EP1597211A2 - Verre phosphate antimicrobien - Google Patents

Verre phosphate antimicrobien

Info

Publication number
EP1597211A2
EP1597211A2 EP04713010A EP04713010A EP1597211A2 EP 1597211 A2 EP1597211 A2 EP 1597211A2 EP 04713010 A EP04713010 A EP 04713010A EP 04713010 A EP04713010 A EP 04713010A EP 1597211 A2 EP1597211 A2 EP 1597211A2
Authority
EP
European Patent Office
Prior art keywords
glass
weight
antimicrobial
composition
powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04713010A
Other languages
German (de)
English (en)
Inventor
Jörg Hinrich FECHNER
José ZEMMER
Karine Seneschal
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Schott AG
Original Assignee
Schott AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE2003108186 external-priority patent/DE10308186B4/de
Priority claimed from DE2003141856 external-priority patent/DE10341856A1/de
Application filed by Schott AG filed Critical Schott AG
Publication of EP1597211A2 publication Critical patent/EP1597211A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q15/00—Anti-perspirants or body deodorants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/005—Antimicrobial preparations
    • 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
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • 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
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/17—Silica-free oxide glass compositions containing phosphorus containing aluminium or beryllium
    • 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
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/253—Silica-free oxide glass compositions containing germanium
    • 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

