DE19726184A1 - Oil-in-water or multiple emulsion with high concentration of suspended UVB filter - Google Patents
Oil-in-water or multiple emulsion with high concentration of suspended UVB filterInfo
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- DE19726184A1 DE19726184A1 DE1997126184 DE19726184A DE19726184A1 DE 19726184 A1 DE19726184 A1 DE 19726184A1 DE 1997126184 DE1997126184 DE 1997126184 DE 19726184 A DE19726184 A DE 19726184A DE 19726184 A1 DE19726184 A1 DE 19726184A1
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- emulsions
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- emulsifiers
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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
-
- 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
-
- 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
- A61K8/062—Oil-in-water emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/066—Multiple emulsions, e.g. water-in-oil-in-water
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- 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
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
- A61K8/496—Triazoles or their condensed derivatives, e.g. benzotriazoles
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
Abstract
Description
Die vorliegende Erfindung betrifft kosmetische und dermatologische Lichtschutzzuberei tungen, insbesondere hautpflegende kosmetische und dermatologische Lichtschutzzu bereitungen.The present invention relates to cosmetic and dermatological light protection tions, in particular skincare cosmetic and dermatological sunscreen preparations.
Die schädigende Wirkung des ultravioletten Teils der Sonnenstrahlung auf die Haut ist allgemein bekannt. Während Strahlen mit einer Wellenlänge, die kleiner als 290 nm ist (der sogenannte UVC-Bereich), von der Ozonschicht in der Erdatmosphäre absorbiert werden, verursachen Strahlen im Bereich zwischen 290 nm und 320 nm, dem soge nannten UVB-Bereich, ein Erythem, einen einfachen Sonnenbrand oder sogar mehr oder weniger starke Verbrennungen.The damaging effect of the ultraviolet part of solar radiation on the skin is well known. While rays with a wavelength smaller than 290 nm (the so-called UVC range), absorbed by the ozone layer in the earth's atmosphere be, cause rays in the range between 290 nm and 320 nm, the soge called UVB, erythema, simple sunburn or even more or less severe burns.
Als ein Maximum der Erythemwirksamkeit des Sonnenlichtes wird der engere Bereich um 308 nm angegeben.As a maximum of the erythema efficiency of sunlight becomes the narrower area indicated at 308 nm.
Zum Schutze gegen UVB-Strahlung sind zahlreiche Verbindungen bekannt, bei denen es sich zumeist um Derivate des 3-Benzylidencamphers, der 4-Aminobenzoesäure, der Zimtsäure, der Salicylsäure, des Benzophenons sowie auch des 2-Phenylbenzimidazols handelt.To protect against UVB radiation, numerous compounds are known in which It is mostly derivatives of 3-Benzylidencamphers, the 4-aminobenzoic acid, the Cinnamic acid, salicylic acid, benzophenone and 2-phenylbenzimidazole is.
Auch für den Bereich zwischen etwa 320 nm und etwa 400 nm, den sogenannten UVA- Bereich, ist es wichtig, Filtersubstanzen zur Verfügung zu haben, da auch dessen Strahlen Schäden hervorrufen können. So ist erwiesen, daß UVA-Strahlung zu einer Schädigung der elastischen und kollagenen Fasern des Bindegewebes führt, was die Haut vorzeitig altern läßt, und daß sie als Ursache zahlreicher phototoxischer und pho toallergischer Reaktionen zu sehen ist. Der schädigende Einfluß der UVB-Strahlung kann durch UVA-Strahlung verstärkt werden.Also for the range between about 320 nm and about 400 nm, the so-called UVA Area, it is important to have filter substances available as well Radiation can cause damage. So it is proven that UVA radiation to a Damage to the elastic and collagen fibers of the connective tissue leads to what the Skin ages prematurely, and that they are the cause of numerous phototoxic and pho allergic reactions can be seen. The damaging influence of UVB radiation can be amplified by UVA radiation.
Die UV-Strahlung kann aber auch zu photochemischen Reaktionen führen, wobei dann die photochemischen Reaktionsprodukte in den Hautmetabolismus eingreifen.The UV radiation can also lead to photochemical reactions, in which case the photochemical reaction products interfere with the skin metabolism.
Vorwiegend handelt es sich bei solchen photochemischen Reaktionsprodukten um radi kalische Verbindungen, z. B. Hydroxylradikale. Auch undefinierte radikalische Photopro dukte, welche in der Haut selbst entstehen, können aufgrund ihrer hohen Reaktivität un kontrollierte Folgereaktionen an den Tag legen. Aber auch Singulettsauerstoff, ein nichtradikalischer angeregter Zustand des Sauerstoffmoleküls kann bei UV-Bestrahlung auftreten, ebenso kurzlebige Epoxide und viele andere. Singulettsauerstoff beispiels weise zeichnet sich gegenüber dem normalerweise vorliegenden Triplettsauerstoff (radikalischer Grundzustand) durch gesteigerte Reaktivität aus. Allerdings existieren auch angeregte, reaktive (radikalische) Triplettzustände des Sauerstoffmoleküls.Predominantly, such photochemical reaction products are radi kalische connections, z. B. hydroxyl radicals. Also undefined radical Photopro Due to their high reactivity, unreacted substances which are formed in the skin itself controlled controlled reactions to the day. But also singlet oxygen, a Non-radical excited state of the oxygen molecule can under UV irradiation occur, as are short-lived epoxides and many others. Singlet oxygen, for example is distinguished from the normally existing triplet oxygen (radical ground state) by increased reactivity. However exist also excited, reactive (radical) triplet states of the oxygen molecule.
Ferner zählt UV-Strahlung zur ionisierenden Strahlung. Es besteht also das Risiko, daß auch ionische Spezies bei UV-Exposition entstehen, welche dann ihrerseits oxidativ in die biochemischen Prozesse einzugreifen vermögen.Furthermore, UV radiation counts as ionizing radiation. So there is a risk that also arise ionic species on UV exposure, which in turn oxidative in to be able to intervene in the biochemical processes.
Ein vorteilhafter UV-Filter ist das 2,2'-Methylen-bis-(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-
tetramethylbutyl)-phenol), welches durch die chemische Strukturformel
An advantageous UV filter is the 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol), which by the chemical structural formula
gekennzeichnet ist. Dennoch ergeben sich auch bei dieser Substanz gewisse, formulie rungstechnisch bedingte Nachteile, denn selbst wenn grundsätzlich ein guter UV-Schutz bei gegebener begrenzter Löslichkeit, (und damit nach herkömmlichen Maßstäben: schlechter Einarbeitbarkeit in eine kosmetische oder dermatologische Zubereitung) er reicht werden kann, kann ein anderes Problem auftreten, die Rekristallisation. Diese tritt gerade bei schlecht löslichen Substanzen vergleichsweise schnell ein, sei es durch Temperaturschwankungen oder andere Einflüsse hervorgerufen. Unkontrollierte Rekri stallisation eines wesentlichen Zubereitungsbestandteiles wie eines UV-Filters hat aber äußerst nachteilige Einwirkungen auf die Eigenschaften der gegebenen Zubereitung und, nicht zuletzt, auf den angestrebten Lichtschutz.is marked. Nevertheless, there are also certain formulas in this substance tion-related disadvantages, because even if basically a good UV protection given given limited solubility (and thus by conventional standards: poor incorporation into a cosmetic or dermatological preparation) he can be enough, another problem may occur, the recrystallization. This occurs especially with poorly soluble substances comparatively quickly, be it through Temperature fluctuations or other influences caused. Uncontrolled Rekri However, installation of an essential preparation component such as a UV filter has extremely adverse effects on the properties of the given preparation and, last but not least, the desired sunscreen.
Weitverbreitete kosmetische und dermatologische Zubereitungsformen sind Emulsio nen. In einfachen Emulsionen liegen in der einen Phase feindisperse, von einer Emulga torhülle umschlossene Tröpfchen der zweiten Phase (Wassertröpfchen in W/O- oder Li pidvesikel in O/W-Emulsionen) vor. In einer multiplen Emulsion (zweiten Grades) hinge gen sind in solchen Tröpfchen feiner disperse Tröpfchen der ersten Phase emulgiert. Auch in diesen Tröpfchen wiederum können noch feiner disperse Tröpfchen vorliegen (multiple Emulsion dritten Grades) und so fort.Common cosmetic and dermatological formulations are emulsions NEN. In simple emulsions are in one phase finely dispersed, by an Emulga Torhülle enclosed droplets of the second phase (water droplets in W / O or Li pidvesicles in O / W emulsions). In a multiple emulsion (second degree) conditions are emulsified in such droplets of fine disperse droplets of the first phase. In turn, even finer disperse droplets may be present in these droplets (third-degree multiple emulsion) and so on.
Es ist bekannt, daß sich multiple Emulsionen - unter anderem - durch eine besonders feine Emulsionstextur auszeichnen können. Diese Eigenschaft eignet sie hervorragend als Basis sowohl für kosmetische wie für medizinische topische Zubereitungen.It is known that multiple emulsions - among others - by a particular fine emulsion texture can distinguish. This property makes it perfect as a base for both cosmetic and medical topical preparations.
So wie man also bei den einfachen Emulsionen von W/O- oder O/W-Emulsionen spricht (Wasser-in-Oel oder Oel-in-Wasser), gibt es bei multiplen Emulsionen W/O/W-, O/W/O-, O/W/O/W-, W/O/W/O-Emulsionen und so fort.Just as one speaks for the simple emulsions of W / O or O / W emulsions (Water-in-oil or oil-in-water), there are multiple emulsions W / O / W-, O / W / O-, O / W / O / W, W / O / W / O emulsions and so on.
Multiple Emulsionen, bei welchen die jeweiligen inneren und äußeren Wasserphasen oder inneren und äußeren Ölphasen (wesentlich) unterschiedlich geartet sind (also z. B. W/O/W'- und O/W/O'-Emulsionen), sind der Präparation durch Zweitopfverfahren zu gängig. Solche Emulsionen, in welchen die inneren und äußeren Wasser- bzw. Ölpha sen nicht unterschiedlich geartet sind, sind sowohl durch Ein- als auch durch Zweitopf verfahren erhältlich.Multiple emulsions in which the respective inner and outer water phases or inner and outer oil phases are (essentially) different in nature (eg W / O / W 'and O / W / O'emulsions) are ready for preparation by two-pot procedures consistently. Such emulsions in which the inner and outer water or Ölpha are not different, are both by one and by two-pot available.
Die multiplen Emulsionen zweiten Grades werden gelegentlich als "bimultiple Systeme", solche dritten Grades als "trimultiple Systeme" usw., bezeichnet (W.Seifriz:, Studies in Emulsions, J.Phys.Chem., 29 (1925) 738-749). The multiple second degree emulsions are sometimes called "bimultiple systems", such third degree as "trimultiple systems", etc., designated (W.Seifriz :, Studies in Emulsions, J. Phys. Chem., 29 (1925) 738-749).
Verfahren zur Herstellung multipler Emulsionen sind dem Fachmann an sich geläufig. So gibt es Zweitopfverfahren, in welchen eine einfache Emulsion (z. B. eine W/O-Emul sion) vorgelegt und durch Zugabe einer weiteren Phase (z. B. eine Wasserphase) mit einem entsprechenden Emulgator (z. B. ein O/W-Emulgator) in eine multiple Emulsion (z. B. eine W/O/W-Emulsion) überführt wird.Processes for the preparation of multiple emulsions are familiar to the person skilled in the art. Thus, there are two-pot processes in which a simple emulsion (eg, a W / O emuls sion) and by adding a further phase (eg., A water phase) with a corresponding emulsifier (eg an O / W emulsifier) into a multiple emulsion (eg, a W / O / W emulsion).
Eine zweites bekanntes Verfahren besteht darin, Emulgatorgemische mit einer Ölphase und einer Wasserphase in einem Eintopfverfahren in eine multiple W/O/W-Emulsion zu überführen. Die Emulgatoren werden in der Ölphase gelöst und mit der Wasserphase vereinigt. Voraussetzung für ein solches Verfahren ist, daß die HLB-Werte (HLB = Hy drophil-Lipophil-Balance) der eingesetzten einzelnen Emulgatoren sich deutlich vonein ander unterscheiden.A second known method is to emulsifier mixtures with an oil phase and a water phase in a one-pot process into a multiple W / O / W emulsion convict. The emulsifiers are dissolved in the oil phase and with the water phase united. A prerequisite for such a method is that the HLB values (HLB = Hy drophil-lipophile balance) of the individual emulsifiers used clearly from a different.
Die Definition für den HLB-Wert ist für Polyolfettsäureester gegeben durch die Formel I
The definition for the HLB value for polyol fatty acid esters is given by the formula I.
HLB = 20.(1-S/A).HLB = 20. (1-S / A).
Für eine Gruppe von Emulgatoren, deren hydrophiler Anteil nur aus Ethylenoxideinhei
ten besteht, gilt die Formel II
For a group of emulsifiers whose hydrophilic portion consists only of Ethylenoxideinhei th, the formula II applies
HLB = E/5
HLB = E / 5
wobei
S = Verseifungszahl des Esters,
A = Säurezahl der zurückgewonnen Säure
E = Massenanteil Ethylenoxid (in %) am
Gesamtmolekül
bedeuten.in which
S = saponification value of the ester,
A = Acid value of the recovered acid
E = mass fraction of ethylene oxide (in%) of the total molecule
mean.
Emulgatoren mit HLB-Werten von 6-8 sind im allgemeinen W/O-Emulgatoren, solche mit HLB-Werten von 8-18 sind im allgemeinen O/W-Emulgatoren.Emulsifiers with HLB values of 6-8 are generally W / O emulsifiers, those with HLB values of 8-18 are generally O / W emulsifiers.
Literatur: "Kosmetik - Entwicklung, Herstellung und Anwendung kosmetischer Mittel"; W.Umbach (Hrsg.), Georg Thieme Verlag 1988.Literature: "Cosmetics - Development, production and use of cosmetic products"; W. Umbach (ed.), Georg Thieme Verlag 1988.
Hydrophile Emulgatoren (mit hohen HLB-Werten) sind in der Regel W/O-Emulgatoren. Demgemäß sind hydrophobe oder lipophile Emulgatoren (mit niedrigen HLB-Werten) in der Regel W/O-Emulgatoren. Hydrophilic emulsifiers (with high HLB values) are usually W / O emulsifiers. Accordingly, hydrophobic or lipophilic emulsifiers (with low HLB values) are in usually W / O emulsifiers.
