WO2003018499A2 - Antimicrobial powdered glass and use thereof - Google Patents

Antimicrobial powdered glass and use thereof Download PDF

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Publication number
WO2003018499A2
WO2003018499A2 PCT/EP2002/009216 EP0209216W WO03018499A2 WO 2003018499 A2 WO2003018499 A2 WO 2003018499A2 EP 0209216 W EP0209216 W EP 0209216W WO 03018499 A2 WO03018499 A2 WO 03018499A2
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WO
WIPO (PCT)
Prior art keywords
weight
glass powder
antimicrobial
glass
powder according
Prior art date
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PCT/EP2002/009216
Other languages
German (de)
French (fr)
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WO2003018499A3 (en
Inventor
Jörg Hinrich FECHNER
José ZIMMER
Original Assignee
Schott Glas
Carl-Zeiss-Stiftung Trading As Schott Glas
Carl-Zeiss-Stiftung
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Priority claimed from DE10213630A external-priority patent/DE10213630A1/en
Application filed by Schott Glas, Carl-Zeiss-Stiftung Trading As Schott Glas, Carl-Zeiss-Stiftung filed Critical Schott Glas
Priority to DE10293768T priority Critical patent/DE10293768B4/en
Publication of WO2003018499A2 publication Critical patent/WO2003018499A2/en
Publication of WO2003018499A3 publication Critical patent/WO2003018499A3/en

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    • 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
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • 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
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • 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
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • 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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass

Definitions

  • the invention relates to an antimicrobial glass powder comprising a glass with a phosphorus content of less than 1% by weight based on the total weight of the glass composition based on oxide.
  • the antibacterial effect is based on added heavy metal ions, such as Cu, Zn or Ag.
  • the antibacterial effect of these compounds does not come from glass, but from the metal ions released.
  • US Pat. No. 5,290,544 describes water-soluble glasses for use in cosmetic products with very low SiO 2 and very high B 2 O 3 or high P 2 ⁇ 5 contents.
  • the glasses have silver concentrations greater than 0.5% by weight.
  • These glasses have an extremely low hydrolytic resistance and tend to completely dissolve in water.
  • the released Ag and / or Cu ions have an antibacterial effect.
  • JP-A-92178433 also describes a water-soluble glass powder with SiO 2 ⁇ 37% by weight as a polymer additive with high silver concentrations> 1% by weight.
  • No. 6,143,318 describes silver-containing phosphate glasses which are used as an antimicrobial material for wound infection treatment with combinations of Cu, Ag and Zn. These are also water-soluble glasses that have low SiO 2 concentrations and very high P 2 O 5 contents.
  • Antimicrobial silver-containing borosilicate glasses or borophosphate glasses are described in JP 10218637, JP 08245240, JP 07291654,
  • JP 03146436, JP 2000264674, JP 2000203876 Most of these glasses have good hydrolytic resistance and can therefore be ground in aqueous media.
  • Zeolites containing silver that is introduced by ion exchange are also used as an antibacterial agent. This is described for example in US 6,245,732 and WO 0038552.
  • Heavy metal-free glasses in which an antimicrobial effect can be demonstrated, are described in DE 19932238, DE 19932239 and WO 01/03650.
  • the glasses known from DE 19932338, DE 19932239 and WO 01/03650 are bioactive glasses with a significant phosphorus content> 1% by weight.
  • bioactive glass differs from conventional lime-sodium-silicate glasses in that it binds living tissue.
  • Bioactive glass refers to a glass that forms a firm bond with body tissue, forming a layer of hydroxyl apatite.
  • the object of the invention is to provide glass powder from glass compositions which avoid the disadvantages of the prior art, in particular can be produced without great effort.
  • a glass powder is understood to mean a powder comprising a large number of glass particles of any shape, including a glass fiber, for example a glass ball with a particle size of ⁇ 1 mm, preferably ⁇ 500 ⁇ m, or a glass fiber with a diameter of ⁇ 1 mm, preferably ⁇ 500 ⁇ m.
  • the glass powder can be added to products.
  • the glass powders are obtained by grinding in different grinding media.
  • the glass compositions of the glasses can be produced on an industrial scale using standard processes and are suitable, for example, for grinding in water, since the glass compositions have sufficient hydrolytic resistance, in contrast to glasses which contain a lot of phosphate, for example.
  • the glass powders according to the invention have a biocidal or biostatic effect on bacteria, fungi and viruses; they are skin-friendly in contact with humans, toxicologically harmless and in particular also suitable for consumption.
  • the glass composition of the Glass powder according to the invention particularly pure.
  • the exposure to heavy metals is low.
  • the maximum concentration in the range of cosmetic products is preferably for Pb ⁇ 20 ppm, Cd ⁇ 5 ppm, As ⁇ 5 ppm, Sb ⁇ 10 ppm, Hg ⁇ 1 ppm, Ni ⁇ 10 ppm.
  • Areas of application for this are, for example, cosmetic products, demo products, food, paints, varnishes, plasters, paper hygiene products, medical products and cleaners.
  • a particular advantage of the glass composition of the glass powder according to the invention is that the glass, owing to the melting and hot-forming process, is suitable for being able to be produced in corresponding large-scale plants.
  • the glass powders with a glass composition according to the invention have an antimicrobial effect which is extremely strong.
  • the antimicrobial properties are also found in glass compositions which have a relatively high hydrolytic resistance as a semi-finished product.
  • alkalis of the glass are replaced by H + ions of the aqueous medium by reactions on the surface of the glass of the glass powder.
  • the antimicrobial effect of the ion exchange is based, among other things, on an increase in the pH value and the osmotic effect on microorganisms.
  • Glass powder comprising ion-exchangeable glasses according to the invention have an antimicrobial effect in aqueous media by increasing the pH value by ion exchange between a metal ion, such as an alkali metal or alkaline earth metal ion and the H + ions of the aqueous solution, and by ion-induced impairment of cell growth (osmotic pressure, Disruption of metabolic processes in the cells).
  • Ground glass powder with particles of small particle size and large surface area show a drastic increase in reactivity, which, due to the ion exchange already described, results in a strong antimicrobial effect.
  • the antimicrobial effect in the glass powders according to the invention is achieved by the ion exchange and not by the antimicrobial effect of the heavy metal ions. However, these can increase the antimicrobial effect as an additive.
  • Particle sizes of ⁇ 100 ⁇ m can be obtained by a 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 glass of the glass powder contains SiO 2 as a network former, preferably between 35 to 80% by weight. At low concentrations, the hydrolytic resistance decreases significantly, so that grinding in aqueous media is no longer guaranteed without significant dissolution of the glass.
