WO2003059834A1 - Composite verre-ceramique contenant des nanoparticules - Google Patents

Composite verre-ceramique contenant des nanoparticules Download PDF

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Publication number
WO2003059834A1
WO2003059834A1 PCT/EP2002/014043 EP0214043W WO03059834A1 WO 2003059834 A1 WO2003059834 A1 WO 2003059834A1 EP 0214043 W EP0214043 W EP 0214043W WO 03059834 A1 WO03059834 A1 WO 03059834A1
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Prior art keywords
glass
weight
composite material
nanoparticles
glass ceramic
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PCT/EP2002/014043
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German (de)
English (en)
Inventor
José ZIMMER
Jörg Hinrich FECHNER
Original Assignee
Schott Glas
Carl-Zeiss-Stiftung Trading As Schott Glas
Carl-Zeiss-Stiftung
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Application filed by Schott Glas, Carl-Zeiss-Stiftung Trading As Schott Glas, Carl-Zeiss-Stiftung filed Critical Schott Glas
Priority to JP2003559943A priority Critical patent/JP2005532972A/ja
Priority to AU2002352237A priority patent/AU2002352237A1/en
Publication of WO2003059834A1 publication Critical patent/WO2003059834A1/fr
Priority to US10/890,682 priority patent/US20050119105A1/en

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    • 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
    • A61Q17/005—Antimicrobial preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—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
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00—Drugs for dermatological disorders
    • A61P17/02—Drugs for dermatological disorders for treating wounds, ulcers, burns, scars, keloids, or the like
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00—Drugs for dermatological disorders
    • A61P17/16—Emollients or protectives, e.g. against radiation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P29/00—Non-central analgesic, antipyretic or antiinflammatory agents, e.g. antirheumatic agents; Non-steroidal antiinflammatory drugs [NSAID]
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04—Antibacterial agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • 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
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C12/00—Powdered glass; Bead compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/006—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of microcrystallites, e.g. of optically or electrically active material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0007—Compositions for glass with special properties for biologically-compatible glass
    • 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
    • C09C1/0078—Pigments consisting of flaky, non-metallic substrates, characterised by a surface-region containing free metal
    • 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
    • A61K2800/62—Coated
    • A61K2800/621—Coated by inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2204/00—Glasses, glazes or enamels with special properties
    • C03C2204/02—Antibacterial glass, glaze or enamel
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/04—Particles; Flakes
    • C03C2214/05—Particles; Flakes surface treated, e.g. coated
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/20—Glass-ceramics matrix
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
    • C03C2217/45—Inorganic continuous phases
    • C03C2217/452—Glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
    • C03C2217/475—Inorganic materials