Definitions

  • the invention relates to antimicrobial glasses, glass ceramics and ceramics obtained therefrom, and glass powder and glass ceramic powder based on phosphate glasses, which have an antimicrobial effect.
  • glass powder is also intended to include glass fibers, glass granules, glass balls.
  • US Pat. No. 5,290,554 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 Os contents.
  • the glasses have silver concentrations of ⁇ 0.5% by weight.
  • These glasses have an extremely low hydrolytic resistance and have the disadvantage of completely dissolving in water.
  • the antibacterial effect in these glasses is caused by the released Ag and / or Cu ions.
  • Phosphate or borophosphate glasses are also from the following
  • JP-A 2001-247335 JP-A 8175843 become known.
  • a disadvantage of these systems is that they are too reactive and that their chemical resistance is too low.
  • JP-A-2001 -247333 describes a glass fiber which is antimicrobially treated with Ag 2 O in a later process step.
  • the glass compositions known from JP-A-2001-247333 have a low content of Na 2 O.
  • Higher alkali contents are achieved in JP-A-2001-247333 or the corresponding US 2001/0023166 by using K 2 O and / or Li 2 O.
  • this has the disadvantage that mixed alkali effects can occur in the glass composition. This results in non-linear changes in reactivity. The reactivity is therefore no longer adjustable.
  • JP-A 2001-247336 and JP-A 2001-247335 also describe a glass composition which is rendered antimicrobial by Ag 2 O in a subsequent process step.
  • the glasses known from JP-A-2001 -247336 or from the corresponding US 2001/0006987 and JP-A-2001-247335 are borophosphate glasses with a proportion of B 2 O 3 .
  • JP-A-2001-247335 is also characterized by a relatively low phosphorus content in the glass.
  • JP-A 8175843 describes a glass which contains ZnO in very high concentrations (35-45 mol% ZnO). These high ZnO concentrations have a negative effect on the chemical resistance of the glasses. The glass has insufficient long-term stability.
  • JP 92338129 describes a soluble glass which achieves its antimicrobial effect solely by adding silver.
  • the glass according to the JP92338129 is also free of Zn. This is disadvantageous because zinc synergistically contributes to the desired antimicrobial effect.
  • a first object of the invention is to provide a glass composition which avoids the disadvantages of the prior art, has an antimicrobial effect, high chemical resistance and high reactivity.
  • the antimicrobial phosphate glasses according to the invention are distinguished by an increased Na 2 O content compared to the glasses from the prior art. As a result, an improved reactivity is associated with a more uniform release of the biocidal ions and thus a higher antimicrobial
  • Tg is understood to mean the transformation temperature of the glass, as for example in VDI-Lexikon Maschinenstoff-Technik (1993), page
  • Na 2 O increases the coefficient of thermal expansion .alpha., So that the polymer is more resistant to thermal shock.
  • a second object of the invention is to provide a glass composition which is free from alkali but nevertheless has a sufficient antimicrobial action and high chemical resistance
  • composition according to the second aspect of the invention is further characterized in that it is largely free of tin, i.e. H. is free of Sn except for impurities. Since Sn in the glass supports the reduction of ionic Ag + to metallic silver, Sn-containing glasses discolor undesirably.
  • the glass preferably contains more than 5
  • the glass is not silver in an oxidatively effective form, for. B. is added as silver nitrate and is not melted under oxidizing conditions and discoloration of the glass should be prevented, since it z. B. upon irradiation with light or by red-ox processes in the glass with such silver-containing glasses can cause discoloration.
  • the addition of silver very often leads to changes in the glass.
  • Such discoloration can be avoided if the glass of silver in the mixture in an oxidatively effective form, for. B. is added as silver nitrate (AgNO 3 ).
  • the glass is preferably used under oxidizing conditions, e.g. B.
  • Alkali alkaline earth
  • alkaline earth can preferably be added to the raw material mixture as nitrates.
  • the total contents of nitrates are preferably more than 0.5 or 1.0% by weight, particularly preferably more than 2.0, very particularly preferably more than 3.0% by weight.
  • a silver concentration of ⁇ 1 wt .-% is particularly preferred if a strong antimicrobial activity with little or no discoloration of the glasses is required and oxidative additives such as. B. nitrates can not be added to the batch during melting.
  • the glass composition in the case of glass compositions with a low alkali content, is free of aluminum and free of heavy metals other than zinc. The addition of zinc increases the antimicrobial effect in such glass compositions. 5a
  • the glass composition or glass ceramics obtained therefrom or glass powder or glass ceramic powder obtained therefrom are toxicologically harmless for use in cosmetics / medicine and are free of heavy metals except for Zn.
  • compositions that are free of alkalis and free of aluminum.
  • the glass compositions or glass ceramics obtained therefrom can be used to preserve the products themselves and to achieve an antimicrobial
  • Outward impact, d. H. a release of antimicrobial substances, in particular ions such. B. zinc or silver can be used.
  • the composition can contain Cr 2 O 3 or CuO.
  • Glass or glass ceramic powder can be used to preserve the products themselves and / or to achieve an antimicrobial effect on the outside, i.e. H. a release of antimicrobial substances, in particular ions such. B. zinc or silver can be used.
  • the glass or the glass ceramic or the glass or glass ceramic powder can - with sufficient high hydrolytic resistance - also as a coating, ie. H. Protective layer to be applied to a polymer.
  • the toxicological harmlessness is not a condition and the composition can contain Cr 2 O 3 or CuO.
  • Alkali-free compositions have the advantage that when used in certain plastics or paints and under certain conditions that 7
  • the polymer chain is not broken and the polymer material is not destroyed locally.
  • polymer chains e.g. B. in polycarbonates, not attacked, so that the mechanical and optical properties of polycarbonates are not adversely affected by the glass powder according to the invention as additives.
  • the phosphate glasses described here have a higher reactivity and thus a better antimicrobial activity. Furthermore, the phosphate glasses described here have a lower Tg and can therefore be processed at lower temperatures and thus more easily.
  • mixtures of the relatively low-melting glasses described here with high-melting polymers can partially or completely melt the glasses, so that the glasses have a more intimate shape
  • melt connection to the polymer which can lead to an extremely homogeneous distribution ⁇ in the polymer.
  • Melting of the glasses as described can be achieved, for example, when processing polymer-glass composite materials according to the invention into plastic semi-finished products or plastic products with biocidal properties.
  • the polymer-glass composite materials according to the invention into plastic semi-finished products or plastic products with biocidal properties.
  • the glass composition according to the invention further have anti-inflammatory and wound healing properties. This is particularly advantageous for use in the field of cosmetics and medicine.
  • the alkali-containing glass composition comprises the following components, in% by weight. on an oxide basis
  • the Na 2 O content is preferably> 9.5% by weight, particularly preferably> 10
  • the alkali-containing glass compositions are preferably free of ü and K except for impurities.
  • the alkali-free glass composition comprises the following components in% by weight on an oxide basis:
  • the sum of the alkali contents being less than 0.4% by weight, preferably less than 0.1% by weight, very preferably less than 0.01% by weight, and the composition being largely Sn-free except for impurities.
  • the glasses or glass ceramics or glass powders according to the invention which are obtained starting from the glass composition mentioned above, Surprisingly, sufficient chemical resistance, high reactivity and a skin-neutral to pH-neutral value are found in the specified composition range.
  • the glass, in particular the glass powder has a biocidal, or at least a biostatic effect. This is due to the skin-neutral to pH-neutral value in aqueous solution
  • the glass is toxicologically safe.
