WO2000069937A1

WO2000069937A1 - Microbicidal copolymers

Info

Publication number: WO2000069937A1
Application number: PCT/EP2000/002818
Authority: WO
Inventors: Peter Ottersbach; Beate Kossmann
Original assignee: Creavis Gesellschaft Für Technologie Und Innovation Mbh
Priority date: 1999-05-12
Filing date: 2000-03-30
Publication date: 2000-11-23
Also published as: DE19921902A1; EP1183288A1; AU4521300A

Abstract

The invention relates to anti-microbial polymers which are obtained by copolymerising aliphatically unsaturated monomers that are functionalised at least once by a primary amino group (component I) with another aliphatically unsaturated monomer that is functionalised at least once by a primary amino group (component II). Component I and II are different from each other. Aliphatically unsaturated monomers can be used as the component III for copolymerisation. The anti-microbial polymers can be used as a microbicidal coating on, inter alia, hygiene articles or in the field of medicine as well as in lacquers or protective coatings of paint.

Description

Microbicidal copolymers

The invention relates to antimicrobial polymers which are obtained by copolymerization of several aliphatic unsaturated monomers which are functionalized at least once by a primary amino group. The invention further relates to a process for the preparation and use of the antimicrobial polymers

Furthermore, the invention relates to antimicrobial polymers which are obtained on a substrate by graft copolymerization of aliphatic unsaturated monomers which are at least simply functionalized by a primary amino group, to a process for their preparation 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 lead

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 genital area and for nursing and elderly care.In addition, bacteria must be kept away from furniture and device surfaces in care stations, particularly in the area of Intensive care and the care of small children, in hospitals, in particular 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 that act as a disinfectant to a greater or lesser extent and have a massive antimicrobial effect degradation products that are harmful to health There are often also intolerances in appropriately sensitized people Another approach against surface bacterial spreading is the incorporation of antimicrobial substances into a matrix

Tert-butylaminoethyl methacrylate is a commercially available monomer of 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 field, 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 ( MtK) 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 developments of germs to counteract effectively must also be developed in the future systems based on new compositions and improved effectiveness

The present invention is therefore based on the object of developing novel, antimicrobial polymers which, if necessary, are intended as a coating to prevent the settlement and spread of bacteria on surfaces It has now surprisingly been found that by copolymerizing several components of aliphatic, unsaturated monomers which are functionalized at least simply by a primary amino group, or by graft copolymerizing these components on a substrate, polymers with a surface which is permanently microbicidal are obtained by solvents and physical stresses are not attacked and no migration shows, it is not necessary to use other biocidal agents

The present invention therefore relates to antimicrobial polymers which, by copolymerizing aliphatic, unsaturated monomers which are at least simply functionalized by a primary amino group (component I), with a further aliphatic unsaturated monomer which is at least simply functionalized by a primary amino group (component II), component I and component II being different from one another, are obtained

The present invention also relates to a process for the preparation of antimicrobial polymers which are graft copolymerized by aliphatic, unsaturated monomers which are at least simply functionalized by a primary amino group (component I), with a further aliphatic unsaturated monomer which is at least simply by a primary amino group is functionalized (component II), component I and component II being different from one another, are obtained

The inventive copolymerization of aliphatic unsaturated monomers which are at least simply functionalized by a primary amino group (components I and II) is also possible with a further aliphatic unsaturated monomer (component III) while largely maintaining the microbicidal action

Suitable comonomer building blocks of components I and II are all aliphatic unsaturated monomers which have at least one primary amino function, such as l-amino-2-propene, N-6-aminohexyl-2-propenamide, N-3-aminopropyl methacrylamide hydrochloride, Methacrylic acid 2-aminoethyl ester hydrochloride and 3-aminopropyl vinyl ether The aliphatic unsaturated monomers functionalized at least simply by a primary amino group in the process according to the invention can have a hydrocarbon radical of up to 50, preferably up to 30, particularly preferably up to 22 carbon atoms. Furthermore, the monomers can also be derived from keto or aldehyde groups such as acrylolyl or oxo groups or cyclic hydrocarbon radicals such as substituted or unsubstituted phenyl or cyclohexyl radicals

In order to achieve a sufficient polymerization rate, the monomers of components I or II used according to the invention should have a molar mass of less than 900, preferably less than 550 g / mol

In a particular embodiment of the present invention, aliphatic unsaturated monomers of the general formula which are functionalized simply by a primary amino group for components I or II

