EP1268580A1

EP1268580A1 - Microbicidal coatings containing acrylo-substituted alkylsulphonic acid polymers

Info

Publication number: EP1268580A1
Application number: EP01911651A
Authority: EP
Inventors: Peter Ottersbach; Beate Kossmann
Original assignee: Creavis Gesellschaft fuer Technologie und Innovation mbH
Current assignee: Creavis Gesellschaft fuer Technologie und Innovation mbH
Priority date: 2000-03-24
Filing date: 2001-02-17
Publication date: 2003-01-02
Also published as: DE10014726A1; WO2001072859A1; AU4062701A

Abstract

The invention relates to microbicidal coatings, obtained by means of a homo-, or co-polymerisation of a monomer of the formula (I) where R1 = H, branched or unbranched aliphatic hydrocarbon residue with 1 - 5 C atoms, R2 = H, branched or unbranched aliphatic hydrocarbon residue with 1 - 5 C atoms, R3 = H, -CH3, R4 = H, branched or unbranched aliphatic hydrocarbon residue with 1 - 5 C atoms, R5 = substituted or unsubstituted, branched or unbranched, aliphatic or aromatic hydrocarbon residue with 1 to 50 C atoms, R6 = H, alkali atom, earth alkali atom, substituted or unsubstituted, branched or unbranched, aliphatic or aromatic hydrocarbon residue with 1 to 50 C atoms, with, in the case of a copolymer, further aliphatic unsaturated monomers and a method for production thereof. Said polymers can be produced by graft co-polymerisation of a substrate, whereby a covalently bonded coating on the substrate is obtained. Said polymers are useful as microbicidal coatings on, amongst other things, hygiene articles or in the medical sphere as well as in paints or protective coatings.

Description

Antimicrobial coatings containing polymers of acrylic-substituted alkyl sulfonic acids

The invention relates to antimicrobial coatings which are obtained by polymerizing acrylic-substituted alkylsulfonic acids, optionally with further monomers. The invention further relates to a method for producing and using these antimicrobial coatings.

Furthermore, the invention relates to antimicrobial coatings which are obtained by graft copolymerization of acrylic-substituted alkylsulfonic acids, optionally with further monomers, on a substrate, to a process for their preparation and their use.

Colonization and spreading of bacteria on the surfaces of pipelines, containers or packaging are highly undesirable. 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 genital area and for nursing and elderly care. In addition, bacteria must be kept away from furniture and device surfaces in care stations, in particular in the area of intensive care and the care of small children, in hospitals, in particular in rooms for medical interventions and in isolation stations for critical infections and in toilets.

Devices, surfaces of furniture and textiles against bacteria are currently being treated as necessary or as a precautionary measure with chemicals or their solutions as well as mixtures that have a more or less broad and massive antimicrobial effect as disinfectants. Such chemical agents have a non-specific effect, are often themselves toxic or irritating or form degradation products which are harmful to health. Frequently, Compatibility with appropriately sensitized people.

Another way of preventing surface bacteria from spreading is to incorporate antimicrobial substances into a matrix.

Thus, e.g. B. US-PS 4,532,269 a terpolymer of butyl methacrylate, tributyltin methacrylate and tert-butylaminoethyl methacrylate. This polymer is used as an antimicrobial marine paint, with the hydrophilic ter - 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 their effect more or less quickly when the necessary “minimum inhibitory concentration” (M-K) is no longer achieved on the surface.

It is also known from European patent applications 0 862 858 and 0 862 859 that homo- and copolymers of tert-butylaminoethyl methacrylate, a methacrylic acid ester with secondary amino function, have inherently milaobicidal properties. In order to effectively counteract undesirable adaptation processes of the milcrobial life forms, especially in view of the resistance development of germs known from antibiotic research, systems based on novel compositions and improved effectiveness must also be developed in the future.

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

Copolymers with acrylic-substituted alkyl sulfonic acids are known from other technical fields. For example, US 5,932,517 describes the use of such compounds as Additives for thermal transfer printing applications. The thermal transfer layer consists of a carrier layer containing basic dyes and a receiver layer containing acid groups for the dyes transported by the thermal printing process. As a receiver layer z. B. copolymers and terpolymers of butyl acrylate and 2-acrylamido-2-methylpropylsulfonic acid or butyl acrylate, allyl methacrylate and 2-acrylamido-2-methylpropylsulfonic acid are used.

