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WO2006035000A1 - Sun protection emulsion comprising a high fraction of sun protection filter pigments - Google Patents

Sun protection emulsion comprising a high fraction of sun protection filter pigments Download PDF

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Publication number
WO2006035000A1
WO2006035000A1 PCT/EP2005/054780 EP2005054780W WO2006035000A1 WO 2006035000 A1 WO2006035000 A1 WO 2006035000A1 EP 2005054780 W EP2005054780 W EP 2005054780W WO 2006035000 A1 WO2006035000 A1 WO 2006035000A1
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WO
WIPO (PCT)
Prior art keywords
pigments
weight
organic
cosmetic
sun protection
Prior art date
Application number
PCT/EP2005/054780
Other languages
German (de)
French (fr)
Inventor
Claudia Mundt
Kerstin Skubsch
Bente Nissen
Anja Sabine Müller
Martin Sugár
Original Assignee
Beiersdorf Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beiersdorf Ag filed Critical Beiersdorf Ag
Priority to EP05789814A priority Critical patent/EP1796620A1/en
Publication of WO2006035000A1 publication Critical patent/WO2006035000A1/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y5/00Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27Zinc; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29Titanium; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/496Triazoles or their condensed derivatives, e.g. benzotriazoles
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4966Triazines or their condensed derivatives
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier 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
    • A61Q17/04Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41Particular ingredients further characterized by their size
    • A61K2800/413Nanosized, i.e. having sizes below 100 nm

Definitions

  • the present invention relates to a cosmetic sunscreen emulsion containing UV sunscreen filter pigments in a concentration of at least 20% by weight, based on the total weight of the preparation.
  • UVA and UVB filters are summarized in most industrialized countries in the form of positive lists such as Appendix 7 of the German Cosmetics Regulation.
  • a special form of UV sunscreen filter substances are the micropigments.
  • the UV protection effect of the micropigments is based on the physical effects of reflection and light scattering.
  • cosmetic preparations are used as micropigments almost exclusively inorganic micropigments of titanium dioxide, zinc oxide or mixed oxides with, for example, iron oxides.
  • the advantages of micropigments as UV filter substance in cosmetic preparations are mainly due to the fact that the pigments, in contrast to dissolved or liquid, do not penetrate into the skin. The occurrence of allergic reactions is excluded.
  • micropigments are difficult to incorporate stable in cosmetic preparations.
  • concentrations concentration above 7% by weight, based on the total weight of the preparation
  • they form pigment agglomerates which precipitate out of the preparation relatively quickly.
  • the storage stability is therefore low.
  • the object of the present invention to overcome the deficiencies of the prior art and to develop stable emulsions with a high content of micropigments as UV light protection filters.
  • the formulations should also have a stable absorption spectrum with a balanced UV-A / UV-B absorption balance when applied to the skin over a prolonged period of use.
  • the preparation according to the invention comprises inorganic and organic UV sunscreen pigments in a concentration of 20 to 40% by weight, and particularly preferred according to the invention if the preparation contains inorganic and organic UV sunscreen pigments in a concentration of 21 to 30% by weight. , in each case based on the total weight of the preparation contains.
  • the weight ratio of inorganic to organic UV photoprotective pigments is preferably from 3: 1 to 1: 3.
  • the organic sunscreen filter pigments are selected from the group 2 J 2'-methylenebis (6- (2H-benzotriazol-2-yl) -4- (1, 1 J 3 J 3-tetramethylbutyl) -phenol) J
  • the micropigments according to the invention may advantageously be present in an aqueous dispersion.
  • C8-C16 alkylpolyglucoside amphiphilic polymers, as described in EP 1093796 B1, can be advantageously used according to the invention as a dispersing aid.
  • Advantageous embodiments of the present invention contain the organic sunscreen filter pigments in a concentration of 1 to 20% by weight, based on the total weight of the preparation.
  • Preferred embodiments of the present invention contain the organic sunscreen filter pigments in a concentration of 2 to 15% by weight, based on the total weight of the preparation.
  • Preferred inorganic pigments are metal oxides and / or other sparingly soluble or insoluble metal compounds in water, in particular oxides of titanium (TiO 2 ), zinc (ZnO), iron (eg Fe 2 O 3 ), zirconium (ZrO 2 ), Silicon (SiO 2 ), manganese (for example MnO), aluminum (Al 2 O 3 ), cerium (for example Ce 2 O 3 ), mixed oxides of the corresponding metals and mixtures of such oxides, and also the sulfate of barium (BaSO 4 ).
  • the titanium dioxide pigments can be present both in the rutile and anatase crystal modifications and can advantageously be surface-treated ("coated") for the purposes of the present invention, with a hydrophilic, amphiphilic or hydrophobic character, for example, being preferred. be formed or should remain preserved character.
  • This surface treatment may consist in providing the pigments with a thin hydrophilic and / or hydrophobic inorganic and / or organic layer by processes known per se.
  • the various surface coating can also contain water for the purposes of the present invention.
  • Coated and uncoated titanium dioxides described in the present invention can also be used in the form of commercially available oily or aqueous predispersions. Dispersants and / or solubilizers may advantageously be added to these predispersions.
  • the titanium dioxides according to the invention are distinguished by a primary particle size of between 10 nm and 200 nm, particle sizes of from 10 nm to 100 nm being preferred according to the invention.
  • titanium dioxides are the MT-100 Z and MT-100 TV from Tayca Corporation, Eusolex T-2000 and Eusolex T-AVO from Merck and the titanium dioxide T 805 from Degussa and the iron / titanium mixed oxide titanium dioxide T817 from Degussa ,
  • zinc oxides can also be used in the form of commercially available oily or aqueous predispersions.
  • Zinc oxide particles and predispersions of zinc oxide particles which are suitable according to the invention are distinguished by a primary particle size of ⁇ 300 nm and can be obtained from the following companies under the following trade names:
  • Particularly preferred zinc oxides in the context of the invention are the Z-Cote HP1 from BASF and the zinc oxide NDM from Haarmann & Reimer.
  • the concentration of inorganic light protection pigments in the preparation is from 1 to 30% by weight and preferably from 2 to 15% by weight, based in each case on the total weight of the preparation.
  • Advantageous further UV filter substances in the sense of the present invention are, for example, those mentioned below which may be present in the water phase and / or the oil phase.
  • UV filter substances which are liquid at room temperature for the purposes of the present invention are homomenthyl salicylate (INCI: homosalates), 2-ethylhexyl 2-hydroxybenzoate (2-ethylhexyl salicylate, octyl salicylate, INCI: octyl salicylates), 2-ethylhexyl-2-cyano-3, 3-diphenyl acrylate (INCI: Octocrylene) and esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester (2-ethylhexyl-4-methoxycinnamate, INCI: octyl methoxycinnamate) and 4-methoxycinnamic acid isopentyl ester (isopentyl 4-methoxycinnamate, INCI: isoamyl p-methoxycinnamate), 3- (4- (2,2-bise
  • UV-A filter substances for the purposes of the present invention are dibenzoyl methane derivatives, in particular 4- (tert-butyl) -4'-methoxydibenzoylmethane (CAS No. 70356-09-1), which has been sold by Givaudan under the trademark Parsol ® 1789 and sold by Merck under the trade name Eusolex® 9020.
  • UV-A filter substances in the context of the present invention are hydroxybenzophenones, which are distinguished by the following structural formula:
  • Cycloalkenyl wherein the substituents R 1 and R 2 together with the nitrogen atom to which they - R 1 and R 2 are independently hydrogen, Ci-C 2 -alkyl, C 3 -C 0 cycloalkyl or C 3 -C 0 are bonded, can form a 5- or 6-membered ring and R 3 is a C 1 -C 20 -alkyl radical.
  • a particularly advantageous hydroxybenzophenone in the context of the present invention is 2- (4'-diethylamino-2 1 -hydroxybenzoyl) -benzoic acid hexyl ester (also: aminobenzophenone), which has the following structure:
  • UV filter substances in the context of the present invention are sulfonated, water-soluble UV filters, such as. B .:
  • Benzene-1,4-di (2-oxo-3-bomylidenemethyl-10-sulfonic acid) becomes.
  • Benzene-1,4-di (2-oxo-3-bornylidenemethyl-10-sulfonic acid) has the INCI name Terephtalidene Dicampher sulfonic acid (CAS No. 90457-82-2) and is, for example, under the trade name
  • UV filter substances for the purposes of the present invention are also so-called broadband filters, ie filter substances which absorb both UV-A and UV-B radiation.
  • An advantageous broadband filter for the purposes of the present invention is also the 2,2'-methyl-bis- (6- (2H-benzotriazol-2-yl) -4- (1, 1 J 3 J 3-tetramethylbutyl) phenol ) J which is available under the trade name Tinosorb® M from CIBA-Chemikalien GmbH.
  • Advantageous broadband filter for the purposes of the present invention is also the 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1,3,3,3-tetramethyl-i - [(trimethylsilyl) oxy] disiloxanyl] propyl] phenol (CAS No .: 155633-54-8) with the INCI name Drometrizole Trisiloxanes.
  • the other UV filter substances can be oil-soluble or water-soluble.
  • Advantageous oil-soluble filter substances are z. B .:
  • 3-benzylidene camphor derivatives preferably 3- (4-methylbenzylidene) camphor, 3-benzylidene camphor;
  • 4-aminobenzoic acid derivatives preferably (2-ethylhexyl) 4- (dimethylamino) benzoate, 4- (dimethylamino) benzoic acid amyl ester;
  • Esters of benzalmalonic acid preferably di-2-ethylhexyl 4-methoxybenzalmalonate;
  • Dioctylbutylamidotriazone (INCI: diethylhexyl butamido triazone), which is available under the trade name UVASORB HEB from Sigma 3V;
  • Esters of cinnamic acid preferably 4-methoxycinnamic acid (2-ethylhexyl) ester 1 4-methoxycinnamic acid isopentyl ester;
  • UV filter substances are: Phenylene-1 J 4-bis (2-benzimidazyl) -3,3'-5 J 5'-tetrasulfonic acid bis-natrium salt (INCI: bisimidazylate, trade name: Neoheliopan AP),
  • dioctylbutylamidotriazone (INCI: Diethylhexyl Butamido Triazone, trade name: Uvasorb HEB), • 2- (4-diethylamino 1 2 1 -hydoxybenzoyl) benzoate (also: aminobenzophenone) (INCI: diethylamino hydroxybenzoyl hexyl benzoate, trade name: Uvinul A plus) .
  • these additional UV filter substances may advantageously be present in a total concentration of from 0.01 to 20% by weight and, preferably, in a total concentration of from 0.5 to 10% by weight, based in each case on the total weight of the preparation.
  • the oil phase of the preparations according to the invention is advantageously selected from the group of polar lipids having a polarity ⁇ 35 mN / m.
