WO2006034982A1 - Light-block concentrate with organic micropigments - Google Patents

Light-block concentrate with organic micropigments Download PDF

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Publication number
WO2006034982A1
WO2006034982A1 PCT/EP2005/054731 EP2005054731W WO2006034982A1 WO 2006034982 A1 WO2006034982 A1 WO 2006034982A1 EP 2005054731 W EP2005054731 W EP 2005054731W WO 2006034982 A1 WO2006034982 A1 WO 2006034982A1
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Prior art keywords
preparation
cosmetic
water
acid
advantageous
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PCT/EP2005/054731
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German (de)
French (fr)
Inventor
Svenja Pfeifer
Claudia Mundt
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Beiersdorf Ag
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Publication of WO2006034982A1 publication Critical patent/WO2006034982A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y5/00Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0216Solid or semisolid forms
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241Containing particulates characterized by their shape and/or structure
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27Zinc; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29Titanium; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/496Triazoles or their condensed derivatives, e.g. benzotriazoles
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4966Triazines or their condensed derivatives
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41Particular ingredients further characterized by their size
    • A61K2800/413Nanosized, i.e. having sizes below 100 nm
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60Particulates further characterized by their structure or composition
    • A61K2800/61Surface treated
    • A61K2800/62Coated
    • A61K2800/622Coated by organic compounds

Definitions

  • the present invention relates to a process for the preparation of a cosmetic preparation based on a dried O / W emulsion and to the process product.
  • the skin is the largest organ in humans. Among its many functions (for example, for heat regulation and as a sense organ) is the barrier function, which prevents the drying of the skin (and thus ultimately the entire organism), probably the most important. At the same time, the skin acts as a protective device against the penetration and absorption of foreign substances and UV radiation. This barrier function is caused by the epidermis, which, as the outermost layer, forms the actual protective cover against the environment. At about one-tenth of the total thickness, it is also the thinnest layer of the skin.
  • Ointments or lotions are usually used to moisturize and restore the skin. Often, agents that regenerate the skin and, for example, prevent and reduce their premature aging (e.g., wrinkles, wrinkles) are added to them.
  • Emulsions are generally understood to mean heterogeneous systems which consist of two liquids which are immiscible or only to a limited extent miscible, which are usually referred to as phases, and in which one of the two liquids is in the form of very fine droplets in the other Liquid is dispersed. Viewed externally and with the naked eye, emulsions appear homogeneous.
  • O / W emulsion oil-in-water emulsion
  • the basic character of an O / W emulsion is characterized by the water.
  • a water-in-oil emulsion (W / O emulsion, eg butter) is the reverse principle, whereby the basic character is determined by the oil.
  • UVA and UVB filters are summarized in most industrialized countries in the form of positive lists such as Appendix 7 of the German Cosmetics Regulation.
  • Conventional cosmetic and / or dermatological emulsions such as sunscreen creams or lotions, have a number of disadvantages due to their water content: ⁇ They are heavy-weight, which results in higher energy consumption and higher costs during transport.
  • a problem of dried emulsions is, in particular, the fact that the oil droplets coalesce during the drying of the emulsion. If the droplets coalesce, no emulsion forms on addition of water.
  • a process for producing a cosmetic preparation which comprises an O / W emulsion comprising a) an aqueous phase, b) an oil phase, c) pigmentary UV light protection filters and d) water-soluble polymers, optionally other cosmetic and / or dermatological active ingredients, auxiliaries and additives, is dried by spray drying, freeze drying and / or drum drying, and by a cosmetic preparation prepared by this method.
  • the preparation prepared by this process is according to the invention.
  • the objects are further achieved by the use of a combination of pigmentary UV photoprotective filters and water-soluble polymers for preparing by spray drying, freeze drying and / or drum drying dried re-emulsifiable O / W emulsions.
  • the inventive method for producing a cosmetic preparation according to the invention is advantageously characterized in that the dried emulsion is then mixed in a mixing device with water-soluble and / or volatile active ingredients, auxiliaries and / or additives.
  • the preparation prepared according to this preparation step is according to the invention.
  • one or more granulating and / or tablet adjuvants can be added to the preparation.
  • the process for the preparation of a preparation which is characterized in that the preparation according to the invention after the addition of one or more tablet excipients are mixed in a mixing device.
  • the preparation prepared according to this preparation step is according to the invention.
  • tablets and / or granules can advantageously be prepared from the preparation in a further process step.
  • the preparation prepared according to this preparation step is according to the invention.
  • a preparation prepared according to one of the above-described process steps may advantageously be used according to the invention for application as a cosmetic with water which may have a temperature of 20 to 100 ° C.
  • the preparation prepared according to this preparation step is according to the invention. Furthermore, it is according to the invention that the user applies the dried emulsion directly without further addition of water, for example as "body powder”.
  • the pigmentary UV light protection filters according to the invention are advantageously used in a concentration of 0.5 to 35% by weight and preferably in a concentration of 2 to 15% by weight, based in each case on the weight of the O / W emulsion before drying or after the re-addition of water used.
  • Embodiments of the present invention that are advantageous according to the invention are characterized in that one or more compounds selected from the group of the compounds 2,4,6-tris (biphenyl) -1,3,5-triazine (in particular 2,4 , 6-tribiphenyl-4-yl-1,3,5-triazine); 2,4,6-tris (terphenyl) -1, 3,5-triazine can be used.
  • the water-soluble polymers according to the invention are advantageously used in a concentration of 1 to 80% by weight and preferably in a concentration of 2 to 50% by weight, based in each case on the weight of the O / W emulsion before drying or after the additional addition of Water, used.
  • water-soluble polymers which are advantageous according to the invention can advantageously be selected from the group of water-soluble or dispersible film formers (for example polyurethanes,
  • Polyvinyl pyrrolidones PVP
  • polyvinyl alcohols e.g., Mowiol 18-88
  • Hydrocolloids e.g., agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins,
  • Hydrocolloids which are preferred according to the invention are, for example, methylcelluloses, which are referred to as the methyl ethers of cellulose. They are characterized by the following structural formula in which R can represent a hydrogen or a methyl group.
  • cellulose mixed ethers which are generally also referred to as methylcelluloses and, in addition to a dominating content of methyl, additionally contain 2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxybutyl groups.
  • Particularly preferred hydroxypropyl methylcelluloses HPMC have an average molecular weight M m ⁇ 50,000 gmol "1 and are, for example, under the name Pharmacoat 603, Pharmacoat 606 and Pharmacoat 645 or under the name Metolose 65 SH 50 or Metolose 60 SH 50 in the FA
  • Other preferred hydroxypropyl methylcelluloses are available under the trade name Methocel K100LV from Dow Chemicals or under the trade name Methocel E5 from Colorcon.
  • (hydroxypropyl) methylcelluloses for example those available under the trade name Methocel E4M from Dow Chemical Comp.
  • sodium carboxymethylcellulose the sodium salt of the glycolic acid ether of cellulose, for which R in structural formula I can be a hydrogen and / or CH 2 -COONa.
  • sodium carboxymethylcellulose also known as cellulose gum, available under the trade name Natrosol Plus 330 CS from Aqualon.
  • the use of maltodextrin preferably with a dextrose equivalent of 10-30, particularly preferably with a dextrose equivalent of 15-20.
  • the use of gum arabic for example, under the trade name spray gum, is also advantageous. Maltodextrin and gum arabic may be used singly or in admixture.
  • the weight ratio of the raw material mixture is advantageously from 1:10 to 10: 1 and according to the invention preferably from 2:10 to 10: 2.
  • the weight ratio of pigmentary UV light protection filters to water-soluble polymers is advantageously from 1:10 to 10: 1 and according to the invention preferably from 3:10 to 10: 3.
  • the preparation according to the present invention contains further UV filter substances.
  • the preparation according to the invention can advantageously contain UV sunscreen filter substances based on inorganic pigments.
  • Preferred inorganic pigments are metal oxides and / or other water-insoluble or insoluble metal compounds, in particular oxides of titanium (TiO 2 ), zinc (ZnO), iron (eg Fe 2 O 3 ), zirconium (ZrO 2 ), silicon ( SiO 2 ), manganese (for example MnO), aluminum (Al 2 O 3 ), cerium (for example Ce 2 O 3 ), mixed oxides of the corresponding metals and mixtures of such oxides and the barium sulfate (BaSO 4 ).
  • the pigments can also be used advantageously in the form of commercially available oily or aqueous predispersions. Dispersants and / or solubilizers may advantageously be added to these pre-dispersions.
  • the pigments may advantageously be surface-treated ("coated"), wherein, for example, a hydrophilic, amphiphilic or hydrophobic character is to be formed or retained.
  • This surface treatment may consist in using a thin film according to methods known per se hydrophilic and / or hydrophobic inorganic and / or organic layer
  • the various surface coatings may also contain water in the sense of the present invention.
  • Inorganic surface coatings for the purposes of the present invention may consist of aluminum oxide (Al 2 O 3 ), aluminum hydroxide Al (OH) 3 or aluminum oxide hydrate (also: Alumina, CAS No .: 1333-84-2), sodium hexametaphosphate (NaPO 3 J 6 , sodium meta-phosphate (NaPO 3 J n , silicon dioxide (SiO 2 ) (also: silica, CAS No .: 7631-86-9), barium sulfate (BaSO 4 ) or iron oxide (Fe 2 O 3 ) Inorganic surface coatings may occur alone, in combination and / or in combination with organic coating materials.
  • Organic surface coatings for the purposes of the present invention can consist of vegetable or animal aluminum stearate, vegetable or animal stearic acid, lauric acid, dimethylpolysiloxane (also: dimethicone), methylpolysiloxane (methicone), simethicone (a mixture of dimethylpolysiloxane having an average molecular weight) Chain length from 200 to 350 dimethylsiloxane units and silica gel) or alginic acid.
  • These organic surface coatings can occur alone, in combination and / or in combination with inorganic coating materials.
  • the titanium dioxide pigments can be present both in the rutile and anatase crystal modifications and can advantageously be surface-treated ("coated") for the purposes of the present invention, with a hydrophilic, amphiphilic or hydrophobic character, for example, being formed or retained
  • This surface treatment may consist in providing the pigments with a thin hydrophilic and / or hydrophobic inorganic and / or organic layer by processes known per se.
  • the various surface coatings may also contain water for the purposes of the present invention.
  • Coated and uncoated titanium dioxides described in the present invention can also be used in the form of commercially available oily or aqueous predispersions. Dispersants and / or solubilizers may advantageously be added to these predispersions.
  • the titanium dioxides according to the invention are distinguished by a primary particle size of between 10 nm and 200 nm, particle sizes of from 10 nm to 100 nm being preferred according to the invention.
  • titanium dioxides are the MT-100 Z and MT-100 TV from Tayca Corporation, Eusolex T-2000 and Eusolex T-AVO from Merck and the titanium dioxide T 805 from Degussa and the iron / titanium mixed oxide titanium dioxide T817 from Degussa ,
  • zinc oxides can also be used in the form of commercially available oily or aqueous predispersions.
  • Zinc oxide particles and predispersions of zinc oxide particles which are suitable according to the invention are distinguished by a primary particle size of ⁇ 300 nm and can be obtained from the following companies under the following trade names:
  • Particularly preferred zinc oxides in the context of the invention are the Z-Cote HP1 from BASF and the zinc oxide NDM from Haarmann & Reimer.
  • UV filter substances which are liquid at room temperature for the purposes of the present invention are homomenthyl salicylate (INCI: homosalates), 2-ethylhexyl 2-hydroxybenzoate (2-ethylhexyl salicylate, octyl salicylate, INCI: octyl salicylates), 2-ethylhexyl-2-cyano-3, 3-diphenyl acrylate (INCI: Octocrylene) and esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester (2-ethylhexyl-4-methoxycinnamate, INCI: octyl methoxycinnamate) and 4-methoxycinnamic acid isopentyl ester (isopentyl-4-methoxycinnamate, INCI: isoamyl p Methoxycinnamate), 3- (4- (2,2-bise
  • UV-A filter substances for the purposes of the present invention are dibenzoyl methane derivatives, in particular 4- (tert-butyl) -4'-methoxydibenzoylmethane (CAS No. 70356-09-1), which has been sold by Givaudan under the trademark Parsol ® 1789 and sold by Merck under the trade name Eusolex® 9020.
  • UV-A filter substances in the context of the present invention are hydroxybenzophenones, which are distinguished by the following structural formula:
  • Cycloalkenyl wherein the substituents R 1 and R 2 together with the nitrogen atom to which they - R 1 and R 2 are independently hydrogen, Ci-C 2 -alkyl, C 3 -C 0 cycloalkyl or C 3 -C 0 are bonded, can form a 5- or 6-membered ring and R 3 is a C 1 -C 20 -alkyl radical.
  • a particularly advantageous hydroxybenzophenone in the context of the present invention is 2- (4'-diethylamino-2 1 -hydroxybenzoyl) -benzoic acid hexyl ester (also: aminobenzophenone), which has the following structure: and Uvinul A Plus is available from BASF.
  • UV filter substances in the context of the present invention are sulfonated, water-soluble UV filters, such as. B .:
  • Phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and its salts especially the corresponding sodium, potassium or triethanolammonium salts, especially the phenylene-1,4 bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt with the INCI name Bisimidazylate (CAS No .: 180898-37-7), which is available, for example, under the trade name Neo Heliopan AP is available from Haarmann &Reimer;
  • Sulfonic acid derivatives of 3-Benzylidencamphers such as. B. 4- (2-oxo-3-bomylidenemethyl) - benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bomylidenemethyl) sulfonic acid and salts thereof.
  • Advantageous UV filter substances for the purposes of the present invention are also so-called broadband filters, ie filter substances which absorb both UV-A and UV-B radiation.
  • An advantageous broadband filter for the purposes of the present invention is also the 2,2'-methyl-bis (6- (2H-benzotriazol-2-yl) -4- (1, 1,3,3-tetramethylbutyl) phenol ), which is available under the trade name Tinosorb® M from CIBA-Chemikalien GmbH.