These receiver layers can optionally consist of the copolymer and a further carrier layer such as polyolefins. The copolymers consist of a maximum of 25 mol% of 2-acrylamido-2-methylpropylsulfonic acid; the use as an antimicrobial coating or the use in an open, non-encapsulated system is not described.

US Pat. No. 5,643,462 describes terpolymers of tannin, an anionic, a cationic and a neutral monomer as a flocculating agent for water treatment. As an anionic monomer u. a. also 2-acrylamido-2-methylpropylsulfonic acid used; the use of such a terpolymer as an antimicrobial polymer has not been described.

It has now surprisingly been found that by polymerizing acrylic-substituted alkylsulfonic acids, optionally with aliphatic unsaturated monomers or by graft-polymerizing these components on a substrate, polymers with a surface that is permanently milcrobicidal are not attacked by solvents and physical stresses and no migration shows. It is not necessary to use other biocidal agents.

The present invention therefore relates to antimicrobial coatings which can be obtained by applying a polymer of monomers of the formula I.

With i = -H, branched or unbranched aliphatic hydrocarbon radical with 1 to 5 carbon atoms

R ₂ = -H, branched or unbranched aliphatic hydrocarbon radical with 1 to 5 carbon atoms R ₃ = -H, -CH ₃ _t = -H, branched or unbranched aliphatic hydrocarbon radical with 1 to 5 carbon atoms

R ₅ = substituted or unsubstituted, branched or unbranched aliphatic or aromatic hydrocarbon radical with 1 to 50 carbon atoms R _ä = -H, alkali metal atom, alkaline earth metal atom, substituted or unsubstituted, branched or unbranched aliphatic or aromatic hydrocarbon radical with 1 to 50 carbon atoms on a substrate.

Alkali atoms are the metals of the 1st main group of the Periodic Table of the Elements, i. H. Li, Na, K, Ca, alkaline earth atoms are correspondingly Mg, Ca, Ba, Sr.

The present invention also relates to antimicrobial coatings which can be obtained by applying a copolymer of monomers of the formula I having the meanings given for R 1, R ₂ , R ₃ , R *., R ₅ and Rs with at least one further aliphatic unsaturated monomer Invention.

The proportion of monomers of the formula I in the copolymer of the coating according to the invention should be between 40 and 99.9 mol%, preferably between 60 and 99.9 mol%, particularly preferably between, in order to obtain a sufficient antimicrobial action of the polymer 80 and 99.9 mol% are.

All monomers which undergo copolymerization with acrylic-substituted alkylsulfonic acids can be used as aliphatic unsaturated monomers. For example, acrylates or methacrylates, e.g. B. acrylic acid, tert-butyl methacrylate or methyl methacrylate, styrene, vinyl chloride, vinyl ether, acrylamides, acrylonitriles, olefins (ethylene, propylene, butylene, isobutylene), allyl compounds, vinyl ketones, vinyl acetic acid, vinyl acetate or vinyl ester, in particular, for example, methyl methacrylate, methyl methacrylate,

Butyl methacrylate, tert-methacrylic acid. -butyl ester, acrylic acid methyl ester,

Acrylic acid ethyl ester, acrylic acid butyl ester, acrylic acid tert. -butyl ester, tert.-

Butylaminoethyl ester, methacrylic acid-3-dimethylaminopropylamide, 2-diethylaminoethyl vinyl ether, methacrylic acid-2-diethylaminoethyl ester, 2-methacryloyloxyethyl trimethylammonium methosulfate and / or 2-methacryloyloxyethyltrimethylammonium chloride.

The aliphatic unsaturated monomers are preferably acrylic acid or methacrylic acid compounds, here in particular methyl methacrylate, butyl methacrylate, tert-methacrylic acid. -butyl ester, acrylic acid methyl ester,

Acrylic acid butyl ester and acrylic acid tert. butyl.

2-Acrylamido-2-methyl-propanesulfonic acid and its alkali metal salts, in particular the sodium salt, are preferably used as the monomer according to formula I as mono- or copolymer for the coatings according to the invention.

The homo- or copolymerization is expediently carried out by a radical initiator or by radiation-induced radiation. Typical procedures are described in the examples.

