DE102005003262A1 - Use of antimicrobial polymers as emulsifiers and emulsifiers containing antimicrobial polymer dispersions - Google Patents

Abstract

The invention relates to the use of amphiphilic copolymers having at least one hydrophobic polymer block and at least one polymer block having antimicrobial activity as emulsifiers for emulsion polymerization, miniemulsion polymerization or suspension polymerization of water-insoluble polymers, polymer networks and polymer composites in water or water-containing media. The invention also relates to emulsifier-containing antimicrobial polymer dispersions.

Description

The The present invention relates to the use of antimicrobial polymers as emulsifiers and emulsifiers containing antimicrobial polymer dispersions. The invention also relates to the use of antimicrobial polymer dispersions for Creation of antimicrobial polymer coatings.

dispersions of polymers in suitable solvents are not just a form of common systems, in the form of these polymers after their preparation, for example in Pathways of emulsion polymerization, miniemulsion polymerization or Incurred suspension polymerization; They are also important intermediates in the production of modern paints, lacquers and coating systems. Because of necessity, for reasons environmental protection and workplace stress on organic solvent to renounce or at least reduce their use more and more polymer dispersions based on water-containing solvent systems or even water-based.

water-based However, polymer dispersions are susceptible to storage upon storage Infestation by microorganisms. They therefore contain biocides on a regular basis. The addition of biocides has, in addition to the function, to prevent that already the dispersions are attacked by microorganisms, including the purpose of the infestation of produced from the water-based polymer dispersions End products, such as the infestation of coatings and paints, which are produced from such polymer dispersions, by microorganisms to aggravate or even completely prevent.

Often used Biocides for these purposes are formaldehyde, glutardialdehyde, other aldehydes and triclosan [5-chloro-2- (2,4-dichlorophenoxy) phenol]. Others too Water compatible biocides are used. Disadvantage of said (and also of most others), as biocidal equipment in water-based polymer dispersions used organic compounds is their water solubility and her more or less low molecular weight. These allow not only that, she can evaporate from the dispersions and thus the working environment unduly burden the production and processing of such systems, but also that she can be washed out, for example, coatings coming into contact with water, made using such dispersions. The latter does not lead only in the industrial sector, but also to the end user too Strains that - partly already on a legal basis - due the expected damage must be prevented.

task the present invention was to provide dispersions of polymers in aqueous systems, which are not volatile Biocides must be added to the polymer dispersions or produced using them Coatings to impart microbicidal properties. Task of Invention was further to propose coating systems that too do not lead to attack by microorganisms prone coatings.

It was surprising found that amphiphiles, not water-soluble Copolymers having at least one hydrophobic polymer block and at least antimicrobial polymer block or - alternatively to the at least one antimicrobial polymer block - at least a non-antimicrobial polymer block with at least one antimicrobial side and / or end group as Emulsifiers in emulsion polymerization, miniemulsion polymerization or suspension polymerization of water-insoluble polymers, polymer networks or polymer composites can be used. Surprising was further that when using the said emulsifiers form dispersions of water-insoluble polymers, which are resistant to the infestation of microorganisms. Next became surprising found that coatings, made using the polymer dispersions thus obtained become permanently antimicrobial equipped and microbes Kill the contact, without that Such dispersions or coatings thus obtained biocides can be released by evaporation or washing.

The The invention therefore relates to the use of amphiphilic copolymers with at least one hydrophobic polymer block and at least one antimicrobial polymer block as emulsifiers for the Emulsion polymerization, miniemulsion polymerization or suspension polymerization of water-insoluble Polymers, polymer networks and polymer composites contained in water or water Media.

Furthermore, the invention relates to the use of amphiphilic copolymers having at least one hydrophobic polymer block and at least one antimicrobial polymer block having at least one antimicrobial side and / or end group as emulsifiers for emulsion polymerization, miniemulsion polymerization or suspension polymerization of water-insoluble polymers, polymer Networks and poly mer composites in media containing water or water.

preferred embodiments the use according to the invention are in the subclaims 3 to 8 claims.

The The invention also relates to a process for the preparation of an aqueous dispersion insoluble in water Polymers, polymer networks or polymer composites with antimicrobial properties Emulsion polymerization, miniemulsion polymerization or suspension polymerization of one or more water-insoluble monomer (s) for the said, insoluble in water Polymers, polymer networks or polymer composites in water or a medium containing water, wherein as emulsifier (s) at least an amphiphilic copolymer having at least one hydrophobic polymer block and at least one polymer block having antimicrobial activity.

Further The invention relates to a process for the preparation of an aqueous dispersion insoluble in water Polymers, polymer networks or polymer composites with antimicrobial properties Emulsion polymerization, miniemulsion polymerization or suspension polymerization of one or more water-insoluble monomer (s) for the said, insoluble in water Polymers, polymer networks or polymer composites in water or a medium containing water, wherein as emulsifier (s) at least an amphiphilic copolymer having at least one hydrophobic polymer block and at least one having no antimicrobial activity Polymer block having at least one antimicrobial side and / or End group used.

preferred Embodiments of the method according to the invention are in the Claims 11 to 16 claims.

The Invention further relates to aqueous dispersions of insoluble in water Polymers, polymer networks or polymer composites with antimicrobial Properties that are available are according to the invention, below described in detail method.

The The invention also relates to the use of aqueous dispersions according to the invention for the production of coatings and materials with antimicrobial Properties.

preferred Embodiments of the invention are claimed in claims 19 to 21.

Of the Term "copolymer" as used in the present Description and used in the claims defined a polymer formed from more than one type of monomer, the recurring units of mostly (but not necessarily) linear linked molecules more than one type of monomers polymerizable with each other. The inventively used Copolymers can random copolymers, block copolymers or so-called "gradient copolymers" (ie, for example Block copolymer - random copolymer - block copolymer sequences encompassing copolymers), but may also include areas in which are hydrophobic monomer units and antimicrobial monomer units directly linked are.

Of the Term "block copolymer" as used in the present Description and used in the claims defined a polymer formed from more than one type of monomer, the recurring units of mostly (but not necessarily) linear linked Molecule blocks exist, which in turn usually (but not necessarily) with each other linear wherein "molecular block" is a portion of the Understood polymer molecule which comprises several identical constitutional units and at least has a constitutional or configurational feature that is included in the immediately adjacent sections (blocks) does not occur.