Definitions

  • the invention relates to an inorganic glass-ceramic composite material comprising a glass or glass ceramic phase and nanoparticles.
  • the composite material is characterized in particular by its antimicrobial, anti-inflammatory, wound-healing and light-absorbing and light-scattering properties.
  • DE 19647 368 A1 shows composite materials containing a substrate and a nanocomposite that is in functional contact therewith.
  • the substrate can consist of glass material and be in the form of powders.
  • the nanocomposite can completely or partially cover the substrate as a coating.
  • a glass powder has become known from US Pat. No. 5,676,720 which comprises 40-60% by weight of SiO 2 , 5-30% by weight of Na 2 0, 10-35% by weight of CaO, 0-12% by weight of P 2 0 5 , a glass ceramic made from a glass of such a composition has also become known.
  • No. 5,981,412 describes a bioactive bioceramic for medical applications with the crystalline phase Na 2 O 2 CaO 3 SiO 2 .
  • the crystallite size is 13 ⁇ m.
  • the ceramization takes place with tempering steps for nucleation and crystallization.
  • the focus is on the mechanical properties such as K 1c .
  • the proportion of crystal phases is between 34 and 60% by volume.
  • Nanoparticles such as Ti0 2 or ZnO are used with particle sizes of approx. 20 - 100 nm for UV blocking in cosmetic and other products. UV blocking is based on absorption, reflection and scattering of the radiation by these nanoparticles.
  • UVA (320 - 400 nm) radiation is scattered more than the radiation in the visible range.
  • the skin in sun protection products can be protected from sunburn.
  • TiO 2 in particular in the crystalline form anatase, is also photocatalytically active.
  • the absorption of photons creates electron-hole pairs that can react with molecules on the TiO 2 particle surface or environment.
  • radicals can develop here, which can have damaging effects on living organisms.
  • TiO 2 nanoparticles are currently coated with SiO 2 or Al 2 O 3 , especially for cosmetic applications.
  • TiO 2 nanoparticles if they get into human cells, can lead to DNA damage.
  • the skin is not a barrier for nanoparticles, since they can also penetrate through the skin.
  • Nanoparticles are provided with capture ions which prevent the formation of radicals on the nanoparticle surface by electron hole interception.
  • the object of the invention is to avoid the disadvantages of the prior art and to provide an inorganic material which, in addition to antimicrobial, anti-inflammatory and skin-regenerating properties, also absorbs, reflects and scatters light, in particular UV radiation, but also radiation in the visible range , radical formation under UV radiation should be avoided and migration of the nanoparticles in the body tissue can be prevented.
  • the object is achieved by using the ceramic-glass composite according to claim 1.
  • the ceramic-glass composite consists of different phases. These are a glass or glass ceramic phase as well as nanocrystals.
  • the nanocrystals are located on or in the surface of the larger glass or glass ceramic particles.
  • the nanopowders have particle sizes with d50 values ⁇ 500 nm, preferably ⁇ 200 nm, more preferably ⁇ 100 nm, most preferably ⁇ 50 nm.
  • the primary particle size can be significantly lower.
  • the glass or glass ceramic phases which contain these nanoparticles on or in the surface are preferably in powder form with particle sizes with d50 ⁇ 100 ⁇ m, preferably ⁇ 50 ⁇ m, more preferably ⁇ 10 ⁇ m.
  • the particle sizes of the glass powders are even more preferably ⁇ 5 ⁇ m, preferably ⁇ 2 ⁇ m, in special cases ⁇ 1 ⁇ m.
  • the crystals of the glass ceramic have crystallite sizes (d50) ⁇ 10 ⁇ m, preferably ⁇ 1 ⁇ m, particularly preferably ⁇ 500 nm, preferably ⁇ 100 nm, in special cases ⁇ 50 nm.
  • the ceramic-glass composite material of the invention is characterized in that the nanoparticles firmly on the surface of larger glass particles.
  • the nanoparticles can be coated with a glassy layer that prevents or suppresses a slight reaction of the nanoparticles with the environment.
  • the chemical resistance of the glass or of the glass ceramic is preferably so high that the glass does not completely dissolve in cosmetic formulations and the nanoparticles coated with glass thus remain coated.
  • the chemical composition of the glass has antimicrobial, anti-inflammatory and skin-care properties.
  • the material can have a biocidal, in any case a biostatic effect against bacteria, fungi and viruses, but can be skin-friendly and toxicologically harmless in contact with humans.
  • Desirable maximum concentrations in the area of cosmetic products are, for example, Pb ⁇ 20 ppm, Cd ⁇ 5 ppm, As ⁇ 5 ppm, Sb ⁇ 10 ppm, Hg ⁇ 1 ppm, Ni ⁇ 10 ppm.
  • the glass or the starting glass of the glass ceramic preferably have the following components:
  • SiO 2 as a network builder between 30-70% by weight. At low concentrations, the spontaneous tendency to crystallize increases sharply and the chemical resistance strongly decreases. At higher SiO 2 values, the crystallization stability can decrease and the processing temperature is increased significantly, so that the hot forming properties deteriorate. Si0 2 is also a component of the crystalline phases formed during a ceramization.
  • Na 2 O is used as a flux when melting the glass. At concentrations ⁇ 5%, the melting behavior is negatively affected. Sodium is part of the phases that form during ceramization. Sodium is released from the powder, inter alia, by ion exchange in aqueous media. K 2 O acts as a flux when melting the glass. In addition, potassium is released in aqueous systems inter alia by ion exchange.
  • the chemical resistance of the glass and thus the release of ions in aqueous media is adjusted via the P 2 0 5 content.
  • the P 2 0 5 content is between 0 and 10% by weight. At higher P 2 O 5 values, the hydrolytic resistance of the glass ceramic becomes too low.
  • the glass can contain up to 5% by weight of B 2 O 3 .
  • Al 2 O 3 should be ⁇ 15% by weight in order to ensure sufficient crystallization stability of the glass for production.
  • Al 2 O 3 should be ⁇ 5% by weight, preferably ⁇ 2% by weight, particularly preferably ⁇ 1% by weight. -% his.
  • antibacterial ions such as e.g. Ag, Au, 1, Ce, Cu, Zn can be contained in concentrations of ⁇ 5% by weight.
  • concentration of these ions is ⁇ 5% by weight, in particular ⁇ 2% by weight in total.
  • Ions such as Ag, Cu, Au, Li can also be included as additives to adjust the high-temperature conductivity of the melt and thus to improve the meltability with HF melting processes.
  • Coloring ions such as Fe, Co, V, Cu, Cr can be added individually or in combination in a total concentration of ⁇ 1% by weight.
  • oxides such as TiO 2 and CeO, which also have an absorbing effect in the UV range, into the base glass, effective blocking of the UV radiation can be achieved, the UV edge being able to be set in a defined manner by adding different contents.
  • the total concentration of these oxides is ⁇ 5% by weight, preferably ⁇ 2% by weight, more preferably ⁇ 1% by weight.
  • the glass can contain ions such as Ce, Mn, Ag, Au, Cu, Zn, Fe, which can act as electron scavengers. In this way, radical formation can be suppressed by the electron-hole pairs generated by Ti0 2 under UV radiation.
  • Certain ions can therefore have a dual function. On the one hand, they reinforce the antimicrobial effect synergistically and can also trap free electrons through redox reactions, which could lead to radical formation.
  • the concentration of the elements is ⁇ 2% by weight, in particular ⁇ 1% by weight, particularly preferably ⁇ 0.1% by weight
  • the glass is melted using conventional melting technologies or high-frequency processes and shaped into block glass or so-called “ribbons”.
  • the glass or the starting glass of the glass ceramic can be ground to powder.
  • the particle size of these powders is preferably ⁇ 100 ⁇ m, particularly preferred ⁇ 50 ⁇ m, in particular ⁇ 10 ⁇ m, in particular ⁇ 5 ⁇ m, in particular ⁇ 1 ⁇ m. Both dry and “wet” grinding technology can be used for this. In the case of "wet” grinding, the powders can then be dried.
  • the glass powders can be mixed with the nanopowders. This can be done dry or the nanopowders are added as a dispersion to the dry or "wet" glass powders.
  • An alternative production route is to add the nanoparticles to the glass during the first grinding process. After the mixing process, the nanoparticles are on the surface of the glass powder. If the nanopowders have been added in dispersion form, drying may be necessary. The mixture is sintered in the oven. The nanopowders combine with the glass powders. Surface diffusion processes coat the nanoparticles with glass during sintering. As a result, the nanoparticles are encapsulated from the environment. The chemical resistance of this glass encapsulation is so high that a surface reaction of the Ti0 2 with the environment is suppressed in cosmetic formulations.
  • the sintering temperatures for viscous sintering are above T g of the starting glass, preferably
  • the sintering can also take place below T g , this is referred to as so-called diffusion-controlled solid-state sintering.
  • the temperatures are preferably 200 ° C. to 0 ° C. below T g , in particular 100 ° C. to 10 ° C. below T g . With this low-temperature sintering, the meal and energy consumption can be reduced by reduced sintering together.
  • the main phases here include Alkali-alkaline earth silicates such as sodium calcium silicates, alkaline earth silicates such as calcium silicate are formed.
  • the sintering can also be carried out in a multi-stage temperature-time program, for example in order to specifically fuse the Nanoparticles with the glass and, if possible, controlled to carry out a ceramicization of the glass.
  • the powders are ground again to adjust the final particle size.
  • the sintering process can be carried out in such a way that the glass phase can be ceramized.
  • the additional scattering or reflection effects can be set by ceramizing the base glass with a defined crystallite size.