  • Particularly advantageous lipids in the context of the present invention are all native lipids, such as. As olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, castor oil, wheat germ oil, grape seed oil, thistle oil, evening primrose oil, macadamia nut oil, corn oil, avocado oil and the like, and those listed below.
  • hydrocarbons in particular paraffin oil and further hydrogenated poly olefins such as hydrogenated polyisobutenes, squalane and squalene are to be used advantageously in the context of the present invention.
  • the content of the lipids is advantageously chosen to be less than 50% by weight, preferably from 1 to 40% by weight, particularly preferably from 5 to 15% by weight, in each case based on the total weight of the preparation.
  • the oil phase of the preparations according to the present invention may optionally be advantageous, although it is not mandatory, if the oil phase of the preparations according to the present invention also contains non-polar lipids.
  • the aqueous phase of the preparations according to the invention may advantageously comprise customary cosmetic adjuvants, for example alcohols, in particular those of low C number, preferably ethanol and / or isopropanol, diols or polyols of low C number and their ethers, preferably propylene glycol, glycerol, ethylene glycol, Propanediol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous products, polymers, foam stabilizers, electrolytes, self-tanning agents, and in particular one or more thickeners, which are advantageously chosen can be selected from the group silicon dioxide, aluminum silicates,
  • xanthan gum As hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, particularly advantageous from the group of polyacrylates, preferably a polyacrylate from the group of so-called carbopols, for example Carbopols types 980, 981, 1382, 2984, 5984, each individually or in combination.
  • Thickeners such as Permulen TR 1, TR 2, Carbopol 1328, Aristoflex AVC, can be advantageously used according to the invention.
  • the cosmetic preparations according to the invention can be composed as usual. Particularly advantageous in the context of the present invention are preparations for the care of the skin: they can be used for cosmetic sunscreen, for cleaning or care of the skin and / or hair and as a make-up product in decorative cosmetics. A further advantageous embodiment of the present invention is Af ter-Sun products.
  • cosmetic compositions in the sense of the present invention can be used, for example, as a skin protection cream, day cream or night cream, etc. It may be possible and advantageous to use the compositions according to the invention as a basis for pharmaceutical formulations.
  • cosmetic preparations whose main purpose is not the protection from sunlight, but which nevertheless contain a content of UV protective substances.
  • So z. B. in day creams or makeup products usually incorporated UV-A or UV-B filter substances.
  • UV protectants, as well as antioxidants and, if desired, preservatives effectively protect the preparations themselves against spoilage.
  • cosmetic preparations which are in the form of a sunscreen agent.
  • the cosmetic preparations according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics.
  • the cosmetic preparations according to the invention may contain cosmetic adjuvants, such as are commonly used in such preparations, for.
  • Advantageous preservatives for the purposes of the present invention are, for example, formaldehyde releasers (such as, for example, DMDM hydantoin, which is available under the trade name Glydant TM from Lonza), iodopropyl butylcarbamates (for example those sold under the trade names Glycacil-L, Glycacil -S. From the company.
  • formaldehyde releasers such as, for example, DMDM hydantoin, which is available under the trade name Glydant TM from Lonza
  • iodopropyl butylcarbamates for example those sold under the trade names Glycacil-L, Glycacil -S. From the company.
  • the preserving system also advantageously also includes preserving aids, such as, for example, ethylhexylglycerol, glycine soya, etc.
  • Advantageous complexing agents for the purposes of the present invention are, for example, EDTA, [S, S] -ethylenediamine disuccinate (EDDS), which is obtainable, for example, under the trade name Octaquest from the company Octel, pentasodium ethylenediamine tetramethylenephosphonate, which, for example, B. under the trade name Dequest 2046 from the company.
  • Monsanto is available and / or iminodisuccinic, which among other things from the company.
  • Bayer AG under the trade name Iminodisuccinat VP OC 370 (about 30% solution) and Baypure CX 100 is permanently available.
  • Particularly advantageous preparations are also obtained when antioxidants are used as additives or active substances.
  • the preparations advantageously contain one or more antioxidants. All antioxidants which are suitable or customary for cosmetic applications can be used as inexpensive but nevertheless optional antioxidants.
  • water-soluble Antioxi ⁇ dantien can be used, such as vitamins, eg. As ascorbic acid and its derivatives.
  • antioxidants are vitamin E and its derivatives as well as vitamin A and its derivatives.
  • the amount of antioxidants (one or more compounds) in the preparations is preferably from 0.001 to 30% by weight, particularly preferably from 0.05 to 20% by weight, in particular from 0.1 to 10% by weight, based on the total weight of the preparation.
  • vitamin E and / or its derivatives are the antioxidant (s), it is advantageous to choose their respective concentrations from the range from 0.001 to 10% by weight, based on the total weight of the formulation.
  • vitamin A or vitamin A derivatives, or carotenes or derivatives thereof are the antioxidant (s), it is advantageous if their respective concentrations are in the range from 0.001 to 10% by weight, based on the total weight of the formulation choose.
  • the cosmetic preparations according to the present invention contain cosmetic active ingredients, preferred active substances being antioxidants which can protect the skin against oxidative stress.
  • active ingredients in the context of the present invention are natural active substances and / or their derivatives, such as.
  • 1, 16-dicarboxylic acid dioic acid, CAS number 20701-68-2, provisional INCI name octadecenedioic acid
  • licochalcone A 1, 16-dicarboxylic acid (dioic acid, CAS number 20701-68-2, provisional INCI name octadecenedioic acid) and / or licochalcone A.
  • Licochalcone can also be used advantageously as a constituent of herbal extracts, in particular of aqueous radix Glycyrrhizae inflatae.
  • the cosmetic preparations contain 0.001 to 10% by weight, in particular 0.05 to 5% by weight, very particularly 0.01 to 2% by weight of an extract of Radix Glycyrrhizae inflatae, in each case on the total weight of the preparation.
  • Inventive formulations which z. B. known anti-wrinkle active ingredients such as flavone glycosides (especially ⁇ -glycosyl rutin), coenzyme Q10, vitamin E and / or derivatives and the like, are particularly advantageous for protection against aesthetically unattractive skin lesions, as z. Skin aging (such as dryness, roughness, dryness wrinkles, itching, decreased refatting (eg, after washing), visible vascular dilation (telangiectasia, cuperosis), slackness and wrinkle and wrinkle formation, localized hypersensitivity). , Hypo and false pigmentation (eg, age spots), increased susceptibility to mechanical stress (eg, cracking), and the like). Furthermore, they are advantageously suitable against the appearance of dry or rough skin.
  • flavone glycosides especially ⁇ -glycosyl rutin
  • coenzyme Q10 vitamin E and / or derivatives and the like
  • the preparations according to the present invention can also advantageously contain self-tanning substances, for example dihydroxyacetone and / or melanin derivatives in concentrations of from 1% by weight to 8% by weight, based on the total weight of the preparation.
  • self-tanning substances for example dihydroxyacetone and / or melanin derivatives in concentrations of from 1% by weight to 8% by weight, based on the total weight of the preparation.
  • the preparations according to the present invention may also contain repellents for protection against mosquitoes, ticks and spiders and the like.
  • repellents for protection against mosquitoes, ticks and spiders and the like.
  • N N-diethyl-3-methylbenzamide (trade name: meta-delphene, "DEET"), dimethyl phthalate (trade name: palatinol M, DMP), 1-piperidinecarboxylic acid 2- (2-hydroxyethyl) -1-methylpropyl ester, and especially 3- (Nn-butyl-N-acetyl-amino) -propionic acid ethyl ester (available from Merck under the tradename Insekt Repellent® 3535.)
  • the repellents can be used either individually or in combination.
  • Moisturizers are substances or mixtures of substances which give cosmetic preparations the property, after application or distribution on the skin surface, to reduce the moisture release of the hom layer (also called transepidermal water loss (TEWL)) and / or to positively influence the hydration of the initial layer ,
  • TEWL transepidermal water loss
  • moisturizers for the purposes of the present invention are, for example, glycerol, lactic acid and / or lactates, in particular sodium lactate, butylene glycol, propylene glycol, methylpropanediol, biosaccharide gum-1, glycine soya, ethylhexyloxyglycerol, pyrrolidonecarboxylic acid and urea.
  • polymeric moisturizers from the group of water-soluble and / or water-swellable and / or water-gellable polysaccharides.
  • the cosmetic preparations according to the invention may also advantageously, although not necessarily, contain fillers which are e.g. B. further improve the sensory and cosmetic properties of the formulations and, for example, cause or enhance a velvety or silky feel on the skin.
  • Advantageous fillers for the purposes of the present invention are starch and starch derivatives (such as, for example, tapioca starch, distarch phosphate, aluminum or sodium starch, octenylsuccinate and the like), pigments which have neither mainly UV filter nor coloring action (such as, for example, US Pat. B. boron nitride etc.) and / or Aerosils ® (CAS no.

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Abstract

The invention relates to a cosmetic sun protection emulsion containing organic and inorganic UV sun protection filter pigments in a concentration of at least 20 wt. %, in relation to the total weight of the preparation. The emulsion is characterised in that the weight ratio of organic to inorganic UV sun protection filter pigments is between 4:1 and 1:4.

Description

Beiersdorf Aktiengesellschaft Hamburg Beiersdorf Aktiengesellschaft Hamburg
Beschreibungdescription
Lichtschutzemulsion mit hohem Anteil an LichtschutzfilterpigmentenSunscreen emulsion with a high proportion of sunscreen filter pigments
Die vorliegende Erfindung betrifft eine kosmetische Lichtschutzemulsion enthaltend UV- Lichtschutzfilterpigmente in einer Konzentration von mindestens 20 Gewichts-%, bezogen auf das Gesamtgewicht der Zubereitung.The present invention relates to a cosmetic sunscreen emulsion containing UV sunscreen filter pigments in a concentration of at least 20% by weight, based on the total weight of the preparation.
Der Trend weg von der vornehmen Blässe hin zur „gesunden, sportlich braunen Haut" ist seit Jahren ungebrochen. Um diese zu erzielen setzen die Menschen ihre Haut der Sonnenstrahlung aus, da diese eine Pigmentbildung im Sinne einer Melaninbildung hervorruft. Die ultraviolette Strahlung des Sonnenlichtes hat jedoch auch eine schädigende Wirkung auf die Haut. Neben der akuten Schädigung (Sonnenbrand) treten Langzeitschäden wie ein erhöhtes Risiko an Hautkrebs zu erkranken bei übermäßiger Bestrahlung mit Licht aus dem UVB-Bereich (Wellenlänge: 280-320 nm) auf. Die übermäßige Einwirkung der UVB- und UVA-Strahlung (Wellenlänge: 320-400 nm) führt darüber hinaus zu einer Schwächung der elastischen und kollagenen Fasern des Bindegewebes. Dies führt zu zahlreichen phototoxischen und photoallergischen Reaktionen und hat eine vorzeitige Hautalterung zur Folge.The trend away from sophisticated paleness to "healthy, sporty brown skin" has been unbroken for years, and people are exposing their skin to sunlight, as it causes pigmentation in the sense of melanin formation, which has ultraviolet radiation from sunlight In addition to the acute injury (sunburn), long-term damage such as an increased risk of developing skin cancer due to excessive exposure to light from the UVB range (wavelength: 280-320 nm) occurs UVB and UVA radiation (wavelength: 320-400 nm) also leads to a weakening of the elastic and collagen fibers of the connective tissue, which leads to numerous phototoxic and photoallergic reactions and leads to premature aging of the skin.