The antimicrobial coatings according to the invention can also be obtained by copolymerizing monomers of the formula I with at least one aliphatic unsaturated monomer on a substrate. A physisorbed coating of the antimicrobial copolymer is obtained on the substrate. An analogous procedure also applies to the coatings consisting of the homopolymer of monomers of the formula I.

All polymeric plastics, such as, for example, are suitable as substrate materials. B. polyurethanes, polyamides, polyesters and ethers, polyether block amides, polystyrene, polyvinyl chloride, polycarbonates, polyorganosiloxanes, polyolefins, polysulfones, polyisoprene, polychloroprene, polytetrafluoroethylene (PTFE), corresponding copolymers and blends and natural and synthetic rubbers, with or without radiation-sensitive groups. The method according to the invention can also be used on surfaces of lacquered or otherwise with plastic Use coated metal, glass or wooden bodies.

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

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 by UV radiation, plasma treatment, corona treatment, flame treatment, ozonization, electrical discharge, γ-radiation are established methods. 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. However, mercury vapor lamps are also suitable for substrate activation if they emit significant amounts of radiation in the areas mentioned. The exposure time is generally 0.1 seconds to 20 minutes, preferably 1 second to 10 minutes.

The standard polymers can also be activated with UV radiation using an additional photosensitizer. 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.

According to the invention, the activation can also be carried out by plasma treatment using an RF or Microwave plasma (Hexagon, Technics Plasma, 85551 Kirchheim, Germany) can be achieved 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 barrier-flain 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, harmful overheating of the substrate must be avoided, which is easily achieved by intimate contact with a cooled metal surface on the substrate surface facing away from the flame side. The activation by flame treatment is accordingly limited to relatively thin, flat substrates. The exposure times are generally 0.1 second to 1 minute, preferably 0.5 to 2 seconds, all of which deal with non-illuminating flames and the distances from the substrate surfaces to the outer flame front are 0.2 to 5 cm, preferably 0.5 to 2 cm.

The substrate surfaces activated in this way are processed using known methods, such as dipping,

Spraying or brushing, with monomers of the formula I (component I) and optionally one or more aliphatic unsaturated monomers (component II), if appropriate in

Solution, coated. Ethanol and water-ethanol mixtures have proven to be solvents. ure, but other solvents can also be used, provided that they have sufficient solubility for the monomers and wet the substrate surfaces well. Solutions with monomer contents of 1 to 10% by weight, for example approximately 5% by weight, have proven themselves in practice and generally result in coherent coats covering the substrate surface with layer thicknesses which can be more than 0.1 μm.

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. The same applies analogously to the homopolymer according to the invention.

Furthermore, graft polymerization can also be achieved by a process which is described in European patent application 0 872 512 and is based on a graft polymerization of swollen monomer and initiator molecules. Both component I and component II can be used for swelling.

The antimicrobial coatings according to the invention made of homo- or copolymers of the monomers of the formula I (component I) and optionally at least one further aliphatic unsaturated monomer (component II) show a milcrobicidal or antimicrobial behavior even without grafting onto a substrate surface.

Another embodiment of the present invention is that the polymerization of components I and optionally II is carried out on a substrate.

The components can be applied to the substrate in solution. Suitable solvents are, for example, water, ethanol, methanol, methyl ethyl ketone, diethyl ether, dioxane, Hexane, heptane, benzene, toluene, chloroform, dichloromethane, tetrahydrofuran and acetonitrile. Component II can also serve as solvent for component I.

The antimicrobial coating according to the invention can also directly, i. H. cannot be applied to a substrate by polymerization of the components. Suitable coating methods are the application of the homo- or copolymers in solution or as a melt.

The solution of the polymers can e.g. B. by dipping, spraying or painting on the substrates.

If the coating according to the invention, i. H. If the polymers are produced directly on the substrate surface without grafting, customary radical initiators can be added. As initiators u. a. Azonitriles, alkyl peroxides, hydroperoxides, acyl peroxides, peroxoketones, peresters, peroxocarbonates, peroxodisulfate, persulfate and all customary photoinitiators such as e.g. B. 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.

