WO2004045570A1 - Light protection concentrate with water-soluble polymers - Google Patents

Light protection concentrate with water-soluble polymers Download PDF

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Publication number
WO2004045570A1
WO2004045570A1 PCT/EP2003/050831 EP0350831W WO2004045570A1 WO 2004045570 A1 WO2004045570 A1 WO 2004045570A1 EP 0350831 W EP0350831 W EP 0350831W WO 2004045570 A1 WO2004045570 A1 WO 2004045570A1
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Prior art keywords
acid
emulsion
weight
advantageous
preparation
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PCT/EP2003/050831
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German (de)
French (fr)
Inventor
Sabine Koopmann
Jens Schulz
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Beiersdorf Ag
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Priority to EP03796021A priority Critical patent/EP1565156A1/en
Publication of WO2004045570A1 publication Critical patent/WO2004045570A1/en

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    • 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
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • A61K8/731Cellulose; Quaternized cellulose derivatives
    • 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
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • 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
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • 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
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A61K8/8176Homopolymers of N-vinyl-pyrrolidones. Compositions of derivatives of such polymers
    • 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
    • A61K2800/54Polymers characterized by specific structures/properties
    • 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
    • A61K2800/56Compounds, absorbed onto or entrapped into a solid carrier, e.g. encapsulated perfumes, inclusion compounds, sustained release forms

Definitions

  • the present invention relates to a process for producing an O / W emulsion, characterized in that an O / W emulsion containing a) a lipid phase in a concentration of 20 to 95% by weight, b) one or more water-soluble polymers in one Total concentration of 1 to 80% by weight, based in each case on the total weight of the preparation, and c) one or more UV light protection filters and d) an aqueous phase, in addition to any other cosmetic and / or dermatological active ingredients, auxiliaries and additives, by spray drying and / or freeze drying.
  • the skin is the largest organ in humans. Among its many functions (for example for heat regulation and as a sensory organ), the barrier function that prevents the skin (and ultimately the entire organism) from drying out is probably the most important. At the same time, the skin acts as a protective device against the penetration and absorption of external substances and UV radiation. This barrier function is brought about by the epidermis, which as the outermost layer forms the actual protective cover against the environment. At around a tenth of the total thickness, it is also the thinnest layer of the skin.
  • Emulsions are generally understood to mean heterogeneous systems which consist of two immiscible or only to a limited extent miscible liquids, which are usually referred to as phases and in which one of the two liquids is dispersed in the form of very fine droplets in the other liquid. When viewed externally and with the naked eye, emulsions appear homogeneous.
  • the two liquids are water and oil and oil droplets are finely distributed in water, then it is an oil-in-water emulsion (O / W emulsion, e.g. milk).
  • O / W emulsion oil-in-water emulsion
  • the basic character of an O / W emulsion is characterized by the water.
  • a water-in-oil emulsion (W / O emulsion, e.g. butter) is the opposite principle, whereby the basic character is determined by the oil.
  • UVB range wavelength: 280-320 nm
  • UVB and UVA radiation wavelength: 320-400 nm
  • UVA and UVB filters summarized in most industrialized countries in the form of positive lists such as Appendix 7 of the Cosmetics Regulation.
  • the application concentrations of the ingredients are already predetermined for the consumer. An individual adaptation to the conditions at the application site is no longer possible.
  • the object is surprisingly achieved by a process for producing an O / W emulsion, characterized in that an O / W emulsion containing a) a lipid phase in a concentration of 20 to 95% by weight, 'b) one or more water-soluble Polymers in a total concentration of 1 to 80% by weight, based in each case on the total weight of the preparation, and c) one or more UV light protection filters and d) an aqueous phase, in addition to any other cosmetic and / or dermatological active ingredients, auxiliaries and additives, is dried by spray drying and / or freeze drying.
  • the lipid phase in a concentration of 25 to 90% by weight and particularly preferably in a concentration of 35 to 80 % By weight, based in each case on the total weight of the preparation, is present in the emulsion according to the invention.
  • one or more water-soluble polymers are contained in a total concentration of 5 to 70% by weight and particularly preferably in a concentration of 10 to 60% by weight, in each case based on the total weight of the emulsion.
  • the water content in the preparation after the spray and / or freeze drying is less than 8% by weight and particularly preferably less than 5% by weight, in each case based on the total weight of the dried emulsion.
  • O / W emulsions produced by such a method are also in accordance with the invention.
  • dry emulsions can be “re-emulsified” by simply adding water, that is to say that an O / W emulsion is formed again, which is usually not the case with “dried” emulsions.
  • the emulsions according to the invention have a particularly pleasant feeling on the skin and can be combined with a large number of cosmetic active ingredients, auxiliaries and additives.
  • the emulsions according to the invention contain UV light protection filters which could not previously be incorporated into re-emulsifiable emulsions.
  • the oil phase of the emulsion according to the invention ie the lipophilic organic constituents, are advantageously chosen from the group of polar oils, for example from the group of lecithins and fatty acid triglycerides, namely the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids Chain length of 8 to 24, especially 12 to 18 carbon atoms.
  • the fatty acid triglycerides can for example be advantageously selected from the group of synthetic, semi-synthetic and natural oils, such as. B.
  • cocoglyceride olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, castor oil, wheat germ oil, grape seed oil, safflower oil, evening primrose oil, macadamia nut oil and the like.
  • z. B natural waxes of animal and vegetable origin, such as beeswax and other insect waxes and berry wax, shea butter and / or lanolin (wool wax).
  • further advantageous polar oil components can also be selected from the group of esters from saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 C atoms and from the group of esters from aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 C atoms.
  • the oil phase can advantageously be selected from the group of dialkyl ethers and dialkyl carbonates.
  • pentylglykoldiheptanoat the one or more oil components from the group consisting of isoeicosane, neopentyl, propylene glycol dicaprylate / dicaprate, caprylic / capric / Diglyceryl- succinate, butylene glycol dicaprylate / dicaprate, cocoglycerides (z. B.
  • Myritol® 331 by Henkel C ⁇ 2 - 13 -Alkyllactate, Di-C ⁇ 2 - 13 -alkyl tartrate, triisostearin, dipentaerythrityl hexacaprylate / hexacaprate, propylene glycol monoisostearate, tricaprylin, dimethyl isosorbide. It is particularly advantageous if the oil phase of the formulations according to the invention has a content of C 12 -is alkyl benzoate or consists entirely of this.
  • Advantageous oil components are also e.g. B. butyl octyl salicylate (for example that available under the trade name Hallbrite BHB from CP Hall), hexadecyl benzoate and butyl octyl benzoate and mixtures thereof (Hallstar AB) and / or diethyl hexyl naphthalate (Corapan®TQ from Haarmann & Reimer).
  • B. butyl octyl salicylate for example that available under the trade name Hallbrite BHB from CP Hall
  • hexadecyl benzoate and butyl octyl benzoate and mixtures thereof Hallstar AB
  • Diethyl hexyl naphthalate Corapan®TQ from Haarmann & Reimer
  • the lipid phase can contain the polar oil components in a concentration of up to 80% by weight based on the total weight of the lipid phase.
  • the weight given relates to the composition of the preparation before drying by means of freeze and / or spray drying.
  • the oil phase can also advantageously also contain non-polar oils, for example those selected from the group of branched and unbranched hydrocarbons and waxes, in particular mineral oil, petroleum jelly (petrolatum), paraffin oil, squalane and squalene, polyolefins, hydrogenated polyisobutenes and isohexa- decane.
  • non-polar oils for example those selected from the group of branched and unbranched hydrocarbons and waxes, in particular mineral oil, petroleum jelly (petrolatum), paraffin oil, squalane and squalene, polyolefins, hydrogenated polyisobutenes and isohexa- decane.
  • non-polar oils for example those selected from the group of branched and unbranched hydrocarbons and waxes, in particular mineral oil, petroleum jelly (petrolatum), paraffin oil, squalane and squalene, polyolefins, hydrogenated polyisobutenes and isohex
  • the non-polar oil components can advantageously be present in the emulsions according to the invention in a concentration of up to 80% by weight, based on the total weight of the lipid phase.
  • the weight specification refers to the Composition of the preparation before drying by freeze and / or spray drying.
  • the oil phase can advantageously also have a content of cyclic or linear silicone oils or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or the silicone oils.
  • Silicone oils are high-molecular synthetic polymeric compounds in which silicon atoms are linked in a chain and / or network-like manner via oxygen atoms and the remaining valences of silicon by hydrocarbon residues (mostly methyl, more rarely ethyl, propyl, phenyl groups, etc.) are saturated.
  • the silicone oils are systematically referred to as polyorganosiloxanes.
  • the methyl-substituted polyorganosiloxanes which are the most important compounds of this group in terms of quantity and are characterized by the following structural formula
  • Dimethicone is available in different chain lengths or with different molecular weights.
  • Particularly advantageous polyorganosiloxanes for the purposes of the present invention are, for example, dimethylpolysiloxanes [polydimethylsiloxane)], which are available, for example, under the trade names Abil 10 to 10,000 from Th. Goldschmidt.
  • Phenylmethylpolysiloxanes INCI: phenyl dimethicone, phenyl trimethicone
  • cyclic silicones octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane
  • cyclomethicones are also advantageous, amino-modified silicones (INCI: amodimethicone and silicone wax).
  • polysiloxane-polyalkylene copolymers (INCI: stearyl dimethicone and cetyl dimethicone) and dialkoxydimethyl polysiloxanes (stearoxy dimethicone and behenoxy stearyl dimethicone), which are available as different Abil-Wax types from Th. Goldschmidt.
  • other silicone oils can also be used advantageously for the purposes of the present invention, for example Cetyldimethicone, hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).
  • Silicones which are particularly preferred according to the invention are dimethicone and cyclomethicone.
  • the silicone oil content of the lipid phase can advantageously be 20 to 100% by weight and particularly preferably 30 to 60% by weight, in each case based on the total weight of the lipid phase.
  • Water-soluble polymers which are advantageous according to the invention can advantageously be inventively selected from the group of water-soluble or dispersible film-formers (for example polyurethanes, dimethicone copolyol polyacrylates, polyvinylpyrrolidone-vinyl acetates PVP / VA, polyvinylpyrrolidones (PVP), see below) and from the group of hydrocolloids (for example Agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, polysaccharide-N-alkyl urethanes, inulin carbamates, gelatin, casein, cellulose ethers, hydroxyethyl and - propyl cellulose derivatives, polysaccharide derivatives , Polyacrylic and polymethacrylic compounds, ammonium acryloyldimethyl taurates / vinyl
  • Hydrocolloids preferred according to the invention are, for example, methyl celluloses, as the methyl ethers of cellulose are referred to. They are characterized by the following structure
  • R can represent a hydrogen or a methyl group.
  • cellulose mixed ethers which are generally also referred to as methyl celluloses and which, in addition to a dominant content of methyl, also contain 2-hydroxyethyl, 2-hydroxypropyl or 2-hy- contain droxybutyl groups.
  • Particularly preferred hydroxypropylmethyl celluloses (HPMC) have an average molar mass M m ⁇ 50,000 g mol "1 and are, for example, under the name Pharmacoat 603, Pharmacoat 606 and Pharmacoat 645 or under the name Metolose 65 SH 50 or Metolose 60 SH 50 from FA Shin Etsu available.
  • (hydroxypropyl) methyl celluloses for example those sold under the trade name Methocel E4M by Dow Chemical Comp. available.
  • sodium carboxymethyl cellulose the sodium salt of the glycolic acid ether of cellulose, for which R in structural formula I can be a hydrogen and / or CH2-COONa.
  • R in structural formula I can be a hydrogen and / or CH2-COONa.
  • Particularly preferred is the sodium carboxymethyl cellulose available under the trade name Natrosol Plus 330 CS from Aqualon, also referred to as cellulose gum.
  • O / W emulsion according to the invention contains water-soluble cosmetic and / or dermatological active ingredients, auxiliaries and / or additives.
  • an O / W emulsion according to the invention is the process for producing an O / W emulsion according to the invention, which is characterized in that an O / W emulsion according to the invention dried by spray drying and / or freeze drying in a mixing device with water-soluble and / or volatile active, auxiliary and / or additives are mixed.
  • volatile means that these compounds have a boiling point of at most 30 ° C.
  • the emulsion according to the invention can thus contain water-soluble and / or water-dispersible ingredients according to the invention. These are advantageously added to the preparation according to the invention after freeze or spray drying.
  • the emulsion according to the invention can contain water-soluble ingredients according to the invention, for example alcohols, diols or polyols of low C number, and their ethers, preferably ethanol, isopropanol, propylene glycol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or mono butyl ether, diethylene glycol monomethyl or monoethyl ether and analog products.
  • water-soluble ingredients according to the invention for example alcohols, diols or polyols of low C number, and their ethers, preferably ethanol, isopropanol, propylene glycol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol
  • the emulsions can contain one or more polyols selected from the group sorbitol, propylene glycol and butylene glycol.
  • the polyols which are particularly preferred according to the invention are sorbitol and mannitol.
  • the cosmetic and / or dermatological emulsion according to the invention has a total amount of polyols of 5.0 to 40.0% by weight, preferably 7.5 to 35.0% by weight and very particularly preferably from 10.0 to 25.0% by weight, based in each case on the total weight of the preparation.
  • the weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying.
  • the emulsion according to the invention is advantageously used as a sunscreen. It is also advantageous for the purposes of the present invention to produce cosmetic and dermatological preparations, the main purpose of which is not protection from sunlight, but which nevertheless contain UV protection substances. So z.
  • UV-A or UV-B filter substances are usually incorporated into day creams or makeup products. UV protection substances, like antioxidants and, if desired, preservatives, also provide effective protection of the preparations themselves against spoilage.
  • cosmetic and dermatological preparations which are in the form of a sunscreen are favorable.
  • the preparations in the sense of the present invention preferably contain at least one UV-A and / or UV-B filter substance.
  • the formulations can, although not necessary, optionally also contain one or more organic and / or inorganic pigments as UV filter substances.
  • Preferred inorganic pigments are metal oxides and / or other metal compounds which are sparingly soluble or insoluble in water, in particular oxides of titanium (Ti0 2 ), zinc (ZnO), iron (e.g. Fe 2 0 3 ), zirconium (Zr0 2 ), silicon ( Si0 2 ), manganese (e.g. MnO), aluminum (Al 2 0 3 ), cerium (e.g. Ce 2 0 3 ), mixed oxides of the corresponding metals and mixtures of such oxides, as well as the sulfate of barium (BaS0 ).
  • the titanium dioxide pigments can be present both in the rutile and anatase crystal modification and, for the purposes of the present invention, can advantageously be surface-treated (“gecoatef”), for example forming or maintaining a hydrophilic, amphiphilic or hydrophobic character.
  • This surface treatment can consist in that the pigments are provided with a thin hydrophilic and / or hydrophobic inorganic and / or organic layer by methods known per se.
  • the various surface coatings can also contain water.
  • Coated and uncoated titanium dioxides described can also be used in the form of the present invention in the form of commercially available oily or aqueous predispersions. Dispersing aids and / or solubilizing agents can advantageously be added to these predispersions.
  • the titanium dioxides according to the invention are distinguished by a primary particle size between 10 nm to 150 nm.
  • titanium dioxides are the MT-100 Z and MT-100 TV from Tayca Corporation, Eusolex T-2000 and Eusolex TS from Merck and the titanium dioxide T 805 from Degussa.
  • zinc oxides can also be used in the form of commercially available oily or aqueous predispersions.
  • Draw suitable zinc oxide particles and predispersions of zinc oxide particles according to the invention are characterized by a primary particle size of ⁇ 300 nm and are available under the following trade names from the companies listed:
  • Z-Cote HP1 from BASF and zinc oxide NDM from Haarmann & Reimer are particularly preferred zinc oxides for the purposes of the invention.
  • the total amount of one or more inorganic pigments in the finished cosmetic preparation is advantageously selected from the range 0.1% by weight to 25% by weight, preferably 0.5% by weight to 18% by weight.
  • An advantageous organic pigment for the purposes of the present invention is 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol) [INCI: bisoctyl-triazole], which is available under the trade name Tinosorb® M from CIBA-Chemicals GmbH.
  • UV-A filter substances for the purposes of the present invention are dibenzoyl methane derivatives, in particular 4- (tert-butylH'-red n ° xydibenzoyl methane (CAS No. 70356-09-1), which is available from Givaudan under the Parsol brand ® 1789 and is sold by Merck under the trade name Eusolex® 9020.
  • 4- tert-butylH'-red n ° xydibenzoyl methane
  • UV-A filter substances are the phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and its salts, especially the corresponding sodium, potassium or triethanolammonium salts , in particular the phenylene-1,4-bis- (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt with the INCI name bisimidazylate, which is available, for example, under the trade name Neo Heliopan AP from Haarmann & Reimer is available.
  • 1,4-di (2-oxo-10-sulfo-3-bornylidenemethyl) benzene and its salts especially the corresponding 10-sulfato compounds, especially the corresponding sodium, potassium or triethanolammonium salt
  • benzene-1,4-di (2-oxo-3-bornylidenemethyl-10-surfonic acid especially the corresponding sodium, potassium or triethanolammonium salt
  • UV-A filter substances are hydroxybenzophenones, which are characterized by the following structural formula:
  • R 1 and R 2 independently of one another are hydrogen, -CC-C2o-alkyl, C 3 -C -o-cycloalkyl or C 3 -C- 0 -cycloalkenyl, the substituents R 1 and R 2 together with the nitrogen atom to which they are bound , can form a 5- or 6-ring and
  • R 3 is a C 1 -C 2 o-alkyl radical.
  • a particularly advantageous hydroxybenzophenone in the sense of the present invention is 2- (4'-diethylamino-2'-hydoxybenzoyl) benzoic acid hexyl ester (also: aminobenzophenone), which is characterized by the following structure:
  • UV filter substances in the sense of the present invention are also so-called broadband filters, ie filter substances that absorb both UV-A and UV-B radiation.
  • Advantageous broadband filters or UV-B filter substances are, for example, bis-resorcinyltriazine derivatives with the following structure:
  • R 1 , R 2 and R 3 are independently selected from the group of branched and unbranched alkyl groups having 1 to 10 carbon atoms or represent a single hydrogen atom. Particularly preferred are the 2,4-bis - ⁇ [4- (2-ethylhexyloxy) -2-hydroxy] phenyl ⁇ -6- (4-methoxyphenyl) -1,3,5-triazine (INCI: Aniso triazine ), which is available under the trade name Tinosorb® S from CIBA-Chemicals GmbH.
  • Particularly advantageous preparations within the meaning of the present invention which are distinguished by a high or very high UV-A protection, preferably contain a plurality of UV-A and / or broadband filters, in particular dibenzoylmethane derivatives [for example 4- (tert-butyl) -4 , -methoxydibenzoylmethane], benzotriazole derivatives [for example 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1, 1, 3,3-tetramethylbutyl) phenol )], Phenylene-1,4-bis (2-benzimidazyl) -3 > 3'-5,5'-tetrasulfonic acid and / or its salts, the 1,4-di (2-oxo-10-sulfo-3 -bomylidene-methyl) -benzene and / or its salts and / or the 2,4-bis - ⁇ [4- (2-ethylhexy
  • UV filter substances which the structural motif
  • R is a branched or unbranched CC 18 alkyl, C 5 -C 12 cycloalkyl radical optionally substituted with one or more C 4 - alkyl groups ⁇ represents,
  • X represents an oxygen atom or an NH group
  • t is a branched or unbranched CC ⁇ alkyl radical, a C 5 -C 12 cycloalkyl radical, optionally substituted with one or more dC 4 alkyl groups, or a hydrogen atom, an alkali metal atom Ammonium group or a 'group of formula means in which
  • A represents a branched or unbranched CrC 18 alkyl radical, a C 5 -C 2 cycloalkyl or aryl radical, optionally substituted by one or more CC 4 alkyl groups
  • R 3 represents a hydrogen atom or a methyl group
  • n is a number 1 to 10 represents a branched or unbranched C 1 -C 8 alkyl radical, a C 5 -Ci2 cycloalkyl radical, optionally substituted with one or more dC - alkyl groups, when X represents the NH group, and a branched or unbranched CC 18 alkyl radical, a C 5 -C 2 cycloalkyl radical, optionally substituted with one or more CC 4 alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of the formula
  • A represents a branched or unbranched Ci-C-i ⁇ -alkyl radical, a Cs-C ⁇ - 2 cycloalkyl or aryl radical, optionally substituted with one or more C 1 -C 4 alkyl groups,
  • R 3 represents a hydrogen atom or a methyl group
  • n represents a number from 1 to 10 when X represents an oxygen atom.
  • a particularly preferred UV filter substance in the sense of the present invention is also an asymmetrically substituted s-triazine, the chemical structure of which is represented by the formula
  • dioctylbutylamidotriazon (INCI: dioctylbutamidotriazone) and is available under the trade name UVASORB HEB from Sigma 3V.
  • Also advantageous in the sense of the present invention is a symmetrically substituted s-triazine, the 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) -t'is-benzoic acid tris ( 2-ethylhexyl ester), synonymous: 2,4,6-tris [anilino- (p-carbo-2'-ethyl-1'-hexyloxy)] - 1,3,5-triazine (INCI: octyl triazone) , which is sold by BASF Aktiengesellschaft under the trade name UVINUL® T 150.
  • European laid-open specification 775698 also describes bis-resorcinyltriazine derivatives which are preferably to be used and whose chemical structure is represented by the generic formula
  • Ri, R 2 and Ai represent a wide variety of organic radicals.
  • An advantageous broadband filter in the sense of the present invention is the 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol), which is available under the trade name Tinosorb® M from CIBA-Chemicals GmbH.
  • Another advantageous broadband filter for the purposes of the present invention is 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1,3,3,3-tetramethyl-1 - [( trimethylsilyl) oxy] disiloxanyl] propyl] phenol (CAS No .: 155633-54-8) with the INCI name Drometrizole Trisiloxane.
  • the UV-B and / or broadband filters can be oil-soluble or water-soluble.
  • Advantageous oil-soluble UV-B and / or broadband filter substances are e.g. B .:
  • 3-benzylidene camphor derivatives preferably 3- (4-methylbenzylidene) camphor, 3-benzylidene camphor;
  • 4-aminobenzoic acid derivatives preferably 4- (dimethylamino) benzoic acid (2-ethylhexyl) ester, 4- (dimethylamino) benzoic acid amyl ester;
  • esters of benzalmalonic acid preferably 4-methoxybenzalmalonic acid di (2-ethylhexyl) este ⁇
  • esters of cinnamic acid preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-methoxycinnamic acid isopentyl ester;
  • benzophenone preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone
  • Advantageous water-soluble UV-B and / or broadband filter substances are e.g. B .:
  • a further light protection filter substance according to the invention to be used advantageously is ethylhexyl-2-cyano-3,3-diphenylacrylate, obtainable (octocrylene) from BASF under the name Uvinul ® N 539th
  • a particularly preferred benzoxazole derivative according to the invention is 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) -imino] -6- (2-ethylhexyl) -imino-1 , 3,5-triazine with CAS No. 288254-16-0, which is characterized by the structural formula
  • the preparations according to the invention advantageously contain the substances which absorb UV radiation in the UV-A and / or UV-B range in a total amount of, for. B. 0.1 wt .-% to 80 wt .-%, preferably 0.5 to 70 wt .-%, in particular 1.0 to 60 wt .-%, each based on the total weight of the preparations to cosmetic preparations To provide that protect the hair or skin from the entire range of ultraviolet radiation. They can also serve as sunscreens for the hair or skin.
  • the weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying.
  • the weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying.
  • Particularly preferred embodiments of the present invention contain one or more triazine derivatives, dibenzoylmethane derivatives, UV filters which are liquid at room temperature and / or inorganic pigments, in particular titanium dioxide, as UV filters.
  • film formers may also be advantageous to incorporate film formers into the emulsion according to the invention, for example in order to improve the water resistance of the preparations or to increase the UV protection performance (UV-A and / or UV-B boosting).
  • Both water-soluble or dispersible and fat-soluble film formers are suitable, in each case individually or in combination with one another.
  • Advantageous water-soluble film formers are e.g. B., the film formers from the group of polymers based on polyvinylpyrrolidone (PVP)
  • copoly of polyvinylpyrrolidone for example the PVP hexadecene copolymer and the PVP eicosen copolymer, which are available under the trade names Antaron V216 and Antaron V220 from GAF Chemicals Cooperation, as well as the Tricontayl PVP and the like.
  • the usual antioxidants can be used in the emulsion.
  • the antioxidants are advantageously selected from the group consisting of amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-camosine, L- Camosin and its derivatives (e.g. anserine), carotenoids, carotenes (e.g. ⁇ -carotene, ⁇ -carotene, lycopene) and their derivatives, aurothioglucose, propylthiouracil and other thiols (e.g.
