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EP1852497A1 - Couche antimicrobienne et son utilisation - Google Patents

Couche antimicrobienne et son utilisation Download PDF

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Publication number
EP1852497A1
EP1852497A1 EP20060015057 EP06015057A EP1852497A1 EP 1852497 A1 EP1852497 A1 EP 1852497A1 EP 20060015057 EP20060015057 EP 20060015057 EP 06015057 A EP06015057 A EP 06015057A EP 1852497 A1 EP1852497 A1 EP 1852497A1
Authority
EP
European Patent Office
Prior art keywords
silver
layer
substance
carrier medium
layer according
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Withdrawn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
EP20060015057
Other languages
German (de)
English (en)
Inventor
Thomas RÜHLE
Dirk W. Schubert
Jürgen Henke
Achim Gruber
Judith Haller
Thomas Schindler
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.)
Carl Freudenberg KG
Original Assignee
Carl Freudenberg KG
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
Application filed by Carl Freudenberg KG filed Critical Carl Freudenberg KG
Priority to PCT/EP2007/001475 priority Critical patent/WO2007124800A1/fr
Publication of EP1852497A1 publication Critical patent/EP1852497A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/049—Cleaning or scouring pads; Wipes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/4935—Impregnated naturally solid product [e.g., leather, stone, etc.]

