WO2003105791A1 - Use of astaxanthin - Google Patents

Use of astaxanthin Download PDF

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Publication number
WO2003105791A1
WO2003105791A1 PCT/EP2003/005969 EP0305969W WO03105791A1 WO 2003105791 A1 WO2003105791 A1 WO 2003105791A1 EP 0305969 W EP0305969 W EP 0305969W WO 03105791 A1 WO03105791 A1 WO 03105791A1
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WO
WIPO (PCT)
Prior art keywords
astaxanthin
acid
hair
derivatives
fatty
Prior art date
Application number
PCT/EP2003/005969
Other languages
German (de)
French (fr)
Inventor
Wolf Eisfeld
Annette Mehling
Original Assignee
Cognis Deutschland Gmbh & Co. Kg.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cognis Deutschland Gmbh & Co. Kg. filed Critical Cognis Deutschland Gmbh & Co. Kg.
Publication of WO2003105791A1 publication Critical patent/WO2003105791A1/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/06Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065Preparations for temporary colouring the hair, e.g. direct dyes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00Medicinal preparations containing organic active ingredients
    • A61K31/045Hydroxy compounds, e.g. alcohols; Salts thereof, e.g. alcoholates
    • A61K31/07Retinol compounds, e.g. vitamin A
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00Medicinal preparations containing organic active ingredients
    • A61K31/33Heterocyclic compounds
    • A61K31/335Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
    • A61K31/35Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having six-membered rings with one oxygen as the only ring hetero atom
    • A61K31/352Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having six-membered rings with one oxygen as the only ring hetero atom condensed with carbocyclic rings, e.g. methantheline 
    • A61K31/3533,4-Dihydrobenzopyrans, e.g. chroman, catechin
    • A61K31/355Tocopherols, e.g. vitamin E
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/31Hydrocarbons
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35Ketones, e.g. benzophenone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/67Vitamins
    • A61K8/678Tocopherol, i.e. vitamin E
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q7/00Preparations for affecting hair growth

Definitions

  • the invention is in the field of cosmetic and pharmaceutical preparations. It relates to the use of astaxanthin, which is obtained primarily from algae, for the preparation of agents which are used against hair loss, for strengthening the hair and for protection against UV light and against graying of the hair.
  • Astaxanthin is a carotenoid obtained from microalgae, which has become known in recent years due to the fact that it has been used increasingly in aquaculture to color the fish meat of trout and salmon.
  • This carotenoid has numerous other areas of application, for example it is used as a radical scavenger, hormone precursor, growth promoter, photoprotector or immunostimulant.
  • one of its most important functions is that of an antioxidant, because it has a 10-fold stronger antioxidative capacity than other carotenoids, for example ß-carotene.
  • astaxanthin includes use for the treatment of benign prostate hyperplasia (BPH) and prostate cancer, which takes place via an inhibition of the enzyme 5 ⁇ -reductase by the carotenoid - as disclosed in US Pat. No. 6,277,417 B1.
  • BPH benign prostate hyperplasia
  • astaxanthin is already known in cosmetic preparations.
  • European Patent EP 0 748 625 B1 describes cosmetic or dermatological preparations with photo-convertible carotenoids such as astaxanthin which, after controlled release, lead to the conversion and increased content of retinol and retinoic acid.
  • formulations with extracts of Haematococcus pluvialis for the treatment of rough, dry skin were disclosed.
  • the preparations can also be used for anti-aging, anti-wrinkle, anti-inflammatory, anti-radical and anti-dandruff treatment.
  • Antioxidants such as tocopherol and carotenoids are known to be used in hair cosmetics - as described in German patent application DE 4139921 A1 - they act against the graying of human hair.
  • the object of the present patent application was to provide active ingredients from renewable raw materials for cosmetic and / or dermatological use, which are accessible in large quantities and which are versatile as care products in the most varied areas of cosmetics, pharmacy and / or Enable dermatology.
  • the invention relates to the use of astaxanthin for the preparation of agents against hair loss, for strengthening the hair to improve properties of the hair shaft, for stimulating hair growth, for protecting against oxidative damage to melanocytes and against graying of the hair, and for preparations with astaxanthin and hair dyes and preparations with astaxanthin and vitamin E.
  • astaxanthin has an outstanding activity against hair loss, in particular in the case of androgenic alopecia, by inhibiting 5- ⁇ -reductase.
  • stimulation of hair growth and strengthening of the hair and hair shaft can also be observed in healthy hair.
  • Preparations against exposure to UV light or to build up the hair offer protection and care for the hair and scalp, which can be attributed, among other things, to the good antioxidative and photoprotective properties of astaxanthine.
  • the coloring properties of astaxanthin can be exploited very well.
  • the hair-damaging properties of hair dyes are balanced by the protective and nourishing effects of small amounts of astaxanthin.
  • astaxanthin for the preparation of preparations for the treatment of acne vulgaris, seborrhea and hirsutism is also advantageous.
  • ROS reactive oxygen species
  • Astaxanthin, astaxanthin derivatives, astaxanthin-containing extracts from algae or animal starting materials can be used in the form of topical or oral preparations.
  • astaxanthine in the preparations, the effect of astaxanthine can be enhanced in a synergistic manner by adding further active ingredients. It has proven to be particularly advantageous if astaxanthin has additionally been combined with a further antioxidant, in particular ⁇ -tocopherol (vitamin E) or its derivatives, preferably the esters of ⁇ -tocopherol, with long-chain fatty acids.
  • a further antioxidant in particular ⁇ -tocopherol (vitamin E) or its derivatives, preferably the esters of ⁇ -tocopherol, with long-chain fatty acids.
  • a particularly intensive and long-lasting color is achieved in the combination of astaxanthin and other hair dyes in coloring hair care products.
  • the agents are particularly well tolerated, particularly as regards the damage to the hair which is often observed with hair dyes.
  • the astaxanthin used according to the invention is obtained from algae, Haematococcus pluvialis serving as the main source for the production from marine origin.
  • Astaxanthin is used in amounts of 0.001 to 10% by weight, preferably 0.05 to 8% by weight and particularly preferably 0.1 to 5% by weight - as pure astaxanthin - based on the overall preparation. Astaxanthin is preferably used in encapsulated form, particularly preferably as microcapsules.
  • astaxanthin, its derivatives, esters and extracts with astaxanthin are preferably dissolved in soft gelatin capsules or dispersed in natural oils, preferably olive oil, safflower oil or semi-synthetic oils such as MCT oils (Miglyol®), and also in formulations with modified release, preferably sustained release formulations.
  • natural oils preferably olive oil, safflower oil or semi-synthetic oils such as MCT oils (Miglyol®)
  • MCT oils Miglyol®
  • a daily dose of 0.1 to 5 mg, preferably 0.5 to 3 mg and particularly preferably 1 to 2 mg of pure astaxanthin is recommended.
  • the preparations according to the invention can either be applied topically or via an oral intake. Encapsulating the preparations has proven useful for both purposes.
  • the active ingredient When applied directly to the skin, the active ingredient is released by mechanical action on the membrane during application, while in the case of oral administration there is a delayed release either through the pores of the membrane or through its gradual dissolution.
  • microcapsule is understood by the person skilled in the art to mean spherical aggregates with a diameter in the range from approximately 0.1 to approximately 5 mm, which contain at least one solid or liquid core which is enclosed by at least one continuous shell. I agree- he said it concerns finely dispersed liquid or solid phases coated with film-forming polymers, in the production of which the polymers are deposited on the material to be encased after emulsification and coacervation or interfacial polymerization. According to another process, melted waxes are taken up in a matrix (“microsponge”), which as microparticles can additionally be coated with film-forming polymers. The microscopic capsules can be dried like powders.
  • multinuclear aggregates also called microspheres.
  • the shell can consist of natural, semi-synthetic or synthetic materials.
  • shell materials are, for example, gum arabic , Agar-agar, agarose, maltodextrins, alginic acid or its salts, for example sodium or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithins, gelatin, albumin, shellac, polysaccharides, such as starch or dextran, polypeptides, protein hydrolysed sate, sucrose and wax e.
  • Stemi-synthetic wrapping materials include chemically modified celluloses, in particular cellulose esters and ethers, e.g.
  • Synthetic covering materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinyl pyrrolidone.
  • microcapsules of the prior art are the following commercial products (the shell material in each case is given in brackets): Hallcrest microcapsules (gelatin, gum arabic), Coletica Thalaspheres (maritime collagen), Lipoiec millicapsules (alginic acid, agar agar), Induchem Unispheres (Lactose, microcrystalline cellulose, hydroxypropylmethylceilulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropylmethylceilulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified agar agar), Kuhs Probiol Nanospheres (phospholipids) as well as Primaspheres and Primasponges (Chitosan), Alginate Phosphate ,
  • chitosan and chitosan derivatives in the form of chitosan microspheres or microcapsules is well known.
  • the protection also extends to encapsulated preparations, in particular to microcapsules with average diameters in the range from 0.1 to 5 mm, consisting of an enveloping membrane and a matrix containing the active ingredients, which can be obtained by
  • microcapsules with average diameters in the range from 0.1 to 5 mm consisting of an envelope membrane and a matrix containing the active ingredients, which can be obtained by:
  • a matrix is prepared from gel formers, anionic polymers and components (a) and (b),
  • the dispersed matrix is treated with aqueous chitosan solutions and, if appropriate, the oil phase is removed in the process.
  • microcapsules according to the invention have the particular advantage that they have high stability with respect to surfactants and can thus also be incorporated stably into cosmetic preparations without being dissolved during storage.
  • the advantage of oral intake is that it is well tolerated by the mucous membrane and completely toxicologically safe.
  • further embodiments of the invention also relate to two processes for producing microcapsules with average diameters in the range from 0.1 to 5 mm, consisting of an envelope membrane and a matrix containing the active ingredients, in which either
  • the dispersed matrix is treated with aqueous solutions of anionic polymers and, if appropriate, the oil phase is removed in the process.
  • a matrix is prepared from gel formers, anionic polymers and components (a) and (b),
  • those substances which have the property of forming gels in aqueous solution at temperatures above 40 ° C. are preferably considered as gel formers.
  • Typical examples are heteropolysaccharides and proteins.
  • Suitable thermogelling heteropolysaccharides are preferably agaroses, which can also be present in the form of the agar agar to be obtained from red algae together with up to 30% by weight of non-gel-forming agar pectins.
  • the main constituent of the agaroses are linear polysaccharides from D-galactose and 3,6-anhydro-L-galactose, which are linked alternately ß-1, 3- and ß-1, 4-glycosidically.
  • the heteropolysaccharides preferably have a molecular weight in the range from 110,000 to 160,000 and are both colorless and tasteless.
  • Alternatives are pectins, xanthans (also xanthan gum) and their mixtures. Preference is furthermore given to those types which still form gels in 1% by weight aqueous solution, which do not melt below 80 ° C. and solidify again above 40 ° C.
  • the various types of gelatin from the group of thermogelating proteins are examples.
  • Chitosans are biopolymers and belong to the group of hydrocolloids. From a chemical point of view, these are partially deacetylated chitins of different molecular weights that contain the following - idealized - monomer unit:
  • chitosans are cationic biopolymers under these conditions.
  • the positively charged chitosans can interact with oppositely charged surfaces and are therefore used in cosmetic hair and body care products and pharmaceuticals Preparations used.
  • the production of chitosans is based on chitin, preferably the shell remains of crustaceans, which are available in large quantities as cheap raw materials.
  • the chitin is usually first deproteinized by adding bases, demineralized by adding mineral acids and finally deacetylated by adding strong bases, it being possible for the molecular weights to be distributed over a broad spectrum.
  • Those types are preferably used which have an average molecular weight of 10,000 to 500,000 or 800,000 to 1,200,000 Daltons and / or a Brookfield viscosity (1% by weight in glycolic acid) below 5000 mPas, a degree of deacetylation in the range of Have 80 to 88% and an ash content of less than 0.3 wt .-%.
  • the chitosans are generally used in the form of their salts, preferably as glycolates.
  • the matrix can optionally be dispersed in an oil phase before the membrane is formed.
  • Guerbet alcohols based on fatty alcohols with 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C6-C22 fatty acids with linear C6-C22 fatty alcohols, esters of branched C6-Ci3-carboxylic acids with linear C6 come as oils for this purpose, for example -C22- fatty alcohols, such as myristyl myristate, myristyl palmitate, myristyl stearate, Myristylisostearat, My- ristyloleat, rat Myristylbehenat, Myristylerucat, cetyl myristate, cetyl palmitate, cetyl stearate, Cetylisostea-, cetyl oleate, cetyl behenate, Cetylerucat, Stearylmyristat, stearyl palmitate, stearyl
  • esters of linear C6-C22 fatty acids with branched alcohols in particular 2-ethylhexanol
  • esters of hydroxycarboxylic acids with linear or branched C6-C22 fatty alcohols in particular dioctyl malates
  • esters of linear and / or branched fatty acids with polyhydric alcohols such as propylene glycol, dimer diol or trimer triol
  • polyhydric alcohols such as propylene glycol, dimer diol or trimer triol
  • Guerbet alcohols triglycerides based on C ⁇ -Cio fatty acids
  • esters of C6-C22 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids especially benzoic acid, esters of C2-C12 dicarboxylic acids with linear or branched alcohols with 1 to 22 carbon atoms or
  • Finsolv® TN linear or branched, symmetrical or asymmetrical dialkyl ethers with 6 to 22 carbon atoms per alkyl group, ring opening products of epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenic hydrocarbons such as squalane, squalene or dialkylcyclohexanes ,
  • the task of the anionic polymers is to form membranes with the chitosans.
  • Salts of alginic acid are preferably suitable for this purpose.
  • Alginic acid is a mixture of carboxyl-containing polysaccharides with the following idealized monomer unit:
  • the average molecular weight of the alginic acids or alginates is in the range from 150,000 to 250,000.
  • Salts of alginic acid are to be understood to mean both their complete and their partial neutralization products, in particular the alkali metal salts and among them preferably the sodium alginate (“algin”) and the ammonium and alkaline earth metal salts, mixed alginates such as sodium / magnesium or sodium being particularly preferred
  • algin sodium alginate
  • algin ammonium and alkaline earth metal salts
  • mixed alginates such as sodium / magnesium or sodium being particularly preferred
  • anionic chitosan derivatives such as carboxylation and, in particular, succinylation products are also suitable for this purpose, or alternatively poly (meth) acrylates with average molecular weights in the range from 5,000 to 50,000 daltons and the various
  • anionic surfactants or low molecular weight inorganic salts such as pyrophosphates, can also be used to form the envelope membrane.
  • the loading of the microcapsules with active ingredients can therefore also be 0.1 to 25% by weight, based on the capsule weight.
  • water-insoluble constituents for example inorganic pigments
  • inorganic pigments can also be added at this point in time to adjust the viscosity, these generally being added in the form of aqueous or aqueous / alcoholic dispersions.
  • emulsifiers and / or solubilizers to the matrix.
  • the matrix After the matrix has been prepared from the gel former, chitosan and active ingredient mixture (components a and b), the matrix can optionally be very finely dispersed in an oil phase under high shear in order to produce particles as small as possible in the subsequent encapsulation. It has proven particularly advantageous to heat the matrix to temperatures in the range from 40 to 60 ° C.
  • the actual encapsulation then takes place, ie the formation of the envelope membrane by bringing the chitosan in the matrix into contact with the anionic polymers.
  • the resulting aqueous preparations generally have a microcapsule content in the range from 1 to 10% by weight.
  • the solution of the polymers contains further ingredients, for example emulsifiers or preservatives.
  • microcapsules After filtration, microcapsules are obtained which have an average diameter in the range of preferably about 1 mm. It is advisable to sieve the capsules to ensure that the size is distributed as evenly as possible.
  • the microcapsules thus obtained can have any shape in the production-related framework, but they are preferably approximately spherical.
  • the anion polymers can also be used to produce the matrix and encapsulated with the chitosans.
  • pro-liposomes can also be used as carriers for the active ingredient mixtures.
  • the pro-liposomes do not contain water and only absorb this with the formation of real liposomes if they are introduced into an aqueous environment.
  • Another object of the invention therefore relates to pro-liposomally encapsulated antioxidant mixtures which have components (a) and (b) and which are obtained by treating the mixtures in cosmetically acceptable solvents with lecithins and / or phospholipids.
  • lecithins as those glycerophospholipids which are formed from fatty acids, glycerol, phosphoric acid and choline by esterification. Lecithins are therefore often referred to in the professional world as phosphatidylcholines (PC).
  • PC phosphatidylcholines
  • a lecithin is shown schematically in the above formula, where R typically stands for linear aliphatic hydrocarbon radicals having 15 to 17 carbon atoms and up to 4 cis double bonds.
  • Examples of natural lecithins that can be encapsulated include the cephalins, which are also referred to as phosphatidic acids and are derivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids.
  • phospholipids are usually understood to be mono- and preferably diesters of phosphoric acid with glycerol (glycerol phosphates), which are generally classed as fats.
  • sphingosines or sphingolipids can also be used for liposomal encapsulation. The use of lecithins or phospholipids for the production of liposomes can be found in the relevant literature.
  • the next object of the invention is directed analogously to a process for the preparation of pro-liposomally encapsulated antioxidant mixtures which have components (a) and (b) and which are obtained by mixing the mixtures in cosmetically acceptable solvents with lecithins and / or Phospholipids treated.
  • the active ingredient mixtures are usually se either in a solvent and brought into contact with the lecithins or phospholipids at temperatures in the range from 30 to 70 ° C, or the anhydrous mixtures are stirred into a solution of the lecithins or phospholipids.
  • the active ingredients and the lecithins and / or phospholipids can be used in a weight ratio of 1:20 to 5: 1, preferably 1: 2 to 4: 1.
  • Suitable solvents are preferably lower alcohols with 1 to 4 carbon atoms, such as ethanol or polyols, which generally have 2 to 15 carbon atoms and at least two hydroxyl groups; propylene glycol is preferred here.
  • Formulations which remain on the hair or scalp for a long time or which frequently contain aggressive chemicals are particularly suitable for the development of the effectiveness. These include hair treatments, hair packs, hair lotions, hair gels, hair colors, bleaching agents, permanent waving agents, sun and after-sun products for hair. The agents are also particularly suitable for long-term use with a prophylactic effect.
  • the preparations are in one
  • the preparations according to the invention have a composition of: 0.001 to 10% by weight of astaxanthin and 0.01 to 8% by weight of hair dyes, based on the overall preparation, preferably as hair colorants
  • hair dyes 0.1 to 5% by weight of astaxanthin and 0.1 to 3% by weight of hair dyes based on the overall preparation. hair dyes
  • ком ⁇ онент keratin fibers preferably human hair
  • direct dyes or oxidation dyes are usually used.
  • the latter consist of a developer (oxidation base) and a coupler component (shader) and are not dyes in the actual sense, but dye precursors.
  • Oxidation bases are aromatic compounds which are nucleus-substituted with at least two electron-donating groups (amino and / or hydroxyl groups).
  • amino and / or hydroxyl groups For example, primary aromatic amines with a further free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and derivatives thereof are used. Special representatives are u. a.
  • shaders are also aromatic compounds, but with groups which are easily oxidizable on the ring in the m position.
  • m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and pyridine derivatives are generally available.
  • Suitable coupler substances are in particular 1-naphthol, pyrogallol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1 -Phenyl-3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2,4-diaminophenoxy) propane, 2-chlororesorcinol, 2-chloro-6-methyl-3 - aminophenol, 2-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxypyridine and 2,6-diaminopyridine.
  • Suitable direct dyes are, for example, dyes from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, such as those with the international names or trade names HC Yellow 2, HC Yellow 4, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16, Basic Brown 17, Picramic Acid and Rodol 9 R known compounds and 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, (N-2,3-dihydroxypropyl-2-nitro-4-trifluoromethyl) - aminobenzene and 4-N-ethyl-1,4-bis (2'-hydroxyethylamino) -2-nitrobenzene hydrochloride.
  • mixtures of dyes from different groups can also be used.
  • other dye components reference is expressly made to the Colipa list, published by the Industry Association for Personal Care and Detergents, Frankfurt.
  • Astaxanthin can - as already partially enumerated above with the agents with a longer duration of action - for the production of cosmetic and / or pharmaceutical preparations, such as hair shampoos, hair lotions, creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, emulsions, stick preparations, powders, Ointments, tablets, dragees, capsules, juices, solutions and granules are used.
  • cosmetic and / or pharmaceutical preparations such as hair shampoos, hair lotions, creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, emulsions, stick preparations, powders, Ointments, tablets, dragees, capsules, juices, solutions and granules are used.
  • agents can also be used as further auxiliaries and additives, mild surfactants, oil bodies, emulsifiers, pearlescent waxes, consistency agents, thickeners, superfatting agents, stabilizers, polymers, silicone compounds, fats, waxes, lecithins, phospholipids, biogenic active ingredients, additional UV light protection factors, additional antioxidants, Contain anti-dandruff agents, film formers, swelling agents, hydrotropes, solubilizers, preservatives, perfume oils, dyes and the like.
  • Anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants can be contained as surface-active substances.
  • anionic surfactants are soaps, alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, fatty acid ether sulfates (fatty ether ether sulfates, hydroxymether amide sulfates, hydroxymether amide sulfates, hydroxymether amide sulfates, hydroxymether amide sulfates, hydroxymether amide sulfates, hydroxymether amide s
  • anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • Typical examples of non-ionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, optionally partially oxidized alk (en) yl oligoglycosides, especially nucylglycolic acid derivatives (N-fatty acid silicate acid derivatives) Wheat-based products), polyolf esters, sugar esters, sorbitan esters, polysorbates and amine oxides.
  • nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • cationic surfactants are quaternary ammonium compounds, such as, for example, dimethyidistearylammonium chloride, and ester quats, in particular quaternized fatty acid trialkanolamine ester salts.
  • amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazoliniumbetaines and sulfobetaines. The surfactants mentioned are exclusively known compounds.
  • Typical examples of particularly suitable mild, ie particularly skin-compatible, surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarosinates, fatty acid taurides, fatty acid glutamates, ⁇ -olefin sulfonates, alkyl fatty amide amides, amide carboxylic acid amide carbamides, fatty carboxamides, or protein fatty acid condensates, the latter preferably based on wheat proteins.
  • esters of linear C6-C22- Fatty acids with branched alcohols in particular 2-ethylhexanol
  • esters of Ci8-C38-alkylhydroxycarboxylic acids with linear or branched C6-C22-fatty alcohols especially dioctylmate
  • esters of linear and / or branched fatty acids with polyhydric alcohols such as propylene glycol , Dimer diol or trimer triol
  • polyhydric alcohols such as propylene glycol , Dimer diol or trimer triol
  • Guerbet alcohols triglycerides based on C ⁇ -Cio fatty acids
  • liquid mono- / di- / triglyceride mixtures based on C6-Ci8 fatty acids
  • esters of C6-C22 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids in particular benzoic acid, esters of C2-Ci2-dicarboxylic acids with linear or branche
  • Suitable emulsifiers are nonionic surfactants from at least one of the following groups:
  • Partial esters of polyglycerol (average degree of self-condensation 2 to 8), polyethylene glycol (molecular weight 400 to 5000), trimethylolpropane, pentaerythritol, sugar alcohols (eg sorbitol), alkyl glucosides (eg methyl glucoside, butyl glucoside, lauryl glucoside) and poly (eg cellulose) saturated and / or unsaturated, linear or branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 mol ethylene oxide;
  • Block copolymers e.g. Polyethylene glycol 30 dipolyhydroxystearate;
  • Polymer emulsifiers e.g. Pemulen types (TR-1, TR-2) from Goodrich;
  • adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols or with castor oil are known, commercially available products. These are mixtures of homologs whose average degree of alkoxylation is the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate, with which the addition reaction is carried out.
  • Ci2 / i8 fatty acid monoesters and diesters of adducts of ethylene oxide with glycerol are known as refatting agents for cosmetic preparations.
  • Alkyl and / or alkenyl oligoglycosides their preparation and their use are known from the prior art. They are manufactured in particular by converting glu cose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms.
  • glycoside residue both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to preferably about 8 are suitable.
  • the degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products,
  • Suitable partial glycerides are hydroxystearic acid monoglyceride, hydroxystearic acid diglyceride, isostearic acid, Isostearinklarediglycerid, oleic acid monoglyceride, oleic acid diglyceride, Ricinolklaremoglycerid, Ricinolklarediglycerid, linoleic acid monoglyceride, Linolklarediglycerid, LinolenTalkremonoglycerid, Linolenchurediglycerid, Erucaklaremonoglycerid, Erucaklarediglycerid, Weinklaremonoglycerid, Weinklarediglyce- chloride, Citronenklamonoglycerid, Citronendiglycerid, ⁇ pfelklamonoglycerid, Malic acid diglyceride and their technical mixtures, which may still contain small amounts of triglyceride from the manufacturing process. Addition products of 1 to 30, preferably 5
  • sorbitan sorbitan, sorbitan sesquiisostearate, sorbitan come diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan dioleate, trioleate, Sorbitanmonoerucat, Sorbitansesquierucat, Sorbitandierucat, Sorbitantrieru- cat, Sorbitanmonoricinoleat, Sorbitansesquiricinoleat, Sorbitandiricinoleat, Sorbitantriricinoleat, Sorbitanmonohydroxystearat, Sorbitansesquihydroxystearat, Sorbitandihydroxystearat, sorting bitantrihydroxystearat , Sorbitan monotartrate, sorbitan sesqui-tartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate,
  • polyglycerol esters are polyglyceryl-2 dipolyhydroxystearates (Dehymuls® PGPH), polyglycerol-3 diisostearates (Lameform® TGI), polyglyceryl-4 isostates (Isolan® Gl 34), polyglyceryl-3 oleates, diisostearoyl polyglyearyl-3 diisostearates (Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010 / 90), Polyglyceryl-3 Cetyl Ether ( Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul® WOL 1403) Polyglyceryl Dimerate I
  • polystyrene resin examples include the mono-, di- and triesters of trimethylolpropane which are optionally reacted with 1 to 30 mol of ethylene oxide. or pentaerythritol with lauric acid, coconut fatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like.
  • Typical anionic emulsifiers are aliphatic fatty acids with 12 to 22 carbon atoms, such as, for example, palmitic acid, stearic acid or behenic acid, and dicarboxylic acids with 12 to 22 carbon atoms, such as, for example, azelaic acid or sebacic acid.
  • Zwitterionic surfactants can also be used as emulsifiers.
  • Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule.
  • Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the coconut alkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the coconut acylaminopropyldimethylammonium glycinate, and 2-alkyl-3 -car- boxylmethyl-3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate.
  • betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the coconut alkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium gly
  • fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine is particularly preferred.
  • Suitable emulsifiers are ampholytic surfactants.
  • Ampholytic surfactants are understood to mean those surface-active compounds which, in addition to a C ⁇ / is-alkyl or acyl group, have at least one free amino group in the molecule and at least one contain a -COOH or -S ⁇ 3H group and are capable of forming internal salts.
  • ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each have about 8 to 18 carbon atoms in the alkyl group.
  • ampholytic surfactants are N-coconut alkylaminopropionate, coconut acylaminoethylamino propionate and Ci2 / ⁇ s acyl sarcosine.
  • cationic surfactants are also suitable as emulsifiers, those of the esterquat type, preferably methylquaternized di-fatty acid triethanolamine ester salts, being particularly preferred.
  • Typical examples of fats are glycerides, i.e. Solid or liquid vegetable or animal products, which consist essentially of mixed glycerol esters of higher fatty acids, come as waxes, among others. natural waxes, e.g. Candelilla wax, carnauba wax, Japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax, beeswax, shellac wax, walnut, lanolin (wool wax), pretzel fat, ceresin, ozokerite (earth wax), petrolatum, paraffin waxes chemically modified waxes (hard waxes), e.g.
  • natural waxes e.g. Candelilla wax, carnauba wax, Japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax, beeswax
  • Montanester waxes Montanester waxes, Sasol waxes, hydrogenated jojoba waxes and synthetic waxes, such as Polyalkylene waxes and polyethylene glycol waxes in question.
  • fat-like substances such as lecithins and phospholipids can also be used as additives.
  • lecithins to mean those glycerophospholipids which are formed from fatty acids, glycerol, phosphoric acid and choline by esterification. Lecithins are therefore often used in the professional world as phosphatidylcholines (PC).
  • Examples of natural lecithins are the cephalins, which are also referred to as phosphatidic acids and are derivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids.
  • phospholipids are usually understood to be mono- and preferably diesters of phosphoric acid with glycerol (glycerol phosphates), which are generally classed as fats.
  • glycerol phosphates glycerol phosphates
  • sphingosines or sphingolipids are also suitable.
  • Pearlescent waxes are: alkylene glycol esters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polyvalent, optionally hydroxy-substituted carbon acids with fatty alcohols with 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which have a total of at least 24 carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring opening products of olefin epoxides with 12 to 22 carbon atoms with fatty alcohols with 12 to 22 carbon atoms and / or polyols with 2 to 15 carbon atoms and 2
  • Suitable consistency agents are primarily fatty alcohols or hydroxy fatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms and, in addition, partial glycerides, fatty acids or hydroxy fatty acids.
  • a combination of these substances with alkyl oligoglucosides and / or fatty acid N-methyl glucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates is preferred.
  • Suitable thickeners are, for example, Aerosil types (hydrophilic silicas), polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl and hydroxypropyl cellulose, as well as higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, (eg Carbopole® and Pemulen types from Goodrich; Synthalene® from Sigma; Keltrol types from Kelco; Sepigel types from Seppic; Salcare types from Allied Colloids), polyacrylamides, polymers, polyvinyl alcohol and polyvinyl pyrrolidone.
  • Aerosil types hydrophilic silicas
  • polysaccharides in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl and hydroxypropyl cellulose
  • Bentonites such as e.g. Bentone® Gel VS-5PC (Rheox) has been proven, which is a mixture of cyclopentasiloxane, disteardimonium hectorite and propylene carbonate.
  • Surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with a narrow homolog distribution or alkyl oligoglucosides as well as electrolytes such as table salt and ammonium chloride are also suitable.
  • Substances such as, for example, lanolin and lecithin and also polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used as superfatting agents, the latter simultaneously serving as foam stabilizers. stabilizers
  • Metal salts of fatty acids such as e.g. Magnesium, aluminum and / or zinc stearate or ricinoleate are used.
  • Suitable cationic polymers are, for example, cationic cellulose derivatives, e.g. a quaternized hydroxyethyl cellulose available under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers such as e.g.
  • Luviquat® condensation products of polyglycols and amines, quaternized collagen polypeptides, such as, for example, lauryl-dimonium hydroxypropyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, e.g.
  • Amodimethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretine® / Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat® 550 / Chemviron), polyaminopolyamides, as well as their crosslinked water-soluble polymers, cationic chitinite crystals such as, for example, quaternized chitin derivatives such as, Condensation products from dihaloalkylene, such as Dibromobutane with bisdialkylamines, e.g.
  • cationic guar gum such as e.g. Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese
  • quaternized ammonium salt polymers such as e.g. Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 from Miranol.
  • Anionic, zwitterionic, amphoteric and nonionic polymers include, for example, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and their polyols, and non-crosslinked polyacrylate and their esters, non-crosslinked acrylate - Trimethylarnmonium chloride / acrylate copolymers, octylacrylamide / methylmethacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, vinylpyrrolidone / dimethylaminoethyl methacrylate and silicate / vinylpoly
  • Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl-modified silicone compounds which can be both liquid and resinous at room temperature.
  • Simethicones which are mixtures of dimethicones with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates, are also suitable.
  • UV light protection factors to be added are understood to mean, for example, organic substances (light protection filters) which are liquid or crystalline at room temperature and are able to absorb ultraviolet rays and absorb the energy absorbed in the form of longer-wave radiation, e.g. To give off heat again.
  • UVB filters can be oil-soluble or water-soluble.
  • oil-soluble substances e.g. to call:
  • 4-aminobenzoic acid derivatives preferably 2-ethyl-hexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate;
  • esters of cinnamic acid preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene);
  • esters of salicylic acid preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbenzyl ester, salicylic acid homomethyl ester;
  • benzophenone preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;
  • esters of benzalmalonic acid preferably 4-methoxybenzmalonic acid di-2-ethylhexyl ester;
  • Triazine derivatives e.g. 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1, 3,5-triazine and octyl triazone, or dioctyl butamido triazone (Uvasorb® HEB);
  • Possible water-soluble substances are: > 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts;
  • benzoylmethane such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl
  • typical UV-A filters -4'- methoxydibenzoylmethane Parsol® 1789
  • 1-phenyl-3- (4'-isopropylphenyl) propane-1, 3-dione and enamine compounds are particularly suitable as typical UV-A filters -4'- methoxydibenzoylmethane (Parsol® 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1, 3-dione and enamine compounds.
  • the UV-A and UV-B filters can of course also be used in mixtures.
  • Particularly favorable combinations consist of the derivatives of benzoylmethane, e.g.
  • insoluble light protection pigments namely finely dispersed metal oxides or salts
  • suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof.
  • Silicates (talc), barium sulfate or zinc stearate can be used as salts.
  • the oxides and salts are used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
  • the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm.
  • the pigments can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or which differ in some other way from the spherical shape.
  • the pigments can also be surface-treated, ie hydrophilized or hydrophobicized. Typical examples are coated titanium dioxide, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. So-called micro- or nanopigments are preferably used in sunscreens. Micronized zinc oxide is preferably used.
  • secondary light stabilizers of the antioxidant type can also be used, which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates the skin.
  • Typical examples of this are amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives,.
  • Imidazoles eg urocanic acid
  • peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine), carotenoids, carotenes (eg ⁇ -carotene, ⁇ -carotene, lycopene) and their derivatives, chlorogenic acid and their derivatives, lipoic acid and their derivatives (e.g. dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (e.g.
  • thioredoxin glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, Propyl, amyl, butyl and lauryl, palmitoyl, oleyl, ⁇ -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 sulfoximine compounds (e.g.
  • buthioninsulfoximine homocysteine sulfoximine, butioninsulfones, penta-, hexa-, heptathionine sulfoximine
  • very low tolerable dosages e.g. pmol to ⁇ mol / kg
  • metal chelators e.g. ⁇ -Hydroxy fatty acids, Pa lmitic acid, phytic acid, lactoferrin
  • ⁇ -hydroxy acids e.g.
  • citric acid 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. ⁇ -linolenic acid, linoleic acid, oleic acid
  • Folic acid and its derivatives ubiquinone and ubiquinol and their derivatives
  • vitamin C and derivatives e.g. ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate
  • tocopherols and derivatives e.g.
  • vitamin E acetate
  • vitamin A and derivatives vitamin A-palmitate
  • biogenic active substances include tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, (deoxy) ribonucleic acid and its fragmentation products, ß-glucans, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudo-essential oils, amide acids To understand plant extracts and vitamin complexes.
  • Common film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or its salts and similar compounds.
  • Piroctone olamine (1-H yd roxy-4-methyl-6- (2, 4, 4-tri my thyipentyl) -2- (1 H) -pyridinone monoethanolamine salt
  • Baypival® (climbazole)
  • Ketoconazol® (4-Acety I- 1 - ⁇ -4- [2- (2.4-dichlorophenyl) r-2- (1 H -imidazol-1-ylmethyl]) - 1, 3-dioxylan-c-4-ylmethoxyphenyl ⁇ piperazine
  • Ketoconazole selenium disulfide, sulfur colloidal, sulfur polyglycol sorbitan monooleate, sulfur ricinolexylate, sulfur tar distillates, salicylic acid (or in combination with hexachlorophene), undexylenic acid, undosulfonate, zinc salt
  • Montmorillonites, clay minerals, pemulene and alkyl-modified carbopol types can serve as swelling agents for aqueous phases.
  • Hydrotropes such as ethanol, isopropyl alcohol, or polyols can also be used to improve the flow behavior.
  • Polyols that come into consideration here preferably have 2 to 15 carbon atoms and at least two hydroxyl groups.
  • the polyols can NEN still contain other functional groups, especially amino groups, or be modified with nitrogen. Typical examples are
  • Alkylene glycols such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols with an average molecular weight of 100 to 1,000 daltons;
  • Methyl compounds such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
  • Dialcohol amines such as diethanolamine or 2-amino-1, 3-propanediol.
  • Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid, as well as the silver complexes known under the name Surfacine® and the other classes of substances listed in Appendix 6, Parts A and B of the Cosmetics Regulation.
  • Perfume oils include mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers (lily, lavender, rose, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel (Be.rgamotte, Lemon, oranges), roots (mace, angelica, celery, cardamom, costus, iris, calmus), woods (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme ), Needles and twigs (spruce, fir, pine, mountain pine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax).
  • Synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.
  • the ethers include, for example, benzylethyl ether
  • the aldehydes include, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal
  • the ketones include, for example, the jonones, ⁇ -isomethylionone and methylcedryl ketone the alcohols ethanol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol
  • the hydrocarbons mainly include the terpenes and balsams.
  • fragrance oils of low volatility which are mostly used as aroma components, are also suitable as perfume oils, for example sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labola oil and lavandin oil.
  • peppermint oil comes as flavors. Spearmint oil, anise oil, star anise oil, caraway oil, eucalyptus oil, fennel oil, lemon oil, wintergreen oil, clove oil, menthol and the like.
  • the dyes which can be used are those which are suitable and approved for cosmetic purposes. Examples are Kochillerot A (Cl 16255), Patent Blue V (C.1.42051), Indigotine (C.1.73015), Chlorophyllin (C.1.75810), Quinoline Yellow (CI47005), Titanium Dioxide (C.1.77891), Indanthrene Blue RS (Cl 69800) and Madder varnish (CI58000). Luminol may also be present as the luminescent dye. example recipes
  • Table 1 Leave-on hair tonic (amounts in% by weight)

