WO2004052328A2 - Emulsions stabilised by glycerophospholipids or sphingolipids for improving the appearance of the skin - Google Patents
Emulsions stabilised by glycerophospholipids or sphingolipids for improving the appearance of the skin Download PDFInfo
- Publication number
- WO2004052328A2 WO2004052328A2 PCT/EP2003/013391 EP0313391W WO2004052328A2 WO 2004052328 A2 WO2004052328 A2 WO 2004052328A2 EP 0313391 W EP0313391 W EP 0313391W WO 2004052328 A2 WO2004052328 A2 WO 2004052328A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oil
- acid
- emulsion
- water emulsion
- insoluble
- Prior art date
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- 239000000839 emulsion Substances 0.000 title claims abstract description 45
- 150000002327 glycerophospholipids Chemical class 0.000 title claims abstract description 29
- 150000003408 sphingolipids Chemical class 0.000 title claims abstract description 26
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- 235000019143 vitamin K2 Nutrition 0.000 description 1
- 239000011728 vitamin K2 Substances 0.000 description 1
- 235000012711 vitamin K3 Nutrition 0.000 description 1
- 239000011652 vitamin K3 Substances 0.000 description 1
- 229940046001 vitamin b complex Drugs 0.000 description 1
- 229940011671 vitamin b6 Drugs 0.000 description 1
- 229940041603 vitamin k 3 Drugs 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/08—Anti-ageing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/062—Oil-in-water emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/55—Phosphorus compounds
- A61K8/553—Phospholipids, e.g. lecithin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/68—Sphingolipids, e.g. ceramides, cerebrosides, gangliosides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
Definitions
- the present invention discloses new oil-in-water emulsions which are stabilized with glycerophospholipids and / or sphingolipids in the absence of emulsifiers with an HLB value greater than 8 and at least one particulate raw material which is insoluble in the emulsion and has an average particle diameter of Contain a maximum of 200 microns and their non-therapeutic use as topical skin care compositions that improve the appearance of the skin by skin imperfections such.
- B. optically conceal fine lines, wrinkles and folds, scars, pimples or rough skin pores.
- Particulate materials such as talc, starch and starch derivatives, cellulose powder, polymer powder (e.g. orgasol) or colored pigments serve to cover up skin imperfections by matching the colors between uneven areas and the surrounding skin.
- the pigment content must account for up to 20% by weight of the cosmetic composition.
- Such compositions have certain disadvantages.
- the relatively high pigment content must be made stable in storage by a high content of emulsifiers, so that the pigments remain evenly dispersed even after prolonged storage and do not settle under the influence of gravity.
- a high content of emulsifier can, depending on the type of emulsifier, lead to intolerance reactions of the skin or limit the application in the particularly sensitive area of the eyes.
- EP 1 136 064 A2 discloses cosmetic compositions which contain a crosslinked silicone elastomer and spherical particles with a difference between maximum and minimum particle size of about 24 ⁇ m in a suitable carrier. Suitable particles are, for. B. silicas (silica) disclosed. Furthermore, methods for improving the aesthetic appearance of the skin, in particular for improving the appearance of the skin texture, for reducing the appearance of fine lines and wrinkles, for improving the skin color and for refining the appearance of the pore size are disclosed. The silicone elastomer is supposed to fill and smooth skin wrinkles; the microparticles deposited on it are said to improve the appearance of the skin by means of light reflections.
- Silicone elastomers are often offered as a compound with volatile silicone oils, for example cyclomethicone, as a commercially available raw material or are easier to formulate as a compound.
- silicone-based raw materials can lead to intolerance reactions, especially in the sensitive eye area.
- they are not accepted as synthetic raw materials by certain consumer groups.
- Glycerophospholipids and sphingolipids are naturally occurring substances on the basis of which stable oil-in-water emulsions can be produced.
- the lecithins in particular are particularly compatible with the skin, eyes and mucous membranes and are also registered as GRAS substances ("Generally Recommended as Safe”).
- Lecithins continue to be commercially and easily available, e.g. B. from egg and especially from soybeans.
- compositions are known from US Pat. No. 4,622,074 which contain pigments coated with hardened lecithin.
- the lecithin coating increases the hydrophobicity of the pigment particles and gives them a soft texture.
- the compositions containing the lecithin-coated pigments are easy to distribute on the skin, impart a soft skin feel, have a moisturizing effect and do not cause any skin irritation.
- the pigments to be coated are mixed in with the lecithin Water heated.
- the deposition of the lecithin on the pigment surfaces is increased by adding a dissolved inorganic salt.
- the pigments are then filtered off or centrifuged and dried at 105 ° C.
- GRAS safe
- Another object was to provide a cosmetic composition for optically improving the skin appearance, which produces a pleasant sensory impression, in particular a pleasant feeling on the skin.
- cosmetic compositions which contain pigments in a carrier based on an emulsion stabilized by glycerophospholipids or sphingolipids are particularly well suited to optically improving the skin texture.
- the present invention relates to an oil-in-water emulsion which is stabilized with at least one glycerophospholipid and / or at least one sphingolipid and contains and free at least one particulate raw material which is insoluble in the emulsion and has an average particle diameter of at most 200 ⁇ m is from emulsifiers with an HLB value greater than 8.
- Another object of the present invention is the non-therapeutic use of oil-in-water emulsions stabilized with at least one glycerophospholipid and / or at least one sphingolipid and containing at least one particulate raw material which is insoluble in the emulsion and has an average particle diameter of at most Contain 200 ⁇ m, to improve the appearance of the skin texture, to visually conceal imperfections, lines, wrinkles, wrinkles, pimples and scars, to achieve an even complexion or to refine the appearance of the pore size.
- the glycerophospholipids and sphingolipids are of vegetable origin.
- a particularly suitable glycerophospholipid source according to the invention are soybeans.
- the glycerophospholipids are selected from phosphatidylcholines, phosphatidylethanolamines, phosphatidylserines and phosphatidylinosites and mixtures of these substances.
- phosphatidylcholines which are particularly preferred according to the invention have the formula (I)
- radicals R 1 and R 2 each independently represent an acyl group of fatty acids with a carbon number of 8-30 C atoms, preferably 10-24 and particularly preferably 12-22 C atoms.
- the fatty acid residues can be saturated as well as mono- or polyunsaturated. The saturated ones are preferred Acyl residues of C 2 - C 2 fatty acids.
- the acyl residues of myristic acid, palmitic acid, stearic acid, arachic acid and behenic acid are particularly preferred.
- phosphatidylethanolamines preferred according to the invention are those of the formula (Ha) or (Ilb),
- radicals R 1 and R 2 have the same meaning as shown for formula (I).
- phosphatidylserines preferred according to the invention are those of the structural formula (purple) or (Illb), CH OR 1
- R 1 and R 2 have the same meaning as shown for formula (I).
- the phosphatidylinositives preferred according to the invention have the structural formula (IVa) or (IVb),
- R 1 and R 2 have the same meaning as set forth for formula (I).
- R 1 acyl residues of palmitic acid, stearic acid and arachic acid are preferred; a stearic acid acyl radical is particularly preferred.
- R 2 represents in a particularly preferred manner a linear saturated C 20 fatty acid acyl residue (arachoyl residue).
- the sphingolipids are selected from glycosphingolipids, sphingophospholipids and ceramides and mixtures of these substances.
- glycosphingolipids suitable according to the invention include the cerebrosides, the sulfatides and the gangliosides. Of these, the cerebrosides having the structural formula (V) are particularly preferred,
- R 1 is a fatty acid residue as set forth for formula (I), which can optionally be hydroxy-substituted in the ⁇ -position
- R 3 is a straight-chain or branched alkyl residue having 8-30, preferably 10-26 and particularly preferably 12-22 carbon atoms represent.
- the alkyl radical can be saturated or mono- or polyunsaturated. Saturated alkyl radicals, in particular an octyl, decyl, dodecyl, lauryl, tetradecyl, myristyl, cetyl, palmityl, stearyl, arachyl or behenyl radical, are preferred according to the invention.
- the radical R 4 represents a ⁇ -D-galactopyranosyl or a ⁇ -D-glucopyranosyl radical.
- the sphingophospholipids suitable according to the invention include, for example
- ceramides preferred according to the invention include those of the structural formula
- the oil-in-water emulsions according to the invention are stabilized with a mixture of hardened glycerophospholipids, which is essentially the composition of hydrogenated natural soy lecithin equivalent.
- the proportion of phosphatidylcholine is about 60-85% by weight, preferably 70-80% by weight, the content of phosphatidylinositol is at most 0.5% by weight and the content of phosphatidylethanolamine is 2-15% by weight, preferably 5-8% by weight .%.
- the glycerophospholipids and / or sphingolipids used according to the invention have an iodine number of at most 10, preferably at most 5.
- the particulate raw materials claimed in accordance with the invention and insoluble in the emulsion and having an average particle diameter of at most 200 ⁇ m are selected from inert inorganic and organic pigments and adsorbents, and from mixtures of these substances.
- the inorganic pigments which are insoluble in the emulsion and have an average particle diameter of at most 200 ⁇ m are selected from the oxides of silicon, titanium, iron, zinc, zirconium, magnesium, cerium and bismuth, boron nitride, mica, fluorspar and water-insoluble pearlescent pigments, which can be coated with at least one inorganic and / or organic compound.
- the pigments can be both colored and colorless. Some of the pigments mentioned below also serve as UV absorbers. Particularly preferred colored pigments are selected from the iron oxides with the color index numbers Cl 77491 (iron oxide red), Cl 77492 (iron oxide hydrate yellow) and CI 77499 (iron oxide black), from Cl 77891 (titanium dioxide) and carbon black. The preferred pigments are selected from the oxides of silicon, titanium, zinc and iron, as well as from bismuth oxychloride. A particularly preferred pigment is the commercial product SB-705 from Miyoshi Kasei, a spherical silica gel with the INCI name silica, which has an average particle diameter of 5-6 ⁇ m and a surface area of approximately 600 m 2 / g. Other pigments preferred according to the invention are mica and pearlescent pigments.
- the inorganic pigments mentioned can be coated.
- the coating can be carried out with the aid of inorganic and / or organic compounds.
- Preferred pigments of this type are selected from silicon dioxide particles which are coated with titanium dioxide and / or iron oxides.
- a particularly preferred pigment of this type is the commercial product Ronasphere ® LDP Merck KGaA. This product is a spherical silica particle coated with titanium dioxide and iron oxide.
- Ronasphere ® LDP has a refractive index that is similar to the skin's refractive index.
- Inorganic coated mica pigments that do not have a pearlescent luster are also suitable.
- inorganic coated inorganic pigments are mica pigments which are coated with titanium dioxide in various layer thicknesses, for example the products of the Timiron ® series from Rona / Merck KGaA, in particular the products Timiron ® MP, Timiron ® Super, Timiron ® Starlight and Timiron ® Silk ,
- the products mentioned have average particle diameters of 5 - 60 ⁇ m or 10 - 60 ⁇ m or 10 - 125 ⁇ m or 5 - 25 ⁇ m.
- mica particles with a coating of titanium dioxide and iron oxide e.g. B. the commercial products Timiron ® MP-20, MP-24, MP-25, MP-28, MP-29, MP-60 and MP-65.
- mica particles coated with titanium dioxide and / or red and / or black iron oxide e.g. B. the products of the Colorona ® series.
- Other preferred pigments are mica pigments coated with silica gel, e.g. , The commercial product Micronasphere ® M.
- suitable pigments are inorganic coated inorganic pigments, the coating of which a proportion of 0.1 - 1% by weight of tin oxide..
- inorganic pigments which are coated with organic substances.
- examples of these are titanium dioxide pigments coated with aluminum stearate (commercial product MT 100 T from Tayca), zinc oxide coated with dimethylpolysiloxane (Dimethicone), boron nitride coated with Dimethicone (Tres BN ® UHP 1106 from Carborundum), with a mixture of dimethylpolysiloxane and silica gel ( Simethicone) and alumina hydrate (alumina) coated titanium dioxide (Eusolex ® T 2000 from Merck), titanium dioxide coated with octylsilanol or spherical polyalkylsesquisiloxane particles (Aerosil ® R972 from Degussa).
- the pigments insoluble in the emulsion are selected with an average particle diameter of at most 200 ⁇ m from water-insoluble organic pigments, of which the color pigments Cl 15510, Cl 15585, Cl 15850, Cl 15985, Cl 45170, Cl 45370, Cl 45380, Cl 45425, Cl 45430, Cl 73360 and Cl 75470 are particularly preferred.
- the particulate raw materials which are insoluble in the emulsion and have an average particle diameter of at most 200 ⁇ m are selected from adsorbents, selected from pyrogenic silicas, for. B. Aerosil ® types, precipitated silicas, for. B. silica gels, silicon dioxide, clays, e.g. B. bentonite or kaolin, magnesium aluminum silicates, e.g. B.
- talc optionally modified starches and starch derivatives, cellulose powders, lactoglobulin derivatives, polymer powders made from polyolefins, polycarbonates, polyurethanes, polyamides, polyesters, polystyrenes, polyacrylates, (meth) acrylate or (meth) acrylate-vinylidene copolymers, which can be crosslinked, Teflon or silicones, as well as mixtures of the substances mentioned.
- Polymer powders based on polyamides are available from Elf Atochem under the names Orgasol ® 1002 (polyamide-6) and Orgasol ® 2002 (polyamide-12).
- Other polymer powders which are suitable for the purpose according to the invention are e.g. B. Polymethacrylate (Micropearl ® M from SEPPIC or Plastic Powder A from NIKKOL), styrene-divinylbenzene copolymers (Plastic Powder FP from NIKKOL), polyethylene and polypropylene powder or silicone polymers (Silicone Powder X2-1605 from Dow Corning).
- Preferred adsorbents are talc, silicon dioxide, silica gel, sodium C 8 .i 6 -soalkylsuccinyllactoglobulin sulfonate, available from Brooks Industries as a commercial product Biopol ® OE, modified starch derivatives of the DRY FLO ® type from the National Starch and Chemical Company and Orgasol ® .
- Talc, silicon dioxide, Biopol ® OE and starch derivatives of the DRY FLO ® type are particularly preferred.
- the particulate raw materials which are suitable according to the invention and are insoluble in the emulsion have an average particle diameter of at most 200 ⁇ m, preferably 0.5-150 ⁇ m, particularly preferably 1-30 ⁇ m and extremely preferably 1-40 ⁇ m.
- the specification of the particle diameter relates to the diameter measured in the longest dimension.
- the oil-in-water emulsions according to the invention contain at least one co-emulsifier with an HLB value less than or equal to 8.
- Co-emulsifiers suitable according to the invention are the mono- and diesters of Glycerol with saturated and unsaturated C 8 -C 18 fatty acids, in particular glycerol monolaurate, glycerol monococoate, glycerol monooleate, glycerol monostearate and glycerol distearate and mixtures of these substances.
- Other suitable co-emulsifiers are plant sterols, e.g. B. the commercial product Generol ® 122.
- suitable co-emulsifiers are the mono-, sesqui- and diesters of sorbitan and sucrose with saturated and unsaturated C 2 -C 1 ⁇ -fatty acids, in particular sorbitan sesquioleate, sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate, sucrose dipalmitate, sorbitan mono-sorbate, sorbitan mono-sorbate and sucrose dioleate.
- Other suitable co-emulsifiers are the mono-, sesqui- and diesters of monosaccharides and alkyl monosaccharides, e.g. B.
- Suitable co-emulsifiers are linear C 12 -C 22 fatty alcohols, e.g. B. cetyl alcohol, stearyl alcohol, oleyl alcohol, erucalcohol, ricinol alcohol, lauryl alcohol, myristyl alcohol, arachidyl alcohol, caprylic alcohol, capric alcohol, linoleyl alcohol, linolenyl alcohol and behenyl alcohol, and their Guerbet alcohols.
- Particularly preferred fatty alcohols are cetyl alcohol, stearyl alcohol or a mixture of these two fatty alcohols, furthermore behenyl alcohol, and technical mixtures of linear C 2 oC 22 fatty alcohols.
- the co-emulsifiers with an HLB value of less than or equal to 8 are each present in amounts of 0.1-3% by weight, preferably 0.2-2% by weight and particularly preferably 0.2-1% by weight on the entire composition.
- compositions according to the invention can contain at least one colloidally dissolved polymer.
- the polymers are selected from natural and synthetic anionic, cationic, nonionic and amphoteric polymers. Synthetic and natural anionic and nonionic polymers are preferred according to the invention.
- Suitable anionic polymers contain carboxylate and / or sulfonate groups and as monomers, for example acrylic acid, methacrylic acid, crotonic acid, maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid.
- the acidic groups can be present in whole or in part as sodium, potassium, ammonium, mono- or triethanolammonium salt.
- Preferred monomers are 2-acrylamido-2-methyl-propanesulfonic acid and acrylic acid.
- copolymers of at least one anionic monomer and at least one nonionic monomer may be preferred to use copolymers of at least one anionic monomer and at least one nonionic monomer.
- anionic monomers reference is made to the substances listed above.
- Preferred nonionic monomers are acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester, vinylpyrrolidone, vinyl ether and vinyl ester.
- Preferred anionic copolymers are acrylic acid-acrylamide copolymers and in particular polyacrylamide copolymers with monomers containing sulfonic acid groups.
- a particularly preferred anionic copolymer consists of 70-55 mol% of acrylamide and 30-45 mol% of 2-acrylamido-2-methylpropanesulfonic acid, the sulfonic acid group being wholly or partly as sodium, potassium, ammonium, mono- or triethanolammonium Salt is present.
- This copolymer can also be crosslinked, the preferred crosslinking agents being polyolefinically unsaturated compounds such as tetraallyloxyethane, allyl sucrose, allylpentaerythritol and methylene-bisacrylamide.
- Such a polymer is contained in the commercial product Sepigel ® 305 from SEPPIC. The use of this compound has proven to be particularly advantageous in the context of the teaching according to the invention.
- polymers are partially or fully neutralized, crosslinked copolymers of 2-methyl-2 [(1-oxo-2-propenyl) amino] -1-propanesulfonic acid (AMPS) and hydroxyethyl acrylate, commercially available in the form of an inverse latex, e.g. B. under the trade name Simulgel ® NS from Seppic.
- AMPS 2-methyl-2 [(1-oxo-2-propenyl) amino] -1-propanesulfonic acid
- acrylamide commercially available in the form of an inverse latex, e.g. B. under the trade name Simulgel ® 600 from Seppic.
- AMPS 2-methyl-2 [(1-oxo-2-propenyl) amino] -1-propanesulfonic acid
- acrylic acid commercially available in the form of an inverse latex, e.g. B. under the trade name Simulgel ® EG from Seppic.
- anionic copolymers are those which contain 2-acrylamido-2-methylpropanesulfonic acid and polyvinylpyrrolidone as monomers, e.g. B. the commercial product Aristoflex ® AVC from Clariant.
- anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Allyl ethers of pentaerythritol, sucrose and propylene can be preferred crosslinking agents. Such compounds are, for example, the commercial products Carbopol ® . Further preferred anionic copolymers are those which contain, as monomers, 80-98% by weight of optionally substituted acrylic acid and 2-20% by weight of C 1-6 -so-fatty alcohol methacrylic acid ester and which can be crosslinked. Such connections are e.g. B. the commercial products Pemulen ® .
- Amphoteric polymers are understood to mean both those polymers which contain both free amino groups and free -COOH or SO 3 H groups in the molecule and are capable of forming internal salts, and also zwitterionic polymers which contain quaternary ammonium groups and -COO " in the molecule. - or -SO 3 " groups or -COOH or SO 3 H groups.
- amphoteric polymer An example of a usable amphoteric polymer according to the invention is obtainable under the name Amphomer ® acrylic resin which is a copolymer of tert-butylaminoethyl methacrylate, N- (1, 1, 3,3- tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid , Methacrylic acid and its simple esters.
- the compositions according to the invention can furthermore contain synthetic nonionic polymers. Suitable nonionic synthetic polymers are polyvinyl pyrrolidones and vinyl pyrrolidone vinyl ester copolymers, e.g. B. the commercial products Luviskol ® (BASF), and polyvinyl alcohols.
- Temporary cationic polymers usually contain an amino group which is present as a quaternary ammonium group at certain pH values.
- Chitosan and its derivatives e.g. B. the products Hydagen ® CMF, Hydagen ® HCMF, Kytamer ® PC and Chitolam ® NB / 101.
- Chitosans which are particularly suitable have a degree of deacetylation of at least 80% and a molecular weight of 5 ⁇ 10 5 to 5 ⁇ 10 6 g / mol.
- the chitosan must be converted into the salt form.
- Suitable acids are z. B. acetic acid, glycolic acid, tartaric acid, malic acid, citric acid, lactic acid, 2-pyrrolidone-5-carboxylic acid, benzoic acid and salicylic acid.
- cationic polymers are, for example, quaternized cellulose derivatives, e.g. B. the commercial products Celquat ® and Polymer JR ® , in particular Celquat ® H 100, Celquat ® L 200 and Polymer JR ® 400, cationic alkyl polyglycosides according to DE-PS 44 13 686, cationized honey, cationic guar derivatives, in particular the products Cosmedia ® Guar and Jaguar ® , polysiloxanes with quaternary groups, such as the commercial products Q2-7224 (Dow Corning), Dow Corning ® 929 Emulsion, SM-2059 (General Electric), SLM-55067 (Wacker) and Abil ® -Quat 3270 and 3272 (Th.
- quaternized cellulose derivatives e.g. B. the commercial products Celquat ® and Polymer JR ® , in particular Celquat ® H 100, Celquat ® L 200 and Polymer JR
- Polyquaternium-2 Polyquaternium-17, Polyquatemium-18 and Polyquaternium-27 with quaternary nitrogen atoms in the main polymer chain.
- the polymers known under the names Polyquatemium-24 can also be used as cationic polymers.
- the crosslinked poly (methacryloyloxyethyltrimethylammonium chloride) with the INCI name Polyquaternium-37 can also be used as a cationic polymer.
- Polyquatium-37 is often used in the form of a non-aqueous polymer dispersion. Such polymer dispersions are commercially available under the names Salcare ® SC 95 and Salcare ® SC 96.
- Copolymers of methacryloyloxyethyltrimethylammonium chloride and nonionic monomers preferably acrylamide, methacrylamide, acrylic acid C 1-4 alkyl ester and methacrylic acid-C ⁇ -alkyl, which may be crosslinked, optionally, are commercially available under the name Salcare ® SC 92nd
- At least one natural, if desired chemically modified polymer is selected from cellulose ethers, e.g. B. methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose or carboxymethyl cellulose, quaternized cellulose derivatives, polyquaternium-24, guar gum, cationic guar derivatives, alginates, xanthan gum, gum arabic, karaya gum, carrageenans,
- cellulose ethers e.g. B. methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose or carboxymethyl cellulose, quaternized cellulose derivatives, polyquaternium-24, guar gum, cationic guar derivatives, alginates, xanthan gum, gum arabic, karaya gum, carrageenans,
- the preparations used contain several, in particular two different polymers of the same charge and / or each contain an ionic and an amphoteric and / or a synthetic nonionic polymer.
- the colloidally dissolved polymers are present in amounts of 0.01-5% by weight, preferably 0.5-4% by weight and particularly preferably 1.0-2.5% by weight of active substance, based on the total weight of the composition ,
- compositions according to the invention enable a particularly uniform distribution not only of pigments but also of selected cosmetic active ingredients.
- Cosmetic sunscreens in particular place high demands on good, homogeneous distributability on the skin.
- the compositions according to the invention therefore furthermore contain at least one active ingredient selected from inorganic and organic UV filter substances, vitamins, provitamins and Vitamin precursors of groups A, B, C, E, H and K or their derivatives, ⁇ -lipoic acid, ⁇ -hydroxycarboxylic acids, allantoin, ⁇ -bisabolol and polysaccharides containing deoxy sugars or deoxy sugar building blocks.
- the organic UV filters used according to the invention are selected from the derivatives of dibenzoylmethane, cinnamic acid esters, diphenylacrylic acid esters, benzophenone, camphor, p-aminobenzoic acid esters, o-aminobenzoic acid esters, salicylic acid esters, benzimidazoles, symmetrically or asymmetrically substituted 1,3,5-triazines, monomers and oligomeric 4,4-diarylbutadienecarboxylic acid esters and carboxamides, ketotricyclo (5.2.1.0) decane, benzalmalonic acid esters and any mixtures of the components mentioned.
- the organic UV filters can be oil-soluble or water-soluble.
- oil-soluble UV filters are 1- (4-tert-butyl phenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione (Parsol ® 1789), 1-phenyl-3- (4 '-Isopropyl-phenyl) -propane-1,3-dione, 3- (4 ' -methylbenzylidene) -D, L-camphor, 4- (dimethylamino) - 2-ethylhexyl benzoate, 4- (dimethylamino) benzoic acid-2 octyl ester, 4- (dimethylamino) benzoic acid amyl ester, 4-methoxycinnamic acid 2-ethylhexyl ester,
- Preferred water-soluble UV filters are 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts, sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5 -sulfonic acid and its salts, sulfonic acid derivatives of 3-benzylidene camphor, such as.
- UV-A filter 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione
- UV-B -Filter solutions of the UV-A filter 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione
- the compositions according to the invention In a further preferred embodiment, therefore, hold 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione in combination with at least one UV-B filter selected from 4-methoxycinnamic acid.
- the weight ratio of UV-B filter to 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione is between 1: 1 and 10: 1, preferably between 2: 1 and 8: 1, the molar ratio is accordingly between 0.3 and 3.8, preferably between 0.7 and 3.0.
- the inorganic light protection pigments preferred according to the invention are finely dispersed or colloidally dispersed metal oxides and metal salts, for example titanium dioxide, zinc oxide, iron oxide, aluminum oxide, cerium oxide, zirconium oxide, silicates (talc) and barium sulfate.
- the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm, so-called nanopigments. They can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or a shape which differs in some other way from the spherical shape.
- the pigments can also be surface-treated, ie hydrophilized or hydrophobicized.
- Typical examples are coated titanium dioxide, such as. B. Titanium dioxide T 805 (Degussa) or Eusolex ® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. Titanium dioxide and zinc oxide are particularly preferred.
- Particularly preferred inorganic light protection pigments are selected from the oxides of titanium, zinc, cerium and iron and any mixtures of the components mentioned, which can be surface-modified.
- Another object of the present invention is the use of an oil-in-water emulsion which is stabilized with at least one glycerophospholipid and / or at least one sphingolipid, at least one particulate raw material which is insoluble in the emulsion and has an average particle diameter of at most 200 ⁇ m and contains at least one inorganic or organic UV filter substance and is free of emulsifiers with an HLB value greater than 8 as sunscreen.
- the compositions according to the invention contain at least one vitamin, pro-vitamin, a vitamin precursor or their derivatives.
- Preferred components are those which are usually assigned to the vitamin groups A, B, C, E, H and K.
- the group of substances called vitamin A includes retinol (vitamin Ai) and 3,4-didehydroretinol (vitamin A 2 ).
- the ß-carotene is the provitamin of retinol.
- vitamin A acid and its esters, vitamin A aldehyde and vitamin A alcohol and its esters, such as retinyl palmitate and retinyl acetate are suitable as vitamin A components.
- the preparations according to the invention preferably contain the vitamin A component in amounts of 0.05-1% by weight, based on the overall composition.
- the vitamin B group or the vitamin B complex include u. a.
- Vitamin B 2 (riboflavin)
- Vitamin B 3 The compounds nicotinic acid and nicotinamide (niacinamide) are often listed under this name. According to the invention, preference is given to nicotinamide, which is preferably present in amounts of 0.05 to 1% by weight, based on the overall composition.
- Vitamin B 5 pantothenic acid and panthenol
- Panthenol is preferably used.
- Derivatives of panthenol which can be used according to the invention are, in particular, the esters and ethers of panthenol and cationically derivatized panthenols.
- derivatives of 2-furanone with the general structural formula (a) can be used instead of and in addition to pantothenic acid or panthenol.
- the 2-furanone derivatives in which the substituents R 1 to R 6 independently of one another are a hydrogen atom, a hydroxyl radical, a methyl, methoxy, aminomethyl or hydroxymethyl radical, a saturated or mono- or di-unsaturated, linear or branched C 2 -C 4 - hydrocarbon residue, a saturated or mono- or di-unsaturated, branched or linear mono-, di- or trihydroxy-C 2 -C 4 - hydrocarbon residue or a saturated or mono- or di-unsaturated, branched or linear mono-, di- or triamino-C 2 -C - hydrocarbon radical.
- the substituents R 1 to R 6 independently of one another are a hydrogen atom, a hydroxyl radical, a methyl, methoxy, aminomethyl or hydroxymethyl radical, a saturated or mono- or di-unsaturated, linear or branched C 2 -C 4 - hydrocarbon residue, a saturated or mono- or di-unsatur
- Particularly preferred derivatives are the commercially available substances dihydro-3-hydroxy-4,4-dimethyl-2 (3H) -furanone with the common name pantolactone (Merck), 4-hydroxymethyl- ⁇ -butyrolactone (Merck), 3.3 -Dimethyl-2-hydroxy- ⁇ -butyrolactone (Aldrich) and 2,5-dihydro-5-methoxy-2-furanone (Merck), all stereoisomers being expressly included.
- the 2-furanone derivative which is extremely preferred according to the invention is pantolactone (dihydro-3-hydroxy-4,4-dimethyl-2 (3H) -furanone), where in formula (a) R 1 is a hydroxyl group, R 2 is a hydrogen atom, R 3 and R 4 represent a methyl group and R 5 and R 6 represent a hydrogen atom.
- the stereoisomer (R) -pantolactone is formed when pantothenic acid is broken down.
- the above-mentioned compounds of the vitamin B 5 type and the 2-furanone derivatives are preferably present in a total amount of 0.05 to 10% by weight, particularly preferably 0.1 to 5% by weight, in each case based on the overall composition ,
- Vitamin B 6 pyridoxine as well as pyridoxamine and pyridoxal.
- Vitamin B 7 also known as vitamin H or "skin vitamin”.
- Biotin is preferably present in amounts of 0.0001 to 1.0% by weight, in particular 0.001 to 0.01% by weight, in each case based on the total composition.
- Vitamin C is preferably used in amounts of 0.1 to 3% by weight, based on the total composition.
- Use in combination with tocopherols may also be preferred.
- the vitamin E group includes tocopherol, in particular ⁇ -tocopherol, and its derivatives.
- esters such as tocopheryl acetate, nicotinate, phosphate, succinate, linoleate, oleate, tocophereth-5, tocophereth-10, tocophereth-12, tocophereth-18, tocophereth-50 and tocopherol.
- Tocopherol and its derivatives are preferably present in amounts of 0.05-1% by weight, based on the total composition.
- Vitamin F is usually understood to mean essential fatty acids, in particular linoleic acid, linolenic acid and arachidonic acid.
- Vitamin H is another name for biotin or vitamin B 7 (see above).
- the fat-soluble vitamins of the vitamin K group which are based on the basic structure of 2-methyl-1, 4-naphthoquinone, include phylloquinone (vitamin K ⁇ , farnoquinone or menaquinone-7 (vitamin K2) and menadione (vitamin K- Vitamin K is preferably present in amounts of 0.0001 to 1.0% by weight, in particular 0.01 to 0.5% by weight, in each case based on the overall composition.
- the agents according to the invention preferably contain vitamins, provitamins and vitamin precursors from groups A, B, C, E and H or their derivatives.
- Vitamin A palmitate retinyl palmitate
- panthenol and its derivatives nicotinamide
- ascorbyl palmitate acetate
- Mg ascorbyl phosphate Na ascorbyl phosphate
- sodium and magnesium ascorbate the tocopherol esters, especially tocopheryl acetate, and biotin are particularly preferred.
- compositions according to the invention contain ⁇ -hydroxycarboxylic acids.
- the ⁇ -hydroxycarboxylic acids are selected from glycolic acid, lactic acid, methyllactic acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid, 2-hydroxyhexanoic acid, 2-hydroxyheptanoic acid, 2-hydroxyoctanoic acid, 2-hydroxynonanoic acid, 2-hydroxydecanoic acid, 2-hydroxy-undecanoic acid, 2-hydroxydodecanoic acid ( ⁇ -hydroxylauric acid), 2-hydroxytetradecanoic acid ( ⁇ -hydroxymyristic acid), 2-hydroxyhexadecanoic acid ( ⁇ -hydroxypalmitic acid), 2-hydroxyoctadecanoic acid ( ⁇ -hydroxystearic acid), 2-hydroxyeicosatetraenoic acid ( ⁇ -hydroxy arachidic acid), phen, hydroxy arachidonic acid, phen, hydroxy arachidic acid, phen, hydroxy arachid acid, phen, hydroxy arachid acid,
- the ⁇ -hydroxycarboxylic acids are used in amounts of 0.01-10% by weight, preferably 0.1-5% by weight and particularly preferably 1-3% by weight, in each case based on the overall composition.
- the compositions according to the invention contain at least one deoxy sugar or at least one polysaccharide containing deoxy sugar building blocks.
- L (-) - fucose and L (+) - rhamnose are preferably deoxy sugar in the sense of the invention.
- Fucose comes e.g. as a building block of polysaccharides that can be isolated from marine brown algae (e.g. Fucus vesiculosus), rhamnose is a polysaccharide building block of arabic acid in gum arabic.
- the polysaccharides containing deoxy sugar or deoxy sugar building blocks are present in amounts of 0.01-10% by weight, preferably 0.1-5% by weight and particularly preferably 1-3% by weight, in each case based on the entire composition , used.
- the oil-in-water emulsions according to the invention can be obtained in that the particulate raw materials which are insoluble in the emulsion and have an average particle diameter of at most 200 ⁇ m of the glycerophospholipid and / or sphingolipid-stabilized emulsion after the homogenization be added.
- the present invention furthermore relates to a process for the preparation of an oil-in-water emulsion which is stabilized with at least one glycerophospholipid and / or at least one sphingolipid and at least one particulate raw material which is insoluble in the emulsion and has an average particle diameter of contains a maximum of 200 ⁇ m, in which the fat phase, which contains the glycerophospholipid and / or the sphingolipid, and the water phase are each separately heated to temperatures of approx. 70 - 85 ° C, the water phase with stirring with a homogenizer to the fat phase is given, if desired the emulsion is cooled to 50 ° C.
- compositions according to the invention were demonstrated in the following comparative experiments. Two different basic recipes were made.
- Base I is an oil-in-water emulsion that is stabilized with an alkyl polyglycoside-fatty alcohol mixture as an emulsifier.
- Base II represents the lecithin-stabilized emulsion according to the invention.
- the software SELS Surface evaluation of the living skin automatically calculates various parameters by default, e.g. B. the scaly, roughness, wrinkles and smoothness.
- the parameter SEW wrinkles / wrinkles was used for the present question. This parameter is calculated from the number and the ratio of horizontal and vertical folds. The more wrinkles there are and the wider they are, the higher the SEW value.
- test samples were applied once in a standardized amount to the defined areas of the forearm and the skin areas were measured before application and one, three and five hours after application.
- An untreated corresponding area was assigned to two formulations (with active ingredient and placebo), so that 24
- Table 3 Mean values (MW), standard deviation (SD) and initial position differences (outgiffiff.) Of the SELS parameter S E w (wrinkle)
Abstract
The invention relates to novel oil-in-water emulsions, which are stabilised by glycerophospholipids and/or sphingolipids and contain at least one particulate raw material that is insoluble in the emulsion and has a maximum average particle diameter of 200 mu m. The invention also relates to the non-therapeutic use of said emulsions as topical skincare compositions for improving the appearance of the skin by optically concealing skin irregularities, e.g. fine lines, wrinkles and folds, scars, pimples or open pores.
Description
"Mit Glycero-Phospholipiden oder Sphingolipiden stabilisierte Emulsionen zur Verbesserung des Hauterscheinungsbildes" "Emulsions stabilized with glycerophospholipids or sphingolipids to improve the appearance of the skin"
Die vorliegende Erfindung offenbart neue ÖI-in-Wasser-Emulsionen, die mit Glycero- Phospholipiden und/oder Sphingolipiden in Abwesenheit von Emulgatoren mit einem HLB-Wert größer 8 stabilisiert sind und mindestens einen in der Emulsion unlöslichen, partikelförmigen Rohstoff mit einem mittleren Teilchendurchmesser von maximal 200 μm enthalten sowie deren nicht-therapeutische Verwendung als topische Hautpflegezusammensetzungen, die das Erscheinungsbild der Haut verbessern, indem sie Hautunebenheiten, z. B. feine Linien, Fältchen und Falten, Narben, Pickel oder grobe Hautporen, optisch kaschieren.The present invention discloses new oil-in-water emulsions which are stabilized with glycerophospholipids and / or sphingolipids in the absence of emulsifiers with an HLB value greater than 8 and at least one particulate raw material which is insoluble in the emulsion and has an average particle diameter of Contain a maximum of 200 microns and their non-therapeutic use as topical skin care compositions that improve the appearance of the skin by skin imperfections such. B. optically conceal fine lines, wrinkles and folds, scars, pimples or rough skin pores.
