DE19940697A1 - Antimicrobial copolymer, used for food packaging, cosmetics, nappies and contact lenses, is prepared by copolymerization of vinylether ammonium salt with aliphatic unsaturated monomer - Google Patents

Abstract

An antimicrobial copolymer is prepared by copolymerization of a vinylether ammonium salt with an aliphatic unsaturated monomer. An antimicrobial copolymer (I) is prepared by copolymerization of (A) a vinylether of formula (1) with (B) an aliphatic unsaturated monomer. R<1> = -H or -CH3; R<2>-R<5> = 1-5C hydrocarbon; and X = CH3SO4<->, NO3<->, F<->, Cl<->, Br<->, I<->, CH3CH2<->, NO2<->, NO<->, CN<->, SCN<->, CNO<->, ClO<->, ClO2<->, ClO3<-> or ClO4<->.

Description

The invention relates to antimicrobial polymers, which by copolymerization of Acryloyloxyalkylammonium salts can be obtained with other monomers. The invention also relates to a method for production and use these antimicrobial polymers.

Furthermore, the invention relates to antimicrobial polymers by Graft copolymerization of acryloyloxyalkylammonium salts with others Monomers are obtained on a substrate, furthermore a process for their Manufacture and its use.

Colonization and spread of bacteria on the surfaces of pipelines, Containers or packaging are highly undesirable. It is formed often layers of mucus that cause the microbe populations to increase extremely Sustainable impairment of water, beverage and food quality and even to the spoilage of the goods as well as damage to the health of the consumer 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 the care of the sick and the elderly. Also are Keeping bacteria away from furniture and equipment surfaces in care wards, especially in the area of intensive care and care for young children, in sick people houses, especially in rooms for medical interventions and in isolation wards for critical cases of infection and in toilets.

Devices, surfaces of furniture and textiles are currently being used against bacteria if necessary or as a precaution with chemicals or their solutions as well Mixtures treated as disinfectants more or less broad and have a massive antimicrobial effect. Such chemical agents are unspecific, they are often toxic or irritating themselves or are harmful to health Degradation products. Often, there are also intolerances with the corresponding sensitized people.

Another approach against superficial bacterial spread 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. Thus, in EP-PS 0 290 676, the use of various polyacrylates and Polymethacrylate as a matrix for the immobilization of bactericidal quaternary Ammonium compounds described.

In another technical area, U.S. Patent No. 4,532,269 discloses a terpolymer from butyl methacrylate, tributyltin methacrylate and tert-butylaminoethyl methacrylate. This polymer is used as an antimicrobial paint for ships, whereby the hydro phile tert-butylaminoethyl methacrylate promotes slow erosion of the polymer and so the highly toxic tributyltin methacrylate as an antimicrobial agent releases.

In these applications the copolymer made with amino methacrylates is only Matrix or carrier substance for added microbicidal active ingredients from the Carrier material can diffuse or migrate. Polymers of this type lose more or their effect less quickly when the necessary on the surface "minimum inhibitory concentration" (MIC) is no longer reached.

From the 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, inherently microbicidal Possess properties. To avoid unwanted adaptation processes of the microbial Life forms, especially in view of those from antibiotic research well-known development of resistance of germs to counteract effectively, must also in the future systems based on novel compositions and improved ones Effectiveness to be developed.

The present invention is therefore based on the object of novel, Develop antimicrobial polymers that promote colonization and Prevent the spread of bacteria on surfaces.

It has now surprisingly been found that by copolymerization of Acryloyloxyalkylammonium salts with aliphatically unsaturated monomers or by graft copolymerization of these components on a substrate with polymers a surface that is permanently microbicidal can be obtained by solvents and physical stress is not attacked and shows no migration. It is not necessary to use other biocidal active ingredients.

