignete Fettsäureester mit 12 - 26 C-Atomen sind z.B. Methyllau¬ rat, Isopropylmyristat, Isopropylpalmitat, n-Hexyllaurat und Iso- octylstearat. Besonders bevorzugt eignet sich als Olkomponente eine Kombination aus Dialkylether und Fettsäureester im Gewichtsverhält¬ nis 1 : 2 bis 2 : 1, z.B. eine Mischung aus gleichen Teilen Di-n- octylether und Isopropylmyristat.Suitable fatty acid esters with 12-26 carbon atoms are e.g. Methyl laurate, isopropyl myristate, isopropyl palmitate, n-hexyl laurate and isooctyl stearate. A combination of dialkyl ether and fatty acid ester in a weight ratio of 1: 2 to 2: 1, e.g. a mixture of equal parts of di-n-octyl ether and isopropyl myristate.
Als Emulgatoren eignen sich alle für die Emulgierung von kosmeti¬ schen oder pharmazeutischen Ölen geeigneten, physiologisch und dermatologisch verträglichen und in der Olphase löslichen Emulga¬ toren. Es ist für die Erzeugung von Mikroemulsionen allerdings er¬ forderlich, die Emulgatoren in höherer Menge einzusetzen als dies für die Herstellung von Makroemulsionen notwendig ist. Bevorzugt wird der Emulgator in einer Menge von ca. 0,2 - 2 Gewichtsteilen pro Gewichtsteil der Olphase (Summe der Olkomponenten) eingesetzt.Suitable emulsifiers are all emulsifiers which are suitable for emulsifying cosmetic or pharmaceutical oils and are physiologically and dermatologically compatible and soluble in the oil phase. For the production of microemulsions, however, it is necessary to use the emulsifiers in a larger amount than is necessary for the production of macroemulsions. The emulsifier is preferably used in an amount of approximately 0.2-2 parts by weight per part by weight of the oil phase (sum of the oil components).
Bevorzugt geeignet sind Emulgatoren vom Typ der nichtionischen Ethylenoxid-Addukte mit einem HLB-Wert von 6 - 10. Unter nicht¬ ionischen Ethylenoxidaddukten werden dabei z.B. die Anlagerungs¬ produkte von Ethylenoxid an Fettsäuren mit 12 - 22 C-Atomen, an Fettalkohole mit 12 - 22 C-Atomen, an Fettsäuremonoester aus Ci2-C22~Eettsäuren und Polyolen mit 2 - 6 C-Atomen und 2 - 6 Hy¬ droxylgruppen, z.B. an Fettsäuremonoglyceride und an Sorbitan-
fettsäureester, an Alkylglycoside, an Methylglucose-Fettsäureester, an Fettsäurealkanolamide und an andere alkoxylierbare Fettderivate verstanden. Unter dem HLB-Wert wird ein aus der Struktur errechenba¬ rer Wert gemäß HLB = 0,2 (100 - L) verstanden, worin L der Anteil der lipophilen Alkyl- oder Acylgruppen in Gew.-% des Gesamtmoleköls ist.Emulsifiers of the type of nonionic ethylene oxide adducts with an HLB value of 6-10 are particularly suitable. Nonionic ethylene oxide adducts include, for example, the adducts of ethylene oxide with fatty acids with 12-22 carbon atoms, with fatty alcohols with 12- 22 C atoms, on fatty acid monoesters from Ci2-C22 ~ fatty acids and polyols with 2-6 C atoms and 2-6 hydroxyl groups, for example on fatty acid monoglycerides and on sorbitan fatty acid esters, on alkyl glycosides, on methyl glucose fatty acid esters, on fatty acid alkanolamides and on other alkoxylatable fat derivatives. The HLB value is understood to be a value which can be calculated from the structure in accordance with HLB = 0.2 (100 −L), where L is the proportion of the lipophilic alkyl or acyl groups in% by weight of the total molecular oil.
Geeignete Emulgatoren sind insbesondere z.B. die Anlagerungsprodukte von 5 Mol Ethylenoxid an Cetyl- und/oder Oleylalkohol-Gemische (Ce- tyl-/01eylalkohol + 5 E0) oder von 3 Mol Ethylenoxid an Lauryl- und/oder Myristylalkohol (Lauryl-/Myristylalkohol + 3 E0).Suitable emulsifiers are especially e.g. the adducts of 5 moles of ethylene oxide with cetyl and / or oleyl alcohol mixtures (cetyl / 01eyl alcohol + 5 E0) or of 3 moles of ethylene oxide with lauryl and / or myristyl alcohol (lauryl / myristyl alcohol + 3 E0).
