EP1159076B1 - Packaging system for cosmetic formulations - Google Patents

Packaging system for cosmetic formulations Download PDF

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Publication number
EP1159076B1
EP1159076B1 EP00916904A EP00916904A EP1159076B1 EP 1159076 B1 EP1159076 B1 EP 1159076B1 EP 00916904 A EP00916904 A EP 00916904A EP 00916904 A EP00916904 A EP 00916904A EP 1159076 B1 EP1159076 B1 EP 1159076B1
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EP
European Patent Office
Prior art keywords
packaging system
micromixer
formulations
supply chambers
mixing
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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.)
Expired - Lifetime
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EP00916904A
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German (de)
French (fr)
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EP1159076A1 (en
Inventor
Joachim BÜNGER
Hans-Jürgen DRILLER
Jutta Zur Lage
Annette Wagner
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Merck Patent GmbH
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Merck Patent GmbH
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Publication of EP1159076A1 publication Critical patent/EP1159076A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D83/00—Containers or packages with special means for dispensing contents
    • B65D83/14—Containers or packages with special means for dispensing contents for delivery of liquid or semi-liquid contents by internal gaseous pressure, i.e. aerosol containers comprising propellant for a product delivered by a propellant
    • B65D83/68—Dispensing two or more contents, e.g. sequential dispensing or simultaneous dispensing of two or more products without mixing them
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B11/00—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use
    • B05B11/0005—Components or details
    • B05B11/0078—Arrangements for separately storing several components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/30—Micromixers

Definitions

  • the invention relates to a packaging system for the in situ production of cosmetic formulations, which has a micromixer.
  • This micromixer can have one or more pantries be connected.
  • Cosmetic formulations often become simple Mixing vessels used with different types of stirrers.
  • the mixing vessels depending on the type of stirrer (e.g. anchor, propeller, inclined blade, Disc, EKATO-MIG stirrer, EKATO-Mizer disc) different Shear forces.
  • the temperature distribution as well as the energy input in the formulation are influenced by the stirrer.
  • the Shear forces, temperature and energy input are not even distributed in the batch vessel and thus influence the structure of the resulting Formulation.
  • Cosmetic formulations are usually commercially available in the form of packaged creams, emulsions, lotions, gels. Problematic in this context is the shelf life and the Stability of the formulations. For this reason, the products contain various additives that are used by very sensitive users can cause irritation or allergic reactions. Can too not the actual ones in various cases for reasons of stability Active ingredients are used in the formulations, but it Suitable derivatives must be used, which are only at the place of action decompose. The latter is delayed on the one hand and associated with the influence or release of another compound. Both together can affect the effectiveness of the actual active ingredients significantly reduce.
  • a packaging system is from French patent application FR-A-2 669 243 known, which has a micromixer in which the mixing chamber at least one Movable deformable wall having the mixing chamber by pressing a button downsized and thus flushes the products into the outlet channel.
  • the object of the present invention is therefore a packaging system to make available by the user in easier Wise high quality creams, emulsions, lotions, gels or others cosmetic formulations can be prepared in situ.
  • the invention is also to provide a packaging system through which the use of various additives such as emulsifiers, Surfactants, preservatives and the like, for sensitive Irritating people or causing allergic reactions can be reduced or completely avoided,
  • the task is solved by a packaging system for in In-situ production of cosmetic formulations using a micromixer having.
  • the present invention therefore relates to a packaging system for in situ Manufacture of cosmetic formulations according to claim 1.
  • the present invention therefore preferably also relates to such a packaging system, one, especially two or more pantries has, which are each provided with a thin tube, the each end in a channel of a micromixer, where mixing the flowable contained in the various pantries Components can take place.
  • the different pantries advantageously have a common one Pump system.
  • the pantries can be under pressure stand.
  • the pantries can be individually attached to the Pump system, which is connected to a micromixer and one Has discharge opening for the mixed product, can be connected.
  • the present invention also relates to a corresponding one Packaging system, the two or more externally connected Has pantries.
  • a component of the packaging system is a micromixer, consisting of two or more firmly connected thin sheet-like structures that are in at least one of the facing surfaces have intersecting channels repeatedly.
  • This micromixer can be made of metal, silicon or plastic structures be made.
  • the packaging system can in a special embodiment be designed that the pump system, which with a micromixer is connected and a discharge opening for the mixed product has, is reusable.
  • the present invention relates to a packaging system for in situ production of cosmetic formulations in the form of lotions, Emulsions, gels or creams or liposome-containing or formulations containing active ingredients.
  • micromixer is manufactured under uniform temperature conditions possible in the micro range.
  • the energy input is in contrast to a large volume stirred kettle, in very small volumes the same for all ingredients.
  • Microemulsions can also be used about the multiple shear conditions of the communicating channels be made better than in a mixing vessel.
  • the micromixer is suitable for the production of very fine and homogeneous formulations.
  • Micromixers are associated with the packaging system according to the invention Connection and locking systems suitable in the patent applications DE 1 95 11 603, DE 1 97 46 583, DE 1 97 46 584, DE 19746585 and DE 1 98 54 096 are described, as well as the Refinements resulting therefrom to a person skilled in the art.
  • Suitable micromixers and associated connection and locking systems can be made from suitable metallic, ceramic, polymeric materials or Silicon exist. They can be mechanically connected or glued his.
  • the connection with the remaining parts of the invention Packaging system is preferably mechanical. It understands by itself that parts under pressure cannot be closed with closing Parts are connected. This means that the present invention includes both packaging systems, their pantries are under pressure and are equipped with sampling valves as well unpressurized, from which the formulations with the help of pump systems be removed.
  • Microemulsions are thermodynamically stable when they arise spontaneously due to extremely low interfacial energy, that is, without the addition of external mechanical energy.
  • the droplet diameters are much smaller than with macroemulsions, they are in the range of 10-30 nm (nanometers), which means below the wavelength of visible light. Microemulsions are therefore colloidally disperse, optically transparent systems. According to POHLER, certain concentration ranges of the oil and water phase as well as the emulsifiers and auxiliary substances must be observed when formulating microemulsions:
  • Surfactants mostly non-ionic surfactants 15 - 40%
  • Mineral oil or vegetable oil 5 - 25% polyalcohols 0 - 20% water 35 - 65%
  • micromixers for the production of microemulsions it is possible to significantly reduce the use of surfactants, so that the tolerance for particularly sensitive skin types can be increased significantly.
  • Stable microemulsions can be already produce with the use of less than 10 wt .-% surfactants. In certain formulations, if desired, completely be used on surfactants.
  • micromixers makes it possible, very much small amounts of the desired cosmetic or pharmaceutical Prepare formulations immediately before use.
  • This has the advantage that the addition of emulsifiers, suspension and Dispersion aids in the form of surfactants and other additives such as.
  • B. Stabilizers can be very limited or their use can be dispensed with entirely. It is also possible in this way not compatible with one another in a formulation for a long time Active ingredients or additives only immediately before use mix. Active ingredients in a formulation only in the form of a derivative are stable, as such, in a separate formulation be presented and only immediately before using the rest of the mixture be added. Also depending on the user Desire for small quantities of a base mixture to be different Various additives can be added at times. This can be both for pharmaceutical as well as for cosmetic formulations of Be interested if different at different times Active ingredients should be applied.
  • Additives can add a cosmetic base formulation for the day Additives are added as for the night. Additives for the day can For example, be a UV filter, but regenerative for the night Additions.
  • FIG Packaging system An example of an embodiment of an inventive device is shown in FIG Packaging system shown, the two different pantries A and A ', from which with a common Pump system B liquid formulations or liquefied by heating can be removed.
  • the pump system B is over thin Lines b, which can consist of thin plastic tubes, connected to a micromixer C; namely the lines b firmly at their ends facing away from the pump system with the micromixer connected and end in the thin channels c of the micromixer.
  • the multiple intersecting or partially overlapping Channels c open into an outlet opening d or in a special one Dispensing tube design. Details of the invention Pump systems are familiar to the person skilled in the art.
  • micromixer used can be those correspond, which are described in the above-mentioned patent applications are. But it can also be modified according to the application Act micromixer.
  • the micromixers are preferably included firmly connected to the pump system. You can as shown in Figure 1 be integrated into a kind of cover, either at the point where the Pump system is operated, is freely movable or tiltable. Corresponding this point may be at a lower level than the dispensing opening are located.
  • Storage vessels can be detachably inserted in the holder E. be and held together at the top with an attachable ring F. be, so that the storage vessels always in the same Position can be connected and the pump system repeated can fit snugly on the connecting tube b.
  • an attachable ring F. be Around to achieve this, it makes sense to close the upper ring with a nose f to which the storage vessels on the right and left with each other facing surface edges g and g 'must lie.
  • On the ring F becomes, if applicable, that having the pump system and the micromixer Lid set.
  • ARLACEL 780 5.0% Liquid paraffin oil 10.0% Miglyol 812 4.0% ARLAMOL HD 5 0% ARLAMOL E 1.0% Perfume (possibly) q.s.
  • the two phases A and B are each separated in one Reservoir submitted with a common Pump system connected with a micromixing are.
  • the phases from the storage containers are used pumped and together through the micromixer led, in which the phases are mixed intensively. It will get a homogeneously mixed milk that is used directly can be.
  • the two are in separate Panels submitted phases for mixing together with the help of a pump system through a thin connection tube connected micromixer pumped.
  • Viscosity 22,800 mPas (Brookfield RVT, Sp. C, 10 rpm) at 25 'C samples contain as a preservative 0.05% propyl 4-hydroxybenzoate (Merck Item No. 7427) 0.17% methyl 4-hydroxybenzoate sodium salt (Merck Art.No. 6756)
  • phase C disperse the Pemulen TR-1 homogeneously in water, Add preservatives and swell.
  • Phase B is under Homogenize entered in phase C and in a storage vessel submitted.
  • Phase A dissolved with heating.
  • Phase D will be added at 35 ° C and presented in a second storage vessel.
  • the storage chamber A / D is heated to about 35 ° C and the contents by means of a pump system together with the contents of the pantry B / C through a micromixer connected to the pump system managed and homogenized.