Die US-Patentschrift 4,931,210 beschreibt ein Verfahren zur Herstellung von W/O/W- Emulsion, wobei als Emulgatoren Polyglycerinpolyricinoleate verwendet werden.US Pat. No. 4,931,210 describes a process for producing W / O / W Emulsion, being used as emulsifiers Polyglycerinpolyricinoleate.
Die Tröpfchendurchmesser der gewöhnlichen "einfachen", also nichtmultiplen Emulsio nen liegen im Bereich von ca. 1 µm bis ca. 50 µm. Solche "Makroemulsionen" sind, ohne weitere färbende Zusätze, milchigweißgefärbt und opak. Feinere ,Makroemulsionen", deren Tröpfchendurchmesser im Bereich von ca. 10-1 µm bis ca. 1 µm liegen, sind, wie derum ohne färbende Zusätze, bläulichweißgefärbt und opak. Solche "Makroemulsio nen" haben für gewöhnlich hohe Viskosität.The droplet diameter of the ordinary "simple", ie non-multiple Emulsio nen are in the range of about 1 micron to about 50 microns. Such "macroemulsions" are, without further coloring additives, milky white colored and opaque. Finer, macroemulsions, whose droplet diameters range from about 10 -1 μm to about 1 μm, are bluish white in color and opaque, as is the case with no coloring additives. Such "macroemulsions" usually have high viscosity.
Mizellaren und molekularen Lösungen mit Partikeldurchmessern kleiner als ca. 10-2 µm, die allerdings nicht mehr als echte Emulsionen aufzufassen sind, ist vorbehalten, klar und transparent zu erscheinen.Micellar and molecular solutions with particle diameters less than about 10 -2 microns, which are no longer considered as true emulsions, however, are reserved to appear clear and transparent.
Der Tröpfchendurchmesser von Mikroemulsionen dagegen liegt im Bereich von etwa 10-2 µm bis etwa 10-1 µm. Mikroemulsionen sind transluzent und meist niedrigviskos. Die Vis kosität vieler Mikroemulsionen vom O/W-Typ ist vergleichbar mit der des Wassers.By contrast, the droplet diameter of microemulsions ranges from about 10 -2 μm to about 10 -1 μm. Microemulsions are translucent and usually low viscosity. The viscosity of many microemulsions of the O / W type is comparable to that of water.
Vorteil von Mikroemulsionen ist, daß in der dispersen Phase Wirkstoffe wesentlich feiner dispers vorliegen können als in der dispersen Phase von "Makroemulsionen". Ein wei terer Vorteil ist, daß sie aufgrund ihrer niedrigen Viskosität versprühbar sind. Werden Mi kroemulsionen als Kosmetika verwendet, zeichnen sich entsprechende Produkte durch hohe kosmetische Eleganz aus.Advantage of microemulsions is that in the disperse phase drugs much finer may be present disperse than in the disperse phase of "macroemulsions". A white terer advantage is that they can be sprayed due to their low viscosity. Be Mi used as cosmetics, are characterized by corresponding products high cosmetic elegance.
Es ist bekannt, daß hydrophile Emulgatoren bei steigender Temperatur ihr Löslichkeits verhalten von wasserlöslich zu fettlöslich ändern. Der Temperaturbereich, in dem die Emulgatoren ihre Löslichkeit geändert haben, wird Phaseninversionstemperaturbereich (PIT) genannt.It is known that hydrophilic emulsifiers with increasing temperature their solubility Change from water-soluble to fat-soluble. The temperature range in which the Emulsifiers have changed their solubility becomes phase inversion temperature range Called (PIT).
S.Matsumoto (Joumal of Colloid and Interface Science, Vol. 94, No.2, 1983) beschreibt, daß die Entwicklung einer W/O/W-Emulsion einer Phaseninversion konzentrierter W/O- Emulsionen, welche durch Span 80, einen ausgeprägten W/O-Emulgator, stabilisiert sind, vorausgeht. Matsumoto geht dabei von einem extrem unpolaren Öl, nämlich flüssi gem Paraffin aus. Darüberhinaus sei eine gewisse Menge hydrophiler Emulgatoren zur Entwicklung einer W/O/W-Emulsion aus einer W/O-Emulsion nötig. S. Matumsumoto (Joumal of Colloid and Interface Science, Vol. 94, No.2, 1983) describes that the development of a W / O / W emulsion of a phase inversion concentrated W / O Emulsions stabilized by Span 80, a pronounced W / O emulsifier are, precedes. Matsumoto goes from an extremely non-polar oil, namely liquid paraffin wax out. In addition, a certain amount of hydrophilic emulsifiers for Development of a W / O / W emulsion from a W / O emulsion necessary.
T.J.Lin, H.Kurihara und H.Ohta (Journal of the Society of Cosmetic Chemists 26, S. 121- 139, März 1975 zeigen bei unpolaren Ölen, daß im Bereich der PIT extrem instabile multiple Emulsionen vorliegen können.T.J. Lin, H. Kurihara and H. Ohta (Journal of the Society of Cosmetic Chemists 26, p. 139, March 1975 show that non-polar oils are extremely unstable in the PIT range multiple emulsions may be present.
Aufgabe der vorliegenden Erfindung war daher, diesen Übelständen Abhilfe zu schaf fen.Object of the present invention was therefore to remedy these evils fen.
Es hat sich überraschenderweise gezeigt, und darin liegt die Lösung der Aufgaben be
gründet, daß O/W-Emulsionen, insbesondere O/W-Mikroemulsionen, oder O/W/O-
Emulsionen oder O/W/O'-Emulsionen, enthaltend
It has surprisingly been found, and therein is the solution of the tasks be based, that O / W emulsions, in particular O / W microemulsions, or O / W / O emulsions or O / W / O'-emulsions containing
- (a) eine Wasserphase,(a) a water phase,
- (b) gegebenenfalls übliche, in Wasser lösliche oder dispergierbare Substanzen,(b) optionally conventional, water-soluble or dispersible substances,
-
(c) eine Ölphase,
- - in welcher mindestens eine kosmetisch oder dermatologische UV-Fil
tersubstanz, gewählt aus der Gruppe der Benzotriazolderivate der all
gemeinen Strukturformel
wiedergegeben wird, wobei R1 und R2 unabhängig voneinander ge wählt werden aus der Gruppe der verzweigten oder unverzweigten C1- C18-Alkylreste, der gegebenenfalls mit einer oder mehreren C1-C4- Al kylgruppen substituierten C5-C15-Cycloalkyl- oder Arylreste, in suspendierter Form vorliegt,
- - In which at least one cosmetic or dermatological UV filter tersubstanz selected from the group of benzotriazole derivatives of all general structural formula
is reproduced, wherein R 1 and R 2 are independently ge selected from the group of branched or unbranched C 1 - C 18 alkyl radicals, optionally substituted with one or more C 1 -C 4 - kylgruppen Al-substituted C 5 -C 15 - Cycloalkyl or aryl radicals, in suspended form,
- - in welcher mindestens eine kosmetisch oder dermatologische UV-Fil
tersubstanz, gewählt aus der Gruppe der Benzotriazolderivate der all
gemeinen Strukturformel
-
(d) mindestens einen Emulgator (Emulgator A), gewählt aus der Gruppe der Emulga
toren mit folgenden Eigenschaften
- - ihre Lipophilie ist entweder abhängig vom pH-Wert, dergestalt daß durch Er höhung oder Senkung des pH-Wertes die Lipophilie zunimmt oder abnimmt, wobei unerheblich ist, welche der beiden Möglichkeiten der Änderung der Li pophilie durch die Erhöhung bzw. Senkung des pH-Wertes bewirkt wird, und/oder
- - ihre Lipophilie ist abhängig von der Temperatur, dergestalt, daß die Lipophi lie mit steigender Temperatur zunimmt und deren Hydrophilie mit sinkender Temperatur zunimmt,
- their lipophilicity is either dependent on the pH, such that increasing or decreasing the pH increases or decreases the lipophilicity, it being irrelevant which of the two possibilities of changing the Li pophilie by increasing or decreasing the pH Value is effected, and / or
- their lipophilicity is dependent on the temperature, such that the lipophilic substance increases with increasing temperature and its hydrophilicity increases with decreasing temperature,
- (e) ferner gegebenenfalls weitere in der Ölphase lösliche oder dispergierbare Sub stanzen, darunter bevorzugt solche, gewählt aus der Gruppe der nicht unter die Definition des Emulgators A fallende Emulgatoren, insbesondere solche, die vor wiegend als W/O-Emulgatoren wirken,(e) further optionally further oil phase soluble or dispersible sub punching, including preferably those selected from the group of non-die Definition of the emulsifier A falling emulsifiers, in particular those before predominantly acting as W / O emulsifiers,
den Nachteilen des Standes der Technik abhelfen.to remedy the disadvantages of the prior art.
Erfindungsgemäß ist möglich, hohe Einsatzkonzentrationen an erfindungsgemäß einge setzten Benzotriazolderivaten, d. h., typischerweise etwa 5 Gew.-%, bezogen auf das Ge samtgewicht einer O/W-Mikroemulsion bzw. einer O/W/O-Emulsion mit einem Ölphasen anteil von etwa 50 Gew.-%, wieder bezogen auf das Gesamtgewicht der Zubereitung, zu erreichen und damit die vorteilhaften Eigenschaften dieses Lichtschutzfilters voll aus zunutzen.According to the invention, it is possible to use high levels of use according to the invention put benzotriazole derivatives, d. h., Typically about 5 wt .-%, based on the Ge total weight of an O / W microemulsion or an O / W / O emulsion with an oil phase proportion of about 50% by weight, again based on the total weight of the preparation, to reach and thus the beneficial properties of this sunscreen filter fully to use.
Erfindungsgemäß bevorzugtes Benzotriazolderivat ist das oben erwähnte 2,2'-Methylen-
bis-(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetrnmethylbutyl)-phenol), welches durch die
chemische Strukturformel
Benzotriazole derivative preferred according to the present invention is the above-mentioned 2,2'-methylenebis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetrnomethylbutyl) phenol) which is represented by the chemical name structural formula
gekennzeichnet ist.is marked.
Als vorteilhafte Verkörperung der vorliegenden Erfindung wird ebenfalls angesehen ein
Verfahren zur Einarbeitung der vorab beschriebenen Benzotriazolderivate in O/W-
Emulsionen, O/W-Mikroemulsionen oder O/W/O-Emulsionen, dadurch gekennzeichnet,
daß
As an advantageous embodiment of the present invention is also considered a method for incorporation of the above-described benzotriazole derivatives in O / W emulsions, O / W microemulsions or O / W / O emulsions, characterized in that
- (a) die Bestandteile einer Wasserphase,(a) the components of a water phase,
- (b) gegebenenfalls übliche, in Wasser lösliche oder dispergierbare Substanzen,(b) optionally conventional, water-soluble or dispersible substances,
- (c) die Bestandteile einer Ölphase(c) the components of an oil phase
- (c1) die vorab beschriebenen Benzotriazolderivate(c1) the benzotriazole derivatives described above
-
(d) mindestens ein Emulgator (Emulgator A), gewählt aus der Gruppe der Emulgato
ren mit folgenden Eigenschaften
- - ihre Lipophilie ist entweder abhängig vom pH-Wert, dergestalt daß durch Er höhung oder Senkung des pH-Wertes die Lipophilie zunimmt oder abnimmt, wobei unerheblich ist, welche der beiden Möglichkeiten der Änderung der Li pophilie durch die Erhöhung bzw. Senkung des pH-Wertes bewirkt wird, und/oder
- - ihre Lipophilie ist abhängig von der Temperatur, dergestalt, daß die Lipophi lie mit steigender Temperatur zunimmt und die Hydrophilie mit sinkender Temperatur zunimmt,
- their lipophilicity is either dependent on the pH, such that increasing or decreasing the pH increases or decreases the lipophilicity, it being irrelevant which of the two possibilities of changing the Li pophilie by increasing or decreasing the pH Value is effected, and / or
- their lipophilicity is dependent on the temperature, such that the lipophil increases with increasing temperature and the hydrophilicity increases with decreasing temperature,
-
(e) ferner gegebenenfalls weitere in der Ölphase lösliche oder dispergierbare Sub
stanzen, darunter bevorzugt solche, gewählt aus der Gruppe der nicht unter die
Definition des Emulgators A fallende Emulgatoren, insbesondere solche, die vor
wiegend als W/O-Emulgatoren wirken,
zusammengegeben werden und unter Agitation ein Gemisch gebildet wird, dergestalt, daß(e) furthermore, if appropriate, further substances which are soluble or dispersible in the oil phase, including preferably those selected from the group of emulsifiers not covered by the definition of emulsifier A, in particular those which predominantly act as W / O emulsifiers,
be combined and formed under agitation a mixture such that - (f) dieses Gemisch durch geeignete Wahl der Parameter, gewählt aus der Gruppe pH-Wert, Temperatur und der Konzentration bzw. Konzentrationen mindestens ei nes der gewählten Emulgatoren, in den Phaseninversionsbereich gebracht wird, in welchem sich W/O-Emulsionen in O/W-Emulsionen umwandeln,(f) this mixture by appropriate choice of the parameters selected from the group pH, temperature and concentration or concentrations at least ei of the emulsifiers selected, is placed in the phase inversion region, in which W / O emulsions convert to O / W emulsions,
- (g) durch Variation mindestens eines Parameters, gewählt aus der Gruppe pH-Wert, Temperatur und der Konzentration bzw. Konzentrationen mindestens eines der gewählten Emulgatoren, die gebildete W/O-Emulsion aus dem Phaseninversions bereich heraus gebracht wird, in welchem sich eine gebildete W/O-Emulsion in ei ne O/W-Emulsion umwandelt, wodurch eine O/W-Emulsion oder O/W-Mikroemul sion erzeugt wird(g) by varying at least one parameter chosen from the group pH value, Temperature and the concentration or concentrations of at least one of selected emulsifiers, the formed W / O emulsion from the phase inversion is brought out in which a formed W / O emulsion in egg ne O / W emulsion, whereby an O / W emulsion or O / W microemuls produced
- (h) gegebenenfalls durch geeignete Wahl der Rahmenbedingungen eine weitere Pha seninversion zur O/W/O-Emulsion eingeleitet wird, (h) if appropriate, by an appropriate choice of framework conditions, another Pha seninversion is initiated to O / W / O emulsion,
- (i) das Gemisch gegebenenfalls weiteren Aufbereitungsschritten, insbesondere ei nem oder mehreren Homogenisierungsschritten unterworfen wird.(i) the mixture optionally further processing steps, in particular ei one or more Homogenisierungsschritten.