Besonders leicht lassen sich Mikroemulsionen dann erhalten, wenn außer dem genannten lipophilen Emulgator noch ein hydrophiler Emul¬ gator eingesetzt wird, z.B. vom Typ der nichtionischen Ethylenoxid- Addukte mit einem HLB-Wert oberhalb von 11 oder vom Typ der wasser¬ löslichen ionischen Tenside.Microemulsions can be obtained particularly easily if, in addition to the lipophilic emulsifier mentioned, a hydrophilic emulsifier is used, e.g. of the type of nonionic ethylene oxide adducts with an HLB value above 11 or of the type of water-soluble ionic surfactants.
Ein weiterer Erfindungsgegenstand ist daher ein Verfahren zur Her¬ stellung zur erfindungsgemäßen Herstellung von Mikroemulsionen, bei dem der Emulgator eine Kombination aus einem lipophilen Emulgator vom Typ der nichtionischen Ethylenoxid-Addukte mit einem HLB-Wert von 6 - 10 und einem hydrophilen Emulgator vom Typ der nichtioni¬ schen Ethylenoxid-Addukte mit einem HLB-Wert oberhalb von.11 oder der wasserlöslichen ionischen Tenside verwendet wird.Another subject of the invention is therefore a process for the production of microemulsions according to the invention, in which the emulsifier is a combination of a lipophilic emulsifier of the nonionic ethylene oxide adduct type with an HLB value of 6-10 and a hydrophilic emulsifier of the type non-ionic ethylene oxide adducts with an HLB value above 11 or the water-soluble ionic surfactants are used.
Als wasserlöslich werden dabei alle jene Tenside angesehen, die bei 20°C zu wenigstens 1 Gew.- in Wasser löslich sind. Als ionische Tenside können anionische, kationische, amphotere oder zwitterioni¬ sche Tenside verwendet werden. Solche Tenside sind in großer Zahl bekannt. Sie zeichnen sich ganz allgemein durch eine lipophile Al¬ kyl- oder Acylgruppe mit 12 - 22 C-Atomen und eine ionische, die
Wasserlöslichkeit bedingende Gruppe aus, die bevorzugt an einem Ende der lipophilen Gruppe gebunden ist.All those surfactants that are at least 1% by weight soluble in water at 20 ° C. are considered water-soluble. Anionic, cationic, amphoteric or zwitterionic surfactants can be used as ionic surfactants. A large number of such surfactants are known. They are generally characterized by a lipophilic alkyl or acyl group with 12-22 C atoms and an ionic group Water solubility-dependent group, which is preferably attached to one end of the lipophilic group.
Geeignete Aniontenside sind z.B. die wasserlöslichen Alkyl-(Ci2~ Ciö)-schwefelsäurehalbester-Salze (Alkylsulfatsalze) , die Alkyl-po- lyglycolethersulfat-Salze, die Monoalkylphosphat-Salze, die Seifen, die Alkyl-polyglycolether-carboxylat-Salze, die Salze von N-acylier- ten Aminosäuren, die Salze von Proteinhydrolysat-Fettsäurekondensa- ten, die Acylisethionat-Salze, die Acyltauride, die Acylsarkosinat- Salze, die Sulfobernsteinsäure-mono-alkyl-(Ci2-Ci8)-ester-Salze und die Sulfobernsteinsäuredialkyl-(C8-Ci6)-ester-Salze und andere be¬ kannte wasserlösliche Salze anionischer Tenside. Geeignete wasser¬ lösliche kationische, zwitterionische und amphotere Tenside sind aus der Fachliteratur bekannt.Suitable anionic surfactants are e.g. the water-soluble alkyl (Ci2 ~ Ciö) sulfuric acid half-ester salts (alkyl sulfate salts), the alkyl polyglycol ether sulfate salts, the monoalkyl phosphate salts, the soaps, the alkyl polyglycol ether carboxylate salts, the salts of N-acylating ten amino acids, the salts of protein hydrolyzate fatty acid condensates, the acyl isethionate salts, the acyl taurides, the acyl sarcosinate salts, the sulfosuccinic acid monoalkyl (Ci2-Ci8) ester salts and the sulfosuccinic acid dialkyl (C8-Ci6) ester salts and other known water-soluble salts of anionic surfactants. Suitable water-soluble cationic, zwitterionic and amphoteric surfactants are known from the specialist literature.