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Cosmetics (AREA)

Abstract

The invention relates to a packaging system for the in situ production of cosmetic formulations. Said packaging system is provided with a micromixer (C) that can be connected to one or more storage chambers (A, A').

Description

Die Erfindung betrifft ein Verpackungssystem zur in situ Herstellung von kosmetischen Formulierungen, welches einen Mikromischer aufweist. Dieser Mikromischer kann mit einer oder mehreren Vorratskammern verbunden sein.The invention relates to a packaging system for the in situ production of cosmetic formulations, which has a micromixer. This micromixer can have one or more pantries be connected.

Zur Herstellung kosmetischer Formulierungen werden häufig einfache Rührgefäße mit verschiedenen Rührertypen verwendet. In den Rührgefäßen treten je nach Rührertyp (z. b. Anker-, Propeller-, Schrägblatt-, Scheiben-, EKATO-MIG-Rührer, EKATO-Mizerscheibe) unterschiedliche Scherkräfte auf. Die Temperaturverteilung sowie auch der Energieeintrag in die Formulierung werden durch den Rührer beeinflußt. die Scherkräfte, Temperatur und eingebrachte Energie sind nicht gleichmäßig im Ansatzgefäß verteilt und beeinflussen so den Aufbau der resultierenden Formulierung.Cosmetic formulations often become simple Mixing vessels used with different types of stirrers. In the mixing vessels depending on the type of stirrer (e.g. anchor, propeller, inclined blade, Disc, EKATO-MIG stirrer, EKATO-Mizer disc) different Shear forces. The temperature distribution as well as the energy input in the formulation are influenced by the stirrer. the Shear forces, temperature and energy input are not even distributed in the batch vessel and thus influence the structure of the resulting Formulation.

