EP1214366A1

EP1214366A1 - Copolymers of aminopropyl vinyl ether

Info

Publication number: EP1214366A1
Application number: EP00953028A
Authority: EP
Inventors: Peter Ottersbach; Beate Kossmann
Original assignee: Creavis Gesellschaft fuer Technologie und Innovation mbH
Current assignee: Creavis Gesellschaft fuer Technologie und Innovation mbH
Priority date: 1999-08-24
Filing date: 2000-07-08
Publication date: 2002-06-19
Also published as: DE19940023A1; WO2001014435A1; CN1382164A; NO20020767L; CA2383030A1; NO20020767D0; AU6562500A; JP2003507542A

Abstract

The invention relates to antimicrobial polymers which can be obtained by copolymerizing vinyl ethers of general formula (I), especially 3-aminopropyl vinyl ethers, with additional aliphatically unsaturated monomers, and to a method for the production thereof. The polymers can also be produced by graft copolymerizing a substrate, whereby a covalently bound coating is obtained on the surface of the substrate. The antimicrobial polymers can be used as a microbicide coating, among other things, on hygiene articles or in the field of medicine, as well as in paints or protective paint coatings.

Description

Copolymers of aminopropyl vinyl ether

The invention relates to antimicrobial polymers which are obtained by copolymerizing amino-functionalized vinyl ethers with further monomers. The invention further relates to a process for the preparation and use of these antimicrobial polymers

Furthermore, the invention relates to antimicrobial polymers which are obtained by graft copolymerization of amino-functionalized vinyl ethers with further monomers on a substrate, a process for their preparation of the graft copolymers and their use

Colonization and spreading of bacteria on the surfaces of pipelines, containers or packaging are highly undesirable.Mucous layers often form, which extremely increase microbial populations, which have a lasting impact on the quality of water, beverages and food, and even spoil the goods and cause health damage the consumer can drive

Bacteria must be kept away from all areas of life in which hygiene is important. This affects textiles for direct body contact, in particular for the intimate area and for nursing and elderly care. Bacteria must also be kept away from furniture and device surfaces in care stations, especially in the Area of intensive care and young child care, in hospitals, especially in rooms for medical interventions and in isolation stations for critical infection cases and in toilets

At present devices, surfaces of mobeine and textiles against bacteria are treated if necessary or as a precautionary measure with chemicals or their solutions as well as mixtures which act as a disinfectant to a greater or lesser extent and have a massive antimicrobial effect.These chemical agents have a non-specific effect, are often themselves toxic or irritating or form degradation products that are harmful to health There are also often incompatibilities with appropriately sensitized people

Another approach against superficial spread of bacteria is the antimicrobial substances into a matrix

Tert-butylaminoethyl methacrylate is a commercially available monomer in methacrylate chemistry and is used in particular as a hydrophilic component in copolymerizations. EP-PS 0 290 676 describes the use of various polyacrylates and polymethacrylates as a matrix for the immobilization of bactericidal quaternary ammonium compounds

From another technical area, US Pat. No. 4,532,269 discloses a terpolymer of butyl methacrylate, tributyltin methacrylate and tert-butylaminoethyl methacrylate. This polymer is used as an antimicrobial marine paint, the hydrophilic tert-butylaminoethyl methacrylate requiring the slow erosion of the polymer and thus the highly toxic tributyltin microbial methacrylate releases

In these applications, the copolymer made with aminomethacrylates is only a matrix or carrier substance for added microbicidal active ingredients that can diffuse or migrate from the carrier substance. Polymers of this type lose their effect more or less quickly if the necessary "minimal inhibitory concentration" on the surface ( MIK) is no longer achieved

From European patent applications 0 862 858 and 0 862 859 it is known that homo- and copolymers of tert-butylaminoethyl methacrylate, a methacrylic acid ester with secondary amino function, have inherent microbicidal properties in order to undesirably adapt the microbial life forms, especially in view of those known from antibiotic research Resistance development of germs to counteract effectively must also be developed in the future systems based on new compositions and improved effectiveness

The object of the present invention is therefore to develop novel, antimicrobial polymers which prevent the settlement and spread of bacteria on surfaces

It has now surprisingly been found that by copolymerization of amino-functionalized vinyl ethers with aliphatic unsaturated monomers or by graft copolymerization of these components on a substrate give polymers with a surface that is permanently microbicidal, is not attacked by solvents and physical stresses and shows no migration. It is not necessary to use further biocidal active ingredients

