DE10022406A1 - New antimicrobial copolymers used for disinfection of water or production of microbicidal coatings, obtained by copolymerisation of amino-functional acrylate or acrylamide with non-functionalised monomers - Google Patents

Abstract

Antimicrobial copolymers of amino-functionalised alkyl or aryl (meth)acrylates or (meth)acrylamides (I) with alkyl or aryl (meth)acrylates or (meth)acrylamides (II), are new. Antimicrobial copolymers (AMC), obtained by copolymerisation of alkyl or aryl (meth)acrylate or (meth)acrylamide monomers of formula (I) and alkyl or aryl (meth)acrylates or (meth)acrylamides of formula (II), are new. R<1>, R<6> = H or methyl; R<2>-R<5>, R<7>, R<8> = optionally substituted, optionally branched 1-50C aliphatic or aromatic hydrocarbyl; X = O, NH or NR<5>, and Y = O, NH or NR<8>. Independent claims are also included for the following: (1) antimicrobial polymer blends containing AMC and other polymer(s), and (2) production of AMC.

Description

The invention relates to antimicrobial coatings made from antimicrobial copolymers. Furthermore, the invention relates to a method for producing and using this anti microbial copolymers, their blends with other polymers and their use as Coating.

Colonization and spread of bacteria on surfaces of pipes, containers or packaging is highly undesirable. Mucus layers often form, make the microbe populations extremely rise, the water, beverage and Permanently affect food quality and even spoil the goods as well can lead to health damage to consumers.

Bacteria must be kept away from all areas of life where hygiene is important. This affects textiles for direct body contact, especially for the intimate area rich and for nursing and elderly care. Bacteria should also be kept away from furniture and device surfaces in care stations, especially in the area of intensive care and Infant care, in hospitals, especially in rooms for medical interventions and in isolation stations for critical infections and in toilets.

Devices, surfaces of furniture and textiles are currently used to fight bacteria in the If necessary or as a precaution with chemicals or their solutions and mixtures treated as a disinfectant more or less broad and massive antimicrobial Act. Such chemical agents have a non-specific effect and are often themselves toxic or irritating or form degradation products that are harmful to health. Un often also show up tolerability in appropriately sensitized people.

Another approach against superficial bacterial spreading is provided by the employees antimicrobial substances into a matrix.

In addition, the prevention of algae growth on surfaces is always a problem  more significant challenge, since there are now many exterior surfaces of buildings Plastic cladding are equipped, which are particularly easy to algae. Next to the Under certain circumstances, the undesired visual impression can also function more appropriately Components are reduced. In this context, e.g. B. an algae from think of photovoltaic functional surfaces.

Another form of microbial contamination, for which there is still none technically satisfactory solution is the infestation of surfaces with fungi. So poses e.g. B. the infestation of joints and walls in damp rooms with Aspergillus niger in addition to impaired optical also represents a serious health-related aspect, because Many people are allergic to the substances released by the fungi, which can go as far as severe chronic respiratory diseases.

In the field of seafaring, fouling the hulls is an economically relevant one Influencing variable because the increased flow resistance associated with the vegetation Ships are associated with a significant increase in fuel consumption. You still meet today such problems generally with the incorporation of toxic heavy metals or others low molecular weight biocides in antifouling coatings to the problems described mitigate. For this purpose, one takes the harmful side effects of such Coatings in purchase, but this in view of the increased ecological sensitivity of the Society turns out to be increasingly problematic.

Thus, e.g. B. US 4,532,269 a terpolymer of butyl methacrylate, tributyltin methacrylate and tert-butylaminoethyl methacrylate. This copolymer is called an antimicrobial Ship paint used, the hydrophilic tert-butylaminoethyl methacrylate the long promotes same erosion of the polymer and so the highly toxic tributyltin methacrylate as antimicrobial agent releases.

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

From European patent applications 0 862 858 it is also known that copolymers of tert-butylaminoethyl methacrylate, a methacrylic acid ester with secondary Amino function, inherently have microbicidal properties. To unwanted Adaptation processes of microbial life forms, especially in view of those from the Antibiotic research effectively counteracts known resistance developments of germs systems based on new compositions and verbes effective effectiveness.

The present invention is therefore based on the object of novel, antimicrobial to develop effective coatings. These are intended to locate and spread Effectively prevent bacteria, algae and fungi on surfaces.

It has now surprisingly been found that by using coatings that contain antimicrobial polymers, surfaces can be equipped so that a antimicrobial effect of these surfaces permanently, and against solvents and physical Resistant to stress, can be generated. These coatings contain no low molecular weight biocides, which means a migration of ecologically problematic substances effectively excludes the entire period of use.

The present invention therefore relates to antimicrobial copolymers obtainable by copolymerizing monomers of the formulas I and II

With
R ¹ , R ⁶ = -H or -CH ₃ ,
R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ = substituted or unsubstituted, branched or unbranched aliphatic or aromatic hydrocarbon radical with 1 to 50 carbon atoms, in each case the same or different,
X = O, NH, NR ⁵ ,
Y = O, NH, NR ⁸ .