  • Another advantageous broadband filter in the context of the present invention is the 2- (2H-benzotriazole) -ylH-methyl-eP-methyl-S-ti.SSS-tetramethyl-i-trimethylsilyoxyldisiloxanyl] propyl] -phenol (CAS). No .: 155633-54-8) with the INCI name Drometrizole Trisiloxane.
  • the other UV filter substances can be oil-soluble or water-soluble.
  • Advantageous oil-soluble filter substances are z. B .:
  • 3-benzylidene camphor derivatives preferably 3- (4-methylbenzylidene) camphor, 3-benzylidene camphor;
  • 4-aminobenzoic acid derivatives preferably (2-ethylhexyl) 4- (dimethylamino) benzoate, 4- (dimethylamino) benzoic acid amyl ester;
  • Esters of benzalmalonic acid preferably di-2-ethylhexyl 4-methoxybenzalmalonate
  • Dioctylbutylamidotriazone (INCI: diethylhexyl butamido triazone), which is available under the trade name UVASORB HEB from Sigma 3V;
  • Esters of cinnamic acid preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-methoxycinnamic acid isopentyl ester;
  • benzophenone preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone and
  • UV filter substances are: phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt (INCI:
  • Dioctylbutylamidotriazone (INCI: diethylhexyl butamido triazone, trade name: Uvasorb HEB),
  • these additional UV filter substances can advantageously be contained in a total concentration of from 0.01 to 20% by weight and, preferably, in a total concentration of from 0.5 to 10% by weight, based in each case on the total weight of the aqueous preparation.
  • the oil phase of the preparations according to the invention is advantageously selected from the group of polar lipids having a polarity ⁇ 35 mN / m.
  • Particularly advantageous lipids in the context of the present invention are all native lipids, such as. As olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, castor oil, wheat germ oil, grape seed oil, thistle oil, evening primrose oil, macadamia nut oil, corn oil, avocado oil and the like, and those listed below.
  • hydrocarbons in particular paraffin oil and further hydrogenated poly olefins such as hydrogenated polyisobutenes, squalane and squalene are to be used advantageously in the context of the present invention.
  • the content of the lipids is advantageously less than 50% by weight, preferably between 1 and 40% by weight, particularly preferably between 5 and 20% by weight, in each case based on the total weight of the water-containing preparation.
  • the lipid phase contains oil-soluble UV filter substances, it is advantageous to choose the content of the lipid phase less than 80% by weight, preferably between 1 and 40% by weight, particularly preferably between 5 and 30% by weight, based in each case on the total weight of the water-containing preparation.
  • oil phase of the preparations according to the present invention also contains non-polar lipids.
  • the aqueous phase of the preparations according to the invention may advantageously comprise customary cosmetic adjuvants, for example alcohols, in particular those of low C number, preferably ethanol and / or isopropanol, diols or polyols of low C number and their ethers, preferably propylene glycol, glycerol, ethylene glycol, Propanediol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous products, polymers, foam stabilizers, electrolytes, self-tanning agents and in particular one or more thickeners, which are advantageously chosen can be selected from the group silicon dioxide, aluminum silicates, polysaccharides or their derivatives, for.
  • customary cosmetic adjuvants for example alcohols, in particular those of low C number, preferably ethanol and / or isopropanol, di
  • hyaluronic acid xanthan gum, hydroxypropylmethylcellulose, particularly advantageous from the group of polyacrylates, preferably a polyacrylate from the group of so-called carbopols, for example Carbopols types 980, 981, 1382, 2984, 5984, each individually or in combination.
  • carbopols for example Carbopols types 980, 981, 1382, 2984, 5984, each individually or in combination.
  • the preparation according to the invention may comprise one or more emulsifiers, it being possible to use for the O / W emulsifiers known for cosmetic emulsions.
  • O / W emulsions which are solids-stabilized and contain no O / W emulsifiers.
  • the cosmetic preparations according to the invention can be composed as usual. Particularly advantageous in the context of the present invention are preparations for Care of the skin: they may be used for cosmetic sunscreen, for cleaning or care of the skin and / or hair and as a make-up product in decorative cosmetics. A further advantageous embodiment of the present invention is Af ter-Sun products.
  • water-containing cosmetic compositions in the sense of the present invention can be used, for example, as skin protection cream, day cream or night cream, etc. It may be possible and advantageous to use the compositions according to the invention as the basis for pharmaceutical formulations.
  • the water-containing preparations according to the invention are used as sunscreen agents.
  • the aqueous preparations according to the invention can be used according to the invention as preparations whose main purpose is not the protection from sunlight but which nevertheless contain a content of UV protective substances.
  • So z. B. in day creams or makeup products usually incorporated UV-A or UV-B filter substances.
  • UV-protective substances, as well as antioxidants and, if desired, preservatives also represent an effective protection of the preparations themselves against spoilage.
  • Cosmetic preparations which are in the form of a sunscreen agent are also favorable.
  • the aqueous cosmetic preparations according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics.
  • the cosmetic preparations according to the invention may contain cosmetic adjuvants, such as are commonly used in such preparations, for.
  • Advantageous preservatives for the purposes of the present invention are, for example, formaldehyde releasers (such as, for example, DMDM hydantoin, which is available under the trade name Glydant TM from Lonza), iodopropyl butylcarbamates (for example those sold under the trade names Glycacil-L, Glycacil -S. From the company.
  • formaldehyde releasers such as, for example, DMDM hydantoin, which is available under the trade name Glydant TM from Lonza
  • iodopropyl butylcarbamates for example those sold under the trade names Glycacil-L, Glycacil -S. From the company.
  • the preserving system also advantageously also comprises preserving aids, such as, for example, ethylhexylglycerol, glycine soya, etc.
  • Advantageous complexing agents for the purposes of the present invention are, for example, EDTA, [S, S] -ethylenediamine disuccinate (EDDS), which is obtainable, for example, under the trade name Octaquest from the company Octel, pentasodium ethylenediamine tetramethylenephosphonate, which, for example, B. under the trade name Dequest 2046 from the company.
  • Monsanto is available and / or iminodisuccinic which u. a.
  • compositions are also obtained when antioxidants are used as additives or active substances.
  • the preparations advantageously contain one or more antioxidants. All antioxidants which are suitable or customary for cosmetic applications can be used as inexpensive but nevertheless optional antioxidants.
  • water-soluble Antioxi ⁇ dantien can be used, such as vitamins, eg. As ascorbic acid and its derivatives.
  • antioxidants are vitamin E and its derivatives as well as vitamin A and its derivatives.
  • the amount of antioxidants (one or more compounds) in the preparations is preferably from 0.001 to 30% by weight, particularly preferably from 0.05 to 20% by weight, in particular from 0.1 to 10% by weight, based on the total weight of the hydrous preparation. If vitamin E and / or its derivatives are the antioxidant (s), it is advantageous to choose their respective concentrations from the range from 0.001 to 10% by weight, based on the total weight of the aqueous formulation.
  • vitamin A or vitamin A derivatives, or carotenes or derivatives thereof are the antioxidant (s), it is advantageous if their respective concentrations are in the range from 0.001 to 10% by weight, based on the total weight of the aqueous formulation to choose.
  • the cosmetic preparations according to the present invention contain cosmetic active ingredients, preferred active substances being antioxidants which can protect the skin against oxidative stress.
  • active ingredients in the context of the present invention are natural active substances and / or their derivatives, such as.
  • 1, 16-dicarboxylic acid dioic acid, CAS number 20701-68-2, provisional INCI name octadecenedioic acid
  • licochalcone A 1, 16-dicarboxylic acid (dioic acid, CAS number 20701-68-2, provisional INCI name octadecenedioic acid) and / or licochalcone A.
  • Licochalcone can also be used advantageously as a constituent of herbal extracts, in particular of aqueous radix Glycyrrhizae inflatae.
  • the cosmetic preparations contain 0.001 to 10% by weight, in particular 0.05 to 5% by weight, very particularly 0.01 to 2% by weight of an extract of Radix Glycyrrhizae inflatae, in each case on the total weight of the preparation.
  • Inventive formulations which z. B. known anti-wrinkle active ingredients such as flavone glycosides (especially ⁇ -glycosylrutin), coenzyme Q10, vitamin E and / or derivatives and the like, are particularly advantageous for protection against aesthetically unattractive skin lesions, as z. Skin aging (such as dryness, roughness, dryness wrinkles, itching, decreased refatting (eg, after washing), visible vascular dilation (telangiectasia, cuperosis), slackness and wrinkle and wrinkle formation, localized hypersensitivity). , Hypo and false pigmentation (eg, age spots), increased susceptibility to mechanical stress (eg, cracking), and the like). Furthermore, they are advantageously suitable against the appearance of dry or rough skin.
  • flavone glycosides especially ⁇ -glycosylrutin
  • coenzyme Q10 vitamin E and / or derivatives and the like
  • the preparations according to the present invention can also advantageously contain self-tanning substances, for example dihydroxyacetone and / or melanin derivatives in concentrations of from 1% by weight to 8% by weight, based on the total weight of the aqueous preparation.
  • self-tanning substances for example dihydroxyacetone and / or melanin derivatives in concentrations of from 1% by weight to 8% by weight, based on the total weight of the aqueous preparation.
  • the preparations according to the present invention may also contain repellents for protection against mosquitoes, ticks and spiders and the like.
  • repellents for protection against mosquitoes, ticks and spiders and the like.
  • N N-diethyl-3-methylbenzamide (trade name: meta-delphene, "DEET"), dimethyl phthalate (trade name: palatinol M, DMP), 1-piperidinecarboxylic acid 2- (2-hydroxyethyl) -1-methylpropyl ester, and especially 3- (Nn-butyl-N-acetyl-amino) -propionic acid ethyl ester (available from Merck under the tradename Insekt Repellent® 3535.)
  • the repellents can be used either individually or in combination.
  • Moisturizers are substances or mixtures of substances which give cosmetic preparations the property, after application or distribution on the skin surface, to reduce the moisture release of the hom layer (also called transepidermal water loss (TEWL)) and / or to positively influence the hydration of the initial layer ,
  • TEWL transepidermal water loss
  • moisturizers for the purposes of the present invention are, for example, glycerol, lactic acid and / or lactates, in particular sodium lactate, butylene glycol, propylene glycol, methylpropanediol, biosaccharide gum-1, glycine soya, ethylhexyloxyglycerol, pyrrolidonecarboxylic acid and urea.
  • polymeric moisturizers from the group of water-soluble and / or water-swellable and / or with To use the aid of water gellable polysaccharides.
  • the cosmetic preparations according to the invention may also advantageously, although not necessarily, contain fillers which are e.g. B. further improve the sensory and cosmetic properties of the formulations and, for example, cause or enhance a velvety or silky feel on the skin.
  • Advantageous fillers for the purposes of the present invention are starch and starch derivatives (such as, for example, tapioca starch, distarch phosphate, aluminum or sodium starch, octenylsuccinate and the like), pigments which have neither chiefly UV filter nor coloring action (such as, for example, US Pat. B. boron nitride etc.) and / or Aerosils ® (CAS no. 7631-86-9).
  • Emulsion preparations after spray / freeze / drum drying Emulsion preparations after spray / freeze / drum drying:

Abstract

The invention relates to a method for preparation of a cosmetic composition, characterised in that an O/W emulsion containing a) an aqueous phase, b) an oil phase, c) pigmented UV-light block filter d) water-soluble polymers, in addition to further optional cosmetic and/or dermatological agents, adjuncts and additives is dried by spray drying, freeze drying and/or drum drying.

Description

Beiersdorf Aktiengesellschaft Hamburg Beiersdorf Aktiengesellschaft Hamburg
Lichtschutzkonzentrat mit organischen MikropigmentenSunscreen concentrate with organic micropigments
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung einer kosmetischen Zubereitung auf der Basis einer getrockneten O/W-Emulsion sowie das Verfahrensprodukt.The present invention relates to a process for the preparation of a cosmetic preparation based on a dried O / W emulsion and to the process product.
Der Wunsch, schön und attraktiv auszusehen, ist von Natur aus im Menschen verwurzelt. Auch wenn das Schönheitsideal im Laufe der Zeit Wandlungen erfahren hat, so ist das Streben nach einem makellosen Äußeren, immer das Ziel der Menschen gewesen. Einen wesentlichen Anteil an einem schönen und attraktiven Äußeren hat dabei der Zustand und das Aussehen der Haut und der Hautanhangsgebilde, d.h. der Haare und der Nägel.The desire to look beautiful and attractive is inherently rooted in man. Even though the ideal of beauty has undergone changes over time, the pursuit of an impeccable appearance has always been the goal of man. An essential part of a beautiful and attractive appearance is the condition and appearance of the skin and the appendages of the skin, i. the hair and the nails.
Die Haut ist das größte Organ des Menschen. Unter ihren vielen Funktionen (beispielsweise zur Wärmeregulation und als Sinnesorgan) ist die Barrierefunktion, die das Austrocknen der Haut (und damit letztlich des gesamten Organismus) verhindert, die wohl wichtigste. Gleich¬ zeitig wirkt die Haut als Schutzeinrichtung gegen das Eindringen und die Aufnahme von au¬ ßen kommender Stoffe und der UV-Strahlung. Bewirkt wird diese Barrierefunktion durch die Epidermis, welche als äußerste Schicht die eigentliche Schutzhülle gegenüber der Umwelt bildet. Mit etwa einem Zehntel der Gesamtdicke ist sie gleichzeitig die dünnste Schicht der Haut.The skin is the largest organ in humans. Among its many functions (for example, for heat regulation and as a sense organ) is the barrier function, which prevents the drying of the skin (and thus ultimately the entire organism), probably the most important. At the same time, the skin acts as a protective device against the penetration and absorption of foreign substances and UV radiation. This barrier function is caused by the epidermis, which, as the outermost layer, forms the actual protective cover against the environment. At about one-tenth of the total thickness, it is also the thinnest layer of the skin.