3-aminopropyl vinyl ether is a commercially available product, the production of which can be found, for example, in European patent application 0 514 710. It is used, inter alia, as an additive for photoresist systems, described, for example, in US 5648194, or as a building block for adhesion promoters in special urethanesilanes, for example in US 5384342 The use of such compounds in antimicrobial polymers is not known

The present invention therefore relates to antimicrobial copolymers which are obtained by copolymerizing a vinyl ether of the general formula

with R ¹ = branched or unbranched hydrocarbon radical with 1 to 5 carbon atoms and R ² , R ³ = H, branched or unbranched hydrocarbon radical with 1 to 5

Carbon atoms, where R ² and R ^{3 may be the} same or different,

can be obtained with at least one aliphatic unsaturated monomer

The proportion of vinyl ether in the reaction mixture should, in order to obtain a sufficient antimicrobial effect of the polymer, between 5 and 98 mol%, preferably between 30-98 mol%, particularly preferably between 50-98 mol%, based on the sum the Monomers

All monomers which undergo copolymerization with vinyl ethers of the general formula can be used as aliphatic unsaturated monomers. Examples include suitable acrylates or methacrylates, such as acrylic acid, tert-butyl methacrylate or methyl methacrylate, styrene, vinyl chloride, vinyl ethers, acrylamides, acrylonitriles, olefins (ethylene, Propylene, butylene, isobutylene), allyl compounds, vinyl ketones, vinyl acetic acid, vinyl acetate or vinyl esters, in particular, for example, methacrylic acid methyl ester, methacrylic acid ethyl ester,

Butyl methacrylate, tert-butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, tert -

Butylaminoethyl ester, 2-diethylaminoethyl methacrylate, 2-diethylaminoethyl vinyl ether, N-3-dimethylaminopropyl methacrylamide, 3-methacryloylaminopropyltrimethylammonium chloride, 2-methacryloyloxyethylrimethylammonium chloride or 2-methacryloyloxyethyltrimethylammonium methosulfate

The aliphatic unsaturated monomers are preferably acrylic acid or methacrylic acid compounds and the vinyl ether of the general formula is 3-aminopropyl vinyl ether

The antimicrobial copolymers according to the invention can be obtained by copolymerization of vinyl ethers of the general formula, in particular with 3-aminopropyl vinyl ether, with one or more aliphatic unsaturated monomers. The polymerization is expediently carried out radically by means of a radical initiator or radiation-induced. Typical procedures are described in the examples

The antimicrobial copolymers according to the invention can also be obtained by copolymerizing vinyl ethers of the general formula, in particular with 3-aminopropyl vinyl ether, and at least one aliphatic unsaturated monomer on a substrate. A physisorbed coating of the antimicrobial copolymer is obtained on the substrate

All polymeric plastics, such as polymers, are particularly suitable as substrate materials. lyurethanes, polyamides, polyesters and ethers, polyether block amides, polystyrene, polyvinyl chloride, polycarbonates, polyorganosiloxanes, polyolefins, polysulfones, polyisoprene, polychloroprene, polytetrafluoroethylene (PTFE), corresponding copolymers and blends as well as natural and synthetic rubbers, with or without radiation-sensitive Groups The method according to the invention can also be applied to surfaces of lacquered or otherwise plastic, metal, glass or wooden bodies

In a further embodiment of the present invention, the copolymers can be obtained by graft-polymerizing a substrate with vinyl ethers of the general formula, in particular with 3-aminopropyl vinyl ether, and at least one aliphatic unsaturated monomer. The grafting of the substrate enables the antimicrobial copolymer to be covalently bound to the substrate as substrates All polymeric materials, such as the plastics already mentioned, can be used

The surfaces of the substrates can be activated by a number of methods before the graft copolymerization.All standard methods for activating polymeric surfaces can be used here.For example, the activation of the substrate before the graft polymerization by UV radiation, plasma treatment, corona treatment, flame treatment , Ozonization, electrical discharge, γ-radiation using established methods The surfaces are expediently freed of oils, fats or other contaminants beforehand in a known manner by means of a solvent

The substrate can be activated by UV radiation in the wavelength range 170-400 nm, preferably 170-250 nm. A suitable radiation source is, for example, a UV excimer device HERAEUS Noblelight, Hanau, Germany. However, mercury vapor lamps are also suitable for substrate activation if they emit significant amounts of radiation in the areas mentioned The exposure time is generally 0 1 seconds to 20 minutes, preferably 1 second to 10 minutes