  • amino acids eg glycine, histidine, tyrosine, tryptophan
  • imidazoles eg urocanic acid
  • peptides such as D, L-carnosine, D-camosine, L- Camosin and its derivatives (e.g. anserine)
  • ⁇ -hydroxy fatty acids palmitic acid, phytin acid, lactoferrin
  • ⁇ -hydroxy acids e.g. citric acid, lactic acid, malic acid
  • humic acid e.g. citric acid, lactic acid, malic acid
  • bile acid e.g. bile extracts
  • bilirubin biliverdin
  • EDTA EDTA
  • EGTA unsaturated fatty acids and their derivatives
  • the amount of the antioxidants (one or more compounds) in the preparations is preferably 0.001 to 30% by weight, particularly preferably 0.025-6.0% by weight, in particular 0.05-3.0% by weight, based on the total weight of the preparation.
  • the weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying.
  • vitamin A or vitamin A derivatives or carotenes or their derivatives represent the antioxidant or antioxidants
  • the weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying.
  • vitamin E and / or its derivatives represent the antioxidant or antioxidants, it is advantageous to choose their respective concentrations from the range from 0.001 to 30% by weight, based on the total weight of the formulation.
  • the weights relate to the composition of the preparation before drying by means of freeze and / or spray drying.
  • active ingredients in the sense of the present invention are natural active ingredients and / or their derivatives, such as. B. alpha-lipoic acid, phytoene, D-biotin, coenzyme Q10, alpha-glucosyl rutin, carnitine, carnosine, natural and / or synthetic isoflavonoids, creatine, fumaric acid ester, ectoine and its derivatives, taurine, and / or ß-alanine.
  • active ingredients can be contained in a concentration of 0.001 to 30% by weight, based on the total weight of the emulsion.
  • the weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying.
  • Recipes according to the invention which, for. B. known anti-wrinkle active ingredients such as flavone glycosides (especially ⁇ -glycosylrutin), coenzyme Q10, vitamin E and / or derivatives and the like are particularly suitable for the prophylaxis and treatment of cosmetic or dermatological skin changes, such as z. B. occur with skin aging (such as dryness, roughness and formation of dry lines, itching, reduced re-greasing (e.g. after washing), visible vasodilation (telangiectasia, cuperosis), flaccidity and formation of wrinkles and fine lines, local hyper- , Hypo and incorrect pigmentation (e.g. age spots), increased susceptibility to mechanical stress (e.g. cracking) and the like). They are also advantageous against the appearance of dry or rough skin.
  • compositions according to the invention include, for example, panthenol, allantoin, tannin, antihistamines (e.g. loratadine, cetirizine, dimetionden, clemastine, capsaicin, HR antagonists, tannin preparations), local anesthetics, opiate antagonists (e.g. naltrexone, naloxone), anti-inflammatory drugs, e.g.
  • Plant active ingredients such as azulene and bisabolol, glycyrrhizin, hamamelin and plant extracts such as chamomile, aloe vera, hamazelis, licorice root.
  • the vitamin D 3 analogues tacalcitol, calcipotriol, tacalcitol, colecalciferol and calcitrol (vitamin D 3 ) and / or fumaric acid esters can also be successful be incorporated into the preparations.
  • These active ingredients can be contained in a concentration of 0.001 to 30% by weight, based on the total weight of the emulsion.
  • the weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying.
  • 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, biosaccaride Gum-1, glycine soybean, 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-gelable polysaccharides.
  • the preparations according to the invention can advantageously contain solid carriers in the form of microfine solid particles. According to the invention, these can advantageously be surface-repellent treated (“gecoatef”), an amphiphilic character of these solid particles being formed or to be retained.
  • the surface treatment can consist in that the solid particles are provided with a thin hydrophobic or hydrophilic layer by methods known per se.
  • the average particle diameter of the microfine solid carrier used as stabilizer is preferably chosen to be less than 100 ⁇ m, particularly advantageously less than 50 ⁇ m. It is essentially irrelevant in which form (platelets, rods, beads, etc.) or modification the solid particles used are present.
  • the microfine solid supports are preferably selected from the group of amphiphilic metal oxide pigments.
  • the following are particularly advantageous: • Titanium dioxides (coated and uncoated): e.g. B. Eusolex T-2000 from Merck, titanium dioxide MT-100 Z from Tayca Corporation
  • microfine solid carriers are selected from the following group: boron nitrides, starch derivatives (Tapioca Starch, Sodium Com Starch octynyl succinate etc.), talc, latex particles.
  • the microfine solid particles are advantageously used in a concentration of 0.5 to 60% by weight, preferably in a concentration of 1 to 50% by weight and particularly preferably in a concentration of 3 to 30% by weight, in each case based on the total weight of the Preparation used.
  • the weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying.
  • the cosmetic or dermatological preparations according to the invention can furthermore advantageously, although not necessarily, contain fillers which, for. B. further improve the sensory and cosmetic properties of the formulations and, for example, cause or intensify a velvety or silky feeling on the skin.
  • Advantageous fillers for the purposes of the present invention are starch and starch derivatives (such as tapioca starch, distarch phosphate, aluminum or sodium starch, octenyl succinate and the like), pigments which have neither mainly UV filter nor coloring effects (such as e.g. B. boron nitride etc.) and / or Aerosile ® (CAS No. 7631-86-9).
  • compositions according to the invention optionally contain the additives customary in cosmetics, for example perfume, colorants, antimicrobial substances, refatting agents, complexing and sequestering agents, pearlescent agents, plant extracts, vitamins, active ingredients, preservatives, bactericides, repellents, Self-tanners (e.g. DHA), depigmenting agents (e.g.
  • 8-hexadecen-1,16-dicarboxylic acid (dioic acid, CAS number 20701-68-2; provisional INCI name Octadecendioic acid)), pigments that have a coloring effect, softening, moisturizing and / or moisturizing substances, or other usual components of a cosmetic or dermatological formulation such as emulsifiers, polymers, foam stabilizers, peeling substances (abrasives, e.g. polymer beads or powder made of polyethylene, polypropylene etc. inorganic oxides, silicates etc.), antiperspirant salts (e.g. acidic aluminum and / or aluminum / zirconium salts such as aluminum chlorohydrate and / or aluminum / zirconium chlorohydrate) and electrolytes.
  • emulsifiers emulsifiers, polymers, foam stabilizers, peeling substances (abrasives, e.g. polymer beads or powder made of polyethylene, polypropylene etc. inorgan
  • repellent active ingredients listed below are preferred:
  • repellent active ingredients for the purposes of the present invention are the active ingredients N, N-diethyl-3-methylbenzamide, 3- (N-n-butyl-N-acetylamino) propionic acid ethyl ester and dimethyl phthalate.
  • the repellent is very particularly preferably ethyl 3- (N-n-butyl-N-acetylamino) propionate.
  • Embodiments of the emulsion according to the invention which are advantageous according to the invention contain one or more repellent active ingredients in a concentration of 1-50% by weight, based on the total weight of the formulation.
  • the weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying.
  • the following can advantageously be used as self-tanners: Glycerol aldehyde, hydroxymethylglyoxal, ⁇ -dialdehyde, erythrulose, 6-aldo-D-fructose, ninhydrin, 5-hydroxy-1,4-naphthoquinone (juglone), 2-hydroxy-1,4-naphthoquinone (Lawson) and particularly preferably 1, 3-dihydroxyacetone.
  • Embodiments which are advantageous according to the invention and have at least one self-tanning substance contain these in a total concentration of 0.1 to 30% by weight, based on the total weight of the emulsion.
  • the weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying.
  • the emulsion according to the invention can advantageously contain one or more preservatives according to the invention.
  • Advantageous preservatives for the purposes of the present invention are, for example, formaldehyde releasers (such as, for example, DMDM hydantoin, which is available, for example, from Lonza under the trade name Glydant TM), iodopropyl butyl carbamates (for example those under the trade names Glycacil-L, Glycacil -S available from Lonza and / or Dekaben LMB from Jan Dekker), parabens (ie alkyl p-hydroxybenzoate such as methyl, ethyl, propyl and / or butyl paraben), phenoxyethanol, ethanol, benzoic acid and the like.
  • formaldehyde releasers such as, for example, DMDM hydantoin, which is available, for example, from Lonza under the trade name Glydant
  • the preservation system according to the invention also advantageously includes preservation aids, such as, for example, octoxyglycerol, glycine soya, etc.
  • preservation aids such as, for example, octoxyglycerol, glycine soya, etc.
  • preservatives or preservation aids such as dibromodicyanobutane (2-bromo-2-bromomethylglutarodinitrile), phenoxyethanol, 3-iodo-2-propynylbutylcarbamate, 2-bromo-2-nitro-propane-1,3-diol and imidazolidinyl - urea, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-chloroacetamide, benzalkonium chloride, benzyl alcohol, salicylic acid and salicylates.
  • dibromodicyanobutane (2-bromo-2-bromomethylglutarodinitrile)
  • phenoxyethanol 3-iodo-2-propynylbutylcarbamate
  • 2-bromo-2-nitro-propane-1,3-diol and imidazolidinyl - urea 2-chloro-2-methyl-4-isothiazolin-3-one
  • iodopropyl butyl carbamates parabens (methyl, ethyl, propyl and / or butyl paraben) and / or phenoxyethanol are used as preservatives.
  • one or more preservatives are advantageous in a concentration of 2% by weight or less than 2% by weight, preferably 1.5% by weight or less than 1.5% by weight and particularly preferably 1% by weight or less than 1% by weight , each based on the total weight of the preparation.
  • the weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying.
  • the emulsion according to the invention advantageously contains one or more conditioners.
  • Preferred conditioners according to the invention are, for example, all compounds which are described in Section 4 below in the International Cosmetic Ingredient Dictionary and Handbook (Volume 4, publisher: RC Pepe, JA Wenninger, GN McEwen, The Cosmetic, Toiletry, and Fragrance Association, 9th edition, 2002) the keywords Hair Conditioning Agents, Humectants, Skin-Condftioning Agents, Skin-Conditioning Agents-Emollient, Skin-Conditioning Agents-Humactant, Skin-Conditioning Agents-Miscellaneous, Skin-Conditioning Agents-Occlusive and Skin Protectans are all listed in the EP 0934956 (p.11-13) under water soluble conditioning agent and oil soluble conditioning agent.
  • the emulsion according to the invention can contain glitter substances and / or other effect substances.
  • hydrocolloids which are advantageous according to the invention and which can be used as water-soluble polymers according to the invention are agar agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, polysaccharide-N-alkyl urethanes, inulin carbamates, gelatin, casein, cellulose ethers, hydroxyethyl and propyl cellulose derivatives, polysaccharides, polyacrylic and polymethacrylic compounds, Ammoniumacryloyldime- thyltaurate / vinyl pyrrolidone copolymers and Ammoniumpolyacryl-dimethyltauramide, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides, polysilicic acids, clay minerals, zeolites, silicas used.
  • xanthan (CAS No. 11138-66-2), also called xanthan gum, which is an anionic heteropolysaccharide which is generally formed from corn sugar by fermentation and is isolated as the potassium salt.
  • An advantageous hydrocolloid in the sense of the present invention is he carrageenan, a gel-forming and similar to agar extract from north Atlantic, belonging to the florida red algae (Chondrus crispus and Gigartina stellata).
  • Polyacrylates are also advantageous hydrocolloids to be used in the sense of the present invention.
  • Polyacrylates which are advantageous according to the invention are acrylate-alkyl acrylate copolymers, in particular those which are selected from the group of the so-called carbomers or carbopols (Carbopol® is actually a registered trademark of NOVEON Inc.).
  • the acrylate-alkyl acrylate copolymers which are advantageous according to the invention are distinguished by the following structure:
  • R ' represents a long-chain alkyl radical and x and y numbers, which symbolize the respective stoichiometric proportion of the respective comonomers.
  • acrylate copolymers and / or acrylate-alkyl acrylate copolymers which are marketed under the trade names Carbopol® 1382, Carbopol® 981 and Carbopol® 5984, Aqua SF-1 by NOVEON Inc. or as Aculyn® 33 by International Specialty Products Corp. are available.
  • the carbomers Carbopol EDT 2001, ETD 2020 and ETD 2050 are also preferred.
  • neutralized or partially neutralized polyacrylates e.g. Carbopole from Noveon.
  • the cosmetic and / or dermatological emulsions according to the invention can contain a number of pigments.
  • the dyes and pigments can be selected from the corresponding positive list in the Cosmetics Ordinance or the EC list of cosmetic colorants. In most cases, they are identical to the colorants approved for food.
  • Advantageous color pigments are, for example, titanium dioxide, mica, iron oxides (e.g. Fe 0 3 , F ⁇ 3 ⁇ , FeO (OH)) and / or tin oxide.
  • Advantageous dyes are, for example, carmine, Berlin blue, chrome oxide green, ultramarine blue and / or manganese violet. It is particularly advantageous to choose the dyes and / or color pigments from the list below.
  • the Color Index Numbers (CIN) are taken from the Rowe Color Index, 3rd edition, Society of Dyers and Colorists, Bradford, England, 1971.
  • 2,4-dihydroxyazobenzene 1- (2'-chloro-4'-nitro-1'-phenylazo) -2-hydroxynaphthalene, ceres red
  • 2- (4-sulfo-1-naphthylazo) -1 -naphthol-4-sulfonic acid calcium salt of 2-hydroxy-1,2 "azonaphthalene-1 '-'ulfonic acid
  • aluminum salt of 1- (4-sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid aluminum salt of 1- (4-sulfo-1-naphthylazo
  • Emulsions according to the invention can contain titanium dioxides, which can be present both in the rutile and anatase crystal modification and, for the purposes of the present invention, are advantageously surface-treated (“gecoatef”), for example a hydrophilic, amphiphilic or hydrophobic character is to be formed or retained.
  • This surface treatment can consist in that the pigments are provided with a thin hydrophilic and / or hydrophobic inorganic and / or organic layer by methods known per se.
  • the various surface coatings can also contain water.
  • Inorganic surface coatings in the sense of the present invention can consist of aluminum oxide (Al 2 0 3 ), aluminum hydroxide Al (OH) 3 , or aluminum oxide hydrate (also: alumina, CAS no .: 1333-84-2), sodium hexametaphosphate (NaP0 3 ) 6 , sodium metaphosphate (NaP0 3 ) n , silicon dioxide (Si0 2 ) (also: silica, CAS No .: 7631-86-9), zirconium oxide (Zr0 2 ) or iron oxide (F ⁇ 2 ⁇ 3 ).
  • These inorganic surface coatings can occur alone, in combination and / or in combination with organic coating materials.
  • oxides, oxide hydrates or phosphates for example of the elements Al, Si, Zr, are struck in dense layers on the pigment surface.
  • the inorganic aftertreatment generally takes place in an aqueous suspension of the pigment by adding soluble aftertreatment chemicals, such as, for example, aluminum sulfate, and then precipitating the hydroxide, which is sparingly soluble in the neutral range, by specifically adjusting the pH with sodium hydroxide solution.
  • soluble aftertreatment chemicals such as, for example, aluminum sulfate
  • the coated pigments are separated from the suspension by filtration and washed carefully to remove the dissolved salts, and then the isolated pigments are dried.
  • titanium dioxides to which aluminum hydroxide has been applied to the surface, such as, for example, titanium dioxide types C47-051 and C47- 5175 available from Sun Chemical.
  • Further preferred pigments are titanium dioxides containing aluminum and / or silicon oxides are coated, such as from Krosnos Titan: Kronos 1071 and 1075 or from Kingfisher: A310.03 Mathematics Aspen.
  • Organic surface coatings in the sense of the present invention can consist of vegetable or animal aluminum stearate, vegetable or animal stearic acid, lauric acid, dimethylpolysiloxane (also: dimethicone), methylpolysiloxane (methicone), simethicone (a mixture of dimethylpolysiloxane with an average chain length of 200 to 350 dimethylsiloxane Units and silica gel) or alginic acid.
  • dimethylpolysiloxane also: dimethicone
  • methicone methylpolysiloxane
  • simethicone a mixture of dimethylpolysiloxane with an average chain length of 200 to 350 dimethylsiloxane Units and silica gel
  • alginic acid can consist of vegetable or animal aluminum stearate, vegetable or animal stearic acid, lauric acid, dimethylpolysiloxane (also: dimethicone), methylpolysiloxan
  • pearlescent pigments according to the invention include natural pearlescent pigments such as B.
  • monocrystalline pearlescent pigments such as B. bismuth oxychloride (BiOCI), layer-substrate pigments: e.g. B. mica / metal oxide
  • Pearlescent pigments are based, for example, on powdered pigments or castor oil dispersions of bismuth oxychloride and / or titanium dioxide and bismuth oxychloride and / or titanium dioxide on mica. Particularly advantageous is e.g. B. the gloss pigment listed under CIN 77163.
  • pearlescent pigment types based on mica / metal oxide are also advantageous:
  • the pearlescent pigments available from Merck under the trade names Timiron, Colorona or Dichrona are particularly preferred.
  • pearlescent pigments which are advantageous in the sense of the present invention can be obtained in numerous ways known per se.
  • other substrates besides mica can be coated with other metal oxides, such as. B. silica and the like.
  • Z are advantageous.
  • Pearlescent pigments which are produced using SiO 2 are particularly preferred. Such pigments, which can also have gonichromatic effects, are e.g. B. available under the trade name Sicopearl Fantastico from BASF.
  • the dyes and pigments can be present both individually and in a mixture and can be mutually coated, different color effects generally being produced by different coating thicknesses.
  • the total amount of dyes and coloring pigments is advantageously from the range of z. B. 0.1 wt .-% to 30 wt .-%, preferably from 0.5 to 15 wt .-%, in particular from 1.0 to 10 wt .-%, each based on the total weight of the preparations.
  • the weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying.
  • the O / W emulsion according to the invention advantageously contains one or more tablet auxiliaries. According to the invention, these can advantageously be in a concentration of 0.1 to 60% by weight, preferably in a concentration of 1 to 50% by weight and very particularly preferably in a concentration of 3 to 35% by weight, in each case based on the total weight of the preparation be used.
  • the weight data relate to the composition of the preparation, the preparation being considered to be the emulsion after freeze and / or spray drying, together with any other water-soluble and / or volatile compounds and tableting materials (including hydrogen carbonates and acids which are solid at room temperature).
  • fillers and compacting aids e.g. starch and / or cellulose derivatives
  • flow agents e.g. highly disperse silicon dioxide
  • flow control agents e.g. highly disperse silicon dioxide
  • all substances can be used that are in the H.P. Fiedler, Lexicon of auxiliaries for pharmacy, cosmetics and related areas, 5th edition, Editio Cantor Verlag, Aulendorf, 2002, under the keywords tablet binders, tablet fillers, tablet lubricants, tablet auxiliaries, tablet disintegrants, tablet Coatings are listed.
  • the preparation according to the invention contains a combination of carbonates and / or hydrogen carbonates and acids which are solid at room temperature (for example citric acid, ascorbic acid, lactic acid, tartaric acid, etc.). Strongly swelling polymers such as crosslinked polyvinylpyrrolidone can also be used advantageously according to the invention.
  • one or more hydrogen carbonates for example sodium hydrogen carbonate, potassium hydrogen carbonate
  • other water-soluble and / or and / or volatile compounds and tableting materials including hydrogen carbonates and acids solid at room temperature
  • one or more acids which are solid at room temperature are advantageous in an amount of 0.1 to 30% by weight, preferably in an amount of 0.5 to 20% by weight and particularly preferably in an amount of 0, 5 to 15% by weight, based in each case on the total weight of the preparation, the emulsion being used after the freeze and / or spray drying together with any further water-soluble and / or volatile compounds and tableting materials (including hydrogen carbonates and solid at room temperature) Acids) is considered.
  • Such an embodiment is particularly advantageous in the sense of the present invention if the emulsion according to the invention is in the form of a tablet (e.g. an effervescent tablet), since the emulsion according to the invention in this embodiment is particularly easy to re-emulsify by adding water.
  • a tablet e.g. an effervescent tablet
  • the invention is also the method for producing such a preparation, which is characterized in that the O / W emulsion according to the invention are mixed with one or more tablet auxiliaries in a mixing device.
  • According to the invention is also a method for producing tablets and / or granules, which is characterized in that an inventive Preparation is pressed or granulated in a press to form one or more tablets, and preparations which are produced by this process.
  • the process for producing a cosmetic is according to the invention, which is characterized in that a preparation according to the invention (an O / W emulsion dried by spray drying and / or freeze drying, optionally with water-soluble and / or volatile active ingredients, auxiliary additives and / or tablet auxiliaries are added and, if appropriate, was tableted or granulated) is mixed with water or emulsified in water.
  • a preparation according to the invention an O / W emulsion dried by spray drying and / or freeze drying, optionally with water-soluble and / or volatile active ingredients, auxiliary additives and / or tablet auxiliaries are added and, if appropriate, was tableted or granulated
  • Cosmetics which are produced by this method are also according to the invention.
  • Such a cosmetic according to the invention is then in the form of an ointment, cream, lotion or an emulsion foam (French mousse) or a sprayable form.
  • a cosmetic according to the invention it can advantageously be used for the treatment and care of the skin, hair and nails.
  • use as a sunscreen is preferred.
  • the examples from Table 1 are mixed homogeneously with mixtures of the water-soluble and dispersible additives (Table 2).
  • the substance mixtures (Tables 1 + 2) can be mixed with tableting and granulating aids (Table 3) and granules and / or tablets according to the invention can be produced by suitable processes.
  • Tablets 1 + 2 can be mixed with tableting and granulating aids (Table 3) and granules and / or tablets according to the invention can be produced by suitable processes.

Abstract

A method for the production of an OIW emulsion, characterized in that an O/W emulsion containing a) a lipid phase at a concentration of 20-95 wt. %, b) one or several water-soluble polymers, the overall concentration thereof being 1-80 wt. % in relation to the overall weight of the preparation, and c) one or several UV light protection filters and d) an aqueous phase, in addition to, optionally, other cosmetic and/or dermatological active ingredients, auxiliary substances and additives, are spray-dried and/or freeze-dried.

Description

Beiersdorf Aktiengesellschaft Hamburg Beiersdorf Aktiengesellschaft Hamburg
Lichtschutzkonzentrat mit wasserlöslichen PolymerenSunscreen concentrate with water-soluble polymers
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung einer O/W-Emulsion, dadurch gekennzeichnet, dass eine O/W-Emulsion enthaltend a) eine Lipidphase in einer Konzentration von 20 bis 95 Gewichts-%, b) ein oder mehrere wasserlösliche Polymere in einer Gesamtkonzentration von 1 bis 80 Gewichts-%, jeweils bezogen auf das Gesamtgewicht der Zubereitung, sowie c) ein oder mehrere UV-Lichtschutzfilter und d) eine wässrige Phase, neben gegebenenfalls weiteren kosmetischen und/oder dermatologischen Wirk-, Hilfsund Zusatzstoffen, durch Sprühtrocknung und/oder Gefriertrocknung getrocknet wird.The present invention relates to a process for producing an O / W emulsion, characterized in that an O / W emulsion containing a) a lipid phase in a concentration of 20 to 95% by weight, b) one or more water-soluble polymers in one Total concentration of 1 to 80% by weight, based in each case on the total weight of the preparation, and c) one or more UV light protection filters and d) an aqueous phase, in addition to any other cosmetic and / or dermatological active ingredients, auxiliaries and additives, by spray drying and / or freeze drying.
Der Wunsch, schön und attraktiv auszusehen, ist von Natur aus im Menschen verwurzelt. Auch wenn das Schönheitsideal im Laufe der Zeit Wandlungen erfahren hat, so ist das Streben nach einem makellosen Äußeren, immer das Ziel der Menschen gewesen. Einen wesentlichen Anteil an einem schönen und attraktiven Äußeren hat dabei der Zustand und das Aussehen der Haut und der Hautanhangsgebilde, d.h. der Haare und der Nägel.The desire to look beautiful and attractive is inherently rooted in people. Even if the ideal of beauty has changed over time, the pursuit of a flawless appearance has always been the goal of people. The condition and the appearance of the skin and the appendages of the skin have an essential part in a beautiful and attractive exterior, i.e. of hair and nails.