Zum Schutz der Haut wurden daher eine Reihe von Lichtschutzfiltersubstanzen entwickelt, die in kosmetischen Zubereitungen eingesetzt werden können. Diese UVA- und UVB-Filter sind in den meisten Industrieländern in Form von Positivlisten wie der Anlage 7 der deutschen Kosmetikverordnung zusammengefasst.To protect the skin, therefore, a number of sunscreen filter substances have been developed which can be used in cosmetic preparations. These UVA and UVB filters are summarized in most industrialized countries in the form of positive lists such as Appendix 7 of the German Cosmetics Regulation.
Eine besondere Form von UV-Lichtschutzfiltersubstanzen stellen die Mikropigmente dar. Die UV-Schutzwirkung der Mikropigmente beruht auf den physikalischen Effekten der Reflexion und Lichtstreuung. In kosmetischen Zubereitungen werden als Mikropigmente fast ausschließlich anorganische Mikropigmente aus Titandioxid, Zinkoxid oder Mischoxiden mit zum Beispiel Eisenoxiden eingesetzt. Die Vorteile von Mikropigmenten als UV-Filtersubstanz in kosmetischen Zubereitungen liegen vor allem darin begründet, dass die Pigmente im Gegensatz zu gelöst oder flüssig vorliegenden, nicht in die Haut penetrieren. Das Auftreten von allergischen Reaktionen ist damit ausgeschlossen.A special form of UV sunscreen filter substances are the micropigments. The UV protection effect of the micropigments is based on the physical effects of reflection and light scattering. In cosmetic preparations are used as micropigments almost exclusively inorganic micropigments of titanium dioxide, zinc oxide or mixed oxides with, for example, iron oxides. The advantages of micropigments as UV filter substance in cosmetic preparations are mainly due to the fact that the pigments, in contrast to dissolved or liquid, do not penetrate into the skin. The occurrence of allergic reactions is excluded.
Nachteilig am Stande der Technik ist jedoch der Umstand, dass Mikropigmente nur schwer stabil in kosmetische Zubereitungen einzuarbeiten sind. Insbesondere wenn Mikropigmente in höheren Konzentrationen (Konzentrationen über 7 Gewichts-%, bezogen auf das Gesamtgewicht der Zubereitung) eingesetzt werden, bilden sie relativ schnell Pigment- Agglomerate, die aus der Zubereitung ausfallen. Die Lagerstabilität ist also gering.A disadvantage of the prior art, however, is the fact that micropigments are difficult to incorporate stable in cosmetic preparations. In particular, when micropigments are used in higher concentrations (concentrations above 7% by weight, based on the total weight of the preparation), they form pigment agglomerates which precipitate out of the preparation relatively quickly. The storage stability is therefore low.
Es war daher die Aufgabe der vorliegenden Erfindung, die Mängel des Standes der Technik zu beseitigen und stabile Emulsionen mit einem hohen Gehalt an Mikropigmenten als UV- Lichtschutzfilter zu entwickeln. Die Formulierungen sollten ferner bei Ihrer Anwendung auf der Haut ein über einen längeren Anwendungszeitraum stabiles Absorptionsspektrum mit einer ausgewogenen UV-A/UV-B-Absorptionsbalance aufweisen.It was therefore the object of the present invention to overcome the deficiencies of the prior art and to develop stable emulsions with a high content of micropigments as UV light protection filters. The formulations should also have a stable absorption spectrum with a balanced UV-A / UV-B absorption balance when applied to the skin over a prolonged period of use.
Überraschend gelöst werden die Aufgaben durch eine kosmetische Lichtschutzemulsion enthaltend organische und anorganische UV-Lichtschutzfilterpigmente in einer Konzentration von mindestens 20 Gewichts-%, bezogen auf das Gesamtgewicht der Zubereitung, dadurch gekennzeichnet, dass das Gewichtsverhältnis von anorganischen zu organischen UV- Lichtschutzfilterpigmenten von 4:1 bis 1 :4 beträgt.Surprisingly, the objects are achieved by a cosmetic sunscreen emulsion containing organic and inorganic UV light protection filter pigments in a concentration of at least 20% by weight, based on the total weight of the preparation, characterized in that the weight ratio of inorganic to organic UV sunscreen filters of 4: 1 to 1: 4.
Es ist erfindungsgemäß bevorzugt, wenn die erfindungsgemäße Zubereitung anorganische und organische UV-Lichtschutzfilterpigmente in einer Konzentration von 20 bis 40 Gewichts- %, und erfindungsgemäß besonders bevorzugt, wenn die Zubereitung anorganische und organische UV-Lichtschutzfilterpigmente in einer Konzentration von 21 bis 30 Gewichts-%, jeweils bezogen auf das Gesamtgewicht der Zubereitung, enthält.It is preferred according to the invention if the preparation according to the invention comprises inorganic and organic UV sunscreen pigments in a concentration of 20 to 40% by weight, and particularly preferred according to the invention if the preparation contains inorganic and organic UV sunscreen pigments in a concentration of 21 to 30% by weight. , in each case based on the total weight of the preparation contains.
Erfindungsgemäß bevorzugt beträgt das Gewichtsverhältnis von anorganischen zu organischen UV-Lichtschutzfilterpigmenten von 3:1 bis 1 :3. Erfindungsgemäß vorteilhafte Ausführungsformen der vorliegenden Erfindung sind dadurch gekennzeichnet, dass die organischen Lichtschutzfilterpigmente gewählt werden aus der Gruppe 2J2'-Methylen-bis-(6-(2H-benzotriazol-2-yl)-4-(1 ,1J3J3-tetramethylbutyl)-phenol)J According to the invention, the weight ratio of inorganic to organic UV photoprotective pigments is preferably from 3: 1 to 1: 3. Embodiments of the present invention which are advantageous according to the invention are characterized in that the organic sunscreen filter pigments are selected from the group 2 J 2'-methylenebis (6- (2H-benzotriazol-2-yl) -4- (1, 1 J 3 J 3-tetramethylbutyl) -phenol) J
2J4J6-Tris-(biphenyl)-1,3J5-triazin und 2J4J6-Tris-(terphenyl)-1,3J5-triazin. Erfindungsgemäß bevorzugt werden als organische UV-Lichtschutzfilterpigmente 2,4,6-Tris-(biphenyl)-1 ,3,5- triazin und/oder 2J4J6-Tris-(terphenyl)-1 ,3J5-triazin eingesetzt.2 J 4 J 6-tris (biphenyl) -1,3 J 5-triazine and 2 J 4 J 6-tris (terphenyl) -1,3 J triazin-5. According to the invention preferred as the organic UV photoprotective filter pigments 2,4,6-tris (biphenyl) -1, 3,5-triazine and / or 2 J 4 J 6-tris (terphenyl) -1, 3 J 5-triazine used ,
Dabei ist es erfindungsgemäß besonders bevorzugt, 2,4,6-Tribiphenyl-4-yl-1 ,3,5-triazin als organisches Lichtschutzfilterpigment einzusetzen.It is particularly preferred according to the invention to use 2,4,6-tribiphenyl-4-yl-1,3,5-triazine as organic sunscreen filter pigment.
Die erfindungsgemäßen Mikropigmente können erfindungsgemäß vorteilhaft in einer wässrigen Dispersion vorliegen. Als Dispergierhilfe sind insbesondere C8-C16 Alkylpolyglucosid amphiphile Polymere, wie sind in EP 1093796 B1 beschrieben sind, erfindungsgemäß vorteilhaft einsetzbar.According to the invention, the micropigments according to the invention may advantageously be present in an aqueous dispersion. C8-C16 alkylpolyglucoside amphiphilic polymers, as described in EP 1093796 B1, can be advantageously used according to the invention as a dispersing aid.
Vorteilhafte Ausführungsformen der vorliegenden Erfindung enthalten die organischen Lichtschutzfilterpigmente in einer Konzentration von 1 bis 20 Gewichts-%, bezogen auf das Gesamtgewicht der Zubereitung. Bevorzugte Ausführungsformen der vorliegenden Erfindung enthalten die organischen Lichtschutzfilterpigmente in einer Konzentration von 2 bis 15 Gewichts-%, bezogen auf das Gesamtgewicht der Zubereitung.Advantageous embodiments of the present invention contain the organic sunscreen filter pigments in a concentration of 1 to 20% by weight, based on the total weight of the preparation. Preferred embodiments of the present invention contain the organic sunscreen filter pigments in a concentration of 2 to 15% by weight, based on the total weight of the preparation.
Es ist dabei erfindungsgemäß von Vorteil, wenn die anorganischen UV- Lichtschutzfilterpigmente gewählt werden aus der Gruppe der folgenden Pigmente:It is advantageous according to the invention if the inorganic UV screening filter pigments are selected from the group of the following pigments:
Bevorzugte anorganische Pigmente sind Metalloxide und/oder andere in Wasser schwerlösli¬ che oder unlösliche Metallverbindungen, insbesondere Oxide des Titans (TiO2), Zinks (ZnO), Eisens (z. B. Fe2O3), Zirkoniums (ZrO2), Siliciums (SiO2), Mangans (z. B. MnO), Aluminiums (AI2O3), Cers (z. B. Ce2O3), Mischoxide der entsprechenden Metalle sowie Abmischungen aus solchen Oxiden, sowie das Sulfat des Bariums (BaSO4).Preferred inorganic pigments are metal oxides and / or other sparingly soluble or insoluble metal compounds in water, in particular oxides of titanium (TiO 2 ), zinc (ZnO), iron (eg Fe 2 O 3 ), zirconium (ZrO 2 ), Silicon (SiO 2 ), manganese (for example MnO), aluminum (Al 2 O 3 ), cerium (for example Ce 2 O 3 ), mixed oxides of the corresponding metals and mixtures of such oxides, and also the sulfate of barium (BaSO 4 ).
