WO2003018499A2 - Poudre de verre antimicrobienne et utilisation - Google Patents
Poudre de verre antimicrobienne et utilisation Download PDFInfo
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- 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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- glass powder
- antimicrobial
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- 239000011521 glass Substances 0.000 title claims abstract description 118
- 230000000845 anti-microbial effect Effects 0.000 title claims abstract description 53
- 239000000843 powder Substances 0.000 claims abstract description 61
- 239000002245 particle Substances 0.000 claims description 14
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 9
- 239000002537 cosmetic Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- 239000011573 trace mineral Substances 0.000 claims description 5
- 235000013619 trace mineral Nutrition 0.000 claims description 5
- 229910001385 heavy metal Inorganic materials 0.000 claims description 4
- 229940127554 medical product Drugs 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000012459 cleaning agent Substances 0.000 claims description 2
- 239000002781 deodorant agent Substances 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 229910018068 Li 2 O Inorganic materials 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 20
- 238000000227 grinding Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000005342 ion exchange Methods 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000003301 hydrolyzing effect Effects 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 239000012736 aqueous medium Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000004599 antimicrobial Substances 0.000 description 4
- 239000005313 bioactive glass Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000002778 food additive Substances 0.000 description 2
- 235000013373 food additive Nutrition 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000003204 osmotic effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 206010048038 Wound infection Diseases 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000002599 biostatic effect Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000006103 coloring component Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000005337 ground glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- -1 plasters Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000005384 silver containing phosphate glass Substances 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 229940032158 sodium silicate Drugs 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Wood Science & Technology (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Plant Pathology (AREA)
- Glass Compositions (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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DE10293768T DE10293768B4 (de) | 2001-08-22 | 2002-08-17 | Antimikrobielles Glaspulver, dessen Verwendung und Verfahren zu dessen Herstellung |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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DE10141116.2 | 2001-08-22 | ||
DE10141116 | 2001-08-22 | ||
DE10213630A DE10213630A1 (de) | 2001-08-22 | 2002-03-27 | Antimikrobielles Glas und dessen Verwendung |
DE10213630.0 | 2002-03-27 |
Publications (2)
Publication Number | Publication Date |
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WO2003018499A2 true WO2003018499A2 (fr) | 2003-03-06 |
WO2003018499A3 WO2003018499A3 (fr) | 2003-04-17 |
Family
ID=26009979
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2002/009216 WO2003018499A2 (fr) | 2001-08-22 | 2002-08-17 | Poudre de verre antimicrobienne et utilisation |
Country Status (2)
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DE (1) | DE10293768B4 (fr) |
WO (1) | WO2003018499A2 (fr) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2004076369A3 (fr) * | 2003-02-25 | 2005-03-31 | Schott Ag | Verre de borosilicate a action antimicrobienne |
WO2006072394A1 (fr) * | 2005-01-08 | 2006-07-13 | Schott Ag | Verre pulverise, en particulier verre pulverise biologiquement actif et procede pour produire du verre pulverise, en particulier du verre pulverise biologiquement actif |
CN100387644C (zh) * | 2003-11-12 | 2008-05-14 | 上海兴雅玻璃材料有限公司 | 抗菌树脂产品及其制造方法 |
EP2189426A1 (fr) | 2004-05-29 | 2010-05-26 | Schott AG | Procédé pour préparer de nanopoudre de verre |
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 |
CN113321956A (zh) * | 2021-05-08 | 2021-08-31 | 河北三棵树涂料有限公司 | 一种具有除醛抗菌抗病毒功能的无机内墙涂料及制备方法 |
CN115135615A (zh) * | 2019-12-17 | 2022-09-30 | Lg电子株式会社 | 抗菌玻璃组合物及其制造方法 |
