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WO2009080427A1 - Procédés de fabrication de matériaux hybrides absorbant les u.v. - Google Patents

Procédés de fabrication de matériaux hybrides absorbant les u.v. Download PDF

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Publication number
WO2009080427A1
WO2009080427A1 PCT/EP2008/066056 EP2008066056W WO2009080427A1 WO 2009080427 A1 WO2009080427 A1 WO 2009080427A1 EP 2008066056 W EP2008066056 W EP 2008066056W WO 2009080427 A1 WO2009080427 A1 WO 2009080427A1
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WIPO (PCT)
Prior art keywords
acid
zinc
oxide
bis
hydroxide
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Ceased
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PCT/EP2008/066056
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German (de)
English (en)
Inventor
Andrey Karpov
Hartmut Hibst
Richard Riggs
Sylke Haremza
Monica Fernandez Gonzalez
Jörg PASTRE
Valerie Andre
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BASF SE
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BASF SE
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Publication of WO2009080427A1 publication Critical patent/WO2009080427A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • A61K8/35—Ketones, e.g. benzophenone
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • 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
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27—Zinc; Compounds 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
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
    • A61K8/368—Carboxylic acids; Salts or anhydrides thereof with carboxyl groups directly bound to carbon atoms of aromatic rings
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/04—Compounds of zinc
    • C09C1/043—Zinc oxide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • 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
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the present invention relates to methods of making UV-absorbing hybrid materials comprising nanoparticles of at least one metal oxide, metal hydroxide, and / or metal oxide hydroxide and at least one organic ultraviolet radiation absorbing compound. Furthermore, the invention relates to the UV radiation-absorbing hybrid materials obtainable by these processes, compositions containing them and the use of the hybrid materials for cosmetic preparations, as UV stabilizer in plastics and as antimicrobial agents.
  • Nanoparticles are particles of the order of nanometers. Their size is in the transition region between atomic or monomolecular systems and continuous macroscopic structures. In addition to their usually very large surface, nanoparticles are characterized by particular physical and chemical properties, which differ significantly from those of larger particles. For example, nanoparticles often have a lower melting point, absorb light only at shorter wavelengths, and have different mechanical, electrical, and magnetic properties than macroscopic particles of the same material. By using nanoparticles as building blocks, many of these special properties can also be used for macroscopic materials (Winnacker / Kuchler, Chemischetechnik: Processes and Products, (Ed .: R. Dittmayer, W. Keim, G. Kreysa, A. Oberholz), Vol. 2: New Technologies, Chapter 9, Wiley-VCH Verlag 2004).
  • nanoparticles refers to particles having an average diameter of from 1 to 500 nm, preferably from 1 to 200 nm, particularly preferably from 10 to 100 nm.
  • TEM transmission electron microscope
  • DLS dynamic light scattering
  • UV absorption wavelength measurements of the UV absorption wavelength
  • the size data for the nanoparticles are based on transmission electron microscopic measurements. With an ideal spherical shape of the nanoparticles, the particle size would correspond to the particle diameter. Agglomerates resulting from the juxtaposition of nanoparticles can be greater than 500 nm.
  • Nanoparticulate zinc oxide with particle sizes below about 100 nm is potentially suitable for use as a UV absorber in transparent organic-inorganic hybrid materials, plastics, paints and coatings.
  • a use for the protection of UV-sensitive organic pigments is possible.
  • finely divided metal oxides for example of zinc oxide
  • dry and wet processes The classical incineration method of zinc, known as the dry process (eg, Gmelin volume 32, 8th Ed., Supplementary Volume, pp. 772 et seq.), Produces aggregated particles with a broad size distribution.
  • dispersions having average particle sizes in the lower nanometer range can only be obtained from such powders with great difficulty by virtue of the shearing forces which can be achieved being too low.
  • Particularly finely divided zinc oxide is mainly produced wet-chemically by precipitation processes.
  • the precipitation in aqueous solution generally yields hydroxide and / or carbonate-containing materials which must be thermally converted to zinc oxide.
  • the thermal aftertreatment has a negative effect on fineness, since the particles are subjected to sintering processes which lead to the formation of micrometer-sized aggregates, which can only be broken down to the primary particles by grinding to an incomplete extent.
  • Nanoparticulate metal oxides can be obtained, for example, by the microemulsion method.
  • a solution of a metal alkoxide is added dropwise to a water-in-oil microemulsion.
  • the hydrolysis of the alkoxides to the nanoparticulate metal oxide takes place.
  • the disadvantages of this method are, in particular, that the metal alkoxides are expensive starting materials, that in addition emulsifiers must be used and that the preparation of the emulsions with droplet sizes in the nanometer range represents a complex process step.
  • DE 199 07 704 describes a nanoparticulate zinc oxide prepared by a precipitation reaction.
  • the nanoparticulate zinc oxide is prepared starting from a zinc acetate solution via an alkaline precipitation.
  • the centrifuged zinc oxide can be redispersed by addition of methylene chloride to a sol.
  • the zinc oxide dispersions prepared in this way have the disadvantage that they have no good long-term stability owing to the lack of surface modification.
  • WO 00/50503 zinc oxide gels are described which contain nanoparticulate zinc oxide with a particle diameter of ⁇ 15 nm and which are redispersible to sols.
  • the solids produced by basic hydrolysis of a zinc compound in alcohol or in an alcohol / water mixture are redispersed by the addition of dichloromethane or chloroform.
  • the disadvantage here is that no stable dispersions are obtained in water or in aqueous dispersants.
  • WO 93/21 127 describes a process for producing surface-modified nanoparticulate ceramic powders.
  • a nanoparticulate ceramic powder is surface-modified by applying a low molecular weight organic compound, for example, propionic acid.
  • a low molecular weight organic compound for example, propionic acid.
  • This method can not be used for the surface modification of zinc oxide, since the modification reactions are carried out in aqueous solution and zinc oxide dissolves in aqueous organic acids. Therefore, this method can not be used for the production of zinc oxide dispersions;
  • zinc oxide in this application is also not mentioned as a possible starting material for nanoparticulate ceramic powders.
  • WO 02/42201 a process for the preparation of nanoparticulate metal oxides is described in which dissolved metal salts are thermally decomposed in the presence of surfactants.
  • the decomposition takes place under conditions under which the surfactants form micelles, and depending on the metal salt chosen, possibly also several hundred degrees Celsius to achieve decomposition.
  • the process is therefore very complex in terms of apparatus and energy.
  • WO 2004/052327 describes surface-modified nanoparticulate zinc oxides in which the surface modification comprises a coating with an organic acid.
  • DE-A 10 2004 020 766 discloses surface-modified nanoparticulate metal oxides prepared in the presence of polyaspartic acid.
  • EP 1455737 describes surface-modified nanoparticulate zinc oxides in which the surface modification comprises a coating with an oligo- or polyethylene glycol acid.
  • Particulate zinc oxide has long been known as a UV light stabilizer in cosmetic preparations.
  • Commercial products are, for example, under the trade names Z-Cote ® (BASF), Creazinc ® (Creations Couliv), Finex-25 ® (Presperse, Inc.), nano Gard ® Zinc Oxide (Nano hybrid Co., LTD), Nano-Zinc ® SL (Sino Lion (USA) Ltd.), O Ristar ® ZO (Orient Stars LLC), oxides de Zinc Micro Pure ® (LCW - Sensient Cosmetic Technologies), Tego ® Sun Z 500 (Degussa Care & Surface Specialties), Unichem ® ZO (Universal preserv-A-Chem, Inc.), USP-1 ® (Zinc Corporation of America) or Zinc oxide NDM ® 106407 (Symrise) available.
  • Z-Cote ® BASF
  • Creazinc ® Creations Coulivities
  • Finex-25 ® Presperse, Inc.
  • UV-A range near ultraviolet light
  • Another object of the present invention was to provide improved UV light stabilizers for the stabilization of plastics.
