EP1183293A1

EP1183293A1 - Microbicidal copolymers

Info

Publication number: EP1183293A1
Application number: EP00929329A
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: 1999-05-12
Filing date: 2000-03-30
Publication date: 2002-03-06
Also published as: NO20015531L; WO2000069934A1; JP2002544347A; AU7236300A; NO20015531D0; DE19921899A1; CN1361797A

Abstract

The invention relates to antimicrobial polymers, obtained by the copolymerisation of aliphatically unsaturated monomers which are at least simply functionalised by a secondary amino group (component I), with an additional aliphatically unsaturated monomer which is at least simply functionalised by a secondary amino group (component II), whereby component I and component II are different from one another. Additional aliphatically unsaturated monomers can be used as component III for copolymerisation. The antimicrobial polymers can be used as a microbicidal coating, among others, on hygiene articles or in the medical field and can also be used in lacquers or protective paint coatings.

Description

Microbicidal copolymers

The invention relates to antimicrobial polymers which are obtained by copolymerization of a plurality of aliphatic unsaturated monomers which are functionalized at least simply by a secondary amino group. The invention further relates to a method for producing and using 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 secondary amino group, to a process for their preparation and their use.

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

Bacteria must be kept away from all areas of life where hygiene is important. This affects textiles for direct body contact, especially 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, in particular 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 infections and in toilets.

Devices, surfaces of furniture and textiles against bacteria are currently being treated as necessary or as a precautionary measure with chemicals or their solutions as well as mixtures that act as a disinfectant, more or less broadly and massively antimicrobially. Such chemical agents have a non-specific effect, are often themselves toxic or irritating or form degradation products which are harmful to health. Often, intolerances also appear in people who are appropriately sensitized. Another way of preventing surface bacteria from spreading is to incorporate 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 ( 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 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 settling and spreading of bacteria on surfaces It has now surprisingly been found that by copolymerizing several components of aliphatic, unsaturated monomers which are at least simply functionalized by a secondary amino group, or by graft copolymerizing these components on a substrate, polymers having 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 copolymerization of aliphatic, unsaturated monomers which are at least simply functionalized by a secondary amino group (component I), with a further aliphatic unsaturated monomer which is at least simply functionalized by a secondary 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 functionalized by graft copolymerization of aliphatic, unsaturated monomers which are at least simply functionalized by a secondary amino group (component I) with a further aliphatic unsaturated monomer which is at least simple by a secondary amino group is functionalized (component II), component I and component II being different from one another, are obtained

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

Suitable comonomer building blocks are, in addition to the secondary amino-functionalized acrylic or .alpha. Described in European applications 0 862 858 and 0 862 859

Methacrylic acid esters, all aliphatic unsaturated monomers which have at least one secondary amino function, such as, for example, 3-phenylmethylamino-2-butenoic acid ethyl ester, 3-ethylamino-2-butenoic acid ethyl ester, 3-methylamino-2-butenoic acid ethyl ester, 3-methylamino-1-phenyl-2 propen-1-one, 2-methyl-N-4-methylamino-1-anthraquinoyl-acrylamide, N-9, 10-dihydro-4- (4- methylphenylamino) -9, 10-dioxo-1-anthrachinyl-2-methyl-propenamide, 2-hydroxy-3 - (3 - triethoxysilylpropylamino) -2-propenoic acid propyl ester, 1 - (1-methylethylamino) -3 - (2- (2nd - propenyl) phenoxy) -2-propanol hydrochloride, 3-phenylamino-2-butenoic acid ethyl ester, 1 - (1 - methylethylamino) -3- (2- (2-propenyloxy) phenoxy) -2-propanol hydrochloride, 2-acrylamido -2-methoxyacetic acid methyl ester, 2-acetamidoacrylic acid methyl ester, acrylic acid tert -butylamide, 2-hydroxy-N-2-propenyl-benzamide, N-methyl-2-propenamide