Die Titandioxid- Pigmente können sowohl in der Kristal I modifikation Rutil als auch Anatas vorliegen und können im Sinne der vorliegenden Erfindung vorteilhaft oberflächlich behandelt („gecoatet") sein, wobei beispielsweise ein hydrophiler, amphiphiler oder hydrophober Cha- rakter gebildet werden bzw. erhalten bleiben soll. Diese Oberflächenbehandlung kann darin bestehen, dass die Pigmente nach an sich bekannten Verfahren mit einer dünnen hydrophilen und/oder hydrophoben anorganischen und/oder organischen Schicht versehen werden. Die verschiedenen Oberflächenbeschichtung können im Sinne der vorliegenden Erfindung auch Wasser enthalten.The titanium dioxide pigments can be present both in the rutile and anatase crystal modifications and can advantageously be surface-treated ("coated") for the purposes of the present invention, with a hydrophilic, amphiphilic or hydrophobic character, for example, being preferred. be formed or should remain preserved character. This surface treatment may consist in providing the pigments with a thin hydrophilic and / or hydrophobic inorganic and / or organic layer by processes known per se. The various surface coating can also contain water for the purposes of the present invention.
Beschriebene beschichtete und un beschichtete Titandioxide können im Sinne vorliegender Erfindung auch in Form kommerziell erhältlicher öliger oder wäßriger Vordispersionen zur Anwendung kommen. Diesen Vordispersionen können vorteilhaft Dispergierhilfmittel und/oder Solubilisationsvermittler zugesetzt sein.Coated and uncoated titanium dioxides described in the present invention can also be used in the form of commercially available oily or aqueous predispersions. Dispersants and / or solubilizers may advantageously be added to these predispersions.
Die erfindungsgemäßen Titandioxide zeichnen sich durch eine Primärpartikelgröße zwischen 10 nm bis 200 nm aus, wobei Partikelgrößen von 10 nm bis 100 nm erfindungsgemäß bevorzugt sind. The titanium dioxides according to the invention are distinguished by a primary particle size of between 10 nm and 200 nm, particle sizes of from 10 nm to 100 nm being preferred according to the invention.
Figure imgf000006_0001
Figure imgf000007_0001
Figure imgf000006_0001
Figure imgf000007_0001
Im Sinne der vorliegenden Erfindung sind besonders bevorzugte Titandioxide das MT-100 Z und MT-100 TV von Tayca Corporation, Eusolex T-2000 und Eusolex T-AVO von Merck und das Titandioxid T 805 von Degussa und das Eisen/Titandmischoxid Titandioxid T817 von Degussa.For the purposes of the present invention, particularly preferred titanium dioxides are the MT-100 Z and MT-100 TV from Tayca Corporation, Eusolex T-2000 and Eusolex T-AVO from Merck and the titanium dioxide T 805 from Degussa and the iron / titanium mixed oxide titanium dioxide T817 from Degussa ,
Zinkoxide können im Sinne der vorliegenden Erfindung auch in Form kommerziell erhältlicher öliger oder wäßriger Vordispersionen zur Anwendung kommen. Erfindungsgemäß geeignete Zinkoxidpartikel und Vordispersionen von Zinkoxidpartikeln zeichnen sich durch eine Primärpartikelgröße von < 300 nm aus und sind unter folgenden Handelsbezeichnungen bei den aufgeführten Firmen erhältlich:For the purposes of the present invention, zinc oxides can also be used in the form of commercially available oily or aqueous predispersions. Zinc oxide particles and predispersions of zinc oxide particles which are suitable according to the invention are distinguished by a primary particle size of <300 nm and can be obtained from the following companies under the following trade names:
Figure imgf000007_0002
Figure imgf000007_0002
Besonderes bevorzugte Zinkoxide im Sinne der Erfindung sind das Z-Cote HP1 von der Firma BASF und das Zinkoxid NDM von der Firma Haarmann & Reimer.Particularly preferred zinc oxides in the context of the invention are the Z-Cote HP1 from BASF and the zinc oxide NDM from Haarmann & Reimer.
Dabei ist es erfindungsgemäß von Vorteil, wenn die Konzentration an anorganischen Lichtschutzpigmenten in der Zubereitung von 1 bis 30 Gewichts-% und bevorzugt von 2 bis 15 Gewichts-%, jeweils bezogen auf das Gesamtgewicht der Zubereitung, beträgt. Vorteilhafte weitere UV-Filtersubstanzen im Sinne der vorliegenden Erfindung sind beispielsweise die im folgenden genannten, welche in der Wasser- und/oder der ölphase vorliegen können.In this case, it is advantageous according to the invention if the concentration of inorganic light protection pigments in the preparation is from 1 to 30% by weight and preferably from 2 to 15% by weight, based in each case on the total weight of the preparation. Advantageous further UV filter substances in the sense of the present invention are, for example, those mentioned below which may be present in the water phase and / or the oil phase.
Vorteilhafte bei Raumtemperatur flüssige UV-Filtersubstanzen im Sinne der vorliegenden Erfindung sind Homomenthylsalicylat (INCI: Homosalate), 2-Ethylhexyl-2-hydroxybenzoat (2- Ethylhexylsalicylat, Octylsalicylat, INCI: Octyl Salicylate), 2-Ethylhexyl-2-cyano-3,3-diphenyl- acrylat (INCI: Octocrylene) und Ester der Zimtsäure, vorzugsweise 4-Methoxyzimtsäure(2- ethylhexyl)ester (2-Ethylhexyl-4-methoxycinnamat, INCI: Octyl Methoxycinnamate) und 4- Methoxyzimtsäureisopentylester (lsopentyl-4-methoxycinnamat, INCI: Isoamyl p-Meth- oxycinnamate), 3-(4-(2,2-bis Ethoxycarbonylvinyl)-phenoxy)propenyl)-methoxysiloxan / Dimethylsiloxan - Copolymer welches beispielsweise unter der Handelsbezeichnung Parsol® SLX bei Hoffmann La Roche erhältlich ist.Advantageous UV filter substances which are liquid at room temperature for the purposes of the present invention are homomenthyl salicylate (INCI: homosalates), 2-ethylhexyl 2-hydroxybenzoate (2-ethylhexyl salicylate, octyl salicylate, INCI: octyl salicylates), 2-ethylhexyl-2-cyano-3, 3-diphenyl acrylate (INCI: Octocrylene) and esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester (2-ethylhexyl-4-methoxycinnamate, INCI: octyl methoxycinnamate) and 4-methoxycinnamic acid isopentyl ester (isopentyl 4-methoxycinnamate, INCI: isoamyl p-methoxycinnamate), 3- (4- (2,2-bisethoxycarbonylvinyl) phenoxy) propenyl) methoxysiloxane / dimethylsiloxane copolymer, which is available, for example, under the trade name Parsol® SLX from Hoffmann La Roche.
Vorteilhafte UV-A-Filtersubstanzen im Sinne der vorliegenden Erfindung sind Dibenzoyl- methanderivate, insbesondere das 4-(tert.-Butyl)-4'-methoxydibenzoylmethan (CAS-Nr. 70356-09-1), welches von Givaudan unter der Marke Parsol® 1789 und von Merck unter der Handelsbezeichnung Eusolex® 9020 verkauft wird.Advantageous UV-A filter substances for the purposes of the present invention are dibenzoyl methane derivatives, in particular 4- (tert-butyl) -4'-methoxydibenzoylmethane (CAS No. 70356-09-1), which has been sold by Givaudan under the trademark Parsol ® 1789 and sold by Merck under the trade name Eusolex® 9020.
Weitere vorteilhafte UV-A-Filtersubstanzen im Sinne der vorliegenden Erfindung sind Hydroxybenzophenone, welche sich durch die folgende Strukturformel auszeichnen:Further advantageous UV-A filter substances in the context of the present invention are hydroxybenzophenones, which are distinguished by the following structural formula:
Figure imgf000008_0001
Figure imgf000008_0001
worinwherein
R1 und R2 unabhängig voneinander Wasserstoff, Ci-C2o-Alkyl, C3-Ci0-Cycloalkyl oder C3-Ci0- Cycloalkenyl bedeuten, wobei die Substituenten R1 und R2 gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, einen 5- oder 6-Ring bilden können und R3 einen CrC20-Alkyl Rest bedeutet. Ein besonders vorteilhaftes Hydroxybenzophenon im Sinne der vorliegenden Erfindung ist das 2-(4'-Diethylamino-21-hydoxybenzoyl)-benzoesäurehexylester (auch: Aminobenzo- phenon), welches sich durch folgende Struktur auszeichnet:Cycloalkenyl, wherein the substituents R 1 and R 2 together with the nitrogen atom to which they - R 1 and R 2 are independently hydrogen, Ci-C 2 -alkyl, C 3 -C 0 cycloalkyl or C 3 -C 0 are bonded, can form a 5- or 6-membered ring and R 3 is a C 1 -C 20 -alkyl radical. A particularly advantageous hydroxybenzophenone in the context of the present invention is 2- (4'-diethylamino-2 1 -hydroxybenzoyl) -benzoic acid hexyl ester (also: aminobenzophenone), which has the following structure:
Figure imgf000009_0001
und unter dem Uvinul A Plus bei der Fa. BASF erhältlich ist.
Figure imgf000009_0001
and Uvinul A Plus is available from BASF.
