DE19921902A1 - Antimicrobial copolymer for medical and hygiene articles, varnishes, paints and coatings comprises monomers with a prim. amino group(s) and further monomers having a prim. amino group(s) - Google Patents

Abstract

Antimicrobial copolymer contains at least two different prim. amino functional monomers. Antimicrobial copolymer is prepared by polymerizing aliphatically unsaturated monomers (I) having a prim. amino group(s) with further aliphatically unsaturated monomers (II) having a prim. amino group(s). An Independent claim is included for the preparation of the above copolymer by copolymerizing monomers (I) and (II).

Description

The invention relates to antimicrobial polymers, which by copolymerization of several aliphatic unsaturated monomers, at least simply by one primary amino group are functionalized can be obtained. Furthermore, the Invention a method for producing and using the antimicrobial Polymers.

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

Colonization and spread of bacteria on pipe surfaces, Containers or packaging are highly undesirable. It is formed often layers of mucus that cause microbial populations to increase extremely Water, beverage and food qualities have a lasting impact and even to spoil the goods and harm the health of consumers being able to lead.

Bacteria are from all areas of life where hygiene is important keep away. This affects textiles for direct body contact, in particular especially for the intimate area and for nursing and elderly care. Also are Keep bacteria away from furniture and device surfaces in care stations, especially in the area of intensive care and care of infants, in the sick houses, especially in rooms for medical interventions and in isolation stations for critical infections and in toilets.  

Devices, surfaces of furniture and textiles are currently used against bacteria if necessary or as a precaution with chemicals or their solutions as well Mixtures treated as a disinfectant more or less wide and have a massive antimicrobial effect. Such chemical agents are non-specific often themselves toxic or irritating or form health-threatening Degradation products. Often there are also intolerances sensitized people.

Another approach against superficial spread of bacteria 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 used. For example, EP-PS 0 290 676 describes the use of various polyacrylates and Polymethacrylates as a matrix for the immobilization of bactericidal quaternaries Ammonium compounds described.

From another technical field, U.S. Patent 4,532,269 discloses a terpolymer from butyl methacrylate, tributyltin methacrylate and tert-butylaminoethyl methacrylate. This polymer is used as an antimicrobial marine paint, the hydro phile tert-butylaminoethyl methacrylate promotes the slow erosion of the polymer and so the highly toxic tributyltin methacrylate as an antimicrobial agent releases.

In these applications, the copolymer made with aminomethacrylates is only Matrix or carrier for added microbicidal active ingredients, which from the Diffuse or migrate carrier. Polymers of this type lose more or less quickly their effect if the necessary on the surface "minimal inhibitory concentration" (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, one  Methacrylic acid ester with secondary amino function, inherently microbicidal Possess properties. To avoid undesirable adaptation processes of the microbial Life forms, especially in view of those from antibiotic research known resistance developments of germs to effectively counteract

systems based on new compositions and improvements Effectiveness to be developed.

The object of the present invention is therefore to develop novel, to develop antimicrobial polymers. If necessary, these should be used as a coating prevent the settlement and spread of bacteria on surfaces.

It has now surprisingly been found that by copolymerizing several Components of aliphatic, unsaturated monomers that are at least simple are functionalized by a primary amino group, or by Graft copolymerization of these components on a substrate with a polymer Surface that is permanently microbicidal, by solvents and physical stress is not attacked and shows no migration. It is not necessary to use other biocidal agents.

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

The present invention also relates to a process for the production antimicrobial polymers obtained by graft copolymerization of aliphatic, unsaturated monomers, at least simply by a primary amino group are functionalized (component I), with another aliphatic unsaturated Monomers that are at least simple through a primary amino group  is functionalized (component II), component I and component II are different from each other.

The copolymerization of aliphatic unsaturated monomer according to the invention, which are at least simply functionalized by a primary amino group (Component I and II), is also aliphatic with another unsaturated Monomers (component III) while largely maintaining the microbicidal action possible.

All aliphatic are suitable as comonomer components of components I and II unsaturated monomers which have at least one primary amino function such as e.g. B. 1-amino-2-propene, N-6-aminohexyl-2-propenamide, N-3-amino propyl methacrylamide hydrochloride, methacrylic acid 2-aminoethyl ester hydrochloride and 3-aminopropyl vinyl ether.

