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WO2000015329A1 - Procede de production de nanoparticules - Google Patents

Procede de production de nanoparticules Download PDF

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Publication number
WO2000015329A1
WO2000015329A1 PCT/EP1999/006527 EP9906527W WO0015329A1 WO 2000015329 A1 WO2000015329 A1 WO 2000015329A1 EP 9906527 W EP9906527 W EP 9906527W WO 0015329 A1 WO0015329 A1 WO 0015329A1
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WO
WIPO (PCT)
Prior art keywords
acid
fatty acids
alcohols
emulsifiers
fatty
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1999/006527
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German (de)
English (en)
Inventor
Christian Kropf
Hans Dolhaine
Thomas Förster
Karlheinz Schaber
Michael Türk
Stephan Cihlar
Peter Christophliemk
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Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AU57455/99A priority Critical patent/AU5745599A/en
Publication of WO2000015329A1 publication Critical patent/WO2000015329A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
    • 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
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • 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
    • A61K8/31—Hydrocarbons
    • 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
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
    • A61K8/365—Hydroxycarboxylic acids; Ketocarboxylic acids
    • 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
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • A61K8/375—Esters of carboxylic acids the alcohol moiety containing more than one hydroxy group
    • 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
    • A61K8/63—Steroids; Derivatives thereof
    • 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
    • A61K8/67—Vitamins
    • A61K8/676—Ascorbic acid, i.e. vitamin C
    • 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
    • A61K8/67—Vitamins
    • A61K8/678—Tocopherol, i.e. vitamin E
    • 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
    • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
    • B01J2/04—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops in a gaseous medium
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/413—Nanosized, i.e. having sizes below 100 nm
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/61—Surface treated
    • A61K2800/614—By macromolecular compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/51—Nanocapsules; Nanoparticles
    • A61K9/5192—Processes