  • Na 2 O is used as a flux when melting the glass. At concentrations less than 5%, the melting behavior is negatively affected. In addition, the necessary mechanism of ion exchange no longer works sufficiently to achieve an antimicrobial effect. At Na 2 O concentrations higher than 30% by weight, a deterioration in the chemical resistance or hydrolytic resistance can be observed, especially in connection with a decrease in the SiO 2 content.
  • Alkali and alkaline earth oxides can in particular be added to increase the ion exchange and thus to increase the antimicrobial effect.
  • the amount of Al 2 O 3 can be added up to a maximum of 8% by weight to increase the chemical stability of the crystallization stability and to control the antimicrobial effect.
  • B 2 O 3 acts as a network builder and can also be used to control the antimicrobial effect.
  • ZnO is an essential component for the hot-forming properties of the glass. It improves crystallization stability and increases surface tension. It can also support the antimicrobial effect. With low SiO 2 contents, it increases the crystallization stability. To achieve an antimicrobial effect, up to 8% by weight of ZnO can be present.
  • a preferred embodiment contains ⁇ 4% by weight ZnO or ⁇ 2 Wt .-%. Designs with ⁇ 1% by weight or 0.5% by weight or ⁇ 0.1% by weight are particularly preferred.
  • CuO can be added as antimicrobial additives that synergistically enhance the intrinsic antimicrobial effect of the base glass.
  • the glass powder according to the invention has no skin-irritating effects. In some cases, however, anti-inflammatory effects can even be observed.
  • a combination of the pH effect and the Ag, Cu or Zn release can achieve a significant increase in the antimicrobial effect, which goes well beyond the sum of the individual effects.
  • the concentration of Ag, Cu, Zn ions released into the product can be well below 1 ppm.
  • the Ag, Cu, Zn can either be introduced during the melt by appropriate salts or else by ion exchange of the glass after the melt.
  • the glasses can be given individual or even several coloring components such as Fe 2 O 3 , CoO, CuO, V 2 O 5 , Cr 2 ⁇ 5 in a total concentration of less than 4% by weight, preferably less than 1% by weight be added.
  • coloring components such as Fe 2 O 3 , CoO, CuO, V 2 O 5 , Cr 2 ⁇ 5 in a total concentration of less than 4% by weight, preferably less than 1% by weight be added.
  • the glasses within the claimed composition range meet all requirements regarding use in the areas of paper hygiene, cosmetics, paints, varnishes, cleaning, medical products, cosmetic applications, food additives and use in deodorant products.
  • An essential property of the glass powder is the surprisingly proven skin tolerance, which is also given at high concentrations with high pH values.
  • the glass powder can be used in any suitable form. Mixtures of different glass powders from the composition range with different compositions are also possible. Mixing with other glass powders is also possible to combine certain effects.
  • components such as fluorine can be added to the glass up to a total concentration of 5% by weight.
  • the glass powder described in this invention is not water-soluble, but acts primarily by ion exchange or ion release, which is associated with a surface reaction, pH increase and metal ion release. Due to the synergistic antimicrobial effect of the glass powder itself and the antimicrobial effect of the metal ions, the amounts of metal ions required are lower in order to achieve a corresponding effect.
  • the glass was smelted from the raw materials in a platinum crucible at 1600 ° C and processed into semi-finished products or ribbons.
  • the ribbons were ground in a drum mill to grain sizes of up to 4 ⁇ m. Grain sizes below 4 ⁇ m were achieved with attritor grinding in an aqueous or non-aqueous medium.
  • Table 1 Table 1 :
  • compositions of glasses in% by weight based on oxide which have an antimicrobial effect, in particular when ground to glass powders:
  • glasses can be melted in large-scale industrial plants and include the following components, the details in% by weight being based on oxide:
  • compositions can optionally contain (if appropriate) trace elements and / or customary refining agents in customary amounts.
  • Trace elements are, for example, impurities contained in the glass, such as Fe 2 0 3 , K 2 O ; usual refining agents, for example Sb 2 O 3 , As 2 O 3 .
  • compositions according to the invention show an antimicrobial or biocidal action after grinding, for example to give a glass powder. This is surprising for the person skilled in the art, since glasses with a phosphorus content of less than 1% by weight based on oxide, for example soda-lime glasses, are unreactive as glass. A biocidal effect was only attributed to glasses containing phosphorus with a phosphorus content> 1% by weight, since these glasses are considered to be very reactive.
  • the glass powders according to the invention have a strong antimicrobial effect and are non-toxic to higher organisms.
  • the glass powders are therefore excellently suitable as an antimicrobial additive for a wide variety of applications, for example as a food additive, in cosmetic products, deoproducts, in medical products, plastics and polymers, paper hygiene, in paints, varnishes and plasters as well as in cleaning agents.

Abstract

The invention relates to a glass powder with anti-microbial effect, whereby the glass of said glass powder comprises the following components: 20-80 wt. % SiO2, 0-40 wt. % Na2O, 0-40 wt. % K2O, 0-40 wt. % Li2O, 0-40 wt. % CaO, 0-40 wt. % MgO, 0-40 wt. % AI2O3, 0-1 wt. % P2O5, 0-40 wt. % B2O3, 0-10 wt. % Fe2O3, 0-30 wt. % XFy, where X can be Li, Na, K, Be, Mg or Ca and y=1 or y=2, where the sum of NaO + K2O + Li2O + CaO + MgO = 15 to 80 wt. %.

Description

Antimikrobielles Glaspulver und dessen Verwendung Antimicrobial glass powder and its use
Die Erfindung betrifft ein antimikrobielles Glaspulver umfassend ein Glas mit einem Phophoranteil kleiner 1 Gew-% bezogen auf das Gesamtgewicht der Glaszusammensetzung bezogen auf Oxidbasis.The invention relates to an antimicrobial glass powder comprising a glass with a phosphorus content of less than 1% by weight based on the total weight of the glass composition based on oxide.
Antimikrobiell wirkende Gläser sind aus einer Vielzahl von Schriften bekanntgeworden.Glasses with an antimicrobial effect have become known from a large number of publications.
