EP1218425A1

EP1218425A1 - Microbicidal additives

Info

Publication number: EP1218425A1
Application number: EP00944020A
Authority: EP
Inventors: Friedrich Sosna; Peter Ottersbach; Beate Kossmann
Original assignee: Creavis Gesellschaft fuer Technologie und Innovation mbH
Current assignee: Creavis Gesellschaft fuer Technologie und Innovation mbH
Priority date: 1999-09-09
Filing date: 2000-07-08
Publication date: 2002-07-03
Also published as: AU5826600A; US6790910B1; CA2384531A1; JP2003508604A; NO20021183D0; CN1387542A; NO20021183L; WO2001018077A1

Abstract

The invention relates to microbicidal polymers and polymer blends, obtained by the polymerization of a monomer of formula (I), wherein R1 = -H or -CH3, R2 = a branched or unbranched aliphatic hydrocarbon radical with between 1 and 5 carbon atoms, R3 = H, a branched or unbranched aliphatic hydrocarbon radical with between 1 and 7 carbon atoms and R4 = H, a branched or unbranched aliphatic hydrocarbon radical with between 1 and 7 carbon atoms, R5 = H, a branched or unbranched aliphatic hydrocarbon radical with between 1 and 7 carbon atoms, X = O, NH, NR5 and by the optional subsequent mixing of said polymers with at least one additional polymer. The microbicidal polymers or polymer blends can be used e.g. as a coating for articles of hygiene or medical articles, or used in lacquers or protective coatings. They can also be used in a method for preventing/reducing biological fouling in water systems.

Description

1

Antimicrobial additives

The invention relates to antimicrobial polymers which are obtained by polymerizing acryloxyalkylamines. The invention further relates to a process for the preparation and use of these antimicrobial polymers

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

Bacteria must be kept away from all areas of life in which hygiene is important. This affects textiles for direct body contact, in particular for the intimate area and for nursing and elderly care. Bacteria must also be kept away from furniture and device surfaces in care stations, especially in the Area of intensive care and young child care, in hospitals, especially in rooms for medical interventions and in isolation stations for critical infection cases and in toilets

At present devices, surfaces of mobeine and textiles against bacteria are treated if necessary or as a precautionary measure with chemicals or their solutions as well as mixtures which act as a disinfectant to a greater or lesser extent and have a massive antimicrobial effect.These chemical agents have a non-specific effect, are often themselves toxic or irritating or form degradation products that are harmful to health There are also often incompatibilities with appropriately sensitized people

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

For example, US Pat. No. 4,532,269 discloses a terpolymer of butyl methacrylate, tributyltin methacrylate and tert-butylaminoethyl methacrylate. This copolymer is used as an antimicrobial marine paint, the hydrophilic tert-butylaminoethyl methacrylate being the long same erosion of the polymer and thus releases the highly toxic tributyltin methacrylate as an antimicrobial agent

In these applications, the copolymer made with aminomethacrylates is only a matrix or carrier substance for added microbicidal active ingredients that can diffuse or migrate from the carrier substance. Polymers of this type lose their effect more or less quickly if the necessary "minimal inhibitory concentration" on the surface ( MIK) is no longer achieved

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

The present invention is therefore based on the object of developing novel, antimicrobially active polymers which, as a coating or coating material, are intended to prevent the settlement and spread of bacteria on surfaces

It has now surprisingly been found that homopolymerization of acryloxyalkylamines or methacryloxyalkylamines gives polymers which are permanently microbicidal, are not attacked by solvents and physical stresses and do not show any migration. It is not necessary to use further biocidal active ingredients for the antimicrobial action of these homopolymers the surface of the polymers is of course important

The present invention therefore relates to antimicrobial polymers which are obtained by polymerizing a monomer of the formula I.

With

Rl = -H or -CH ₃ R2 - branched or unbranched ahphatic hydrocarbon residue with 1 to 5

Carbon atoms, R3 = H, branched or unbranched aliphatic hydrocarbon radical with 1 to 7

Carbon atoms and R4 = H, branched or unbranched aliphatic hydrocarbon radical having 1 to 7 carbon atoms,

R5 = H, branched or unbranched aliphatic hydrocarbon with 1 to 7

Carbon atoms, X = O, NH, NR5 can be obtained

Acryloyloxyaikylamines (X = O) and alkylaminoacrylamides (X = NH) are particularly suitable for producing the polymers according to the invention

The radicals R3 and R4 can have the same or different meanings. If R3 and / or R4 denote hydrocarbon groups, these can in particular be methyl, ethyl, i-propyl, n-propyl or tert-butyl groups

Preferred monomers of the formula I are methacrylic acid-2-tert-butylaminoethyl ester, methacrylic acid-2-diethylaminoethyl ester, methacrylic acid-2-dimethylaminomethyl ester, acrylic acid-2-tert-butylaminoethyl ester, acrylic acid-3-dimethylaminopropyl ester, acrylic acid 2-diethylaminoethylester -dimethylaminoethyl ester, methacrylic acid-3-dimethylaminopropylamide, methacrylic acid-3-diethylaminopropylamide, acrylic acid-3-dimethylaminopropylamide or acrylic acid-3-diethylaminopropylamide The antimicrobial polymers according to the invention can be obtained by homopolymerizing monomers of the formula I. The free-radical polymerization is expediently carried out chemically by means of a free-radical initiator or radiation-induced. Typical procedures are described in the examples

The present invention furthermore relates to antimicrobial polymer blends which can be obtained by mixing one or more antimicrobial polymers, in each case by polymerizing monomers of the formula I, where R 1, R 2, R 3, R 4, R 5 and X have the meanings already mentioned, with at least one other polymers can be produced