Nach dem erfindungsgemäßen Verfahren lassen sich Mikroemulsionen herstellen, die dem Typ Wasser-in-Öl angehören und solche, die dem Typ Öl-in-Wasser angehören. Für beide Typen von Mikroemulsionen sind bestimmte Konzentrationsbereiche der Komponenten bevorzugt:Microemulsions belonging to the water-in-oil type and those belonging to the oil-in-water type can be produced by the process according to the invention. For both types of microemulsions, certain concentration ranges of the components are preferred:
Mikroemulsionen vom Typ Wasser-in-Öl sind dadurch gekennzeichnet, daß sieMicroemulsions of the water-in-oil type are characterized in that they
(A) 20 - 60 Gew.-% eines Dialkylethers mit insgesamt 12 - 24 C-Ato¬ men(A) 20-60% by weight of a dialkyl ether with a total of 12-24 carbon atoms
(B) 0 - 40 Gew.-% eines Fettsäureesters mit insgesamt 12 - 26 C-Ato¬ men oder eines Kohlenwasserstoffδls(B) 0 to 40% by weight of a fatty acid ester with a total of 12 to 26 carbon atoms or a hydrocarbon oil
(C) 20 - 35 Gew.-% eines Ethylenoxid-Addukts mit einem HLB-Wert von(C) 20-35% by weight of an ethylene oxide adduct with an HLB value of
6 - 10
(D) 1 - 10 Gew.-% eines nichtionischen Ethylenoxid-Addukts mit einem6-10 (D) 1-10% by weight of a nonionic ethylene oxide adduct with a
HLB-Wert oberhalb 11 oder eines wasserlöslichen ionischen TensidsHLB value above 11 or a water-soluble ionic surfactant
(E) 1 - 10 Gew.-% eines Diols oder Polyols mit 2 - 6 C-Atomen und(E) 1-10% by weight of a diol or polyol with 2-6 C atoms and
1 - 20 Gew.-% Wasser enthalten.Contain 1 - 20 wt .-% water.
Durch den Zusatz der Komponente (E), also eines Diols oder Polyols mit 2 - 6 C-Atomen, wird der Existenzbereich der Mikroemulsion noch weiter vergrößert. Geeignete Diole oder Polyole sind z.B. Ethylen- glycol, 1,2-Propylenglycol, 1,3-Propylenglycol, Glycerin, Erythrit, Trimethylolpropan, Sorbit, Pentaerythrit, Butandiol, Diglycerin, Diethylenglycol, Glycerin-monomethylether oder Methylglucose.The area of existence of the microemulsion is further increased by adding component (E), that is to say a diol or polyol having 2-6 carbon atoms. Suitable diols or polyols are e.g. Ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, glycerol, erythritol, trimethylolpropane, sorbitol, pentaerythritol, butanediol, diglycerol, diethylene glycol, glycerol monomethyl ether or methyl glucose.
Mikroemulsionen des Typs Öl-in-Wasser lassen sich bevorzugt in fol¬ genden Konzentrationsbereichen erhalten:Microemulsions of the oil-in-water type can preferably be obtained in the following concentration ranges:
(A) 3 - 30 Gew.-% eines Dialkylethers mit insgesamt 12 - 24 C-Atomen(A) 3 to 30% by weight of a dialkyl ether with a total of 12 to 24 carbon atoms
(B) 0 - 20 Gew.- ,aber nicht mehr als 70 Gew.-% der Olphase, eines Fettsäureesters mit insgesamt 12 - 26 C-Atomen oder eines KohlenwasserstoffÖls(B) 0-20% by weight, but not more than 70% by weight of the oil phase, a fatty acid ester with a total of 12-26 carbon atoms or a hydrocarbon oil
(C) 10 - 20 Gew.-% eines Ethylenoxid-Addukts mit einem HLB-Wert von(C) 10-20% by weight of an ethylene oxide adduct with an HLB value of
6 - 106-10
(D) 1 - 10 Gew.-% eines Ethylenoxid-Addukts mit einem HLB-Wert ober¬ halb 11 oder eines wasserlöslichen ionischen Tensids(D) 1-10% by weight of an ethylene oxide adduct with an HLB value above 11 or a water-soluble ionic surfactant
(E) 1 - 10 Gew.-% eines Diols oder Polyols mit 2 - 6 C-Atomen.