Bei den aus dem Stand der Technik bekannten Gläsern bzw. Glaspulvem beruht die antibakterielle Wirkung auf zugesetzten Schwermetallionen wie z.B. Cu, Zn oder Ag. Die antibakterielle Wirkung geht bei diesen Verbindungen nicht von Glas, sondern von den freigesetzten Metallionen aus.In the glasses or glass powders known from the prior art, the antibacterial effect is based on added heavy metal ions, such as Cu, Zn or Ag. The antibacterial effect of these compounds does not come from glass, but from the metal ions released.
So werden in der US 5,290,544 wasserlösliche Gläser für die Anwendungen in kosmetischen Produkten mit sehr geringen SiO2 und sehr hohen B2O3 bzw. hohen P2θ5-Gehalten beschrieben. Die Gläser weisen Silberkonzentrationen größer 0,5 Gew.-% auf. Diese Gläser besitzen eine extrem niedrige hydrolytische Beständigkeit und neigen dazu, sich in Wasser komplett aufzulösen. Die hierbei freiwerdenden Ag- und/oder Cu-Ionen wirken antibakteriell. Auch in der JP-A- 92178433 wird ein wasserlösliches Glaspulver mit Si02 < 37 Gew.% als Polymerzusatz mit hohen Silberkonzentrationen > 1 Gew.% beschrieben.For example, US Pat. No. 5,290,544 describes water-soluble glasses for use in cosmetic products with very low SiO 2 and very high B 2 O 3 or high P 2 θ 5 contents. The glasses have silver concentrations greater than 0.5% by weight. These glasses have an extremely low hydrolytic resistance and tend to completely dissolve in water. The released Ag and / or Cu ions have an antibacterial effect. JP-A-92178433 also describes a water-soluble glass powder with SiO 2 <37% by weight as a polymer additive with high silver concentrations> 1% by weight.
In der US 6,143,318 werden silberhaltige Phosphatgläser beschrieben, die als antimikrobielles Material für die Wundinfektionsbehandlung mit Kombinationen aus Cu, Ag und Zn verwendet werden. Hierbei handelt es sich ebenfalls um wasserlösliche Gläser, die niedrige SiO2-Konzentrationen und sehr hohe P2O5- Gehalte aufweisen.No. 6,143,318 describes silver-containing phosphate glasses which are used as an antimicrobial material for wound infection treatment with combinations of Cu, Ag and Zn. These are also water-soluble glasses that have low SiO 2 concentrations and very high P 2 O 5 contents.
Diese Gläser sind aufgrund ihrer niedrigen hydrolytischen Beständigkeit nur sehr beschränkt für eine Mahlung in wäßrigen Medien geeignet. Antimikrobielle silberhaltige Borosilikatgläser bzw. Borophosphatgläser werden in den Schriften JP 10218637, JP 08245240, JP 07291654,Due to their low hydrolytic stability, these glasses are only suitable for grinding in aqueous media to a very limited extent. Antimicrobial silver-containing borosilicate glasses or borophosphate glasses are described in JP 10218637, JP 08245240, JP 07291654,
JP 03146436, JP 2000264674, JP 2000203876 beschrieben. Diese Gläser weisen größtenteils eine gute hydrolytische Beständigkeit auf und können daher in wäßrigen Medien gemahlen werden.JP 03146436, JP 2000264674, JP 2000203876. Most of these glasses have good hydrolytic resistance and can therefore be ground in aqueous media.
Zeolithe, die Silber enthalten, das durch lonenaustausch eingebracht wird, finden ebenfalls als antibakterielles Mittel Verwendung. Dies wird beispielsweise in der US 6,245,732 und WO 0038552 beschrieben.Zeolites containing silver that is introduced by ion exchange are also used as an antibacterial agent. This is described for example in US 6,245,732 and WO 0038552.
Schwermetallfreie Gläser, bei denen eine antimikrobielle Wirkung nachgewiesen werden kann, sind in der DE 19932238, der DE 19932239 und der WO 01/03650 beschrieben.Heavy metal-free glasses, in which an antimicrobial effect can be demonstrated, are described in DE 19932238, DE 19932239 and WO 01/03650.
Bei den aus der DE 19932338, der DE 19932239 sowie der WO 01/03650 bekannten Gläsern handelt es sich um bioaktive Gläser mit einem signifikanten Phosphoranteil > 1 Gew.-%.The glasses known from DE 19932338, DE 19932239 and WO 01/03650 are bioactive glasses with a significant phosphorus content> 1% by weight.
Die wesentlichen Eigenschaften von bioaktivem Glas sind dem Fachmann bekannt und beispielsweise in der US-A 5,074,916 beschrieben. Danach unterscheidet sich bioaktives Glas von herkömmlichen Kalk-Natrium-Silicat- Gläsern dadurch, daß es lebendes Gewebe bindet.The essential properties of bioactive glass are known to the person skilled in the art and are described, for example, in US Pat. No. 5,074,916. According to this, bioactive glass differs from conventional lime-sodium-silicate glasses in that it binds living tissue.
Bioaktives Glas bezeichnet ein Glas, das eine feste Bindung mit Körpergewebe eingeht, wobei eine Hydroxyl-Apatitschicht ausgebildet wird.Bioactive glass refers to a glass that forms a firm bond with body tissue, forming a layer of hydroxyl apatite.
Nachteilg an diesen Gläsern ist der hohe Phosphoranteil, der beim Erschmelzen der Gläser zu Fertigungproblemen führt.The disadvantage of these glasses is the high phosphorus content, which leads to manufacturing problems when the glasses melt.
Ein weiterer Nachteil der im Stand der Technik beschriebenen Gläser ist, daß diese Substanzen unerwünschte Nebenwirkungen aufweisen und gesundheitlich nicht unbedenklich sind. Sie können alfergieauslösend, hautreizend oder in anderer Form belastend für den menschlichen Körper oder die Umwelt sein.Another disadvantage of the glasses described in the prior art is that these substances have undesirable side effects and are not harmless to health. They can trigger alfergia, irritating to the skin or be otherwise harmful to the human body or the environment.
Aufgabe der Erfindung ist es Glaspulver aus Glaszusammensetzungen anzugeben, die die Nachteile des Standes der Technik vermeiden, inbesondere ohne großen Aufwand darstellbar sind.The object of the invention is to provide glass powder from glass compositions which avoid the disadvantages of the prior art, in particular can be produced without great effort.
Unter einem Glaspulver wird ein Pulver umfassend eine Vielzahl von Glaspartikeln beliebiger Form, worunter auch eine Glasfaser fallen, verstanden, beispielsweise eine Glaskugel mit Partikelgröße < 1mm bevorzugt < 500μm oder eine Glasfaser mit einem Durchmesser von <1mm bevorzugt < 500μm.A glass powder is understood to mean a powder comprising a large number of glass particles of any shape, including a glass fiber, for example a glass ball with a particle size of <1 mm, preferably <500 μm, or a glass fiber with a diameter of <1 mm, preferably <500 μm.