The use of 2-methacryloyloxyethyl derivatives as a cationic component in copolymerizations is known from other technical fields. EP 0 322 234 describes in this context the synthesis of terpolymers, which in addition to 2- Methacryloyloxyethyl derivatives residues from its manufacture and others Contain monomers as a drainage aid. Polymers with an undefined In particular, compositions cannot be used in the medical field. Of Further find 2-Methacryloyloxyethyldimethylbenzylammoniumsalze z. B. Use as an aid for the preparation of polymer dispersions, as in No. 5,696,194 is explained in more detail, or as an aid for dye systems, as in U.S. 4,168,976.

The present invention therefore provides antimicrobial copolymers which, by copolymerization of a monomer of the formula I

with
R ¹ = -H or -CH ₃ ,
R ² = branched or unbranched aliphatic hydrocarbon test with 1 to 5 carbon atoms,
R ³ , R ⁴ , R ⁵ branched or unbranched aliphatic hydrocarbon radical with 1 to 5 carbon atoms, where R ³ , R ⁴ and R ^{5 can be} identical or different and
X ^- = CH ₃ SO ^- ₄ , NO ^- ₃ , F ^- , Cl ^- , Br ^- , I ^- , CH ₃ CH ₂ ^- , NO ₂ ^- , NO ^- , CN ^- , SCN ^- , CNO ^- , ClO ^- , C1O ₂ ^- , ClO ₃ ^- , ClO ₄ ^-
can be obtained with at least one further aliphatically unsaturated monomer.

The present invention also relates to a process for the production of antimicrobial copolymers, in which a copolymerization of monomers of the formula I

with
R ¹ = -H or -CH ₃ ,
R ² = branched or unbranched aliphatic hydrocarbon radical with 1 to 5 carbon atoms,
R ³ , R ⁴ , R ⁵ = branched or unbranched aliphatic hydrocarbon radical with 1 to 5 carbon atoms, where R ³ , R ⁴ and R ^{5 can be} identical or different and
X ^- = CH ₃ SO ^- ₄ , NO ^- ₃ , F ^- , Cl ^- , Br ^- , I ^- , CH ₃ CH ₂ ^- , NO ₂ ^- , NO ^- , CN ^- , SCN ^- , CNO ^- , ClO ^- , ClO ₂ ^- , ClO ₃ ^- , ClO ₄ ^{- is} carried out with at least one further aliphatically unsaturated monomer.

The proportion of monomers according to formula I in the reaction mixture should be around to obtain a sufficient, antimicrobial effect of the polymer, between 5 and 98 mol%, preferably between 30 and 98 mol%, particularly preferred between 50 and 98 mol.%, based on the sum of the monomers.

All monomers can be used as aliphatically unsaturated monomers which enter into a copolymerization with the monomers according to formula I. Suitable are z. B. acrylates or methacrylates, such as acrylic acid, tert-butyl methacrylate or Methyl methacrylate, styrene, vinyl chloride, vinyl ethers, acrylamides, acrylonitriles, olefins (Ethylene, propylene, butylene, isobutylene), allyl compounds, vinyl ketones, Vinyl acetic acid, vinyl acetate or vinyl ester, especially e.g. B. Methyl methacrylate, ethyl methacrylate, butyl methacrylate, Methacrylic acid tert-butyl ester, acrylic acid methyl ester, acrylic acid ethyl ester, Acrylic acid butyl ester, acrylic acid tert-butyl ester, tert-butylminoethyl ester, 2-di ethylaminoethyl methacrylate, 2-diethylaminoethyl vinyl ether, N-3-diethylminoropvl ethacrylamide or 3-methacryloylaminopropyltrimethylammonium chloride.

The aliphatically unsaturated monomers are preferably Acrylic acid or methacrylic acid compounds.

Preferred monomers according to formula I are Methacryloyloxyalkyltrialkylammonium salts, particularly preferably 2- Methacryloyloxyethyltrimethylammonium salts, especially the corresponding one Methyl sulfate (2-methacryloyloxyethyltrimethylammonium methosulfate) is used.

The antimicrobial copolymers of the invention can by Copolymerization of monomers of the formula I with one or more aliphatic unsaturated monomers are obtained. The polymerization is expediently carried out radical by a radical initiator or radiation-induced. Typical Procedures are described in the examples.