  • UV radiation-absorbing hybrid materials comprising nanoparticles of at least one oxide, hydroxide and / or oxide hydroxide of at least one metal selected from the group consisting of aluminum, magnesium, cerium, iron, manganese, cobalt, nickel, titanium, zinc, Zirconium and mixtures thereof, and at least one organic UV-absorbing compound obtainable by precipitating the oxide, hydroxide and / or oxide hydroxide from a solution containing a suitable salt of the metal, characterized in that the precipitation is carried out in the presence of at least one organic compound , UV-absorbing compound takes place.
  • the invention thus provides a process for producing UV radiation-absorbing hybrid materials comprising a) nanoparticles of at least one oxide, hydroxide and / or oxide hydroxide of at least one metal selected from the group consisting of aluminum, magnesium, cerium, iron, manganese, cobalt, nickel , Titanium, zinc, zirconium and mixtures thereof, and b) at least one organic, ultraviolet radiation absorbing compound, by precipitating the oxide, hydroxide and / or oxide hydroxide from a solution containing a suitable salt of the metal, characterized in that the precipitation in Presence of at least one organic UV-absorbing compound takes place.
  • Two preferred embodiments of the invention are the methods A) basic induced precipitation and
  • the UV radiation-absorbing hybrid materials according to the invention are also referred to as surface-modified nanoparticulate hybrid materials or surface-modified nanoparticulate particles.
  • the metal salts, metal oxides, metal hydroxides and metal oxide hydroxides may be both anhydrous compounds and water containing compounds such as hydrates.
  • Preferred metal salts are halides, for example zinc chloride or titanium tetrachloride, benzoates, for example zinc benzoate, carboxylate-containing salts, for example zinc acetate, and nitrates, for example zinc nitrate.
  • Particularly preferred metal salts are Ti (OH) 4 , Ti (OC2Hs) 4 , titanium tetrapropoxide, titanium tetraisopropoxide, zinc acetate, zinc benzoate, zinc chloride, zinc bromide, zinc nitrate or mixtures thereof.
  • Very particularly preferred metal salts are zinc acetate dihydrate, zinc chloride and zinc nitrate.
  • a particularly preferred metal oxide according to the invention is zinc oxide.
  • a subject of the invention is a process for producing UV radiation-absorbing hybrid materials comprising a) nanoparticles of at least one oxide, hydroxide and / or oxide hydroxide of at least one metal selected from the group consisting of aluminum, magnesium, cerium, iron, manganese, cobalt, nickel, Titanium, zinc, zirconium and their mixtures, as well b) at least one organic ultraviolet radiation absorbing compound comprising the steps of 1) preparing a first solution containing at least one salt of a metal selected from the group consisting of aluminum, magnesium, cerium, iron, manganese, cobalt, nickel, titanium , Zinc, zirconium and mixtures thereof and a second solution containing at least one strong base, at least one of the two solutions containing at least one ultraviolet absorbing compound; 2) mixing the solutions prepared in step 1) at a temperature in the range of 0 to 120 0 C, wherein the UV radiation-absorbing hybrid materials formed and precipitate to form a suspension of the solution, optionally heating the suspension,
  • step 3 optionally drying of the UV radiation-absorbing hybrid materials obtained in step 3).
  • the metal salts in process step 1) may be metal halides, acetates, sulfates or nitrates.
  • Preferred metal salts are halides, for example zinc chloride or titanium tetrachloride, acetates, for example zinc acetate and nitrates, for example zinc nitrate.
  • a particularly preferred metal salt is zinc chloride or zinc nitrate.
  • the solvents for the first solution should be selected so that the metal salts used as starting materials in the range of 0.05 to 1 mol / l, preferably in the range of 0.1 to 0.5 mol / l, particularly preferably 0.2 to 0.4 mol / l are soluble therein, but the oxides, hydroxides or oxide hydroxide resulting from the reaction with the base are at most slightly, preferably sparingly soluble and precipitate out of the solution.
  • Suitable solvents are preferably selected from water, water-miscible organic solvents and mixtures thereof.
  • Preferred water-miscible organic solvents are water-miscible alcohols, especially those suitable for the solvolysis process, as detailed below. These include, for example, ethanol, isopropanol or 1, 2-propanediol.
  • the solvent should be chosen such that the UV-absorbing compound is in the range of 0.1 to 20 g / l, preferably 1 to 10 g / l , more preferably from 1, 5 to 5 g / l at least dispersible, preferably soluble.
  • Preferred solvents are water-miscible alcohols, especially those suitable for the solvolysis process, as detailed below.
  • soluble is understood to mean the property of a material which is clear to the human eye in the respectively indicated solvent at respectively given temperature and given pressure (preferably at 20.degree. C. and 1013 mbar) in the respectively indicated concentration. to produce transparent solution.
  • the bases to be used may be any substances capable of producing in aqueous solution, depending on their concentration, a pH of from about 8 to about 13, preferably from about 9 to about 12.5. These may be, for example, metal oxides or hydroxides as well as ammonia or amines. Preference is given to using alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide or ammonia. More preferably, sodium hydroxide, potassium hydroxide and ammonia are used. In a preferred embodiment of the invention, ammonia may also be formed by thermal decomposition of urea in situ during process steps 1) and / or 2).
  • the concentration of the base in the second solution prepared in process step 1) is generally selected so that in the second solution a Hydroxylionenkon- concentration in the range of 0.1 to 2 mol / l, preferably from 0.2 to 1 mol / l and more preferably from 0.4 to 0.8 mol / l sets.
  • c is a concentration and M n + is at least one metal ion of valency n.
  • M n + is at least one metal ion of valency n.
  • a second solution having a hydroxyl ion concentration of 0.4 mol / l is preferably used.
  • the mixing of the two solutions in process step 2) is carried out at a temperature in the range from 0 0 C to 120 0 C, preferably in the range of 10 0 C to 100 ° C, more preferably in the range from 15 ° C to 80 0 C.
  • mixing may be carried out at a pH in the range of 3 to 13.
  • the pH at the time of mixing is in the range of 7 to 13.
  • the time for the mixing of the two solutions in process step 2) according to the invention is in the range of 1 second to 6 hours, preferably in the range of 1 minute to 2 hours. In general, the mixing time for discontinuous driving is longer than for continuous driving.
  • the mixing in process step 2) can be carried out, for example, by combining a solution of a metal salt, for example zinc chloride or zinc nitrate, with a solution of a mixture of a UV radiation-absorbing compound and an alkali metal hydroxide or ammonium hydroxide, in particular sodium hydroxide.
  • a solution of a mixture of a UV-absorbing compound and a metal salt, such as zinc chloride or zinc nitrate may be combined with a solution of an alkali metal hydroxide or ammonium hydroxide, especially sodium hydroxide.
  • a solution of a mixture of a UV-absorbing compound and a metal salt for example of zinc chloride or zinc nitrate
  • a solution of a mixture of a UV-absorbing compound and an alkali metal hydroxide or ammonium hydroxide, in particular sodium hydroxide can be combined.
  • the mixing in process step 2) takes place by metering in a solution of a mixture of a UV Radiation absorbing compound and an alkali metal hydroxide or ammonium hydroxide, in particular sodium hydroxide, to a solution of a metal salt, such as zinc chloride or zinc nitrate, or by dosing a solution of an alkali metal hydroxide or ammonium hydroxide, in particular sodium hydroxide, to a solution of a mixture of a UV-absorbing compound and a metal salt, for example, zinc chloride or zinc nitrate.
  • a metal salt such as zinc chloride or zinc nitrate
  • the surface-modified nanoparticulate particles form, which precipitate out of the solution to form a suspension.
  • the mixing is carried out while stirring the mixture. After complete union of the two solutions 1 and 2, the stirring is preferably continued for a time between 30 minutes and 5 hours at a temperature in the range of 0 0 C to 120 0 C.