Damit die Haut ihre biologischen Funktionen im vollen Umfang erfüllen kann, bedarf sie der regelmäßigen Reinigung und Pflege. Die Reinigung der Haut dient dabei der Entfernung vonFor the skin to fulfill its biological functions to the full extent, it needs regular cleaning and care. The cleaning of the skin serves the removal of
Schmutz, Schweiß und Resten abgestorbener Hautpartikel, die einen idealen Nährboden fürDirt, sweat and residues of dead skin particles, which provide an ideal breeding ground for
Krankheitserreger und Parasiten aller Art bilden. Hautpflegeprodukte, in der Regel Cremes,Form pathogens and parasites of all kinds. Skin care products, usually creams,
Salben oder Lotionen, dienen meist der Befeuchtung und Rückfettung der Haut. Häufig sind ihnen Wirkstoffe zugesetzt, welche die Haut regenerieren und beispielsweise ihre vorzeitige Alterung (z.B. das Entstehen von Fältchen, Falten) verhindern und vermindern sollen.Ointments or lotions, are usually used to moisturize and restore the skin. Often, agents that regenerate the skin and, for example, prevent and reduce their premature aging (e.g., wrinkles, wrinkles) are added to them.
Hautpflegeprodukte bestehen in der Regel aus Emulsionen. Unter Emulsionen versteht man im allgemeinen heterogene Systeme, die aus zwei nicht oder nur begrenzt miteinander mischbaren Flüssigkeiten bestehen, die üblicherweise als Phasen bezeichnet werden und bei denen eine der beiden Flüssigkeiten in Form feinster Tröpfchen in der anderen Flüssigkeit dispergiert ist. Äußerlich und mit bloßem Auge betrachtet erscheinen Emulsionen homogen.Skin care products usually consist of emulsions. Emulsions are generally understood to mean heterogeneous systems which consist of two liquids which are immiscible or only to a limited extent miscible, which are usually referred to as phases, and in which one of the two liquids is in the form of very fine droplets in the other Liquid is dispersed. Viewed externally and with the naked eye, emulsions appear homogeneous.
Sind die beiden Flüssigkeiten Wasser und öl und liegen öltröpfchen fein verteilt in Wasser vor, so handelt es sich um eine öl-in-Wasser-Emulsion (O/W-Emulsion, z. B. Milch). Der Grundcharakter einer O/W-Emulsion ist durch das Wasser geprägt. Bei einer Wasser-in-öl- Emulsion (W/O-Emulsion, z. B. Butter) handelt es sich um das umgekehrte Prinzip, wobei der Grundcharakter hier durch das öl bestimmt wird.If the two liquids are water and oil and oil droplets are finely distributed in water, then it is an oil-in-water emulsion (O / W emulsion, eg milk). The basic character of an O / W emulsion is characterized by the water. A water-in-oil emulsion (W / O emulsion, eg butter) is the reverse principle, whereby the basic character is determined by the oil.
Der Trend weg von der vornehmen Blässe hin zur „gesunden, sportlich braunen Haut" ist seit Jahren ungebrochen. Um diese zu erzielen setzen die Menschen ihre Haut der Sonnenstrahlung aus, da diese eine Pigmentbildung im Sinne einer Melaninbildung hervorruft. Die ultraviolette Strahlung des Sonnenlichtes hat jedoch auch eine schädigende Wirkung auf die Haut. Neben der akuten Schädigung (Sonnenbrand) treten Langzeitschäden wie ein erhöhtes Risiko an Hautkrebs zu erkranken bei übermäßiger Bestrahlung mit Licht aus dem UVB-Bereich (Wellenlänge: 280-320 nm) auf. Die übermäßige Einwirkung der UVB- und UVA-Strahlung (Wellenlänge: 320-400 nm) führt darüber hinaus zu einer Schwächung der elastischen und kollagenen Fasern des Bindegewebes. Dies führt zu zahlreichen phototoxischen und photoallergischen Reaktionen und hat eine vorzeitige Hautalterung zur Folge.The trend away from sophisticated paleness to "healthy, sporty brown skin" has been unbroken for years, and people are exposing their skin to sunlight, as it causes pigmentation in the sense of melanin formation, which has ultraviolet radiation from sunlight In addition to the acute injury (sunburn), long-term damage such as an increased risk of developing skin cancer due to excessive exposure to light from the UVB range (wavelength: 280-320 nm) occurs UVB and UVA radiation (wavelength: 320-400 nm) also leads to a weakening of the elastic and collagen fibers of the connective tissue, which leads to numerous phototoxic and photoallergic reactions and leads to premature aging of the skin.
Zum Schutz der Haut wurden daher eine Reihe von Lichtschutzfiltern entwickelt, die in kosmetischen Zubereitungen eingesetzt werden können. Diese UVA- und UVB-Filter sind in den meisten Industrieländern in Form von Positivlisten wie der Anlage 7 der deutschen Kosmetikverordnung zusammengefasst.To protect the skin, therefore, a number of sunscreen filters have been developed that can be used in cosmetic preparations. These UVA and UVB filters are summarized in most industrialized countries in the form of positive lists such as Appendix 7 of the German Cosmetics Regulation.
Herkömmliche kosmetische und/oder dermatologische Emulsionen, beispielsweise Sonnenschutzcremes oder -lotionen, haben aufgrund Ihres Wassergehaltes eine Reihe von Nachteilen: ■ Sie besitzen ein hohes Gewicht, was beim Transport zu höherem Energieverbrauch und höheren Kosten führt.Conventional cosmetic and / or dermatological emulsions, such as sunscreen creams or lotions, have a number of disadvantages due to their water content: ■ They are heavy-weight, which results in higher energy consumption and higher costs during transport.
■ Sie besitzen ein größeres Volumen, was beim Transport zu geringeren Transportkapazitäten führt.■ They have a larger volume, resulting in lower transport capacities during transport.
■ Insbesondere dünnflüssige Emulsionen sind wesentlich aufwendiger zu lagern und transportieren, da die Zubereitungen „auslaufen" können. ■ Die Anwendungskonzentrationen der Inhaltsstoffe (z.B. UV-Filterkonzentration und damit UV-Filterleistung) sind dem Verbraucher bereits vorgegeben. Eine individuelle Anpassung an die Gegebenheiten am Anwendungsort sind nicht mehr möglich.■ In particular, low-viscosity emulsions are much more expensive to store and transport because the preparations can "leak". ■ The application concentrations of the ingredients (eg UV filter concentration and thus UV filter performance) are already given to the consumer. An individual adaptation to the conditions at the place of application are no longer possible.
Es war daher die Aufgabe der vorliegenden Erfindung, die Nachteile des Standes der Technik zu beseitigen und eine „trockene" Emulsion sowie ein Verfahren zur Herstellung derselben zu entwickeln.It was therefore the object of the present invention to eliminate the disadvantages of the prior art and to develop a "dry" emulsion and a method for producing the same.
Zwar sind dem Fachmann derartige „Instant-Emulsionen" an sich bekannt. So beschreibt die DE 102 54 334 und DE 102 54 335 „trockene" Emulsionen mit einem Gehalt an Lichtschutzfiltern. Doch konnten diese Schriften ebenso wenig den Weg zur vorliegenden Erfindung weisen wie die WO 00/26280, WO 02/32563, WO 02/47624 und WO 02/047620.Although such "instant emulsions" are known per se to the person skilled in the art, DE 102 54 334 and DE 102 54 335 describe "dry" emulsions containing sunscreen filters. However, these documents could just as little point the way to the present invention as WO 00/26280, WO 02/32563, WO 02/47624 and WO 02/047620.
Ein Problem getrockneter Emulsionen besteht insbesondere in dem Umstand, dass es bei der Trocknung der Emulsion zu einer Koaleszenz der öltröpfchen kommt. Koaleszieren die Tröpfchen, bildet sich beim Zusatz von Wasser keine Emulsion mehr zurück.A problem of dried emulsions is, in particular, the fact that the oil droplets coalesce during the drying of the emulsion. If the droplets coalesce, no emulsion forms on addition of water.
Es war daher die Aufgabe der vorliegenden Erfindung, die Mängel des Standes der Technik zu beseitigen und Emulsionen zu entwickeln, die sich problemlos trocknen und nach erneutem Zusatz von Wasser re-emulgieren lassen.It was therefore the object of the present invention to eliminate the deficiencies of the prior art and to develop emulsions that dry easily and re-emulsify after re-addition of water.
Überraschend gelöst wird die Aufgabe durch ein Verfahren zur Herstellung einer kosmetischen Zubereitung, dadurch gekennzeichnet, dass eine O/W-Emulsion enthaltend a) eine wässrige Phase, b) eine ölphase, c) pigmentäre UV-Lichtschutzfilter und d) wasserlösliche Polymere, neben gegebenenfalls weiteren kosmetischen und/oder dermatologischen Wirk-, Hilfs- und Zusatzstoffen, durch Sprühtrocknung, Gefriertrocknung und/oder Walzentrocknung getrocknet wird, sowie durch eine kosmetische Zubereitung, die nach diesem Verfahren hergestellt ist.The object is surprisingly achieved by a process for producing a cosmetic preparation, which comprises an O / W emulsion comprising a) an aqueous phase, b) an oil phase, c) pigmentary UV light protection filters and d) water-soluble polymers, optionally other cosmetic and / or dermatological active ingredients, auxiliaries and additives, is dried by spray drying, freeze drying and / or drum drying, and by a cosmetic preparation prepared by this method.
Die nach diesem Verfahren hergestellte Zubereitung ist erfindungsgemäß. Die Aufgaben werden ferner gelöst durch die Verwendung einer Kombination aus pigmentären UV-Lichtschutzfiltern und wasserlöslichen Polymeren zur Herstellung durch Sprühtrocknung, Gefriertrocknung und/oder Walzentrocknung getrockneter re-emulgierbarer O/W-Emulsionen.The preparation prepared by this process is according to the invention. The objects are further achieved by the use of a combination of pigmentary UV photoprotective filters and water-soluble polymers for preparing by spray drying, freeze drying and / or drum drying dried re-emulsifiable O / W emulsions.
Das erfindungsgemäße Verfahren zur Herstellung einer kosmetischen Zubereitung ist erfindungsgemäß vorteilhaft dadurch gekennzeichnet, dass die getrocknete Emulsion anschließend in einer Mischungsvorrichtung mit wasserlöslichen und/oder leichtflüchtigen Wirk-, Hilfs- und/oder Zusatzstoffen vermischt wird.The inventive method for producing a cosmetic preparation according to the invention is advantageously characterized in that the dried emulsion is then mixed in a mixing device with water-soluble and / or volatile active ingredients, auxiliaries and / or additives.
Die nach diesem Herstellungsschritt hergestellte Zubereitung ist erfindungsgemäß.The preparation prepared according to this preparation step is according to the invention.
Erfindungsgemäß vorteilhaft können der Zubereitung ein oder mehrere Granulier- und/oder Tablettenhilfsstoffe zugesetzt werden.Advantageously according to the invention, one or more granulating and / or tablet adjuvants can be added to the preparation.
Erfindungsgemäß ist das Verfahren zur Herstellung einer Zubereitung, welches dadurch gekennzeichnet ist, dass der erfindungsgemäßen Zubereitung nach dem Zusatz eines oder mehrerer Tablettenhilfsstoffe in einer Mischungsvorrichtung vermischt werden.According to the invention, the process for the preparation of a preparation, which is characterized in that the preparation according to the invention after the addition of one or more tablet excipients are mixed in a mixing device.
Die nach diesem Herstellungsschritt hergestellte Zubereitung ist erfindungsgemäß.The preparation prepared according to this preparation step is according to the invention.
Nach dem Mischvorgang können erfindungsgemäß vorteilhaft in einem weiteren Verfahrensschritt aus der Zubereitung Tabletten und/oder Granulate hergestellt werden. Dies geschieht erfindungsgemäß vorteilhaft dadurch, dass die Zubereitung in einer Presse zu einer oder mehreren Tabletten gepresst oder mittels geeigneter Granuliervorrichtungen granuliert werden.After the mixing process, according to the invention, tablets and / or granules can advantageously be prepared from the preparation in a further process step. This is done according to the invention advantageously characterized in that the preparation are pressed in a press to one or more tablets or granulated by means of suitable granulation.
Die nach diesem Herstellungsschritt hergestellte Zubereitung ist erfindungsgemäß.The preparation prepared according to this preparation step is according to the invention.
Eine nach einem der oben beschriebenen Verfahrensschritten hergestellte Zubereitung kann zur Anwendung als Kosmetikum erfindungsgemäß vorteilhaft mit Wasser, das eine Temperatur von 20 bis 100 °C haben kann, versetzt werden.A preparation prepared according to one of the above-described process steps may advantageously be used according to the invention for application as a cosmetic with water which may have a temperature of 20 to 100 ° C.
Die nach diesem Herstellungsschritt hergestellte Zubereitung ist erfindungsgemäß. Desweiteren ist es erfindungsgemäß, dass der Anwender die getrocknete Emulsion ohne weiteren Wasserzusatz direkt z.B. als „Körper-Puder" anwendet.The preparation prepared according to this preparation step is according to the invention. Furthermore, it is according to the invention that the user applies the dried emulsion directly without further addition of water, for example as "body powder".
Die erfindungsgemäßen pigmentären UV-Lichtschutzfilter werden erfindungsgemäß vorteilhaft in einer Konzentration von 0,5 bis 35 Gewichts-% und bevorzugt in einer Konzentration von 2 bis 15 Gewichts-%, jeweils bezogen auf das Gewicht der O/W-Emulsion vor der Trocknung beziehungsweise nach dem erneuten Zusatz von Wasser, eingesetzt.According to the invention, the pigmentary UV light protection filters according to the invention are advantageously used in a concentration of 0.5 to 35% by weight and preferably in a concentration of 2 to 15% by weight, based in each case on the weight of the O / W emulsion before drying or after the re-addition of water used.
