WO2001087998A2 - Antimicrobial polymers and polymer blends made of polymer alkyl acrylamides - Google Patents

Abstract

The invention relates to antimicrobial polymers or polymer blends thereof which can be obtained by polymerising a monomer of formula (I) wherein R1 = -H or CH3, R2 = H, a branched or unbranched aliphatic hydrocarbon radical with 1 - 10 carbon atoms and R3 = H, a branched or unbranched aliphatic hydrocarbon radical with 1 - 10 carbon atoms, and optionally mixing the product thereof with at least at least one other polymer. The antimicrobial polymers or polymer blends can be used as a coating for substrates in lacquers or protective paints. The invention also relates to a method for disinfecting water circuits with antimicrobial polymers or blends.

Description

Antimicrobial polymers and polymer blends made from polymers of alkyl acrylamides

The invention relates to antimicrobial polymers made from alkyl acrylamides. The invention further relates to a method for producing and using these antimicrobial polymers, in particular in polymer blends.

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 can even lead to product spoilage and consumer health damage.

Bacteria must be kept away from all areas of life where hygiene is important. This affects textiles for direct body contact, especially for the intimate 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.

In addition, the avoidance of algae growth on surfaces is becoming an increasingly important challenge, since many exterior surfaces of buildings are now included Plastic cladding are equipped, which are particularly easy to handle. In addition to the undesirable visual impression, the function of corresponding components can also be reduced under certain circumstances. In this context, for example, algae growth of photovoltaic functional areas should be considered.

Another form of microbial contamination, for which there is still no technically satisfactory solution, is the infestation of surfaces with fungi. For example, The infestation of joints and walls in damp rooms with Aspergillus niger, in addition to the impaired visual appearance, is also a serious health-related aspect, since many people are allergic to the substances released by the fungi, which can lead to serious chronic respiratory diseases.

In the field of seafaring, the fouling of the hulls is an economically relevant influencing factor, since the increased flow resistance of the ships associated with the vegetation results in a significant increase in fuel consumption. To date, such problems have generally been countered by incorporating toxic heavy metals or other low-molecular biocides in antifouling coatings in order to alleviate the problems described. For this purpose, the harmful side effects of such coatings are accepted, but this is becoming increasingly problematic given the increased ecological sensitivity of society.

Thus, e.g. B. U.S. Patent 4,532,269, a terpolymer of butyl methacrylate, tributyltin methacrylate and tert-butylaminoethyl methacrylate. This copolymer is used as an antimicrobial marine paint, with the hydrophilic tert-butylaminoethyl methacrylate promoting the slow erosion of the polymer and thus releasing the highly toxic tributyltin methacrylate as an antimicrobial agent.

In these applications, the copolymer produced with aminomethacrylates is only a matrix or carrier substance for added microbicidal active substances which can diffuse or migrate from the carrier substance. Polymers of this type lose theirs more or less quickly

Effect if the necessary "minimal inhibitory concentration" on the surface (MTK) is no longer achieved.

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

The present invention is therefore based on the object, novel, antimicrobially active polymers, for. B. to develop as coatings. These are intended to effectively prevent the settlement and spread of bacteria, algae and fungi on surfaces.

It has now surprisingly been found that coatings which contain antimilσobielle polymers, surfaces can be equipped so that an antimicrobial effect of these surfaces can be generated permanently, and resistant to solvents and physical stresses. These coatings do not contain low molecular weight biocides, which effectively rules out the migration of ecologically problematic substances over the entire period of use.

The present invention therefore relates to antimicrobial polymers which can be obtained by polymerizing a monomer of the formula I:

With

R ¹ = -H or -CH ₃ R ² = branched or unbranched aliphatic hydrocarbon radical with 1 to 10

Carbon atoms or -HR ³ = branched or unbranched aliphatic hydrocarbon radical with 1 to 10

Carbon atoms or -H.