  • the resulting suspension after mixing, to a temperature in the range of 10 to 200 0 C, preferably 50 to 150 0 C, more preferably heated from 80 to 150 0 C.
  • a further preferred embodiment of the method according to the invention is characterized in that at least one of the method steps 1) to 4) is carried out continuously.
  • the process step 2) is preferably carried out in a tubular reactor.
  • the continuous process is carried out in the form that the mixing in step 2) takes place in a first reaction space at a temperature T1 in which a first solution of at least one metal salt and a second solution of at least one strong base are introduced continuously, at least one contains at least one ultraviolet radiation absorbing compound of the two solutions from which the suspension formed is removed continuously and transferred into a second reaction space for temperature control at a temperature T2, forming the UV radiation absorbing hybrid materials.
  • the continuous process is carried out in the form that the temperature T2 is higher than the temperature T1.
  • the methods described above are particularly suitable for the production of UV radiation-absorbing hybrid materials containing titanium dioxide and / or zinc oxide, in particular zinc oxide.
  • the precipitation takes place from a, preferably aqueous, solution of zinc acetate, zinc chloride or zinc nitrate at a pH in the range from 8 to 13 in the presence of at least one UV-absorbing compound.
  • US 4,410,446 describes the preparation of stable zinc oxide-containing suspensions by heating zinc acetate in a low-volatility inert liquid. Magnesium naphthenate is used as the dispersing aid.
  • No. 4,193,769 describes the preparation of stable zinc oxide-containing suspensions by heating zinc carbonate in a low-volatility inert liquid.
  • dispersing agents unsaturated fatty acids, sulfonic acid, alkoxylated long-chain amines, etc. are used.
  • DE 102 97 544 describes metal oxide dispersions comprising a metal oxide having a particle diameter of less than 200 nm and a dispersing medium, wherein the dispersing medium comprises a polyhydric alcohol and / or a polyether compound.
  • JP 2003268368 describes a UV emitter comprising zinc oxide particles.
  • the zinc oxide particles are free of alkali metals and halides and are obtained by heating a mixture of Zn carboxylates (eg Zn formates, acetates, oxalates, adipates, terephthalates) and alcohols (eg methanol, Ethanol, ethylene glycol, 1, 4-butanediol, polyethylene glycol) at about 100 - 300 0 C produced.
  • Zn carboxylates eg Zn formates, acetates, oxalates, adipates, terephthalates
  • alcohols eg methanol, Ethanol, ethylene glycol, 1, 4-butanediol, polyethylene glycol
  • JP 07-232919 describes a process for producing zinc oxide particles, which zinc oxide particles are prepared by heating a mixture of zinc or a zinc compound (eg zinc oxide, zinc hydroxide, zinc hydroxide carbonate, zinc acetate), a compound having at least one Carboxyl group (eg formic acid, oxalic acid, maleic acid) acid, terephthalic acid) and alcohols (eg., Methanol, ethanol, ethylene glycol, 1, 4-butanediol, polyethylene glycol) at about 100 - 300 0 C are prepared.
  • a zinc compound eg zinc oxide, zinc hydroxide, zinc hydroxide carbonate, zinc acetate
  • Carboxyl group eg formic acid, oxalic acid, maleic acid
  • alcohols eg., Methanol, ethanol, ethylene glycol, 1, 4-butanediol, polyethylene glycol
  • Jezequel et al. J. Mater. Res. Vol. 10, No.1, Jan 1995
  • a method for producing UV radiation-absorbing hybrid materials comprising a) nanoparticles of at least one oxide, hydroxide and / or oxide hydroxide of at least one metal selected from the group consisting of aluminum, magnesium, cerium, iron, manganese, cobalt, nickel, titanium, Zinc, zirconium and mixtures thereof, and b) at least one organic UV-absorbing compound, by precipitation of the oxide, hydroxide and / or oxide hydroxide from a suitable salt of the metal-containing solution, characterized in that the precipitation of the oxide, hydroxide and / or oxide of the metal metal by decomposition of a carboxylate-containing metal salt in the presence of alcohol.
  • the reaction mixture essentially comprises a liquid phase.
  • the liquid phase in turn preferably comprises at least one alcohol and optionally water.
  • the reaction mixture in a preferred embodiment of the invention in the range of 0.1 to 20, preferably from 0.5 to 15 and in particular from 1 to 10 wt .-% water, with the proviso that the sum of the amounts of all components of the reaction mixture 100 wt .-% is.
  • water is added to the reaction mixture in particular if the metal salt itself contains no water, for example in the form of water of crystallization.
  • the mixture is heated to a temperature T1 at a heating rate r1, left at this temperature T1 for a certain time t1, and then heated at a heating rate r2 to a temperature T2 greater than temperature T1 and at T2 again leave for a certain time t2.
  • the temperatures T1 and T2 of the metal salt, the alcohol and the organic ultraviolet radiation absorbing compound comprising mixture be at least 50 0 C, preferably at least 70 0 C, particularly preferably at least 100 ° C and in particular at least 120 0 C, wherein T2 is greater than T1.
  • the temperatures T1 and T2 of the metal salt, the alcohol and the organic ultraviolet radiation absorbing compound comprising mixture exceed 300 0 C, preferably not more than 250 0 C, particularly preferably at most 200 0 C and in particular at most 150 0 C, wherein T2 is greater than T1.
  • a preferred embodiment of the invention is also a method according to the invention, characterized in that the mixture is successively heated to two different temperatures T1 and T2 in the range of 50 to 300 ° C, more preferably in the range of 70 to 200 ° C, wherein T2 is greater than T1. After a residence time t2 at temperature T2, the mixture is cooled. This cooling can be done at different speeds. Among other things, the cooling rate influences the shape and size of the forming particles.
  • the organic UV-absorbing compound is preferably added to the mixture prior to heating to the temperature T1, the compound preferably being provided in a suitable solvent or dispersant which is at least partially miscible with the liquid phase, provided that Compound itself is not already soluble or dispersible in the liquid phase.
  • the organic UV-absorbing compound is added to the mixture after heating the mixture to the temperature T1 and before heating to the temperature T2.
  • the organic UV-absorbing compound is added to the mixture after heating the mixture to the temperature T2 and before cooling.
  • the organic UV-absorbing compound is added to the mixture during cooling.
  • the mixture containing metal salt, alcohol and organic UV-absorbing compound is first heated to a temperature T1 of at least 50 ° C., preferably at least 70 ° C., particularly preferably at least 100 ° C.
  • the mixture heated to T1 is then added in the range of 0.1 to 20, preferably 0.5 to 10 wt .-% of water.
  • the reaction mixture is then heated to a temperature T2 of at most 300 0 C, preferably not more than 250 0 C, particularly preferably at most 200 0 C and in particular at most 150 0 C heated, wherein T2 is greater than T1.
  • the reaction mixture is stirred at temperature T2 for a time t2 of at least 5, preferably at least 10, more preferably at least 30 and at most 300, preferably at most 180, more preferably at most 120 and in particular at most 60 minutes. Subsequently, the reaction mixture is preferably cooled to 10 0 C to 120 0 C.
  • the separation of the precipitated particles from the dispersion can be carried out in a manner known per se, for example by decantation, filtration or preferably centrifugation, or spray drying. If necessary, prior to separation of the precipitated particles, the dispersion may be concentrated by means of a membrane process such as nano-, ultra-, micro- or cross-flow filtration and optionally at least partially freed of undesired constituents.
  • the liquid phase is removed by evaporation under normal pressure or reduced pressure, by freezing, freeze-drying, filtering and subsequent drying or drying at elevated temperature at atmospheric pressure or preferably at reduced pressure. This is particularly advantageous since this method on the one hand accelerates and on the other hand a gentle handling of the hybrid material is ensured, as well as a possibility of solvent recovery is given.