Solche Öl-in-Wasser-Emulsionen lassen sich auch aus den weiter oben beschriebenen Wasser-in-Öl-Emulsionen durch entsprechende Erhöhung des Wasseranteils erhalten.(E) 1-10% by weight of a diol or polyol with 2-6 C atoms. Such oil-in-water emulsions can also be obtained from the water-in-oil emulsions described above by increasing the water content accordingly.
Die Konsistenz der Mikroemulsionen bei 20°C ist überwiegend flüssig, solche Mikroemulsionen, die einen hohen Wassergehalt und solche, die einen Anteil ionischer Emulgatoren aufweisen, können jedoch recht dickflüssig (Beispiel 3) oder gar gelförmig erstarrt (Beispiel 4 - 6) sein.The consistency of the microemulsions at 20 ° C is predominantly liquid, but those microemulsions which have a high water content and those which have a proportion of ionic emulsifiers can be quite viscous (example 3) or even solidified in gel form (examples 4-6).
Die Mikroemulsionen lassen sich auf einfache Weise dadurch herstel¬ len, daß man die Olkomponenten mischt, die lipophilen Emulgatoren und die hydrophilen nichtionischen Emulgatoren darin löst und diese Mischung mit der Mischung von Wasser und ggf. Polyol und ionischem Tensid mischt und - falls erforderlich - homogenisiert.The microemulsions can be produced in a simple manner by mixing the oil components, dissolving the lipophilic emulsifiers and the hydrophilic nonionic emulsifiers therein and mixing this mixture with the mixture of water and optionally polyol and ionic surfactant and - if necessary - homogenizing .
Das Gemisch aus Dialkylether, Fettsäureester und nichtionischen Ethylenoxid-Addukten eignet sich auch als Mikroemulsionskonzentrat, das sich durch einfaches Vermischen mit Wasser und ggf. Polyolen und ggf. hydrophilen nichtionischen oder ionischen Tensiden in stabile Mikroemulsionen überführen läßt.The mixture of dialkyl ether, fatty acid ester and nonionic ethylene oxide adducts is also suitable as a microemulsion concentrate which can be converted into stable microemulsions by simple mixing with water and, if appropriate, polyols and, if appropriate, hydrophilic nonionic or ionic surfactants.
Ein solches Emulsionskonzentrat zur Herstellung von Mikroemulsionen nach dem erfindungsgemäßen Verfahren enthält z.B.Such an emulsion concentrate for the production of microemulsions by the process according to the invention contains e.g.
(A) 25 - 35 Gew.-% eines Dialkylethers mit insgesamt 12 - 24 C-Ato¬ men(A) 25-35% by weight of a dialkyl ether with a total of 12-24 carbon atoms
(B) 25 - 35 Gew.-% eines Fettsäureesters mit insgesamt 12 - 26 C-(B) 25-35% by weight of a fatty acid ester with a total of 12-26 C-
Atomen und
(C) 30 - 40 Gew.- eines Emulgators vom Typ der nichtionischenAtoms and (C) 30-40% by weight of a nonionic type emulsifier
Ethylenoxid-Addukte mit einem HLB-Wert von 6 - 10Ethylene oxide adducts with an HLB value of 6-10
(D) 1 - 10 Gew.-% eines Emulgators vom Typ der nichtionischen Ethy¬ lenoxid-Addukte mit einem HLB-Wert oberhalb von 11.(D) 1-10% by weight of an emulsifier of the nonionic ethylene oxide adduct type with an HLB value above 11.
Zur Verwendung als Mikroemulsions-Badeöl wird ein Teil der Olkom¬ ponente durch ein ätherisches Öl oder durch ein Gemisch syntheti¬ scher Duftstofföle ersetzt.For use as a microemulsion bath oil, part of the oil component is replaced by an essential oil or by a mixture of synthetic fragrance oils.
