EP1453768A1 - Vitroceramique alcali-silicate antimicrobienne et son utilisation - Google Patents
Vitroceramique alcali-silicate antimicrobienne et son utilisationInfo
- Publication number
- EP1453768A1 EP1453768A1 EP02798328A EP02798328A EP1453768A1 EP 1453768 A1 EP1453768 A1 EP 1453768A1 EP 02798328 A EP02798328 A EP 02798328A EP 02798328 A EP02798328 A EP 02798328A EP 1453768 A1 EP1453768 A1 EP 1453768A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- glass ceramic
- glass
- weight
- ceramic powder
- starting
- 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- Withdrawn
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
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/25—Silicon; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/0007—Compositions for glass with special properties for biologically-compatible glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/0007—Compositions for glass with special properties for biologically-compatible glass
- C03C4/0021—Compositions for glass with special properties for biologically-compatible glass for dental use
-
- 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 an antimicrobial glass ceramic or an antimicrobial glass ceramic powder.
- the starting glass for the glass ceramic or the glass ceramic powder comprises 30-65 wt.% Si0 2 , 5-30 wt.%
- a glass powder has become known from US Pat. No. 5,676,720 which contains 40-60% by weight.
- No. 5,981,412 describes a bioactive bioceramic for medical applications with the crystalline phase Na 2 O 2CaO 3SiO 2 .
- the crystallite size is 13 ⁇ m.
- the ceramization takes place with tempering steps for nucleation and crystallization.
- the focus is on the mechanical properties such as K 1c .
- the proportion of crystal phases is between 34 and 60% by volume.
- US Pat. No. 5,981,412 describes only a crystalline phase which is a high-temperature phase and which only arises under the special conditions specified in this document.
- the object of the invention is to provide a glass ceramic or a powder of such a glass ceramic that in addition to the antimicrobial Properties also have anti-inflammatory, skin-regenerating and light-scattering properties.
- a glass ceramic according to claim 1 wherein the crystalline main phase consists of alkali-earth alkali silicates and / or earth alkali silicates and / or alkali silicates.
- the glass ceramic according to the invention or the glass ceramic powder according to the invention is characterized in that it exhibits a defined scattering and reflection effect in the visible wavelength range of the light. This can reduce the visual appearance of skin folds when used cosmetically. Furthermore, the glass ceramic shows a biocidal, in any case a biostatic effect against bacteria, fungi and viruses. However, the glass ceramic according to the invention is skin-friendly and toxicologically harmless in contact with humans.
- the maximum concentration of heavy metals is, for example, for Pb ⁇ 20 ppm, Cd ⁇ 5 ppm, As ⁇ 5 ppm, Sb ⁇ 10 ppm, Hg ⁇ 1 ppm, Ni ⁇ 10 ppm.
- the unceramized starting glass which is used for the production of the glass ceramic according to the invention, contains SiO 2 as a network former between 30-65% by weight. At lower concentrations, the spontaneous tendency to crystallize increases sharply and the chemical resistance decreases sharply. At higher Si0 2 values, the crystallization stability can decrease and the
- Si0 2 is also a component of the crystalline phases formed during the ceramization and must be present in the glass in correspondingly high concentrations if high crystalline phase fractions are to be set by the ceramization.
- Na 2 0 is used as a flux when melting the glass. At concentrations less than 5%, the melting behavior is negatively affected.
- Sodium is part of the phases formed during the ceramization and, if high crystalline phase fractions are to be set by the ceramization, must be present in the glass in correspondingly high concentrations.
- K 2 0 acts as a flux when melting the glass. Potassium is also released in aqueous systems. If there are high potassium concentrations in the glass, potassium-containing phases such as potassium silicates are also eliminated.
- the K 2 O content can be in the range 0-40% by weight, preferably 0-25% by weight, particularly preferably 0-10% by weight.
- the chemical resistance of the glass and thus the release of ions in aqueous media is adjusted via the P 2 0 ⁇ content.