  • the hybrid material particles are dispersed in highly viscous alcohols (viscosity> 5 mPa ⁇ s), it is advantageous to carry out the separation from the highly viscous alcohol or the partial removal of the high-viscosity alcohol (constriction) at elevated temperature, since in this way the viscosity is lowered and thereby the times required for the separation or narrowing can be reduced.
  • the reaction mixture is preferably more preferably cooled to 10 ° C to 50 0 C, to room temperature.
  • the precipitated and optionally separated from the liquid phase metal oxide, metal hydroxide and / or metal oxide hydroxide can be washed by methods known in the art, for example by dispersing once or more in a C1 to C4 alcohol, preferably ethanol or isopropanol, and after separation of the - This liquid washing phase are dried in a conventional manner, for example in a drying oven at temperatures between 40 and 100 0 C, preferably between 50 and 80 0 C under atmospheric pressure to constant weight.
  • the resulting dispersions of metal oxide, metal hydroxide and / or metal oxide hydroxide can also be used without at least one or more of the further workup steps such as separation, purification and Drying be used for the preparation of, for example, a cosmetic preparation.
  • Suitable metal salts for the production of zinc oxide by solvolysis are, for example, zinc carboxylates. These are in the broadest sense zinc compounds which possess at least one carboxylate group per zinc atom in a stoichiometric manner. These are preferably partial or complete zinc salts of saturated or unsaturated monocarboxylic acids, saturated or unsaturated polycarboxylic acids, alicyclic or aromatic monocarboxylic or polycarboxylic acids, all of these acids also having further substituents, such as, for example, hydroxyl, cyano, halogen, amino, nitro, alkenyl or polycarboxylic acids. can carry koxy, sulfone or halogen.
  • Preferred zinc carboxylates are those which have hydroxy groups in the crystal lattice and are represented by the following general formula I.
  • a particularly preferred method is therefore the inventive method, which is characterized in that the metal salt is selected from compounds of the general formula I.
  • Formula I does not reflect any water or solvent molecules that may be present in the crystal lattice. According to the invention, however, compounds containing such water or solvent molecules should also be encompassed by the general formula I.
  • a preferred metal salt is zinc acetate dihydrate of the formula Zn (OCOCH3) 2 * 2 H2O.
  • reaction mixture is the mixture of all components used for the reaction.
  • the reaction mixture used for the process according to the invention preferably comprises at least 1, particularly preferably at least 2 and in particular at least 5% by weight and preferably at most 50, particularly preferably at most 20 and in particular at most 15% by weight of the metal salt, with the proviso that the sum of the amounts of all components of the reaction mixture is 100% by weight.
  • Alcohols suitable for the processes according to the invention have one (monohydric alcohols), preferably at least two OH groups per molecule.
  • Suitable monohydric alcohols are selected from methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-
  • Suitable monohydric alcohols are selected from partial ethers of glycols, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monopropyl ether.
  • glycols such as ethylene glyco
  • Suitable diols are preferably selected from 1, 2-ethanediol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 2,3-butanediol, 1, 4-butanediol, but-2-en-1, 4-diol, 1, 2-pentanediol, 1, 5-pentanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 1, 2-hexanediol, 1, 6-hexanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, octanediol, 1, 10-decanediol, 1, 2-dodecane
  • Suitable diols are also OH-terminated polyether homopolymers such as polyethylene glycol, polypropylene glycol and polybutylene glycol, binary copolymers such as ethylene glycol / propylene glycol and ethylene glycol / butylene glycol copolymers, straight-chain tertiary copolymers such as ternary ethylene glycol / propylene glycol / ethylene glycol, propylene glycol / Ethylene glycol / propylene glycol and ethylene glycol / butylene glycol / ethylene glycol copolymers.
  • Suitable diols are also OH-terminated polyether block copolymers, such as binary block copolymers, such as polyethylene glycol / polypropylene glycol and polyethylene glycol / polybutylene glycol, straight-chain, ternary block copolymers, such as polyethylene glycol / polypropylene glycol / polyethylene glycol, polypropylene glycol / polyethylene glycol / polypropylene glycol and polyethylene glycol / polybutylene glycol. col / polyethylene glycol terpolymers.
  • polyethers may also be substituted and / or have different end groups from OH.
  • Particularly preferred polyhydric alcohols are those having 10 or less carbon atoms. Of these, preference is given to those alcohols which are in the liquid state at 25 ° C. and 1013 mbar and have such low viscosity that they can be used as the sole solvent and dispersion medium as part of the reaction mixture without the aid of a further liquid phase.
  • polyhydric alcohols examples include ethylene glycol, diethylene glycol, 1, 2 Propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2,3-butanediol, pentanediol, hexanediol and octanediol, wherein ethylene glycol (1, 2-ethanediol) and 1, 2-propanediol are particularly preferred.
  • Suitable higher alcohols are also triols such as 1, 1, 1 -Tris-
  • polyhydric alcohols which can be used are also sugar alcohols, such as glycerol, threitol, erythritol, pentaerythritol, pentitol, the pentitol including XyNt, ribitol and arabitol, hexitol, the hexitol including mannitol, sorbitol and dulcitol, glyceraldehyde, dioxyacetone, threose, Erythrulose, erythrose, arabinose, ribose, ribulose, xylose, xylulose, lyxose, glucose, fructose, mannose, idose, sorbose, gulose, talose, tagatose, galactose, allose, altrose, lactose, xylose, arabinose, isomaltose, glucose heptose,
  • sugar alcohols such as glycerol, threitol, erythritol, pentaerythritol, pentitol and hexitol are preferred, since they lead to increased agglomeration resistance of the fine metal oxide particles in the metal oxide dispersion.
  • the aforementioned alcohols can be used according to the invention alone or in mixtures thereof.
  • the reaction mixture preferably comprises at least 10, particularly preferably at least 40 and in particular at least 60% by weight and preferably at most 98, particularly preferably at most 95 and in particular at most 90% by weight of alcohol, with the proviso that the sum of the amounts of all Components of the reaction mixture 100 wt .-% is.
  • reaction mixture may contain, in addition to metal salt, UV-absorbing compound and alcohol, at least one further cosmetically acceptable organic solvent and / or water.
  • Suitable further organic solvents are, for example, liquid ketone solvents, amide solvents, ester solvents and ether solvents.
  • the ketone solvents can be selected, for example, from acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone , Dibutyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-heptanedione, acetophenone, acetylacetone, 2,4-hexanedione, 2,5-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2 , 4-octanedione, 3,5-octanedione, 2,4-nonanedione,
  • the amide solvents can be selected, for example, from formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N -
  • the ester solvents can be selected, for example, from diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, ⁇ -butyrolactone, ⁇ -valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate , n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl
  • the ether solvents can be selected, for example, from dipropyl ether, diisopropyl ether, dioxane, tetrahydrofuran, tetrahydropyran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol dimethacrylate, propylene glycol diethyl ether, propylene glycol dipropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol dipropyl ether.
  • the aforementioned solvents may each be used alone or as mixtures thereof.
  • reaction mixture contains a further solvent which is different from alcohol and water, these are preferably at least 1, more preferably at least 2 and in particular at least 5% by weight and preferably at most 70, more preferably at most 50 and in particular at most 10% by weight. -% of the other solvent, with the proviso that the sum of the amounts of all components of the reaction mixture is 100 wt .-%.
  • the reaction mixture contains at most 1, preferably at most 0.1, more preferably at most 0.01 wt .-% of a further, different from alcohol and water solvent.
  • the reaction mixture contains no solvent other than alcohol and water.
  • Such other solvents can be used in Type A) and Type B) processes.
  • UV-absorbing compounds mentioned below are suitable for the processes A) and B).
  • UV-radiation absorbing compounds are commercially available commercial products, such as Uvinul ® brands (BASF).
  • Uvinul ® light stabilizers include compounds of the classes of benzophenones, benzotriazoles, cyanoacrylates, hindered amines (HALS-compounds), triazines, cinnamic esters, para-aminobenzoates, naphthalimides.
