Antimicrobial aqueous dispersions, useful e.g. for treating medical equipment, are obtained by mixing aqueous dispersions of polymer and metal or metal compound

The Invention relates to a process for the preparation of an antimicrobially acting aqueous dispersion, a solid intermediate product produced therefrom as well as a antimicrobial plastic object that with such methods producible products and their use.

It are, for example from <patcit><text>DE 10331324 A1</text></patcit> various metals and metal compounds known the antimicrobial effect. It also highlights plastic products for the described medical needs that such antimicrobial metals and metal compounds. There are slurries colloidal metals mixed with sparingly soluble metal salts either applied directly to plastics, but what unsatisfactory to Efficacy results, or the admixture is to support materials such as barium sulfate applied and then processed elaborately and in the plastic incorporated.

In <patcit><text>WO 03/080231</text></patcit> is a method for the preparation of silver nanoparticles using water-soluble Polymers described for colloid stabilization. The polymers all concern water-soluble Substances, which are added in small amounts. On the use of silver nanoparticles in sprays and glue is pointed. On A process for producing silver nanoparticles containing water-insoluble polymer or plastics is not mentioned.

In <patcit><text>DE 10351611</text></patcit> is a method for the preparation of silver-containing liquid phases nanoscaligem high purity for the antimicrobial application described. In<patcit><text>DE 10359338</text></patcit> describes the preparation of a silver nanoparticle-containing polymerizable dental material describe. The incorporation of silver nanoparticles in a complex Kneading performed. In <patcit><text>DE 10315720</text></patcit> are antimicrobial coatings with nanoscale silver particles and a varnish base listed. A description or a method for preparing the coating formulations is not specified.

It Therefore, there is a need for a simple and cost-effective A process for the manufacture of plastic products, the nanoscale Particles of antimicrobial metals or metal compounds contain.

moreover , the products according to the prior art nor a satisfactory reproducible effect on behavior, which manifests itself in the fact that the antimicrobial effect of production lot to production lot can vary significantly.

task the invention is thus to provide a simple and cost-effective A process for the manufacture of plastic products, the nanoscale Particles of antimicrobial metals or metal compounds to find containing that the disadvantages of the prior art not having.

The The method according to the invention is first therein, an aqueous Dispersing nanoscale particles of antimicrobial metals or metal compounds with an aqueous dispersion of an addition polymerization, Polycondensation or polyaddition product mix down. The thereby forming aqueous Dispersion of antimicrobial modified latex can directly for coating purposes be used and only then is dried. The drying can be but also take place directly after mixing. The finished coating or the finished plastic product according to the invention is represented by obtained simply by heating after drying, and has a very good reproducibility on the antimicrobial activity behavior.

The objects of the invention and its preferred embodiments are defined in independent and the dependent of claims described.

object of the present invention is a method for preparing a antimicrobial aqueous Dispersion, characterized in that i) an aqueous dispersion of nanoscale particles of antimicrobial metals or metal compounds with an aqueous Dispersion of a polymerization, polycondensation or polyaddition is mixed.

object The invention also provides an antimicrobial aqueous dispersion, characterized in that it comprises nanoscale particles antimicrobially acting metals or metal compounds and particles of a polymerization, Polycondensation or polyaddition product comprises and preferably is prepared by the method described above.

Of the dispersion can yet added according to the intended use of other additives are, for example, to their durability, dispersion stability, odor or altering appearance. To improve the dispersion stability can preferably ionic or nonionic surfactants such as alkylsulfonates, arylsulfonates, alkylarylsulfonates, added alkyl polyethylene oxides, ethylene oxide propylenxoidblockcopolymere will.

In a preferred embodiment, of the present invention, the dispersion of a paint, a varnish, a primer or a wood preservative added, so appropriate it&lt;?page 3?&gt;inventive products with antimicrobial to obtain effect.

A aqueous Dispersion according to the invention is a dispersion phase as an external contains as a main ingredient water. The water may be less than 50 wt .-%, preferably less than 20 wt .-% water miscible organic solvents such as Methanol, ethanol, i-propanol, n-propanol, acetone, tetrahydrofuran, Dioxane, dimethylformamide, N-methylpyrrolidone or Formanid.

The Polymer dispersions may high-boiling or low-boiling water-insoluble solvents. The high boiling solvent be in an amount of 0.01 to 50 wt .-%, based on the polymer, used. Particularly preferred is a range of 0.1-30 wt .-%. examples for high-boiling solvents are phthalates such as dibutyl phthalate, dinonyl, phthalate, phosphoric esters as tricresyl phosphate, adipic as adipate, Adipate. The low boiling solvent be in an amount of 0.01 to 100 wt .-%, based on the polymer, used. Particularly preferred is a range of 1.0 to 50% by weight. The low boiling solvent preferably only during the the inventive method for the production of nanoscale silver or silver halide containing polymerization, polycondensation or polyaddition used. They are in the drying process together with the water removed. examples for low boiling solvents are n-hexane, n-heptane, cyclohexane, ethyl acetate, methyl acetate, methylene chloride, methanol, Ethanol, isopropanol, dioxane, acetonitrile, tetrahydrofuran, chloroform, Benzene, toluene. The use of mixtures of low- and high-boiling Mixtures is possible.

The weight ratio of nanoscale particles of antimicrobial metals or Metal compounds to the polymerization, polycondensation or Polyaddition can vary within wide ranges. Prefers is a weight ratio of antimicrobial metals or metal compounds to Polymer from 0.1 to 10^-10 1 and particularly preferably a ratio of 10^-2 until 10^-6 to 1.

The dispersion of the invention as can for Coating purposes are used to with conventional and Methods on any object be applied. Thus, eg medical equipment by conventional Methods such as spraying, Dipping or brushing and antimicrobial coating as follows described by simple drying and heating with an efficient antimicrobial protection are provided.