The activation of the substrate before the graft polymerization with UV radiation can also be carried out with an additional photosensitizer. For this purpose, the photosensitizer, such as benzophenone, is applied to the substrate surface and irradiated. This can also be done with a mercury vapor lamp with exposure times of 0 1 seconds to 20 minutes, preferably 1 second to 10 minutes

According to the invention, the activation can also be achieved by plasma treatment using an RF or microwave plasma (Hexagon, Fa Technics Plasma, 85551 Kirchheim, Germany) in air, nitrogen or argon atmosphere. The exposure times are generally 2 seconds to 30 minutes, preferably 5 seconds up to 10 minutes The energy input for laboratory devices is between 100 and 500 W, preferably between 200 and 300 W.

Corona devices (SOFTAL, Hamburg, Germany) can also be used for activation. The exposure times in this case are generally 1 to 10 minutes, preferably 1 to 60 seconds

Activation by electrical discharge, electron or γ-rays (e.g. from a cobalt 60 source) and ozonization enable short exposure times, which are generally 0 1 to 60 seconds

Flaming substrate surfaces also leads to their activation. Suitable devices, in particular those with a barrier flame front, can be easily built or, for example, obtained from ARCOTEC, 71297 Monsheim, Germany. They can be operated with hydrocarbons or hydrogen as fuel gas In any case, damaging overheating of the substrate must be avoided, which is easily achieved by intimate contact with a cooled metal surface on the substrate surface facing away from the flame side. The activation by flame is accordingly limited to relatively thin, flat substrates. The exposure times are in the generally to 0 1 second to 1 minute, preferably 0 5 to 2 seconds, all of which are non-luminous flames and the distance from the substrate surfaces to the outer flame front is 0 2 to 5 cm, preferably 0 5 to 2 cm

The substrate surfaces activated in this way are produced using known methods, such as dipping, Spraying or brushing, coated with vinyl ethers of the general formula (component I), in particular with 3-aminopropyl vinyl ether, and one or more aliphatic unsaturated monomers (component II), optionally in solution, water, ethanol and water-ethanol mixtures have been used as solvents Preserved, but other solvents can also be used, provided they have sufficient bulk for the monomers and the substrate surfaces wet well. Solutions with monomer contents of 1 to 10% by weight, for example about 5% by weight, have been retained in practice and result in general coherent coats covering the substrate surface with layer thicknesses that can be more than 0 1 μm

The graft copolymerization of the monomers applied to the activated surfaces can expediently be initiated by radiation in the short-wave segment of the visible region or in the long-wave segment of the UV region of the electromagnetic radiation. For example, radiation from a UV excimer of the wavelengths 250 to 500 nm is very suitable. preferably from 290 to 320 nm Here too, mercury vapor lamps are suitable, provided they emit considerable amounts of radiation in the areas mentioned. The exposure times are generally 10 seconds to 30 minutes, preferably 2 to 15 minutes

Furthermore, graft copolymerization of the comonomer compositions according to the invention can also be achieved by a process which is described in European patent application 0 872 512 and is based on a graft polymerization of swollen monomer and initiator molecules. The monomer used for swelling can be component II

The antimicrobial copolymers of vinyl ethers of the general formula (component I), in particular 3-aminopropyl vinyl ether, and at least one aliphatic unsaturated monomer (component II) according to the invention exhibit a microbicidal or antimicrobial behavior even without grafting onto a substrate surface. Another embodiment of the present invention consists in this that the copolymerization of components I and II is carried out on a substrate

The components can be applied in solution to the substrate as a solvent For example, water, ethanol, methanol, methyl ethyl ketone, diethyl ether, dioxane, hexane, heptane, benzene, toluene, chloroform, dichloromethane, tetrahydrofuran and acetonitrile are suitable as solvents for component I, component II can also be used

The antimicrobial copolymers according to the invention can also be used directly, ie not by polymerizing the components on a substrate, but rather as an antimicrobial coating. Suitable coating methods are the application of the copolymers in solution or as a melt

The solution of the polymers according to the invention can be applied to the substrates, for example by dipping, spraying or painting

If the polymers according to the invention are produced directly on the substrate surface without grafting, customary radical initiators can be added