- the P 2 0 5 content is between 0 and 15% by weight. At higher P 2 0 5 values, the hydrolytic resistance of the
- the glass can contain up to 5% by weight of B 2 0 3 .
- the amount of Al 2 0 3 should be less than 3% by weight in order to avoid a chemical that is too high
- Al 2 0 3 is used to adjust the chemical resistance of the glass.
- antimicrobial ions such as. B. Ag
- Au, I, Ce, Cu, Zn, Sn can be contained in concentrations of less than 5% by weight.
- the addition of Ag is particularly preferred.
- particularly preferred crystalline phases such.
- Silver phosphates such as AgPO 3 or silicon phosphates SiP 2 O are formed in the glass ceramic.
- ions such as B. Ag, Cu, Au, Li to adjust the high temperature conductivity of the melt and thus to improve Meltability with high frequency melting processes may be included as additives.
- concentration of these ions should be less than 5% by weight.
- Coloring ions such as B. Fe, Cr, Co, V, can be contained individually or combined in a total concentration of less than 1 wt.%.
- the glass ceramic according to the invention is usually used in powder form.
- the ceramization can be done either with a glass block or glass ribbons or with glass powder. After ceramization, the glass ceramic blocks or ribbons must be ground to powder. If the powder has been ceramized, it may also have to be ground again in order to remove agglomerates which have formed during the ceramization step.
- ceramization in powder form is a very small crystallite size with high overall phase proportions.
- crystallites on surface defects that are generated during grinding grow from the surface.
- a large number of surface nuclei are generated by grinding, so that a large number of crystals begin to grow at the same time and thus an extremely small one
- Crystallite size can still be achieved with high crystalline phase fractions.
- a separate additional annealing treatment for nucleation e.g. US Pat. No. 5,981,412 is therefore not necessary.
- the grindings can be dry as well as in aqueous or non-aqueous
- the particle sizes are usually less than 500 ⁇ m. Particle sizes of ⁇ 100 ⁇ m or ⁇ 20 ⁇ m have proven to be expedient. Particle sizes ⁇ 10 ⁇ m and smaller than 5 ⁇ m and smaller than 2 ⁇ m are particularly suitable. Particle sizes ⁇ 1 ⁇ m have been found to be particularly suitable. Mixtures of different glass powders from the composition range with different compositions and grain sizes are possible to combine certain effects.
- the crystallization takes place very quickly.
- the ceramization temperatures are between 50 ° C and 400 ° C above Tg, preferably 50 ° C - 200 ° C above Tg in a particularly preferred range 50 - 100 ° C above Tg.
- the ceramization can also be carried out in multi-stage thermal processes.
- the crystallization is primarily surface-controlled. Acicular crystallites grow from the surface into the glass interior. Few crystallites also begin to grow inside the glass. They are spherulitic.
- the ceramization of the powders primarily results in needle-shaped crystals due to the high surface areas.
- the ceramization of the initial glass is surface-controlled. If the ribbons or blocks of the starting glass are ground into powders before the ceramization, the crystallization temperatures shift to significantly lower values. The crystals begin to grow from the surfaces of the powder particles inside.
- the ceramization can be carried out in such a way that the particles only have an outer crystalline layer and remain amorphous on the inside. The choice of particle size determines the average crystallite size.
- the crystal phase proportions in the glass after the ceramization are greater than 5
- a preferred range is a phase proportion greater than 10% by weight and greater than 30% by weight.
- the range is more preferably greater than 50% by weight.
- the main crystal phases are alkali-alkaline earth silicates and / or alkaline earth silicates, in particular NaCa silicates and Ca silicates, it being possible for these phase fractions to be influenced by the ceramization.
- crystal secondary phases which can contain silver and / or phosphorus and / or silicon such as AgPO 3 , SiP 2 O, SiO 2 can, depending on the specific one
- Composition of the starting glass also occur.