Erfindungsgemäß gleichermaßen vorteilhaft sind Verfahren, bei welchen die Variation
des Parameters oder der Parameter darin besteht, daß
Equally advantageous according to the invention are methods in which the variation of the parameter or of the parameters consists in that
- (1) bei vorgegebenem pH-Wert und vorgegebener Konzentration des Emulgators A bzw. der Vielzahl an Emulgatoren A die Temperatur des Gemisches sowie gege benenfalls zusätzlich die Konzentration mindestens eines weiteren Emulgators A variiert wird, daß(1) at a given pH and concentration of the emulsifier A or the plurality of emulsifiers A, the temperature of the mixture and Gege if appropriate, in addition, the concentration of at least one further emulsifier A. is varied, that
- (2) bei vorgegebener Temperatur und vorgegebener Konzentration des Emulgators A bzw. der Vielzahl an Emulgatoren A der pH-Wert des Gemisch es sowie gegebe nenfalls zusätzlich die Konzentration mindestens eines weiteren Emulgators A va riiert wird, daß(2) at a given temperature and given concentration of the emulsifier A. or the plurality of emulsifiers A, the pH of the mixture it as well as give If appropriate, in addition, the concentration of at least one further emulsifier A va is riiert that
- (3) bei vorgegebener Temperatur und vorgegebenem pH-Wert die Konzentration min destens eines Emulgators A sowie gegebenenfalls zusätzlich die Konzentration mindestens eines weiteren Emulgators A variiert wird, daß(3) at a given temperature and pH, the concentration min at least one emulsifier A and optionally in addition the concentration at least one further emulsifier A is varied, that
- (4) bei vorgegebenem pH-Wert die Temperatur des Gemisches sowie zusätzlich die Konzentration mindestens eines Emulgators A sowie gegebenenfalls zusätzlich die Konzentration mindestens eines weiteren Emulgators A variiert werden, daß(4) at a given pH, the temperature of the mixture and additionally the Concentration of at least one emulsifier A and optionally in addition the concentration of at least one further emulsifier A can be varied, that
- (5) bei vorgegebener Temperatur des Gemisches der pH-Wert des Gemisches sowie zusätzlich die Konzentration mindestens eines Emulgators A sowie gegebenen falls zusätzlich die Konzentration mindestens eines weiteren Emulgators A variiert werden, daß(5) at a given temperature of the mixture, the pH of the mixture as well in addition, the concentration of at least one emulsifier A and given if, in addition, the concentration of at least one further emulsifier A varies be that
- (6) bei vorgegebener Konzentration mindestens eines Emulgators A der pH-Wert so wie zusätzlich die Temperatur des Gemisches sowie gegebenenfalls zusätzlich die Konzentration mindestens eines weiteren Emulgators A variiert werden.(6) at a predetermined concentration of at least one emulsifier A, the pH value so as in addition the temperature of the mixture and possibly additionally the Concentration of at least one further emulsifier A can be varied.
Grundsätzlich ist zwar möglich und vorteilhaft, das oder die Benzotriazolderivate zu je dem beliebigen Zeitpunkt dem den Emulsionen zugrundeliegenden Gemisch zuzuge ben. Es wird allerdings ein erfindungsgemäßes Verfahren bevorzugt, welches dadurch gekennzeichnet ist, daß die Benzotriazolderivate vor dem Emulgierungsvorgang in der Ölphase gegebenenfalls unter Erwärmen, dispergiert werden und die übrigen Schritte des Verfahrens nachgeschaltet werden. In principle, although possible and advantageous, the benzotriazole derivatives or each ever at any time zuge the mixture underlying the emulsions ben. However, a method according to the invention is preferred which is characterized characterized in that the benzotriazole derivatives prior to the emulsification in the Oil phase, optionally with heating, and the remaining steps be followed by the process.
Es ist dabei bevorzugt, zunächst die Löslichkeit des oder der Benzotriazolderivate in der Gesamtheit der Ölkomponenten zu bestimmen, wobei es von Vorteil ist, solche Ölkom ponenten auszuwählen, in denen das oder die Benzotriazolderivate zu höchstens 5 Gew.-% löslich sind. Diese Vorauswahl zu treffen, übersteigt nicht das allgemeine Wis sen des Fachmannes.It is preferred, first, the solubility of the benzotriazole or the derivatives in the To determine totality of the oil components, it being advantageous to such Ölkom components in which the benzotriazole derivative or % By weight are soluble. To make this preselection does not exceed the general wis sen of the professional.
Es ist bevorzugt, das oder die vorab beschriebenen Benzotriazolderivate unter Erwär men in der Ölphase, insbesondere vorteilhaft in einer unpolaren Ölkomponente bzw. einem Gemisch aus unpolaren Ölkomponenten, zu dispergieren.It is preferred that the benzotriazole derivative (s) described above are heated under heating in the oil phase, in particular advantageously in a non-polar oil component or a mixture of non-polar oil components to disperse.
Sofern die Phaseninversion im wesentlichen durch Variation der Temperatur eingeleitet wird, sind O/W-Emulsionen, insbesondere O/W-Mikroemulsionen erhältlich, wobei die Größe der Öltröpfchen im wesentlichen durch die Konzentration des oder der eingesetz ten Emulgatoren bestimmt wird, dergestalt, daß eine höhere Emulgatorkonzentration kleinere Tröpfchen bewirkt und geringere Emulgatorkonzentration zu größeren Tröpf chen führt. Es ist, wenn die Phaseninversion im wesentlichen durch Variation der Tem peratur eingeleitet wird, durchaus vorteilhaft, auf weitere, nicht unter die Definition des Emulgators A fallende, weitere Emulgatoren, namentlich W/O-Emulgatoren, zu verzich ten.Insofar as the phase inversion is initiated essentially by varying the temperature are O / W emulsions, in particular O / W microemulsions available, the Size of the oil droplets essentially by the concentration of or used emulsifiers is determined, such that a higher emulsifier concentration smaller droplets causes lower emulsifier concentration and larger droplets leads. It is when the phase inversion is essentially due to variation of the tem It is quite advantageous, for others, not under the definition of Emulsifier A falling, further emulsifiers, namely W / O emulsifiers, verzich th.
Sofern die Phaseninversion im wesentlichen durch Variation des pH-Wertes eingeleitet wird, sind O/W-Emulsionen, insbesondere O/W-Mikroemulsionen, aber auch O/W/O- Emulsionen erhältlich. Es ist, wenn die Phaseninversion im wesentlichen durch Variation des pH-Wertes eingeleitet wird, durchaus vorteilhaft, einen oder mehrere weitere, nicht unter die Definition des Emulgators A fallende, weitere Emulgatoren, namentlich W/O- Emulgatoren, einzusetzen.Provided that the phase inversion initiated essentially by varying the pH are O / W emulsions, in particular O / W microemulsions, but also O / W / O emulsions. Emulsions available. It is when the phase inversion is essentially due to variation the pH is initiated, quite beneficial, one or more others, not under the definition of emulsifier A, other emulsifiers, namely W / O Emulsifiers, use.
Erfindungsgemäß können O/W/O-Emulsionen erhalten werden, wenn der Ölphasenan teil höher als etwa 15 Gew.-%, insbesondere höher als etwa 20 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitung liegt, mehr als etwa 5 Gew.-%, insbesondere etwa 5-10 Gew.-% eines zusätzlichen, nicht unter die Definition des Emulgators A fallenden W/O-Emulgators vorliegen und/oder wenn die Ölphase einen niedrigen Anteil an pola ren Ölen aufweist. In the present invention, O / W / O emulsions can be obtained when the oil phase Part higher than about 15 wt .-%, in particular higher than about 20 wt .-%, based on the total weight of the composition is more than about 5% by weight, especially about 5-10 wt .-% of an additional, not falling under the definition of the emulsifier A. W / O emulsifier present and / or if the oil phase, a low proportion of pola ren oils has.
Erfindungsgemäß können O/W-Mikroemulsionen erhalten werden, wenn der Ölphasen anteil unter etwa 20 Gew.-%, insbesondere unter etwa 15 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitung liegt, weniger als etwa 5 Gew.-% eines zusätzlichen, nicht unter die Definition des Emulgators A fallenden W/O-Emulgators vorliegen und/oder wenn die Ölphase einen hohen Anteil an polaren Ölen aufweist.According to the invention, O / W microemulsions can be obtained when the oil phase proportion below about 20% by weight, in particular below about 15% by weight, based on the Total weight of the preparation, less than about 5% by weight of an additional, not covered by the definition of the emulsifier A W / O emulsifier and / or when the oil phase has a high proportion of polar oils.
Erfindungsgemäß können O/W-Emulsionen ("Makroemulsionen") erhalten werden, wenn weniger als etwa 5 Gew.-% eines zusätzlichen nicht unter die Definition des Emulgators A fallenden W/O-Emulgators und mehr als etwa 20 Gew.-% einer polaren Ölphase vor liegen. Vorteilhaft können zusätzliche Gelbildner (z. B. Carbopole, Xanthangummi, Cel lulosederivate) eingesetzt werden.According to the invention, O / W emulsions ("macroemulsions") can be obtained when less than about 5% by weight of an additional not under the definition of the emulsifier A falling W / O emulsifier and more than about 20 wt .-% of a polar oil phase before lie. Advantageously, additional gelling agents (eg, carbopols, xanthan gum, cel lulosederivatives).
Es ist dabei im Einzelfalle möglich, daß die vorgenannten Konzentrationsgrenzen leicht über- oder unterschritten werden und dennoch die betreffenden Emulsionstypen erhal ten werden. Dies kommt angesichts der breit streuenden Vielfalt an geeigneten Emulga toren und Ölbestandteilen für den Fachmann nicht unerwartet, so daß er weiß, daß bei solchen Über- oder Unterschreitungen der Boden der vorliegenden Erfindung nicht ver lassen wird.It is possible in an individual case that the aforementioned concentration limits easily exceeded or fallen below and still the respective emulsion types erhal be. This comes in the face of the wide variety of suitable Emulga Doors and oil components for the expert not unexpected, so he knows that at such overrun or underruns the soil of the present invention is not ver will let.
Es hat sich in erstaunlicher Weise herausgestellt, daß das oder die erfindungsgemäß eingesetzten Benzotriazolderivate als Festkörper, und zwar gewissermaßen "erkap selt", nämlich abgetrennt von anderen Bestandteilen der Zubereitungen vorliegen, in welchen sie teilweise sogar begrenzte Löslichkeit besitzen können. Es wird angenom men, daß die Festkörperpartikel der schwerlöslichen UV-Filtersubstanzen durch das er findungsgemäße Einarbeitungsverfahren einen Hüllfilm erhalten, welcher vermutlich als wesentlichen Bestandteil Emulgatormolekeln enthält.It has surprisingly been found that the or the invention used Benzotriazolderivate as a solid, in a sense "erkap separated from other constituents of the preparations, in which they may sometimes even have limited solubility. It is assumed men that the solid particles of the poorly soluble UV filter substances by the he inventive incorporation process obtained a cladding film, which probably as essential ingredient contains emulsifier.
Erfindungsgemäß kann die Rekristallisation des oder der erfindungsgemäß eingesetzten s-Triazinderivate verhindert werden. Darüberhinaus sind erfindungsgemäß Lichtschutz zubereitungen erhältlich, welche vorzügliche Anwendungseigenschaften aufweisen.According to the invention, the recrystallization of the invention or the used s-triazine derivatives are prevented. In addition, according to the invention light protection available formulations which have excellent application properties.
Der Phaseninversionsbereich läßt sich mathematisch darstellen als Punktmenge inner
halb des geradlinigen Koordinatensystems Σ, welches durch die Größen Temperatur,
pH-Wert und Konzentration eines geeigneten Emulgators bzw. eines Emulgatorengemi
sches in der Zubereitung gebildet wird, gemäß:
Σ= {O, θ, a, m},
mit
O - Koordinatenursprung
θ - Temperatur
a - pH-Wert
m - Konzentration.The phase inversion range can be represented mathematically as a point quantity within the rectilinear coordinate system Σ, which is formed by the variables temperature, pH and concentration of a suitable emulsifier or of an emulsifier mixture in the preparation, according to:
Σ = {O, θ, a, m},
With
O - coordinate origin
θ - temperature
a - pH
m - concentration.
Dabei muß genaugenommen natürlich in einem mehrkomponentigen Emulgatorensy
stem der Beitrag m jedes einzelnen Emulgators zur Gesamtfunktion berücksichtigt wer
den, was bei einem i-komponentigen Emulgatorensystem zur Beziehung
Σ = }O, θ, a, m1, m2. . .mi} führt.To be exact, of course, in a multi-component emulsifier system, the contribution of each emulsifier to the overall function must be taken into account for the overall function of what, in the case of an i-component emulsifier system, is the relationship
Σ =} O, θ, a, m 1 , m 2 . , .m i } leads.
Der Phaseninversionsbereich Φ stellt dabei im mathematischen Sinne ein zusammen hängendes Gebiet oder eine Vielzahl zusammenhängender Gebiete innerhalb des Koor dinatensystems Σ dar. Φ repräsentiert die Gesamtmenge der Koordinatenpunkte K(θ, a, m1, m2. . .mi), welche erfindungsgemäße Gemische aus Wasser- und Ölphase, i erfin dungsgemäßen Emulgatoren der Konzentration mi bei der Temperatur θ und dem pH- Wert a bestimmen, und für welche gilt, daß beim Übergang von einer Koordinate K1 ∉ Φ zu einer Koordinate K2 ∈ Φ Phaseninversion eintritt, wie in Fig. 1 beschrieben. Als va riable Koordinaten in Fig. 1 wurden Temperatur und pH-Wert eines gegebenen Gemi sches unter Konstanthaltung der Konzentration von m1 - mi angegeben. Beim Übergang von K1 nach K2 wird lediglich die Temperatur erhöht.The phase inversion range Φ represents here in the mathematical sense a contiguous area or a plurality of contiguous areas within the coor ordinate line Σ represents. Φ represents the total amount of the coordinate points K (θ, a, m 1, m 2.. .M i), which according to the invention Mixtures of water and oil phase, i inventions to the invention emulsifiers concentration m i at the temperature θ and the pH determine a, and for which holds that when moving from a coordinate K 1 ∉ Φ to a coordinate K 2 ∈ Φ phase inversion occurs, as described in Fig. 1. . As a va riable coordinates in Figure 1 the temperature and pH value of a given Gemi ULTRASONIC were held constant, the concentration of m 1 - m i indicated. In the transition from K 1 to K 2 , only the temperature is increased.