Die Haut ist das größte Organ des Menschen. Unter ihren vielen Funktionen (beispielsweise zur Wärmeregulation und als Sinnesorgan) ist die Barrierefunktion, die das Austrocknen der Haut (und damit letztlich des gesamten Organismus) verhindert, die wohl wichtigste. Gleichzeitig wirkt die Haut als Schutzeinrichtung gegen das Eindringen und die Aufnahme von außen kommender Stoffe und der UV-Strahlung. Bewirkt wird diese Barrierefunktion durch die Epidermis, welche als äußerste Schicht die eigentliche Schutzhülle gegenüber der Umwelt bildet. Mit etwa einem Zehntel der Gesamtdicke ist sie gleichzeitig die dünnste Schicht der Haut.The skin is the largest organ in humans. Among its many functions (for example for heat regulation and as a sensory organ), the barrier function that prevents the skin (and ultimately the entire organism) from drying out is probably the most important. At the same time, the skin acts as a protective device against the penetration and absorption of external substances and UV radiation. This barrier function is brought about by the epidermis, which as the outermost layer forms the actual protective cover against the environment. At around a tenth of the total thickness, it is also the thinnest layer of the skin.
Damit die Haut ihre biologischen Funktionen im vollen Umfang erfüllen kann, bedarf sie der regelmäßigen Reinigung und Pflege. Die Reinigung der Haut dient dabei der Entfernung von Schmutz, Schweiß und Resten abgestorbener Hautpartikel, die einen idealen Nährboden für Krankheitserreger und Parasiten aller Art bilden. Hautpflegeprodukte, in der Regel Cremes, Salben oder Lotionen, dienen meist der Befeuchtung und Rückfettung der Haut. Häufig sind ihnen Wirkstoffe zugesetzt, welche die Haut regenerieren und beispielsweise ihre vorzeitige Alterung (z.B. das Entstehen von Fältchen, Falten) verhindern und vermindern sollen.In order for the skin to fully fulfill its biological functions, it needs regular cleaning and care. The cleaning of the skin serves to remove dirt, sweat and residues of dead skin particles, which can form an ideal breeding ground for pathogens and parasites of all kinds. Skin care products, usually creams, ointments or lotions, mostly serve to moisturize and regrease the skin. Active ingredients that regenerate the skin and, for example, prevent and reduce its premature aging (for example the appearance of wrinkles, wrinkles) are often added to them.
Hautpflegeprodukte bestehen in der Regel aus Emulsionen. Unter Emulsionen versteht man im allgemeinen heterogene Systeme, die aus zwei nicht oder nur begrenzt miteinander mischbaren Flüssigkeiten bestehen, die üblicherweise als Phasen bezeichnet werden und bei denen eine der beiden Flüssigkeiten in Form feinster Tröpfchen in der anderen Flüssigkeit dispergiert ist. Äußerlich und mit bloßem Auge betrachtet erscheinen Emulsionen homogen.Skin care products usually consist of emulsions. Emulsions are generally understood to mean heterogeneous systems which consist of two immiscible or only to a limited extent miscible liquids, which are usually referred to as phases and in which one of the two liquids is dispersed in the form of very fine droplets in the other liquid. When viewed externally and with the naked eye, emulsions appear homogeneous.
Sind die beiden Flüssigkeiten Wasser und Öl und liegen Öltröpfchen fein verteilt in Wasser vor, so handelt es sich um eine öl-in-Wasser-Emulsion (O/W-Emulsion, z. B. Milch). Der Grundcharakter einer O/W-Emulsion ist durch das Wasser geprägt. Bei einer Wasser-in-öl-Emulsion (W/O-Emulsion, z. B. Butter) handelt es sich um das umgekehrte Prinzip, wobei der Grundcharakter hier durch das Öl bestimmt wird.If the two liquids are water and oil and oil droplets are finely distributed in water, then it is an oil-in-water emulsion (O / W emulsion, e.g. milk). The basic character of an O / W emulsion is characterized by the water. A water-in-oil emulsion (W / O emulsion, e.g. butter) is the opposite principle, whereby the basic character is determined by the oil.
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 the paleness towards "healthy, sporty brown skin" has been going on for years. In order to achieve this, people expose their skin to the sun's radiation, since this causes pigment formation in the sense of melanin formation. The ultraviolet radiation of sunlight has However, in addition to the acute damage (sunburn), long-term damage such as an increased risk of skin cancer occurs with excessive exposure to light from the UVB range (wavelength: 280-320 nm) 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 results in premature skin aging.
Zum Schutz der Haut wurden daher eine Reihe von Lichtschutzfiltern 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 Kosmetikverordnung zusammengefasst.To protect the skin, a number of light protection filters have therefore been developed that can be used in cosmetic preparations. These are UVA and UVB filters summarized in most industrialized countries in the form of positive lists such as Appendix 7 of the Cosmetics Regulation.
Herkömmliche kosmetische und/oder dermatologische Emulsionen, beispielsweise Sonnenschutzcremes oder -lotionen, haben aufgrund Ihres Wassergehaltes eine Reihe von Nachteilen:Conventional cosmetic and / or dermatological emulsions, for example sunscreen creams or lotions, have a number of disadvantages due to their water content:
■ Sie besitzen ein hohes Gewicht, was beim Transport zu höherem Energieverbrauch und höheren Kosten führt.■ They are heavy, which leads to higher energy consumption and higher costs during transport.
■ Sie besitzen ein größeres Volumen, was beim Transport zu geringeren Transportkapazitäten führt.■ They have a larger volume, which leads to lower transport capacities during transport.
■ Insbesondere dünnflüssige Emulsionen sind wesentlich aufwendiger zu lagern und transportieren, da die Zubereitungen „auslaufen" können.■ In particular, low-viscosity emulsions are much more difficult to store and transport because the preparations can "leak".
■ Die Anwendungskonzentrationen der Inhaltsstoffe (z.B. UV-Filterkonzentration und damit UV-Filterleistung) sind dem Verbraucher bereits vorgegeben. Eine individuelle Anpassung an die Gegebenheiten am Anwendungsort sind nicht mehr möglich.■ The application concentrations of the ingredients (e.g. UV filter concentration and thus UV filter performance) are already predetermined for the consumer. An individual adaptation to the conditions at the application site is no longer possible.
Es war daher die Aufgabe der vorliegenden Erfindung, die Nachteile des Standes der Technik zu beseitigen und eine „trockene" Emulsion sowie ein Verfahren zur Herstellung derselben zu entwickeln.It was therefore the object of the present invention to eliminate the disadvantages of the prior art and to develop a “dry” emulsion and a process for producing the same.
Überraschend gelöst wird die Aufgabe durch ein Verfahren zur Herstellung einer O/W- Emulsion, dadurch gekennzeichnet, dass eine O/W-Emulsion enthaltend a) eine Lipidphase in einer Konzentration von 20 bis 95 Gewichts-%, ' b) ein oder mehrere wasserlösliche Polymere in einer Gesamtkonzentration von 1 bis 80 Gewichts-%, jeweils bezogen auf das Gesamtgewicht der Zubereitung, sowie c) ein oder mehrere UV-Lichtschutzfilter und d) eine wässrige Phase, neben gegebenenfalls weiteren kosmetischen und/oder dermatologischen Wirk-, Hilfsund Zusatzstoffen, durch Sprühtrocknung und/oder Gefriertrocknung getrocknet wird.The object is surprisingly achieved by a process for producing an O / W emulsion, characterized in that an O / W emulsion containing a) a lipid phase in a concentration of 20 to 95% by weight, 'b) one or more water-soluble Polymers in a total concentration of 1 to 80% by weight, based in each case on the total weight of the preparation, and c) one or more UV light protection filters and d) an aqueous phase, in addition to any other cosmetic and / or dermatological active ingredients, auxiliaries and additives, is dried by spray drying and / or freeze drying.
Dabei ist es erfindungsgemäß bevorzugt, wenn die Lipidphase in einer Konzentration von 25 bis 90 Gewichts-% und besonders bevorzugt in einer Konzentration von 35 bis 80 Gewichts-%, jeweils bezogen auf das Gesamtgewicht der Zubereitung, in der erfindungsgemäßen Emulsion enthalten ist.It is preferred according to the invention if the lipid phase in a concentration of 25 to 90% by weight and particularly preferably in a concentration of 35 to 80 % By weight, based in each case on the total weight of the preparation, is present in the emulsion according to the invention.
Es ist des weiteren erfindungsgemäß bevorzugt, wenn ein oder mehrere wasserlösliche Polymere in einer Gesamtkonzentration von 5 bis 70 Gewichts-% und besonders bevorzugt in einer Konzentration von 10 bis 60 Gewichts-%, jeweils bezogen auf das Gesamtgewicht der Emulsion enthalten sind.It is further preferred according to the invention if one or more water-soluble polymers are contained in a total concentration of 5 to 70% by weight and particularly preferably in a concentration of 10 to 60% by weight, in each case based on the total weight of the emulsion.
Ferner ist es erfindungsgemäß bevorzugt, wenn der Wassergehalt in der Zubereitung nach der Sprüh- und/oder Gefriertrocknung weniger als 8 Gewichts-% und besonders bevorzugt weniger als 5 Gewichts-%, jeweils bezogen auf das Gesamtgewicht der getrockneten Emulsion beträgt.Furthermore, it is preferred according to the invention if the water content in the preparation after the spray and / or freeze drying is less than 8% by weight and particularly preferably less than 5% by weight, in each case based on the total weight of the dried emulsion.
Auch sind nach einem derartigen Verfahren hergestellte O/W-Emulsionen erfindungsgemäß.O / W emulsions produced by such a method are also in accordance with the invention.
Überraschend ist insbesondere, dass sich die trockenen Emulsionen durch einfachen Zusatz von Wasser „reemulgieren" lassen, das heißt, dass wieder eine O/W-Emulsion ausgebildet wird, was für gewöhnlich bei „eingetrockneten" Emulsionen nicht der Fall ist.It is particularly surprising that the dry emulsions can be “re-emulsified” by simply adding water, that is to say that an O / W emulsion is formed again, which is usually not the case with “dried” emulsions.
Zwar beschreiben Y. Kawashima et al [Int. J. Pharmazeut, 86 (1992) 25-33, Drug Development and Industrial Pharmacy, 18(9), 919-937 (1992) und Chem. Pharm. Bull. 39(6) 1528-1531 (1991)] sowie H.G. Kristensen et al. [Euro. J. Pharmaceutis and Biopharmaceutics 53 (2002) 147-153 und Int. J. Pharmaceutics 212 (2001) 187-194, 195- 202] getrocknete, redispergierbare Emulsionen. Auch diese Emulsionen werden mit Hilfe von Hydroxypropylmethylcellulose stabilisiert. Doch sind die dort beschriebenen Emulsionen bei weitem nicht so komplex aufgebaut wie kosmetische und/oder dermatologische Emulsionen. Daher konnten diese Schriften keinen Weg zur vorliegenden Erfindung weisen. Die erfindungsgemäßen Emulsionen weisen gegenüber den bisher bekannten, redispergierbaren Emulsionen ein besonders angenehmes Hautgefühl auf und lassen sich mit einer Vielzahl kosmetischer Wirk-, Hilfs- und Zusatzstoffen kombinieren. So enthalten die erfindungsgemäßen Emulsionen UV- Lichtschutzfilter, die sich bisher nicht in reemulgierbare Emulsionen einarbeiten ließen. Die Ölphase der erfindungsgemäßen Emulsion, d.h. die lipophilen organischen Bestandteile, werden vorteilhaft gewählt aus der Gruppe der polaren Öle, beispielsweise aus der Gruppe der Lecithine und der Fettsäuretriglyceride, namentlich der Triglycerin- ester gesättigter und/oder ungesättigter, verzweigter und/oder unverzweigter Alkancarbonsauren einer Kettenlänge von 8 bis 24, insbesondere 12 bis 18 C-Atomen. Die Fettsäuretriglyceride können beispielsweise vorteilhaft gewählt werden aus der Gruppe der synthetischen, halbsynthetischen und natürlichen Öle, wie z. B. Cocoglycerid, Olivenöl, Sonnenblumenöl, Sojaöl, Erdnußöl, Rapsöl, Mandelöl, Palmöl, Kokosöl, Rizinusöl, Weizenkeimöl, Traubenkernol, Distelöl, Nachtkerzenöl, Macadamianußöl und dergleichen mehr.Although Y. Kawashima et al [Int. J. Pharmkonom, 86 (1992) 25-33, Drug Development and Industrial Pharmacy, 18 (9), 919-937 (1992) and Chem. Pharm. Bull. 39 (6) 1528-1531 (1991)] and HG Kristensen et al. [Euro. J. Pharmaceutis and Biopharmaceutics 53 (2002) 147-153 and Int. J. Pharmaceutics 212 (2001) 187-194, 195-202] dried, redispersible emulsions. These emulsions are also stabilized with the help of hydroxypropylmethyl cellulose. However, the emulsions described there are nowhere near as complex as cosmetic and / or dermatological emulsions. Therefore, these writings could not point to the present invention. Compared to the previously known, redispersible emulsions, the emulsions according to the invention have a particularly pleasant feeling on the skin and can be combined with a large number of cosmetic active ingredients, auxiliaries and additives. For example, the emulsions according to the invention contain UV light protection filters which could not previously be incorporated into re-emulsifiable emulsions. The oil phase of the emulsion according to the invention, ie the lipophilic organic constituents, are advantageously chosen from the group of polar oils, for example from the group of lecithins and fatty acid triglycerides, namely the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids Chain length of 8 to 24, especially 12 to 18 carbon atoms. The fatty acid triglycerides can for example be advantageously selected from the group of synthetic, semi-synthetic and natural oils, such as. B. cocoglyceride, olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, castor oil, wheat germ oil, grape seed oil, safflower oil, evening primrose oil, macadamia nut oil and the like.
Erfindungsgemäß vorteilhaft sind ferner z. B. natürliche Wachse tierischen und pflanzlichen Ursprungs, wie beispielsweise Bienenwachs und andere Insektenwachse sowie Beerenwachs, Sheabutter und/oder Lanolin (Wollwachs).According to the invention, z. B. natural waxes of animal and vegetable origin, such as beeswax and other insect waxes and berry wax, shea butter and / or lanolin (wool wax).
Weitere vorteilhafte polare Ölkomponenten können im Sinne der vorliegenden Erfindung ferner gewählt werden aus der Gruppe der Ester aus gesättigten und/oder ungesättigten, verzweigten und/oder unverzweigten Alkancarbonsauren einer Kettenlänge von 3 bis 30 C-Atomen und gesättigten und/oder ungesättigten, verzweigten und/oder unverzweigten Alkoholen einer Kettenlänge von 3 bis 30 C-Atomen sowie aus der Gruppe der Ester aus aromatischen Carbonsäuren und gesättigten und/oder ungesättigten, verzweigten und/oder unverzweigten Alkoholen einer Kettenlänge von 3 bis 30 C-Atomen. Solche Esteröle können dann vorteilhaft gewählt werden aus der Gruppe Octylpalmitat, Octylco- coat, Octylisostearat, Octyldodeceylmyristat, Octyldodekanol, Cetearylisononanoat, Isopropylmyristat, Isopropylpalmitat, Isopropylstearat, Isopropyloleat, n-Butylstearat, n- Hexyllaurat, n-Decyloleat, Isooctylstearat, Isononylstearat, Isononylisononanoat, 2-Ethyl- hexylpalmitat, 2-Ethylhexyllaurat, 2-Hexyldecylstearat, 2-Octyldodecylpalmitat, Stearyl- heptanoat, Oleyloleat, Oleylerucat, Erucyloleat, Erucylerucat, Tridecylstearat, Tridecyltri- mellitat, sowie synthetische, halbsynthetische und natürliche Gemische solcher Ester, wie z. B. Jojobaöl.In the context of the present invention, further advantageous polar oil components can also be selected from the group of esters from saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 C atoms and from the group of esters from aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 C atoms. Such ester oils can then advantageously be selected from the group octyl palmitate, octyl co-coat, octyl isostearate, octyl dodeceyl myristate, octyl dodecanol, cetearyl isononanoate, isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-stonolate, n-stonolate, n-stonyl-n-stonate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, stearyl heptanoate, oleyl oleate, olerlerucate, erucyl oleate, erucylerucate, tridecyl stearate, tridecyltrimic gemellate, as well as synthetic such as. B. Jojoba oil.
Ferner kann die Ölphase vorteilhaft gewählt werden aus der Gruppe der Dialkylether und Dialkylcarbonate, vorteilhaft sind z. B. Dicaprylylether (Cetiol OE) und/oder Dicaprylyl- carbonat, beispielsweise das unter der Handelsbezeichnung Cetiol CC bei der Fa. Cognis erhältliche.Furthermore, the oil phase can advantageously be selected from the group of dialkyl ethers and dialkyl carbonates. B. dicaprylyl ether (Cetiol OE) and / or dicaprylyl carbonate, for example that available under the trade name Cetiol CC from Cognis.
Es ist ferner bevorzugt, das oder die ölkomponenten aus der Gruppe Isoeikosan, Neo- pentylglykoldiheptanoat, Propylenglykoldicaprylat/dicaprat, Caprylic/Capric/Diglyceryl- succinat, Butylenglykol Dicaprylat/Dicaprat, Cocoglyceride (z. B. Myritol® 331 von Henkel), Cι2-13-Alkyllactat, Di-Cι2-13-Alkyltartrat, Triisostearin, Dipentaerythrityl Hexa- caprylat/Hexacaprat, Propylenglykolmonoisostearat, Tricaprylin, Dimethylisosorbid. Es ist insbesondere vorteilhaft, wenn die ölphase der erfindungsgemäßen Formulierungen einen Gehalt an C12-ιs-Alkylbenzoat aufweist oder vollständig aus diesem besteht.It is further preferred pentylglykoldiheptanoat the one or more oil components from the group consisting of isoeicosane, neopentyl, propylene glycol dicaprylate / dicaprate, caprylic / capric / Diglyceryl- succinate, butylene glycol dicaprylate / dicaprate, cocoglycerides (z. B. Myritol® 331 by Henkel), Cι 2 - 13 -Alkyllactate, Di-Cι 2 - 13 -alkyl tartrate, triisostearin, dipentaerythrityl hexacaprylate / hexacaprate, propylene glycol monoisostearate, tricaprylin, dimethyl isosorbide. It is particularly advantageous if the oil phase of the formulations according to the invention has a content of C 12 -is alkyl benzoate or consists entirely of this.
Vorteilhafte Ölkomponenten sind ferner z. B. Butyloctylsalicylat (beispielsweise das unter der Handelsbezeichnung Hallbrite BHB bei der Fa. CP Hall erhältliche), Hexadecylben- zoat und Butyloctylbenzoat und Gemische davon (Hallstar AB) und/oder Diethylhexyl- naphthalat (Corapan®TQ von Haarmann & Reimer).Advantageous oil components are also e.g. B. butyl octyl salicylate (for example that available under the trade name Hallbrite BHB from CP Hall), hexadecyl benzoate and butyl octyl benzoate and mixtures thereof (Hallstar AB) and / or diethyl hexyl naphthalate (Corapan®TQ from Haarmann & Reimer).
Auch beliebige Abmischungen solcher öl- und Wachskomponenten sind vorteilhaft im Sinne der vorliegenden Erfindung einzusetzen.Any mixtures of such oil and wax components can also be used advantageously for the purposes of the present invention.
Die Lipidphase kann die polaren Ölkomponenten erfindungsgemäß in einer Konzentration von bis zu 80 Gewichts-% bezogen auf das Gesamtgewicht der Lipidphase enthalten. Die Gewichtsangabe bezieht sich dabei auf die Zusammensetzung der Zubereitung vor der Trocknung mittels Gefrier- und/oder Sprühtrocknung.According to the invention, the lipid phase can contain the polar oil components in a concentration of up to 80% by weight based on the total weight of the lipid phase. The weight given relates to the composition of the preparation before drying by means of freeze and / or spray drying.
Ferner kann die Ölphase ebenfalls vorteilhaft auch unpolare öle enthalten, beispielsweise solche, welche gewählt werden aus der Gruppe der verzweigten und unverzweigten Kohlenwasserstoffe und -wachse, insbesondere Mineralöl, Vaseline (Petrolatum), Paraffinöl, Squalan und Squalen, Polyolefine, hydrogenierte Polyisobutene und Isohexa- decan. Unter den Polyolefinen sind Polydecene und hydrierte Polyisobutene die bevorzugten Substanzen.The oil phase can also advantageously also contain non-polar oils, for example those selected from the group of branched and unbranched hydrocarbons and waxes, in particular mineral oil, petroleum jelly (petrolatum), paraffin oil, squalane and squalene, polyolefins, hydrogenated polyisobutenes and isohexa- decane. Among the polyolefins, polydecenes and hydrogenated polyisobutenes are the preferred substances.
Die unpolaren ölkomponenten können vorteilhaft in einer Konzentration von bis zu 80 Gewichts-% bezogen auf das Gesamtgewicht der Lipidphase in den erfindungsgemäßen Emulsionen enthalten sein. Die Gewichtsangabe bezieht sich dabei auf die Zusammensetzung der Zubereitung vor der Trocknung mittels Gefrier- und/oder Sprühtrocknung.The non-polar oil components can advantageously be present in the emulsions according to the invention in a concentration of up to 80% by weight, based on the total weight of the lipid phase. The weight specification refers to the Composition of the preparation before drying by freeze and / or spray drying.
Vorteilhaft kann die ölphase ferner einen Gehalt an cyclischen oder linearen Silikonölen aufweisen oder vollständig aus solchen Ölen bestehen, wobei allerdings bevorzugt wird, außer dem Silikonöl oder den Silikonölen einen zusätzlichen Gehalt an anderen Ölpha- senkomponenten zu verwenden.The oil phase can advantageously also have a content of cyclic or linear silicone oils or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or the silicone oils.
Silikonöle sind hochmolekulare synthetische polymere Verbindungen, in denen Silicium- Atome über Sauerstoff-Atome ketten- und/oder netzartig verknüpft und die restlichen Valenzen des Siliciums durch Kohlenwasserstoff-Reste (meist Methyl-, seltener Ethyl-, Propyl-, Phenyl-Gruppen u. a.) abgesättigt sind. Systematisch werden die Silikonöle als Polyorganosiloxane bezeichnet. Die methylsubstituierten Polyorganosiloxane, welche die mengenmäßig bedeutendsten Verbindungen dieser Gruppe darstellen und sich durch die folgende Strukturformel auszeichnenSilicone oils are high-molecular synthetic polymeric compounds in which silicon atoms are linked in a chain and / or network-like manner via oxygen atoms and the remaining valences of silicon by hydrocarbon residues (mostly methyl, more rarely ethyl, propyl, phenyl groups, etc.) are saturated. The silicone oils are systematically referred to as polyorganosiloxanes. The methyl-substituted polyorganosiloxanes, which are the most important compounds of this group in terms of quantity and are characterized by the following structural formula
Figure imgf000008_0001
werden auch als Polydimethylsiloxan bzw. Dimethicon (INCI) bezeichnet. Dimethicone gibt es in verschiedenen Kettenlängen bzw. mit verschiedenen Molekulargewichten.
Figure imgf000008_0001
are also known as polydimethylsiloxane or dimethicone (INCI). Dimethicone is available in different chain lengths or with different molecular weights.
Besonders vorteilhafte Polyorganosiloxane im Sinne der vorliegenden Erfindung sind beispielsweise Dimethylpolysiloxane [Polydimethylsiloxan)], welche beispielsweise unter den Handelsbezeichnungen Abil 10 bis 10 000 bei Th. Goldschmidt erhältlich sind. Ferner vorteilhaft sind Phenylmethylpolysiloxane (INCI: Phenyl Dimethicone, Phenyl Tri- methicone), cyclische Silikone (Octamethylcyclotetrasiloxan bzw. Decamethylcyclopenta- siloxan), welche nach INCI auch als Cyclomethicone bezeichnet werden, aminomodifi- zierte Silikone (INCI: Amodimethicone) und Silikonwachse, z. B. Polysiloxan-Polyalkylen- Copolymere (INCI: Stearyl Dimethicone und Cetyl Dimethicone) und Dialkoxydimethyl- polysiloxane (Stearoxy Dimethicone und Behenoxy Stearyl Dimethicone), welche als verschiedene Abil-Wax-Typen bei Th. Goldschmidt erhältlich sind. Aber auch andere Silikonöle sind vorteilhaft im Sinne der vorliegenden Erfindung zu verwenden, beispielsweise Cetyldimethicon, Hexamethylcyclotrisiloxan, Polydimethylsiloxan, Poly(methylphenylsilo- xan).Particularly advantageous polyorganosiloxanes for the purposes of the present invention are, for example, dimethylpolysiloxanes [polydimethylsiloxane)], which are available, for example, under the trade names Abil 10 to 10,000 from Th. Goldschmidt. Phenylmethylpolysiloxanes (INCI: phenyl dimethicone, phenyl trimethicone), cyclic silicones (octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane), which according to INCI are also referred to as cyclomethicones, are also advantageous, amino-modified silicones (INCI: amodimethicone and silicone wax). B. polysiloxane-polyalkylene copolymers (INCI: stearyl dimethicone and cetyl dimethicone) and dialkoxydimethyl polysiloxanes (stearoxy dimethicone and behenoxy stearyl dimethicone), which are available as different Abil-Wax types from Th. Goldschmidt. However, other silicone oils can also be used advantageously for the purposes of the present invention, for example Cetyldimethicone, hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).