Advantageous can also objects daily Use, such as door- and window handles, light switches, railings, keyboards, toilet lids, Toilet brushes, Shower fittings, telephone receivers, Children's toys, particularly plastic toys, films, fibers, Fabrics, textiles or other frequently touched surfaces with a protection according to the present Plated invention , whereby a stubborn counteracted adherence of pathogens on surfaces becomes. This avoids especially in public areas such as eg in toilets, and especially in swimming pools and Hospitals, a significant risk of infection and can be a regular and necessary disinfection replace or at least reduce its necessary frequency or less aggressive disinfectants allow.

in the Construction, the dispersion of the invention is advantageous for fight and prevention of mold used by the walls or Wallcoverings with the dispersion of the invention are treated. Advantageously also sealants, roofing tiles and insulation materials so antimicrobial equipped.

furthermore it is advantageous to container and equipment for the Crop production and generally sanitized held vessel as z. B. Petri dishes using the dispersion of the invention antimicrobial equip.

Around from the dispersion of the invention a Plastic article or a plastic coating according to the present to obtain invention is first the water from the dispersion such an extent that a water content of at most 20 wt .-%, preferably of at most 10 wt .-%, more preferably of 5 wt .-% and in particular of at most 1 wt .-% remains. The Removal of the water is preferably by distillation or Drying such as convection drying, radiation drying, Belt drying, spray drying or freeze-drying performed.

The to be obtained from the dispersion as solid intermediate is also an object of the present invention and can for later use stored or directly further processed to a plastic object will. It is also possible, to obtain the intermediate product in powder form and for coating purposes apply in this form or at first in water or solvents, where it is not soluble, or only to a small extent, again suspend. In addition, the solid intermediate can be converted to melting in a granulate and in this form &lt;?page 4?&gt;be stored and processed.

In a preferred embodiment, of the present invention, the solid intermediate in addition the polymerization of the invention, Polycondensation or polyaddition product have at least one further on plastic, which already added to the aqueous dispersion and can be left after drying them in an intermediate. Preferably, however, the more plastic is the first obtained solid intermediate product is mixed to a preferred intermediate to obtain. The further plastic is preferably not with antimicrobial loaded and made possible by the blending acting particles a more precise adjustment of the antimicrobial action.

As for the described dispersion can also the solid intermediate in accordance with the intended use further additives are added, for example, its durability, Further processing, odor or changing appearance.

In a further preferred embodiment of the present invention, the solid intermediate product a Paint, a varnish, a primer, one or a wood preservative added to as corresponding products according to the invention with antimicrobial to obtain effect. In aqueous the intermediate product is preferably in paint formulations solid powder form dispersed in the paint or An aqueous Dispersing nanoscale particles of antimicrobial metals or metal compounds with the paint stirred waterborne. at Paints, solvent-based the intermediate is dissolved directly in the paint or previously in an organic solvent or solvent mixture dissolved and then stirred with the paint. Here, a convenient solvent or solvent mixture used, which is included in the paint.

For the solid Intermediate according to the present Invention and its preparations are, for example, the same Areas of application in question that described above for the dispersion were.

Out the solid intermediate product is a plastic or a plastic object or a plastic coating according to the present invention obtained by subjecting the intermediate product is subjected to conditions which are at least partially coalesced.

Has been Intermediate admixed another plastic, for example in The form of granules, the plastic article and the plastic coating can also in the for Additional plastic usual Processing can be made, especially if the further plastic predominates. Preferably, a granulate or powder of the intermediate product with granules of farther plastic, mixed and after Melting by the known methods such as extrusion, coextrusion, further processed spinning or injection molding into sheets, fibers, plates, rods, filaments will. When are prepared by co-extrusion multilayer films preferably only the outer layers of biocidal equipped. examples for Other plastics are polyester, PET, polycarbonates, polyurethanes, polyamides, Polyalkylenes such as PE, PP, polystyrene, poly (meth) acrylates, ABS, cellulose triacetate, Fluorine polymers, polyethers, POM, elastomers.

For the plastic article or the plastic coating according to the present invention come as the same fields of application in question, the above for the Dispersion were described. by way of example the case of products such as there said antimicrobially finished objects of daily use, such as door and Window handles, light switches, railings, keyboards, toilet lids, Toilet brushes, Shower fittings, telephone receivers, Children's toys, particularly plastic toys, films, fibers, Fabrics, textiles or other frequently touched surfaces, Wall coatings, wall coverings, sealants, roof tiles and insulation materials, container and equipment for the Crop production and generally sterile-held container or wrappings such as petri dishes, water tanks, water pipes or Isolierzelte, is it to inventive plastic objects, if the Products at least partially made of a plastic according to the invention or are coated therewith.

The by the novel process manufactured products can the case of polymers commonly Additives used such as stabilizers, UV absorbers, Dyes, optical brighteners, metal or metal oxide nanoparticles, plasticizers, Lubricants or pigments are added, which is in itself the Metal or metal oxide nanoparticles to other than antimicrobial acting particles according to the present can act invention. The addition of the additives may be damaged during Manufacturing process or afterwards.

The by the novel process manufactured products can other polymerization, polycondensation or polyaddition for antimicrobial finishing are mixed. By coating methods or coextrusion can Also films are produced, in which only the upper and / or lower layer of antimicrobial metals or Me&lt;?page 5?&gt;metal compounds contain / contains.

The by the novel process manufactured products can also contain a residual amount of water. The water content based on the polymerization, polycondensation or polyaddition is less than preferably less than 10 weight percent, and especially 2 weight percent.

The Removing water from the dispersion of the invention and the initiation coalescence can in one process step, be at a sufficiently high temperature, performed eg. If the glass or melting temperature of the polymerization, polycondensation or polyaddition below room temperature, is a heating is not absolutely necessary. The co-melting can then be effected at room temperature.