Definitions

  • the invention is in the field of nanoparticles and relates to particles with a diameter in the range from 10 to 300 nm, which are obtained by dissolving organic active substances under supercritical or near-critical conditions and then spraying in the presence of emulsifiers and / or protective colloids.
  • nanoparticles are currently one of the most expanding research topics in the field of cosmetic active ingredients. Representing the large number of publications on the subject of finely divided organic active substances, the so-called “nanoorganics”, reference is made to the Australian patent AU-B 10708/88 (BASF), from which a process for the production of nanoparticles is known in which organic substances are known , in this case carotenoids, together with suitable emulsifiers, dissolve in water-miscible solvents and edible oils and stir into an aqueous protective colloid solution The nanoparticles are then isolated by distillation and spray drying, but this process is technically very complex.
  • BASF Australian patent AU-B 10708/88
  • the object of the method according to the invention was to provide an improved method for producing organic nanoparticles (“nanoorganics”) which avoids the disadvantages of the prior art and thereby in particular with as little effort as possible, delivers nanoparticles of the desired grain size range that do not agglomerate during storage.
  • the process should ensure that there is no process-related decomposition of the starting materials.
  • the invention relates to a method for producing nanoparticles with diameters in the range from 10 to 300, preferably 50 to 150 nm, in which
  • Sterols are animal or vegetable steroids to be understood which only carry a hydroxyl group at C-3, but no other functional groups. As a rule, the sterols have 27 to 30 carbon atoms and a double bond in 5/6, optionally 7/8, 8/9 or other positions. In addition to these unsaturated species, sterols also include the saturated compounds obtainable by curing, which are referred to as stanoia and are included in the present invention. An example of a suitable animal sterol is cholesterol.
  • phytosterols which are preferred for technical reasons, are, for example, ergosterols, Campesterols, stigmasterols, brassica sterols and preferably sitosterols or sitostanols and in particular ß-sitosterols or ß-sitostanoia.
  • esters are preferably used.
  • the acid component of the ester can be traced back to carboxylic acids of the formula (I)
  • R 1 CO is an aliphatic, linear or branched acyl radical having 2 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds.
  • Typical examples are acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, 2-ethyl hexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, conjugated linoleic acid (CLA) , Linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, which are obtained, for example, in the pressure splitting of natural fats and oils, in the reduction of aldehydes from Ro
  • esters with 12 to 18 carbon atoms such as coconut, palm, palm kernel or tallow fatty acids, are preferred.
  • the use of esters of ⁇ -sitosterol or ⁇ -sitostanol with fatty acids having 12 to 18 carbon atoms is particularly preferred.
  • These esters can be prepared either by direct esterification of the phytostenols with the fatty acids or by transesterification with fatty acid lower alkyl esters or triglycerides in the presence of suitable catalysts, such as sodium ethylate or especially also enzymes [cf. EP-A2 0195311 (Yoshikawa)].
  • antioxidants are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-camosine, L-camosine and their derivatives (e.g. anserine ), Carotenoids, carotenes (e.g. ⁇ -carotene, ß-carotene, lycopene) and their derivatives, chlorogenic acid and their derivatives, lipoic acid and their derivatives (e.g.
  • amino acids e.g. glycine, histidine, tyrosine, tryptophan
  • imidazoles e.g. urocanic acid
  • peptides such as D, L-carnosine, D-camosine, L-camosine and their derivatives (e.g. anserine )
  • Carotenoids e.g
  • thiols e.g. thioredoxin, glutathione, cysteine, cystine , Cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, ⁇ -linoleyl,
  • Cholesteryl and glyceryl esters and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (for example Buthioninsulfoximine, homocysteine sulfoximine, Butioninsulfone, penta-, hexa-, Heptathioninsuifoximin) in very low tolerable doses (e.g. pmol to ⁇ mol / kg), further (metal) chelators (e.g.
  • ⁇ -hydroxy fatty acids palmitic acid, phytic acid, lactoferrin
  • ⁇ -hydroxy acids e.g. citric acid, Lactic acid, malic acid
  • humic acid bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives
  • unsaturated fatty acids and their derivatives e.g. ⁇ -linolenic acid, linoleic acid, oleic acid
  • folic acid and its derivatives ubiquinone and ubiquinol and their derivatives
  • Vitamin C and derivatives e.g.