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Abstract

The invention relates to the use of astaxanthin for producing agents against hair loss, for strengthening hair, for improving the properties of hair, for stimulating hair growth, for preventing the melanocytes from oxidative damage and thus preventing hair from going gray. The invention also relates to preparations that contain astaxanthin and hair dyes or astaxanthin and α tocopherol. The astaxanthin used preferably originates from marine sources and is present in the formulations in encapsulated form.

Description

Verwendung von AstaxanthinUse of astaxanthin
Die Erfindung befindet sich auf dem Gebiet der kosmetischen und pharmazeutischen Zubereitungen. Sie betrifft die Verwendung von Astaxanthin, das vornehmlich aus Algen gewonnen wird, zur Herstellung von Mitteln, die gegen Haarausfall, zur Kräftigung des Haares sowie zum Schutz gegen UV-Lichteinwirkung und gegen Ergrauen der Haare eingesetzt werden.The invention is in the field of cosmetic and pharmaceutical preparations. It relates to the use of astaxanthin, which is obtained primarily from algae, for the preparation of agents which are used against hair loss, for strengthening the hair and for protection against UV light and against graying of the hair.
Stand der TechnikState of the art
Astaxanthin ist ein Carotinoid, das aus Mikroalgen gewonnen wird, welches in den letzten Jahren bekannt geworden, dadurch dass es zunehmend in der Aquakultur zum Färben des Fischfleisches von Forellen und Lachsen eingesetzt wurde. Dieses Carotinoid hat zahlreiche weitere Einsatzgebiete, so wird es unter anderem als Radikalfänger, Hormonvorläufer, Wachtumsförderer, Photoprotektor oder Immunstimulans eingesetzt. Daneben ist eine seiner wichtigsten Funktionen die als Antioxidans, denn es hat eine 10fach stärkere antioxidative Kapazität als andere Carotinoide, beispielsweise ß-Carotin.Astaxanthin is a carotenoid obtained from microalgae, which has become known in recent years due to the fact that it has been used increasingly in aquaculture to color the fish meat of trout and salmon. This carotenoid has numerous other areas of application, for example it is used as a radical scavenger, hormone precursor, growth promoter, photoprotector or immunostimulant. In addition, one of its most important functions is that of an antioxidant, because it has a 10-fold stronger antioxidative capacity than other carotenoids, for example ß-carotene.
95 % des derzeit auf dem Markt eingesetzten Astaxanthins kommt aus synthetischer Herstellung. Da die Nachfrage nach natürlichen Produkten und deren Einsatz in Nahrungsmitteln, pharmazeutischen und kosmetischen Zubereitungen ständig wächst, wird in letzter Zeit vermehrt Astaxanthin aus marinem Urspung gewonnen, wobei die Microalge Haematococcus pluvialis die natürliche Quelle darstellt, die den höchsten Gehalt an Astaxanthin aufweist.95% of the astaxanthine currently on the market comes from synthetic production. Since the demand for natural products and their use in food, pharmaceutical and cosmetic preparations is constantly growing, astaxanthin has recently been obtained from marine origin, with the microalgae Haematococcus pluvialis being the natural source with the highest astaxanthin content.
Die medizinische Anwendung von Astaxanthin umfasst den Einsatz zur Behandlung von Benigner Prostata Hyperplasie (BPH) und Prostatakrebs, die über eine Inhibierung des Enzyms 5α- Reduktase durch das Carotinoid stattfindet - so offenbart in dem US-Patent US 6277 417 B1. Auch in kosmetischen Zubereitungen ist der Einsatz von Astaxanthin bereits bekannt. So wurden in dem Europäischen Patent EP 0 748 625 B1 kosmetische oder dermatologische Zubereitungen mit photo - konvertiblen Carotinoiden wie Astaxanthin beschrieben, die nach kontrollierter Freisetzung zur einer Umwandlung und erhöhtem Gehalt von Retinol und Retinolsäure führen. In der Internationalen Patentanmeldung WO 99/13855 wurden Formulierungen mit Extrakten von Haematococcus pluvialis zur Behandlung von rauher, trockener Haut offenbart. Die Zubereitungen können ebenfalls zur Anti-aging- , Antifalten-, Anti-Entzündungs-, Anti-Radikal- und Antischuppen- Behandlung eingesetzt werden. Antioxidantien wie Tocopherol und Carotinoide werden bekanntermaßen im haarkosmetischen Bereich verwendet - wie in der deutschen Patentanmeldung DE 4139921 A1 beschrieben - wirken sie gegen das Ergrauen menschlicher Haare.The medical use of astaxanthin includes use for the treatment of benign prostate hyperplasia (BPH) and prostate cancer, which takes place via an inhibition of the enzyme 5α-reductase by the carotenoid - as disclosed in US Pat. No. 6,277,417 B1. The use of astaxanthin is already known in cosmetic preparations. For example, European Patent EP 0 748 625 B1 describes cosmetic or dermatological preparations with photo-convertible carotenoids such as astaxanthin which, after controlled release, lead to the conversion and increased content of retinol and retinoic acid. In the international patent application WO 99/13855, formulations with extracts of Haematococcus pluvialis for the treatment of rough, dry skin were disclosed. The preparations can also be used for anti-aging, anti-wrinkle, anti-inflammatory, anti-radical and anti-dandruff treatment. Antioxidants such as tocopherol and carotenoids are known to be used in hair cosmetics - as described in German patent application DE 4139921 A1 - they act against the graying of human hair.
Kosmetische Zubereitungen stehen dem Verbraucher heute in einer Vielzahl von Kombinationen zur Verfügung. Dennoch besteht im Markt das Bedürfnis nach Produkten mit einem verbesserten Leistungsspektrum. Hierbei sind Hautverträglichkeit sowie der Einsatz natürlicher Produkte beim Kunden gefragt. Für die Herstellung von Produkten, die gleichzeitig eine Vielzahl von Anwendungen erlauben, besteht bisher das Problem, dass ihren Zubereitungen eine große Zahl an Wirkstoffen zugesetzt werden müssen, die gemeinsam das gewünschte Anforderungsprofil ergeben, ohne sich dabei gegenseitig zu stören oder gar unerwünschte Nebeneffekte zu erzeugen. Dem entsprechend besteht ein besonderes Interesse an Pflegemitteln, die die gewünschten Eigenschaften in sich vereinigen. Daneben ist es wünschenswert durch das Auffinden neuer Einsatzgebiete bereits bekannter Substanzklassen deutlich bessere Produkte zu erhalten. Besonders Extrakte von nachwachsenden Rohstoffen und deren Inhaltstoffe finden immer häufiger Einsatz in der Kosmetik.Cosmetic preparations are available to the consumer in a variety of combinations today. Nevertheless, there is a need in the market for products with an improved range of services. Skin compatibility and the use of natural products by the customer are required here. For the manufacture of products that allow a multitude of applications at the same time, there has been the problem that a large number of active ingredients have to be added to their preparations, which together produce the desired profile of requirements, without interfering with one another or even producing undesirable side effects , Accordingly, there is a particular interest in care products that combine the desired properties. In addition, it is desirable to find significantly better products by finding new areas of use for already known substance classes. Extracts of renewable raw materials and their ingredients are used more and more frequently in cosmetics.
Die Aufgabe der vorliegenden Patentanmeldung hat darin bestanden, Wirkstoffe aus nachwachsenden Rohstoffen für die kosmetische und/oder dermatologische Anwendung zur Verfügung zu stellen, die in großen Mengen zugänglich sind und die eine vielseitige Anwendung als Pflegemittel in den unterschiedlichsten Bereichen der Kosmetik, Pharmazie und/oder Dermatologie ermöglichen.The object of the present patent application was to provide active ingredients from renewable raw materials for cosmetic and / or dermatological use, which are accessible in large quantities and which are versatile as care products in the most varied areas of cosmetics, pharmacy and / or Enable dermatology.
Beschreibung der ErfindungDescription of the invention
Gegenstand der Erfindung ist die Verwendung von Astaxanthin zur Herstellung von Mitteln gegen Haarausfall, zur Kräftigung des zur Verbesserung der Haarschafteigenschaften, zur Stimulierung des Haarwachstums, zum Schutz vor oxidativen Schädigungen von Melanocyten und gegen das Ergrauen der Haare, sowie Zubereitungen mit Astaxanthin und Haarfarbstoffen und Zubereitungen mit Astaxanthin und Vitamin E.The invention relates to the use of astaxanthin for the preparation of agents against hair loss, for strengthening the hair to improve properties of the hair shaft, for stimulating hair growth, for protecting against oxidative damage to melanocytes and against graying of the hair, and for preparations with astaxanthin and hair dyes and preparations with astaxanthin and vitamin E.
Überraschenderweise wurde gefunden, dass Astaxanthin über die Inhibierung der 5-α-Reduktase eine hervorragende Wirksamkeit gegen Haarausfall, insbesondere bei androgener Alopecie, aufweist. Dabei ist zusätzlich bei Auftreten dieser Krankheitsform jedoch auch bei gesundem Haar eine Stimulation des Haarwachstums und eine Kräftigung des Haares und Haarschaftes zu beobachten. Zubereitungen gegen UV-Lichteinwirkung oder zum Aufbau des Haares bieten Schutz und Pflege von Haar und Kopfhaut, die unter anderem auf die guten antioxidativen und photoprotektiven Eigenschaften des Astaxanthins zurückzuführen sind. Zusätzlich dazu können die färbenden Eigenschaften von Astaxanthin sehr gut ausgenutzt werden. Die haarschädigenden Eigenschaften von Haarfärbemitteln werden durch die schützenden und pflegenden Effekte von bereits kleinen Mengen Astaxanthin ausgeglichen.Surprisingly, it was found that astaxanthin has an outstanding activity against hair loss, in particular in the case of androgenic alopecia, by inhibiting 5-α-reductase. When this type of disease occurs, however, stimulation of hair growth and strengthening of the hair and hair shaft can also be observed in healthy hair. Preparations against exposure to UV light or to build up the hair offer protection and care for the hair and scalp, which can be attributed, among other things, to the good antioxidative and photoprotective properties of astaxanthine. In addition, the coloring properties of astaxanthin can be exploited very well. The hair-damaging properties of hair dyes are balanced by the protective and nourishing effects of small amounts of astaxanthin.
Bedingt durch die inhibierende Wirkung auf die 5-α-Reduktase ist auch die Verwendung von Astaxanthin zur Herstellung von Zubereitungen zur Behandlung von Akne vulgaris, Seborrhea und Hirsutismus vorteilhaft.Due to the inhibitory effect on 5-α-reductase, the use of astaxanthin for the preparation of preparations for the treatment of acne vulgaris, seborrhea and hirsutism is also advantageous.
Durch UV-Lichteinfluss oder oxidativen Stress wird die Menge an ROS (reactive oxygen species) erhöht. ROS führen zu Schädigungen von Melanocyten, die in Haut und Haaren vorliegen. Es konnte daher festgestellt werden, dass Astaxanthin durch seine antioxidative Wirkung ebenfalls einen schützenden Einfluss auf Melanocyten hat und deshalb zur Verzögerung des Ergrauens der Haare eingesetzt werden kann.The amount of ROS (reactive oxygen species) is increased by the influence of UV light or oxidative stress. ROS damage melanocytes that are present in the skin and hair. It was therefore found that astaxanthin also has a protective effect on melanocytes due to its antioxidant effect and can therefore be used to delay graying of the hair.
Der Einsatz von Astaxanthin, Astaxanthin-Derivaten, Astaxanthin enthaltenen Extrakten aus Algen oder tierischen Ausgangsstoffen kann in Form von topischen oder oral zu applizierenden Zubereitungen erfolgen.Astaxanthin, astaxanthin derivatives, astaxanthin-containing extracts from algae or animal starting materials can be used in the form of topical or oral preparations.
In den Zubereitungen kann die Wirkung des Astaxanthins durch Zugabe weiterer Wirkstoffe in synergistischer Weise verstärkt werden. Es hat sich als besonders vorteilhaft erwiesen, wenn Astaxanthin zusätzlich mit einem weiteren Antioxidans, insbesondere α-Tocopherol (Vitamin E) oder seinen Derivaten, vorzugsweise den Estern von α-Tocopherol mit langkettigen Fettsäuren kombiniert wurde.In the preparations, the effect of astaxanthine can be enhanced in a synergistic manner by adding further active ingredients. It has proven to be particularly advantageous if astaxanthin has additionally been combined with a further antioxidant, in particular α-tocopherol (vitamin E) or its derivatives, preferably the esters of α-tocopherol, with long-chain fatty acids.
Ebenso wird in färbenden Haarpflegemitteln eine besonders intensive und anhaltende Färbung bei der Kombination von Astaxanthin und weiteren Haarfarbstoffen erreicht. Die Mittel zeichnen sich durch eine besonders gute Verträglichkeit aus, insbesondere was die bei Haarfärbemitteln oft beobachtete Schädigung des Haares betrifft.A particularly intensive and long-lasting color is achieved in the combination of astaxanthin and other hair dyes in coloring hair care products. The agents are particularly well tolerated, particularly as regards the damage to the hair which is often observed with hair dyes.
Astaxanthinastaxanthin
Vorzugsweise jedoch nicht ausschließlich wird das erfindungsgemäß eingesetzte Astaxanthin aus Algen gewonnen, wobei Haematococcus pluvialis als Hauptquelle für die Herstellung aus marinem Ursprung dient. Preferably, but not exclusively, the astaxanthin used according to the invention is obtained from algae, Haematococcus pluvialis serving as the main source for the production from marine origin.
Figure imgf000005_0001
Figure imgf000005_0001
Möglich ist selbstverständlich auch die Verwendung von synthetisch hergestelltem Astaxanthin, sowie von Derivaten des Astaxanthins, insbesondere den Estern.Of course, it is also possible to use synthetically produced astaxanthin and derivatives of astaxanthin, in particular the esters.
Astaxanthin wird in Mengen von 0,001 bis 10 Gew. %, vorzugsweise 0,05 bis 8 Gew.% und besonders bevorzugt 0,1 bis 5 Gew. % - als reines Astaxanthin - bezogen auf die Gesamtzubereitung - eingesetzt. Vorzugsweise wird Astaxanthin in verkapselter Form, besonders bevorzugt als Mikrokapseln eingesetzt.Astaxanthin is used in amounts of 0.001 to 10% by weight, preferably 0.05 to 8% by weight and particularly preferably 0.1 to 5% by weight - as pure astaxanthin - based on the overall preparation. Astaxanthin is preferably used in encapsulated form, particularly preferably as microcapsules.
In pharmazeutischen Zubereitungen für die orale Applikation wird Astaxanthin, seine Derivate, Ester und Extrakte mit Astaxanthin vorzugsweise in Weichgelatinekapsein, gelöst oder dispergiert in natürlichen Ölen, vorzugsweise Olivenöl, Saffloröl oder halbsynthetischen Ölen wie beispielsweise MCT- Ölen (Miglyol®), sowie auch in Formulierungen mit modifizierter Freisetzung, bevorzugt Retardformulierungen, eingesetzt. Eine tägliche Dosis von 0,1 bis 5 mg, vorzugsweise 0,5 bis 3 mg und besonders bevorzugt 1 bis 2 mg reines Astaxanthin wird empfohlen.In pharmaceutical preparations for oral administration, astaxanthin, its derivatives, esters and extracts with astaxanthin are preferably dissolved in soft gelatin capsules or dispersed in natural oils, preferably olive oil, safflower oil or semi-synthetic oils such as MCT oils (Miglyol®), and also in formulations with modified release, preferably sustained release formulations. A daily dose of 0.1 to 5 mg, preferably 0.5 to 3 mg and particularly preferably 1 to 2 mg of pure astaxanthin is recommended.
Mikrokapselnmicrocapsules
Die erfindungsgemäßen Zubereitungen können entweder topisch angewendet werden oder über eine orale Aufnahme. Zu beiden Zwecken hat es sich als nützlich erwiesen, die Zubereitungen zu verkapseln. Die Freisetzung des Wirkstoffes erfolgt bei direkter Anwendung auf der Haut durch mechanische Einwirkung auf die Membran beim Auftragen, während im Fall der oralen Applikation eine verzögerte Freisetzung entweder durch die Poren der Membran oder durch deren allmähliche Auflösung geschieht.The preparations according to the invention can either be applied topically or via an oral intake. Encapsulating the preparations has proven useful for both purposes. When applied directly to the skin, the active ingredient is released by mechanical action on the membrane during application, while in the case of oral administration there is a delayed release either through the pores of the membrane or through its gradual dissolution.
Unter dem Begriff "Mikrokapsel" werden vom Fachmann sphärische Aggregate mit einem Durchmesser im Bereich von etwa 0,1 bis etwa 5 mm verstanden, die mindestens einen festen oder flüssigen Kern enthalten, der von mindestens einer kontinuierlichen Hülle umschlossen ist. Genau- er gesagt handelt es sich um mit filmbildenden Polymeren umhüllte feindisperse flüssige oder feste Phasen, bei deren Herstellung sich die Polymere nach Emulgierung und Koazervation oder Grenzflächenpolymerisation auf dem einzuhüllenden Material niederschlagen. Nach einem anderen Verfahren werden geschmolzene Wachse in einer Matrix aufgenommen („microsponge"), die als Mikropartikel zusätzlich mit filmbildenden Polymeren umhüllt sein können. Die mikroskopisch kleinen Kapseln lassen sich wie Pulver trocknen. Neben einkernigen Mikrokapseln sind auch mehrkernige Aggregate, auch Mikrosphären genannt, bekannt, die zwei oder mehr Kerne im kontinuierlichen Hüllmaterial verteilt enthalten. Ein- oder mehrkernige Mikrokapseln können zudem von einer zusätzlichen zweiten, dritten etc. Hülle umschlossen sein. Die Hülle kann aus natürlichen, halbsynthetischen oder synthetischen Materialien bestehen. Natürlich Hüllmaterialien sind beispielsweise Gummi Arabicum, Agar-Agar, Agarose, Maltodextrine, Alginsäure bzw. ihre Salze, z.B. Natrium- oder Calciumalginat, Fette und Fettsäuren, Cetylalkohol, Collagen, Chitosan, Lecithine, Gelatine, Albumin, Schellack, Polysaccaride, wie Stärke oder Dextran, Polypeptide, Proteinhydroly- sate, Sucrose und Wachse. Halbsynthetische Hüllmaterialien sind unter anderem chemisch modifizierte Cellulosen, insbesondere Celluloseester und -ether, z.B. Celluloseacetat, Ethylcellulose, Hydroxypropylcellulose, Hydroxypropylmethylceilulose und Carboxymethylcellulose, sowie Stärkederivate, insbesondere Stärkeether und -ester. Synthetische Hüllmaterialien sind beispielsweise Polymere wie Polyacrylate, Polyamide, Polyvinylalkohol oder Polyvinylpyrrolidon.The term “microcapsule” is understood by the person skilled in the art to mean spherical aggregates with a diameter in the range from approximately 0.1 to approximately 5 mm, which contain at least one solid or liquid core which is enclosed by at least one continuous shell. I agree- he said it concerns finely dispersed liquid or solid phases coated with film-forming polymers, in the production of which the polymers are deposited on the material to be encased after emulsification and coacervation or interfacial polymerization. According to another process, melted waxes are taken up in a matrix (“microsponge”), which as microparticles can additionally be coated with film-forming polymers. The microscopic capsules can be dried like powders. In addition to mononuclear microcapsules, there are also multinuclear aggregates, also called microspheres. Known, which contain two or more cores distributed in the continuous shell material. Single or multi-core microcapsules can also be enclosed by an additional second, third, etc. The shell can consist of natural, semi-synthetic or synthetic materials. Of course, shell materials are, for example, gum arabic , Agar-agar, agarose, maltodextrins, alginic acid or its salts, for example sodium or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithins, gelatin, albumin, shellac, polysaccharides, such as starch or dextran, polypeptides, protein hydrolysed sate, sucrose and wax e.Semi-synthetic wrapping materials include chemically modified celluloses, in particular cellulose esters and ethers, e.g. cellulose acetate, ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylceilulose and carboxymethyl cellulose, as well as starch derivatives, especially starch ethers and esters. Synthetic covering materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinyl pyrrolidone.