Rι NH ₂

with Ri branched, unbranched or cyclic, aliphatic unsaturated

Hydrocarbon radicals with up to 50 carbon atoms, which can be substituted by O, N or S atoms, are used

The monomers of components I and II must be different. A molecular weight difference of at least 23 g / mol can exist between these monomers. Exemplary combinations of monomers of components I, II and possibly III are described in the examples

The antimicrobial copolymers according to the invention can also be carried out by copolymerizing components I and II or I, II and III on a substrate. A physisorbed coating of the antimicrobial copolymer is obtained on the substrate All polymeric plastics, such as, for example, are suitable as substrate materials. B Polyurethanes, 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 components I and II or components I, II and III. Grafting the substrate enables the antimicrobial copolymer to be covalently bound to the substrate. All polymeric materials can be used as substrates how the plastics already mentioned are used

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

The substrates 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 standard polymers 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 carried out by plasma treatment using an RF or microwave plasma (Hexagon, Fa Technics Plasma, 85551 Kirchheim, Germany) in air.

Nitrogen or argon atmosphere can be reached. The exposure times are generally 2 seconds to 30 minutes, preferably 5 seconds to 10 minutes. The energy input in 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 surface of the substrate facing away from the flame side. Activation by flame is accordingly limited to relatively thin, flat substrates. The exposure times generally amount to 0 1 second to 1 minute, preferably 0 5 to 2 seconds, all of which deal with non-luminous flames and the distances between the substrate surfaces and the outer flame front are 0 2 to 5 cm, preferably 0.5 to 2 cm The substrate surfaces thus activated are, according to known methods, such as dipping, spraying or brushing, with aliphatic unsaturated monomers which are at least simply functionalized by a primary amino group (component I), with one or more aliphatic unsaturated monomers, at least one of which is by a primary amino group is functionalized (component II), component I and component II being different from one another, if appropriate in solution, coated Water and water / ethanol mixtures have proven to be suitable as solvents, but other solvents can also be used, provided they have a sufficient capacity 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 found to be effective in practice and generally result in coherent coats covering the substrate surface with layers thicker than layers 0 1 m can be

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 significant amounts of radiation in the areas mentioned: n The exposure times are generally 10 seconds to 30 minutes, preferably 2 to 15 minutes

Furthermore, a 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 III

The antimicrobial copolymers of aliphatic unsaturated according to the invention

Monomers which are at least simply functionalized by a primary amino group (components I and II) and optionally a further aliphatic unsaturated monomer

(Component III), component I and component II being different from one another, show microbicidal or antimicrobial behavior even without grafting onto a substrate surface

A further embodiment of the present invention consists in that the copolymerization of components I and II or I, II and II, component I and component II being different from one another, is carried out on a substrate

Components I, II and III, if applicable, can be applied to the substrate in solution. Examples of suitable solvents are water, ethanol, methanol, methyl ethyl ketone, diethyl ether, dioxane, hexane, heptane, benzene, toluene, chloroform, dichloromethane, tetrahydrofuran and acetonitrile Component III can also serve for components I and II

All aliphatic unsaturated monomers which undergo copolymerization with components I and II can be used as component III. Further aliphatic unsaturated monomers which are at least simply functionalized by a primary amino group can also be used as component III, in which case components I , II and III are all different from one another. In addition, as component III, acrylates or methacrylates, for example 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 are 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

The initiators that can be used include azonitriles, alkyl peroxides, hydroperoxides, acyl peroxides, peroxoketones, peresters, peroxocarbonates, peroxodisulfate, persulfate and all the usual photoinitiators such as acetophenones, α-hydroxyketones, dimethyl ketals and and benzophenone

The polymerization can also be initiated 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 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, polyolefins, 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 roofing, basement, walls, facades, greenhouses, sun protection, garden fence, wood protection

Sanitary Public toilets, bathrooms, shower curtains, toiletries,

Swimming pool, sauna, joints, sealing compounds

Food machines, kitchen, cake items, sponges, toys, food packaging, milk processing, drinking water systems, cosmetics - machine parts air conditioning, ion exchangers, process water, solar systems,

Heat exchangers, bioreactors, membranes, medical technology, contact lenses, diapers, membranes, implants

Articles of daily use car seats, clothing (stockings, sportswear),

Hospital facilities, door handles, telephone receiver, public transport, animal cages, cash registers, carpeting, wallpaper