Under Coalescence is to be understood that the product contained in the intermediate polymeric particles flow together slowly and glue or merge, what observable under the light or electron micrographs is. This process is also referred to as film formation. Prefers are based on the number of at least 20% of the particles, especially preferably at least 50% of the particles, and more preferably at least 70% of the particles coalesced.

The Coalescence can be for example caused by the action of pressure, However, it is preferred to suspend the intermediate product at a temperature which is high enough to cause the coalescence.

This Process is usually carried out above the glass transition temperature of the polymerization, polycondensation or polyaddition product, and in particular near to above its melting point.

Under nanoscale particles of antimicrobial metals or metal compounds For the purposes of the invention to understand all particles having a have diameters of sphere of equal volume of no more than about 500 nm and the at least one antimicrobial metal or exhibit antimicrobial metal compound. There are for this principle all metals or metal compounds suitable for the antimicrobial have effect. Whether such an effect is present, you can easily on the basis of cultures to be controlled the Exciting find. inhibit Suitable metals or metal compounds the growth when the cultures are mixed with it.

Especially suitable metals are zinc, noble metals such as palladium, silver, Platinum and gold, osmium, iridium, copper, zirconium, bismuth, and sparingly soluble cerium and in water Compounds of these metals such as zinc sulfide, zinc oxide, silver sulfate, silver phosphate, Silver halides and silver.

The nanoscale particles can essentially only of a antimicrobial metal or an antimicrobial metal compound exist, but they can also different antimicrobial metals and / or metal compounds have to enable a wider spectrum of action. In addition to containing particles comprise other substances, such as inorganic excipients such as silica gel or barium sulfate. Furthermore, the particles can, if they contain more than one component, homogeneously or heterogeneously composed be, in the latter case, also in the form of a core-shell structure.

In a preferred embodiment, of the present invention have the nanoscale particles when they mainly consist of one or more antimicrobial metals, a maximum diameter of about 300 nm, in particular less than about 150 nm and particularly preferably of a maximum of about 100 nm. It has also shown to be advantageous if the diameter is at least about 5 nm, preferably at least about 10 nm. If the nanoscale particles predominantly of one or more antimicrobial metal compounds exist, it is preferred if the diameter of a maximum of about 800 nm, in particular less than about 600 nm, and particularly preferably is a maximum of about 300 nm. It has also shown to be advantageous if the diameter at least about 15 nm, in particular at least about 30 nm. As Diameter of the particles in this context is the average Diameter of the balls to be understood, the volume of which coincides with that of the particles.

Will Metal compounds used, must at least in the form of nanoscale Particles whose water be low in order for Preparation process of the invention to be suitable. By choosing suitable support materials or by a suitable design of the particles, the solubility of the metal compounds reducing it in a known manner. Particularly suitable Metal compounds as part of the nanoscale particles in the aqueous Dispersion according to the present Invention at a concentration of metal ions in the aqueous Phase of less than 0.1 g / l and in particular of less than 0.02 g / L lead.

In a particularly preferred embodiment the present invention, the nanoscale particles in essentially of silver and / or silver compounds, in particular out &lt;?page 6?&gt;Silver and / or silver halides.

silver is an effective anti-microbial metal at an extremely low toxicity for the People. Nanosilver has here a broad spectrum of activity against Bacteria, yeasts and fungi, and is therefore in modern antibiotics a sense superior.

nanosilver is extremely fine silver. The surface of the silver is the nanoparticles potentiated by a multiple. This makes it possible with the smallest Amounts large of nanosilver For example plastic antibacterial equip amounts.

The common Methods for preparing silver nanoparticles are the reduction of silver salts, with or without protective colloids or the electrochemical resolution of metallic silver. If the reaction conditions and the reducing agent selected, that during the reduction of a silver salt, the silver in a very fine Form is deposited, it is called colloidal silver or Silver hydrosol. The silver particles are then so small that they because of the large relationship between surface to volume in water or aqueous brines hover. The diameter of such Silberhydrosolteilchen typically between 20 and 80 nm.

The History of documented procedures for the production of nanoscale Silver goes far back into the 19th century. So first described<nplcit><text>H. Rose in Pogg. Ann., 14,183 (1828)</text></nplcit> the production of a Silver hydrosol by introducing phosgene into a silver salt solution. In Subsequently, a variety of methods with different Reducing agents and silver compounds described.

Wider Attention was primarily the reduction with iron citrate of silver nitrate produced Carey Lea silver (<nplcit><text>At the. J. Sci., (3) 37.476 (1889)</text></nplcit>) And with of Kohlschütter by reducing Silberhydroxidlösung Hydrogen produced silver sol (<nplcit><text>Z. electrochemistry., 14, 49 (1908)</text></nplcit>).

The for the Preparation of dispersions aqueous used Dispersions of a polymerization polycondensation or polyaddition product are known and are also under the name of Polymer Latex described in the literature.