Üblicherweise werden im Handel kosmetische Formulierungen in Form von verpackten Cremes, Emulsionen, Lotionen, Gelen angeboten. Problematisch ist in diesem Zusammenhang die Lagerfähigkeit und die Stabilität der Formulierungen. Aus diesem Grund enthalten die Produkte verschiedenste Additive, die bei sehr empfindlichen Anwendern zu Reizungen oder allergischen Reaktionen führen können. Auch können aus Stabilitätsgründen in verschiedenen Fällen nicht die eigentlichen Wirkstoffe in den Formulierungen eingesetzt werden, sondern es müssen geeignete Derivate verwendet werden, die sich erst am Wirkort zersetzen. Letzteres ist einerseits mit einer zeitlichen Verzögerung und mit dem Einfluß bzw. Freisetzung einer weiteren Verbindung verbunden. Beides gemeinsam kann die Wirksamkeit des eigentlichen Wirkstoffe deutlich reduzieren.Cosmetic formulations are usually commercially available in the form of packaged creams, emulsions, lotions, gels. Problematic in this context is the shelf life and the Stability of the formulations. For this reason, the products contain various additives that are used by very sensitive users can cause irritation or allergic reactions. Can too not the actual ones in various cases for reasons of stability Active ingredients are used in the formulations, but it Suitable derivatives must be used, which are only at the place of action decompose. The latter is delayed on the one hand and associated with the influence or release of another compound. Both together can affect the effectiveness of the actual active ingredients significantly reduce.

Um diesen Problemen aus dem Wege zu gehen, wurden verschiedene Systeme entwickelt bei denen in unterschiedlichen Gefäßen oder Vorratskammern getrennt Formulierungen vorgehalten werden. Die Vermischung der getrennten Formulierungen erfolgt erst direkt vor der Verwendung, indem entweder die Formulierungen aus den verschiedenen Vorratskammern zusammengegeben und durch Schütteln oder Rühren miteinander vermischt werden. In manchen Fällen müssen die Formulierungen vorab in der Hand miteinander vermischt werden. Eine andere Möglichkeit besteht darin, die getrennten Formulierungen durch ein miteinander verbundenes Pumpsystem aus den Vorratsgefäßen über Kanäle oder dünne Schläuche in einer Ausgabeöffnung zusammenzuführen.In order to avoid these problems, various Systems developed in those in different vessels or pantries separate formulations are kept. The mixing the separate formulations are made just before use, by either using the wording from the different Panels are put together and by shaking or stirring be mixed together. In some cases, the wording be mixed in hand beforehand. Another Possibility is to separate the formulations by one another connected pump system from the storage vessels via channels or to bring thin tubes together in a dispensing opening.

Aus der Französischen Patentanmeldung FR-A-2 669 243 ist ein Verpackungssystem bekannt, das einen Mikromischer aufweist, bei dem die Mischkammer mindestens eine bewegliche verformbare Wand aufweist, die durch Drücken eines Knopfes die Mischkammer verkleinert und so die Produkte in den Auslasskanal spült.A packaging system is from French patent application FR-A-2 669 243 known, which has a micromixer in which the mixing chamber at least one Movable deformable wall having the mixing chamber by pressing a button downsized and thus flushes the products into the outlet channel.

Diese Systeme weisen alle den Nachteil auf, daß nur eine eingeschränkte Durchmischung der vorgelegten Formulierungen möglich ist und die Bildung von hochwertigen Emulsionen durch das so erfolgende Vermischen, insbesondere von Mikroemulsionen, nicht möglich ist, es sei denn es wird eine vorgelegte Emulsion nur noch mit einer wirkstoffhaltigen Formulierung vermischt.These systems all have the disadvantage of being limited Mixing of the formulations presented is possible and the formation of high quality emulsions by the resultant Mixing, especially of microemulsions, is not possible unless a submitted emulsion is only with an active ingredient Formulation mixed.

Aufgabe der vorliegenden Erfindung ist es daher, ein Verpackungssystem zur Verfügung zu stellen, durch das vom Anwender in einfacher Weise hochwertige Cremes, Emulsionen, Lotionen, Gele oder andere kosmetische Formulierungen in situ hergestellt werden können. Aufgabe der Erfindung ist es auch, ein Verpackungssystem zur Verfügung zu stellen, durch das der Einsatz von verschiedenen Additven, wie Emulgatoren, Tenside, Konservierungsmittel und dergleichen, die für empfindliche Personen reizend wirken oder allergische Reaktionen hervorrufen können, reduziert oder völlig vermieden werden kann,The object of the present invention is therefore a packaging system to make available by the user in easier Wise high quality creams, emulsions, lotions, gels or others cosmetic formulations can be prepared in situ. task the invention is also to provide a packaging system through which the use of various additives such as emulsifiers, Surfactants, preservatives and the like, for sensitive Irritating people or causing allergic reactions can be reduced or completely avoided,

Die Lösung der Aufgabe erfolgt durch ein Verpackungssystem zur in situ Herstellung von kosmetischen Formulierungen, welches einen Mikromischer aufweist.The task is solved by a packaging system for in In-situ production of cosmetic formulations using a micromixer having.

Gegenstand der vorliegenden Erfindung ist daher ein Verpackungssystem zur in situ Herstellung von kosmetischen Formulierungen gemäß Anspruch 1.The present invention therefore relates to a packaging system for in situ Manufacture of cosmetic formulations according to claim 1.

Gegenstand der vorliegenden Erfindung ist daher vorzugsweise auch ein solches Verpakkungssystem, das ein, insbesondere zwei oder mehre Vorratskammern aufweist, welche jeweils mit einem dünnen Röhrchen versehen sind, die jeweils in einem Kanal eines Mikromischer enden, worin eine Vermischung der aus den verschiedenen Vorratskammern enthaltenen fließfähigen Komponenten stattfinden kann. The present invention therefore preferably also relates to such a packaging system, one, especially two or more pantries has, which are each provided with a thin tube, the each end in a channel of a micromixer, where mixing the flowable contained in the various pantries Components can take place.

Vorteilhafterweise weisen die verschiedenen Vorratskammern ein gemeinsames Pumpsystem auf. Die Vorratskammern können unter Druck stehen.The different pantries advantageously have a common one Pump system. The pantries can be under pressure stand.

Die Vorratskammern können einzeln zum Zweck des Gebrauchs an das Pumpsystem, welches mit einem Mikromischer verbunden ist und eine Abgabeöffnung für das vermischte Produkt aufweist, anschließbar sein.The pantries can be individually attached to the Pump system, which is connected to a micromixer and one Has discharge opening for the mixed product, can be connected.

Gegenstand der vorliegenden Erfindung ist auch ein entsprechendes Verpackungssystem, das zwei oder mehr miteinander äußerlich verbundene Vorratskammern aufweist.The present invention also relates to a corresponding one Packaging system, the two or more externally connected Has pantries.