  • HALS-compounds hindered amines
  • triazines cinnamic esters
  • para-aminobenzoates naphthalimides
  • Other known UV-absorbing compounds are, for example, hydroxyphenyltriazines or oxalanilides. Such compounds are usually used alone or in mixtures with other light stabilizers in cosmetic applications such as in sunscreens or for the stabilization of organic polymers such as plastics.
  • UV radiation absorbing compounds are:
  • Substituted acrylates e.g. Ethyl or isooctyl- ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate (mainly 2-ethylhexyl- ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate), methyl- ⁇ -methoxycarbonyl- ⁇ -phenylacrylate, methyl- ⁇ -methoxycarbonyl- ⁇ - ( p-methoxyphenyl) acrylate, methyl or butyl ⁇ -cyano- ⁇ -methyl- ⁇ - (p-methoxyphenyl) acrylate, N- ( ⁇ -methoxycarbonyl- ⁇ -cyanovinyl) -2-methylindoline, octyl-p-methoxycinnamate, isopentyl-4-methoxycinnamate, urocaninic acid or its salts or esters;
  • acrylates e.g. Ethyl or isooctyl- ⁇ -cyano
  • Derivatives of p-aminobenzoic acid in particular their esters e.g. 4-aminobenzoic acid ethyl ester or ethoxylated ethyl 4-aminobenzoate, salicylates, substituted cinnamates (cinnamates) such as ethylhexyl p-methoxycinnamate or 4-isopentyl-4-methoxycinnamate, 2-phenylbenzimidazole-5-sulfonic acid or its salts.
  • esters e.g. 4-aminobenzoic acid ethyl ester or ethoxylated ethyl 4-aminobenzoate
  • salicylates e.g. 4-aminobenzoic acid ethyl ester or ethoxylated ethyl 4-aminobenzoate
  • substituted cinnamates cinnamates
  • 2-hydroxybenzophenone derivatives e.g. 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4, 2 ', 4'-trihydroxy, 2'-hydroxy-4,4' - dimethoxy-2-hydroxybenzophenone and 4-methoxy-2-hydroxybenzophenone-sulfonic acid sodium salt;
  • Esters of 4,4-diphenylbutadiene-1, 1-dicarboxylic acid e.g. the bis (2-ethylhexyl) ester;
  • Benzylidene camphor or its derivatives as described, for. As mentioned in DE-A 38 36 630, e.g. 3-Benzylidene camphor, 3 (4'-methylbenzylidene) d-1-camphor;
  • Dibenzoylmethanes e.g. 4-tert-butyl-4'-methoxydibenzoylmethane
  • 2,4,6-triaryltriazine compounds such as 2,4,6-tris ⁇ N- [4- (2-ethylhex-1-yl) oxycarbonylphenyl] amino ⁇ -1, 3,5-triazine, 4,4 ' - ((6- ((tert. Butyl) aminocarbonyl) phenylamino) -1, 3,5-triazine-2,4-diyl) imino) bis (benzoic acid 2'-ethylhexyl ester);
  • Sterically hindered amines such as N, N'-bis-formyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) hexamethylenediamine (CAS No. 124172-53-8), bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate (CAS No. 52829-07-9), bis (1, 2,2,6,6-pentamethyl-4-piperidyl) sebacate (CAS No. 41556-26-7), methyl (1, 2,2,6,6-pentamethyl-4-piperidyl) sebacate (CAS No. 82919-37-7), oligomeric hindered amines, under the trade name Uvinul ® 5050 H (CAS-No. 152261-33-1) and Uvinul ® 5062 H (CAS-No. 65447-77-0) are commercially available.
  • Uvinul ® 5050 H CAS-No. 152261-33-1
  • UV radiation-absorbing compounds can be found in the document Cosmetic Legislation, Vol. 1, Cosmetic Products, European Commission 1999, pp. 64-66, to which reference is hereby made.
  • UV radiation-absorbing compounds are also described in lines 14 to 30 ([003O]) on page 6 of EP 1 191 041 A2. These are incorporated herein by reference, and this reference is made to the disclosure of the present invention. Further suitable UV radiation-absorbing compounds are described, for example, on page 39, line 20 to page 41, line 10 of WO 2006/106140. This text is incorporated by reference in its entirety and this text is made the disclosure content of the present invention.
  • the method according to the invention is characterized in that the UV-absorbing compound is selected from benzophenones, benzotriazoles, benzoyl benzoates, 4-aminobenzoates, cyanoacrylates, sterically hindered amines, triazines, cinnamic esters and mixtures thereof.
  • the UV-absorbing compound is selected from benzophenones, benzotriazoles, benzoyl benzoates, 4-aminobenzoates, cyanoacrylates, sterically hindered amines, triazines, cinnamic esters and mixtures thereof.
  • the method according to the invention is characterized in that the UV radiation absorbing compound is selected from compounds containing at least one aromatic C ⁇ ring.
  • the method according to the invention is characterized in that the UV-absorbing compound is selected from 4-aminobenzoic acid,
  • Salicylic acid 2-ethylhexyl ester (CAS no. 18-60-5 1, Eusolex ® OS), 4-methoxy cinnamic acid-2-isoamyl (CAS no. 71617-10-2, Neo Heliopan E 1000 ®) 2- ethylhexyl-4-methoxycinnamate (CAS no. 5466-77-3, Uvinul ® MC80, Neo Helio- pan ® AV)
  • Neo Heliopan ® AP Neo Heliopan ® AP
  • the reaction mixture in particular for process B), preferably comprises at least 0.01, particularly preferably at least 0.1, more preferably at least 1 and in particular at least 2% by weight and preferably at most 20, particularly preferably at most 10 and in particular at most 5% by weight of the UV radiation absorbing compound, with the proviso that the sum of the amounts of all components of the reaction mixture is 100% by weight.
  • the precipitations can be carried out in the presence of at least one dispersant.
  • the dispersants may, for example, be:
  • Polyethers such as polyethylene glycol, organic acids as described in WO 2004/052327, in particular claim 1, to which reference is hereby made in its entirety;
  • the dispersant used is a nonionic dispersant.
  • This nonionic dispersant is preferably selected from one of the following groups:
  • Alkylphenols having 8 to 15 carbon atoms in the alkyl group having 8 to 15 carbon atoms in the alkyl group
  • Alkylmono- and -oligoglycosides having 8 to 22 carbon atoms in the alkyl radical, - castor oil and / or hydrogenated castor oil,
  • Partial esters based on linear, branched, unsaturated or saturated fatty acids having 12 to 22 carbon atoms,
  • Pentaerythritol - dipentaerythritol
  • Sugar alcohols eg sorbitol
  • Alkyl glucosides eg methyl glucoside, butyl glucoside, lauryl glucoside
  • polyglucosides eg cellulose
  • wool wax alcohols having 24 to 36 carbon atoms
  • Guerbet alcohols having 6 to 22 carbon atoms
  • - polyalkylene glycols whose structure comprises between 2 and 80 ethylene glycol units
  • the nonionic dispersant used is at least one substance from one of the following groups:
  • Non-ionic dispersants are under the brand name Cremophor ® (Fa. BASF Aktiengesellschaft) are commercially available.
  • the technical grade of the ethylene oxide adducts can always also contain a small proportion of the free hydroxyl or carboxyl group-containing substrates listed above by way of example. In general, this proportion is less than 20 wt .-%, preferably less than 5 wt .-%, based on the total amount of the dispersant.
  • the concentration of the nonionic dispersants based on the solution from which the precipitation is carried out is generally in the range from 0.1 to 20 g / l, preferably from 1 to 10 g / l, more preferably from 1, 5 to 5 g / l.
  • a preferred embodiment of the process according to the invention is characterized in that the precipitation of the oxides, hydroxides or oxide hydroxides in the presence of at least one nonionic dispersant, which is obtained by reacting hydrogenated castor oil or fatty alcohols with about 35 to about 50 equivalents of ethylene oxide.