Die nicht-therapeutische Behandlung von Hautunebenheiten durch kosmetische Zusammensetzungen ist im Stand der Technik bereits bekannt. So dienen partikelförmige Materialien, wie Talkum, Stärke und Stärkederivate, Cellulosepulver, Polymerpulver (z. B. Orgasol) oder farbige Pigmente dazu, Hautunebenheiten durch farbliches Angleichen zwischen unebenen Stellen und umgebender Haut zu verdecken. Um eine länger anhaltende abdeckende Wirkung zu erreichen, muss der Pigmentgehalt einen Anteil von bis zu 20 Gew.% an der kosmetischen Zusammensetzung ausmachen. Derartige Zusammensetzungen weisen gewisse Nachteile auf. So muss der relativ hohe Pigmentgehalt durch einen hohen Gehalt an Emulgatoren lagerstabil gemacht werden, damit die Pigmente auch bei längerer Lagerung gleichmäßig dispergiert bleiben und sich nicht unter dem Einfluss der Schwerkraft absetzen. Ein hoher Gehalt an Emulgator kann aber, je nach Art des Emulgators, zu Unverträglichkeitsreaktionen der Haut führen bzw. die Anwendungsmöglichkeit im besonders empfindlichen Augenbereich einschränken.The non-therapeutic treatment of skin imperfections by cosmetic compositions is already known in the prior art. Particulate materials such as talc, starch and starch derivatives, cellulose powder, polymer powder (e.g. orgasol) or colored pigments serve to cover up skin imperfections by matching the colors between uneven areas and the surrounding skin. In order to achieve a long-lasting covering effect, the pigment content must account for up to 20% by weight of the cosmetic composition. Such compositions have certain disadvantages. The relatively high pigment content must be made stable in storage by a high content of emulsifiers, so that the pigments remain evenly dispersed even after prolonged storage and do not settle under the influence of gravity. A high content of emulsifier can, depending on the type of emulsifier, lead to intolerance reactions of the skin or limit the application in the particularly sensitive area of the eyes.
Zur optischen Faltenbehandlung wurde in der Druckschrift US 4,255,416 vorgeschlagen, eine pigmenthaltige Zusammensetzung mit einem filmbildenden Polymer und einem höheren Anteil an flüchtigem Lösemittel auf die Haut aufzutragen. Der Film, der sich nach Verdunsten des Lösemittels auf der Haut bildet, soll zu einer mechanischen
Straffung der Haut führen und dadurch feine Fältchen und Linien glätten. Derartige Zusammensetzungen weisen häufig nur einen geringen Tragekomfort auf.For optical wrinkle treatment, it was proposed in US Pat. No. 4,255,416 to apply a pigment-containing composition to the skin with a film-forming polymer and a higher proportion of volatile solvent. The film that forms on the skin after the solvent has evaporated is said to become a mechanical one Tighten the skin and thereby smooth fine lines and wrinkles. Such compositions often have only a low level of comfort.
In der Druckschrift EP 1 136 064 A2 sind kosmetische Zusammensetzungen offenbart, die in einem geeignetem Träger ein vernetztes Silicon-Elastomer und sphärische Partikel mit einer Differenz zwischen maximaler und minimaler Partikelgröße von etwa 24 μm enthalten. Als geeignete Partikel sind z. B. Kieselsäuren (Silica) offenbart. Weiterhin werden Verfahren zur Verbesserung des ästhetischen Erscheinungsbildes der Haut, insbesondere zur Verbesserung des Erscheinungsbilds der Hauttextur, zur Verminderung des Erscheinungsbildes von feinen Linien und Falten, zur Verbesserung der Hautfarbe und zur Verfeinerung des Erscheinungsbildes der Porengröße offenbart. Das Silicon-Elastomer soll dabei Hautfältchen ausfüllen und ebnen; die sich darauf ablagernden Mikropartikel sollen durch Lichtreflexionen das Erscheinungsbild der Haut verbessern.EP 1 136 064 A2 discloses cosmetic compositions which contain a crosslinked silicone elastomer and spherical particles with a difference between maximum and minimum particle size of about 24 μm in a suitable carrier. Suitable particles are, for. B. silicas (silica) disclosed. Furthermore, methods for improving the aesthetic appearance of the skin, in particular for improving the appearance of the skin texture, for reducing the appearance of fine lines and wrinkles, for improving the skin color and for refining the appearance of the pore size are disclosed. The silicone elastomer is supposed to fill and smooth skin wrinkles; the microparticles deposited on it are said to improve the appearance of the skin by means of light reflections.
Siliconelastomere werden häufig als Compound mit flüchtigen Siliconölen, beispielsweise Cyclomethicone, als handelsüblicher Rohstoff angeboten bzw. sind als Compound einfacher zu formulieren. Rohstoffe auf Siliconbasis können allerdings zu Unverträglichkeitsreaktionen insbesondere im empfindlichen Augenbereich führen. Außerdem werden sie als synthetische, körperfremde Rohstoffe von bestimmten Verbrauchergruppen nicht akzeptiert.Silicone elastomers are often offered as a compound with volatile silicone oils, for example cyclomethicone, as a commercially available raw material or are easier to formulate as a compound. However, silicone-based raw materials can lead to intolerance reactions, especially in the sensitive eye area. In addition, they are not accepted as synthetic raw materials by certain consumer groups.
Glycero-Phospholipide und Sphingolipide sind natürlich vorkommende Substanzen, auf deren Basis sich stabile ÖI-in-Wasser-Emulsionen herstellen lassen. Insbesondere die Lecithine sind besonders haut-, äugen- und schleimhautverträglich und außerdem als GRAS-Substanzen ("Generally Recommended as Safe") registriert. Lecithine sind weiterhin kommerziell leicht und günstig verfügbar, z. B. aus Ei und insbesondere aus Sojabohnen.Glycerophospholipids and sphingolipids are naturally occurring substances on the basis of which stable oil-in-water emulsions can be produced. The lecithins in particular are particularly compatible with the skin, eyes and mucous membranes and are also registered as GRAS substances ("Generally Recommended as Safe"). Lecithins continue to be commercially and easily available, e.g. B. from egg and especially from soybeans.
Aus der US- Patentschrift US 4,622,074 sind kosmetische Zusammensetzungen bekannt, die mit gehärtetem Lecithin beschichtete Pigmente enthalten. Die Lecithin-Beschichtung erhöht die Hydrophobie der Pigmentteilchen und verleiht ihnen eine weiche Textur. Die Zusammensetzungen, die die Lecithin-beschichteten Pigmente enthalten, lassen sich gut auf der Haut verteilen, vermitteln ein weiches Hautgefühl, haben einen feuchtigkeitsspendenden Effekt und rufen keinerlei Hautirritationen hervor. Für die Herstellung werden die zu beschichtenden Pigmente zusammen mit dem Lecithin in
Wasser erhitzt. Die Abscheidung des Lecithins auf den Pigmentoberflächen wird durch Zugabe eines gelösten anorganischen Salzes verstärkt. Die Pigmente werden anschließend abfiltriert bzw. abzentrifugiert und bei 105 °C getrocknet. Die US 4,622,074 liefert allerdings keinen Hinweis darauf, dass stabile, pigmenthaltige ÖI-in-Wasser- Emulsionen nur mittels Glycero-Phospholipiden und/oder Sphingolipiden ohne weitere hydrophile Emulgatoren mit einem HLB-Wert größer 8 hergestellt werden können. Die Offenlegungsschrift WO 96/03964 A1 offenbart pigmenthaltige ÖI-in-Wasser- Emulsionen, die Lecithin bzw. ein Gemisch aus Lecithin und hydroxyliertem Lecithin und 10 - 20 Gew.% an Pigmenten enthalten. Diese Zusammensetzungen enthalten weiterhin jedoch 2,5 - 7 Gew.% an hydrophilen, ethoxylierten Emulgatoren mit einem HLB-Wert von deutlich mehr als 8. Somit weist auch diese Schrift dem Fachmann keinen Weg zur vorliegenden Erfindung.Cosmetic compositions are known from US Pat. No. 4,622,074 which contain pigments coated with hardened lecithin. The lecithin coating increases the hydrophobicity of the pigment particles and gives them a soft texture. The compositions containing the lecithin-coated pigments are easy to distribute on the skin, impart a soft skin feel, have a moisturizing effect and do not cause any skin irritation. For the production, the pigments to be coated are mixed in with the lecithin Water heated. The deposition of the lecithin on the pigment surfaces is increased by adding a dissolved inorganic salt. The pigments are then filtered off or centrifuged and dried at 105 ° C. US Pat. No. 4,622,074 does not, however, provide any indication that stable, oil-in-water emulsions containing pigments can only be prepared using glycerophospholipids and / or sphingolipids without further hydrophilic emulsifiers with an HLB value greater than 8. The published patent application WO 96/03964 A1 discloses pigment-containing oil-in-water emulsions which contain lecithin or a mixture of lecithin and hydroxylated lecithin and 10-20% by weight of pigments. However, these compositions furthermore contain 2.5-7% by weight of hydrophilic, ethoxylated emulsifiers with an HLB value of significantly more than 8. Thus, this document also shows the skilled person no way to the present invention.
Eine Aufgabe der vorliegenden Erfindung war es, eine kosmetische Zusammensetzung zur optischen Verbesserung des Hauterscheinungsbildes zur Verfügung zu stellen, die auf einem besonders haut- und schleimhautverträglichen Träger basiert. Eine weitere Aufgabe war es, eine kosmetische Zusammensetzung zur optischen Verbesserung des Hauterscheinungsbildes zur Verfügung zu stellen, die mit einem natürlichen, im besten Falle als sicher anerkannten (GRAS), günstig verfügbaren Emulgator stabilisiert ist.It was an object of the present invention to provide a cosmetic composition for optically improving the skin appearance, which is based on a carrier which is particularly compatible with the skin and mucous membranes. Another object was to provide a cosmetic composition for optically improving the skin appearance, which is stabilized with a natural, at best recognized as safe (GRAS), cheaply available emulsifier.
Eine weitere Aufgabe war es, eine kosmetische Zusammensetzung zur optischen Verbesserung des Hauterscheinungsbildes zur Verfügung zu stellen, die einen angenehmen sensorischen Eindruck, insbesondere ein angenehmes Hautgefühl, hervorruft.Another object was to provide a cosmetic composition for optically improving the skin appearance, which produces a pleasant sensory impression, in particular a pleasant feeling on the skin.
Überraschend wurde nun gefunden, dass kosmetische Zusammensetzungen, die Pigmente in einem Träger auf Basis einer durch Glycero-Phospholipide oder Sphingolipide stabilisierten Emulsion enthalten, besonders gut geeignet sind, die Hauttextur optisch zu verbessern.Surprisingly, it has now been found that cosmetic compositions which contain pigments in a carrier based on an emulsion stabilized by glycerophospholipids or sphingolipids are particularly well suited to optically improving the skin texture.
Gegenstand der vorliegenden Erfindung ist eine ÖI-in-Wasser-Emulsion, die mit mindestens einem Glycero-Phospholipid und/oder mindestens einem Sphingolipid stabilisiert ist, mindestens einen in der Emulsion unlöslichen, partikelförmigen Rohstoff mit einem mittleren Teilchendurchmesser von maximal 200 μm enthält und frei ist von Emulgatoren mit einem HLB-Wert größer 8.
Ein weiterer Gegenstand der vorliegenden Erfindung ist die nicht-therapeutische Verwendung von mit mindestens einem Glycero-Phospholipid und/oder mindestens einem Sphingolipid stabilisierten ÖI-in-Wasser-Emulsionen, die mindestens einen in der Emulsion unlöslichen, partikelförmigen Rohstoff mit einem mittleren Teilchendurchmesser von maximal 200 μm enthalten, zur Verbesserung des Erscheinungsbildes der Hauttextur, zur optischen Kaschierung von Hautunebenheiten, Linien, Fältchen, Falten, Pickeln und Narben, zur Erzielung eines ebenmäßigen Teints oder zur Verfeinerung des Erscheinungsbildes der Porengröße.The present invention relates to an oil-in-water emulsion which is stabilized with at least one glycerophospholipid and / or at least one sphingolipid and contains and free at least one particulate raw material which is insoluble in the emulsion and has an average particle diameter of at most 200 μm is from emulsifiers with an HLB value greater than 8. Another object of the present invention is the non-therapeutic use of oil-in-water emulsions stabilized with at least one glycerophospholipid and / or at least one sphingolipid and containing at least one particulate raw material which is insoluble in the emulsion and has an average particle diameter of at most Contain 200 μm, to improve the appearance of the skin texture, to visually conceal imperfections, lines, wrinkles, wrinkles, pimples and scars, to achieve an even complexion or to refine the appearance of the pore size.
In einer ersten bevorzugten Ausführungsform der Erfindung sind die Glycero- Phospholipide und Sphingolipide pflanzlichen Ursprungs. Eine erfindungsgemäß besonders geeignete Glycero-Phospholipidquelle sind Sojabohnen.In a first preferred embodiment of the invention, the glycerophospholipids and sphingolipids are of vegetable origin. A particularly suitable glycerophospholipid source according to the invention are soybeans.
In einer weiteren bevorzugten Ausführungsform der Erfindung sind die Glycero-Phospholipide ausgewählt aus Phosphatidylcholinen, Phosphatidylethanolaminen, Phosphatidyl- serinen und Phosphatidylinositen sowie Mischungen dieser Substanzen.In a further preferred embodiment of the invention, the glycerophospholipids are selected from phosphatidylcholines, phosphatidylethanolamines, phosphatidylserines and phosphatidylinosites and mixtures of these substances.
Die erfindungsgemäß besonders bevorzugten Phosphatidylcholine weisen die Formel (I) auf,The phosphatidylcholines which are particularly preferred according to the invention have the formula (I)
(I)(I)
in der die Reste R1 und R2 jeweils unabhängig voneinander eine Acylgruppe aus Fettsäuren mit einer Kohlenstoffanzahl von 8 - 30 C-Atomen, bevorzugt 10 - 24 und besonders bevorzugt 12 - 22 C-Atomen, darstellen. Die Fettsäurereste können sowohl gesättigt als auch einfach oder mehrfach ungesättigt sein. Bevorzugt sind die gesättigten
Acylreste von C 2 - C 2-Fettsäuren. Besonders bevorzugt sind die Acylreste der Myristinsäure, Palmitinsäure, Stearinsäure, Arachinsäure und Behensäure.in which the radicals R 1 and R 2 each independently represent an acyl group of fatty acids with a carbon number of 8-30 C atoms, preferably 10-24 and particularly preferably 12-22 C atoms. The fatty acid residues can be saturated as well as mono- or polyunsaturated. The saturated ones are preferred Acyl residues of C 2 - C 2 fatty acids. The acyl residues of myristic acid, palmitic acid, stearic acid, arachic acid and behenic acid are particularly preferred.
Die erfindungsgemäß bevorzugten Phosphatidylethanolamine sind solche der Formel (Ha) bzw. (Ilb),The phosphatidylethanolamines preferred according to the invention are those of the formula (Ha) or (Ilb),
CH O RlCH O Rl
R2 — o- CH OR2 - o- CH O
CH- O O CH. CH, NH.CH- OO CH. CH , NH.
OHOH
(Ha)(Ha)
CH 2 O R1 CH 2 OR 1
R2 O CH OR 2 O CH O
CH, O P O CH, CH7 NH.CH, OPO CH, CH 7 NH.
O" O "
(Ilb)(IIb)
in denen die Reste R1 und R2 dieselbe Bedeutung haben wie für Formel (I) dargestellt. Besonders bevorzugt sind Phosphatidylethanolamine, bei denen R1 und R2 unabhängig voneinander gesättigte Acylreste von Fettsäuren mit 16 oder 18 Kohlenstoffatomen, insbesondere einen Palmitoyl- oder Stearoyl-Rest, darstellen.in which the radicals R 1 and R 2 have the same meaning as shown for formula (I). Phosphatidylethanolamines in which R 1 and R 2 independently of one another are saturated acyl radicals of fatty acids having 16 or 18 carbon atoms, in particular a palmitoyl or stearoyl radical, are particularly preferred.
Die erfindungsgemäß bevorzugten Phosphatidylserine sind solche der Strukturformel (lila) bzw. (Illb),
CH O R1 The phosphatidylserines preferred according to the invention are those of the structural formula (purple) or (Illb), CH OR 1
R^ O- CH OR ^ O- CH O
CH2 O P O CH2 CH(NH2)-COOHCH 2 OPO CH 2 CH (NH 2 ) -COOH
OHOH
(lila)(purple)
CH O R1 CH OR 1
R^ O- CH OR ^ O- CH O
CH2 O P O CH2 CH(NH2)-COO" CH 2 OPO CH 2 CH (NH 2 ) -COO "
O" O "
(lllb)(IIIb)
in denen R1 und R2 dieselbe Bedeutung haben wie für Formel (I) dargestellt. Besonders bevorzugt sind Phosphatidylserine, bei denen R1 und R2 unabhängig voneinander gesättigte Acylreste von Fettsäuren mit 16 oder 18 Kohlenstoffatomen, insbesondere einen Palmitoyl- oder Stearoyl-Rest, darstellen.in which R 1 and R 2 have the same meaning as shown for formula (I). Phosphatidylserines in which R 1 and R 2 independently of one another are saturated acyl residues of fatty acids having 16 or 18 carbon atoms, in particular a palmitoyl or stearoyl residue, are particularly preferred.
Die erfindungsgemäß bevorzugten Phosphatidylinosite weisen die Strukturformel (IVa) bzw. (IVb) auf,
The phosphatidylinositives preferred according to the invention have the structural formula (IVa) or (IVb),
OHOH
(IVa)(IVa)
(IVb)(IVb)
bei der die Reste R1 und R2 dieselbe Bedeutung haben wie für Formel (I) dargelegt. Für R1 sind Acylreste aus Palmitinsäure, Stearinsäure und Arachinsäure bevorzugt; besonders bevorzugt ist ein Stearinsäureacylrest. R2 stellt in besonders bevorzugter Weise einen linearen gesättigten C20-Fettsäureacylrest (Arachoylrest) dar.in which the radicals R 1 and R 2 have the same meaning as set forth for formula (I). For R 1 , acyl residues of palmitic acid, stearic acid and arachic acid are preferred; a stearic acid acyl radical is particularly preferred. R 2 represents in a particularly preferred manner a linear saturated C 20 fatty acid acyl residue (arachoyl residue).
In einer weiteren bevorzugten Ausführungsform der Erfindung sind die Sphingolipide ausgewählt aus Glycosphingolipiden, Sphingophospholipiden und Ceramiden sowie Mischungen dieser Substanzen.In a further preferred embodiment of the invention, the sphingolipids are selected from glycosphingolipids, sphingophospholipids and ceramides and mixtures of these substances.