The aqueous Dispersion of a polymerisation may, for example, in <nplcit><text>"Giesla Henrici-Olive-S.Oliver Polymerization Verlag Chemie 1969 Cape. 1.11.3. emulsion "</text></nplcit> described, be obtained by an emulsion polymerization process. A ethylenically unsaturated Compound, also referred to as a monomer, with addition of an Emulsifier such as sodium palmitate or C₁₂-C₁₄Sulfonate introduced into water. polymerization is a water-soluble Initiator started. The polymerization does not in the monomer but in the formed of the emulsifier takes micelles. The polymer falls as finely divided in dispersion or latex. Depending on the monomer used or monomer mixtures are different polymer or copolymer latexes receive. By the type and amount of the emulsifier is the particle size of the latex particles controlled. examples for Monomers for the production of polymer latices or copolymer latexes are 2-hydroxypropyl acrylate, methacrylic acid salt, acrylonitrile, α-chloroacrylonitrile, Methacrylonitrile, 2-hydroxypropyl methacrylate, N-vinyl-2-pyrrolidone, 1,3-butadiene, vinyl ethers, Acrylamide, allyl alcohol, N-methylolacrylamide, pentyl acrylate, n-butyl acrylate, Benzyl, 1-butyl, 5-methyl-1,3,6-heptatriene, 1,1-dihydroperfluorobutyl acrylate, Benzyl methacrylate, 3-0xo-n-butyl acrylate, Cyclohexyl acrylate, cyclopentyl acrylate, cetyl acrylate, cyclohexyl methacrylate, Cyclopentadiene, 2-Norbomylmethylacrylat, 2-Norbomylmethylmethacrylat, Ethyl methacrylate, ethylene, chlorostyrene, isobutyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-isobornyl methacrylate, chloroprene, n-butyl methacrylate, Isobutyl methacrylate, 3-0xo-n-butyl methacrylate, isopropyl methacrylate, Lauryl acrylate, lauryl methacrylate, methyl acrylate, methyl methacrylate, Methyl vinyl ketone, n-octyl acrylate, n-octadecyl acrylate, n-octadecyl methacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, n-octyl methacrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl acrylate ,, ethyl acrylate, Propyl acrylate, dicyclopentenyl acrylate, 2,2,2-trifluoroethyl n-hexyl acrylate, styrene, sec-butyl acrylate, p-bromostyrene, p-chlorostyrene, p-fluorostyrene, m-chlorostyrene, Neohexylacrylat, vinyl acetate, vinyl chloride, vinylidene chloride, m- and p-vinyltoluene, alpha-methylstyrene ,, acrylic acid, methacrylic acid, vinylsulfonic acid Na-salt, Mono-methyl itaconate, p-styrenesulfonic acid sodium salt, 2-acrylamido-2-methylpropane sulfonic acid Na salt, Methylenebisacrylamide, ethylene dimethacrylate, divinylbenzene, allyl acrylate, Ethylidendiacrylat, 1,6-hexamethylene dimethacrylate, 2-acetoacetoxyethyl methacrylate, methacrylic acid, Acrylic acid, methacrylamide and triallyl. In addition, also latexes with special structure as core-shell latexes or latexes suitable with Pfropfcopolymerstrukturen.

dispersions polyester and copolyesters as Polyesterlatizes and Copolyesterlatizes designates, for example, are known from <patcit><text>EP 78559</text></patcit> and <patcit><text>EP 29620</text></patcit>, Copolyesterlatizes be by polycondensation from bifunctional or polyfunctional Alcohols and di- or poly-carboxylic acids or poly Carboxylic acid derivatives produced. examples for dicarboxylic acids or Dicarbondäure&lt;?page 7?&gt;derivatives are terephthalic acid, dimethyl terephthalate, Succinic acid, maleic acid, adipate, cyclohexane, Phthalic acid dimethyl esters. examples for polyfunctional alcohols are glycol, butanediol, hexanediol, neopentyl alcohol. For the preparation of emulsifiable or self-emulsifying copolyesters additionally Carboxyl or sulfo-containing dicarboxylic acids or dicarboxylic used such as sulfoisophthalic or sodium dimethyl-5-sulfoisophtalat.

These Copolyesters are suited to aqueous dispersions in a Selbstemulgierprozess form. The Copolester be in a low boiling solvent dissolved. subsequently is water and an emulsifier is added and then the solvent evaporated. There are finely dispersed in this way without the use of dispersion devices get Copolyesterlatizes.

The for the purpose of the invention suitable polyadducts are preferably ionically modified. In particular, ionomeric polyaddition or polycondensation used. Ionomers polyaddition of<patcit><text>US 6,313,196</text></patcit> and <patcit><text>EP 049 399</text></patcit> known.

The used in this invention contain ionomeric polyaddition or polycondensation per 100 g of 4 to 180 milliequivalents, preferably 4 to 100 milliequivalents ionic group or to be converted into ionic groups and optionally 1 to 20 wt .-% to within a polyether built alkylene of the formula -CH₂-CH₂-O, Where the polyether pendant or may be contained in the main chain.

To the useful invention ionomeric polyaddition or polycondensation, hereinafter should this the term "ionomeric Products "used will include, Polyurethanes, polyesters, polyamides, polyureas, polycarbonates, Polyacetals or polyethers, also more ionomeric products simultaneously 2 or more polymer types belong, such as polyester polyurethanes, polyether or Polyesterpolyharnstoffe.

ionomers Products as used in the invention be, are known as such and for example in <nplcit><text>Applied Macromolecular Chemie 26 (1972), pages 45-106</text></nplcit>; <nplcit><text>Applied Macromolecular Chemistry 82 (1979), pages 53 et seq; J. Oil. Col. Chem. Assoc. 53 (1970), pages 363</text></nplcit> described. Other descriptions suitable ionomeric products are found in German Offenlegungsschriften (<patcit><text>DE-A) 26 37 690</text></patcit>. <patcit><text>26 42 973</text></patcit>. <patcit><text>26 51 505</text></patcit>. <patcit><text>26 51 506.</text></patcit>. <patcit><text>26 59 617</text></patcit>. <patcit><text>27 29 245</text></patcit>. <patcit><text>27 30 514</text></patcit>. <patcit><text>27 32 131</text></patcit>. <patcit><text>27 34 576</text></patcit> and <patcit><text>28 11 148</text></patcit>,

ionomers Products with anionic groups are preferred. For the process the invention in a special way are suitable ionomeric products in the <patcit><text>DE-B2-1 472 746</text></patcit> described. These ionomeric products are based on polyurethanes from Compounds containing several reactive hydrogen atoms with a molecular weight from 300 to 10,000, polyisocyanates and optionally chain extenders, containing reactive hydrogen atoms are obtained. In the preparation of these polyurethanes or subsequently in these remaining isocyanate groups with a compound at least one salt-like active hydrogen atom and at least one or capable of salt formation Groups reacted. In the case of use of compounds having capable of salt formation Groups, the resulting anionic polyurethanes then in manner known per se at least partially converted into the salt form.