As blend material, ie as a further polymer with which the polymer according to the invention is mixed, for example polyurethanes, PVC, polyolefins such as polyethylene or polypropylene, polysiloxanes, polystyrenes, polyacrylates, polymethacrylates or engineering plastics, such as polyamides or polyterephahates, come into question To obtain a sufficient antimicrobial effect of a polymer blend, the proportion of the antimicrobial polymer according to the invention should be 0.2 to 90, preferably 40-90% by weight

The production of the antimicrobially active polymer blends can in principle be carried out by all processes known in the art, such as are described in detail in, for example, "HG Elias, Macromolecules, Vol. 2, 5th Edition, S 620 ff" Schemlzmischen two pre-formed polymers the granular or powder polymers on roller mills, in kneaders or with extruders mixed. For thermoplastics, this is heated above the glass or melting temperatures. Solution mixing is based on independently prepared solutions of the two polymers in the same solvent

In specific embodiments of the present invention, it is possible for the proportion of the one or more antimicrobial polymers according to the invention in a blend to be less than 40-90% by weight, such as 0 2-70, preferably 0.2 to 30, particularly preferably 0 , 2 to 15, very particularly preferably 0.2-10% by weight

A preferred method for producing the antimicrobial polymers according to the invention or polymer blends is the radical polymerization of monomers of the formula I in solution with a radical initiator. The antimicrobial polymers obtained in this way can, if necessary, be mixed on a surface by mixing with other polymers by known methods, such as dipping, spraying or brushing. Methanol, water-alcohol mixtures, methyl ethyl ketone, diethyl ether, dioxane, hexane, heptane, benzene, toluene, chloroform, dichloromethane, tetrahydrofuran and acetonitrile are preserved, but other solvents can also be used, provided that they have a sufficient bulk ratio for the polymers and the substrate surfaces wet well solutions with polymer contents of 3 to 20% by weight, for example about 5% by weight, have been found to be effective in practice and generally give coherent coatings covering the substrate surface with layer thicknesses of more than 0.1 μm can be

Furthermore, the antimicrobial polymers or polymer blends according to the invention can also be applied to the substrates as a melt, for example by coextrusion, by dipping, spraying or painting

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, far lower concentrations, for example in the lower percent or per mille range, may be sufficient

Use of the modified polymer substrates The present invention further relates to the use of the antimicrobial polymers or polymer blends according to the invention for the production of antimicrobially active products and the products thus produced as such. The products May contain or consist of antimicrobial polymers according to the invention. Such products are preferably based on polyamides, polyurethanes, polyether block amides, polyester amides or imides, PVC, polyolefins, silicones, polysiloxanes, polymethacrylate or polyterephthalates, which have surfaces coated with polymers according to the invention or with polymers according to the invention in the form of a polymer blend were processed

Antimicrobial products of this type are, for example, machine parts for food processing, components of air conditioning systems, roofing, bathroom and toilet articles, cake articles, components of sanitary facilities, components of animal cages and dwellings, toys, components in water systems, food packaging, operating elements (touch panel) of devices and contact lenses

The polymers or polymer blends according to the invention can be used wherever bacteria-free, ie microbicidal surfaces or surfaces with non-stick properties are important. Examples of uses for the polymers or polymer blends according to the invention are, in particular, paints, protective coatings or coatings in the following areas

- Marine hull, port facilities, buoys, drilling platforms, ballast water tanks

House roofing, basement, walls, facades, greenhouses, sun protection, garden fences, wood protection, tarpaulins, textile fabrics

Sanitary Public toilets, bathrooms, shower curtains, toiletries, swimming pool, sauna, joints, sealants - food machinery, kitchen, cake 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 - everyday objects car seats, clothing (stockings, sportswear), hospital equipment, door handles, telephone receiver, public transport, animal cages, cash registers, carpeting, wallpaper 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, in particular here in salt-containing seawater

In addition, the antimicrobial polymers or polymer blends according to the invention can be used as additives in the formulation of cosmetic products, for example for pastes and ointments. Here, the proportion of polymers or polymer blends according to the invention, depending on the effectiveness of the polymer and the formulation, can be up to the lower percentages. or alcohol range can be lowered

Furthermore, the polymers or polymer blends according to the invention are used as biofouling inhibitors in cooling circuits. In order to avoid damage to cooling circuits caused by algae or bacteria, they often have to be cleaned or built accordingly oversized. The addition of microbicidal substances such as formalin is in open cooling systems, such as in power plants or chemical Plants are common, not possible. 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 into the process water in finely dispersed form. 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 This effectively prevents algae on system parts. This results in a completely new process for avoiding or reducing bifouling in service water systems

The present invention therefore furthermore relates to processes for the disinfection of cooling water streams, in which antimicrobial polymers or their polymer blends are added in dispersed form to the cooling water. Cooling water in the sense of the present invention is all process water streams which are used for heating or cooling purposes in closed or open circulation systems The dispersed form of the copolymers or their blends can be obtained in the production process itself, for example by emulsion polymerization, precipitation or suspension polymerization or subsequently by grinding, for example in a jet mill. The particles obtained in this way are preferred in a size distribution of 0.001 to 3 mm (as a spherical diameter) used so that, on the one hand, a large surface is available for killing the bacteria or algae, on the other hand, where necessary, separation from the cooling water is easily possible, e.g. by filtering. The process can, for example, be carried out in such a way that a part (5- 10%) of the copolymers / blends used are removed from the system and replaced by an appropriate amount of fresh material. Alternatively, while checking the bacterial count of the water, further antimicrobial copolymer / blend can be added if required. The amount used - depending on the water quality - is 0.1 -100 g antimicrobial copolyme r or their blends per ITT cooling water