The copolymers according to the invention can in addition to the monomers of the formulas I and II at least one further aliphatic unsaturated monomer such as acrylic or Contain methacrylic acid compounds, i.e. H. the copolymerization is carried out with monomers Formulas I and II and the other aliphatic unsaturated monomers carried out.

Preferred monomers of the formulas I or II are 2-tert-methacrylic acid. butylaminoethyl ester, methacrylic acid 2-diethylaminoethyl ester, methacrylic acid 2-diethyl aminomethyl ester, 2-tert-butylaminoethyl acrylic acid, 3-dimethyl acrylic acid aminopropyl ester, 2-diethylaminoethyl acrylate, 2-acrylic acid dimethylaminoethyl ester, methacrylic acid 3-dimethylaminopropylamide, acrylic acid 3 dimethylaminopropylamide, methacrylic acid-2-dimethylaminoethyl ester, N-3- Dimethylaminopropyl methacrylamide; Methacrylic acid isopropylamide, acrylic acid-3 dimethylaminopropylamide, acrylic acid tert-butylamide, N, N-dimethylacrylamide, N- Isopropylacrylamide used.  

As a monomer of formula II or as another aliphatic unsaturated monomer z. B. Methyl methacrylate, methyl acrylate, methacrylic acid tert-butyl ester, acrylic acid tert-butyl ester, Butyl methacrylate, butyl acrylate, ethyl methacrylate, ethyl acrylate, Propyl methacrylic acid, isopropyl methacrylic acid, propyl methacrylic acid, Propyl acrylate and isopropyl acrylate are used.

The invention therefore also relates to a method for producing these antimicrobial Copolymers by chemically, thermally or radiation-chemically induced copolymerization of monomers of the formulas I, II and optionally further aliphatic unsaturated monomers. The method can be used to manufacture the various embodiments of the copolymers according to the invention can be used.

Another object of the present invention are antimicrobial polymer blends that the above Copolymers of monomers of the formulas I, II and at least one further polymer contain. Optionally, the antimicrobial copolymers are polymerized by Monomers of the formulas I and II with at least one further aliphatically unsaturated Monomers made. They can already be used as further aliphatic unsaturated monomers mentioned acrylic acid or methacrylic acid compounds are used. The further Polymer in polymer blend usually has no antimicrobial effect.

The production of the antimicrobial polymer blends can in principle be done by everyone in the Technology known methods, such as. B. in "H.G.-Elias, Macromolecules, Vol. 2, 5th Edition, P. 620 ff ", are described in detail Melt mixing two pre-formed polymers which are present as granules or powder Polymers on roller mills, in kneaders or mixed with extruders. For thermoplastics is heated to above the glass or melting temperature. When mixing solutions you go from independently prepared solutions of the two polymers in the same solvent.

As a further polymer z. B. polyurethanes, polyamides, polyesters and ethers, Polyether block amides, polystyrene, polyvinyl chloride, polycarbonates, polyorganosiloxanes,  Polyolefins, polysulfones, polyisoprene, poly-chloroprene, polytetrafluoroethylene (PTFE) or Polyterephthalates and / or their copolymers are used.

To obtain a sufficient antimicrobial effect of the polymer blends, the proportion the antimicrobial copolymers in the polymer blend from 0.2 to 70, preferably 0.2 to 30, are particularly preferably 1 to 20% by weight.

The antimicrobial copolymers according to the invention or the corresponding blends can as a coating by known methods, such as dipping, spraying or painting Coating formulation to be applied to a surface. As Solvent component of the coating formulation have ethanol, methanol, water Alcohol mixtures, methyl ethyl ketone, diethyl ether, dioxane, hexane, heptane, benzene, toluene, Chloroform, dichloromethane, tetrahydrofuran and acetonitrile are tried and tested, but there are also others Solvents can be used, provided they have sufficient solvent power for the copolymers or their blends and any other coating components and the Wet the substrate surfaces well. Solutions with solids contents of 3 to 80% by weight, for example with about 10 wt .-% have proven themselves in practice and result in generally connected in one pass and covering the substrate surface Coatings with layer thicknesses that can be more than 0.1 µm.

Furthermore, the antimicrobial coatings according to the invention can also be used as a melt, e.g. B. by coextrusion, by dipping, spraying or painting on the substrates be applied.

Furthermore, the antimicrobial polymers or Polymer blends also as additives and components for the formulation of polymer blends, Use paints, varnishes and biocides.

In the case of polymer blends, a particularly advantageous compounding by extrusion is optionally also by coextrusion of the antimicrobial copolymer with others Polymers possible.  

Are polymers according to the invention or polymer blends as an additive or component in Paints, varnishes or biocides used can be much lower concentrations such. B. in lower percentile or alcohol range should be sufficient.

In a further embodiment of the present invention, the copolymers can by Graft polymerization of a substrate with monomers of the formula I and II, and optional at least one aliphatic unsaturated monomer can be obtained. The grafting of the Substrate enables the antimicrobial copolymer to be covalently bound to the Substrate. All polymeric materials, such as those already mentioned, can be used as substrates Plastics.