Under The term "salt-like Group "are preferred means the following groups: -SO₃^- or -COO^-,

As Output components the preparation of the anionic polyurethanes are, for example, the compounds described in the following useful:

I. compounds with active hydrogen atoms

These Compounds are substantially linear and have a molecular weight from about 300 to 10,000, preferably from 500 to 4 000. The known Compounds have terminal Hydroxyl and / or amino groups. Preferred polyhydroxyl such as polyesters, polyacetals, polyethers, polyamides and polyesteramides. The hydroxyl number of these compounds corresponds to about 370 to 10, especially 225-28.

As eg polyether, the polymerization products of ethylene oxide, Propylene oxide, tetrahydrofuran, butylene oxide and copolymerization or graft, and by condensation from polyhydric alcohols or mixtures thereof obtained Condensates and obtained by alkoxylation of polyhydric alcohols mentioned products.

As Polyacetals such as the compounds obtainable from hexanediol and formaldehyde Compounds. As polyesters, polyester and polyamides are consisting of polyvalent saturated Carboxylic acids and polyvalent saturated Alcohols, amino alcohols, diamines and their mixtures obtained mainly linear condensates suitable.

&lt;?page 8?&gt;

Also already containing urethane or urea group-containing polyhydroxyl compounds and optionally modified natural polyols such as castor oil or carbohydrates are usable.

Of course, can contribute to the Varying the lyophilicity or the hydrophobicity and the mechanical Characteristics of the products, mixtures of various polyhydroxyl compounds used will.

II. Polyisocyanates

As Polyisocyanates are all aromatic and aliphatic diisocyanates suitable such as 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, di- and tetraalkyldiphenylmethane, 4,4'-dibenzyl, 1,3-Phenylendiidocyanat, 1,4-phenylene diisocyanate, the isomers of tolylene diisocyanate, optionally in admixture, Preferably, the aliphatic diisocyanates, butane-1,4-diisocyanate, Hexane-1,6-diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate and isophorone.

III. Chain extender

To The chain extenders with reactive Hydrogen atoms include: <ul><li>1. The usual Glycols such as ethylene glycol or condensates of ethylene glycol, butanediol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, hexanediol, bis-hydroxymethylcyclohexane;</li><li>2. the aliphatic, cycloaliphatic and aromatic diamines such as ethylenediamine, hexamethylenediamine, 1,4-cyclohexyldiamine, benzidine, Diaminodiphenylmethane, the isomers of phenylenediamine, hydrazine, Ammonia;</li><li>3. aminoalcohols such as ethanolamine, propanolamine, butanolamine;</li><li>4. polyfunctional amines or hydroxy compounds such as diethylenetriamine, Triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, Glycerol, pentaerythritol, 1,3-Diaminoisopropanol, 1,2-diaminopropanol, the monooxalkylierten polyamines such as N-Oxethylethylendiamin, N-Oxethylhydrazin, N-Oxethylhexamethylendiamin;</li><li>5. Water.</li></ul>

IV. For salt capable of forming compounds

<ul><li>1. Compounds with fully trained acidic moiety.</li><li>a) Hydroxysäurem such as glyceric acid, Lactic acid, Trichlormilchsäure, Malic acid, Dioxymaleinsäure, Dioxyfumarsäure, Tartaric acid, Dioxyweinsäure, Citric acid, dimethylolpropionic and dimethylol, the aliphatic, cycloaliphatic, aromatic and heterocyclic Mono- and diamino such as glycine, α- and β-alanine, 6-aminocaproic acid, 4-aminobutyric acid, the isomeric mono- and diaminobenzoic, the isomeric mono- and Diaminonaphthaoesäuren;</li><li>b) hydroxy and carboxy-; 2-hydroxyethanesulfonic acid, phenolsulfonic (2), Phenolsulfonic (3), Phenolsulfonic (4), Phenolsulfonic (2.4), sulfoacetic, m-sulfobenzoic p-sulfobenzoic Benzoic acid (1) -disulfonsäure- (3.5), 2-chloro-benzoic acid (1) -sulfonsäure- (4), 2-hydroxybenzoic acid (1) -sulfonic acid (5) Naphthol (1) sulfonic acid, naphthol (1) disulfonic acid, 8-Chlornaphtol- (1) disulphonic acid, naphthol (1) -trisulfonsäure, naphthol (2) sulfonic acid (1) and naphthol (2) -trisulfonsäure;</li><li>c) amino sulfonic acids; sulfamic Hydroylamin monosulfonic acid, Hydrazindisulfonsäure, sulfanilic acid, N-phenylamino-methanesulfonic acid, 4,6-dichloroaniline-sulfonic acid (2), Phenylene diamine (1.3) -disulfonsäure- (4.6), Naphthylenamin- (1) -sulfonic acid, Naphthylamine (2) sulfonic acid, naphthylamine disulfonic, naphthylamine trisulphonic, 4,4'-di- (p-aminobenzoylamino) diphenyl urea-disulphonic (3,3 '), phenylhydrazine-disulphonic (2.5 ) Taurine, methyl taurine, Butyltaurin, 3-amino-benzoic acid (1) -sulfonsäure- (5), 3-amino-toluene-N-methane sulfonic acid, 4,6-diaminobenzene-disulphonic acid (1,3), 2,4-diamino-toluene-sulfonic acid (5) 4,4'-Diaminodiphenyl-disulphonic acid (2,2 '), 2-aminophenol-sulphonic acid (4) 4,4'-diamino-diphenylethersulfonsäure- (2), 2-aminoanisole-N-methanesulfonic, 2-aminodiphenylamine-sulfonic acid, Ethylenglykolsulfonsäure, 2,4-diaminobenzene, N-Sulfonatoethylethylenamin;</li><li>d) further include to the hydroxyl and amino carboxylic acid and sulfonic acids, Polycarboxylic and sulfonic acids the (optionally hydrolyzed) addition products of unsaturated acids such as acrylic acid, methacrylic acid, vinylsulfonic styrenesulfonic and unsaturated Nitriles such as acrylonitrile, of cyclic dicarboxylic acid anhydrides such as maleic acid, phthalic acid, Succinic anhydride, of Sulfo carboxylic as Sulfoessigsäure-, o-sulfobenzoic, lactones such as β-propiolactone, γ-butyrolactone, the addition products from the reaction products of olefins with Sulfur trioxide as carbyl sulfate, of Epoxycarbon- and sulfonic acids such as Glycidic acid, 2,3-epoxypropane, of Sultones such as 1,3-propane, 1,4-butane sultone, 1,8-Naphthylsulton, cyclic sulfates such as glycol sulfate, of Disulfonsäureanhydriden as Benzoldisulfonsäure- (1,2) anhydride to aliphatic and aromatic amines such as 1,2-ethylenediamine, 1,6-hexamethylene-diamine, the isomeric phenylenediamines, diethylene triamine, triethylene tetramine, Tetraethy&lt;?page 9?&gt;lenpentamin, furthermore the addition products of sodium bisulphite of olefinically unsaturated compounds such as allyl alcohol, maleic acid, Maleic acid-bis-ethylene- and bis-propylene glycol ester;</li><li>e) Hydrazincarbonsäuren.</li><li>2. Reactive Compounds having 3 to 7 ring members, the salt-like or ring opening Capable of forming salts comprise groups: </li><li>a) dicarboxylic as succinic anhydride, maleic anhydride, optionally hydrogenated phthalic anhydride;</li><li>b) tetracarboxylic as 1,2,4,5-benzene tetracarboxylic anhydride;</li><li>c) Disulfonsäureanhydride such as benzene disulfonic acid (1,2) anhydride;</li><li>d) Sulfocarbonsäureanhydride as Sulfoessigsäureanhydrid, o-sulfobenzoic;</li><li>e) sultones such as 1,3-propane, 1,4-butane sultone, 1,8-Naphthsulton;</li><li>f) lactones such as β-propiolactone, γ-butyrolactone;</li><li>g) epoxycarboxylic as Glycidsäuren, optionally in the form of their alkali metal salts;</li><li>h) Epoxysulfonsäuren such as 2,3-epoxypropane-sulphonic acid-1, optionally in the form of their alkali metal salts, and the adducts of Epoxyaldehydes and alkali metal hydrogen sulfites, such as the bisulphite the glycidaldehyde.</li></ul>