Beispiele für Mikrokapseln des Stands der Technik sind folgende Handelsprodukte (in Klammern angegeben ist jeweils das Hüllmaterial) : Hallcrest Microcapsules (Gelatine, Gummi Arabicum), Coletica Thalaspheres (maritimes Collagen), Lipoiec Millicapseln (Alginsäure, Agar-Agar), Indu- chem Unispheres (Lactose, mikrokristalline Cellulose, Hydroxypropylmethylceilulose); Unicerin C30 (Lactose, mikrokristalline Cellulose, Hydroxypropylmethylceilulose), Kobo Glycospheres (modifizierte Stärke, Fettsäureester, Phospholipide), Softspheres (modifiziertes Agar-Agar), Kuhs Probiol Nanospheres (Phospholipide) sowie Primaspheres und Primasponges (Chitosan, Alginate) und Primasys (Phospholipide).Examples of microcapsules of the prior art are the following commercial products (the shell material in each case is given in brackets): Hallcrest microcapsules (gelatin, gum arabic), Coletica Thalaspheres (maritime collagen), Lipoiec millicapsules (alginic acid, agar agar), Induchem Unispheres (Lactose, microcrystalline cellulose, hydroxypropylmethylceilulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropylmethylceilulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified agar agar), Kuhs Probiol Nanospheres (phospholipids) as well as Primaspheres and Primasponges (Chitosan), Alginate Phosphate ,
Die Verwendung von Chitosan und Chitosanderivaten ist in Form von Chitosanmikrosphären oder Mikrokapseln hinlänglich bekannt.The use of chitosan and chitosan derivatives in the form of chitosan microspheres or microcapsules is well known.
Im Sinne der vorliegenden Erfindung erstreckt sich der Schutz auch auf verkapselte Zubereitungen, speziell auf Mikrokapseln mit mittleren Durchmessern im Bereich von 0,1 bis 5 mm, bestehend aus einer Hüllmembran und einer die Wirkstoffe enthaltenden Matrix, welche erhältlich sind, indem manFor the purposes of the present invention, the protection also extends to encapsulated preparations, in particular to microcapsules with average diameters in the range from 0.1 to 5 mm, consisting of an enveloping membrane and a matrix containing the active ingredients, which can be obtained by
(i) aus Gelbildnern, Chitosanen und den Komponenten (a) und (b) eine Matrix zubereitet, (ii) gegebenenfalls die Matrix in einer Ölphase dispergiert, (iii) die dispergierte Matrix mit wässrigen Lösungen anionischer Polymeren behandelt und gegebenenfalls dabei die Ölphase entfernt.(i) preparing a matrix from gel formers, chitosans and components (a) and (b), (ii) optionally dispersing the matrix in an oil phase, (iii) the dispersed matrix is treated with aqueous solutions of anionic polymers and, if necessary, the oil phase is removed.
In einer alternativen Ausführungsform werden weiterhin Mikrokapseln mit mittleren Durchmessern im Bereich von 0,1 bis 5 mm, bestehend aus einer Hüllmembran und einer die Wirkstoffe enthaltenden Matrix, welche erhältlich sind, indem manIn an alternative embodiment, microcapsules with average diameters in the range from 0.1 to 5 mm, consisting of an envelope membrane and a matrix containing the active ingredients, which can be obtained by:
(i) aus Gelbildnern, anionischen Polymeren und den Komponenten (a) und (b) eine Matrix zubereitet,(i) a matrix is prepared from gel formers, anionic polymers and components (a) and (b),
(ii) gegebenenfalls die Matrix in einer Ölphase dispergiert,(ii) optionally dispersing the matrix in an oil phase,
(iii) die dispergierte Matrix mit wässrigen Chitosanlösungen behandelt und gegebenenfalls dabei die Ölphase entfernt.(iii) the dispersed matrix is treated with aqueous chitosan solutions and, if appropriate, the oil phase is removed in the process.
Die erfindungsgemäßen Mikrokapseln besitzen den besonderen Vorteil, dass sie gegenüber Ten- siden eine hohe Stabilität aufweisen und auf diese Weise auch stabil in kosmetische Zubereitungen eingearbeitet werden können ohne schon während der Lagerung aufgelöst zu werden. Bei der oralen Aufnahme besteht der Vorteil in einer hohen Schleimhautverträglichkeit bei völliger toxikologischer Unbedenklichkeit.The microcapsules according to the invention have the particular advantage that they have high stability with respect to surfactants and can thus also be incorporated stably into cosmetic preparations without being dissolved during storage. The advantage of oral intake is that it is well tolerated by the mucous membrane and completely toxicologically safe.
Analog betreffen weitere Ausgestaltungsformen der Erfindung auch zwei Verfahren zur Herstellung von Mikrokapseln mit mittleren Durchmessern im Bereich von 0,1 bis 5 mm, bestehend aus einer Hüllmembran und einer die Wirkstoffe enthaltenden Matrix, bei dem man entwederAnalogously, further embodiments of the invention also relate to two processes for producing microcapsules with average diameters in the range from 0.1 to 5 mm, consisting of an envelope membrane and a matrix containing the active ingredients, in which either
(i) aus Gelbildnern, Chitosanen und den Komponenten (a) und (b) eine Matrix zubereitet, (ii) gegebenenfalls die Matrix in einer Ölphase dispergiert,(i) preparing a matrix from gel formers, chitosans and components (a) and (b), (ii) optionally dispersing the matrix in an oil phase,
(iii) die dispergierte Matrix mit wässrigen Lösungen anionischer Polymeren behandelt und gegebenenfalls dabei die Ölphase entfernt.(iii) the dispersed matrix is treated with aqueous solutions of anionic polymers and, if appropriate, the oil phase is removed in the process.
oderor
(i) aus Gelbildnern, anionischen Polymeren und den Komponenten (a) und (b) eine Matrix zubereitet,(i) a matrix is prepared from gel formers, anionic polymers and components (a) and (b),
(ii) gegebenenfalls die Matrix in einer Ölphase dispergiert,(ii) optionally dispersing the matrix in an oil phase,
(iii) die dispergierte Matrix mit wässrigen Chitosanlösungen behandelt und gegebenenfalls dabei die Ölphase entfernt. Gelbildner(iii) the dispersed matrix is treated with aqueous chitosan solutions and, if appropriate, the oil phase is removed in the process. gelling agent
Im Sinne der Erfindung werden als Gelbildner vorzugsweise solche Stoffe in Betracht gezogen, welche die Eigenschaft zeigen in wässriger Lösung bei Temperaturen oberhalb von 40 °C Gele zu bilden. Typische Beispiele hierfür sind Heteropolysaccharide und Proteine. Als thermogelierende Heteropolysaccharide kommen vorzugsweise Agarosen in Frage, welche in Form des aus Rotalgen zu gewinnenden Agar-Agar auch zusammen mit bis zu 30 Gew.-% nicht-gelbildenden Agaro- pektinen vorliegen können. Hauptbestandteil der Agarosen sind lineare Polysaccharide aus D- Galaktose und 3,6-Anhydro-L-galaktose, die alternierend ß-1 ,3- und ß-1 ,4-glykosidisch verknüpft sind. Die Heteropolysaccharide besitzen vorzugsweise ein Molekulargewicht im Bereich von 110.000 bis 160.000 und sind sowohl färb- als auch geschmacklos. Als Alternativen kommen Pektine, Xanthane (auch Xanthan Gum) sowie deren Mischungen in Frage. Es sind weiterhin solche Typen bevorzugt, die noch in 1-Gew.-%iger wässriger Lösung Gele bilden, die nicht unterhalb von 80 °C schmelzen und sich bereits oberhalb von 40 °C wieder verfestigen. Aus der Gruppe der thermogelierenden Proteine seien exemplarisch die verschiedenen Gelatine-Typen genannt.For the purposes of the invention, those substances which have the property of forming gels in aqueous solution at temperatures above 40 ° C. are preferably considered as gel formers. Typical examples are heteropolysaccharides and proteins. Suitable thermogelling heteropolysaccharides are preferably agaroses, which can also be present in the form of the agar agar to be obtained from red algae together with up to 30% by weight of non-gel-forming agar pectins. The main constituent of the agaroses are linear polysaccharides from D-galactose and 3,6-anhydro-L-galactose, which are linked alternately ß-1, 3- and ß-1, 4-glycosidically. The heteropolysaccharides preferably have a molecular weight in the range from 110,000 to 160,000 and are both colorless and tasteless. Alternatives are pectins, xanthans (also xanthan gum) and their mixtures. Preference is furthermore given to those types which still form gels in 1% by weight aqueous solution, which do not melt below 80 ° C. and solidify again above 40 ° C. The various types of gelatin from the group of thermogelating proteins are examples.
Chitosanechitosan
Chitosane stellen Biopolymere dar und werden zur Gruppe der Hydrokolloide gezählt. Chemisch betrachtet handelt es sich um partiell deacetylierte Chitine unterschiedlichen Molekulargewichtes, die den folgenden - idealisierten - Monomerbaustein enthalten:Chitosans are biopolymers and belong to the group of hydrocolloids. From a chemical point of view, these are partially deacetylated chitins of different molecular weights that contain the following - idealized - monomer unit:
Figure imgf000008_0001
Figure imgf000008_0001
Im Gegensatz zu den meisten Hydrokolloiden, die im Bereich biologischer pH-Werte negativ geladen sind, stellen Chitosane unter diesen Bedingungen kationische Biopolymere dar. Die positiv geladenen Chitosane können mit entgegengesetzt geladenen Oberflächen in Wechselwirkung treten und werden daher in kosmetischen Haar- und Körperpflegemitteln sowie pharmazeutischen Zubereitungen eingesetzt. Zur Herstellung der Chitosane geht man von Chitin, vorzugsweise den Schalenresten von Krustentieren aus, die als billige Rohstoffe in großen Mengen zur Verfügung stehen. Das Chitin wird dabei üblicherweise zunächst durch Zusatz von Basen deproteiniert, durch Zugabe von Mineralsäuren demineralisiert und schließlich durch Zugabe von starken Basen deacetyliert, wobei die Molekulargewichte über ein breites Spektrum verteilt sein können. Vorzugsweise werden solche Typen eingesetzt, die ein durchschnittliches Molekulargewicht von 10.000 bis 500.000 bzw. 800.000 bis 1.200.000 Dalton aufweisen und/oder eine Viskosität nach Brookfield (1 Gew.-%ig in Glycolsäure) unterhalb von 5000 mPas, einen Deacetylierungsgrad im Bereich von 80 bis 88 % und einem A- schegehalt von weniger als 0,3 Gew.-% besitzen. Aus Gründen der besseren Wasserlöslichkeit werden die Chitosane in der Regel in Form ihrer Salze, vorzugsweise als Glycolate eingesetzt.In contrast to most hydrocolloids, which are negatively charged in the range of biological pH values, chitosans are cationic biopolymers under these conditions. The positively charged chitosans can interact with oppositely charged surfaces and are therefore used in cosmetic hair and body care products and pharmaceuticals Preparations used. The production of chitosans is based on chitin, preferably the shell remains of crustaceans, which are available in large quantities as cheap raw materials. The chitin is usually first deproteinized by adding bases, demineralized by adding mineral acids and finally deacetylated by adding strong bases, it being possible for the molecular weights to be distributed over a broad spectrum. Those types are preferably used which have an average molecular weight of 10,000 to 500,000 or 800,000 to 1,200,000 Daltons and / or a Brookfield viscosity (1% by weight in glycolic acid) below 5000 mPas, a degree of deacetylation in the range of Have 80 to 88% and an ash content of less than 0.3 wt .-%. For reasons of better water solubility, the chitosans are generally used in the form of their salts, preferably as glycolates.
Ölphaseoil phase
Die Matrix kann vor der Bildung der Membran optional in einer Ölphase dispergiert werden. Als Öle kommen für diesen Zweck beispielsweise Guerbetalkohole auf Basis von Fettalkoholen mit 6 bis 18, vorzugsweise 8 bis 10 Kohlenstoffatomen, Ester von linearen C6-C22-Fettsäuren mit linearen C6-C22-Fettalkoholen, Ester von verzweigten C6-Ci3-Carbonsäuren mit linearen C6-C22- Fettalkoholen, wie z.B. Myristylmyristat, Myristylpalmitat, Myristylstearat, Myristylisostearat, My- ristyloleat, Myristylbehenat, Myristylerucat, Cetylmyristat, Cetylpalmitat, Cetylstearat, Cetylisostea- rat, Cetyloleat, Cetylbehenat, Cetylerucat, Stearylmyristat, Stearylpalmitat, Stearylstearat, Stearyli- sostearat, Stearyloleat, Stearylbehenat, Stearylerucat, Isostearylmyristat, Isostearylpalmitat, I- sostearylstearat, Isostearylisostearat, Isostearyloleat, Isostearylbehenat, Isostearyloleat, Oleylmy- ristat, Oleylpalmitat, Oleylstearat, Oleylisostearat, Oleyloleat, Oleylbehenat, Oleylerucat, Behenyl- myristat, Behenylpalmitat, Behenylstearat, Behenylisostearat, Behenyloleat, Behenylbehenat, Be- henylerucat, Erucylmyristat, Erucylpalmitat, Erucylstearat, Erucylisostearat, Erucyloleat, Erucylbe- henat und Erucylerucat. Daneben eignen sich Ester von linearen C6-C22-Fettsäuren mit verzweigten Alkoholen, insbesondere 2-Ethylhexanol, Ester von Hydroxycarbons uren mit linearen oder verzweigten C6-C22-Fettalkoholen, insbesondere Dioctyl Malate, Ester von linearen und/oder verzweigten Fettsäuren mit mehrwertigen Alkoholen (wie z.B. Propylenglycol, Dimerdiol oder Tri- mertriol) und/oder Guerbetalkoholen, Triglyceride auf Basis Cδ-Cio-Fettsäuren, flüssige Mono-/Di- /Triglycerid-mischungen auf Basis von Cε-Ciδ-Fettsäuren, Ester von C6-C22-Fettalkoholen und/oder Guerbetalkoholen mit aromatischen Carbonsäuren, insbesondere Benzoesäure, Ester von C2-C12- Dicarbonsäuren mit linearen oder verzweigten Alkoholen mit 1 bis 22 Kohlenstoffatomen oder Po- lyolen mit 2 bis 10 Kohlenstoffatomen und 2 bis 6 Hydroxylgruppen, pflanzliche Öle, verzweigte primäre Alkohole, substituierte Cyclohexane, lineare und verzweigte Cδ-C22-Fettalkoholcarbonate, Guerbetcarbonate, Ester der Benzoesäure mit linearen und/oder verzweigten C6-C22-Alkoholen (z.B. Finsolv® TN), lineare oder verzweigte, symmetrische oder unsymmetrische Dialkylether mit 6 bis 22 Kohlenstoffatomen pro Alkylgruppe, Ringöffnungsprodukte von epoxidierten Fettsäureestern mit Polyolen, Siliconöle und/oder aliphatische bzw. naphthenische Kohlenwasserstoffe, wie z.B. wie Squalan, Squalen oder Dialkylcyclohexane in Betracht.The matrix can optionally be dispersed in an oil phase before the membrane is formed. Guerbet alcohols based on fatty alcohols with 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C6-C22 fatty acids with linear C6-C22 fatty alcohols, esters of branched C6-Ci3-carboxylic acids with linear C6 come as oils for this purpose, for example -C22- fatty alcohols, such as myristyl myristate, myristyl palmitate, myristyl stearate, Myristylisostearat, My- ristyloleat, rat Myristylbehenat, Myristylerucat, cetyl myristate, cetyl palmitate, cetyl stearate, Cetylisostea-, cetyl oleate, cetyl behenate, Cetylerucat, Stearylmyristat, stearyl palmitate, stearyl stearate, Stearyli- sostearat, stearyl oleate , stearyl, sostearylstearat Stearylerucat, isostearyl, isostearyl, I, isostearyl isostearate, Isostearyloleat, isostearyl behenate, Isostearyloleat, Oleylmy- ristat, myristate oleyl palmitate, oleyl stearate, oleyl isostearate, oleate, Oleylbehenat, oleyl, behenyl, behenyl, behenyl, Behenylisostearat, behenyl oleate, behenyl , Behenyleruc at, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. In addition, esters of linear C6-C22 fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C6-C22 fatty alcohols, in particular dioctyl malates, esters of linear and / or branched fatty acids with polyhydric alcohols ( such as propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides based on Cδ-Cio fatty acids, liquid mono- / di- / triglyceride mixtures based on Cε-Ciδ fatty acids, esters of C6-C22 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, especially benzoic acid, esters of C2-C12 dicarboxylic acids with linear or branched alcohols with 1 to 22 carbon atoms or polyols with 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched Cδ-C22 fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and / or ver branched C6-C22 alcohols (e.g. Finsolv® TN), linear or branched, symmetrical or asymmetrical dialkyl ethers with 6 to 22 carbon atoms per alkyl group, ring opening products of epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenic hydrocarbons such as squalane, squalene or dialkylcyclohexanes ,
Anionpolymereanionic polymers
Die anionische Polymere haben die Aufgabe, mit den Chitosanen Membranen zu bilden. Für diesen Zweck eignen sich vorzugsweise Salze der Alginsäure. Bei der Alginsäure handelt es sich um ein Gemisch carboxylgruppenhaltiger Polysaccharide mit folgendem idealisierten Monomerbaustein:The task of the anionic polymers is to form membranes with the chitosans. Salts of alginic acid are preferably suitable for this purpose. Alginic acid is a mixture of carboxyl-containing polysaccharides with the following idealized monomer unit:
Figure imgf000010_0001
Figure imgf000010_0001
Das durchschnittliche Molekulargewicht der Alginsäuren bzw. der Alginate liegt im Bereich von 150.000 bis 250.000. Dabei sind als Salze der Alginsäure sowohl deren vollständige als auch deren partiellen Neutralisationsprodukte zu verstehen, insbesondere die Alkalisalze und hierunter vorzugsweise das Natriumalginat („Algin") sowie die Ammonium- und Erdalkalisalze, besonders bevorzugt sind Mischalginate, wie z.B. Natrium/Magnesium- oder Natrium/Caiciumalginate. In einer alternativen Ausführungsform der Erfindung kommen für diesen Zweck jedoch auch anionische Chitosanderivate, wie z.B. Carboxylierungs- und vor allem Succinylierungsprodukte in Frage. Alternativ kommen auch Poly(meth)acrylate mit durchschnittlichen Molekulargewichten im Bereich von 5.000 bis 50.000 Dalton sowie die verschiedenen Carboxymethylcellulosen in Frage. Anstelle der anionischen Polymeren können für die Ausbildung der Hüllmembran auch anionische Tenside oder niedermolekulare anorganische Salze, wie beispielsweise Pyrophosphate eingesetzt werden. Herstellverfahren MikrokapselnThe average molecular weight of the alginic acids or alginates is in the range from 150,000 to 250,000. Salts of alginic acid are to be understood to mean both their complete and their partial neutralization products, in particular the alkali metal salts and among them preferably the sodium alginate (“algin”) and the ammonium and alkaline earth metal salts, mixed alginates such as sodium / magnesium or sodium being particularly preferred In an alternative embodiment of the invention, however, anionic chitosan derivatives, such as carboxylation and, in particular, succinylation products are also suitable for this purpose, or alternatively poly (meth) acrylates with average molecular weights in the range from 5,000 to 50,000 daltons and the various In place of the anionic polymers, anionic surfactants or low molecular weight inorganic salts, such as pyrophosphates, can also be used to form the envelope membrane. Manufacturing process microcapsules