  • the heavy metal load is preferably less than 20 ppm for Pb, less than 5 ppm for Cd, less than 5 ppm for As, less than 10 ppm for Sb, less than 1 ppm for Hg, less than 10 ppm for Ni.
  • an ion exchange takes place, for example of Na ions or of Ca ions between the glass surface and the liquid medium.
  • the alkali-containing glass preferably contains Al 2 O 3 in concentrations> 6% by weight.
  • the ratio between Na / Al is preferably between 2: 1 and 1: 1% by weight.
  • Na and - AI contribute to the structure of the glass network in a molar ratio of 1: 1. Excess Na then acts as a network modifier. The reactivity of the glass can thus be set directly via the Na / Al ratio.
  • Na 2 O levels are> 10 wt .-% if the glass matrix alone contains Na 2 O and Na 2 O> 5 wt .-% and CaO> 5 percent .-% ⁇ for installation of Na 2 and CaO exposed. 11
  • the targeted incorporation of network-modifying alkaline earth ions interrupts the network formation and the reactivity of the glass, since the network is looser with a high alkaline earth content and the biocidal ions such as Zn that are introduced can be released more easily.
  • the pH value can be adjusted to a skin-neutral value through the ion exchange of the Na ions or Ca ions in aqueous solution and the OH groups of the phosphorus oxide which do not contribute to the formation of the glass network.
  • the proportion of the OH groups of the phosphorus oxide which do not contribute to the construction of the glass network can be defined on the one hand by the mixture composition, on the other hand by melting parameters such as e.g. B. melting time, purity of raw materials, etc. can be influenced.
  • the pH of the glass in contact with water can be set in a defined manner by varying the glass composition or by varying the melting parameters.
  • a setting over a wide pH range from 4.0 to 8.5 is achieved, particularly preferably 4.5 to 7. 12
  • Glasses which have a proportion of CaO> 5% by weight are particularly preferred since the Ca has a special function. If Ca is present, the glass can become bioactive.
  • the bioactivity is characterized by the fact that forms a mineral layer on the particle surface, the so-called hydroxyapatite layer. This layer is very similar to the hard tissue of the human organism and is therefore very compatible with both the hard tissue and the soft tissue.
  • Glass composition Ca and Zn in the ratio of 1: 1 to 1: 2 in% by weight are achieved by an embodiment which contains 8% by weight of CaO and 8.5% by weight of ZnO.
  • This preferred embodiment with Ca and Zn in a ratio of 1: 1 to 1: 2 is distinguished by the fact that it has the desired antimicrobial activity on the one hand, and on the other hand it is particularly “biocompatible”, that is to say particularly compatible in contact with body tissue.
  • Marking harmlessness is particularly suitable for use in creams or lotions or similar dosage forms in order to apply them to the skin.
  • Another field of application is the preservation of food.
  • the glass is preferably free of other heavy metals. Particularly pure raw materials are preferably used in such applications.
  • the biocidal or biostatic effect of the glass according to the invention or of the glass powder obtained therefrom or of the glass ceramics according to the invention obtained from these starting glasses is caused by the release of ions in a liquid medium, in particular in water.
  • the glasses or the glass powder and glass ceramics obtained therefrom have a biocidal action against bacteria, fungi and viruses. This effect is caused in particular by the presence of zinc.
  • the glasses or glass powder or glass ceramics according to the invention can be used to achieve this.
  • Such - heavy metal ions are Ag, Cu, Ge, Te and Cr. Glasses or glass powder or glass ceramics according to the invention can be added to polymers, paints and lacquers.
  • a preferred field of application of the glasses or the glass ceramic, glass powder or glass ceramic powder obtained therefrom according to the invention is the use in polymers to achieve a biocidal or biostatic effect.
  • the preservation of the polymer itself can be in the foreground, ie to protect the polymer from bacteria and fungal attack.
  • it can be used to create a biostatic or biocidal polymer surface, where possible no biocidally active substances, e.g. B. ions, to the environment 14 are to be delivered.
  • Another goal can be the provision of a polymer which in particular releases biocidally active substances.
  • plastic-glass composite material comprising:
  • a strong antimicrobial effect is also achieved when alkali-free glasses are used, even without the presence of alkalis in the glass matrix.
  • the reactivity of the glass and thus the strength of the antimicrobial effect are usually adjusted both in terms of time and quantitatively via the content of alkali ions.
  • a different reactivity can be set even without alkali ions.
  • Alkaline earth content as well as the antimicrobial effect can be set by the antimicrobial zinc.
  • alkali-free such as alkali-containing glass compositions or glass ceramics or glass powder or
  • Glass ceramic powder from such glass compositions in polymers is expected to be due to the shielding of aqueous media only 15 are insufficiently antimicrobial because they are encapsulated by polymers.
  • the glass can partially melt, depending on the processing temperature set, which increases the antimicrobial effect.
  • the glass composition also comprises Ca and Zn and the sum of CaO and ZnO is in the range 5-40% by weight in this glass composition.
  • the ZnO content is preferably more than 0.1% by weight, preferably more than 1% by weight.
  • the glasses with the compositions according to the invention or the glass ceramics, glass powder or glass ceramic powder obtained therefrom have a biostatic or biocidal action in polymers.
  • an antimicrobial surface should, as far as possible, not release or release antimicrobial substances, in particular ions to the outside, ie outside the polymer surface.
  • the glasses according to the invention in particular also the alkali-free glasses, enable slow release of antimicrobial ions from a polymer matrix.
  • the water content of the polymer and the diffusion of the ions mobile in the polymer matrix play a decisive role here.
  • the levels of biocidal ions in the glass matrix or the concentration of the glass in the polymer are higher than in the above-mentioned application. This release can be associated with a partial or complete
  • the polymer matrix also partially or completely dissolves. This is particularly the case when the polymer matrix is water-soluble.
  • Glass, the glass ceramic obtained therefrom and the glass or glass ceramic powder obtained therefrom, with sufficient hydrolytic resistance, is not contained in the polymer itself, but can also be applied to the polymer as a coating or protective layer.
  • the proportion of CaO is preferably more than 1% by weight, preferably more than 7.7% by weight. Another advantage of a CaO content greater than 1% by weight is the increase in the temperature resistance of the glass.
  • the glasses, glass powder, glass ceramics or glass ceramic powder according to the invention can have a biocidal effect 17 also have a bioactive effect due to ion exchange or ion release.
  • the glasses, glass ceramics, glass powder or glass ceramic powder according to the invention are therefore particularly biocompatible, ie particularly compatible with body tissue.
  • the heavy metal content can be reduced by completely or partially replacing Zn, preferably with Ca, but also with Mg. Such substances ensure good environmental compatibility.
  • ions are exchanged or released by reactions on the glass surface or partial dissolution of the glass.
  • the antimicrobial effect is based, among other things, on the release of ions.
  • Glass surface also plays a role.
  • the antimicrobial effect of the glass surface is also based on the presence of antimicrobial ions.
  • Gram negative bacteria have an antimicrobial effect because positive surface charges attract bacteria, but gram negative bacteria do not
  • the release rate of the glass can be adjusted by varying the glass-forming, that is to say the network-forming P 2 O 5 component.
  • the release rate of biocidal ions is set by the ion exchange and the dissolution of the glass.
  • the release of phosphates in aqueous solution allows the pH to be adjusted in a targeted manner, in particular to a skin-neutral value.
  • the network formation is interrupted and the reactivity of the glass is adjusted, since the network is looser with a high Na 2 O content and the biocidal ions such as Zn, Ag that are introduced are lighter can be delivered.
  • the reactivity is controlled by the targeted incorporation of CaO or ZnO.