The antimicrobial copolymers of the invention can also by Copolymerization of monomers of the formula I with at least one aliphatic unsaturated monomers are obtained on a substrate. It will be a physisorbed coating of the antimicrobial copolymer on the substrate obtain.

All polymeric plastics are particularly suitable as substrate materials, such as. B. Polyurethanes, polyamides, polyesters and ethers, polyether block amides, polystyrene, Polyvinyl chloride, polycarbonates, polyorganosiloxanes, polyolefins, polysulfones, Polyisoprene, poly-chloroprene, polytetrafluoroethylene (PTFE), appropriate Copolymers and blends as well as natural and synthetic rubbers, with or without radiation-sensitive groups. The inventive method can also on surfaces of painted or otherwise with plastic coated metal, glass or wooden bodies.

In a further embodiment of the present invention, the Copolymers by graft polymerization of a substrate with monomers of the formula I and at least one aliphatically unsaturated monomer can be obtained. the Grafting of the substrate allows covalent attachment of the antimicrobial Copolymers to the substrate. All polymeric materials can be used as substrates, such as the plastics already mentioned are used.

The surfaces of the substrates can before the graft copolymerization after a Set of methods to be activated. All standard methods for Activation of polymer surfaces are used; for example can the activation of the substrate before the graft polymerization by UV radiation, Plasma treatment, corona treatment, flame treatment, ozonization, electrical Discharge, γ-radiation can be carried out. The surfaces become functional beforehand in a known manner by means of a solvent of oils, fats or others Freed impurities.

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, provided they are significant Emit radiation components in the areas mentioned. The exposure time is generally 0.1 seconds to 20 minutes, preferably 1 second to 10 Minutes.

The activation of the substrate before the graft polymerization with UV radiation can continue to be done with an additional photosensitizer. For this purpose, the Photosensitizer, e.g. B. Benzophenone applied to the substrate surface and irradiated. This can also be done with a mercury vapor lamp Exposure times from 0.1 seconds to 20 minutes, preferably 1 second to 10 Minutes.

According to the invention, activation can also be achieved 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 (from SOFTAL, Hamburg, Germany) can also be used. use to activate. In this case, the exposure times are in 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) as well as the ozonization enables 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 opened build easily or, for example, obtain from ARCOTEC, 71297 Mönsheim, Germany. You can use hydrocarbons or hydrogen as a Fuel gas are operated. In any case, harmful overheating of the Avoided by intimate contact with a cooled substrate Metal surface on the substrate surface facing away from the flaming side is easily achieved. The activation by flaming is accordingly on limited relatively thin, flat substrates. The exposure times are in general from 0.1 second to 1 minute, preferably 0.5 to 2 seconds, all of which are non-luminous flames and the distances of the substrate surfaces to the outer flame front 0.2 to 5 cm, preferably 0.5 to 2 cm.

The substrate surfaces activated in this way are by known methods, such as Dipping, spraying or brushing with monomers of the formula I (component I) and one or more aliphatically unsaturated monomers (component II), optionally in solution, coated. The solvents used have been water and Water-ethanol mixtures proven, but other solvents can also be used, provided they have sufficient solvency for the monomers and the Wet substrate surfaces well. Solutions with monomer contents from 1 to 10 % By weight, for example with about 5% by weight, have proven themselves in practice and generally result in a single pass, the sub Coatings covering the surface of the substrate with layer thicknesses greater than 0.1 µm can be.

The graft copolymerization of those applied to the activated surfaces Monomers can expediently by radiation in the short-wave segment of the visible range or in the long-wave segment of the UV range of the electromagnetic radiation can be initiated. Well suited is z. B. the radiation a UV excimer with wavelengths from 250 to 500 nm, preferably from 290 to 320 nm. Here, too, mercury vapor lamps are suitable, provided they are significant Emit radiation components in the areas mentioned. The exposure times are generally 10 seconds to 30 minutes, preferably 2 to 15 minutes Minutes.