Zur Herstellung der Mikrokapseln stellt man üblicherweise eine 1 bis 10, vorzugsweise 2 bis 5 Gew.-%ige wässrige Lösung des Gelbildners, vorzugsweise des Agar-Agars her und erhitzt diese unter Rückfluss. In der Siedehitze, vorzugsweise bei 80 bis 100°C, wird eine zweite wässrige Lösung zugegeben, welche das Chitosan in Mengen von 0,1 bis 2, vorzugsweise 0,25 bis 0,5 Gew.- % und den Wirkstoff (Komponenten a und b) in Mengen von 0,1 bis 25 und insbesondere 0,25 bis 10 Gew,-% enthält; diese Mischung wird als Matrix bezeichnet. Die Beladung der Mikrokapseln mit Wirkstoffen kann daher ebenfalls 0,1 bis 25 Gew.-% bezogen auf das Kapselgewicht betragen. Falls gewünscht, können zu diesem Zeitpunkt zur Viskositätseinstellung auch wasserunlösliche Bestandteile, beispielsweise anorganische Pigmente zugegeben werden, wobei man diese in der Regel in Form von wässrigen oder wässrig/alkoholischen Dispersionen zusetzt. Zur Emulgierung bzw. Dispergierung der Wirkstoffe kann es ferner von Nutzen sein, der Matrix Emulgatoren und/oder Lösungsvermittler hinzuzugeben. Nach der Herstellung der Matrix aus Gelbildner, Chitosan und Wirkstoffmischung (Komponenten a und b) kann die Matrix optional in einer Ölphase unter starker Scherung sehr fein dispergiert werden, um bei der nachfolgenden Verkapselung möglichst kleine Teilchen herzustellen. Dabei hat es sich als besonders vorteilhaft erwiesen, die Matrix auf Temperaturen im Bereich von 40 bis 60 °C zu erwärmen, während man die Ölphase auf 10 bis 20 °C kühlt. Im letzten, nun wieder obligatorischen Schritt erfolgt dann die eigentliche Verkapselung, d.h. die Ausbildung der Hüllmembran durch Inkontaktbringen des Chitosans in der Matrix mit den anionischen Polymeren. Hierzu empfiehlt es sich, die gegebenenfalls in der Ölphase dispergierte Matrix bei einer Temperatur im Bereich von 40 bis 100, vorzugsweise 50 bis 60 °C mit einer wässrigen, etwa 1 bis 50 und vorzugsweise 10 bis 15 Gew.-%ige wässrigen Lösung des Anionpolymers zu behandeln und dabei - falls erforderlich - gleichzeitig oder nachträglich die Ölphase zu entfernen. Die dabei resultierenden wässrigen Zubereitungen weisen in der Regel einen Mikrokapselge- halt im Bereich von 1 bis 10 Gew.-% auf. In manchen Fällen kann es dabei von Vorteil sein, wenn die Lösung der Polymeren weitere Inhaltsstoffe, beispielsweise Emulgatoren oder Konservierungsmittel enthält. Nach Filtration werden Mikrokapseln erhalten, welche im Mittel einen Durchmesser im Bereich von vorzugsweise etwa 1 mm aufweisen. Es empfiehlt sich, die Kapseln zu sieben, um eine möglichst gleichmäßige Größenverteilung sicherzustellen. Die so erhaltenen Mikrokapseln können im herstellungsbedingten Rahmen eine beliebige Form aufweisen, sie sind jedoch bevorzugt näherungsweise kugelförmig. Alternativ kann man die Anionpolymere auch zur Herstellung der Matrix einsetzen und die Verkapselung mit den Chitosanen durchführen. Pro-LiposomenTo produce the microcapsules, a 1 to 10, preferably 2 to 5% by weight aqueous solution of the gel former, preferably the agar, is usually prepared and heated under reflux. At boiling point, preferably at 80 to 100 ° C, a second aqueous solution is added, which contains the chitosan in amounts of 0.1 to 2, preferably 0.25 to 0.5% by weight and the active ingredient (components a and b) in amounts of 0.1 to 25 and in particular 0.25 to 10% by weight; this mixture is called the matrix. The loading of the microcapsules with active ingredients can therefore also be 0.1 to 25% by weight, based on the capsule weight. If desired, water-insoluble constituents, for example inorganic pigments, can also be added at this point in time to adjust the viscosity, these generally being added in the form of aqueous or aqueous / alcoholic dispersions. To emulsify or disperse the active ingredients, it may also be useful to add emulsifiers and / or solubilizers to the matrix. After the matrix has been prepared from the gel former, chitosan and active ingredient mixture (components a and b), the matrix can optionally be very finely dispersed in an oil phase under high shear in order to produce particles as small as possible in the subsequent encapsulation. It has proven particularly advantageous to heat the matrix to temperatures in the range from 40 to 60 ° C. while the oil phase is cooled to 10 to 20 ° C. In the last step, which is now mandatory again, the actual encapsulation then takes place, ie the formation of the envelope membrane by bringing the chitosan in the matrix into contact with the anionic polymers. For this purpose, it is advisable to optionally disperse the matrix in the oil phase at a temperature in the range from 40 to 100, preferably 50 to 60 ° C. with an aqueous, about 1 to 50 and preferably 10 to 15% by weight aqueous solution of the anion polymer to treat and - if necessary - to remove the oil phase at the same time or subsequently. The resulting aqueous preparations generally have a microcapsule content in the range from 1 to 10% by weight. In some cases it can be advantageous if the solution of the polymers contains further ingredients, for example emulsifiers or preservatives. After filtration, microcapsules are obtained which have an average diameter in the range of preferably about 1 mm. It is advisable to sieve the capsules to ensure that the size is distributed as evenly as possible. The microcapsules thus obtained can have any shape in the production-related framework, but they are preferably approximately spherical. Alternatively, the anion polymers can also be used to produce the matrix and encapsulated with the chitosans. Pro-liposomes
Anstelle der beschriebenen Mikrokapseln kommen als Träger für die Wirkstoffgemische auch Pro- Liposomen in Frage. Zur Begriffsklärung sei darauf hingewiesen, dass die Pro-Liposomen kein Wasser enthalten und dieses erst dann unter Bildung von echten Liposomen aufnehmen, wenn sie in eine wässrige Umgebung eingebracht werden. Ein weiterer Gegenstand der Erfindung betrifft daher pro-liposomal verkapselte Antioxidantsgemische, die die Komponenten (a) und (b) aufweisen, und welche man erhält, indem man die Gemische in kosmetisch akzeptablen Lösemitteln mit Lecithinen und/oder Phospholipiden behandelt.Instead of the described microcapsules, pro-liposomes can also be used as carriers for the active ingredient mixtures. To clarify the term, it should be noted that the pro-liposomes do not contain water and only absorb this with the formation of real liposomes if they are introduced into an aqueous environment. Another object of the invention therefore relates to pro-liposomally encapsulated antioxidant mixtures which have components (a) and (b) and which are obtained by treating the mixtures in cosmetically acceptable solvents with lecithins and / or phospholipids.
Unter der Bezeichnung Lecithine versteht der Fachmann diejenigen Glycero-Phospholipide, die sich aus Fettsäuren, Glycerin, Phosphorsäure und Cholin durch Veresterung bilden. Lecithine werden in der Fachwelt daher auch häufig als Phosphatidylcholine (PC) bezeichnet.The person skilled in the art understands the term lecithins as those glycerophospholipids which are formed from fatty acids, glycerol, phosphoric acid and choline by esterification. Lecithins are therefore often referred to in the professional world as phosphatidylcholines (PC).
Figure imgf000012_0001
Figure imgf000012_0001
In der obigen Formel ist ein Lecithin schematisch angegeben, wobei R typischerweise für lineare aliphatische Kohlenwasserstoffreste mit 15 bis 17 Kohlenstoffatomen und bis zu 4 cis- Doppelbindungen steht. Als Beispiele für natürliche Lecithine, die zur Verkapselung in Frage kommen, seien die Kephaline genannt, die auch als Phosphatidsäuren bezeichnet werden und Derivate der 1,2-Diacyl-sn-glycerin-3-phosphorsäuren darstellen. Dem gegenüber versteht man unter Phospholipiden gewöhnlich Mono- und vorzugsweise Diester der Phosphorsäure mit Glycerin (Gly- cerinphosphate), die allgemein zu den Fetten gerechnet werden. Daneben kommen auch zur lipo- somalen Verkapselung Sphingosine bzw. Sphingolipide in Frage. Der Einsatz von Lecithinen bzw. Phospholipiden zur Herstellung von Liposomen ist der einschlägigen Literatur zu entnehmen.A lecithin is shown schematically in the above formula, where R typically stands for linear aliphatic hydrocarbon radicals having 15 to 17 carbon atoms and up to 4 cis double bonds. Examples of natural lecithins that can be encapsulated include the cephalins, which are also referred to as phosphatidic acids and are derivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids. In contrast, phospholipids are usually understood to be mono- and preferably diesters of phosphoric acid with glycerol (glycerol phosphates), which are generally classed as fats. In addition, sphingosines or sphingolipids can also be used for liposomal encapsulation. The use of lecithins or phospholipids for the production of liposomes can be found in the relevant literature.
Herstellverfahren Pro-LiposomenPro liposome manufacturing process
Ein nächster Gegenstand der Erfindung ist analog auf ein Verfahren zur Herstellung von pro- liposomal verkapselten Antioxidantsgemischen gerichtet, die die Komponenten (a) und (b) aufweisen, und welche man erhält, indem man die Gemische in kosmetisch akzeptablen Lösemitteln mit Lecithinen und/oder Phospholipiden behandelt. Hierzu werden die Wirkstoffgemische üblicherwei- se entweder in einem Lösungsmittel vorgelegt und mit den Lecithinen bzw. Phospholipiden bei Temperaturen im Bereich von 30 bis 70 °C in Kontakt gebracht oder aber die wasserfreien Gemische werden in eine Lösung der Lecithine bzw.Phospholipide eingerührt. Die Wirkstoffe und die Lecithine und/oder Phospholipide können dabei im Gewichtsverhältnis 1 : 20 bis 5 : 1, vorzugsweise 1 : 2 bis 4 : 1 eingesetzt werden. Als Lösemittel eignen sich vorzugsweise niedere Alkohole mit 1 bis 4 Kohlenstoffatome, wie z.B. Ethanol oder Polyole, welche in der Regel 2 bis 15 Kohlenstoffatome und mindestens zwei Hydroxylgruppen besitzen; hier ist Propylenglycol bevorzugt.The next object of the invention is directed analogously to a process for the preparation of pro-liposomally encapsulated antioxidant mixtures which have components (a) and (b) and which are obtained by mixing the mixtures in cosmetically acceptable solvents with lecithins and / or Phospholipids treated. For this purpose, the active ingredient mixtures are usually se either in a solvent and brought into contact with the lecithins or phospholipids at temperatures in the range from 30 to 70 ° C, or the anhydrous mixtures are stirred into a solution of the lecithins or phospholipids. The active ingredients and the lecithins and / or phospholipids can be used in a weight ratio of 1:20 to 5: 1, preferably 1: 2 to 4: 1. Suitable solvents are preferably lower alcohols with 1 to 4 carbon atoms, such as ethanol or polyols, which generally have 2 to 15 carbon atoms and at least two hydroxyl groups; propylene glycol is preferred here.
Gewerbliche AnwendbarkeitIndustrial applicability
Für die Entfaltung der Wirksamkeit sind insbesondere Formulierungen geeignet, die für längere Zeit auf dem Haar bzw. auf der Kopfhaut verbleiben, oder die häufig aggressive Chemikalien enthalten. Dazu zählen Haarkuren, Haarpackungen, Haarwässer, Haargele, Haarfarben, Blondie- rungsmittel, Dauerwellmittel, Sun- und After-Sun-Produkte für Haare. Die Mittel eignen sich insbesondere auch zur Langzeitanwendung mit prophylaktischer Wirkung.Formulations which remain on the hair or scalp for a long time or which frequently contain aggressive chemicals are particularly suitable for the development of the effectiveness. These include hair treatments, hair packs, hair lotions, hair gels, hair colors, bleaching agents, permanent waving agents, sun and after-sun products for hair. The agents are also particularly suitable for long-term use with a prophylactic effect.
In einer üblichen Ausführungsform der erfindungsgemäßen Mittel liegen die Zubereitungen in einerIn a common embodiment of the agents according to the invention, the preparations are in one
Zusammensetzung von:Composition of:
0,001 bis 10 Gew. % Astaxanthin und 0,01 bis 3 Gew. % Tocopherol bezogen auf die Gesamtzubereitung vor, bevorzugt enthalten sie0.001 to 10% by weight of astaxanthin and 0.01 to 3% by weight of tocopherol, based on the total preparation, preferably contain them
0,05 bis 8 Gew. % Astaxanthin und 0,03 bis 2 Gew. % Tocopherol bezogen auf die Gesamtzubereitung und besonders bevorzugt0.05 to 8% by weight of astaxanthin and 0.03 to 2% by weight of tocopherol based on the total preparation and particularly preferred
0,1 bis 5 Gew. % Astaxanthin und 0,05 bis 1 Gew. % Tocopherol bezogen auf die Gesamtzubereitung.0.1 to 5% by weight of astaxanthin and 0.05 to 1% by weight of tocopherol, based on the total preparation.
Als Haarfärbemittel haben die erfindungsgemäßen Zubereitungen eine Zusammensetzung von: 0,001 bis 10 Gew. % Astaxanthin und 0,01 bis 8 Gew. % Haarfarbstoffe bezogen auf die Gesamtzubereitung vor, bevorzugt enthalten sieThe preparations according to the invention have a composition of: 0.001 to 10% by weight of astaxanthin and 0.01 to 8% by weight of hair dyes, based on the overall preparation, preferably as hair colorants
0,05 bis 8 Gew. % Astaxanthin und 0,05 bis 5 Gew. % Haarfarbstoffe bezogen auf die Gesamtzubereitung und besonders bevorzugt0.05 to 8% by weight of astaxanthin and 0.05 to 5% by weight of hair dyes based on the overall preparation and particularly preferred
0,1 bis 5 Gew. % Astaxanthin und 0,1 bis 3 Gew. % Haarfarbstoffe bezogen auf die Gesamtzubereitung. Haarfarbstoffe0.1 to 5% by weight of astaxanthin and 0.1 to 3% by weight of hair dyes based on the overall preparation. hair dyes
Zur Färbung von Keratinfasern, vorzugsweise menschlichen Haaren, werden üblicherweise entweder sogenannte direktziehende Farbstoffe oder Oxidationsfärbemittel eingesetzt. Letztere setzen sich aus einer Entwickler- (Oxidationsbase) und einer Kupplerkomponente (Nuancierer) zusammen und stellen keine Farbstoffe im eigentlichen Sinne dar, sondern Farbstoffvorprodukte.To dye keratin fibers, preferably human hair, either so-called direct dyes or oxidation dyes are usually used. The latter consist of a developer (oxidation base) and a coupler component (shader) and are not dyes in the actual sense, but dye precursors.
Oxidationsbasen sind aromatische Verbindungen, die mit mindestens zwei elektronenabgebenden Gruppen (Amino- und/oder Hydroxy-Gruppen) kernsubstituiert sind. Es werden beispielsweise primäre aromatische Amine mit einer weiteren, in para- oder ortho-Position befindlichen freien oder substituierten Hydroxy- oder Aminogruppe, Diaminopyridinderivate, heterocyclische Hydrazone, 4- Aminopyrazolonderivate sowie 2,4,5,6-Tetraaminopyrimidin und dessen Derivate eingesetzt. Spezielle Vertreter sind u. a. p-Toluylendiamin, p-Aminophenol, N, N-Bis-(2-hydroxy-ethyl)-p- phenylendiamin, 2- (2,5-Diamino-phenoxy)-ethanol, 1-Phenyl-3-carboxyamido-4-amino-pyrazolon- 5 und 4-Amino-3-methylphenol, 2-(2-Hydroxyethyl)-1,4-aminobenzol und 2,4,5,6- Tetraaminopyrimidin.Oxidation bases are aromatic compounds which are nucleus-substituted with at least two electron-donating groups (amino and / or hydroxyl groups). For example, primary aromatic amines with a further free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and derivatives thereof are used. Special representatives are u. a. p-toluenediamine, p-aminophenol, N, N-bis (2-hydroxyethyl) p-phenylenediamine, 2- (2,5-diamino-phenoxy) -ethanol, 1-phenyl-3-carboxyamido-4- amino-pyrazolone-5 and 4-amino-3-methylphenol, 2- (2-hydroxyethyl) -1,4-aminobenzene and 2,4,5,6-tetraaminopyrimidine.
Nuancierer sind in der Regel ebenfalls aromatische Verbindungen, jedoch mit am Ring in m- Position leicht oxidierbaren Gruppen. Als Komponenten stehen in der Regel m- Phenylendiaminderivate, Naphthole, Resorcin und Resorcinderivate, Pyrazolone, m-Aminophenole sowie Pyridin-Derivate zur Verfügung. Als Kupplersubstanzen eignen sich insbesondere 1- Naphthol, Pyrogallol, 1,5-, 2,7- und 1,7-Dihydroxynaphthalin, 5-Amino-2-methylphenol, m- Ami- nophenol, Resorcin, Resorcinmonomethylether, m-Phenylendiamin, 1-Phenyl-3-methyl-pyrazolon- 5, 2,4-Dichlor-3-aminophenol, 1,3-Bis-(2,4-diaminophenoxy)-propan, 2-Chlorresorcin, 2-Chlor-6- methyl-3- aminophenol, 2-Methylresorcin, 2,5-Dimethylresorcin, 2,6-Dihydroxypyridin und 2,6- Diaminopyridin.As a rule, shaders are also aromatic compounds, but with groups which are easily oxidizable on the ring in the m position. As components, m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and pyridine derivatives are generally available. Suitable coupler substances are in particular 1-naphthol, pyrogallol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1 -Phenyl-3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2,4-diaminophenoxy) propane, 2-chlororesorcinol, 2-chloro-6-methyl-3 - aminophenol, 2-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxypyridine and 2,6-diaminopyridine.
Als direktziehende Farbstoffe kommen dabei beispielsweise Farbstoffe aus der Gruppe der Ni- trophenylendiamine, Nitroaminophenole, Anthrachinone oder Indophenole in Betracht, wie z.B. die unter den internationalen Bezeichnungen bzw. Handelsnamen HC Yellow 2, HC Yellow 4, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16, Basic Brown 17, Pikraminsäure und Rodol 9 R bekannten Verbindungen sowie 4-Amino-2- nitrodiphenylamin-2'-carbonsäure, 6-Nitro-1,2,3,4-tetrahydrochinoxalin, (N-2,3-Dihydroxypropyl-2- nitro-4-trifluormethyl)-aminobenzol und 4-N-Ethyl-1,4-bis(2'-hydroxyethylamino)-2-nitrobenzol- hydrochlorid. Neben synthetischen Farbstoffen können auch in der Natur vorkommende Farbstoffe wie beispielsweise Henna rot, Henna neutral, Henna schwarz, Kamillenblüte, Sandelholz, schwarzer Tee, Faulbaumrinde, Salbei, Blauholz, Krappwurzel, Catechu, Sedre, Alkannawurzel, Curcumin, Hä- matoxylin, und Autin zum Einsatz kommen. Die natürlichen Farbstoffe können nicht eindeutig den beiden Gruppen zugeordnet werden, fallen jedoch in den häufigsten Fällen in die Gruppe der direktziehenden Färbemittel.Suitable direct dyes are, for example, dyes from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, such as those with the international names or trade names HC Yellow 2, HC Yellow 4, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16, Basic Brown 17, Picramic Acid and Rodol 9 R known compounds and 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, (N-2,3-dihydroxypropyl-2-nitro-4-trifluoromethyl) - aminobenzene and 4-N-ethyl-1,4-bis (2'-hydroxyethylamino) -2-nitrobenzene hydrochloride. In addition to synthetic dyes, naturally occurring dyes such as henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre, alkanna root, curcumin, hematoxylin, and autin are used. The natural dyes cannot be clearly assigned to the two groups, but in the most common cases fall into the group of direct dyes.
Neben Farbstoffmischungen innerhalb der Gruppen sind auch Mischungen von Farbstofffen aus verschiedenen Gruppen einsetzbar. Bezüglich weiterer Farbstöffkomponenten wird ausdrücklich auf die Colipa-Liste, herausgegeben vom Industrieverband Körperpflege und Waschmittel, Frankfurt, verwiesen.In addition to dye mixtures within the groups, mixtures of dyes from different groups can also be used. With regard to other dye components, reference is expressly made to the Colipa list, published by the Industry Association for Personal Care and Detergents, Frankfurt.
Kosmetische und/oder pharmazeutische ZubereitungenCosmetic and / or pharmaceutical preparations
Astaxanthin kann - wie bereits zuvor bei den Mitteln mit längerer Wirkdauer teilweise aufgezählt - zur Herstellung von kosmetischen und/oder pharmazeutischen Zubereitungen, wie beispielsweise Haarshampoos, Haarlotionen, Cremes, Gele, Lotionen, alkoholische und wäßrig/alkoholische Lösungen, Emulsionen, Stiftpräparaten, Pudern, Salben, Tabletten, Dragees, Kapseln, Säfte, Lösungen und Granulaten dienen. Diese Mittel können ferner als weitere Hilfs- und Zusatzstoffe milde Tenside, Ölkörper, Emulgatoren, Perlglanzwachse, Konsistenzgeber, Verdickungsmittel, Überfettungsmittel, Stabilisatoren, Polymere, Siliconverbindungen, Fette, Wachse, Lecithine, Phospholipide, biogene Wirkstoffe, zusätzliche UV-Lichtschutzfaktoren, zusätzliche Antioxidantien, Anti- schuppenmittel, Filmbildner, Quellmittel, Hydrotrope, Solubilisatoren, Konservierungsmittel, Parfümöle, Farbstoffe und dergleichen enthalten.Astaxanthin can - as already partially enumerated above with the agents with a longer duration of action - for the production of cosmetic and / or pharmaceutical preparations, such as hair shampoos, hair lotions, creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, emulsions, stick preparations, powders, Ointments, tablets, dragees, capsules, juices, solutions and granules are used. These agents can also be used as further auxiliaries and additives, mild surfactants, oil bodies, emulsifiers, pearlescent waxes, consistency agents, thickeners, superfatting agents, stabilizers, polymers, silicone compounds, fats, waxes, lecithins, phospholipids, biogenic active ingredients, additional UV light protection factors, additional antioxidants, Contain anti-dandruff agents, film formers, swelling agents, hydrotropes, solubilizers, preservatives, perfume oils, dyes and the like.