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

Use of the modified polymer substrates The present invention further relates to the use of the antimicrobial coatings according to the invention for the production of antimicrobially active products and the products thus produced as such. The products can contain or consist of modified polymer substrates according to the invention. Such products are preferably based on polyamides, polyurethanes, polyether block amides, polyester amides or imides, PVC, polyolefins, silicones, polysiloxanes, polymethacrylate or polyterephthalates, the surfaces modified with polymers according to the invention exhibit.

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 of sanitary facilities, components of animal cages and houses, toys, components in water systems, food packaging, operating elements (touch panel ) of devices and contact lenses.

The coatings according to the invention made from the homo- or copolymers or corresponding graft polymers of the monomers of the formula I, optionally with further aliphatic monomers, can be used wherever it is possible to use bacteria-free, ie. H. microbicidal surfaces or surfaces with non-stick properties. Examples of uses for the coatings according to the invention are, in particular, paints, protective coatings or coatings in the following areas:

Marine: hulls, port facilities, buoys, drilling platforms, 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 transport, animal cages, cash registers, carpeting, wallpapers.

The present invention also relates to the use of the Coatings according to the invention or processes for producing the coatings of polymer substrates modified on the surface for producing hygiene products or medical articles. The above statements regarding preferred materials apply accordingly. Such hygiene products include toothbrushes, toilet seats, combs and packaging materials. Other items that may come into contact with many people, such as telephone receivers, handrails of stairs, door and window handles as well as holding belts and handles in public transport, also fall under the name of hygiene articles. Medical articles are e.g. B. catheters, tubes, cover sheets or surgical cutlery.

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

Example 1 :

6 g of 2-acrylamido-2-methyl-l-ρropansulfonic acid (from Aldrich), 6 ml of methyl methacrylate (from Aldrich), 40 ml of ethanol and 20 ml of water are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.15 g of azobisisobutyronitrile dissolved in 4 ml of ethyl methyl ketone are slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours, during which the product precipitates out. The polymeric product is filtered off and the filter residue is rinsed with 100 ml of ethanol in order to remove any remaining monomers. The product is then dried in vacuo at 50 ° C for 24 hours.

Example la:

0.05 g of the product from Example 1 are placed in 20 ml of a test 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 lb: 0.05 g of the product from Example 1 are placed in 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After this time the number of germs has dropped from 10 ⁷ to 10 ² .

Example 2:

6 g of 2-acrylamido-2-methyl-l-propanesulfonic acid (from Aldrich), 6 ml of butyl methacrylate (from Aldrich), 40 ml of ethanol and 20 ml of water are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.15 g of azobisisobutyronitrile dissolved in 4 ml of ethyl methyl ketone are slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours, during which the product precipitates out. The polymeric product is filtered off and the filter residue is rinsed with 100 ml of ethanol in order to remove any remaining monomers. The product is then dried in vacuo at 50 ° C for 24 hours.

Example 2a:

0.05 g of the product from Example 2 are placed in 20 ml of a test 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 ² .

Example 3:

5 g of 2-acrylamido-2-methyl-l-propanesulfonic acid (Aldrich), 7 ml of methacrylic acid tert. - Butyl ester (from Aldrich), 40 ml of ethanol and 20 ml of water are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.15 g Azobisisobutyronitrile dissolved in 4 ml of ethyl methyl ketone was slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours, during which the product precipitates out. The polymeric product is filtered off and the filter residue is rinsed with 100 ml of ethanol in order to remove any remaining monomers. The product is then dried in vacuo at 50 ° C for 24 hours.

Example 3a:

0.05 g of the product from Example 3 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 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 ³ .

Example 4: 10 g of 2-acrylamido-2-methyl-l-propanesulfonic acid (Aldrich), 35 ml of ethanol and 15 ml of water are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.15 g of azobisisobutyronitrile dissolved in 4 ml of ethyl methyl ketone are slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. The polymeric product is precipitated with cyclohexane, filtered off and the filter residue is rinsed with 100 ml of ethanol in order to remove any remaining monomers. The product is then dried in vacuo at 50 ° C for 24 hours.

Example 4a

0.05 g of the product from Example 4 are dissolved in 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of

Test microbial suspension removed, and the number of bacteria in the test batch determined. After expiration during this time the number of germs dropped from 10 ⁷ to 10 ² .