  • the effects can be controlled by process parameters such as the temperature-time profile of the process, but also by the amount of crystal former added.
  • the composite material is usually used as a powder, particle sizes of ⁇ 100 ⁇ m being obtained by a final grinding process.
  • Particle sizes of ⁇ 50 ⁇ m or ⁇ 20 ⁇ m have proven to be expedient.
  • Particle sizes ⁇ 10 ⁇ m and smaller than 5 ⁇ m are particularly suitable.
  • Particle sizes ⁇ 1 ⁇ m have been found to be particularly suitable.
  • the grinding process can be carried out dry as well as with aqueous and non-aqueous grinding media.
  • the total amount of nanoparticles in the composite material is ⁇ 20% by weight, preferably ⁇ 10% by weight, more preferably ⁇ 5% by weight.
  • the light-influencing effects are achieved on the one hand by the nanoparticles, which lead intrinsically to the absorption and scattering of the light, on the other hand by the surface morphology of the glass or glass-ceramic particles, which lead to scattering of the light, and by bulk characteristics of the glass or glass-ceramic particles ,
  • the sintered nanoparticles can simultaneously act as heterogeneous nuclei for the crystallization of the glass phase. The crystallization with the nanoparticles can thus be influenced.
  • nanoparticles with biologically active glass leads to a UV blocker with positive skin properties.
  • the disadvantages of nanoparticles cannot be compensated for, but overcompensated.
  • the coating of the glass particles with nanopowders leads to additional light-scattering effects which are not observed in the pure glass or glass ceramic powders and which can be attributed to the changed surface morphology.
  • the powders are ideally suited to be used in the field of cosmetic products. This can include Products in the field of color cosmetics or UV protection products.
  • Fig. 1 wide-angle X-ray diagram of a sample with a base glass according to
  • Fig. 2 SEM image of a base glass according to embodiment 1 without sintered TiO 2 nanoparticles 3 - 5 SEM images of a basic glass according to embodiment 1 with 5% by weight of TiO 2 nanoparticles sintered at 560 ° C. for one
  • Table 1 Compositions in% by weight of the base glasses
  • the 4 ⁇ m glass powder of type 1 was dry-mixed in a drum mill with 5% by weight of TiO 2 nanopowder with a secondary particle size of approximately 100 nm.
  • the powder mixture was then sintered in a chamber furnace at 580 ° C. for 2 hours.
  • the sintered powder was then briefly ground again in a drum mill, so that a particle size of approximately 5 ⁇ m was set.
  • the nanopowders are firmly sintered into the surface of the glass powder and largely completely coated with a glassy phase. This could be demonstrated using SEM and TEM.
  • FIG. 1 shows an X-ray diagram of a base glass according to embodiment 1 with sintered TiO 2 on (rutile) nanoparticles. Sintering took place at 560 ° C for one hour.
  • the x-ray diagram clearly shows the amorphous structure of the base glass and the crystalline structure of the sintered Ti0 2 particles.
  • the X-ray reflections of the sintered TiO 2 particles are given the reference number 1.
  • FIG. 2 shows an SEM image of a base glass according to embodiment 1 without sintered nanoparticles.
  • the glass powder was sintered at 560 ° C for one hour. A smooth surface without sintered nanoparticles can be seen.
  • FIGS. 3-5 show a base glass according to embodiment 1 with 5% by weight of TiO 2 nanoparticles (rutile).
  • This composition like the comparative sample whose surface is shown in FIG. 2, was sintered at 560 ° C. for one hour. In contrast to the comparison sample shown in FIG. 2, the surface is no longer smooth.
  • the solid bond between the individual nanoparticles, in this case the rutile and the base glass powder, can be clearly seen in FIG. 3.
  • the solid bond between the nanoparticles and the base glass powder can also be clearly seen in FIGS. 4 and 5.
  • the sample composition is the same sample as in the SEM image according to FIG. 3.
  • FIG. 6 shows a transmission electron microscopy TEM image of a base glass according to embodiment 1 with 5% by weight of TiO 2 nanoparticles sintered at 560 ° C. for one hour. It can be seen on this TEM image that the Ti0 2 (rutile) nanoparticles designated by the reference number 10 is surrounded by a glassy phase which is given the reference number 20.
  • the antimicrobial anti-inflammatory UV-radiation-reducing glass-ceramic composite materials can preferably be used in powder form as an additive in the cosmetic industry, for example in sun protection creams and day creams and creams against skin aging.
  • the invention provides a material in which different properties are combined in one material. Protection of the radical formation is achieved by coating the TiO 2 with an antimicrobial, anti-inflammatory and skin-regenerating layer. This happens in particular because the nanoparticles are bound to glass and thus no skin penetration can occur.
  • the material In powder form, the material has special light-scattering, absorbing, reflective properties due to surface modification.