Diese Aufgabe wird durch ein Glaspulver gemäß einem der Ansprüche 4 oder 5 gelöst, wobei das Glaspulver aus einer weitgehend phosphatfreien Zusammensetzung erhalten wird.This object is achieved by a glass powder according to one of claims 4 or 5, the glass powder being obtained from a largely phosphate-free composition.
Die Glaspulver können Produkten zugesetzt werden. Die Glaspulver werden durch Mahlung in unterschiedlichen Mahlmedien erhalten.The glass powder can be added to products. The glass powders are obtained by grinding in different grinding media.
Die Glaszusammensetzungen der Gläser können in großtechnischem Maßstab mit Standardverfahren hergestellt werden und sind zum Beispiel zur Mahlung in Wasser, geeignet, da die Glaszusammensetzungen eine hinreichende hydrolytische Beständigkeit aufweisen, im Gegensatz zum Beispiel zu stark phophathaltigen Gläsern.The glass compositions of the glasses can be produced on an industrial scale using standard processes and are suitable, for example, for grinding in water, since the glass compositions have sufficient hydrolytic resistance, in contrast to glasses which contain a lot of phosphate, for example.
Die erfindungsgemäßen Glaspulver zeigen gegenüber Bakterien, Pilzen sowie Viren eine biozide bzw. eine biostatische Wirkung; sie sind im Kontakt mit dem Menschen hautverträglich, toxikologisch unbedenklich und insbesondere auch zum Verzehr geeignet.The glass powders according to the invention have a biocidal or biostatic effect on bacteria, fungi and viruses; they are skin-friendly in contact with humans, toxicologically harmless and in particular also suitable for consumption.
Aufgrund der Anforderungen an die toxikologische Unbedenklichkeit des Glaspulvers sowie deren Eignung zum Verzehr ist die Glaszusammensetzung des erfindungsgemäßen Glaspulvers besonders rein. Die Belastung durch Schwermetalle ist gering. So beträgt die Maximaikonzentration im Bereich kosmetischer Produkte vorzugsweise für Pb < 20 ppm, Cd < 5 ppm, As < 5 ppm, Sb < 10 ppm, Hg < 1 ppm, Ni < 10 ppm.Due to the requirements for the toxicological harmlessness of the glass powder and its suitability for consumption, the glass composition of the Glass powder according to the invention particularly pure. The exposure to heavy metals is low. The maximum concentration in the range of cosmetic products is preferably for Pb <20 ppm, Cd <5 ppm, As <5 ppm, Sb <10 ppm, Hg <1 ppm, Ni <10 ppm.
Mit den antimikrobiellen Substanzen kann eine Konservierung von Produkten selbst erzielt oder eine antimikrobielle Wirkung nach außen erreicht werden.With the antimicrobial substances, products can be preserved themselves or an antimicrobial effect can be achieved externally.
Anwendungsbereiche hierfür sind zum Beispiel kosmetische Produkte, Deoprodukte, Lebensmittel, Farben, Lacke, Putze, Papierhygieneprodukte, Medizinprodukte und Reiniger.Areas of application for this are, for example, cosmetic products, demo products, food, paints, varnishes, plasters, paper hygiene products, medical products and cleaners.
Im kosmetischen Bereich spielen Hautirritationen eine wesentliche Rolle. Daher ist es vorteilhaft, wenn der antimikrobielle Glaszusatz besonders hautfreundlich ist.Skin irritation plays an important role in the cosmetic field. It is therefore advantageous if the antimicrobial glass additive is particularly skin-friendly.
Ein besonderer Vorteil der Glaszusammensetzung des erfindungsgemäßen Glaspulvers ist, daß das Glas aufgrund des Schmelz- und Heißformgebungsverhaitens geeignet ist, um in entsprechenden großtechnischen Anlagen hergestellt werden zu können.A particular advantage of the glass composition of the glass powder according to the invention is that the glass, owing to the melting and hot-forming process, is suitable for being able to be produced in corresponding large-scale plants.
Da die Prozeßtemperaturen bzw. die Viskosität des Glases niedrig ist, können kostengünstige Werkstoffe bei Schmelze und Heißformgebung eingesetzt werden.Since the process temperatures and the viscosity of the glass are low, inexpensive materials can be used for melting and hot forming.
Neben der Herstellung über ein Schmelzverfahren sind auch alternative Hersteilungsverfahren über die Sol-Gel- oder Reaktionssinter-Route denkbar.In addition to production using a melting process, alternative production processes using the sol-gel or reaction sinter route are also conceivable.
Überraschenderweise ergibt sich bei den Glaspulvern mit Glaszusammensetzung gemäß der Erfindung eine antimikrobielle Wirkung, die extrem stark ist. Je geringer die mittlere Partikelgröße des Glaspulvers, desto höher die antimikrobille Wirkung wegen der Erhöhung der reaktiven Oberfläche des Glases. Die antimikrobiellen Eigenschaften werden auch bei Glaszusammensetzungen gefunden, die als Halbzeug eine relativ hohe hydrolytische Beständigkeit besitzen. Bei den erfindungsgemäßen Glaspulvern werden durch Reaktionen an der Oberfläche des Glases des Glaspulvers Alkalien des Glases durch H+-lonen des wäßrigen Mediums ausgetauscht. Die antimikrobielle Wirkung des lonenaustausches beruht unter anderem auf einer Erhöhung des pH-Wertes und dem osmotischen Effekt auf Mikroorganismen.Surprisingly, the glass powders with a glass composition according to the invention have an antimicrobial effect which is extremely strong. The smaller the average particle size of the glass powder, the higher the antimicrobial effect due to the increase in the reactive surface of the glass. The antimicrobial properties are also found in glass compositions which have a relatively high hydrolytic resistance as a semi-finished product. In the glass powders according to the invention, alkalis of the glass are replaced by H + ions of the aqueous medium by reactions on the surface of the glass of the glass powder. The antimicrobial effect of the ion exchange is based, among other things, on an increase in the pH value and the osmotic effect on microorganisms.