  • at least one nonionic dispersant which is obtained by reacting hydrogenated castor oil or fatty alcohols with about 35 to about 50 equivalents of ethylene oxide.
  • Cremophor ® CO 40 Fa. BASF Aktiengesellschft
  • an addition product of 40 equivalents of ethylene oxide with hydrogenated castor oil or Cremophor ® A 25 is (Fa. BASF Aktiengesellschaft), an addition product of 25 equivalents of ethylene oxide with cetyl stearyl alcohol, as nonionic dispersant used.
  • the precipitation takes place in the presence of a polyacrylate as a dispersant.
  • the polyacrylates are polymers based on at least one ⁇ , ⁇ -unsaturated carboxylic acid, for example acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, maleic acid, citraconic acid, methylene malonic acid, crotonic acid, isocrotonic acid, fumaric acid, mesaconic acid and itaconic acid.
  • polyacrylates based on acrylic acid, methacrylic acid, maleic acid or mixtures thereof are used.
  • the proportion of the at least one ⁇ , ⁇ -unsaturated carboxylic acid in the polyacrylates is generally between 20 and 100 mol%, preferably between 50 and 100 mol%, particularly preferably between 75 and 100 mol%.
  • the polyacrylates can be used both in the form of the free acid and partially or completely neutralized in the form of their alkali metal, alkaline earth metal or ammonium salts. However, they can also be used as salts of the respective polyacrylic acid and triethylamine, ethanolamine, diethanolamine, triethanolamine, morpholine, diethylenetriamine or tetraethylenepentamine.
  • the polyacrylates may contain other comonomers which are einpolysiert in the polymer chain, for example, the esters, amides and nitriles of the above-mentioned carboxylic acids, eg.
  • Suitable as further copolymerizable comonomers are allylacetic acid, vinylacetic acid, acrylamidoglycolic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate or acrylamidomethylpropanesulfonic acid, and phosphonic acid-containing monomers such as vinylphosphonic acid , Allylphosphonic acid or acrylamidomethanepropanephosphonic acid.
  • the monomers containing acid groups can be used in the polymerization in the form of the free acid groups and in partially or completely neutralized with bases form.
  • copolymerizable compounds are N-vinylcaprolactam, N-vinylimidazole, N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, vinyl acetate, vinyl nylpropionate, isobutene or styrene and compounds having more than one polymerizable double bond such as diallyl ammonium chloride, ethylene glycol dimethacrylate, diethylene glycol diacrylate, allyl methacrylate, trimethylolpropane triacrylate, triallylamine, tetraallyloxyethane, triallyl cyanurate, maleic acid diallyl ester, tetraallylethylenediamine, Divinylidenharnstoff, pentaerythritol, pentaerythritol triacrylate and pentaerythritol tetraallyl, N, N-methylenebisacrylamide or N, N '-Methylen
  • mixtures of said comonomers are suitable for the preparation of the polyacrylates.
  • mixtures of 50 to 100 mol% of acrylic acid and 0 to 50 mol% of one or more of the comonomers mentioned are suitable for the preparation of the polyacrylates.
  • the concentration of the polyacrylates is based on the solution from which the precipitation takes place, as a rule in the range from 0.1 to 20 g / l, preferably from 1 to 10 g / l, particularly preferably from 1, 5 to 5 g / l.
  • the polyacrylates must of course be at least partially, preferably completely soluble in the solvents used.
  • the molecular weight of the dispersants suitable as polyacrylates is generally in the range of 800 to 250,000 g / mol, preferably in the range of 1000 to 100,000 g / mol, more preferably in the range of 1000 to 20,000 g / mol.
  • a preferred embodiment of the process according to the invention is characterized in that the precipitation of the metal oxide, metal hydroxide and / or the metal oxide hydroxide takes place in the presence of a polyacrylate which is obtained from pure acrylic acid.
  • Sokalan ® PA 15 (Fa. BASF Aktiengesellschaft), the sodium salt of a polyacrylic acid is used.
  • the precipitation takes place in the presence of an oligo- or polyethylene glycol acid as a dispersant.
  • an oligo- or polyethylene glycol acid as a dispersant.
  • a further subject of the present invention is UV-absorbing hybrid materials comprising a) nanoparticles of at least one oxide, hydroxide and / or oxide hydroxide of at least one metal selected from the group consisting of aluminum, magnesium, cerium, iron, manganese, cobalt, nickel, Titanium, zinc, zirconium and mixtures thereof; and b) at least one organic ultraviolet absorbing compound obtainable by precipitating the oxide, hydroxide and / or oxide hydroxide from a solution containing a suitable salt of the metal in the presence of at least one organic UV Radiation absorbing compound.
  • the surface-modified nanoparticulate particles have a diameter of 10 to 200 nm. This is particularly advantageous since good redispersibility is ensured within this size distribution.
  • the surface-modified nanoparticulate particles have a diameter of 20 to 100 nm.
  • This size range is particularly advantageous because, for example, after redispersing of, for example, zinc oxide nanoparticles of this size, the resulting suspensions are transparent and thus do not affect the color when added to cosmetic formulations.
  • transparent films such as plastic films.
  • a particularly preferred embodiment of the hybrid materials according to the invention is characterized in that their dispersions are largely transparent. This is particularly advantageous because the dispersions are thereby incorporated in incorporation into other products, e.g. Plastic moldings have no influence on the color scheme.
  • the dispersions can be used in films because they also do not affect the transparency of these films.
  • Another object of the present invention is the use of obtainable by the novel UV radiation-absorbing hybrid materials as UV light stabilizers in cosmetic preparations, as stabilizers in plastics and as antimicrobial agents.
  • Another object of the present invention are cosmetic preparations containing the obtainable by the novel UV radiation-absorbing hybrid materials and dispersions thereof.
  • a further subject of the present invention are plastics and films, in particular plastic films, containing the UV radiation-absorbing hybrid materials obtainable by the process according to the invention.
  • the UV radiation-absorbing hybrid materials obtainable by the process according to the invention are redispersible in a liquid medium and form stable suspensions.
  • the UV radiation-absorbing hybrid materials obtainable by the process according to the invention are redispersible in polar organic solvents and form stable suspensions. This is particularly advantageous, since this uniform incorporation, for example, in plastics and films, in particular plastic films, is possible.
  • the UV radiation-absorbing hybrid materials obtainable by the process according to the invention are redispersible in alcohol and / or water and form stable suspensions there. This is particularly advantageous, since this opens up the possibility of using the UV radiation-absorbing hybrid materials, for example in cosmetic formulations, wherein dispensing with further organic solvents other than alcohols is optionally advantageous.
  • a further subject of the present invention is a process for the preparation of preparations, in particular cosmetic preparations, comprising a) nanoparticles of at least one oxide, hydroxide and / or oxide hydroxide of at least one metal selected from the group consisting of aluminum, magnesium, cerium, iron, Manganese, cobalt, nickel, titanium, zinc, zirconium and mixtures thereof, and b) at least one organic ultraviolet radiation absorbing compound, the process comprising at least the steps of: i) reacting a suitable salt of the metal in an alcohol-containing reaction mixture, wherein the reaction of the metal salt is in the presence of at least one organic ultraviolet radiation absorbing material Ii) optionally removing up to 90% by weight of the volatile constituents of the reaction mixture obtained from step i), iii) optionally at least partially exchanging the first liquid phase of the reaction mixture for a second liquid phase different from the first liquid phase, iv) Use of the reaction mixture obtained according to steps i), optionally ii) and optionally iii) for the preparation of
  • a further preferred embodiment of the method according to the invention is characterized in that at least one of the method steps ii) and iii) is carried out continuously.
  • a further subject of the present invention are suspensions of UV radiation-absorbing hybrid materials comprising a) nanoparticles of at least one oxide, hydroxide and / or oxide hydroxide of at least one metal selected from the group consisting of aluminum, magnesium, cerium, iron, manganese, cobalt, nickel, titanium , Zinc, zirconium and mixtures thereof, and b) at least one organic ultraviolet radiation absorbing compound, these suspensions being obtainable by the methods described above.