Erfindungsgemäß besonders bevorzugte Silikone sind Dimethicon und Cyclomethicon.Silicones which are particularly preferred according to the invention are dimethicone and cyclomethicone.
Der Silikonölanteil der Lipidphase kann vorteilhaft 20 bis 100 Gewichts-% und besonders bevorzugt von 30 bis 60 Gewichts-%, jeweils bezogen auf das Gesamtgewicht der Lipidphase betragen.The silicone oil content of the lipid phase can advantageously be 20 to 100% by weight and particularly preferably 30 to 60% by weight, in each case based on the total weight of the lipid phase.
Erfindungsgemäß vorteilhafte wasserlösliche Polymere können erfindungsgemäß vorteilhaft aus der Gruppe der wasserlöslichen bzw. dispergierbaren Filmbildner (z. B. Polyurethane, Dimethicone Copolyol Polyacrylate, Polyvinylpyrrolidon-Vinylacetate PVP/VA, Polyvinylpyrrolidone (PVP), siehe unten) und aus der Gruppe der Hydrokolloide (z.B. Agar-Agar, Carrageen, Tragant, Gummi arabicum, Alginate, Pektine, Polyosen, Guar-Mehl, Johannisbrotbaumkernmehl, Stärke, Dextrine, Polysaccharid-N- alkylurethane, Inulincarbamate, Gelatine, Casein, Celluloseether, Hydroxyethyl- und - propyl-cellulosederivate, Polysaccharide, Polyacryl- und Polymethacryl-Verbindungen, Ammoniumacryloyldimethyltaurate/Vinylpyrrolidoncopolymere und Ammoniumpolyacryl- dimethyltauramide, Vinylpolymere, Polycarbonsäuren, Polyether, Polyimine, Polyamide, Polykieselsäuren, Tonmineralien, Zeolithe, Kieselsäuren, siehe unten) gewählt werden.Water-soluble polymers which are advantageous according to the invention can advantageously be inventively selected from the group of water-soluble or dispersible film-formers (for example polyurethanes, dimethicone copolyol polyacrylates, polyvinylpyrrolidone-vinyl acetates PVP / VA, polyvinylpyrrolidones (PVP), see below) and from the group of hydrocolloids (for example Agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, polysaccharide-N-alkyl urethanes, inulin carbamates, gelatin, casein, cellulose ethers, hydroxyethyl and - propyl cellulose derivatives, polysaccharide derivatives , Polyacrylic and polymethacrylic compounds, ammonium acryloyldimethyl taurates / vinyl pyrrolidone copolymers and ammonium polyacrylic dimethyl tauramides, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides, polysilicic acids, clay minerals, zeolites, silicas, see below).
Erfindungsgemäß bevorzugte Hydrokolloide sind beispielsweise Methylcellulosen, als welche die Methylether der Cellulose bezeichnet werden. Sie zeichnen sich durch die folgende StruktuHydrocolloids preferred according to the invention are, for example, methyl celluloses, as the methyl ethers of cellulose are referred to. They are characterized by the following structure
Figure imgf000009_0001
in der R ein Wasserstoff oder eine Methylgruppe darstellen kann.
Figure imgf000009_0001
in which R can represent a hydrogen or a methyl group.
Insbesondere vorteilhaft im Sinne der vorliegenden Erfindung sind die im allgemeinen ebenfalls als Methylcellulosen bezeichneten Cellulosemischether, die neben einem dominierenden Gehalt an Methyl- zusätzlich 2-Hydroxyethyl-, 2-Hydroxypropyl- oder 2-Hy- droxybutyl-Gruppen enthalten. Besonders bevorzugte Hydroxypropylmethylcellulosen (HPMC) weisen eine mittlere Molmasse Mm < 50000g mol"1 auf und sind beispielsweise unter der Bezeichnung Pharmacoat 603, Pharmacoat 606 und Pharmacoat 645 oder unter der Bezeichnung Metolose 65 SH 50 bzw. Metolose 60 SH 50 bei der FA Shin Etsu erhältlich.Particularly advantageous for the purposes of the present invention are the cellulose mixed ethers, which are generally also referred to as methyl celluloses and which, in addition to a dominant content of methyl, also contain 2-hydroxyethyl, 2-hydroxypropyl or 2-hy- contain droxybutyl groups. Particularly preferred hydroxypropylmethyl celluloses (HPMC) have an average molar mass M m <50,000 g mol "1 and are, for example, under the name Pharmacoat 603, Pharmacoat 606 and Pharmacoat 645 or under the name Metolose 65 SH 50 or Metolose 60 SH 50 from FA Shin Etsu available.
Des weiteren bevorzugt sind (Hydroxypropyl)methylcellulosen, beispielsweise die unter der Handelsbezeichnung Methocel E4M bei der Dow Chemical Comp. erhältlichen.Also preferred are (hydroxypropyl) methyl celluloses, for example those sold under the trade name Methocel E4M by Dow Chemical Comp. available.
Erfindungsgemäß ferner vorteilhaft ist Natriumcarboxymethylcellulose, das Natrium-Salz des Glykolsäureethers der Cellulose, für welches R in Strukturformel I ein Wasserstoff und/oder CH2-COONa darstellen kann. Besonders bevorzugt ist die unter der Handelsbezeichnung Natrosol Plus 330 CS bei Aqualon erhältliche, auch als Cellulose Gum bezeichnete Natriumcarboxymethylcellulose.Also advantageous according to the invention is sodium carboxymethyl cellulose, the sodium salt of the glycolic acid ether of cellulose, for which R in structural formula I can be a hydrogen and / or CH2-COONa. Particularly preferred is the sodium carboxymethyl cellulose available under the trade name Natrosol Plus 330 CS from Aqualon, also referred to as cellulose gum.
Ferner ist es erfindungsgemäß, wenn eine derartige erfindungsgemäße O/W-Emulsion wasserlösliche kosmetische und/oder dermatologische Wirk-, Hilfs- und/oder Zusatzstoffe enthält.It is furthermore according to the invention if such an O / W emulsion according to the invention contains water-soluble cosmetic and / or dermatological active ingredients, auxiliaries and / or additives.
Erfindungsgemäß ist das Verfahren zur Herstellung einer erfindungsgemäßen O/W- Emulsion, welches dadurch gekennzeichnet ist, dass eine durch Sprühtrocknung und/oder Gefriertrocknung getrocknete erfindungsgemäße O/W-Emulsion in einer Mischungsvorrichtung mit wasserlöslichen und/oder leichflüchtigen Wirk-, Hilfs- und/oder Zusatzstoffen vermischt wird.According to the invention is the process for producing an O / W emulsion according to the invention, which is characterized in that an O / W emulsion according to the invention dried by spray drying and / or freeze drying in a mixing device with water-soluble and / or volatile active, auxiliary and / or additives are mixed.
Dabei bedeutet „leichtflüchtig" erfindungsgemäß, dass diese Verbindungen einen Siedepunkt von höchstens 30°C aufweisen.According to the invention, “volatile” means that these compounds have a boiling point of at most 30 ° C.
Auch eine O/W-Emulsion, die nach einem solchen Verfahren hergestellt wird, ist erfindungsgemäß.An O / W emulsion which is produced by such a process is also in accordance with the invention.
Die erfindungsgemäße Emulsion kann damit erfindungsgemäß wasserlösliche und/ oder wasserdispergierbare Inhaltsstoffe enthalten. Diese werden der erfindungsgemäßen Zubereitung dabei vorteilhaft nach der Gefrier- bzw. Sprühtrocknung zugesetzt. Die erfindungsgemäße Emulsion kann erfindungsgemäß wasserlösliche Inhaltsstoffe enthalten, beispielsweise Alkohole, Diole oder Polyole niedriger C-Zahl, sowie deren Ether, vorzugsweise Ethanol, Isopropanol, Propylenglykol, Ethylenglykol, Ethylenglykol- monoethyl- oder -monobutylether, Propylenglykolmonomethyl, -monoethyl- oder -mono- butylether, Diethylenglykolmonomethyl- oder -monoethylether und analoge Produkte.The emulsion according to the invention can thus contain water-soluble and / or water-dispersible ingredients according to the invention. These are advantageously added to the preparation according to the invention after freeze or spray drying. The emulsion according to the invention can contain water-soluble ingredients according to the invention, for example alcohols, diols or polyols of low C number, and their ethers, preferably ethanol, isopropanol, propylene glycol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or mono butyl ether, diethylene glycol monomethyl or monoethyl ether and analog products.
Die Emulsionen können ein oder mehrere Polyole gewählt aus der Gruppe Sorbitol, Propylen Glycol sowie Butylen Glycol, enthalten.The emulsions can contain one or more polyols selected from the group sorbitol, propylene glycol and butylene glycol.
Die erfindungsgemäß besonders bevorzugten Polyole sind Sorbitol und Mannitol.The polyols which are particularly preferred according to the invention are sorbitol and mannitol.
Es ist vorteilhaft im Sinne der vorliegenden Erfindung, wenn die erfindungsgemäße kosmetische und/oder dermatologische Emulsion eine Gesamtmenge an Polyolen von 5,0 bis 40,0 Gewichts-%, bevorzugt von 7,5 bis 35,0 Gewichts-% und ganz besonders bevorzugt von 10,0 bis 25,0 Gewichts-%, jeweils bezogen auf das Gesamtgewicht der Zubereitung, enthält. Die Gewichtsangaben beziehen sich dabei auf die Zusammensetzung der Zubereitung vor der Trocknung mittels Gefrier- und/oder Sprühtrocknung.It is advantageous in the sense of the present invention if the cosmetic and / or dermatological emulsion according to the invention has a total amount of polyols of 5.0 to 40.0% by weight, preferably 7.5 to 35.0% by weight and very particularly preferably from 10.0 to 25.0% by weight, based in each case on the total weight of the preparation. The weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying.
Die erfindungsgemäße Emulsion wird vorteilhaft als Sonnenschutzmittel eingesetzt. Es ist auch vorteilhaft im Sinne der vorliegenden Erfindung, kosmetische und dermatologische 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-Filtersub- stanzen eingearbeitet. Auch stellen UV-Schutzsubstanzen, ebenso wie Antioxidantien und, gewünschtenfalls, Konservierungsstoffe, einen wirksamen Schutz der Zubereitungen selbst gegen Verderb dar. Günstig sind femer kosmetische und dermatologische Zubereitungen, die in der Form eines Sonnenschutzmittels vorliegen.The emulsion according to the invention is advantageously used as a sunscreen. It is also advantageous for the purposes of the present invention to produce cosmetic and dermatological preparations, the main purpose of which is not protection from sunlight, but which nevertheless contain UV protection substances. So z. For example, UV-A or UV-B filter substances are usually incorporated into day creams or makeup products. UV protection substances, like antioxidants and, if desired, preservatives, also provide effective protection of the preparations themselves against spoilage. Furthermore, cosmetic and dermatological preparations which are in the form of a sunscreen are favorable.
Dementsprechend enthalten die Zubereitungen im Sinne der vorliegenden Erfindung vorzugsweise mindestens eine UV-A- und/oder UV-B-Filtersubstanz. Die Formulierungen können, obgleich nicht notwendig, gegebenenfalls auch ein oder mehrere organische und/oder anorganische Pigmente als UV-Filtersubstanzen enthalten. Bevorzugte anorganische Pigmente sind Metalloxide und/oder andere in Wasser schwerlösliche oder unlösliche Metallverbindungen, insbesondere Oxide des Titans (Ti02), Zinks (ZnO), Eisens (z. B. Fe203), Zirkoniums (Zr02), Siliciums (Si02), Mangans (z. B. MnO), Aluminiums (Al203), Cers (z. B. Ce203), Mischoxide der entsprechenden Metalle sowie Abmischungen aus solchen Oxiden, sowie das Sulfat des Bariums (BaS0 ).Accordingly, the preparations in the sense of the present invention preferably contain at least one UV-A and / or UV-B filter substance. The formulations can, although not necessary, optionally also contain one or more organic and / or inorganic pigments as UV filter substances. Preferred inorganic pigments are metal oxides and / or other metal compounds which are sparingly soluble or insoluble in water, in particular oxides of titanium (Ti0 2 ), zinc (ZnO), iron (e.g. Fe 2 0 3 ), zirconium (Zr0 2 ), silicon ( Si0 2 ), manganese (e.g. MnO), aluminum (Al 2 0 3 ), cerium (e.g. Ce 2 0 3 ), mixed oxides of the corresponding metals and mixtures of such oxides, as well as the sulfate of barium (BaS0 ).
Die Titandioxid- Pigmente können sowohl in der Kristallmodifikation Rutil als auch Anatas vorliegen und können im Sinne der vorliegenden Erfindung vorteilhaft oberflächlich behandelt („gecoatef) sein, wobei beispielsweise ein hydrophiler, amphiphiler oder hydrophober Charakter 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 modification and, for the purposes of the present invention, can advantageously be surface-treated (“gecoatef”), for example forming or maintaining a hydrophilic, amphiphilic or hydrophobic character. This surface treatment can consist in that the pigments are provided with a thin hydrophilic and / or hydrophobic inorganic and / or organic layer by methods known per se. For the purposes of the present invention, the various surface coatings can also contain water.
Beschriebene beschichtete und unbeschichtete Titandioxide können im Sinne voriiegender Erfindung auch in Form kommerziell erhältlicher öliger oder wäßriger Vordispersionen zur Anwendung kommen. Diesen Vordispersionen können vorteilhaft Dispergierhilfmittel und/oder Solubilisationsvermittler zugesetzt sein. Die erfindungsgemäßen Titandioxide zeichnen sich durch eine Primärpartikelgröße zwischen 10 nm bis 150 nm aus.Coated and uncoated titanium dioxides described can also be used in the form of the present invention in the form of commercially available oily or aqueous predispersions. Dispersing aids and / or solubilizing agents can advantageously be added to these predispersions. The titanium dioxides according to the invention are distinguished by a primary particle size between 10 nm to 150 nm.
Figure imgf000012_0001
Figure imgf000013_0001
Figure imgf000012_0001
Figure imgf000013_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 TS von Merck und das Titandioxid T 805 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 TS from Merck and the titanium dioxide T 805 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. Draw suitable zinc oxide particles and predispersions of zinc oxide particles according to the invention are characterized by a primary particle size of <300 nm and are available under the following trade names from the companies listed:
Figure imgf000014_0001
Figure imgf000014_0001
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.Z-Cote HP1 from BASF and zinc oxide NDM from Haarmann & Reimer are particularly preferred zinc oxides for the purposes of the invention.
Die Gesamtmenge an einem oder mehreren anorganischen Pigmenten in der fertigen kosmetischen Zubereitung wird vorteilhaft aus dem Bereich 0,1 Gew.-% bis 25 Gew.-% gewählt, vorzugsweise 0,5 Gew.-% bis 18 Gew.-%.The total amount of one or more inorganic pigments in the finished cosmetic preparation is advantageously selected from the range 0.1% by weight to 25% by weight, preferably 0.5% by weight to 18% by weight.
Vorteilhaftes organisches Pigment im Sinne der vorliegenden Erfindung ist das 2,2'-Me- thylen-bis-(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol) [INCI: Bisoctyl- triazol], welches unter der Handelsbezeichnung Tinosorb® M bei der CIBA-Chemikalien GmbH erhältlich ist.An advantageous organic pigment for the purposes of the present invention is 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol) [INCI: bisoctyl-triazole], which is available under the trade name Tinosorb® M from CIBA-Chemicals GmbH.
Vorteilhafte UV-A-Filtersubstanzen im Sinne der vorliegenden Erfindung sind Dibenzoyl- methanderivate, insbesondere das 4-(tert.-ButylH'-roetn°xydibenzoylmethan (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-butylH'-red n ° xydibenzoyl methane (CAS No. 70356-09-1), which is available from Givaudan under the Parsol brand ® 1789 and is sold by Merck under the trade name Eusolex® 9020.
Weitere vorteilhafte UV-A-Filtersubstanzen sind die Phenylen-1,4-bis-(2-benzimidazyl)- 3,3'-5,5'-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, welches beispielsweise unter der Handelsbezeichnung Neo Heliopan AP bei Haarmann & Reimer erhältlich ist. Ferner vorteilhaft sind das 1,4-di(2-oxo-10-Sulfo-3-bornylidenmethyl)-Benzol und dessen Salze (besonders die entprechenden 10-Sulfato-verbindungen, insbesondere das entsprechende Natrium-, Kalium- oder Triethanolammonium-Salz), das auch als Benzol-1,4- di(2-oxo-3-bornylidenmethyl-10-surfonsäure) bezeichnet wird.Further advantageous UV-A filter substances are the phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and its salts, especially the corresponding sodium, potassium or triethanolammonium salts , in particular the phenylene-1,4-bis- (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt with the INCI name bisimidazylate, which is available, for example, under the trade name Neo Heliopan AP from Haarmann & Reimer is available. Also advantageous are the 1,4-di (2-oxo-10-sulfo-3-bornylidenemethyl) benzene and its salts (especially the corresponding 10-sulfato compounds, especially the corresponding sodium, potassium or triethanolammonium salt) , which is also known as benzene-1,4-di (2-oxo-3-bornylidenemethyl-10-surfonic acid).
Weitere vorteilhafte UV-A-Filtersubstanzen sind Hydroxybenzophenone, die sich durch die folgende Strukturformel auszeichnen:Further advantageous UV-A filter substances are hydroxybenzophenones, which are characterized by the following structural formula:
Figure imgf000015_0001
Figure imgf000015_0001
wonnWonn
• R1 und R2 unabhängig voneinander Wasserstoff, Cι-C2o-Alkyl, C3-Cιo-Cycloalkyl oder C3-Cι0-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• R 1 and R 2 independently of one another are hydrogen, -CC-C2o-alkyl, C 3 -C -o-cycloalkyl or C 3 -C- 0 -cycloalkenyl, the substituents R 1 and R 2 together with the nitrogen atom to which they are bound , can form a 5- or 6-ring and
• R3 einen C1-C2o-Alkyl Rest bedeutet.• R 3 is a C 1 -C 2 o-alkyl radical.
Ein besonders vorteilhaftes Hydroxybenzophenon im Sinne der vorliegenden Erfindung ist der 2-(4'-Diethylamino-2'-hydoxybenzoyl)-benzoesäurehexylester (auch: Aminobenzo- phenon), welcher sich durch folgende Struktur auszeichnet:A particularly advantageous hydroxybenzophenone in the sense of the present invention is 2- (4'-diethylamino-2'-hydoxybenzoyl) benzoic acid hexyl ester (also: aminobenzophenone), which is characterized by the following structure:
Figure imgf000015_0002
und unter dem Handelsnamen Uvinul A Plus bei der Fa. BASF erhältlich ist. Vorteilhafte UV-Filtersubstanzen im Sinne der vorliegenden Erfindung sind ferner sogenannte Breitbandfilter, d.h. Filtersubstanzen, die sowohl UV-A- als auch UV-B-Strahlung absorbieren.
Figure imgf000015_0002
and is available under the trade name Uvinul A Plus from BASF. Advantageous UV filter substances in the sense of the present invention are also so-called broadband filters, ie filter substances that absorb both UV-A and UV-B radiation.
Vorteilhafte Breitbandfilter oder UV-B-Filtersubstanzen sind beispielsweise Bis-Resorci- nyltriazinderivate mit der folgenden Struktur:Advantageous broadband filters or UV-B filter substances are, for example, bis-resorcinyltriazine derivatives with the following structure:
Figure imgf000016_0001
wobei R1, R2 und R3 unabhängig voneinander gewählt werden aus der Gruppe der verzweigten und unverzweigten Alkylgruppen mit 1 bis 10 Kohlenstoffatomen bzw. ein einzelnes Wasserstoffatom darstellen. Insbesondere bevorzugt sind das 2,4-Bis-{[4-(2-Ethyl- hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazin (INCI: Aniso Triazin), welches unter der Handelsbezeichnung Tinosorb® S bei der CIBA-Chemikalien GmbH erhältlich ist.
Figure imgf000016_0001
where R 1 , R 2 and R 3 are independently selected from the group of branched and unbranched alkyl groups having 1 to 10 carbon atoms or represent a single hydrogen atom. Particularly preferred are the 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine (INCI: Aniso triazine ), which is available under the trade name Tinosorb® S from CIBA-Chemicals GmbH.
Besonders vorteilhafte Zubereitungen im Sinne der vorliegenden Erfindung, die sich durch einen hohen bzw. sehr hohen UV-A-Schutz auszeichnen, enthalten bevorzugt mehrere UV-A- und/oder Breitbandfilter, insbesondere Dibenzoylmethanderivate [beispielsweise das 4-(tert.-Butyl)-4,-methoxydibenzoylmethan], Benzotriazolderivate [beispielsweise das 2,2'-Methylen-bis-(6-(2H-benzotriazol-2-yl)-4-(1 ,1 ,3,3-tetrame- thylbutyl)-phenol)], Phenylen-1 ,4-bis-(2-benzimidazyl)-3>3'-5,5'-tetrasulfonsäure und/oder ihre Salze, das 1,4-di(2-oxo-10-Sulfo-3-bomylidenmethyl)-Benzol und/oder dessen Salze und/oder das 2,4-Bis-{[4-(2-Ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)- 1 ,3,5-triazin, jeweils einzeln oder in beliebigen Kombinationen miteinander.Particularly advantageous preparations within the meaning of the present invention, which are distinguished by a high or very high UV-A protection, preferably contain a plurality of UV-A and / or broadband filters, in particular dibenzoylmethane derivatives [for example 4- (tert-butyl) -4 , -methoxydibenzoylmethane], benzotriazole derivatives [for example 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1, 1, 3,3-tetramethylbutyl) phenol )], Phenylene-1,4-bis (2-benzimidazyl) -3 > 3'-5,5'-tetrasulfonic acid and / or its salts, the 1,4-di (2-oxo-10-sulfo-3 -bomylidene-methyl) -benzene and / or its salts and / or the 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) - 1, 3,5-triazine, individually or in any combination with one another.
Auch andere UV-Filtersubstanzen, welche das Strukturmotiv Also other UV filter substances, which the structural motif
Figure imgf000017_0001
aufweisen, sind vorteilhafte UV-Filtersubstanzen im Sinne der vorliegenden Erfindung, beispielsweise die in der Europäischen Offenlegungsschrift EP 570 838 A1 beschriebe¬ nen s-Triazinderivate, deren chemische Struktur durch die generische Formel
Figure imgf000017_0001
have, are advantageous UV filter substances for the purposes of the present invention, for example, the descriptions in the European Published Patent Application EP 570 838 A1 ¬ NEN s-triazine derivatives, the chemical structure by the generic formula
Figure imgf000017_0002
wiedergegeben wird, wobei
Figure imgf000017_0002
is reproduced, whereby
R einen verzweigten oder unverzweigten C C18-Alkylrest, einen C5-C12-Cycloalkyl- rest, gegebenenfalls substituiert mit einer oder mehreren d-C4- Alkylgruppen dar¬ stellt,R is a branched or unbranched CC 18 alkyl, C 5 -C 12 cycloalkyl radical optionally substituted with one or more C 4 - alkyl groups ¬ represents,
X ein Sauerstoffatom oder eine NH-Gruppe darstellt, t einen verzweigten oder unverzweigten C C^-Alkylrest, einen C5-C12-Cycloalkyl- rest, gegebenenfalls substituiert mit einer oder mehreren d-C4- Alkylgruppen, oder ein Wasserstoffatom, ein Alkalimetallatom, eine Ammoniumgruppe oder eine ' Gruppe der Formel
Figure imgf000018_0001
bedeutet, in welcher
X represents an oxygen atom or an NH group, t is a branched or unbranched CC ^ alkyl radical, a C 5 -C 12 cycloalkyl radical, optionally substituted with one or more dC 4 alkyl groups, or a hydrogen atom, an alkali metal atom Ammonium group or a 'group of formula
Figure imgf000018_0001
means in which
A einen verzweigten oder unverzweigten CrC18-Alkylrest, einen C5-Cι2-Cyclo- alkyl- oder Arylrest darstellt, gegebenenfalls substituiert mit einer oder mehreren C C4- Alkylgruppen, R3 ein Wasserstoffatom oder eine Methylgruppe darstellt, n eine Zahl von 1 bis 10 darstellt, einen verzweigten oder unverzweigten Cι-Cι8-Alkylrest, einen C5-Ci2-Cycloalkyl- rest, gegebenenfalls substituiert mit einer oder mehreren d-C - Alkylgruppen, darstellt, wenn X die NH-Gruppe darstellt, und einen verzweigten oder unverzweigten C C18-Alkylrest, einen C5-Cι2-Cycloalkyl- rest, gegebenenfalls substituiert mit einer oder mehreren C C4- Alkylgruppen, oder ein Wasserstoffatom, ein Alkalimetallatom, eine Ammoniumgruppe oder eine Gruppe der FormelA represents a branched or unbranched CrC 18 alkyl radical, a C 5 -C 2 cycloalkyl or aryl radical, optionally substituted by one or more CC 4 alkyl groups, R 3 represents a hydrogen atom or a methyl group, n is a number 1 to 10 represents a branched or unbranched C 1 -C 8 alkyl radical, a C 5 -Ci2 cycloalkyl radical, optionally substituted with one or more dC - alkyl groups, when X represents the NH group, and a branched or unbranched CC 18 alkyl radical, a C 5 -C 2 cycloalkyl radical, optionally substituted with one or more CC 4 alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of the formula
Figure imgf000018_0002
bedeutet, in welcher
Figure imgf000018_0002
means in which
A einen verzweigten oder unverzweigten Ci-C-iβ-Alkylrest, einen Cs-Cι2-Cyclo- alkyl- oder Arylrest darstellt, gegebenenfalls substituiert mit einer oder mehreren C1-C4- Alkylgruppen,A represents a branched or unbranched Ci-C-iβ-alkyl radical, a Cs-Cι- 2 cycloalkyl or aryl radical, optionally substituted with one or more C 1 -C 4 alkyl groups,
R3 ein Wasserstoffatom oder eine Methylgruppe darstellt, n eine Zahl von 1 bis 10 darstellt, wenn X ein Sauerstoffatom darstellt.R 3 represents a hydrogen atom or a methyl group, n represents a number from 1 to 10 when X represents an oxygen atom.