The present invention also relates to the use of the polymer substrates modified on the surface with polymers or polymer blends according to the invention for the production of hygiene products or medical articles. The above statements regarding preferred materials apply accordingly. Such hygiene products are, for example, toothbrushes, toilet seats, combs and packaging materials Hygiene articles also include other objects that may come into contact with many people, such as telephone receivers, handrails of stairs, door and window handles as well as hand straps and handles in public transport. Medical technology articles include catheters, tubes, cover foils or surgical cutlery

The uses mentioned for the antimicrobial polymers apply accordingly to the polymer blends according to the invention

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

Example 1: 60 ml of 2-diethylaminoethyl methacrylate (Aldrich) and 250 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.74 g of azobisisobutyrometril dissolved in 20 ml of ethyl methyl ketone are slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 1.5 l of demineralized water, the polymer product precipitating. After filtering off the product, the filter residue is rinsed with 100 ml of a 10% solution of ethanol in water. to remove residual monomers that are still present. 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 microbial suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined Staphylococcus aureus more detectable

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 bacteria in the test mixture is determined 10 ⁷ dropped to 10 "

Example 2:

90 ml of methacrylic acid-2-tert-butylaminoethyl ester (from Aldrich) and 180 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.745 g of azobisisobutyrometrile dissolved in 20 ml of ethyl methyl ketone are then slowly added dropwise with stirring. The mixture is brought to 70 ° C heated and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 1 l of demineralized water, the polymer product precipitating. After filtering off the product, the filter residue is rinsed with 100 ml of a 10% solution of ethanol in water. to remove residual monomers that are still present. The product is then dried in vacuo at 50 ° C. for 24 hours Example 2a

0.05 g of the product from Example 2 are placed in 20 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined Staphylococcus aureus more detectable

Example 2b

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

Example 3:

20 ml of 3-dimethylaminopropyl acrylate (Aldrich) and 70 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.2 g of azobisisobutyrometrile dissolved in 5 ml of ethyl methyl ketone is slowly added dropwise with stirring. The mixture is brought to 70 ° C heated and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 0.5 l of demineralized water, the polymer product precipitating. After filtering off the product, the filter residue is washed with 100 ml of a 10% solution of ethanol in water spooled to remove any remaining monomers. The product is then dried in vacuo at 50 ° C. for 24 hours

Example 3 a

0.05 g of the product from Example 3 are placed in 20 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined 10 ⁷ dropped to 10 ³

Example 3b 0.05 g of the product from Example 3 is placed in 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined by After this time, the number of bacteria has dropped from 10 ⁷ to 10 ^J.

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 (from Aldrich), which has also previously been heated to 165 ° C. The two polymers are mixed thoroughly and at a rate of 20 ° C cooled to room temperature per hour

Example 4a 0.05 g of the product from Example 4 is placed in 20 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined Germ count decreased from 10 to 10 ^J.

Example 4b

0.05 g of the product from Example 4 are placed in 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined 10 ⁷ dropped to 10 ⁴

Example 5:

90 ml of methacrylic acid-2-tert-butylaminoethyl ester (from Aldrich) and 180 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.745 g of azobisisobutyrometrile dissolved in 20 ml of ethyl methyl ketone are then slowly added dropwise with stirring. The mixture is brought to 70 ° C heated and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 1 liter of demineralized water, the polymer product precipitating. After filtering off the product, the filter residue is rinsed with 100 ml of a 10% solution of ethanol in water. In order to remove any residual monomers still present, the product is then dried in vacuo for 24 hours at 50 ° C. 5 g of the product are dissolved in 32 g of di-isononyl phthalate. Then 64 g of polyvinyl chloride granules are added to this mixture and the mixture is thoroughly stirred until it becomes pasty 20 g of the paste obtained are knife-coated spread on a metal plate so that a layer thickness of 0.7 mm is obtained. 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 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 2 hours, 1 ml of the test germ suspension is removed, and the Number of bacteria determined in the test batch After this time, no bacteria from Staphylococcus aureus can be detected

Example 5b

A 3 x 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 4 hours, 1 ml of the test germ suspension is removed, and the Number of bacteria determined in the test batch After this time no more Pseudomonas aeruginosa germs can be detected

Example 6: 90 ml of methacrylic acid-2-tert-butylaminoethyl ester (from Aldrich) and 180 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.745 g of azobisisobutyrometrile dissolved in 20 ml of ethyl methyl ketone are then slowly added dropwise with stirring. The mixture is added heated to 70 ° C and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 1 liter of demineralized water, whereby the polymeric product precipitates. After filtering off the product, the filter residue is washed with 100 ml of a 10% solution of ethanol in Rinsed water to remove any residual monomers still present. The product is then dried in vacuo for 24 hours at 50 ° C. 2 g of the product are dissolved in 32 g of di-isononyl phthalate. Then 64 g of polyvinyl chloride granules are added to this mixture and the mixture is thoroughly stirred until she will be pasty 20 g of the paste obtained with a squeegee so on a meta Spread the plate so that a layer thickness of 0.7 mm is obtained. The plate with the paste on it is then heated to 200 ° C. for 2 minutes, the Gelled paste and a soft PVC film is created

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 2 hours, 1 ml of the test germ suspension is removed, and the Number of bacteria determined in the test batch After this time, no bacteria from Staphylococcus aureus can be detected