Vorteilhafte weitere UV-Filtersubstanzen im Sinne der vorliegenden Erfindung sind sulfo- nierte, wasserlösliche UV-Filter, wie z. B.:Advantageous further UV filter substances in the context of the present invention are sulfonated, water-soluble UV filters, such as. B .:
• Phenylen-1,4-bis-(2-benzimidazyl)-3,3'-5J5'-tetrasulfonsäure und ihre Salze, besonders die entsprechenden Natrium-, Kalium- oder Triethanolammonium-Salze, insbesondere das Phenylen-1,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfonsäure-bis-natriumsalz mit der INCI-Bezeichnung Bisimidazylate (CAS-Nr.: 180898-37-7), welches beispielsweise unter der Handelsbezeichnung Neo Heliopan AP bei Haarmann & Reimer erhältlich ist;• phenylene-1,4-bis- (2-benzimidazyl) -3,3'-5 J 5'-tetrasulfonic acid and its salts, particularly the corresponding sodium, potassium or triethanolammonium salts, in particular phenylene-1,4 bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt with the INCI name Bisimidazylate (CAS No .: 180898-37-7), which is sold, for example, under the trade name Neo Heliopan AP is available from Haarmann &Reimer;
• Salze der 2-Phenylbenzimidazol-5-sulfonsäure, wie ihr Natrium-, Kalium- oder ihr Trietha- nolammonium-Salz sowie die Sulfonsäure selbst mit der INCI Bezeichnung Phe- nylbenzimidazole Sulfonsäure (CAS.-Nr. 27503-81-7), welches beispielsweise unter der Handelsbezeichnung Eusolex 232 bei Merck oder unter Neo Heliopan Hydro bei Haarmann & Reimer erhältlich ist;Salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or triethanolammonium salt, and the sulfonic acid itself with the INCI name phenylbenzimidazole sulfonic acid (CAS No. 27503-81-7), which is available, for example, under the trade name Eusolex 232 from Merck or under Neo Heliopan Hydro from Haarmann &Reimer;
• 1 ,4-di(2-oxo-10-Sulfo-3-bomylidenmethyl)-Benzol (auch: 3,3'-(1 ,4-Phenylendimethylene)- bis-(7,7-dimethyl-2-oxo-bicyclo-[2.2.1]hept-1-ylmethan Sulfonsäure) und dessen Salze1, 4-di (2-oxo-10-sulfo-3-bomylidenemethyl) benzene (also: 3,3 '- (1,4-phenylenedimethylene) bis (7,7-dimethyl-2-oxo) bicyclo [2.2.1] hept-1-ylmethane sulfonic acid) and its salts
(besonders die entprechenden 10-Sulfato-verbindungen, insbesondere das entspre¬ chende Natrium-, Kalium- oder Triethanolammonium-Salz), das auch als Benzol-1,4-di(2- oxo-3-bornylidenmethyl-10-sulfonsäure) bezeichnet wird. Benzol-1,4-di(2-oxo-3-bornyli- denmethyl-10-sulfonsäure) hat die INCI-Bezeichnung Terephtalidene Dicampher Sulfonsäure (CAS.-Nr.: 90457-82-2) und ist beispielsweise unter dem Handelsnamen(Especially the entprechenden 10-sulfato compounds, in particular the corre sponding sodium, potassium or triethanolammonium salt), which also referred to as benzene-1,4-di (2-oxo-3-bomylidenemethyl-10-sulfonic acid) becomes. Benzene-1,4-di (2-oxo-3-bornylidenemethyl-10-sulfonic acid) has the INCI name Terephtalidene Dicampher sulfonic acid (CAS No. 90457-82-2) and is, for example, under the trade name
Mexoryl SX von der Fa. Chimex erhältlich;Mexoryl SX available from Chimex;
• Sulfonsäure-Derivate des 3-Benzylidencamphers, wie z. B. 4-(2-Oxo-3-bomylidenmethyl)- benzolsulfonsäure, 2-Methyl-5-(2-oxo-3-bomylidenmethyl)sulfonsäure und deren Salze. Vorteilhafte UV-Filtersubstanzen im Sinne der vorliegenden Erfindung sind ferner soge¬ nannte Breitbandfilter, d.h. Filtersubstanzen, die sowohl UV-A- als auch UV-B-Strahlung ab¬ sorbieren.Sulfonic acid derivatives of 3-Benzylidencamphers, such as. B. 4- (2-oxo-3-bomylidenemethyl) - benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bomylidenemethyl) sulfonic acid and salts thereof. Advantageous UV filter substances for the purposes of the present invention are also so-called broadband filters, ie filter substances which absorb both UV-A and UV-B radiation.
Ein vorteilhafter Breitbandfilter im Sinne der vorliegenden Erfindung ist auch das 2,2'-Me- thylen-bis-(6-(2H-benzotriazol-2-yl)-4-(1 ,1J3J3-tetramethylbutyl)-phenol)J welches unter der Handelsbezeichnung Tinosorb® M bei der CIBA-Chemikalien GmbH erhältlich ist.An advantageous broadband filter for the purposes of the present invention is also the 2,2'-methyl-bis- (6- (2H-benzotriazol-2-yl) -4- (1, 1 J 3 J 3-tetramethylbutyl) phenol ) J which is available under the trade name Tinosorb® M from CIBA-Chemikalien GmbH.
Vorteilhafter Breitbandfilter im Sinne der vorliegenden Erfindung ist ferner das 2-(2H-benzo- triazol-2-yl)-4-methyl-6-[2-methyl-3-[1 ,3,3,3-tetramethyl-i -[(trimethylsilyl)oxy]disiloxa- nyl]propyl]-phenol (CAS-Nr.: 155633-54-8) mit der INCI-Bezeichnung Drometrizole Trisilo- xane.Advantageous broadband filter for the purposes of the present invention is also the 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1,3,3,3-tetramethyl-i - [(trimethylsilyl) oxy] disiloxanyl] propyl] phenol (CAS No .: 155633-54-8) with the INCI name Drometrizole Trisiloxanes.
Die weiteren UV-Filtersubstanzen können öllöslich oder wasserlöslich sein. Vorteilhafte öllösliche Filtersubstanzen sind z. B.:The other UV filter substances can be oil-soluble or water-soluble. Advantageous oil-soluble filter substances are z. B .:
• 3-Benzylidencampher-Derivate, vorzugsweise 3-(4-Methylbenzyliden)campher, 3-Benzyli- dencampher;3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3-benzylidene camphor;
• 4-Aminobenzoesäure-Derivate, vorzugsweise 4-(Dimethylamino)-benzoesäure(2-ethylhe- xyl)ester, 4-(Dimethylamino)benzoesäureamylester; • Ester der Benzalmalonsäure, vorzugsweise 4-Methoxybenzalmalonsäuredi(2-ethylhexyl)- ester;4-aminobenzoic acid derivatives, preferably (2-ethylhexyl) 4- (dimethylamino) benzoate, 4- (dimethylamino) benzoic acid amyl ester; Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzalmalonate;
• Dioctylbutylamidotriazon (INCI: Diethylhexyl Butamido Triazone), welches unter der Han¬ delsbezeichnung UVASORB HEB bei Sigma 3V erhältlich ist;Dioctylbutylamidotriazone (INCI: diethylhexyl butamido triazone), which is available under the trade name UVASORB HEB from Sigma 3V;
• Ester der Zimtsäure, vorzugsweise 4-Methoxyzimtsäure(2-ethylhexyl)ester1 4-Methoxy- zimtsäureisopentylester;Esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester 1 4-methoxycinnamic acid isopentyl ester;
• Derivate des Benzophenons, vorzugsweise 2-Hydroxy-4-methoxybenzophenon, 2- Hydroxy-4-methoxy-4'-methylbenzophenon, 2,21-Dihydroxy-4-methoxybenzophenon sowie• derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2 1 -dihydroxy-4-methoxybenzophenone and
• an Polymere gebundene UV-Filter,Polymer-bound UV filters,
• Homomenthylsalicylat (INCI: Homosalate) und • 2-Ethylhexyl-2-hydroxybenzoat (2-Ethylhexylsalicylat, Octylsalicylat, INCI: Octyl Salicy- late).• Homomenthyl salicylate (INCI: Homosalate) and • 2-Ethylhexyl-2-hydroxybenzoate (2-ethylhexyl salicylate, octyl salicylate, INCI: Octyl salicylate).
Besonders vorteilhafte UV-Filtersubstanzen sind: • Phenylen-1 J4-bis-(2-benzimidazyl)-3,3'-5J5'-tetrasulfonsäure-bis-natriunnsalz (INCI: Bisimidazylate, Handelsname: Neoheliopan AP),Particularly advantageous UV filter substances are: Phenylene-1 J 4-bis (2-benzimidazyl) -3,3'-5 J 5'-tetrasulfonic acid bis-natrium salt (INCI: bisimidazylate, trade name: Neoheliopan AP),
• Dioctylbutylamidotriazon (INCI: Diethylhexyl Butamido Triazone, Handelsname: Uvasorb HEB), • 2-(41-Diethylamino-21-hydoxybenzoyl)-benzoesäurehexylester (auch: Aminobenzophenon) (INCI: Diethylamino Hydroxybenzoyl Hexyl Benzoat, Handelsname: Uvinul A plus),• dioctylbutylamidotriazone (INCI: Diethylhexyl Butamido Triazone, trade name: Uvasorb HEB), • 2- (4-diethylamino 1 2 1 -hydoxybenzoyl) benzoate (also: aminobenzophenone) (INCI: diethylamino hydroxybenzoyl hexyl benzoate, trade name: Uvinul A plus) .
• (3Z)-1 ,7,7-trimethyl-3-(4-methylbenzylidene)bicyclo[2.2.1]heptan-2-one (INCI: 4-Methyl- benzylidene Campher, Handelsname: Eusolex 6300),• (3Z) -1,7,7-trimethyl-3- (4-methylbenzylidenes) bicyclo [2.2.1] heptan-2-one (INCI: 4-methylbenzylidenes camphor, trade name: Eusolex 6300),
• 2-Ethylhexyl-2-cyano-3,3-diphenylacrylat (INCI: Octocrylene, Handelsname: Uvinul N- 539),2-ethylhexyl-2-cyano-3,3-diphenylacrylate (INCI: Octocrylene, trade name: Uvinul N-539),
• Benzol-1,4-di(2-oxo-3-bomylidenmethyl-10-sulfonsäure) (INCI: Terephtalidene Dicampher Sulfonsäure, Handelsname: Mexoryl SX),Benzene-1,4-di (2-oxo-3-bomylidenemethyl-10-sulfonic acid) (INCI: Terephtalidene dicampher sulfonic acid, trade name: Mexoryl SX),
• 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1 ,3,3,3-tetramethyl-i -[(trimethyl- silyl)oxy]disiloxanyl]propyl]-phenol (INCI: Drometrizole Trisiloxane, Handelsname: Mexoryl XL).2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1,3,3,3-tetramethyl-i - [(trimethylsilyl) oxy] disiloxanyl] propyl ] -phenol (INCI: Drometrizole Trisiloxane, trade name: Mexoryl XL).
Ganz besonders vorteilhafte UV-Filtersubstanzen im Sinne der vorliegenden Erfindung sind:Very particularly advantageous UV filter substances in the context of the present invention are:
• 2-Ethylhexyl-4-methoxycinnamat (INCI: Octyl Methoxycinnamat, Handelsname: Parsol MCX), • 4-(tert.-Butyl)-4'-methoxydibenzoylmethan (INCI: Butylmethoxydibenzoylmethan, Han¬ delsname: Parsol 1789),2-ethylhexyl-4-methoxycinnamate (INCI: octyl methoxycinnamate, trade name: Parsol MCX), 4- (tert-butyl) -4'-methoxydibenzoylmethane (INCI: butylmethoxydibenzoylmethane, trade name: Parsol 1789),
• Salze der 2-Phenylbenzimidazol-5-sulfonsäure, wie ihr Natrium-, Kalium- oder ihr Trietha- nolammonium-Salz sowie die Sulfonsäure selbst mit der INCI Bezeichnung Phe- nylbenzimidazole Sulfonsäure (Handelsname: Eusolex 232). • 2,4-Bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazin (INCI: Aniso Triazin, erhältlich unter dem Handelsnamen Tinosorb S) in gelöster Form,Salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or triethanolammonium salt, and also the sulfonic acid itself with the INCI name phenylbenzimidazole sulfonic acid (trade name: Eusolex 232). 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine (INCI: aniso triazine, available at the trade name Tinosorb S) in dissolved form,
• 2,4-bis-[5-1 (dimethylpropyl)benzoxazol-2-yl-(4-phenyl)-imino]-6-(2-ethylhexyl)-imino-1 ,3,5- triazin mit der (CAS Nr. 288254-16-0, erhältlich bei 3V Sigma unter der Handelsbezeichnung Uvasorb® K2A) in gelöster Form, • 4,4',4"-(1 ,3,5-Triazin-2,4,6-triyltriimino)-tris-benzoesäure-tris(2-ethylhexylester) (auch: 2,4,6-Tris-[anilino-(p-carbo-2'-ethyl-1'-hexyloxy)]-1,3,5-triazin (INCI: Octyl Triazone), welches von der BASF Aktiengesellschaft unter der Warenbezeichnung UVINUL® T 150 vertrieben wird) in gelöster Form, • Dioctylbutylamidotriazon (INCI: Diethylhexyl Butamido Triazone, Handelsname: Uvasorb HEB).• 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) -imino] -6- (2-ethylhexyl) -imino-1,3,5-triazine having the (CAS No. 288254-16-0, available from 3V Sigma under the trade name Uvasorb® K2A) in dissolved form, 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) - tris-benzoic acid tris (2-ethylhexyl ester) (also: 2,4,6-tris [anilino- (p-carbo-2'-ethyl-1'-hexyloxy)] - 1,3,5-triazine (INCI : Octyl Triazone) sold by BASF Aktiengesellschaft under the trade name UVINUL® T 150) in dissolved form, Dioctylbutylamidotriazone (INCI: diethylhexyl butamido triazone, trade name: Uvasorb HEB).