Besonders bevorzugte UV-Filtersubstanz im Sinne der vorliegenden Erfindung ist ferner ein unsymmetrisch substituiertes s-Triazin, dessen chemische Struktur durch die Formel A particularly preferred UV filter substance in the sense of the present invention is also an asymmetrically substituted s-triazine, the chemical structure of which is represented by the formula
Figure imgf000019_0001
wiedergegeben wird, welches im Folgenden auch als Dioctylbutylamidotriazon (INCI: Dioctylbutamidotriazone) bezeichnet wird und unter der Handelsbezeichnung UVASORB HEB bei Sigma 3V erhältlich ist.
Figure imgf000019_0001
is reproduced, which is also referred to below as dioctylbutylamidotriazon (INCI: dioctylbutamidotriazone) and is available under the trade name UVASORB HEB from Sigma 3V.
Vorteilhaft im Sinne der vorliegenden Erfindung ist auch ein symmetrisch substituiertes s- Triazin, das 4,4',4"-(1 ,3,5-Triazin-2,4,6-triyltriimino)-t'is-benzoesäure-tris(2-ethylhexyl- ester), synonym: 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.Also advantageous in the sense of the present invention is a symmetrically substituted s-triazine, the 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) -t'is-benzoic acid tris ( 2-ethylhexyl ester), synonymous: 2,4,6-tris [anilino- (p-carbo-2'-ethyl-1'-hexyloxy)] - 1,3,5-triazine (INCI: octyl triazone) , which is sold by BASF Aktiengesellschaft under the trade name UVINUL® T 150.
Auch in der Europäischen Offenlegungsschrift 775698 werden bevorzugt einzusetzende Bis-Resorcinyltriazinderivate beschrieben, deren chemische Struktur durch die generische FormelEuropean laid-open specification 775698 also describes bis-resorcinyltriazine derivatives which are preferably to be used and whose chemical structure is represented by the generic formula
Figure imgf000019_0002
wiedergegeben wird, wobei Ri , R2 und A-i verschiedenste organische Reste repräsentieren.
Figure imgf000019_0002
is reproduced, wherein Ri, R 2 and Ai represent a wide variety of organic radicals.
Vorteilhaft im Sinne der vorliegenden Erfindung sind femer das 2,4-Bis-{[4-(3-sulfonato)- 2-hydroxy-propyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazin Natriumsalz, das 2,4-Bis-{[4-(3-(2-Propyloxy)-2-hydroxy-propyloxy)-2-hydroxy]-phenyl}-6-(4-methoxy- phenyl)-1 ,3,5-triazin, das 2,4-Bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-[4-(2-meth- oxyethyl-carboxyl)-phenylamino]-1 ,3,5-triazin, das 2,4-Bis-{[4-(3-(2-propyloxy)-2-hydroxy- propyloxy)-2-hydroxy]-phenyl}-6-[4-(2-ethyl-carboxyl)-phenylamino]-1 ,3,5-triazin, das 2,4- Bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(1 -methyl-pyrrol-2-yl)-1 ,3,5-triazin, das 2,4-Bis-{[4-tris(trimethylsiloxy-silylpropyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)- 1 ,3,5-triazin, das 2,4-Bis-{[4-(2"-methylpropenyloxy)-2-hydroxy]-phenyl}-6-(4-methoxy- phenyl)-1,3,5-triazin und das 2,4-Bis-{[4-(1',1',1,,3',5,,5't5'-Heptamethylsiloxy-2"-methyl- propyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazin. Ein vorteilhafter Breitbandfilter im Sinne der vorliegenden Erfindung ist das 2,2'-Methylen- bis-(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol), welches unter der Handelsbezeichnung Tinosorb® M bei der CIBA-Chemikalien GmbH erhältlich ist.For the purposes of the present invention, 2,4-bis - {[4- (3-sulfonato) - 2-hydroxypropyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine sodium salt, the 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxypropyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl ) -1, 3,5-triazine, the 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- [4- (2-methoxyethyl carboxyl ) -phenylamino] -1, 3,5-triazine, the 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxypropyloxy) -2-hydroxy] phenyl} -6- [4- (2-ethylcarboxyl) phenylamino] -1, 3,5-triazine, the 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6 - (1-methyl-pyrrol-2-yl) -1, 3,5-triazine, the 2,4-bis - {[4-tris (trimethylsiloxysilylpropyloxy) -2-hydroxy] phenyl} -6- ( 4-methoxyphenyl) - 1, 3,5-triazine, the 2,4-bis - {[4- (2 "-methylpropenyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1 , 3,5-triazine and 2,4-bis - {[4- (1 ', 1', 1, 3 ', 5, 5' 5 't Heptamethylsiloxy-2 "-methyl-propyloxy) - 2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine. An advantageous broadband filter in the sense of the present invention is the 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol), which is available under the trade name Tinosorb® M from CIBA-Chemicals GmbH.
Vorteilhafter Breitbandfilter im Sinne der vorliegenden Erfindung ist ferner das 2-(2H- benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]di- siloxanyl]propyl]-phenol (CAS-Nr.: 155633-54-8) mit der INCI-Bezeichnung Drometrizole Trisiloxane.Another advantageous broadband filter for the purposes of the present invention is 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1,3,3,3-tetramethyl-1 - [( trimethylsilyl) oxy] disiloxanyl] propyl] phenol (CAS No .: 155633-54-8) with the INCI name Drometrizole Trisiloxane.
Die UV-B- und/oder Breitband-Filter können öllöslich oder wasserlöslich sein. Vorteilhafte öllösiiche UV-B- und/oder Breitband-Filtersubstanzen sind z. B.:The UV-B and / or broadband filters can be oil-soluble or water-soluble. Advantageous oil-soluble UV-B and / or broadband 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-benzylidene camphor;
■ 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;
- 2,4,6-Trianilino-(p-carbo-2'-ethyl-1 '-hexyloxy)-1 ,3,5-triazin;- 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1, 3,5-triazine;
■ Ester der Benzalmalonsäure, vorzugsweise 4-Methoxybenzalmalonsäuredi(2-ethylhe- xyl)esteπ■ Esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid di (2-ethylhexyl) esteπ
■ Ester der Zimtsäure, vorzugsweise 4-Methoxyzimtsäure(2-ethylhexyl)ester, 4-Meth- oxyzimtsäureisopentylester; ■ Derivate des Benzophenons, vorzugsweise 2-Hydroxy-4-methoxybenzophenon, 2- Hydroxy-4-methoxy-4'-methylbenzophenon, 2,2'-Dihydroxy-4-methoxybenzophenon■ esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-methoxycinnamic acid isopentyl ester; ■ Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone
■ sowie an Polymere gebundene UV-Filter.■ and UV filters bound to polymers.
Vorteilhafte wasserlösliche UV-B- und/oder Breitband-Filtersubstanzen sind z. B.:Advantageous water-soluble UV-B and / or broadband filter substances are e.g. B .:
■ Salze der 2-Phenylbenzimidazol-5-sulfonsäure, wie ihr Natrium-, Kalium- oder ihr Tri- ethanolammonium-Salz, sowie die Sulfonsäure selbst;■ salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or triethanolammonium salt, and the sulfonic acid itself;
■ Sulfonsäure-Derivate des 3-Benzylidencamphers, wie z. B.4-(2-Oxo-3-bornylidenme- thyl)benzolsulfonsäure, 2-Methyl-5-(2-oxo-3-bornylidenmethyl)sulfonsäure und deren Salze.■ Sulfonic acid derivatives of 3-benzylidene camphor, such as. B.4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidene methyl) sulfonic acid and their salts.
Besonders 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), 4- Isopropylbenzylsalicylat 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 (INCI: Dimethicodiethylbenzalmalonat) welches beispielsweise unter der Handelsbezeichnung Parsol® SLX bei Hoffmann La Röche erhältlich ist.Particularly advantageous UV filter substances which are liquid at room temperature for the purposes of the present invention are homomenthyl salicylate (INCI: homosalate), 2-ethylhexyl-2-hydroxybenzoate (2-ethylhexyl salicylate, octyl salicylate, INCI: octyl salicylate), 4-isopropyl benzyl salicylate, and preferably esters of cimyl 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-bis-ethoxycarbonylvinyl) -phenoxy) propenyl) -methoxysiloxane / dimethylsiloxane - copolymer (INCI: Dimethicodiethylbenzalmalonat) which is available, for example, under the trade name Parsol® SLX from Hoffmann La Röche.
Eine weiterere erfindungsgemäß vorteilhaft zu verwendende Lichtschutzfiltersubstanz ist das Ethylhexyl-2-cyano-3,3-diphenylacrylat (Octocrylen), welches von BASF unter der Bezeichnung Uvinul® N 539 erhältlich ist.A further light protection filter substance according to the invention to be used advantageously is ethylhexyl-2-cyano-3,3-diphenylacrylate, obtainable (octocrylene) from BASF under the name Uvinul ® N 539th
Ein erfindungsgemäß besonders bevorzugtes Benzoxazol-Derivat ist das 2,4-bis-[5-1(di- methylpropyl)benzoxazol-2-yl-(4-phenyl)-imino]-6-(2-ethylhexyl)-imino-1 ,3,5-triazin mit der CAS Nr. 288254-16-0, welches sich durch die Strukturformel
Figure imgf000022_0001
A particularly preferred benzoxazole derivative according to the invention is 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) -imino] -6- (2-ethylhexyl) -imino-1 , 3,5-triazine with CAS No. 288254-16-0, which is characterized by the structural formula
Figure imgf000022_0001
auszeichnet und bei 3V Sigma unter der Handelsbezeichnung Uvasorb® K2A erhältlich ist.distinguished and is available from 3V Sigma under the trade name Uvasorb® K2A.
Es kann auch von erheblichem Vorteil sein, polymergebundene oder polymere UV-Filtersubstanzen in Zubereitungen gemäß der vorliegenden Erfindung zu verwenden, insbesondere solche, wie sie in der WO-A-92/20690 beschrieben werden.It can also be of considerable advantage to use polymer-bound or polymeric UV filter substances in preparations according to the present invention, in particular those as described in WO-A-92/20690.
Die Liste der genannten UV-Filter, die im Sinne der vorliegenden Erfindung eingesetzt werden können, soll selbstverständlich nicht limitierend sein.The list of the UV filters mentioned, which can be used in the sense of the present invention, should of course not be limiting.
Vorteilhaft enthalten die erfindungsgemäßen Zubereitungen die Substanzen, die UV- Strahlung im UV-A- und/oder UV-B-Bereich absorbieren, in einer Gesamtmenge von z. B. 0,1 Gew.-% bis 80 Gew.-%, vorzugsweise 0,5 bis 70 Gew.-%, insbesondere 1,0 bis 60 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Zubereitungen, um kosmetische Zubereitungen zur Verfügung zu stellen, die das Haar bzw. die Haut vor dem gesamten Bereich der ultravioletten Strahlung schützen. Sie können auch als Sonnenschutzmittel fürs Haar oder die Haut dienen.The preparations according to the invention advantageously contain the substances which absorb UV radiation in the UV-A and / or UV-B range in a total amount of, for. B. 0.1 wt .-% to 80 wt .-%, preferably 0.5 to 70 wt .-%, in particular 1.0 to 60 wt .-%, each based on the total weight of the preparations to cosmetic preparations To provide that protect the hair or skin from the entire range of ultraviolet radiation. They can also serve as sunscreens for the hair or skin.
Die Gewichtsangaben beziehen sich dabei auf die Zusammensetzung der Zubereitung vor der Trocknung mittels Gefrier- und/oder Sprühtrocknung. Die Gewichtsangaben beziehen sich dabei auf die Zusammensetzung der Zubereitung vor der Trocknung mittels Gefrier- und/oder Sprühtrocknung. Besonders bevorzugte Ausführungsformen der vorliegenden Erfindung enthalten als UV- Filter ein oder mehrere Triazin-Derivate, Dibenzoylmethanderivate, bei Raumtemperatur flüssige UV-Filter und/oder anorganische Pigmente, insbesondere Titandioxid.The weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying. The weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying. Particularly preferred embodiments of the present invention contain one or more triazine derivatives, dibenzoylmethane derivatives, UV filters which are liquid at room temperature and / or inorganic pigments, in particular titanium dioxide, as UV filters.
Ferner kann es gegebenenfalls von Vorteil sein, Filmbildner in die erfindungsgemäße Emulsion einzuarbeiten, beispielsweise um die Wasserfestigkeit der Zubereitungen zu verbessern oder die UV-Schutzleistung zu erhöhen (UV-A- und/oder UV-B-Boosting). Geeignet sind sowohl wasserlösliche bzw. dispergierbare als auch fettlösliche Filmbildner, jeweils einzeln oder in Kombination miteinander.It may also be advantageous to incorporate film formers into the emulsion according to the invention, for example in order to improve the water resistance of the preparations or to increase the UV protection performance (UV-A and / or UV-B boosting). Both water-soluble or dispersible and fat-soluble film formers are suitable, in each case individually or in combination with one another.
Erfindungsgemäß vorteilhafte wasserlöslich bzw. dispergierbare Filmbildner, welche auch als erfindungsgemäße wasserlösliche Polymere eingesetzt werden können, sind z. B. Polyurethane (z. B. die Avalure® -Typen von Goodrich), Dimethicone Copolyol Polyacrylate (Silsoft Surface® von der Witco Organo Silicones Group), PVPΛ/A (VA = Vinylacetat) Copolymer (Luviscol VA 64 Powder der BASF) etc.Advantageously water-soluble or dispersible film formers according to the invention, which can also be used as water-soluble polymers according to the invention, are e.g. B. Polyurethanes (e.g. Avalure® types from Goodrich), Dimethicone Copolyol Polyacrylate (Silsoft Surface® from the Witco Organo Silicones Group), PVPΛ / A (VA = vinyl acetate) copolymer (Luviscol VA 64 Powder from BASF) etc ,
Vorteilhafte wasseriösliche Filmbildner sind z. B., die Filmbildner aus der Gruppe der Polymere auf Basis von Polyvinylpyrrolidon (PVP)Advantageous water-soluble film formers are e.g. B., the film formers from the group of polymers based on polyvinylpyrrolidone (PVP)
Figure imgf000023_0001
Figure imgf000023_0001
Besonders bevorzugt sind Copoly des Polyvinylpyrrolidons, beispielsweise das PVP Hexadecen Copolymer und das PVP Eicosen Copolymer, welche unter den Handelsbezeichnungen Antaron V216 und Antaron V220 bei der GAF Chemicals Cooperation erhältlich sind, sowie das Tricontayl PVP und dergleichen mehr.Particularly preferred are copoly of polyvinylpyrrolidone, for example the PVP hexadecene copolymer and the PVP eicosen copolymer, which are available under the trade names Antaron V216 and Antaron V220 from GAF Chemicals Cooperation, as well as the Tricontayl PVP and the like.
Erfindungsgemäß können in der Emulsion die üblichen Antioxidantien eingesetzt werden.According to the invention, the usual antioxidants can be used in the emulsion.
Vorteilhaft werden die Antioxidantien gewählt aus der Gruppe bestehend aus Aminosäuren (z.B. Glycin, Histidin, Tyrosin, Tryptophan) und deren Derivate, Imidazole (z.B. Uroca- ninsäure) und deren Derivate, Peptide wie D,L-Carnosin, D-Camosin, L-Camosin und deren Derivate (z.B. Anserin), Carotinoide, Carotine (z.B. α-Carotin, ß-Carotin, Lycopin) und deren Derivate, Aurothioglucose, Propylthiouracil und andere Thiole (z.B. Thiored- oxin, Glutathion, Cystein, Cystin, Cystamin und deren Glycosyl-, N-Acetyl-, Methyl-, Ethyl- , Propyl-, Amyl-, Butyl- und Lauryl-, Palmitoyl-, Oleyl-, γ-Linoleyl-, Cholesteryl- und Gly- cerylester) sowie deren Salze, Dilaurylthiodipropionat, Distearylthiodipropionat, Thiodi- propionsäure und deren Derivate (Ester, Ether, Peptide, Lipide, Nukleotide, Nukleoside und Salze) sowie (Metall)-Chelatoren (z.B. α-Hydroxyfettsäuren, Palmitinsäure, Phytin- säure, Lactoferrin), α-Hydroxysäuren (z.B. Citronensäure, Milchsäure, Apfelsäure), Huminsäure, Gallensäure, Gallenextrakte, Bilirubin, Biliverdin, EDTA, EGTA und deren Derivate, ungesättigte Fettsäuren und deren Derivate (z.B. γ-Linolensäure, Linolsäure, ölsäure), Folsäure und deren Derivate, Alanindiessigsäure, Flavonoide, Polyphenole, Catechine, Vitamin C und Derivate (z.B. Ascorbylpalmitat, Mg-Ascorbylphosphat, Ascor- bylacetat), Tocopherole und Derivate (z.B. Vitamin-E-acetat), sowie Koniferylbenzoat des Benzoeharzes, Rutinsäure und deren Derivate, Ferulasäure und deren Derivate, Butylhy- droxytoluol, Butylhydroxyanisol, Nordihydroguajakharzsäure, Nordihydroguajaretsäure, Trihydroxybutyrophenon, Harnsäure und deren Derivate, Mannose und deren Derivate, Zink und dessen Derivate (z.B. ZnO, ZnS0 ) Selen und dessen Derivate (z.B. Se- lenmethionin), 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.The antioxidants are advantageously selected from the group consisting of amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-camosine, L- Camosin and its derivatives (e.g. anserine), carotenoids, carotenes (e.g. α-carotene, β-carotene, lycopene) and their derivatives, aurothioglucose, propylthiouracil and other thiols (e.g. Thiored- oxine, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as (metal) chelators (e.g. α-hydroxy fatty acids, palmitic acid, phytin acid, lactoferrin), α-hydroxy acids (e.g. 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 (e.g. γ-linolenic acid, linoleic acid, oleic acid), Folic acid and its derivatives, alanine diacetic acid, flavonoids, polyphenols, catechins, vitamin C and derivatives (eg ascorbyl palmitate, Mg ascorbyl phosphate, ascorbate acetate), tocopherols and derivatives (eg vitamin E acetate), and coniferyl benzoate of benzoin, rutinic acid and their derivatives, ferulic acid and its derivatives, butylhydroxytoluene, butylhydroxyanisole, nordihydroguajakharzäure, nordihydroguajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (eg ZnO, ZnS0) selenium and its derivatives ), Stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active substances.
Die Menge der Antioxidantien (eine oder mehrere Verbindungen) in den Zubereitungen beträgt vorzugsweise 0,001 bis 30 Gew.-%, besonders bevorzugt 0,025 —6.0 Gew.-%, insbesondere 0.05 —3.0 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitung. Die Gewichtsangaben beziehen sich dabei auf die Zusammensetzung der Zubereitung vor der Trocknung mittels Gefrier- und/oder Sprühtrocknung.The amount of the antioxidants (one or more compounds) in the preparations is preferably 0.001 to 30% by weight, particularly preferably 0.025-6.0% by weight, in particular 0.05-3.0% by weight, based on the total weight of the preparation. The weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying.
Sofern Vitamin A bzw. Vitamin-A-Derivate, bzw. Carotine bzw. deren Derivate das oder die Antioxidantien darstellen, ist es vorteilhaft, deren jeweilige Konzentrationen aus dem Bereich von 0,001 bis 30 Gew.-%, bezogen auf das Gesamtgewicht der Formulierung, zu wählen. Die Gewichtsangaben beziehen sich dabei auf die Zusammensetzung der Zubereitung vor der Trocknung mittels Gefrier- und/oder Sprühtrocknung.If vitamin A or vitamin A derivatives or carotenes or their derivatives represent the antioxidant or antioxidants, it is advantageous to use their respective concentrations in the range from 0.001 to 30% by weight, based on the total weight of the formulation. to choose. The weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying.
Sofern Vitamin E und/oder dessen Derivate das oder die Antioxidantien darstellen, ist es vorteilhaft, deren jeweilige Konzentrationen aus dem Bereich von 0,001 bis 30 Gew.-%, bezogen auf das Gesamtgewicht der Formulierung, zu wählen. Die Gewichtsangaben beziehen sich dabei auf die Zusammensetzung der Zubereitung vor der Trocknung mittels Gefrier- und/oder Sprühtrocknung.If vitamin E and / or its derivatives represent the antioxidant or antioxidants, it is advantageous to choose their respective concentrations from the range from 0.001 to 30% by weight, based on the total weight of the formulation. The weights relate to the composition of the preparation before drying by means of freeze and / or spray drying.
Weitere vorteilhafte Wirkstoffe im Sinne der vorliegenden Erfindung sind natürliche Wirkstoffe und/oder deren Derivate, wie z. B. alpha-Liponsäure, Phytoen, D-Biotin, Coenzym Q10, alpha-Glucosylrutin, Carnitin, Carnosin, natürliche und/oder synthetische Isoflavo- noide, Kreatin, Fumarsäureester, Ectoin und dessen Derivate, Taurin, und/oder ß-Alanin. Diese Wirkstoffe können in einer Konzentration von 0,001 bis 30 Gewichts-%, bezogen auf das Gesamtgewicht der Emulsion, in dieser enthalten sein. Die Gewichtsangaben beziehen sich dabei auf die Zusammensetzung der Zubereitung vor der Trocknung mittels Gefrier- und/oder Sprühtrocknung.Further advantageous active ingredients in the sense of the present invention are natural active ingredients and / or their derivatives, such as. B. alpha-lipoic acid, phytoene, D-biotin, coenzyme Q10, alpha-glucosyl rutin, carnitine, carnosine, natural and / or synthetic isoflavonoids, creatine, fumaric acid ester, ectoine and its derivatives, taurine, and / or ß-alanine. These active ingredients can be contained in a concentration of 0.001 to 30% by weight, based on the total weight of the emulsion. The weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying.
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 zur Prophylaxe und Behandlung kosmetischer oder dermatologischer 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.Recipes according to the invention, which, for. B. known anti-wrinkle active ingredients such as flavone glycosides (especially α-glycosylrutin), coenzyme Q10, vitamin E and / or derivatives and the like are particularly suitable for the prophylaxis and treatment of cosmetic or dermatological skin changes, such as z. B. occur with skin aging (such as dryness, roughness and formation of dry lines, itching, reduced re-greasing (e.g. after washing), visible vasodilation (telangiectasia, cuperosis), flaccidity and formation of wrinkles and fine lines, local hyper- , Hypo and incorrect pigmentation (e.g. age spots), increased susceptibility to mechanical stress (e.g. cracking) and the like). They are also advantageous against the appearance of dry or rough skin.