Erfindungsgemäß ist ein Bestandteil des Verpackungssystems ein Mikromischer, bestehend aus zwei oder mehr fest miteinander verbundenen dünnen flächenförmigen Strukturen, die in mindestens einer der einander zugewandten Flächen sich wiederholt kreuzende Kanäle aufweisen.According to the invention, a component of the packaging system is a micromixer, consisting of two or more firmly connected thin sheet-like structures that are in at least one of the facing surfaces have intersecting channels repeatedly.

Dieser Mikromischer kann aus Metall-, Silizium- oder Kunststoffstrukturen hergestellt sein.This micromixer can be made of metal, silicon or plastic structures be made.

Des Verpackungssystem kann in einer besonderen Ausführungsform so ausgestaltet sein, daß das Pumpsystem, welches mit einem Mikromischer verbunden ist und eine Abgabeöffnung für das vermischte Produkt aufweist, wiederverwendbar ist.The packaging system can in a special embodiment be designed that the pump system, which with a micromixer is connected and a discharge opening for the mixed product has, is reusable.

Gegenstand der vorliegenden Erfindung ist ein Verpackungssystem zur in situ Herstellung von kosmetischen Formulierungen in Form von Lotionen, Emulsionen, Gelen oder Cremes oder von liposomenhaltigen oder wirkstoffhaltigen Formulierungen.The present invention relates to a packaging system for in situ production of cosmetic formulations in the form of lotions, Emulsions, gels or creams or liposome-containing or formulations containing active ingredients.

Für bestimmte Formulierungen ist die gleichmäßige Durchmischung, Temperatur und Energieeintrag bereits im Mikrobereich wichtig. Durch einen Mikromischer ist die Herstellung unter gleichmäßigen Temperaturbedingungen im Mikrobereich möglich. Der Energieeintrag ist im Gegensatz zu einem großvolumigen Rührkessel, in den sehr kleine Volumina für alle Inhaltsstoffe gleich. Des weiteren können Mikroemulsionen über die multiplen Scherbedingungen der kommunizierenden Kanäle besser hergestellt werden als in einem Rührgefäß. Der Mikromischer eignet sich für die Herstellung sehr feiner und homogener Formulierungen.For certain formulations, uniform mixing is Temperature and energy input are important in the micro range. By A micromixer is manufactured under uniform temperature conditions possible in the micro range. The energy input is in contrast to a large volume stirred kettle, in very small volumes the same for all ingredients. Microemulsions can also be used about the multiple shear conditions of the communicating channels be made better than in a mixing vessel. The micromixer is suitable for the production of very fine and homogeneous formulations.

Es wurde nun gefunden, daß durch den Einsatz von Mikromischern die Herstellung von Mischungen in Form von Emulsionen, Suspensionen und Dispersionen, Lotionen, Lösungen Gelen und Cremes in situ möglich ist, in denen alle Inhaltsstoffe auch in kleinsten Volumenteilen gleich verteilt sind.It has now been found that through the use of micromixers Production of mixtures in the form of emulsions, suspensions and dispersions, lotions, solutions, gels and creams possible in situ is where all ingredients are the same even in the smallest parts by volume are distributed.

Die Herstellung dieser Mischungen ist unter gleichmäßigen Temperaturbedingungen im Mikrobereich möglich, da sich in den dünnen, gegebenenfalls laminatartigen Kanälen aufgrund der geringen Volumina so gut wie kein Temperaturgefälle ausbildet, wenn die getrennt vorgelegten Formulierungen erwärmt werde. Weiterhin ist der Energieeintrag in jedem, d. h. auch im kleinsten Volumenteil, gleich. Es wurde auch gefunden, daß Emulsionen mit einer wesentlich homogeneren Tröpfchengrößenverteilung hergestellt werden können als in einem Rührgefäß. Aufgrund der multiplen Scherbedingungen der kommunizierenden Kanäle im Mikromischer werden zwangsläufig Tröpfchengrößen im Mikrobereich vorgegeben, so daß Mikroemulsionen erhalten werden, die in einem Rührgefäß nur sehr aufwendig hergestellt werden könnten. Die Verwendung eines Mikromischers eignet sich daher zur Herstellung sehr feiner homogener Formulierungen. Vorteilhafterweise ist dieses in situ möglich.The preparation of these mixtures is under uniform temperature conditions possible in the micro range, as in the thin, if necessary laminate-like channels because of the small volumes so good like no temperature gradient when the separately presented Formulations are warmed. Furthermore, the energy input in everyone d. H. even in the smallest part of the volume, the same. It was also found that emulsions with a much more homogeneous droplet size distribution can be produced as in a stirred vessel. by virtue of the multiple shear conditions of the communicating channels droplet sizes in the micro range are inevitable in the micromixer given so that microemulsions are obtained which are in one Mixing vessel could only be produced with great effort. The usage A micromixer is therefore suitable for the production of very fine ones homogeneous formulations. This is advantageously possible in situ.

Für das erfindungsgemäße Verpackungssystem sind Mikromischer, dazugehörende An- und Verschlußsysteme geeignet, die in den Patentanmeldungen DE 1 95 11 603, DE 1 97 46 583, DE 1 97 46 584, DE 19746585 und DE 1 98 54 096 beschrieben sind, sowie sich dem Fachmann daraus ergebenden Ausgestaltungen. Geeignete Mikromischer und dazugehörende An- und Verschlußsysteme können aus geeigneten metallischen, keramischen, polymeren Werkstoffen oder aus Silicium bestehen. Sie können mechanisch verbunden oder verklebt sein. Die Verbindung mit den übrigen Teilen des erfindungsgemäßen Verpackungssystems erfolgt vorzugsweise mechanisch. Es versteht dabei von selbst, daß unter Druck stehende Teile unlösbar mit schließenden Teilen verbunden sind. Dieses bedeutet, daß die vorliegende Erfindung sowohl Verpackungssysteme einschließt, deren Vorratskammern unter Druck stehen und mit Entnahmeventilen versehen sind als auch drucklose, aus denen die Formulierungen mit Hilfe von Pumpsystemen entnommen werden.Micromixers are associated with the packaging system according to the invention Connection and locking systems suitable in the patent applications DE 1 95 11 603, DE 1 97 46 583, DE 1 97 46 584, DE 19746585 and DE 1 98 54 096 are described, as well as the Refinements resulting therefrom to a person skilled in the art. Suitable micromixers and associated connection and locking systems can be made from suitable metallic, ceramic, polymeric materials or Silicon exist. They can be mechanically connected or glued his. The connection with the remaining parts of the invention Packaging system is preferably mechanical. It understands by itself that parts under pressure cannot be closed with closing Parts are connected. This means that the present invention includes both packaging systems, their pantries are under pressure and are equipped with sampling valves as well unpressurized, from which the formulations with the help of pump systems be removed.