  • Flavones such as Flavon (primrose), chrysin (poplar), galangin (glagantroot), apigenin (snapdragon, chamomile, dahlia), luteolin (foxglove, dahlia), camphor oil (buckthorn, delphinium, sloe), quercutin (oak, gold lacquer, pansy), quercetin (Oak, gold lacquer, pansies), morin (mulberry), robinetin (acacia), gossynetin (cotton, hibiscus), myricetin (currant, hamameiis), fisetin (fisetholz), rutin (citrus fruits, pansies, linden flowers, tea, St.
  • Flavon primaryrose
  • chrysin poplar
  • galangin glagantroot
  • apigenin snapdragon, chamomile, dahlia
  • luteolin
  • Synthetic or natural waxes can also be used, e.g. Paraffin waxes, hydrogenated castor oil, cetyl plasticity, ethylene oxide waxes, pearlescent waxes, camauba wax, beeswax, sunflower wax and apple wax.
  • fatty acids and fatty alcohols having 12 to 22 carbon atoms which are solid at room temperature such as, for example, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, stearic acid and behenic acid and their technical mixtures, or cetyl alcohol, palmoleyl alcohol, stearyl alcohol and behenyl alcohol and their technical mixtures .
  • Mixtures of the fatty alcohols mentioned with alkylpolyglucosides are also suitable, mixtures of cetearyl alcohol with cetearylglucosides in a mixing ratio of 10:90 to 90:10 being particularly preferred.
  • Metal soaps such as the calcium, magnesium, aluminum and / or zinc salts of carboxylic acids having 10 to 18 carbon atoms, in particular undecylenic acid, stearic acid, hydroxystearic acid or ricmolic acid, are also suitable as starting materials for the process according to the invention
  • Suitable dyes are, for example, direct dyes from the group of nitrophylenediamines, nitroaminophenols, anthrachmones or indophenols, such as, for example, those with the international names or trade names HC Yellow 2, HC Yellow 4, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16, Basic Brown 17, Picramic Acid and Rodol 9 R known compounds and 4-amino-2-nitro-phenylamine-2'-carboxylic acid 6-nitro-1, 2,3,4-tetrahydro-chlorooxaline, (N-2,3-dihydroxypropyl-2-nitro-4-trifluoromethyl) aminobenzene and 4-N-ethyl-1, 4-b ⁇ s (2'-hydroxyethylam ⁇ no) -2-n ⁇ trobenzol- hydrochlo
  • Oxidation dyes consisting of developer and coupler components can be used.
  • the developer components are, for example, aromatic aromatic nurse with another free or substituted one that is in the para or ortho position Hydroxy or amino group, diaminopy ⁇ dinde ⁇ vate heterocyclic hydrazones, 4-aminopyrazolone de ⁇ vate and 2,4,5,6-tetraaminopy ⁇ midine and its derivatives used.
  • Ku Plpler substances are particularly suitable 1-naphthol pyrogallol, 1, 5-, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenoi resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3- methyl-pyrazolon-5 2,4-dichloro-3-aminophenol, 1, 3-bis (2,4-diminophenoxy) propane, 2-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methyl resorcinol , 2,5-Dimethylresorc ⁇ n, 2,6-Dihydroxypy ⁇ dm and 2,6-D ⁇ am ⁇ nopy ⁇ d ⁇ n
  • natural color pigments from plants such as chlorophylls carotenes and anthocyanins, can also be used
  • UV light barrier factors suitable for the production of nanopigments are, for example 3-benzylidene camphor or 3-benzylidene norcampher and its derivatives, for example 3- (4-methylbenzylidene) camphor as described in EP-B1 0693471;
  • 4-aminobenzoic acid derivatives preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate;
  • Esters of cinnamic acid preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene);
  • esters of salicylic acid preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylic acid, homomenthyl salicylic acid;
  • esters of benzalmalonic acid preferably di-2-ethylhexyl 4-methoxybenzmalonate
  • Triazine derivatives e.g. 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1, 3,5-triazine and octyl triazone, as described in EP-A1 0818450;
  • Propane-1,3-dione e.g. 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione;
  • Sulfonic acid derivatives of benzophenones preferably 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid and their salts;
  • Sulfonic acid derivatives of 3-benzyiide camphor e.g. 4- (2-oxo-3-bornylidene-methyl) be ⁇ zolsulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.
  • Benzoylmethane derivatives such as, for example, 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl-4'-methoxydibenzoylmethane (Parsol 1789), or 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione.
  • UV light protection filters can be found in the overview by P.Finkel in S ⁇ FW-Journal 122, 543 (1996).
  • Suitable starting materials are also fragrances.
  • Natural fragrances are extracts of flowers (lily, lavender, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel (bergamot, lemon, Oranges), Roots (Macis, Angelica, Celery, Cardamom, Costus, Iris, Calmus), Woods (Pine, San del, Guaiac, Cedar, Rosewood), Herbs and Grasses (Tarragon, Lemongrass, Sage, Thyme ), Needles and twigs (spruce, fir, pine, mountain pine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax).
  • Typical Synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl benzylatepylatepylatepylatepylatepylatepylatepylatepylatepylatepylate, stylatepylatepylate.