WO2025103555A1 (fr) * | 2023-11-17 | 2025-05-22 | TROVOcare GmbH & Co. KG | Poudres de verre à taux de libération d'ions métalliques accrus de différentes combinaisons d'ions métalliques pour une réduction plus rapide de micro-organismes et/ou de virus et pour supporter une régénération cellulaire et/ou prolifération cellulaire, et procédé de production de telles poudres de verre |
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CN111604483A (zh) * | 2020-04-23 | 2020-09-01 | 华北理工大学 | 中碳低合金钢用超高拉速薄板坯连铸保护渣 |
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JPH0714825B2 (ja) * | 1989-11-01 | 1995-02-22 | ユー・エイチ・アイ システムズ株式会社 | 抗菌・殺菌用ガラス |
US5074916A (en) * | 1990-05-18 | 1991-12-24 | Geltech, Inc. | Alkali-free bioactive sol-gel compositions |
JP2827051B2 (ja) * | 1990-11-13 | 1998-11-18 | 石塚硝子 株式会社 | 抗菌抗黴性を有する樹脂フイルム |
JP3057773B2 (ja) * | 1991-02-05 | 2000-07-04 | 不二製油株式会社 | パイの製造方法 |
JP3486919B2 (ja) * | 1993-07-09 | 2004-01-13 | 日本板硝子株式会社 | 抗菌性を有するフレーク状ガラス |
JPH07291654A (ja) * | 1994-04-22 | 1995-11-07 | Nippon Sheet Glass Co Ltd | 抗菌性ガラス粉末 |
DE19503167A1 (de) * | 1995-02-01 | 1996-08-08 | Gruenzweig & Hartmann | Glasfaserzusammensetzungen |
FI101129B (sv) * | 1995-01-13 | 1998-04-30 | Vivoxid Oy | Nya bioaktiva glas och deras användning |
GB9502253D0 (en) * | 1995-02-06 | 1995-03-29 | Giltech Ltd | The effects of antibacterial agents on the behaviour of mouse fibroblasts in vitro |
JPH08245240A (ja) * | 1995-03-06 | 1996-09-24 | Koa Glass Kk | 抗菌性複合ガラス粒子 |
JP3378014B2 (ja) * | 1996-03-22 | 2003-02-17 | ザ、プロクター、エンド、ギャンブル、カンパニー | 放出抑制剤を装填したゼオライトを含む配送系およびその製造方法 |
JPH10218637A (ja) * | 1997-01-31 | 1998-08-18 | Nippon Glass Fiber Co Ltd | 抗菌・抗かび性ガラス及びそのガラスを含有する樹脂組成物 |
ES2142249B1 (es) * | 1997-12-02 | 2001-04-01 | Esmaltes S A | Esmalte ceramico bactericida y sus aplicaciones. |
JP3845852B2 (ja) * | 1998-02-18 | 2006-11-15 | 日本電気硝子株式会社 | 抗菌性ガラス及び樹脂組成物 |
JPH11236241A (ja) * | 1998-02-25 | 1999-08-31 | Ishizuka Glass Co Ltd | 抗菌性を有する建材用結晶化ガラスビーズ |
JP2000203876A (ja) * | 1998-12-28 | 2000-07-25 | Nippon Sheet Glass Co Ltd | 抗菌性ガラス及びそのガラスを含有する樹脂組成物 |
WO2000038552A1 (fr) * | 1998-12-31 | 2000-07-06 | Healthshield Technologies Llc | Boitier antimicrobien pour lentille de contact |
JP2000264674A (ja) * | 1999-03-12 | 2000-09-26 | Nippon Sheet Glass Co Ltd | 抗菌性ガラス及び樹脂組成物 |
ES2245644T3 (es) * | 1999-06-14 | 2006-01-16 | Imperial College Innovations | Composiciones de biovidrio derivadas de sol-gel que contienen plata. |
CA2374395A1 (fr) * | 1999-07-09 | 2001-01-18 | Carl-Zeiss-Stiftung Trading As Schott Glas | Agent conservateur destine a des preparations perissables, notamment des preparations cosmetiques et pharmaceutiques |
-
2002
- 2002-08-17 WO PCT/EP2002/009216 patent/WO2003018499A2/fr not_active Application Discontinuation
- 2002-08-17 DE DE10293768T patent/DE10293768B4/de not_active Expired - Fee Related
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004076369A3 (fr) * | 2003-02-25 | 2005-03-31 | Schott Ag | Verre de borosilicate a action antimicrobienne |
CN100387644C (zh) * | 2003-11-12 | 2008-05-14 | 上海兴雅玻璃材料有限公司 | 抗菌树脂产品及其制造方法 |
EP2189426A1 (fr) | 2004-05-29 | 2010-05-26 | Schott AG | Procédé pour préparer de nanopoudre de verre |
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 |
WO2006072394A1 (fr) * | 2005-01-08 | 2006-07-13 | Schott Ag | Verre pulverise, en particulier verre pulverise biologiquement actif et procede pour produire du verre pulverise, en particulier du verre pulverise biologiquement actif |
DE102005001078A1 (de) * | 2005-01-08 | 2006-07-20 | Schott Ag | Glaspulver, insbesondere biologisch aktives Glaspulver und Verfahren zur Herstellung von Glaspulver, insbesondere biologisch aktivem Glaspulver |
DE102005001078A8 (de) * | 2005-01-08 | 2006-11-02 | Schott Ag | Glaspulver, insbesondere biologisch aktives Glaspulver und Verfahren zur Herstellung von Glaspulver, insbesondere biologisch aktivem Glaspulver |
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 |
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 (zh) * | 2019-12-17 | 2022-09-30 | Lg电子株式会社 | 抗菌玻璃组合物及其制造方法 |
CN115135615B (zh) * | 2019-12-17 | 2023-11-17 | Lg电子株式会社 | 抗菌玻璃组合物及其制造方法 |
CN113321956A (zh) * | 2021-05-08 | 2021-08-31 | 河北三棵树涂料有限公司 | 一种具有除醛抗菌抗病毒功能的无机内墙涂料及制备方法 |
WO2025103555A1 (fr) * | 2023-11-17 | 2025-05-22 | TROVOcare GmbH & Co. KG | Poudres de verre à taux de libération d'ions métalliques accrus de différentes combinaisons d'ions métalliques pour une réduction plus rapide de micro-organismes et/ou de virus et pour supporter une régénération cellulaire et/ou prolifération cellulaire, et procédé de production de telles poudres de verre |
Also Published As
Publication number | Publication date |
---|---|
DE10293768B4 (de) | 2011-05-12 |
DE10293768D2 (de) | 2004-11-04 |
WO2003018499A3 (fr) | 2003-04-17 |
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