Erfindungsgemäß vorteilhafte Ausführungsformen der vorliegenden Erfindung sind dadurch gekennzeichnet, dass als pigmentäre UV-Lichtschutzfilter eine oder mehrere Verbindungen gewählt aus der Gruppe der Verbindungen 2,4,6-Tris-(biphenyl)-1,3,5-triazin (insbesondere 2,4,6-Tribiphenyl-4-yl-1 ,3,5-triazin); 2,4,6-Tris-(terphenyl)-1 ,3,5-triazin eingesetzt werden.Embodiments of the present invention that are advantageous according to the invention are characterized in that one or more compounds selected from the group of the compounds 2,4,6-tris (biphenyl) -1,3,5-triazine (in particular 2,4 , 6-tribiphenyl-4-yl-1,3,5-triazine); 2,4,6-tris (terphenyl) -1, 3,5-triazine can be used.
Die erfindungsgemäßen wasserlöslichen Polymere werden erfindungsgemäß vorteilhaft in einer Konzentration von 1 bis 80 Gewichts-% und bevorzugt in einer Konzentration von 2 bis 50 Gewichts-%, jeweils bezogen auf das Gewicht der O/W-Emulsion vor der Trocknung beziehungsweise nach dem erneuten Zusatz von Wasser, eingesetzt.According to the invention, the water-soluble polymers according to the invention are advantageously used in a concentration of 1 to 80% by weight and preferably in a concentration of 2 to 50% by weight, based in each case on the weight of the O / W emulsion before drying or after the additional addition of Water, used.
Erfindungsgemäß vorteilhafte wasserlösliche Polymere können erfindungsgemäß vorteilhaft aus der Gruppe der wasserlöslichen bzw. dispergierbaren Filmbildner (z. B. Polyurethane,According to the invention, water-soluble polymers which are advantageous according to the invention can advantageously be selected from the group of water-soluble or dispersible film formers (for example polyurethanes,
Dimethicone Copolyol Polyacrylate, Polyvinylpyrrolidon-Vinylacetate PVP/VA,Dimethicone Copolyol Polyacrylate, Polyvinylpyrrolidone Vinyl Acetate PVP / VA,
Polyvinylpyrrolidone (PVP), Polyvinylalkohole (z.B. Mowiol 18-88) und aus der Gruppe derPolyvinyl pyrrolidones (PVP), polyvinyl alcohols (e.g., Mowiol 18-88) and from the group of
Hydrokolloide (z.B. Agar-Agar, Carrageen, Tragant, Gummi arabicum, Alginate, Pektine,Hydrocolloids (e.g., agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins,
Polyosen, Guar-Mehl, Johannisbrotbaumkernmehl, Stärke, Dextrine, Polysaccharid-N- alkylurethane, Inulincarbamate, Gelatine, Casein, Celluloseether, Hydroxyethyl- und -propyl- cellulosederivate, Polysaccharide, Polyacryl- und Polymethacryl-Verbindungen, Ammonium- acryloyldimethyltaurate/Vinylpyrrolidoncopolymere und Ammoniumpolyacryl- dimethyltauramide, Vinylpolymere, Polycarbonsäuren, Polyether, Polyimine, Polyamide,Polyols, guar gum, locust bean gum, starch, dextrins, polysaccharide N-alkyl urethanes, inulin carbamates, gelatin, casein, cellulose ethers, hydroxyethyl and propylcellulose derivatives, polysaccharides, polyacrylic and polymethacrylic compounds, ammonium acryloyldimethyltaurates / vinylpyrrolidone copolymers and ammonium polyacrylic dimethyltauramides, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides,
Polykieselsäuren, Tonmineralien, Zeolithe, Kieselsäuren, siehe unten) gewählt werden.Polysilicic acids, clay minerals, zeolites, silicas, see below).
Erfindungsgemäß bevorzugte Hydrokolloide sind beispielsweise Methylcellulosen, als welche die Methylether der Cellulose bezeichnet werden. Sie zeichnen sich durch die folgende Strukturformel aus
Figure imgf000007_0001
in der R ein Wasserstoff oder eine Methylgruppe darstellen kann.
Hydrocolloids which are preferred according to the invention are, for example, methylcelluloses, which are referred to as the methyl ethers of cellulose. They are characterized by the following structural formula
Figure imgf000007_0001
in which R can represent a hydrogen or a methyl group.
Insbesondere vorteilhaft im Sinne der vorliegenden Erfindung sind die im allgemeinen eben¬ falls als Methylcellulosen bezeichneten Cellulosemischether, die neben einem dominieren¬ den Gehalt an Methyl- zusätzlich 2-Hydroxyethyl-, 2-Hydroxypropyl- oder 2-Hydroxybutyl- Gruppen enthalten. Besonders bevorzugte Hydroxypropyl methylcellulosen (HPMC) weisen eine mittlere Molmasse Mm < 50.000 gmol"1 auf und sind beispielsweise unter der Bezeichnung Pharmacoat 603, Pharmacoat 606 und Pharmacoat 645 oder unter der Bezeichnung Metolose 65 SH 50 bzw. Metolose 60 SH 50 bei der FA Shin Etsu erhältlich. Weitere bevorzugte Hydroxypropylmethylcellulosen sind unter dem Handelsnamen Methocel K100LV bei der Firma Dow Chemicals oder unter dem Handelsnamen Methocel E5 bei der Firma Colorcon erhältlich.Particularly advantageous for the purposes of the present invention are the cellulose mixed ethers which are generally also referred to as methylcelluloses and, in addition to a dominating content of methyl, additionally contain 2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxybutyl groups. Particularly preferred hydroxypropyl methylcelluloses (HPMC) have an average molecular weight M m <50,000 gmol "1 and are, for example, under the name Pharmacoat 603, Pharmacoat 606 and Pharmacoat 645 or under the name Metolose 65 SH 50 or Metolose 60 SH 50 in the FA Other preferred hydroxypropyl methylcelluloses are available under the trade name Methocel K100LV from Dow Chemicals or under the trade name Methocel E5 from Colorcon.
Des weiteren bevorzugt sind (Hydroxypropyl)methylcellulosen, beispielsweise die unter der Handelsbezeichnung Methocel E4M bei der Dow Chemical Comp, erhältlichen.Also preferred are (hydroxypropyl) methylcelluloses, for example those available under the trade name Methocel E4M from Dow Chemical Comp.
Erfindungsgemäß ferner vorteilhaft ist Natriumcarboxymethylcellulose, das Natrium-Salz des Glykolsäureethers der Cellulose, für welches R in Strukturformel I ein Wasserstoff und/oder CH2-COONa darstellen kann. Besonders bevorzugt ist die unter der Handelsbezeichnung Natrosol Plus 330 CS bei Aqualon erhältliche, auch als Cellulose Gum bezeichnete Natrium¬ carboxymethylcellulose.Also advantageous according to the invention is sodium carboxymethylcellulose, the sodium salt of the glycolic acid ether of cellulose, for which R in structural formula I can be a hydrogen and / or CH 2 -COONa. Especially preferred is sodium carboxymethylcellulose, also known as cellulose gum, available under the trade name Natrosol Plus 330 CS from Aqualon.
Erfindungsgemäß ferner vorteilhaft ist der Einsatz von Maltodextrin , bevorzugt mit einem Dextrose-Äquivalent von 10-30, besonders bevorzugt mit einem Dextrose-Äquivalent von 15- 20. Desweiteren vorteilhaft ist der Einsatz vom Gummi Arabicum z.B. unter dem Handelsnamen Spray Gum erhältlich. Maltodextrin und Gummi Arabicum können einzeln oder im Gemisch eingesetzt werden. Erfindungsgemäß vorteilhaft beträgt das Gewichtsverhältnis des Rohstoffgemisches von 1 :10 bis 10:1 und erfindungsgemäß bevorzugt von 2:10 bis 10:2. Erfindungsgemäß vorteilhaft beträgt das Gewichtsverhältnis von pigmentären UV- Lichtschutzfiltern zu wasserlöslichen Polymeren von 1 :10 bis 10:1 und erfindungsgemäß bevorzugt von 3:10 bis 10:3 .Also advantageous according to the invention is the use of maltodextrin, preferably with a dextrose equivalent of 10-30, particularly preferably with a dextrose equivalent of 15-20. The use of gum arabic, for example, under the trade name spray gum, is also advantageous. Maltodextrin and gum arabic may be used singly or in admixture. According to the invention, the weight ratio of the raw material mixture is advantageously from 1:10 to 10: 1 and according to the invention preferably from 2:10 to 10: 2. According to the invention, the weight ratio of pigmentary UV light protection filters to water-soluble polymers is advantageously from 1:10 to 10: 1 and according to the invention preferably from 3:10 to 10: 3.
Es ist erfindungsgemäß vorteilhaft, wenn die Zubereitung gemäß der vorliegenden Erfindung, weitere UV-Filtersubstanzen enthält.It is advantageous according to the invention if the preparation according to the present invention contains further UV filter substances.
Ferner kann die erfindungsgemäße Zubereitung vorteilhaft UV-Lichtschutzfiltersubstanzen auf der Basis anorganischer Pigmente enthalten. Bevorzugte anorganische Pigmente sind Metalloxide und/oder andere in Wasser schwerlösliche oder unlösliche Metallverbindungen, insbesondere Oxide des Titans (TiO2), Zinks (ZnO), Eisens (z. B. Fe2O3), Zirkoniums (ZrO2), Siliciums (SiO2), Mangans (z. B. MnO), Aluminiums (AI2O3), Cers (z. B. Ce2O3), Mischoxide der entsprechenden Metalle sowie Abmischungen aus solchen Oxiden sowie das Sulfat des Bariums (BaSO4).Furthermore, the preparation according to the invention can advantageously contain UV sunscreen filter substances based on inorganic pigments. Preferred inorganic pigments are metal oxides and / or other water-insoluble or insoluble metal compounds, in particular oxides of titanium (TiO 2 ), zinc (ZnO), iron (eg Fe 2 O 3 ), zirconium (ZrO 2 ), silicon ( SiO 2 ), manganese (for example MnO), aluminum (Al 2 O 3 ), cerium (for example Ce 2 O 3 ), mixed oxides of the corresponding metals and mixtures of such oxides and the barium sulfate (BaSO 4 ).
Die Pigmente können vorteilhaft im Sinne der vorliegenden Erfindung auch in Form kommer¬ ziell erhältlicher öliger oder wäßriger Vordispersionen zur Anwendung kommen. Diesen Vor¬ dispersionen können vorteilhaft Dispergierhilfsmittel und/oder Solubilisationsvermittler zuge¬ setzt sein.For the purposes of the present invention, the pigments can also be used advantageously in the form of commercially available oily or aqueous predispersions. Dispersants and / or solubilizers may advantageously be added to these pre-dispersions.
Die Pigmente können erfindungsgemäß vorteilhaft oberflächlich behandelt („gecoatet") sein, wobei beispielsweise ein hydrophiler, amphiphiler oder hydrophober Charakter gebildet wer¬ den bzw. erhalten bleiben soll. Diese Oberflächenbehandlung kann darin bestehen, dass die Pigmente nach an sich bekannten Verfahren mit einer dünnen hydrophilen und/oder hydro- phoben anorganischen und/oder organischen Schicht versehen werden. Die verschiedenen Oberflächenbeschichtungen können im Sinne der vorliegenden Erfindung auch Wasser ent¬ halten.According to the invention, the pigments may advantageously be surface-treated ("coated"), wherein, for example, a hydrophilic, amphiphilic or hydrophobic character is to be formed or retained.This surface treatment may consist in using a thin film according to methods known per se hydrophilic and / or hydrophobic inorganic and / or organic layer The various surface coatings may also contain water in the sense of the present invention.
Anorganische Oberflächenbeschichtungen im Sinne der vorliegenden Erfindung können be- stehen aus Aluminiumoxid (AI2O3), Aluminiumhydroxid AI(OH)3, bzw. Aluminiumoxidhydrat (auch: Alumina, CAS-Nr.: 1333-84-2), Natriumhexametaphosphat (NaPO3J6, Natriummeta¬ phosphat (NaPO3Jn, Siliciumdioxid (SiO2) (auch: Silica, CAS-Nr.: 7631-86-9), Bariumsulfat (BaSO4) oder Eisenoxid (Fe2O3). Diese anorganischen Oberflächenbeschichtungen können allein, in Kombination und/oder in Kombination mit organischen Beschichtungsmaterialien vorkommen. Organische Oberflächenbeschichtungen im Sinne der vorliegenden Erfindung können beste¬ hen aus pflanzlichem oder tierischem Aluminiumstearat, pflanzlicher oder tierischer Stearin¬ säure, Laurinsäure, Dimethylpolysiloxan (auch: Dimeticone), Methyl polysiloxan (Methi- cone), Simethicone (einem Gemisch aus Dimethylpolysiloxan mit einer durchschnittlichen Kettenlänge von 200 bis 350 Dimethylsiloxan-Einheiten und Silicagel) oder Alginsäure. Diese organischen Oberflächenbeschichtungen können allein, in Kombination und/oder in Kombi¬ nation mit anorganischen Beschichtungsmaterialien vorkommen.Inorganic surface coatings for the purposes of the present invention may consist of aluminum oxide (Al 2 O 3 ), aluminum hydroxide Al (OH) 3 or aluminum oxide hydrate (also: Alumina, CAS No .: 1333-84-2), sodium hexametaphosphate (NaPO 3 J 6 , sodium meta-phosphate (NaPO 3 J n , silicon dioxide (SiO 2 ) (also: silica, CAS No .: 7631-86-9), barium sulfate (BaSO 4 ) or iron oxide (Fe 2 O 3 ) Inorganic surface coatings may occur alone, in combination and / or in combination with organic coating materials. Organic surface coatings for the purposes of the present invention can consist of vegetable or animal aluminum stearate, vegetable or animal stearic acid, lauric acid, dimethylpolysiloxane (also: dimethicone), methylpolysiloxane (methicone), simethicone (a mixture of dimethylpolysiloxane having an average molecular weight) Chain length from 200 to 350 dimethylsiloxane units and silica gel) or alginic acid. These organic surface coatings can occur alone, in combination and / or in combination with inorganic coating materials.