- Glass ceramics containing phosphorus from this composition range can be bioactive in aqueous media, i.e. they form a hydroxyapatite layer on their surface and also on foreign surfaces in aqueous systems.
- Such powders are particularly suitable for use as biomaterials or in applications in which remineralization processes play an important role, such as e.g. B. in the field of hair cosmetics, nail cosmetics and dental care.
- the chemical reactivity or the ion release is influenced by the phases and phase fractions. Chemical reactivity and ion release can thus be controlled, so that the main tolerance, the pH value and the antimicrobial and anti-inflammatory effect can be adjusted.
- the crystalline phases show a significantly different chemical resistance than the glass phase.
- the chemical resistance can be both increased and decreased.
- the mechanical, abrasive and optical properties are also modified in accordance with the main crystal phase properties.
- the resulting crystalline phases sometimes show a much higher solubility in water than the glass phase.
- the ionic release of the powder and the pH value in aqueous solution and thus also the biological effect can be influenced by the targeted adjustment of the phase fractions.
- Light scattering effects to achieve optical effects such as transparency, reflection, scattering result from the different refractive indices of glass phase and crystal phase as well as the set crystallite sizes.
- honeycomb or porous surface structures remain, which in particular influence the optical properties such as transmission, reflection and light scattering of the powders in formulations.
- formation of nanoparticles is also observed.
- the glass ceramic powders are ideally suited to be used in the field of cosmetic products. This can include Products in the field of color cosmetics.
- the antimicrobial effect enables use in the area of deodorant and antiperspirant.
- Other applications in the cosmetics sector are hair and skin care.
- the powder is also suitable for use in the medical field as an implant material and in the field of wound care.
- the material is suitable for being used as a carrier substance in the production of artificial three-dimensional tissue structures.
- the powder can also be added to polymers, for example as an antimicrobial agent.
- Such glass ceramic powders can also be used in the fields of paints and varnishes, foods, cleaning agents, paper hygiene, medical devices, organic products, cosmetic products and oral care
- Fig. 1 X-ray diffraction pattern of a powder crystallized
- Fig. 9 X-ray diffraction diagram of a crystallized starting glass with a composition according to embodiment 8, annealed for four hours at 700 ° C.
- Fig. 10 X-ray diffraction diagram of a crystallized starting glass with a composition according to embodiment 8, annealed for four hours at 900 ° C.
- Fig. 12 X-ray diffraction diagram of a crystallized starting glass with a composition according to embodiment 9, annealed for four hours at 700 ° C.
- Fig. 17 SEM image of the surface crystals on the surface of a glass ceramic, according to the tempering of a starting glass
- Embodiment 1 was obtained at 660 ° C for 4 h
- Fig. 18 SEM image of a section through a glass ceramic, through
- Fig. 20A -B surface of a glass ceramic ribbons, ceramized at 700 ° C, then treated in water for 24 h.
- FIG. 21 A -B surface of a glass ceramic ribbons, ceramized at 900 ° C, then treated in water for 24 h.
- a glass was melted from the raw materials.
- the melt was carried out in platinum crucibles at 1550 ° C.
- Table 1 shows the compositions of the starting glasses in% by weight for all of the glass ceramics described below.
- Table 1 Compositions (synthesis values) [% by weight]
- the starting glasses specified in Table 1 are used for the production of glass ceramics, it is found that the glasses according to working examples 2 and 9 already tend to crystallize strongly when the glass melts. It is therefore necessary to cool particularly quickly with these starting glasses. If partial or complete ceramization already occurs during the melting of the glass, the glass ceramic can be subjected to renewed tempering at the temperatures indicated in order to obtain the crystal phases described in this application.
- FIGS. 1-3 show the X-ray diffraction diagrams of starting glasses crystallized in powder form according to embodiment 1 in Table 1, annealed for 5 h at 650 ° C. (FIG. 1), 590 ° C. (FIG. 2) and 560 ° C. (FIG. 3).
- the decrease in intensity of the diffraction orders 1 due to the crystal phases can be clearly seen, which is synonymous with a falling crystal content in the glass ceramic.