Definitions

  • the invention relates to a layer comprising a carrier medium, wherein the carrier medium is associated with at least one antimicrobial substance.
  • the invention further relates to the use of a layer as a cleaning article or in a cleaning article.
  • Layers and cleaning articles are known from the prior art which comprise a carrier medium to which an antimicrobial substance is assigned.
  • an antimicrobial substance acts antibacterial, antiviral, antifungal and / or against spores.
  • the invention is therefore based on the object to provide a layer of the type mentioned, which is characterized by a high reactivity of the antimicrobial substance.
  • the above object is achieved with the features of claim 1.
  • the antimicrobial substance is present colloidally and / or nanoscale.
  • a colloidally and / or nanoscale substance exhibits a particularly high reactivity when the substance is brought into contact with bacteria, viruses, fungi or spores. Furthermore, it has been recognized that the layer according to the invention very easily delivers the acting substance to media which come into contact with the layer. In that regard, the situation according to the invention is characterized by a high dispensability with respect to the antimicrobial substance.
  • Colloids are disperse systems in which substances are distributed in a dispersion medium such that their particles have an extent of from 10 to 1000 angstroms in at least one spatial direction and consist of from 10 3 to 10 9 atoms.
  • Nanoscale structures are understood to mean regions of any morphology that have dimensions in the nanometer range, at least in one spatial direction.
  • Colloids are an intermediate state of heterogeneous and homogeneous mixtures.
  • the ratio of interface to volume is at colloidal and nanoscale structures very high, whereby a high reactivity is ensured.
  • the colloidal distribution also allows easy diffusion or dissolution of the particles from a carrier medium.
  • the antimicrobial substance can show a high mobility and neutralize bacteria or viruses and spores effectively and quickly or kill.
  • the particle shape, the particle size, the layer thickness and the degree of coverage of the antimicrobial substance can be adjusted by subsequent treatment of the deposited substance particles.
  • the temporal release profile and thus the reactivity of the antimicrobial substance is precisely adjustable.
  • the substance could be distributed in the carrier medium.
  • the entire effectively effective surface could be covered with the substance.
  • the antimicrobial substance is distributed homogeneously over the entire layer. This causes the fabric to be effective at all interfaces of the layer.
  • the substance could be distributed in a layer applied to the carrier medium or assigned to such a layer. It is conceivable that the substance is colloidally distributed both in the carrier medium and the carrier medium is also provided with a coating which comprises the substance colloidally or in non-colloidal state. By this combination, a particularly long-lasting antimicrobial effect of the situation is feasible, since first the substances from the carrier medium are effective before the coating is removed.
  • a printing paste could act.
  • the provision of a printing paste allows a particularly cost-effective production process. As a result, process costs, as they arise, for example, during vapor deposition of the active substance, effectively avoided.
  • the layer could be interrupted at least in certain areas or consist of non-coherent partial layers.
  • coherent layers the substance can not be sufficiently mobilized due to closed surfaces and therefore can not freely develop its reactivity. Interruptions of the layer result in edge areas where the antimicrobial substance is significantly more reactive and thus faster mobilizable.
  • the formation of partial layers also causes a variety of edges and fissures, where the effect described can occur.
  • the layer or the partial layers could be formed as island structures.
  • the formation of island structures could be achieved by sputter deposition. In this method, a substrate is brought into the vicinity of a target, so that atoms knocked out of the target can condense on the substrate and form a layer. The ejected atoms are atoms of the antimicrobial substance. Island structures can be formed by this method. The islands form clusters or monoclusters. These island structures in their entirety show a very large surface area, forming a multiplicity of edges, at which molecules or atoms of the antimicrobial substance are mobilized sufficiently quickly can, for example, interact with bacteria and neutralize or kill them.
  • the layer by means of a silver-containing printing paste.
  • the printing paste could comprise a silver dispersion.
  • This specific embodiment allows cost-effective application of patterns, letters or symbols to give the consumer an indication of the technical use of the situation. Letters, symbols or patterns must often be applied to indicate their intended use.
  • no separate coating of the layer is necessary because the patterns or symbols themselves can act as an antimicrobial layer.
  • the application of the layer takes place wet-chemically by impregnation with a silver precursor and subsequent conversion of the precursor into metallic silver.
  • silver precursors silver nitrate (AgNO3), silver sulfate (AgSO4) 2, organometallic complexes or metallocenes can function.
  • AgNO3 silver nitrate
  • AgSO4 silver sulfate
  • organometallic complexes or metallocenes can function.
  • the use of these silver precursors permits locally selective creation of zones and regions, optionally through masks or templates in which the silver is metallic. In the remaining areas, if necessary after removal of a mask or stencil, the silver precursor is still present.
  • Impregnate a layer with a silver dispersion or a cleansing lotion comprising a silver dispersion can then be dried or used in the wet state, for example as a disposable cleaning article. Impregnation is a cost effective and rapidly practicable method of applying silver to a layer.
  • the layer or sub-layers could have a thickness of 0.05 to 1000 nm. This layer thickness range has proved to be particularly advantageous in order to realize sufficient mobility of the atoms or molecules of an antibacterial and / or antimicrobial or antimycotic substance.