Zu den erfindungsgemäß geeigneten Glycosphingolipiden gehören die Cerebroside, die Sulfatide und die Ganglioside. Erfindungsgemäß besonders bevorzugt sind hiervon die Cerebroside mit der Strukturformel (V),
The glycosphingolipids suitable according to the invention include the cerebrosides, the sulfatides and the gangliosides. Of these, the cerebrosides having the structural formula (V) are particularly preferred,
(V)(V)
in der R1 einen Fettsäurerest wie für Formel (I) dargelegt, der gewünschtenfalls in α- Position Hydroxy-substituiert sein kann, und R3 einen geradkettigen oder verzweigten Alkylrest mit 8 - 30, bevorzugt 10 - 26 und besonders bevorzugt 12 - 22 Kohlenstoffatomen darstellen. Der Alkylrest kann gesättigt oder einfach oder mehrfach ungesättigt sein. Gesättigte Alkylreste, insbesondere ein Octyl-, Decyl-, Dodecyl-, Lauryl-, Tetradecyl-, Myristyl-, Cetyl-, Palmityl-, Stearyl-, Arachyl- oder Behenylrest, sind erfindungsgemäß bevorzugt. Der Rest R4 stellt einen ß-D-Galactopyranosyl- oder einen ß-D-Glucopyrano- syl-Rest dar.in which R 1 is a fatty acid residue as set forth for formula (I), which can optionally be hydroxy-substituted in the α-position, and R 3 is a straight-chain or branched alkyl residue having 8-30, preferably 10-26 and particularly preferably 12-22 carbon atoms represent. The alkyl radical can be saturated or mono- or polyunsaturated. Saturated alkyl radicals, in particular an octyl, decyl, dodecyl, lauryl, tetradecyl, myristyl, cetyl, palmityl, stearyl, arachyl or behenyl radical, are preferred according to the invention. The radical R 4 represents a β-D-galactopyranosyl or a β-D-glucopyranosyl radical.
Zu den erfindungsgemäß geeigneten Sphingophospholipiden gehören beispielsweise dieThe sphingophospholipids suitable according to the invention include, for example
Sphingomyeline und die Inosit-Sphingophospholipide.Sphingomyeline and the inositol sphingophospholipids.
Zu den erfindungsgemäß bevorzugten Ceramiden gehören solche der StrukturformelThe ceramides preferred according to the invention include those of the structural formula
(VI),(VI)
(VI)(VI)
bei denen der Rest R1 einen Substituenten wie für Formel (I) dargelegt darstellt..in which the radical R 1 represents a substituent as set out for formula (I).
In einer besonders bevorzugten Ausführungsform sind die erfindungsgemäßen ÖI-in- Wasser-Emulsionen mit einer Mischung aus gehärteten Glycero-Phospholipiden stabilisiert, die im wesentlichen der Zusammensetzung von hydriertem natürlichem Sojalecithin
entspricht. Hierbei beträgt der Anteil an Phosphatidylcholin etwa 60 - 85 Gew.%, bevorzugt 70 - 80 Gew.%, der Gehalt an Phosphatidylinosit maximal 0,5 Gew.% und der Gehalt an Phosphatidylethanolamin 2 - 15 Gew.%, bevorzugt 5 - 8 Gew.%.In a particularly preferred embodiment, the oil-in-water emulsions according to the invention are stabilized with a mixture of hardened glycerophospholipids, which is essentially the composition of hydrogenated natural soy lecithin equivalent. The proportion of phosphatidylcholine is about 60-85% by weight, preferably 70-80% by weight, the content of phosphatidylinositol is at most 0.5% by weight and the content of phosphatidylethanolamine is 2-15% by weight, preferably 5-8% by weight .%.
Die erfindungsgemäß verwendeten Glycero-Phospholipide und/oder Sphingolipide weisen eine Jodzahl von maximal 10, bevorzugt von maximal 5 auf.The glycerophospholipids and / or sphingolipids used according to the invention have an iodine number of at most 10, preferably at most 5.
Die erfindungsgemäß beanspruchten, in der Emulsion unlöslichen partikelförmigen Rohstoffe mit einem mittleren Teilchendurchmesser von maximal 200 μm sind ausgewählt aus inerten anorganischen und organischen Pigmenten und Adsorbentien, sowie aus Mischungen dieser Substanzen.The particulate raw materials claimed in accordance with the invention and insoluble in the emulsion and having an average particle diameter of at most 200 μm are selected from inert inorganic and organic pigments and adsorbents, and from mixtures of these substances.
In einer bevorzugten Ausführungsform der Erfindung sind die in der Emulsion unlöslichen anorganischen Pigmente mit einem mittleren Teilchendurchmesser von maximal 200 μm ausgewählt aus den Oxiden von Silicium, Titan, Eisen, Zink, Zirkonium, Magnesium, Cer und Bismut, aus Bornitrid, Glimmer, Flussspat und wasserunlöslichen Perlglanzpigmenten, die mit mindestens einer anorganischen und/oder organischen Verbindung beschichtet sein können.In a preferred embodiment of the invention, the inorganic pigments which are insoluble in the emulsion and have an average particle diameter of at most 200 μm are selected from the oxides of silicon, titanium, iron, zinc, zirconium, magnesium, cerium and bismuth, boron nitride, mica, fluorspar and water-insoluble pearlescent pigments, which can be coated with at least one inorganic and / or organic compound.
Die Pigmente können sowohl farbig als auch farblos sein. Einige der im folgenden genannten Pigmente dienen auch als UV-Absorber. Besonders bevorzugte farbige Pigmente sind ausgewählt aus den Eisenoxiden mit den Colour Index-Nummern Cl 77491 (Eisenoxid rot), Cl 77492 (Eisenoxidhydrat gelb) und CI 77499 (Eisenoxid schwarz), aus Cl 77891 (Titandioxid) und Ruß. Die bevorzugten Pigmente sind ausgewählt aus den Oxiden von Silicium, Titan, Zink und Eisen, sowie aus Bismutoxychlorid. Ein besonders bevorzugtes Pigment ist das Handelsprodukt SB-705 der Firma Miyoshi Kasei, ein sphärisches Kieselgel mit der INCI-Bezeichnung Silica, das einen durchschnittlichen Teilchendurchmesser von 5 - 6 μm und eine Oberfläche von etwa 600 m2/g aufweist. Weitere erfindungsgemäß bevorzugte Pigmente sind Glimmer und Perlglanzpigmente.The pigments can be both colored and colorless. Some of the pigments mentioned below also serve as UV absorbers. Particularly preferred colored pigments are selected from the iron oxides with the color index numbers Cl 77491 (iron oxide red), Cl 77492 (iron oxide hydrate yellow) and CI 77499 (iron oxide black), from Cl 77891 (titanium dioxide) and carbon black. The preferred pigments are selected from the oxides of silicon, titanium, zinc and iron, as well as from bismuth oxychloride. A particularly preferred pigment is the commercial product SB-705 from Miyoshi Kasei, a spherical silica gel with the INCI name silica, which has an average particle diameter of 5-6 μm and a surface area of approximately 600 m 2 / g. Other pigments preferred according to the invention are mica and pearlescent pigments.
Die genannten anorganischen Pigmente können beschichtet sein. Die Beschichtung kann mit Hilfe von anorganischen und/oder organischen Verbindungen erfolgen. Erfindungsgemäß bevorzugt sind anorganische Pigmente, die eine anorganische Beschichtung aufweisen.
Bevorzugte Pigmente dieser Art sind ausgewählt aus Siliciumdioxid-Partikeln, die mit Titandioxid und/oder Eisenoxiden beschichtet sind. Ein besonders bevorzugtes Pigment dieser Art ist das Handelsprodukt Ronasphere®LDP der Firma Merck KGaA. Bei diesem Produkt handelt es sich um sphärische Siliciumdioxid-Partikel, die mit Titandioxid und Eisenoxid beschichtet sind. Ronasphere®LDP weist einen Brechungsindex auf, der dem Brechungsindex der Haut ähnelt.The inorganic pigments mentioned can be coated. The coating can be carried out with the aid of inorganic and / or organic compounds. According to the invention, preference is given to inorganic pigments which have an inorganic coating. Preferred pigments of this type are selected from silicon dioxide particles which are coated with titanium dioxide and / or iron oxides. A particularly preferred pigment of this type is the commercial product Ronasphere ® LDP Merck KGaA. This product is a spherical silica particle coated with titanium dioxide and iron oxide. Ronasphere ® LDP has a refractive index that is similar to the skin's refractive index.
Weiterhin geeignet sind anorganisch beschichtete Glimmerpigmente, die keinen Perlglanz aufweisen.Inorganic coated mica pigments that do not have a pearlescent luster are also suitable.
Weitere bevorzugte anorganisch beschichtete anorganische Pigmente sind Glimmerpigmente, die mit Titandioxid in verschiedenen Schichtdicken beschichtet sind, beispielsweise die Produkte der Timiron®-Serie von Rona/Merck KGaA, insbesondere die Produkte Timiron® MP, Timiron® Super, Timiron® Starlight und Timiron® Silk. Die genannten Produkte weisen durchschnittliche Teilchendurchmesser von 5 - 60 μm bzw. 10 - 60 μm bzw. 10 - 125 μm bzw. 5 - 25 μm auf. Ebenfalls bevorzugt sind Glimmerpartikel mit einer Beschichtung aus Titandioxid und Eisenoxid, z. B. die Handelsprodukte Timiron® MP-20, MP-24, MP-25, MP-28, MP-29, MP-60 und MP-65. Weiterhin erfindungsgemäß geeignet sind mit Titandioxid und/oder rotem und/oder schwarzem Eisenoxid beschichtete Glimmerpartikel, z. B. die Produkte der Colorona®- Serie. Weitere bevorzugte Pigmente sind mit Kieselgel beschichtete Glimmerpigmente, z. B. das Handelsprodukt Micronasphere® M. Weitere erfindungsgemäß geeignete Pigmente sind anorganisch beschichtete anorganische Pigmente, deren Beschichtung einen Anteil von 0,1 - 1 Gew.% Zinnoxid aufweist.Further preferred inorganic coated inorganic pigments are mica pigments which are coated with titanium dioxide in various layer thicknesses, for example the products of the Timiron ® series from Rona / Merck KGaA, in particular the products Timiron ® MP, Timiron ® Super, Timiron ® Starlight and Timiron ® Silk , The products mentioned have average particle diameters of 5 - 60 μm or 10 - 60 μm or 10 - 125 μm or 5 - 25 μm. Also preferred are mica particles with a coating of titanium dioxide and iron oxide, e.g. B. the commercial products Timiron ® MP-20, MP-24, MP-25, MP-28, MP-29, MP-60 and MP-65. Also suitable according to the invention are mica particles coated with titanium dioxide and / or red and / or black iron oxide, e.g. B. the products of the Colorona ® series. Other preferred pigments are mica pigments coated with silica gel, e.g. , The commercial product Micronasphere ® M. Further according to the invention suitable pigments are inorganic coated inorganic pigments, the coating of which a proportion of 0.1 - 1% by weight of tin oxide..
Ebenfalls erfindungsgemäß geeignet, wenngleich weniger bevorzugt, sind anorganische Pigmente, die mit organischen Substanzen beschichtet sind. Beispiele hierfür sind mit Aluminiumstearat beschichtete Titandioxid-Pigmente (Handelsprodukt MT 100 T von der Firma Tayca), mit Dimethylpolysiloxan (Dimethicone) beschichtetes Zinkoxid, mit Dimethicone beschichtetes Bornitrid (Tres BN® UHP 1106 von Carborundum), mit einem Gemisch aus Dimethylpolysiloxan und Silicagel (Simethicone) und Aluminiumoxidhydrat (Alumina) beschichtetes Titandioxid (Eusolex® T 2000 von Merck), mit Octylsilanol beschichtetes Titandioxid oder sphärische Polyalkylsesquisiloxan-Partikel (Aerosil® R972 von Degussa).Also suitable according to the invention, although less preferred, are inorganic pigments which are coated with organic substances. Examples of these are titanium dioxide pigments coated with aluminum stearate (commercial product MT 100 T from Tayca), zinc oxide coated with dimethylpolysiloxane (Dimethicone), boron nitride coated with Dimethicone (Tres BN ® UHP 1106 from Carborundum), with a mixture of dimethylpolysiloxane and silica gel ( Simethicone) and alumina hydrate (alumina) coated titanium dioxide (Eusolex ® T 2000 from Merck), titanium dioxide coated with octylsilanol or spherical polyalkylsesquisiloxane particles (Aerosil ® R972 from Degussa).
In einer weiteren Ausführungsform der Erfindung sind die in der Emulsion unlöslichen Pigmente mit einem mittleren Teilchendurchmesser von maximal 200 μm ausgewählt
aus wasserunlöslichen organischen Pigmenten, von denen die Farbpigmente Cl 15510, Cl 15585, Cl 15850, Cl 15985, Cl 45170, Cl 45370, Cl 45380, Cl 45425, Cl 45430, Cl 73360 und Cl 75470 besonders bevorzugt sind.In a further embodiment of the invention, the pigments insoluble in the emulsion are selected with an average particle diameter of at most 200 μm from water-insoluble organic pigments, of which the color pigments Cl 15510, Cl 15585, Cl 15850, Cl 15985, Cl 45170, Cl 45370, Cl 45380, Cl 45425, Cl 45430, Cl 73360 and Cl 75470 are particularly preferred.
In einer bevorzugten Ausführungsform der Erfindung sind die in der Emulsion unlöslichen partikelförmigen Rohstoffe mit einem mittleren Teilchendurchmesser von maximal 200 μm ausgewählt aus Adsorbentien, ausgewählt aus pyrogenen Kieselsäuren, z. B. Aerosil®-Typen, Fällungskieselsäuren, z. B. Kieselgelen, Siliciumdioxid, Tonen, z. B. Bentonite oder Kaolin, Magnesiumaluminiumsilikaten, z. B. Talkum, gegebenenfalls modifizierten Stärken und Stärkederivaten, Cellulosepulvern, Lactoglobulinderivaten, Polymerpulvern aus Polyolefinen, Polycarbonaten, Polyurethanen, Polyamiden, Polyestern, Polystyrolen, Polyacrylaten, (Meth)acrylat- oder (Meth)acrylat-Vinyliden-Copolymeren, die vernetzt sein können, Teflon oder Siliconen, sowie Mischungen der genannten Substanzen.In a preferred embodiment of the invention, the particulate raw materials which are insoluble in the emulsion and have an average particle diameter of at most 200 μm are selected from adsorbents, selected from pyrogenic silicas, for. B. Aerosil ® types, precipitated silicas, for. B. silica gels, silicon dioxide, clays, e.g. B. bentonite or kaolin, magnesium aluminum silicates, e.g. B. talc, optionally modified starches and starch derivatives, cellulose powders, lactoglobulin derivatives, polymer powders made from polyolefins, polycarbonates, polyurethanes, polyamides, polyesters, polystyrenes, polyacrylates, (meth) acrylate or (meth) acrylate-vinylidene copolymers, which can be crosslinked, Teflon or silicones, as well as mixtures of the substances mentioned.
Polymerpulver auf Basis von Polyamiden sind unter der Bezeichnung Orgasol® 1002 (Polyamid-6) und Orgasol® 2002 (Polyamid-12) von Elf Atochem erhältlich. Weitere Polymerpulver, die sich für den erfindungsgemäßen Zweck eignen, sind z. B. Polymethacry- late (Micropearl® M von SEPPIC oder Plastic Powder A von NIKKOL), Styrol-Divinylben- zol-Copolymeren (Plastic Powder FP von NIKKOL), Polyethylen- und Polypropylen- Pulver oder auch Siliconpolymere (Silicone Powder X2-1605 von Dow Corning). Bevorzugte Adsorbentien sind Talkum, Siliciumdioxid, Kieselgel, Natrium-C8.i6-lsoalkyl- succinyllactoglobulinsulfonat, von Brooks Industries erhältlich als Handelsprodukt Biopol® OE, modifizierte Stärkederivate vom Typ DRY FLO® der National Starch and Chemical Company und Orgasol®. Besonders bevorzugt sind Talkum, Siliciumdioxid, Biopol® OE und Stärkederivate vom Typ DRY FLO®.Polymer powders based on polyamides are available from Elf Atochem under the names Orgasol ® 1002 (polyamide-6) and Orgasol ® 2002 (polyamide-12). Other polymer powders which are suitable for the purpose according to the invention are e.g. B. Polymethacrylate (Micropearl ® M from SEPPIC or Plastic Powder A from NIKKOL), styrene-divinylbenzene copolymers (Plastic Powder FP from NIKKOL), polyethylene and polypropylene powder or silicone polymers (Silicone Powder X2-1605 from Dow Corning). Preferred adsorbents are talc, silicon dioxide, silica gel, sodium C 8 .i 6 -soalkylsuccinyllactoglobulin sulfonate, available from Brooks Industries as a commercial product Biopol ® OE, modified starch derivatives of the DRY FLO ® type from the National Starch and Chemical Company and Orgasol ® . Talc, silicon dioxide, Biopol ® OE and starch derivatives of the DRY FLO ® type are particularly preferred.
Die erfindungsgemäß geeigneten, in der Emulsion unlöslichen, partikelförmigen Rohstoffe weisen einen mittleren Teilchendurchmesser von maximal 200 μm, bevorzugt 0,5 - 150 μm, besonders bevorzugt 1 - 30 μm und außerordentlich bevorzugt 1 - 40 μm, auf. Die Angabe des Teilchendurchmesser bezieht sich dabei auf den in der längsten Ausdehnung gemessenen Durchmesser.The particulate raw materials which are suitable according to the invention and are insoluble in the emulsion have an average particle diameter of at most 200 μm, preferably 0.5-150 μm, particularly preferably 1-30 μm and extremely preferably 1-40 μm. The specification of the particle diameter relates to the diameter measured in the longest dimension.