Glaspulver umfassend ionenaustauschbare Gläser gemäß der Erfindung wirken in wäßrigen Medien antimikrobiell durch pH-Wert-Erhöhung durch lonenaustausch zwischen einem Metallion, wie beispielsweise einem Alkali- oder Erdalkalimetallion und den H+-lonen der wäßrigen Lösung sowie durch ionenbedingte Beeinträchtigung des Zellwachstums (osmotischer Druck, Störung von Stoffwechselvorgängen der Zellen). Gemahlene Glaspulver mit Teilchen geringer Partikelgröße und großer Oberfläche zeigen eine drastische Reaktivitätserhöhung, woraus, durch den schon beschriebenen lonenaustausch, eine starke antimikrobielle Wirkung resultiert. Die antmikrobieile Wirkung wird bei den erfindungsgemäßen Glaspulvern durch den lonenaustausch erzielt und nicht durch die antimikrobille Wirkung der Schwermetallionen. Diese können aber als Zusatz die antimikrobielle Wirkung verstärken.Glass powder comprising ion-exchangeable glasses according to the invention have an antimicrobial effect in aqueous media by increasing the pH value by ion exchange between a metal ion, such as an alkali metal or alkaline earth metal ion and the H + ions of the aqueous solution, and by ion-induced impairment of cell growth (osmotic pressure, Disruption of metabolic processes in the cells). Ground glass powder with particles of small particle size and large surface area show a drastic increase in reactivity, which, due to the ion exchange already described, results in a strong antimicrobial effect. The antimicrobial effect in the glass powders according to the invention is achieved by the ion exchange and not by the antimicrobial effect of the heavy metal ions. However, these can increase the antimicrobial effect as an additive.
Durch einen Mahlprozeß können Partikelgrößen < 100 μm erhalten werden. Als zweckmäßig haben sich Partikelgrößen < 50 μm bzw. 20 μm erwiesen. Besonders geeignet sind Partikelgrößen < 10 μm sowie kleiner 5 μm. Als ganz besonders geeignet haben sich Partikelgrößen < 1 μm herausgestellt.Particle sizes of <100 μm can be obtained by a grinding process. Particle sizes of <50 μm or 20 μm have proven to be expedient. Particle sizes <10 μm and smaller than 5 μm are particularly suitable. Particle sizes <1 μm have been found to be particularly suitable.
Der Mahlprozeß kann sowohl trocken als auch mit wäßrigen und nichtwäßrigen Mahlmedien durchgeführt werden.The grinding process can be carried out dry as well as with aqueous and non-aqueous grinding media.
Mischungen verschiedener Glaspulver aus dem Zusammensetzungsbereich mit unterschiedlichen Zusammensetzungen und Korngrößen sind möglich, um bestimmte Effekte zu kombinieren. Je nach Partikelgröße, Konzentration und der Zusammensetzung des Pulvers werden pH-Werte von bis zu 13 erreicht.Mixtures of different glass powders from the composition range with different compositions and grain sizes are possible to combine certain effects. Depending on the particle size, concentration and the composition of the powder, pH values of up to 13 are achieved.
Das Glas des Glaspulvers enthält SiO2 als Netzwerkbildner, bevorzugt zwischen 35 bis 80 Gew.-%. Bei niedrigen Konzentrationen nimmt die hydrolytische Beständigkeit stark ab, so daß das Mahlen in wäßrigen Medien nicht mehr ohne signifikante Auflösung des Glases gewährleistet ist.The glass of the glass powder contains SiO 2 as a network former, preferably between 35 to 80% by weight. At low concentrations, the hydrolytic resistance decreases significantly, so that grinding in aqueous media is no longer guaranteed without significant dissolution of the glass.
Na2O wird als Flußmittel beim Schmelzen des Glases eingesetzt. Bei Konzentrationen kleiner 5 % wird das Schmelzverhalten negativ beeinflußt. Außerdem wirkt der notwendige Mechanismus des lonenaustausches nicht mehr hinreichend, um eine antimikrobielle Wirkung zu erzielen. Bei höheren Na2O- Konzentrationen als 30 Gew.-% ist eine Verschlechterung der chemischen Resistenz bzw. hydrolytischen Beständigkeit, insbesondere in Verbindung einer Abnahme des SiO2-Anteils, zu beobachten.Na 2 O is used as a flux when melting the glass. At concentrations less than 5%, the melting behavior is negatively affected. In addition, the necessary mechanism of ion exchange no longer works sufficiently to achieve an antimicrobial effect. At Na 2 O concentrations higher than 30% by weight, a deterioration in the chemical resistance or hydrolytic resistance can be observed, especially in connection with a decrease in the SiO 2 content.
Alkali- und Erdalkalioxide können insbesondere hinzugesetzt werden, um den lonenaustausch zu erhöhen und so die antimikrobille Wirkung zu verstärken. Die Menge an AI2O3 kann zur Erhöhung der chemischen Beständigkeit der Kristallisationsstabilität sowie der Steuerung der antimikrobiellen Wirkung bis zu maximal 8 Gew.-% hinzugegeben werden.Alkali and alkaline earth oxides can in particular be added to increase the ion exchange and thus to increase the antimicrobial effect. The amount of Al 2 O 3 can be added up to a maximum of 8% by weight to increase the chemical stability of the crystallization stability and to control the antimicrobial effect.
B2O3 wirkt als Netzwerkbildner und kann auch der Steuerung der antimikrobiellen Wirkung dienen.B 2 O 3 acts as a network builder and can also be used to control the antimicrobial effect.
ZnO ist eine wesentliche Komponente für die Heißformgebungseigen-schaften des Glases. Es verbessert die Kristallisationsstabilität und erhöht die Oberflächenspannung. Außerdem kann es den antimikrobiellen Effekt unterstützen. Bei geringen SiO2-Gehalten erhöht es die Kristallisationsstabilität. Zur Erzielung einer antimikrobiellen Wirkung können bis zu 8 Gew.-% ZnO enthalten sein. Eine bevorzugte Ausführung enthält < 4 Gew.-% ZnO oder < 2 Gew.-%. Ausführungen mit < 1 Gew.-% oder 0,5 Gew.-% bzw. < 0,1 Gew.-% sind besonders bevorzugt.ZnO is an essential component for the hot-forming properties of the glass. It improves crystallization stability and increases surface tension. It can also support the antimicrobial effect. With low SiO 2 contents, it increases the crystallization stability. To achieve an antimicrobial effect, up to 8% by weight of ZnO can be present. A preferred embodiment contains <4% by weight ZnO or <2 Wt .-%. Designs with <1% by weight or 0.5% by weight or <0.1% by weight are particularly preferred.