The used in the method according to the invention, at least simply by one primary amino group functionalized, aliphatic unsaturated monomers can have a hydrocarbon residue of up to 50, preferably up to 30, especially preferably have up to 22 carbon atoms. Furthermore, the Monomers also by keto or aldehyde groups such as acrylolyl or Oxo groups or cyclic hydrocarbon radicals such as substituted unsubstituted phenyl or cyclohexyl radicals are substituted.

In order to achieve a sufficient rate of polymerization, the Monomers of components I or II used according to the invention have a molecular weight 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 by a primary amino group can be used for components I or II

R ₁ NH ₂

with branched, unbranched or cyclic, aliphatic unsaturated hydrocarbon radical with up to 50 C atoms, which can be substituted by O, N or S atoms,
be used.

The monomers of components I and II must be different. So can a molar mass difference of at least 23 g / mol between these monomers consist. 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 by Copolymerization of components I and II or I, II and III on a substrate be performed. It becomes a physisorbed coating from the antimicrobial copolymer 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, poly-chloroprene, 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 used on surfaces of painted or otherwise with plastic Use coated metal, glass or wooden bodies.

In a further embodiment of the present invention, the Copolymers by graft polymerization of a substrate with components I and II or components I, II and III can be obtained. The grafting of the substrate enables the antimicrobial copolymer to be covalently bound to the  Substrate. All polymeric materials, such as those already mentioned, can be used as substrates Plastics are used.

The surfaces of the substrates can be after a graft copolymerization Set of methods to be activated. All standard methods for Activation of polymeric surfaces are used; For example, the Activation of the substrate before the graft polymerization by UV radiation, Plasma treatment, corona treatment, flame treatment, ozonization, electrical Discharge of γ radiation, methods used. The are expedient Surfaces previously in a known manner using a solvent of oils, fats or other contaminants.

The substrates can be activated by UV radiation in the wavelength range 170-400 nm, preferably 170-250 nm. A suitable radiation source is e.g. B. a UV excimer device HERAEUS Noblelight, Hanau, Germany. But also Mercury vapor lamps are suitable for substrate activation if they are significant Emit 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 continue with a additional photosensitizer. For this, the photosensitizer, such as B. Benzophenone applied to the substrate surface and irradiated. This can also be used 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 a RF or microwave plasma (Hexagon, Technics Plasma, 85551 Kirchheim, Germany) in air, nitrogen or argon atmosphere. The Exposure times are generally 2 seconds to 30 minutes, preferably  5 seconds 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. use for activation. The exposure times in this case are Usually 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 enables 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 flame barrier, can be opened easily build or, for example, obtain from ARCOTEC, 71297 Mönsheim, Germany. You can use hydrocarbons or hydrogen as Fuel gas operated. In any case, harmful overheating of the Avoid substrate, which is due to intimate contact with a cooled Metal surface on the substrate surface facing away from the flame side is easily achieved. The activation by flame is accordingly on relatively thin, flat substrates limited. The exposure times are generally 0.1 seconds to 1 minute, preferably 0.5 to 2 seconds, all of which deal with non-glowing flames and the distances the substrate surfaces to the outer flame front 0.2 to 5 cm, preferably 0.5 up to 2 cm.

The substrate surfaces activated in this way are processed using known methods such as Dip, spray or brush with aliphatic unsaturated monomers that 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 functionalized by a primary amino group (Component II), component I and component II being different from one another  are, optionally in solution, coated. Water and Water-ethanol mixtures have proven their worth, but other solvents can also be used, provided they have sufficient solvency for the monomers and the Wet the substrate surfaces well. Solutions with monomer contents from 1 to 10 % By weight, for example about 5% by weight, have proven themselves in practice and generally result in coherent in one pass that Coatings covering the substrate surface with layer thicknesses of more than 0.1 µm can be.

The graft copolymerization of those applied to the activated surfaces Monomers can be expediently by radiation in the short-wave segment of the visible range or in the long-wave segment of the UV range electromagnetic radiation can be initiated. Z. B. the radiation a UV excimer of the wavelengths 250 to 500 nm, preferably from 290 to 320 nm. Mercury vapor lamps are also suitable here, provided they are significant Emit 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 invention Comonomer compositions can also be achieved by a method which is in the European patent application 0 872 512 is described, and on a Graft polymerization of swollen monomer and initiator molecules is based. The monomer used for swelling can be component III.