Acrylic acid amide, methacrylic acid amide, methacrylic acid isopropylamide, acrylic acid tert-butylamide, N, N-dimethylacrylamide or N-isopropylacrylamide are preferably used as monomers of the formula I.

The invention therefore also relates to a process for the preparation of these antimilα-objective polymers by chemically, thermally or radiation-chemically induced radical polymerization of monomers of the formula I, optionally with at least one further aliphatic unsaturated monomer.

As further aliphatic unsaturated monomers, acrylic acid or methacrylic acid compounds, such as. Example, methyl methacrylate, methyl acrylate, tert-butyl methacrylate, tert-butyl acrylate, butyl methacrylate, butyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, isopropyl methacrylate, propyl methacrylate, propyl acrylate and acrylic acid propyl ester are used.

The process can be carried out to produce the various embodiments of the polymers or copolymers according to the invention which will be described below.

The present invention further relates to antimilcrobial polymer blends which contain the abovementioned polymers of monomers of the formula I and at least one further polymer. Optionally, the antimicrobial polymers are produced by polymerizing monomers of the formula I with at least one further aliphatic unsaturated monomer. The acrylic acid or methacrylic acid compounds already mentioned can be used as further aliphatic unsaturated monomers. The other polymer in the polymer blend generally has no antimicrobial effect. The production of the antimicrobial polymer blends can in principle by all methods known in the art, such as. B. "HG-Elias, Macromolecules, Vol. 2, 5th Edition, pp. 620 ff.", Are described in detail. For example, when melt-mixing two pre-formed polymers, the polymers present as granules or powder on roller mills, in kneaders or with extruders. In the case of thermoplastics, this is heated above the glass or melting temperature. When mixing solutions, independently prepared solutions of the two polymers in the same solvent are used.

As a further polymer z. B. polyurethanes, polyamides, polyesters and ethers, polyether block amides, polystyrene, polyvinyl chloride, polycarbonates, polyorganosiloxanes, polyolefins, polysulfones, polyisoprene, polychloroprene, polytetrafluoroethylene (PTFE), polyterephthalates and / or their copolymers.

In order to obtain a sufficient antimicrobial effect of the polymer blend, the antimilcrobial polymer in the polymer blend should have a proportion of 0.2 to 70, preferably 0.2 to 30, particularly preferably 1 to 20% by weight.

The antimicrobial polymers according to the invention or the corresponding blends can be applied to a surface as a coating by known methods, such as dipping, spraying or brushing the coating formulation. Ethanol, methanol, water-alcohol mixtures, methyl ethyl ketone, diethyl ether, dioxane, hexane, heptane, benzene, toluene, chloroform, dichloromethane, tetrahydrofuran and acetonitrile have proven themselves as solvent constituents of the coating formulation, but other solvents can also be used if they are sufficient Have dissolving power for the polymers or their blends as well as any other constituents that may be present and wet the substrate surfaces well. Solutions with solids contents of 3 to 80% by weight, for example approximately 10% by weight, have proven themselves in practice and generally result in coherent coatings covering the substrate surface with layer thicknesses which can be more than 0.1 μm. Furthermore, the antimicrobial polymers according to the invention or the polymer blends as a coating can also be used as a melt, for. B. by coextrusion by dipping, spraying or Painting can be applied to the substrates.

Furthermore, the antimicrobial polymers or polymer blends according to the invention can also be used as additives and components for the formulation of polymer blends, paints, varnishes and biocides.

In the case of polymer blends, particularly advantageous compounding by extrusion, if appropriate also by coextrusion with further polymers, is possible.

If polymers or polymer blends according to the invention are used as an additive or component in paints, lacquers or biocides, lower concentrations, for. B. in the lower percentage or alcohol range may be sufficient for an antimilcrobial effect.

In a further embodiment of the present invention, the polymers can be obtained by graft-polymerizing a substrate with monomers of the formula I and optionally at least one aliphatic unsaturated monomer. The grafting of the substrate enables the antimicrobial polymer to be covalently bound to the substrate. All polymeric materials, such as the plastics already mentioned, can be used as substrates.