In die erfindungsgemäßen Zubereitungen können aber auch andere pharmazeutisch oder dermatologisch wirkende Substanzen wie beispielsweise die Haut beruhigende und pflegende Substanzen eingearbeitet sein. Hierzu zählen beispielsweise Panthenol, Allantoin, Tannin, Antihistaminika (z.B. Loratadin, Cetirizin, Dimetionden, Clemastin, Capsaicin, HrAntagonisten, Gerbstoffpräparate), Lokalanästhetika, Opiatantagonisten (z.B. Naltrexon, Naloxon), Antiphlogistika, Glucocorticoide (z.B. Hydrocortison, Tacrolimus, Ciclosporin A) sowie Pflanzenwirkstoffe wie Azulen und Bisabolol, Glycyrrhizin, Hamamelin und Pflanzenextrakte wie Kamille, aloe vera, Hamazelis, Süßholzwurzel. Auch die Vitamin D3-analoga Tacalcitol, Calcipotriol, Tacalcitol, Colecalciferol sowie Calcitrol (Vitamin D3) und/oder Fumarsäureester können erfolgreich in die Zubereitungen eingearbeitet werden.However, other pharmaceutically or dermatologically active substances such as, for example, substances that soothe and care for the skin can also be incorporated into the preparations according to the invention. These include, for example, panthenol, allantoin, tannin, antihistamines (e.g. loratadine, cetirizine, dimetionden, clemastine, capsaicin, HR antagonists, tannin preparations), local anesthetics, opiate antagonists (e.g. naltrexone, naloxone), anti-inflammatory drugs, e.g. Plant active ingredients such as azulene and bisabolol, glycyrrhizin, hamamelin and plant extracts such as chamomile, aloe vera, hamazelis, licorice root. The vitamin D 3 analogues tacalcitol, calcipotriol, tacalcitol, colecalciferol and calcitrol (vitamin D 3 ) and / or fumaric acid esters can also be successful be incorporated into the preparations.
Diese Wirkstoffe können in einer Konzentration von 0,001 bis 30 Gewichts-%, bezogen auf das Gesamtgewicht der Emulsion, in dieser enthalten sein. Die Gewichtsangaben beziehen sich dabei auf die Zusammensetzung der Zubereitung vor der Trocknung mittels Gefrier- und/oder Sprühtrocknung.These active ingredients can be contained in a concentration of 0.001 to 30% by weight, based on the total weight of the emulsion. The weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying.
Vorteilhafte anfeuchtende bzw. feuchthaltende Mittel (sogenannte Moisturizer) im Sinne der vorliegenden Erfindung sind beispielsweise Glycerin, Milchsäure und/oder Lactate, insbesondere Natriumlactat, Butylenglykol, Propylenglykol, Biosaccaride Gum-1, Glycine Soja, Ethylhexyloxyglycerin, Pyrrolidoncarbonsäure 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 Fuco- gel®1000 von der Gesellschaft SOLABIA S.A. erhältlich ist.Advantageous moisturizing or moisturizing agents (so-called 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, biosaccaride Gum-1, glycine soybean, 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-gelable polysaccharides. Particularly advantageous are, for example, hyaluronic acid, chitosan and / or a fucose-rich polysaccharide, which is filed in the Chemical Abstracts under the registration number 178463-23-5 and z. B. under the name Fucogel®1000 from the company SOLABIA S.A. is available.
Vorteilhaft können die erfindungsgemäßen Zubereitungen Feststoffträger in Form von mikrofeinen Feststoffteilchen enthalten. Diese können erfindungsgemäß vorteilhaft oberflächlich wasserabwiesend behandelt („gecoatef) sein, wobei ein amphiphiler Charakter dieser Feststoffteilchen gebildet werden bzw. erhalten bleiben soll. Die Oberflächenbehandlung kann darin bestehen, daß die Feststoffteilchen nach an sich bekannten Verfahren mit einer dünnen hydrophoben bzw. hydrophilen Schicht versehen werden.The preparations according to the invention can advantageously contain solid carriers in the form of microfine solid particles. According to the invention, these can advantageously be surface-repellent treated (“gecoatef”), an amphiphilic character of these solid particles being formed or to be retained. The surface treatment can consist in that the solid particles are provided with a thin hydrophobic or hydrophilic layer by methods known per se.
Der mittlere Partikeldurchmesser der als Stabilisator verwendeten mikrofeinen Feststoffträger wird vorzugsweise kleiner als 100 μm, besonders vorteilhaft kleiner als 50 μm gewählt. Dabei ist es im wesentlichen unerheblich, in welcher Form (Plättchen, Stäbchen, Kügelchen etc.) bzw. Modifikation die verwendeten Feststoffteilchen vorliegen.The average particle diameter of the microfine solid carrier used as stabilizer is preferably chosen to be less than 100 μm, particularly advantageously less than 50 μm. It is essentially irrelevant in which form (platelets, rods, beads, etc.) or modification the solid particles used are present.
Vorzugsweise werden die mikrofeinen Feststoffträger aus der Gruppe der amphiphilen Metalloxidpigmente gewählt. Vorteilhaft sind insbesondere: • Titandioxide (gecoatet und ungecoatet): z. B. Eusolex T-2000 von der Fa. Merck, Titandioxid MT-100 Z von der Fa. Tayca CorporationThe microfine solid supports are preferably selected from the group of amphiphilic metal oxide pigments. The following are particularly advantageous: • Titanium dioxides (coated and uncoated): e.g. B. Eusolex T-2000 from Merck, titanium dioxide MT-100 Z from Tayca Corporation
• Zinkoxide z. B. Z-Cote und Z-Cote HP1 von der BASF AG, MZ -300, MZ -500 und MZ-505M von der Fa. Tayca Corporation• zinc oxides z. B. Z-Cote and Z-Cote HP1 from BASF AG, MZ-300, MZ-500 and MZ-505M from Tayca Corporation
• Eisenoxide• iron oxides
Des weiteren ist es vorteilhaft, wenn die mikrofeinen Feststoffträger aus der folgenden Gruppe gewählt werden: Bornitride, Stärkederivate (Tapioca Starch, Sodium Com Starch Octynylsuccinat etc.), Talkum, Latexpartikel.Furthermore, it is advantageous if the microfine solid carriers are selected from the following group: boron nitrides, starch derivatives (Tapioca Starch, Sodium Com Starch octynyl succinate etc.), talc, latex particles.
Die mikrofeinen Feststoffteilchen werden erfindungsgemäß vorteilhaft in einer Konzentration von 0,5 bis 60 Gewichts-%, bevorzugt in einer Konzentration von 1 bis 50 Gewichts-% und besonders bevorzugt in einer Konzentration von 3 bis 30 Gewichts-%, jeweils bezogen auf das Gesamtgewicht der Zubereitung eingesetzt. Die Gewichtsangaben beziehen sich dabei auf die Zusammensetzung der Zubereitung vor der Trocknung mittels Gefrier- und/oder Sprühtrocknung.According to the invention, the microfine solid particles are advantageously used in a concentration of 0.5 to 60% by weight, preferably in a concentration of 1 to 50% by weight and particularly preferably in a concentration of 3 to 30% by weight, in each case based on the total weight of the Preparation used. The weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying.
Die erfindungsgemäßen kosmetischen oder dermatologischen Zubereitungen können femer 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).The cosmetic or dermatological preparations according to the invention can furthermore advantageously, although not necessarily, contain fillers which, for. B. further improve the sensory and cosmetic properties of the formulations and, for example, cause or intensify a velvety or silky feeling on the skin. Advantageous fillers for the purposes of the present invention are starch and starch derivatives (such as tapioca starch, distarch phosphate, aluminum or sodium starch, octenyl succinate and the like), pigments which have neither mainly UV filter nor coloring effects (such as e.g. B. boron nitride etc.) and / or Aerosile ® (CAS No. 7631-86-9).
Die Zusammensetzungen enthalten gemäß der Erfindung außer den vorgenannten Substanzen gegebenenfalls die in der Kosmetik üblichen Zusatzstoffe, beispielsweise Parfüm, Farbstoffe, antimikrobielle Stoffe, rückfettende Agentien, Komplexierungs- und Se- questrierungsagentien, Perlglanzagentien, Pflanzenextrakte, Vitamine, Wirkstoffe, Konservierungsmittel, Bakterizide, Repellentien, Selbstbräuner (z.B. DHA), Depigmentiermittel (z.B. 8-Hexadecen-1,16-dicarbonsäure (Dioic acid, CAS-Nummer 20701-68-2; vorläufige INCI-Bezeichnung Octadecendioic acid)), Pigmente, die eine färbende Wirkung haben, weichmachende, anfeuchtende und/oder feuchthaltende Substanzen, oder andere übliche Bestandteile einer kosmetischen oder dermatologischen Formulierung wie Emulgatoren, Polymere, Schaumstabilisatoren, Peeling-Stoffe (Abrasiva, z.B. Polymerkügelchen oder -pulver aus Polyethylen, Polypropylen etc. anorganischen Oxiden, Silikaten usw.), Antitranspirant-Salze (z.B. saure Aluminium- und/oder Aluminium/Zirkoniumsalze wie Aluminiumchlorhydrat und/oder Aluminium/Zirkoniumchlorhydrat) und Elektrolyte.In addition to the substances mentioned above, the compositions according to the invention optionally contain the additives customary in cosmetics, for example perfume, colorants, antimicrobial substances, refatting agents, complexing and sequestering agents, pearlescent agents, plant extracts, vitamins, active ingredients, preservatives, bactericides, repellents, Self-tanners (e.g. DHA), depigmenting agents (e.g. 8-hexadecen-1,16-dicarboxylic acid (dioic acid, CAS number 20701-68-2; provisional INCI name Octadecendioic acid)), pigments that have a coloring effect, softening, moisturizing and / or moisturizing substances, or other usual components of a cosmetic or dermatological formulation such as emulsifiers, polymers, foam stabilizers, peeling substances (abrasives, e.g. polymer beads or powder made of polyethylene, polypropylene etc. inorganic oxides, silicates etc.), antiperspirant salts (e.g. acidic aluminum and / or aluminum / zirconium salts such as aluminum chlorohydrate and / or aluminum / zirconium chlorohydrate) and electrolytes.
Erfindungsgemäß bevorzugt sind die im folgenden aufgelisteten Repellent-Wirkstoffe:According to the invention, the repellent active ingredients listed below are preferred:
Figure imgf000028_0001
Figure imgf000029_0001
wirkt als Synergist bei verschiedenen Repellents
Figure imgf000028_0001
Figure imgf000029_0001
acts as a synergist with various repellents
Besonders vorteilhafte Repellent-Wirkstoffe im Sinne der vorliegenden Erfindung sind die obengenannten Wirkstoffe N,N-Diethyl-3-methylbenzamid, 3-(N-n-Butyl-N-acetyl-amino)- propionsäureethylester und Dimethylphthalat. Ganz besonders bevorzugt ist das Repellent 3-(N-n-B utyl-N-acetyl-amino)propionsäureethylester.Particularly advantageous repellent active ingredients for the purposes of the present invention are the active ingredients N, N-diethyl-3-methylbenzamide, 3- (N-n-butyl-N-acetylamino) propionic acid ethyl ester and dimethyl phthalate. The repellent is very particularly preferably ethyl 3- (N-n-butyl-N-acetylamino) propionate.
Erfindungsgemäß vorteilhafte Ausführungsformen der erfindungsgemäßen Emulsion enthalten ein oder mehrere Repellent-Wirkstoffe in einer Konzentration von 1-50 Gewichts-%, bezogen auf das Gesamtgewicht der Formulierung. Die Gewichtsangaben beziehen sich dabei auf die Zusammensetzung der Zubereitung vor der Trocknung mittels Gefrier- und/oder Sprühtrocknung.Embodiments of the emulsion according to the invention which are advantageous according to the invention contain one or more repellent active ingredients in a concentration of 1-50% by weight, based on the total weight of the formulation. The weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying.
Als Selbstbräuner können erfindungsgemäß vorteilhaft unter anderem eingesetzt werden: Glycerolaldehyd, Hydroxymethylglyoxal, γ-Dialdehyd, Erythrulose, 6-Aldo-D-Fructose, Ninhydrin, 5-Hydroxy-1,4-naphtochinon (Juglon), 2-Hydroxy-1,4-naphtochinon (Lawson) und besonders bevorzugt 1,3-Dihydroxyaceton.According to the invention, the following can advantageously be used as self-tanners: Glycerol aldehyde, hydroxymethylglyoxal, γ-dialdehyde, erythrulose, 6-aldo-D-fructose, ninhydrin, 5-hydroxy-1,4-naphthoquinone (juglone), 2-hydroxy-1,4-naphthoquinone (Lawson) and particularly preferably 1, 3-dihydroxyacetone.
Erfindungsgemäß vorteilhafte Ausführungsformen mit mindestens einer Selbstbräunungssubstanz, enthalten diese in einer Gesamtkonzentration von 0,1 bis 30 Gewichts-%, bezogen auf das Gesamtgewicht der Emulsion. Die Gewichtsangaben beziehen sich dabei auf die Zusammensetzung der Zubereitung vor der Trocknung mittels Gefrier- und/oder Sprühtrocknung.Embodiments which are advantageous according to the invention and have at least one self-tanning substance contain these in a total concentration of 0.1 to 30% by weight, based on the total weight of the emulsion. The weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying.
Die erfindungsgemäße Emulsion kann erfindungsgemäß vorteilhaft ein oder mehrere Konservierungsstoffe enthalten. Vorteilhafte Konservierungsstoffe 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-Hydroxybenzoesäurealkylester, wie Methyl-, Ethyl-, Propyl- und/oder Butylparaben), Phenoxyethanol, Ethanol, Benzoesäure und dergleichen mehr. Üblicherweise umfaßt das Konservierungssystem erfindungsgemäß femer vorteilhaft auch Konservierungshelfer, wie beispielsweise Octoxyglycerin, Glycine Soja etc. Die nachfolgende Tabelle gibt einen Überblick über einige erfindungsgemäß vorteilhafte Konservierungsstoffe:The emulsion according to the invention can advantageously contain one or more preservatives according to the invention. Advantageous preservatives for the purposes of the present invention are, for example, formaldehyde releasers (such as, for example, DMDM hydantoin, which is available, for example, from Lonza under the trade name Glydant ™), iodopropyl butyl carbamates (for example those under the trade names Glycacil-L, Glycacil -S available from Lonza and / or Dekaben LMB from Jan Dekker), parabens (ie alkyl p-hydroxybenzoate such as methyl, ethyl, propyl and / or butyl paraben), phenoxyethanol, ethanol, benzoic acid and the like. Usually, the preservation system according to the invention also advantageously includes preservation aids, such as, for example, octoxyglycerol, glycine soya, etc. The following table provides an overview of some preservatives which are advantageous according to the invention:
Figure imgf000030_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000031_0001
Ferner vorteilhaft sind in der Kosmetik gebräuchliche Konservierungsmittel oder Konservierungshilfsstoffe, wie Dibromdicyanobutan (2-Brom-2-brommethylglutarodinitril), Phenoxyethanol, 3-lod-2-propinylbutylcarbamat, 2-Brom-2-nitro-propan-1,3-diol, Imidazolidinyl- harnstoff, 5-Chlor-2-methyl-4-isothiazolin-3-on, 2 -Chloracetamid, Benzalkoniumchlorid, Benzylalkohol, Salicylsäure und Salicylate.Also useful in cosmetics are preservatives or preservation aids, such as dibromodicyanobutane (2-bromo-2-bromomethylglutarodinitrile), phenoxyethanol, 3-iodo-2-propynylbutylcarbamate, 2-bromo-2-nitro-propane-1,3-diol and imidazolidinyl - urea, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-chloroacetamide, benzalkonium chloride, benzyl alcohol, salicylic acid and salicylates.
Es ist dabei erfindungsgemäß besonders bevorzugt, wenn als Konservierungsstoffe lodopropylbutylcarbamate, Parabene (Methyl-, Ethyl-, Propyl- und/oder Butylparaben) und/oder Phenoxyethanol eingesetzt werden.It is particularly preferred according to the invention if iodopropyl butyl carbamates, parabens (methyl, ethyl, propyl and / or butyl paraben) and / or phenoxyethanol are used as preservatives.
Erfindungsgemäß vorteilhaft sind ein oder mehrere Konservierungsstoffe in einer Konzentration von 2 Gewichts-% oder kleiner 2 Gewichts-%, bevorzugt 1,5 Gewichts-% oder kleiner 1,5 Gewichts-% und besonders bevorzugt 1 Gewichts-% oder kleiner 1 Gewichts-%, jeweils bezogen auf das Gesamtgewicht der Zubereitung enthalten. Die Gewichtsangaben beziehen sich dabei auf die Zusammensetzung der Zubereitung vor der Trocknung mittels Gefrier- und/oder Sprühtrocknung.According to the invention, one or more preservatives are advantageous in a concentration of 2% by weight or less than 2% by weight, preferably 1.5% by weight or less than 1.5% by weight and particularly preferably 1% by weight or less than 1% by weight , each based on the total weight of the preparation. The weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying.
Die erfindungsgemäße Emulsion enthält vorteilhafter Weise einen oder mehrere Konditionierer. Erfindungsgemäß bevorzugte Konditionierer sind beispielsweise alle Verbindungen, welche im International Cosmetic Ingredient Dictionary and Handbook (Volume 4, Herausgeber: R. C. Pepe, J.A. Wenninger, G. N. McEwen, The Cosmetic, Toiletry, and Fragrance Association, 9. Auflage, 2002) unter Section 4 unter den Stichworten Hair Conditioning Agents, Humectants, Skin-Condftioning Agents, Skin- Conditioning Agents-Emollient, Skin-Conditioning Agents-Humactant, Skin-Conditioning Agents-Miscellaneous, Skin-Conditioning Agents-Occlusive und Skin Protectans aufgeführt sind sowie alle in der EP 0934956 (S.11-13) unter water soluble conditioning agent und oil soluble conditioning agent aufgeführten Verbindungen. Ein Teil dieser Verbindungen wird unter den Bestandteilen der wässrigen Phase und der ölphase namentlich aufgeführt. Weitere erfindungsgemäß vorteilhafte Konditionierer stellen beispielsweise die nach der internationalen Nomenklatur für kosmetische Inhaltsstoffe (INCI) als Polyquatemium benannten Verbindungen dar (insbesondere Polyquaternium-1 bis Polyquaternium-56). Erfindungsgemäß vorteilhaft kann die erfindungsgemäße Emulsion Glittersoffe und/oder andere Effektstoffe enthalten.The emulsion according to the invention advantageously contains one or more conditioners. Preferred conditioners according to the invention are, for example, all compounds which are described in Section 4 below in the International Cosmetic Ingredient Dictionary and Handbook (Volume 4, publisher: RC Pepe, JA Wenninger, GN McEwen, The Cosmetic, Toiletry, and Fragrance Association, 9th edition, 2002) the keywords Hair Conditioning Agents, Humectants, Skin-Condftioning Agents, Skin-Conditioning Agents-Emollient, Skin-Conditioning Agents-Humactant, Skin-Conditioning Agents-Miscellaneous, Skin-Conditioning Agents-Occlusive and Skin Protectans are all listed in the EP 0934956 (p.11-13) under water soluble conditioning agent and oil soluble conditioning agent. Some of these compounds are listed under the constituents of the aqueous phase and the oil phase. Further conditioners which are advantageous according to the invention are, for example, the compounds named polyquaternium according to the international nomenclature for cosmetic ingredients (INCI) (in particular polyquaternium-1 to polyquaternium-56). Advantageously according to the invention, the emulsion according to the invention can contain glitter substances and / or other effect substances.
Als erfindungsgemäß vorteilhafte Hydrokolloide, die als erfindungsgemäße wasserlösliche Polymere eingesetzt werden können, werden Agar-Agar, Carrageen, Tragant, Gummi arabicum, Alginate, Pektine, Polyosen, Guar-Mehl, Johannisbrotbaumkernmehl, Stärke, Dextrine, Polysaccharid-N-alkylurethane, Inulincarbamate, Gelatine, Casein, Celluloseether, Hydroxyethyl- und -propyl-cellulosederivate, Polysaccharide, Polyacryl- und Polymethacryl-Verbindungen, Ammoniumacryloyldime- thyltaurate/Vinylpyrrolidoncopolymere und Ammoniumpolyacryl-dimethyltauramide, Vinylpolymere, Polycarbonsäuren, Polyether, Polyimine, Polyamide, Polykieselsäuren, Tonmineralien, Zeolithe, Kieselsäuren eingesetzt.The hydrocolloids which are advantageous according to the invention and which can be used as water-soluble polymers according to the invention are agar agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, polysaccharide-N-alkyl urethanes, inulin carbamates, gelatin, casein, cellulose ethers, hydroxyethyl and propyl cellulose derivatives, polysaccharides, polyacrylic and polymethacrylic compounds, Ammoniumacryloyldime- thyltaurate / vinyl pyrrolidone copolymers and Ammoniumpolyacryl-dimethyltauramide, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides, polysilicic acids, clay minerals, zeolites, silicas used.
Ein vorteilhaftes Hydrokolloid im Sinne der vorliegenden Erfindung ist femer Xanthan (CAS-Nr. 11138-66-2), auch Xanthan Gummi genannt, welches ein anionisches Heteropolysaccharid ist, das in der Regel durch Fermentation aus Maiszucker gebildet und als Kaliumsalz isoliert wird.An advantageous hydrocolloid for the purposes of the present invention is also xanthan (CAS No. 11138-66-2), also called xanthan gum, which is an anionic heteropolysaccharide which is generally formed from corn sugar by fermentation and is isolated as the potassium salt.
Ein vorteilhaftes Hydrokolloid im Sinne der vorliegenden Erfindung ist fe er Carrageen, ein gelbildender und ähnlich wie Agar aufgebauter Extrakt aus nordatlant, zu den Florideen zählenden Rotalgen (Chondrus crispus u. Gigartina stellata).An advantageous hydrocolloid in the sense of the present invention is he carrageenan, a gel-forming and similar to agar extract from north Atlantic, belonging to the florida red algae (Chondrus crispus and Gigartina stellata).
Polyacrylate sind ebenfalls vorteilhaft im sinne der vorliegenden Erfindung zu verwendende Hydrokolloide. Erfindungsgemäß vorteilhafte Polyacrylate sind Acrylat- Alkylacrylat-Copolymere, insbesondere solche, die aus der Gruppe der sogenannten Carbomere oder Carbopole (Carbopol® ist eigentlich eine eingetragene Marke der NOVEON Inc.) gewählt werden. Insbesondere zeichnen sich das oder die erfindungsgemäß vorteilhaften Acrylat-Alkylacrylat-Copolymere durch die folgende Struktur aus:
Figure imgf000033_0001
Polyacrylates are also advantageous hydrocolloids to be used in the sense of the present invention. Polyacrylates which are advantageous according to the invention are acrylate-alkyl acrylate copolymers, in particular those which are selected from the group of the so-called carbomers or carbopols (Carbopol® is actually a registered trademark of NOVEON Inc.). In particular, the acrylate-alkyl acrylate copolymers which are advantageous according to the invention are distinguished by the following structure:
Figure imgf000033_0001
Darin stellen R' einen langkettigen Alkylrest und x und y Zahlen dar, welche den jewieli- gen stöchiometrischen Anteil der jeweiligen Comonomere symbolisieren.R 'represents a long-chain alkyl radical and x and y numbers, which symbolize the respective stoichiometric proportion of the respective comonomers.
Erfindungsgemäß bevorzugt sind Acrylat-Copolymere und/oder Acrylat-Alkylacrylat-Co- polymere, welche unter den Handelbezeichnungen Carbopol® 1382, Carbopol® 981 und Carbopol® 5984, Aqua SF-1 von der NOVEON Inc. bzw. als Aculyn® 33 von International Specialty Products Corp. erhältlich sind. Weiterhin bevorzugt sind die Carbomere Carbopol EDT 2001 , ETD 2020 und ETD 2050.According to the invention, preference is given to acrylate copolymers and / or acrylate-alkyl acrylate copolymers which are marketed under the trade names Carbopol® 1382, Carbopol® 981 and Carbopol® 5984, Aqua SF-1 by NOVEON Inc. or as Aculyn® 33 by International Specialty Products Corp. are available. The carbomers Carbopol EDT 2001, ETD 2020 and ETD 2050 are also preferred.
Ferner vorteilhaft sind Copoiymere aus C10-30-Alkylacrylaten und einem oder mehreren Monomeren der Acrylsäure, der Methacrylsäure oder deren Ester, die kreuzvernetzt sind mit einem Allylether der Saccharose oder einem Allylether des Pentaerythrit.Also advantageous are copolymers of C10-30 alkyl acrylates and one or more monomers of acrylic acid, methacrylic acid or their esters, which are cross-linked with an allyl ether of sucrose or an allyl ether of pentaerythritol.