Unter den erfindungsgemäßen Bedingungen ist dieser Prozeß nicht notwendig reversi bel, d. h., kehrt das System von der Koordinate K2 ∈ Φ wieder zur Koordinate K1 ∉ Φ zurück, können erfindungsgemäß andere Emulsionstypen erhalten werden, als der Stand der Technik hätte erwarten lassen. Beispielsweise wird durch Erhöhen der Tem peratur eines erfindungsgemäßen Gemisches aus Wasser- und Ölphase, i erfindungs gemäßen Emulgatoren der Konzentrationen mi, wobei der pH-Wert a konstant bleibt, ausgehend von einer Temperatur welche für Phaseninversion zu niedrig ist (Bedingun gen also, wo eine herkömmliche O/W-Emulsion vorläge, welche auch beim Abkühlen auf Raumtemperatur eine solche bliebe), erwärmt wird, so daß Phaseninversion eintritt, wird nach Abkühlen, z. B. auf Raumtemperatur, keine herkömmliche O/W-Emulsion er halten, sondern eine erfindungsgemäße O/W-Mikroemulsion. Oder, mutatis mutandis: eine erfindungsgemäße O/W/O-Emulsion.Under the conditions according to the invention, this process is not necessarily reversible, ie if the system returns from the coordinate K 2 ∈ Φ back to the coordinate K 1 ∉ Φ, other types of emulsion can be obtained according to the invention than the prior art would have expected. For example, by increasing the temperature of a mixture according to the invention of water and oil phase, according to the invention emulsifiers of concentrations m i , the pH a remains constant, starting from a temperature which is too low for phase inversion conditions a conventional O / W emulsion vorläge, which would remain on cooling to room temperature such), is heated, so that phase inversion occurs, after cooling, z. B. at room temperature, no conventional O / W emulsion he hold, but an inventive O / W microemulsion. Or, mutatis mutandis: an O / W / O emulsion according to the invention.
Unerheblich ist dabei, ob der Phaseninversionsbereich eines gegebenen Systems ein einziges zusammenhängendes (i + 2)-dimensionales Gebiet darstellt oder aus mehreren zusammenhängenden, aber voneinander getrennten solchen Gebieten besteht, also mehreren Phaseninversionsbereichen eines gegebenen Systems entsprechend. Im Rahmen der hiermit vorgelegten Offenbarung wird daher stets verallgemeinernd von ei nem Phaseninversionsbereich gesprochen, auch bei Vorliegen zweier oder mehrerer voneinander getrennter solcher Bereiche.It is irrelevant whether the phase inversion range of a given system is a represents the single contiguous (i + 2) -dimensional domain or of several coherent, but separate, such areas multiple phase inversion regions of a given system accordingly. in the The scope of the disclosure presented here is therefore always generalized by ei spoken phase inversion, even in the presence of two or more separate such areas.
Die Praxis der Herstellung einer erfindungsgemäßen Emulsion besteht vorteilhaft darin, nach Auswahl geeigneter Rohstoffe, d. h., Wasser- und Ölphase, ein oder mehrere Emulgatoren vom Typ A, letzterer oder letztere vorliegend in Konzentrationen, bei wel chen Phaseninversion für das gegebene Gemisch möglich ist, und gegebenenfalls wei tere Substanzen, die Einzelkomponenten unter Agitation auf eine Temperatur zu erwär men, bei welcher Phaseninversion für das gegebene Gemisch möglich ist, und durch Er höhung oder Erniedrigung des pH-Wertes des Gemisches Phaseninversion herbeizu führen, hernach unter fortwährender Agitation das Gemisch auf Raumtemperatur ab kühlen zu lassen. Ein oder mehrere zwischengeschaltete Homogenisierungsschritte sind vorteilhaft, aber nicht zwingend notwendig.The practice of preparing an emulsion according to the invention is advantageously after selection of suitable raw materials, d. h., water and oil phase, one or more Emulsifiers of type A, the latter or the latter present in concentrations where wel phase inversion for the given mixture is possible, and optionally white ture the individual components under agitation to a temperature in which phase inversion is possible for the given mixture, and by Er increase or decrease in the pH of the mixture causes phase inversion Afterwards, under constant agitation, the mixture is cooled down to room temperature to cool. One or more intermediary homogenization steps are advantageous, but not mandatory.
Eine weitere vorteilhafte Ausführungsform des erfindungsgemäßen Verfahrens besteht darin, nach der Auswahl geeigneter Rohstoffe, d. h., Wasser- und Ölphase, ein oder mehrere Emulgatoren vom Typ A letzterer oder letztere vorliegend in Konzentrationen, bei welchen Phaseninversion für das gegebene Gemisch möglich ist, und gegebenen falls weitere Substanzen, die Einzelkomponenten unter Agitation auf einen pH-Wert zu bringen, bei welchem Phaseninversion für das gegebene Gemisch möglich ist, und durch Erhöhung der Temperatur des Gemisches Phaseninversion herbeizuführen, her nach unter fortwährender Agitation das Gemisch auf Raumtemperatur abkühlen zu las sen. Ein oder mehrere zwischengeschaltete Homogenisierungsschritte sind vorteilhaft, aber nicht zwingend notwendig.A further advantageous embodiment of the method according to the invention exists therein, after the selection of suitable raw materials, d. h., water and oil phase, one or a plurality of emulsifiers of type A the latter or the latter present in concentrations, in which phase inversion is possible for the given mixture, and given if further substances, the individual components under agitation to a pH value in which phase inversion is possible for the given mixture, and by inducing phase inversion by raising the temperature of the mixture after continuing to cool the mixture to room temperature while continuing agitation sen. One or more intermediary homogenization steps are advantageous, but not mandatory.
Eine dritte vorfeilhafte Ausführungsform des erfindungsgemäßen Verfahrens besteht darin, nach der Auswahl geeigneter Rohstoffe, d. h., Wasser- und Ölphase, ein oder mehrere Emulgatoren vom Typ A und gegebenenfalls weitere Substanzen, die Einzel komponenten unter Agitation auf einen pH-Wert und eine Temperatur zu bringen, bei welchen Phaseninversion für das gegebene Gemisch möglich ist, und durch Zugabe des Emulgators A oder der Emulgatoren A zum Gemisch Phaseninversion herbeizufüh ren, hernach unter fortwährender Agitation das Gemisch auf Raumtemperatur abkühlen zu lassen. Ein oder mehrere zwischengeschaltete Homogenisierungsschritte sind vorteil haft, aber nicht zwingend notwendig.A third vorfeilhafte embodiment of the method according to the invention consists therein, after the selection of suitable raw materials, d. h., water and oil phase, one or several emulsifiers type A and optionally other substances, the individual to bring components under agitation to a pH and a temperature at which phase inversion is possible for the given mixture, and by addition of the emulsifier A or of the emulsifiers A to the mixture causes phase inversion Thereafter, under constant agitation, cool the mixture to room temperature allow. One or more intermediary homogenization steps are advantageous liable, but not mandatory.
In der Praxis ist möglich und gegebenenfalls sogar vorteilhaft, bei der Herstellung einer erfindungsgemäßen Emulsion den Temperaturbereich, der dem Phaseninversionsbe reich zugeordnet werden kann auch zu übersteigen, da beim Abkühlen auf Raumtempe ratur dieser Bereich dann zwangsläufig durchlaufen wird.In practice it is possible and possibly even advantageous in the production of a emulsion of the invention, the temperature range of the Phaseninversionsbe can also be assigned to rich, because when cooling on Raumtempe then this area will inevitably go through.
Die Emulgatoren A werden bevorzugt gewählt aus der Gruppe der Emulgatoren, welche gute Protonendonoren bzw. Protonenakzeptoren darstellen, wobei gewährleistet sein muß, daß ihre Lipophilie entweder abhängig ist vom pH-Wert, dergestalt daß durch Er höhung oder Senkung des pH-Wertes die Lipophilie zunimmt oder abnimmt, wobei un erheblich ist, welche der beiden Möglichkeiten der Änderung der Lipophilie durch die Erhöhung bzw. Senkung des pH-Wertes bewirkt wird, oder ihre Lipophilie abhängig ist von der Temperatur, dergestalt, daß die Lipophilie mit steigender Temperatur zunimmt und deren Hydrophilie mit sinkender Temperatur zunimmt, oder ihre Lipophilie abhängig ist von pH-Wert und der Temperatur, dergestalt daß durch Erhöhung oder Senkung des pH-Wertes die Lipophilie zunimmt oder abnimmt, wobei unerheblich ist, welche der bei den Möglichkeiten der Änderung der Lipophilie durch die Erhöhung bzw. Senkung des pH-Wertes bewirkt wird, und daß die Lipophilie mit steigender Temperatur zunimmt und deren Hydrophilie mit sinkender Temperatur zunimmt.The emulsifiers A are preferably selected from the group of emulsifiers, which represent good proton donors or proton acceptors, being ensured must that their lipophilicity be either dependent on the pH, so that by Er increasing or decreasing the pH, the lipophilicity increases or decreases, where un It is significant which of the two possibilities of lipophilicity change Increasing or lowering the pH is caused, or their lipophilicity is dependent from the temperature, such that the lipophilicity increases with increasing temperature and whose hydrophilicity increases with decreasing temperature, or their lipophilicity dependent is of pH and temperature, such that by increasing or decreasing the pH increases or decreases the lipophilicity, which is irrelevant which of the possibilities of changing the lipophilicity by increasing or decreasing the pH is effected, and that the lipophilicity increases with increasing temperature and whose hydrophilicity increases with decreasing temperature.
Vorteilhaft werden die Emulgatoren des Typs A gewählt aus der Gruppe der Sorbitan ester und Saccharoseester, insbesondere der verzweigten und unverzweigten Alkylester und Alkenylester mit Kohlenstoffketten von 4-24 Kohlenstoffatomen, bevorzugt Sorbi tanstearat, Sorbitanoleat, Glycerylsorbitanstearat, Saccharosemonostearat, Saccharo semonolaurat, Saccharosepalmitat. Advantageously, the emulsifiers of the type A are selected from the group of sorbitan ester and sucrose esters, in particular the branched and unbranched alkyl esters and alkenyl esters having carbon chains of 4-24 carbon atoms, preferably sorbi tanstearat, sorbitan oleate, glyceryl sorbitan stearate, sucrose monostearate, sucrose semolaurate, sucrose palmitate.
Vorteilhaft können die Emulgatoren des Typs A gewählt aus der Gruppe der Mono
glycerin-monocarbonsäure-monoester gewählt werden, insbesondere solche, welche
durch die Strukturen
Advantageously, the emulsifiers of the type A can be selected from the group of mono-glycerol-monocarboxylic monoesters, in particular those which are characterized by the structures
gekennzeichnet sind, wobei R' einen verzweigten oder unverzweigten Acylrest mit 6-14 Kohlenstoffatomen darstellt. Vorteilhaft wird R' gewählt aus der Gruppe der unverzweig ten Acylreste.wherein R 'is a branched or unbranched acyl radical having 6-14 Represents carbon atoms. Advantageously, R 'is selected from the group of unbranched th acyl radicals.
Die diesen Estern zugrundeliegenden Säuren sind die
The acids underlying these esters are the
Besonders vorteilhaft stellt R' den Octanoylrest (Caprylsäurerest) bzw. den Decanoyl
rest (Caprinsäurerest) dar, wird also also durch die Formeln
Particularly advantageous R 'is the octanoyl (CaprylsÄureurer) or the Decanoyl rest (CaprinsÄureest), that is so by the formulas
R' = -C7H15 bzw. R' = -C9H19
R '= -C 7 H 15 or R' = -C 9 H 19
repräsentiert.represents.
Vorteilhaft können die Emulgatoren des Typs A auch aus der Gruppe der Di- und Tri glycerin-monocarbonsäure-monoester gewählt werden. Erfindungsgemäß liegen die Di- bzw. Triglycerineinheiten der erfindungsgemäßen Diglycerin-monocarbonsäure monoester bzw. Triglycerin-monocarbonsäure-monoester als lineare, unverzweigte Moleküle, also über die jeweiligen OH-Gruppen in 1- bzw. 3-Stellung veretherte "Mo noglycerinmoleküle" vor. Advantageously, the emulsifiers of the type A also from the group of di- and tri glycerol monocarboxylic monoester can be selected. According to the invention are the Di- or triglycerol units of the inventive diglycerol monocarboxylic acid monoester or triglycerol monocarboxylic monoester as linear, unbranched Molecules, ie etherified via the respective OH groups in the 1- or 3-position "Mo noglycerin molecules ".
Ein geringer Anteil zyklischer Di- bzw. Triglycerineinheiten sowie über die OH-Grup pen in 2-Stellung veretherte Glycerinmoleküle kann geduldet werden. Es ist jedoch von Vorteil, solche Verunreinigungen so gering wie nur möglich zu halten.A small proportion of cyclic di- or triglycerol units and the OH group 2-etherified glycerol molecules can be tolerated. However, it is advantageous to keep such impurities as low as possible.
Die erfindungsgemäßen Monocarbonsäuremonoester sind bevorzugt durch folgende
Struktur gekennzeichnet:
The monocarboxylic acid monoesters according to the invention are preferably characterized by the following structure:
wobei R'' einen Kohlenwasserstoffrest, vorteilhaft einen verzweigten oder unver zweigten Alkyl- oder Alkenylrest von 5 bis 17 C-Atomen darstellt.where R "is a hydrocarbon radical, advantageously a branched or unbranched branched alkyl or alkenyl radical of 5 to 17 carbon atoms.
Die erfindungsgemäßen Monocarbonsäureester des Triglycerins sind bevorzugt
durch folgende Struktur gekennzeichnet:
The monocarboxylic acid esters of triglycerin according to the invention are preferably characterized by the following structure:
wobei R''' einen Kohlenwasserstoffrest, vorteilhaft einen verzweigten oder unver zweigten Alkyl- oder Alkenylrest Alkylrest von 5 bis 17 C-Atomen darstellt.where R '' 'is a hydrocarbon radical, preferably a branched or unbranched branched alkyl or alkenyl radical alkyl radical of 5 to 17 carbon atoms.
Die diesen Estern zugrundeliegenden Säuren sind die
The acids underlying these esters are the
Besonders günstig werden R'' und R''' gewählt aus der Gruppe der unverzweigten Al kylreste mit ungeraden C-Zahlen, insbesondere mit 9, 11 und 13 C-Atomen.Particularly favorable R '' and R '' 'are selected from the group of unbranched Al kylreste with odd C numbers, in particular with 9, 11 and 13 C atoms.
Im allgemeinen sind die Monocarbonsäure-monoester des Diglycerins denen des Tri glycerins bevorzugt.In general, the monocarboxylic acid monoesters of diglycerol are those of tri glycerol is preferred.