The surfaces of the substrates can be activated by a number of methods before the graft polymerization. All standard methods for activating polymer surfaces can be used here; For example, the activation of the substrate before the graft polymerization can be carried out by UV radiation, plasma treatment, corona treatment, flame treatment, ozonization, electrical discharge or γ radiation. 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 e.g. B a UV excimer device

HERAEUS Noblelight, Hanau, Germany. But mercury vapor lamps are also suitable for substrate activation, provided that 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.

An additional photosensitizer can also be used to activate the substrate before the graft polymerization with UV radiation. For this, the photosensitizer, such as. B. Benzophenone applied to the substrate surface and irradiated. This can also be done with a mercury vapor lamp with exposure times of 0.1 seconds to 20 minutes, preferably 1 second to 10 minutes.

The activation can also be achieved according to the invention 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 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 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 enable short exposure times, which are generally 0.1 to 60 seconds.

Flaming substrate surfaces also leads to their activation. Suitable devices, in particular those with a flame barrier front, can be built in a simple manner or, for example, can be obtained from ARCOTEC, 71297 Mönsheim, Germany. They can be operated with hydrocarbons or hydrogen as fuel gas. In any case, damaging overheating of the substrate must be avoided, which is due to intimate contact with a cooled metal surface on the side facing away from the flame side Substrate surface is easily reached. The activation by flame treatment is accordingly limited to relatively thin, flat substrates. The exposure times generally range from 0.1 second to 1 minute, preferably 0.5 to 2 seconds, all of which deal with non-luminous flames and the distances between the substrate surfaces and the outer flame front are 0.2 to 5 cm, preferably 0.5 to 2 cm.

The graft polymerization 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. Z. B. the radiation of a UV excimer of the wavelengths 250 to 500 nm, preferably from 290 to 320 nm. Mercury vapor lamps are also suitable here, provided that they emit considerable amounts of radiation in the ranges mentioned. The exposure times are generally 10 seconds to 30 minutes, preferably 2 to 15 minutes. As initiators in the manufacture of the polymers according to the invention, u. a. Azonitriles, alkyl peroxides, hydroperoxides, acyl peroxides, peroxoketones, peresters, peroxocarbonates, peroxodisulfate, persulfate and all customary photoinitiators such as e.g. B. use acetophenones, α-hydroxy ketones, dimethyl ketals and and benzophenone. The polymerization initiation can also be carried out thermally or, as already stated, by electromagnetic radiation, such as. B. UV light or γ radiation.

Use of the polymers or the polymer blends

Further objects of the present invention are the use of the antimicrobial polymers or polymer blends according to the invention for the production of antimicrobially active products. Such products are preferably based on polyamides, polyurethanes, polyether block amides, polyester amides or imides, PVC, polyolefins, silicones, polysiloxanes, polymethacrylate or polyterephthalates, metals, glasses and ceramics, which have surfaces coated with polymers or blends according to the invention.

Antimilcrobially active products of this type are, for example, machine parts for food processing, components of air conditioning systems, coated pipes, semi-finished products, Roofing, bathroom and toilet articles, kitchen 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 polymers or blends according to the invention can be used wherever there is a lack of bacteria, algae and fungi, i.e. microbicidal surfaces or surfaces with non-stick properties. Examples of use for the polymers or polymer blends according to the invention, for. B. as a coating of a substrate can be found in the following areas:

Marine: ship hulls, port facilities, buoys, drilling platforms, ballast water tanks House: roofs, cellars, walls, facades, greenhouses, sun protection, garden fences, wood protection, tarpaulins, textile fabrics - 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, catheters, tubes, cover foils, surgical cutlery

Articles of daily use: car seats, clothing (stockings, sportswear), hospital furnishings, door handles, telephone receivers, public transport, animal cages, cash registers, carpeting, wallpapers, telephone receivers, handrails for meetings, door and door handles

Window handles and straps and handles in public transport Hygiene products: toothbrushes, toilet seats, combs and packaging materials

The polymers or polymer blends can also be used in the form of lacquers, protective coatings or coatings. Here it makes sense to use existing paint systems such as B. to use acrylic paints. The polymers or polymer blends can also be used as a paint additive in the maritime sector, in particular when avoiding barnacle larvae on ship hulls, generally as an additive in an antifouling paint, here in particular in saline seawater.