  • the network formation is interrupted and the reactivity of the glass is adjusted, since the network is looser at a high CaO content and the biocidal ions such as Zn, Ag that are introduced can be released more easily.
  • Glasses according to the invention which comprise CaO are particularly preferred, in particular with a weight fraction greater than 5% by weight, because if Ca is present, the glass becomes bioactive.
  • Particularly preferred embodiments contain Ca and Zn in a ratio of 1: 1 to 1: 2% by weight.
  • the biocidal or biostatic effect of the glass according to the invention or glass powder obtained therefrom or of the glass ceramics or glass ceramic powder obtained from these starting glasses is caused by the release of ions in a liquid medium, in particular in water.
  • the glasses or the glass powder and glass ceramics obtained therefrom have a biocidal action against bacteria, fungi and viruses.
  • Glass ceramics or ceramics can be obtained from the glasses described here. These are produced by means of a subsequent tempering step either on the semi-finished product (for example the glass ribbons or ribbons) or on the product, for example on the glass powder or the glass fibers. After the tempering step, renewed grinding may be necessary to set the desired particle size.
  • the glass compositions can be ground to glass powder with particle sizes ⁇ 100 ⁇ m.
  • 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 ⁇ 2 ⁇ m have proven to be particularly suitable.
  • the grinding process can be carried out dry as well as with non-aqueous or aqueous grinding media.
  • pH values from 4.0 to 8.0 are achieved.
  • Grain sizes can be combined synergistically to adjust the special properties of the individual glass powders. For example, it is possible to control the antimicrobial effect of the glass powder by the particle size.
  • the glass of the glass powder contains P 2 O 5 as a network former, the
  • Degree of crosslinking can be influenced, inter alia, by melting parameters.
  • Na 2 O is used as a flux when melting the glass.
  • the melting behavior is negatively influenced at concentrations of less than 5% by weight.
  • the necessary mechanism of ion exchange no longer works sufficiently to achieve an antimicrobial effect.
  • Na 2 O concentrations higher than 30% by weight the chemical resistance is too low or the reactivity is too high.
  • the melting behavior is also negatively influenced.
  • alkaline earth oxides are necessary to build up the glass network.
  • the desired reactivity of the glass can be set by the proportion of alkaline earth oxides in the glass composition.
  • Glasses according to the invention which comprise CaO are particularly preferred, in particular with a weight fraction greater than 5% by weight, since at 21
  • Presence of Ca the glass is particularly compatible with body tissues.
  • the amount of AI 2 O 3 serves to increase the chemical resistance of the crystallization stability and to control the antimicrobial effect. »It also partially contributes to the development of the glass network.
  • more than 6.2% by weight of AI 2 O 3 is added to an alkali-containing glass composition.
  • the reactivity is too high when the Al 2 O 3 content is ⁇ 6.2%, ie the glass reacts too quickly, a long-term effect in the release of antimicrobial ions is not achieved.
  • the very low Al 2 O 3 content ⁇ 3.9% by weight increases the reactivity of the alkali-free glass, so that surprisingly a long-term effect in the release of antimicrobial ions is achieved. Due to the A ⁇ Os content, a long-term effect in the release of antimicrobial ions can be achieved in alkali-containing as well as alkali-free glasses.
  • ZnO is an essential component for the hot forming properties of the glass. It improves the crystallization stability and increases the
  • ZnO has antimicrobial properties and is used in a preferred embodiment of the invention to achieve an antimicrobial effect, preferably in a composition which is free of other heavy metals apart from zinc.
  • ZnO ZnO
  • Version contains> 10% by weight ZnO or> 12% by weight ZnO.
  • the glass matrix can also be built up without zinc 22 Instead of Zn, the glass then preferably comprises Ca.
  • an antimicrobial effect by biocidally active ions such.
  • these ions can also only be introduced into the surface areas of the glass via an ion exchange.
  • CuO can be added as antimicrobial additives.
  • the glass according to the invention has no skin-irritating effects.
  • a combination of the pH effect, the effect through surface effects 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 - using appropriate salts or by ion exchange of the glass after the melt.
  • Varnishes can give the glasses individual or multiple coloring components such as B. Fe 2 O 3 , CoO, CuO, V 2 O 5 , Cr 2 O 5 in a total concentration less than 4 wt .-%, preferably less than 1 wt .-% are added.
  • Glasses, glass powder, glass ceramics or glass ceramic powder with a composition within the claimed composition range 23 meet all requirements for use in the areas of paper hygiene, cosmetics, paints, varnishes, plasters, medical products, cosmetic applications, food additives and use in deoproducts, anti-perspirants and in products for the treatment of skin irritations, acute and chronic wounds and in the area of
  • Dental care / dental hygiene and oral care / oral hygiene as well as dental material e.g. for tooth fillings, crowns, inlets etc.
  • 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.
  • Embodiment is used particularly in the field of dental care and dental hygiene, since in addition to the antimicrobial and anti-inflammatory effect, fluorine can be released in small concentrations by this embodiment, which hardens the tooth enamel.
  • a particularly preferred application in the dental field is the use of the glasses described for dental materials.
  • the glasses according to the invention are suitable on their own or in combination with other materials for tooth fillings, crowns, inlets. It is particularly preferred here to use the glasses or glass ceramics according to the invention and those obtained therefrom.
  • Glass or glass ceramic powder as a composite material with polymer materials Glass or glass ceramic powder as a composite material with polymer materials.
  • polymers that are particularly suitable for adding bioglass. These are in particular PMMA; PVC; PTFE; PEEK; polystyrene;
  • polyacrylate polyethylene; Polyester; polycarbonate; PGA biodegradable polymer; LGA biodegradable polymer or the biopolymer collagen; Fibrin; chitin; 24 chitosan; polyamides; polycarbonates; Polyester; polyimides; polyurea; polyurethanes; Organic fluoropolymers; Polyacrylamides and polyacrylic acids; polyacrylates; polymethacrylates; polyolefins; Polystyrene and styrene copolymers; polyvinyl; polyvinyl ether; polyvinylidene chloride; Vinyl polymers; polyoxymethylene; polyaziridines; polyoxyalkylenes; Synthetic resins or alkyl
  • Resins amino resins, epoxy resins, phenolic resins or unsaturated polyester resins; electrically conductive polymers; High temperature polymers; inorganic polymers; Polyphenylene oxide silicones; Biopolymers such as cellulose, cellulose esters, cellulose ethers, enzymes, gelatin, natural resins, nucleic acids, polysaccharides, proteins, silk, starch or wool.
  • the glasses according to the invention preferably have for use with alkali-sensitive polymers, such as, for. B. polycarbonates have a low alkali content or are alkali-free in a preferred embodiment.
  • alkali-sensitive polymers such as, for. B. polycarbonates have a low alkali content or are alkali-free in a preferred embodiment.
  • Cutlery for example chopsticks
  • Glass ceramic powder can also be used in the clothing industry, preferably as an additive to synthetic fibers.
  • the ⁇ antimicrobial glass powder as an admixture to the fibers is particularly suitable for use in fibers for carpets.
  • the glass described in this invention or the glass ceramic obtained therefrom or the glass or glass ceramic powder obtained therefrom, which is obtained by grinding, is water-soluble, but has sufficient chemical resistance.
  • the glass or glass powder acts primarily by ion exchange or ion release, which is associated with a surface reaction and metal ion release.
  • the glass or glass ceramic powders according to the invention show a high reactivity and a higher antimicrobial effect than that 27 Group of bioactive glasses described in the prior art or glass powders made from such glasses.
  • alkali-containing glass compositions with an antimicrobial effect are described.
  • the glasses were melted from the raw materials in a platinum crucible and then processed into ribbons.
  • Table 1 shows the compositions and properties of glasses which can be ground to the glass powders according to the invention and which have an antimicrobial effect.