Furthermore, a graft copolymerization of the invention Comonomer compositions can also be achieved by a process described in US Pat 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 II.

The antimicrobial copolymers according to the invention from monomers according to Formula I (component I) and at least one other aliphatically unsaturated one Monomers (component II), even without grafting, point to one Substrate surface exhibits microbicidal or antimicrobial behavior. Another Embodiment of the present invention is that the copolymers ization of components I and II is carried out on a substrate.

The components can be applied to the substrate in solution. As Lö 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 can also Component II serve.

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 as 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, conventional free radical initiators can be added. As initiators in the preparation of the copolymers according to the invention, inter alia. Azonitriles, alkyl peroxides, hydroperoxides, acyl peroxides, peroxoketones, peresters, Peroxocarbonates, peroxodisulfate, persulfate and all common photoinitiators such. B. Acetophenones, α-hydroxy ketones, dimethyl ketals and and benzophenone use. The polymerization can also be initiated thermally or as already stated, by electromagnetic radiation, such as. B. UV light or γ- Radiation take place.

Use of the modified polymer substrates

Further objects of the present invention are the use of antimicrobial polymers according to the invention for the production of antimicrobial effective products and the products manufactured in this way as such. the Products can contain polymer substrates modified according to the invention or 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, machine parts for food processing, components of air conditioning systems, roofing, Bathroom and toilet articles, kitchen articles, components of Sanitary facilities, components of animal cages and housing, 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 use for the copolymers or graft polymers according to the invention are, in particular, pools, protective paints or coatings in the following areas:

• - Marine: Hulls, docks, buoys, drilling platforms, Ballast water tanks
• - House: roofing, basement, walls, facades, greenhouses, Sun protection, garden fences, wood protection
• - Sanitary: public toilets, bathrooms, shower curtains, toiletries, Swimming pool, sauna, joints, sealants
• - Food: machines, kitchen, kitchen items, sponges, toys, Food packaging, milk processing, drinking water systems, Cosmetics
• - Machine parts: air conditioning systems, ion exchangers, industrial 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 receivers, public Transportation, animal cages, cash registers, carpeting, wallpaper

The copolymers according to the invention or coatings made from these copolymers can also be found as components for the formulation of paints and varnishes, e.g. B. as Aggregate or as a coating of an aggregate or pigment Use.

In addition, objects of the present invention are the use of according to the invention with polymers according to the invention or processes at the Surface modified polymer substrates for the manufacture of hygiene products or medical technology articles. The above statements about preferred Materials apply accordingly. Such hygiene products are for example Toothbrushes, toilet seats, combs and packaging materials. Under the The term hygiene items also includes other items that may come with many People come into contact, such as telephone receivers, handrails on stairs, door and window handles as well as straps and handles in public transport. Medi interest technical articles are z. B. catheters, hoses, cover films or else surgical utensils.

To further describe the present invention, the following are made Examples are given which illustrate the invention further, but not its scope should limit as set out in the claims.

example 1

3 g of 2-methacryloyloxyethyltrimethylammonium methosulfate (80% by weight solution in Water) (from Aldrich), 9 g of methyl methacrylate (from Aldrich), and 60 ml Ethanol are placed in a three-necked flask and under a stream of argon on 65 ° C heated. Then 0.15 g of azobisisobutyronitrile are dissolved in 4 ml Ethyl methyl ketone was slowly added dropwise with stirring. The mixture is brought to 70 ° C heated and stirred for 72 hours at this temperature. After this time has elapsed the reaction mixture is stirred into 0.5 l of deionized water, the polymeric product fails. After filtering off the product, the filter residue is mixed with 100 ml of VE- Rinsed with water to remove any residual monomers. Afterwards the product was dried in vacuo at 50 ° C. for 24 hours.

Example 1a

0.05 g of the product from Example 1 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 germ suspension is removed and the germ count in the test batch is determined. After this time, the number of germs has dropped ^{from 10 7} to 10 ^4.