Problematische Formulierungen sind im W/O-Bereich Emulsionen insbesondere solche mit hohen Gehalten an pflanzlichen Triglyceriden. Emulsionen ohne stabilisierende Wachse zeichnen sich häufig durch ungenügende Langzeitviskositätskonstanz aus und O/W-Lotionen sind generell schwieriger zu stabilisieren als Cremes. Diese Emulsionen lassen sich daher besonders gut herstellen unter Verwendung von Mikromischern. Von besonderem Vorteil ist hierbei, daß durch Verwendung von Mikromischern besonders geringe Mengen hergestellt werden können, die vorteilhafter Weise in situ, d. h. direkt vor der Verwendung hergestellt werden können.Problematic formulations are particularly in the W / O area emulsions those with high levels of vegetable triglycerides. Emulsions without stabilizing waxes are often characterized insufficient long-term viscosity constancy and O / W lotions generally more difficult to stabilize than creams. These emulsions can therefore be produced particularly well using micromixers. It is particularly advantageous here that through use particularly small quantities are produced by micromixers can, advantageously in situ, d. H. right before use can be produced.

Mikroemulsionen sind dann thermodynamisch stabil, wenn sie aufgrund extrem geringer Grenzflächenenergie spontan entstehen, das heißt, ohne Zufuhr von äußerer mechanischer Energie. Die Tröpfchendurchmesser sind wesentlich geringer als bei Makroemulsionen, sie liegen im Bereich von 10-30 nm (Nanometer), das bedeutet unterhalb der Wellenlänge des sichtbaren Lichtes. Mikroemulsionen sind daher kolloid-disperse, optisch transparente Systeme. Nach POHLER sind zur Formulierung von Mikroemulsionen bestimmte Konzentrationsbereiche der Öl- und der Wasserphase sowie der Emulgatoren und Hilfsstoffe einzuhalten: Tenside (meist Niotenside) 15 - 40% Mineralöl bzw. Pflanzenöl 5 - 25% Polyalkohole 0 - 20% Wasser 35 - 65% Microemulsions are thermodynamically stable when they arise spontaneously due to extremely low interfacial energy, that is, without the addition of external mechanical energy. The droplet diameters are much smaller than with macroemulsions, they are in the range of 10-30 nm (nanometers), which means below the wavelength of visible light. Microemulsions are therefore colloidally disperse, optically transparent systems. According to POHLER, certain concentration ranges of the oil and water phase as well as the emulsifiers and auxiliary substances must be observed when formulating microemulsions: Surfactants (mostly non-ionic surfactants) 15 - 40% Mineral oil or vegetable oil 5 - 25% polyalcohols 0 - 20% water 35 - 65%

Durch den Einsatz von Mikromischern zur Herstellung von Mikroemulsionen ist es möglich, den Einsatz von Tensiden erheblich zu reduzieren, so daß die Verträglichkeit für besonders empfindliche Hauttypen wesentlich erhöht werden kann. Stabile Mikroemulsionen lassen sich bereits bei Verwendung von weniger als 10 Gew.-% Tensiden herstellen. In bestimmten Formulierungen kann auch, falls gewünscht, völlig auf Tenside verwendet werden.Through the use of micromixers for the production of microemulsions it is possible to significantly reduce the use of surfactants, so that the tolerance for particularly sensitive skin types can be increased significantly. Stable microemulsions can be already produce with the use of less than 10 wt .-% surfactants. In certain formulations, if desired, completely be used on surfactants.

Üblicherweise sind die wichtigsten Anforderungen an Emulgiergeräte ausreichende und insbesondere variable Emulgierleistung, genügend Scher- bzw. Schlag- und Prallkräfte, Ausstattung für eine gleichmäßige Bearbeitung des Ansatzes, Vakuumvorrichtung, Heizung und Kühlung (14).Diese Probleme lassen sich erfindungsgemäß in einfacher Weise durch den Einsatz von geeigneten Mikromischern lösen, die einen gezielten Energieeintrg in jedem Volumenelement gewährleisten und in denen unter Einwirkung intensiver Scherkräfte in den dünnen Kanälen eine intensive Vermischung stattfindet.The most important requirements for emulsifying devices are usually sufficient and in particular variable emulsification performance, sufficient Shear or impact and impact forces, equipment for a uniform Processing of the approach, vacuum device, heating and cooling (14) These problems can be solved in a simple manner according to the invention by using suitable micromixers that solve a specific problem Ensure energy input in every volume element and in those under the action of intense shear forces in the thin channels intensive mixing takes place.

Weiterhin ist es durch die Verwendung von Mikromischern möglich, sehr kleine Mengen der gewünschten kosmetischen oder pharmazeutischen Formulierungen unmittelbar vor der Verwendung herzustellen. Dieses hat den Vorteil, daß der Zusatz von Emulgatoren, Suspensions- und Dispersionshilfen in Form von Tensiden und anderen Additiven wie z. B. Stabilisatoren sehr eingeschränkt werden kann bzw. auf ihre Verwendung ganz verzichtet werden kann. Es ist auf diese Weise auch möglich, über längere Zeit nicht miteinander in einer Formulierung verträgliche Wirkstoffe oder Zusätze erst direkt vor der Verwendung miteinander zu vermischen. Wirkstoffe, die in einer Formulierung nur in Form eines Derivats stabil sind, können als solche in einer getrennten Formulierung vorgelegt werden und erst direkt vor der Verwendung der übrigen Mischung zugefügt werden. Auch können so vom Anwender je nach Wunsch zu kleinen Mengen einer Basismischung zu unterschiedlichen Zeitpunkten verschiedene Zusätze zugefügt werden. Dieses kann sowohl für pharmazeutische als auch für kosmetische Formulierungen von Interesse sein, wenn zu verschiedenen Zeitpunkten unterschiedliche Wirkstoffe appliziert werden sollen. Furthermore, the use of micromixers makes it possible, very much small amounts of the desired cosmetic or pharmaceutical Prepare formulations immediately before use. This has the advantage that the addition of emulsifiers, suspension and Dispersion aids in the form of surfactants and other additives such as. B. Stabilizers can be very limited or their use can be dispensed with entirely. It is also possible in this way not compatible with one another in a formulation for a long time Active ingredients or additives only immediately before use mix. Active ingredients in a formulation only in the form of a derivative are stable, as such, in a separate formulation be presented and only immediately before using the rest of the mixture be added. Also depending on the user Desire for small quantities of a base mixture to be different Various additives can be added at times. This can be both for pharmaceutical as well as for cosmetic formulations of Be interested if different at different times Active ingredients should be applied.