Of the Term "antimicrobial" as used in the present Description and used in the claims defined a property (in the context of the present invention: of a polymer), not to be exposed to attack by microbes, because these can not unfold their effect. The microbes can do this in the context of the present invention, bacteria, viruses, fungi (including yeasts), Algae, without the invention on these groups or on special Species or even strains to restrict these groups. there According to the invention, the microbial Attack the (co) polymer coating in any of its Properties worsening attack or just a try of the respective microbium, the coating as a transfer medium at the transition from an earlier one Host (for example, a carrier of the bacterium or fungus) to a new host (e.g. a living being to be infected). The term "antimicrobial" therefore concludes According to the invention, the terms "antibacterial", "antiviral", "antifungal", etc., is, however not limited to this.

In the context of the present description and in the patent claims, "non-water-soluble" is understood to mean that the amphiphilic block copolymer used in accordance with the invention does not dissolve in water or only sparingly, preferably in water vanishingly small amounts. According to the invention, the water solubility of the antimicrobial copolymers is less than 1 g / l, preferably less than 0.1 g / l, even more preferably less than 0.05 g / l. The low water solubility of the amphiphilic copolymers used as emulsifier means that they do not dissolve in aqueous media used for emulsion polymerization, miniemulsion polymerization or suspension polymerization, but rather at the interface between the aqueous phase and the organic (hydrophobic) phase.

amphiphilic Copolymers having at least one hydrophobic polymer block and at least antimicrobial polymer block or alternatively to the latter - at least a non-antimicrobial polymer block with at least one antimicrobial side and / or end group are as such known from the prior art; For example, reference is made to the document WO 02 / 085,542.

The used according to the invention, not water-soluble amphiphilic copolymer at least one hydrophobic polymer block. It can be a hydrophobic Polymer block or can several hydrophobic polymer blocks be present. In the latter case, these can be made up of several polymer blocks same monomer building blocks or different monomer building blocks best hen, or it can same and different monomer building blocks to blocks different Be combined degree of polymerization. The position of the hydrophobic Polymer blocks / hydrophobic polymer blocks in the molecule of the invention used, not water-soluble amphiphilic coplymers or - specifically preferred but not limited to block copolymers can be arbitrary, and it is possible according to the invention, terminal or pendant hydrophobic polymer blocks or middle-class to realize hydrophobic polymer blocks.

In a preferred embodiment The invention is in the amphiphilic copolymer used as an emulsifier or block copolymer of the at least one hydrophobic polymer block a hydrophobic repeating units formed oligomer, Homopolymer or copolymer block.

The term "oligomer block" or "homopolymer block" or "copolymer block" in the context of the present description and in the claims, a chain (ie, substantially linear) or reticulated (ie, substantially flat) or star-shaped (ie substantially three-dimensional) structures of a few ("oligomer") or many repeating homogeneous ("homopolymer") or different from each other ("copolymer"), polymerizable in the ground state with each other and in the oligomer block, homopolymer block or copolymer block understood to be polymerized monomer units, which are connected by covalent bonds to one another with a larger structure compared to the / the monomer unit (s) significantly higher molecular weight. According to the invention, the monomer units recurring in the polymer or copolymer can be of any desired character and can be selected from hydrocarbon units comprising only carbon and hydrogen, which are mostly hydrophobic molecules, or in addition to carbon and hydrogen also heteroatoms such as O, N, S and /. or P (preferably at least O) comprising units having at least regions of some hydrophilicity besides larger hydrophobic areas. The pure hydrocarbon units may be, for example but not limited to, ethylene groups, n-propylene groups and / or i-propylene groups, n-butylene groups and / or i-butylene groups and / or t Butyl groups and / or higher homologs, but also styrene groups, α-methylstyrene groups and / or divinylbenzene groups may be selected. The backbones may consist of homopolymers of one monomer unit or copolymers of several monomer units, the latter being able to be regular, random or block copolymers. Heteroatom-containing units are usually more hydrophilic; they have at least areas with some hydrophilicity. Exemplary (but not limiting) examples of monomers of this type are ethylene oxide, propylene oxide, vinyl chloride, acrylic chloride, methacrylic chloride, acrylic acid, methacrylic acid, C ₁ to C ₆ alkyl acrylate (such as methyl acrylate or ethyl acrylate or propyl acrylate or n-butyl acrylate or 2-ethylhexyl acrylate ), C ₁ to C ₆ alkyl methacrylate (such as methyl methacrylate or ethyl methacrylate or propyl methacrylate or n-butyl methacrylate or 2-ethylhexyl methacrylate), acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, heptyloxazoline, nonyloxazoline and phenyloxazoline. From such monomer units existing oligomers, homopolymers or copolymers have at least partially a certain hydrophilicity. Copolymers of this type may also be regular, random or block copolymers. Of course, it is also possible to combine monomer units containing hydrocarbons and heteroatoms with one another to form copolymer backbones, it also being possible for such copolymers to be regular, random or block copolymers. In particular, block copolymers of the latter type can include highly hydrophobic (predominantly hydrocarbon moieties) regions of the backbone adjacent more hydrophilic regions of the backbone.

According to the invention, such amphiphilic copolymers are preferably used as emulsifiers having an oligomer, homopolymer or copolymer block formed from hydrophobic repeating units having a degree of polymerisation ranging from 5 to 10,000. When using such emulsifiers not only a good emulsifying effect for the (co) polymerization step in the preparation of the dispersion can be achieved, but there is also a targeted transfer of the antimicrobial action-based groups on the target polymer instead.

by virtue of the good results of the antimicrobial action more preferred comprises the amphiphilic copolymer molecule or block copolymer molecule used as an emulsifier formed from hydrophobic repeating units oligomer, Homopolymer or copolymer block, wherein the hydrophobic recurring Units selected are from the group of one or more of the units ethylene, propylene, Propylene oxide, vinyl chloride, vinyl acetate, vinyl versatate, styrene, Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, acrylonitrile, Heptyloxazoline, nonyloxazoline and phenyloxazoline. It can be one of mentioned units or it can a plurality of said units as hydrophobic repeating units chosen become.

The Fact that the according to the invention as an emulsifier used non-water soluble amphiphilic copolymers to an antimicrobial effect in the Target polymers, polymer networks or polymer composites is closely related to the presence of at least one antimicrobial effect having polymer blocks or no antimicrobial action containing polymer blocks having one or more antimicrobial side and / or end groups connected. In the context of emulsion polymerization, miniemulsion polymerization or suspension polymerization in the presence of one or more Emulsifiers in the form of the amphiphilic copolymers used according to the invention be antimicrobial effect of the target polymers, polymer networks or polymer composites causing groups on the target polymers grafted and covalently bound there.