The antimicrobial copolymers of aliphatic unsaturated according to the invention Monomers that are simply functionalized by a primary amino group (Component I and II), and optionally another aliphatic unsaturated Monomers (component III), component I and component II are different from one another, point to one even without grafting Microbicidal or antimicrobial behavior.  

Another embodiment of the present invention is that the Copolymerization of components I and II or I, II and II, component I and component II are different from one another, carried out on a substrate becomes.

Components I, II and optionally III can be applied to the substrate in solution become. Suitable solvents are, for example, water, ethanol, methanol, Methyl ethyl ketone, diethyl ether, dioxane, hexane, heptane, benzene, toluene, Chloroform, dichloromethane, tetrahydrofuran and acetonitrile. As a solvent for Component I and II can also serve component III.

All aliphatic unsaturated monomers can be used as component III be that undergo a copolymerization with components I and II. Further aliphatic unsaturated monomers that are at least simple by a primary Amino group are functionalized, can also be used as component III, in which case components I, II and III are all different from one another are. In addition, as component III, acrylates or methacrylates, e.g. B. 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, i.e. H. Not by polymerizing the components on a substrate, rather than antimicrobial coating can be used. 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, for. B. by diving, Spraying or painting can be applied to the substrates.  

Are the polymers of the invention without grafting directly on the Generated substrate surface, so conventional radical initiators can be added. As initiators u. a. Azonitriles, alkyl peroxides, hydroperoxides, acylper oxides, peroxoketones, peresters, peroxocarbonates, peroxodisulfate, persulfate and all usual photoinitiators such. B. acetophenones, α-hydroxy ketones, dimethyl ketals and use benzophenone.

The polymerization can also be initiated thermally or as already executed by electromagnetic radiation, such as. B. UV light or γ radiation respectively.

Furthermore, the antimicrobial polymers according to the invention can also be used as Use 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 antimicrobial effective products and the products so manufactured as such. The Products can contain or modified polymer substrates according to the invention consist of these. Such products are preferably based on polyamides, Polyurethanes, polyether block amides, polyester amides or imides, PVC, Polyolefins, silicones, polysiloxanes, polymethacrylate or polyterephthalates, the 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, kitchen articles, components from Sanitary facilities, components of animal cages and dwellings, Toys, components in water systems, food packaging, Control 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: ship hulls, port facilities, buoys, drilling platform, Ballast water tanks
• - House: roofs, cellars, walls, facades, greenhouses, Sun protection, garden fences, wood protection
• - Sanitary: public toilets, bathrooms, shower curtains, toiletries, Swimming pool, sauna, joints, sealing compounds
• - Food: machines, kitchen, kitchen 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
• - Articles of daily use: car seats, clothing (stockings, sportswear) Hospital facilities, door handles, telephone receivers, public Transportation, animal cages, cash registers, carpeting, wallpaper

The present invention also relates to the use of the according to the invention with polymers or processes according to the invention Surface modified polymer substrates for the production of Hygiene products or medical devices. The above statements about 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 U. with many people come into contact, like telephone receivers, handrails from stairs, Door and window handles as well as straps and handles in public transport.  

Medical technology articles are e.g. B. catheters, tubes, cover films or surgical cutlery.

To further describe the present invention, the following Given examples that further illustrate the invention, but not its scope limit as set out in the claims.

example 1

6 g of methacrylic acid-2-aminoethyl ester hydrochloride (Aldrich), 6 g of 3-amino propyl vinyl ether (Aldrich) and 60 ml of ethanol are combined in one Three-necked flask placed and heated to 65 ° C under a stream of argon. After that 0.15 g of azobisisobutyronitrile dissolved in 4 ml of ethyl methyl ketone while stirring slowly dripped. The mixture is heated to 70 ° C and 72 hours at this Temperature stirred. After this time, the reaction mixture in 0.5 l n-He xan stirred in, the polymeric product precipitates. After filtering off the Product, the filter residue is rinsed with 100 ml of n-hexane to still remove existing residual monomers. The product is then used for 4 Dried in vacuo at 50 ° C for hours.