The present invention also relates to the use of the polymer substrates modified according to the invention with the inventive polymers or processes on the surface for the production of hygiene products or medical articles. The above statements regarding preferred materials apply accordingly. Such hygiene products are, for example, toothbrushes, toilet seats, combs and packaging materials other objects, which may come into contact with many people, such as telephone handset, handrail of stairs, door and window handles as well as holding straps and handles in public transport, medical technology articles are e.g. 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 methacrylic acid-2-aminoethyl ester hydrochloride (Aldrich), 6 g of 3-aminopropyl vinyl ether (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 slowly added dropwise in 4 ml of ethyl methyl ketone with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After this time, the reaction mixture is stirred into 0.5 l of n-hexane, the polymeric product precipitating out. After filtering off the product the filter residue is rinsed with 100 ml of n-hexane in order 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 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, no Staphylococcus germs are found aureus more detectable

Example lb

0.05 g of the product from Example 1 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. After this time, the number of bacteria is 10 ⁷ dropped to 10 ⁴

Example 2

4 g of methacrylic acid-2-aminoethyl ester hydrochloride (Aldrich), 4 g of N-3-aminopropyl methacrylamide hydrochloride (Polysciences Ine) and 50 ml of ethanol are in placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.1 g of azobisisobutyronitrile dissolved in 4 ml of ethyl methyl ketone is then slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After this time, the reaction mixture is stirred in 0.5 l of n-hexane, the polymeric product precipitating. After filtering off the product, the filter residue is rinsed with 100 ml of n-hexane in order to remove residual monomers that are still present. The product is then left in vacuo at 50 ° C. for 24 hours dried

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. After this time the number of bacteria is 10 ⁷ dropped to 10 ²

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. After this time, the number of bacteria is 10 ⁷ dropped to 10 ⁴

Example 3

6 g of 3-aminopropyl vinyl ether (Aldrich), 4 g of N-3-aminopropyl methacrylamide hydrochloride

(Polysciences Ine) and 60 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.14 g of azobisisobutyronitrile dissolved in 4 ml of ethyl methyl ketone is slowly added dropwise with stirring. The mixture is heated to 70 ° C. and for 72 hours stirred at this temperature. After this time, the reaction mixture is stirred into 0.5 l of n-hexane, the polymeric product precipitating. After filtering off the product, the filter residue is rinsed with 100 ml of n-hexane in order to remove any residual monomers still present the product dried for 24 hours at 50 ° C in a vacuum Example 3a

0.05 g of the product from Example 3 is 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. After this time, no Staphylococcus aureus bacteria are found more detectable

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. After this time, the number of bacteria is 10 ⁷ dropped to 10 ²

Example 4 4 g of 3-aminopropyl vinyl ether (Aldrich), 2 g of N-3-aminopropyl methacrylamide hydrochloride (Polysciences Ine), 3 g of 2-aminoethyl methacrylate hydrochloride (Aldrich), and 70 ml of ethanol are combined in one Three-necked flasks were introduced and heated to 65 ° C. under a stream of argon. 0.18 g of azobisisobutyronitrile dissolved in 4 ml of ethyl methyl ketone were then slowly added dropwise with stirring. The mixture was heated to 70 ° C. and stirred at this temperature for 72 hours. After this time, the reaction mixture was dissolved in 0.6 l of n-hexane is stirred in, the polymeric product precipitating. After filtering off the product, the filter residue is rinsed with 140 ml of n-hexane in order to remove residual monomers still present. The product is 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 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 the number of bacteria is 10 ⁷ dropped to 10 ¹ 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 bacteria in the test mixture is determined. After this time, the number of bacteria is 10 ⁷ dropped to 10 ¹

Example 5

4 g of methacrylic acid 2-aminoethyl ester hydrochloride (Aldrich), 5 g of 3-aminopropyl vinyl ether (Aldrich), 3 g of methyl methacrylate (Aldrich) and 65 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 dissolved in 4 ml of ethyl methyl ketone is 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 1 n-hexane, during which time the polymeric product precipitates after filtering off the product, the filter residue is rinsed with 100 ml of n-hexane in order to remove any residual monomers still present. The product is then dried in vacuo at 50 ° C. for 24 hours

Example 5a 0.05 g of the product from Example 5 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 ³

Example 5b

0.05 g of the product from Example 5 is 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. After this time, the number of bacteria is 10 ⁷ dropped to 10 ⁴ Example 6:

4 g of methacrylic acid 2-aminoethyl ester hydrochloride (from Aldrich), 4 g of 3-aminopropyl vinyl ether (from Aldrich), 2.5 g of butyl methacrylate (from Aldrich) and 65 ml of ethanol are placed in a three-necked flask and under a stream of argon heated to 65 ° C. Then 0.15 g of azobisisobutyronitrile dissolved in 4 ml of ethyl methyl ketone are slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After this time, the reaction mixture is stirred into 0.5 l of n-hexane, the polymeric product precipitating; after filtering off the product, the filter residue is rinsed with 100 ml of n-hexane in order to remove any residual monomers still present. The product is then dried in vacuo at 50 ° C. for 24 hours.

Example 6a

0.05 g of the product from Example 6 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 is removed and the number of microbes in the test mixture is determined. After this time the number of germs has dropped from 10 ⁷ to 10 ⁴ .

Example 6b

0.05 g of the product from Example 6 are placed in 20 ml of a test germ 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. After this time the number of germs has dropped from 10 ⁷ to 10 ⁴ .

In addition to the above-described microbicidal activity against cells from Pseudomonas aeruginosa and Staphylococcus aureus, all samples also showed microbicidal activity against cells from Klebsiella pneumoniae, Escherichia coli, Rhizopus oryzae, Candida tropicalis and Tetrahymena pyriformis.

Claims

Claims:

1 Antimicrobial polymers, obtainable by copolymerization of aliphatic unsaturated monomers which are at least simply functionalized by a primary amino group (component I), with a further aliphatic unsaturated monomer which is at least simply functionalized by a primary amino group (component II), component I and component II are different from each other

2 antimicrobial polymers according to claim 1, characterized in that the copolymerization is carried out with further, aliphatic unsaturated monomers (component III)

3 antimicrobial polymers according to one of claims 1 or 2, characterized in that for component I and II functionalized by a primary amino group aliphatic unsaturated monomers of the general formula

Rι NH ₂

with Ri branched, unbranched or cyclic, aliphatic unsaturated

Hydrocarbon radicals with up to 50 carbon atoms, which can be substituted by O, N or S atoms

4 antimicrobial polymers according to one of claims 1 to 3, characterized in that there is a molecular weight difference of at least 23 g / mol between the monomers of components I and II

5 antimicrobial polymers according to one of claims 1 to 4, characterized in that the copolymerization is carried out on a substrate

Antimicrobial polymers according to one of claims 1 to 4, characterized in that the copolymerization is carried out as a graft polymerization of a substrate

Antimicrobial polymers according to claim 6, 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 6, characterized in that the substrate before the graft polymerization by UV radiation with a

Photoinitiator is activated

Process for the preparation of antimicrobial polymers by copolymerization of aliphatic unsaturated monomers which are at least simply functionalized by a primary amino group (component I), with a further aliphatic unsaturated monomer which is at least simply functionalized by a primary amino group (component II), component I and component II are different from each other

Process according to claim 9, characterized in that the copolymerization is carried out with further aliphatic unsaturated monomers (component III)

Method according to one of claims 9 or 10, characterized in that that for component I and II each functionalized by a primary amino group aliphatic unsaturated monomers of the general formula

Rι NH ₂

with Ri branched, unbranched or cyclic, aliphatic unsaturated

Method according to one of claims 9 to 11, characterized in that there is a molecular weight difference of at least 23 g / mol between the monomers of components I and II

Method according to one of claims 9 to 12, characterized in that the copolymerization is carried out on a substrate

Method according to one of claims 9 to 12, characterized in that the copolymerization is carried out as a graft polymerization of a substrate

A method according to claim 14, characterized in that the substrate before the graft polymerization by UV radiation, plasma treatment,

Corona treatment, flame treatment, ozonization, electrical discharge or γ-radiation is activated

A method according to claim 14, characterized in that the substrate is activated by UV radiation with a photoinitiator before the graft polymerization.

17. Use of the antimicrobial polymers according to one of claims 1 to 8 for the production of products with an antimicrobial coating from the polymer.

18. Use of the antimicrobial polymers according to one of claims 1 to 8 for the production of medical articles with an antimicrobial coating from the polymer.

19. Use of the antimicrobial polymers according to one of claims 1 to 8 for the production of hygiene articles with an antimicrobial coating from the polymer.

20. Use of the antimicrobial polymers according to one of claims 1 to 8 in paints, protective coatings and coatings.