Neben den geannten obligatorischen Komponenten können die erfin¬ dungsgemäß hergestellten Mikroemulsionen auch weitere, für den je¬ weiligen Verwendungszweck bestimmte Hilfs- und Wirkstoffe enthalten. Hierzu gehören hautkosmetische Wirkstoffe, Vitamine, Feuchthalte¬ mittel, Antioxidantien, Konservierungsmittel, antimikrobielle und fungizide Wirkstoffe, dermatologische Wirkstoffe und Konfektio- nierungshilfsmittel, wie z.B. Elektrolyte, pH-Puffersubstanzen, Komplexbildner, wasserlösliche, polymere Verdickungs ittel, Schaumbildner oder Schauminhibitoren, perlglanzbildende oder trü¬ bende Stoffe und Farbstoffe.In addition to the compulsory components mentioned, the microemulsions produced according to the invention can also contain other auxiliaries and active ingredients which are intended for the particular intended use. These include skin cosmetic active ingredients, vitamins, humectants, antioxidants, preservatives, antimicrobial and fungicidal active ingredients, dermatological active ingredients and packaging aids such as e.g. Electrolytes, pH buffer substances, complexing agents, water-soluble, polymeric thickeners, foaming agents or foam inhibitors, pearlescent or opacifying substances and dyes.
Die folgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern.
The following examples are intended to explain the subject matter of the invention in more detail.
B e i s p i e l eB e i s p i e l e
1. Nichtionogene Mikroemulsionen W/01. Nonionic microemulsions W / 0
' 1 ' 1
Di-n-octylether 26 ,5 Gew.-%Di-n-octyl ether 26.5% by weight
I sopropy Imyr i stat 26,5 Gew.-%I sopropy Imyr i stat 26.5% by weight
Cety oleylalkohol + 5 EO 29,8 Gew.-%Cety oleyl alcohol + 5 EO 29.8% by weight
Cetyl-/oleylalkohol + 10 EO 3 , 3 Gew. -%Cetyl / oleyl alcohol + 10 EO 3.3% by weight
Glycerin 6,0 Gew.-Glycerin 6.0 wt.
Wasser 8,0 Gew.-%Water 8.0% by weight
Herstellung:Manufacturing:
Di-n-octylether, Isopropylmyristat und die nichtionischen Emulga¬ toren werden bei 40°C gemischt. Wasser und Glycerin werden ebenfalls gemischt und die Mischung dann unter Rühren in die Olphase einemul- giert. Es bildet sich eine homogene, optisch isotrope Mikroemulsion.Di-n-octyl ether, isopropyl myristate and the nonionic emulsifiers are mixed at 40 ° C. Water and glycerin are also mixed and the mixture is then emulsified into the oil phase with stirring. A homogeneous, optically isotropic microemulsion is formed.
2. Nichtionische Mikroemulsion 0/W2. Nonionic microemulsion 0 / W
22
Di-n-Octylether 14,2 Gew.-%Di-n-octyl ether 14.2% by weight
Isopropylmyristat 14,2 Gew.-%Isopropyl myristate 14.2% by weight
CetyWoleylalkohol + 5 EO 15,9 Gew.-%CetyWoleyl alcohol + 5 EO 15.9% by weight
CetyWoleylalkohol + 10 E0 1 ,8 Gew.-%CetyWoleyl alcohol + 10 E0 1.8% by weight
Glycerin 6,0 Gew.-%Glycerin 6.0% by weight
Wasser 48,0 Gew.-%
3. Anionische Mikroemulsion 0/WWater 48.0% by weight 3. Anionic microemulsion 0 / W
3 4 5 63 4 5 6
Di-n-Octylether 4,0 4,0 4,0 4,0 Isopropyl yristat 4,0 4,0 4,0 4,0 CetyWoleylalkohol + 5 EO 12,0 12,0 - - LauryWmyristylalkohol + 3 EO - - 7,0 7,5 LauryWmyristylalkohol + 2 E0- sulfat, Na-Salz 3,0 3,0 8,0 7,5 Glycerin 7,0 10,0 7,0 7,0 Wasser 70,0 67,0 70,0 70,0Di-n-octyl ether 4.0 4.0 4.0 4.0 isopropyl yristat 4.0 4.0 4.0 4.0 Cety-woleyl alcohol + 5 EO 12.0 12.0 - - Laury-wmyristyl alcohol + 3 EO - - 7 .0 7.5 Laury wmyristyl alcohol + 2 E0 sulfate, Na salt 3.0 3.0 8.0 7.5 Glycerin 7.0 10.0 7.0 7.0 Water 70.0 67.0 70.0 70.0