Zu einer kosmetischen Basisformulierung können für den Tag andere Zusätze hinzugefügt werden als für die Nacht. Zusätze für den Tag können beispielsweise UV-Filter sein, für die Nacht dagegen regenerierende Zusätze.Others can add a cosmetic base formulation for the day Additives are added as for the night. Additives for the day can For example, be a UV filter, but regenerative for the night Additions.

Zum besseren Verständnis und zur Verdeutlichung der Erfindung werden im folgenden Beispiele gegeben, die im Rahmen des Schutzbereichs der vorliegenden Erfindung liegen. Diese sind jedoch aufgrund der allgemeinen Gültigkeit des beschriebenen Erfindungsprinzips nicht geeignet, den Schutzbereich der vorliegenden Anmeldung nur auf diese Beispiele zu reduzieren. Weiterhin ist der Inhalt der zitierten Patentanmeldungen als Teil der Offenbarung der Erfindung der vorliegenden Beschreibung anzusehen.For better understanding and clarification of the invention given in the following examples, which are part of the Scope of the present invention. However, these are due to the general validity of the principle of the invention described not suitable, the scope of the present application only to reduce to these examples. Furthermore, the content of the quoted Patent applications as part of the disclosure of the invention of the present View description.

Beispielhaft ist in Figur 1 eine Ausführungsform eines erfindungsgemäßen Verpackungssystems dargestellt, das zwei verschiedene Vorratskammern A und A' aufweist, aus denen mit einem gemeinsamen Pumpsystem B flüssige bzw. durch Erwärmen verflüssigte Formulierungen entnommen werden können. Das Pumpsystem B ist über dünne Leitungen b, welche aus dünnen Kunststoffröhrchen bestehen können, mit einem Mikromischer C verbunden; und zwar sind die Leitungen b an ihren vom Pumpsystem abgewandten Enden fest mit dem Mikromischer verbunden und enden in den dünnen Kanälen c des Mikromischers. Die sich mehrfach kreuzenden bzw. teilweise überlappenden Kanäle c münden in eine Auslaßöffnung d oder in einer besonderen Ausgestaltung in ein Abgaberöhrchen. Einzelheiten des erfindungsgemäßen Pumpsystems sind dem Fachmann geläufig.An example of an embodiment of an inventive device is shown in FIG Packaging system shown, the two different pantries A and A ', from which with a common Pump system B liquid formulations or liquefied by heating can be removed. The pump system B is over thin Lines b, which can consist of thin plastic tubes, connected to a micromixer C; namely the lines b firmly at their ends facing away from the pump system with the micromixer connected and end in the thin channels c of the micromixer. The multiple intersecting or partially overlapping Channels c open into an outlet opening d or in a special one Dispensing tube design. Details of the invention Pump systems are familiar to the person skilled in the art.

Die Ausgestaltungen des eingesetzten Mikromischers können denen entsprechen, die in den oben angegebenen Patentanmeldungen beschrieben sind. Es kann sich aber auch um anwendungsgemäß veränderte Mikromischer handeln. Vorzugsweise sind die Mikromischer mit dem Pumpsystem fest verbundenen. Sie können wie in Figur 1 gezeigt in eine Art Deckel integriert sein, der entweder an der Stelle, an der das Pumpsystem betätigt wird, frei beweglich oder kippbar ist. Entsprechend kann diese Stelle sich in einer tieferen Ebene als die Ausgabeöffnung befinden.The configurations of the micromixer used can be those correspond, which are described in the above-mentioned patent applications are. But it can also be modified according to the application Act micromixer. The micromixers are preferably included firmly connected to the pump system. You can as shown in Figure 1 be integrated into a kind of cover, either at the point where the Pump system is operated, is freely movable or tiltable. Corresponding this point may be at a lower level than the dispensing opening are located.

Die in dem dargestellten Verpackungssystem (Fig. 1) miteinander verbundenen Vorratsgefäße können lösbar in der Halterung E eingesetzt sein und am oberen Rand mit einem aufsetzbaren Ring F zusammengehalten werden, so daß die Vorratsgefäße immer wieder in gleicher Position miteinander verbunden werden und das Pumpsystem wiederholt paßgenau auf die Anschlußröhrchen b gesetzt werden können. Um dieses zu erreichen ist es sinnvoll, den oberen Ring mit einer Nase f zu versehen, an die die Vorratsgefäße rechts und links mit den einander zugewandten Flächenrändern g und g' anliegen müssen. Auf den Ring F wird gegebenenfalls der das Pumpsystem und den Mikromischer aufweisende Deckel gesetzt.The interconnected in the packaging system shown (Fig. 1) Storage vessels can be detachably inserted in the holder E. be and held together at the top with an attachable ring F. be, so that the storage vessels always in the same Position can be connected and the pump system repeated can fit snugly on the connecting tube b. Around to achieve this, it makes sense to close the upper ring with a nose f to which the storage vessels on the right and left with each other facing surface edges g and g 'must lie. On the ring F becomes, if applicable, that having the pump system and the micromixer Lid set.

Beispiel 1example 1

W/O Körperpflegemilch (KALT-HERSTELLUNG)W / O body care milk (COLD PRODUCTION) A.A. ARLACEL 780ARLACEL 780 5.0 %5.0% Paraffinöl dünnflüssigLiquid paraffin oil 10.0 %10.0% Miglyol 812Miglyol 812 4.0 %4.0% ARLAMOL HDARLAMOL HD 5 0 %5 0% ARLAMOL EARLAMOL E 1.0 %1.0% Parfüm (evtl.)Perfume (possibly) q.s.q.s. B.B. Glyceringlycerin 2.5 %2.5% ATLAS G-2330ATLAS G-2330 1.5 %1.5% Mg SO4 Mg SO 4 0.5 %0.5% Demin. WasserDemin. water 70.5 %70.5% Konservierung (evtl.)Conservation (possibly) q.s.q.s.