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Abstract

L'invention concerne un matériau composite comprenant une phase verre ou une phase verre-céramique. L'invention est caractérisée en ce que le matériau composite inorganique comprend des nanoparticules, et en ce que la phase verre ou verre-céramique est recouverte de nanoparticules sur/ ou dans la surface.
PCT/EP2002/014043 2002-01-18 2002-12-11 Composite verre-ceramique contenant des nanoparticules WO2003059834A1 (fr)

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JP2003559943A JP2005532972A (ja) 2002-01-18 2002-12-11 ナノ粒子を含むガラスセラミック複合材料
AU2002352237A AU2002352237A1 (en) 2002-01-18 2002-12-11 Glass-ceramic composite containing nanoparticles
US10/890,682 US20050119105A1 (en) 2002-01-18 2004-07-14 Glass-ceramic composite containing nanoparticles

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DE10201747A DE10201747C1 (de) 2002-01-18 2002-01-18 Glas-Keramik-Komposit, Verfahren zu seiner Herstellung und Verwendungen
DE10201747.6 2002-01-18

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DE10332011A1 (de) * 2003-07-14 2005-02-17 Schott Ag Verwendung von Glaszusammensetzungen zum Erzielen eines antioxidativen Effektes
WO2005115936A2 (fr) * 2004-05-29 2005-12-08 Schott Ag Nanopoudre de verre et son utilisation, notamment poudre de verre a composants multiples, de grandeur particulaire moyenne inferieure a 1 $g(m)m
WO2006089738A1 (fr) * 2005-02-23 2006-08-31 Carl Zeiss Smt Ag Materiau composite optique et procede de production correspondant
JP2007507426A (ja) * 2003-09-29 2007-03-29 ショット アクチエンゲゼルシャフト 組織研磨剤
EP1779855A1 (fr) * 2005-10-28 2007-05-02 Abdula Kurkayev Nanoparticules de minéraux hétérocristallins et leur méthode de fabrication
US8784845B2 (en) 2006-09-12 2014-07-22 Prophy Med Ab Selective chemokine modulation
EP4234503A1 (fr) * 2022-02-24 2023-08-30 Corning Incorporated Vitrocéramiques de combeite transparentes

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DE102004008931B4 (de) * 2003-02-25 2008-01-17 Schott Ag Verwendung von porösen Gläsern, Glaskeramiken, Glaspulvern oder Glaskeramikpulvern in kosmetrischen, medizinischen, bioziden Formulierungen
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9173822B2 (en) 2003-07-14 2015-11-03 Schott Ag Use of glass compositions for achieving an antioxidative effect
DE10332011A1 (de) * 2003-07-14 2005-02-17 Schott Ag Verwendung von Glaszusammensetzungen zum Erzielen eines antioxidativen Effektes
JP2007507426A (ja) * 2003-09-29 2007-03-29 ショット アクチエンゲゼルシャフト 組織研磨剤
US7816292B2 (en) 2004-05-29 2010-10-19 Schott Ag Nano glass powder and use thereof, in particular multicomponent glass powder with a mean particle size of less than 1 μm
WO2005115936A2 (fr) * 2004-05-29 2005-12-08 Schott Ag Nanopoudre de verre et son utilisation, notamment poudre de verre a composants multiples, de grandeur particulaire moyenne inferieure a 1 $g(m)m
WO2005115936A3 (fr) * 2004-05-29 2006-02-16 Schott Ag Nanopoudre de verre et son utilisation, notamment poudre de verre a composants multiples, de grandeur particulaire moyenne inferieure a 1 $g(m)m
US7907347B2 (en) 2005-02-23 2011-03-15 Carl Zeiss Smt Ag Optical composite material and method for its production
WO2006089738A1 (fr) * 2005-02-23 2006-08-31 Carl Zeiss Smt Ag Materiau composite optique et procede de production correspondant
WO2007048634A3 (fr) * 2005-10-28 2007-12-06 Abdula Kurkayev Nanoparticules de mineral heterocristallin en tant que medicaments
WO2007048634A2 (fr) 2005-10-28 2007-05-03 Abdula Kurkayev Nanoparticules de mineral heterocristallin en tant que medicaments
EP1779855A1 (fr) * 2005-10-28 2007-05-02 Abdula Kurkayev Nanoparticules de minéraux hétérocristallins et leur méthode de fabrication
US8784845B2 (en) 2006-09-12 2014-07-22 Prophy Med Ab Selective chemokine modulation
US9649426B2 (en) 2006-09-12 2017-05-16 Prophy Med Ab Selective chemokine modulation
US9656015B2 (en) 2006-09-12 2017-05-23 Prophy Med Ab Selective chemokine modulation
EP4234503A1 (fr) * 2022-02-24 2023-08-30 Corning Incorporated Vitrocéramiques de combeite transparentes

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