Under "grafted" is under the This description and the claims understood that the one or the plurality of antimibrobially active groups by way of a Graft copolymerization grafted onto the polymer or copolymer are / are, with essentially such groups of the polymer / copolymer and / or the antimicrobially active group for the formation of covalent Bonds between polymer / copolymer and antimicrobial effective or effective group (s) can be used, which by way of a graft copolymerization link to let. Without limitation it is believed that this essentially groups with multiple bonds between two adjacent ones Atoms, in particular C = C double bonds and / or C≡C triple bonds in the interlinked molecules of the polymer or copolymer on the one hand and in the antimicrobial effective grafting molecules, on the other hand.

According to the invention it a preferred embodiment, that in the amphiphilic copolymer used as the emulsifier of at least an antimicrobial polymer block of amphiphilic Copolymer is a hydrophilic polymer block. It may be in the copolymer or preferably block copolymer a single antimicrobial effect be present, or there may be several be present antimicrobial polymer blocks. In the latter Case can the several blocks same, different in their antimicrobial action, but otherwise the same or in every respect (especially in theirs antimicrobial action) may be different polymer blocks. With different polymer blocks can For example, different antimicrobial efficiencies realized be, for example, antimicrobial efficacy of different intensity and / or against different microorganisms (eg different Bacteria and / or different viruses and / or different Fungi or yeasts and / or different algae) directed efficiencies.

The Position of the antimicrobial polymer block / s having antimicrobial polymer blocks in the molecule of the invention used, not water-soluble amphiphilic coplymer or block copolymer can be arbitrary, and it is possible according to the invention, terminal or pendant antimicrobial polymer blocks or median antimicrobial Effecting polymer blocks to realize.

Yet more preferred is in the amphiphilic used as an emulsifier Copolymer having at least one antimicrobial effect Polymer block hydrophilic antimicrobial oligomer, homopolymer or copolymer block. With particular advantage lies in the existing hydrophilic oligomer, Homopolymer or copolymer block the degree of polymerization in the range from 5 to 10,000.

Most preferably, in the amphiphilic copolymer or block copolymer used as the emulsifier, the at least one antimicrobial polymer block is a hydrophilic oligomer, homopolymer or copolymer block whose polymer is selected from the group of one or more the polymers poly-N- (C ₁ to C ₂₂ ) alkyl-4-vinylpyridines, poly-N- (C ₈ to C ₂₂ ) alkylethyleneimines and polyhexylbiguanidines. It may be one or several (even several identical, different only in molecular weight) of said polymers can be used.

in the Framework of the use according to the invention not water-soluble amphiphilic copolymers, it is moreover preferred that the at least a non-antimicrobial polymer block with at least one antimicrobial side and / or end group hydrophilic oligomer, homopolymer or copolymer block having a or more antimicrobial side and / or end groups. It may or may not several non-antimicrobial polymer block / polymer blocks in the emulsifiers be used. In the same way, it is possible according to the invention that the at least one no antimicrobial polymer block one or more several antimicrobial side groups or one or more antimicrobial end groups or one or more antimicrobial side groups in addition to one or more antimicrobial end groups. Furthermore becomes the definition of oligomers, homopolymers and copolymers The above definitions are referenced.

one particularly preferred use according to the invention amphiphilic copolymers or block copolymers as emulsifiers, in which the non-antimicrobial polymer block hydrophilic oligomer, homopolymer or copolymer block having a Degree of polymerization in the range of 30 to 10,000 with one or several antimicrobial side and / or end groups is.

In the inventive use of the amphiphilic copolymers or block copolymers as emulsifiers, the non-antimicrobial polymer block having at least one antimicrobial side and / or end group is particularly advantageously a hydrophilic oligomer, homopolymer or copolymer block whose polymer (e ) is selected from the group of one or more of the polymers polyethylene glycol, polyvinyl alcohol, Polymethyloxazolin, Polyethyloxazolin and Polypropyloxazolin, with one or more side and / or end groups, which are selected from one or more of the groups antibiotics, quaternary ammonium salts, quaternary phosphonium salts , tertiary sulfonium salts, guanidines and biguanidines. The compounds of the abovementioned groups which are suitable for the side and / or end groups can be selected as desired and in particular for particular antimicrobial effectiveness, without this being subject to any restrictions according to the invention. In all cases, the said antimicrobial efficacy side and / or end groups are attached via covalent bonds to the hydrophilic oligomer, homopolymer or copolymer block, thus providing them permanently and resistant to abrasion or delamination (e.g., hydrolyzing) the antimicrobial group. According to the invention, at least one of the organic substituents of the quaternary ammonium salts, quaternary phosphonium salts and / or tertiary sulfonium salts used as antimicrobial side and / or end group (s) is preferably a C ₄ -alkyl radical, ie an alkyl radical having more than 4 carbon atoms, preferably one Alkyl radical having more than 8 carbon atoms, for example an alkyl radical having 12 to 22 carbon atoms.

The use according to the invention the amphiphilic copolymers as emulsifiers in the emulsion polymerization, Miniemulsionspolymerisation or suspension polymerization takes place in water or water containing media, even more preferably in Water or mostly, for example more than 50% by volume or more preferably more than 70% by volume, Water containing media. The residual amounts of medium can - without restriction and the Person skilled in the field of emulsion and suspension polymerization well-known and easily selectable - any liquids and are particularly preferably water-compatible organic Solvent. It corresponds to a particular embodiment of the invention, in addition one or more of the emulsifiers according to the invention one or several, known per se and in the emulsion polymerization, miniemulsion polymerization or suspension polymerization commonly used (also not antimicrobial or in any way none bioactivity having) emulsifiers as co-emulsifiers to use. these can either the emulsifying effect of the invention or the used Reinforce emulsifiers / emulsifiers or modify. The concentration of the co-emulsifier / co-emulsifiers is not limited and may be obtained by one skilled in the art of emulsion polymerization or suspension polymerization easily and without much effort determined experimentally or adjusted according to his experience.

According to a further preferred embodiment of the use according to the invention, the amphiphilic copolymers - optionally together with the abovementioned co-emulsifiers - are used in an amount of at least 2 ppm. Preferred amounts are at least 10 ppm, with further advantage in the range of 20 to 50,000 ppm and even more preferably in the range of 50 to 1,000 ppm emulsifier (in the sense of the amphiphilic copolymer used according to the invention). The above information is based on the mass of the used, insoluble in water Monomers used to make the polymers, polymer networks or polymer composites.