Die Titandioxid- Pigmente können sowohl in der Kristal I modifikation Rutil als auch Anatas vorliegen und können im Sinne der vorliegenden Erfindung vorteilhaft oberflächlich behandelt („gecoatet") sein, wobei beispielsweise ein hydrophiler, amphiphiler oder hydrophober Cha¬ rakter gebildet werden bzw. erhalten bleiben soll. Diese Oberflächenbehandlung kann darin bestehen, dass die Pigmente nach an sich bekannten Verfahren mit einer dünnen hydrophilen und/oder hydrophoben anorganischen und/oder organischen Schicht versehen werden. Die verschiedenen Oberflächenbeschichtung können im Sinne der vorliegenden Erfindung auch Wasser enthalten.The titanium dioxide pigments can be present both in the rutile and anatase crystal modifications and can advantageously be surface-treated ("coated") for the purposes of the present invention, with a hydrophilic, amphiphilic or hydrophobic character, for example, being formed or retained This surface treatment may consist in providing the pigments with a thin hydrophilic and / or hydrophobic inorganic and / or organic layer by processes known per se.The various surface coatings may also contain water for the purposes of the present invention.
Beschriebene beschichtete und un beschichtete Titandioxide können im Sinne vorliegender Erfindung auch in Form kommerziell erhältlicher öliger oder wäßriger Vordispersionen zur Anwendung kommen. Diesen Vordispersionen können vorteilhaft Dispergierhilfmittel und/oder Solubilisationsvermittler zugesetzt sein.Coated and uncoated titanium dioxides described in the present invention can also be used in the form of commercially available oily or aqueous predispersions. Dispersants and / or solubilizers may advantageously be added to these predispersions.
Die erfindungsgemäßen Titandioxide zeichnen sich durch eine Primärpartikelgröße zwischen 10 nm bis 200 nm aus, wobei Partikelgrößen von 10 nm bis 100 nm erfindungsgemäß bevorzugt sind. The titanium dioxides according to the invention are distinguished by a primary particle size of between 10 nm and 200 nm, particle sizes of from 10 nm to 100 nm being preferred according to the invention.
Figure imgf000010_0001
Figure imgf000011_0001
Figure imgf000010_0001
Figure imgf000011_0001
Im Sinne der vorliegenden Erfindung sind besonders bevorzugte Titandioxide das MT-100 Z und MT-100 TV von Tayca Corporation, Eusolex T-2000 und Eusolex T-AVO von Merck und das Titandioxid T 805 von Degussa und das Eisen/Titandmischoxid Titandioxid T817 von Degussa.For the purposes of the present invention, particularly preferred titanium dioxides are the MT-100 Z and MT-100 TV from Tayca Corporation, Eusolex T-2000 and Eusolex T-AVO from Merck and the titanium dioxide T 805 from Degussa and the iron / titanium mixed oxide titanium dioxide T817 from Degussa ,
Zinkoxide können im Sinne der vorliegenden Erfindung auch in Form kommerziell erhältlicher öliger oder wäßriger Vordispersionen zur Anwendung kommen. Erfindungsgemäß geeignete Zinkoxidpartikel und Vordispersionen von Zinkoxidpartikeln zeichnen sich durch eine Primärpartikelgröße von < 300 nm aus und sind unter folgenden Handelsbezeichnungen bei den aufgeführten Firmen erhältlich:For the purposes of the present invention, zinc oxides can also be used in the form of commercially available oily or aqueous predispersions. Zinc oxide particles and predispersions of zinc oxide particles which are suitable according to the invention are distinguished by a primary particle size of <300 nm and can be obtained from the following companies under the following trade names:
Figure imgf000011_0002
Figure imgf000011_0002
Besonderes bevorzugte Zinkoxide im Sinne der Erfindung sind das Z-Cote HP1 von der Firma BASF und das Zinkoxid NDM von der Firma Haarmann & Reimer.Particularly preferred zinc oxides in the context of the invention are the Z-Cote HP1 from BASF and the zinc oxide NDM from Haarmann & Reimer.
Vorteilhafte weitere UV-Filtersubstanzen im Sinne der vorliegenden Erfindung sind beispielsweise die im folgenden genannten, welche in der Wasser- und/oder der ölphase vorliegen können.Advantageous further UV filter substances in the sense of the present invention are, for example, those mentioned below which may be present in the water phase and / or the oil phase.
Vorteilhafte bei Raumtemperatur flüssige UV-Filtersubstanzen im Sinne der vorliegenden Erfindung sind Homomenthylsalicylat (INCI: Homosalate), 2-Ethylhexyl-2-hydroxybenzoat (2- Ethylhexylsalicylat, Octylsalicylat, INCI: Octyl Salicylate), 2-Ethylhexyl-2-cyano-3,3-diphenyl- acrylat (INCI: Octocrylene) und Ester der Zimtsäure, vorzugsweise 4-Methoxyzimtsäure(2- ethylhexyl)ester (2-Ethylhexyl-4-methoxycinnamat, INCI: Octyl Methoxycinnamate) und 4- Methoxyzimtsäureisopentylester (lsopentyl-4-methoxycinnamat, INCI: Isoamyl p-Meth- oxycinnamate), 3-(4-(2,2-bis Ethoxycarbonylvinyl)-phenoxy)propenyl)-methoxysiloxan / Dimethylsiloxan - Copolymer welches beispielsweise unter der Handelsbezeichnung Parsol® SLX bei Hoffmann La Roche erhältlich ist.Advantageous UV filter substances which are liquid at room temperature for the purposes of the present invention are homomenthyl salicylate (INCI: homosalates), 2-ethylhexyl 2-hydroxybenzoate (2-ethylhexyl salicylate, octyl salicylate, INCI: octyl salicylates), 2-ethylhexyl-2-cyano-3, 3-diphenyl acrylate (INCI: Octocrylene) and esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester (2-ethylhexyl-4-methoxycinnamate, INCI: octyl methoxycinnamate) and 4-methoxycinnamic acid isopentyl ester (isopentyl-4-methoxycinnamate, INCI: isoamyl p Methoxycinnamate), 3- (4- (2,2-bisethoxycarbonylvinyl) phenoxy) propenyl) methoxysiloxane / dimethylsiloxane copolymer, which is available, for example, under the trade name Parsol® SLX from Hoffmann La Roche.
Vorteilhafte UV-A-Filtersubstanzen im Sinne der vorliegenden Erfindung sind Dibenzoyl- methanderivate, insbesondere das 4-(tert.-Butyl)-4'-methoxydibenzoylmethan (CAS-Nr. 70356-09-1), welches von Givaudan unter der Marke Parsol® 1789 und von Merck unter der Handelsbezeichnung Eusolex® 9020 verkauft wird.Advantageous UV-A filter substances for the purposes of the present invention are dibenzoyl methane derivatives, in particular 4- (tert-butyl) -4'-methoxydibenzoylmethane (CAS No. 70356-09-1), which has been sold by Givaudan under the trademark Parsol ® 1789 and sold by Merck under the trade name Eusolex® 9020.
Weitere vorteilhafte UV-A-Filtersubstanzen im Sinne der vorliegenden Erfindung sind Hydroxybenzophenone, welche sich durch die folgende Strukturformel auszeichnen:Further advantageous UV-A filter substances in the context of the present invention are hydroxybenzophenones, which are distinguished by the following structural formula:
Figure imgf000012_0001
Figure imgf000012_0001
worinwherein
R1 und R2 unabhängig voneinander Wasserstoff, Ci-C2o-Alkyl, C3-Ci0-Cycloalkyl oder C3-Ci0- Cycloalkenyl bedeuten, wobei die Substituenten R1 und R2 gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, einen 5- oder 6-Ring bilden können und R3 einen CrC20-Alkyl Rest bedeutet.Cycloalkenyl, wherein the substituents R 1 and R 2 together with the nitrogen atom to which they - R 1 and R 2 are independently hydrogen, Ci-C 2 -alkyl, C 3 -C 0 cycloalkyl or C 3 -C 0 are bonded, can form a 5- or 6-membered ring and R 3 is a C 1 -C 20 -alkyl radical.
Ein besonders vorteilhaftes Hydroxybenzophenon im Sinne der vorliegenden Erfindung ist das 2-(4'-Diethylamino-21-hydoxybenzoyl)-benzoesäurehexylester (auch: Aminobenzo- phenon), welches sich durch folgende Struktur auszeichnet:
Figure imgf000013_0001
und unter dem Uvinul A Plus bei der Fa. BASF erhältlich ist.
A particularly advantageous hydroxybenzophenone in the context of the present invention is 2- (4'-diethylamino-2 1 -hydroxybenzoyl) -benzoic acid hexyl ester (also: aminobenzophenone), which has the following structure:
Figure imgf000013_0001
and Uvinul A Plus is available from BASF.
Vorteilhafte weitere UV-Filtersubstanzen im Sinne der vorliegenden Erfindung sind sulfo- nierte, wasserlösliche UV-Filter, wie z. B.:Advantageous further UV filter substances in the context of the present invention are sulfonated, water-soluble UV filters, such as. B .:
• Phenylen-1,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfonsäure und ihre Salze, besonders die entsprechenden Natrium-, Kalium- oder Triethanolammonium-Salze, insbesondere das Phenylen-1,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfonsäure-bis-natriumsalz mit der INCI-Bezeichnung Bisimidazylate (CAS-Nr.: 180898-37-7), welches beispielsweise unter der Handelsbezeichnung Neo Heliopan AP bei Haarmann & Reimer erhältlich ist;Phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and its salts, especially the corresponding sodium, potassium or triethanolammonium salts, especially the phenylene-1,4 bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt with the INCI name Bisimidazylate (CAS No .: 180898-37-7), which is available, for example, under the trade name Neo Heliopan AP is available from Haarmann &Reimer;
• Salze der 2-Phenylbenzimidazol-5-sulfonsäure, wie ihr Natrium-, Kalium- oder ihr Trietha- nolammonium-Salz sowie die Sulfonsäure selbst mit der INCI Bezeichnung Phe- nylbenzimidazole Sulfonsäure (CAS.-Nr. 27503-81-7), welches beispielsweise unter der Handelsbezeichnung Eusolex 232 bei Merck oder unter Neo Heliopan Hydro bei Haarmann & Reimer erhältlich ist;Salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or triethanolammonium salt, and the sulfonic acid itself with the INCI name phenylbenzimidazole sulfonic acid (CAS No. 27503-81-7), which is available, for example, under the trade name Eusolex 232 from Merck or under Neo Heliopan Hydro from Haarmann &Reimer;
• 1 ,4-di(2-oxo-10-Sulfo-3-bomylidenmethyl)-Benzol (auch: 3,3'-(1 ,4-Phenylendimethylene)- bis-(7,7-dimethyl-2-oxo-bicyclo-[2.2.1]hept-1-ylmethan Sulfonsäure) und dessen Salze (besonders die entprechenden 10-Sulfato-verbindungen, insbesondere das entspre¬ chende Natrium-, Kalium- oder Triethanolammonium-Salz), das auch als Benzol-1 ,4-di(2- oxo-3-bomylidenmethyl-10-sulfonsäure) bezeichnet wird. Benzol-1,4-di(2-oxo-3-bomyli- denmethyl-10-sulfonsäure) hat die INCI-Bezeichnung Terephtalidene Dicampher Sulfonsäure (CAS.-Nr.: 90457-82-2) und ist beispielsweise unter dem Handelsnamen Mexoryl SX von der Fa. Chimex erhältlich;1, 4-di (2-oxo-10-sulfo-3-bomylidenemethyl) benzene (also: 3,3 '- (1,4-phenylenedimethylene) bis (7,7-dimethyl-2-oxo) bicyclo [2.2.1] hept-1-ylmethane sulfonic acid) and its salts (especially the corresponding 10-sulfato compounds, in particular the corresponding sodium, potassium or triethanolammonium salt), which is also known as benzene-1, Benzo-1,4-di (2-oxo-3-bomylidenemethyl-10-sulfonic acid) has the INCI name Terephtalidene Dicampher sulfonic acid ( CAS No .: 90457-82-2) and is available, for example, under the trade name Mexoryl SX from Chimex;
• Sulfonsäure-Derivate des 3-Benzylidencamphers, wie z. B. 4-(2-Oxo-3-bomylidenmethyl)- benzolsulfonsäure, 2-Methyl-5-(2-oxo-3-bomylidenmethyl)sulfonsäure und deren Salze.Sulfonic acid derivatives of 3-Benzylidencamphers, such as. B. 4- (2-oxo-3-bomylidenemethyl) - benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bomylidenemethyl) sulfonic acid and salts thereof.
Vorteilhafte UV-Filtersubstanzen im Sinne der vorliegenden Erfindung sind ferner soge¬ nannte Breitbandfilter, d.h. Filtersubstanzen, die sowohl UV-A- als auch UV-B-Strahlung ab¬ sorbieren. Ein vorteilhafter Breitbandfilter im Sinne der vorliegenden Erfindung ist auch das 2,2'-Me- thylen-bis-(6-(2H-benzotriazol-2-yl)-4-(1 ,1,3,3-tetramethylbutyl)-phenol), welches unter der Handelsbezeichnung Tinosorb® M bei der CIBA-Chemikalien GmbH erhältlich ist.Advantageous UV filter substances for the purposes of the present invention are also so-called broadband filters, ie filter substances which absorb both UV-A and UV-B radiation. An advantageous broadband filter for the purposes of the present invention is also the 2,2'-methyl-bis (6- (2H-benzotriazol-2-yl) -4- (1, 1,3,3-tetramethylbutyl) phenol ), which is available under the trade name Tinosorb® M from CIBA-Chemikalien GmbH.