Tensidesurfactants
Als oberflächenaktive Stoffe können anionische, nichtionische, kationische und/oder amphotere bzw. zwitterionische Tenside enthalten sein. Typische Beispiele für anionische Tenside sind Seifen, Alkylbenzolsulfonate, Alkansulfonate, Olefinsulfonate, Alkylethersulfonate, Glycerinethersulfo- nate, α-Methylestersulfonate, Sulfofettsäuren, Alkylsulfate, Fettalkoholethersulfate, Glyce- rinethersulfate, Fettsäureethersulfate, Hydroxymischethersulfate, Monoglycerid(ether)sulfate, Fett- säureamid(ether)sulfate, Mono- und Dialkylsulfosuccinate, Mono- und Dialkylsulfosuccinamate, Sulfotriglyceride, Amidseifen, Ethercarbonsäuren und deren Salze, Fettsäureisethionate, Fettsäu- resarcosinate, Fettsäuretauride, N-Acylaminosäuren, wie beispielsweise Acyllactylate, Acyltartrate, Acylglutamate und Acylaspartate, Alkyloligoglucosidsulfate, Proteinfettsäurekondensate (insbesondere pflanzliche Produkte auf Weizenbasis) und Alkyl(ether)phosphate. Sofern die anionischen Tenside Polyglycoletherketten enthalten, können diese eine konventionelle, vorzugsweise jedoch eine eingeengte Homologenverteilung aufweisen. Typische Beispiele für nichtionische Tenside sind Fettalkoholpolyglycolether, Alkylphenolpolyglycolether, Fettsäurepolyglycolester, Fettsäurea- midpolyglycolether, Fettaminpolygiycolether, alkoxylierte Triglyceride, Mischether bzw. Mischformale, gegebenenfalls partiell oxidierte Alk(en)yloligoglykoside bzw. Glucoronsäurederivate, Fett- säure-N-alkylgiucamide, Proteinhydrolysate (insbesondere pflanzliche Produkte auf Weizenbasis), Polyolf ettsäu reester , Zuckerester, Sorbitanester, Polysorbate und Aminoxide. Sofern die nichtionischen Tenside Polyglycoletherketten enthalten, können diese eine konventionelle, vorzugsweise jedoch eine eingeengte Homologenverteilung aufweisen. Typische Beispiele für kationische Tenside sind quartäre Ammoniumverbindungen, wie beispielsweise das Dimethyidistearylammoni- umchlorid, und Esterquats, insbesondere quatemierte Fettsäuretrialkanolaminestersalze. Typische Beispiele für amphotere bzw. zwitterionische Tenside sind Alkylbetaine, Alkylamidobetaine, Ami- nopropionate, Aminoglycinate, Imidazoliniumbetaine und Sulfobetaine. Bei den genannten Tensi- den handelt es sich ausschließlich um bekannte Verbindungen. Typische Beispiele für besonders geeignete milde, d.h. besonders hautverträgliche Tenside sind Fettalkoholpolyglycolethersulfate, Monoglyceridsulfate, Mono- und/oder Dialkylsulfosuccinate, Fettsäureisethionate, Fettsäuresarco- sinate, Fettsäuretauride, Fettsäureglutamate, α-Olefinsulfonate, Ethercarbonsäuren, Alkyloli- goglucoside, Fettsäuregfucamide, Alkylamidobetaine, Amphoacetale und/oder Proteinfettsäurekondensate, letztere vorzugsweise auf Basis von Weizenproteinen.Anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants can be contained as surface-active substances. Typical examples of anionic surfactants are soaps, alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, fatty acid ether sulfates (fatty ether ether sulfates, hydroxymether amide sulfates, hydroxymether amide sulfates, hydroxymether amide sulfates, hydroxymether amide sulfates, hydroxymether amide sulfates, hydroxymether amide sulfates, hydroxymether amide sulfates, fatty ether ether sulfates, hydroxyl ether sulfates, hydroxymether amide sulfates, hydroxymether ether sulfates, hydroxyl ether sulfates, hydroxyl ether sulfates, hydroxymether ether sulfates, fatty ether ether sulfates, hydroxymether ether sulfates, hydroxyl ether sulfates, hydroxymether ether sulfates, hydroxymether ether sulfates, hydroxymether sulfates, sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino acids, such as acyl lactylates, acyl tartrates Acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable products based on wheat) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Typical examples of non-ionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, optionally partially oxidized alk (en) yl oligoglycosides, especially nucylglycolic acid derivatives (N-fatty acid silicate acid derivatives) Wheat-based products), polyolf esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Typical examples of cationic surfactants are quaternary ammonium compounds, such as, for example, dimethyidistearylammonium chloride, and ester quats, in particular quaternized fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazoliniumbetaines and sulfobetaines. The surfactants mentioned are exclusively known compounds. Typical examples of particularly suitable mild, ie particularly skin-compatible, surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarosinates, fatty acid taurides, fatty acid glutamates, α-olefin sulfonates, alkyl fatty amide amides, amide carboxylic acid amide carbamides, fatty carboxamides, or protein fatty acid condensates, the latter preferably based on wheat proteins.
Ölkörperoil body
Als Ölkörper kommen beispielsweise Guerbetalkohole auf Basis von Fettalkoholen mit 6 bis 18, vorzugsweise 8 bis 10 Kohlenstoffatomen, Ester von linearen C6-C22-Fettsäuren mit linearen oder verzweigten C6-C22-Fettalkoholen bzw. Ester von verzweigten C6-Ci3-Carbonsäuren mit linearen oder verzweigten C6-C22-Fettalkoholen, wie z.B. Myristylmyristat, Myristylpalmitat, Myristylstearat, Myristylisostearat, Myristyloleat, Myristylbehenat, Myristylerucat, Cetylmyristat, Cetylpalmitat, Ce- tylstearat, Cetylisostearat, Cetyloleat, Cetylbehenat, Cetylerucat, Stearylmyristat, Stearylpalmitat, Stearylstearat, Stearylisostearat, Stearyloleat, Stearylbehenat, Stearylerucat, Isostearylmyristat, Isostearylpalmitat, Isostearylstearat, Isostearylisostearat, Isostearyloleat, Isostearylbehenat, I- sostearyloleat, Oleylmyristat, Oleylpalmitat, Oleylstearat, Oleylisostearat, Oleyloleat, Oleylbehenat, Oleylerucat, Behenylmyristat, Behenylpalmitat, Behenylstearat, Behenylisostearat, Behenyloleat, Behenylbehenat, Behenylerucat, Erucylmyristat, Erucylpalmitat, Erucylstearat, Erucylisostearat, Erucyloleat, Erucylbehenat und Erucylerucat. Daneben eignen sich Ester von linearen C6-C22- Fettsäuren mit verzweigten Alkoholen, insbesondere 2-Ethylhexanol, Ester von Ci8-C38-Alkylhy- droxycarbonsäuren mit linearen oder verzweigten C6-C22-Fettalkoholen, insbesondere Dioctyl Ma- late, Ester von linearen und/oder verzweigten Fettsäuren mit mehrwertigen Alkoholen (wie z.B. Propylenglycol, Dimerdiol oder Trimertriol) und/oder Guerbetalkoholen, Triglyceride auf Basis CΘ- Cio-Fettsäuren, flüssige Mono-/Di-/Triglyceridmischungen auf Basis von C6-Ci8-Fettsäuren, Ester von C6-C22-Fettalkoholen und/oder Guerbetalkoholen mit aromatischen Carbonsäuren, insbesondere Benzoesäure, Ester von C2-Ci2-Dicarbonsäuren mit linearen oder verzweigten Alkoholen mit 1 bis 22 Kohlenstoffatomen oder Polyolen mit 2 bis 10 Kohlenstoffatomen und 2 bis 6 Hydroxylgruppen, pflanzliche Öle, verzweigte primäre Alkohole, substituierte Cyclohexane, lineare und verzweigte C6-C22-Fettalkoholcarbonate, wie z.B. Dicaprylyl Carbonate (Cetiöl® CC), Guer^ betcarbonate auf Basis von Fettalkoholen mit 6 bis 18, vorzugsweise 8 bis 10 C Atomen, Ester der Benzoesäure mit linearen und/oder verzweigten C6-C22-Alkoholen (z.B. Finsolv® TN), lineare oder verzweigte, symmetrische oder unsymmetrische Dialkylether mit 6 bis 22 Kohlenstoffatomen pro Alkylgruppe, wie z.B. Dicaprylyl Ether (Cetiol® OE), Ringöffnungsprodukte von epoxidierten Fettsäureestern mit Polyolen, Siliconöle (Cyclomethicone, Siliciummethicontypen u.a.) und/oder a- liphatische bzw. naphthenische Kohlenwasserstoffe, wie z.B. wie Squalan, Squalen oder Dialkyl- cyclohexane in Betracht.Guerbet alcohols based on fatty alcohols with 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C6-C22 fatty acids with linear or branched C6-C22 fatty alcohols or esters of branched C6-Ci3 carboxylic acids with linear or branched C6-C22-fatty alcohols, such as myristyl myristate, myristyl palmitate, myristyl stearate, Myristylisostearat, myristyl, Myristylbehenat, Myristylerucat, cetyl myristate, cetyl palmitate, Ce tylstearat, Cetylisostearat, cetyl oleate, cetyl behenate, Cetylerucat, Stearylmyristat, stearyl palmitate, stearyl stearate, Stearylisostearat, stearyl oleate, stearyl behenate , Stearylerucat, isostearyl, isostearyl palmitate, Isostearylstearat, isostearyl isostearate, Isostearyloleat, isostearyl behenate, Isostearyloleat, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, Oleylbehenat, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl, Behenylisostearat, behenyl oleate, Behenylbehen at, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. In addition, esters of linear C6-C22- Fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of Ci8-C38-alkylhydroxycarboxylic acids with linear or branched C6-C22-fatty alcohols, especially dioctylmate, esters of linear and / or branched fatty acids with polyhydric alcohols (such as propylene glycol , Dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides based on CΘ-Cio fatty acids, liquid mono- / di- / triglyceride mixtures based on C6-Ci8 fatty acids, esters of C6-C22 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids , in particular benzoic acid, esters of C2-Ci2-dicarboxylic acids with linear or branched alcohols with 1 to 22 carbon atoms or polyols with 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C6-C22 -Fatty alcohol carbonates, such as dicaprylyl carbonates (Cetiöl® CC), Guer ^ betcarbonate based on fatty alcohols with 6 to 1 8, preferably 8 to 10 C atoms, esters of benzoic acid with linear and / or branched C6-C22 alcohols (eg Finsolv® TN), linear or branched, symmetrical or unsymmetrical dialkyl ethers with 6 to 22 carbon atoms per alkyl group, such as dicaprylyl ether (Cetiol® OE), ring opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicones, silicon methicone types, etc.) and / or aliphatic or naphthenic hydrocarbons, such as, for example, squalane, squalene or dialkylcyclohexanes.
Emulgatorenemulsifiers
Als Emulgatoren kommen beispielsweise nichtionogene Tenside aus mindestens einer der folgenden Gruppen in Frage:Examples of suitable emulsifiers are nonionic surfactants from at least one of the following groups:
> Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/ oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen, an Alkylphe- nole mit 8 bis 15 C-Atomen in der Alkylgruppe sowie Alkylamine mit 8 bis 22 Kohlenstoffatomen im Alkylrest;> Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms, with alkylphenols with 8 to 15 C atoms in the Alkyl group and alkylamines with 8 to 22 carbon atoms in the alkyl radical;
> Alkyl- und/oder Alkenyloligoglykoside mit 8 bis 22 Kohlenstoffatomen im Alk(en)ylrest und deren ethoxylierte Analoga;> Alkyl and / or alkenyl oligoglycosides with 8 to 22 carbon atoms in the alk (en) yl radical and their ethoxylated analogs;
> Anlagerungsprodukte von 1 bis 15 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinu- söl; Anlagerungsprodukte von 15 bis 60 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl; > Partialester von Glycerin und/oder Sorbitan mit ungesättigten, linearen oder gesättigten, verzweigten Fettsäuren mit 12 bis 22 Kohlenstoffatomen und/oder Hydroxycarbonsauren mit 3 bis 18 Kohlenstoffatomen sowie deren Addukte mit 1 bis 30 Mol Ethylenoxid;> Addition products of 1 to 15 mol ethylene oxide onto castor oil and / or hardened castor oil; Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil; > Partial esters of glycerol and / or sorbitan with unsaturated, linear or saturated, branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 mol ethylene oxide;
> Partialester von Polyglycerin (durchschnittlicher Eigenkondensationsgrad 2 bis 8), Polyethy- lenglycol (Molekulargewicht 400 bis 5000), Trimethylolpropan, Pentaerythrit, Zuckeralkoholen (z.B. Sorbit), Alkylglucosiden (z.B. Methylglucosid, Butylglucosid, Laurylglucosid) sowie Po- lyglucosiden (z.B. Cellulose) mit gesättigten und/oder ungesättigten, linearen oder verzweigten Fettsäuren mit 12 bis 22 Kohlenstoffatomen und/oder Hydroxycarbonsauren mit 3 bis 18 Kohlenstoffatomen sowie deren Addukte mit 1 bis 30 Mol Ethylenoxid;> Partial esters of polyglycerol (average degree of self-condensation 2 to 8), polyethylene glycol (molecular weight 400 to 5000), trimethylolpropane, pentaerythritol, sugar alcohols (eg sorbitol), alkyl glucosides (eg methyl glucoside, butyl glucoside, lauryl glucoside) and poly (eg cellulose) saturated and / or unsaturated, linear or branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 mol ethylene oxide;
> Mischester aus Pentaerythrit, Fettsäuren, Citronensäure und Fettalkohol und/oder Mischester von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, Methylglucose und Polyolen, vorzugsweise Glycerin oder Polyglycerin.> Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol.
> Mono-, Di- und Trialkylphosphate sowie Mono-, Di- und/oder Tri-PEG-alkylphosphate und deren Salze;> Mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts;
> Wollwachsalkohole;> Wool wax alcohols;
> Polysiloxan-Polyalkyl-Polyether-Copolymere bzw. entsprechende Derivate;> Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;
> Block-Copolymere z.B. Polyethylenglycol-30 Dipolyhydroxystearate;> Block copolymers e.g. Polyethylene glycol 30 dipolyhydroxystearate;
> Polymeremulgatoren, z.B. Pemulen-Typen (TR-1 ,TR-2) von Goodrich;> Polymer emulsifiers, e.g. Pemulen types (TR-1, TR-2) from Goodrich;
> Polyalkylenglycole sowie> Polyalkylene glycols as well
> Glycerincarbonat.> Glycerine carbonate.
> Ethylenoxidanlagerunqsprodukte> Ethylene oxide addition products
Die Anlagerungsprodukte von Ethylenoxid und/oder von Propylenoxid an Fettalkohole, Fettsäuren, Alkylphenole oder an Ricinusöl stellen bekannte, im Handel erhältliche Produkte dar. Es handelt sich dabei um Homologengemische, deren mittlerer Alkoxylierungsgrad dem Verhältnis der Stoffmengen von Ethylenoxid und/ oder Propylenoxid und Substrat, mit denen die Anlagerungsreaktion durchgeführt wird, entspricht. Ci2/i8-Fettsäuremono- und -diester von Anlagerungsprodukten von Ethylenoxid an Glycerin sind als Rückfettungsmittel für kosmetische Zubereitungen bekannt.The adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols or with castor oil are known, commercially available products. These are mixtures of homologs whose average degree of alkoxylation is the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate, with which the addition reaction is carried out. Ci2 / i8 fatty acid monoesters and diesters of adducts of ethylene oxide with glycerol are known as refatting agents for cosmetic preparations.
> Alkyl- und/oder Alkenyloliqoqlykoside> Alkyl and / or alkenyl olefin glycosides
Alkyl- und/oder Alkenyloligoglycoside, ihre Herstellung und ihre Verwendung sind aus dem Stand der Technik bekannt. Ihre Herstellung erfolgt insbesondere durch Umsetzung von Glu- cose oder Oligosacchariden mit primären Alkoholen mit 8 bis 18 Kohlenstoffatomen. Bezüglich des Glycosidrestes gilt, daß sowohl Monoglycoside, bei denen ein cyclischer Zuckerrest glycosidisch an den Fettalkohol gebunden ist, als auch oligomere Glycoside mit einem Oligo- merisationsgrad bis vorzugsweise etwa 8 geeignet sind. Der Oligomerisierungsgrad ist dabei ein statistischer Mittelwert, dem eine für solche technischen Produkte übliche Homologenverteilung zugrunde liegt,Alkyl and / or alkenyl oligoglycosides, their preparation and their use are known from the prior art. They are manufactured in particular by converting glu cose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms. With regard to the glycoside residue, both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to preferably about 8 are suitable. The degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products,
> Partialglyceride> Partial glycerides
Typische Beispiele für geeignete Partialglyceride sind Hydroxystearinsäuremonoglycerid, Hydroxystearinsäurediglycerid, Isostearinsäuremonoglycerid, Isostearinsäurediglycerid, Öl- säuremonoglycerid, Ölsäurediglycerid, Ricinolsäuremoglycerid, Ricinolsäurediglycerid, Linol- säuremonoglycerid, Linolsäurediglycerid, Linolensäuremonoglycerid, Linolensäurediglycerid, Erucasäuremonoglycerid, Erucasäurediglycerid, Weinsäuremonoglycerid, Weinsäurediglyce- rid, Citronensäuremonoglycerid, Citronendiglycerid, Äpfelsäuremonoglycerid, Äpfelsäuredigly- cerid sowie deren technische Gemische, die untergeordnet aus dem Herstellungsprozeß noch geringe Mengen an Triglycerid enthalten können. Ebenfalls geeignet sind Anlagerungsprodukte von 1 bis 30, vorzugsweise 5 bis 10 Mol Ethylenoxid an die genannten Partialglyceride.Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride, hydroxystearic acid diglyceride, isostearic acid, Isostearinsäurediglycerid, oleic acid monoglyceride, oleic acid diglyceride, Ricinolsäuremoglycerid, Ricinolsäurediglycerid, linoleic acid monoglyceride, Linolsäurediglycerid, Linolensäuremonoglycerid, Linolensäurediglycerid, Erucasäuremonoglycerid, Erucasäurediglycerid, Weinsäuremonoglycerid, Weinsäurediglyce- chloride, Citronensäuremonoglycerid, Citronendiglycerid, Äpfelsäuremonoglycerid, Malic acid diglyceride and their technical mixtures, which may still contain small amounts of triglyceride from the manufacturing process. Addition products of 1 to 30, preferably 5 to 10, mol of ethylene oxide onto the partial glycerides mentioned are also suitable.
> Sorbitanester> Sorbitan esters
Als Sorbitanester kommen Sorbitanmonoisostearat, Sorbitansesquiisostearat, Sorbitan- diisostearat, Sorbitantriisostearat, Sorbitanmonooleat, Sorbitansesquioleat, Sorbitan-dioleat, Sorbitantrioleat, Sorbitanmonoerucat, Sorbitansesquierucat, Sorbitandierucat, Sorbitantrieru- cat, Sorbitanmonoricinoleat, Sorbitansesquiricinoleat, Sorbitandiricinoleat, Sorbitantriricinoleat, Sorbitanmonohydroxystearat, Sorbitansesquihydroxystearat, Sorbitandihydroxystearat, Sor- bitantrihydroxystearat, Sorbitanmonotartrat, Sorbitansesqui-tartrat, Sorbitanditartrat, Sorbi- tantritartrat, Sorbitanmonocitrat, Sorbitansesquicitrat, Sorbitandicitrat, Sorbitantricitrat, Sorbi- tanmonomaleat, Sorbitansesquimaleat, Sorbitan-dimaleat, Sorbitantrimaleat sowie deren technische Gemische. Ebenfalls geeignet sind Anlagerungsprodukte von 1 bis 30, vorzugsweise 5 bis 10 Mol Ethylenoxid an die genannten Sorbitanester. PolyglycerinesterAs sorbitan sorbitan, sorbitan sesquiisostearate, sorbitan come diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan dioleate, trioleate, Sorbitanmonoerucat, Sorbitansesquierucat, Sorbitandierucat, Sorbitantrieru- cat, Sorbitanmonoricinoleat, Sorbitansesquiricinoleat, Sorbitandiricinoleat, Sorbitantriricinoleat, Sorbitanmonohydroxystearat, Sorbitansesquihydroxystearat, Sorbitandihydroxystearat, sorting bitantrihydroxystearat , Sorbitan monotartrate, sorbitan sesqui-tartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan technical sorbitan and sorbitan dittrate. Addition products of 1 to 30, preferably 5 to 10, mol of ethylene oxide onto the sorbitan esters mentioned are also suitable. polyglycerol
Typische Beispiele für geeignete Polyglycerinester sind Polyglyceryl-2 Dipolyhydroxystearate (Dehymuls® PGPH), Polyglycerin-3-Diisostearate (Lameform® TGI), Polyglyceryl-4 Isostea- rate (Isolan® Gl 34), Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3 Diisostearate (Iso- lan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450), Polyglyceryl-3 Bees- wax (Cera Bellina®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010/90), Polyglyceryl-3 Cetyl Ether (Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) und Polygly- ceryl Polyricinoleate (Admul® WOL 1403) Polyglyceryl Dimerate Isostearate sowie deren Gemische. Beispiele für weitere geeignete Polyolester sind die gegebenenfalls mit 1 bis 30 Mol Ethylenoxid umgesetzten Mono-, Di- und Triester von Trimethylolpropan. oder Pentaerythrit mit Laurinsäure, Kokosfettsäure, Taigfettsäure, Palmitinsäure, Stearinsäure, Ölsäure, Behensäure und dergleichen.Typical examples of suitable polyglycerol esters are polyglyceryl-2 dipolyhydroxystearates (Dehymuls® PGPH), polyglycerol-3 diisostearates (Lameform® TGI), polyglyceryl-4 isostates (Isolan® Gl 34), polyglyceryl-3 oleates, diisostearoyl polyglyearyl-3 diisostearates (Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010 / 90), Polyglyceryl-3 Cetyl Ether ( Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul® WOL 1403) Polyglyceryl Dimerate Isostearate and their mixtures. Examples of other suitable polyol esters are the mono-, di- and triesters of trimethylolpropane which are optionally reacted with 1 to 30 mol of ethylene oxide. or pentaerythritol with lauric acid, coconut fatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like.