Will be according to a further preferred embodiment of the use according to the invention one or more, referred to above as "co-emulsifiers" (optionally not bioactive) compound (s) used in such a system excellent emulsification for the later polymerization process solely due to the emulsifying action of the co-emulsifiers, or optionally it may also be completely dispensed with an additional co-emulsifier be, for example in the surfactant-free miniemulsion polymerization. In other words: on an emulsifying effect of otherwise according to the invention as emulsifiers used copolymers or block copolymers can be completely dispensed with and thereby their concentration are greatly reduced. In this If necessary, the concentration of the copolymers may even fall to a value below the minimum value of 2 above ppm copolymer can be lowered, but may also be higher, for example in the aforementioned area.

One Part of the knowledge on which the present invention is based exists in that amphiphilic Copolymers or block copolymers with at least one hydrophobic Molecule block and at least one hydrophilic molecule block that is either antimicrobial effective oligomer or polymer is or is not antimicrobial effective oligomer or polymer with one or more antimicrobially active Side and / or end groups is, when setting a certain, slightly experimental for the Professional determinable molar ratio from hydrophobic block or hydrophobic blocks to hydrophilic block or hydrophilic blocks no longer soluble in water is. If such (by definition due to the presence of the antimicrobial oligomer and / or polymer or antimicrobial inactive oligomer and / or polymer having one or more antimicrobial side and / or end groups antimicrobial effective) amphiphilic molecules used as emulsifiers, for example in an emulsion of a or more hydrophobic (i.e., less soluble in the aqueous emulsion) Monomers in an aqueous solvent system or in water, dissolve they are in the aqueous phase not, but arrange themselves at the interface of the aqueous with the hydrophobic (Monomer-) phase, with the hydrophilic side or the more hydrophilic end of the amphiphilic molecule aligned to the aqueous phase and with the more hydrophobic side or the more hydrophobic end of the amphiphilic one molecule aligned to the hydrophobic monomer phase. That's how they stabilize the emulsion. Upon subsequent adjustment of suitable polymerization conditions in the system (for example adding an initiator, heating, exposing, other polymerization activation, without these being a restriction according to the invention) form from the (hydrophobic) monomer polymer molecules, on the antimicrobial oligomer and / or polymer or the non-antimicrobial oligomer and / or polymer with a or several antimicrobial side and / or end groups grafted. As a result, the antimicrobial effectiveness mediating moiety covalently linked to the polymer backbone or copolymer backbone. It can neither by evaporation nor by washing low molecular weight antimicrobial substance from the prepared dispersion or released from the emulsion polymerized product.

The inventive method relates to the preparation of an aqueous dispersion insoluble in water Polymers, polymer networks or polymer composites with antimicrobial properties Emulsion polymerization, miniemulsion polymerization or suspension polymerization one or more water-insoluble monomers (s) for the said, insoluble in water Polymers, polymer networks or polymer composites in water or a medium containing water. Such methods are as such known from the prior art, for example from the document WO 02/085/542, the disclosure of which by reference to the disclosure taken over the present application becomes. The in the prior art and in particular in the aforementioned document mentioned polymers, polymer networks and polymer composites can also be produced in the context of the present process, if one for one emulsion polymerization, miniemulsion polymerization or suspension polymerization used as emulsifiers, the copolymers according to the invention.

In the process according to the invention, therefore, the emulsifier (s) used is at least one copolymer or, preferably, but not limiting, block copolymer having at least one hydrophobic polymer block and at least one polymer block having antimicrobial activity. According to the invention, a copolymer or block copolymer is selected for the process, or one can use two or more different copolymers or block copolymers or also one or more copolymer (s) in addition to one or more block copolymer (s). This is advantageous not only for emulsification in emulsion, miniemulsion or suspension polymerization, since good emulsification is achieved in the aqueous or aqueous medium, but can also be used for transfer of antimicrobial activity or responsible for the specific setting of an antimicrobial action against certain microorganisms.

alternative you choose in the method according to the invention as emulsifier (s) at least one amphiphilic copolymer or block copolymer with at least one hydrophobic polymer block and at least one no antimicrobial polymer block with at least an antimicrobial side and / or end group. According to select one for the Process a copolymer or block copolymer, or you can two or more different copolymers or block copolymers or a or use more copolymers besides one or more block copolymers. This is not just for emulsification in emulsion, miniemulsion or suspension polymerization advantageous because good emulsification in the aqueous or hydrous Medium is achieved, but can also be used for the transmission of antimicrobial Effect of the produced polymer responsible group (s) or for the targeted setting of an antimicrobial effect against certain Be desirable microorganisms.

In a preferred embodiment The invention is in the amphiphilic copolymer used as an emulsifier the at least one hydrophobic polymer block is made of hydrophobic repeating units of formed oligomer, homopolymer or Copolymer block.

The The terms "oligomer", "homopolymer" and "copolymer" have been defined above, and it will work for too the inventive method referred to this definition.

According to the invention, the monomer units recurring in the polymer or copolymer can be of any desired character and can be selected from hydrocarbon units comprising only carbon and hydrogen, which are mostly hydrophobic molecules, or in addition to carbon and hydrogen also heteroatoms such as O, N, S and /. or P (preferably at least O) comprising at least regions having some hydrophilicity adjacent larger hydrophobic regions. The pure hydrocarbon units may be, for example but not limited to, ethylene groups, n-propylene groups and / or i-propylene groups, n-butylene groups and / or i-butylene groups and / or t Butyl groups and / or higher homologs, but also styrene groups, α-methylstyrene groups and / or divinylbenzene groups may be selected. The backbones may consist of homopolymers of one monomer unit or copolymers of several monomer units, the latter being able to be regular, random or block copolymers. Heteroatom-containing units are usually more hydrophilic; they have at least areas with some hydrophilicity. Exemplary (but not limiting) examples of monomers of this type are ethylene oxide, propylene oxide, vinyl chloride, acrylic chloride, methacrylic chloride, acrylic acid, methacrylic acid, C ₁ to C ₆ alkyl acrylate (such as methyl acrylate or ethyl acrylate or propyl acrylate or n-butyl acrylate or 2-ethylhexyl acrylate ), C ₁ to C ₆ alkyl methacrylate (such as methyl methacrylate or ethyl methacrylate or propyl methacrylate or n-butyl methacrylate or 2-ethylhexyl methacrylate), acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, heptyloxazoline, nonyloxazoline and phenyloxazoline. From such monomer units existing oligomers, homopolymers or copolymers have at least partially a certain hydrophilicity. Copolymers of this type may also be regular, random or block copolymers. Of course, it is also possible to combine monomer units containing hydrocarbons and heteroatoms with one another to form copolymer backbones, it also being possible for such copolymers to be regular, random or block copolymers. In particular, block copolymers of the latter type can include highly hydrophobic (predominantly hydrocarbon moieties) regions of the backbone adjacent more hydrophilic regions of the backbone.