Example 1a

0.05 g of the product from Example 1 are in 20 ml of a test microbial suspension of Staphylococcus aureus inserted and shaken. After a contact time of 15 Minutes, 1 ml of the test microbial suspension is removed, and the bacterial count in Experimental approach determined. After this time there are no germs from Staphylococcus aureus more detectable.

Example 1b

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 microbes in the test mixture is determined. After this time the number of germs has dropped from 10 ⁷ to 10 ⁴ .

Example 2

4 g of methacrylic acid 2-aminoethyl ester hydrochloride (Aldrich), 4 g of N-3 amino propyl methacrylamide hydrochloride (from Polysciences Inc.) and 50 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.1 g of azobisisobutyronitrile is dissolved in 4 ml of ethyl methyl ketone Stir slowly added dropwise. The mixture is heated to 70 ° C and 72 hours stirred at this temperature. After this time, the reaction mixture stirred in 0.5 l of n-hexane, the polymeric product precipitating, after filtering off of the product, the filter residue is rinsed with 100 ml of n-hexane remove existing residual monomers. The product will then be available for 24 Dried in vacuo at 50 ° C for hours.

Example 2a

0.05 g of the product from Example 2 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 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 microbes in the test mixture is determined. After this time the number of germs has dropped from 10 ⁷ to 10 ⁴ .

Example 3

6 g of 3-aminopropyl vinyl ether (from Aldrich) (from Aldrich), 4 g of N-3-amino propyl methacrylamide hydrochloride (from Polysciences Inc.) 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 Stir slowly added dropwise. The mixture is heated to 70 ° C and 72 hours stirred at this temperature. After this time, the reaction mixture stirred in 0.5 l of n-hexane, whereby the polymeric product precipitates. After filtering of the product, the filter residue is rinsed with 100 ml of n-hexane remove existing residual monomers. The product will then be available for 24 Dried in vacuo at 50 ° C for hours.

Example 3a

0.05 g of the product from Example 3 are in 20 ml of a test microbial suspension of Staphylococcus aureus inserted and shaken. After a contact time of 15 Minutes, 1 ml of the test microbial suspension is removed, and the bacterial count in Experimental approach determined. After this time there are no germs from Staphylococcus aureus 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 microbes in the test mixture is determined. After this time the number of germs has dropped from 10 ⁷ to 10 ² .

Example 4

4 g of 3-aminopropyl vinyl ether (Aldrich), 2 g of N-3-aminopropyl methacrylamide hydrochloride (from Polysciences Inc.), 3 g of 2-aminoethyl methacrylic acid hydrochloride (Aldrich), and 70 ml of ethanol are in a three-necked flask  submitted and heated to 650 C under a stream of argon. Then 0.18 g Azobisisobutyronitrile dissolved in 4 ml of ethyl methyl ketone while stirring slowly dripped. The mixture is heated to 70 ° C and 72 hours at this Temperature stirred. After this time, the reaction mixture in 0.6 l of n-hexane stirred in, the polymeric product precipitates after filtering off the Product, the filter residue is rinsed with 140 ml of n-hexane to still remove existing residual monomers. The product will then be 24 Dried in vacuo at 50 ° C for 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 is removed and the number of microbes in the test mixture is determined. After this time, the number of bacteria has dropped from 10 ⁷ 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 microbes in the test mixture is determined. After this time, the number of bacteria has dropped from 10 ⁷ to 10 ¹ .

Example 5

4 g of methacrylic acid-2-aminoethyl ester hydrochloride (Aldrich), 5 g of 3-amino propyl vinyl ether (Aldrich), 3 g methyl methacrylate (Aldrich) and 65 ml Ethanol are placed in a three-necked flask and opened under a stream of argon Heated to 65 ° C. Then 0.15 g of azobisisobutyronitrile is dissolved in 4 ml Ethyl methyl ketone slowly added dropwise with stirring. The mixture is brought to 70 ° C heated and stirred for 72 hours at this temperature. After that time will  the reaction mixture was stirred into 0.5 l of n-hexane, the polymeric product fails, after filtering off the product, the filter residue is washed with 100 ml of n-hexane rinsed to remove any remaining monomers. After that, Product dried for 24 hours at 50 ° C in a vacuum.

Example 5a

0.05 g of the product from Example 5 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 ³ .

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 microbes in the test mixture is determined. After this time the number of germs has dropped from 10 ⁷ to 10 ⁴ .