AgO, CuO können als antimikrobiell wirkende Zusätze, die synergistisch die intrinsische antimikrobielle Wirkung des Grundglases verstärken, zugegeben werden.AgO, CuO can be added as antimicrobial additives that synergistically enhance the intrinsic antimicrobial effect of the base glass.
Das erfindungsgemäße Glaspulver ruft keine hautirritierenden Wirkungen hervor. Teilweise sind hingegen sogar entzündungshemmende Wirkungen zu beobachten.The glass powder according to the invention has no skin-irritating effects. In some cases, however, anti-inflammatory effects can even be observed.
Durch eine Kombination der pH-Wirkung und der Ag, Cu oder Zn-Abgabe kann eine erheblichen Steigerung der antimikrobiellen Wirkung erzielt werden, die über die Summe der Einzelwirkungen deutlich hinausgeht. Die in das Produkt freigesetzte Konzentration von Ag, Cu, Zn-Ionen kann hierbei deutlich unter 1 ppm liegen.A combination of the pH effect and the Ag, Cu or Zn release can achieve a significant increase in the antimicrobial effect, which goes well beyond the sum of the individual effects. The concentration of Ag, Cu, Zn ions released into the product can be well below 1 ppm.
Die Einbringung des Ag, Cu, Zn kann hierbei entweder bereits bei der Schmelze durch entsprechende Salze erfolgen oder aber durch lonenaustausch des Glases nach der Schmelze.The Ag, Cu, Zn can either be introduced during the melt by appropriate salts or else by ion exchange of the glass after the melt.
Zur Erzielung von Farbwirkungen können den Gläsern einzelne oder auch mehrere farbgebende Komponenten wie z.B. Fe2O3, CoO, CuO, V2O5, Cr2θ5 in einer Gesamtkonzentration kleiner 4 Gew.-%, vorzugsweise kleiner 1 Gew.-% zugesetzt werden.To achieve color effects, the glasses can be given individual or even several coloring components such as Fe 2 O 3 , CoO, CuO, V 2 O 5 , Cr 2 θ 5 in a total concentration of less than 4% by weight, preferably less than 1% by weight be added.
Die innerhalb des beanspruchten Zusammensetzungsbereiches liegenden Gläser erfüllen alle Anforderungen bezüglich eines Einsatzes in den Bereichen Papierhygiene, Kosmetik, Farben, Lacken, Putzen, Medizinprodukten, kosmetischen Anwendungen, Nahrungsmittelzusatz sowie Verwendung in Deo Produkten. Wesentliche Eigenschaft des Glaspulvers ist die überraschenderweise nachgewiesene Hautverträglichkeit, die auch bei hohen Konzentrationen mit hohen pH-Werten gegeben ist.The glasses within the claimed composition range meet all requirements regarding use in the areas of paper hygiene, cosmetics, paints, varnishes, cleaning, medical products, cosmetic applications, food additives and use in deodorant products. An essential property of the glass powder is the surprisingly proven skin tolerance, which is also given at high concentrations with high pH values.
Das Glaspulver kann in jeder geeigneten Form eingesetzt werden. Mischungen unterschiedlicher Glaspulver aus dem Zusammensetzungsbereich mit unterschiedlichen Zusammensetzungen sind ebenfalls möglich. Die Mischung mit anderen Glaspulvern ist ebenfalls möglich, um bestimmte Effekte zu kombinieren.The glass powder can be used in any suitable form. Mixtures of different glass powders from the composition range with different compositions are also possible. Mixing with other glass powders is also possible to combine certain effects.
Komponenten wie Fluor können je nach Anwendungsgebiet dem Glas bis zu Konzentrationen von in Summe 5 Gew.-% zugesetzt werden.Depending on the field of application, components such as fluorine can be added to the glass up to a total concentration of 5% by weight.
Das in dieser Erfindung beschriebene Glaspulver ist nicht wasserlöslich, sondern wirkt in erster Linie durch lonenaustausch bzw. lonenabgabe, was mit einer Oberflächenreaktion, pH-Erhöhung und Metallionen-Freisetzung verbunden ist. Durch die synergistische antimikrobielle Wirkung des Glaspulvers selbst sowie die antimikrobielle Wirkung der Metallionen sind die benötigten Mengen an Metallionen geringer, um eine entsprechende Wirkung zu erzielen.The glass powder described in this invention is not water-soluble, but acts primarily by ion exchange or ion release, which is associated with a surface reaction, pH increase and metal ion release. Due to the synergistic antimicrobial effect of the glass powder itself and the antimicrobial effect of the metal ions, the amounts of metal ions required are lower in order to achieve a corresponding effect.
Die Erfindung soll nachfolgend anhand der Ausführungsbeispiele beschrieben werden.The invention will be described below using the exemplary embodiments.
AusführungsbeispieieAusführungsbeispieie
Aus den Rohstoffen wurde das Glas in einem Platintiegel bei 1600° C erschmozlen und zu Halbzeug oder Ribbons verarbeitet. Die Ribbons wurden in einer Trommelmühle auf Korngrößen von bis zu 4 μm gemahlen. Korngrößen unter 4 μm wurden mit Attritormahlungen in wäßrigem oder nicht wäßrigem Medium erreicht. Tabelle 1 :The glass was smelted from the raw materials in a platinum crucible at 1600 ° C and processed into semi-finished products or ribbons. The ribbons were ground in a drum mill to grain sizes of up to 4 μm. Grain sizes below 4 μm were achieved with attritor grinding in an aqueous or non-aqueous medium. Table 1 :
Zusammensetzungen von Gläser in Gew-% bezogen auf Oxidbasis, die insbesondere zu Glaspulvern gemahlen eine antimikrobielle Wirkung aufweisen:Compositions of glasses in% by weight based on oxide, which have an antimicrobial effect, in particular when ground to glass powders:
Figure imgf000010_0001
Figure imgf000010_0001
Besonders einfach herzustellen, großtechnisch verfügbar, da in großtechnischen Anlagen erschmelzbar sind Gläser die nachfolgende Komponenten umfassen, wobei die Angabe in Gew-% auf Oxidbasis bezogen sind:Particularly easy to manufacture, available on an industrial scale, since glasses can be melted in large-scale industrial plants and include the following components, the details in% by weight being based on oxide:
SiO2 : 68-75 Gew-%; Na2O:10-20 Gew-%; AI2O3: 0-3 Gew-%, CaO: 5-15 Gew-%; MgO 0-10 Gew-%. Diese Zusammensetzungen können gegebenenfalls (ggf.) Spurenelemente und/oder übliche Läutermittel in üblichen Mengen enthalten. Spurenelemente sind beispilesweise im Glas enthaltene Verunreinigungen wie Fe203 , K2O; übliche Läutermittel beispielsweise Sb2O3 , As2O3.SiO 2 : 68-75% by weight; Na 2 O: 10-20% by weight; Al2O3: 0-3% by weight, CaO: 5-15% by weight; MgO 0-10% by weight. These compositions can optionally contain (if appropriate) trace elements and / or customary refining agents in customary amounts. Trace elements are, for example, impurities contained in the glass, such as Fe 2 0 3 , K 2 O ; usual refining agents, for example Sb 2 O 3 , As 2 O 3 .