Prefers be in the process of the invention as emulsifiers such amphiphilic copolymers or block copolymers used, which formed a hydrophobic repeating units Oligomer, homopolymer or Copolymer block having a degree of polymerization ranging from 5 to 10,000. When using such emulsifiers can not only a good emulsifying effect for the (co) polymerization step be achieved in the preparation of the dispersion, but it finds also a targeted transfer of the antimicrobial effect based Groups on the target polymer instead.

Further, due to the good results of the antimicrobial action, an amphiphilic copolymer molecule comprising an oligomer, homopolymer or copolymer block formed from hydrophobic repeating units, wherein the hydrophobic repeating units are selected from the group of one or more, is used as the emulsifier the units ethylene, propylene, propylene oxide, vinyl chloride, vinyl acetate, vinyl versatate, styrene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, acrylonitrile, heptyloxazoline, nonyloxazoline and phenyloxazoline. It may be one of the units mentioned or it is possible to select a plurality of the units mentioned as hydrophobic repeating units.

That according to the invention as an emulsifier used non-water soluble amphiphilic copolymers or block copolymers to an antimicrobial Effect on the target polymers, polymer networks or polymer composites lead, go on the presence of at least one antimicrobial effect having polymer blocks or having no antimicrobial activity Back polymer blocks with one or more antimicrobial side and / or end groups. As part of emulsion polymerization, miniemulsion polymerization or suspension polymerization in the presence of one or more emulsifiers in the form of the amphiphilic compounds used according to the invention Copolymers become antimicrobial action of the target polymers, polymer networks grafted polymer or polymer composing groups on the target polymers grafted and there covalently bound.

According to the invention it a preferred embodiment, that in the amphiphilic copolymer or block copolymer used as emulsifier the at least one antimicrobial polymer block of the amphiphilic block copolymer is a hydrophilic polymer block. It may have a single antimicrobial effect in the copolymer Be present in the polymer block, or it can several polymer blocks containing antimicrobial activity be. In the latter case can the several blocks same, different in their antimicrobial action, but otherwise the same or in every respect (especially in theirs antimicrobial action) may be different polymer blocks. For example, with different polymer blocks different antimicrobial efficiencies are realized, For example, antimicrobial efficacy of different intensity and / or against different microorganisms (eg different bacteria and / or different viruses and / or different fungi or yeasts and / or different algae) directed efficiencies

Yet is further preferred in the inventive method that in the or the amphiphilic copolymer (s) used as emulsifier (s) or Block copolymer (s) having at least one antimicrobial effect comprising polymer block a hydrophilic antimicrobial oligomer, Homopolymer or copolymer block. With particular advantage in the existing hydrophilic oligomer, homopolymer or copolymer block the degree of polymerization in the range of 5 to 10,000.

The amphiphilic copolymer or block copolymer used as emulsifier is very particularly preferably used as the at least one antimicrobial polymer block a hydrophilic oligomer, homopolymer or copolymer block whose polymer is selected from the group of one or more of the polymers poly -N- (C ₁ to C ₂₂ ) alkyl-4-vinylpyridines, poly-N- (C ₈ to C ₂₂ ) alkylethyleneimines and polyhexylbiguanidines. It may be one or several (even several identical, different only in molecular weight) of said polymers can be used.

in the Framework of the method according to the invention using water-insoluble Furthermore, it is amphiphilic copolymers or block copolymers preferred that the at least one non-antimicrobial polymer block with at least one antimicrobial side and / or end group a hydrophilic oligomer, homopolymer or copolymer block with one or more antimicrobial side and / or end groups is. It may or may not a plurality of non-antimicrobial polymer block / polymer blocks in the Emulsifiers are used. In the same way, it is possible according to the invention that the at least a non-antimicrobial polymer block one or more several antimicrobial side groups or one or more antimicrobials End groups or one or more antimicrobial side groups having one or more antimicrobial end groups. About that addition, the definition of oligomers, homopolymers and copolymers referred to the above definitions.

one particularly preferred method of the invention correspond amphiphilic copolymers or block copolymers as emulsifiers, in those of the antimicrobial polymer block a hydrophilic oligomer, homopolymer or copolymer block with a degree of polymerization in the range of 30 to 10,000 with a or more antimicrobial side and / or end groups.

With particular advantage in the process according to the invention using the amphiphilic copolymers or block copolymers as emulsifiers, the non-antimicrobial polymer block having at least one antimicrobial side and / or end group is a hydrophilic oligomer, homopolymer or copolymer block whose polymer (e) is selected from the group of one or more of the polymers polyethylene glycol, polyvinyl alcohol, polymethyloxazoline, polyethyloxazoline and polypropyloxazoline, having one or more side and / or end groups, which are selected from one or more of the groups antibiotics, quaternary ammonium salts, quaternary phosphonium salts, tertiary Other sulfonium salts, guanidines and biguanidines. The compounds of the abovementioned groups which are suitable for the side and / or end groups can be selected as desired and in particular for particular antimicrobial effectiveness, without this being subject to any restrictions according to the invention. In all cases, said side and / or end groups, which confer antimicrobial efficacy, are attached via covalent bonds to the hydrophilic oligomer, homopolymer or copolymer block, thus providing them with lasting resistance to diffusion or detachment (eg, hydrolyzation) antimicrobial group. According to the invention, in the quaternary ammonium salts, quaternary phosphonium salts and / or tertiary sulfonium salts used as antimicrobial side and / or end group (s), at least one of the organic substituents is preferably a C ₄ -alkyl radical, ie an alkyl radical having 4 or more carbon atoms, preferably one Alkyl radical having more than 8 carbon atoms, for example an alkyl radical having 12 to 22 carbon atoms.