  • the ethers include, for example, benzylethyl ether
  • the aldehydes include, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal
  • the ketones include, for example, the jonones, ⁇ -isomethylionone and methyl cedryl ketone , the alcohols anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and te ⁇ ineol
  • the hydrocarbons mainly include the terpenes and balsams.
  • Ambroxan, heliotropin, vanillin, ethylvanillin, coumarin, camphor, menthol, indole and maltol as well as the extracts of rice, rice husks, myrrh, olibanum, mistletoe and salvia sclarea are also suitable.
  • Enzymes can also be used in the process, e.g. Choline oxidase (from bacteria), peroxidase (from soybeans), laccases and tyrosinases (from fungi); Suitable enzyme inhibitors are e.g. Phenylboronic acid and its derivatives, Gly-Pro-Phe-Pro-Leu pentapeptides and peptides containing this sequence, bacitracin, aminoethylbenzenesulfonyl fluoride, all of which are effective as serine protease inhibitors for regulating skin flaking.
  • Choline oxidase from bacteria
  • peroxidase from soybeans
  • laccases from laccases
  • tyrosinases from fungi
  • Suitable enzyme inhibitors are e.g. Phenylboronic acid and its derivatives, Gly-Pro-Phe-Pro-Leu pentapeptides and peptides containing this sequence, bacitracin, aminoe
  • Koji acid, arbutin, epicatechin gallate, bacelaine, dihydromyrecitin, ascorbic acid and 1000-1500 D proteins from silk protein hydroylsates can be used as tyrosinase inhibitors (skin whiteners).
  • tyrosinase inhibitors skin whiteners
  • cholesterol and phytosterol sulfate can be used as elastase inhibitors for skin rejuvenation
  • Chitin and chitin derivatives e.g. Chitosan
  • Phospholipids (lecithins),
  • Inulin can be converted into nanoparticles by the process according to the invention.
  • liquids or gases are heated under pressure, they finally get into the supercritical or fluid state above their respective critical conditions, in which they are present as liquids which are distinguished by a particularly low density, low viscosity and a very high diffusion coefficient.
  • Typical examples of liquids or gases which are considered as supercritical solvents in the context of the invention are carbon dioxide, ethylene, propane, ammonia, methanol, nitrous oxide, nitrous oxide, sulfur hexafluoride, difluoromethane, trifluoromethane, water, toluene and a number of nitrogen heterocycles; Mixtures of the gases mentioned can also be used.
  • Information on the behavior of supercritical liquids and gases can be found, for example, in Angew.Chem.
  • the conditions under which a substance changes to the supercritical state are of course substance-specific.
  • carbon dioxide for the preferred solvent carbon dioxide, however, a temperature range of 0 to 200 and preferably 40 to 100 ° C. and a pressure range of 10 to 300, preferably 20 to 200 bar are recommended; in principle, these areas can also be transferred to other substances.
  • the sterols and sterol esters are placed in a suitable pressure vessel, the reactor is closed and the solvent, preferably carbon dioxide, is injected until the desired pressure is reached. The temperature is then increased until the mixture changes to the supercritical state.
  • the organic active ingredients are dissolved together with emulsifiers and / or protective colloids, which may be present in substance as aqueous or alcoholic solutions or in mixtures with cosmetic oils.
  • the solutions are sprayed through a nozzle, which results in the production of particles with a particularly fine particle size, namely so-called nanoparticles .
  • the process which is also referred to as “jet spraying” or “rapid expansion of supercritical solutions (RESS)", can be carried out in a manner known per se, ie the reactor is discharged with a suitable fine nozzle and the spraying is carried out continuously by you open the exit and the The reactor is carefully relaxed. The same conditions apply for the spray temperature as for the dissolving process.
  • the teaching of the invention is to relax the substances not in air or water, but in aqueous and / or alcoholic solutions of emulsifiers and / or protective colloids in order to prevent undesirable caking of the To prevent particles. It is also possible to relax the fluid mixtures directly into the protective colloid, for example in polyethylene glycol, so that the use of water or alcohol is unnecessary. Finally, it is also possible to dissolve the emulsifiers and / or protective colloids in cosmetic oils and to relax the active ingredients in these mixtures.
  • Suitable emulsifiers are nonionic surfactants from at least one of the following groups:
  • alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogs
  • polyol and especially polyglycerol esters such as e.g. Polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate. Mixtures of compounds from several of these classes of substances are also suitable;