Erfindungsgemäß ganz besonders günstig sind
According to the invention are very particularly favorable
Als bevorzugter erfindungsgemäßer Monocarbonsäuremonoester des Diglycerins hat sich das Diglycerinmonocaprinat (DMC) erwiesen.As preferred monocarboxylic monoester of the invention diglycerol has the diglycerol monocaprinate (DMC) proved.
Nach einer vorteilhaften Ausführungsform der vorliegenden Erfindung wird ein zu sätzlicher Anteil an in anderen Stellen verestertem Di- oder Triglycerin, ebenso wie gegebenenfalls ein Anteil an den verschiedenen Diestern des Di- bzw. Triglycerins verwendet.According to an advantageous embodiment of the present invention, an additional proportion of di- or triglycerin esterified in other places, as well as optionally a proportion of the different diesters of di- or triglycerol used.
Vorteilhaft sind auch Triglyceryldiisostearat (Nomenklatur analog CTFA: Polyglyceryl-3- diisostearat), Isostearyldiglycerylsuccinat, Diglycerylsesquiisostearat (Nomenklatur ana log CTFA: Polyglyceryl-2-sesquiisostearat), Triglycerylpolyhydroxystearat (Nomenklatur analog CTFA: Polyglyceryl-2-polyhydroxystearat).Also advantageous are triglyceryl diisostearate (nomenclature analog CTFA: polyglyceryl-3 diisostearate), isostearyl diglyceryl succinate, diglyceryl sesquiisostearate (nomenclature ana log CTFA: polyglyceryl-2-sesquiisostearate), triglyceryl polyhydroxystearate (nomenclature analogous to CTFA: polyglyceryl-2-polyhydroxystearate).
Auch Cetearylisononanoat, Dicocoyl-pentaerythrityl-distearylcitrat, ferner die Methicon copolyole, Cyclomethiconcopolyle, Alkylmethiconcopolyole, insbesondere Lau rylmethi concopolyol, Cetyldimethiconcopolyol, haben sich erfindungsgemäß als vorteilhaft er wiesen.Also cetearyl isononanoate, dicocoyl-pentaerythrityl-distearyl citrate, furthermore the methicon Copolyols, Cyclomethiconcopolyle, Alkylmethiconcopolyole, in particular Lau rylmethi concopolyol, Cetyldimethiconcopolyol, have inventively advantageous he grasslands.
Besonders vorteilhaft werden der oder die Emulgatoren des Typs A gewählt aus der Gruppe der verzweigten oder unverzweigten Alkylmonocarbonsäuren, Alkenylmonocar bonsäuren und Alkylendicarbonsäuren mit 4 bis 30 Kohlenstoffatomen, insbesondere Stearinsäure, Ölsäure, Bernsteinsäure, Hexansäure (Capronsäure), Heptansäure (Önanthsäure), Octansäure (Caprylsäure), Nonansäure (Pelargonsäure), Decansäure (Caprinsäure), Undecansäure, Undecensäure (Undecylensäure), Dodecansäure (Laurin säure), Tridecansäure, Tetradecansäure (Myristinsäure), Pentadecansäure, Hexadecan säure (Palmitinsäure), Heptadecansäure (Margarinsäure), Octadecansäure (Stearin säure), Isostearinsäure, Behensäure. Es ist auch vorteilhaft, die Emulgatoren A aus der Gruppe der kosmetisch bzw. pharmazeutisch akzeptablen Salze der vorstehend ge nannten Carbonsäuren zu wählen, insbesondere der Alkali-, Ammonium-, Monoalkylam monium, Dialkylammonium-, Trialkylammonium- und Tetraalkylammoniumsalze.Particularly advantageous are the emulsifiers or the type A selected from the Group of branched or unbranched alkyl monocarboxylic acids, alkenyl monocar Bonsäuren and alkylenedicarboxylic acids having 4 to 30 carbon atoms, in particular Stearic acid, oleic acid, succinic acid, hexanoic acid (caproic acid), heptanoic acid (Enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (Capric acid), undecanoic acid, undecenoic acid (undecylenic acid), dodecanoic acid (laurin acid), tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecane acid (palmitic acid), heptadecanoic acid (margaric acid), octadecanoic acid (stearin acid), isostearic acid, behenic acid. It is also advantageous to use the emulsifiers A from the Group of cosmetically or pharmaceutically acceptable salts of the above ge called carboxylic acids to choose, in particular the alkali, ammonium, monoalkylam monium, dialkylammonium, trialkylammonium and tetraalkylammonium salts.
Ebenfalls besonders vorteilhaft werden der oder die Emulagtoren A gewählt aus der Gruppe der mono-, oligo und polyethoxylierten Verbindungen, insbesondere der poly ethoxylierten ein- oder mehrbasigen Alkohole oder Fettsäuren, beispielsweise Cetea reth-20, PEG-20-Glycerylstearat, Steareth-20, P EG-20-Stearat, P EG-30-Stearat, PEG- 40-Rizinusöl, PEG-1-Glycerin-Sorbitan-Oleostearat, PEG-7 hydriertes Rizinusöl, PEG- 40-Sorbitan peroleat, PEG-45-Dodecyl-Glycol-Copolymer.Also particularly advantageous or the Emulagtoren A are selected from the Group of mono-, oligo and polyethoxylated compounds, in particular poly ethoxylated monohydric or polybasic alcohols or fatty acids, for example cetea reth-20, PEG-20 glyceryl stearate, steareth-20, P EG-20 stearate, P EG-30 stearate, PEG- 40-castor oil, PEG-1-glycerol sorbitan oleostearate, PEG-7 hydrogenated castor oil, PEG- 40 sorbitan peroleate, PEG-45 dodecyl glycol copolymer.
Die erfindungsgemäßen Emulsionen sind vorteilhaft dadurch gekennzeichnet, daß der Emulgator A oder die Emulgatoren A in Konzentrationen von 0,01-20 Gew.-%, bevor zugt 0,05-10 Gew.-%, besonders bevorzugt 0,1-5 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Zusammensetzung, vorliegt oder vorliegen.The emulsions according to the invention are advantageously characterized in that the Emulsifier A or the emulsifiers A in concentrations of 0.01-20 wt .-%, before zugt 0.05-10 wt .-%, particularly preferably 0.1-5 wt .-%, each based on the Total weight of the composition, whether present or present.
Es ist erfindungsgemäß möglich, die Einsatzmengen von an sich in Ölkomponenten schwerlöslichen oder unlöslichen UV-Filtern, insbesondere 4,4',4''-(1,3,5-Triazin-2,4,6- triyltriimino)-tris-benzoesäure-tris(2-ethylhexylester), aber auch 2-Phenylbenzimidazol-5- sulfonsäure bzw. deren Salze in kosmetischen oder dermatologischen Zubereitungen gegenüber dem Stande der Technik zu vervielfachen.It is possible according to the invention, the amounts of in per se in oil components poorly soluble or insoluble UV filters, especially 4,4 ', 4' '- (1,3,5-triazine-2,4,6- triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester), but also 2-phenylbenzimidazole-5 sulfonic acid or salts thereof in cosmetic or dermatological preparations to multiply over the prior art.
Die Gesamtmenge an in Ölkomponenten an sich schwerlöslichen UV-Filtersubstanzen, insbesondere 4,4',4''-(1,3,5-Triazin-2,4,6-triyltriimino)-tris-benzoesäure-tris(2-ethylhexyl ester), aber auch 2-Phenylbenzimidazol-5-sulfonsäure bzw. deren Salze in den fertigen kosmetischen oder dermatologischen Zubereitungen wird vorteilhaft aus dem Bereich von 0,1-10,0 Gew.-%, bevorzugt 0,5-6,0 Gew.-% gewählt, bezogen auf das Gesamt gewicht der Zubereitungen. The total amount of UV filter substances sparingly soluble in oil components, in particular 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester), but also 2-phenylbenzimidazole-5-sulfonic acid or salts thereof in the finished Cosmetic or dermatological preparations will be advantageous in the field from 0.1 to 10.0% by weight, preferably 0.5 to 6.0% by weight, based on the total weight of the preparations.
Es ist erfindungsgemäß vorteilhaft, in den erfindungsgemäßen Zubereitungen zusätzli che öllösliche UVA-Filter und/oder UVB-Filter in der Lipidphase und/oder wasserlösliche UVA-Filter und/oder UVB-Filter in der wäßrigen Phase einzusetzen.It is advantageous according to the invention, in the preparations according to the invention addi oil-soluble UVA filters and / or UVB filters in the lipid phase and / or water-soluble Use UVA filter and / or UVB filter in the aqueous phase.
Vorteilhaft können die erfindungsgemäßen Lichtschutzformulierungen weitere Substan zen enthalten, die UV-Strahlung im UVB-Bereich absorbieren, wobei die Gesamtmenge der Filtersubstanzen z. B. 0,1 Gew.-% bis 30 Gew.-%, vorzugsweise 0,5 bis 10 Gew.-%, insbesondere 1 bis 6 Gew.-% beträgt, bezogen auf das Gesamtgewicht der Zubereitun gen, um kosmetische Zubereitungen zur Verfügung zu stellen, die die Haut vor dem gesamten Bereich der ultravioletten Strahlung schützen.Advantageously, the sunscreen formulations according to the invention can be further substituents containing UV radiation in the UVB range, the total amount the filter substances z. 0.1% to 30% by weight, preferably 0.5 to 10% by weight, in particular 1 to 6 wt .-%, based on the total weight of the preparation to provide cosmetic preparations that protect the skin from the skin protect entire area of ultraviolet radiation.
Die zusätzlichen UVB-Filter können öllöslich oder wasserlöslich sein. Vorteilhafte öllösli
che UVB-Filtersubstanzen sind z. B.:
The additional UVB filters can be oil-soluble or water-soluble. Advantageous oil-soluble UVB filter substances are e.g. B .:
- - 3-Benzylidencampher-Derivate, vorzugsweise 3-(4-Methylbenzyliden)campher, 3- Benzylidencampher;3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3 benzylidenecamphor;
- - 4-Aminobenzoesäure-Derivate, vorzugsweise 4-(Dimethylamino)-benzoesäure(2- ethylhexyl)ester, 4-(Dimethylamino)benzoesäureamylester;4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid (2- ethylhexyl) ester, 4- (dimethylamino) benzoic acid amyl ester;
- - Ester der Zimtsäure, vorzugsweise 4-Methoxyzimtsäure(2-ethylhexyl)ester, 4- Methoxyzimtsäureisopentylester;Esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4- methoxycinnamate;
- - Derivate des Benzophenons, vorzugsweise 2-Hydroxy-4-methoxybenzophenon, 2- Hydroxy-4-methoxy-4'-methylbenzophenon, 2,2'-Dihydroxy-4-methoxybenzophenon;Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2- Hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;
- - Ester der Benzalmalonsäure, vorzugsweise 4-Methoxybenzalmalonsäu redi(2-ethylhe xyl)ester;Esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid (2-ethylhe xyl ester);
- - 4,4',4''-(1,3,5-Triazin-2,4,6-triyltriimino)-tris-benzoesäure-tris(2-ethylhexylester).4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester).
Vorteilhafte wasserlösliche UVB-Filtersubstanzen sind z. B.:
Advantageous water-soluble UVB filter substances are z. B .:
- - Salze der 2-Phenylbenzimidazol-5-sulfonsäure wie ihr Natrium-, Kalium- oder ihr Tri ethanolammonium-Salz, sowie die Sulfonsäure selbst, sofern der pH-Wert so gewählt wird, daß diese in wasserlöslicher Form vorliegen,Salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or tri ethanolammonium salt, as well as the sulfonic acid itself, provided that the pH chosen is that these are present in water-soluble form,
- - Sulfonsäure-Derivate von Benzophenonen, vorzugsweise 2-Hydroxy-4-methoxyben zophenon-5-sulfonsäure und deren Salze, sofern der pH-Wert so gewählt wird, daß diese in wasserlöslicher Form vorliegen,Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzene zophenone-5-sulfonic acid and its salts, provided that the pH is chosen such that these are present in water-soluble form,
- - Sulfonsäure-Derivate des 3-Benzylidencamphers, wie z. B. 4-(2-Oxo-3-bornylidenme thyl)benzolsulfonsäure, 2Methyl-5-(2-oxo-3-bornylidenmethyl)sulfönsäure und deren Salze, sofern der pH-Wert so gewählt wird, daß diese in wasserlöslicher Form vorlie gen.- Sulfonic acid derivatives of 3-Benzylidencamphers, such as. B. 4- (2-oxo-3-bornylidenme thyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bomylidenemethyl) sulfonic acid and their Salts, provided that the pH is chosen so that they are present in water-soluble form gene.
Die Liste der genannten UVB-Filter, die in Kombination mit den erfindungsgemäßen Wirkstoffkombinationen verwendet werden können, soll selbstverständlich nicht limitie rend sein.The list of said UVB filters used in combination with the invention Drug combinations can be used, of course, not limitie be his.
Es kann auch von Vorteil sein, zusätzliche UVA-Filter in den erfindungsgemäßen Zube reitungen einzusetzen, welche bisher üblicherweise in kosmetischen Zubereitungen ent halten sind. Bei diesen Substanzen handelt es sich vorzugsweise um Derivate des Di benzoylmethans, insbesondere um 1-(4'-tert.Butylphenyl)-3-(4'-methoxyphenyl)propan- 1,3-dion und um 1-Phenyl-3-(4'-isopropylphenyl)propan-1,3-dion. Auch diese Kombina tionen bzw. Zubereitungen, die diese Kombinationen enthalten, sind Gegenstand der Erfindung. Es können die für die UVB-Kombination verwendeten Mengen eingesetzt werden.It may also be advantageous to add additional UVA filters in the invention use preparations that have traditionally been ent in cosmetic preparations ent are holding. These substances are preferably derivatives of di benzoylmethane, in particular 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane 1,3-dione and 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione. Also this Kombina tions or preparations containing these combinations are the subject of Invention. The quantities used for the UVB combination can be used become.
Erfindungsgemäße kosmetische und dermatologische Zubereitungen enthalten vorteil haft außerdem anorganische Pigmente auf Basis von Metalloxiden und/oder anderen in Wasser schwerlöslichen oder unlöslichen Metallverbindungen, insbesondere der Oxide des Titans (TiO2), Zinks (ZnO), Eisens (z. B. Fe2O3), Zirkoniums (ZrO2), Siliciums (SiO2), Mangans (z. B. MnO), Aluminiums (Al2O3), Cers (z. B. Ce2O3), Mischoxiden der entspre chenden Metalle sowie Abmischungen aus solchen Oxiden. Besonders bevorzugt han delt es sich um Pigmente auf der Basis von TiO2.Cosmetic and dermatological preparations according to the invention also advantageously contain inorganic pigments based on metal oxides and / or other sparingly soluble or insoluble metal compounds, in particular the oxides of titanium (TiO 2 ), zinc (ZnO), iron (eg Fe 2 O) 3 ), zirconium (ZrO 2 ), silicon (SiO 2 ), manganese (eg MnO), aluminum (Al 2 O 3 ), cerium (eg Ce 2 O 3 ), mixed oxides of the corresponding metals and Blends of such oxides. Particular preference is given to pigments based on TiO 2 .