- the intensity peaks 1 can For example, Na2CaSi0 4 / Na 2 OCaOSi ⁇ 2 and Na2CaSi 3 08 crystal phases can be assigned.
- Ca silicates can also form at temperatures> 900 ° C.
- FIGS. 4 and 5 show the DTA thermal analysis of initial glass ceramized as a ribbon according to exemplary embodiment 1 in Table 1 (FIG. 4) and initial glass ceramized in powder form (FIG. 5) with heating rates of 10 K / min.
- the crystallization peak 3 for the crystal phase which is shifted to lower temperatures for the starting glass ceramized in the powder, can be clearly seen.
- FIG. 7 shows high-temperature X-ray diagrams for a glass ceramic powder which was obtained from an initial glass according to exemplary embodiment 7 as a function of the temperature. At higher temperatures greater than 900 ° C, recrystallization takes place. , The x-ray measurements were taken while heating up. Ca silicates can also form at these temperatures.
- 2000.1 and 2000.2 denote the Na 2 CaSiO 4 phase that can be assigned according to the JCPDS database
- 2002.1 and 2002.2 denote the Na 2 CaSi 3 ⁇ 8 phase that can be assigned according to the JCPDS database.
- the Na 2 As will be seen from FIG 7 3 8 phase ⁇ formed CaSi only at temperatures above about 900 ° C.
- Table 2 Properties of glass ceramics according to embodiment 1
- Table 3 shows the antibacterial effect of a glass ceramic powder which was annealed for 5 hours at 580 ° C. with a grain size of 4 ⁇ m.
- Table 3 Antibacterial effect of the powders according to Europ. Pharmacopoeia (3rd edition): Embodiment 1 (grain size 4 ⁇ m)
- FIGS. 8-10 show the X-ray diffraction diagrams of starting glasses crystallized in powder form according to embodiment 8 in Table 1, annealed for 4 hours at 560 ° C. (FIG. 8), 700 ° C. (FIG. 9) and 900 ° C. (FIG. 10).
- the phase that can be determined from the intensity peaks is an Na-Ca silicate, specifically Na 6 Ca 3 Si 6 O 8 (JCPDS 77-2189) as the crystalline phase.
- JCPDS 77-2189 Na 6 Ca 3 Si 6 O 8
- FIGS. 11-13 show the X-ray diffraction diagrams of starting glasses crystallized in powder form according to exemplary embodiment 9 in Table 1, annealed for 4 hours at 560 ° C ( Figure 11), 700 ° C ( Figure 12) and 900 ° C ( Figure 13).
- Silicon phosphate SiP 2 O 7 (JCPDS 39-0189) and cristobalite SiO 2 (JCPDS 82-0512) can be identified.
- a further crystalline phase is contained in the samples produced at 700 ° C. and 900 ° C., which are shown in FIGS. 12 and 13, namely silver phosphate AgPO 3 (JCPDS 11-0641). The proportion of this phase is greater in the sample produced at 900 ° C than in the sample produced at 700 ° C.
- FIG. 14 shows the DTA thermal analysis of initial glass ceramized as a ribbon according to working examples 8 and 9 in Table 1 with heating rates of 10 K / min.
- the crystallization peak 3 for the crystal phase can be clearly seen for the exemplary embodiment 8.
- Starting glass according to embodiment example ⁇ Is a glass ceramic that is already crystallizing from the melt.
- a strongly exothermic signal can no longer be observed in the DTA, since the further or recrystallization only releases a little heat. This is due to the fact that the starting glass in this exemplary embodiment tends to spontaneously crystallize when it melts.
- Table 5 shows the antibacterial effect of a glass ceramic powder which, starting from an initial glass according to embodiment 8, was annealed at 560 ° C. with a grain size of 4 ⁇ m.