In einer besonders bevorzugten Ausführungsform enthalten die erfindungsgemäßen ÖI- in-Wasser-Emulsionen mindestens einen Co-Emulgator mit einem HLB-Wert kleiner oder gleich 8. Erfindungsgemäß geeignete Co-Emulgatoren sind die Mono- und Diester von
Glycerin mit gesättigten und ungesättigten C8 - C18-Fettsäuren, insbesondere Glycerin- monolaurat, Glycerinmonococoat, Glycerinmonooleat, Glycerinmonostearat und Glycerindistearat sowie Mischungen dieser Substanzen. Weitere geeignete Co- Emulgatoren sind pflanzliche Sterine, z. B. das Handelsprodukt Generol® 122. Weitere geeignete Coemulgatoren sind die Mono-, Sesqui- und Diester von Sorbitan und Sucrose mit gesättigten und ungesättigten Cι2-C1δ-Fettsäuren, insbesondere Sorbitansesquioleat, Sorbitanmonolaurat, Sorbitanmonooleat, Sorbitanmonopalmitat, Sucrosedipalmitat, Sorbitanmonostearat, Sucrosedistearat und Sucrosedioleat. Weitere geeignete Coemulgatoren sind die Mono-, Sesqui- und Diester von Monosacchariden und Alkylmonosacchariden, z. B. Methylglucosesesquistearat, σ-Butylglucosidcocoat oder σ-Butylglucosidcaprat. Weitere geeignete Coemulgatoren sind lineare C12-C22- Fettalkohole, z. B. Cetylalkohol, Stearylalkohol, Oleylalkohol, Erucaalkohol, Ricinol- alkohol, Laurylalkohol, Myristylalkohol, Arachidylalkohol, Caprylalkohol, Caprinalkohol, Linoleylalkohol, Linolenylalkohol und Behenylalkohol, sowie deren Guerbetalkohole. Besonders bevorzugte Fettalkohole sind Cetylalkohol, Stearylalkohol oder ein Gemisch dieser beiden Fettalkohole, desweiteren Behenylalkohol sowie technische Gemische aus linearen C2o-C22-Fettalkoholen.In a particularly preferred embodiment, the oil-in-water emulsions according to the invention contain at least one co-emulsifier with an HLB value less than or equal to 8. Co-emulsifiers suitable according to the invention are the mono- and diesters of Glycerol with saturated and unsaturated C 8 -C 18 fatty acids, in particular glycerol monolaurate, glycerol monococoate, glycerol monooleate, glycerol monostearate and glycerol distearate and mixtures of these substances. Other suitable co-emulsifiers are plant sterols, e.g. B. the commercial product Generol ® 122. Further suitable co-emulsifiers are the mono-, sesqui- and diesters of sorbitan and sucrose with saturated and unsaturated C 2 -C 1 δ -fatty acids, in particular sorbitan sesquioleate, sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate, sucrose dipalmitate, sorbitan mono-sorbate, sorbitan mono-sorbate and sucrose dioleate. Other suitable co-emulsifiers are the mono-, sesqui- and diesters of monosaccharides and alkyl monosaccharides, e.g. B. methyl glucose sesquistearate, σ-butyl glucoside cocoate or σ-butyl glucoside caprate. Other suitable co-emulsifiers are linear C 12 -C 22 fatty alcohols, e.g. B. cetyl alcohol, stearyl alcohol, oleyl alcohol, erucalcohol, ricinol alcohol, lauryl alcohol, myristyl alcohol, arachidyl alcohol, caprylic alcohol, capric alcohol, linoleyl alcohol, linolenyl alcohol and behenyl alcohol, and their Guerbet alcohols. Particularly preferred fatty alcohols are cetyl alcohol, stearyl alcohol or a mixture of these two fatty alcohols, furthermore behenyl alcohol, and technical mixtures of linear C 2 oC 22 fatty alcohols.
Die Co-Emulgatoren mit einem HLB-Wert kleiner oder gleich 8 sind erfindungsgemäß in Mengen von 0,1 - 3 Gew.%, bevorzugt 0,2 - 2 Gew.% und besonders bevorzugt 0,2 - 1 Gew.%, jeweils bezogen auf die gesamte Zusammensetzung, enthalten.According to the invention, the co-emulsifiers with an HLB value of less than or equal to 8 are each present in amounts of 0.1-3% by weight, preferably 0.2-2% by weight and particularly preferably 0.2-1% by weight on the entire composition.
In einer weiteren besonders bevorzugten Ausführungsform können die erfindungsgemäßen Zusammensetzungen mindestens ein kolloidal gelöstes Polymer enthalten. Die Polymere sind ausgewählt aus natürlichen und synthetischen anionischen, kationischen, nichtionischen und amphoteren Polymeren. Erfindungsgemäß bevorzugt sind synthetische und natürliche anionische und nichtionische Polymere.In a further particularly preferred embodiment, the compositions according to the invention can contain at least one colloidally dissolved polymer. The polymers are selected from natural and synthetic anionic, cationic, nonionic and amphoteric polymers. Synthetic and natural anionic and nonionic polymers are preferred according to the invention.
Geeignete anionische Polymere enthalten Carboxylat- und/oder Sulfonatgruppen und als Monomere beispielsweise Acrylsäure, Methacrylsäure, Crotonsäure, Maleinsäure- anhydrid und 2-Acrylamido-2-methylpropansulfonsäure. Dabei können die sauren Gruppen ganz oder teilweise als Natrium-, Kalium-, Ammonium-, Mono- oder Triethanolammonium-Salz vorliegen. Bevorzugte Monomere sind 2-Acrylamido-2-methyl- propansulfonsäure und Acrylsäure.Suitable anionic polymers contain carboxylate and / or sulfonate groups and as monomers, for example acrylic acid, methacrylic acid, crotonic acid, maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid. The acidic groups can be present in whole or in part as sodium, potassium, ammonium, mono- or triethanolammonium salt. Preferred monomers are 2-acrylamido-2-methyl-propanesulfonic acid and acrylic acid.
Innerhalb dieser Ausführungsform kann es bevorzugt sein, Copolymere aus mindestens einem anionischen Monomer und mindestens einem nichtionischen Monomer einzuset-
zen. Bezüglich der anionischen Monomere wird auf die oben aufgeführten Substanzen verwiesen. Bevorzugte nichtionische Monomere sind Acrylamid, Methacrylamid, Acryl- säureester, Methacrylsäureester, Vinylpyrrolidon, Vinylether und Vinylester. Bevorzugte anionische Copolymere sind Acrylsäure-Acrylamid-Copolymere sowie insbesondere Polyacrylamidcopolymere mit Sulfonsäuregruppen-haltigen Monomeren. Ein besonders bevorzugtes anionisches Copolymer besteht aus 70 - 55 Mol-% Acrylamid und 30 - 45 Mol-% 2-Acrylamido-2-methylpropansulfonsäure, wobei die Sulfonsäuregruppe ganz oder teilweise als Natrium-, Kalium-, Ammonium-, Mono- oder Triethanolammonium-Salz vorliegt. Dieses Copolymer kann auch vernetzt vorliegen, wobei als Ver- netzungsagentien bevorzugt polyolefinisch ungesättigte Verbindungen wie Tetraallyl- oxyethan, Allylsucrose, Allylpentaerythrit und Methylen-bisacrylamid zum Einsatz kommen. Ein solches Polymer ist in dem Handelsprodukt Sepigel®305 der Firma SEPPIC enthalten. Die Verwendung dieses Compounds hat sich im Rahmen der erfindungsgemäßen Lehre als besonders vorteilhaft erwiesen.In this embodiment, it may be preferred to use copolymers of at least one anionic monomer and at least one nonionic monomer. Zen. With regard to the anionic monomers, reference is made to the substances listed above. Preferred nonionic monomers are acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester, vinylpyrrolidone, vinyl ether and vinyl ester. Preferred anionic copolymers are acrylic acid-acrylamide copolymers and in particular polyacrylamide copolymers with monomers containing sulfonic acid groups. A particularly preferred anionic copolymer consists of 70-55 mol% of acrylamide and 30-45 mol% of 2-acrylamido-2-methylpropanesulfonic acid, the sulfonic acid group being wholly or partly as sodium, potassium, ammonium, mono- or triethanolammonium Salt is present. This copolymer can also be crosslinked, the preferred crosslinking agents being polyolefinically unsaturated compounds such as tetraallyloxyethane, allyl sucrose, allylpentaerythritol and methylene-bisacrylamide. Such a polymer is contained in the commercial product Sepigel ® 305 from SEPPIC. The use of this compound has proven to be particularly advantageous in the context of the teaching according to the invention.
Weitere bevorzugte Polymere sind teilweise oder vollständig neutralisierte, vernetzte Copolymere aus 2-Methyl-2[(1-oxo-2-propenyl)amino]-1-propansulfonsäure (AMPS) und Hydroxyethylacrylat, in Form eines inversen Latex kommerziell erhältlich, z. B. unter dem Handelsnamen Simulgel® NS von der Firma Seppic. Weiterhin bevorzugt sind teilweise oder vollständig neutralisierte, vernetzte Copolymere aus 2-Methyl-2[(1-oxo-2-propenyl) amino]-1-propansulfonsäure (AMPS) und Acrylamid, in Form eines inversen Latex kommerziell erhältlich, z. B. unter dem Handelsnamen Simulgel® 600 von der Firma Seppic. Weiterhin bevorzugt sind teilweise oder vollständig neutralisierte, vernetzte Copolymere aus 2-Methyl-2[(1-oxo-2-propenyl)amino]-1-propansulfonsäure (AMPS) und Acrylsäure, in Form eines inversen Latex kommerziell erhältlich, z. B. unter dem Handelsnamen Simulgel® EG von der Firma Seppic.Other preferred polymers are partially or fully neutralized, crosslinked copolymers of 2-methyl-2 [(1-oxo-2-propenyl) amino] -1-propanesulfonic acid (AMPS) and hydroxyethyl acrylate, commercially available in the form of an inverse latex, e.g. B. under the trade name Simulgel ® NS from Seppic. Also preferred are partially or completely neutralized, crosslinked copolymers of 2-methyl-2 [(1-oxo-2-propenyl) amino] -1-propanesulfonic acid (AMPS) and acrylamide, commercially available in the form of an inverse latex, e.g. B. under the trade name Simulgel ® 600 from Seppic. Also preferred are partially or fully neutralized, crosslinked copolymers of 2-methyl-2 [(1-oxo-2-propenyl) amino] -1-propanesulfonic acid (AMPS) and acrylic acid, commercially available in the form of an inverse latex, e.g. B. under the trade name Simulgel ® EG from Seppic.
Weitere bevorzugte anionische Copolymere sind solche, die als Monomere 2-Acryl- amido-2-methylpropansulfonsäure und Polyvinylpyrrolidon enthalten, z. B. das Handelsprodukt Aristoflex® AVC von Clariant.Further preferred anionic copolymers are those which contain 2-acrylamido-2-methylpropanesulfonic acid and polyvinylpyrrolidone as monomers, e.g. B. the commercial product Aristoflex ® AVC from Clariant.
Ebenfalls bevorzugte anionische Homopolymere sind unvemetzte und vernetzte Poly- acrylsäuren. Dabei können Allylether von Pentaerythrit, von Sucrose und von Propylen bevorzugte Vernetzungsagentien sein. Solche Verbindungen sind beispielsweise die Handelsprodukte Carbopol®. Weitere bevorzugte anionische Copolymere sind solche, die als Monomere 80 - 98 Gew.-% gewünschtenfalls substituierte Acrylsäure und 2 - 20 Gew.-% C^-Cso-Fettalkoholmethacrylsäureester enthalten und vernetzt sein können. Solche Verbindungen sind z. B. die Handelsprodukte Pemulen®.
Unter amphoteren Polymeren versteht man sowohl solche Polymere, die im Molekül sowohl freie Aminogruppen als auch freie -COOH- oder SO3H-Gruppen enthalten und zur Ausbildung innerer Salze befähigt sind, als auch zwitterionische Polymere, die im Molekül quartäre Ammoniumgruppen und -COO"- oder -SO3 "-Gruppen bzw. -COOH- oder SO3H-Gruppen enthalten. Ein Beispiel für ein erfindungsgemäß einsetzbares amphoteres Polymer ist das unter der Bezeichnung Amphomer® erhältliche Acrylharz, das ein Copolymeres aus tert.-Butylaminoethylmethacrylat, N-(1 , 1 ,3,3- Tetramethylbutyl)acrylamid sowie zwei oder mehr Monomeren aus der Gruppe Acrylsäure, Methacrylsäure und deren einfachen Estern darstellt. Die erfindungsgemäßen Zusammensetzungen können weiterhin synthetische nichtionische Polymere enthalten. Geeignete nichtionische synthetische Polymere sind Polyvinyl- pyrrolidone und Vinylpyrrolidon Vinylester-Copolymere, z. B. die Handelsprodukte Luviskol® (BASF), sowie Polyvinylalkohole.Also preferred anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Allyl ethers of pentaerythritol, sucrose and propylene can be preferred crosslinking agents. Such compounds are, for example, the commercial products Carbopol ® . Further preferred anionic copolymers are those which contain, as monomers, 80-98% by weight of optionally substituted acrylic acid and 2-20% by weight of C 1-6 -so-fatty alcohol methacrylic acid ester and which can be crosslinked. Such connections are e.g. B. the commercial products Pemulen ® . Amphoteric polymers are understood to mean both those polymers which contain both free amino groups and free -COOH or SO 3 H groups in the molecule and are capable of forming internal salts, and also zwitterionic polymers which contain quaternary ammonium groups and -COO " in the molecule. - or -SO 3 " groups or -COOH or SO 3 H groups. An example of a usable amphoteric polymer according to the invention is obtainable under the name Amphomer ® acrylic resin which is a copolymer of tert-butylaminoethyl methacrylate, N- (1, 1, 3,3- tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid , Methacrylic acid and its simple esters. The compositions according to the invention can furthermore contain synthetic nonionic polymers. Suitable nonionic synthetic polymers are polyvinyl pyrrolidones and vinyl pyrrolidone vinyl ester copolymers, e.g. B. the commercial products Luviskol ® (BASF), and polyvinyl alcohols.
Bei kationischen Polymeren unterscheidet man "temporär" und "permanent" kationische Polymere. Temporär kationische Polymere enthalten üblicherweise eine Aminogruppe, die bei bestimmten pH-Werten als quartäre Ammoniumgruppe vorliegt. Bevorzugt sind Chitosan und dessen Derivate, z. B. die Produkte Hydagen® CMF, Hydagen® HCMF, Kytamer® PC und Chitolam® NB/101. Besonders gut geeignete Chitosane weisen einen Deacetylierungsgrad von wenigstens 80 % und ein Molekulargewicht von 5 ■ 105 bis 5 • 106 g/mol auf. Zur Herstellung erfindungsgemäßer Zubereitungen muß das Chitosan in die Salzform überführt werden. Hierzu geeignete Säuren sind z. B. Essigsäure, Glycol- säure, Weinsäure, Apfelsäure, Citronensäure, Milchsäure, 2-Pyrrolidon-5-carbonsäure, Benzoesäure und Salicylsäure.In the case of cationic polymers, a distinction is made between "temporary" and "permanent" cationic polymers. Temporary cationic polymers usually contain an amino group which is present as a quaternary ammonium group at certain pH values. Chitosan and its derivatives, e.g. B. the products Hydagen ® CMF, Hydagen ® HCMF, Kytamer ® PC and Chitolam ® NB / 101. Chitosans which are particularly suitable have a degree of deacetylation of at least 80% and a molecular weight of 5 × 10 5 to 5 × 10 6 g / mol. To prepare preparations according to the invention, the chitosan must be converted into the salt form. Suitable acids are z. B. acetic acid, glycolic acid, tartaric acid, malic acid, citric acid, lactic acid, 2-pyrrolidone-5-carboxylic acid, benzoic acid and salicylic acid.
Weitere verwendbare kationische Polymere sind beispielsweise quaternisierte Cellulose- Derivate, z. B. die Handelsprodukte Celquat® und Polymer JR®, insbesondere Celquat® H 100, Celquat® L 200 und Polymer JR®400, kationische Alkylpolyglycoside gemäß der DE-PS 44 13 686, kationisierter Honig, kationische Guar-Derivate, insbesondere die Produkte Cosmedia®Guar und Jaguar®, Polysiloxane mit quatemären Gruppen, wie z.B. die Handelsprodukte Q2-7224 (Dow Corning), Dow Corning® 929 Emulsion, SM-2059 (General Electric), SLM-55067 (Wacker) sowie Abil®-Quat 3270 und 3272 (Th. Goldschmidt), sowie die unter den Bezeichnungen Polyquaternium-2, Polyquaternium-17, Polyquatemium-18 und Polyquaternium-27 bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette. Gleichfalls als kationische Polymere eingesetzt werden können die unter den Bezeichnungen Polyquatemium-24 bekannten Polymere.
Ebenfalls als kationisches Polymer verwendbar ist das, gewünschtenfalls vernetzte, Poly(methacryloyloxyethyltrimethylammoniumchlorid) mit der INCI-Bezeichnung Polyquaternium-37. Polyquatemium-37 wird häufig in Form einer nichtwässrigen Polymerdispersion eingesetzt. Solche Polymerdispersionen sind unter den Bezeichnungen Salcare® SC 95 und Salcare® SC 96 im Handel erhältlich. Copolymere aus Methacryloyloxyethyltrimethylammoniumchlorid und nichtionischen Monomeren, bevorzugt Acrylamid, Methacrylamid, Acrylsäure-C1-4-alkylester und Meth- acrylsäure-C^-alkylester, die gegebenenfalls vernetzt sein können, sind im Handel unter dem Namen Salcare® SC 92 erhältlich.Further usable cationic polymers are, for example, quaternized cellulose derivatives, e.g. B. the commercial products Celquat ® and Polymer JR ® , in particular Celquat ® H 100, Celquat ® L 200 and Polymer JR ® 400, cationic alkyl polyglycosides according to DE-PS 44 13 686, cationized honey, cationic guar derivatives, in particular the products Cosmedia ® Guar and Jaguar ® , polysiloxanes with quaternary groups, such as the commercial products Q2-7224 (Dow Corning), Dow Corning ® 929 Emulsion, SM-2059 (General Electric), SLM-55067 (Wacker) and Abil ® -Quat 3270 and 3272 (Th. Goldschmidt), as well as the polymers known under the names Polyquaternium-2, Polyquaternium-17, Polyquatemium-18 and Polyquaternium-27 with quaternary nitrogen atoms in the main polymer chain. The polymers known under the names Polyquatemium-24 can also be used as cationic polymers. The crosslinked poly (methacryloyloxyethyltrimethylammonium chloride) with the INCI name Polyquaternium-37 can also be used as a cationic polymer. Polyquatium-37 is often used in the form of a non-aqueous polymer dispersion. Such polymer dispersions are commercially available under the names Salcare ® SC 95 and Salcare ® SC 96. Copolymers of methacryloyloxyethyltrimethylammonium chloride and nonionic monomers, preferably acrylamide, methacrylamide, acrylic acid C 1-4 alkyl ester and methacrylic acid-C ^ -alkyl, which may be crosslinked, optionally, are commercially available under the name Salcare ® SC 92nd
In einer weiteren bevorzugten Ausführungsform der Erfindung ist mindestens ein natürliches, gewünschtenfalls chemisch modifiziertes Polymer, ausgewählt aus Celluloseethem, z. B. Methylcellulose, Hydroxypropylcellulose, Hydroxyethylcellulose, Hydroxypropylmethylcellulose oder Carboxymethylcellulose, quaternisierten Cellulose- Derivaten, Polyquaternium-24, Guar-Gum, kationischen Guar-Derivaten, Alginaten, Xanthan-Gum, Gummi arabicum, Karaya-Gummi, Carrageenanen,In a further preferred embodiment of the invention, at least one natural, if desired chemically modified polymer is selected from cellulose ethers, e.g. B. methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose or carboxymethyl cellulose, quaternized cellulose derivatives, polyquaternium-24, guar gum, cationic guar derivatives, alginates, xanthan gum, gum arabic, karaya gum, carrageenans,
Johannisbrotkernmehl, Leinsamengummen, Dextranen, Schellack, Amylose, Amylopektin, Dextrinen, chemisch und/oder thermisch modifizierte Stärken, Gelatine, Agar-Agar, sowie Chitosan und dessen Derivaten, enthalten.Locust bean gum, linseed gums, dextrans, shellac, amylose, amylopectin, dextrins, chemically and / or thermally modified starches, gelatin, agar agar, and chitosan and its derivatives.