  • the compositions relate to synthesis values in% by weight on an oxide basis.
  • Table 1 Compositions (synthesis values) [% by weight] of glass compositions according to the invention containing alkalis:
  • Table 2 shows pH values and conductivities of glass powders of the composition as in Examples 1 and 2 according to the table in a 1% by weight aqueous suspension after 60 min:
  • Table 3 shows the antimicrobial activity for embodiment 2 according to Table 1.
  • the value 0 shows that compared to the initial starting value of, for example, 260,000 E. coli bacteria, there are no longer any bacteria in the suspension, that is to say the antimicrobial action of the glass powder has killed off all colony-forming units.
  • Table 3 Antibacterial effect of the powders according to Europ. Pharmacopoeia (3rd edition) in 0.001 wt.% Aqueous suspension: Example 2 grain size 4 ⁇ m:
  • the glass composition according to embodiment 3 in Table 1 represents a particularly preferred form, since it shows a pH-neutral value, combined with an antimicrobial and anti-inflammatory effect and a particular compatibility with body tissue.
  • a proliferation test is a test procedure that can be used to quantify the effectiveness of antimicrobial surfaces.
  • the antimicrobial effectiveness of the surface is characterized by whether and how many daughter cells are released into a surrounding nutrient medium. The implementation of the test is described in
  • the glass powder was introduced homogeneously into different polymers.
  • the polymers used were polypropylene (PP), acrylonitrile butadiene styrene
  • ABS ABS
  • polyamide PA polyamide
  • Staphylococcus epidermidis was used as the germ. This germ is a bacterium that occurs on the skin.
  • Table 4 shows the observed proliferation over 48 h for a glass powder with a particle size between d50 of 4 ⁇ m and a glass composition 31 according to embodiment 1 in table 1, which was introduced homogeneously in the concentrations (% by weight) specified in polypropylene (PP).
  • Onset OD means the optical density in the surrounding nutrient medium. Proliferation (formation of daughter cells) and release of the cells from the surface into the surrounding nutrient medium impair the transmission of the nutrient medium. This absorption at certain wavelengths correlates with the antimicrobial effectiveness of the surface. The higher the Onset OD value, the more antimicrobial the surface is. This definition of size OD also applies to all of the following tables.
  • Polymer used polypropylene (PP)
  • Table 5 shows the proliferation observed over 48 h for a glass powder with a particle size between d50 of 4 ⁇ m and a glass composition according to exemplary embodiment 7 in Table 1, which is homogeneous in the concentrations (% by weight) given in polypropylene ( PP) was introduced.
  • Glass powder of a glass composition according to exemplary embodiment 7 polymer used: polypropylene (PP)
  • Table 6 shows the proliferation observed over 48 h for a glass powder with a particle size between d50 of 4 ⁇ m and a glass composition according to exemplary embodiment 1 in Table 1, which is homogeneous in the respectively stated concentrations (% by weight) in acrylonitrile butadiene styrene ( ABS) was introduced.
  • ABS acrylonitrile butadiene styrene
  • Table 7 shows the observed proliferation over 48 h for a glass powder with a particle size between d50 of 4 ⁇ m and a glass composition according to exemplary embodiment 2 in Table 1, which is homogeneous in the respectively stated concentrations (% by weight) in acrylonitrile butadiene styrene ( ABS) was introduced.
  • ABS Acrylonitrile Butadiene Styrene
  • Table 8 shows the proliferation observed over 48 h for a glass powder with a particle size between d50 of 4 ⁇ m and a glass composition according to exemplary embodiment 1 in Table 1, which is homogeneous in the concentrations (% by weight) given in polyamide (PA) was introduced.
  • Glass powder of a glass composition according to embodiment 1 polymer used: polyamide (PA)
  • Table 9 shows the proliferation observed over 48 h for a glass powder with a particle size between d50 of 4 ⁇ m and a glass composition according to embodiment 2 in Table 1, which is homogeneous in the concentrations (% by weight) specified in polyamide (PA) was introduced.
  • Polymer used polyamide (PA)
  • the alkali-free glasses described can also be produced using the sol-gel process.
  • the alkali-free glasses were melted from the raw materials in a platinum crucible and then processed into ribbons.
  • Table 10 shows the compositions and properties of alkali-free glasses which can be ground to the glass powders according to the invention.
  • the compositions relate to synthesis values in% by weight on an oxide basis.
  • Table 10 Compositions (synthesis values) [% by weight] of alkali-free glass compositions according to the invention
  • Table 11 shows the antimicrobial effect for embodiment 1 in accordance with
  • Table 11 Antibacterial effect of the powders according to Europ. Pharmacopoeia (3rd edition) in 0.001% by weight aqueous suspension: Example 1 according to Table 9; Grain size 4 ⁇ m
  • Table 12 Antibacterial effect of the powders according to Europ. Pharmacopoeia (3rd edition) in 0.01% by weight aqueous suspension: Example 2 according to Table 9: particle size 4 ⁇ m
  • a proliferation test is a test procedure that can be used to quantify the effectiveness of antimicrobial surfaces.
  • the antimicrobial effectiveness of the surface is characterized by whether and how many daughter cells are released into a surrounding nutrient medium.
  • the implementation of the test is described in T. Bechert, P. Steinschreibe, G. Guggenbichler, Nature Medicine, Volume 6, Number
  • the glass powder was introduced homogeneously into a polymer.
  • Staphylococcus epidermidis was used as the germ. This germ is a bacterium that occurs on the skin.
  • Impairment of the transmission of the nutrient medium correlates with the antimicrobial effectiveness of the surface.
  • ABS acrylonitrile-butadiene-styrene
  • Example 1 Polymer used: PS (polystyrene)
  • PS polystyrene
  • a glass composition is shown for the first time that has a long-term antimicrobial effect.
  • glass powder or glass ceramic powder of such a glass composition also have an antimicrobial effect if they are enclosed in a polymer matrix.
  • a polymer-glass composite which comprises such a glass composition and is characterized by a high antimicrobial
  • Such polymer-glass composite materials are particularly preferably produced in that 39 a polymer is mixed with a glass powder resulting in a polymer-glass powder mixture. This polymer-glass powder mixture is then subjected to a heat treatment in a mixer, for example by heating the polymer-glass powder mixture to a temperature in the range from + 50 ° C. to + 350 ° C. with mechanical mixing. A plastic-glass composite material is then formed, in which the glass can partially melt and there is an intimate connection of the glasses with a particularly high-melting polymer, which leads to an extremely homogeneous distribution of the glass in the polymer.
  • the plastic-glass composite material obtained can be ground by grinding z. B. be further processed into granules or directly to a semi-finished plastic or finished plastic product, for example by spraying.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Animal Behavior & Ethology (AREA)
  • Inorganic Chemistry (AREA)
  • Zoology (AREA)
  • Pest Control & Pesticides (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • Dermatology (AREA)
  • Wood Science & Technology (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Glass Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Cosmetics (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne un verre phosphaté antimicrobien présentant la composition suivante en % en poids, sur une base d'oxyde : P2O5 > 66-80 % en poids; SO3 0-40 % en poids; B203 0-1 % en poids; A12O3 > 6,2-10 % en poids; SiO2 0-10 % en poids; Na2O > 9-20 % en poids; CaO 0-25 % en poids; MgO 0-15 % en poids; SrO 0-15 % en poids; BaO 0-15 % en poids; ZnO > 0-25 % en poids; Ag2O 0-5 % en poids; CuO 0-10 % en poids; GeO2 0-10 % en poids; TeO2 0-15 % en poids; Cr2O3 0-10 % en poids; J 0-10 % en poids; F 0-3 % en poids.
EP04713010A 2003-02-25 2004-02-20 Verre phosphate antimicrobien Withdrawn EP1597211A2 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE10308186 2003-02-25
DE2003108186 DE10308186B4 (de) 2003-02-25 2003-02-25 Antimikrobiell wirkendes Phosphatglas und dessen Verwendungen
DE2003141856 DE10341856A1 (de) 2003-09-09 2003-09-09 Antimikrobiell wirkendes alkalifreies Phosphatglas
DE10341856 2003-09-09
PCT/EP2004/001670 WO2004076371A2 (fr) 2003-02-25 2004-02-20 Verre phosphate antimicrobien