- Table 5 Antibacterial effect of the powders according to Europ. Pharmacopoeia (3rd
- Example 8 annealed at 560 ° C, (grain size 4 ⁇ m)
- Table 6 shows the antibacterial effect of a glass ceramic powder which, based on a starting glass according to embodiment 9, was annealed at 900 ° C. with a grain size of 4 ⁇ m.
- Table 7 shows the main crystalline phases found in the samples produced in tabular form, the general formula x Na 2 O xy CaO xz SiO 2
- a silicon phosphate phase is found in addition to the Na-Ca phases.
- a silver phosphate phase is found at high temperatures from 700 ° C.
- Table 7 Crystalline main phases of glass ceramics, working examples 8 and 9
- Table 8 shows the pH values and the conductivities of a 1% suspension of a glass ceramic powder, which comprises a base glass according to embodiment 7 in Table 1, for various tempering conditions for the production of the glass ceramic.
- the annealing times and the annealing temperatures are given in the annealing conditions. Depending on the tempering time and tempering temperature, different main crystal phases appear in the glass ceramic.
- Table 8 pH value and conductivity of a glass ceramic powder crystallized from a starting glass according to embodiment 7
- the standardized base strength or standardized conductivity is understood to mean the base strength or conductivity standardized to the surface. This is independent of the actual particle size and considers the conductivity per area (cm 2 ) and mass (g) of the powder.
- Table 9 shows the ionic permeability of non-ceramized powder and glass ceramic powder in 1% suspension which comprises a glass according to embodiment 7 in Table 1 as the starting glass.
- the glass ceramic powder was prepared by annealing at 650 ° C for 4 h.
- the surface crystals on the ribbon are clearly visible. Parts of these surface crystals can be water-soluble, so that when treated with water, these be removed and a honeycomb structure remains. Furthermore, certain phases can be extracted as nanoparticles from this crystalline surface, which are important, among other things, for oral gare applications, ie use of the glass ceramics of the invention in the field of dental and oral care. Furthermore, the crystalline shown in this figure has
- FIG. 17 is a section of FIG. 18.
- the section is designated 3000 in FIG.
- the crystallites formed can be seen in FIG. 18 as round dots.
- the crystals formed in bulk have light-scattering properties which can be used for certain applications.
- crystallization was carried out in the glass block (ribbon). Both FIG. 17 and FIG. 18 show a cross section through the surface of the block or ribbon. 17 is a detail from FIG. 18 and shows in detail the surface,
- FIG. 19 shows the surface of a glass ceramic ribbons which was obtained by ceramizing an initial glass in accordance with exemplary embodiment 1 by tempering at 700 ° C. for 4 h. The glass ceramic was then treated with H 2 O for 15 min. The easily soluble crystalline phases, comprising essentially Na-Ca silicate, are dissolved out. As can be clearly seen in FIG. 19, a “honeycomb” structure remains.
- FIGS. 20A and B show the surface of a glass ceramic powder which was obtained by ceramizing a starting glass according to embodiment 1 by ceramizing at 700 ° C. for 4 h in the powder.
- the surface shown was obtained by the glass ceramic powder being in water for 24 h was treated.
- Surface roughness can also be seen in FIGS. 20A and 28B. As can be seen from the figures, the surface is relatively homogeneous and hardly shows the formation of nanoparticles.
- FIGS. 21A and 21B show the surface of a glass ceramic powder which was obtained in the powder by ceramizing an initial glass in accordance with exemplary embodiment 1 by ceramizing at 900 ° C. for 4 h.
- FIGS. 20A and 20B nanocrystals detached in FIGS. 21A and 21B and a porous structure of the surface can be seen.
- the crystalline nanoparticles are less soluble in water.
- the nanoparticles were formed during the annealing step and have been removed from the surface.
- the extracted nanoparticles include important for oral care applications as they have a desensitizing effect on tooth nerves.
- the densifying effect is achieved by the nanoparticles being able to close the tubulin channels.
- the invention provides for the first time a glass ceramic powder and a glass ceramic that can be used in a large number of areas, for example in the field of cosmetics, nutritional supplements and in the medical field.