The aliphatic unsaturated monomers of components I or II functionalized according to the invention and functionalized at least once by a secondary amino group can have a hydrocarbon radical of up to 50, preferably up to 30, particularly preferably up to 22 carbon atoms. The substituents of the amino group can have aliphatic or vinyl hydrocarbon radicals such as methyl, ethyl, propyl or acrylic radicals or cyclic hydrocarbon radicals such as substituted or unsubstituted phenyl or cyclohexyl radicals having up to 25 carbon atoms. Furthermore, the amino group can also be substituted by keto or aldehyde groups such as acryloyl or oxo groups

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 secondary amino group for components I or II

with R _x branched, unbranched or cyclic, saturated or unsaturated hydrocarbon radical with up to 50 carbon atoms, which can be substituted by O, N or S atoms and R ₂ branched, unbranched or cyclic, saturated or unsaturated hydrocarbon radical with up to 25 C atoms, which can be substituted by O, N or S atoms, be 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 are particularly suitable as substrate materials, such as, for example, polyurethanes, polyamides, polyesters and ethers, polyether block amides, polystyrene, polyvinyl chloride, polycarbonates, polyorganosiloxanes, polyolefms, 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 wood bodies

In a further embodiment of the present invention, the copolymers can be prepared by graft-polymerizing a substrate with components I and II or components I, II and III. The grafting of the substrate enables the antimicrobial copolymer to be covalently bonded 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 up 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, especially 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 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 treatment is accordingly limited to relatively thin, flat substrates.The exposure times are generally 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 substrates and the outer flame front are 0 2 to 5 cm, preferably 0 5 to 2 cm

The substrate surfaces activated in this way are, according to known methods, such as dipping, spraying or brushing, with aliphatic unsaturated monomers which are at least simply functionalized by a secondary amino group (component I), with one or more aliphatic unsaturated monomers, at least one of which is by a secondary 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 coatings covering the substrate surface with layer thicknesses of more than 0Can be 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, a graft copolymerization of the comonomer compositions according to the invention can also be achieved by a process which is known in Europe Patent application 0 872 512 is described, 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 monomers according to the invention, which are functionalized at least simply by a secondary amino group (component I and II), and optionally a further aliphatic unsaturated monomer (component III), component I and component II being different from one another, also show microbicidal or antimicrobial behavior 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 functionalized at least simply by a secondary 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, component III can be acrylates or methacrylates, for example acrylic acid, tert-butyl methacrylate or methyl methacrylate, styrene, vinyl chloride, vinyl ether, 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 Further objects of the present invention are 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 present invention also relates to the use of the polymer substrates modified on the surface with polymers or processes according to the invention 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 also other objects that may come into contact with many people, such as a telephone handset, handrails of stairs, door and window handles, and holding straps and handles in public transport. Medical technology items include catheters, tubes, cover foils or surgical cutlery

The copolymers or graft polymers according to the invention can be used wherever bacterial-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 machinery, kitchen, cake items, sponges, toys,

Food packaging, milk processing, drinking water systems, cosmetics Machine parts Air conditioning systems, ion exchangers, process water, solar systems, heat exchangers, bioreactors, membranes, medical technology, contact lenses, diapers, membranes, implants, utensils, car seats, clothing (stockings, sportswear), hospital facilities, door handles, telephone receiver, public transport,

Animal cages, cash registers, carpeting, wallpaper

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

5 g of 2-acrylamido-2-methoxyacetic acid methyl ester (Aldrich), 5 g of 2-acetamidoacrylic acid methyl ester (Aldrich) and 55 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 is dissolved slowly added dropwise in 4 ml of ethyl methyl ketone 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, 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 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 is placed in 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 30 minutes, 1 ml of the test germ suspension is removed, and the number of bacteria in the test mixture is determined 10 ⁷ dropped to 10 ³

Example lb

0.05 g of the product from Example 1 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 bacterial count in the test mixture is determined. After this time, the bacterial count has dropped from 10 ⁷ to 10 ⁴