Anionische EmulgatorenAnionic emulsifiers
Typische anionische Emulgatoren sind aliphatische Fettsäuren mit 12 bis 22 Kohlenstoffatomen, wie beispielsweise Palmitinsäure, Stearinsäure oder Behensäure, sowie Dicarbonsäuren mit 12 bis 22 Kohlenstoffatomen, wie beispielsweise Azelainsäure oder Sebacinsäure.Typical anionic emulsifiers are aliphatic fatty acids with 12 to 22 carbon atoms, such as, for example, palmitic acid, stearic acid or behenic acid, and dicarboxylic acids with 12 to 22 carbon atoms, such as, for example, azelaic acid or sebacic acid.
Amphothere und kationische EmulgatorenAmphoteric and cationic emulsifiers
Weiterhin können als Emulgatoren zwitterionische Tenside verwendet werden. Als zwitterionische Tenside werden solche oberflächenaktiven Verbindungen bezeichnet, die im Molekül mindestens eine quartäre Ammoniumgruppe und mindestens eine Carboxylat- und eine Sul- fonatgruppe tragen. Besonders geeignete zwitterionische Tenside sind die sogenannten Betaine wie die N-Alkyl-N,N-dimethylammoniumglycinate, beispielsweise das Kokosalkyldi- methylammoniumglycinat, N-Acylaminopropyl-N,N-dimethylammonium-glycinate, beispielsweise das Kokosacylaminopropyldimethyl-ammoniumglycinat, und 2-Alkyl-3-car- boxylmethyl-3-hydroxyethylimidazoline mit jeweils 8 bis 18 C-Atomen in der Alkyl- oder A- cylgruppe sowie das Kokosacylaminoethylhydroxyethylcarboxymethylglycinat. Besonders bevorzugt ist das unter der CTFA-Bezeichnung Cocamidopropyl Betaine bekannte Fettsäurea- mid-Derivat. Ebenfalls geeignete Emulgatoren sind ampholytische Tenside. Unter ampholyti- schen Tensiden werden solche oberflächenaktiven Verbindungen verstanden, die außer einer Cδ/is-Alkyl- oder Acylgruppe im Molekül mindestens eine freie Aminogruppe und mindestens eine -COOH- oder -Sθ3H-Gruppe enthalten und zur Ausbildung innerer Salze befähigt sind. Beispiele für geeignete ampholytische Tenside sind N-Alkylglycine, N-Alkylpropion-säuren, N- Alkylaminobuttersäuren, N-Alkyliminodipropionsäuren, N-Hydroxyethyl-N-alkylamidopropylg- lycine, N-Alkyltaurine, N-Alkylsarcosine, 2-Alkylaminopropionsäuren und Alkylaminoessigsäu- ren mit jeweils etwa 8 bis 18 C-Atomen in der Alkylgruppe.. Besonders bevorzugte ampholytische Tenside sind das N-Kokosalkylaminopropionat, das Kokosacylaminoethylamino- propionat und das Ci2/ιs-Acylsarcosin. Schließlich kommen auch Kationtenside als Emulgatoren in Betracht, wobei solche vom Typ der Esterquats, vorzugsweise methylquaternierte Di- fettsäuretriethanolaminester-Salze, besonders bevorzugt sind.Zwitterionic surfactants can also be used as emulsifiers. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the coconut alkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the coconut acylaminopropyldimethylammonium glycinate, and 2-alkyl-3 -car- boxylmethyl-3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. The fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine is particularly preferred. Suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are understood to mean those surface-active compounds which, in addition to a Cδ / is-alkyl or acyl group, have at least one free amino group in the molecule and at least one contain a -COOH or -Sθ3H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each have about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-coconut alkylaminopropionate, coconut acylaminoethylamino propionate and Ci2 / ιs acyl sarcosine. Finally, cationic surfactants are also suitable as emulsifiers, those of the esterquat type, preferably methylquaternized di-fatty acid triethanolamine ester salts, being particularly preferred.
Fette und WachseFats and waxes
Typische Beispiele für Fette sind Glyceride, d.h. feste oder flüssige pflanzliche oder tierische Produkte, die im wesentlichen aus gemischten Glycerinestern höherer Fettsäuren bestehen, als Wachse kommen u.a. natürliche Wachse, wie z.B. Candelillawachs, Carnaubawachs, Japanwachs, Espartograswachs, Korkwachs, Guarumawachs, Reiskeimölwachs, Zuckerrohrwachs, Ouricury- wachs, Montanwachs, Bienenwachs, Schellackwachs, Walrat, Lanolin (Wollwachs), Bürzelfett, Ceresin, Ozokerit (Erdwachs), Petrolatum, Paraffinwachse, Mikrowachse; chemisch modifizierte Wachse (Hartwachse), wie z.B. Montanesterwachse, Sasolwachse, hydrierte Jojobawachse sowie synthetische Wachse, wie z.B. Polyalkylenwachse und Polyethylenglycolwachse in Frage. Neben den Fetten kommen als Zusatzstoffe auch fettähnliche Substanzen, wie Lecithine und Phospholipide in Frage. Unter der Bezeichnung Lecithine versteht der Fachmann diejenigen Glycero- Phospholipide, die sich aus Fettsäuren, Glycerin, Phosphorsäure und Cholin durch Veresterung bilden. Lecithine werden in der Fachwelt daher auch häufig als Phosphatidylcholine (PC). Als Beispiele für natürliche Lecithine seien die Kephaline genannt, die auch als Phosphatidsäuren bezeichnet werden und Derivate der 1,2-Diacyl-sn-glycerin-3-phosphorsäuren darstellen. Dem gegenüber versteht man unter Phospholipiden gewöhnlich Mono- und vorzugsweise Diester der Phosphorsäure mit Glycerin (Glycerinphosphate), die allgemein zu den Fetten gerechnet werden. Daneben kommen auch Sphingosine bzw. Sphingolipide in Frage.Typical examples of fats are glycerides, i.e. Solid or liquid vegetable or animal products, which consist essentially of mixed glycerol esters of higher fatty acids, come as waxes, among others. natural waxes, e.g. Candelilla wax, carnauba wax, Japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax, beeswax, shellac wax, walnut, lanolin (wool wax), pretzel fat, ceresin, ozokerite (earth wax), petrolatum, paraffin waxes chemically modified waxes (hard waxes), e.g. Montanester waxes, Sasol waxes, hydrogenated jojoba waxes and synthetic waxes, such as Polyalkylene waxes and polyethylene glycol waxes in question. In addition to fats, fat-like substances such as lecithins and phospholipids can also be used as additives. The skilled worker understands the term lecithins to mean those glycerophospholipids which are formed from fatty acids, glycerol, phosphoric acid and choline by esterification. Lecithins are therefore often used in the professional world as phosphatidylcholines (PC). Examples of natural lecithins are the cephalins, which are also referred to as phosphatidic acids and are derivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids. In contrast, phospholipids are usually understood to be mono- and preferably diesters of phosphoric acid with glycerol (glycerol phosphates), which are generally classed as fats. In addition, sphingosines or sphingolipids are also suitable.
Perlqlanzwachse' Pearlescent waxes '
Als Perlglanzwachse kommen beispielsweise in Frage: Alkylenglycolester, speziell Ethylenglycoldi- stearat; Fettsäurealkanolamide, speziell Kokosfettsäurediethanolamid; Partialglyceride, speziell Stearinsäuremonoglycerid; Ester von mehrwertigen, gegebenenfalls hydroxy-substituierte Carbon- säuren mit Fettalkoholen mit 6 bis 22 Kohlenstoffatomen, speziell langkettige Ester der Weinsäure; Fettstoffe, wie beispielsweise Fettalkohole, Fettketone, Fettaldehyde, Fettether und Fettcarbonate, die in Summe mindestens 24 Kohlenstoffatome aufweisen, speziell Lauron und Distearylether; Fettsäuren wie Stearinsäure, Hydroxystearinsäure oder Behensäure, Ringöffnungsprodukte von Olefinepoxiden mit 12 bis 22 Kohlenstoffatomen mit Fettalkohoien mit 12 bis 22 Kohlenstoffatomen und/oder Polyolen mit 2 bis 15 Kohlenstoffatomen und 2 bis 10 Hydroxylgruppen sowie deren Mischungen.Pearlescent waxes, for example, are: alkylene glycol esters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polyvalent, optionally hydroxy-substituted carbon acids with fatty alcohols with 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which have a total of at least 24 carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring opening products of olefin epoxides with 12 to 22 carbon atoms with fatty alcohols with 12 to 22 carbon atoms and / or polyols with 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.
Konsistenzgeber und VerdickunqsmittelConsistency and thickening agents
Als Konsistenzgeber kommen in erster Linie Fettalkohole oder Hydroxyfettalkohole mit 12 bis 22 und vorzugsweise 16 bis 18 Kohlenstoffatomen und daneben Partialglyceride, Fettsäuren oder Hydroxyfettsäuren in Betracht. Bevorzugt ist eine Kombination dieser Stoffe mit Alkyloligoglucosi- den und/oder Fettsäure-N-methylglucamiden gleicher Kettenlänge und/oder Polyglycerinpoly-12- hydroxystearaten. Geeignete Verdickungsmittel sind beispielsweise Aerosil-Typen (hydrophile Kieselsäuren), Polysaccharide, insbesondere Xanthan-Gum, Guar-Guar, Agar-Agar, Alginate und Tylosen, Carboxymethylcellulose und Hydroxyethyl- und Hydroxypropylcellulose, ferner höhermolekulare Polyethylenglycolmono- und -diester von Fettsäuren, Polyacrylate, (z.B. Carbopo- le® und Pemulen-Typen von Goodrich; Synthalene® von Sigma; Keltrol-Typen von Kelco; Sepigel-Typen von Seppic; Salcare-Typen von Allied Colloids), Polyacrylamide, Polymere, Polyvi- nylalkohol und Polyvinylpyrrolidon. Als besonders wirkungsvoll haben sich auch Bentonite, wie z.B. Bentone® Gel VS-5PC (Rheox) erwiesen, bei dem es sich um eine Mischung aus Cyclopentasilo- xan, Disteardimonium Hectorit und Propylencarbonat handelt. Weiter in Frage kommen Tenside, wie beispielsweise ethoxylierte Fettsäureglyceride, Ester von Fettsäuren mit Polyolen wie beispielsweise Pentaerythrit oder Trimethylolpropan, Fettalkoholethoxylate mit eingeengter Homologenverteilung oder Alkyloligoglucoside sowie Elektrolyte wie Kochsalz und Ammoniumchlorid.Suitable consistency agents are primarily fatty alcohols or hydroxy fatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms and, in addition, partial glycerides, fatty acids or hydroxy fatty acids. A combination of these substances with alkyl oligoglucosides and / or fatty acid N-methyl glucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates is preferred. Suitable thickeners are, for example, Aerosil types (hydrophilic silicas), polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl and hydroxypropyl cellulose, as well as higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, (eg Carbopole® and Pemulen types from Goodrich; Synthalene® from Sigma; Keltrol types from Kelco; Sepigel types from Seppic; Salcare types from Allied Colloids), polyacrylamides, polymers, polyvinyl alcohol and polyvinyl pyrrolidone. Bentonites, such as e.g. Bentone® Gel VS-5PC (Rheox) has been proven, which is a mixture of cyclopentasiloxane, disteardimonium hectorite and propylene carbonate. Surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with a narrow homolog distribution or alkyl oligoglucosides as well as electrolytes such as table salt and ammonium chloride are also suitable.
Überfettungsmittelsuperfatting
Als Überfettungsmittel können Substanzen wie beispielsweise Lanolin und Lecithin sowie polye- thoxylierte oder acylierte Lanolin- und Lecithinderivate, Polyolfettsaureester, Monoglyceride und Fettsäurealkanolamide verwendet werden, wobei die letzteren gleichzeitig als Schaumstabilisatoren dienen. StabilisatorenSubstances such as, for example, lanolin and lecithin and also polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used as superfatting agents, the latter simultaneously serving as foam stabilizers. stabilizers
Als Stabilisatoren können Metallsalze, von Fettsäuren, wie z.B. Magnesium-, Aluminium- und/oder Zinkstearat bzw. -ricinoleat eingesetzt werden.Metal salts of fatty acids, such as e.g. Magnesium, aluminum and / or zinc stearate or ricinoleate are used.
Polymerepolymers
Geeignete kationische Polymere sind beispielsweise kationische Cellulosederivate, wie z.B. eine quaternierte Hydroxyethylcellulose, die unter der Bezeichnung Polymer JR 400® von Amerchol erhältlich ist, kationische Stärke, Copolymere von Diallylammoniumsalzen und Acrylamiden, quaternierte Vinylpyrrolidon/Vinylimidazol-Polymere, wie z.B. Luviquat® (BASF), Kondensationsprodukte von Polyglycolen und Aminen, quaternierte Kollagenpolypeptide, wie beispielsweise Lauryl- dimonium Hydroxypropyl Hydrolyzed Collagen (Lamequat®L/Grünau), quaternierte Weizenpoly- peptide, Polyethylenimin, kationische Siliconpolymere, wie z.B. Amodimethicone, Copolymere der Adipinsäure und Dimethylaminohydroxypropyldiethylentriamin (Cartaretine®/Sandoz), Copolymere der Acrylsäure mit Dimethyl-diallylammoniumchlorid (Merquat® 550/Chemviron), Polyaminopoly- amide, sowie deren vernetzte wasserlöslichen Polymere, kationische Chitinderivate wie beispielsweise quatemiertes Chitosan, gegebenenfalls mikrokristallin verteilt, Kondensationsprodukte aus Dihalogenalkylen, wie z.B. Dibrombutan mit Bisdialkylaminen, wie z.B. Bis-Dimethylamino-1 ,3- propan, kationischer Guar-Gum, wie z.B. Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 der Firma Celanese, quaternierte Ammoniumsalz-Polymere, wie z.B. Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 der Firma Miranol.Suitable cationic polymers are, for example, cationic cellulose derivatives, e.g. a quaternized hydroxyethyl cellulose available under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers such as e.g. Luviquat® (BASF), condensation products of polyglycols and amines, quaternized collagen polypeptides, such as, for example, lauryl-dimonium hydroxypropyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, e.g. Amodimethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretine® / Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat® 550 / Chemviron), polyaminopolyamides, as well as their crosslinked water-soluble polymers, cationic chitinite crystals such as, for example, quaternized chitin derivatives such as, Condensation products from dihaloalkylene, such as Dibromobutane with bisdialkylamines, e.g. Bis-dimethylamino-1,3-propane, cationic guar gum, such as e.g. Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese, quaternized ammonium salt polymers such as e.g. Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 from Miranol.
Als anionische, zwitterionische, amphotere und nichtionische Polymere kommen beispielsweise Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidon/Vinylacrylat-Copolymere, Vinylace- tat/Butylmaleat/ Isobornylacrylat-Copolymere, Methylvinylether/Maleinsäureanhydrid-Copolymere und deren Ester, unvemetzte und mit Polyolen vernetzte Polyacrylsäuren, Acrylamidopropyl- trimethylarnmoniumchlorid/ Acrylat-Copolymere, Octylacrylamid/Methylmeth-acry- lat/tert.Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere, Polyvinylpyrrolidon, Vinylpyrrolidon/Vinylacetat-Copolymere, Vinylpyrrolidon/ Dimethylaminoethylmethacrylat/Vinyl- caprolactam-Terpolymere sowie gegebenenfalls derivatisierte Celluloseether und Silicone in Frage. SiliconverbindungenAnionic, zwitterionic, amphoteric and nonionic polymers include, for example, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and their polyols, and non-crosslinked polyacrylate and their esters, non-crosslinked acrylate - Trimethylarnmonium chloride / acrylate copolymers, octylacrylamide / methylmethacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, vinylpyrrolidone / dimethylaminoethyl methacrylate and silicate / vinylpolymers as well as derivatives / vinylpolymers as well as derivatives / vinylpolymers as well , silicone compounds
Geeignete Siliconverbindungen sind beispielsweise Dimethylpolysiloxane, Methylphenylpolysiloxa- ne, cyclische Silicone sowie amino-, fettsäure-, alkohol-, polyether-, epoxy-, fluor-, glykosid- und/oder alkylmodifizierte Siliconverbindungen, die bei Raumtemperatur sowohl flüssig als auch harzförmig vorliegen können. Weiterhin geeignet sind Simethicone, bei denen es sich um Mischungen aus Dimethiconen mit einer durchschnittlichen Kettenlänge von 200 bis 300 Dimethylsi- loxan-Einheiten und hydrierten Silicaten handelt.Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl-modified silicone compounds which can be both liquid and resinous at room temperature. Simethicones, which are mixtures of dimethicones with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates, are also suitable.
UV-Lichtschutzfilter und AntioxidantienUV light protection filters and antioxidants
Unter den zusätzlich zuzusetzenden UV-Lichtschutzfaktoren sind beispielsweise bei Raumtemperatur flüssig oder kristallin vorliegende organische Substanzen (Lichtschutzfilter) zu verstehen, die in der Lage sind, ultraviolette Strahlen zu absorbieren und die aufgenommene Energie in Form längerwelliger Strahlung, z.B. Wärme wieder abzugeben. UVB-Filter können öllöslich oder wasserlöslich sein. Als öllösliche Substanzen sind z.B. zu nennen:The additional UV light protection factors to be added are understood to mean, for example, organic substances (light protection filters) which are liquid or crystalline at room temperature and are able to absorb ultraviolet rays and absorb the energy absorbed in the form of longer-wave radiation, e.g. To give off heat again. UVB filters can be oil-soluble or water-soluble. As oil-soluble substances e.g. to call:
> 3-Benzylidencampher bzw. 3-Benzylidennorcampher und dessen Derivate, z.B. 3-(4- Methylbenzyliden)campher;> 3-benzylidene camphor or 3-benzylidene norcampher and its derivatives, e.g. 3- (4-methylbenzylidene) camphor;
> 4-Aminobenzoesäurederivate, vorzugsweise 4-(Dimethylamino)benzoesäure-2-ethyl- hexylester, 4-(Dimethylamino)benzoesäure-2-octylester und 4-(Dimethylamino)benzoe- säureamylester;> 4-aminobenzoic acid derivatives, preferably 2-ethyl-hexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate;
> Ester der Zimtsäure, vorzugsweise 4-Methoxyzimtsäure-2-ethylhexylester, 4-Methoxy- zimtsäurepropylester, 4-Methoxyzimtsäureisoamylester 2-Cyano-3,3-phenylzimtsäure-2- ethylhexylester (Octocrylene);> Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene);
> Ester der Salicylsäure, vorzugsweise Salicylsäure-2-ethylhexylester, Salicylsäure-4-iso- propylbenzylester, Salicylsäurehomomenthylester;> Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbenzyl ester, salicylic acid homomethyl ester;
> Derivate des Benzophenons, vorzugsweise 2-Hydroxy-4-methoxybenzophenon, 2-Hydroxy-4- methoxy-4'-methylbenzophenon, 2,2'-Dihydroxy-4-methoxybenzophenon;> Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;
> Ester der Benzalmalonsäure, vorzugsweise 4-Methoxybenzmalonsäuredi-2-ethylhexyl-ester;> Esters of benzalmalonic acid, preferably 4-methoxybenzmalonic acid di-2-ethylhexyl ester;
> Triazinderivate, wie z.B. 2,4,6-Trianilino-(p-carbo-2'-ethyl-1 '-hexyloxy)-1 ,3,5-triazin und Octyl Triazon, oder Dioctyl Butamido Triazone (Uvasorb® HEB);> Triazine derivatives, e.g. 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1, 3,5-triazine and octyl triazone, or dioctyl butamido triazone (Uvasorb® HEB);
> Propan-1 ,3-dione, wie z.B. 1-(4-tert.Butylphenyl)-3-(4'methoxyphenyl)propan-1 ,3-dion;> Propane-1,3-dione, e.g. 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione;
> Ketotricyclo(5.2.1.0)decan-Derivate.> Ketotricyclo (5.2.1.0) decane derivatives.
Als wasserlösliche Substanzen kommen in Frage: > 2-Phenylbenzimidazol-5-sulfonsäure und deren Alkali-, Erdalkali-, Ammonium-, Alkylammoni- um-, Alkanolammonium- und Glucammoniumsalze;Possible water-soluble substances are: > 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts;
> Sulfonsäurederivate von Benzophenonen, vorzugsweise 2-Hydroxy-4-methoxybenzo-phenon- 5-sulfonsäure und ihre Salze;> Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzo-phenone-5-sulfonic acid and its salts;