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Abstract
L'invention concerne une vitrocéramique, le verre de départ comprenant 30 à 65 % en poids de SiO2, 5 à 30 % en poids de Na2O, 5 à 30 % en poids de CaO, 0 à 15 % en poids de P2O5. Les phases cristallines principales comprennent alcali-alcali terreux-silicate et/ou alcali-silicate et/ou alcali terreux-silicate. L'invention est caractérisée en ce que la vitrocéramique présentant une phase cristalline unique 1 Na2O ? 2 CaO ? 3 SiO2 est exclue, ou la grosseur des cristallites de la vitrocéramique est < à 10 νm, ou la proportion en poids de SiO2 est < à 47 %.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10161074 | 2001-12-12 | ||
DE10161074 | 2001-12-12 | ||
DE10241495 | 2002-09-07 | ||
DE10241495A DE10241495B4 (de) | 2001-12-12 | 2002-09-07 | Antimikrobielle Alkalisilicat-Glaskeramik, Glaskeramikpulver, Verfahren zu dessen Herstellung und Verwendung |
PCT/EP2002/014044 WO2003050051A1 (fr) | 2001-12-12 | 2002-12-11 | Vitroceramique alcali-silicate antimicrobienne et son utilisation |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1453768A1 true EP1453768A1 (fr) | 2004-09-08 |
Family
ID=26010764
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02798328A Withdrawn EP1453768A1 (fr) | 2001-12-12 | 2002-12-11 | Vitroceramique alcali-silicate antimicrobienne et son utilisation |
Country Status (5)
Country | Link |
---|---|
US (1) | US7141520B2 (fr) |
EP (1) | EP1453768A1 (fr) |
CN (1) | CN1599702A (fr) |
AU (1) | AU2002363868A1 (fr) |
WO (1) | WO2003050051A1 (fr) |
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US7597900B2 (en) * | 2001-03-27 | 2009-10-06 | Schott Ag | Tissue abrasives |
US7141520B2 (en) * | 2001-12-12 | 2006-11-28 | Schott Ag | Antimicrobial alkali-silicate glass ceramic and the use thereof |
SG103933A1 (en) * | 2002-07-15 | 2004-05-26 | Pentax Corp | Cao-sio2-based bioactive glass and sintered calcium phosphate glass using same |
JP3793532B2 (ja) * | 2003-10-14 | 2006-07-05 | ペンタックス株式会社 | CaO−MgO−SiO2系生体活性ガラス及びそれを用いたリン酸カルシウム焼結体 |
DE102004026433A1 (de) * | 2004-05-29 | 2005-12-22 | Schott Ag | Nanoglaspulver und deren Verwendung |
US7754194B2 (en) * | 2005-04-06 | 2010-07-13 | L'oréal | Hair relaxer compositions utilizing bioactive glass |
US20070258916A1 (en) * | 2006-04-14 | 2007-11-08 | Oregon Health & Science University | Oral compositions for treating tooth hypersensitivity |
US8063754B2 (en) * | 2006-12-15 | 2011-11-22 | Honda Motor Co., Ltd. | Vehicle state information transmission apparatus using tactile device |
WO2011038312A1 (fr) * | 2009-09-28 | 2011-03-31 | E. I. Du Pont De Nemours And Company | Poudres de particules de verre cristallin comprenant un composant de verre et un composant cristallin |
US8545733B2 (en) * | 2009-09-28 | 2013-10-01 | E I Du Pont De Nemours And Company | Methods of making glass-crystalline particles including a glass component and a crystalline component |