Example 6b

A 3 x 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 from Pseudomonas aeruginosa and shaken. After a contact time of 4 hours, 1 ml of the test germ suspension is removed, and the Number of bacteria determined in the test batch After this time, the number of bacteria has dropped from 10 ⁷ to 10 ³

Example 7:

90 ml of methacrylic acid-2-tert-butylaminoethyl ester (from Aldrich) and 180 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.745 g of azobisisobutyrometrile dissolved in 20 ml of ethyl methyl ketone are then slowly added dropwise with stirring. The mixture is brought to 70 ° C heated and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 1 l of demineralized water, the polymer product precipitating. After filtering off the product, the filter residue is rinsed with 100 ml of a 10% solution of ethanol in water. In order to remove any residual monomers still present, the product is then dried in vacuo for 24 hours at 50 ° C. 5 g of the product are stirred into 95 g of an acrylic varnish called Rowacryl G-31293 from ROWA

Example 7a Using a brush, a 5 x 5 cm aluminum plate is coated with the acrylic lacquer treated in this way from Example 7 and then dried in a drying cabinet at 35 ° C. for a period of 24 hours. This coated aluminum plate is coated placed upwards on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken After a contact time of 2 hours, 1 ml of the test germ suspension is removed and the number of germs in the test mixture is determined After this time no more Staphylococcus aureus germs are left detectable

Example 7b

Using a brush, a 5 x 5 cm aluminum plate is coated with the acrylic lacquer treated in this way from Example 7 and then dried in a drying cabinet at 35 ° C. for 24 hours. This coated aluminum plate is placed on the bottom of a beaker with its coated side up that contains 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken After a contact time of 2 hours, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined. After this time, no Pseudomonas aeruginosa germs are detectable

Example 8:

90 ml of methacrylic acid-2-tert-butylaminoethyl ester (from Aldrich) and 180 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.745 g of azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone are then slowly added dropwise with stirring. The mixture is brought to 70 ° C heated and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 1 liter of demineralized water, the polymer product precipitating. After filtering off the product, the filter residue is rinsed with 100 ml of a 10% solution of ethanol in water In order to remove any residual monomers still present, the product is subsequently dried in vacuo at 50 ° C. for 24 hours. 2 g of the product are stirred into 98 g of an acrylic lacquer called Rowacryl G-31293 from ROWA

Example 8a

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 a period of 24 hours. This coated aluminum plate is placed on the bottom of a beaker with its coated side up that contains 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 2 hours, 1 ml of the test microbial suspension was removed, and the number of bacteria in the test mixture was determined. After this time, no bacteria from Staphylococcus aureus can be detected

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 a period of 24 hours. This aluminum plate is coated with the coated side upwards on the floor placed in a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 2 hours, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined. After this time the number of bacteria has dropped from 10 to 10 ³

Example 9:

90 ml of methacrylic acid-2-tert-butylaminoethyl ester (from Aldrich) and 180 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.745 g of azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone are then slowly added dropwise with stirring. The mixture is brought to 70 ° C heated and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 1 l of demineralized water, the polymer product precipitating. After filtering off the product, the filter residue is rinsed with 100 ml of a 10% solution of ethanol in water. In order to remove any residual monomers still present, the product is then dried in vacuo for 24 hours at 50 ° C. 5 g of the product are stirred into 95 g of Plextol D 510 from PolymerLatex, an aqueous dispersion of a methacrylic ester / acrylic acid ester copolymer

Example 9a

Using a brush, a 5 x 5 cm aluminum plate is coated with the dispersion from Example 9 treated in this way and then dried in a drying cabinet at 35 ° C. for 24 hours. This coated aluminum plate is placed on the bottom of a beaker with its coated side up placed, which contains 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 2 hours, 1 ml of the test germ suspension is removed, and the bacterial count in the test mixture is determined after After this time, no Staphylococcus aureus germs can be detected

Example 9b

Using a brush, a 5 x 5 cm aluminum plate is coated with the dispersion from Example 9 treated in this way and then dried in a drying cabinet at 35 ° C. for 24 hours. This coated aluminum plate is placed on the bottom of a beaker with its coated side up placed, which contains 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 2 hours, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined. After this time, the number of bacteria has dropped from 10 to 10

Example 10:

90 ml of methacrylic acid-2-tert-butylaminoethyl ester (from Aldrich) and 180 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.745 g of azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone are then slowly added dropwise with stirring. The mixture is brought to 70 ° C heated and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 1 l of demineralized water, the polymer product precipitating. After filtering off the product, the filter residue is rinsed with 100 ml of a 10% solution of ethanol in water. In order to remove any residual monomers still present, the product is then dried in vacuo for 24 hours at 50 ° C. 2 g of the product are stirred into 98 g of Plextol D 510 from PolymerLatex, an aqueous dispersion of a methacrylic ester / acrylic acid ester copolymer

Example 10a

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 coated aluminum plate is placed on the bottom of a beaker with its coated side up that contains 20 ml of a test microbial suspension of Staphylococcus aureus and shaken After a contact time of 2 hours, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined. After this time, no bacteria of Staphylococcus aureus are detectable 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 24 hours. This coated aluminum plate is placed on the bottom of a beaker with its coated side up placed, which contains 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 2 hours, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined. After this time, the number of bacteria has dropped from 10 ⁷ to 10 ²

Example 11:

90 ml of methacrylic acid-2-tert-butylaminoethyl ester (from Aldrich) and 180 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.745 g of azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone are then slowly added dropwise with stirring. The mixture is brought to 70 ° C heated and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 1 l of demineralized water, the polymer product precipitating. After filtering off the product, the filter residue is rinsed with 100 ml of a 10% solution of ethanol in water. In order to remove any residual monomers that are still present, the product is then dried in vacuo for 24 hours at 50 ° C. 1 g of the product is dissolved in 99 g of ethanol. Six cotton pads, each with a diameter of 3 cm, are immersed in this solution for 1 second, removed and 24 Dried for hours at room temperature

Example 1 1 a In each case a coated cotton pad from Example 11 is inoculated with Chlorella sp, Trentepohlia sp, Gloeocapsa sp Calothrix sp and Aspergilus niger. These samples are then placed in an incubator for 3 weeks. In contrast to accompanying control samples, none of the coated cotton pads fouling is noticeable

Example 12:

60 ml of 2-diethylaminoethyl methacrylate (Aldrich) and 250 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.74 g of azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone are slowly added dropwise with stirring The mixture is heated to 70 ° C. and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 1.5 l of demineralized water, the polymeric product precipitating. After filtering off the product, the filter residue is washed with 100 ml of a 10% solution Solution of ethanol rinsed in water to remove any residual monomers still present. The product is then dried in vacuo for 24 hours at 50 ° C. 2 g of the product are dissolved in 10 g of tetrahydrofuran and applied to a 0.5 cm with a 100 micron doctor blade thick and 2 x 2 cm large aluminum plate applied The plate is then dried at 50 ° C for 24 hours

Example 12a

The aluminum plate from Example 12 is placed with its coated side upward on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 2 hours, 1 ml of the test germ suspension is removed, and the number of germs in the test mixture is determined according to After this time, no Staphylococcus aureus germs can be detected

Example 12b

The aluminum plate from Example 12 is placed with its coated side upward on the bottom of a beaker containing 20 ml of a test germ suspension from Pseudomonas aeruginosa and shaken. After a contact time of 4 hours, 1 ml of the test germ suspension is removed, and the bacterial count in the test mixture is determined according to No more Pseudomonas aeruginosa germs can be detected after this time

Example 13: 90 ml of methacrylic acid-2-tert-butylaminoethyl ester (Aldrich) and 180 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.745 g of azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone are then slowly added dropwise with stirring. The mixture is added heated to 70 ° C and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 1 liter of demineralized water, whereby the polymeric product precipitates. After filtering off the product, the filter residue is washed with 100 ml of a 10% solution of ethanol in Water rinsed to remove residual monomers still present. The product is then left for 24 hours Dried in vacuo at 50 ° C. 2 g of the product are dissolved in 10 g of tetrahydrofuran and applied to a 0.5 cm thick and 2 × 2 cm aluminum plate using a 100 micrometer doctor blade. The plate is then dried at 50 ° C. for 24 hours

Example 13a

The coated aluminum side of Example 13 is placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 2 hours, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test batch is determined according to After this time, no Staphylococcus aureus germs can be detected

Example 13b

The coated aluminum side of Example 13 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 4 hours, 1 ml of the test microbial suspension is removed and the number of bacteria in the test batch is determined according to No more Pseudomonas aeruginosa germs can be detected after this time

Example 14: 20 ml of 3-dimethylaminopropyl acrylate (Aldrich) and 70 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.2 g of azobisisobutyronitrile dissolved in 5 ml of ethyl methyl ketone is slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 0.5 l of demineralized water, the polymeric product precipitates After filtering off the product, the filter residue is rinsed with 100 ml of a 10% solution of ethanol in water in order to remove any remaining monomers. The product is then dried in vacuo at 50 ° C. for 24 hours, and 2 g of the product are dried dissolved in 10 g of tetrahydrofuran and applied with a 100 micrometer doctor blade to a 0.5 cm thick and 2 by 2 cm large aluminum plate. The plate is then dried at 50 ° C. for 24 hours

Example 14a The coated aluminum side of Example 14 is placed on the bottom of a beaker containing 20 ml of a test microbial 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 bacteria in the test batch is determined according to After this time, no Staphylococcus aureus germs can be detected

Example 14b

The coated aluminum side of Example 14 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 bacteria in the test batch is determined according to No more Pseudomonas aeruginosa germs can be detected after this time

Example 15: 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 on an aluminum plate 0.5 cm thick and 2 x 2 cm in size and cooled at a rate of 20 ° C per hour to room temperature

Example 15a

The coated aluminum side of Example 15 is placed on the bottom of a beaker containing 20 ml of a test microbial 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 bacteria in the test batch is determined according to After this time, no Staphylococcus aureus germs can be detected

Example 15b

The aluminum plate from Example 15 is placed with its coated side up on the bottom of a beaker containing 20 ml of a test germ suspension of Pseudomonas aeruginosa and shaken. After a contact time of 8 hours, 1 ml of the

Test microbial suspension removed, and the number of microbes in the test batch determined after expiration During this time, Pseudomonas aeruginosa germs can no longer be detected

Example 16:

50 ml of dimethylaminopropyl methacrylamide (Aldrich) and 250 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.6 g of azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone are then slowly added dropwise with stirring. The mixture is heated to 70 ° C. and 72 Stirred at this temperature for h hours. After this time, the reaction mixture is stirred into 1.5 l of cyclohexane, the polymer product precipitating. After filtering off the product, the filter residue is rinsed with 100 ml of n-hexane in order to remove residual monomers still present the product dried in vacuo for 24 hours at 50 ° C. 2 g of the product are dissolved in 10 g of tetrahydrofuran and applied to a 0.5 cm thick and 2 × 2 cm aluminum plate using a 100 micrometer doctor blade ° C dried for 24 hours