The inventive method using the amphiphilic copolymers or block copolymers as emulsifiers in the emulsion polymerization, miniemulsion or Suspension polymerization is carried out in water or water-containing Media, more preferably in water or predominantly, for example more as 50% by volume, or more preferably more than 70% by volume, of water Media. In a likewise preferred alternative of the method according to the invention is used as a solvent for the emulsion polymerization reaction according to the invention used pure water. It is understood that the skilled person specifically used solvents from a variety of conceivable solvents and select their mixtures can without the Invention in this regard Restrictions imposed. This concludes also the purity of the water used: Basically Tap water, demineralised water or distilled water, possibly also in addition from disturbing Gases liberated water, preferred; the purity of the water can However, also selected by the expert on the basis of the intended use and in doubt be determined experimentally without effort. Most in the process distilled and optionally additionally degassed is preferred Water used. The residual amounts of medium can - without limitation and The person skilled in the art of emulsion and suspension polymerization is well known and easily selectable - any liquids and are particularly preferably water-compatible organic Solvent.

there it corresponds to a particular embodiment of the invention, in addition one or more of the emulsifiers according to the invention one or several, known per se and in the emulsion polymerization, miniemulsion or Suspension polymerization usually used (possibly also non-bioactive) emulsifiers as To use co-emulsifiers. These can be either the emulsifying Effect of the invention used Reinforce emulsifiers / emulsifiers or modify. The concentration of the co-emulsifier / co-emulsifiers is not limited and may be obtained by one skilled in the art of emulsion polymerization or suspension polymerization easily and without much effort determined experimentally or adjusted according to his experience.

Corresponding a further preferred embodiment the method according to the invention are the amphiphilic copolymers and / or block copolymers - optionally together with the aforementioned co-emulsifiers - in one Quantity of at least 2 ppm used. Preferred amounts are included at least 10 ppm, with further advantage in the range of 20 to 50,000 ppm and more preferably in the range of 50 to 1000 ppm emulsifier (in the sense of the invention used amphiphilic Block copolymer). The above information is based on the mass of the used, insoluble in water Monomers used to make the polymers, polymer networks or Polymer composites are used.

If, in accordance with a further preferred embodiment of the process according to the invention, one or more compounds (if appropriate also non-bioactive) referred to above as "coemulsifiers" are used in such a system, excellent emulsification for the later polymerization process can be achieved solely on the basis of In other words, it is possible to completely dispense with an emulsifying effect of the block copolymers otherwise used as emulsifiers in the process according to the invention, thereby greatly reducing their concentration In this case, the concentration of the copolymers or block copolymers used according to the invention may even be below the minimum value of 2 ppm (block) copolymer mentioned above may be higher, but may also be higher, for example in the aforementioned range. This can easily be determined by a person skilled in the art on the basis of his specialist knowledge or can be determined experimentally without much effort. Among other things, the need may be guiding, on the produced polymers, polymer networks or polymer composites from a to confer sufficient antimicrobial efficacy by grafting the groups derived from the emulsifier (s).

The Choice of the other conditions of the emulsion polymerization process may also be within the scope of the present invention to those skilled in the art are incumbent without any restrictions be predetermined by the invention. This is especially true for the temperature, the pressure, any initiators used or initiating acting Conditions (irradiation, wavelength and intensity of the used Radiation), any catalysts used, the agitation (e.g. stir or shaking) of the reaction system and other variables. Particularly preferred according to the invention in the presence from (frequently water-soluble) Initiators such as potassium persulfate or 2,2'-azobis (2-methyl-propionamide) dihydrochloride and at elevated Temperature (for example 30 to 100 ° C, more preferably 50 to 80 ° C, for example 50 to 60 ° C) with stirring worked the reaction mixture.

The The invention also relates to an aqueous dispersion at least one water-insoluble polymer, polymer network or polymer composites with antimicrobial properties in one Water-containing, more preferably in a predominantly (even more preferred in a> 50 vol .-% water containing, more preferably in a> 70 vol .-% water-containing) solvent system or in water. Such a dispersion is as described above Method available, in particular by means of the emulsion polymerization, miniemulsion polymerization or suspension polymerization process, the use of a or more amphiphilic copolymers and / or block copolymers of at least one hydrophobic polymer block and at least one antimicrobial Effect having polymer block as emulsifiers or from at least a hydrophobic polymer block and at least one no antimicrobial Having effective polymer block with at least one antimicrobial side and / or end group as emulsifier (s).

such inventive dispersions are particularly advantageous in terms of their properties in the production by emulsion polymerization, miniemulsion polymerization or suspension polymerization (low viscosity, good stirrability, good discharge the heat of reaction of the Polymerization step, as far as possible guiding the reaction to the products, low residual amounts of educts, in particular monomers), their storage under usual as under extraordinary Storage conditions and their properties in the processing of in the dispersion present polymers, polymer networks or Polymer composites with grafted antimicrobial groups too Coatings or materials with antimicrobial properties. In particular, according to the invention can be permanently antimicrobial Apply effective coatings to any objects that are permanent are antimicrobial and neither biocides by evaporating into the environment Release even by water (such as rainwater) washed out become. Furthermore, antimicrobial properties are also found inside the coating (this is very important for thicker coatings) before, because the antimicrobial effect groups throughout Polymer are distributed. The antimicrobial effect therefore remains then get a piece of it when worn off or by scratching it off Will get removed.

The dispersions according to the invention can in addition to the abovementioned components (predominantly (co) polymer, residual amounts Starting materials, initiator residues or secondary products in small amounts, emulsifier residues) additionally contain further substances. These are, for example, co-emulsifiers, dyes, Stabilizers and others, familiar to those skilled, the properties are not impairing Be substances.

The The invention also relates to the use of a dispersion with the aforementioned (and possibly further) components for Preparation of coatings and articles with antimicrobial properties. This can be any coatings; non-limiting examples are colors as coatings, paints as coatings or coatings, whose purpose is primarily the antimicrobial finish of a surface Subject is. preferred dimensions The emulsions find use in the application of coatings on medical devices.

The basis for the application of the coatings of the copolymer according to the invention and / or block copolymer can in principle be any desired basis. Preferably, according to the invention, the coatings are applied to a solid material, preferably a solid material selected from metal or alloys thereof, plastic, glass, ceramics, porcelain, natural fibers, synthetic fibers, stone or concrete, to just any non-limiting choice to call. For example, it is particularly preferable to apply coatings on any basis in the construction sector (eg building walls outside and inside or parts of structures), on vehicles (eg cars, ships) or on metallic materials (eg on medical devices or equipment or machinery). The application of the coatings by means of the emulsions according to the invention is carried out after known methods.

The coatings applied in this way are then followed by customary fixing steps, for example drying and / or curing subjected. After such aftertreatment steps, coatings, containing one or more polymer (s) according to the invention, a thickness in the range of 100 nm to 10 cm, preferably 1 μm to 1 cm, indicated as the thickness after the drying step.