  • partial esters based on linear, branched, unsaturated or saturated C6 / 22 fatty acids, ricinoleic acid as well as 12-hydroxystearic acid and glycerin, polyglycerin, pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucoside (e.g. methyl glucoside), butyl glucoside Polyglucosides (eg cellulose); (9) mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts;
  • the adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters as well as sorbitan mono- and diesters of fatty acids or with castor oil are known, commercially available products. These are homogeneous mixtures, the medium of which Degree of alkoxylation corresponds to the ratio of the amounts of substance of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out.
  • Ci2 / i8 fatty acid monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE-PS 2024051 as refatting agents for cosmetic preparations.
  • C ⁇ -alkyl mono- and oligoglycosides their preparation and their use are known from the prior art. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms.
  • glycoside residue both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to about 8 are suitable.
  • the degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.
  • Zwitterionic surfactants can also be used as emulsifiers.
  • Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule.
  • Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethyl-ammonium glycinate, for example the coconut alkydimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the coconut acyl aminopropyldimethylammonium 2-cyanate -Alkyl-3-carboxylmethyl-3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate.
  • betaines such as the N-alkyl-N, N-dimethyl-ammonium glycinate, for example the coconut alkydimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glyc
  • Suitable emulsifiers are ampholytic surfactants.
  • Ampholytic surfactants are understood to mean those surface-active compounds which, apart from a C ⁇ s alkyl or acyl group, at least in the molecule contain a free amino group and at least one -COOH or -S0 3 H group and are capable of forming internal salts.
  • ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 bisacid acids 18 carbon atoms in the alkyl group.
  • ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and Ci2 / i8-acylsarcosine.
  • ampholytic emulsifiers quaternary emulsifiers are also suitable, those of the esterquat type, preferably methylquaternized difatty acid triethanolamine ester salts, being particularly preferred.
  • protective colloid and emulsifier can be used interchangeably.
  • protective colloids are, however, lyophilic colloids such as, for example, gelatin, casein, gum arabic, lysalbic acid, starch and polymers, such as polyvinyl alcohols, polyvinyl pyrrolidones, polyalkylene glycols and polyacrylates.
  • lyophilic colloids such as, for example, gelatin, casein, gum arabic, lysalbic acid, starch and polymers, such as polyvinyl alcohols, polyvinyl pyrrolidones, polyalkylene glycols and polyacrylates.
  • emulsifiers and the “real” protective colloids either in substance or in the form of aqueous, occasionally also aqueous-alcoholic solutions in amounts of 0.1 to 20, preferably 5 to 15,% by weight, based on the organic active substances. used.
  • Cosmetic oils include, for example, Guerbet alcohols based on fatty alcohols with 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C ⁇ -C ⁇ fatty acids with linear C6-C22 fatty alcohols, esters of branched C6-Ci3 carboxylic acids with linear C6 -C22- fatty alcohols, esters of linear C6-C 2 fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C ⁇ -C ⁇ fatty alcohols, in particular dioctyl malates, esters of linear and / or branched Fatty acids with polyhydric alcohols (such as propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides based on C ⁇ -Cio fatty acids, liquid mono- / di- / triglyceride mixtures based on C6-Ci8-
  • Finsolv® TN linear or branched, symmetrical or asymmetrical dialkyl ethers with 6 to 22 carbon atoms per alkyl group, ring opening products of epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenic hydrocarbons.
  • Examples 1 to 14 The gaseous solvent was removed from a reservoir at a constant pressure of 60 bar and purified over a column with an activated carbon and a molecular sieve packing. After the liquefaction, the solvent was compressed to the desired supercritical pressure p using a diaphragm pump at a constant flow rate of 3.5 l / h. The solvent was then brought to the required temperature T1 in a preheater and passed into an extraction column (steel, 400 ml) which was loaded with the organic active ingredient. The resulting supercritical, i.e.
  • the fluid mixture was sprayed through a laser-drawn nozzle (length 830 ⁇ m, diameter 45 ⁇ m) at a temperature T2 into a plexiglass expansion chamber which contained a 4% by weight aqueous solution of the emulsifier or protective colloid.
  • the fluid medium evaporated and the dispersed nanoparticles enclosed in the protective colloid remained.
  • the process conditions and the mean particle size range are given in Table 1 below.