Example 1b

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 germ suspension is removed and the germ count in the test batch is determined. After this time, the number of germs has dropped ^{from 10 7} to 10 ^4.

Example 2

6 g of 2-methacryloyloxyethyltrimethylammonium methosulfate (80% by weight solution in Water) (from Aldrich), 6 g of butyl methacrylate (from Aldrich), and 60 ml of ethanol are placed in a three-necked flask and exposed to a stream of argon 65 ° C heated. Then 0.15 g of azobisisobutyronitrile are dissolved in 4 ml Ethyl methyl ketone was slowly added dropwise with stirring. The mixture is brought to 70 ° C heated and stirred for 72 hours at this temperature. After this time has elapsed the reaction mixture is stirred into 0.5 l of isopropanol, the polymeric product fails. After filtering off the product, the filter residue is made up with 100 ml Isopropanol rinsed to remove residual monomers that are still present. In connection the product is dried in vacuo at 50 ° C. for 24 hours.

Example 2a

0.05 g of the product from Example 2 are in 20 ml of a test germ suspension of Staphylococcus aureus inserted and shaken. After a contact time of 15 Minutes 1 ml of the test germ suspension is removed, and the germ count im Experimental approach determined. After this time there are no germs of Staphylococcus aureus more detectable.

Example 2b

0.05 g of the product from Example 2 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 germ suspension is removed and the germ count in the test batch is determined. After this time, the number of bacteria has dropped ^{from 10 7} to 10 ^2.

Example 3

6 g of 2-methacryloyloxyethyltrimethylammonium methosulfate (80% by weight solution in Water) (from Aldrich), 6 g of tert-butyl methacrylate (from Aldrich) and 60 ml Ethanol are placed in a three-necked flask and under a stream of argon on 65 ° C heated. 0.15 g of azobisisobutyronitrile are then dissolved in 4 ml of ethylme ethyl ketone was 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 stirred into 0.5 l of cyclohexane, the polymeric product fails. After filtering off the product, the filter residue is made up with 100 ml Cyclohexane rinsed to remove residual monomers still present. In connection the product is dried in vacuo at 50 ° C. for 24 hours.

Example 3a

0.05 g of the product from Example 3 are in 20 ml of a test germ suspension of Staphylococcus aureus inserted and shaken. After a contact time of 15 Minutes 1 ml of the test germ suspension is removed, and the germ count im Experimental approach determined. After this time has elapsed, the number of germs is from 107 to 102 fallen off.

Example 3b

0.05 g of the product from Example 3 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 germ suspension is removed and the germ count in the test batch is determined. After this time, the number of bacteria has dropped ^{from 10 7} to 10 ^2.

Example 4

4 g of 2-methacryloyloxyethyltrimethylammonium methosulfate (80% by weight solution in Water) (Aldrich), 8 g of ethyl methacrylate (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 are 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 into 0.5 l of deionized water, the polymeric product precipitating. To Filter off the product, the filter residue is rinsed with 100 ml of deionized water, to remove residual monomers still present. The product is then used for Dryed in vacuo at 50 ° C. for 24 hours.

Example 4a

0.05 g of the product from Example 4 are in 20 ml of a test germ suspension of Staphylococcus aureus inserted and shaken. After a contact time of 15 Minutes 1 ml of the test germ suspension is removed, and the germ count im Experimental approach determined. After this time there are no germs of Staphylococcus aureus more detectable.

Example 4b

0.05 g of the product from Example 4 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 germ suspension is removed and the germ count in the test batch is determined. After this time, the number of bacteria has dropped ^{from 10 7} to 10 ^3.