Diese zusätzlichen UV-Filtersubstanzen können erfindungsgemäß vorteilhaft in einer Gesamtkonzentration von 0,01 bis 20 Gewichts-% und erfindungsgemäß bevorzugt in einer Gesamtkonzentration von 0,5 bis 10 Gewichts-%, jeweils bezogen auf das Gesamtgewicht er Zubereitung in dieser enthalten sein.According to the invention, these additional UV filter substances may advantageously be present in a total concentration of from 0.01 to 20% by weight and, preferably, in a total concentration of from 0.5 to 10% by weight, based in each case on the total weight of the preparation.
Erfindungsgemäß besonders bevorzugt sind jedoch Zubereitungen, die außer den erfindungsgemäßen, pigmentären Lichtschutzfiltem keine weiteren UV- Lichtschutzfiltersubstanzern enthalten.However, particularly preferred according to the invention are preparations which, apart from the pigmentary sunscreen filters according to the invention, contain no further UV sunscreen filter substances.
Die ölphase der erfindungsgemäßen Zubereitungen wird vorteilhaft gewählt aus der Gruppe der polaren Lipide mit einer Polarität < 35 mN/m Besonders vorteilhafte Lipide im Sinne der vorliegenden Erfindung sind alle nativen Lipide, wie z. B. Olivenöl, Sonnenblumenöl, Sojaöl, Erdnußöl, Rapsöl, Mandelöl, Palmöl, Kokosöl, Rizinusöl, Weizenkeimöl, Traubenkemöl, Distelöl, Nachtkerzenöl, Macadamianußöl, Maiskeimöl, Avocadoöl und dergleichen sowie die im folgenden aufgelisteten. The oil phase of the preparations according to the invention is advantageously selected from the group of polar lipids having a polarity <35 mN / m. Particularly advantageous lipids in the context of the present invention are all native lipids, such as. As olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, castor oil, wheat germ oil, grape seed oil, thistle oil, evening primrose oil, macadamia nut oil, corn oil, avocado oil and the like, and those listed below.
Figure imgf000013_0001
Figure imgf000013_0001
Von den Kohlenwasserstoffen sind insbesondere Paraffinöl sowie weitere hydrierte PoIy- olefine wie hydriertes Polyisobutene, Squalan und Squalen vorteilhaft im Sinne der vor- liegenden Erfindung zu verwenden.Of the hydrocarbons, in particular paraffin oil and further hydrogenated poly olefins such as hydrogenated polyisobutenes, squalane and squalene are to be used advantageously in the context of the present invention.
Die Gehalt der Lipide wird vorteilhaft kleiner als 50 Gew.-% gewählt, bevorzugt zwischen 1 und 40 Gew.-%, insbesondere bevorzugt zwischen 5 und 15 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Zubereitung.The content of the lipids is advantageously chosen to be less than 50% by weight, preferably from 1 to 40% by weight, particularly preferably from 5 to 15% by weight, in each case based on the total weight of the preparation.
Es kann gegebenenfalls vorteilhaft sein, wenngleich es nicht zwingend ist, wenn die ölphase der Zubereitungen im Sinne der vorliegenden Erfindung auch unpolare Lipide enthält. Die Wasserphase der erfindungsgemäßen Zubereitungen kann vorteilhaft übliche kosmeti¬ sche Hilfsstoffe enthalten, wie beispielsweise Alkohole, insbesondere solche niedriger C- Zahl, vorzugsweise Ethanol und/oder Isopropanol, Diole oder Polyole niedriger C-Zahl sowie deren Ether, vorzugsweise Propylenglykol, Glycerin, Ethylenglykol, Propandiol, Ethylengly- kolmonoethyl- oder -monobutylether, Propylenglykol monomethyl, -monoethyl- oder -monobu- tylether, Diethylenglykolmonomethyl- oder -monoethylether und analoge Produkte, Polymere, Schaumstabilisatoren, Elektrolyte, Selbstbräuner sowie insbesondere ein oder mehrere Verdickungsmittel, welches oder welche vorteilhaft gewählt werden können aus der Gruppe Siliciumdioxid, Aluminiumsilikate, Polysaccharide bzw. deren Derivate, z. B. Hy- aluronsäure, Xanthangummi, Hydroxypropylmethylcellulose, besonders vorteilhaft aus der Gruppe der Polyacrylate, bevorzugt ein Polyacrylat aus der Gruppe der sogenannten Carbopole, beispielsweise Carbopole der Typen 980, 981 , 1382, 2984, 5984, jeweils einzeln oder in Kombination. Auch Verdicker, wie Permulen TR 1 , TR 2, Carbopol 1328, Aristoflex AVC, können erfindungsgemäß vorteilhaft eingesetzt werden.It may optionally be advantageous, although it is not mandatory, if the oil phase of the preparations according to the present invention also contains non-polar lipids. The aqueous phase of the preparations according to the invention may advantageously comprise customary cosmetic adjuvants, for example alcohols, in particular those of low C number, preferably ethanol and / or isopropanol, diols or polyols of low C number and their ethers, preferably propylene glycol, glycerol, ethylene glycol, Propanediol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous products, polymers, foam stabilizers, electrolytes, self-tanning agents, and in particular one or more thickeners, which are advantageously chosen can be selected from the group silicon dioxide, aluminum silicates, polysaccharides or their derivatives, for. As hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, particularly advantageous from the group of polyacrylates, preferably a polyacrylate from the group of so-called carbopols, for example Carbopols types 980, 981, 1382, 2984, 5984, each individually or in combination. Thickeners, such as Permulen TR 1, TR 2, Carbopol 1328, Aristoflex AVC, can be advantageously used according to the invention.
Die erfindungsgemäßen kosmetischen Zubereitungen können wie üblich zusammengesetzt sein. Besonders vorteilhaft im Sinne der vorliegenden Erfindung sind Zubereitungen zur Pflege der Haut: sie können dem kosmetischen Lichtschutz, ferner zur Reinigung oder Pflege der Haut und/oder der Haare und als Schminkprodukt in der dekorativen Kosmetik dienen. Eine weitere vorteilhafte Ausführungsform der vorliegenden Erfindung besteht in Af- ter-Sun-Produkten.The cosmetic preparations according to the invention can be composed as usual. Particularly advantageous in the context of the present invention are preparations for the care of the skin: they can be used for cosmetic sunscreen, for cleaning or care of the skin and / or hair and as a make-up product in decorative cosmetics. A further advantageous embodiment of the present invention is Af ter-Sun products.
Entsprechend ihrem Aufbau können kosmetische Zusammensetzungen im Sinne der vor¬ liegenden Erfindung, beispielsweise verwendet werden als Hautschutzcreme, Tages- oder Nachtcreme usw. Es ist gegebenenfalls möglich und vorteilhaft, die erfindungsgemäßen Zu¬ sammensetzungen als Grundlage für pharmazeutische Formulierungen zu verwenden.According to their structure, cosmetic compositions in the sense of the present invention can be used, for example, as a skin protection cream, day cream or night cream, etc. It may be possible and advantageous to use the compositions according to the invention as a basis for pharmaceutical formulations.
Es ist auch vorteilhaft im Sinne der vorliegenden Erfindung, kosmetische Zubereitungen zu erstellen, deren hauptsächlicher Zweck nicht der Schutz vor Sonnenlicht ist, die aber dennoch einen Gehalt an UV-Schutzsubstanzen enthalten. So werden z. B. in Tagescremes oder Makeup-Produkten gewöhnlich UV-A- bzw. UV-B-Filtersubstanzen eingearbeitet. Auch stellen UV-Schutzsubstanzen, ebenso wie Antioxidantien und, gewünschtenfalls, Kon¬ servierungsstoffe, einen wirksamen Schutz der Zubereitungen selbst gegen Verderb dar. Günstig sind ferner kosmetische Zubereitungen, die in der Form eines Sonnenschutzmittels vorliegen.It is also advantageous in the context of the present invention to prepare cosmetic preparations whose main purpose is not the protection from sunlight, but which nevertheless contain a content of UV protective substances. So z. B. in day creams or makeup products usually incorporated UV-A or UV-B filter substances. UV protectants, as well as antioxidants and, if desired, preservatives, effectively protect the preparations themselves against spoilage. Also favorable are cosmetic preparations which are in the form of a sunscreen agent.
Zur Anwendung werden die erfindungsgemäßen kosmetischen Zubereitungen in der für Kosmetika üblichen Weise auf die Haut und/oder die Haare in ausreichender Menge aufgebracht.For use, the cosmetic preparations according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics.
Die kosmetischen Zubereitungen gemäß der Erfindung können kosmetische Hilfsstoffe enthalten, wie sie üblicherweise in solchen Zubereitungen verwendet werden, z. B. Konservierungsmittel, Konservierungshelfer, Komplexbildner, Bakterizide, Parfüme, Substanzen zum Verhindern oder Steigern des Schäumens, Farbstoffe, Pigmente, die eine färbende Wirkung haben, Verdickungsmittel, anfeuchtende und/oder feuchhaltende Substanzen, Füllstoffe, die das Hautgefühl verbessern, Fette, öle, Wachse oder andere übliche Bestandteile einer kosmetischen Formulierung wie Alkohole, Polyole, Polymere, Schaumstabilisatoren, Elektrolyte, organische Lösungsmittel oder Silikonderivate.The cosmetic preparations according to the invention may contain cosmetic adjuvants, such as are commonly used in such preparations, for. Preservatives, preservatives, complexing agents, bactericides, perfumes, substances for preventing or increasing foaming, dyes, pigments which have a coloring effect, thickeners, moisturizing and / or moisturizing substances, fillers which improve the feel on the skin, fats, oils, Waxes or other common ingredients of a cosmetic formulation such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.