Es ist erfindungsgemäß auch möglich, dass die verwendeten Zubereitungen mehrere, insbesondere zwei verschiedene Polymere gleicher Ladung und/oder jeweils ein ionisches und ein amphoteres und/oder ein synthetisches nichtionisches Polymer enthalten.It is also possible according to the invention that the preparations used contain several, in particular two different polymers of the same charge and / or each contain an ionic and an amphoteric and / or a synthetic nonionic polymer.
Die kolloidal gelösten Polymere sind erfindungsgemäß in Mengen von 0,01 - 5 Gew.%, bevorzugt 0,5 - 4 Gew.% und besonders bevorzugt 1,0 - 2,5 Gew.% Aktivsubstanz, bezogen auf das Gesamtgewicht der Zusammensetzung, enthalten.According to the invention, the colloidally dissolved polymers are present in amounts of 0.01-5% by weight, preferably 0.5-4% by weight and particularly preferably 1.0-2.5% by weight of active substance, based on the total weight of the composition ,
Weiterhin wurde überraschend gefunden, dass die erfindungsgemäßen Zusammensetzungen eine besonders gleichmäßige Verteilung nicht nur von Pigmenten, sondern auch von ausgewählten kosmetischen Wirkstoffen ermöglichen. Insbesondere an kosmetische Sonnenschutzmittel werden hohe Anforderungen an eine gute, homogene Verteilbarkeit auf der Haut gestellt. In einer bevorzugten Ausführungsform enthalten die erfindungsgemäßen Zusammensetzungen daher weiterhin mindestens einen Wirkstoff, ausgewählt aus anorganischen und organischen UV-Filtersubstanzen, Vitaminen, Provitaminen und
Vitaminvorstufen der Gruppen A, B, C, E, H und K oder deren Derivaten, α-Liponsäure, α-Hydroxycarbonsäuren, Allantoin, α-Bisabolol sowie Desoxyzuckern oder Desoxyzucker-Bausteine enthaltenden Polysacchariden.Furthermore, it has surprisingly been found that the compositions according to the invention enable a particularly uniform distribution not only of pigments but also of selected cosmetic active ingredients. Cosmetic sunscreens in particular place high demands on good, homogeneous distributability on the skin. In a preferred embodiment, the compositions according to the invention therefore furthermore contain at least one active ingredient selected from inorganic and organic UV filter substances, vitamins, provitamins and Vitamin precursors of groups A, B, C, E, H and K or their derivatives, α-lipoic acid, α-hydroxycarboxylic acids, allantoin, α-bisabolol and polysaccharides containing deoxy sugars or deoxy sugar building blocks.
Die erfindungsgemäß verwendeten organischen UV-Filter sind ausgewählt aus den Derivaten von Dibenzoylmethan, Zimtsäureestern, Diphenylacrylsäureestern, Benzophenon, Campher, p-Aminobenzoesäureestem, o-Aminobenzoesäureestem, Salicylsäureestern, Benzimidazolen, symmetrisch oder unsymmetrisch substituierten 1,3,5-Triazinen, mono- meren und oligomeren 4,4-Diarylbutadiencarbonsäureestern und -carbonsäureamiden, Ketotricyclo(5.2.1.0)decan, Benzalmalonsäureestern sowie beliebigen Mischungen der genannten Komponenten. Die organischen UV-Filter können öllöslich oder wasserlöslich sein. Erfindungsgemäß besonders bevorzugte öllösliche UV-Filter sind 1-(4-tert.-Butyl- phenyl)-3-(4'-methoxyphenyl)propan-1 ,3-dion (Parsol® 1789), 1-Phenyl-3-(4'-isopropyl- phenyl)-propan-1 ,3-dion, 3-(4'-Methylbenzyliden)-D,L-campher, 4-(DimethyIamino)- benzoesäure-2-ethylhexylester, 4-(Dimethylamino)benzoesäure-2-octylester, 4- (Dimethylamino)-benzoesäureamylester, 4-Methoxyzimtsäure-2-ethylhexylester,The organic UV filters used according to the invention are selected from the derivatives of dibenzoylmethane, cinnamic acid esters, diphenylacrylic acid esters, benzophenone, camphor, p-aminobenzoic acid esters, o-aminobenzoic acid esters, salicylic acid esters, benzimidazoles, symmetrically or asymmetrically substituted 1,3,5-triazines, monomers and oligomeric 4,4-diarylbutadienecarboxylic acid esters and carboxamides, ketotricyclo (5.2.1.0) decane, benzalmalonic acid esters and any mixtures of the components mentioned. The organic UV filters can be oil-soluble or water-soluble. According to the invention particularly preferred oil-soluble UV filters are 1- (4-tert-butyl phenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione (Parsol ® 1789), 1-phenyl-3- (4 '-Isopropyl-phenyl) -propane-1,3-dione, 3- (4 ' -methylbenzylidene) -D, L-camphor, 4- (dimethylamino) - 2-ethylhexyl benzoate, 4- (dimethylamino) benzoic acid-2 octyl ester, 4- (dimethylamino) benzoic acid amyl ester, 4-methoxycinnamic acid 2-ethylhexyl ester,
4-Methoxyzimtsäurepropylester, 4-Methoxyzimtsäureisopentylester, 2-Cyano-3,3-phenyl- zimtsäure-2-ethylhexylester (Octocrylene), Salicylsäure-2-ethylhexylester, Salicylsäure- 4-isopropylbenzylester, Salicylsäurehomomenthylester (3,3,5-Trimethyl-cyclohexyl- salicylat), 2-Hydroxy-4-methoxybenzophenon, 2-Hydroxy-4-methoxy-4'-methylbenzophe- non, 2,2'-Dihydroxy-4-methoxybenzophenon, 4-Methoxybenzmalonsäuredi-2-ethylhexyl- ester, 2,4,6-Trianilino-(p-carbo-2'-ethyl-1'-hexyloxy)-1,3,5-triazin (Octyl Triazone) und Dioctyl Butamido Triazone (Uvasorb® HEB) sowie beliebige Mischungen der genannten Komponenten.4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isopentyl ester, 2-cyano-3,3-phenyl-cinnamic acid-2-ethylhexyl ester (octocrylene), salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbenzyl ester, salicylic acid homomethyl methyl ester (3,3,5) - salicylate), 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 4-methoxybenzmalonic acid di-2-ethylhexyl ester, 2, 4,6-Trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine (octyl triazone) and dioctyl butamido triazone (Uvasorb ® HEB) as well as any mixtures of the components mentioned.
Bevorzugte wasserlösliche UV-Filter sind 2-Phenylbenzimidazol-5-sulfonsäure und deren Alkali-, Erdalkali-, Ammonium-, Alkylammonium-, Alkanolammonium- und Glucammoni- umsalze, Sulfonsäurederivate von Benzophenonen, vorzugsweise 2-Hydroxy-4-methoxy- benzophenon-5-sulfonsäure und ihre Salze, Sulfonsäurederivate des 3-Benzyliden- camphers, wie z. B. 4-(2-Oxo-3-bornylidenmethyl)benzolsulfonsäure und 2-Methyl-5-(2- oxo-3-bornyliden)sulfonsäure und deren Salze.Preferred water-soluble UV filters are 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts, sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5 -sulfonic acid and its salts, sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and salts thereof.
Einige der öllöslichen UV-Filter können selbst als Lösungsmittel oder Lösungsvermittler für andere UV-Filter dienen. So lassen sich beispielsweise Lösungen des UV-A-Filters 1-(4-tert.-Butylphenyl)-3-(4'methoxyphenyl)propan-1 ,3-dion (z. B. Parsol® 1789) in verschiedenen UV-B-Filtern herstellen. Die erfindungsgemäßen Zusammensetzungen ent-
halten daher in einer weiteren bevorzugten Ausführungsform 1-(4-tert.-Butylphenyl)-3- (4'-methoxyphenyl)propan-1 ,3-dion in Kombination mit mindestens einem UV-B-Filter, ausgewählt aus 4-Methoxyzimtsäure-2-ethylhexylester, 2-Cyano-3,3-phenylzimtsäure-2- ethylhexylester, Salicylsäure-2-ethylhexylester und 3,3,5-Trimethyl-cyclohexylsalicylat. In diesen Kombinationen liegt das Gewichtsverhältnis von UV-B-Filter zu 1-(4-tert- Butylphenyl)-3-(4'methoxyphenyl)propan-1 ,3-dion zwischen 1:1 und 10:1 , bevorzugt zwischen 2:1 und 8:1 , das molare Verhältnis liegt entsprechend zwischen 0,3 und 3,8, bevorzugt zwischen 0,7 und 3,0.Some of the oil-soluble UV filters can themselves serve as solvents or solubilizers for other UV filters. For example, solutions of the UV-A filter 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione (e.g. Parsol ® 1789) can be used in various UV-B -Filter. The compositions according to the invention In a further preferred embodiment, therefore, hold 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione in combination with at least one UV-B filter selected from 4-methoxycinnamic acid. 2-ethylhexyl ester, 2-cyano-3,3-phenylcinnamic acid-2-ethylhexyl ester, salicylic acid-2-ethylhexyl ester and 3,3,5-trimethyl-cyclohexyl salicylate. In these combinations, the weight ratio of UV-B filter to 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione is between 1: 1 and 10: 1, preferably between 2: 1 and 8: 1, the molar ratio is accordingly between 0.3 and 3.8, preferably between 0.7 and 3.0.
Bei den erfindungsgemäß bevorzugten anorganischen Lichtschutzpigmenten handelt es sich um feindisperse oder kolloiddisperse Metalloxide und Metallsalze, beispielsweise Titandioxid, Zinkoxid, Eisenoxid, Aluminiumoxid, Ceroxid, Zirkoniumoxid, Silicate (Talk) und Bariumsulfat. Die Partikel sollten dabei einen mittleren Durchmesser von weniger als 100 nm, vorzugsweise zwischen 5 und 50 nm und insbesondere zwischen 15 und 30 nm aufweisen, so genannte Nanopigmente. Sie können eine sphärische Form aufweisen, es können jedoch auch solche Partikel zum Einsatz kommen, die eine ellipsoide oder in sonstiger Weise von der sphärischen Gestalt abweichende Form besitzen. Die Pigmente können auch oberflächenbehandelt, d.h. hydrophilisiert oder hydrophobiert vorliegen. Typische Beispiele sind gecoatete Titandioxide, wie z. B. Titandioxid T 805 (Degussa) oder Eusolex® T2000 (Merck). Als hydrophobe Coatingmittel kommen dabei vor allem Silicone und dabei speziell Trialkoxyoctylsilane oder Simethicone in Frage. Besonders bevorzugt sind Titandioxid und Zinkoxid.The inorganic light protection pigments preferred according to the invention are finely dispersed or colloidally dispersed metal oxides and metal salts, for example titanium dioxide, zinc oxide, iron oxide, aluminum oxide, cerium oxide, zirconium oxide, silicates (talc) and barium sulfate. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm, so-called nanopigments. They can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or a shape which differs in some other way from the spherical shape. The pigments can also be surface-treated, ie hydrophilized or hydrophobicized. Typical examples are coated titanium dioxide, such as. B. Titanium dioxide T 805 (Degussa) or Eusolex ® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. Titanium dioxide and zinc oxide are particularly preferred.
Besonders bevorzugte anorganische Lichtschutzpigmente sind ausgewählt aus den Oxiden von Titan, Zink, Cer und Eisen sowie beliebigen Mischungen der genannten Komponenten, die oberflächenmodifiziert sein können.Particularly preferred inorganic light protection pigments are selected from the oxides of titanium, zinc, cerium and iron and any mixtures of the components mentioned, which can be surface-modified.
Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung einer Öl-inWasser-Emulsion, die mit mindestens einem Glycero-Phospholipid und/oder mindestens einem Sphingolipid stabilisiert ist, mindestens einen in der Emulsion unlöslichen, partikelförmigen Rohstoff mit einem mittleren Teilchendurchmesser von maximal 200 μm sowie mindestens einen anorganischen oder organischen UV-Filtersubstanzen enthält und frei ist von Emulgatoren mit einem HLB-Wert größer 8, als Sonnenschutzmittel.Another object of the present invention is the use of an oil-in-water emulsion which is stabilized with at least one glycerophospholipid and / or at least one sphingolipid, at least one particulate raw material which is insoluble in the emulsion and has an average particle diameter of at most 200 μm and contains at least one inorganic or organic UV filter substance and is free of emulsifiers with an HLB value greater than 8 as sunscreen.
In einer weiteren bevorzugten Ausführungsform enthalten die erfindungsgemäßen Zusammensetzungen mindestens ein Vitamin, Pro-Vitamin, eine Vitaminvorstufe oder deren Derivate. Hierbei sind solche Komponenten bevorzugt, die üblicherweise den Vitamingruppen A, B, C, E, H und K zugeordnet werden.
Zur Gruppe der als Vitamin A bezeichneten Substanzen gehören das Retinol (Vitamin A-i) sowie das 3,4-Didehydroretinol (Vitamin A2). Das ß-Carotin ist das Provitamin des Retinols. Als Vitamin A-Komponente kommen erfindungsgemäß beispielsweise Vitamin A-Säure und deren Ester, Vitamin A-Aldehyd und Vitamin A-Alkohol sowie dessen Ester, wie Retinylpalmitat und Retinylacetat in Betracht. Die erfindungsgemäßen Zubereitungen enthalten die Vitamin A-Komponente bevorzugt in Mengen von 0,05 - 1 Gew.-%, bezogen auf die gesamte Zusammensetzung.In a further preferred embodiment, the compositions according to the invention contain at least one vitamin, pro-vitamin, a vitamin precursor or their derivatives. Preferred components are those which are usually assigned to the vitamin groups A, B, C, E, H and K. The group of substances called vitamin A includes retinol (vitamin Ai) and 3,4-didehydroretinol (vitamin A 2 ). The ß-carotene is the provitamin of retinol. According to the invention, vitamin A acid and its esters, vitamin A aldehyde and vitamin A alcohol and its esters, such as retinyl palmitate and retinyl acetate, are suitable as vitamin A components. The preparations according to the invention preferably contain the vitamin A component in amounts of 0.05-1% by weight, based on the overall composition.
Zur Vitamin B-Gruppe oder zu dem Vitamin B-Komplex gehören u. a.The vitamin B group or the vitamin B complex include u. a.
• Vitamin B^ (Thiamin)Vitamin B ^ (thiamine)
• Vitamin B2 (Riboflavin)Vitamin B 2 (riboflavin)
• Vitamin B3. Unter dieser Bezeichnung werden häufig die Verbindungen Nicotinsäure und Nicotinsäureamid (Niacinamid) geführt. Erfindungsgemäß bevorzugt ist das Nicotinsäureamid, das bevorzugt in Mengen von 0,05 bis 1 Gew.-%, bezogen auf die gesamte Zusammensetzung, enthalten ist.Vitamin B 3 . The compounds nicotinic acid and nicotinamide (niacinamide) are often listed under this name. According to the invention, preference is given to nicotinamide, which is preferably present in amounts of 0.05 to 1% by weight, based on the overall composition.
• Vitamin B5 (Pantothensäure und Panthenol). Bevorzugt wird Panthenol eingesetzt. Erfindungsgemäß einsetzbare Derivate des Panthenols sind insbesondere die Ester und Ether des Panthenols sowie kationisch derivatisierte Panthenole. In einer weiteren bevorzugten Ausführungsform der Erfindung können an Stelle von sowie zusätzlich zu Pantothensäure oder Panthenol auch Derivate des 2-Furanon mit der allgemeinen Strukturformel (a) eingesetzt werden.• Vitamin B 5 (pantothenic acid and panthenol). Panthenol is preferably used. Derivatives of panthenol which can be used according to the invention are, in particular, the esters and ethers of panthenol and cationically derivatized panthenols. In a further preferred embodiment of the invention, derivatives of 2-furanone with the general structural formula (a) can be used instead of and in addition to pantothenic acid or panthenol.
(a)(A)
Bevorzugt sind die 2-Furanon-Derivate, in denen die Substituenten R1 bis R6 unabhängig voneinander ein Wasserstoffatom, einen Hydroxylrest, einen Methyl-, Methoxy-, Aminomethyl- oder Hydroxymethylrest, einen gesättigten oder ein- oder zweifach ungesättigten, linearen oder verzweigten C2-C4 - Kohlenwasserstoffrest, einen gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxy-C2-C4 - Kohlenwasserstoffrest oder einen gesättigten
oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Triamino-C2-C - Kohlenwasserstoffrest darstellen. Besonders bevorzugte Derivate sind die auch im Handel erhältlichen Substanzen Dihydro-3-hydroxy-4,4-dimethyI- 2(3H)-furanon mit dem Trivialnamen Pantolacton (Merck), 4-Hydroxymethyl-γ- butyrolacton (Merck), 3,3-Dimethyl-2-hydroxy-γ-butyrolacton (Aldrich) und 2,5- Dihydro-5-methoxy-2-furanon (Merck), wobei ausdrücklich alle Stereoisomeren eingeschlossen sind. Das erfindungsgemäß außerordentlich bevorzugte 2-Furanon- Derivat ist Pantolacton (Dihydro-3-hydroxy-4,4-dimethyl-2(3H)-furanon), wobei in Formel (a) R1 für eine Hydroxylgruppe, R2 für ein Wasserstoffatom, R3 und R4 für eine Methylgruppe und R5 und R6 für ein Wasserstoffatom stehen. Das Stereoisomer (R)-Pantolacton entsteht beim Abbau von Pantothensäure.Preferred are the 2-furanone derivatives in which the substituents R 1 to R 6 independently of one another are a hydrogen atom, a hydroxyl radical, a methyl, methoxy, aminomethyl or hydroxymethyl radical, a saturated or mono- or di-unsaturated, linear or branched C 2 -C 4 - hydrocarbon residue, a saturated or mono- or di-unsaturated, branched or linear mono-, di- or trihydroxy-C 2 -C 4 - hydrocarbon residue or a saturated or mono- or di-unsaturated, branched or linear mono-, di- or triamino-C 2 -C - hydrocarbon radical. Particularly preferred derivatives are the commercially available substances dihydro-3-hydroxy-4,4-dimethyl-2 (3H) -furanone with the common name pantolactone (Merck), 4-hydroxymethyl-γ-butyrolactone (Merck), 3.3 -Dimethyl-2-hydroxy-γ-butyrolactone (Aldrich) and 2,5-dihydro-5-methoxy-2-furanone (Merck), all stereoisomers being expressly included. The 2-furanone derivative which is extremely preferred according to the invention is pantolactone (dihydro-3-hydroxy-4,4-dimethyl-2 (3H) -furanone), where in formula (a) R 1 is a hydroxyl group, R 2 is a hydrogen atom, R 3 and R 4 represent a methyl group and R 5 and R 6 represent a hydrogen atom. The stereoisomer (R) -pantolactone is formed when pantothenic acid is broken down.