The above acid groups can in customary Manner by reacting with the compounds listed below be converted into the salt form: inorganic bases, basically reacting or compounds basenabspaltende as monovalent metal hydroxides, carbonates and oxides such as sodium hydroxide, Potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate. Further, organic bases such as tertiary amines, for example trimethylamine, triethylamine, Dimethylaminoethanol, Dimethylaminpropanol, ammonia and the like.

Suitable Structural components are further example within polyether built-containing ethylene oxide mono- or divalent Alcohols.

at Addition of such, monofunctional, nonionically hydrophilic Polyether it may often be advantageous to co-use of more than difunctional structural components premature Chain termination to prevent. The monofunctional polyethers of latter formula are known to se Method, as described for example in the <patcit><text>US Patents 3,905,929</text></patcit>. <patcit><text>4190566</text></patcit> or <patcit><text>4237264</text></patcit> are described prepared.

Such Synthesis components impart the inventive use polyurethanes additional, selective hydrophilization, electrolyte stability, freeze stability and improved Gliding.

The Amount of polyisocyanates is preferably selected such that all reactive with isocyanate groups react.

The Reaction is optionally using solvents carried out, wherein low boiling solvents having a boiling point less than 120 ° C, such as acetone, Methyl ethyl ketone, acetonitrile, tetrahydrofuran, dioxane, preferably are suitable, which may contain water, optionally proportionately. As solvent inorganic Bases and compounds with at least one isocyanate group with reacting hydrogen and at least one salt-like or Capable of forming salts Group can optionally water without additives of organic solvents be used.

The predominantly linear high molecular weight anionic polyurethanes generally fall as a clear to slightly opalescent solutions in the stated polar solvents at. is your solids about 5 to 50 wt .-% of the ionic polyurethane. Preferably Polyester or polyether polyurethanes used.

The average particle size of the dispersions of used in this invention Polymerisation polycondensation or polyaddition products is in The range of 30 nm to 1000 nm preferably in the range of 50 nm to 200 nm. There are both homodisperse and dispersions polydiperse usable.

The Manufacture of inventively used Polymer latexes, polyester and ionomeric polyaddition should illustrated by the following examples will.

Polymer Dispersion 1

Under Passage of nitrogen, a solution of 1.0 g of Dowfax 2A1, an emulsifier of Messrs. Dow Chemical Company, and 350 g of water on 90 ° C heated. at pH 6-7 is metered into this solution simultaneously within 2 hours 50 g of methyl methacrylate and aqueous 50 g of a 1% to pH 7 adjusted Azobiscyanvaleriansäurelösung. Thereafter more 4 hours at 90 ° C touched. After Distilling 50 g of water is a finely divided Polymethylmethacrylatlatex receive. The solids content is adjusted by adding water.<tables><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1*" /><tbody><row><entry colname="1">Data:</entry><entry colname="2"> Solid: 10 wt .-%</entry></row><row><entry colname="2">Particle size: 75 nm</entry></row></tbody></tgroup></table></tables>

&lt;?page 10?&gt;

Polymer Dispersion 2

Under Passage of nitrogen, a solution of 800 mg dodecylbenzenesulfonate and 250 g of water at 90 ° C heated. At pH 6-7 is metered into this solution within 2 hours at the same time aqueous 50 g styrene and 50 g of a 1% to pH 7 adjusted potassium peroxodisulfate. Thereafter more 4 hours at 90 ° C touched. After distillation of 40 g of water is a finely divided polystyrene latex receive. The solids content is adjusted by adding water.<tables><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1*" /><tbody><row><entry colname="1">Data:</entry><entry colname="2"> Solid: 15 wt .-%</entry></row><row><entry colname="2">Particle size: 60 nm</entry></row></tbody></tgroup></table></tables>