WO2011038311A1 (fr) * | 2009-09-28 | 2011-03-31 | E. I. Du Pont De Nemours And Company | Particules vitreuses-cristallines comprenant un composant vitreux et un composant cristallin |
KR101034685B1 (ko) * | 2010-01-28 | 2011-05-16 | 주식회사 금비 | 식품, 막걸리 보관용 항균성 유리 |
ES2406354B1 (es) | 2011-09-20 | 2014-04-09 | Consejo Superior De Investigaciones Científicas (Csic) - | Combinación y procedimiento de obtención de esmaltes cerámicos bactericidas para productos cerámicos |
EP2765856A1 (fr) * | 2011-10-12 | 2014-08-20 | Corning Incorporated | Vitrocéramiques antimicrobiennes |
KR101174402B1 (ko) | 2012-05-30 | 2012-08-16 | 주식회사 휴코텍 | 항균유리 제조방법 및 그에 의하여 제조되는 항균유리 |
US20140031949A1 (en) * | 2012-06-27 | 2014-01-30 | Signal Medical Corporation | Ceramic antibacterial |
CN104072841A (zh) * | 2013-03-25 | 2014-10-01 | 北京工业大学 | 一种长效抑菌塑片及制作方法 |
CN104074231B (zh) * | 2013-03-25 | 2016-04-27 | 北京工业大学 | 一种应急避难场所应急净水供水装置及供水方法 |
CN104650908A (zh) * | 2015-02-11 | 2015-05-27 | 浙江科技学院 | Led用红色荧光粉及其制备方法 |
CN106746675B (zh) * | 2017-02-10 | 2019-04-26 | 长春理工大学 | 高强度抑菌抗菌二硅酸锂玻璃陶瓷及其制备方法 |
CN107235634A (zh) * | 2017-07-06 | 2017-10-10 | 江西草珊瑚口腔护理用品有限公司 | 一种生物活性玻璃陶瓷材料及其制备方法和一种牙膏 |
US10273183B2 (en) * | 2017-07-14 | 2019-04-30 | Owens-Brockway Glass Container Inc. | Soda-lime-silica glass-ceramic |
US10399886B2 (en) | 2017-07-14 | 2019-09-03 | Owens-Brockway Glass Container Inc. | Feedstock gel and method of making glass-ceramic articles from the feedstock gel |
WO2020112404A1 (fr) * | 2018-11-26 | 2020-06-04 | Corning Incorporated | Verres bioactifs au silicate |
CN112390528A (zh) | 2019-08-13 | 2021-02-23 | 康宁股份有限公司 | 生物活性玻璃组合物 |
CN110937807A (zh) * | 2019-12-02 | 2020-03-31 | 陈果 | 高强度抗菌玻璃及其制备方法 |
CN111919857A (zh) * | 2020-08-12 | 2020-11-13 | 高时(厦门)石业有限公司 | 杀菌粉的制备方法、其杀菌粉及使用其的抗菌无机人造石 |
EP4201900A3 (fr) | 2021-12-23 | 2023-07-05 | Ivoclar Vivadent AG | Vitrocéramique à base de silicate de lithium et contenant de l'étain |
EP4201901A3 (fr) | 2021-12-23 | 2023-07-12 | Ivoclar Vivadent AG | Vitrocéramique à base de silicate de lithium et contenant du cuivre |
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US7141520B2 (en) * | 2001-12-12 | 2006-11-28 | Schott Ag | Antimicrobial alkali-silicate glass ceramic and the use thereof |
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2002
- 2002-12-11 US US10/498,244 patent/US7141520B2/en not_active Expired - Lifetime
- 2002-12-11 AU AU2002363868A patent/AU2002363868A1/en not_active Abandoned
- 2002-12-11 CN CNA028242653A patent/CN1599702A/zh active Pending
- 2002-12-11 WO PCT/EP2002/014044 patent/WO2003050051A1/fr active Application Filing
- 2002-12-11 EP EP02798328A patent/EP1453768A1/fr not_active Withdrawn
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US20050009682A1 (en) | 2005-01-13 |
CN1599702A (zh) | 2005-03-23 |
AU2002363868A1 (en) | 2003-06-23 |
WO2003050051A1 (fr) | 2003-06-19 |
US7141520B2 (en) | 2006-11-28 |
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