Out However, the dispersions of the invention can Also solid materials are made by mixing the water or the aqueous solvent system removed. This can also be done according to known procedures, for example, by pressing and molding the solid polymeric material. As a result, solid objects thus formed become antimicrobial equipped Obtained polymer. Their antimicrobial properties are aimed after the grafted on the polymer antimicrobial groups and are due to the covalently bound to the (co) polymer antimicrobial Groups present throughout the polymer. Therefore, such objects hold one Microbial attack even then stand if surface damage occurs.

Surprisingly have the resulting coatings and materials after the Applying and curing antimicrobial properties. Due to the fact that the not provide antimicrobial properties molecules in the solvent system remain, but on the polymer of the coating or the article can be grafted they are neither removed by evaporation nor by aqueous systems or washed out directly by water. The polymer and the coatings and articles obtained from it are therefore theoretical permanently antimicrobial. In particular, the antimicrobial properties can bactericidal, virucidal, fungicidal and / or algicidal properties without limiting the invention thereto. In particular, it is possible according to coatings from one or more (co) polymer (s), due to the special choice of the grafted group determining emulsifier antimicrobial properties against very specific microbes (bacteria, Including viruses, fungi Yeasts, algae).

The Invention is further illustrated by the following examples, which preferred embodiments of the invention, but without being limited to these.

example 1

For the emulsion polymerization of polymethyl methacrylate became a block copolymer as emulsifier used, consisting of a polymethylmethacrylate block and a methylated polyvinylpyridine block duration.

The Preparation of the block copolymer polymethylmethacrylate (degree of polymerization 60) -blk-poly-4-vinyl-N-metylpyridinium iodide (degree of polymerization 350) he followed by living anionic polymerization of methyl methacrylate and subsequently 4-vinylpyridine followed by alkylation with methyl iodide.

In A 100 ml round-bottomed flask was charged with 50 ml of degassed, demineralized Water and 90 mg of block copolymer (corresponding to 2.5% by weight based on the methyl methacrylate weight). Within a half 4 ml of methyl methacrylate were added dropwise with stirring into the flask, being a white one Emulsion formed. When the addition was complete, 29 mg of 2,2'-azobis (2-methylpropionamide) dihydrochloride (0.8% by weight, based on the methyl methacrylate weight) was added, and the mixture was heated to 60 ° C with stirring.

To a reaction time of four hours, the oil bath was removed. Both the white ones stable emulsion as well as the coatings produced therefrom showed antimicrobial properties against the bacterium Staphylococcus aureus, as by literature tests (refer, for example to document WO 02 / 085,542).

Example 2

For the emulsion polymerization of polymethyl methacrylate became a block copolymer as emulsifier used. This was a polyphenyloxazoline-blk polymethyloxazoline block copolymer with a dimethyldodecylammonium antimicrobial end group.

The Preparation of the block copolymer polyphenyloxazoline (degree of polymerization 60) -blk polymethyloxazoline (degree of polymerization 70) terminated with a quaternary N, N-dimethyldodecylammonium triflate was made by living cationic Polymerization of phenyloxazoline followed by methyl oxazoline and termination of the reaction with N, N-dimethyldodecylamine.

In a 100 ml round bottom flask, 50 ml of degassed, demineralized water and 90 mg of block copolymer (equivalent to 2.5% by weight based on the methyl methacrylate weight). Within half an hour, 4 ml of methyl methacrylate were added dropwise with stirring into the flask, forming a white emulsion. After completion of the addition, 29 mg of 2,2'-azobis (2-methylpropionamide) dihydrochloride (0.8% by weight based on the weight of methyl methacrylate) was added, and the mixture was heated to 60 ° C with stirring.

To a reaction time of four hours, the oil bath was removed. Both the white ones stable emulsion as well as the coatings produced therefrom showed antimicrobial properties against the bacterium Staphylococcus aureus, as by literature tests (refer, for example to document WO 02 / 085,542).

Example 3

Production of films

to Preparation of films from the dispersions became more commercially available Paintbrush dipped in the dispersion. The absorbed polymer dispersion was even on deleted a slide. Subsequently one left the painted surface air dry. After two hours, one received a mechanical durable, homogeneous, white film. This showed antimicrobial properties across from the bacterium Staphylococcus aureus as known from the literature Tests (refer, for example, to document WO 02 / 085,542) was detected.

Claims (21)