Example 5

A polyamide 12 film is applied for 2 minutes at a pressure of 1 mbar of the 172 nm Radiation from an excimer radiation source from Heraeus. The so activated film is placed in an irradiation reactor under protective gas and fixed. Then the film is in a protective gas countercurrent with 20 ml of a mixture to 6 g 2-Methacryloyloxyethyltrimethylammonium methosulfate (80% by weight solution in Water) (from Aldrich), 6 g of butyl methacrylate (from Aldrich) and 60 g of ethanol layered. The irradiation chamber is closed and at a distance of 10 cm placed under an excimer irradiation unit from Heraeus, which produces an emission with a wavelength of 308 nm. The irradiation is started, the Exposure time is 15 minutes. The film is then removed and rinsed off with 30 ml of ethanol. The film is then 12 hours at 50 ° C in a vacuum dried. The film is then immersed in water for 5 times 6 hours at 30.degree extracted, then dried at 50 ° C for 12 hours.

The back of the film is then treated in the same way so that one Finally, a polyamide film coated on both sides with grafted polymer receives.

Example 5a

A coated piece of film from Example 5 (5 by 4 cm) is in 30 ml of a Test germ suspension of Staphylococcus aureus inserted and shaken. To a contact time of 15 minutes, 1 ml of the test germ suspension is removed, and the number of germs in the test batch is determined. After this time there are none Staphylococcus aureus germs more detectable.

Example 5b

A coated piece of film from Example 5 (5 by 4 cm) is in 30 ml of a Test germ suspension of Pseudomonas aeruginosa inserted and shaken. To a contact time of 60 minutes, 1 ml of the test germ suspension is removed, and the number of germs in the test batch is determined. After this time, the The number of germs dropped from 107 to 103.

Example 6

A polyamide 12 film is applied for 2 minutes at a pressure of 1 mbar of the 172 nm Radiation from an excimer radiation source from Heraeus. The so activated film is placed in an irradiation reactor under protective gas and fixed. Then the film is in a protective gas countercurrent with 20 ml of a mixture to 6 g 2-Methacryloyloxyethyltrimethylammonium methosulfate (80% by weight solution in Water) (from Aldrich), 6 g of tert-butyl methacrylate (from Aldrich) and 60 g Ethanol overlaid. The irradiation chamber is closed and at a distance of 10 cm placed under an excimer irradiation unit from Heraeus, the one Has emission of wavelength 308 nm. The irradiation is started, the Exposure time is 15 minutes. The film is then removed and rinsed off with 30 ml of ethanol. The film is then 12 hours at 50 ° C in a vacuum dried. The film is then immersed in water for 5 times 6 hours at 30.degree extracted, then dried at 50 ° C for 12 hours.

The back of the film is then treated in the same way so that one Finally, a polyamide film coated on both sides with grafted polymer receives.

Example 6a

A coated piece of film from Example 6 (5 by 4 cm) is in 30 ml of a Test germ suspension of Staphylococcus aureus inserted and shaken. To a contact time of 15 minutes, 1 ml of the test germ suspension is removed, and the number of germs in the test batch is determined. After this time there are none Staphylococcus aureus germs more detectable.

Example 6b

A coated piece of film from Example 6 (5 by 4 cm) is placed in 30 ml of a test germ suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test germ suspension is removed and the germ count in the test batch is determined. After this time, the number of germs has dropped ^{from 10 7} to 10 ^4.

Claims (22)