Vorteilhafte Konservierungsmittel im Sinne der vorliegenden Erfindung sind beispielsweise Formaldehydabspalter (wie z. B. DMDM Hydantoin, welches beispielsweise unter der Handelsbezeichnung Glydant ™ von der Fa. Lonza erhältlich ist), lodopropylbutylcarbamate (z. B. die unter den Handelsbezeichnungen Glycacil-L, Glycacil-S von der Fa. Lonza erhältlichen und/oder Dekaben LMB von Jan Dekker), Parabene (d. h. p-Hydroxy- benzoesäurealkylester, wie Methyl-, Ethyl-, Propyl- und/oder Butylparaben), Phenoxyethanol, Ethanol, Benzoesäure und dergleichen mehr. Üblicherweise umfaßt das Konser¬ vierungssystem erfindungsgemäß ferner vorteilhaft auch Konservierungshelfer, wie bei- spielsweise Ethylhexylglycerin, Glycine Soja etc.Advantageous preservatives for the purposes of the present invention are, for example, formaldehyde releasers (such as, for example, DMDM hydantoin, which is available under the trade name Glydant ™ from Lonza), iodopropyl butylcarbamates (for example those sold under the trade names Glycacil-L, Glycacil -S. From the company. Lonza available and / or Dekaben LMB from Jan Dekker), parabens (ie p-hydroxy-benzoic acid alkyl esters, such as methyl, ethyl, propyl and / or butylparaben), phenoxyethanol, ethanol, benzoic acid and the like , According to the invention, the preserving system also advantageously also includes preserving aids, such as, for example, ethylhexylglycerol, glycine soya, etc.
Vorteilhafte Komplexbildner im Sinne der vorliegenden Erfindung sind beispielsweise EDTA, [S,S]-Ethylendiamindisuccinat (EDDS), welches beispielsweise unter der Handels¬ bezeichnung Octaquest von der Fa. Octel erhältlich ist, Pentanatrium-Ethylendiamin- tetramethylenphosphonat, welches z. B. unter dem Handelsnamen Dequest 2046 von der Fa. Monsanto erhältlich ist und/oder Iminodibersteinsäure, welche u. a. von der Fa. Bayer AG unter den Handelsnamen Iminodisuccinat VP OC 370 (ca. 30% ige Lösung) und Baypure CX 100 fest erhältlich ist. Besonders vorteilhafte Zubereitungen werden ferner erhalten, wenn als Zusatz- oder Wirk¬ stoffe Antioxidantien eingesetzt werden. Erfindungsgemäß enthalten die Zubereitungen vorteilhaft eines oder mehrere Antioxidantien. Als günstige, aber dennoch fakultativ zu ver¬ wendende Antioxidantien können alle für kosmetische Anwendungen geeigneten oder gebräuchlichen Antioxidantien verwendet werden.Advantageous complexing agents for the purposes of the present invention are, for example, EDTA, [S, S] -ethylenediamine disuccinate (EDDS), which is obtainable, for example, under the trade name Octaquest from the company Octel, pentasodium ethylenediamine tetramethylenephosphonate, which, for example, B. under the trade name Dequest 2046 from the company. Monsanto is available and / or iminodisuccinic, which among other things from the company. Bayer AG under the trade name Iminodisuccinat VP OC 370 (about 30% solution) and Baypure CX 100 is permanently available. Particularly advantageous preparations are also obtained when antioxidants are used as additives or active substances. According to the invention, the preparations advantageously contain one or more antioxidants. All antioxidants which are suitable or customary for cosmetic applications can be used as inexpensive but nevertheless optional antioxidants.
Besonders vorteilhaft im Sinne der vorliegenden Erfindung können wasserlösliche Antioxi¬ dantien eingesetzt werden, wie beispielsweise Vitamine, z. B. Ascorbinsäure und deren Derivate.Particularly advantageous in the context of the present invention, water-soluble Antioxi¬ dantien can be used, such as vitamins, eg. As ascorbic acid and its derivatives.
Bevorzugte Antioxidantien sind ferner Vitamin E und dessen Derivate sowie Vitamin A und dessen Derivate.Further preferred antioxidants are vitamin E and its derivatives as well as vitamin A and its derivatives.
Die Menge der Antioxidantien (eine oder mehrere Verbindungen) in den Zubereitungen be- trägt vorzugsweise 0,001 bis 30 Gew.-%, besonders bevorzugt 0,05 bis 20 Gew.-%, insbe¬ sondere 0,1 bis 10 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitung.The amount of antioxidants (one or more compounds) in the preparations is preferably from 0.001 to 30% by weight, particularly preferably from 0.05 to 20% by weight, in particular from 0.1 to 10% by weight, based on the total weight of the preparation.
Sofern Vitamin E und/oder dessen Derivate das oder die Antioxidantien darstellen, ist vor¬ teilhaft, deren jeweilige Konzentrationen aus dem Bereich von 0,001 bis 10 Gew.-%, bezo- gen auf das Gesamtgewicht der Formulierung, zu wählen.If vitamin E and / or its derivatives are the antioxidant (s), it is advantageous to choose their respective concentrations from the range from 0.001 to 10% by weight, based on the total weight of the formulation.
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 bis 10 Gew.-%, bezogen auf das Gesamtgewicht der Formulierung, zu wählen.If vitamin A or vitamin A derivatives, or carotenes or derivatives thereof, are the antioxidant (s), it is advantageous if their respective concentrations are in the range from 0.001 to 10% by weight, based on the total weight of the formulation choose.
Es ist insbesondere vorteilhaft, wenn die kosmetischen Zubereitungen gemäß der vorlie¬ genden Erfindung kosmetische Wirkstoffe enthalten, wobei bevorzugte Wirkstoffe Antioxidantien sind, welche die Haut vor oxidativer Beanspruchung schützen können.It is particularly advantageous if the cosmetic preparations according to the present invention contain cosmetic active ingredients, preferred active substances being antioxidants which can protect the skin against oxidative stress.
Weitere vorteilhafte Wirkstoffe im Sinne der vorliegenden Erfindung sind natürliche Wirk¬ stoffe und/oder deren Derivate, wie z. B. alpha-Liponsäure, Phytoen, Niacinamid, Panthenol, D-Biotin, Coenzym Q10, alpha-Glucosylrutin, Camitin, Camosin, natürliche und/oder synthetische Isoflavonoide, Kreatin, Kreatinin, Taurin und/oder ß-Alanin sowie 8-Hexadecen- 1 ,16-dicarbonsäure (Dioic acid, CAS-Nummer 20701-68-2; vorläufige INCI-Bezeichnung Octadecendioic acid) und/oder Licochalcon A.Further advantageous active ingredients in the context of the present invention are natural active substances and / or their derivatives, such as. Alpha-lipoic acid, phytoene, niacinamide, panthenol, D-biotin, coenzyme Q10, alpha-glucosylrutin, camitine, camosine, natural and / or synthetic isoflavonoids, creatine, creatinine, taurine and / or beta-alanine, and 8-hexadecene. 1, 16-dicarboxylic acid (dioic acid, CAS number 20701-68-2, provisional INCI name octadecenedioic acid) and / or licochalcone A.
Licochalcon kann vorteilhaft auch als Bestandteil von pflanzlichen Extrakten, insbesondere von wäßrigen Radix Glycyrrhizae inflatae, eingesetzt werden.Licochalcone can also be used advantageously as a constituent of herbal extracts, in particular of aqueous radix Glycyrrhizae inflatae.
Es ist erfindungsgemäß vorteilhaft, wenn die kosmetischen Zubereitungen 0,001 bis 10 Gew.-%, insbesondere 0,05 bis 5 Gew.-%, ganz besonders 0,01 bis 2 Gew.-% an einem Extrakt aus Radix Glycyrrhizae inflatae enthalten, jeweils bezogen auf das Gesamtgewicht der Zubereitung.It is advantageous according to the invention if the cosmetic preparations contain 0.001 to 10% by weight, in particular 0.05 to 5% by weight, very particularly 0.01 to 2% by weight of an extract of Radix Glycyrrhizae inflatae, in each case on the total weight of the preparation.
Ganz besonders vorteilhaft ist es, von einem Extrakt auszugehen, der unter der Bezeichnung Polyol Soluble Licorice Extract PU (INCI-Bezeichnung Glycyrrhiza Inflata) von der Firma Maruzen zu erhalten ist. Der Extrakt aus Radix Glycyrrhizae inflatae enthält einen Anteil von ca. 25 % Licochalcone A.It is particularly advantageous to start from an extract which is obtainable from Maruzen under the name Polyol Soluble Licorice Extract PU (INCI name Glycyrrhiza Inflata). The extract of Radix Glycyrrhizae inflatae contains about 25% licochalcone A.
Erfindungsgemäße Rezepturen, welche z. B. bekannte Antifaltenwirkstoffe wie Flavon- glycoside (insbesondere α-Glycosylrutin), Coenzym Q10, Vitamin E und/oder Derivate und dergleichen enthalten, eignen sich insbesondere vorteilhaft zum Schutz vor ästhetisch unattraktiven Hautveränderungen, wie sie z. B. bei der Hautalterung auftreten (wie beispielsweise Trockenheit, Rauhigkeit und Ausbildung von Trockenheitsfältchen, Juckreiz, verminderte Rückfettung (z. B. nach dem Waschen), sichtbare Gefäßerweiterungen (Teleangiektasien, Cuperosis), Schlaffheit und Ausbildung von Falten und Fältchen, lokale Hyper-, Hypo- und Fehlpigmentierungen (z. B. Altersflecken), vergrößerte Anfälligkeit gegenüber mechanischem Stress (z. B. Rissigkeit) und dergleichen). Weiterhin vorteilhaft eignen sie sich gegen das Erscheinungsbild der trockenen bzw. rauhen Haut.Inventive formulations which z. B. known anti-wrinkle active ingredients such as flavone glycosides (especially α-glycosyl rutin), coenzyme Q10, vitamin E and / or derivatives and the like, are particularly advantageous for protection against aesthetically unattractive skin lesions, as z. Skin aging (such as dryness, roughness, dryness wrinkles, itching, decreased refatting (eg, after washing), visible vascular dilation (telangiectasia, cuperosis), slackness and wrinkle and wrinkle formation, localized hypersensitivity). , Hypo and false pigmentation (eg, age spots), increased susceptibility to mechanical stress (eg, cracking), and the like). Furthermore, they are advantageously suitable against the appearance of dry or rough skin.