  • Another object of the present invention is the use of these suspensions as UV light stabilizers in cosmetic preparations, for the stabilization of plastics or as antimicrobial agents.
  • the preparations according to the invention serve to care for or protect the skin, in particular for sun protection or care in sunlight exposure, and are in the form of an emulsion, a dispersion, a suspension, an aqueous surfactant preparation, a milk, a lotion, a cream, a balm, an ointment, a gel, a granule, a powder, one Pen preparations, such as a lipstick, a foam, an aerosol or a spray.
  • Suitable emulsions are oil-in-water emulsions and W / O emulsions or microemulsions.
  • the hybrid material according to the invention is very suitable for use in sunscreens, since the particles can be produced in a size that makes them appear transparent to the human eye. This results in no white veil on the skin when applied.
  • the cosmetic preparation is used for topical application on the skin.
  • Topical preparations are to be understood as meaning those preparations which are suitable for applying the active ingredients to the skin in fine distribution and preferably in a form resorbable by the skin.
  • aqueous and aqueous-alcoholic solutions sprays, foams, foam aerosols, ointments, aqueous gels, emulsions of the O / W or W / O type, microemulsions or cosmetic stick preparations.
  • the preparation contains a carrier.
  • a carrier is water, a gas, a water-based liquid, an oil, a gel, an emulsion or microemulsion, a dispersion or mixtures thereof.
  • the mentioned carriers show good skin tolerance.
  • Particularly advantageous for topical preparations are aqueous gels, emulsions or microemulsions.
  • Nonionic surfactants, zwitterionic surfactants, ampholytic surfactants or anionic emulsifiers can be used as emulsifiers.
  • the emulsifiers may be present in the compositions according to the invention in amounts of from 0.1 to 10% by weight, preferably from 1 to 5% by weight, based on the composition.
  • Suitable emulsifiers / surfactants for cosmetic preparations are disclosed in paragraphs [0052] to [0054] of EP 1455737 B1, to which reference is hereby made in its entirety.
  • the cosmetic preparations may be used in addition to the hybrid materials contain further light protection filters.
  • These may be the abovementioned organic light stabilizers but also pigments, for example finely dispersed metal oxides or salts such as, for example, titanium dioxide, iron oxide, aluminum oxide, cerium oxide, zirconium oxide, silicates (talc), barium sulfate and zinc stearate.
  • the particles should have an average diameter of less than 100 nm, preferably from 5 to 50 nm and in particular from 15 to 30 nm.
  • secondary light stabilizers of the antioxidant type which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates into the skin. Typical examples include superoxide dismutase, tocopherols (vitamin E) and ascorbic acid (vitamin C).
  • the total amount of light stabilizer in the sunscreen according to the invention is usually from 1 to 20, preferably from 5 to 15 wt .-%.
  • the preparation according to the invention may contain from 1 to 95, preferably from 5 to 80, and in particular from 10 to 60,% by weight of water.
  • the cosmetic preparation according to the invention further contains nourishing substances, other cosmetic active ingredients and / or auxiliaries and additives.
  • Skin-moisturizing agents, antimicrobial substances and / or deodorising or antiperspirant substances are used in particular as further cosmetic active ingredients.
  • This has the advantage that it is possible to obtain further desired effects which contribute to the care or treatment of the skin or, for example, increase the sense of well-being of the user of the cosmetic composition when using this composition.
  • the hybrid material, water and physiologically suitable solvents including caring ingredients, such as oils, waxes, fats, moisturizers, thickeners, emulsifiers and fragrances may be included.
  • a high proportion of caring substances is particularly advantageous for the topical prophylactic or cosmetic treatment of the skin. It is particularly advantageous if the composition contains further care components in addition to the animal and vegetable fats and oils, which in many cases also have care properties.
  • the group of active ingredients that can be used includes, for example: fatty alcohols having 8 to 22 C atoms, in particular fatty alcohols of natural fatty acids; animal and vegetable protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein, silk protein, oat protein, pea protein, almond protein and wheat protein; Vitamins, provitamins and vitamin precursors, especially those of vitamin A and B; Mono-, di- and oligosaccharides; Plant extracts; Honey extracts; ceramides; phospholipids; Vaseline, paraffin and silicone oils; Fatty acid and fatty alcohol esters, in particular the monoesters of the fatty acids with alcohols having 3 to 24 carbon atoms.
  • auxiliaries and additives serve to improve the esthetic, application-technical and / or cosmetic properties.
  • auxiliaries and additives are e.g. Co-emulsifiers, organic solvents, super-greases, stabilizers, antioxidants, waxes or greases, bodying agents, thickeners, tanning agents, vitamins, cationic polymers, biogenic agents, preservatives, hydrotropes, solubilizers, dyes and fragrances.
  • further auxiliaries and additives reference is hereby made to the disclosure of EP 1455737 B1, paragraphs [0075] to [0077], to which reference is hereby made in its entirety.
  • hybrid materials obtainable according to the invention in particular the zinc oxide dispersions
  • hair cosmetics such as shampoos, conditioners, rinses, hair lotions, hair gels, hair sprays etc.
  • leave-on products which remain on the hair or scalp after application are particularly suitable.
  • the hybrid material applied in this way to the scalp and the hair, in particular the hybrid material comprising zinc oxide can therefore also act there as a UV protection agent or unfold its skin-soothing effect on the scalp.
  • the cosmetic preparation according to the invention is applied topically to the surface of the body to be treated or protected.
  • This form of application is particularly advantageous because it is easy to handle, so that incorrect dosages are largely excluded. Furthermore, an additional nourishing effect for the skin can be achieved.
  • the sunscreen can only be applied specifically to these parts of the body.
  • Another object of the present invention is the use of the hybrid materials according to the invention as antimicrobial agents.
  • the use of Materials are particularly advantageous for this purpose, because on the one hand due to the fineness of the particles and the resulting large surface, the antimicrobial effect is greatly improved and on the other hand, the material is present in finely divided form due to the good dispersing properties.
  • the material can be easily used in various dosage forms such as creams, skin milk, lotions or Tonics.
  • Another object of the present invention is a pharmaceutical agent containing a hybrid material according to the invention or its dispersion.
  • This pharmaceutical agent is characterized in that due to the fineness of the particles, the pharmaceutical activity is greatly increased.
  • the pharmaceutical agent according to the invention has the advantage that due to the good long-term stability of the hybrid materials can be dispensed with the addition of stabilizers to prevent segregation. Thus, in addition, the compatibility of the pharmaceutical agent is increased.
  • a mixture of 100 g of Zn acetate dihydrate, and 1000 g of 1, 2-propanediol was heated with stirring (400 rpm) within 15 minutes in air at 100 0 C. After reaching the temperature of 100 0 C, 20 ml of water were added, the mixture was heated to 150 ° C, held for 1 hour under reflux at this temperature and then cooled to room temperature.
  • the resulting suspension was centrifuged in a Sorvall centrifuge type ® RC-6 (Fa. Thermo) at 13,000 rpm.
  • the settled ZnO powder was separated from the 1, 2-propanediol, redispersed twice in ethanol and then dried at about 50 0 C for 12 hours in a drying oven.
  • the obtained ZnO powder was mixed in a mortar with 2.7 g of 2- (2-hydroxy-5-methylbenzoyl) benzoic acid. In comparison to Example 1, the mixture showed markedly lower absorption in the UV and lower transparency in the VIS.
  • a mixture of 100 g Zn acetate dihydrate, 2.7 g of benzoic acid and 1000 g of 1, 2- propanediol was heated under stirring (400 rpm) over 15 minutes in air at 100 0 C. After reaching the temperature of 100 0 C, 20 ml of water were added, the mixture was heated to 150 0 C, held for 1 hour under reflux at this temperature and then cooled to room temperature.