Mikroemu1sionskonzentrate MikroemulsionsbadeöleMicroemulsion concentrates Microemulsion bath oils
7 87 8
Di-n-Octylether 30,5 28Di-n-octyl ether 30.5 28
Isoproyplmyristat 30,5 28Isoproyplmyristat 30.5 28
Parfü öl - 5Perfume oil - 5
CetyWoleylalkohol + 5 E0 35 35CetyWoleyl alcohol + 5 E0 35 35
CetyWoleylalkohol + 10 E0 4 4
CetyWoleyl alcohol + 10 E0 4 4
Claims
1. Verfahren zur Herstellung von Mikroemulsionen mit einem Gehalt an Olkomponenten, Emulgatoren und Wasser, dadurch gekennzeich¬ net, daß man als Olkomponente einen Dialkylether mit insgesamt 12 - 24 C-Atomen in einer Menge von wenigstens 30 Gew.-% der Olphase verwendet.1. Process for the preparation of microemulsions containing oil components, emulsifiers and water, characterized in that a dialkyl ether having a total of 12-24 carbon atoms in an amount of at least 30% by weight of the oil phase is used as the oil component.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Di¬ alkylether ein linearer Di-n-alkylether mit jeweils 6 - 10 C- Atomen pro Alkylgruppe ist.2. The method according to claim 1, characterized in that the di-alkyl ether is a linear di-n-alkyl ether, each with 6 - 10 carbon atoms per alkyl group.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß als weitere Olkomponenten Fettsäureester mit insgesamt 12 - 26 C-Atomen oder Kohlenwasserstoffe in einer Menge von höchstens 70 Gew.-% der Olphase verwendet wird.3. The method according to claim 1 or 2, characterized in that as further oil components fatty acid esters with a total of 12 - 26 carbon atoms or hydrocarbons in an amount of at most 70 wt .-% of the oil phase is used.
4. Verfahren nach einem der Ansprüche 1 - 3, dadurch gekennzeich¬ net, daß als Emulgatoren eine Kombination aus einem lipophilen Emulgator vom Typ der nichtionischen Ethylenoxid-Addukte mit einem HLB-Wert von 6 - 10 und einem hydrophilen Emulgator vom Typ der nichtionischen Ethylenoxid-Addukte mit einem HLB-Wert oberhalb von 11 oder der wasserlöslichen ionischen Tenside ver¬ wendet wird.4. The method according to any one of claims 1-3, characterized in that the emulsifiers are a combination of a lipophilic emulsifier of the nonionic ethylene oxide adduct type with an HLB value of 6-10 and a hydrophilic emulsifier of the nonionic ethylene oxide type Adducts with an HLB value above 11 or the water-soluble ionic surfactants are used.
5. Mikroemulsion vom Typ Wasser-in-Öl, dadurch gekennzeichnet, daß sie5. Microemulsion of the water-in-oil type, characterized in that it
(A) 20 - 60 Gew.-% eines Dialkylethers mit insgesamt 12 - 24(A) 20-60% by weight of a dialkyl ether with a total of 12-24
C-Atomen (B) 0 - 40 Gew.-% eines Fettsäureesters mit insgesamt 12 - 26C atoms (B) 0-40% by weight of a fatty acid ester with a total of 12-26
C-Atomen oder eines KohlenwasserstoffölsCarbon atoms or a hydrocarbon oil
(C) 20 - 35 Gew.-% eines Ethylenoxid-Addukts mit einem HLB-Wert von 6 - 10(C) 20-35% by weight of an ethylene oxide adduct with an HLB value of 6-10
(D) 1 - 10 Gew.-% eines nichtionischen Ethylenoxid-Addukts mit einem HLB-Wert oberhalb 11 oder eines wasser¬ löslichen ionischen Tensids(D) 1-10% by weight of a nonionic ethylene oxide adduct with an HLB value above 11 or a water-soluble ionic surfactant
(E) 1 - 10 Gew.-% eines Diols oder Polyols mit 2 - 6 C-Atomen und(E) 1-10% by weight of a diol or polyol with 2-6 C atoms and
1 - 20 Gew.-% Wasser1 - 20 wt .-% water
enthält.contains.