Es ist besonders vorteilhaft im Sinne der vorliegenden Erfindung, wenngleich nicht zwin gend, wenn die anorganischen Pigmente in hydrophober Form vorliegen, d. h., daß sie oberflächlich wasserabweisend behandelt sind. Diese Oberflächenbehandlung kann darin bestehen, daß die Pigmente nach an sich bekannten Verfahren mit einer dünnen hydrophoben Schicht versehen werden.It is particularly advantageous in the context of the present invention, although not zwin when the inorganic pigments are in hydrophobic form, d. h. that she are superficially treated water-repellent. This surface treatment can consist in that the pigments according to known methods with a thin be provided hydrophobic layer.
Eines solcher Verfahren besteht beispielsweise darin, daß die hydrophobe Oberflächen
schicht nach einer Reaktion gemäß
One such method is, for example, that the hydrophobic surface layer after a reaction according to
nTiO2 + m(RO)3Si-R' → nTiO2 (oberfl.)
erzeugt wird. n und m sind dabei nach Belieben einzusetzende stöchiometrische Para
meter, R und R' die gewünschten organischen Reste. Beispielsweise in Analogie zu DE-
OS 33 14 742 dargestellte hydrophobisierte Pigmente sind von Vorteil.nTiO 2 + m (RO) 3 Si-R '→ nTiO 2 (surface)
is produced. n and m are to be used at will stoichiometric para meter, R and R 'are the desired organic radicals. For example, in analogy to DE-OS 33 14 742 illustrated hydrophobized pigments are advantageous.
Vorteilhafte TiO2-Pigmente sind beispielsweise unter den Handelsbezeichnungen MT 100 T von der Firma TAYCA erhältlich.Advantageous TiO 2 pigments are available, for example, under the trade names MT 100 T from TAYCA.
Die erfindungsgemäßen kosmetischen und/oder dermatologischen Lichtschutzformulie rungen können wie üblich zusammengesetzt sein und dem kosmetischen und/oder der matologischen Lichtschutz, ferner zur Behandlung, der Pflege und der Reinigung der Haut und/oder der Haare und als Schminkprodukt in der dekorativen Kosmetik dienen.The cosmetic and / or dermatological sunscreen formulation according to the invention ments may be composed as usual and the cosmetic and / or the Photological light protection, furthermore for the treatment, care and cleaning of the Skin and / or hair and serve as a make-up product in decorative cosmetics.
Zur Anwendung werden die erfindungsgemäßen kosmetischen und dermatologischen Zubereitungen in der für Kosmetika üblichen Weise auf die Haut und/oder die Haare in ausreichender Menge aufgebracht.For use, the cosmetic and dermatological according to the invention Preparations in the usual way for cosmetics on the skin and / or hair in applied sufficient amount.
Besonders bevorzugt sind solche kosmetischen und dermatologischen Zubereitungen, die in der Form eines Sonnenschutzmittels vorliegen. Vorteilhaft können diese zusätzlich mindestens einen weiteren UVA-Filter und/oder mindestens einen weiteren UVB-Filter und/oder mindestens ein anorganisches Pigment, bevorzugt ein anorganisches Mikro pigment, enthalten.Particularly preferred are such cosmetic and dermatological preparations, which are in the form of a sunscreen. Advantageously, these can additionally at least one further UVA filter and / or at least one further UVB filter and / or at least one inorganic pigment, preferably an inorganic micro pigment, included.
Die erfindungsgemäßen kosmetischen und dermatologischen Zubereitungen können kosmetische Hilfsstoffe enthalten, wie sie üblicherweise in solchen Zubereitungen ver wendet werden, z. B. Konservierungsmittel, Bakterizide, Parfüme, Substanzen zum Ver hindern des Schäumens, Farbstoffe, Pigmente, die eine färbende Wirkung haben, Ver dickungsmittel, anfeuchtende und/oder feuchhaltende Substanzen, Fette, Öle, Wachse oder andere übliche Bestandteile einer kosmetischen oder dermatologischen Formulie rung wie Alkohole, Polyole, Polymere, Schaumstabilisatoren, Elektrolyte, organische Lösungsmittel oder Silikonderivate.The cosmetic and dermatological preparations according to the invention can contain cosmetic excipients, as ver usually in such preparations ver be used, for. As preservatives, bactericides, perfumes, substances for Ver foaming, dyes, pigments having a coloring effect, Ver thickeners, moisturizing and / or moisturizing substances, fats, oils, waxes or other common ingredients of a cosmetic or dermatological formulation Such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic Solvent or silicone derivatives.
Ein zusätzlicher Gehalt an Antioxidantien ist im allgemeinen bevorzugt. Erfindungsge mäß können als günstige Antioxidantien alle für kosmetische und/oder dermatologische Anwendungen geeigneten oder gebräuchlichen Antioxidantien verwendet werden. An additional content of antioxidants is generally preferred. Erfindungsge As favorable antioxidants, they can all be used for cosmetic and / or dermatological purposes Applications of suitable or common antioxidants can be used.
Vorteilhaft werden die Antioxidantien gewählt aus der Gruppe bestehend aus Aminosäu ren (z. B. Glycin, Histidin, Tyrosin, Tryptophan) und deren Derivate, Imidazole (z. B. Uro caninsäure) und deren Derivate, Peptide wie D,L-Carnosin, D-Carnosin, L-Carnosin und deren Derivate (z. B. Anserin), Carotinoide, Carotine (z. B. β-Carotin, p-Carotin, Lycopin) und deren Derivate, Chlorogensäure und deren Derivate, Liponsäure und deren Deri vate (z. B. Dihydroliponsäure), Aurothioglucose, PropyIthiouracil und andere Thiole (z. B. Thioredoxin, Glutathion, Cystein, Cystin, Cystamin und deren Glycosyl-, N-Acetyl-, Methyl-, EthyI-, Propyl-, Amyl-, Butyl- und Lauryl-, Palmitoyl-, Oleyl-, γ-Linoleyl-, Chole steryl- und Glycerylester) sowie deren Salze, Dilaurylthiodipropionat, Distearylthiodipro pionat, Thiodipropionsäure und deren Derivate (Ester, Ether, Peptide, Lipide, Nukleoti de, Nukleoside und Salze) sowie Sulfoximinverbindungen (z. B. Buthioninsulfoximine, Homocysteinsulfoximin, Buthioninsulfone, Penta-, Hexa-, Heptathioninsulfoximin) in sehr geringen verträglichen Dosierungen (z. B. µmol bis µmol/kg), ferner (Metall)-Chelatoren (z. B. α-Hydroxyfettsäurnn, Palmitinsäure, Phytinsäure, Lactoferrin), a-Hydroxysäuren (z. B. Citronensäure, Milchsäure, Apfelsäure), Huminsäure, Gallensäure, Gallenextrakte, Bilirubin, Biliverdin, EDTA, EGTA und deren Derivate, ungesättigte Fettsäuren und de ren Derivate (z. B. γ-Linolensäure, Linolsäure, Ölsäure), Folsäure und deren Derivate, Ubichinon und Ubichinol und deren Derivate, Vitamin C und Derivate (z. B. Ascorbylpal mitat, Mg-Ascorbylphosphat, Ascorbylacetat), Tocopherole und Derivate (z. B. Vitamin-E- acetat), Vitamin A und Derivate (Vitamin-A-palmitat) sowie Koniferylbenzoat des Ben zoeharzes, Rutinsäure und deren Derivate, α-Glycosylrutin, Ferulasäure, Furfuryliden glucitol, Carnosin, Butylhydroxytoluol, Butylhydroxyanisol, Nordihydroguajakharzsäure, Nordihydroguajaretsäure, Trihydroxybutyrophenon, Harnsäure und deren Derivate, Mannose und deren Derivate, Zink und dessen Derivate (z. B. ZnO, ZnSO4) Selen und dessen Derivate (z. B. Selenmethionin), Stilbene und deren Derivate (z. B. Stilbenoxid, Trans-Stilbenoxid) und die erfindungsgemäß geeigneten Derivate (Salze, Ester, Ether, Zucker, Nukleotide, Nukleoside, Peptide und Lipide) dieser genannten Wirkstoffe.Advantageously, the antioxidants are selected from the group consisting of amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urotroic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine), carotenoids, carotenes (eg β-carotene, p-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and derivatives thereof (eg dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (eg thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, Butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesterol and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and Salts) as well as sulfoximine compounds (eg buthionine sulfoximines, homocysteinesulfoximine, buthioni sulfones, penta, hexa, heptathionine sulfoximine) in very low tolerated dosages (eg. (Μmol to μmol / kg), furthermore (metal) chelators (eg α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acid, Bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (eg γ-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives ( eg ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (for example vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and also coniferyl benzoate of the benzine resin, rutinic acid and derivatives thereof , α-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordihydroguaiacetic acid, nordihydroguiaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (eg ZnO, ZnSO 4 ) Selenium and its derivatives (z. B. selenium methionine), stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide) and the inventively suitable derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these drugs.
Die Menge der vorgenannten Antioxidantien (eine oder mehrere Verbindungen) in den Zubereitungen beträgt vorzugsweise 0,001 bis 30 Gew.-%, besonders bevorzugt 0,05- 20 Gew.-%, insbesondere 1-10 Gew.-%, bezogen auf das Gesamtgewicht der Zuberei tung. The amount of the aforementioned antioxidants (one or more compounds) in the Preparations is preferably from 0.001 to 30% by weight, particularly preferably from 0.05 to 20 wt .-%, in particular 1-10 wt .-%, based on the total weight of Zuberei tung.
Sofern Vitamin E und/oder dessen Derivate das oder die Antioxidantien darstellen, ist vorteilhaft, deren jeweilige Konzentrationen aus dem Bereich von 0,001-10 Gew.-%, bezogen auf das Gesamtgewicht der Formulierung, zu wählen.If vitamin E and / or its derivatives are the antioxidant (s) advantageous, their respective concentrations in the range of 0.001-10 wt .-%, based on the total weight of the formulation to choose.
Sofern Vitamin A, bzw. Vitamin-A-Derivate, bzw. Carotine bzw. deren Derivate das oder die Antioxidantien darstellen, ist vorteilhaft, deren jeweilige Konzentrationen aus dem Bereich von 0,001-10 Gew.-%, bezogen auf das Gesamtgewicht der Formulierung, zu wählen.If vitamin A, or vitamin A derivatives, or carotenes or their derivatives, the or which are antioxidants is advantageous, their respective concentrations from the Range of 0.001-10% by weight based on the total weight of the formulation choose.
Die Lipidphase kann vorteilhaft gewählt werden aus folgender Substanzgruppe:
The lipid phase can advantageously be selected from the following substance group:
- - Öle, wie Triglyceride der Caprin- oder der Caprylsäure- Oils, such as triglycerides of capric or caprylic acid
- - Fette, Wachse und andere natürliche und synthetische Fettkörper, vorzugsweise Ester von Fettsäuren mit Alkoholen niedriger C-Zahl, z. B. mit Isopropanol, Propy lenglykol oder Glycerin, oder Ester von Fettalkoholen mit Alkansäuren niedriger C-Zahl oder mit Fettsäuren;- Fats, waxes and other natural and synthetic fats, preferably Esters of fatty acids with lower C-number alcohols, e.g. B. with isopropanol, propy glycol or glycerol, or esters of fatty alcohols with lower alkanoic acids C number or with fatty acids;
- - Alkylbenzoate.- alkyl benzoates.
Ganz besonders vorteilhaft kann die Lipidphase gewählt werden aus der Gruppe der Si likonöle wie Dimethylpolysiloxane, Diethylpolysiloxane, Diphenylpolysiloxane sowie Mischformen daraus.Most preferably, the lipid phase can be selected from the group of Si silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and Mixed forms thereof.
Die wäßrige Phase der erfindungsgemäßen Zubereitungen enthält gegebenenfalls vor
teilhaft
The aqueous phase of the preparations according to the invention may contain some geous
- - Alkohole, Diole oder Polyole niedriger C-Zahl, sowie deren Ether, vorzugsweise Ethanol, Isopropanol, Propylenglykol, Glycerin, Ethylenglykol, Ethylenglykolmo noethyl- oder -monobutylether, Propylenglykolmonomethyl, -monoethyl- oder -monobutylether, Diethylenglykolmonomethyl- oder -monoethylether und analoge Produkte, ferner Alkohole niedriger C-Zahl, z. B. Ethanol, Isopropanol, 1,2-Pro pandiol, Glycerin sowie insbesondere ein oder mehrere Verdickungsmittel, wel ches oder welche vorteilhaft gewählt werden können aus der Gruppe Siliciumdi oxid, Aluminiumsilikate, Polysaccharide bzw. deren Derivate, z. B. Hyaluronsäure, Xanthangummi, Hydroxypropylmethylcellulose, besonders vorteilhaft aus der Gruppe der Polyacrylate, bevorzugt ein Polyacrylat aus der Gruppe der soge nannten Carbopole, beispielsweise Carbopole der Typen 980, 981, 1382, 2984, 5984, jeweils einzeln oder in Kombination.- Alcohols, diols or polyols low C number, and their ethers, preferably Ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol mo noethyl or monobutyl ether, propylene glycol monomethyl, -monoethyl- or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous Products, also low C-number alcohols, e.g. For example, ethanol, isopropanol, 1,2-Pro pandiol, glycerol and in particular one or more thickening agents, wel Ches or which can be advantageously selected from the group silicon di oxide, aluminum silicates, polysaccharides or their derivatives, for. Hyaluronic acid, Xanthan gum, hydroxypropylmethylcellulose, particularly advantageous from the Group of polyacrylates, preferably a polyacrylate from the group of soge named carbopols, for example carbopols of types 980, 981, 1382, 2984, 5984, each individually or in combination.
Die kosmetischen oder dermatologischen Lichtschutzzubereitungen enthalten vorteilhaft anorganische Pigmente, insbesondere Mikropigmente, z. B. in Mengen von 0,1 Gew.-% bis 30 Gew.-%, vorzugsweise in Mengen von 0,5 Gew.-% bis 10 Gew.-%, insbesondere aber 1 Gew.-% bis 6 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitungen.The cosmetic or dermatological sunscreen preparations contain advantageous inorganic pigments, in particular micropigments, for. B. in amounts of 0.1 wt .-% to 30 wt .-%, preferably in amounts of 0.5 wt .-% to 10 wt .-%, in particular but 1 wt .-% to 6 wt .-%, based on the total weight of the preparations.