Initiators which can be used in the preparation of the copolymers according to the invention are, inter alia, azonitriles, alkyl peroxides, hydroperoxides, acyl peroxides, peroxoketones, peresters, peroxocarbonates, peroxodisulfate, persulfate and all customary photoinitiators such as acetophenones, α-hydroxyketones, dimethyl ketones and benzophenone. Polymerization initiation can also be used also thermally or, as already stated, by electromagnetic radiation, such as UV light or γ radiation

Furthermore, the antimicrobial polymers according to the invention can also be used as components for the formulation of paints and varnishes

Use of the modified polymer substrates

The present invention further relates to the use of the antimicrobial polymers or copolymers according to the invention for the production of antimicrobially active products and the products thus produced as such. The products can contain or consist of modified polymer substrates according to the invention. Such products are preferably based on polyamides, polyurethanes, polyether block amides, polyester amides or imides, PVC, polyolefms, silicones, polysiloxanes, polymethacrylate or polyterephthalates which have surfaces modified with polymers according to the invention

Antimicrobial products of this type are, for example, and in particular machine parts for food processing, components of air conditioning systems, roofing, bathroom and toilet articles, cake articles, components of sanitary facilities, components of animal cages and dwellings, toys, components in water systems, food packaging, operating elements (touch panel ) of devices and contact lenses

The copolymers or graft copolymers according to the invention can be used wherever bacteria-free, ie microbicidal surfaces or surfaces with non-stick properties are important. Examples of uses for the copolymers or graft polymers according to the invention are, in particular, paints, protective coatings or coatings in the following areas

Marine hull, port facilities, buoys, drilling platforms, ballast water tanks, house roofs, basements, walls, facades, greenhouses, sun protection, garden fences, wood protection - sanitary Public toilets, bathrooms, shower curtains, toiletries,

Swimming pool, sauna, joints, sealing compounds

Food machinery, kitchen, cake items, sponges, toys, food packaging, milk processing, drinking water systems, cosmetics, machine parts, air conditioners, ion exchangers, process water, solar systems, heat exchangers, bioreactors, membranes

Medical technology contact lenses, diapers, membranes, implants, everyday items, car seats, clothing (stockings, sportswear), hospital facilities, door handles, telephone receiver, public transport, animal cages, cash registers, carpets, wallpaper

The present invention furthermore relates to the use of the surface of the polymers or processes modified according to the invention, according to the invention Polymer substrates for the production of hygiene products or medical technology articles The above explanations regarding preferred materials apply accordingly. Such hygiene products are, for example, toothbrushes, toilet seats, combs and packaging materials. The term hygiene articles also includes other objects that may come into contact with many people, such as telephone receivers, handrails of stairs, door and window handles as well as holding belts and handles in public transport. Medical technology items include catheters, tubes, cover foils or surgical cutlery

To further describe the present invention, the following examples are given, which further illustrate the invention but are not intended to limit its scope as set out in the claims

Example 1:

6 g of 3-aminopropyl vinyl ether (Aldrich), 6 g of methacrylic acid methyl ester (Aldrich), and 60 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.15 g of azobisisobutyronitrile is dissolved in 4 ml of ethyl methyl ketone Stirring slowly added dropwise The mixture is heated to 70 ° C. and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 0.5 l of demineralized water, the polymer product precipitating. After filtering off the product, the filter residue becomes 100 ml of demineralized water rinsed to remove any remaining monomers. The product is then dried in vacuo at 50 ° C. for 24 hours

Example la:

0.05 g of the product from Example 1 are placed in 20 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined Staphylococcus aureus more detectable

Example lb:

0.05 g of the product from Example 1 are dissolved in 20 ml of a test germ suspension of pseudo- monas aeruginosa inserted and shaken After a contact time of 60 minutes, 1 ml of the test germ suspension is removed, and the number of bacteria in the test mixture is determined. After this time, the number of bacteria has dropped from 10 ⁷ to 10 ²

Example 2:

6 g of 3-aminopropyl vinyl ether (from Aldrich), 6 g of methacrylic acid butyl ester (from Aldrich), and 60 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.15 g of azobisisobutyronitrile is then dissolved in 4 ml of ethyl methyl ketone Stirring slowly added dropwise The mixture is heated to 70 ° C. and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 0.5 l of demineralized water, the polymer product precipitating. After filtering off the product, the filter residue becomes 100 ml deionized water rinsed to remove any residual monomers still present. The product is then dried in vacuo at 50 ° C. for 24 hours