Herstellungsmethode:Production Method:

Die beide Phasen A und B werden jeweils getrennt in einem Vorratsbehälter vorgelegt, die mit einem gemeinsamen Pumpsystem versehen mit einem Mikromischen verbunden sind. Zur Verwendung werden die Phasen aus den Vorratsbehältern gepumpt und gemeinsam durch den Mikromischer geführt, worin die Phasen intensiv vermischt werden. Es wird eine homogen vermischte Milch erhalten, die direkt verwendet werden kann.The two phases A and B are each separated in one Reservoir submitted with a common Pump system connected with a micromixing are. The phases from the storage containers are used pumped and together through the micromixer led, in which the phases are mixed intensively. It will get a homogeneously mixed milk that is used directly can be.

Viskosität:Viscosity:

10 000 mPa s (Brookfield LVT Helipath, Spindel C, 6 upm, 1 Min.)10,000 mPa s (Brookfield LVT Helipath, spindle C, 6 rpm, 1 Min.)

Bezugsquellen:Sources: (1) ICI Surfactants(1) ICI surfactants Beispiel 2Example 2

Sonnenschutzmilch (W/S) (Wasser in Silikon)Sun protection milk (W / S) (water in silicone) AA Eusolex 2292 (Art.-Nr. 5382)Eusolex 2292 (Art.No. 5382) (1)(1) 2,002.00 DC 1401DC 1401 (2)(2) 10,0010.00 DC 3225 CDC 3225 C. (2)(2) 10,0010.00 Dow Corning 344Dow Corning 344 (2)(2) 10,0010.00 q.s.q.s. BB Eusolex 232 (Art.-Nr. 5372)Eusolex 232 (Item No. 5372) (1)(1) 2,002.00 Tris(hydroxymethyl)-Tris (hydroxymethyl) - (1)(1) 0,880.88 aminomethan (Art.-Nr. 8386)aminomethane (art.no.8386) Natriumchlorid (Art.-Nr. 6400)Sodium chloride (item no.6400) (1)(1) 2,002.00 Glycerin (Art.-Nr. 4093)Glycerin (Art.No. 4093) (1)(1) 5,005.00 Konservierungsmittel (evtl.)Preservative (possibly) q.s.q.s. Wasser, demineralisiertWater, demineralized ad 100,00ad 100.00

Herstellung:production:

Zur Herstellung der Sonnenschutzmilch werden die beiden in getrennten Vorratskammern vorgelegten Phasen zum Vermischen gemeinsam mit Hilfe eines Pumpsystems durch einen über dünne Anschlußröhrchen angeschlossenen Mikromischer gepumpt.To make the sunscreen milk, the two are in separate Panels submitted phases for mixing together with the help of a pump system through a thin connection tube connected micromixer pumped.

BemerkungenRemarks

Viskosität 22.800 mPas (Brookfield RVT, Sp. C, 10 Upm) bei 25 'C Muster enthalten als Konservierungsmittel
0,05 % Propyl-4-hydroxybenzoat (Merck Art.-Nr. 7427)
0, 17 % Methyl-4-hydroxybenzoat Natriumsalz (Merck Art.-Nr. 6756)Viscosity 22,800 mPas (Brookfield RVT, Sp. C, 10 rpm) at 25 'C samples contain as a preservative
0.05% propyl 4-hydroxybenzoate (Merck Item No. 7427)
0.17% methyl 4-hydroxybenzoate sodium salt (Merck Art.No. 6756)

Bezugsquellen:Sources:

  • (1) E. Merck, Darmstadt(1) E. Merck, Darmstadt
  • (2) Dow Corning, Düsseldorf(2) Dow Corning, Düsseldorf

    • Beispiel 3Example 3

    Transparente MikroemulsionTransparent microemulsion Handelsnametrade name INClINCI Gew.-%Wt .-% Eumulgin B2Eumulgin B2 Ceteareth-20Ceteareth-20 19,519.5 Cetiol RECetiol RE PEG-7 Glyceryl CocoatePEG-7 glyceryl cocoate 20.020.0 Uniphen P-23Uniphen P-23 Phenoxyethanol + Methyl-/ Ethyl-/Propyl-/ButylparabenPhenoxyethanol + methyl / ethyl / propyl / butyl paraben 0.30.3 Mineralölmineral oil Mineral OilMineral Oil 5.05.0 Glyceringlycerin Glyceringlycerin 20.020.0 Wasser, demin.Water, demin. WaterWater 35.235.2

    Herstellung:production:

  • 1. Eumulgin B2, Cetiol HE, Uniphen P-23 und das Paraffinöl werden in einem Vorratsgefäß vorgelegt und vor der Verwendung zum Schmelzen auf ca. 95°C-105°C erhitzt.1. Eumulgin B2, Cetiol HE, Uniphen P-23 and the paraffin oil are in submitted to a storage container and before use for Melt heated to approx. 95 ° C-105 ° C.
  • 2. Wasser und das Glycerin werden in einem zweiten Vorratsgefäß zusammengegeben und ebenfalls auf ca. 95°C-100°C erwärmt. 2. Water and the glycerin are in a second storage vessel put together and also heated to approx. 95 ° C-100 ° C.
  • 3. Die Wasserphase und die Fettphase werden zur intensiven Durchmischung durch einen Mikromischer gepumpt. Das entstandene Mikroemulsionsgel wird zum Erkalten gerührt.3. The water phase and the fat phase become intensive mixing pumped through a micromixer. The resulting Microemulsion gel is stirred to cool.