Example 16a

The coated aluminum side of Example 16 is placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 2 hours, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test batch is determined according to After this time, no Staphylococcus aureus germs can be detected

Example 16b

The coated aluminum side of Example 16 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 4 hours, 1 ml of the test microbial suspension is removed and the number of bacteria in the test batch is determined according to Over this time, the number of germs has decreased from 10 ⁷ to 10 ³ germs per ml

Example 17:

50 ml of diethylaminopropyl methacrylamide (Aldrich) and 250 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.6 g Azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone is slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 1.5 l of cyclohexane, the polymeric product precipitating. After filtering off the product the filter residue is rinsed with 100 ml of n-hexane in order to remove any residual monomers still present. The product is then dried in vacuo for 24 hours at 50 ° C. 2 g of the product are dissolved in 10 g of tetrahydrofuran and with a 100 micron doctor blade on a 0.5 cm thick and 2 x 2 cm large aluminum plate applied The plate is then dried at 50 ° C for 24 hours

Example 17a

The coated aluminum side of Example 17 is placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 2 hours, 1 ml of the test microbial suspension is removed and the number of microbes in the test batch is determined according to After this time, no Staphylococcus aureus germs can be detected

Example 17b

The coated aluminum side of Example 17 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 4 hours, 1 ml of the test microbial suspension is removed and the number of microbes in the test batch is determined according to Over this time, the number of bacteria has decreased from 10 to 10 bacteria per ml

Example 18:

45 ml of acrylic acid-3-dimethylaminopropylamide (Aldrich) and 250 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.6 g of azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone are then slowly added dropwise with stirring. The mixture is brought to 70 ° C heated and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 1.5 l of cyclohexane, the polymer product precipitating. After filtering off the product, the filter residue is rinsed with 100 ml of n-hexane in order to add residual monomers still present Then remove the Product dried in a vacuum for 24 hours at 50 ° C. 2 g of the product are dissolved in 10 g of tetrahydrofuran and applied to a 0.5 cm thick and 2 × 2 cm aluminum plate using a 100 micrometer doctor blade. The plate is then at 50 ° C dried for 24 hours

Example 18a

The coated aluminum side of Example 18 is placed on the bottom of a beaker containing 20 ml of a test microbial 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 bacteria in the test batch is determined according to After this time, no Staphylococcus aureus germs can be detected

Example 18b

The coated aluminum side of Example 18 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 bacteria in the test batch is determined according to Over this time the number of germs has decreased from 10 ⁷ to 10 ⁴ germs per ml

Example 19:

10 g of the polymer from Example 16 are heated to 165 ° C. Then this heated polymer is mixed with 3 g of polymethyl methacrylate (Aldrich), which was also previously heated to 165 ° C. The two polymers are mixed thoroughly, on an aluminum plate with 0, 5 cm thick and 2 x 2 cm in size and cooled at a rate of 20 ° C per hour to room temperature

Example 19a

The coated aluminum side of Example 19 is placed on the bottom of a beaker containing 20 ml of a test microbial 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 bacteria in the test batch is determined according to After this time, no Staphylococcus aureus germs can be detected Example 19b

The coated aluminum side of Example 19 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 bacteria in the test batch is determined according to Over this time, the number of germs has decreased from 10 ⁷ to 10 germs per ml

Example 20: 50 ml of dimethylaminopropyl methacrylamide (Aldrich) and 250 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.6 g of azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone are then slowly added dropwise with stirring. The mixture is brought to 70 ° C. heated and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 1.5 l of cyclohexane, the polymer product precipitating. After filtering off the product, the filter residue is rinsed with 100 ml of n-hexane in order to remove any residual monomers still present The product is then dried in vacuo for 24 hours at 50 ° C. 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 with a squeegee on a metal plate so that they are one layer thick n Sets the thickness to 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 20a A 3 by 3 cm piece of the soft PVC film from Example 20 is placed on the bottom of a

Beaker placed containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 2 hours, 1 ml of the test germ suspension is removed, and the number of germs in the test mixture is determined. After this time there are none

Staphylococcus aureus germs more detectable

Example 20b

A 3 by 3 cm piece of the soft PVC film from Example 20 is placed on the bottom of a Beaker placed containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 4 hours, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined. After this time, the number of bacteria has decreased from 10 to 10 bacteria per ml

Example 21:

50 ml of dimethylaminopropyl methacrylamide (Aldrich) and 250 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.6 g of azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone are then slowly added dropwise with stirring. The mixture is heated to 70 ° C. and 72 Stirred at this temperature for h hours. After this time, the reaction mixture is stirred into 1.5 l of cyclohexane, the polymer product precipitating. After filtering off the product, the filter residue is rinsed with 100 ml of n-hexane in order to remove residual monomers still present the product dried for 24 hours at 50 ° C. in vacuo. 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 mixed with a Spread the squeegee onto a metal plate so that it is 0.7 mm thick 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 created

Example 21a

A 3 by 3 cm piece of the soft PVC film from Example 21 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 2 hours, 1 ml of the test germ suspension is removed, and the Number of bacteria determined in the test batch After this time, no bacteria from Staphylococcus aureus can be detected

Example 21b

A 3 x 3 cm piece of the soft PVC film from Example 21 is placed on the bottom of a beaker containing 20 ml of a test germ suspension from Pseudomonas aeruginosa and shaken. After a contact time of 4 hours, 1 ml of the test germ suspension is removed, and the Number of bacteria determined in the test batch After this time the Germ count decreased from 10 ⁷ to 10 "

Example 22:

50 ml of diethylaminopropyl methacrylamide (Aldrich) and 250 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.6 g of azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone are then slowly added dropwise with stirring. The mixture is heated to 70 ° C. and 72 Stirred at this temperature for h hours. After this time, the reaction mixture is stirred into 1.5 l of cyclohexane, the polymer product precipitating. After filtering off the product, the filter residue is rinsed with 100 ml of n-hexane in order to remove residual monomers still present the product dried for 24 hours at 50 ° C. in vacuo. 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 mixed with a Spread the squeegee onto a metal plate so that it is 0.7 mm thick 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 created

Example 22a

A 3 x 3 cm piece of the soft PVC film from Example 22 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 2 hours, 1 ml of the test germ suspension is removed and the Number of bacteria determined in the test batch After this time, no bacteria from Staphylococcus aureus can be detected

Example 22b

A 3 x 3 cm piece of the soft PVC film from Example 22 is placed on the bottom of a beaker containing 20 ml of a test germ suspension from Pseudomonas aeruginosa and shaken. After a contact time of 4 hours, 1 ml of the test germ suspension is removed, and the Number of bacteria determined in the test batch After this time, the number of bacteria has dropped from 10 ⁷ to 10 ¹

Example 23: 50 ml of dimethylaminopropyl methacrylamide (Aldrich) and 250 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.6 g of azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone are then slowly added dropwise with stirring. The mixture is heated to 70 ° C. and 72 Stirred at this temperature for h hours. After this time, the reaction mixture is stirred into 1.5 l of cyclohexane, the polymer product precipitating. After filtering off the product, the filter residue is rinsed with 100 ml of n-hexane in order to remove residual monomers still present the product dried in vacuo for 24 hours at 50 ° C. 5 g of the product are stirred into 95 g of an acrylic varnish called Rowacryl G-31293 from ROWA

Example 23 a

Using a brush, a 5 x 5 cm aluminum plate is coated with the acrylic lacquer treated in this way from Example 23 and then dried in a drying cabinet at 35 ° C. for 24 hours. This coated aluminum plate is placed on the bottom of a beaker with its coated side up that contains 20 ml of a test microbial suspension of Staphylococcus aureus and shaken After a contact time of 2 hours, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined. After this time, no bacteria of Staphylococcus aureus are detectable

Example 23b

Using a brush, a 5 x 5 cm aluminum plate is coated with the acrylic lacquer treated in this way from Example 23 and then dried in a drying cabinet at 35 ° C. for 24 hours. This coated aluminum plate is placed on the bottom of a beaker with its coated side up placed, which contains 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 2 hours, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined. After this time, the number of bacteria has dropped from 10 ⁷ to 10 ⁴

Example 24: 45 ml of acrylic acid-3-dimethylaminopropylamide (Aldrich) and 250 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.6 g of azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone are then 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 1.5 l of cyclohexane, the polymer product precipitating. After filtering off the product, the filter residue is rinsed with 100 ml of n-hexane In order to remove any residual monomers still present, the product is subsequently dried in vacuo at 50 ° C. for 24 hours. 2 g of the product are stirred into 98 g of an acrylic lacquer called Rowacryl G-31293 from ROWA

Example 24a

Using a brush, a 5 x 5 cm aluminum plate is coated with the acrylic lacquer treated in this way from Example 24 and then dried in a drying cabinet at 35 ° C. for 24 hours. This coated aluminum plate is placed on the bottom of a beaker with its coated side up placed, which contains 20 ml of a test germ suspension of Staphylococcus aureus and shaken After a contact time of 2 hours, 1 ml of the test germ suspension is removed, and the number of germs in the test mixture is determined

Example 24b

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

Brush acrylic paint from Example 24 and then dry in a drying cabinet at 35 ° C for 24 hours.This coated 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 The contact time of 2 hours is taken from 1 ml of the test microbial suspension, and the number of bacteria in the test mixture is determined. After this time, the number of bacteria has dropped from 10 to 10 ³

Example 25:

50 ml of dimethylaminopropyl methacrylamide (Aldrich) and 250 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.6 g of azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone are then slowly added dropwise with stirring. The mixture is heated to 70 ° C. and 72 Stirred at this temperature for h hours. After this time, the reaction mixture is stirred into 1.5 l of cyclohexane, the polymer product precipitating. After filtering off the product, the filter residue is washed with 100 ml of n-hexane rinsed to remove any residual monomers still present. The product is then dried in vacuo for 24 hours at 50 ° C. 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 25a

Using a brush, a 5 x 5 cm aluminum plate is coated with the dispersion from Example 25 treated in this way and then dried in a drying cabinet at 35 ° C. for 24 hours. This coated aluminum plate is placed on the bottom of a beaker with its coated side up placed, which contains 20 ml of a test germ suspension of Staphylococcus aureus and shaken After a contact time of 2 hours, 1 ml of the test germ suspension is removed, and the number of germs in the test mixture is determined. After this time, no germs of Staphylococcus aureus are detectable

Example 25b

Using a brush, a 5 x 5 cm aluminum plate is coated with the dispersion from Example 25 treated in this way and then dried in a drying cabinet at 35 ° C. for 24 hours. This coated aluminum plate is placed on the bottom of a beaker with its coated side up placed, which contains 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 2 hours, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined. After this time, the number of bacteria has dropped from 10 ⁷ to 10 ⁴