Example 2

5 g of 2-acrylamido-2-methoxyacetic acid methyl ester (Aldrich), 3 g of tert-butylamide (Aldrich) and 55 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.12 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 for 72 hours at this temperature. After this time, the reaction mixture is stirred into 0.5 1 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 remaining monomers. 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 30 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 ³

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 ³

Example 3 4 g of methyl 2-acetamidoacrylate (Aldrich), 5 g of tert-butyl acrylate (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 is dissolved in 5 ml Ethyl methyl ketone was slowly added dropwise with stirring. The mixture was heated to 70 ° C. and stirred for 72 hours at this temperature. After this time, the reaction mixture was stirred into 0.5 1 n-hexane, the polymeric product precipitating. After filtering off the product, the filter residue became rinsed with 100 ml of n-hexane to remove any residual monomers still present. The product is then dried in vacuo at 50 ° C. for 24 hours

Example 3 a

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 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 10 ⁷ dropped to 10 ³

Example 4

1.5 g of 3-ethylamino-2-butenoic acid ethyl ester (from Sigma), 1.5 g of 3-methylamino-2-butenoic acid ethyl ester (from Sigma) and 35 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon 0.1 g of azobisisobutyronitrile dissolved in 3 ml of ethyl methyl ketone is 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 0.35 l of n-hexane, the polymer Product precipitates after filtering off the product, the filter residue is rinsed with 70 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 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, no Staphylococcus aureus bacteria are found more detectable

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 ²

Example 5

4 g of 2-acrylamido-2-methoxyacetic acid methyl ester (from Aldrich), 5 g of 2-acetamidoacrylic acid methyl ester (from Aldrich), 3 g of methyl methacrylate (from 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. After this time, no Staphylococcus aureus bacteria are found more detectable Example 5b

0.05 g of the product from Example 5 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 6

4 g of 2-acrylamido-2-methoxyacetic acid methyl ester (from Aldrich), 4 g of 2-acetamidoacrylic acid methyl ester (from Aldrich), 2.5 g of butyl methacrylate (from Aldrich) and 65 ml of ethanol are placed in a three-necked flask and brought to 65 ° under a stream of argon C. 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 at this temperature for 72 hours. After this time, the reaction mixture is stirred into 0.5 l of n-hexane , whereby 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 remaining monomers. 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 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 6b

0.05 g of the product from Example 6 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

In addition to the microbicidal activity against cells of Pseudomonas aeruginosa and Staphylococcus aureus described above, all samples also showed one microbicidal activity against cells of 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 secondary amino group (component I), with a further aliphatic unsaturated monomer which is at least simply functionalized by a secondary 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 secondary amino group aliphatic unsaturated monomers of the general formula

with Ri-branched, unbranched or cyclic, saturated or unsaturated hydrocarbon radical with up to 50 C atoms, which can be substituted by O, N or S atoms and

R: Branched, unbranched or cyclic, saturated or unsaturated hydrocarbon radical with up to 25 C atoms, which can be substituted by O, N or S atoms, are used.

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.

6. 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.

7. 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.

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

9. A process for the preparation of antimicrobial polymers by copolymerization of aliphatic unsaturated monomers which are at least simply functionalized by a secondary amino group (component I), with a further aliphatic unsaturated monomer which is at least simply functionalized by a secondary amino group (component II), where Component I and component II are different from each other.

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

11. The method according to any one of claims 9 or 10, characterized in that for component I and II each functionalized by a secondary amino group aliphatic unsaturated monomers of the general formula

with Ri branched, unbranched or cyclic, saturated or unsaturated hydrocarbon radical with up to 50 carbon atoms, which can be substituted by O, N or S atoms and R ₂ branched, unbranched or cyclic, saturated or unsaturated hydrocarbon radical with up to 25 carbon atoms, which can be substituted by O, N or S atoms

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

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

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 lacquers, protective coatings or coatings.