  • the layer or the partial layers could have a surface density of 5-1000 mg / m 2 .
  • This loading is just enough for a few applications so that it can be used as a disposable or disposable item.
  • the carrier medium could comprise fibers.
  • the carrier medium provides a fissured surface for the attachment of antimicrobial substances.
  • layers of the active substance which are deposited on the carrier medium are subjected to a fracture.
  • the active substance could be increasingly assigned to individual fiber types, with other fiber types having a significantly lower occupancy by the active substance.
  • the zerklwestungs bin is still increased.
  • the nanoscale and / or colloidal structures of the substance could preferably be deposited on hydrophobic, in particular polyolefinic, fibers of a nonwoven, with hydrophilic, in particular viscose, fibers being largely free of material. This makes it possible, on a nonwoven fabric comprising a fiber mixture, to selectively deposit the active substance on a specific type of fiber. The fracture of the fabric layer or the fabric occupancy then results from the fiber structure of the support medium.
  • the carrier medium could comprise a nonwoven fabric.
  • the use of a nonwoven fabric allows adjustment of porosity by appropriate selection of fiber density or fiber thicknesses. It is conceivable that the nonwoven fabric is also constructed of nanofibers, which ensure a very small pore size. Nanofibers usually have a diameter which is less than 1 ⁇ m and preferably between 50 and 500 nm. By using nanofibers, the fracture effect described above can be increased even more.
  • nonwovens are characterized by a high absorbency and can therefore act as cleaning wipes, which absorb liquids.
  • such wipes could comprise multi-ply nonwovens, where each ply could have a different pore size, fibrous material, or other average fiber diameter.
  • at least one layer could comprise split fibers. This type of fiber can be easily split and / or solidified by water jet treatment. At least one layer could comprise staple fibers or continuous fibers. These types of fibers can be easily solidified by water jet treatment and / or devour each other.
  • the carrier medium could comprise polymers.
  • thermoplastics such as polypropylene, polyethylene or polyester and polyamide are used. These materials are particularly suitable for the production of fiber-containing nonwovens, since the existing of these polymers fibers can be fused together by thermal action and thus firmly connected. This allows the consolidation of knitted fabrics from fibers.
  • Polypropylene and polyethylene are particularly suitable for the addition of silver.
  • Silver can be easily attached to polypropylene or polyethylene and forms a firm bond with these materials.
  • Sputtering in particular allows silver to be easily deposited on these materials.
  • a firm bond results from van der Waals forces or a chemical bond Binding.
  • Thermal or plasma treatment of polypropylene and / or polyethylene activates their surfaces and improves the adhesion of silver to the surfaces.
  • the carrier medium could be configured as a reusable latex glove. This embodiment advantageously allows the use of existing products and their cost-effective equipment with antimicrobial substances.
  • the carrier medium could include chitosans and / or cyclodextrins. These materials have proven to be particularly suitable for the incorporation of colloidal silver and other substances, such as fragrances.
  • fragrances could be assigned to the carrier medium.
  • bad odors can be neutralized, absorbed or suppressed or covered.
  • the chitosans and / or cyclodextrins can be exposed to silver and / or fragrances and fixed on the actual carrier medium.
  • the chitosans and / or cyclodextrins allow a targeted and long-lasting release of embedded colloidal silver or of stored fragrances.
  • Metallic silver which is not in ionic form, could be deposited in sheet silicates or zeolites. It is advantageous that the silver can be present in the form of nanoclusters in channel structures of the layered silicates or of the zeolites. At the edge of these channel structures, silver oxide is initially formed, which is diffused away and converted into ionic silver. Then, the next layer of a nanocluster is converted to silver oxide, repeating the process described above. As a result, a depot effect can be achieved in which defined over a long period of time and targeted ionic silver can be released.
  • a silver salt solution in particular an aqueous silver nitrate solution, is produced.
  • the zeolite or the carrier medium is impregnated with the solution. This is followed by a two-stage thermal treatment. First, the silver salt is converted to silver oxide under an atmospheric oxygen atmosphere. The silver oxide is reduced to metallic silver under a hydrogen atmosphere. Thus, there is then within the pores of the layered silicate metallic silver.
  • This concrete method enables a particularly homogeneous and uniform distribution of metallic silver within very fine channel structures. Depending on the pore size or the channel diameter, different sized clusters of metallic silver can be formed. In that regard, a polymodal distribution of nanoscale silver structures within a layered silicate is possible.
  • fragrance molecules colloidal silver is incorporated into the cyclodextrins and chitosans.
  • silver exits and in return odors are trapped by the resulting gaps in the cyclodextrins and chitosans. This embodiment allows a saving of expensive fragrances.
  • the antimicrobial agent could comprise silver.
  • Silver is particularly useful as an antimicrobial agent because it is virtually non-toxic to humans. Furthermore, silver has a relatively low allergenic potential. Silver acts as an antiseptic substance in low concentrations over a long period on a variety of infectious agents. In addition, most known bacteria show no resistance to silver.
  • the substance could comprise at least one sub-group element.