Vorteilhafter Breitbandfilter im Sinne der vorliegenden Erfindung ist ferner das 2-(2H-benzo- triazol^-ylH-methyl-e-P-methyl-S-ti.S.S.S-tetramethyl-i-^trimethylsilyOoxyldisiloxa- nyl]propyl]-phenol (CAS-Nr.: 155633-54-8) mit der INCI-Bezeichnung Drometrizole Trisilo- xane.Another advantageous broadband filter in the context of the present invention is the 2- (2H-benzotriazole) -ylH-methyl-eP-methyl-S-ti.SSS-tetramethyl-i-trimethylsilyoxyldisiloxanyl] propyl] -phenol (CAS). No .: 155633-54-8) with the INCI name Drometrizole Trisiloxane.
Die weiteren UV-Filtersubstanzen können öllöslich oder wasserlöslich sein. Vorteilhafte öllösliche Filtersubstanzen sind z. B.:The other UV filter substances can be oil-soluble or water-soluble. Advantageous oil-soluble filter substances are z. B .:
• 3-Benzylidencampher-Derivate, vorzugsweise 3-(4-Methylbenzyliden)campher, 3-Benzyli- dencampher;3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3-benzylidene camphor;
• 4-Aminobenzoesäure-Derivate, vorzugsweise 4-(Dimethylamino)-benzoesäure(2-ethylhe- xyl)ester, 4-(Dimethylamino)benzoesäureamylester;4-aminobenzoic acid derivatives, preferably (2-ethylhexyl) 4- (dimethylamino) benzoate, 4- (dimethylamino) benzoic acid amyl ester;
• Ester der Benzalmalonsäure, vorzugsweise 4-Methoxybenzalmalonsäuredi(2-ethylhexyl)- ester;Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzalmalonate;
• Dioctylbutylamidotriazon (INCI: Diethylhexyl Butamido Triazone), welches unter der Han¬ delsbezeichnung UVASORB HEB bei Sigma 3V erhältlich ist; • Ester der Zimtsäure, vorzugsweise 4-Methoxyzimtsäure(2-ethylhexyl)ester, 4-Methoxy- zimtsäureisopentylester;Dioctylbutylamidotriazone (INCI: diethylhexyl butamido triazone), which is available under the trade name UVASORB HEB from Sigma 3V; Esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-methoxycinnamic acid isopentyl ester;
• Derivate des Benzophenons, vorzugsweise 2-Hydroxy-4-methoxybenzophenon, 2- Hydroxy-4-methoxy-4'-methylbenzophenon, 2,2'-Dihydroxy-4-methoxybenzophenon sowieDerivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone and
• an Polymere gebundene UV-Filter, • Homomenthylsalicylat (INCI: Homosalate) und• polymer-bound UV filters, • homomenthyl salicylate (INCI: homosalates) and
• 2-Ethylhexyl-2-hydroxybenzoat (2-Ethylhexylsalicylat, Octylsalicylat, INCI: Octyl Salicy- late).• 2-ethylhexyl 2-hydroxybenzoate (2-ethylhexyl salicylate, octyl salicylate, INCI: octyl salicylate).
Besonders vorteilhafte UV-Filtersubstanzen sind: • Phenylen-1,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfonsäure-bis-natriumsalz (INCI:Particularly advantageous UV filter substances are: phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt (INCI:
Bisimidazylate, Handelsname: Neoheliopan AP),Bisimidazylate, trade name: Neoheliopan AP),
• Dioctylbutylamidotriazon (INCI: Diethylhexyl Butamido Triazone, Handelsname: Uvasorb HEB),Dioctylbutylamidotriazone (INCI: diethylhexyl butamido triazone, trade name: Uvasorb HEB),
• 2-(4'-Diethylamino-21-hydoxybenzoyl)-benzoesäurehexylester (auch: Aminobenzophenon) (INCI: Diethylamino Hydroxybenzoyl Hexyl Benzoat, Handelsname: Uvinul A plus), • (3Z)-1 ,7,7-trinnethyl-3-(4-nnethylbenzylidene)bicyclo[2.2.1]heptan-2-one (INCI: 4-Methyl- benzylidene Campher, Handelsname: Eusolex 6300),• 2- (4'-diethylamino-2 1 -hydroxybenzoyl) -benzoic acid hexyl ester (also: aminobenzophenone) (INCI: diethylamino hydroxybenzoyl hexyl benzoate, trade name: Uvinul A plus), (3Z) -1,7,7-trimethyl-3- (4-niethylbenzylidene) bicyclo [2.2.1] heptan-2-one (INCI: 4-methylbenzylidenes camphor, trade name: Eusolex 6300),
• 2-Ethylhexyl-2-cyano-3,3-diphenylacrylat (INCI: Octocrylene, Handelsname: Uvinul N- 539), • Benzol-1,4-di(2-oxo-3-bomylidenmethyl-10-sulfonsäure) (INCI: Terephtalidene Dicampher Sulfonsäure, Handelsname: Mexoryl SX),2-ethylhexyl-2-cyano-3,3-diphenylacrylate (INCI: Octocrylene, trade name: Uvinul N-539), benzene-1,4-di (2-oxo-3-bomylidenemethyl-10-sulfonic acid) (INCI : Terephtalidene Dicampher sulfonic acid, trade name: Mexoryl SX),
• 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1 ,3,3,3-tetramethyl-i -[(trimethyl- silyl)oxy]disiloxanyl]propyl]-phenol (INCI: Drometrizole Trisiloxane, Handelsname: Mexoryl XL). 2,4-bis-[5-1(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)-imino]-6-(2-ethylhexyl)-imino- 1 ,3,5-triazin mit der (CAS Nr. 288254-16-0, erhältlich bei 3V Sigma unter der2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1,3,3,3-tetramethyl-i - [(trimethylsilyl) oxy] disiloxanyl] propyl ] -phenol (INCI: Drometrizole Trisiloxane, trade name: Mexoryl XL). 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) -imino] -6- (2-ethylhexyl) -imino-1,3,5-triazine having the (CAS No 288254-16-0, available at 3V Sigma under the
Handelsbezeichnung Uvasorb® K2A) in gelöster Form.Trade name Uvasorb® K2A) in dissolved form.
Ganz besonders vorteilhafte UV-Filtersubstanzen im Sinne der vorliegenden Erfindung sind:Very particularly advantageous UV filter substances in the context of the present invention are:
• 2-Ethylhexyl-4-methoxycinnamat (INCI: Octyl Methoxycinnamat, Handelsname: Parsol MCX),2-ethylhexyl-4-methoxycinnamate (INCI: octyl methoxycinnamate, trade name: Parsol MCX),
• 4-(tert.-Butyl)-4'-methoxydibenzoylmethan (INCI: Butylmethoxydibenzoylmethan, Han¬ delsname: Parsol 1789),4- (tert-butyl) -4'-methoxydibenzoylmethane (INCI: butylmethoxydibenzoylmethane, tradename: Parsol 1789),
• Salze der 2-Phenylbenzimidazol-5-sulfonsäure, wie ihr Natrium-, Kalium- oder ihr Trietha- nolammonium-Salz sowie die Sulfonsäure selbst mit der INCI Bezeichnung Phe- nylbenzimidazole Sulfonsäure (Handelsname: Eusolex 232).Salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or triethanolammonium salt, and also the sulfonic acid itself with the INCI name phenylbenzimidazole sulfonic acid (trade name: Eusolex 232).
• Phenylen-1,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfonsäure und ihre Salze, besonders die entsprechenden Natrium-, Kalium- oder Triethanolammonium-Salze, insbesondere das Phenylen-1 ,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfonsäure-bis-natriumsalz mit der INCI-Bezeichnung Bisimidazylate (CAS-Nr.: 180898-37-7), welches beispielsweise unter der Handelsbezeichnung Neo Heliopan AP bei Haarmann & Reimer erhältlich ist;Phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and its salts, especially the corresponding sodium, potassium or triethanolammonium salts, in particular phenylene-1,4 bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt with the INCI name Bisimidazylate (CAS No .: 180898-37-7), which is available, for example, under the trade name Neo Heliopan AP is available from Haarmann &Reimer;
• 2,4-Bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1 ,3,5-triazin (INCI: Aniso Triazin, erhältlich unter dem Handelsnamen Tinosorb S) in gelöster Form,2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine (INCI: aniso triazine, available at the trade name Tinosorb S) in dissolved form,
• 4,4',4"-(1 ,3,5-Triazin-2,4,6-triyltriimino)-tris-benzoesäure-tris(2-ethylhexylester) (auch: 2,4,6-Tris-[anilino-(p-carbo-2'-ethyl-1'-hexyloxy)]-1,3,5-triazin (INCI: Octyl Triazone), welches von der BASF Aktiengesellschaft unter der Warenbezeichnung UVINUL® T 150 vertrieben wird) in gelöster Form,• 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester) (also: 2,4,6-tris [anilino - (p-carbo-2'-ethyl-1'-hexyloxy)] - 1,3,5-triazine (INCI: Octyl Triazone), which is marketed by BASF Aktiengesellschaft under the trade name UVINUL® T 150) in dissolved form .
• Dioctylbutylamidotriazon (INCI: Diethylhexyl Butamido Triazone, Handelsname: Uvasorb HEB). Diese zusätzlichen UV-Filtersubstanzen können erfindungsgemäß vorteilhaft in einer Gesamtkonzentration von 0,01 bis 20 Gewichts-% und erfindungsgemäß bevorzugt in einer Gesamtkonzentration von 0,5 bis 10 Gewichts-%, jeweils bezogen auf das Gesamtgewicht der wasserhaltigen Zubereitung in dieser enthalten sein.Dioctylbutylamidotriazone (INCI: diethylhexyl butamido triazone, trade name: Uvasorb HEB). According to the invention, these additional UV filter substances can advantageously be contained in a total concentration of from 0.01 to 20% by weight and, preferably, in a total concentration of from 0.5 to 10% by weight, based in each case on the total weight of the aqueous preparation.
Die ölphase der erfindungsgemäßen Zubereitungen wird vorteilhaft gewählt aus der Gruppe der polaren Lipide mit einer Polarität < 35 mN/m Besonders vorteilhafte Lipide im Sinne der vorliegenden Erfindung sind alle nativen Lipide, wie z. B. Olivenöl, Sonnenblumenöl, Sojaöl, Erdnußöl, Rapsöl, Mandelöl, Palmöl, Kokosöl, Rizinusöl, Weizenkeimöl, Traubenkemöl, Distelöl, Nachtkerzenöl, Macadamianußöl, Maiskeimöl, Avocadoöl und dergleichen sowie die im folgenden aufgelisteten. The oil phase of the preparations according to the invention is advantageously selected from the group of polar lipids having a polarity <35 mN / m. Particularly advantageous lipids in the context of the present invention are all native lipids, such as. As olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, castor oil, wheat germ oil, grape seed oil, thistle oil, evening primrose oil, macadamia nut oil, corn oil, avocado oil and the like, and those listed below.
Figure imgf000017_0001
Figure imgf000017_0001
Von den Kohlenwasserstoffen sind insbesondere Paraffinöl sowie weitere hydrierte PoIy- olefine wie hydriertes Polyisobutene, Squalan und Squalen vorteilhaft im Sinne der vor- liegenden Erfindung zu verwenden. Die Gehalt der Lipide wird vorteilhaft kleiner als 50 Gew.-% gewählt, bevorzugt zwischen 1 und 40 Gew.-%, insbesondere bevorzugt zwischen 5 und 20 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Wasser enthaltenden Zubereitung.Of the hydrocarbons, in particular paraffin oil and further hydrogenated poly olefins such as hydrogenated polyisobutenes, squalane and squalene are to be used advantageously in the context of the present invention. The content of the lipids is advantageously less than 50% by weight, preferably between 1 and 40% by weight, particularly preferably between 5 and 20% by weight, in each case based on the total weight of the water-containing preparation.
Falls die Lipidphase öllösliche UV-Filtersubstanzen enthält, ist es vorteilhaft den Gehalt der Lipidphase kleiner als 80 Gew.-% zu wählen, bevorzugt zwischen 1 und 40 Gew.-%, insbesondere bevorzugt zwischen 5 und 30 Gew.-%, jeweils bezogen auf das Gesamt¬ gewicht der wasserhaltigen Zubereitung.If the lipid phase contains oil-soluble UV filter substances, it is advantageous to choose the content of the lipid phase less than 80% by weight, preferably between 1 and 40% by weight, particularly preferably between 5 and 30% by weight, based in each case on the total weight of the water-containing preparation.
Es kann gegebenenfalls vorteilhaft sein, wenngleich es nicht zwingend ist, wenn die ölphase der Zubereitungen im Sinne der vorliegenden Erfindung auch unpolare Lipide enthält.It may optionally be advantageous, although it is not mandatory, if the oil phase of the preparations according to the present invention also contains non-polar lipids.
Die Wasserphase der erfindungsgemäßen Zubereitungen kann vorteilhaft übliche kosmeti¬ sche Hilfsstoffe enthalten, wie beispielsweise Alkohole, insbesondere solche niedriger C- Zahl, vorzugsweise Ethanol und/oder Isopropanol, Diole oder Polyole niedriger C-Zahl sowie deren Ether, vorzugsweise Propylenglykol, Glycerin, Ethylenglykol, Propandiol, Ethylengly- kolmonoethyl- oder -monobutylether, Propylenglykol monomethyl, -monoethyl- oder -monobu- tylether, Diethylenglykolmonomethyl- oder -monoethylether und analoge Produkte, Polymere, Schaumstabilisatoren, Elektrolyte, Selbstbräuner sowie insbesondere ein oder mehrere Verdickungsmittel, welches oder welche vorteilhaft gewählt werden können aus der Gruppe Siliciumdioxid, Aluminiumsilikate, Polysaccharide bzw. deren Derivate, z. B. Hy- aluronsäure, Xanthangummi, Hydroxypropylmethylcellulose, besonders vorteilhaft aus der Gruppe der Polyacrylate, bevorzugt ein Polyacrylat aus der Gruppe der sogenannten Carbopole, beispielsweise Carbopole der Typen 980, 981 , 1382, 2984, 5984, jeweils einzeln oder in Kombination.The aqueous phase of the preparations according to the invention may advantageously comprise customary cosmetic adjuvants, for example alcohols, in particular those of low C number, preferably ethanol and / or isopropanol, diols or polyols of low C number and their ethers, preferably propylene glycol, glycerol, ethylene glycol, Propanediol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous products, polymers, foam stabilizers, electrolytes, self-tanning agents and in particular one or more thickeners, which are advantageously chosen can be selected from the group silicon dioxide, aluminum silicates, polysaccharides or their derivatives, for. As hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, particularly advantageous from the group of polyacrylates, preferably a polyacrylate from the group of so-called carbopols, for example Carbopols types 980, 981, 1382, 2984, 5984, each individually or in combination.