> Sulfonsäurederivate des 3-Benzylidencamphers, wie z.B. 4-(2-Oxo-3-bornylidenme- thyl)benzolsulfonsäure und 2-Methyl-5-(2-oxo-3-bornyliden)sulfonsäure und deren Salze.> Sulfonic acid derivatives of 3-benzylidene camphor, e.g. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.
Als typische UV-A-Filter kommen insbesondere Derivate des Benzoylmethans in Frage, wie beispielsweise 1-(4'-tert.Butylphenyl)-3-(4'-methoxyphenyl)propan-1 ,3-dion, 4-tert.-Butyl-4'- methoxydibenzoylmethan (Parsol® 1789), 1-Phenyl-3-(4'-isopropylphenyl)-propan-1 ,3-dion sowie Enaminverbindungen. Die UV-A und UV-B-Filter können selbstverständlich auch in Mischungen eingesetzt werden. Besonders günstige Kombinationen bestehen aus den Derivate des Benzoylmethans,, z.B. 4-tert.-Butyl-4'-methoxydibenzoylmethan (Parsol® 1789) und 2-Cyano-3,3- phenylzimtsäure-2-ethyl-hexylester (Octocrylene) in Kombination mit Ester der Zimtsäure, vorzugsweise 4-Methoxyzimtsäure-2-ethylhexylester und/oder 4-Methoxyzimtsäurepropylester und/oder 4-Methoxyzimtsäureisoamylester. Vorteilhaft werden deartige Kombinationen mit wasserlöslichen Filtern wie z.B. 2-Phenylbenzimidazol-5-sulfonsäure und deren Alkali-, Erdalkali-, Ammonium-, Alkylammonium-, Alkanolammonium- und Glucammoniumsalze kombiniert.Derivatives of benzoylmethane, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl, are particularly suitable as typical UV-A filters -4'- methoxydibenzoylmethane (Parsol® 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1, 3-dione and enamine compounds. The UV-A and UV-B filters can of course also be used in mixtures. Particularly favorable combinations consist of the derivatives of benzoylmethane, e.g. 4-tert-butyl-4'-methoxydibenzoylmethane (Parsol® 1789) and 2-cyano-3,3-phenylcinnamic acid-2-ethyl-hexyl ester (octocrylene) in combination with ester of cinnamic acid, preferably 4-methoxycinnamic acid-2-ethylhexyl ester and / or propyl 4-methoxycinnamate and / or isoamyl 4-methoxycinnamate. Such combinations with water-soluble filters such as e.g. 2-Phenylbenzimidazole-5-sulfonic acid and their alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts combined.
Neben den genannten löslichen Stoffen kommen für diesen Zweck auch unlösliche Lichtschutzpigmente, nämlich feindisperse Metalloxide bzw. Salze in Frage. Beispiele für geeignete Metalloxide sind insbesondere Zinkoxid und Titandioxid und daneben Oxide des Eisens, Zirkoniums, Silici- ums, Mangans, Aluminiums und Cers sowie deren Gemische. Als Salze können Silicate (Talk), Bariumsulfat oder Zinkstearat eingesetzt werden. Die Oxide und Salze werden in Form der Pigmente für hautpflegende und hautschützende Emulsionen und dekorative Kosmetik verwendet. Die Partikel sollten dabei einen mittleren Durchmesser von weniger als 100 nm, vorzugsweise zwischen 5 und 50 nm und insbesondere zwischen 15 und 30 nm aufweisen. Sie können eine sphärische Form aufweisen, es können jedoch auch solche Partikel zum Einsatz kommen, die eine el- lipsoide oder in sonstiger Weise von der sphärischen Gestalt abweichende Form besitzen. Die Pigmente können auch oberflächenbehandelt, d.h. hydrophilisiert oder hydrophobiert vorliegen. Typische Beispiele sind geeoatete Titandioxide, wie z.B. Titandioxid T 805 (Degussa) oder Eusolex® T2000 (Merck). Als hydrophobe Coatingmittel kommen dabei vor allem Silicone und dabei speziell Trialkoxyoctylsilane oder Simethicone in Frage. In Sonnenschutzmitteln werden bevorzugt sogenannte Mikro- oder Nanopigmente eingesetzt. Vorzugsweise wird mikronisiertes Zinkoxid verwendet. Neben den beiden vorgenannten Gruppen primärer Lichtschutzstoffe können auch sekundäre Lichtschutzmittel vom Typ der Antioxidantien eingesetzt werden, die die photochemische Reaktionskette unterbrechen, welche ausgelöst wird, wenn UV-Strahlung in die Haut eindringt. Typische Beispiele hierfür sind Aminosäuren (z.B. Glycin, Histidin, Tyrosin, Tryptophan) und deren Derivate, . Imidazole (z.B. Urocaninsäure) und deren Derivate, Peptide wie D,L-Carnosin, D-Carnosin, L- Carnosin und deren Derivate (z.B. Anserin), Carotinoide, Carotine (z.B. α-Carotin, ß-Carotin, Ly- copin) und deren Derivate, Chlorogensaure und deren Derivate, Liponsaure und deren Derivate (z.B. Dihydroliponsäure), Aurothioglucose, Propylthiouracil und andere Thiole (z.B. Thioredoxin, Glutathion, Cystein, Cystin, Cystamin und deren Glycosyl-, N-Acetyl-, Methyl-, Ethyl-, Propyl-, A- myl-, Butyl- und Lauryl-, Palmitoyl-, Oleyl-, γ-Linoleyl-, Cholesteryl- und Glycerylester) sowie deren Salze, Dilaurylthiodipropionat, Distearylthiodipropionat, Thiodipropionsäure und deren Derivate (Ester, Ether, Peptide, Lipide, Nukleotide, Nukleoside und Salze) sowie Sulfoximinverbindungen (z.B. Buthioninsulfoximine, Homocysteinsulfoximin, Butioninsulfone, Penta-, Hexa-, Heptathionin- sulfoximin) in sehr geringen verträglichen Dosierungen (z.B. pmol bis μmol/kg), ferner (Metall)- Chelatoren (z.B. α-Hydroxyfettsäuren, Palmitinsäure, Phytinsäure, Lactoferrin), α-Hydroxysäuren (z.B. Citronensäure, Milchsäure, Äpfelsäure), Huminsäüre, Gallensäure, Gallenextrakte, Bilirubin, Biliverdin, EDTA, EGTA und deren Derivate, ungesättigte Fettsäuren und deren Derivate (z.B. γ- Linolensäure, Linolsäure, Ölsäure), Folsäure und deren Derivate, Ubichinon und Ubichinol und deren Derivate, Vitamin C und Derivate (z.B. Ascorbylpalmitat, Mg-Ascorbylphosphat, Ascorbyla- cetat), Tocopherole und Derivate (z.B. Vitamin-E-acetat), Vitamin A und Derivate (Vitamin-A- palmitat) sowie Koniferylbenzoat des Benzoeharzes, Rutinsäure und deren Derivate, α- Glycosylrutin, Ferulasäure, Furfurylidenglucitol, Carnosin, Butylhydroxytoluol, Butylhydroxyanisol, Nordihydroguajakharzsäure, Nordihydroguajaretsäure, Trihydroxybutyrophenon, Harnsäure und deren Derivate, Mannose und deren Derivate, Superoxid-Dismutase, Zink und dessen Derivate (z.B. ZnO, ZnS0 ) Selen und dessen Derivate (z.B. Selen-Methionin), 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. In addition to the soluble substances mentioned, insoluble light protection pigments, namely finely dispersed metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. Silicates (talc), barium sulfate or zinc stearate can be used as salts. The oxides and salts are used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or which differ in some other way from the spherical shape. The pigments can also be surface-treated, ie hydrophilized or hydrophobicized. Typical examples are coated titanium dioxide, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. So-called micro- or nanopigments are preferably used in sunscreens. Micronized zinc oxide is preferably used. In addition to the two aforementioned groups of primary light stabilizers, secondary light stabilizers of the antioxidant type can also be used, which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates the skin. Typical examples of this are amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives,. Imidazoles (eg urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine), carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and their derivatives, lipoic acid and their derivatives (e.g. dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, 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 sulfoximine compounds (e.g. buthioninsulfoximine, homocysteine sulfoximine, butioninsulfones, penta-, hexa-, heptathionine sulfoximine) in very low tolerable dosages (e.g. pmol to μmol / kg), also (metal) chelators (e.g. α -Hydroxy fatty acids, Pa lmitic acid, phytic 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, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (e.g. ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (vitamin A-palmitate) and coniferyl benzoate of benzoin, rutinic acid and its derivatives, α-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordihydroguajakh resin acid, nordihydroguajaretic acid, trihydroxybutomate and derivate, superficial derivatives and their derivatives, urea and derivatives of superficial acid and its derivatives, urea and derivatives of superficial acid and its derivatives, superficial and synthetic derivatives, its derivatives (eg ZnO, ZnS0) selenium and its derivatives (eg selenium methionine), stilbenes and their derivatives ate (eg stilbene oxide, trans-stilbene oxide) and the derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active substances which are suitable according to the invention.
Biogene WirkstoffeBiogenic agents
Unter biogenen Wirkstoffen sind beispielsweise Tocopherol, Tocopherolacetat, Tocopherolpalmitat, Ascorbinsäure, (Desoxy)Ribonucleinsäure und deren Fragmentierungsprodukte, ß-Glucane, Retinol, Bisabolol, Allantoin, Phytantriol, Panthenol, AHA-Säuren, Aminosäuren, Ceramide, Pseudoce- ramide, essentielle Öle, Pflanzenextrakte und Vitaminkomplexe zu verstehen.Examples of biogenic active substances include tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, (deoxy) ribonucleic acid and its fragmentation products, ß-glucans, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudo-essential oils, amide acids To understand plant extracts and vitamin complexes.
Filmbildnerfilm formers
Gebräuchliche Filmbildner sind beispielsweise Chitosan, mikrokristallines Chitosan, quaterniertes Chitosan, Polyvinylpyrrolidon, Vinylpyrrolidon-Vinylacetat-Copolymerisate, Polymere der Acrylsäu- rereihe, quaternäre Cellulose-Derivate, Kollagen, Hyaluronsäure bzw. deren Salze und ähnliche Verbindungen.Common film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or its salts and similar compounds.
AntischuppenwirkstoffeAntidandruff agents
Als Antischuppenwirkstoffe kommen Pirocton Olamin ( 1 -H yd roxy-4-methy l-6-(2 ,4 ,4-tri my thyipentyl)- 2-(1 H)-pyridinonmonoethanolaminsalz), Baypival® (Climbazole), Ketoconazol®, (4-Acety I- 1 - { -4-[2- (2.4-dichlorphenyl) r-2-(1 H-imidazol-1 -ylmethy])-1 ,3-dioxylan-c-4-ylmethoxyphenyl}piperazin, Ketoconazol, Elubiol, Selendisuifid, Schwefel kolloidal, Schwefelpolyehtylenglykolsorbitanmonooleat, Schwefelrizinolpolyehtoxylat, Schwfel-teer Destillate, Salicylsäure (bzw. in Kombination mit He- xachlorophen), Undexylensäure Monoethanolamid Sulfosuccinat Na-Salz, Lamepon® UD (Prote- in-Undecylensäurekondensat), Zinkpyrithion, Aluminiumpyrithion und Magnesiumpyrithion / Dipy- rithion-Magnesiumsulfat in Frage.Piroctone olamine (1-H yd roxy-4-methyl-6- (2, 4, 4-tri my thyipentyl) -2- (1 H) -pyridinone monoethanolamine salt), Baypival® (climbazole), Ketoconazol®, (4-Acety I- 1 - {-4- [2- (2.4-dichlorophenyl) r-2- (1 H -imidazol-1-ylmethyl]) - 1, 3-dioxylan-c-4-ylmethoxyphenyl} piperazine, Ketoconazole, selenium disulfide, sulfur colloidal, sulfur polyglycol sorbitan monooleate, sulfur ricinolexylate, sulfur tar distillates, salicylic acid (or in combination with hexachlorophene), undexylenic acid, undosulfonate, zinc salt Aluminum pyrithione and magnesium pyrithione / dipyrithione magnesium sulfate in question.
Quellmittelswelling agent
Als Quellmittel für wäßrige Phasen können Montmorillonite, Clay Mineralstoffe, Pemulen sowie alkylmodifizierte Carbopoltypen (Goodrich) dienen.Montmorillonites, clay minerals, pemulene and alkyl-modified carbopol types (Goodrich) can serve as swelling agents for aqueous phases.
HvdrotropeHvdrotrope
Zur Verbesserung des Fließverhaltens können ferner Hydrotrope, wie beispielsweise Ethanol, I- sopropylalkohol, oder Polyole eingesetzt werden. Polyole, die hier in Betracht kommen, besitzen vorzugsweise 2 bis 15 Kohlenstoffatome und mindestens zwei Hydroxylgruppen. Die Polyole kön- nen noch weitere funktionelle Gruppen, insbesondere Aminogruppen, enthalten bzw. mit Stickstoff modifiziert sein. Typische Beispiele sindHydrotropes, such as ethanol, isopropyl alcohol, or polyols can also be used to improve the flow behavior. Polyols that come into consideration here preferably have 2 to 15 carbon atoms and at least two hydroxyl groups. The polyols can NEN still contain other functional groups, especially amino groups, or be modified with nitrogen. Typical examples are
> Glycerin; .> Glycerin; ,
> Alkylenglycole, wie beispielsweise Ethylenglycol, Diethylenglycol, Propylenglycol, Butylengly- col, Hexylenglycol sowie Polyethylenglycole mit einem durchschnittlichen Molekulargewicht von 100 bis 1.000 Dalton;> Alkylene glycols, such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols with an average molecular weight of 100 to 1,000 daltons;
> technische Oligoglyceringemische mit einem Eigenkondensationsgrad von 1,5 bis 10 wie etwa technische Diglyceringemische mit einem Diglyceringehalt von 40 bis 50 Gew.-%;> technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10 such as technical diglycerol mixtures with a diglycerol content of 40 to 50% by weight;
> Methyolverbindungen, wie insbesondere Trimethylolethan, Trimethylolpropan, Trimethylolbu- tan, Pentaerythrit und Dipentaerythrit;> Methyl compounds, such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
> Niedrigalkylglucoside, insbesondere solche mit 1 bis 8 Kohlenstoffen im Alkylrest, wie beispielsweise Methyl- und Butylglucosid;> Lower alkyl glucosides, especially those with 1 to 8 carbons in the alkyl radical, such as methyl and butyl glucoside;
> Zuckeralkohole mit 5 bis 12 Kohlenstoffatomen, wie beispielsweise Sorbit oder Mannit,> Sugar alcohols with 5 to 12 carbon atoms, such as sorbitol or mannitol,
> Zucker mit 5 bis 12 Kohlenstoffatomen, wie beispielsweise Glucose oder Saccharose;> Sugar with 5 to 12 carbon atoms, such as glucose or sucrose;
> Aminozucker, wie beispielsweise Glucamin;> Aminosugars such as glucamine;
> Dialkoholamine, wie Diethanolamin oder 2-Amino-1 ,3-propandiol.> Dialcohol amines, such as diethanolamine or 2-amino-1, 3-propanediol.
Konservierungsmittelpreservative
Als Konservierungsmittel eignen sich beispielsweise Phenoxyethanol, Formaldehydlösung, Para- bene, Pentandiol oder Sorbinsäure sowie die unter der Bezeichnung Surfacine® bekannten Silberkomplexe und die in Anlage 6, Teil A und B der Kosmetikverordnung aufgeführten weiteren Stoffklassen.Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid, as well as the silver complexes known under the name Surfacine® and the other classes of substances listed in Appendix 6, Parts A and B of the Cosmetics Regulation.
Parfümöle und AromenPerfume oils and flavors
Als Parfümöle seien genannt Gemische aus natürlichen und synthetischen Riechstoffen. Natürliche Riechstoffe sind Extrakte von Blüten (Lilie, Lavendel, Rosen, Jasmin, Neroli, Ylang-Ylang), Stengeln und Blättern (Geranium, Patchouli, Petitgrain), Früchten (Anis, Koriander, Kümmel, Wacholder), Fruchtschalen (Be.rgamotte, Zitrone, Orangen), Wurzeln (Macis, Angelica, Sellerie, Kardamon, Costus, Iris, Calmus), Hölzern (Pinien-, Sandel-, Guajak-, Zedern-, Rosenholz), Kräutern und Gräsern (Estragon, Lemongras, Salbei, Thymian), Nadeln und Zweigen (Fichte, Tanne, Kiefer, Latschen), Harzen und Balsamen (Galbanum, Elemi, Benzoe, Myrrhe, Olibanum, Opoponax). Weiterhin kommen tierische Rohstoffe in Frage, wie beispielsweise Zibet und Castoreum. Typische synthetische Riechstoffverbindungen sind Produkte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe. Riechstoffverbindungen vom Typ der Ester sind z.B. Benzyla- cetat, Phenoxyethylisobutyrat, p-tert. -B u tylcy cio hexylacetat , Linalylacetat, Dimethylbenzylcarbiny- lacetat, Phenylethylacetat, Linalylbenzoat, Benzylformiat, Ethylmethylphenylglycinat, Allylcyclohe- xylpropionat, Styrallylpropionat und Benzylsalicylat. Zu den Ethern zählen beispielsweise Benzy- lethylether, zu den Aldehyden z.B. die linearen Alkanale mit 8 bis 18 Kohlenstoffatomen, Citral, Citronellal, Citronellyloxyacetaldehyd, Cyclamenaldehyd, Hydroxycitronellal, Lilial und Bourgeonal, zu den Ketonen z.B. die Jonone, α-lsomethylionon und Methylcedrylketon, zu den Alkoholen A- nethol, Citronellol, Eugenol, Isoeugenol, Geraniol, Linalool, Phenylethylal ohol und Terpineol, zu den Kohlenwasserstoffen gehören hauptsächlich die Terpene und Balsame. Bevorzugt werden jedoch Mischungen verschiedener Riechstoffe verwendet, die gemeinsam eine ansprechende Duftnote erzeugen. Auch ätherische Öle geringerer Flüchtigkeit, die meist als Aromakomponenten verwendet werden, eignen sich als Parfümöle, z.B. Salbeiöl, Kamillenöl, Nelkenöl, Melissenöl, Min- zenöl, Zimtblätteröl, Lindenblütenöl, Wacholderbeerenöl, Vetiveröl, Olibanöl, Galbanumöl, Labola- numöl und Lavandinöl. Vorzugsweise werden Bergamotteöl, Dihydromyrcenol, Lilial, Lyral, Citro- „nello Phenylethylalkohol, α-Hexylzimtaldehyd, Geraniol, Benzylaceton, Cyclamenaldehyd, Linalool, Boisambrene Forte, Ambroxan, Indol, Hedione, Sandelice, Citronenöl, Mandarinenöl, Oran- genöl, Allylamylglycolat, Cyelovertal, Lavandinöl, Muskateller Salbeiöl, ß-Damascone, Geraniumol Bourbon, Cyclohexylsalicylat, Vertofix Coeur, Iso-E-Super, Fixolide NP, Evernyl, Iraldein gamma, Phenylessigsäure, Geranylacetat, Benzylacetat, Rosenoxid, Romilllat, Irotyl und Floramat allein oder in Mischungen, eingesetzt.Perfume oils include mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers (lily, lavender, rose, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel (Be.rgamotte, Lemon, oranges), roots (mace, angelica, celery, cardamom, costus, iris, calmus), woods (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme ), Needles and twigs (spruce, fir, pine, mountain pine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials, such as civet and castoreum, are also suitable. typical Synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert. -B u tylcy cio hexylacetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzylethyl ether, the aldehydes include, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones include, for example, the jonones, α-isomethylionone and methylcedryl ketone the alcohols ethanol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes and balsams. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Essential oils of low volatility, which are mostly used as aroma components, are also suitable as perfume oils, for example sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labola oil and lavandin oil. Bergamot oil, dihydromyrcenol, lilial, lyral, citro-nello phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzylacetone, cyclamenaldehyde, linalool, boisambrene forte, ambroxan, indole, hedione, sandelice, lemon oil, mandarin alcohol, allyl glycolate, orangelol glycol oil are preferred , Lavandin oil, muscatel sage oil, ß-damascone, geraniumol bourbon, cyclohexyl salicylate, vertofix coeur, iso-e-super, fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilllate, irotyl and floramate alone or in mixtures, used.
Als Aromen kommen beispielsweise Pfefferminzöl,. Krauseminzöl, Anisöl, Sternanisöl, Kümmelöl, Eukalyptusöl, Fenchelöl, Citronenöl, Wintergrünöl, Nelkenöl, Menthol und dergleichen in Frage.For example, peppermint oil comes as flavors. Spearmint oil, anise oil, star anise oil, caraway oil, eucalyptus oil, fennel oil, lemon oil, wintergreen oil, clove oil, menthol and the like.
Farbstoffedyes
Als Farbstoffe können die für kosmetische Zwecke geeigneten und zugelassenen Substanzen verwendet werden. Beispiele sind Kochenillerot A (C.l. 16255), Patentblau V (C.1.42051), Indigotin (C.1.73015), Chlorophyllin (C.1.75810), Chinolingelb (C.I.47005), Titandioxid (C.1.77891), Indanthrenblau RS (C.l. 69800) und Krapplack (C.I.58000). Als Lumineszenzfarbstoff kann auch Luminol enthalten sein. BeispielrezepturenThe dyes which can be used are those which are suitable and approved for cosmetic purposes. Examples are Kochillerot A (Cl 16255), Patent Blue V (C.1.42051), Indigotine (C.1.73015), Chlorophyllin (C.1.75810), Quinoline Yellow (CI47005), Titanium Dioxide (C.1.77891), Indanthrene Blue RS (Cl 69800) and Madder varnish (CI58000). Luminol may also be present as the luminescent dye. example recipes
Tabelle 1: Leave-on Haartonic (Mengenangaben in Gew.%)Table 1: Leave-on hair tonic (amounts in% by weight)
Figure imgf000030_0001
Figure imgf000030_0001
Mengenangabe von „Astaxanthin verkapselt" entspricht der Menge der reinen Aktivsubstanz Astaxanthin Quantity of "astaxanthin encapsulated" corresponds to the amount of the pure active substance astaxanthin