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Abstract

L'invention concerne un procédé de production de nanoparticules dont le diamètre est compris entre 10 et 300 nm. Ce procédé consiste (a) à dissoudre des principes actifs organiques dans des conditions surcritiques ou quasi-critiques dans un solvant, (b) à relaxer le mélange fluide dans un gaz ou un liquide par une buse, et (c) simultanément à évaporer le solvant. Ce procédé est caractérisé en ce que l'on utilise des émulsifiants et/ou des matières colloïdales de protection.
PCT/EP1999/006527 1998-09-15 1999-09-04 Procede de production de nanoparticules Ceased WO2000015329A1 (fr)

Priority Applications (1)

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AU57455/99A AU5745599A (en) 1998-09-15 1999-09-04 Method for producing nanoparticles

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US10046698P 1998-09-15 1998-09-15
US60/100,466 1998-09-15

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000035415A1 (fr) * 1998-12-11 2000-06-22 Cognis Deutschland Gmbh Utilisation de filtres organiques a nanoparticules, pour la protection contre les uv
WO2000047177A1 (fr) * 1999-02-09 2000-08-17 Cognis Deutschland Gmbh Utilisation de nanoparticules de chitosanes et/ou de derives de chitosanes
WO2000067702A1 (fr) * 1999-05-05 2000-11-16 Cognis Deutschland Gmbh Utilisation cosmetique ou pharmaceutique de savons metalliques sous forme de nanoparticules
WO2001043706A1 (fr) * 1999-12-18 2001-06-21 Cognis Deutschland Gmbh & Co. Kg Utilisation d"agents antipelliculaires nanometriques
WO2001045652A1 (fr) * 1999-12-22 2001-06-28 Cognis Deutschland Gmbh & Co. Kg Utilisation de colorants capillaires nanometriques
FR2827510A1 (fr) * 2001-07-18 2003-01-24 Oreal Filtres uv organiques insolubles de type aryl vinylene cetone et leur utilisation en cosmetique
WO2003103633A1 (fr) * 2002-06-10 2003-12-18 Elan Pharma International, Ltd. Preparation de sterols nanoparticulaires et nouvelles combinaisons de sterols
WO2004087645A1 (fr) * 2003-03-28 2004-10-14 Kuraray Co., Ltd. Procede de production d'une emulsion carotenoide
EP2226062A1 (fr) * 2009-03-06 2010-09-08 Linde AG Procédé de fabrication de cosmétique
WO2010099966A3 (fr) * 2009-03-06 2011-12-29 Linde Aktiengesellschaft Procédé de fabrication de cosmétiques
US8137683B2 (en) 2001-06-19 2012-03-20 Dsm Ip Assets B.V. Process for the preparation of dispersions

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EP0322687A2 (fr) * 1987-12-28 1989-07-05 Schwarz Pharma Ag Procédé de préparation d'un produit ayant au moins un agent thérapeutique encastré dans véhicule
WO1997014407A1 (fr) * 1995-10-17 1997-04-24 Research Triangle Pharmaceuticals Administration de medicaments insolubles
WO1998016204A1 (fr) * 1996-10-14 1998-04-23 F. Hoffmann-La Roche Ag Procede destine a la fabrication d'une preparation en poudre
US5874029A (en) * 1996-10-09 1999-02-23 The University Of Kansas Methods for particle micronization and nanonization by recrystallization from organic solutions sprayed into a compressed antisolvent
WO1999052504A1 (fr) * 1998-04-09 1999-10-21 F. Hoffmann-La Roche Ag Procede de production de particules submicroniques par dissolution dans du gaz comprime et des tensioactifs