Publications (1)

Publication Number Publication Date
EP1597211A2 true EP1597211A2 (fr) 2005-11-23

Family

ID=32928835

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04713010A Withdrawn EP1597211A2 (fr) 2003-02-25 2004-02-20 Verre phosphate antimicrobien

Country Status (4)

Country Link
US (1) US8080490B2 (fr)
EP (1) EP1597211A2 (fr)
JP (1) JP4602320B2 (fr)
WO (1) WO2004076371A2 (fr)

Families Citing this family (49)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060142413A1 (en) * 2003-02-25 2006-06-29 Jose Zimmer Antimicrobial active borosilicate glass
DE10308227A1 (de) * 2003-02-25 2004-09-09 Schott Glas Antimikrobiell wirkendes Sulfophosphatglas
DE102004011520A1 (de) * 2004-03-08 2005-10-06 Schott Ag Antimikrobiell brechzahlangepasstes Phosphatglas
ATE517643T1 (de) * 2005-08-12 2011-08-15 Univ Limerick Synthetisches transplantat mit einem glasnetz
US20070199890A1 (en) * 2006-02-27 2007-08-30 Agion Technologies, Inc. Antimicrobial activated carbon and use thereof
US8034732B2 (en) * 2006-03-17 2011-10-11 Koa Glass Co., Ltd. Antimicrobial glass and method of producing antimicrobial glass
US7651966B2 (en) * 2006-04-18 2010-01-26 Mo-Sci Corporation Alkaline resistant phosphate glasses and method of preparation and use thereof
JP5079273B2 (ja) * 2006-07-03 2012-11-21 Ｈｏｙａ株式会社 リン酸塩ガラス、フツリン酸塩ガラス、精密プレス成形用プリフォーム、光学素子およびそれぞれの製造方法
MX2009003218A (es) 2006-09-25 2009-04-06 Orthovita Inc Compuestos que soportan carga bioactiva.
WO2008104964A2 (fr) * 2007-02-26 2008-09-04 University Of Limerick Greffe osseuse synthétique
JP5111906B2 (ja) * 2007-03-19 2013-01-09 旭ファイバーグラス株式会社 抗菌剤を含む樹脂組成物及び成形品
CN101497496B (zh) * 2008-02-02 2011-06-15 比亚迪股份有限公司 一种搪瓷釉料组合物与一种镀膜材料及其制备方法
US20100168798A1 (en) * 2008-12-30 2010-07-01 Clineff Theodore D Bioactive composites of polymer and glass and method for making same
GB2470088B (en) * 2009-11-10 2011-06-29 Landmark Innovations Ltd Root canal therapy
ES2361695B1 (es) * 2009-12-09 2012-04-27 CONSEJO SUPERIOR DE INVESTIGACIONES CIENT�?FICAS (CSIC) (Titular al 50%) Polvo de composición v�?trea con actividad biocida.
DE102010023339A1 (de) 2010-06-10 2011-12-15 Siemens Aktiengesellschaft Beschleuniger für zwei Teilchenstrahlen zum Erzeugen einer Kollision
TWI540111B (zh) 2011-03-28 2016-07-01 康寧公司 Ｃｕ、ＣｕＯ與ＣｕＯ奈米顆粒在玻璃表面與耐久塗層上的抗微生物作用
TW201321031A (zh) * 2011-10-12 2013-06-01 Corning Inc 抗菌的玻璃陶瓷
JP5667970B2 (ja) 2011-12-26 2015-02-12 株式会社日立製作所 複合材料
JP5712123B2 (ja) 2011-12-26 2015-05-07 株式会社日立製作所 複合材料
US9169153B2 (en) 2012-05-07 2015-10-27 Nippon Electric Glass Co., Ltd. Optical glass and optical element
US10350013B2 (en) * 2012-06-21 2019-07-16 Globus Medical, Inc. Surgical tool systems and methods
US9408383B2 (en) 2012-06-28 2016-08-09 Certainteed Corporation Roofing granules
US10131574B2 (en) 2013-06-17 2018-11-20 Corning Incorporated Antimicrobial glass articles and methods of making and using same
US20160106109A1 (en) * 2013-07-02 2016-04-21 Koa Glass Co., Ltd. Antibacterial glass
US9724440B2 (en) 2013-11-15 2017-08-08 GE Lighting Solutions, LLC Environmental cleaning and antimicrobial lighting component and fixture
US9642358B2 (en) * 2013-12-12 2017-05-09 Ge Lighting Solutions Llc Antimicrobial lighting system
IN2013CH05760A (fr) * 2013-12-12 2015-08-07 Pandian Bio Medical Res Ct
EP2886520A1 (fr) * 2013-12-19 2015-06-24 Nanobiomatters Bactiblock, S.L. Verre antibactérien
CN106164004B (zh) 2014-02-13 2019-12-10 康宁股份有限公司 具有增强的强度和抗微生物性质的玻璃，及其制造方法
US11039621B2 (en) 2014-02-19 2021-06-22 Corning Incorporated Antimicrobial glass compositions, glasses and polymeric articles incorporating the same
US9622483B2 (en) 2014-02-19 2017-04-18 Corning Incorporated Antimicrobial glass compositions, glasses and polymeric articles incorporating the same
US11039620B2 (en) 2014-02-19 2021-06-22 Corning Incorporated Antimicrobial glass compositions, glasses and polymeric articles incorporating the same
CN105613582B (zh) * 2014-10-31 2019-11-22 住友大阪水泥股份有限公司 抗菌性组合物及抗菌性釉料组合物以及抗菌性物品
US20170342383A1 (en) 2016-05-27 2017-11-30 Corning Incorporated Lithium disilicate glass-ceramic compositions and methods thereof
US10751367B2 (en) 2016-05-27 2020-08-25 Corning Incorporated Bioactive glass microspheres
US10647962B2 (en) 2016-05-27 2020-05-12 Corning Incorporated Bioactive aluminoborate glasses
US10676713B2 (en) 2016-05-27 2020-06-09 Corning Incorporated Bioactive borophosphate glasses
DE102017207253B3 (de) 2017-04-28 2018-06-14 Schott Ag Filterglas
EP3717030A1 (fr) 2017-11-28 2020-10-07 Corning Incorporated Compositions de verre bioactif et restauration de l'hypersensibilité de la dentine
EP3717427A1 (fr) 2017-11-28 2020-10-07 Corning Incorporated Verre bioactif à viscosité de liquidus élevée
EP3717426A1 (fr) 2017-11-28 2020-10-07 Corning Incorporated Vitrocéramiques bioactives chimiquement renforcées
WO2019108557A1 (fr) 2017-11-28 2019-06-06 Corning Incorporated Verre à base de borate bioactif et procédés associés
EP3883896A1 (fr) * 2018-11-20 2021-09-29 Corning Incorporated Verres au phosphate bioactifs
WO2021049269A1 (fr) * 2019-09-13 2021-03-18 株式会社ジーシー Poudre de verre et initiateur de polymérisation chimique
DE102020116036B4 (de) * 2020-06-17 2022-05-05 Damir Ibrahimovic Lackzusammensetzung und Verwendung derselben
GB2597480B (en) * 2020-07-22 2022-08-17 Matthew Thorn Daniel Antimicrobial compositions and eyewear
CN112830678A (zh) * 2021-01-22 2021-05-25 深圳市尤佳环境科技有限公司 陶瓷抗菌添加剂及其制备方法、陶瓷釉料
KR20230051863A (ko) * 2021-10-12 2023-04-19 휴먼켐 주식회사 기능성 항균 파우더 및 이의 제조 방법