Claims

Patentansprüche claims
1. Verwendung von Astaxanthin zur Herstellung von Mitteln gegen Haarausfall.1. Use of astaxanthin for the preparation of hair loss remedies.
2. Verwendung von Astaxanthin zur Herstellung von Mitteln zur Kräftigung des Haares und Verbesserung der Haarschafteigenschaften.2. Use of astaxanthin for the preparation of agents for strengthening the hair and improving the properties of the hair.
3. Verwendung von Astaxanthin zur Herstellung von Mitteln zur Stimulierung des Haarwachstums.3. Use of astaxanthin for the preparation of agents for stimulating hair growth.
4. Verwendung von Astaxanthin zur Herstellung von Mitteln zum Schutz des Haares vor UV- Licht-Einwirkung.4. Use of astaxanthin for the preparation of agents for protecting the hair from exposure to UV light.
5. Verwendung von Astaxanthin in Haarfärbemitteln.5. Use of astaxanthin in hair dyes.
6. . Verwendung von Astaxanthin zur Herstellung von Mitteln zum Schutz vor oxidativen Schädigungen von Melanocyten.6.. Use of astaxanthin for the preparation of agents for protection against oxidative damage to melanocytes.
7. Verwendung von Astaxanthin zur Herstellung von Mitteln gegen Ergrauen der Haare.7. Use of astaxanthin for the manufacture of anti-graying agents.
8. Verwendung nach mindestens einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass Astaxanthin aus Algen gewonnen wird.8. Use according to at least one of claims 1 to 7, characterized in that astaxanthin is obtained from algae.
9. Verwendung nach mindestens einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, das Astaxanthin in Mengen von 0,001 bis 10 Gew. % - bezogen auf die Mittel - eingesetzt wird.9. Use according to at least one of claims 1 to 8, characterized in that the astaxanthin is used in amounts of 0.001 to 10% by weight, based on the composition.
10. Verwendung nach mindestens einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass Astaxanthin in verkapselter Form eingesetzt wird.10. Use according to at least one of claims 1 to 9, characterized in that astaxanthin is used in encapsulated form.
11. Haarpflegemittel, enthaltend a) Astaxanthin und b) mindestens einen Haarfarbstoff.11. Hair care composition containing a) astaxanthin and b) at least one hair dye.
12. Zubereitungen, enthaltend a) Astaxanthin und b) α-Tocopherol oder α-Tocopherolderivate 12. Preparations containing a) astaxanthin and b) α-tocopherol or α-tocopherol derivatives
PCT/EP2003/005969 2002-06-15 2003-06-06 Use of astaxanthin WO2003105791A1 (en)

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JP2008273874A (en) * 2007-04-27 2008-11-13 Fuji Chem Ind Co Ltd External preparation for scalp
WO2009080572A1 (en) * 2007-12-21 2009-07-02 Unilever Plc Topical composition comprising coloring antioxidants
US20110059192A1 (en) * 2005-08-09 2011-03-10 Glynn Kelly M Methods and Compositions for Modulating Hair Growth or Regrowth
US20120251458A1 (en) * 2011-03-29 2012-10-04 Kemin Industries, Inc. Dyes for Membranes and Biological Structures
WO2014112219A1 (en) * 2013-01-21 2014-07-24 富士フイルム株式会社 External preparation for skin
US8834855B2 (en) 2005-01-21 2014-09-16 Promar As Sunscreen compositions comprising carotenoids
WO2016026723A3 (en) * 2014-08-19 2016-04-14 Cutech Srl Extracts of nannochloropsis sp. and their applications

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EP0748625A1 (en) * 1995-06-16 1996-12-18 L'oreal Cosmetic or dermatologic compositions with controlled release of the active agent containing a photoconvertible carotenoid
US6277417B1 (en) * 2000-04-07 2001-08-21 Triarco Industries, Inc. Method of inhibiting 5α-reductase with astaxanthin
EP1213013A2 (en) * 2000-11-29 2002-06-12 Basf Aktiengesellschaft Process for preparing solid compositions of water-soluble, hardly water-soluble or water-insoluble active agents

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EP0586303A1 (en) * 1992-09-01 1994-03-09 L'oreal Cosmetic or pharmaceutical composition containing an association between a peroxydase and an anti-singlet oxygen agent
EP0748625A1 (en) * 1995-06-16 1996-12-18 L'oreal Cosmetic or dermatologic compositions with controlled release of the active agent containing a photoconvertible carotenoid
US6277417B1 (en) * 2000-04-07 2001-08-21 Triarco Industries, Inc. Method of inhibiting 5α-reductase with astaxanthin
EP1213013A2 (en) * 2000-11-29 2002-06-12 Basf Aktiengesellschaft Process for preparing solid compositions of water-soluble, hardly water-soluble or water-insoluble active agents

Cited By (12)

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Publication number Priority date Publication date Assignee Title
US8834855B2 (en) 2005-01-21 2014-09-16 Promar As Sunscreen compositions comprising carotenoids
US20110059192A1 (en) * 2005-08-09 2011-03-10 Glynn Kelly M Methods and Compositions for Modulating Hair Growth or Regrowth
US8197865B2 (en) 2005-08-09 2012-06-12 Access Business Group International Llc Methods and compositions for modulating hair growth or regrowth
JP2008273874A (en) * 2007-04-27 2008-11-13 Fuji Chem Ind Co Ltd External preparation for scalp
WO2009080572A1 (en) * 2007-12-21 2009-07-02 Unilever Plc Topical composition comprising coloring antioxidants
CN101951871B (en) * 2007-12-21 2013-05-22 荷兰联合利华有限公司 Topical composition comprising coloring antioxidants
US20120251458A1 (en) * 2011-03-29 2012-10-04 Kemin Industries, Inc. Dyes for Membranes and Biological Structures
WO2014112219A1 (en) * 2013-01-21 2014-07-24 富士フイルム株式会社 External preparation for skin
JP5931223B2 (en) * 2013-01-21 2016-06-08 富士フイルム株式会社 Skin preparation
WO2016026723A3 (en) * 2014-08-19 2016-04-14 Cutech Srl Extracts of nannochloropsis sp. and their applications
US20170246229A1 (en) * 2014-08-19 2017-08-31 Cutech Srl Extracts of nannochloropsis sp. and their applications
US11141371B2 (en) 2014-08-19 2021-10-12 Symrise Ag Extracts of Nannochloropsis sp. and their applications

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