Die erfindungsgemäße Zubereitung kann erfindungsgemäß ein oder mehrere Emulgatoren enthalten, wobei für die für kosmetische Emulsionen bekannten O/W-Emulgatoren eingesetzt werden können.According to the invention, the preparation according to the invention may comprise one or more emulsifiers, it being possible to use for the O / W emulsifiers known for cosmetic emulsions.
Erfindungsgemäß bevorzugt sind jedoch O/W-Emulsionen, die Feststoff-stabilisiert sind und keine O/W-Emulgatoren enthalten.According to the invention, however, preferred are O / W emulsions which are solids-stabilized and contain no O / W emulsifiers.
Die erfindungsgemäßen kosmetischen Zubereitungen können wie üblich zusammengesetzt sein. Besonders vorteilhaft im Sinne der vorliegenden Erfindung sind Zubereitungen zur Pflege der Haut: sie können dem kosmetischen Lichtschutz, ferner zur Reinigung oder Pflege der Haut und/oder der Haare und als Schminkprodukt in der dekorativen Kosmetik dienen. Eine weitere vorteilhafte Ausführungsform der vorliegenden Erfindung besteht in Af- ter-Sun-Produkten.The cosmetic preparations according to the invention can be composed as usual. Particularly advantageous in the context of the present invention are preparations for Care of the skin: they may be used for cosmetic sunscreen, for cleaning or care of the skin and / or hair and as a make-up product in decorative cosmetics. A further advantageous embodiment of the present invention is Af ter-Sun products.
Entsprechend ihrem Aufbau können wasserhaltige kosmetische Zusammensetzungen im Sinne der vorliegenden Erfindung, beispielsweise verwendet werden als Hautschutzcreme, Tages- oder Nachtcreme usw. Es ist gegebenenfalls möglich und vorteilhaft, die erfin¬ dungsgemäßen Zusammensetzungen als Grundlage für pharmazeutische Formulierungen zu verwenden.According to their structure, water-containing cosmetic compositions in the sense of the present invention can be used, for example, as skin protection cream, day cream or night cream, etc. It may be possible and advantageous to use the compositions according to the invention as the basis for pharmaceutical formulations.
Es ist vorteilhaft im Sinne der vorliegenden Erfindung, wenn die wasserhaltigen erfindungsgemäßen Zubereitungen als Sonnenschutzmittel verwendet werden. Auch sind die wasserhaltigen erfindungsgemäßen Zubereitungen erfindungsgemäß verwendbar als Zubereitungen, deren hauptsächlicher Zweck nicht der Schutz vor Sonnenlicht ist, die aber dennoch einen Gehalt an UV-Schutzsubstanzen enthalten. So werden z. B. in Tagescremes oder Makeup-Produkten gewöhnlich UV-A- bzw. UV-B-Filtersubstanzen eingearbeitet. Auch stellen UV-Schutzsubstanzen, ebenso wie Antioxidantien und, gewünschtenfalls, Kon¬ servierungsstoffe, einen wirksamen Schutz der Zubereitungen selbst gegen Verderb dar. Günstig sind ferner kosmetische Zubereitungen, die in der Form eines Sonnenschutzmittels vorliegen.It is advantageous for the purposes of the present invention if the water-containing preparations according to the invention are used as sunscreen agents. Also, the aqueous preparations according to the invention can be used according to the invention as preparations whose main purpose is not the protection from sunlight but which nevertheless contain a content of UV protective substances. So z. B. in day creams or makeup products usually incorporated UV-A or UV-B filter substances. UV-protective substances, as well as antioxidants and, if desired, preservatives, also represent an effective protection of the preparations themselves against spoilage. Cosmetic preparations which are in the form of a sunscreen agent are also favorable.
Zur Anwendung werden die wasserhaltigen, erfindungsgemäßen kosmetischen Zube¬ reitungen in der für Kosmetika üblichen Weise auf die Haut und/oder die Haare in ausrei- chender Menge aufgebracht.For use, the aqueous cosmetic preparations according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics.
Die kosmetischen Zubereitungen gemäß der Erfindung können kosmetische Hilfsstoffe enthalten, wie sie üblicherweise in solchen Zubereitungen verwendet werden, z. B. Konservierungsmittel, Konservierungshelfer, Komplexbildner, Bakterizide, Parfüme, Substanzen zum Verhindern oder Steigern des Schäumens, Farbstoffe, Pigmente, die eine färbende Wirkung haben, Verdickungsmittel, anfeuchtende und/oder feuchhaltende Substanzen, Füllstoffe, die das Hautgefühl verbessern, Fette, öle, Wachse oder andere übliche Bestandteile einer kosmetischen Formulierung wie Alkohole, Polyole, Polymere, Schaumstabilisatoren, Elektrolyte, organische Lösungsmittel oder Silikonderivate. Vorteilhafte Konservierungsmittel im Sinne der vorliegenden Erfindung sind beispielsweise Formaldehydabspalter (wie z. B. DMDM Hydantoin, welches beispielsweise unter der Handelsbezeichnung Glydant ™ von der Fa. Lonza erhältlich ist), lodopropylbutylcarbamate (z. B. die unter den Handelsbezeichnungen Glycacil-L, Glycacil-S von der Fa. Lonza erhältlichen und/oder Dekaben LMB von Jan Dekker), Parabene (d. h. p-Hydroxy- benzoesäurealkylester, wie Methyl-, Ethyl-, Propyl- und/oder Butylparaben), Phenoxyethanol, Ethanol, Benzoesäure und dergleichen mehr. Üblicherweise umfaßt das Konser¬ vierungssystem erfindungsgemäß ferner vorteilhaft auch Konservierungshelfer, wie bei¬ spielsweise Ethylhexylglycerin, Glycine Soja etc.The cosmetic preparations according to the invention may contain cosmetic adjuvants, such as are commonly used in such preparations, for. Preservatives, preservatives, complexing agents, bactericides, perfumes, substances for preventing or increasing foaming, dyes, pigments which have a coloring effect, thickeners, moisturizing and / or moisturizing substances, fillers which improve the feel on the skin, fats, oils, Waxes or other common ingredients of a cosmetic formulation such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives. Advantageous preservatives for the purposes of the present invention are, for example, formaldehyde releasers (such as, for example, DMDM hydantoin, which is available under the trade name Glydant ™ from Lonza), iodopropyl butylcarbamates (for example those sold under the trade names Glycacil-L, Glycacil -S. From the company. Lonza available and / or Dekaben LMB from Jan Dekker), parabens (ie p-hydroxy-benzoic acid alkyl esters, such as methyl, ethyl, propyl and / or butylparaben), phenoxyethanol, ethanol, benzoic acid and the like , According to the invention, the preserving system also advantageously also comprises preserving aids, such as, for example, ethylhexylglycerol, glycine soya, etc.
Vorteilhafte Komplexbildner im Sinne der vorliegenden Erfindung sind beispielsweise EDTA, [S,S]-Ethylendiamindisuccinat (EDDS), welches beispielsweise unter der Handels¬ bezeichnung Octaquest von der Fa. Octel erhältlich ist, Pentanatrium-Ethylendiamin- tetramethylenphosphonat, welches z. B. unter dem Handelsnamen Dequest 2046 von der Fa. Monsanto erhältlich ist und/oder Iminodibersteinsäure, welche u. a. von der Fa. Bayer AG unter den Handelsnamen Iminodisuccinat VP OC 370 (ca. 30% ige Lösung) und Baypure CX 100 fest erhältlich ist.Advantageous complexing agents for the purposes of the present invention are, for example, EDTA, [S, S] -ethylenediamine disuccinate (EDDS), which is obtainable, for example, under the trade name Octaquest from the company Octel, pentasodium ethylenediamine tetramethylenephosphonate, which, for example, B. under the trade name Dequest 2046 from the company. Monsanto is available and / or iminodisuccinic which u. a. Bayer AG under the trade names Iminodisuccinat VP OC 370 (about 30% solution) and Baypure CX 100 is permanently available.
Besonders vorteilhafte Zubereitungen werden ferner erhalten, wenn als Zusatz- oder Wirk- Stoffe Antioxidantien eingesetzt werden. Erfindungsgemäß enthalten die Zubereitungen vorteilhaft eines oder mehrere Antioxidantien. Als günstige, aber dennoch fakultativ zu ver¬ wendende Antioxidantien können alle für kosmetische Anwendungen geeigneten oder gebräuchlichen Antioxidantien verwendet werden.Particularly advantageous preparations are also obtained when antioxidants are used as additives or active substances. According to the invention, the preparations advantageously contain one or more antioxidants. All antioxidants which are suitable or customary for cosmetic applications can be used as inexpensive but nevertheless optional antioxidants.
Besonders vorteilhaft im Sinne der vorliegenden Erfindung können wasserlösliche Antioxi¬ dantien eingesetzt werden, wie beispielsweise Vitamine, z. B. Ascorbinsäure und deren Derivate.Particularly advantageous in the context of the present invention, water-soluble Antioxi¬ dantien can be used, such as vitamins, eg. As ascorbic acid and its derivatives.
Bevorzugte Antioxidantien sind ferner Vitamin E und dessen Derivate sowie Vitamin A und dessen Derivate.Further preferred antioxidants are vitamin E and its derivatives as well as vitamin A and its derivatives.
Die Menge der Antioxidantien (eine oder mehrere Verbindungen) in den Zubereitungen be¬ trägt vorzugsweise 0,001 bis 30 Gew.-%, besonders bevorzugt 0,05 bis 20 Gew.-%, insbe¬ sondere 0,1 bis 10 Gew.-%, bezogen auf das Gesamtgewicht der wasserhaltigen Zu- bereitung. Sofern Vitamin E und/oder dessen Derivate das oder die Antioxidantien darstellen, ist vor¬ teilhaft, deren jeweilige Konzentrationen aus dem Bereich von 0,001 bis 10 Gew.-%, bezo¬ gen auf das Gesamtgewicht der wasserhaltigen Formulierung, zu wählen.The amount of antioxidants (one or more compounds) in the preparations is preferably from 0.001 to 30% by weight, particularly preferably from 0.05 to 20% by weight, in particular from 0.1 to 10% by weight, based on the total weight of the hydrous preparation. If vitamin E and / or its derivatives are the antioxidant (s), it is advantageous to choose their respective concentrations from the range from 0.001 to 10% by weight, based on the total weight of the aqueous formulation.
Sofern Vitamin A bzw. Vitamin-A-Derivate, bzw. Carotine bzw. deren Derivate das oder die Antioxidantien darstellen, ist vorteilhaft, deren jeweilige Konzentrationen aus dem Bereich von 0,001 bis 10 Gew.-%, bezogen auf das Gesamtgewicht der wasserhaltigen Formulie¬ rung, zu wählen.If vitamin A or vitamin A derivatives, or carotenes or derivatives thereof, are the antioxidant (s), it is advantageous if their respective concentrations are in the range from 0.001 to 10% by weight, based on the total weight of the aqueous formulation to choose.
Es ist insbesondere vorteilhaft, wenn die kosmetischen Zubereitungen gemäß der vorlie¬ genden Erfindung kosmetische Wirkstoffe enthalten, wobei bevorzugte Wirkstoffe Antioxidantien sind, welche die Haut vor oxidativer Beanspruchung schützen können.It is particularly advantageous if the cosmetic preparations according to the present invention contain cosmetic active ingredients, preferred active substances being antioxidants which can protect the skin against oxidative stress.
Weitere vorteilhafte Wirkstoffe im Sinne der vorliegenden Erfindung sind natürliche Wirk¬ stoffe und/oder deren Derivate, wie z. B. alpha-Liponsäure, Phytoen, Niacinamid, Panthenol, D-Biotin, Coenzym Q10, alpha-Glucosylrutin, Camitin, Camosin, natürliche und/oder synthetische Isoflavonoide, Kreatin, Kreatinin, Taurin und/oder ß-Alanin sowie 8-Hexadecen- 1 ,16-dicarbonsäure (Dioic acid, CAS-Nummer 20701-68-2; vorläufige INCI-Bezeichnung Octadecendioic acid) und/oder Licochalcon A.Further advantageous active ingredients in the context of the present invention are natural active substances and / or their derivatives, such as. Alpha-lipoic acid, phytoene, niacinamide, panthenol, D-biotin, coenzyme Q10, alpha-glucosylrutin, camitine, camosine, natural and / or synthetic isoflavonoids, creatine, creatinine, taurine and / or beta-alanine, and 8-hexadecene. 1, 16-dicarboxylic acid (dioic acid, CAS number 20701-68-2, provisional INCI name octadecenedioic acid) and / or licochalcone A.
Licochalcon kann vorteilhaft auch als Bestandteil von pflanzlichen Extrakten, insbesondere von wäßrigen Radix Glycyrrhizae inflatae, eingesetzt werden.Licochalcone can also be used advantageously as a constituent of herbal extracts, in particular of aqueous radix Glycyrrhizae inflatae.