  • Subgroup elements are distinguished by antimicrobial action. Against this background, it is conceivable that several subgroup elements are present together in the layers and / or the carrier medium in order to selectively counteract different bacterial species. It has been shown in test series that there is a ranking of the substances used in terms of antimicrobial effectiveness. This can be represented as follows. Silver is the most effective substance, followed by mercury, copper, cadmium, chromium, lead, cobalt, gold, zinc, iron and finally manganese. against this background, it is conceivable to use also main group elements which show an antimicrobial effect.
  • the antimicrobial agent could comprise a gold-silver mixture or consist solely of a gold-silver mixture. Mixtures of this type show a particularly high antimicrobial activity. It has surprisingly been found that the presence of gold further enhances the antimicrobial effect of silver. Against this background, it is conceivable to dope silver with gold. It is also conceivable to form islands or clusters that comprise either only gold or only silver but also mixtures of these substances. In this case, islands or clusters of different composition can coexist.
  • the substance could be aluminum mixed.
  • aluminum causes brightening and / or improved appearance of the coating, since silver, for example, turns brown as a result of oxidation processes. This leads to an ugly appearance of the coating or the entire situation.
  • Aluminum also causes a modification of the release rate of the antimicrobial agent.
  • the substance could be the subject of a supported system. This is understood to mean a system in which the actually antimicrobial substance is assigned to carrier substrates.
  • the support substrates may be carbon blacks or oxides. Due to the attachment of material particles to carrier substrates, it is ensured that the individual substance particles do not agglomerate. As a result, the reactivity of the active substance is significantly improved.
  • the carrier substrates themselves can be assigned to the actual carrier medium.
  • the layer could be provided with a plasma coating.
  • a plasma coating is a production process in which materials are coated with thin layers, which are extracted from a plasma by the action of an electrical voltage.
  • a workpiece to be treated is introduced after a very thorough cleaning in a vacuum chamber and fixed there.
  • the chamber is evacuated until a residual gas pressure in the high vacuum or ultrahigh vacuum is reached.
  • a working gas usually argon, admitted and ignited by various methods of energy input, such as microwaves, high frequency, electrical discharge, a low-pressure plasma.
  • a layer described here as a cleaning article or in a cleaning article is particularly advantageous since the antimicrobial substance has a high reactivity and the layer shows a high fabric release capacity.
  • the layer according to the invention it is therefore particularly ensured that the antimicrobial substance remains on a cleaned surface. As a result, a long-lasting and lasting disinfecting and cleaning effect is achieved.
  • the cleaning article is configured as a cleaning cloth, in particular as a disposable cleaning cloth. Due to the extremely low loading with antimicrobial substance, its effect may be exhausted after one or a few uses of the cleaning cloth.
  • the design of a cleaning cloth as a disposable cleaning cloth is particularly cost-effective, since the usually very expensive antimicrobial substances can be applied extremely finely dosed.
  • Disposable cleaning wipes have the advantage over multiple wipes that they can not form a source of contamination after a single use because they are disposed of immediately after use.
  • Multi-purpose wipes are more expensive than disposable wipes because they include more antimicrobial fabric. Nevertheless, multiple wipes can not be used in proportion to the amount of antimicrobial agent, as they are often no longer functional due to contamination after relatively few cycles of use.
  • a mop usually comprises textile strips which serve to absorb liquid. These strips could be formed by the layers according to the invention. This specific embodiment allows the use of the antimicrobial substance in hospitals, nursing homes and other places, such as in commercial kitchens, in which undesirable bacteria can form on the floor.
  • the layer is configured as a nonwoven fabric, woven fabric, knitted fabric, knitted fabric or yarn.
  • a nonwoven fabric is advantageous in terms of adjustable porosity.
  • Fabrics and knits are characterized by a high mechanical stability and can have different types of fibers in mixture.
  • the use of different types of fibers, namely fibers of different materials, allows the selective attachment of the active substance to individual fibers.
  • Yarns are advantageous when the situation in mops, especially loop mops, is used. The yarns replace the previously described strips.
  • the layer is designed as a film.
  • the layer is designed as a cling film or packaging film for food.
  • the coating of the layer with antimicrobial substances effectively allows the suppression of bacterial growth, which can spoil food.
  • the carrier medium is designed as a foam body.
  • the interior of the foam body is impregnated with the antimicrobial active substance.
  • the foam body could be used as a cleaning sponge. This ensures that liquid absorbed by a foam body is disinfected or that the growth taking place in it is inhibited by bacteria. This is advantageous when the foam body is used as a sponge in food-related areas such as counters or tables in restaurants.
  • hygienic conditions can be easily improved, i. Bacterial growth can be suppressed or in extreme cases a bactericide be achieved.
  • the layers described here can be used in almost all hygiene or cosmetic products due to their antimicrobial effect.
  • baby wipes, diapers, wipes, facial tissues or products for incontinence patients are conceivable.
  • microbiologically active silver ions are formed as silver oxide on the nanoparticle surface by the action of atmospheric oxygen and moisture from the environment.
  • the oxide layer itself has a substantially constant thickness regardless of the particle size. This means that the microbiologically effective volume of the total volume increases significantly with decreasing particle size.
  • Nanoscale silver can be used to equip materials that would otherwise be inaccessible to silver equipment. So can grosspartteilige For example, silver particles may not be spun in all polymer fibers because the nozzles become clogged.