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EP0322687A2 (fr) * 1987-12-28 1989-07-05 Schwarz Pharma Ag Procédé de préparation d'un produit ayant au moins un agent thérapeutique encastré dans véhicule
WO1997014407A1 (fr) * 1995-10-17 1997-04-24 Research Triangle Pharmaceuticals Administration de medicaments insolubles
US5874029A (en) * 1996-10-09 1999-02-23 The University Of Kansas Methods for particle micronization and nanonization by recrystallization from organic solutions sprayed into a compressed antisolvent
WO1998016204A1 (fr) * 1996-10-14 1998-04-23 F. Hoffmann-La Roche Ag Procede destine a la fabrication d'une preparation en poudre
WO1999052504A1 (fr) * 1998-04-09 1999-10-21 F. Hoffmann-La Roche Ag Procede de production de particules submicroniques par dissolution dans du gaz comprime et des tensioactifs

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HIRAI H ET AL: "Characterization of palladium nanoparticles protected with polymer as hydrogenation catalyst", REACTIVE & FUNCTIONAL POLYMERS,NL,ELSEVIER SCIENCE PUBLISHERS BV, vol. 37, no. 1-3, pages 121-131, XP004127874, ISSN: 1381-5148 *
SUN Y -P ET AL: "PREPARATIONS OF NICKEL, COBALT, AND IRON NANOPARTICLES THROUGH THE RAPID EXPANSION OF SUPERCRITICAL FLUID SOLUTIONS (RESS) AND CHEMICAL REDUCTION", CHEMISTRY OF MATERIALS,US,AMERICAN CHEMICAL SOCIETY, WASHINGTON, vol. 11, no. 1, pages 7-9, XP000792066, ISSN: 0897-4756 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000035415A1 (fr) * 1998-12-11 2000-06-22 Cognis Deutschland Gmbh Utilisation de filtres organiques a nanoparticules, pour la protection contre les uv
WO2000047177A1 (fr) * 1999-02-09 2000-08-17 Cognis Deutschland Gmbh Utilisation de nanoparticules de chitosanes et/ou de derives de chitosanes
WO2000067702A1 (fr) * 1999-05-05 2000-11-16 Cognis Deutschland Gmbh Utilisation cosmetique ou pharmaceutique de savons metalliques sous forme de nanoparticules
WO2001043706A1 (fr) * 1999-12-18 2001-06-21 Cognis Deutschland Gmbh & Co. Kg Utilisation d"agents antipelliculaires nanometriques
WO2001045652A1 (fr) * 1999-12-22 2001-06-28 Cognis Deutschland Gmbh & Co. Kg Utilisation de colorants capillaires nanometriques
US8137683B2 (en) 2001-06-19 2012-03-20 Dsm Ip Assets B.V. Process for the preparation of dispersions
FR2827510A1 (fr) * 2001-07-18 2003-01-24 Oreal Filtres uv organiques insolubles de type aryl vinylene cetone et leur utilisation en cosmetique
EP1281391A1 (fr) * 2001-07-18 2003-02-05 L'oreal Filtres UV organiques insolubles de type aryl vinylène cétone et leur utilisation en cosmétique
WO2003103633A1 (fr) * 2002-06-10 2003-12-18 Elan Pharma International, Ltd. Preparation de sterols nanoparticulaires et nouvelles combinaisons de sterols
WO2004087645A1 (fr) * 2003-03-28 2004-10-14 Kuraray Co., Ltd. Procede de production d'une emulsion carotenoide
EP2226062A1 (fr) * 2009-03-06 2010-09-08 Linde AG Procédé de fabrication de cosmétique
WO2010099966A3 (fr) * 2009-03-06 2011-12-29 Linde Aktiengesellschaft Procédé de fabrication de cosmétiques

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