6. Mikroemulsion vom Typ Öl-in-Wasser, dadurch gekennzeichnet, daß sie6. Oil-in-water type microemulsion, characterized in that it
(A) 3 - 30 Gew.-% eines Dialkylethers mit insgesamt 12 - 24 C-(A) 3 to 30% by weight of a dialkyl ether with a total of 12 to 24 C
AtomenAtoms
(B) 0 - 20 Gew.-% , aber nicht mehr als 70 Gew.-% der Olkom¬ ponenten (A + B), eines Fettsäureesters mit insgesamt 12 - 26 C-Atomen oder eines Kohlen¬ wasserstoffÖls(B) 0-20% by weight, but not more than 70% by weight, of the oil components (A + B), a fatty acid ester with a total of 12-26 carbon atoms or a hydrocarbon oil
(C) 10 - 20 Gew.-% eines Ethylenoxid-Addukts mit einem HLB-Wert von 6 - 10 (D) 1 - 10 Gew.-% eines Ethylenoxid-Addukts mit einem HLB-Wert oberhalb 11 oder eines wasserlöslichen ioni¬ schen Tensids(C) 10-20% by weight of an ethylene oxide adduct with an HLB value of 6-10 (D) 1-10% by weight of an ethylene oxide adduct with an HLB value above 11 or a water-soluble ionic surfactant
(E) 1 - 10 Gew.-% eines Diols oder Polyols mit 2 - 6 C-Atomen(E) 1-10% by weight of a diol or polyol with 2-6 C atoms
enthält.contains.
7. Emulsionskonzentrat zur Herstellung von Mikroemulsionen nach dem Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß es7. emulsion concentrate for the preparation of microemulsions by the process according to claim 1, characterized in that it
(A) 25 - 35 Gew.-% eines Dialkylethers mit insgesamt 12 - 24(A) 25-35% by weight of a dialkyl ether with a total of 12-24
C-AtomenC atoms
(B) 25 - 35 Gew.-% eines Fettsäureesters mit insgesamt 12 - 26(B) 25-35% by weight of a fatty acid ester with a total of 12-26
C-AtomenC atoms
(C) 30 - 40 Gew.-% eines Emulgators vom Typ der nichtionischen(C) 30-40% by weight of a nonionic type emulsifier
Ethylenoxid-Addukte mit einem HLB-Wert von 6 - 10 undEthylene oxide adducts with an HLB value of 6 - 10 and
(D) 1 - 10 Gew.-% eines Emulgators vom Typ der nichtionischen(D) 1-10% by weight of a nonionic type emulsifier
Ethylenoxid-Addukte mit einem HLB-Wert ober¬ halb von 11Ethylene oxide adducts with an HLB value above 11
enthält. contains.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4411557.1 | 1994-04-02 | ||
| DE19944411557 DE4411557A1 (en) | 1994-04-02 | 1994-04-02 | Process for the preparation of microemulsions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1995026707A1 true WO1995026707A1 (en) | 1995-10-12 |
Family
ID=6514556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1995/001134 WO1995026707A1 (en) | 1994-04-02 | 1995-03-25 | Dialkyl ether-containing micro-emulsions |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE4411557A1 (en) |
| WO (1) | WO1995026707A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19619036A1 (en) * | 1996-04-30 | 1997-11-13 | Schering Ag | New vitamin D derivatives with carbo- or heterocyclic substituents at C-25, process for their preparation and their use in the manufacture of medicinal products |
| DE19929505A1 (en) * | 1999-06-29 | 2001-01-11 | Cognis Deutschland Gmbh | Cosmetic emulsions |
| EP1849453A1 (en) * | 2006-04-28 | 2007-10-31 | L'Oréal | Composition for washing keratinous material and cosmetic treatment method using said compositio |
| US7811594B2 (en) | 2002-03-28 | 2010-10-12 | Beiersdorf Ag | Crosslinked oil droplet-based cosmetic or pharmaceutical emulsions |
| US8470754B2 (en) | 2008-07-08 | 2013-06-25 | L'oreal | Detergent cosmetic compositions comprising at least one amino silicone, and uses thereof |
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|---|---|---|---|---|
| DE19602902A1 (en) * | 1996-01-27 | 1997-07-31 | Henkel Kgaa | Oil-based soap gel preparation |
| DE19623383C2 (en) | 1996-06-12 | 1999-07-01 | Henkel Kgaa | Use of fatty substances as a silicone substitute for the production of cosmetic and / or pharmaceutical preparations |