  • thermoplastics and elastomers there are basically two ways of application:
  • nanoscale silver to a substrate surface chemically or by vapor deposition. Since the silver sits here on the surface, it can act very quickly. In addition, the morphology (shape, size) of the silver nanostructures allows the silver release profile to be set very well.
  • nanoscale silver is compounded with other fillers at the same time.
  • concentrations of 500-2000 ppm of silver may be necessary here for a sufficient effect.
  • a part of the silver is not accessible in the volume.
  • the effect is delayed because the silver must first diffuse to the polymer surface.
  • the nonwoven comprises polymeric fibers.
  • the nonwoven fabric further contains natural fibers, namely cellulose fibers. Concretely, nonwoven fabrics containing viscose, polypropylene and polyethylene terephthalate fibers in mixture have been used.
  • Sample 2 has a silver loading of 10.5 mg / m 2 .
  • Samples 3 to 6 each have 29.4; 56.7; 115.5 and 231 mg / m 2 silver loading on.
  • Sample 1 has no silver loading and represents a so-called blank.
  • the carrier medium has an antimicrobial active substance silver, which is colloidal and / or nanoscale. This is accomplished by creating substantially cuboid nanoparticle island structures of silver with an edge length in the range of 5 nm.
  • the island structures formed on the carrier medium have a specific surface area which is larger than the surface of a closed nanolayer with a thickness of 5 nm.
  • the cuboid island structures were detected by SIMS.
  • the nanoscale and / or colloidal silver structures are preferably deposited on the polyolefinic fibers of the nonwoven fabric used.
  • the viscous fibers are largely free of silver. This makes it possible, on a nonwoven fabric comprising a fiber mixture, to selectively deposit silver on a specific type of fiber.
  • the size of the islands and the width of their size distribution can be controlled.
  • the specific surface and thus the release profile of the antimicrobial silver is adjustable.
  • polymodal distributed nanostructures can be generated by targeted adjustment of the process parameters. These each have a different number of unsaturated surface atoms. As a result, they have a different reactivity or microbiological activity.
  • Samples 1 to 6 were subjected to an antimicrobial finish test according to the well-known AATCC Method 100, which is used on textile materials.
  • Table 1 shows the kill rate of Escherichia coli cells as a function of silver loading.
  • Table 1 the silver loading in mg / m 2 is plotted in the first column.
  • the second column of the table shows the number of bacteria in the unit CFU / ml (colony forming units / ml) after 24 hours and the third column shows the kill rate after 24 hours in percent.
  • the fourth and fifth columns are constructed analogously.
  • Table 2 shows the results of a microbiological test conducted on spores of the Aspergillus niger type on Samples 1-6. Samples 1 to 6 served as a pattern for dishcloths (dishcloth pattern).
  • Aspergillus niger is also called black mold because of its dark spores. Aspergillus niger is a widespread food spoiler and material destroyer. He is found worldwide in the ground. This fungus can destroy paper and packaging, as well as leather and paint, and even plastics and optical glasses. Diseases caused by Aspergillus niger include, in addition to allergic reactions, infections of the external auditory canal, lung aspergillosis, peritonitis, inflammation of the inner lining of the skin, diseases of the nails and infections of the skin.
  • the first column of Table 2 shows the silver loading in mg / m 2 .
  • the second column indicates by the size B qualitatively, whether the respective sample is overgrown with spores after two days.
  • the third column indicates by analogy whether the sample is overgrown after four days. (B) expresses only qualitatively that the
  • the samples designed as cloths were stored at 32 ° C. for 48 hours in 100 ml of 10% milk solutions. Subsequently, the samples were taken out and dried. The milk solutions and the dried and re-wetted with 100 ul of water after drying them were evaluated olfactometrically.
  • Table 3 shows the results of the evaluation.
  • the samples 1 to 6 with a size of 2.5 x 5 cm were stored in each 100 ml of water with pH values of 3, 7 and 11 and the silver concentration was determined. It was found that within the first hour of storage time the delivery rate is the highest. The antibacterial effect is therefore very quickly effective, so that after 24 hours already a complete kill of bacteria can be achieved. Nevertheless, a moderate delivery is observed even after the first hour, which also ensures a medium to long-term effect.
  • a reference sample with a silver loading of 55 mg / m 2 was subjected to two full standard washes with a commercially available washing machine and commercially available washing powder. After the first wash, about 30% of the silver was still on the cloth. After the second wash, about 30% of the silver was still on the cloth. After the second wash, kill rates of up to 91.17% for Escherichia coli bacteria and 99.33% for Staphylococcus aureus bacteria could still be detected on the cloth.
  • Table 4 shows the results of a test in which glass sheets were treated with different samples.
  • Layers with a carrier medium of nonwoven fabric were soaked with a nano-silver dispersants. These layers served as wipes for the disinfection of glass panes.
  • silver is colloidally dispersed on the support medium. The silver is homogeneously distributed in the carrier medium.
  • This standard floor cleaner was applied to 10 x 10 cm samples, which were overlaid for about 17 hrs. Overnight in a test tube at room temperature. After 17 hours each sample was divided.
  • glass wafers were wiped with Type B (cloth) samples, which were steamed with 120 mg / m 2 of silver.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Apparatus For Disinfection Or Sterilisation (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
EP20060015057 2006-05-03 2006-07-19 Couche antimicrobienne et son utilisation Withdrawn EP1852497A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2007/001475 WO2007124800A1 (fr) 2006-05-03 2007-02-21 Linge à effet antimicrobien et utilisation de ce linge