Polymer Dispersion 3

407.4 g (0.2396 mol) hexanediol / Neopentylglykolpolyadipat be at 120 ° C in a water jet vacuum dewatered. At 70-80 ° C is treated with 77.7 g (0.4625 mol) and 1,6-diisocyanatohexane at 100 ° C stirred 1.5 h. The prepolymer has an NCO content of 3.4%. After 33% sodium cashing in acetone at 50 ° C with 75.0 g (0.1924 mol) of 2-aminoethyl-β-aminopropionic acid sodium salt (39.5% in water) and, after 7 minutes with 1160 ml of deionized Water dispersed. After the acetone distilled under water pump vacuum receives to a very fine dispersion. <tables><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1*" /><tbody><row><entry colname="1">Data:</entry><entry colname="2"> Solid: 30 wt .-%</entry></row><row><entry colname="2">Particle size: 60 nm</entry></row></tbody></tgroup></table></tables>

The nanoscale invention Particles containing at least one antibacterial metal or have at least one antimicrobial metal compound, can be prepared by known methods.

The Preparing nanoscale silver and gold particles, referred to herein as example for preparing nanoscale metal particles is described, is preferably carried out by reduction of silver and gold salts in aqueous solution and in the case of silver salts at pH values ​​greater than 10. As silver salts are in particular silver nitrate and the gold salts those of chloroauric. Suitable reducing agents have phenylenediamines, hydroquinones, hydrazine and hydrazine derivatives, hydrides, especially borohydrides, hydrogen, Hydroxylamine, Dimethylaminoborane, iron II-citrate, formaldehyde, hydrogen peroxide, ascorbic acid, Stannous salts, dextrins, tannin, alginates found to be advantageous. If the dispersion of silver nanoparticles before further use supported a stabilization of the dispersion is useful. Especially suitable for the stabilization is sodium chloride. The in this way Silver nanoparticles produced have a particle size of 10 nm to 100 nm, preferably 20-60 nm. The content of silver is in the range of 50 to 500 mmol of silver in 1 kg of water. The on this Way prepared aqueous Dispersions of silver nanoparticles directly in step A of the inventive method be used.

In The following examples the preparation of aqueous Silver nanoparticle dispersions described as an example.

Ag-Sol 1

In 400 ml of distilled water, 12 g of solid sodium hydroxide and 40 g of dextrin were dissolved in portions with weak stirring and two hours at 40 ° C touched. subsequently is allowed at 25 ° C a Mixture of 30 g of silver nitrate in 50 ml of water and 50 ml of 25% ammonia solution run in 3 seconds under vigorous stirring. After a contains reaction time of 20 min the reaction solution 300 mmol Ag as silver nanoparticles per kg aqueous solution. The solution is treated with 2.05 g of sodium chloride stabilized and neutralized with concentrated acetic acid. The middle Particle size of the silver nanoparticles is 50 nm.

Ag Sol 2

In a reaction vessel, 8.5 g of silver nitrate at 35 ° C in 350 dissolved ml of distilled water with gentle stirring and 75 ml of 25% ammonia solution is added. Then allowed to with vigorous stirring within 5 seconds a solution of 0.75 g of sodium borohydride enter distilled water in 100 ml. The pH of this borohydride solution was adjusted with ammonia to 12th The Reaktionsge is mixed then 45min at 40 ° C touched and obtained a reaction solution with 92 mmol Ag as silver nanoparticles per kg aqueous solution. The solution is treated with 1.2 g of sodium chloride stabilized and neutralized with concentrated acetic acid. The average particle size of the silver nanoparticles is 80 nm.

Ag-Sol 3

In a reaction vessel 25 g of dextrin and 22 g of solid at 25 ° C Sodium hydroxide dissolved in 500 ml of distilled water with gentle agitation. After a break of 10 min, a solution of 40 g of silver nitrate in 150 ml of distilled water within 5 seconds and the mixture stirred 40 minutes. Then, at 40 ° C heated and stirred for another 25 min. Leave to 20 g of a 10% hydroxylamine solution accrue, within 3 seconds and the mixture for another 15 minutes stirring.

one receives a reaction solution 200 mmol Ag as silver nanoparticles per kg aqueous solution. The solution is treated with 3.6 g of sodium chloride stabilized and neutralized with concentrated acetic acid. &lt;?page 11?&gt;The middle Particle size of the silver nanoparticles is at 30 nm.

Ag Sol 4

In a reaction vessel, 8.5 g of silver nitrate at 35 ° C in 350 dissolved ml of distilled water with gentle stirring and 75 ml of 25% ammonia solution is added. Then allowed to with vigorous stirring within 5 seconds a solution of 2.25 g trimethylaminoborane in a mixture of 140 ml methanol shrink and 140 ml of distilled water. The reaction mixture is then further 45min at 55 ° C touched and obtained a reaction solution 69 mmol Ag as silver nanoparticles per kg aqueous solution. The solution is stabilized with 1.2 g of sodium chloride and with concentrated acetic acid neutralized. The average particle size of the silver nanoparticles is at 25 nm.

Au Sol 1

In a 3 liter glass flask are heated in 2200 ml of distilled water at 80 ° C. Then 75 ml of a 0.01456 molar HAuCl₄solution and 90 ml of a 0.18 molar K₂CO₃solution in Every few seconds added under stirring. After 5 minutes is the solution to 65 ° C chilled and 60 ml of a 0.04 molar formalin under strong stirring within 2 seconds, respectively. After 2 minutes a further 60 ml of formalin solution are added stirred 40 minutes. You get a clear red gold sol with particle size diameters of 10-30 nm. The gold content of the reaction solution is about 0.09 g Au / l. If necessary, the content can by ultracentrifugation be concentrated to up to 2 g Au / l.