| FR2751532B1 (en) * | 1996-07-23 | 1998-08-28 | Oreal | WASHING AND CONDITIONING COMPOSITIONS BASED ON SILICONE AND DIALKYLETHER |
| US6667044B1 (en) | 1996-10-04 | 2003-12-23 | Beiersdorf Ag | Cosmetic or dermatological gels based on microemulsions |
| DE19641672A1 (en) * | 1996-10-10 | 1998-04-16 | Beiersdorf Ag | Cosmetic or dermatological preparations based on ethylene oxide-free and propylene oxide-free emulsifiers for the production of microemulsion gels |
| DE19646869C1 (en) | 1996-11-13 | 1997-12-04 | Henkel Kgaa | Cosmetic formulation containing cationic polymer, especially pearly shampoo, giving stable aqueous formulation |
| DE19719504C1 (en) | 1997-05-12 | 1998-12-10 | Henkel Kgaa | Process for the manufacture of hair coloring agents |
| DE19755491C1 (en) | 1997-12-13 | 1999-05-12 | Henkel Kgaa | Preparation of thickened hair dye compositions |
| DE19843876A1 (en) * | 1998-09-25 | 2000-04-13 | Cognis Deutschland Gmbh | Self-emulsifying W / O emulsion bases |
| DE19927076A1 (en) | 1999-06-15 | 2000-12-21 | Cognis Deutschland Gmbh | Hair dye preparations |
| DE10213957A1 (en) * | 2002-03-28 | 2003-10-09 | Beiersdorf Ag | Crosslinked cosmetic or pharmaceutical phospholipid-containing gels and emulsions based on ethylene oxide-containing or propylene oxide-containing emulsifiers |
| DE10213956A1 (en) * | 2002-03-28 | 2003-10-09 | Beiersdorf Ag | Cosmetic or pharmaceutical emulsions based on cross-linked oil droplets |
| DE10226990A1 (en) * | 2002-06-18 | 2004-03-18 | Sanguibiotech Ag | Topically applicable micro-emulsions with binary phase and active substance differentiation, their production and their use, in particular for supplying the skin with bioavailable oxygen |
| DE10300506A1 (en) * | 2003-01-08 | 2004-07-22 | Cognis Deutschland Gmbh & Co. Kg | wax dispersions |
| WO2005046626A2 (en) * | 2003-11-07 | 2005-05-26 | L'oreal | Make-up or lip care composition comprising an oil in water emulsion and a hydrophilic active agent |
| JP2008525333A (en) * | 2004-12-23 | 2008-07-17 | ユニリーバー・ナームローゼ・ベンノートシヤープ | Water-in-oil microemulsion for hair treatment |
| US8404218B2 (en) | 2004-12-23 | 2013-03-26 | Conopco, Inc. | Gelled water-in-oil microemulsions for hair treatment |
| WO2012051727A2 (en) | 2010-10-01 | 2012-04-26 | Swissdent Cosmetics Ag | Oxidative stable micellar compositions |
| CN111700877A (en) | 2014-09-03 | 2020-09-25 | 吉倪塞思公司 | Therapeutic nanoparticles and related compositions, methods and systems |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19619036A1 (en) * | 1996-04-30 | 1997-11-13 | Schering Ag | New vitamin D derivatives with carbo- or heterocyclic substituents at C-25, process for their preparation and their use in the manufacture of medicinal products |
| DE19929505A1 (en) * | 1999-06-29 | 2001-01-11 | Cognis Deutschland Gmbh | Cosmetic emulsions |
| DE19929505B4 (en) * | 1999-06-29 | 2004-08-26 | Cognis Deutschland Gmbh & Co. Kg | Cosmetic emulsions |
| US7811594B2 (en) | 2002-03-28 | 2010-10-12 | Beiersdorf Ag | Crosslinked oil droplet-based cosmetic or pharmaceutical emulsions |
| EP1849453A1 (en) * | 2006-04-28 | 2007-10-31 | L'Oréal | Composition for washing keratinous material and cosmetic treatment method using said compositio |
| FR2900336A1 (en) * | 2006-04-28 | 2007-11-02 | Oreal | KERATINIC WASHING COMPOSITION AND COSMETIC TREATMENT METHOD USING THE SAME |
| US8470754B2 (en) | 2008-07-08 | 2013-06-25 | L'oreal | Detergent cosmetic compositions comprising at least one amino silicone, and uses thereof |
| US8476212B2 (en) | 2008-07-08 | 2013-07-02 | L'oreal | Detergent cosmetic compositions comprising at least one amino silicone, and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4411557A1 (en) | 1995-10-05 |
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