In addition, the antimicrobial polymers or polymer blends according to the invention can be used as additives in the formulation of cosmetic products, e.g. for pastes and ointments. The proportion of polymers or polymer blends according to the invention can be reduced here, depending on the effectiveness of the polymer and the formulation, down to the lower percent or per mille range.

The polymers or polymer blends according to the invention are furthermore used as a biofouling inhibitor, in particular in cooling circuits. To avoid damage to cooling circuits caused by algae or bacteria, they often have to be cleaned or oversized. The addition of microbicidal substances such as formalin is not possible with open cooling systems, as are common in power plants or chemical plants.

Other microbicidal substances are often highly corrosive or foam-forming, which prevents use in such systems.

In contrast, it is possible to feed polymers according to the invention or their blends with the other polymers mentioned in finely dispersed form into the process water. The bacteria are killed on the antimicrobial polymers and, if necessary, removed from the system by filtering off the dispersed polymer / blend. A deposit of bacteria or algae on system parts can be effectively prevented.

Further objects of the present invention are therefore methods for the disinfection of cooling water flows, in which antimicrobial polymers or their polymer blends are added in dispersed form to the cooling water.

The dispersed form of the polymers or their blends can be in the manufacturing process itself z. B. by emulsion polymerization, precipitation or suspension polymerization or subsequently by grinding z. B. can be obtained in a jet mill. The particles obtained in this way are preferably used in a size distribution of 0.001 to 3 mm (as ball diameter), so that on the one hand a large surface is available for killing the bacteria or algae, and on the other hand where necessary, the separation from the cooling water, for. B. is easily possible by filtration. The method can e.g. B. be exercised in such a way that part (5-10%) of the polymers / blends used are continuously removed from the system and replaced by a corresponding amount of fresh material. As an alternative, further antimicrobial copolymer / blend can be added, if necessary, while checking the bacterial count of the water. Depending on the water quality, 0.1 - 100 g of antimicrobial polymer or its blends per m ^{3 of} cooling water are sufficient.

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

Example 1:

12 g of acrylic acid tert-butylamide (from Aldrich) and 90 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.23 g of azobisisobutyronitrile dissolved in 6 ml of ethyl methyl ketone are slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After this time, the reaction mixture is stirred into 0.5 1 of water, the polymeric product precipitating. After filtering off the product, the filter residue is rinsed with 20 ml of n-hexane in order to remove any remaining monomers. The product is then dried in vacuo at 50 ° C. for 24 hours. 2 g of the product are dissolved in 10 g of tetrahydrofuran and applied to a 0.5 cm thick and 2 by 2 cm aluminum plate using a 100 micrometer doctor blade. The plate is then dried at 50 ° C for 24 hours.

Example la: The coated side of the aluminum plate from Example 1 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus contains and shaken. After a contact time of 3 hours, 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 decreased from 10 ⁷ to 10 ³ germs per ml.

Example lb:

The coated aluminum side of Example 1 is placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 6 hours, 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 decreased from 10 ⁷ to 10 ⁴ germs per ml.