Nachfolgend soll kurz noch auf einige Besonderheiten und Unterschiede der Vorausset zungen für erfindungsgemäß O/W-Emulsionen, O/W-Mikroemulsionen bzw. O/W/O- Emulsionen eingegangen werden.Below is briefly to some specifics and differences of the Vorausset for O / W emulsions, O / W microemulsions or O / W / O emulsions according to the invention. Emulsions are received.
Öle und Fette unterscheiden sich unter anderem in ihrer Polarität, welche schwierig zu definieren ist. Es wurde bereits vorgeschlagen, die Grenzflächenspannung gegenüber Wasser als Maß für den Polaritätsindex eines Öls bzw. einer Ölphase anzunehmen. Da bei gilt, daß die Polarität der betreffenden Ölphase umso größer ist, je niedriger die Grenzflächenspannung zwischen dieser Ölphase und Wasser ist. Erfindungsgemäß wird die Grenzflächenspannung als ein mögliches Maß für die Polarität einer gegebenen Ölkomponente angesehen.Among other things, oils and fats differ in their polarity, which is difficult to achieve is defined. It has already been proposed to oppose the interfacial tension To assume water as a measure of the polarity index of an oil or an oil phase. because in that the polarity of the relevant oil phase is greater, the lower the Interfacial tension between this oil phase and water is. According to the invention the interfacial tension is given as a possible measure of the polarity of a given Oil component considered.
Die Grenzflächenspannung ist diejenige Kraft, die an einer gedachten, in der Grenzflä che zwischen zwei Phasen befindlichen Linie der Länge von einem Meter wirkt. Die phy sikalische Einheit für diese Grenzflächenspannung errechnet sich klassisch nach der Beziehung Kraft/Länge und wird gewöhnlich in mN/m (Millinewton geteilt durch Meter) wiedergegeben. Sie hat positives Vorzeichen, wenn sie das Bestreben hat, die Grenz fläche zu verkleinern. Im umgekehrten Falle hat sie negatives Vorzeichen.The interfacial tension is the force that is at an imaginary, in the Grenzflä between the two-phase line of one meter length. The phy The physical unit for this interfacial tension is calculated classically according to the Relationship force / length and is usually expressed in mN / m (millinewton divided by meters) played. It has a positive sign, if it has the endeavor, the limit area to zoom out. In the opposite case, it has a negative sign.
Als Grenze, unterhalb derer eine Ölphase als "polar" und oberhalb derer eine Ölphase als "unpolar" gilt, werden erfindungsgemäß 30 mN/m angesehen.As a limit, below which an oil phase as "polar" and above which an oil phase is considered to be "non-polar", 30 mN / m are considered according to the invention.
Erfindungsgemäß wird für O/W-Mikroemulsionen die Ölphase vorteilhaft gewählt aus der Gruppe der polaren Ölkomponenten, welche eine Polarität zwischen 10 und 30 mN/m aufweisen, wobei gewährleistet sein muß, daß mindestens eine nichtpolare Ölkompo nente vorhanden ist.According to the invention, the oily phase is advantageously selected from O-W microemulsions Group of polar oil components, which have a polarity between 10 and 30 mN / m it must be ensured that at least one non-polar Ölkompo is present.
Vorteilhafte O/W-Mikroemulsionen werden erhalten, wenn die Ölphase gewählt wird aus der Gruppe der polaren Ölkomponenten, besonders bevorzugt aus der Gruppe der na türlichen, synthetischen oder halbsynthetischen Ölkomponenten, welche eine Polarität zwischen 10 und 20 mN/m aufweisen, wobei gewährleistet sein muß, daß mindestens eine nichtpolare Ölkomponente vorhanden ist.Advantageous O / W microemulsions are obtained when the oil phase is selected the group of polar oil components, more preferably from the group of na natural, synthetic or semi-synthetic oil components which have one polarity between 10 and 20 mN / m, it being necessary to ensure that at least a non-polar oil component is present.
Vorteilhaft ist auch, polare pflanzliche Öle als polare Öle der erfindungsgemäßen O/W- Emulsionen zu verwenden. Die pflanzlichen Öle können vorteilhaft gewählt werden aus der Gruppe der Öle der Pflanzenfamilien Euphorbiaceae, Poaceae, Fabaceae, Brassi caceae, Pedalaceae, Asteraceae, Linaceae, Flacourticaceae, Violales, vorzugsweise gewählt aus der Gruppe natives Rizinusöl, Weizenkeimöl, Traubenkernöl, Kukuinußöl, Safloröl, Distelöl, Nachtkerzenöl und weiteren Ölen, welche mindestens 1,5 Gew.-% an Linolsäureglyceriden enthalten.It is also advantageous to use polar vegetable oils as polar oils of the O / W invention. To use emulsions. The vegetable oils can be chosen favorably from the group of oils of the plant families Euphorbiaceae, Poaceae, Fabaceae, Brassi caceae, Pedalaceae, Asteraceae, Linaceae, Flacourticaceae, Violales, preferably selected from the group of virgin castor oil, wheat germ oil, grapeseed oil, kukui nut oil, Safflower oil, safflower oil, evening primrose oil and other oils which at least 1.5 wt .-% of Linoleic acid glycerides included.
Im Gegenzuge sollen erfindungsgemäße O/W/O-Emulsionen von solchen Ölkomponen ten nur untergeordnete Mengen aufweisen und statt deren hauptsächlich solche, deren Polaritätswert höher liegt als 30 mN/m. Als vorteilhaft haben sich gleichermaßen natürli che, synthetische und halbsynthetische Öle, Fette und Wachse erwiesen.In contrast, according to the invention O / W / O emulsions of such oil components have only minor amounts and instead mainly those whose Polarity value is higher than 30 mN / m. As beneficial have alike naturli che, synthetic and semi-synthetic oils, fats and waxes.
Der Zusatz von Elektrolyten bewirkt eine Veränderung des Löslichkeitsverhaltens eines hydrophilen Emulgators. Die hydrophilen Emulgatoren mit den vorab beschriebenen Strukturen bzw. Eigenschaften durchlaufen eine partielle Phaseninversion, in der es zu einer Solubilisierung von Wasser durch die Ölphase kommt, welche in einer stabilen Mi kroemulsion oder, im gewünschten Falle, auch einer stabilen O/W/O-Emulsion resultiert.The addition of electrolytes causes a change in the solubility behavior of a hydrophilic emulsifier. The hydrophilic emulsifiers with the previously described Structures or properties go through a partial phase inversion, in which it too a solubilization of water through the oil phase occurs, which in a stable Mi Kroemulsion or, if desired, also results in a stable O / W / O emulsion.
Die erfindungsgemäßen Mikroemulsionen enthalten daher vorteilhaft Elektrolyte, insbe sondere eines oder mehrere Salze mit folgenden Anionen: Chloride, ferner anorgani sche Oxo-Element-Anionen, von diesen insbesondere Sulfate, Carbonate, Phosphate, Borate und Aluminate. Auch auf organischen Anionen basierende Elektrolyte können vorteilhaft verwendet werden, beispielsweise Lactate, Acetate, Benzoate, Propionate, Tartrate, Citrate und andere mehr. Vergleichbare Effekte sind auch durch Ethylendi amintetraessigsäure und deren Salze zu erzielen.The microemulsions according to the invention therefore advantageously contain electrolytes, esp in particular one or more salts having the following anions: chlorides, also inorganic of these oxo-element anions, in particular sulfates, carbonates, phosphates, Borates and aluminates. Also on organic anions based electrolytes can be used advantageously, for example, lactates, acetates, benzoates, propionates, Tartrates, citrates and more. Similar effects are also due to ethylene di Amintetraessigsäure and their salts to achieve.
Als Kationen der Salze werden bevorzugt Ammonium,- Alkylammonium,- Alkalimetall-, Erdalkalimetall,- Magnesium-, Eisen- bzw. Zinkionen verwendet. Es bedarf an sich kei ner Erwähnung, daß in Kosmetika nur physiologisch unbedenkliche Elektrolyte verwen det werden sollten. Spezielle medizinische Anwendungen der erfindungsgemäßen Mikroemulsionen können andererseits, wenigstens grundsätzlich, die Verwendung von Elektrolyten bedingen, welche nicht ohne ärztliche Aufsicht verwendet werden sollten. Preferred cations of the salts are ammonium, alkylammonium, alkali metal, Alkaline earth metal, - used magnesium, iron or zinc ions. It does not take care of itself mentions that only physiologically harmless electrolytes are used in cosmetics should be. Special medical applications of the invention On the other hand, microemulsions can, at least in principle, the use of Electrolytes condition, which should not be used without medical supervision.
Besonders bevorzugt sind Kaliumchlorid, Kochsalz, Magnesiumsulfat, Zinksulfat und Mi schungen daraus. Ebenfalls vorteilhaft sind Salzmischungen wie sie im natürlichen Salz vom Toten Meer auftreten.Particularly preferred are potassium chloride, common salt, magnesium sulfate, zinc sulfate and Mi. from it. Also advantageous are salt mixtures as in natural salt occur from the Dead Sea.
Die Konzentration des Elektrolyten oder der Elektrolyte sollte etwa 0,01-10,0 Gew.-%, besonders vorteilhaft etwa 0,03-8,0 Gew.-% betragen, bezogen auf das Gesamtgewicht der Zubereitung.The concentration of the electrolyte or electrolytes should be about 0.01-10.0% by weight, particularly advantageously about 0.03-8.0 wt .-%, based on the total weight the preparation.
Die Emulgatoren des Typs A können landsläufig als O/W-Emulgatoren angesehen wer den. Ein Gehalt von etwa 5-10 Gew.-% an üblichen W/O-Emulgatoren fördert in vorteil hafter Weise die Bildung von O/W/O-Emulsionen, ein Gehalt von deutlich über 10 Gew. % an solchen Emulgatoren führt zur Destabilisierung der O/W/O-Emulsionen.The emulsifiers of type A can universally considered as O / W emulsifiers who the. A content of about 5-10 wt .-% of conventional W / O emulsifiers promotes beneficial way, the formation of O / W / O emulsions, a content of well above 10 wt. % of such emulsifiers leads to the destabilization of the O / W / O emulsions.
Ferner ist gewünschtenfalls für die Herstellung erfindungsgemäßer O/W/O-Emulsionen von Vorteil, hydrophile und/oder lipophile Gelbildner einzusetzen. Diese tragen zwar in der Regel nicht zur Bildung multipler Tröpfchen bei, fördern aber die Stabilität einmal ge bildeter multipler Tröpfchen.Further, if desired, for the preparation of inventive O / W / O emulsions advantageous to use hydrophilic and / or lipophilic gelling agents. Although they carry in usually do not contribute to the formation of multiple droplets, but promote stability once formed multiple droplets.
Wenn bei einem erfindungsgemäßen Herstellungsverfahren für O/W/O-Emulsionen der pH-Wert variiert werden soll, um ein ansonsten vorbestimmtes System in den Phasenin versionsbereich zu bringen, so ist von Vorteil, zu Beginn des Verfahrens zunächst mög lichst geringe Elektrolytkonzentration in der Wasserphase einzusetzen, möglichst zu nächst ganz darauf zu verzichten. Weiterhin ist von Vorteil, den Emulgator A in der Öl phase vorzulegen, beispielsweise für Stearinsäure im Konzentrationsbereich von 0,5-5 Gew.-%, insbesondere 2 Gew.-%. Vorteilhaft ist die Gegenwart eines nicht unter die Definition des Emulgators A fallenden Emulgators im Konzentrationsbereich von ca. 5- 10 Gew.-%, insbesondere etwa 7 Gew.-%.When in a production method for O / W / O emulsions of the present invention pH should be varied to an otherwise predetermined system in the phases To bring version range, it is advantageous at the beginning of the process initially possible Use as low as possible electrolyte concentration in the water phase, if possible to next to refrain entirely. It is also advantageous, the emulsifier A in the oil phase, for example for stearic acid in the concentration range of 0.5-5 Wt .-%, in particular 2 wt .-%. Advantageous is the presence of a not under the Definition of Emulsifier A falling emulsifier in the concentration range of about 5 10 wt .-%, in particular about 7 wt .-%.
Die Variation des pH-Wertes sollte vorteilhaft erst erfolgen, wenn die W/O-Emulsion sich gebildet hat, beispielsweise durch Zufügen von NaOH.The variation of the pH value should advantageously be done only when the W / O emulsion is has formed, for example by adding NaOH.
Dabei liegt im allgemeinen Fachwissen des Fachmannes und bedarf keinerlei erfinderi schen Dazutuns, für einen gegebenen Emulgator oder ein gegebenes Emulgatorsystem in einem gegebenen Wasser/Ölphasensystem den Temperatur- bzw. pH-Bereich zu ermitteln, in welchem Phaseninversion stattfindet. Als allgemeiner Richtwert für den PIT bei üblichen Emulgatorkonzentrationen kann ein Temperaturbereich von etwa 40-90°C angegeben werden. Im allgemeinen sinkt der PIT bei steigender Emulgatorkonzentra tion.This is generally the expertise of the skilled person and requires no erfinderi for a given emulsifier or emulsifier system in a given water / oil phase system the temperature or pH range determine in which phase inversion takes place. As a general guideline for the PIT at usual emulsifier concentrations, a temperature range of about 40-90 ° C. be specified. In general, the PIT decreases with increasing emulsifier concentration tion.
Es können während dieses Verfahrens gewünschtenfalls ferner die in der Kosmetik oder medizinischen Galenik üblichen Grund-, Hilfs-, Zusatz-, und/oder Wirkstoffe zugegeben werden. Es ist dem Fachmann klar, zu welchem Zeitpunkt solche Stoffe dem Prozeß beigegeben werden können, ohne daß die Eigenschaften der zu erzielenden Emulsion wesentlich beeinträchtigt werden.If desired, it is also possible, during this process, to use those in cosmetics or medical galenics usual basic, auxiliary, additional, and / or active ingredients added become. It will be clear to those skilled in the art at which time such substances will be in the process can be added without the properties of the emulsion to be achieved be significantly affected.
Die nachfolgenden Beispiele sollen das Wesen der vorliegenden Erfindung näher umrei ßen, ohne die Erfindung einzuschränken. Der Begriff "MBTTBP" steht dabei für 2,2'- Methylen-bis-(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol).The following examples are intended to delineate the nature of the present invention without limiting the invention. The term "MBTTBP" stands for 2,2'- Methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) -phenol).