Family Cites Families (99)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1294337A (en) 1969-11-05 1972-10-25 Arthur Terence Ranson Process for treating glass
GB1316160A (en) 1970-10-15 1973-05-09 Hollandsche Betongroep Nv Concrete reinforcement
JPS5116446B1 (fr) 1971-05-21 1976-05-24
JPS5138727B1 (fr) 1971-07-23 1976-10-23
DE2239307A1 (de) 1972-08-10 1974-02-21 Owens Illinois Inc Verfahren zur verstaerkung von festen glasgegenstaenden und nach dem verfahren hergestellte gegenstaende
CA1016724A (en) 1972-09-18 1977-09-06 Smc Corporation Flux for continuous casting of steel
US3926246A (en) 1972-09-18 1975-12-16 Scm Corp Flux for continuous casting of steel
JPS5829262B2 (ja) * 1976-12-02 1983-06-21 株式会社保谷硝子 緑色フイルタ−ガラス
US4092139A (en) 1977-03-16 1978-05-30 Corning Glass Works Process for making colored photosensitive glass
JPS5438311A (en) * 1977-08-31 1979-03-22 Hoya Glass Works Ltd Low temperature melting coating glass capable of highly absorbing laser
JPS6049142B2 (ja) * 1978-04-17 1985-10-31 株式会社保谷硝子 カラ−・テレビジョン・カメラ用近赤外吸収フイルタ−
GB8327949D0 (en) 1983-10-19 1983-11-23 Holmes A Glass ceramic materials
JPS61133813A (ja) 1984-12-03 1986-06-21 Matsushita Electric Ind Co Ltd 面形状測定装置
JPS61186248A (ja) 1985-02-13 1986-08-19 Nippon Electric Glass Co Ltd ガラスセラミツク
GB2178422B (en) 1985-08-02 1990-02-14 Stc Plc Prosthesis formed from water-soluble phosphate glass.
EP0220333B1 (fr) 1985-10-26 1990-03-21 Schott Glaswerke Vitrocéramique transparente colorée à bonne tenue à la température et à transmission variable et réglable dans le domaine de l'infrarouge
US4831074A (en) * 1987-05-11 1989-05-16 Kishimoto Sangyo Company Ltd. Plastic composite and the process for manufactring the same
JPH02149447A (ja) 1988-12-01 1990-06-08 Nippon Electric Glass Co Ltd 歯科用結晶化ガラス
JPH02264074A (ja) * 1989-04-05 1990-10-26 Yoshio Ichikawa 抗菌性コーティング用組成物および抗菌性布帛
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
DE3936284A1 (de) 1989-11-01 1991-05-02 Bayer Ag Emailfritten mit verbesserter haftung fuer stahlblech
DD302011A9 (de) 1989-11-13 1994-11-03 Biovision Gmbh Entwicklung Glasiges oder glasig-kristallines Material mit schneller Loeslichkeit und Verfahren zu seiner Herstellung
US5196381A (en) 1990-01-16 1993-03-23 E. I. Du Pont De Nemours And Company Metaphosphate glass composition
US5074916A (en) 1990-05-18 1991-12-24 Geltech, Inc. Alkali-free bioactive sol-gel compositions
DE69123312T2 (de) * 1990-08-21 1997-03-20 Asahi Glass Co Ltd Kalziumphosphat Glaskeramik
US5022921A (en) 1990-10-19 1991-06-11 Corning Incorporated Phosphate glasses for glass molds
JP3146436B2 (ja) 1990-10-30 2001-03-19 日立マクセル株式会社 Ｉｃモジユール
US6123743A (en) 1991-01-07 2000-09-26 Norton Company Glass-ceramic bonded abrasive tools
JP3057773B2 (ja) 1991-02-05 2000-07-04 不二製油株式会社 パイの製造方法
PL167664B1 (pl) 1991-03-16 1995-10-31 Torf Ets Sposób ekstrakcji torfu oraz urzadzenie do ekstrakcji torfu PL PL PL PL PL
JPH0788236B2 (ja) 1991-05-10 1995-09-27 石塚硝子株式会社 合成樹脂添加用硝子組成物
US5234871A (en) 1991-11-27 1993-08-10 Schott Glass Technologies, Inc. Vanadium- and copper-containing glasses for use as filters for light sources intended for use with night vision devices
JPH06340445A (ja) 1993-05-28 1994-12-13 Kirin Brewery Co Ltd 黄色着色ガラス
US5807641A (en) 1993-05-31 1998-09-15 Sumitomo Osaka Cement Co., Ltd. Anti-bacterial and anti-fungal glaze composition for ceramic products
US5544695A (en) 1993-06-01 1996-08-13 Harasym; Michael Antivortexing nozzle system for pouring molten metal
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
JP3428080B2 (ja) 1993-08-05 2003-07-22 日本板硝子株式会社 銀イオン含有ガラスの製造方法
US5328874A (en) 1993-10-18 1994-07-12 Corning Incorporated Zinc sulfophosphate glasses
JPH07291654A (ja) 1994-04-22 1995-11-07 Nippon Sheet Glass Co Ltd 抗菌性ガラス粉末
JPH0827404A (ja) * 1994-05-09 1996-01-30 Nippon Sheet Glass Co Ltd 抗菌性コーティング用組成物、そのコーティング法、および抗菌性被覆物品
JP3486951B2 (ja) 1994-05-09 2004-01-13 日本板硝子株式会社 抗菌性ガラス組成物
DE19503167A1 (de) 1995-02-01 1996-08-08 Gruenzweig & Hartmann Glasfaserzusammensetzungen
JPH0848539A (ja) 1994-06-02 1996-02-20 Nippon Sheet Glass Co Ltd 抗菌性ガラス組成物
JP3110963B2 (ja) 1994-12-20 2000-11-20 石塚硝子株式会社 耐久性を有する抗菌剤
GB9502253D0 (en) 1995-02-06 1995-03-29 Giltech Ltd The effects of antibacterial agents on the behaviour of mouse fibroblasts in vitro
JP3026732B2 (ja) 1995-02-08 2000-03-27 神鋼パンテツク株式会社 抗菌性を有するガラス被覆の施工方法
JPH08245240A (ja) 1995-03-06 1996-09-24 Koa Glass Kk 抗菌性複合ガラス粒子
DE69613941T2 (de) 1995-11-06 2001-11-22 Corning Inc Dreikomponenten-Glas-/Polymer-Mischungen
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
JPH1059788A (ja) 1996-08-21 1998-03-03 Tokyo Yogyo Co Ltd 抗菌器具
US5834008A (en) 1996-09-19 1998-11-10 U.S. Biomaterials Corp. Composition and method for acceleration of wound and burn healing
JP3772414B2 (ja) 1996-09-26 2006-05-10 旭硝子株式会社 有機樹脂に燃焼時の発煙抑止機能を付与する低融点ガラス
US6074984A (en) 1996-11-18 2000-06-13 Bulldog Technologies U.S.A., Inc. SOx Additive systems based upon use of multiple particle species
JPH10158037A (ja) 1996-11-27 1998-06-16 Asahi Glass Co Ltd 抗菌性ガラス及びその製造方法
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
JPH10231187A (ja) 1997-02-21 1998-09-02 Toto Ltd 抗菌性釉薬、この釉薬を用いた陶磁器製品及び抗菌性釉薬の調製方法
JP3845959B2 (ja) 1997-07-07 2006-11-15 日本電気硝子株式会社 抗菌性ガラス粉末及び樹脂成形体
JPH1160277A (ja) 1997-08-18 1999-03-02 Nippon Electric Glass Co Ltd 抗菌性結晶化ガラス物品及びその製造方法
ES2142249B1 (es) 1997-12-02 2001-04-01 Esmaltes S A Esmalte ceramico bactericida y sus aplicaciones.
JP4163778B2 (ja) 1998-01-23 2008-10-08 石塚硝子株式会社 抗菌性ガラス繊維
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
JPH11278866A (ja) 1998-03-31 1999-10-12 Nihon Yamamura Glass Co Ltd ガラス容器の抗菌処理方法
US6509057B2 (en) 1998-04-01 2003-01-21 Sumitomo Osaka Cement, Co., Ltd. Antibacterial, antifungal or antialgal article and process for producing same
JP3453515B2 (ja) 1998-05-12 2003-10-06 東洋佐々木ガラス株式会社 抗菌性強化ガラス物品
JP2000053451A (ja) 1998-08-05 2000-02-22 Sumitomo Osaka Cement Co Ltd 抗菌性ガラス製品およびその製造方法
JP2000191339A (ja) 1998-12-28 2000-07-11 Koa Glass Kk 溶解性ガラス、抗菌性樹脂組成物、および抗菌性成形品
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
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
JP2001048595A (ja) 1999-03-19 2001-02-20 Inax Corp ガラス層をもつ基体の表面処理方法及びその製品
JP2000327369A (ja) 1999-05-21 2000-11-28 Asahi Glass Co Ltd リン酸スズ系ガラス含有結晶性組成物
JP2001026466A (ja) 1999-07-13 2001-01-30 Nippon Sheet Glass Co Ltd 抗菌ガラスの製造方法
DE19960548A1 (de) 1999-12-15 2001-06-21 Siemens Ag Glas/Kunststoff-Compounds
JP2001247335A (ja) 1999-12-28 2001-09-11 Ishizuka Glass Co Ltd 抗菌性付与用ガラス組成物、抗菌性高分子複合材料及び抗菌性繊維
JP4689019B2 (ja) 1999-12-28 2011-05-25 石塚硝子株式会社 抗菌性付与用ガラス組成物、及びそれを用いた抗菌性高分子複合材料、抗菌性高分子複合材料成形体
JP2001247336A (ja) 1999-12-28 2001-09-11 Ishizuka Glass Co Ltd 抗菌性付与用ガラス組成物、及びそれを用いた抗菌性高分子複合材料、抗菌性高分子複合材料成形体
JP2001247333A (ja) * 1999-12-28 2001-09-11 Ishizuka Glass Co Ltd 抗菌性付与用ガラス組成物、抗菌性繊維、抗菌性撚糸及び抗菌性布状物
JP2001247334A (ja) * 1999-12-28 2001-09-11 Ishizuka Glass Co Ltd 抗菌性付与用ガラス組成物及び抗菌性繊維
WO2001051426A1 (fr) 2000-01-14 2001-07-19 Inax Corporation Produit constitue d'une couche de verre et son procede d'obtention
WO2001072262A2 (fr) * 2000-03-27 2001-10-04 Schott Glas Nouvelles compositions de produits cosmetiques, d'hygiene personnelle, d'agents de nettoyage et de supplements nutritionnels contenant du verre bioactif, et procedes de fabrication et d'utilisation de ces dernieres
DE10017701C2 (de) 2000-04-08 2002-03-07 Schott Glas Gefloatetes Flachglas
CN1323527A (zh) 2000-05-16 2001-11-28 顾浩 银、铜无机抗菌剂
JP2002012442A (ja) 2000-06-23 2002-01-15 Asahi Glass Co Ltd 低融点ガラス
US6409396B1 (en) * 2000-08-02 2002-06-25 Schott Glass Technologies, Inc. Interference filter having a glass substrate
JP3622752B2 (ja) * 2000-09-29 2005-02-23 興亜硝子株式会社 抗菌性ガラスおよびその製造方法
US20040166172A1 (en) 2001-03-27 2004-08-26 Coni Rosati Bioctive tissue abrasives
DE10122262A1 (de) 2001-05-08 2002-11-21 Schott Glas Polymere mit bioaktivem Glas mit antimikrobieller Wirkung
DE10293767B4 (de) 2001-08-22 2017-06-08 Schott Ag Desinfektionsglaspulver mit antimikrobieller, entzündungshemmender, wundheilender Wirkung und dessen Verwendung
EP1419118B1 (fr) 2001-08-22 2006-07-12 Schott Ag Poudre de verre antimicrobienne, anti-inflammatoire, cicatrisante et utilisation
DE10141117A1 (de) 2001-08-22 2003-03-13 Schott Glas Antimikrobielles Silicatglas und dessen Verwendung
JP4052836B2 (ja) 2002-01-15 2008-02-27 日本電気硝子株式会社 抗菌性ガラス微小球及びその製造方法
US20050119105A1 (en) 2002-01-18 2005-06-02 Schott Ag Glass-ceramic composite containing nanoparticles
CN1379146A (zh) 2002-05-20 2002-11-13 朱红军 复合型(Ag+Ag2O)防集聚纳米银抗菌非织造布及工业化生产工艺
US6921546B2 (en) 2003-02-20 2005-07-26 Gemtron Corporation Antimicrobial glass and glass-like products and method of preparing same
DE10308227A1 (de) 2003-02-25 2004-09-09 Schott Glas Antimikrobiell wirkendes Sulfophosphatglas
US20060142413A1 (en) 2003-02-25 2006-06-29 Jose Zimmer Antimicrobial active borosilicate glass
DE10309826B4 (de) 2003-03-05 2009-11-12 Schott Ag Verfahren zum Strukturieren von Phosphatgläsern durch zerstörungsfreien Ionenaustausch, strukturierte Phosphatgläser und deren Verwendung
JP4338129B2 (ja) 2003-09-12 2009-10-07 フジノン株式会社 超音波内視鏡
DE102004011520A1 (de) 2004-03-08 2005-10-06 Schott Ag Antimikrobiell brechzahlangepasstes Phosphatglas
DE102004026432A1 (de) 2004-05-29 2005-12-22 Schott Ag Glaszusammensetzungen als antimikrobieller Zusatz für Dentalmaterialien und deren Verwendung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004076371A2 *