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102006020791 2006-05-03

Publications (1)

Publication Number Publication Date
EP1852497A1 true EP1852497A1 (fr) 2007-11-07

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US (1) US20070259196A1 (fr)
EP (1) EP1852497A1 (fr)

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DE102009023459B4 (de) * 2009-06-02 2017-08-31 Aap Implantate Ag Osteosynthese mit Nanosilber
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GB2511528A (en) 2013-03-06 2014-09-10 Speciality Fibres And Materials Ltd Absorbent materials
CN104695209A (zh) * 2013-12-05 2015-06-10 江南大学 一种新型抗菌纺织面料的制备方法
CN104727139A (zh) * 2013-12-20 2015-06-24 江南大学 一种抗电磁辐射新型纺织面料及其制备方法

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WO2001094687A2 (fr) * 2000-06-02 2001-12-13 Milliken & Company Fils et tissus presentant un appret a base metallique, a application topique, non electroconducteurs et resistants au lavage
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* Cited by examiner, † Cited by third party
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EP4201204A1 (fr) * 2021-12-21 2023-06-28 Atomos Master Key GmbH Objet antibactérien et son procédé de fabrication
WO2023117348A1 (fr) * 2021-12-21 2023-06-29 Atomos Master Key Gmbh Objet antibactérien et son procédé de production

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