Die Bestandteile der Ölphase werden vereinigt und homogenisiert, dann mit der Wasser phase vereinigt und auf eine Temperatur von 80-85°C (d. h., in den Phaseninversions temperaturbereich des Systems) gebracht, hernach auf Raumtemperatur abgekühlt (also aus dem Phaseninversionstemperaturbereich des Systems wieder heraus ge bracht).The components of the oil phase are combined and homogenized, then with the water phase and at a temperature of 80-85 ° C (i.e., in the phase inversions temperature range of the system), then cooled to room temperature (ie out of the phase inversion temperature range of the system introduced).
Die Bestandteile der Ölphase werden vereinigt und homogenisiert, dann mit der Wasser phase vereinigt und auf eine Temperatur von 80-85°C (d. h., in den Phaseninversions temperaturbereich des Systems) gebracht, hernach auf Raumtemperatur abgekühlt (also aus dem Phaseninversionstemperaturbereich des Systems wieder heraus ge bracht). The components of the oil phase are combined and homogenized, then with the water phase and at a temperature of 80-85 ° C (i.e., in the phase inversions temperature range of the system), then cooled to room temperature (ie out of the phase inversion temperature range of the system introduced).
MBTTBP wird im Mineralöl vorsuspendiert und mit der restlichen Ölphase vereinigt, worauf diese und homogenisiert und dann mit der Wasserphase vereinigt und auf eine Temperatur von 80-85°C (d. h., in den Phaseninversionstemperaturbereich des Systems) gebracht, hernach auf Raumtemperatur abgekühlt (also aus dem Phasen in versionstemperaturbereich des Systems wieder heraus gebracht) wird.MBTTBP is pre-suspended in mineral oil and combined with the remaining oil phase, whereupon and homogenized and then combined with the water phase and placed on a Temperature of 80-85 ° C (i.e., in the phase inversion temperature range of Systems), then cooled to room temperature (ie from the phases in version temperature range of the system brought out).
MBTTBP wird im Mineralöl vorsuspendiert und mit der restlichen Ölphase vereinigt, worauf diese und homogenisiert und dann mit der Wasserphase vereinigt und auf eine Temperatur von 80-85°C (d. h., in den Phaseninversionstemperaturbereich des Systems) gebracht, hernach auf Raumtemperatur abgekühlt (also aus dem Phasenin versionstemperaturbereich des Systems wieder heraus gebracht) wird. MBTTBP is pre-suspended in mineral oil and combined with the remaining oil phase, whereupon and homogenized and then combined with the water phase and placed on a Temperature of 80-85 ° C (i.e., in the phase inversion temperature range of Systems), then cooled to room temperature (ie from the Phasenin version temperature range of the system brought out).
Die Bestandteile der Ölphase werden vereinigt und homogenisiert, dann mit der Wasser phase vereinigt und auf eine Temperatur von 80-85°C (d. h., in den Phaseninversions temperaturbereich des Systems) gebracht, hernach auf Raumtemperatur abgekühlt (also aus dem Phaseninversionstemperaturbereich des Systems wieder heraus ge bracht). The components of the oil phase are combined and homogenized, then with the water phase and at a temperature of 80-85 ° C (i.e., in the phase inversions temperature range of the system), then cooled to room temperature (ie out of the phase inversion temperature range of the system introduced).
MBTTBP wird im Mineralöl vorsuspendiert und mit der restlichen Ölphase vereinigt, worauf diese und homogenisiert und dann mit der Wasserphase vereinigt und auf eine Temperatur von 80-85°C (d. h., in den Phaseninversionstemperaturbereich des Systems) gebracht, hernach auf Raumtemperatur abgekühlt (also aus dem Phasenin versionstemperaturbereich des Systems wieder heraus gebracht) wird.MBTTBP is pre-suspended in mineral oil and combined with the remaining oil phase, whereupon and homogenized and then combined with the water phase and placed on a Temperature of 80-85 ° C (i.e., in the phase inversion temperature range of Systems), then cooled to room temperature (ie from the Phasenin version temperature range of the system brought out).
MBTTBP wird in der Ölphase dispergiert. Wasser wird zugegeben und das System auf ca. 40°C erwärmt. NaOH wird zugegeben bis ein pH-Wert von 7 erreicht ist, hernach wird auf Raumtemperatur abgekühlt. MBTTBP is dispersed in the oil phase. Water is added and the system on heated to about 40 ° C. NaOH is added until a pH of 7 is reached, afterwards is cooled to room temperature.
MBTTBP wird im Mineralöl vorsuspendiert und mit der restlichen Ölphase vereinigt. Wasser wird zugegeben und das System auf ca. 40°C erwärmt. NaOH wird zugegeben bis ein pH-Wert von 7 erreicht ist, hernach wird auf Raumtemperatur abgekühlt.MBTTBP is pre-suspended in mineral oil and combined with the remaining oil phase. Water is added and the system is heated to about 40 ° C. NaOH is added until a pH of 7 is reached, then cooled to room temperature.
MBTTBP wird in der Ölphase dispergiert. Wasser wird zugegeben und das System auf ca. 40°C erwärmt. NaOH wird zugegeben bis ein pH-Wert von 7 erreicht ist, hernach wird auf Raumtemperatur abgekühlt. MBTTBP is dispersed in the oil phase. Water is added and the system on heated to about 40 ° C. NaOH is added until a pH of 7 is reached, afterwards is cooled to room temperature.
MBTTBP wird im Mineralöl vorsuspendiert und mit der restlichen Ölphase vereinigt. Wasser wird zugegeben und das System auf ca. 40°C erwärmt. NaOH wird zugegeben bis ein pH-Wert von 7 erreicht ist, hernach wird auf Raumtemperatur abgekühlt.MBTTBP is pre-suspended in mineral oil and combined with the remaining oil phase. Water is added and the system is heated to about 40 ° C. NaOH is added until a pH of 7 is reached, then cooled to room temperature.
Claims (9)
- (a) eine Wasserphase,
- (b) gegebenenfalls übliche, in Wasser lösliche oder dispergierbare Substanzen,
- (c) eine Ölphase,
- - in welcher mindestens eine kosmetisch oder dermatologische UV-Fil
tersubstanz, gewählt aus der Gruppe der Benzotriazolderivate der all
gemeinen Strukturformel
wiedergegeben wird, wobei R1 und R2 unabhängig voneinander ge wählt werden aus der Gruppe der verzweigten oder unverzweigten C1- C18-Alkylreste, der gegebenenfalls mit einer oder mehreren C1-C4-Al kylgruppen substituierten C5-C12-Cycloalkyl oder Arylreste, in suspendierter Form vorliegt,
- - in welcher mindestens eine kosmetisch oder dermatologische UV-Fil
tersubstanz, gewählt aus der Gruppe der Benzotriazolderivate der all
gemeinen Strukturformel
- (d) mindestens einen Emulgator (Emulgator A), gewählt aus der Gruppe der Emulga
toren mit folgenden Eigenschaften
- - ihre Lipophilie ist entweder abhängig vom pH-Wert, dergestalt daß durch Er höhung oder Senkung des pH-Wertes die Lipophilie zunimmt oder abnimmt, wobei unerheblich ist, welche der beiden Möglichkeiten der Änderung der Li pophilie durch die Erhöhung bzw. Senkung des pH-Wertes bewirkt wird, und/oder
- - ihre Lipophilie ist abhängig von der Temperatur, dergestalt, daß die Lipophi lie mit steigender Temperatur zunimmt und deren Hydrophilie mit sinkender Temperatur zunimmt,
- (e) ferner gegebenenfalls weitere in der Ölphase lösliche oder dispergierbare Sub stanzen, darunter bevorzugt solche, gewählt aus der Gruppe der nicht unter die Definition des Emulgators A fallende Emulgatoren, insbesondere solche, die vor wiegend als W/O-Emulgatoren wirken.
- (a) a water phase,
- (b) optionally conventional, water-soluble or dispersible substances,
- (c) an oil phase,
- - In which at least one cosmetic or dermatological UV filter tersubstanz selected from the group of benzotriazole derivatives of all general structural formula
is reproduced, wherein R 1 and R 2 are independently ge selected from the group of branched or unbranched C 1 - C 18 alkyl radicals which optionally kylgruppen with one or more C 1 -C 4 -alkyl substituted C 5 -C 12 - Cycloalkyl or aryl radicals, in suspended form,
- - In which at least one cosmetic or dermatological UV filter tersubstanz selected from the group of benzotriazole derivatives of all general structural formula
- (D) at least one emulsifier (emulsifier A), selected from the group of Emulga factors having the following properties
- their lipophilicity is either dependent on the pH, such that increasing or decreasing the pH increases or decreases the lipophilicity, it being irrelevant which of the two possibilities of changing the Li pophilie by increasing or decreasing the pH Value is effected, and / or
- their lipophilicity is dependent on the temperature, such that the lipophilic substance increases with increasing temperature and its hydrophilicity increases with decreasing temperature,
- (E) further optionally further in the oil phase soluble or dispersible sub stances, including preferably those selected from the group of not falling under the definition of the emulsifier A emulsifiers, in particular those which act predominantly as W / O emulsifiers.
wobei R1 und R2 unabhängig voneinander gewählt werden aus der Gruppe der ver zweigten oder unverzweigten C1-C18-Alkylreste, der gegebenenfalls mit einer oder meh reren C1-C4- Alkylgruppen substituierten C5-C12-Cycloalkyl- oder Arylreste, in O/W-Emulsionen, O/W-Mikroemulsionen oder O/W/O-Emulsionen, dadurch gekenn zeichnet, daß
- (a) die Bestandteile einer Wasserphase,
- (b) gegebenenfalls übliche, in Wasser lösliche oder dispergierbare Substanzen,
- (c) die Bestandteile einer Ölphase
- (c1) die vorab beschriebenen Benzotriazolderivate
- (d) mindestens ein Emulgator (Emulgator A), gewählt aus der Gruppe der Emulgato
ren mit folgenden Eigenschaften
- - ihre Lipophilie ist entweder abhängig vom pH-Wert, dergestalt daß durch Er höhung oder Senkung des pH-Wertes die Lipophilie zunimmt oder abnimmt, wobei unerheblich ist, welche der beiden Möglichkeiten der Änderung der Li pophilie durch die Erhöhung bzw. Senkung des pH-Wertes bewirkt wird, und/oder
- - ihre Lipophilie ist abhängig von der Temperatur, dergestalt, daß die Lipophi lie mit steigender Temperatur zunimmt und die Hydrophilie mit sinkender Temperatur zunimmt,
- (e) ferner gegebenenfalls weitere in der Ölphase lösliche oder dispergierbare Sub
stanzen, darunter bevorzugt solche, gewählt aus der Gruppe der nicht unter die
Definition des Emulgators A fallende Emulgatoren, insbesondere solche, die vor
wiegend als W/O-Emulgatoren wirken,
zusammengegeben werden und unter Agitation ein Gemisch gebildet wird, dergestalt, daß - (f) dieses Gemisch durch geeignete Wahl der Parameter, gewählt aus der Gruppe pH-Wert, Temperatur und der Konzentration bzw. Konzentrationen mindestens ei nes der gewählten Emulgatoren, in den Phaseninversionsbereich gebracht wird, in welchem sich W/O-Emulsionen in O/W-Emulsionen umwandeln,
- (g) durch Variation mindestens eines Parameters, gewählt aus der Gruppe pH-Wert, Temperatur und der Konzentration bzw. Konzentrationen mindestens eines der gewählten Emulgatoren, die gebildete W/O-Emulsion aus dem Phaseninversions bereich heraus gebracht wird, in welchem sich eine gebildete W/O-Emulsion in ei ne O/W-Emulsion umwandelt, wodurch eine O/W-Emulsion oder O/W-Mikroemul sion erzeugt wird,
- (h) gegebenenfalls durch geeignete Wahl der Rahmenbedingungen eine weitere Pha seninversion zur O/W/O-Emulsion eingeleitet wird,
- (i) das Gemisch gegebenenfalls weiteren Aufbereitungsschritten, insbesondere einem oder mehreren Homogenisierungsschritten unterworfen wird.
where R 1 and R 2 are independently selected from the group of the branched or unbranched C 1 -C 18 -alkyl radicals which are optionally substituted by one or more C 1 -C 4 -alkyl-substituted C 5 -C 12 -cycloalkyl or Aryl radicals, in O / W emulsions, O / W microemulsions or O / W / O emulsions, characterized in that
- (a) the components of a water phase,
- (b) optionally conventional, water-soluble or dispersible substances,
- (c) the components of an oil phase
- (c1) the benzotriazole derivatives described above
- (d) at least one emulsifier (emulsifier A) selected from the group of emulsifiers having the following properties
- their lipophilicity is either dependent on the pH, such that increasing or decreasing the pH increases or decreases the lipophilicity, it being irrelevant which of the two possibilities of changing the Li pophilie by increasing or decreasing the pH Value is effected, and / or
- their lipophilicity is dependent on the temperature, such that the lipophil increases with increasing temperature and the hydrophilicity increases with decreasing temperature,
- (e) furthermore, if appropriate, further substances which are soluble or dispersible in the oil phase, including preferably those selected from the group of emulsifiers not covered by the definition of emulsifier A, in particular those which predominantly act as W / O emulsifiers,
be combined and formed under agitation a mixture such that - (f) this mixture is brought into the phase inversion range by suitable choice of the parameters selected from the group of pH, temperature and concentration or concentrations of at least one of the emulsifiers chosen, in which W / O emulsions in O / Convert W emulsions,
- (G) by varying at least one parameter selected from the group pH, temperature and the concentration or concentrations of at least one of the selected emulsifiers, the formed W / O emulsion is brought out of the phase inversion area, in which a formed Converts W / O emulsion into an O / W emulsion to form an O / W emulsion or O / W microemulsion,
- (h) optionally initiating a further phase inversion to the O / W / O emulsion by suitable choice of the framework conditions,
- (i) the mixture is optionally subjected to further treatment steps, in particular one or more homogenization steps.
Priority Applications (1)
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DE1997126184 DE19726184A1 (en) | 1997-06-20 | 1997-06-20 | Oil-in-water or multiple emulsion with high concentration of suspended UVB filter |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1997126184 DE19726184A1 (en) | 1997-06-20 | 1997-06-20 | Oil-in-water or multiple emulsion with high concentration of suspended UVB filter |
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DE19726184A1 true DE19726184A1 (en) | 1998-12-24 |
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DE1997126184 Withdrawn DE19726184A1 (en) | 1997-06-20 | 1997-06-20 | Oil-in-water or multiple emulsion with high concentration of suspended UVB filter |
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