Example 2:

12 g of isopropyl methacrylamide (from Aldrich) and 90 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.23 g of azobisisobutyronitrile dissolved in 6 ml of ethyl methyl ketone are slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After this time, the reaction mixture is stirred into 0.5 1 n-hexane, the polymeric product precipitating. After filtering off the product, the filter residue is rinsed with 20 ml of n-hexane in order to remove any remaining monomers. The product is then dried for 24 hours at 50 ° C. in a vacuum. 2 g of the product are dissolved in 10 g of tetrahydrofuran and applied to a 0.5 cm thick and 2 by 2 cm aluminum plate using a 100 micrometer doctor blade. After a contact time of 6 hours, 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 decreased from 10 ⁷ to 10 ³ germs per ml.

Example 2a:

The coated aluminum side of Example 2 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 3 hours, 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 decreased from 10 ⁷ to 10 ⁴ germs per ml. Example 2b

The coated aluminum side of Example 2 is placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 6 hours, 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 decreased from 10 ⁷ to 10 ⁴ germs per ml.

Example 3:

12 g of acrylic acid tert-butylamide (from Aldrich) and 90 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.23 g of azobisisobutyronitrile dissolved in 6 ml of ethyl methyl ketone are slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After this time, the reaction mixture is stirred into 0.5 1 n-hexane, the polymeric product precipitating. After filtering off the product, the filter residue is rinsed with 20 ml of n-hexane in order to remove any remaining monomers. The product is then dried in vacuo at 50 ° C. for 24 hours. 2 g of the product are dissolved in 10 g of tetrahydrofuran and applied to a 0.5 cm thick and 2 by 2 cm aluminum plate using a 100 micrometer doctor blade. The plate is then dried at 50 ° C for 24 hours.

Example 3 a:

The coated aluminum side of Example 3 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 4 hours, 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 decreased from 10 ⁷ to 10 ³ germs per ml.

Example 3b

The aluminum plate from Example 3 is placed with its coated side up on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 8 hours, 1 ml of Test microbial suspension removed, and the number of bacteria in the test batch determined. After this time the number of germs has decreased from 10 ⁷ to 10 ⁴ germs per ml.

Example 4;

10 g of the polymer from Example 1 are heated to 165 ° C. This heated polymer is then mixed with 3 g of polymethyl methacrylate (Aldrich), which was also previously heated to 165 ° C. The two polymers are mixed thoroughly, applied to an aluminum plate 0.5 cm thick and 2 by 2 cm in size and cooled to room temperature at a rate of 20 ° C. per hour.

Example 4a

The coated aluminum side of Example 4 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 4 hours, 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 decreased from 10 ⁷ to 10 ⁴ germs per ml.

Example 4b

The coated aluminum side of Example 4 is placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 8 hours, 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 decreased from 10 ⁷ to 10 ⁴ germs per ml.

Example 5:

12 g of acrylic acid tert-butylamide (from Aldrich) and 90 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.23 g of azobisisobutyronitrile dissolved in 6 ml of ethyl methyl ketone are slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After this time, the reaction mixture is stirred into 0.5 1 of water, the polymeric product precipitating. After filtering off the product, the filter residue is rinsed with 20 ml of n-hexane, to remove remaining monomers. The product is then dried in vacuo at 50 ° C. for 24 hours. 6 g of the product are dissolved in 32 g of diisononyl phthalate. Then 64 g of polyvinyl chloride granules are added to this mixture, the mixture being stirred intimately until it becomes pasty. 20 g of the paste obtained are spread onto a metal plate using a doctor blade in such a way that a layer thickness of 0.7 mm is established. The plate with the paste on it is then heated to 200 ° C. for 2 minutes, during which the paste gels and a soft PVC film is formed.

Example 5a: A 3 by 3 cm piece of the soft PVC film from Example 5 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 3 hours, 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 decreased from 10 ⁷ to 10 ⁴ germs per ml.

Example 5b

A 3 by 3 cm piece of the soft PVC film from Example 5 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Pseudomonas aeruginosa and shaken. After a contact time of 6 hours, 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 decreased from 10 ⁷ to 10 ⁴ germs per ml.