Example 6

4 g of methacrylic acid-2-aminoethyl ester hydrochloride (Aldrich), 4 g of 3-amino propyl vinyl ether (Aldrich), 2.5 g butyl methacrylate (Aldrich) and 65 ml Ethanol are placed in a three-necked flask and opened under a stream of argon Heated to 65 ° C. Then 0.15 g of azobisisobutyronitrile is dissolved in 4 ml Ethyl methyl ketone slowly added dropwise with stirring. The mixture is brought to 70 ° C heated and stirred for 72 hours at this temperature. After that time will the reaction mixture was stirred into 0.5 l of n-hexane, the polymeric product fails. After filtering off the product, the filter residue is washed with 100 ml of n-hexane rinsed to remove any remaining monomers. After that, Product dried for 24 hours at 50 ° C in a vacuum.  

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 1 minute, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After this time, the bacterial count has dropped from 10 ⁷ to 10 ¹ .

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 microbicidal activity against cells of Pseudomonas aeruginosa and Staphylococcus aureus also showed all samples a microbicidal action against cells from Klebsiella pneumoniae, Escherichia coli, Rhizopus oryzae, Candida tropicalis and Tetrahymena pyriformis.

Claims (20)

1. Antimicrobial polymers, obtainable by copolymerization of aliphatic unsaturated monomers, at least simply by a primary Amino group are functionalized (component I), with another aliphatic unsaturated monomers, at least simply by a primary Amino group is functionalized (component II), component I and Component II are different from each other. 2. Antimicrobial polymers according to claim 1, characterized, that the copolymerization with further, aliphatic unsaturated monomers (Component III) is carried out. 3. Antimicrobial polymers according to one of claims 1 or 2, characterized in that
that for component I and II each functionalized by a primary amino group aliphatic unsaturated monomers of the general formula
R ₁ NH ₂
with R ₁ : branched, unbranched or cyclic, aliphatic unsaturated hydrocarbon radical with up to 50 C atoms, which can be substituted by O, N or S atoms. 4. Antimicrobial polymers according to one of claims 1 to 3, characterized, that between the monomers of components I and II a Molar mass difference of at least 23 g / mol.   5. Antimicrobial polymers according to one of claims 1 to 4, characterized, that the copolymerization is carried out on a substrate. 6. Antimicrobial polymers according to one of claims 1 to 4, characterized, that the copolymerization is carried out as a graft polymerization of a substrate becomes. 7. antimicrobial polymers according to claim 6, characterized, that the substrate before the graft polymerization by UV radiation, Plasma treatment, corona treatment, flame treatment, ozonization, electrical Discharge or γ-radiation is activated. 8. antimicrobial polymers according to claim 6, characterized, that the substrate before the graft polymerization by UV radiation with a Photoinitiator is activated. 9. Process for the preparation of antimicrobial polymers by copolymerization of aliphatic unsaturated monomers, which are at least simply identified by a primary amino group are functionalized (component I), with another aliphatic unsaturated monomers that are at least simple by a primary Amino group is functionalized (component II), component I and Component II are different from each other. 10. The method according to claim 9, characterized, that the copolymerization with further, aliphatic unsaturated monomers (Component III) is carried out.   11. The method according to any one of claims 9 or 10, characterized in that aliphatic unsaturated monomers of the general formula which are functionalized by a primary amino group for component I and II
R ₁ NH ₂
with R ₁ : branched, unbranched or cyclic, aliphatic unsaturated hydrocarbon radical with up to 50 C atoms, which can be substituted by O, N or S atoms,
be used. 12. The method according to any one of claims 9 to 11, characterized, that between the monomers of components I and II a Molar mass difference of at least 23 g / mol. 13. The method according to any one of claims 9 to 12, characterized, that the copolymerization is carried out on a substrate. 14. The method according to any one of claims 9 to 12, characterized, that the copolymerization is carried out as a graft polymerization of a substrate becomes.   15. The method according to claim 14, characterized, 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, that the substrate before the graft polymerization by UV radiation with a Photoinitiator is activated. 17. Use of the antimicrobial polymers according to one of claims 1 to 8 for the manufacture of products with an antimicrobial coating the polymer. 18. Use of the antimicrobial polymers according to one of claims 1 to 8 for the manufacture of medical articles with an antimicrobial Polymer coating. 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.