Vorteilhaft sind Verbindungen, die die INCI-Bezeichnung „Acrylates/C 10-30 Alkyl Acrylate Crosspolymer" tragen. Insbesondere vorteilhaft sind die unter den Handelsbezeichnungen Pemulen TR1 und Pemulen TR2 bei der NOVEON Inc. erhältlichen.Compounds which have the INCI name "Acrylates / C 10-30 Alkyl Acrylate Crosspolymer" are advantageous. Those which are available under the trade names Pemulen TR1 and Pemulen TR2 from NOVEON Inc. are particularly advantageous.
Vorteilhaft sind Verbindungen, die die INCI- AcrylatesΛ/inyl Isodecanoate Crosspolymer" tragen. Insbesondere vorteilhaft sind die unter den Handelsbezeichnungen Stabylen 30 von 3V Sigma erhältlichen.Compounds which carry the INCI-AcrylatesΛ / inyl isodecanoate crosspolymer "are advantageous. Particularly advantageous are those available from 3V Sigma under the trade names Stabylen 30.
Vorteilhaft sind ferner Verbindungen, die die INCI-Bezeichnung „acrylates/C12-24 pareth- 25 acrylate copolymer" (unter der Handelsbezeichnungen Synthalen® W2000 bei der 3V Inc. erhältlich), die die INCI-Bezeichnung „acrylates/steareth-20 methacrylate copolymer" (unter der Handelsbezeichnungen Aculyn® 22 bei der International Specialty Products Corp. erhältlich), die die INCI-Bezeichnung „acrylates/steareth-20 itaconate copolymer" (unter der Handelsbezeichnungen Structure 2001® bei der National Starch erhältlich), die die INCI-Bezeichnung „acrylates/aminoacrylates/C 10-30 alkyl PEG-20 itaconate copolymer" (unter der Handelsbezeichnungen Structure Plus® bei der National Starch erhältlich) und ähnliche Polymere.Also advantageous are compounds which have the INCI name "acrylates / C12-24 pareth-25 acrylate copolymer" (available under the trade names Synthalen® W2000 from 3V Inc.) and the INCI name "acrylates / steareth-20 methacrylate copolymer""(available under the trade names Aculyn® 22 from International Specialty Products Corp.), the INCI name" acrylates / steareth-20 itaconate copolymer "(available under the trade names Structure 2001® from National Starch), the INCI Name "acrylates / aminoacrylates / C 10-30 alkyl PEG-20 itaconate copolymer "(available under the trade names Structure Plus® from National Starch) and similar polymers.
Erfindungsgemäß bevorzugt ist es insbesondere, neutralisierte oder teilneutralisierte Polyacrylate (z.B. Carbopole der Firma Noveon) einzusetzen.According to the invention, it is particularly preferred to use neutralized or partially neutralized polyacrylates (e.g. Carbopole from Noveon).
Die erfindungsgemäßen kosmetischen und/oder dermatologischen Emulsionen können eine Reihe von Pigmenten enthalten.The cosmetic and / or dermatological emulsions according to the invention can contain a number of pigments.
Die Farbstoffe und -pigmente können aus der entsprechenden Positivliste der Kosmetikverordnung bzw. der EG-Liste kosmetischer Färbemittel ausgewählt werden. In den meisten Fällen sind sie mit den für Lebensmittel zugelassenen Farbstoffen identisch. Vorteilhafte Farbpigmente sind beispielsweise Titandioxid, Glimmer, Eisenoxide (z. B. Fe 03, Fβ3θ , FeO(OH)) und/oder Zinnoxid. Vorteilhafte Farbstoffe sind beispielsweise Carmin, Berliner Blau, Chromoxidgrün, Ultramarinblau und/oder Manganviolett. Es ist insbesondere vorteilhaft, die Farbstoffe und/oder Farbpigmente aus der folgenden Liste zu wählen. Die Colour Index Nummern (CIN) sind dem Rowe Colour Index, 3. Auflage, Society of Dyers and Colourists, Bradford, England, 1971 entnommen.The dyes and pigments can be selected from the corresponding positive list in the Cosmetics Ordinance or the EC list of cosmetic colorants. In most cases, they are identical to the colorants approved for food. Advantageous color pigments are, for example, titanium dioxide, mica, iron oxides (e.g. Fe 0 3 , Fβ 3 θ, FeO (OH)) and / or tin oxide. Advantageous dyes are, for example, carmine, Berlin blue, chrome oxide green, ultramarine blue and / or manganese violet. It is particularly advantageous to choose the dyes and / or color pigments from the list below. The Color Index Numbers (CIN) are taken from the Rowe Color Index, 3rd edition, Society of Dyers and Colorists, Bradford, England, 1971.
Chemische oder sonstige Bezeichnung CIN FarbeChemical or other name CIN color
Pigment Green 10006 GrünPigment Green 10006 Green
Acid Green 1 10020 GrünAcid Green 1 10020 Green
2,4-Dinitrohydroxynaphthalin-7-sulfosäure 10316 Gelb2,4-dinitrohydroxynaphthalene-7-sulfonic acid 10316 yellow
Pigment Yellow 1 11680 GelbPigment Yellow 1 11680 yellow
Pigment Yellow 3 11710 GelbPigment Yellow 3 11710 yellow
Pigment Orange 1 11725 OrangePigment Orange 1 11725 Orange
2,4-Dihydroxyazobenzol 11920 Orange2,4-dihydroxyazobenzene 11920 orange
Solvent Red 3 12010 RotSolvent Red 3 12010 Red
1 -(2'-Chlor-4'-nitro-1 '-phenylazo)-2-hydroxynaphthalin 12085 Rot1 - (2'-chloro-4'-nitro-1 '-phenylazo) -2-hydroxynaphthalene 12085 red
Pigment Red 3 12120 RotPigment Red 3 12120 red
Ceresrot; Sudanrot; Fettrot G 12150 RotCeresrot; Sudan Red; Fat red G 12150 red
Pigment Red 112 12370 RotPigment Red 112 12370 Red
Pigment Red 7 12420 RotPigment Red 7 12420 red
Pigment Brown 1 12480 BraunPigment Brown 1 12480 Brown
4-(2'-Methoxy-5'-sulfosäurediethylamid-1'-phenylazo)-3-hy- 12490 Rot droxy-5"-chloro-2",4"-dimethoxy-2-naphthoesäureanilid4- (2'-Methoxy-5'-sulfonic acid diethylamide-1'-phenylazo) -3-hy- 12490 red hydroxy-5 "-chloro-2", 4 "-dimethoxy-2-naphthoic acid anilide
Disperse Yellow 16 12700 GelbDisperse Yellow 16 12700 Yellow
1 -(4-Sulfo-1 -phenylazoH-amiπo-benzol-δ-sulfosäure 13015 Gelb1 - (4-Sulfo-1-phenylazoH-amino-benzene-δ-sulfonic acid 13015 yellow
2,4-Dihydroxy^azobenzol-4'-sulfosäure 14270 Orange2,4-Dihydroxy ^ azobenzene-4'-sulfonic acid 14270 orange
2-(2,4-Dimethylphenylazo-5-sulfosäure)-1-hydroxynaphthalin- 14700 Rot2- (2,4-dimethylphenylazo-5-sulfonic acid) -1-hydroxynaphthalene-14700 red
4-sulfosäure4-sulfonic acid
2-(4-Sulfo-1 -naphthylazo)-1 -naphthol-4-sulfosäure 14720 Rot2- (4-sulfo-1-naphthylazo) -1 -naphthol-4-sulfonic acid 14720 red
2-(6-Sulfo-2,4-xylylazo)-1-naphthol-5-sulfosäure 14815 Rot2- (6-sulfo-2,4-xylylazo) -1-naphthol-5-sulfonic acid 14815 red
1-(4'-Sulfophenylazo)-2-hydroxynaphthalin 15510 Orange Chemische oder sonstige Bezeichnung CIN Farbe1- (4'-Sulfophenylazo) -2-hydroxynaphthalene 15510 orange Chemical or other name CIN color
1 -(2-Sulfosäure-4-chlor-5-carbonsäure-1 -phenylazo)-2- 15525 Rot hydroxynaphthalin1 - (2-sulfonic acid-4-chloro-5-carboxylic acid-1-phenylazo) -2- 15525 red hydroxynaphthalene
1-(3-Methyl-phenylazo-4-sulfosäure)-2-hydroxynaphthalin 15580 Rot1- (3-methyl-phenylazo-4-sulfonic acid) -2-hydroxynaphthalene 15580 red
1-(4',(8')-Sulfosäurenaphthylazo)-2-hydroxynaphthalin 15620 Rot1- (4 ', (8') - sulfonic acid naphthylazo) -2-hydroxynaphthalene 15620 red
2-Hydroxy-1 ,2'-azonaphthalin-1 '-sulfosäure 15630 Rot2-hydroxy-1, 2'-azonaphthalene-1 'sulfo acid 15630 red
3-Hydroxy-4-phenylazo-2-naphthylcarbonsäure 15800 Rot3-Hydroxy-4-phenylazo-2-naphthylcarboxylic acid 15800 red
1 -(2-Sulfo-4-methyl-1 -phenylazo)-2-naphthylcarbonsäure 15850 Rot1 - (2-Sulfo-4-methyl-1-phenylazo) -2-naphthylcarboxylic acid 15850 red
1 -(2-Sulfo-4-methyl-5-chlor-1 -phenylazo)-2-hydroxy- 15865 Rot naphthalin-3-carbonsäure1 - (2-Sulfo-4-methyl-5-chloro-1-phenylazo) -2-hydroxy- 15865 red naphthalene-3-carboxylic acid
1 -(2-Sulfo-1 -naphthylazo)-2-hydroxynaphthalin-3-carbonsäure 15880 Rot1 - (2-sulfo-1-naphthylazo) -2-hydroxynaphthalene-3-carboxylic acid 15880 red
1 -(3-Sulfo-1 -phenylazo)-2-naphthol-6-sulfosäure 15980 Orange1 - (3-Sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid 15980 orange
1 -(4-Sulfo-1 -phenylazo)-2-naphthol-6-sulfosäure 15985 Gelb1 - (4-Sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid 15985 yellow
Allura Red 16035 RotAllura Red 16035 red
1 -(4-Sulfo-1 -naphthylazo)-2-naphthol-3,6-disulfosäure 16185 Rot1 - (4-Sulfo-1-naphthylazo) -2-naphthol-3,6-disulfonic acid 16185 red
Acid Orange 10 16230 OrangeAcid Orange 10 16230 Orange
1 -(4-Sulfo-1 -naphthylazo)-2-naphthol-6,8-disulfosäure 16255 Rot1 - (4-Sulfo-1-naphthylazo) -2-naphthol-6,8-disulfonic acid 16255 red
1 -(4-Sulfo-1 -naphthylazo)-2-naphthol-3,6,8-trisulfosäure 16290 Rot1 - (4-Sulfo-1-naphthylazo) -2-naphthol-3,6,8-trisulfonic acid 16290 red
8-Amino-2 -phenylazo- 1 -naphthol-3,6-disulfosäure 17200 Rot8-amino-2-phenylazo-1-naphthol-3,6-disulfonic acid 17200 red
Acid Red 1 18050 RotAcid Red 1 18050 Red
Acid Red 155 18130 RotAcid Red 155 18 130 Red
Acid Yellow 121 18690 GelbAcid Yellow 121 18690 yellow
Acid Red 180 18736 RotAcid Red 180 18736 Red
Acid Yellow 11 18820 GelbAcid Yellow 11 18820 Yellow
Acid Yellow 17 18965 GelbAcid Yellow 17 18965 yellow
4-(4-Sulfo-1 -phenylazo)-1 -(4-sulfophenyl)-5-hydroxy- 19140 Gelb pyrazolon-3-carbonsäure4- (4-Sulfo-1-phenylazo) -1 - (4-sulfophenyl) -5-hydroxy-19140 yellow pyrazolone-3-carboxylic acid
Pigment Yellow 16 20040 GelbPigment Yellow 16 20040 yellow
2,6-(4'-Sulfo-2", 4"-dimethyl)-bis-phenylazo)1 ,3-dihydroxy- 20170 Orange benzol2,6- (4'-sulfo-2 ", 4" -dimethyl) bis-phenylazo) 1, 3-dihydroxy- 20170 orange benzene
Acid Black 1 20470 SchwärAcid Black 1 20470 Black
Pigment Yellow 13 21100 GelbPigment Yellow 13 21 100 yellow
Pigment Yellow 83 21108 GelbPigment Yellow 83 21 108 Yellow
Solvent Yellow 21230 GelbSolvent Yellow 21230 yellow
Acid Red 163 24790 RotAcid Red 163 24790 Red
Acid Red 73 27290 RotAcid Red 73 27 290 Red
2-[4'-(4"-Sulfo-1"-phenylazo)-7'-sulfo-1 '-naphthylazo]-1 - 27755 Schwarz hydroxy-7-aminonaphthalin-3,6-disulfosäure2- [4 '- (4 "-sulfo-1" -phenylazo) -7'-sulfo-1' -naphthylazo] -1 - 27755 black hydroxy-7-aminonaphthalene-3,6-disulfonic acid
4'-[(4"-Sulfo-1 "-phenylazo)-7'-sulfo-1 '-naphthylazo]-1 -hydroxy- 28440 Schwarz4 '- [(4 "-sulfo-1" -phenylazo) -7'-sulfo-1' -naphthylazo] -1 -hydroxy- 28440 black
8-acetyl-aminonaphthalin-3,5-disulfosäure8-acetyl-aminonaphthalene-3,5-disulfonic acid
Direct Orange 34, 39, 44, 46, 60 40215 OrangeDirect Orange 34, 39, 44, 46, 60 40215 Orange
Food Yellow 40800 Orange trans-ß-Apo-8'-Carotinaldehyd (C30) 40820 Orange trans-Apo-8'-Carotinsäure (C3o)-ethylester 40825 OrangeFood Yellow 40800 orange trans-beta-apo-8'-Carotinaldehyd (C30) 40820 orange trans-Apo-8'-carotene acid (C 3 o) ethyl ester 40825 orange
Canthaxanthin 40850 OrangeCanthaxanthin 40850 orange
Acid Blue 1 42045 BlauAcid Blue 1 42045 Blue
2,4-Disulfo-5-hydroxy-4'-4"-bis-(diethylamino)triphenyl- 42051 Blau carbinol2,4-disulfo-5-hydroxy-4'-4 "-bis- (diethylamino) triphenyl- 42051 blue carbinol
4-[(-4-N-Ethyl-p-sulfobenzylamino)-phenyl-(4-hydroxy-2-sulfo- 42053 Grün phenyl)-(methylen)-1-(N-ethylN-p-sulfobenzyl)-2,5- Chemische oder sonstige Bezeichnung CIN Farbe cyclohexadienimin]4 - [(- 4-N-ethyl-p-sulfobenzylamino) phenyl- (4-hydroxy-2-sulfo-42053 green phenyl) - (methylene) -1- (N-ethylN-p-sulfobenzyl) -2, 5 Chemical or other name CIN color cyclohexadienimine]
Acid Blue 7 42080 BlauAcid Blue 7 42080 Blue
(N-Ethyl-p-sulfobenzyl-amino)-phenyl-(2-sulfophenyl)- 42090 Blau methylen-(N-ethyl-N-p-sulfo-benzyl)Δ2, -cyclohexadienimin(N-ethyl-p-sulfobenzylamino) phenyl- (2-sulfophenyl) - 42090 blue methylene- (N-ethyl-Np-sulfobenzyl) Δ 2, -cyclohexadienimine
Acid Green 9 42100 GrünAcid Green 9 42 100 Green
Diethyl-di-sulfobenzyl-di-4-amino-2-chlor-di-2-methyl- 42170 Grün fuchsonimmoniumDiethyl-di-sulfobenzyl-di-4-amino-2-chloro-di-2-methyl- 42170 green foxsonmonium
Basic Violet 14 42510 ViolettBasic Violet 14 42510 Violet
Basic Violet 2 42520 ViolettBasic Violet 2 42520 Violet
2'-Methyl-4'-(N-ethyl-N-m-sulfobenzyl)-amino-4"-(N-diethyl)- 42735 Blau amino-2-methyl-N-ethylN-m-sulfobenzyl-fuchsonimmonium2'-Methyl-4 '- (N-ethyl-N-m-sulfobenzyl) -amino-4 "- (N-diethyl) - 42735 Blue amino-2-methyl-N-ethylN-m-sulfobenzyl-fuchsonimmonium
4'-(N-Dimethyl)-amino-4"-(N-phenyl)-aminonaphtho-N- 44045 Blau dimethyl-fuchsonimmonium4 '- (N-Dimethyl) -amino-4 "- (N-phenyl) -aminonaphtho-N- 44045 blue dimethyl-fuchsonimmonium
2-Hydroxy-3,6-disulfo-4,4'-bis-dimethylamino- 44090 Grün naphthofuchsonimmonium2-hydroxy-3,6-disulfo-4,4'-bis-dimethylamino- 44090 green naphthofuchsonimmonium
Acid Red 52 45100 RotAcid Red 52 45 100 Red
3-(2'-Methylphenylamino)-6-(2'-methyl-4'-sulfophenylamino)- 45190 Violett3- (2'-Methylphenylamino) -6- (2'-methyl-4'-sulfophenylamino) - 45190 Violet
9-(2"-carboxyphenyl)-xantheniumsalz9- (2 'carboxyphenyl) -xantheniumsalz
Acid Red 50 45220 RotAcid Red 50 45 220 Red
Phenyl-2-oxyfluoron-2-carbonsäure 45350 GelbPhenyl-2-oxyfluoron-2-carboxylic acid 45350 yellow
4,5-Dibromfluorescein 45370 Orange4,5-dibromofluorescein 45370 orange
2,4,5,7-Tetrabromfluorescein 45380 Rot2,4,5,7-tetrabromofluorescein 45380 red
Solvent Dye 45396 OrangeSolvent Dye 45396 Orange
Acid Red 98 45405 RotAcid Red 98 45405 Red
3',4',5',6'-Tetrachlor-2,4,5,7-tetrabromfluorescein 45410 Rot3 ', 4', 5 ', 6'-tetrachloro-2,4,5,7-tetrabromofluorescein 45410 red
4,5-Diiodfluorescein 45425 Rot4,5-diiodofluorescein 45425 red
2,4,5,7-Tetraiodfluorescein 45430 Rot2,4,5,7-tetraiodofluorescein 45430 red
Chinophthalon 47000 GelbQuinophthalone 47000 yellow
Chinophthalon-disulfosäure 47005 GelbQuinophthalone disulfonic acid 47005 yellow
Es kann femer günstig sein, als Farbstoff eine oder mehrer Substanzen aus der folgenden Gruppe zu wählen: 2,4-Dihydroxyazobenzol, 1-(2'-Chlor-4'-nitro-1'- phenylazo)-2-hydroxynaphthalin, Ceresrot, 2-(4-Sulfo-1 -naphthylazo)-1 -naphthol-4-sulfo- säure, Calciumsalz der 2-Hydroxy-1,2"azonaphthalin-1 '-'ulfosäure, Caicium- und Bariumsalze der 1-(2-Sulfo-4-methyl-1-phenylazo)-2-naphthylcarbonsäure, Calciumsalz der 1-(2-Surfo-1-naphthylazo)-2-hydroxynaphthalin-3-carbonsäure, Aluminiumsalz der 1- (4-Sulfo-1-phenylazo)-2-naphthol-6-sulfosäure, Aluminiumsalz der 1-(4-Sulfo-1- naphthylazo)-2-naphthol-3,6-disulfosäure, 1 -(4-Surfo-1 -naphthylazo)-2-naphthol-6,8- disulfosäure, Aluminiumsalz der 8-Amino-2 -phenylazo- 1 -naphthol-3,6-disurfosäure , Aluminiumsalz der 4-(4-Sulfo-1-phenylazo)-1-(4-sulfophenyl)-5-hydroxy-pyrazolon-3- carbonsäure, 4'-[(4"-Sulfo-1 "-phenylazo)-7'-sulfo-1 '-naphthylazo]-1 -hydroxy-8-acetyl- aminonaphthalin-3,5-disulfosäure, Aluminium- und Zirkoniumsalze von 4,5-Dibromflu- orescein, Aluminium- und Zirkoniumsalze von 2,4,5,7-Tetrabromfluorescein, 3"4"5"6"Te- trachlor-2,4,5,7-tetrabromfluorescein und sein Aluminiumsalz, Aluminiumsalz von 2,4,5,7-Tetraiodfluorescein, Aluminiumsalz der Chinophthalon-disulfosäure, Aluminiumsalz der Indigo-disulfosäure, 4,4'-Di'ethyl-6,6'-di'hlorthioindigo, Komplexsalz (Na, AI, Ca) der Karminsäure, rotes und schwarzes Eisenoxid (CIN: 77491 (rot) und 77499 (schwarz)), Eisenoxidhydrat (CIN: 77 492), Manganammoniumdiphosphat (CIN 77745), Ultramarin (CIN 77007) und Titandioxid.It may also be favorable to choose one or more substances from the following group as the dye: 2,4-dihydroxyazobenzene, 1- (2'-chloro-4'-nitro-1'-phenylazo) -2-hydroxynaphthalene, ceres red, 2- (4-sulfo-1-naphthylazo) -1 -naphthol-4-sulfonic acid, calcium salt of 2-hydroxy-1,2 "azonaphthalene-1 '-'ulfonic acid, calcium and barium salts of 1- (2- Sulfo-4-methyl-1-phenylazo) -2-naphthylcarboxylic acid, calcium salt of 1- (2-surfo-1-naphthylazo) -2-hydroxynaphthalene-3-carboxylic acid, aluminum salt of 1- (4-sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid, aluminum salt of 1- (4-sulfo-1-naphthylazo) -2-naphthol-3,6-disulfonic acid, 1 - (4-surfo-1-naphthylazo) -2-naphthol-6 , 8-disulfonic acid, aluminum salt of 8-amino-2-phenylazo-1-naphthol-3,6-disurfonic acid, aluminum salt of 4- (4-sulfo-1-phenylazo) -1- (4-sulfophenyl) -5-hydroxy -pyrazolone-3-carboxylic acid, 4 '- [(4 "-sulfo-1" -phenylazo) -7'-sulfo-1' -naphthylazo] -1 -hydroxy-8-acetylaminonaphthalene-3,5-disulfonic acid, Aluminum and zirconium salts of 4.5 -Dibromofluorescein, aluminum and zirconium salts of 2,4,5,7-tetrabromofluorescein, 3 "4" 5 "6" Te- trachloro-2,4,5,7-tetrabromofluorescein and its aluminum salt, aluminum salt of 2,4,5,7-tetraiodofluorescein, aluminum salt of quinophthalone disulfonic acid, aluminum salt of indigo disulfonic acid, 4,4'-di'ethyl-6, 6'-di'hlorthioindigo, complex salt (Na, Al, Ca) of carminic acid, red and black iron oxide (CIN: 77491 (red) and 77499 (black)), iron oxide hydrate (CIN: 77 492), manganese ammonium diphosphate (CIN 77745), Ultramarine (CIN 77007) and titanium dioxide.
Erfindungsgemäße Emulsionen können Titandioxide enthalten, die sowohl in der Kristallmodifikation Rutil als auch Anatas vorliegen können und im Sinne der vorliegenden Erfindung vorteilhaft oberflächlich behandelt („gecoatef) ist, wobei beispielsweise ein hydrophiler, amphiphiler oder hydrophober Charakter 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 Oberflächenbeschichtungen können im Sinne der vorliegenden Erfindung auch Wasser enthalten.Emulsions according to the invention can contain titanium dioxides, which can be present both in the rutile and anatase crystal modification and, for the purposes of the present invention, are advantageously surface-treated (“gecoatef”), for example a hydrophilic, amphiphilic or hydrophobic character is to be formed or retained. This surface treatment can consist in that the pigments are provided with a thin hydrophilic and / or hydrophobic inorganic and / or organic layer by methods known per se. For the purposes of the present invention, the various surface coatings can also contain water.
Anorganische Oberflächenbeschichtungen im Sinne der vorliegenden Erfindung können bestehen aus Aluminiumoxid (Al203), Aluminiumhydroxid AI(OH)3, bzw. Aluminiumoxidhydrat (auch: Alumina, CAS-Nr.: 1333-84-2), Natriumhexametaphosphat (NaP03)6, Natriummetaphosphat (NaP03)n, Siliciumdioxid (Si02) (auch: Silica, CAS-Nr.: 7631-86-9), Zirkoniumoxid (Zr02) oder Eisenoxid (Fβ2θ3). Diese anorganischen Oberflächenbeschichtungen können allein, in Kombination und/oder in Kombination mit organischen Beschichtungsmaterialien vorkommen.Inorganic surface coatings in the sense of the present invention can consist of aluminum oxide (Al 2 0 3 ), aluminum hydroxide Al (OH) 3 , or aluminum oxide hydrate (also: alumina, CAS no .: 1333-84-2), sodium hexametaphosphate (NaP0 3 ) 6 , sodium metaphosphate (NaP0 3 ) n , silicon dioxide (Si0 2 ) (also: silica, CAS No .: 7631-86-9), zirconium oxide (Zr0 2 ) or iron oxide (Fβ2θ 3 ). These inorganic surface coatings can occur alone, in combination and / or in combination with organic coating materials.