Example 6:

12 g of acrylic acid tert-butylamide (from Aldrich) and 90 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.23 g of azobisisobutyronitrile dissolved in 6 ml of ethyl methyl ketone are slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After this time, the reaction mixture is stirred into 0.5 1 of water, the polymeric product precipitating. After filtering off the product, the filter residue is rinsed with 20 ml of n-hexane in order to remove any remaining monomers. The product is then dried in vacuo at 50 ° C. for 24 hours. 2 g of the product are mixed in 32 g of Isononyl phthalate dissolved. Then 64 g of polyvinyl chloride granules are added to this mixture, the mixture being stirred intimately until it becomes pasty. 20 g of the paste obtained are spread onto a metal plate using a doctor blade in such a way that a layer thickness of 0.7 mm is established. The plate with the paste on it is then heated to 200 ° C. for 2 minutes, during which the paste gels and a soft PVC film is formed.

Example 6a

A 3 by 3 cm piece of the soft PVC film from Example 6 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 3 hours, 1 ml of the test microbial suspension is removed and the number of microbes in the test mixture is determined. After this time the number of germs has dropped from 10 ⁷ to 10 ⁴ .

Example 6b: A 3 by 3 cm piece of the soft PVC film from Example 6 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Pseudomonas aeruginosa and shaken. After a contact time of 6 hours, 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 ⁵ .

Example 7:

12 g of isopropyl methacrylamide (from Aldrich) and 90 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.23 g of azobisisobutyronitrile dissolved in 6 ml of ethyl methyl ketone are slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After this time, the reaction mixture is stirred into 0.5 1 n-hexane, the polymeric product precipitating. After filtering off the product, the filter residue is rinsed with 20 ml of n-hexane in order to remove any remaining monomers. The product is then dried in vacuo at 50 ° C. for 24 hours. 2 g of the product are dissolved in 32 g of diisononyl phthalate. Then 64 g of polyvinyl chloride granules are added to this mixture, the mixture being stirred intimately until it becomes pasty. 20 g of the paste obtained are spread onto a metal plate with a squeegee in such a way that they set a layer thickness of 0.7 mm. The plate with the paste on it is then heated to 200 ° C. for 2 minutes, the paste gelling and a soft PVC film being produced.

Example 7a

A 3 by 3 cm piece of the soft PVC film from Example 7 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 3 hours, 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 7b

A 3 by 3 cm piece of the soft PVC film from Example 7 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Pseudomonas aeruginosa and shaken. After a contact time of 6 hours, 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 ⁵ .

Example 8: 12 g of acrylic acid tert-butylamide (from Aldrich) and 90 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.23 g of azobisisobutyronitrile dissolved in 6 ml of ethyl methyl ketone are slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After this time, the reaction mixture is stirred into 0.5 1 of water, the polymeric product precipitating. After filtering off the product, the filter residue is rinsed with 20 ml of n-hexane in order to remove any remaining monomers. The product is then dried for 24 hours at 50 ° C in a vacuum. 5 g of the product are stirred into 95 g of an acrylic varnish called Rowacryl G-31293 from ROWA.

Example 8a

Using a brush, a 5 x 5 cm aluminum plate is treated with the one treated in this way Brush acrylic paint from Example 8 and then dry in a drying cabinet at 35 ° C for 24 hours. This aluminum plate is placed with its coated side up on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 3 hours, 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 8b

Using a brush, a 5 x 5 cm aluminum plate is coated with the acrylic lacquer treated in this way from Example 8 and then dried in a drying cabinet at 35 ° C. for 24 hours. This aluminum plate is placed with its coated side up on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 6 hours, 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 9:

12 g of isopropyl methacrylamide (from Aldrich) and 90 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.23 g of azobisisobutyronitrile dissolved in 6 ml of ethyl methyl ketone are slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After this time, the reaction mixture is stirred into 0.5 1 n-hexane, the polymeric product precipitating. After filtering off the product, the filter residue is rinsed with 20 ml of n-hexane in order to remove any remaining monomers. The product is then dried in vacuo at 50 ° C. for 24 hours. 2 g of the product are stirred into 98 g of an acrylic varnish called Rowacryl G-31293 from ROWA.