Example 4b

0.05 g of the product from Example 4 are dissolved 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 5: 4.5 g of 2-acrylamido-2-methyl-l-propanesulfonic acid (from Aldrich), 7.5 ml of methyl methacrylate (from Aldrich), 40 ml of ethanol and 20 ml of water are placed in a three-necked flask and under a stream of argon heated to 65 ° C. Then 0.15 g of azobisisobutyronitrile dissolved in 4 ml of ethyl methyl ketone are slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours, during which the product precipitates out. The polymeric product is filtered off and the filter residue is rinsed with 100 ml of ethanol in order to remove any remaining monomers. The product is then dried in vacuo at 50 ° C for 24 hours.

Example 5a: 0.05 g of the product from Example 5 is 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 ³ .

Example 6: A polyamide 12 film is exposed to the 172 nm radiation of an excimer radiation source from Heraeus for 2 minutes at a pressure of 1 mbar. The film activated in this way is placed under protective gas in an irradiation reactor and fixed. The film is then covered with 20 ml of a mixture of 15 g of 2-acrylamido-2-methyl-l-propanesulfonic acid (from Aldrich), 3 ml of methyl methacrylate (from Aldrich), 60 ml of ethanol and 30 ml of water in a protective gas countercurrent. The radiation chamber is closed and placed at a distance of 10 cm below an excimer radiation unit from Heraeus, which has an emission of 308 nm. The radiation is started and the exposure time is 15 minutes. The film is then removed and rinsed with 30 ml of ethanol. The film is then dried in vacuo at 50 ° C. for 12 hours. The film is then extracted in water 5 times 6 hours at 30 ° C., then dried at 50 ° C. for 12 hours.

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

Example 6a

A coated piece of film from Example 6 (5 × 4 cm) is placed in 30 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 6b

A coated piece of film from Example 6 (5 × 4 cm) is placed in 30 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 ³ .

Claims

claims:

1. Antimicrobial coating, obtainable by applying a polymer of monomers of the formula I.

(I) with

Rl = -H, branched or unbranched aliphatic hydrocarbon radical with 1 to 5

Carbon atoms

R2 = -H, branched or unbranched aliphatic hydrocarbon radical with 1 to 5 carbon atoms

R3 = -H, -CH ₃

R4 = -H, branched or unbranched aliphatic hydrocarbon radical with 1 to 5

Carbon atoms

R5 = substituted or unsubstituted, branched or unbranched aliphatic or aromatic hydrocarbon radical with 1 to 50 carbon atoms

R6 = -H, alkali atom, alkaline earth atom, substituted or unsubstituted, branched or unbranched aliphatic or aromatic hydrocarbon radical with 1 to 50 carbon atoms on a substrate.

2. Antimicrobial coating, obtainable by applying a copolymer of monomers of the formula I.

(I) with Rl = -H, branched or unbranched aliphatic hydrocarbon radical with 1 to 5 carbon atoms

R2 = -H, branched or unbranched aliphatic hydrocarbon radical with 1 to 5 carbon atoms R3 = -H, -CH ₃

R4 = -H, branched or unbranched aliphatic hydrocarbon radical with 1 to 5 carbon atoms

R5 = substituted or unsubstituted, branched or unbranched aliphatic or aromatic hydrocarbon radical having 1 to 50 carbon atoms R6 = -H, alkali metal atom, alkaline earth metal atom, substituted or unsubstituted, branched or unbranched aliphatic or aromatic hydrocarbon radical having 1 to 50 carbon atoms with at least one further aliphatically unsaturated monomer on a substrate.

3. Antimicrobial coating according to claim 2, characterized in that the copolymers contain between 40 and 99.5 mol% of monomers according to formula I.

4. Antimicrobial coatings according to claim 2 or 3, characterized in that the aliphatic unsaturated monomers are methacrylic acid compounds.

5. Antimicrobial coatings according to claim 2 or 3, characterized in that it is acrylic acid compounds in the aliphatic unsaturated monomers.

6. Antimicrobial coatings according to claim 2 to 5, characterized in that as aliphatic unsaturated monomers methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid butyl ester, methacrylic acid tert. -butyl ester, acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid butyl ester, acrylic acid tert. -butyl ester, tert-butylaminoethyl ester, 2-diethylaminoethyl vinyl ether, N-3-dimethylaminopropyl methacrylamide, 2-methacryloyloxyethyltrimethylammonium methosulfate, 2-diethylaminoethyl methacrylic acid and / or 2-methacryloyloxyethyltrimethylammonium chloride.