Example 2a:

0.05 g of the product from Example 2 are placed in 20 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined Staphylococcus aureus more detectable

Example 2b

0.05 g of the product from Example 2 are placed in 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined 10 ⁷ dropped to 10 ²

Example 3: 6 g of 3-aminopropyl vinyl ether (Aldrich), 6 g of 2-diethylaminoethyl methacrylate (Aldrich) and 60 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.15 g of azobisisobutyronitrile is then dissolved in 4 ml of ethyl methyl ketone under Stirring slowly added dropwise The mixture is heated to 70 ° C. and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 0.5 l demineralized water, the polymer product precipitating. After filtering off the product, the filter residue becomes 100 ml of demineralized water rinsed to remove any remaining monomers. The product is then dried in vacuo at 50 ° C. for 24 hours

Example 3a:

0.05 g of the product from Example 3 are placed in 20 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined 10 ⁷ dropped to 10 ²

Example 3b

0.05 g of the product from Example 3 are placed in 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined 10 ⁷ dropped to 10 ²

Example 4:

6 g of 3-aminopropyl vinyl ether (Aldrich), 6 g of tert-butyl methacrylic acid (Aldrich) and 60 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.15 g of azobisisobutyronitrile are then dissolved in 4 ml of ethyl methyl ketone slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 0.5 l of deionized water, the polymer product precipitating. After filtering off the product, the The filter residue was rinsed with 100 ml of demineralized water to remove any residual monomers that were still present. The product was then dried in vacuo at 50 ° C. for 24 hours

Example 4a

0.05 g of the product from Example 4 are placed in 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the Test microbial suspension removed and the number of bacteria in the test batch determined. After this time, no bacteria from Staphylococcus aureus can be detected

Example 4b: 0.05 g of the product from Example 4 are placed in 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined the bacterial count dropped from 10 ⁷ to 10 ²

Example 5:

A polyamide 12 film is exposed for 2 minutes at a pressure of 1 mbar to 172 nm radiation from an excimer radiation source from Heraeus. The film activated in this way is placed in an irradiation reactor under protective gas and fixed thereupon the film is exposed to 20 ml of a mixture in a protective gas countercurrent 6 g of 3-aminopropyl vinyl ether (Aldrich), 6 g of butyl methacrylate (Aldrich) and 60 g of ethanol are coated. The radiation chamber is closed and placed at a distance of 10 cm under an excimer radiation unit from Heraeus, which has an emission of the wavelength 308 nm The irradiation is started, the exposure time is 15 minutes. The film is then removed and rinsed with 30 ml of ethanol. The film is then dried in vacuo at 50 ° C. for 12 hours. The film is then extracted 5 times 6 hours at 30 ° C. in water. then dried at 50 ° C for 12 hours

The back of the film is then treated in the same way, so that finally a polyamide film coated on both sides with grafted polymer is obtained

Example 5a

A coated piece of film from Example 5 (5 × 4 cm) is placed in 30 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined. After this time there are no germs more detectable from Staphylococcus aureus Example 5b

A coated piece of film from Example 5 (5 × 4 cm) is placed in 30 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined dropped from 10 to 10

Example 6: A polyamide 12 film is exposed for 2 minutes at a pressure of 1 mbar to 172 nm radiation from an excimer radiation source from Heraeus. The film activated in this way is placed in an irradiation reactor under protective gas and fixed thereupon, the film is then counter-currented with 20 ml a mixture of 6 g of 3-aminopropyl vinyl ether (from Aldrich), 4 g of methacrylic acid tert-butyl ester (from Aldrich) and 60 g of ethanol. The radiation chamber is closed and placed at a distance of 10 cm under an excimer radiation unit from Heraeus, which has an emission of the wavelength 308 nm. The irradiation is started, the exposure time is 15 minutes. The film is then removed and rinsed with 30 ml of ethanol. The film is then dried in vacuo for 12 hours at 50 ° C. The film is then 5 times 6 in water Extracted hours at 30 ° C, then dried at 50 ° C for 12 hours

Example 6a

A coated piece of film from Example 6 (5 × 4 cm) is placed in 30 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test batch is determined more detectable from Staphylococcus aureus

Example 6b A coated piece of film from Example 6 (5 × 4 cm) is placed in 30 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined dropped from 10 ⁷ to 10 ⁴

Claims

claims:

1 Antimicrobial copolymers, obtainable by copolymerization of a vinyl ether of the general formula

with R ¹ = branched or unbranched hydrocarbon residue with 1 to 5

Carbon atoms and

R ² , R ³ = H, branched or unbranched hydrocarbon radical having 1 to 5 carbon atoms, where R ² and R ^{3 can be the} same or different,

with at least one aliphatic unsaturated monomer

2 antimicrobial copolymers according to claim 1, characterized in that 3-aminopropyl vinyl ether is used as vinyl ether

3 antimicrobial polymers according to claim 1 or 2, characterized in that the aliphatic unsaturated monomers are methacrylic acid compounds

4 antimicrobial polymers according to claim 1 or 2, characterized in that the aliphatic unsaturated monomers are acrylic acid compounds Antimicrobial polymers according to Claim 1 or 2, characterized in that the aliphatic unsaturated monomers are methyl methacrylate, ethyl methacrylate, butyl methacrylate, tert-butyl methacrylate, methyl acrylate, ethyl acrylate, 2-acrylate, tert-butyl methyl acrylate, tert-butyl methacrylate, tert-butyl methacrylate, Diethylamino-ethyl vinyl ether, N-3-dimethylaminopropyl methacrylamide, 3-methacryloyl-aminopropyltrimethylammonium chloride, 2-methacryloyloxyethyltrimethylammonium chloride or 2-methacryloyloxyethyltrimethylammonium methosulfate can be used

Antimicrobial polymers according to one of claims 1 to 5, characterized in that the copolymerization is carried out on a substrate

Antimicrobial polymers according to one of claims 1 to 5, characterized in that the copolymerization is carried out as a graft polymerization of a substrate

Antimicrobial polymers according to claim 7, characterized in that the substrate is activated before the graft polymerization by UV radiation, plasma treatment, corona treatment, flame treatment, ozonization, electrical discharge or γ-radiation

Antimicrobial polymers according to Claim 7, characterized in that the substrate is activated with a photoinitiator by UV radiation before the graft polymerization

Process for the preparation of antimicrobial copolymers, characterized in that a copolymerization of a vinyl ether of the general formula H

/

H, C:

\

N

with R ¹ = branched or unbranched hydrocarbon residue with 1 to 5

Carbon atoms and

is carried out with at least one aliphatic unsaturated monomer

A method according to claim 10, characterized in that 3-aminopropyl vinyl ether is used as the vinyl ether

A method according to claim 10 or 11, characterized in that the aliphatic unsaturated monomers are methacrylic acid compounds

A method according to claim 10 or 11, characterized in that the aliphatic unsaturated monomers are acrylic acid compounds

A process as claimed in claim 10 or 11, characterized in that the aliphatic unsaturated monomers are methyl methacrylate, ethyl methacrylate, butyl methacrylate, tert-butyl methacrylate, Acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid butyl ester, acrylic acid tert-butyl ester, tert-butylaminoethyl ester, 2-diethylaminoethyl methacrylate, 2-di-ethylaminoethyl vinyl ether, N-3-dimethylaminopropyl methacrylamide, 3-methacryloylaminopropyltrimethylethyl-methylethylmethyl-methyl-methyl-methyl-methyl-methoxy-2-methylethyl-methylethyl-methoxy-2-methylethyl-methoxy-2-methyl-methyl-imid-3-methyl-methyl-imid-methyl-methyl-imid-3-methyl-methoxy-2-methyl-methoxy-1-methoxyethyl become

Method according to one of claims 10 to 14, characterized in that the copolymerization is carried out on a substrate

Method according to one of claims 10 to 14, characterized in that the copolymerization is carried out as a graft polymerization of a substrate

A method according to claim 16, characterized in that the substrate is activated before the graft polymerization by UV radiation, plasma treatment, corona treatment, flame treatment, ozonization, electrical discharge or γ-radiation

A method according to claim 16, characterized in that the substrate is activated by UV radiation with a photoinitiator before the graft polymerization

Use of the antimicrobial polymers according to one of claims 1 to 9 for the production of products with an antimicrobial coating from the polymer

Use of the antimicrobial polymers according to one of claims 1 to 9 for the production of medical articles with an antimicrobial coating from the polymer Use of the antimicrobial polymers according to one of claims 1 to 9 for the production of hygiene articles with an antimicrobial coating from the polymer

Use of the antimicrobial polymers according to one of claims 1 to 9 in paints, protective coatings and coatings