Example 9a

Using a brush, a 5 x 5 cm aluminum plate is coated with the acrylic lacquer treated in this way from Example 9 and then dried in a drying cabinet at 35 ° C. for 24 hours. This aluminum plate is with its coated side facing up placed on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 3 hours, 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 9b

Using a brush, a 5 x 5 cm aluminum plate is coated with the acrylic lacquer treated in this way from Example 9 and then dried in a drying cabinet at 35 ° C. for 24 hours. This aluminum plate is placed with its coated side up on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 6 hours, 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 ⁵ .

Example 10;

12 g of acrylic acid tert-butylamide (from Aldrich) and 90 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.23 g of azobisisobutyronitrile dissolved in 6 ml of ethyl methyl ketone are slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After this time, the reaction mixture is stirred into 0.5 1 of water, the polymeric product precipitating. After filtering off the product, the filter residue is rinsed with 20 ml of n-hexane in order to remove any remaining monomers. The product is then dried for 24 hours at 50 ° C in a vacuum. 5 g of the product are stirred into 95 g of Plextol D 510 from PolymerLatex, an aqueous dispersion of a methacrylic acid ester / acrylic acid ester copolymer.

Example 10a

Using a brush, a 5 x 5 cm aluminum plate is treated with the one treated in this way

Spread the dispersion from Example 10 and then dry it in a drying cabinet at 35 ° C. for 24 hours. This aluminum plate is placed with its coated side up on the bottom of a beaker containing 20 ml of a test microbial suspension Contains and shaken Staphylococcus aureus. After a contact time of 3 hours, 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 10b

Using a brush, a 5 x 5 cm aluminum plate is coated with the dispersion from Example 10 treated in this way and then dried in a drying cabinet at 35 ° C. for a period of 24 hours. This aluminum plate is placed with its coated side up on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 6 hours, 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 ⁵ .

Example 11: 12 g of isopropyl methacrylamide (Aldrich) and 90 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.23 g of azobisisobutyronitrile dissolved in 6 ml of ethyl methyl ketone are slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After this time, the reaction mixture is stirred into 0.5 1 n-hexane, the polymeric product precipitating. After filtering off the product, the filter residue is rinsed with 20 ml of n-hexane in order to remove any remaining monomers. The product is then dried for 24 hours at 50 ° C in a vacuum. 2 g of the product are stirred into 98 g of Plextol D 510 from PolymerLatex, an aqueous dispersion of a methacrylic acid ester / acrylic acid ester copolymer.

Example Ha:

Using a brush, a 5 by 5 cm aluminum plate is coated with the dispersion from Example 11 treated in this way and then dried in a drying cabinet at 35 ° C. for 24 hours. This aluminum plate is placed with its coated side up on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 3 hours, 1 ml taken from the test microbial suspension, and the number of microbes determined in the test batch. After this time, the number of germs has dropped from 10 ⁷ to 10 ⁵ .

Example 11b: Using a brush, a 5 by 5 cm aluminum plate is coated with the dispersion from Example 11 treated in this way and then dried in a drying cabinet at 35 ° C. for a period of 24 hours. This aluminum plate is placed with its coated side up on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 6 hours, 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 ⁵ .

Claims

claims: 1. Antimicrobial polymers obtainable by polymerizing a monomer of the formula I.