Die genannten Verbindungen des Vitamin B5-Typs sowie die 2-Furanonderivate sind bevorzugt in einer Gesamtmenge von 0,05 bis 10 Gew.-%, besonders bevorzugt 0,1 bis 5 Gew.-%, jeweils bezogen auf die gesamte Zusammensetzung, enthalten.The above-mentioned compounds of the vitamin B 5 type and the 2-furanone derivatives are preferably present in a total amount of 0.05 to 10% by weight, particularly preferably 0.1 to 5% by weight, in each case based on the overall composition ,
• Vitamin B6 (Pyridoxin sowie Pyridoxamin und Pyridoxal).• Vitamin B 6 (pyridoxine as well as pyridoxamine and pyridoxal).
• Vitamin B7 (Biotin), auch als Vitamin H oder "Hautvitamin" bezeichnet. Biotin ist bevorzugt in Mengen von 0,0001 bis 1,0 Gew.-%, insbesondere 0,001 bis 0,01 Gew.- %, jeweils bezogen auf die gesamte Zusammensetzung, enthalten.• Vitamin B 7 (biotin), also known as vitamin H or "skin vitamin". Biotin is preferably present in amounts of 0.0001 to 1.0% by weight, in particular 0.001 to 0.01% by weight, in each case based on the total composition.
Vitamin C (Ascorbinsäure) wird bevorzugt in Mengen von 0,1 bis 3 Gew.-%, bezogen auf die gesamte Zusammensetzung, eingesetzt. Die Verwendung der Derivate Ascorbyl- palmitat, -stearat, -dipalmitat, -acetat, Mg-Ascorbylphosphat, Na-Ascorbylphosphat, Natrium- und Magnesiumascorbat, Dinatriumascorbylphosphat und -sulfat, Kalium- ascorbyltocopherylphosphat, Chitosanascorbat oder Ascorbylglucosid kann bevorzugt sein. Die Verwendung in Kombination mit Tocopherolen kann ebenfalls bevorzugt sein. Zur Vitamin E-Gruppe zählen Tocopherol, insbesondere α-Tocopherol, und seine Derivate. Bevorzugte Derivate sind insbesondere die Ester, wie Tocopherylacetat, -nicotinat, -phosphat, -succinat, -linoleat, -oleat, Tocophereth-5, Tocophereth-10, Tocophereth-12, Tocophereth-18, Tocophereth-50 und Tocophersolan. Tocopherol und seine Derivate sind bevorzugt in Mengen von 0,05 - 1 Gew.-%, bezogen auf die gesamte Zusammensetzung, enthalten.Vitamin C (ascorbic acid) is preferably used in amounts of 0.1 to 3% by weight, based on the total composition. The use of the derivatives ascorbyl palmitate, stearate, dipalmitate, acetate, Mg ascorbyl phosphate, Na ascorbyl phosphate, sodium and magnesium ascorbate, disodium ascorbyl phosphate and sulfate, potassium ascorbyltocopheryl phosphate, chitosan sorbyl glucosate or ascorbic ascorbyl. Use in combination with tocopherols may also be preferred. The vitamin E group includes tocopherol, in particular α-tocopherol, and its derivatives. Preferred derivatives are in particular the esters, such as tocopheryl acetate, nicotinate, phosphate, succinate, linoleate, oleate, tocophereth-5, tocophereth-10, tocophereth-12, tocophereth-18, tocophereth-50 and tocopherol. Tocopherol and its derivatives are preferably present in amounts of 0.05-1% by weight, based on the total composition.
Unter Vitamin F werden üblicherweise essentielle Fettsäuren, insbesondere Linolsäure, Linolensäure und Arachidonsäure, verstanden.
Vitamin H ist eine andere Bezeichnung für Biotin oder Vitamin B7 (siehe oben).Vitamin F is usually understood to mean essential fatty acids, in particular linoleic acid, linolenic acid and arachidonic acid. Vitamin H is another name for biotin or vitamin B 7 (see above).
Zu den fettlöslichen Vitaminen der Vitamin K-Gruppe, denen das Grundgerüst des 2-Methyl-1 ,4-naphthochinons zugrunde liegt, gehören Phyllochinon (Vitamin K^, Farno- chinon oder Menachinon-7 (Vitamin K2) und Menadion (Vitamin K-). Vitamin K ist bevorzugt in Mengen von 0,0001 bis 1 ,0 Gew.-%, insbesondere 0,01 bis 0,5 Gew.-%, jeweils bezogen auf die gesamte Zusammensetzung, enthalten.The fat-soluble vitamins of the vitamin K group, which are based on the basic structure of 2-methyl-1, 4-naphthoquinone, include phylloquinone (vitamin K ^, farnoquinone or menaquinone-7 (vitamin K2) and menadione (vitamin K- Vitamin K is preferably present in amounts of 0.0001 to 1.0% by weight, in particular 0.01 to 0.5% by weight, in each case based on the overall composition.
Bevorzugt enthalten die erfindungsgemäßen Mittel Vitamine, Provitamine und Vitaminvorstufen aus den Gruppen A, B, C, E und H oder deren Derivate. Vitamin A-palmitat (Retinylpalmitat), Panthenol und seine Derivate, Nicotinsäureamid, Ascorbylpalmitat, -acetat, Mg-Ascorbylphosphat, Na-Ascorbylphosphat, Natrium- und Magnesiumascorbat, die Tocopherolester, besonders Tocopherylacetat, und Biotin sind besonders bevorzugt.The agents according to the invention preferably contain vitamins, provitamins and vitamin precursors from groups A, B, C, E and H or their derivatives. Vitamin A palmitate (retinyl palmitate), panthenol and its derivatives, nicotinamide, ascorbyl palmitate, acetate, Mg ascorbyl phosphate, Na ascorbyl phosphate, sodium and magnesium ascorbate, the tocopherol esters, especially tocopheryl acetate, and biotin are particularly preferred.
In einer weiteren bevorzugten Ausführungsform enthalten die erfindungsgemäßen Zusammensetzungen α-Hydroxycarbonsäuren. Die α-Hydroxycarbonsäuren sind erfindungsgemäß ausgewählt aus Glycolsäure, Milchsäure, Methylmilchsäure, 2-Hydroxy- butansäure, 2-Hydroxypentansäure, 2-Hydroxyhexansäure, 2-Hydroxyheptansäure, 2-Hydroxyoctansäure, 2-Hydroxynonansäure, 2-Hydroxydecansäure, 2-Hydroxy- undecansäure, 2-Hydroxydodecansäure (α-Hydroxylaurinsäure), 2-Hydroxytetradecan- säure (α-Hydroxymyristinsäure), 2-Hydroxyhexadecansäure (α-Hydroxypalmitinsäure), 2-Hydroxyoctadecansäure (α-Hydroxystearinsäure), 2-Hydroxyeicosatetraensäure (α-Hydroxyarachidonsäure), Mandelsäure, Phenylmilchsäure, Glycerinsäure, 2,3,4-Tri- hydroxybutansäure mit den Isomeren Erythonsäure und Threonsäure, Ribonsäure, Arabinonsäure, Xylonsäure, Lyxonsäure, Allonsäure, Altronsäure, Gluconsäure, Mannonsäure, Gulonsäure, Idonsäure, Galactonsäure, Talonsäure, Glucoheptonsäure, Galactoheptonsäure, Tartronsäure, Äpfelsäure, Weinsäure, Zitronensäure, Schleimsäure (Galactarsäure), Glucarsäure sowie den physiologisch verträglichen Salzen der vorgenannten Säuren und ihren Lactonformen, insbesondere Gluconolacton, Galactolacton, Glucuronolacton, Galacturonolacton, Gulonolacton, Ribonolacton, Glucoheptonolacton, Mannonolacton, Galactoheptonolacton und Pantoyllacton.In a further preferred embodiment, the compositions according to the invention contain α-hydroxycarboxylic acids. According to the invention, the α-hydroxycarboxylic acids are selected from glycolic acid, lactic acid, methyllactic acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid, 2-hydroxyhexanoic acid, 2-hydroxyheptanoic acid, 2-hydroxyoctanoic acid, 2-hydroxynonanoic acid, 2-hydroxydecanoic acid, 2-hydroxy-undecanoic acid, 2-hydroxydodecanoic acid (α-hydroxylauric acid), 2-hydroxytetradecanoic acid (α-hydroxymyristic acid), 2-hydroxyhexadecanoic acid (α-hydroxypalmitic acid), 2-hydroxyoctadecanoic acid (α-hydroxystearic acid), 2-hydroxyeicosatetraenoic acid (α-hydroxy arachidic acid), phen, hydroxy arachidonic acid, phen, hydroxy arachidic acid, phen, hydroxy arachid acid, phenyl arachid acid , Glyceric acid, 2,3,4-tri-hydroxybutanoic acid with the isomers erythonic acid and threonic acid, ribonic acid, arabinonic acid, xylonic acid, lyxonic acid, allonic acid, altronic acid, gluconic acid, mannonic acid, gulonic acid, idonic acid, galactonic acid, talonic acid, glucoheptonic acid, galactoheptonic acid, tartronic acid, malic acid , Tartaric acid, citric acid, mucic acid (galactaric acid), glucaric acid s and the physiologically tolerable salts of the aforementioned acids and their lactone forms, in particular gluconolactone, galactolactone, glucuronolactone, galacturonolactone, gulonolactone, ribonolactone, glucoheptonolactone, mannonolactone, galactoheptonolactone and pantoyl lactone.
Die α-Hydroxycarbonsäuren werden erfindungsgemäß in Mengen von 0,01 - 10 Gew.-%, bevorzugt 0,1 - 5 Gew.-% und besonders bevorzugt 1 - 3 Gew.-%, jeweils bezogen auf die gesamte Zusammensetzung, eingesetzt.
In einer weiteren bevorzugten Ausführungsform enthalten die erfindungsgemäßen Zusammensetzungen mindestens einen Desoxyzucker oder mindestens ein Des- oxyzucker-Bausteine enthaltendes Polysaccharid.According to the invention, the α-hydroxycarboxylic acids are used in amounts of 0.01-10% by weight, preferably 0.1-5% by weight and particularly preferably 1-3% by weight, in each case based on the overall composition. In a further preferred embodiment, the compositions according to the invention contain at least one deoxy sugar or at least one polysaccharide containing deoxy sugar building blocks.
Als Desoxyzucker im Sinne der Erfindung werden vorzugsweise die L(-)-Fucose und die L(+)-Rhamnose verstanden. Fucose kommt z.B. als Baustein von Polysacchariden vor, die aus marinen Braunalgen (z. B. Fucus vesiculosus) isoliert werden können, Rhamnose stellt einen Polysaccharid-Baustein der Arabinsäure in Gummi arabicum dar. Entsprechende Handelsprodukte sind z. B. Fucogel 1000 (INCI-Bezeichnung Biosaccharide Gum-1) oder Rhamnosoft (INCI-Bezeichnung Biosaccharide Gum-2), beide von der Firma Solabia erhältlich.L (-) - fucose and L (+) - rhamnose are preferably deoxy sugar in the sense of the invention. Fucose comes e.g. as a building block of polysaccharides that can be isolated from marine brown algae (e.g. Fucus vesiculosus), rhamnose is a polysaccharide building block of arabic acid in gum arabic. B. Fucogel 1000 (INCI name Biosaccharide Gum-1) or Rhamnosoft (INCI name Biosaccharide Gum-2), both available from Solabia.
Die Desoxyzucker oder Desoxyzucker-Bausteine enthaltenden Polysaccharide werden erfindungsgemäß in Mengen von 0,01 - 10 Gew.-%, bevorzugt 0,1 - 5 Gew.-% und besonders bevorzugt 1 - 3 Gew.-%, jeweils bezogen auf die gesamte Zusammensetzung, eingesetzt.According to the invention, the polysaccharides containing deoxy sugar or deoxy sugar building blocks are present in amounts of 0.01-10% by weight, preferably 0.1-5% by weight and particularly preferably 1-3% by weight, in each case based on the entire composition , used.
In einer besonders bevorzugten Ausführungsform sind die erfindungsgemäßen ÖI-in- Wasser-Emulsionen dadurch erhältlich, dass die in der Emulsion unlöslichen, partikelförmigen Rohstoffe mit einem mittleren Teilchendurchmesser von maximal 200 μm der Glycero-Phospholipid- und/oder Sphingolipid-stabilisierten Emulsion nach der Homogenisierung zugefügt werden.In a particularly preferred embodiment, the oil-in-water emulsions according to the invention can be obtained in that the particulate raw materials which are insoluble in the emulsion and have an average particle diameter of at most 200 μm of the glycerophospholipid and / or sphingolipid-stabilized emulsion after the homogenization be added.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung einer ÖI-in-Wasser-Emulsion, die mit mindestens einem Glycero-Phospholipid und/oder mindestens einem Sphingolipid stabilisiert ist und mindestens einen in der Emulsion unlöslichen, partikelförmigen Rohstoff mit einem mittleren Teilchendurchmesser von maximal 200 μm enthält, bei dem die Fettphase, die das Glycero-Phopholipid und/oder das Sphingolipid enthält, und die Wasserphase jeweils getrennt voneinander auf Temperaturen von ca. 70 - 85 °C erhitzt werden, die Wasserphase unter Rühren mit einem Homogenisator zur Fettphase gegeben wird, gewünschtenfalls die Emulsion auf 50 °C abgekühlt wird und mindestens ein verdickendes Polymer zugegeben wird, die Emulsion bis 30 °C abgekühlt wird und die unlöslichen, partikelförmigen Rohstoffe mit einem mittleren Teilchendurchmesser von maximal 200 μm sowie gewünschtenfalls weitere Wirkstoffe zugefügt werden. Bevorzugt ist dieses Verfahren für Emulsionen, die frei sind von Emulgatoren mit einem HLB-Wert größer 8.
Die folgenden Beispiele sollen die Erfindung verdeutlichen, ohne sie hierauf zu beschränken:
The present invention furthermore relates to a process for the preparation of an oil-in-water emulsion which is stabilized with at least one glycerophospholipid and / or at least one sphingolipid and at least one particulate raw material which is insoluble in the emulsion and has an average particle diameter of contains a maximum of 200 μm, in which the fat phase, which contains the glycerophospholipid and / or the sphingolipid, and the water phase are each separately heated to temperatures of approx. 70 - 85 ° C, the water phase with stirring with a homogenizer to the fat phase is given, if desired the emulsion is cooled to 50 ° C. and at least one thickening polymer is added, the emulsion is cooled to 30 ° C. and the insoluble, particulate raw materials with an average particle diameter of at most 200 μm and, if desired, further active ingredients are added. This method is preferred for emulsions that are free from emulsifiers with an HLB value greater than 8. The following examples are intended to illustrate the invention without restricting it thereto:
Wirkungsnachweiseffect detection
Die verbesserte Wirkung der erfindungsgemäßen Zusammensetzungen wurde in folgenden Vergleichsversuchen nachgewiesen. Es wurden zwei verschiedene Basisrezepturen hergestellt.The improved effect of the compositions according to the invention was demonstrated in the following comparative experiments. Two different basic recipes were made.
Basis I stellt eine ÖI-in-Wasser-Emulsion dar, die mit einem Alkylpolyglycosid- Fettalkohol-Gemisch als Emulgator stabilisiert ist. Basis II stellt die erfindungsgemäße Lecithin-stabilisierte Emulsion dar.Base I is an oil-in-water emulsion that is stabilized with an alkyl polyglycoside-fatty alcohol mixture as an emulsifier. Base II represents the lecithin-stabilized emulsion according to the invention.
Von beiden Basisrezepturen wurden 3 Varianten hergestellt:3 variants of both basic formulations were produced:
1. Placebo-Formulierung: ohne erfindungsgemäßes Pigment (Ronasphere® LDP)1. placebo formulation: without inventive pigment (® Ronasphere LDP)
2. Rezeptur mit 1 Gew.% eines erfindungsgemäßen Pigmentes (Ronasphere® LDP)2. Recipe with 1% by weight of a pigment according to the invention (Ronasphere ® LDP)
3. Rezeptur mit 3 Gew.% eines erfindungsgemäßen Pigmentes (Ronasphere® LDP)3. formulation with 3 wt.% Of a pigment (® Ronasphere LDP) of the invention
Die Untersuchungen wurden an 6 Probandinnen am Unteram mittels eines Visioscan- Gerätes (Courage & Khazaka) durchgeführt. Dieses Gerät in Kombination mit der Software "SELS 2000" stellt ein System zur Analyse von Oberflächenprofilen dar. Mit einer CCD-Kamera werden Bilder der Oberfläche (Haut) aufgenommen und über einen Bildspeicher in verschiedene Graustufen umgewandelt. Über die Analyse dieser Graustufenverteilung können Höhen und Tiefen in einer Aufnahme berechnet werden. Indirekt erhält man somit das Profil der Oberfläche.The examinations were carried out on 6 test persons in the Unteram using a Visioscan device (Courage & Khazaka). This device in combination with the "SELS 2000" software represents a system for the analysis of surface profiles. Images of the surface (skin) are recorded with a CCD camera and converted into various shades of gray via an image memory. By analyzing this grayscale distribution, heights and depths can be calculated in one image. The profile of the surface is thus obtained indirectly.
Die Software SELS ("Surface evaluation of the living skin") berechnet automatisch verschiedene Parameter standardmäßig, z. B. die Schuppigkeit, Rauhigkeit, Faltigkeit und Glätte. Für die vorliegende Fragestellung wurde der Parameter SEW (Faltigkeit/Wrinkles) herangezogen. Dieser Parameter berechnet sich aus der Anzahl und dem Verhältnis von horizontalen und vertikalen Falten. Je mehr Falten vorliegen und je breiter diese sind, desto höher ist der SEW-Wert.The software SELS ("Surface evaluation of the living skin") automatically calculates various parameters by default, e.g. B. the scaly, roughness, wrinkles and smoothness. The parameter SEW (wrinkles / wrinkles) was used for the present question. This parameter is calculated from the number and the ratio of horizontal and vertical folds. The more wrinkles there are and the wider they are, the higher the SEW value.
Die Testmuster wurden in standardisierter Menge einmalig auf die definierten Areale des Unterarms aufgetragen und die Hautareale vor der Applikation sowie eine, drei und fünf Stunden nach der Applikation vermessen. Jeweils zwei Formulierungen (mit Wirkstoff und Placebo) wurde ein unbehandeltes korrespondierendes Areal zugeordnet, so dass
24The test samples were applied once in a standardized amount to the defined areas of the forearm and the skin areas were measured before application and one, three and five hours after application. An untreated corresponding area was assigned to two formulations (with active ingredient and placebo), so that 24
bei der statistischen Analyse ein Many-to-one-Vergleich der Ausgangslagendifferenzen ausgeführt werden konnte.in the statistical analysis a many-to-one comparison of the initial position differences could be carried out.