Use of amphiphilic copolymers with at least a hydrophobic polymer block and at least one antimicrobial Having effect polymer block as emulsifiers for the emulsion polymerization, Miniemulsion polymerization or suspension polymerization of water-insoluble Polymers, polymer networks and polymer composites in water or Water containing media. Use of amphiphilic copolymers with at least a hydrophobic polymer block and at least one no antimicrobial Effectively having polymer block with at least one antimicrobial Side and / or End group as emulsifiers for emulsion polymerization, miniemulsion polymerization or suspension polymerization of water-insoluble Polymers, polymer networks and polymer composites in water or Water containing media. Use according to claim 1 or claim 2, wherein the at least one hydrophobic polymer block is made of hydrophobic formed from repeating units oligomer, homopolymer or copolymer block is, preferably one of hydrophobic repeating units formed oligomer, homopolymer or copolymer block with a Degree of polymerization in the range of 5 to 10,000, more preferred a hydrophobic repeating units formed oligomer, homopolymer or copolymer block selected from the group of or more of the units ethylene, propylene, propylene oxide, vinyl chloride, Vinyl acetate, vinyl versatate, styrene, methyl acrylate, methyl methacrylate, Ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, Acrylonitrile, heptyloxazoline, nonyloxazoline and phenyloxazoline. Use according to any one of claims 1 to 3, wherein the at least an antimicrobial polymer block of amphiphilic Copolymer and / or block copolymer, a hydrophilic polymer block is. Use according to any one of claims 1 to 4, wherein the polymer block having at least one antimicrobial activity is a hydrophilic antimicrobial oligomer, homopolymer or copolymer block, preferably a hydrophilic oligomer, homopolymer or copolymer block having a degree of polymerization in the range from 5 to 10,000, more preferably a hydrophilic oligomer, homopolymer or copolymer block whose polymer is selected from the group of one or more of the polymers poly-N- (C ₁ to C ₂₂ ) alkyl-4 vinylpyridines, poly-N- (C ₈ to C ₂₂ ) alkyl ethyleneimines and polyhexyl biguanidines. Use according to any one of claims 1 to 4, wherein the at least one non-antimicrobial polymer block having at least one antimicrobial side and / or end group is a hydrophilic oligomer, homopolymer or copolymer block having one or more antimicrobial side and / or end groups. or end groups, preferably a hydrophilic oligomer, homopolymer or copolymer block having a degree of polymerization ranging from 30 to 10,000 with one or more antimicrobial side and / or end groups, more preferably a hydrophilic oligomer, homopolymer or copolymer. A block whose polymer (s) is / are selected from the group of one or more of the polymers polyethylene glycol, polyvinyl alcohol, polymethyloxazoline, polyethyloxazoline and polypropyloxazoline, having one or more side and / or end groups selected from one or more of the groups Antibiotics, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, Guanidines and biguanidines, even more preferred, wherein the quaternary ammonium salts, quaternary phosphonium salts and / or ter tiary sulfonium salts are substituted with at least one C _{> 4} alkyl radical. Use according to one of claims 1 to 6 in water or predominantly Water containing media, preferably in water or predominantly water containing media, more preferably in the presence of at least one Co-emulsifier and / or at least one stabilizer and / or at least another additive. Use according to one of claims 1 to 7 in an amount of at least 2 ppm, preferably in an amount of at least 10 ppm, more preferably in an amount of 20 to 50,000 ppm, still further preferably from 50 to 1000 ppm, of the emulsifier, based on the Mass of water-insoluble monomers used for the polymers, Polymer networks or polymer composites. Process for the preparation of an aqueous dispersion in water insoluble Polymers, polymer networks or polymer composites with antimicrobial Properties by emulsion polymerization, miniemulsion polymerization or suspension polymerization of one or more in water insoluble Monomer (s) for the aforesaid, insoluble in water Polymers, polymer networks or polymer composites in water or a medium containing water, wherein as emulsifier (s) at least an amphiphilic copolymer having at least one hydrophobic polymer block and at least one antimicrobial polymer block used. Process for the preparation of an aqueous dispersion insoluble in water Polymers, polymer networks or polymer composites with antimicrobial Properties by emulsion polymerization, miniemulsion polymerization or suspension polymerization of one or more in water insoluble Monomer (s) for the aforesaid, insoluble in water Polymers, polymer networks or polymer composites in water or a medium containing water, wherein as emulsifier (s) at least an amphiphilic copolymer having at least one hydrophobic polymer block and at least one having no antimicrobial activity Polymer block with used at least one antimicrobial side and / or end group. A method according to claim 9 or claim 10, wherein as the at least one hydrophobic polymer block of the as emulsifier used at least one amphiphilic copolymer and / or block copolymer a hydrophobic repeating units formed oligomer, Homopolymer or Copolymer block selected is, preferably a hydrophobic repeating units formed oligomer, homopolymer or copolymer block with a Degree of polymerization is chosen in the range of 5 to 10,000, more preferably a hydrophobic repeating units formed Oligomer, homopolymer or copolymer block selected from the group of one or more of the units ethylene, propylene, Propylene oxide, vinyl chloride, vinyl acetate, vinyl versatate, styrene, Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, Acrylonitrile, heptyloxazoline, nonyloxazoline and phenyloxazoline. A method according to any one of claims 9 to 11, wherein as the at least one antimicrobial polymer block of the emulsifier used, at least one amphiphilic copolymer and / or block copolymers a hydrophilic polymer block is chosen. A method according to any one of claims 9 to 12, wherein as the at least one antimicrobial polymer block of the emulsifier used, at least one amphiphilic copolymer and / or block copolymer, a hydrophilic antimicrobial oligomer, homopolymer or copolymer block is selected, Preferably, a hydrophilic oligomer, homopolymer or copolymer block is selected with a degree of polymerization in the range of 5 to 10,000, more preferably a hydrophilic oligomer, homopolymer or copolymer block is selected, the polymer is selected from the group of one or more the polymers poly-N- (C ₁ to C ₂₂ ) alkyl-4-vinylpyridines, poly-N- (C ₈ to C ₂₂ ) alkylethyleneimines and polyhexylbiguanidines. A method according to any one of claims 9 to 12, wherein as the at least one antimicrobial polymer block having at least one antimicrobial side and / or end group in the emulsifier used, at least one amphiphilic copolymer and / or block copolymer, a hydrophilic oligomer , Homopolymer or copolymer block having one or more antimicrobial side and / or end groups, preferably a hydrophilic oligomer, homopolymer or copolymer block having a degree of polymerization ranging from 30 to 10,000 with one or more antimicrobial side chains. and / or end groups, more preferably a hydrophilic oligomer, homopolymer or copolymer block whose polymer (s) is / are selected from the group of one or more of the polymers polyethylene glycol, polyvinyl alcohol, polymethyloxazoline, polyethyloxazoline and polypropyloxazoline, having a or multiple page and / or end groups is selected t is / are from one or more of the groups antibiotics, quaternary ammonium salts, quaternary phosphonium salts, tertiary Other sulfonium salts, guanidines and biguanidines, even more preferred, wherein the quaternary ammonium salts, quaternary phosphonium salts and / or tertiary sulfonium salts are substituted with at least one C _{> 4} alkyl. A method according to any one of claims 9 to 14, wherein as the reaction medium Water or a predominantly Water-containing medium is used, preferably wherein additionally at least one Co-emulsifier and / or at least one stabilizer and / or at least another additive is added. A method according to any one of claims 9 to 15, wherein the at least one emulsifier in an amount of at least 2 ppm, preferably in an amount of at least 10 ppm, more preferably in an amount of from 20 to 50,000 ppm, even more preferably from 50 to 1,000 ppm, of the emulsifier, based on the mass the used, insoluble in water Monomers for the polymers, polymer networks or polymer composites. Aqueous dispersions of insoluble in water Polymers, polymer networks or polymer composites having antimicrobial properties, obtainable according to the method according to any one of claims 9 to 16. Use of aqueous dispersions according to claim 17 for the production of coatings and materials with antimicrobial properties. Use according to claim 18, wherein the coatings with antimicrobial properties applied to solid materials be, preferably on metal, plastic, glass, ceramics, natural fibers, synthetic fibers, Stone or concrete. Use according to claim 18 or claim 19, wherein the coatings with antimicrobial properties have a thickness in the range of 100 nm to 10 cm, in terms of thickness after Dry. Use according to any one of claims 18 to 20, wherein the coatings bactericidal, virucidal, fungicidal and / or algicidal properties to have.