Die Zubereitungen gemäß der vorliegenden Erfindung können ferner vorteilhaft auch Selbst¬ bräunungssubstanzen enthalten, wie beispielsweise Dihydroxyaceton und/oder Melaninderivate in Konzentrationen von 1 Gew.-% bis zu 8 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitung.The preparations according to the present invention can also advantageously contain self-tanning substances, for example dihydroxyacetone and / or melanin derivatives in concentrations of from 1% by weight to 8% by weight, based on the total weight of the preparation.
Ferner vorteilhaft können die Zubereitungen gemäß der vorliegenden Erfindung auch Repellenten zum Schutz vor Mücken, Zecken und Spinnen und dergleichen enthalten. Vorteilhaft sind z. B. N,N-Diethyl-3-methylbenzamid (Handelsbezeichnung: Meta-delphene, „DEET"), Dimethylphtalat (Handelsbezeichnung: Palatinol M, DMP), 1-Piperidincarbonsäure- 2-(2-hydroxyethyl)-1-methylpropylester sowie insbesondere 3-(N-n-Butyl-N-acetyl-amino)- propionsäureethylester (unter dem Handelsnamen Insekt Repellent® 3535 bei der Fa. Merck erhältlich). Die Repellenten können sowohl einzeln als auch in Kombination eingesetzt werden.Further advantageously, the preparations according to the present invention may also contain repellents for protection against mosquitoes, ticks and spiders and the like. Advantageous z. N, N-diethyl-3-methylbenzamide (trade name: meta-delphene, "DEET"), dimethyl phthalate (trade name: palatinol M, DMP), 1-piperidinecarboxylic acid 2- (2-hydroxyethyl) -1-methylpropyl ester, and especially 3- (Nn-butyl-N-acetyl-amino) -propionic acid ethyl ester (available from Merck under the tradename Insekt Repellent® 3535.) The repellents can be used either individually or in combination.
Als Moisturizer werden Stoffe oder Stoffgemische bezeichnet, welche kosmetischen Zubereitungen die Eigenschaft verleihen, nach dem Auftragen bzw. Verteilen auf der Hautoberfläche die Feuchtigkeitsabgabe der Homschicht (auch transepidermal water loss (TEWL) genannt) zu reduzieren und/oder die Hydratation der Homschicht positiv zu beeinflussen.Moisturizers are substances or mixtures of substances which give cosmetic preparations the property, after application or distribution on the skin surface, to reduce the moisture release of the hom layer (also called transepidermal water loss (TEWL)) and / or to positively influence the hydration of the initial layer ,
Vorteilhafte Moisturizer im Sinne der vorliegenden Erfindung sind beispielsweise Glycerin, Milchsäure und/oder Lactate, insbesondere Natriumlactat, Butylenglykol, Propylenglykol, Methylpropandiol, Biosaccaride Gum-1 , Glycine Soja, Ethylhexyloxyglycerin, Pyr- rolidoncarbonsäure und Harnstoff. Ferner ist es insbesondere von Vorteil, polymere Moisturizer aus der Gruppe der wasserlöslichen und/oder in Wasser quellbaren und/oder mit Hilfe von Wasser gelierbaren Polysaccharide zu verwenden. Insbesondere vorteilhaft sind beispielsweise Hyaluronsäure, Chitosan und/oder ein fucosereiches Polysaccharid, welches in den Chemical Abstracts unter der Registraturnummer 178463-23-5 abgelegt und z. B. unter der Bezeichnung Fucogel®1000 von der Gesellschaft SOLABIA S.A. erhältlich ist. Moisturizer können vorteilhaft auch als Antifaltenwirkstoffe zum Schutz kosmetischer Haut¬ veränderungen, wie sie z. B. bei der Hautalterung auftreten, verwendet werden.Advantageous moisturizers for the purposes of the present invention are, for example, glycerol, lactic acid and / or lactates, in particular sodium lactate, butylene glycol, propylene glycol, methylpropanediol, biosaccharide gum-1, glycine soya, ethylhexyloxyglycerol, pyrrolidonecarboxylic acid and urea. Furthermore, it is particularly advantageous to use polymeric moisturizers from the group of water-soluble and / or water-swellable and / or water-gellable polysaccharides. Hyaluronic acid, chitosan and / or a fucose-rich polysaccharide, for example, which are filed in the Chemical Abstracts under the registry number 178463-23-5 and z. B. under the name Fucogel®1000 from the company SOLABIA S.A. is available. Moisturizers may advantageously also be used as anti-wrinkle agents for protecting cosmetic skin changes, as described, for example, in US Pat. B. occur during skin aging, can be used.
Die erfindungsgemäßen kosmetischen Zubereitungen können ferner vorteilhaft, wenngleich nicht zwingend, Füllstoffe enthalten, welche z. B. die sensorischen und kosmetischen Eigenschaften der Formulierungen weiter verbessern und beispielsweise ein samtiges oder seidiges Hautgefühl hervorrufen oder verstärken. Vorteilhafte Füllstoffe im Sinne der vorliegenden Erfindung sind Stärke und Stärkederivate (wie z. B. Tapiocastärke, Distärkephosphat, Aluminium- bzw. Natrium-Stärke Octenylsuccinat und dergleichen), Pigmente, die weder hauptsächlich UV-Filter- noch färbende Wirkung haben (wie z. B. Bornitrid etc.) und/oder Aerosile® (CAS-Nr. 7631-86-9) und/oder Nylon 12 und/oder Covabead LH 85 und/oder Mearlmica SVA. Die nachfolgenden Beispiele sollen die vorliegende Erfindung verdeutlichen, ohne sie einzu¬ schränken. Alle Mengenangaben, Anteile und Prozentanteile sind, soweit nicht anders an¬ gegeben, auf das Gewicht und die Gesamtmenge bzw. auf das Gesamtgewicht der Zube¬ reitungen bezogen. The cosmetic preparations according to the invention may also advantageously, although not necessarily, contain fillers which are e.g. B. further improve the sensory and cosmetic properties of the formulations and, for example, cause or enhance a velvety or silky feel on the skin. Advantageous fillers for the purposes of the present invention are starch and starch derivatives (such as, for example, tapioca starch, distarch phosphate, aluminum or sodium starch, octenylsuccinate and the like), pigments which have neither mainly UV filter nor coloring action (such as, for example, US Pat. B. boron nitride etc.) and / or Aerosils ® (CAS no. 7631-86-9) and / or nylon 12 and / or 85 Covabead LH and / or Mearlmica SVA. The following examples are intended to illustrate the present invention without restricting it. All amounts, proportions and percentages are, unless stated otherwise, based on the weight and the total amount or on the total weight of Zube¬ preparations.
Beispiele W/O EmulsionExamples W / O emulsion
Figure imgf000020_0001
Figure imgf000021_0001
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Figure imgf000023_0001
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000025_0001
O/W EmulsionO / W emulsion
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000030_0001
Figure imgf000031_0001

Claims

Patentansprüche claims
1. Kosmetische Lichtschutzemulsion enthaltend organische und anorganische UV- Lichtschutzfilterpigmente in einer Konzentration von mindestens 20 Gewichts-%, bezogen auf das Gesamtgewicht der Zubereitung, dadurch gekennzeichnet, dass das Gewichtsverhältnis von anorganischen zu organischen UV-Lichtschutzfilterpigmenten von 4:1 bis 1 :4 beträgt.1. Cosmetic light protection emulsion containing organic and inorganic UV photoprotective pigments in a concentration of at least 20% by weight, based on the total weight of the preparation, characterized in that the weight ratio of inorganic to organic UV photoprotective pigments of 4: 1 to 1: 4 ,
2. Kosmetische Zubereitung nach Anspruch 1 , dadurch gekennzeichnet, dass die organischen Lichtschutzfilterpigmente gewählt werden aus der Gruppe 2,2'-Methylen- bis-(6-(2H-benzotriazol-2-yl)-4-(1 , 1 ,3,3-tetramethylbutyl)-phenol), 2,4,6-Tris- (biphenyl)-1,3,5-triazin und 2J4J6-Tris-(terphenyl)-1 ,3J5-triazin.2. Cosmetic preparation according to claim 1, characterized in that the organic sunscreen filter pigments are selected from the group of 2,2'-methylenebis (6- (2H-benzotriazol-2-yl) -4- (1, 1, 3 , 3-tetramethylbutyl) -phenol), 2,4,6-tris (biphenyl) -1,3,5-triazine and 2 J 4 J 6 -tris (terphenyl) -1,3 3 J 5-triazine.
3. Kosmetische Zubereitung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass als organische UV-Lichtschutzfilterpigmente 2,4,6-Tris- (biphenyl)-1,3,5-triazin und/oder 2,4,6-Tris-(terphenyl)-1 ,3,5-triazin eingesetzt werden. 3. Cosmetic preparation according to one of the preceding claims, characterized in that as organic UV photoprotective pigments 2,4,6-tris (biphenyl) -1,3,5-triazine and / or 2,4,6-tris ( terphenyl) -1, 3,5-triazine can be used.
4. Kosmetische Zubereitung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die organischen UV-Lichtschutzfilterpigmente in einer Gesamtkonzentration von 2 bis 10 Gewichts-%, bezogen auf das Gesamtgewicht der Zubereitung, in dieser enthalten sind. 4. Cosmetic preparation according to one of the preceding claims, characterized in that the organic UV photoprotective pigments in a total concentration of 2 to 10% by weight, based on the total weight of the preparation, are contained in this.
5. Kosmetische Zubereitung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die anorganischen Lichtschutzfilterpigmente gewählt werden aus der Gruppe der Oxide des Titans (TiO2), Zinks (ZnO), Eisens (z. B. Fe2O3), Zirkoniums (ZrO2), Siliciums (SiO2), Mangans (z. B. MnO), Aluminiums (AI2O3), Cers (z. B. Ce2O3), Mischoxide der entsprechenden Metalle sowie Abmischungen aus sol¬ chen Oxiden sowie das Sulfat des Bariums (BaSO4). 5. Cosmetic preparation according to one of the preceding claims, characterized in that the inorganic sunscreen filter pigments are selected from the group of the oxides of titanium (TiO 2 ), zinc (ZnO), iron (eg Fe 2 O 3 ), zirconium ( ZrO 2 ), silicon (SiO 2 ), manganese (for example MnO), aluminum (Al 2 O 3 ), cerium (for example Ce 2 O 3 ), mixed oxides of the corresponding metals and mixtures of such oxides and the sulfate of barium (BaSO 4 ).
6. Kosmetische Zubereitung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Zubereitung weitere UV-Lichtschutzfilter enthält. 6. Cosmetic preparation according to one of the preceding claims, characterized in that the preparation contains further UV light protection filters.
PCT/EP2005/054780 2004-09-27 2005-09-23 Sun protection emulsion comprising a high fraction of sun protection filter pigments WO2006035000A1 (en)

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