Es ist erfindungsgemäß vorteilhaft, wenn die kosmetischen Zubereitungen 0,001 bis 10 Gew.-%, insbesondere 0,05 bis 5 Gew.-%, ganz besonders 0,01 bis 2 Gew.-% an einem Extrakt aus Radix Glycyrrhizae inflatae enthalten, jeweils bezogen auf das Gesamtgewicht der Zubereitung.It is advantageous according to the invention if the cosmetic preparations contain 0.001 to 10% by weight, in particular 0.05 to 5% by weight, very particularly 0.01 to 2% by weight of an extract of Radix Glycyrrhizae inflatae, in each case on the total weight of the preparation.
Ganz besonders vorteilhaft ist es, von einem Extrakt auszugehen, der unter der Bezeichnung Polyol Soluble Licorice Extract PU (INCI-Bezeichnung Glycyrrhiza Inflata) von der Firma Maruzen zu erhalten ist. Der Extrakt aus Radix Glycyrrhizae inflatae enthält einen Anteil von ca. 25 % Licochalcone A.It is particularly advantageous to start from an extract which is obtainable from Maruzen under the name Polyol Soluble Licorice Extract PU (INCI name Glycyrrhiza Inflata). The extract of Radix Glycyrrhizae inflatae contains about 25% licochalcone A.
Erfindungsgemäße Rezepturen, welche z. B. bekannte Antifaltenwirkstoffe wie Flavon- glycoside (insbesondere α-Glycosylrutin), Coenzym Q10, Vitamin E und/oder Derivate und dergleichen enthalten, eignen sich insbesondere vorteilhaft zum Schutz vor ästhetisch unattraktiven Hautveränderungen, wie sie z. B. bei der Hautalterung auftreten (wie beispielsweise Trockenheit, Rauhigkeit und Ausbildung von Trockenheitsfältchen, Juckreiz, verminderte Rückfettung (z. B. nach dem Waschen), sichtbare Gefäßerweiterungen (Teleangiektasien, Cuperosis), Schlaffheit und Ausbildung von Falten und Fältchen, lokale Hyper-, Hypo- und Fehlpigmentierungen (z. B. Altersflecken), vergrößerte Anfälligkeit gegenüber mechanischem Stress (z. B. Rissigkeit) und dergleichen). Weiterhin vorteilhaft eignen sie sich gegen das Erscheinungsbild der trockenen bzw. rauhen Haut.Inventive formulations which z. B. known anti-wrinkle active ingredients such as flavone glycosides (especially α-glycosylrutin), coenzyme Q10, vitamin E and / or derivatives and the like, are particularly advantageous for protection against aesthetically unattractive skin lesions, as z. Skin aging (such as dryness, roughness, dryness wrinkles, itching, decreased refatting (eg, after washing), visible vascular dilation (telangiectasia, cuperosis), slackness and wrinkle and wrinkle formation, localized hypersensitivity). , Hypo and false pigmentation (eg, age spots), increased susceptibility to mechanical stress (eg, cracking), and the like). Furthermore, they are advantageously suitable against the appearance of dry or rough skin.
Die Zubereitungen gemäß der vorliegenden Erfindung können ferner vorteilhaft auch Selbst¬ bräunungssubstanzen enthalten, wie beispielsweise Dihydroxyaceton und/oder Melaninderivate in Konzentrationen von 1 Gew.-% bis zu 8 Gew.-%, bezogen auf das Gesamtgewicht der wasserhaltigen Zubereitung.The preparations according to the present invention can also advantageously contain self-tanning substances, for example dihydroxyacetone and / or melanin derivatives in concentrations of from 1% by weight to 8% by weight, based on the total weight of the aqueous preparation.
Ferner vorteilhaft können die Zubereitungen gemäß der vorliegenden Erfindung auch Repellenten zum Schutz vor Mücken, Zecken und Spinnen und dergleichen enthalten. Vorteilhaft sind z. B. N,N-Diethyl-3-methylbenzamid (Handelsbezeichnung: Meta-delphene, „DEET"), Dimethylphtalat (Handelsbezeichnung: Palatinol M, DMP), 1-Piperidincarbonsäure- 2-(2-hydroxyethyl)-1-methylpropylester sowie insbesondere 3-(N-n-Butyl-N-acetyl-amino)- propionsäureethylester (unter dem Handelsnamen Insekt Repellent® 3535 bei der Fa. Merck erhältlich). Die Repellenten können sowohl einzeln als auch in Kombination eingesetzt werden.Further advantageously, the preparations according to the present invention may also contain repellents for protection against mosquitoes, ticks and spiders and the like. Advantageous z. N, N-diethyl-3-methylbenzamide (trade name: meta-delphene, "DEET"), dimethyl phthalate (trade name: palatinol M, DMP), 1-piperidinecarboxylic acid 2- (2-hydroxyethyl) -1-methylpropyl ester, and especially 3- (Nn-butyl-N-acetyl-amino) -propionic acid ethyl ester (available from Merck under the tradename Insekt Repellent® 3535.) The repellents can be used either individually or in combination.
Als Moisturizer werden Stoffe oder Stoffgemische bezeichnet, welche kosmetischen Zubereitungen die Eigenschaft verleihen, nach dem Auftragen bzw. Verteilen auf der Hautoberfläche die Feuchtigkeitsabgabe der Homschicht (auch transepidermal water loss (TEWL) genannt) zu reduzieren und/oder die Hydratation der Homschicht positiv zu beeinflussen.Moisturizers are substances or mixtures of substances which give cosmetic preparations the property, after application or distribution on the skin surface, to reduce the moisture release of the hom layer (also called transepidermal water loss (TEWL)) and / or to positively influence the hydration of the initial layer ,
Vorteilhafte Moisturizer im Sinne der vorliegenden Erfindung sind beispielsweise Glycerin, Milchsäure und/oder Lactate, insbesondere Natriumlactat, Butylenglykol, Propylenglykol, Methylpropandiol, Biosaccaride Gum-1 , Glycine Soja, Ethylhexyloxyglycerin, Pyr- rolidoncarbonsäure und Harnstoff. Ferner ist es insbesondere von Vorteil, polymere Moisturizer aus der Gruppe der wasserlöslichen und/oder in Wasser quellbaren und/oder mit Hilfe von Wasser gelierbaren Polysaccharide zu verwenden. Insbesondere vorteilhaft sind beispielsweise Hyaluronsäure, Chitosan und/oder ein fucosereiches Polysaccharid, welches in den Chemical Abstracts unter der Registraturnummer 178463-23-5 abgelegt und z. B. unter der Bezeichnung Fucogel®1000 von der Gesellschaft SOLABIA S.A. erhältlich ist. Moisturizer können vorteilhaft auch als Antifaltenwirkstoffe zum Schutz kosmetischer Haut¬ veränderungen, wie sie z. B. bei der Hautalterung auftreten, verwendet werden.Advantageous moisturizers for the purposes of the present invention are, for example, glycerol, lactic acid and / or lactates, in particular sodium lactate, butylene glycol, propylene glycol, methylpropanediol, biosaccharide gum-1, glycine soya, ethylhexyloxyglycerol, pyrrolidonecarboxylic acid and urea. Furthermore, it is particularly advantageous to use polymeric moisturizers from the group of water-soluble and / or water-swellable and / or with To use the aid of water gellable polysaccharides. Hyaluronic acid, chitosan and / or a fucose-rich polysaccharide, for example, which are filed in the Chemical Abstracts under the registry number 178463-23-5 and z. B. under the name Fucogel®1000 of the company SOLABIA SA is available. Moisturizers may advantageously also be used as anti-wrinkle agents for protecting cosmetic skin changes, as described, for example, in US Pat. B. occur during skin aging, can be used.
Die erfindungsgemäßen kosmetischen Zubereitungen können ferner vorteilhaft, wenngleich nicht zwingend, Füllstoffe enthalten, welche z. B. die sensorischen und kosmetischen Eigenschaften der Formulierungen weiter verbessern und beispielsweise ein samtiges oder seidiges Hautgefühl hervorrufen oder verstärken. Vorteilhafte Füllstoffe im Sinne der vorliegenden Erfindung sind Stärke und Stärkederivate (wie z. B. Tapiocastärke, Distärkephosphat, Aluminium- bzw. Natrium-Stärke Octenylsuccinat und dergleichen), Pigmente, die weder hauptsächlich UV-Filter- noch färbende Wirkung haben (wie z. B. Bornitrid etc.) und/oder Aerosile® (CAS-Nr. 7631-86-9).The cosmetic preparations according to the invention may also advantageously, although not necessarily, contain fillers which are e.g. B. further improve the sensory and cosmetic properties of the formulations and, for example, cause or enhance a velvety or silky feel on the skin. Advantageous fillers for the purposes of the present invention are starch and starch derivatives (such as, for example, tapioca starch, distarch phosphate, aluminum or sodium starch, octenylsuccinate and the like), pigments which have neither chiefly UV filter nor coloring action (such as, for example, US Pat. B. boron nitride etc.) and / or Aerosils ® (CAS no. 7631-86-9).
Die nachfolgenden Beispiele sollen die vorliegende Erfindung verdeutlichen, ohne sie einzu¬ schränken. Alle Mengenangaben, Anteile und Prozentanteile sind, soweit nicht anders an¬ gegeben, auf das Gewicht und die Gesamtmenge bzw. auf das Gesamtgewicht der Zube- reitungen bezogen. The following examples are intended to illustrate the present invention without restricting it. All quantities, proportions and percentages are, unless stated otherwise, based on the weight and the total amount or on the total weight of the preparations.
BeispieleExamples
Emulsionszubereitungen nach Sprüh-/ Gefrier-/ oder Walzentrocknung:Emulsion preparations after spray / freeze / drum drying:
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001

Claims

Patentansprüche claims
1. Verfahren zur Herstellung einer kosmetischen Zubereitung, dadurch gekennzeichnet, dass eine O/W-Emulsion enthaltend a) eine wässrige Phase, b) eine ölphase, c) pigmentäre UV-Lichtschutzfilter und d) wasserlösliche Polymere, neben gegebenenfalls weiteren kosmetischen und/oder dermatologischen Wirk-, Hilfs¬ und Zusatzstoffen, durch Sprühtrocknung, Gefriertrocknung und/oder Walzentrocknung getrocknet wird.1. A process for the preparation of a cosmetic preparation, which comprises an O / W emulsion comprising a) an aqueous phase, b) an oil phase, c) pigmentary UV light protection filters and d) water-soluble polymers, optionally further cosmetic and / or dermatologischen Wirk-, Hilfs¬ and additives, by spray drying, freeze drying and / or drum drying is dried.
2. Kosmetische Zubereitung hergestellt nach einem Verfahren nach Anspruch 1.2. Cosmetic preparation prepared by a process according to claim 1.
3. Verfahren zur Herstellung einer kosmetischen Zubereitung, dadurch gekennzeichnet, dass eine O/W-Emulsion nach einem der Ansprüche 1 oder 2 in einer Mischungsvorrichtung mit wasserlöslichen und/oder leichtflüchtigen Wirk-, Hilfs- und/oder Zusatzstoffen vermischt wird.3. A process for the preparation of a cosmetic preparation, characterized in that an O / W emulsion according to any one of claims 1 or 2 in a mixing device with water-soluble and / or volatile active ingredients, auxiliaries and / or additives is mixed.
4. Zubereitung hergestellt nach einem Verfahren nach Anspruch 3.4. Preparation prepared by a process according to claim 3.
5. Zubereitung enthaltend eine O/W-Emulsion nach einem der Ansprüche 2 oder 4 sowie einen oder mehrere Granulier- und/oder Tablettenhilfsstoffe.5. A preparation comprising an O / W emulsion according to any one of claims 2 or 4 and one or more granulation and / or tablet excipients.
6. Verfahren zur Herstellung einer Zubereitung nach Anspruch 5, dadurch gekennzeichnet, dass eine O/W-Emulsion nach einem der Ansprüche 2 oder 4 mit einem oder mehreren6. A process for the preparation of a preparation according to claim 5, characterized in that an O / W emulsion according to one of claims 2 or 4 with one or more
Tablettenhilfsstoffen in einer Mischungsvorrichtung vermischt werden.Tablet excipients are mixed in a mixing device.
7. Zubereitung hergestellt nach einem Verfahren nach Anspruch 6.7. Preparation prepared by a process according to claim 6.
8. Verfahren zur Herstellung von Tabletten und/oder Granulaten, dadurch gekennzeichnet, dass eine Zubereitung nach Anspruch 7 in einer Presse zu einer oder mehreren Tabletten gepresst oder mittels geeigneter Granuliervorrichtungen granuliert werden.8. A process for the preparation of tablets and / or granules, characterized in that a preparation according to claim 7 pressed in a press to one or more tablets or granulated by means of suitable granulation.
9. Zubereitung hergestellt nach einem Verfahren nach Anspruch 8.9. Preparation prepared by a process according to claim 8.
10. Verfahren zur Herstellung einer kosmetische Formulierung dadurch gekennzeichnet, dass eine Zubereitung nach einem der Ansprüche 2, 4, 5, 7 und/oder 9 mit Wasser versetzt werden. 10. A process for the preparation of a cosmetic formulation, characterized in that a preparation according to any one of claims 2, 4, 5, 7 and / or 9 are mixed with water.
11. Kosmetische Formulierung hergestellt nach einem Verfahren nach Anspruch 10. 11. Cosmetic formulation prepared by a process according to claim 10.
12. Verfahren oder Zubereitung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, das als pigmentäre UV-Lichtschutzfilter eine oder mehrere Verbindungen gewählt aus der Gruppe der Verbindungen 2,4,6-Tris-(biphenyl)-1 ,3,5- triazin; 2,4,6-Tris-(terphenyl)-1 ,3,5-triazin. 12. A method or preparation according to any one of the preceding claims, characterized in that as pigmentary UV light protection filter one or more compounds selected from the group of compounds 2,4,6-tris (biphenyl) -1, 3,5-triazine; 2,4,6-tris- (terphenyl) -1, 3,5-triazine.
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