Die Ergebnisse der Visioscan-Untersuchungen sind in Tabelle 3 zusammengefasst. Die Rezepturen auf Lecithin-Basis zeigen, je nach Gehalt an erfindungsgemäßem Pigment, die größte Verbesserung des Faltigkeitswertes.The results of the Visioscan examinations are summarized in Table 3. The lecithin-based formulations show the greatest improvement in wrinkle value, depending on the pigment content of the invention.
Tabelle 3: Mittelwerte (MW), Standardabweichung (SD) und Ausgangslagendifferenzen (Ausgidiff.) des SELS-Parameters SEw (Faltigkeit)Table 3: Mean values (MW), standard deviation (SD) and initial position differences (outgiffiff.) Of the SELS parameter S E w (wrinkle)
Tabelle 4: Weitere erfindungsgemäße Rezepturbeispiele Table 4: Further recipe examples according to the invention
Claims
1. ÖI-in-Wasser-Emulsion, die mit mindestens einem Glycero-Phospholipid und/öder mindestens einem Sphingolipid stabilisiert ist, mindestens einen in der Emulsion unlöslichen, partikelförmigen Rohstoff mit einem mittleren Teilchendurchmesser von maximal 200 μm enthält und frei ist von Emulgatoren mit einem HLB-Wert größer 8.1. Oil-in-water emulsion which is stabilized with at least one glycerophospholipid and/or at least one sphingolipid, contains at least one particulate raw material which is insoluble in the emulsion and has an average particle diameter of a maximum of 200 μm and is free of emulsifiers an HLB value greater than 8.
2. ÖI-in-Wasser-Emulsion gemäß Anspruch 1, dadurch gekennzeichnet, dass die Glycero-Phospholipide und/oder Sphingolipide pflanzlichen Ursprungs sind.2. Oil-in-water emulsion according to claim 1, characterized in that the glycerophospholipids and / or sphingolipids are of plant origin.
3. Öl-in-Wasser Emulsion gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Glycero-Phospholipide ausgewählt sind aus Phosphatidylcholinen, Phosphatidyl- ethanolaminen, Phosphatidylserinen und Phosphatidylinositen sowie Mischungen dieser Substanzen.3. Oil-in-water emulsion according to claim 1 or 2, characterized in that the glycerophospholipids are selected from phosphatidylcholines, phosphatidylethanolamines, phosphatidylserines and phosphatidylinositols and mixtures of these substances.
4. ÖI-in-Wasser-Emulsion gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Sphingolipide ausgewählt sind aus Glycosphingolipiden, Sphingophospholipiden und Ceramiden sowie Mischungen dieser Substanzen.4. Oil-in-water emulsion according to one of the preceding claims, characterized in that the sphingolipids are selected from glycosphingolipids, sphingophospholipids and ceramides and mixtures of these substances.
5. ÖI-in-Wasser-Emulsion gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Glycero-Phospholipide und/oder Sphingolipide eine Jodzahl von maximal 10 aufweisen.5. Oil-in-water emulsion according to one of the preceding claims, characterized in that the glycerophospholipids and / or sphingolipids have an iodine number of a maximum of 10.
6. ÖI-in-Wasser-Emulsion gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Glycero-Phospholipide und/oder Sphingolipide eine Jodzahl von maximal 5 aufweisen.6. Oil-in-water emulsion according to one of the preceding claims, characterized in that the glycerophospholipids and / or sphingolipids have an iodine number of a maximum of 5.
7. ÖI-in-Wasser-Emulsion gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die in der Emulsion unlöslichen, partikelförmigen Rohstoffe mit einem mittleren Teilchendurchmesser von maximal 200 μm ausgewählt sind aus inerten anorganischen und organischen Pigmenten und Adsorbentien, sowie aus Mischungen dieser Substanzen.
7. Oil-in-water emulsion according to one of the preceding claims, characterized in that the particulate raw materials insoluble in the emulsion with an average particle diameter of a maximum of 200 μm are selected from inert inorganic and organic pigments and adsorbents, as well as from mixtures of these substances.
8. ÖI-in-Wasser-Emulsion gemäß Anspruch 7, dadurch gekennzeichnet, dass die anorganischen Pigmente ausgewählt sind aus den Oxiden von Silicium, Titan, Eisen, Zink, Zirkonium, Magnesium, Cer und Bismut, aus Bornitrid, Glimmer, Flussspat und wasserunlöslichen Perlglanzpigmenten, die mit mindestens einer anorganischen und/oder organischen Verbindung beschichtet sein können.8. Oil-in-water emulsion according to claim 7, characterized in that the inorganic pigments are selected from the oxides of silicon, titanium, iron, zinc, zirconium, magnesium, cerium and bismuth, from boron nitride, mica, fluorspar and water-insoluble Pearlescent pigments that can be coated with at least one inorganic and/or organic compound.
9. ÖI-in-Wasser-Emulsion nach einem der Ansprüche 7 oder 8, dadurch gekennzeichnet, dass die anorganischen Pigmente ausgewählt sind aus Siliciumdioxid-Partikeln, die mit Titandioxid und/oder Eisenoxiden beschichtet sind.9. Oil-in-water emulsion according to one of claims 7 or 8, characterized in that the inorganic pigments are selected from silicon dioxide particles which are coated with titanium dioxide and / or iron oxides.
10. ÖI-in-Wasser-Emulsion gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die in der Emulsion unlöslichen, partikelförmigen Rohstoffe mit einem mittleren Teilchendurchmesser von maximal 200 μm der Glycero- Phospholipid- und/oder Sphingolipid-stabilisierten Emulsion nach der Homogenisierung zugefügt werden.10. Oil-in-water emulsion according to one of the preceding claims, characterized in that the particulate raw materials insoluble in the emulsion with an average particle diameter of a maximum of 200 μm of the glycero-phospholipid- and / or sphingolipid-stabilized emulsion after homogenization be added.
11. ÖI-in-Wasser-Emulsion gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die in der Emulsion unlöslichen, partikelförmigen Rohstoffe einen mittleren Teilchendurchmesser von 0,5 - 150 μm aufweisen.11. Oil-in-water emulsion according to one of the preceding claims, characterized in that the particulate raw materials insoluble in the emulsion have an average particle diameter of 0.5 - 150 μm.
12. ÖI-in-Wasser-Emulsion gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die in der Emulsion unlöslichen, partikelförmigen Rohstoffe einen mittleren Teilchendurchmesser von 1 - 40 μm aufweisen.12. Oil-in-water emulsion according to one of the preceding claims, characterized in that the particulate raw materials insoluble in the emulsion have an average particle diameter of 1 - 40 μm.
13. ÖI-in-Wasser-Emulsion gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass weiterhin mindestens ein kolloidal gelöstes Polymer enthalten ist.13. Oil-in-water emulsion according to one of the preceding claims, characterized in that at least one colloidally dissolved polymer is also contained.
14. ÖI-in-Wasser-Emulsion gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass weiterhin mindestens ein Wirkstoff, ausgewählt aus anorganischen und organischen UV-Filtersubstanzen, Vitaminen, Provitaminen und Vitaminvorstufen der Gruppen A, B, C, E, H und K oder deren Derivaten, α- Liponsäure, α-Hydroxycarbonsäuren, Allantoin, α-Bisabolol sowie Desoxyzuckem oder Desoxyzucker-Bausteine enthaltenden Polysacchariden, enthalten ist.
14. Oil-in-water emulsion according to one of the preceding claims, characterized in that at least one active ingredient selected from inorganic and organic UV filter substances, vitamins, provitamins and vitamin precursors of groups A, B, C, E, H and K or its derivatives, α-lipoic acid, α-hydroxycarboxylic acids, allantoin, α-bisabolol and polysaccharides containing deoxysugar or deoxysugar building blocks.
15. Verwendung einer ÖI-in-Wasser-Emulsion, die mit mindestens einem Glycero- Phospholipid und/oder mindestens einem Sphingolipid stabilisiert ist, mindestens einen in der Emulsion unlöslichen, partikelförmigen Rohstoff mit einem mittleren Teilchendurchmesser von maximal 200 μm sowie mindestens einen anorganischen oder organischen UV-Filtersubstanzen enthält und frei ist von Emulgatoren mit einem HLB-Wert größer 8, als Sonnenschutzmittel.15. Use of an oil-in-water emulsion that is stabilized with at least one glycerophospholipid and / or at least one sphingolipid, at least one particulate raw material insoluble in the emulsion with an average particle diameter of a maximum of 200 μm and at least one inorganic or contains organic UV filter substances and is free of emulsifiers with an HLB value greater than 8, as a sunscreen.
16. Nicht-therapeutische Verwendung von mit mindestens einem Glycero-Phospholipid und/oder mindestens einem Sphingolipid stabilisierten ÖI-in-Wasser-Emulsionen, die mindestens einen in der Emulsion unlöslichen, partikelförmigen Rohstoff mit einem mittleren Teilchendurchmesser von maximal 200 μm enthalten,16. Non-therapeutic use of oil-in-water emulsions stabilized with at least one glycerophospholipid and/or at least one sphingolipid, which contain at least one particulate raw material that is insoluble in the emulsion and has an average particle diameter of a maximum of 200 μm,
- zur Verbesserung des Erscheinungsbildes der Hauttextur,- to improve the appearance of skin texture,
- zur optischen Kaschierung von Hautunebenheiten, Linien, Fältchen, Falten, Pickeln und Narben,- for the optical concealment of skin imperfections, lines, wrinkles, pimples and scars,
- zur Erzielung eines ebenmäßigen Teints oder- to achieve an even complexion or
- zur Verfeinerung des Erscheinungsbildes der Porengröße.- to refine the appearance of pore size.
17. Nicht-therapeutische Verwendung gemäß Anspruch 16, dadurch gekennzeichnet, dass die ÖI-in-Wasser-Emulsionen frei sind von Emulgatoren mit einem HLB-Wert größer 8.17. Non-therapeutic use according to claim 16, characterized in that the oil-in-water emulsions are free of emulsifiers with an HLB value greater than 8.
18. Nicht-therapeutische Verwendung gemäß einem der Ansprüche 15 - 17, dadurch gekennzeichnet, dass die Glycero-Phospholipide und/oder Sphingolipide pflanzlichen Ursprungs sind.18. Non-therapeutic use according to one of claims 15 - 17, characterized in that the glycerophospholipids and / or sphingolipids are of plant origin.
19. Nicht-therapeutische Verwendung gemäß einem der Ansprüche 15 - 18, dadurch gekennzeichnet, dass die Glycero-Phospholipide ausgewählt sind aus Phosphatidyl- cholinen, Phosphatidylethanolaminen, Phosphatidylserinen und Phosphatidylinositen sowie Mischungen dieser Substanzen.19. Non-therapeutic use according to one of claims 15 - 18, characterized in that the glycerophospholipids are selected from phosphatidylcholines, phosphatidylethanolamines, phosphatidylserines and phosphatidylinositols and mixtures of these substances.
20. Nicht-therapeutische Verwendung gemäß einem der Ansprüche 15 - 19, dadurch gekennzeichnet, dass die Sphingolipide ausgewählt sind aus Glycosphingolipiden, Sphingophospholipiden und Ceramiden sowie Mischungen dieser Substanzen.
20. Non-therapeutic use according to one of claims 15 - 19, characterized in that the sphingolipids are selected from glycosphingolipids, sphingophospholipids and ceramides and mixtures of these substances.
1. Verfahren zur Herstellung einer ÖI-in-Wasser-Emulsion, die mit mindestens einem Glycero-Phospholipid und/oder mindestens einem Sphingolipid stabilisiert ist und mindestens einen in der Emulsion unlöslichen, partikelförmigen Rohstoff mit einem mittleren Teilchendurchmesser von maximal 200 μm enthält, das dadurch gekennzeichnet ist, dass die Fettphase, die das Glycero-Phopholipid und/oder das Sphingolipid enthält, und die Wasserphase jeweils getrennt voneinander auf Temperaturen von ca. 70 - 85 °C erhitzt werden, die Wasserphase unter Rühren mit einem Homogenisator zur Fettphase gegeben wird, gewünschtenfalls die Emulsion auf 50 °C abgekühlt wird und mindestens ein verdickendes Polymer zugegeben wird, die Emulsion auf 30 °C abgekühlt wird und die unlöslichen, partikelförmigen Rohstoffe mit einem mittleren Teilchendurchmesser von maximal 200 μm sowie gewünschtenfalls weitere Wirkstoffe zugefügt werden.1. Process for producing an oil-in-water emulsion which is stabilized with at least one glycerophospholipid and/or at least one sphingolipid and contains at least one particulate raw material which is insoluble in the emulsion and has an average particle diameter of a maximum of 200 μm characterized in that the fat phase, which contains the glycero-phospholipid and/or the sphingolipid, and the water phase are each heated separately from one another to temperatures of approximately 70 - 85 ° C, and the water phase is added to the fat phase while stirring with a homogenizer , if desired, the emulsion is cooled to 50 ° C and at least one thickening polymer is added, the emulsion is cooled to 30 ° C and the insoluble, particulate raw materials with an average particle diameter of a maximum of 200 μm and, if desired, other active ingredients are added.
22. Verfahren gemäß Anspruch 21, dadurch gekennzeichnet ist, dass die Emulsion frei ist von Emulgatoren mit einem HLB-Wert größer 8.
22. The method according to claim 21, characterized in that the emulsion is free of emulsifiers with an HLB value greater than 8.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE10258103.7 | 2002-12-11 | ||
DE2002158103 DE10258103A1 (en) | 2002-12-11 | 2002-12-11 | Oil-in-water emulsions for use in sunscreens and non-therapeutic skin treatment and containing particulate material are stabilized using a glycero-phospholipid and/or sphingolipid |
Publications (2)
Publication Number | Publication Date |
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WO2004052328A2 true WO2004052328A2 (en) | 2004-06-24 |
WO2004052328A3 WO2004052328A3 (en) | 2004-09-10 |
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Application Number | Title | Priority Date | Filing Date |
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PCT/EP2003/013391 WO2004052328A2 (en) | 2002-12-11 | 2003-11-28 | Emulsions stabilised by glycerophospholipids or sphingolipids for improving the appearance of the skin |
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DE (1) | DE10258103A1 (en) |
WO (1) | WO2004052328A2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2006090301A1 (en) | 2005-02-23 | 2006-08-31 | Philips Intellectual Property & Standards Gmbh | Electroluminescent device with iridium complex |
JP2008291014A (en) * | 2007-04-27 | 2008-12-04 | Fancl Corp | Milky lotion-like cosmetic |
WO2008148672A1 (en) * | 2007-06-06 | 2008-12-11 | Henkel Ag & Co. Kgaa | Emulsion containing particles and surfactant |
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US4760096A (en) * | 1985-09-27 | 1988-07-26 | Schering Corporation | Moisturizing skin preparation |
US5219560A (en) * | 1989-03-20 | 1993-06-15 | Kobayashi Kose Co., Ltd. | Cosmetic composition |
US5599547A (en) * | 1994-11-22 | 1997-02-04 | The Procter & Gamble Company | Mascara compositions |
US5817298A (en) * | 1988-11-30 | 1998-10-06 | The Boots Company Plc | Titanium dioxide sunscreens |
US5853712A (en) * | 1994-07-30 | 1998-12-29 | The Procter & Gamble Company | Cosmetic compositions containing water dispersible pigment which is surface treated with a polymer and process |
US6106847A (en) * | 1996-09-13 | 2000-08-22 | Lancaster Group Gmbh | Stable multiple phase emulsion of the type O1 /W/O2 |
DE10031704A1 (en) * | 2000-06-29 | 2002-01-10 | Beiersdorf Ag | Use of lecithins to enhance the sun protection factor and / or the UV-A protection performance of cosmetic or dermatological sunscreens |
US20020048597A1 (en) * | 1998-06-13 | 2002-04-25 | Rainer Kropke | Cosmetic and dermatological preparations with a content of chitosan and phospholipids |
FR2816852A1 (en) * | 2000-11-21 | 2002-05-24 | Nuxe Lab | Combination of colorant and emulsifier capable of forming stable lamellar emulsion, giving enhanced colorant stability in cosmetic or dermatological compositions |
-
2002
- 2002-12-11 DE DE2002158103 patent/DE10258103A1/en not_active Ceased
-
2003
- 2003-11-28 WO PCT/EP2003/013391 patent/WO2004052328A2/en active Application Filing
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US4760096A (en) * | 1985-09-27 | 1988-07-26 | Schering Corporation | Moisturizing skin preparation |
US5817298A (en) * | 1988-11-30 | 1998-10-06 | The Boots Company Plc | Titanium dioxide sunscreens |
US5219560A (en) * | 1989-03-20 | 1993-06-15 | Kobayashi Kose Co., Ltd. | Cosmetic composition |
US5853712A (en) * | 1994-07-30 | 1998-12-29 | The Procter & Gamble Company | Cosmetic compositions containing water dispersible pigment which is surface treated with a polymer and process |
US5599547A (en) * | 1994-11-22 | 1997-02-04 | The Procter & Gamble Company | Mascara compositions |
US6106847A (en) * | 1996-09-13 | 2000-08-22 | Lancaster Group Gmbh | Stable multiple phase emulsion of the type O1 /W/O2 |
US20020048597A1 (en) * | 1998-06-13 | 2002-04-25 | Rainer Kropke | Cosmetic and dermatological preparations with a content of chitosan and phospholipids |
DE10031704A1 (en) * | 2000-06-29 | 2002-01-10 | Beiersdorf Ag | Use of lecithins to enhance the sun protection factor and / or the UV-A protection performance of cosmetic or dermatological sunscreens |
FR2816852A1 (en) * | 2000-11-21 | 2002-05-24 | Nuxe Lab | Combination of colorant and emulsifier capable of forming stable lamellar emulsion, giving enhanced colorant stability in cosmetic or dermatological compositions |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2006090301A1 (en) | 2005-02-23 | 2006-08-31 | Philips Intellectual Property & Standards Gmbh | Electroluminescent device with iridium complex |
JP2008291014A (en) * | 2007-04-27 | 2008-12-04 | Fancl Corp | Milky lotion-like cosmetic |
JP2013227353A (en) * | 2007-04-27 | 2013-11-07 | Fancl Corp | Milky lotion cosmetic |
WO2008148672A1 (en) * | 2007-06-06 | 2008-12-11 | Henkel Ag & Co. Kgaa | Emulsion containing particles and surfactant |
Also Published As
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DE10258103A1 (en) | 2004-06-24 |
WO2004052328A3 (en) | 2004-09-10 |
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