Zusammensetzungen gemäß der Erfindung, insbesondere die oben angegebenen zeigen nach dem Aufmahlen beispielsweise zu einem Glaspulver eine antmikrobielle bzw. biozide Wirkung. Dies ist für den Fachmann überraschend, da Gläser mit einem Phosphoranteil kleiner 1 Gew-% bezogen auf Oxidbasis, beispielsweise Kalk-Natron-Gläser als Glas inreaktiv sind. Eine biozide Wirkung wurde lediglich phosphorhaltigen Gläsern mit einem Phosphoranteil > 1 Gew-% zugeschrieben, da diese Gläser als sehr reaktiv gelten.Compositions according to the invention, in particular those given above, show an antimicrobial or biocidal action after grinding, for example to give a glass powder. This is surprising for the person skilled in the art, since glasses with a phosphorus content of less than 1% by weight based on oxide, for example soda-lime glasses, are unreactive as glass. A biocidal effect was only attributed to glasses containing phosphorus with a phosphorus content> 1% by weight, since these glasses are considered to be very reactive.
Für das Ausführungsbeispiel 1 ergab sich die in Tabelle 2 niedergelegte antimikrobielle Wirkung eines Pulvers mit einer mittleren Korngröße von 4 μm nach Europ. Pharmakopoe (3. Auflage).For example 1, the antimicrobial effect of a powder with an average grain size of 4 μm according to Europ was shown in Table 2. Pharmacopoeia (3rd edition).
Tabelle 2:Table 2:
Figure imgf000011_0001
Wie aus den Tabelle 1 und 2 hervorgeht, besitzen die erfindungsgemäßen Glaspulver eine stark antimikrobielle Wirkung bei Ungiftigkeit für höhere Organismen.
Figure imgf000011_0001
As can be seen from Tables 1 and 2, the glass powders according to the invention have a strong antimicrobial effect and are non-toxic to higher organisms.
Damit sind die Glaspulver hervorragend geeignet als antimikrobieller Zusatz für , unterschiedlichste Anwendungen, beispielsweise als Nahrungsmittelzusatz, in kosmetischen Produkten, Deoprodukten, in Medizinprodukten, Kunststoffen und Polymeren, Papierhygiene, in Farben, Lacken sowie Putzen sowie in Reinigungsmitteln. The glass powders are therefore excellently suitable as an antimicrobial additive for a wide variety of applications, for example as a food additive, in cosmetic products, deoproducts, in medical products, plastics and polymers, paper hygiene, in paints, varnishes and plasters as well as in cleaning agents.

Claims

Patentansprüche claims
1. Antimikrobiell wirkendes Glaspulver, wobei das Glas des Glaspulvers die nachfolgenden Komponenten umfasst:1. Antimicrobial glass powder, the glass of the glass powder comprising the following components:
20 - 80 Gew.-% Si02 20-80% by weight Si0 2
0 - 40 Gew.-% Na200 - 40% by weight Na 2 0
0 - 40 Gew.-% K2O0 - 40 wt% K 2 O
0 - 40 Gew.-% Li200 - 40% by weight of Li 2 0
0 - 40 Gew.-% CaO0 - 40 wt% CaO
0 - 40 Gew.-% MgO0 - 40 wt% MgO
0 - 40 Gew.-% Al203
Figure imgf000013_0001
0 - 40% by weight Al 2 0 3
Figure imgf000013_0001
0 - 40 Gew.-% B203 0 - 40% by weight B 2 0 3
0 - 10 Gew-% Fe203 0 - 10 wt% Fe 2 0 3
0 - 30 Gew.-% XFy, wobei X Li, Na, K, Be, Mg, Ca sein kann und y=1 oder y=2 und gegebenenfalls Spurenelemente und/oder übliche Läutermittel in üblichen Mengen, wobei die Summe Na20 + K20 + Li20 + CaO + MgO 15 bis 80 Gew.% beträgt.0 - 30% by weight XF y , where X can be Li, Na, K, Be, Mg, Ca and y = 1 or y = 2 and optionally trace elements and / or customary refining agents in customary amounts, the sum being Na 2 0 + K 2 0 + Li 2 0 + CaO + MgO is 15 to 80% by weight.
2. Antimikrobiell wirkendes Glaspulver nach Anspruch 1 , wobei die Summe Na20+K20+Li2O 5 bis 50 Gew% beträgt.2. Antimicrobial glass powder according to claim 1, wherein the sum Na 2 0 + K 2 0 + Li 2 O is 5 to 50% by weight.
3. Antimikrobiell wirkendes Glaspulver nach Anspruch 1 , wobei die Summe CaO+MgO 5 bis 50 Gew.% beträgt.3. Antimicrobial glass powder according to claim 1, wherein the total CaO + MgO is 5 to 50 wt.%.
4. Antimikrobiell wirkendes Glaspulver, wobei das Glas des Glaspulvers die nachfolgenden Komponenten umfasst:4. Antimicrobial glass powder, the glass of the glass powder comprising the following components:
68 - 75 Gew.-% Si02 10 - 20 Gew.-% Na20 5 - 15 Gew.-% CaO 0 - 10 Gew.-% MgO68-75% by weight Si0 2 10-20% by weight Na 2 0 5-15% by weight CaO 0-10 wt% MgO
0 - 3 Gew.-% Al203 und gegebenenfalls Spurenelemente und/oder übliche Läutermittel in üblichen Mengen.0-3% by weight of Al 2 0 3 and optionally trace elements and / or customary refining agents in customary amounts.