1. Antimicrobial copolymers obtainable by copolymerizing a monomer of the formula I.
with
R ¹ = -H or -CH ₃ ,
R ² = branched or unbranched aliphatic hydrocarbon radical with 1 to 5 carbon atoms,
R ³ , R ⁴ , R ⁵ = branched or unbranched aliphatic hydrocarbon radical with 1 to 5 carbon atoms, where R ³ , R ⁴ and R ^{5 can be} identical or different and
X ^- = CH ₃ SO ^- ₄ , NO ^- ₃ , F ^- Cl ^- , Br ^- , I ^- , CH ₃ CH ₂ ^- , NO ₂ ^- , NO ^- , CN ^- , SCN ^- , CNO ^- , ClO ^- , ClO ₂ ^- , ClO ₃ ^- , ClO ₄ ^- with at least one further aliphatically unsaturated monomer. 2. Antimicrobial polymers according to claim 1, characterized, that the aliphatically unsaturated monomers are methacrylic acid compounds. 3. Antimicrobial polymers according to claim 1, characterized, that the aliphatically unsaturated monomers are acrylic acid compounds. 4. Antimicrobial polymers according to claim 1, characterized, that as aliphatically unsaturated monomers methyl methacrylate, Methacrylic acid ethyl ester, methacrylic acid butyl ester, methacrylic acid tert- butyl ester, methyl acrylate, ethyl acrylate, butyl acrylate, Acrylic acid tert-butyl ester, tert-butylaminoethyl ester, 2-diethylamino ethyl methacrylate, 2-diethylaminoethyl vinyl ether, N-3-dimethyl aminopropyl methacrylamide or 3-methacryloylaminopropyl tri methylammonium chloride are used. 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 will. 7. Antimicrobial polymers according to claim 6, characterized, that the substrate is exposed to UV radiation prior to graft polymerization, 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. Antimicrobial polymers according to one of claims 1 to 8, characterized, that as a monomer of formula I 2-Methacryloyloxyethyltrimethylammonium methosulfate is used. 10. Process for the preparation of antimicrobial copolymers, characterized in that a copolymerization of a monomer of the formula I.
with
R ¹ = -H or -CH ₃ ,
R ² = branched or unbranched aliphatic hydrocarbon radical with 1 to 5 carbon atoms,
R ³ , R ⁴ , R ⁵ = branched or unbranched aliphatic hydrocarbon radical with 1 to 5 carbon atoms, where R ³ , R ⁴ and R ^{5 can be} identical or different and
X ^- = CH ₃ SO ^- ₄ , NO ^- ₃ , F ^- , Cl ^- , Br ^- , I ^- , CH ₃ CH ₂ ^- , NO ₂ ^- , NO ^- , CN ^- , SCN ^- , CNO ^- , ClO ^- , ClO ₂ ^- , ClO ₃ ^- , ClO ₄ ^{- is} carried out with at least one further aliphatically unsaturated monomer. 11. The method according to claim 10, characterized, that the aliphatically unsaturated monomers are methacrylic acid compounds. 12. The method according to claim 10, characterized, that the aliphatically unsaturated monomers are acrylic acid compounds. 13. The method according to claim 10, characterized, that as aliphatically unsaturated monomers methacrylic acid methylsier, Methacrylic acid ethyl ester, methacrylic acid butyl ester, methacrylic acid tert- butyl ester, methyl acrylate, ethyl acrylate, butyl acrylate, Acrylic acid tert-butyl ester, tert-butylaminoethyl ester, 2- Diethylaminoethyl methacrylate, 2-diethylaminoethyl vinyl ether, N-3- Dimethylaminopropyl methacrylamide or 3-methacrylaylaminopropyl trim thylammonium chloride are used. 14. The method according to any one of claims 10 to 13, characterized, that the copolymerization is carried out on a substrate. 15. The method according to any one of claims 10 to 13, characterized, that the copolymerization is carried out as a graft polymerization of a substrate will. 16. The method according to claim 15, characterized, that the substrate is exposed to UV radiation prior to graft polymerization, Plasma treatment, corona treatment, flame treatment, ozonization, electrical Discharge or γ-radiation is activated. 17. The method according to claim 15, characterized, that the substrate before the graft polymerization by UV radiation with a Photoinitiator is activated. 18. The method according to any one of claims 10 to 17, characterized, that as a monomer of the formula I 2-Methacryloyloxyethyltri methylammonium methosulfate is used. 19. Use of the antimicrobial polymers according to any one of claims 1 to 9 for the manufacture of products with an antimicrobial coating the polymer. 20. Use of the antimicrobial polymers according to any one of claims 1 to 9 for the manufacture of medical articles with an antimicrobial Coating from the polymer. 21. Use of the antimicrobial polymers according to any one of claims 1 to 9 for the production of hygiene articles with an antimicrobial coating from the polymer. 22. Use of the antimicrobial polymers according to any one of claims 1 to 9 in paints, protective paints and coatings.