Also Published As

Publication number Publication date
JP2006518697A (ja) 2006-08-17
US20060172877A1 (en) 2006-08-03
WO2004076371A3 (fr) 2005-04-28
JP4602320B2 (ja) 2010-12-22
US8080490B2 (en) 2011-12-20
WO2004076371A2 (fr) 2004-09-10

Similar Documents

Publication Publication Date Title
EP1597211A2 (fr) Verre phosphate antimicrobien
EP1580172B1 (fr) anti-microbiel, indice de refraction-adapte verre phosphate
DE10308186B4 (de) Antimikrobiell wirkendes Phosphatglas und dessen Verwendungen
EP1470088B1 (fr) Poudre de verre de silicate antimicrobienne, insoluble dans l'eau et melange de poudres de verre
WO2004076370A1 (fr) Verre phosphate antimicrobien
WO2004076369A2 (fr) Verre de borosilicate a action antimicrobienne
EP1419118B1 (fr) Poudre de verre antimicrobienne, anti-inflammatoire, cicatrisante et utilisation
EP1419119B1 (fr) Verre de silice antimicrobien insoluble dans l'eau et utilisation
EP1667941B1 (fr) Surfaces en verre antimicrobiennes de poudres de verre
DE10293767B4 (de) Desinfektionsglaspulver mit antimikrobieller, entzündungshemmender, wundheilender Wirkung und dessen Verwendung
DE602004000926T2 (de) Antimikrobielle Glaszusammensetzung und diese enthaltende antimikrobielle Polymerzusammensetzung
US20060142413A1 (en) Antimicrobial active borosilicate glass
WO2002090278A1 (fr) Polymeres comportant du verre bioactif presentant une action antimicrobienne
DE102015214431B3 (de) Bor-armes Zirkonium-freies Neutralglas mit optimiertem Alkaliverhältnis
DE10293768B4 (de) Antimikrobielles Glaspulver, dessen Verwendung und Verfahren zu dessen Herstellung
EP1498395B1 (fr) Utilisation d'une composition vitreuse pour obtenir un effet antioxydant
DE10213630A1 (de) Antimikrobielles Glas und dessen Verwendung
DE10241495B4 (de) Antimikrobielle Alkalisilicat-Glaskeramik, Glaskeramikpulver, Verfahren zu dessen Herstellung und Verwendung
DE10341856A1 (de) Antimikrobiell wirkendes alkalifreies Phosphatglas
WO2003082358A1 (fr) Utilisation de poudre ou de fibres de verre et / ou de vitroceramique pour l'emission regulee d'ions
DE112020006174T5 (de) Antibakterielle Glaszusammensetzung und Verfahren zu deren Herstellung
DE10322444A1 (de) Formulierung kosmetischer Produkte mit Glaspulver

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20050704

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

DAX Request for extension of the european patent (deleted)
RBV Designated contracting states (corrected)

Designated state(s): DE

RIN1 Information on inventor provided before grant (corrected)

Inventor name: SENESCHAL-MERZ, KARINE

Inventor name: ZEMMER, JOSE

Inventor name: FECHNER, JOERG, HINRICH

17Q First examination report despatched

Effective date: 20110119

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20110730