  • the resulting suspension was centrifuged in a Sorvall centrifuge type ® RC-6 (Fa. Thermo) at 13,000 rpm.
  • the settled ZnO powder was from 1, 2-propanediol separated, redispersed twice in ethanol and then dried at about 50 0 C for 12 hours in a drying oven.
  • the resulting suspension was centrifuged in a Sorvall centrifuge type ® RC-6 (Fa. Thermo) at 13,000 rpm.
  • the settled ZnO powder was separated from the 1, 2-propanediol, redispersed twice in ethanol and then dried at about 50 0 C for 12 hours in a drying oven.
  • the resulting suspension was centrifuged in a Sorvall centrifuge type ® RC-6 (Fa. Thermo) at 13,000 rpm.
  • the settled ZnO powder was from 1, 2-propanediol separated, redispersed twice in ethanol and then dried at about 50 0 C for 12 hours in a drying oven.
  • the resulting suspension was centrifuged in a Sorvall centrifuge type ® RC-6 (Fa. Thermo) at 13,000 rpm.
  • the settled ZnO powder was separated from the 1, 2-propanediol, redispersed twice in ethanol and then dried at about 50 0 C for 12 hours in a drying oven.
  • a mixture of 100 g Zn acetate dihydrate, 2.7 g Uvinul ® 5050H (BASF, CAS 152261- 33-1) and 1000 g of 1, 2-propanediol was added with stirring (400 rpm) over 15 minutes in air at 100 ° C heated. After reaching the temperature of 100 0 C, 20 ml of water were added, the mixture was heated to 150 0 C, held for 1 hour under reflux at this temperature and then cooled to room temperature.
  • the resulting suspension was centrifuged in a Sorvall centrifuge type ® RC-6 (Fa. Thermo) at 13,000 rpm.
  • the deposited ZnO powder was separated from the 1, 2-propanediol, redispersed twice in ethanol and then dried at about 50 ° C for 12 hours in a drying oven. Examples of cosmetic formulations
  • phase A and C were heated separately to about 85 0 C. Subsequently, phase C and the hybrid material were stirred into phase A with homogenization. After brief post-homogenization, the emulsion was cooled to room temperature with stirring and bottled. All amounts are based on the total weight of the preparations.
  • Emulsion A comprising 3 wt .-% Uvinul ® T150 and 4 wt .-% hybrid material prepared according to Example 1
  • Example 8 Emulsion B containing 3 wt .-% Uvinul ® T150, 2 wt .-% Uvinul ® A Plus and 4 wt .-% hybrid material according to Example 1
  • Emulsion A comprising 3 wt .-% Uvinul ® T150 and 4 wt .-% hybrid material according to Example 1
  • Emulsion B containing 3 wt .-% Uvinul ® T150, 2 wt .-% Uvinul ® A Plus and 4 wt .-% hybrid material according to Example 1

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Abstract

L'invention concerne des procédés de fabrication de matériaux hybrides absorbant les U.V., matériaux qui comprennent : des nanoparticules d'au moins un oxyde métallique, un hydroxyde métallique et/ou un oxyhydroxyde métallique; et au moins un composé organique absorbant le rayonnement ultraviolet. L'invention concerne en outre : les matériaux hybrides absorbant les U.V. qui peuvent être obtenus d'après ces procédés; des compositions contenant ces matériaux; et l'utilisation des matériaux hybrides pour des préparations cosmétiques, comme agent anti-UV dans des matières plastiques et comme principes actifs antimicrobiens.
PCT/EP2008/066056 2007-12-21 2008-11-24 Procédés de fabrication de matériaux hybrides absorbant les u.v. Ceased WO2009080427A1 (fr)

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Cited By (11)

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WO2011016139A1 (fr) * 2009-08-04 2011-02-10 L'oreal Pigment composite et procédé de préparation de celui-ci
CN102040561A (zh) * 2010-11-30 2011-05-04 浙江工业大学 一种苯并三唑紫外线吸收剂的合成方法
US20130143033A1 (en) * 2010-04-29 2013-06-06 Mitsubishi Plastics, Inc. Laminated polyester film
CN106046415A (zh) * 2016-05-27 2016-10-26 广州煌垅生物科技有限公司 一种光稳定剂组合物及其制备方法
FR3070163A1 (fr) * 2017-08-21 2019-02-22 Commissariat A L'energie Atomique Et Aux Energies Alternatives Particules fonctionnalisees absorbant le rayonnement ultra-violet et leur procede de preparation
FR3079237A1 (fr) * 2018-03-20 2019-09-27 Commissariat A L'energie Atomique Et Aux Energies Alternatives Particules inorganiques greffees par des composes organiques specifiques presentant des proprietes de protection contre les rayons uv
US11229422B2 (en) 2015-10-01 2022-01-25 Global Life Sciences Solutions Operations Uk Ltd. Micro-needle sampling device and use thereof
US11357713B2 (en) 2015-07-14 2022-06-14 Conopco, Inc. Antimicrobial composition
WO2023139038A1 (fr) * 2022-01-18 2023-07-27 Basf Se Compositions de filtre uv comprenant des particules d'oxyde métallique hybride
US20230374313A1 (en) * 2022-05-20 2023-11-23 University Of South Florida Spectrally selective zinc oxide particles and methods of making thereof
US12485072B1 (en) * 2024-11-24 2025-12-02 Imam Mohammad Ibn Saud Islamic University Eco-friendly and biocompatible hybrid nanomaterials in sunscreen

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102471605A (zh) * 2009-08-04 2012-05-23 莱雅公司 复合颜料及其制备方法
US20130259912A1 (en) * 2009-08-04 2013-10-03 L'oreal Composite pigment and method for preparation thereof
US8882902B2 (en) 2009-08-04 2014-11-11 L'oreal Composite pigment and method for preparation thereof
CN102471605B (zh) * 2009-08-04 2015-06-17 莱雅公司 复合颜料及其制备方法
WO2011016139A1 (fr) * 2009-08-04 2011-02-10 L'oreal Pigment composite et procédé de préparation de celui-ci
US20130143033A1 (en) * 2010-04-29 2013-06-06 Mitsubishi Plastics, Inc. Laminated polyester film
CN102040561A (zh) * 2010-11-30 2011-05-04 浙江工业大学 一种苯并三唑紫外线吸收剂的合成方法
US11357713B2 (en) 2015-07-14 2022-06-14 Conopco, Inc. Antimicrobial composition
US11229422B2 (en) 2015-10-01 2022-01-25 Global Life Sciences Solutions Operations Uk Ltd. Micro-needle sampling device and use thereof
CN106046415A (zh) * 2016-05-27 2016-10-26 广州煌垅生物科技有限公司 一种光稳定剂组合物及其制备方法
FR3070163A1 (fr) * 2017-08-21 2019-02-22 Commissariat A L'energie Atomique Et Aux Energies Alternatives Particules fonctionnalisees absorbant le rayonnement ultra-violet et leur procede de preparation
FR3079237A1 (fr) * 2018-03-20 2019-09-27 Commissariat A L'energie Atomique Et Aux Energies Alternatives Particules inorganiques greffees par des composes organiques specifiques presentant des proprietes de protection contre les rayons uv
WO2023139038A1 (fr) * 2022-01-18 2023-07-27 Basf Se Compositions de filtre uv comprenant des particules d'oxyde métallique hybride
US20230374313A1 (en) * 2022-05-20 2023-11-23 University Of South Florida Spectrally selective zinc oxide particles and methods of making thereof
US12492309B2 (en) * 2023-05-22 2025-12-09 University Of South Florida Spectrally selective zinc oxide particles and methods of making thereof
US12485072B1 (en) * 2024-11-24 2025-12-02 Imam Mohammad Ibn Saud Islamic University Eco-friendly and biocompatible hybrid nanomaterials in sunscreen

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