7. Antimicrobial coatings according to one of claims 1 to 6, characterized in that the polymerization of the monomers is carried out on a substrate.

8. Antimicrobial coatings according to one of claims 1 to 6, characterized in that the polymerization of the monomers is carried out as a graft polymerization of a substrate.

9. Antimicrobial coatings according to claim 8, characterized in that the substrate before the graft polymerization by UV radiation, plasma treatment,

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

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

11. Antimicrobial coatings according to one of claims 1 to 10, characterized in that as the monomer of formula I 2-Acrylamido-2-methyl-l-propanesulfonic acid or the corresponding sodium salt is used.

12. A method for producing antimicrobial coatings, characterized in that a polymer of monomers of the formula I with

(I) Rl = -H, branched or unbranched aliphatic hydrocarbon radical with 1 to 5 carbon atoms R2 = -H, branched or unbranched aliphatic hydrocarbon radical with 1 to 5

Carbon atoms R3 = -H, -CH ₃

R4 = -H, branched or unbranched aliphatic hydrocarbon radical with 1 to 5 carbon atoms R5 = substituted or unsubstituted, branched or unbranched aliphatic or aromatic hydrocarbon radical with 1 to 50 carbon atoms R6 = -H, alkali atom, alkaline earth metal atom, substituted or unsubstituted, branched or unbranched aliphatic or aromatic hydrocarbon radical having 1 to 50 carbon atoms and applied to a substrate.

13. A process for the preparation of antimicrobial coatings, characterized in that a copolymer of monomers of the formula I

With

Rl ^■ = -H, branched or unbranched aliphatic hydrocarbon radical with 1 to 5

Carbon atoms

R2 = -H, branched or unbranched aliphatic hydrocarbon est with 1 to 5 carbon atoms

R3 = -H, -CH ₃

R4 = -H, branched or unbranched aliphatic hydrocarbon radical with 1 to 5

Carbon atoms

R6 - H, alkali atom, alkaline earth atom, substituted or unsubstituted, branched or unbranched aliphatic or aromatic hydrocarbon radical having 1 to 50 carbon atoms with at least one further aliphatic unsaturated monomer and produced and applied to a substrate.

14. The method according to claim 13, characterized in that the copolymers contain between 40 and 99 mol% of monomers according to formula I.

15. The method according to claim 13 or 14, characterized in that the aliphatic unsaturated monomers are methacrylic acid compounds.

16. The method according to claim 13 or 14, characterized in that the aliphatic unsaturated monomers are acrylic acid compounds.

17. The method according to any one of claims 13 to 16, characterized in that, as aliphatic unsaturated monomers, methacrylic acid methyl ester, methacrylic acid reethylester, butyl methacrylate, tert-methacrylic acid. -butyl ester, acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid butyl ester, acrylic acid tert. -butyl ester, tert-butylaminoethyl ester, 2-diethylaminoethyl vinyl ether, N-3-dimethylaminopropyl methacrylamide, 2-methacryloyloxyethyltrimethylammonium methosulfate, methacrylic acid e-2-diethylaminoethyl ester and / or 2-methacryloyloxyethyltrimethylammonium chloride, are used.

18. The method according to any one of claims 13 to 17, characterized in that the polymerization of the monomers is carried out on a substrate.

19. The method according to any one of claims 12 to 17, characterized in that the polymerization of the monomers is carried out as a graft polymerization of a substrate.

20. The method according to claim 19, 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.

21. The method according to claim 19, characterized in that the substrate before the graft polymerization by UV radiation with a

Photoinitiator is activated.

22. The method according to any one of claims 12 to 21, characterized in that 2-acrylamido-2-methyl-l-propane sulfonic acid or the corresponding sodium salt is used as the monomer of the formula I.

23. Use of the antimicrobial coatings according to one of claims 1 to 11 for the production of medical articles.

24. Use of the antimicrobial coatings according to one of claims 1 to 11 for the production of hygiene articles.

25. Use of the antimilcrobial coatings according to one of claims 1 to 11 in paints, protective coatings and other coatings.