5. Antimikrobiell wirkendes Glaspulver, wobei das Glas des Glaspulvers die nachfolgenden Komponenten umfasst:5. Antimicrobial glass powder, the glass of the glass powder comprising the following components:
20 - 80 Gew.-% Si02 20-80% by weight Si0 2
0 - 30 Gew.-% Na200-30% by weight Na 2 0
0 - 30 Gew.-% K2O0-30% by weight K 2 O
0 - 30 Gew.-% CaO0-30% by weight CaO
0 - 30 Gew.-% MgO
Figure imgf000014_0001
0-30% by weight of MgO
Figure imgf000014_0001
0 - 1 Gew.-% P2O5 0-1% by weight of P 2 O 5
0 - 40 Gew.-% B203 0 - 40% by weight B 2 0 3
0 - 10 Gew-% Fe203 und gegegbenenfalls Spurenelemente und/oder übliche Läutermittel in üblichen Mengen.0 - 10% by weight Fe 2 0 3 and, if appropriate, trace elements and / or customary refining agents in customary amounts.
6. Antimikrobiell wirkendes Glaspulver nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das Glas des weiteren Schwermetallionen, ausgewählt aus der Klasse der nachfolgenden Elemente:6. Antimicrobial glass powder according to one of claims 1 to 5, characterized in that the glass further heavy metal ions, selected from the class of the following elements:
Ag, Cu, Zn umfaßt.Ag, Cu, Zn.
7. Antimikrobiell wirkendes Glaspulver nach einem der Ansprüche 1 bis 6 , dadurch gekennzeichnet, daß die Größe der Glaspartikel im Mittel < 20 μm ist.7. Antimicrobial glass powder according to one of claims 1 to 6, characterized in that the size of the glass particles is on average <20 microns.
8. Antimikrobiell wirkendes Glaspulver nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Größe der Partikel des Glaspulvers im Mittel < 10 μm ist. 8. Antimicrobial glass powder according to one of claims 1 to 6, characterized in that the size of the particles of the glass powder is on average <10 microns.
9. Antimikrobiell wirkendes Glaspulver nach einem der Ansprüche 1 bis 6 , dadurch gekennzeichnet, daß die Größe der Glaspartikel < 5 μm ist.9. Antimicrobial glass powder according to one of claims 1 to 6, characterized in that the size of the glass particles is <5 microns.
10. Antimikrobiell wirkendes Glaspulver nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Größe der Glaspartikel des Glaspulvers im Mittel < 1 μm ist.10. Antimicrobial glass powder according to one of claims 1 to 6, characterized in that the size of the glass particles of the glass powder is on average <1 micron.
11. Antimikrobiell wirkendes Glaspulver nach einem der Ansprüche 1 bis 10 zur Verwendung in Kosmetikprodukten.11. Antimicrobial glass powder according to one of claims 1 to 10 for use in cosmetic products.
12. Antimikrobiell wirkendes Glaspulver nach einem der Ansprüche 1 bis 10 zur Verwendung in Deodorantprodukten.12. Antimicrobial glass powder according to one of claims 1 to 10 for use in deodorant products.
13. Antimikrobiell wirkendes Glaspulver nach einem der Ansprüche 1 bis 10 zur Verwendung in medizinischen Produkten und Präparaten.13. Antimicrobial glass powder according to one of claims 1 to 10 for use in medical products and preparations.
14. Antimikrobiell wirkendes Glaspulver nach einem der Ansprüche 1 bis 10 zur Verwendung in Kunststoffen und Polymeren.14. Antimicrobial glass powder according to one of claims 1 to 10 for use in plastics and polymers.
15. Antimikrobiell wirkendes Glaspulver nach einem der Ansprüche 1 bis 10 zur Verwendung im Bereich der Papierhygiene.15. Antimicrobial glass powder according to one of claims 1 to 10 for use in the field of paper hygiene.
16. Antimikrobiell wirkendes Glaspulver nach einem der Ansprüche 1 bis 10 zur Verwendung in Nahrungsmitteln.16. Antimicrobial glass powder according to one of claims 1 to 10 for use in food.
17. Antimikrobiell wirkendes Glaspulver nach einem der Ansprüche 1 bis 10 zur Verwendung in Reinigungsmitteln. 17. Antimicrobial glass powder according to one of claims 1 to 10 for use in cleaning agents.
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CN113321956A (en) * 2021-05-08 2021-08-31 河北三棵树涂料有限公司 Inorganic interior wall coating with aldehyde-removing, antibacterial and antiviral functions and preparation method thereof
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WO2004076369A2 (en) * 2003-02-25 2004-09-10 Schott Ag Antimicrobial active borosilicate glass
CN100387644C (en) * 2003-11-12 2008-05-14 上海兴雅玻璃材料有限公司 Antibiotic resin product and its producing method
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
EP2189426A1 (en) 2004-05-29 2010-05-26 Schott AG Process for preparing a nanoscale glass or glass-ceramic powder
US7905115B2 (en) 2005-01-08 2011-03-15 Schott Ag Glass powder, especially biologically active glass powder, and method for producing glass powder, especially biologically active glass powder
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DE102005001078A1 (en) * 2005-01-08 2006-07-20 Schott Ag Glass powder, in particular biologically active glass powder and process for the production of glass powder, in particular biologically active glass powder
WO2006072394A1 (en) * 2005-01-08 2006-07-13 Schott Ag Glass powder, especially biologically active glass powder, and method for producing glass powder, especially biologically active glass powder
US9446983B2 (en) 2009-08-03 2016-09-20 Ppg Industries Ohio, Inc. Glass compositions and fibers made therefrom
US9556059B2 (en) 2009-08-03 2017-01-31 Hong Li Glass compositions and fibers made therefrom
US9593038B2 (en) 2009-08-03 2017-03-14 Ppg Industries Ohio, Inc. Glass compositions and fibers made therefrom
US9862638B2 (en) 2009-08-03 2018-01-09 Ppg Industries Ohio, Inc. Methods to make glass compositions and fibers made therefrom
US10377663B2 (en) 2009-08-03 2019-08-13 Ppg Industries Ohio, Inc. Methods to make glass compositions and fibers made therefrom
US10487007B2 (en) 2009-08-03 2019-11-26 Ppg Industries Ohio, Inc. Glass compositions and fibers made therefrom
CN115135615A (en) * 2019-12-17 2022-09-30 Lg电子株式会社 Antibacterial glass composition and method for producing same
CN115135615B (en) * 2019-12-17 2023-11-17 Lg电子株式会社 Antibacterial glass composition and manufacturing method thereof
CN113321956A (en) * 2021-05-08 2021-08-31 河北三棵树涂料有限公司 Inorganic interior wall coating with aldehyde-removing, antibacterial and antiviral functions and preparation method thereof

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