The Producing Silberhalogenidnanopartikeln so-called Silberhalogenidsole (AgX brine), the nanoscale here as an example of the preparation Particles is described by metal compounds are expediently produced by Mixing a water-soluble Silver salt and a water-soluble Alkali metal halide in the presence of a protective colloid, which is preferred is gelatin. The resulting Silberhalogenidsol can then cleaned in a flock / wash process or by ultrafiltration will.

In The following examples the preparation of an aqueous Silberhalogenidsols of silver chloride, silver bromide and silver iodide described as an example.

AgX Sol 1

In 250 ml of water and 0.3 ml of decanol are 10 g low molecular weight bone gelatin and 0.4 g of sodium chloride dissolved. At 40 ° C allowed to then under vigorous stirring a solution of 13.8 g of sodium chloride in 95 ml of water and a solution of 40 g of silver nitrate in 90 ml of water at the same time within 2 minutes enter. After 3 minutes, cooled one to 20 ° C and the pH-value with sulfuric acid to 3.2. Then aqueous sodium 3.5 g of 15% Polystyrenesulfonic (mean Molecular weight of 3000) was added within 5 min. It forms a precipitate. you can 10 min to settle and sucks on the precipitation supernatant from. The precipitate is washed with 200 ml of water with vigorous stirring 5 min washed and allowed then again settle for 10 minutes and sucks the standing above the precipitate solution from. This washing procedure is repeated twice. The washed Precipitate is slurried with water to 500 ml, to heated 35 ° C and adjusted with sodium hydroxide to a pH of 7.5-8. Than it will be added 0.15 g trypsin and stirred for 60 minutes. The dispersion thus obtained contains 450 mmol of silver per kg as silver chloride nanoparticles with a average diameter of 50 nm.

A2X Sol 2

In 250 ml of water and 0.3 ml of decanol are 10 g low molecular weight bone gelatin and 0.4 g of potassium chloride dissolved. At 40 ° C allowed to then under vigorous stirring a solution of 28.1 g of potassium chloride in 85 ml of water and a solution of 40 g of silver nitrate in 90 ml of water at the same time within 2 minutes enter. After 3 minutes, cooled one to 20 ° C and the pH-value with sulfuric acid to 3.2. Then aqueous sodium 3.5 g of 15% Polystyrenesulfonic (mean Molecular weight of 3000) was added within 5 min. It forms a precipitate. you can 10 min to settle and sucks on the precipitation supernatant from. The precipitate is washed with 200 ml of water with vigorous stirring 5 min washed and allowed then again settle for 10 minutes and sucks the standing above the precipitate solution from. This washing procedure is repeated twice. The washed Precipitate is slurried with water to 500 ml, to heated 35 ° C and adjusted with sodium hydroxide to a pH of 7.5-8. Than it will be added 0.15 g trypsin and stirred for 60 minutes. The dispersion thus obtained contains 450 mmol of silver per kg as silver chloride nanoparticles with a average diameter of 60 nm.

AgX Sol 3

In 250 ml of water and 0.3 ml of decanol are 10 g low molecular weight bone gelatin and 0.3 g of potassium iodide dissolved. At 40 ° C allowed to then under vigorous stirring a solution of 39.1 g of potassium iodide in 85 ml of water and a solution of 40 g of silver nitrate run into 90 ml of water at the same time within 2 minutes. After 3 minutes, cooled one at 20 ° C from and &lt;?page 12?&gt;is the one with sulfuric acid to 3.2 pH. Then aqueous sodium 3.5 g of 15% Polystyrenesulfonic (mean Molecular weight of 3000) was added within 5 min. It imagines Precipitation. you can 10 minutes to settle and sucks the above Precipitation supernatant from.

Of the Precipitate with 200 ml of water with vigorous stirring 5 min washed and allowed then again settle for 10 minutes and sucks the standing above the precipitate solution from. This washing procedure is repeated twice. The washed Precipitate is slurried with water to 500 ml, to heated 35 ° C and adjusted with sodium hydroxide to a pH of 7.5-8. intestine added 0.15 g trypsin and stirred for 60 minutes. The dispersion thus obtained contains 450 mmol of silver per kg as silver chloride nanoparticles with a average diameter of 40 nm.

Examples

The following examples, to which the present invention is in no means restricted is showing how biozidausgerüstete by the novel process transparent Polymerization, polycondensation or polyaddition can be prepared in a simple manner. The thus prepared Products exhibit very good reproducibility in antimicrobial Effect behavior.

example 1

To 200 g of polymer dispersion 1 are 0.625 g Ag-Sol 1 was added at 25 ° C stirred and 10 minutes. subsequently the water is distilled off in a rotary evaporator. The resulting powder is at 180 ° C melted and poured into a 0.5 mm thick layer. The after cooling down resulting layer is completely transparent.

example 2

To 100 g of the polymer dispersion 3 are 3.06 g Ag-Sol 2 added at 25 ° C stirred and 10 minutes. A PET film is then coated with said mixture and dried at 50 ° C. The result is a completely transparent biocidal coating.

example 3

100 g polymer dispersion 2 are mixed with 15 g of ethyl acetate and 2 Hours at 50 ° C stirred vigorously. subsequently be 3.1 g AgX Sol 1 was added and stirred for a further 15 minutes. After that is coated with this dispersion a polystyrene plate and at 70 ° C dried. You get a transparent polystyrene board having a biocidal equipped surface.

example 4

To 200 g of polymer dispersion 1 3.5 g Ag-Sol 3 was added at 25 ° C stirred and 10 minutes. subsequently the water by spray drying away. 1.5g of the obtained powder is melted with 1 kg of a polycarbonate melt and mixed for the preparation of biocidal equipped Injection molded parts used.