Example 26: 45 ml of acrylic acid-3-dimethylaminopropylamide (Aldrich) and 250 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.6 g of azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone is slowly added dropwise with stirring. The mixture is added heated to 70 ° C and stirred for 72 h at this temperature. After this time, the reaction mixture is stirred into 1.5 l of cyclohexane, the polymeric product precipitating. After filtering off the product, the filter residue is rinsed with 100 ml of n-hexane to still Remove existing residual monomers. The product is subsequently dried in vacuo at 50 ° C. for 24 hours. 2 g of the product are dissolved in 98 g of Plextol D 510 from PolymerLatex, an aqueous dispersion of a methacrylic acid ester. / Acrylic acid ester copolymers, stirred in

Example 26a

Using a brush, a 5 x 5 cm aluminum plate is coated with the dispersion from Example 26 treated in this way and then dried in a drying cabinet at 35 ° C. for 24 hours. This coated aluminum plate is placed on the bottom of a beaker with its coated side up placed, which contains 20 ml of a test germ suspension of Staphylococcus aureus and shaken After a contact time of 2 hours, 1 ml of the test germ suspension is removed, and the number of germs in the test mixture is determined

Example 26b

Spread the dispersion from Example 26 and then dry in a drying cabinet at 35 ° C. for 24 hours. This coated aluminum plate is placed with its coated side up on the bottom of a beaker containing 20 ml of a test germ suspension of Pseudomonas aeruginosa and shaken Contact time of 2 hours, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined. After this time, the number of bacteria has dropped from 10 ⁷ to 10 ³

Claims

claims:

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

With

Rl = -H or -CH ₃

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

R3 = H, branched or unbranched aliphatic hydrocarbon radical with 1 to 7

Carbon atoms and R4 = H, branched or unbranched aliphatic hydrocarbon radical with 1 to 7

Carbon atoms, R5 = H, branched or unbranched aliphatic hydrocarbon radical with 1 to 7

Carbon atoms, X = O, NH, NR5

2 antimicrobial polymers according to claim 1, characterized in that as monomer of formula I methacrylic acid-2-tert-butylaminoethyl ester, methacrylic acid-2-diethylaminoethyl ester, methacrylic acid-2-dimethylaminomethyl ester, acrylic acid-2-tert-butylaminoethyl ester, acrylic acid-3-dimethylaminopropylester Acrylic acid 2-diethylaminoethyl ester, acrylic acid 2-dimethylaminoethyl ester, methacrylic acid 3-dimethylaminopropylamide, methacrylic acid 3-diethylaminopropylamide, acrylic acid 3-dimethylaminopropylamide or acrylic acid 3-diethylaminopropalymide

3 antimicrobial polymer according to claim 1, characterized in that as the monomer of formula I methacrylic acid-2-tert-butylaminoethyl ester, 2-diethylaminoethyl methacrylate, 2-dimethylaminomethyl methacrylate, 2-tert-butylaminoethyl acrylate, 3-dimethylaminopropyl acrylate, 2-diethylaminoethyl acrylate, 2-dimethylaminoethyl acrylate, 3-dimethyl methacrylate, methacrylate 3-dimethylamino diethylaminopropylamide, acrylic acid-3-dimethylaminopropylamide or acrylic acid-3-diethylaminopropylamide can be used

Antimicrobial polymer blend, characterized in that one or more antimicrobial polymers, each obtainable by polymerizing a monomer of the formula I.

with Rl = -H or -CH ₃

R2 = branched or unbranched aliphatic hydrocarbon radical with 1 to 5

Carbon atoms, R3 = H, branched or unbranched aliphatic hydrocarbon radical with 1 to 7 carbon atoms and R4 = H, branched or unbranched aliphatic hydrocarbon radical with 1 to 7

Carbon atoms, X = O, NH, NR5 is mixed with at least one other polymer

Antimicrobial polymer blend according to claim 4, characterized in that the polymer blend consists of 0.2 to 90% by weight of one or more antimicrobial polymers Antimicrobial polymer blend according to Claim 4 or 5, characterized in that polyurethanes, polyolefins, polyethylene, polypropylene, polysiloxane, polystyrene, polyacrylates, polymethyl methacrylate, PVC, polyamide or polyterephthalate are used as further polymer

Use of the antimicrobial polymers according to one of claims 1 to 3 for the manufacture of medical articles

Use of the antimicrobial polymers according to one of claims 1 to 3 for the production of hygiene articles

Use of the antimicrobial polymers according to one of Claims 1 to 3 in paints, protective coatings and coatings

Use of the antimicrobial polymers according to one of claims 1 to 3 in biocide formulations

Use of the antimicrobial polymers according to one of claims 1 to 3, characterized in that for the production of films, tarpaulins, fabrics and fibers

Use of the antimicrobial polymers according to one of claims 1 to 3 in formulations for ointments and pastes

Use of the antimicrobial polymers according to one of claims 1 to 3 for the production of products with an antimicrobial coating from the antimicrobial polymer

Use of the antimicrobial polymer blends according to one of claims 4 to 6 for the manufacture of medical articles Use of the antimicrobial polymer blends according to one of claims 4 to 6 for the production of hygiene articles

Use of the antimicrobial polymer blends according to one of claims 4 to 6 in lacquers, protective coatings and coatings

Use of the antimicrobial polymer blends according to one of claims 4 to 6 in biocide formulations

Use of the antimicrobial polymer blends according to one of claims 4 to 6 for the production of films, tarpaulins, fabrics and fibers

Use of the antimicrobial polymer blends according to one of claims 4 to 6 in formulations for ointments and pastes

Process for the disinfection of cooling water flows, characterized in that antimicrobial polymers according to claims 1 to 3 are added to the cooling water in dispersed form

Process for the disinfection of cooling water streams, characterized in that antimicrobial polymer blends according to claims 4 to 6 are added to the cooling water in dispersed form