    • Beispiel 4Example 4

    Sonnenschutzgel (Emulgator-frei)Sun protection gel (emulsifier-free) SPF 3,21 UVA PF 2.5 (Sun protection factor, Diffey Methode)SPF 3.21 UVA PF 2.5 (Sun protection factor, Diffey method) Gew.-%Wt .-% AA Eusolex 2292 (Art.-Nr. 105382)Eusolex 2292 (Art.no.105382) (1)(1) 1,0001,000 Luvitol EHOLuvitol EHO (2)(2) 9,0009,000 Dow Corning 200 (100 cs)Dow Corning 200 (100 cs) (3)(3) 2,0002,000 Antaron V-220Antaron V-220 (4)(4) 2,0002,000 Jojobaöljojoba oil (5)(5) 5,0005,000 DL-α-TocopherolacetatDL-α-tocopherol acetate (1)(1) 0,5000,500 (Art. Nr. 500952)(Art. No. 500952) BB Tris(hydroxymethyl)-aminomethanTris (hydroxymethyl) aminomethane (1)(1) 0,7000,700 (Art.-Nr. 108386)(Art.no.108386) Wasser, demineralisiertWater, demineralized 14,30014,300 Wasser, demineralisiertWater, demineralized ad 100, 000ad 100, 000 DD Aloe Vera Gel 1: 10Aloe vera gel 1:10 (7)(7) 1,0001,000

    Herstellung:production:

    Für Phase C das Pemulen TR-1 im Wasser homogen dispergieren, Konservierungsmittel hinzufügen und vorquellen. Phase B wird unter Homogenisieren in Phase C eingetragen und in einem Vorratsgefäß vorgelegt. Phase A unter Erhitzen gelöst. Bei 35°C wird Phase D zusetzen und in einem zweiten Vorratsgefäß vorgelegt. Zur Verwendung wird die Vorratskammer A/D auf etwa 35 °C erwärmt und der Inhalt mittels eines Pumpsystems gemeinsam mit dem Inhalt der Vorratskammer B/C durch einen mit dem Pumpsystem verbundenen Mikromischer geführt und homogenisiert. For phase C, disperse the Pemulen TR-1 homogeneously in water, Add preservatives and swell. Phase B is under Homogenize entered in phase C and in a storage vessel submitted. Phase A dissolved with heating. Phase D will be added at 35 ° C and presented in a second storage vessel. For use the storage chamber A / D is heated to about 35 ° C and the contents by means of a pump system together with the contents of the pantry B / C through a micromixer connected to the pump system managed and homogenized.

    Bemerkungen:Remarks:

    Viskosität 67.000 mPas (Brookfield RVT, Sp. C, 5 Upm) bei 25°C PH25°C = 6,9
    Als Konservierungsmittel kann gegebenenfalls1,0 % Phenoxyethanol (Merck-Art.-Nr. 807291) hinzugefügt werden.    Viscosity 67,000 mPas (Brookfield RVT, Sp. C, 5 rpm) at 25 ° C PH 25 ° C = 6.9
    1.0% phenoxyethanol (Merck art. No. 807291) can optionally be added as a preservative.

    BezugsguellenBezugsguellen

    (1)(1) Merck KGaA, DarmstadtMerck KGaA, Darmstadt (2)(2) BASF, LudwigshafenBASF, Ludwigshafen (3)(3) Dow Corning, DüsseldorfDow Corning, Düsseldorf (4)(4) GAF, FrechenGAF, cheeky (5)(5) Henry Lamotte, BremenHenry Lamotte, Bremen (6)(6) Goodrich, NeussGoodrich, Neuss (7)(7) Rahn, MaintalRahn, Main Valley

    Claims (11)

    1. Packaging system which is intended for the in-situ production of cosmetic formulations and, for mixing free-flowing components, contains a micromixer (C), comprising two or more thin sheet-like structures which are fixed to one another, characterized in that the structures, in at least one of the surfaces which are directed towards one another, have channels (c) which cross over one another repeatedly.
    2. Packaging system according to Claim 1, characterized in that it has two or more supply chambers (A), which are each provided with a thin tube, these tubes terminating in each case in a channel (c) of a micromixer (C) and mixing of the free-flowing components from the various supply chambers being brought about therein.
    3. Packaging system according to Claim 2, characterized in that the various supply chambers (A) have a common pumping system (B).
    4. Packaging system according to Claim 2, characterized in that the supply chambers (A) are subjected to pressure.
    5. Packaging system according to Claim 3, characterized in that the supply chambers (A) can be connected individually, for use purposes, to the pumping system (B), which is connected to a micromixer (C) and has an outlet opening (d) for the mixed product.
    6. Packaging system according to Claims 1 to 4, characterized in that it has two or more supply chambers (A) which are connected externally to one another.
    7. Packaging system according to Claims 1 to 6, characterized in that it has a micromixer (C) produced from metal, silicon or plastic structures.
    8. Packaging system according to Claims 3 and 5 to 7, characterized in that the pumping system (B), which is connected to a micromixer (C) and has an outlet opening (d) or discharge tube for the mixed product, is reusable.
    9. Packaging system according to Claims 1 to 8 for the in-situ production of cosmetic formulations in the form of lotions, emulsions, gels or creams.
    10. Packaging system according to Claims 1 to 8 for the in-situ production of liposome-containing formulations.
    11. Packaging system according to Claims 1 to 8 for the in-situ production of active-ingredient-containing formulations.
    EP00916904A 1999-03-17 2000-03-07 Packaging system for cosmetic formulations Expired - Lifetime EP1159076B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    DE19911776A DE19911776A1 (en) 1999-03-17 1999-03-17 Packaging systems for cosmetic formulations
    DE19911776 1999-03-17
    PCT/EP2000/001976 WO2000054890A1 (en) 1999-03-17 2000-03-07 Packaging system for cosmetic formulations

    Publications (2)

    Publication Number Publication Date
    EP1159076A1 EP1159076A1 (en) 2001-12-05
    EP1159076B1 true EP1159076B1 (en) 2004-05-12

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    US (1) US6817753B2 (en)
    EP (1) EP1159076B1 (en)
    JP (1) JP2002538909A (en)
    CN (1) CN1118332C (en)
    AU (1) AU760488B2 (en)
    CA (1) CA2367724C (en)
    DE (2) DE19911776A1 (en)
    ES (1) ES2220444T3 (en)
    WO (1) WO2000054890A1 (en)

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    AU3809000A (en) 2000-10-04
    WO2000054890A1 (en) 2000-09-21
    DE50006410D1 (en) 2004-06-17
    CA2367724A1 (en) 2000-09-21
    JP2002538909A (en) 2002-11-19
    US6817753B2 (en) 2004-11-16
    CA2367724C (en) 2007-07-03
    ES2220444T3 (en) 2004-12-16
    CN1343143A (en) 2002-04-03
    EP1159076A1 (en) 2001-12-05
    DE19911776A1 (en) 2000-09-21
    US20030048693A1 (en) 2003-03-13
    CN1118332C (en) 2003-08-20
    AU760488B2 (en) 2003-05-15

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