Hierzu werden Oxide, Oxidhydrate oder Phosphate beispielsweise der Elemente AI, Si, Zr in dichten Schichten auf die Pigmentoberfläche aufgefällt.For this purpose, oxides, oxide hydrates or phosphates, for example of the elements Al, Si, Zr, are struck in dense layers on the pigment surface.
Die anorganische Nachbehandlung geschieht im allgemeinen in einer wässrigen Suspension des Pigmentes durch Zugabe löslicher Nachbehandlungschemikalien, wie z.B. Aluminiumsulfat, und anschließende Ausfällung des im neutralen Bereich schwerlöslichen Hydroxides durch gezielte Einstellung des pH-Wertes mit Natronlauge. Nach der anorganischen Nachbehandlung werden die gecoateten Pigmente durch Filtration aus der Suspension abgetrennt und sorgfältig gewaschen, um die gelösten Salze zu entfernen, anschließend werden die isolierten Pigmente getrocknet. Besonders bevorzugt im Sinne dieser Erfindung sind Titandioxide, auf die Aluminiumhydroxid auf die Oberfläche aufgebracht worden ist, wie z.B. die von Sun Chemical erhältlichen Titandioxid Typen C47-051 und C47- 5175. Weiterhin bevorzugte Pigmente sind Titandioxide, die mit Aluminium- und / oder Siliziumoxiden gecoated sind, wie z.B. von der Firma Krosnos Titan: Kronos 1071 und 1075 oder von der Firma Kingfisher: A310.03 Tudor Aspen.The inorganic aftertreatment generally takes place in an aqueous suspension of the pigment by adding soluble aftertreatment chemicals, such as, for example, aluminum sulfate, and then precipitating the hydroxide, which is sparingly soluble in the neutral range, by specifically adjusting the pH with sodium hydroxide solution. After the inorganic aftertreatment, the coated pigments are separated from the suspension by filtration and washed carefully to remove the dissolved salts, and then the isolated pigments are dried. For the purposes of this invention, particular preference is given to titanium dioxides to which aluminum hydroxide has been applied to the surface, such as, for example, titanium dioxide types C47-051 and C47- 5175 available from Sun Chemical. Further preferred pigments are titanium dioxides containing aluminum and / or silicon oxides are coated, such as from Krosnos Titan: Kronos 1071 and 1075 or from Kingfisher: A310.03 Tudor Aspen.
Organische Oberflächenbeschichtungen im Sinne der vorliegenden Erfindung können bestehen aus pflanzlichem oder tierischem Aluminiumstearat, pflanzlicher oder tierischer Stearinsäure, Laurinsäure, Dimethylpolysiloxan (auch: Dimethicone), Methylpolysiloxan (Methicone), Simethicone (einem Gemisch aus Dimethylpolysiloxan mit einer durchschnittlichen Kettenlänge von 200 bis 350 Dimethylsiloxan-Einheiten und Silicagel) oder Alginsäure. Diese organischen Oberflächenbeschichtungen können allein, in Kombination und/oder in Kombination mit anorganischen Beschichtungsmaterialien vorkommen.Organic surface coatings in the sense of the present invention can consist of vegetable or animal aluminum stearate, vegetable or animal stearic acid, lauric acid, dimethylpolysiloxane (also: dimethicone), methylpolysiloxane (methicone), simethicone (a mixture of dimethylpolysiloxane with an average chain length of 200 to 350 dimethylsiloxane Units and silica gel) or alginic acid. These organic surface coatings can occur alone, in combination and / or in combination with inorganic coating materials.
Ferner kann es erfindungsgemäß vorteilhaft sein Perlglanzpigmente einzusetzen. Dazu zählen natürliche Perlglanzpigmente, wie z. B.Furthermore, it can be advantageous to use pearlescent pigments according to the invention. These include natural pearlescent pigments such as B.
„Fischsilber" (Guanin/Hypoxanthin-Mischkristalle aus Fischschuppen) und"Fish silver" (guanine / hypoxanthine mixed crystals from fish scales) and
„Perlmutt" (vermahlene Muschelschalen),"Mother-of-pearl" (milled mussel shells),
monokristalline Perlglanzpigmente wie z. B. Bismuthoxychlorid (BiOCI), Schicht-Substrat Pigmente: z. B. Glimmer / Metalloxidmonocrystalline pearlescent pigments such as B. bismuth oxychloride (BiOCI), layer-substrate pigments: e.g. B. mica / metal oxide
Basis für Perlglanzpigmente sind beispielsweise pulverförmige Pigmente oder Ricinusöldispersionen von Bismutoxychlorid und/oder Titandioxid sowie Bismutoxychlorid und/oder Titandioxid auf Glimmer. Insbesondere vorteihaft ist z. B. das unter der CIN 77163 aufgelistete Glanzpigment.Pearlescent pigments are based, for example, on powdered pigments or castor oil dispersions of bismuth oxychloride and / or titanium dioxide and bismuth oxychloride and / or titanium dioxide on mica. Particularly advantageous is e.g. B. the gloss pigment listed under CIN 77163.
Vorteilhaft sind ferner beispielsweise die folgenden Perlglanzpigmentarten auf Basis von Glimmer/Metalloxid:The following pearlescent pigment types based on mica / metal oxide are also advantageous:
Figure imgf000038_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000039_0001
Besonders bevorzugt sind die von der Firma Merck unter den Handelsnamen Timiron, Colorona oder Dichrona erhältlichen Perlglanzpigmente.The pearlescent pigments available from Merck under the trade names Timiron, Colorona or Dichrona are particularly preferred.
Die Liste der genannten Perlglanzpigmente soll selbstverständlich nicht limitierend sein. Im Sinne der vorliegenden Erfindung vorteilhafte Perlglanzpigmente sind auf zahlreichen, an sich bekannten Wegen erhältlich. Beispielsweise lassen sich auch andere Substrate außer Glimmer mit weiteren Metalloxiden beschichten, wie z. B. Silica und dergleichen mehr. Vorteilhaft sind z. B. mit Ti02 und Fe2θ3 beschichtete Si02-Partikel („Ronaspheren"), die von der Firma Merck vertrieben werden.The list of the pearlescent pigments mentioned is of course not intended to be limiting. Pearlescent pigments which are advantageous in the sense of the present invention can be obtained in numerous ways known per se. For example, other substrates besides mica can be coated with other metal oxides, such as. B. silica and the like. Z are advantageous. B. with Ti0 2 and Fe 2 θ3 coated Si0 2 particles ("Ronaspheren"), which are sold by Merck.
Es kann darüber hinaus von Vorteil sein, gänzlich auf ein Substrat wie Glimmer zu verzichten. Besonders bevorzugt sind Perlglanzpigmente, welche unter der Verwendung von Si02 hergestellt werden. Solche Pigmente, die auch zusätzlich gonichromatische Effekte haben können, sind z. B. unter dem Handelsnamen Sicopearl Fantastico bei der Firma BASF erhältlich.It can also be advantageous to completely do without a substrate such as mica. Pearlescent pigments which are produced using SiO 2 are particularly preferred. Such pigments, which can also have gonichromatic effects, are e.g. B. available under the trade name Sicopearl Fantastico from BASF.
Weiterhin vorteilhaft können Pigmente der Firma Engelhard / Mearl auf Basis von Caicium Natrium Borosilikat, die mit Titandioxid beschichtet sind, eingesetzt werden. Diese sind unter dem Namen Reflecks erhältlich. Sie weisen durch ihrer Partikelgröße von 40 - 180 μm zusätzlich zu der Farbe einen Glitzereffekt auf.Pigments from Engelhard / Mearl based on calcium sodium borosilicate, which are coated with titanium dioxide, can also be used advantageously. These are available under the name Reflecks. Due to their particle size of 40 - 180 μm, they have a glitter effect in addition to the color.
Die Farbstoffe und Pigmente können sowohl einzeln als auch im Gemisch vorliegen sowie gegenseitig miteinander beschichtet sein, wobei durch unterschiedliche Be- schichtungsdicken im allgemeinen verschiedene Farbeffekte hervorgerufen werden. Die Gesamtmenge der Farbstoffe und farbgebenden Pigmente wird vorteilhaft aus dem Bereich von z. B. 0,1 Gew.-% bis 30 Gew.-%, vorzugsweise von 0,5 bis 15 Gew.-%, insbesondere von 1,0 bis 10 Gew.-% gewählt, jeweils bezogen auf das Gesamtgewicht der Zubereitungen. Die Gewichtsangaben beziehen sich dabei auf die Zusammensetzung der Zubereitung vor der Trocknung mittels Gefrier- und/oder Sprühtrocknung.The dyes and pigments can be present both individually and in a mixture and can be mutually coated, different color effects generally being produced by different coating thicknesses. The The total amount of dyes and coloring pigments is advantageously from the range of z. B. 0.1 wt .-% to 30 wt .-%, preferably from 0.5 to 15 wt .-%, in particular from 1.0 to 10 wt .-%, each based on the total weight of the preparations. The weight data relate to the composition of the preparation before drying by means of freeze and / or spray drying.
Vorteilhaft im Sinne der vorliegenden Erfindung enthält die erfindungsgemäße O/W- Emulsion einen oder mehrere Tablettenhilfsstoffe. Diese können erfindungsgemäß vorteilhaft in einer Konzentration von 0,1 bis 60 Gewichts-%, bevorzugt in einer Konzentration von 1 bis 50 Gewichts-% und ganz besonders bevorzugt in einer Konzentration von 3 bis 35 Gewichts-%, jeweils bezogen auf das Gesamtgewicht der Zubereitung eingesetzt werden. Die Gewichtsangaben beziehen sich dabei auf die Zusammensetzung der Zubereitung wobei als Zubereitung die Emulsion nach der Gefrier- und/oder Sprühtrocknung zusammen mit evtl. weiteren wasserlöslichen und/oder leichtflüchtigen Verbindungen und Tablettierstoffen (inkl. Hydrogencarbonaten und bei Raumtemperatur festen Säuren) angesehen wird.The O / W emulsion according to the invention advantageously contains one or more tablet auxiliaries. According to the invention, these can advantageously be in a concentration of 0.1 to 60% by weight, preferably in a concentration of 1 to 50% by weight and very particularly preferably in a concentration of 3 to 35% by weight, in each case based on the total weight of the preparation be used. The weight data relate to the composition of the preparation, the preparation being considered to be the emulsion after freeze and / or spray drying, together with any other water-soluble and / or volatile compounds and tableting materials (including hydrogen carbonates and acids which are solid at room temperature).
Als Tablettenhilfsstoffe können beispielsweise Füll- und Kopaktierhilfsstoffe (z.B. Stärke- und/oder Cellulosederivate), Fließmittel (z.B.hochdisperse Siliziumdioxide), Fließreguliermittel, Schmiermittel, Formtrennmittel eingesetzt werden.For example, fillers and compacting aids (e.g. starch and / or cellulose derivatives), flow agents (e.g. highly disperse silicon dioxide), flow control agents, lubricants, mold release agents can be used as tablet auxiliaries.
Erfindungsgemäß vorteilhaft können alle Stoffe eingesetzt werden, die im H.P. Fiedler, Lexikon der Hilfsstoffe für Pharmazie, Kosmetik und angrenzenden Gebiete, 5. Auflage, Editio Cantor Verlag, Aulendorf, 2002, unter den Stichworten Tabletten-Bindemittel, Tabletten-Füllstoffe, Tabletten-Gleitmittel, Tabletten-Hilfsstoffe, Tabletten-Sprengmittel, Tabletten-Überzüge aufgelistetet sind.Advantageously according to the invention, all substances can be used that are in the H.P. Fiedler, Lexicon of auxiliaries for pharmacy, cosmetics and related areas, 5th edition, Editio Cantor Verlag, Aulendorf, 2002, under the keywords tablet binders, tablet fillers, tablet lubricants, tablet auxiliaries, tablet disintegrants, tablet Coatings are listed.
In einer erfindungsgemäß besonders bevorzugten Ausführungsform enthält die erfindungsgemäße Zubereitung eine Kombination aus Carbonaten und/oder Hydrogencarbonaten sowie bei Raumtemperatur festen Säuren (z.B. Zitronensäure, Ascorbinsäure, Milchsäure, Weinsäure, etc). Auch stark quellende Polymere wie beispielsweise vernetztes Polyvinylpyrrolidon kann erfindungsgemäß vorteilhaft eingesetzt werden. Erfindungsgemäß vorteilhaft werden ein oder mehrere Hydrogencarbonate (z.B. Natriumhydrogencarbonat, Kaliumhydrogencarbonat) in einer Menge von 0,1 bis 30 Gewichts-%, bevorzugt in einer Menge von 0,5 bis 20 Gewichts-% und besonders bevorzugt in einer Menge von 0,5 bis 15 Gewichts-%, jeweils bezogen auf das Gesamtgewicht der Zubereitung eingesetzt, wobei als Zubereitung die Emulsion nach der Gefrier- und/oder Sprühtrocknung zusammen mit evi. weiteren wasserlöslichen und/oder und/oder leichtflüchtigen Verbindungen und Tablettierstoffen (inkl. Hydrogencarbonaten und bei Raumtemperatur festen Säuren) angesehen wird.In a particularly preferred embodiment according to the invention, the preparation according to the invention contains a combination of carbonates and / or hydrogen carbonates and acids which are solid at room temperature (for example citric acid, ascorbic acid, lactic acid, tartaric acid, etc.). Strongly swelling polymers such as crosslinked polyvinylpyrrolidone can also be used advantageously according to the invention. According to the invention, one or more hydrogen carbonates (for example sodium hydrogen carbonate, potassium hydrogen carbonate) are advantageous in an amount of 0.1 to 30% by weight, preferably in an amount of 0.5 to 20% by weight and particularly preferably in an amount of 0.5 to 15% by weight, based in each case on the total weight of the preparation, the emulsion being the preparation after the freeze and / or spray drying together with evi. other water-soluble and / or and / or volatile compounds and tableting materials (including hydrogen carbonates and acids solid at room temperature) is considered.
Erfindungsgemäß vorteilhaft werden ein oder mehrere bei Raumtemperatur feste Säuren (besonders bevorzugt Zitronensäure) in einer Menge von 0,1 bis 30 Gewichts-%, bevorzugt in einer Menge von 0,5 bis 20 Gewichts-% und besonders bevorzugt in einer Menge von 0,5 bis 15 Gewichts-%, jeweils bezogen auf das Gesamtgewicht der Zubereitung eingesetzt, wobei als Zubereitung die Emulsion nach der Gefrier- und/oder Sprühtrocknung zusammen mit evtl. weiteren wasseriöslichen und/oder leichtflüchtigen Verbindungen und Tablettierstoffen (inkl. Hydrogencarbonaten und bei Raumtemperatur festen Säuren) angesehen wird.According to the invention, one or more acids which are solid at room temperature (particularly preferably citric acid) are advantageous in an amount of 0.1 to 30% by weight, preferably in an amount of 0.5 to 20% by weight and particularly preferably in an amount of 0, 5 to 15% by weight, based in each case on the total weight of the preparation, the emulsion being used after the freeze and / or spray drying together with any further water-soluble and / or volatile compounds and tableting materials (including hydrogen carbonates and solid at room temperature) Acids) is considered.
Eine derartige Ausführungeform ist insbesondere dann vorteilhaft im Sinne der vorliegenden Erfindung, wenn die erfindungsgemäße Emulsion in Form einer Tablette (z.B. einer Brausetablette) vorliegt, da sich die erfindungsgemäße Emulsion in dieser Ausführungsform besonders leicht durch Zusatz von Wasser reemulgieren läßt.Such an embodiment is particularly advantageous in the sense of the present invention if the emulsion according to the invention is in the form of a tablet (e.g. an effervescent tablet), since the emulsion according to the invention in this embodiment is particularly easy to re-emulsify by adding water.
Erfindungsgemäß ist auch das Verfahren zur Herstellung einer derartigen Zubereitung, welches dadurch gekennzeichnet ist, dass die erfindungsgemäße O/W-Emulsion mit einem oder mehreren Tablettenhilfsstoffen in einer Mischungsvorrichtung vermischt werden.According to the invention is also the method for producing such a preparation, which is characterized in that the O / W emulsion according to the invention are mixed with one or more tablet auxiliaries in a mixing device.
Erfindungsgemäß sind auch Zubereitungen, die nach diesem erfindungsgemäßen Verfahren hergestellt werden.Preparations which are produced by this process according to the invention are also according to the invention.
Erfindungsgemäß ist ferner ein Verfahren zur Herstellung von Tabletten und/oder Granulaten, welches dadurch gekennzeichnet ist, dass eine erfindungsgemäße Zubereitung in einer Presse zu einer oder mehreren Tabletten gepresst oder granuliert wird, sowie Zubereitungen, die nach diesem Verfahren hergestellt werden.According to the invention is also a method for producing tablets and / or granules, which is characterized in that an inventive Preparation is pressed or granulated in a press to form one or more tablets, and preparations which are produced by this process.
Erfindungsgemäß ist nicht zuletzt das Verfahren zur Herstellung eines Kosmetikums, welches dadurch gekennzeichnet ist, dass eine erfindungsgemäße Zubereitung (eine durch Sprühtrocknung und/oder Gefriertrocknung getrocknete O/W-Emulsion, die gegebenenfalls mit wasserlöslichen und/oder leichtflüchtigen Wirk-, Hilfs- Zusatzstoffen und/oder Tablettenhilfsstoffen versetzt sowie gegebenenfalls tabletiert bzw. granuliert wurde) mit Wasser versetzt bzw. in Wasser emulgiert wird. Erfindungsgemäß sind auch Kosmetika, die nach diesem Verfahren hergestellt werden.Last but not least, the process for producing a cosmetic is according to the invention, which is characterized in that a preparation according to the invention (an O / W emulsion dried by spray drying and / or freeze drying, optionally with water-soluble and / or volatile active ingredients, auxiliary additives and / or tablet auxiliaries are added and, if appropriate, was tableted or granulated) is mixed with water or emulsified in water. Cosmetics which are produced by this method are also according to the invention.
Ein derartiges erfindungsgemäßes Kosmetikum liegt dann in Form einer Salbe, Creme, Lotion oder eines Emulsionsschaumes (franz. Mousse) oder einer sprühbaren Form vor. Es kann erfindungsgemäß vorteilhaft zur Behandlung und Pflege der Haut, Haare und Nägel eingesetzt werden. Erfindungsgemäß bevorzugt ist dabei die Verwendung als Sonnenschutzmittel.Such a cosmetic according to the invention is then in the form of an ointment, cream, lotion or an emulsion foam (French mousse) or a sprayable form. According to the invention, it can advantageously be used for the treatment and care of the skin, hair and nails. According to the invention, use as a sunscreen is preferred.
Die nachfolgenden Beispiele sollen die vorliegende Erfindung verdeutlichen, ohne sie einzuschränken. Alle Mengenangaben, Anteile und Prozentanteile sind, soweit nicht anders angegeben, auf das Gewicht und die Gesamtmenge bzw. auf das Gesamtgewicht der Zubereitungen bezogen.The following examples are intended to illustrate the present invention without restricting it. Unless otherwise stated, all quantities, parts and percentages are based on the weight and the total amount or on the total weight of the preparations.
Die Beispiele aus Tabelle 1 (Emulsions- Zubereitungen nach Sprühtrocknung) werden erfindungsgemäß mit Stoffmischungen der wasserlöslichent-dipergierbaren Zusätze (Tabelle 2) homogen vermischt.According to the invention, the examples from Table 1 (emulsion preparations after spray drying) are mixed homogeneously with mixtures of the water-soluble and dispersible additives (Table 2).
Optional können die Stoffmischungen (Tabelle 1+2) mit Tablettier- und Granulierhilfsstoffen (Tabelle 3) vermischt und erfindungsgemäße Granulate und/oder Tabletten nach geeigneten Verfahren hergestellt werden. Beispiele:Optionally, the substance mixtures (Tables 1 + 2) can be mixed with tableting and granulating aids (Table 3) and granules and / or tablets according to the invention can be produced by suitable processes. Examples:
Tabelle 1: Emulsionszubereitung nach Sprüh-/ bzw. GefriertrocknungTable 1: Emulsion preparation after spray or freeze drying
Figure imgf000043_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000045_0001

Claims

Patentansprüche claims
1. Verfahren zur Herstellung einer O/W-Emulsion, dadurch gekennzeichnet, dass eine O/W-Emulsion enthaltend a) eine Lipidphase in einer Konzentration von 20 bis 95 Gewichts-%, b) ein oder mehrere wasserlösliche Polymere in einer Gesamtkonzentration von 1 bis 80 Gewichts-%, jeweils bezogen auf das Gesamtgewicht der Zubereitung, sowie c) ein oder mehrere UV-Lichtschutzfilter und d) eine wässrige Phase, neben gegebenenfalls weiteren kosmetischen und/oder dermatologischen Wirk-, Hilfs- und Zusatzstoffen, durch Sprühtrocknung und/oder Gefriertrocknung getrocknet wird.1. A process for producing an O / W emulsion, characterized in that an O / W emulsion containing a) a lipid phase in a concentration of 20 to 95% by weight, b) one or more water-soluble polymers in a total concentration of 1 up to 80% by weight, in each case based on the total weight of the preparation, and c) one or more UV light protection filters and d) an aqueous phase, in addition to any other cosmetic and / or dermatological active ingredients, auxiliaries and additives, by spray drying and / or freeze drying.
2. O/W-Emulsion hergestellt nach einem Verfahren nach Anspruch 1.2. O / W emulsion produced by a process according to claim 1.
3. Verfahren zur Herstellung einer O/W-Emulsion, dadurch gekennzeichnet, dass eine O/W-Emulsion nach einem der Ansprüche 1 oder 2 in einer Mischungsvorrichtung mit wasserlöslichen und/oder leichtflüchtigen Wirk-, Hilfs- und/oder Zusatzstoffen vermischt wird.3. A process for producing an O / W emulsion, characterized in that an O / W emulsion according to one of claims 1 or 2 is mixed in a mixing device with water-soluble and / or volatile active ingredients, auxiliaries and / or additives.
4. O/W-Emulsion hergestellt nach einem Verfahren nach Anspruch 3.4. O / W emulsion produced by a method according to claim 3.
5. Zubereitung enthaltend eine O/W-Emulsion nach einem der Ansprüche 2 oder 4 sowie einen oder mehrere Granulier- und/oder Tablettenhilfsstoffe.5. Preparation containing an O / W emulsion according to one of claims 2 or 4 and one or more granulating and / or tablet auxiliaries.
6. Verfahren zur Herstellung einer Zubereitung nach Anspruch 5, dadurch gekennzeichnet, dass eine O/W-Emulsion nach einem der Ansprüche 2 oder 4 mit einem oder mehreren Tablettenhilfsstoffen in einer Mischungsvorrichtung vermischt werden.6. A method for producing a preparation according to claim 5, characterized in that an O / W emulsion according to one of claims 2 or 4 is mixed with one or more tablet excipients in a mixing device.
7. Zubereitung hergestellt nach einem Verfahren nach Anspruch 6.7. Preparation prepared by a method according to claim 6.
8. Verfahren zur Herstellung von Tabletten und/oder Granulaten, dadurch gekennzeichnet, dass eine Zubereitung nach Anspruch 7 in einer Presse zu einer oder mehreren Tabletten gepresst oder mittels geeigneter Granuliervorrichtungen granuliert werden.8. A process for the production of tablets and / or granules, characterized in that a preparation according to claim 7 is pressed in a press to form one or more tablets or granulated by means of suitable granulating devices.
9. Zubereitung hergestellt nach einem Verfahren nach Anspruch 8.9. Preparation produced by a method according to claim 8.
10. Verfahren zur Herstellung eines Kosmetikums dadurch gekennzeichnet, dass eine Zubereitung nach einem der Ansprüche 2, 4, 5, 7 und/oder 9 mit Wasser versetzt werden.10. A method for producing a cosmetic, characterized in that a preparation according to one of claims 2, 4, 5, 7 and / or 9 are mixed with water.
11. Kosmetikum hergestellt nach einem Verfahren nach Anspruch 10. 11. Cosmetic manufactured by a method according to claim 10.
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WO2010060776A1 (en) * 2008-11-25 2010-06-03 L'oreal Photoprotective composition containing an unmodified gelling starch and polyamide particles
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US20140287005A1 (en) * 2008-11-25 2014-09-25 L'oreal Photoprotective composition containing an unmodified gelling starch and polyamide particles
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