With R ¹ = -H or -CH ₃ R ² = H, branched or unbranched aliphatic hydrocarbon radical having 1 to 10 carbon atoms and R ³ = H, branched or unbranched aliphatic hydrocarbon radical having 1 to 10 carbon atoms. 2. Antimilcrobial polymers according to claim 1, characterized in that acrylic acid amide, methacrylic acid amide, methacrylic acid isopropylamide, acrylic acid tert-butylamide, N, N-dimethylacrylamide or N-isopropylacrylamide are used as the monomer of formula I. 3. Antimicrobial polymer according to claim 1 or 2, characterized in that the polymerization of the monomers of the formula I is carried out with additionally at least one further aliphatic unsaturated monomer. 4. Antimicrobial polymer according to claim 3, characterized in that the aliphatic unsaturated monomers are methacrylic acid compounds. 5. Antimicrobial polymer according to claim 3, characterized in that the aliphatic unsaturated monomers are acrylic acid compounds. 6. Antimicrobial polymer according to one of claims 1 to 5, characterized in that the polymerization is carried out as a graft polymerization of a substrate. 7. Antimicrobial polymer 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 polymer blends containing an antimicrobial polymer obtainable by polymerizing a monomer of the formula I.

with R ¹ = -H or -CH ₃ R ² = H, branched or unbranched aliphatic hydrocarbon radical with 1 to 10 Carbon atoms and R ³ = H, branched or unbranched aliphatic hydrocarbon radical with 1 to 10 carbon atoms and at least one further polymer. 9. antimicrobial polymer blends according to claim 8, characterized in that the polymerization of the monomers of the formula I is carried out with additionally at least one further aliphatic unsaturated monomer. 10. Antimicrobial polymer blend according to claim 8 or 9, characterized in that the antimicrobial polymer has a proportion of 0.2 to 70 wt .-% in the polymer blend. 11. Antimicrobial polymer blend according to one of claims 8 to 10, characterized in that as another polymer polyurethanes, polyamides, polyesters and ethers, polyether block amides, polystyrene, polyvinyl chloride, polycarbonates, polyorganosiloxanes, polyolefins, polysulfones, polyisoprene, poly-chloroprene, polyterephthalates, Polytetrafluoroethylene (PTFE) and / or their copolymers is used. 12. A process for the preparation of antimicrobial polymers, characterized in that a radical polymerization of monomers of the formula I

With R ¹ = -H or -CH ₃ R ² = H, branched or unbranched aliphatic hydrocarbon radical having 1 to 10 carbon atoms and R ³ = H, branched or unbranched aliphatic hydrocarbon radical having 1 to 10 carbon atoms is carried out chemically, thermally or radiation-chemically induced. 13. The method according to claim 12, characterized in that the polymerization of the monomers of the formula I is carried out with additionally at least one further aliphatic unsaturated monomer. 14. The method according to claim 12 or 13, characterized in that the polymerization is carried out as a graft polymerization of a substrate. 15. The method according to claim 14, 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. 16. Use of the antimicrobial polymers according to one of claims 1 to 7 for the production of products with an antimicrobial coating from the polymer. 17. Use of the antimicrobial polymers according to one of claims 1 to 7 for the production of medical articles with an antimicrobial coating made of the polymer. 18. Use of the antimicrobial polymers according to one of claims 1 to 7 for the production of hygiene articles with an antimicrobial coating from the polymer. 19. Use of the antimicrobial polymers according to one of claims 1 to 7 in lacquers, protective coatings and coatings. 20. Use of the antimicrobial polymer blends according to one of claims 8 to 11 for Manufacture of products with an antimicrobial coating from the polymer. 21. Use of the antimilαobial polymer blends according to one of claims 8 to 11 for the production of medical articles with an antimicrobial coating from the polymer. 22. Use of the antimicrobial polymer blends according to one of claims 8 to 11 for the production of hygiene articles with an antimicrobial coating made of the polymer. 23. Use of the antimilαobial polymer blends according to one of claims 8 to 11 in paints, protective coatings and coatings. 24. A process for the disinfection of cooling water flows, characterized in that antimicrobial polymers according to claims 1 to 5 are added in dispersed form to the cooling water. 25. A process for the disinfection of cooling water flows, characterized in that antimicrobial polymer blends according to claims 8 to 11 are added to the cooling water in dispersed form.