The surfaces of the substrates can be modified a number of times before the graft copolymerization Methods are activated. All standard methods for activating polyme surfaces are used; for example, the activation of the substrate may occur graft polymerization by UV radiation, plasma treatment, corona treatment, loading Flame, ozonization, electrical discharge or γ-radiation can be carried out. The surfaces are expediently removed beforehand in a known manner by means of a solvent Free from oils, greases or other contaminants.

The substrates can be activated by UV radiation in the wavelength range 170-400 nm, preferably 170-250 nm. A suitable radiation source is e.g. B. a UV excimer device HERAEUS Noblelight, Hanau, Germany. But mercury vapor lamps are also suitable for substrate activation, provided that there is considerable radiation in the areas mentioned emit. The exposure time is generally 0.1 seconds to 20 minutes, preferably 1 second to 10 minutes.

The activation of the substrate before the graft polymerization with UV radiation can continue with an additional photosensitizer. For this, the photosensitizer, such as B. Benzophenone applied to the substrate surface and irradiated. This can also with a mercury vapor lamp with exposure times from 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) in air, Nitrogen or argon atmosphere can be achieved. The exposure times are in total generally 2 seconds to 30 minutes, preferably 5 seconds to 10 minutes. The Ener The input for laboratory devices is between 100 and 500 W, preferably between 200 and 300 W.

Corona devices (from SOFTAL, Hamburg, Germany) can also be used for Akti Use the crossing. In this case, the exposure times 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 in general mean 0.1 to 60 seconds.

Flaming substrate surfaces also leads to their activation. Suitable Devices, especially those with a flame barrier, can be easily operated build or obtain, for example, from ARCOTEC, 71297 Mönsheim, Germany. They can be operated with hydrocarbons or hydrogen as fuel gas. In in any case, harmful overheating of the substrate must be avoided, which is caused by intimate contact with a cooled metal surface on the distant from the flame side facing substrate surface is easily achieved. The activation by flame is accordingly limited to relatively thin, flat substrates. The exposure times are generally 0.1 seconds to 1 minute, preferably 0.5 to 2 Seconds, all of which deal with non-glowing flames and the Ab stands of the substrate surfaces to the outer flame front 0.2 to 5 cm, preferably 0.5 to 2 cm.

The graft copolymerization of the monomers applied to the activated surfaces can expediently by rays in the short-wave segment of the visible range or in long-wave segment of the UV range of electromagnetic radiation can be initiated.  

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, if they emit significant amounts of radiation in the areas mentioned. The exposure times are generally 10 seconds to 30 minutes, preferably 2 to 15 minutes.

As initiators in the preparation of the copolymers according to the invention u. a. Azonitriles, alkyl peroxides, hydroperoxides, acyl peroxides, peroxoketones, peresters, Peroxocarbonate, Peroxodisulfat, Persulfat and all usual photoinitiators such as. B. Use acetophenones, α-hydroxy ketones, dimethyl ketals and and benzophenone. The Polymerization initiation can also be carried out thermally or, as already stated, by electromagnetic radiation, such as B. UV light or γ radiation.

Use of the copolymers or the polymer blends

Further objects of the present invention are the use of the invention ß antimicrobial copolymers or polymer blends for the production of antimicrobial effective products. Such products are preferably based on polyamides, Polyurethanes, polyether block amides, polyester amides or imides, PVC, polyolefins, Silicones, polysiloxanes, polymethacrylate or polyterephthalates, metals, glasses and Ceramics, the surfaces coated with copolymers or blends according to the invention exhibit.

Antimicrobial products of this type are, for example, machine parts for the Food processing, components of air conditioning systems, coated pipes, semi-finished products, Roofing, bathroom and toilet articles, kitchen articles, components from Sanitary facilities, components of animal cages and dwellings, toys, Components in water systems, food packaging, controls (touch panel) of devices and contact lenses.

The copolymers or blends according to the invention can be used wherever bacteria-free, algae- and fungus-free, ie microbicidal surfaces or surfaces with non-stick properties are important. Examples of use for the copolymers or polymer blends according to the invention, for. B. as a coating of a substrate can be found in the following areas:

• - Marine: hulls, port facilities, buoys, drilling platforms, ballast water tanks
• - House: roofs, cellars, walls, facades, greenhouses, sun protection, gar Fences, wood protection, tarpaulins, textile fabrics
• - Sanitary: public toilets, bathrooms, shower curtains, toiletries, Swimming pool, sauna, joints, sealing compounds
• - Food: machines, kitchen, kitchen items; Sponges, toys, life medium packaging, milk processing, drinking water systems, cosmetics
• - Machine parts: air conditioners, ion exchangers, process water, solar systems, heat exchangers, bioreactors, membranes
• - Medical technology: contact lenses, diapers, membranes, implants, catheters, tubes, Cover films, surgical cutlery
• - Articles of daily use: car seats, clothing (stockings, sportswear), sick people home furnishings, door handles, telephone receivers, public transport, animal cages, Cash registers, carpets, wallpapers, telephone receivers, handrails from meetings, door and Window handles and straps and handles in public transport
• - Hygiene products: toothbrushes, toilet seats, combs and packaging materials.

The copolymers or polymer blends can also be in the form of lacquers, protective coatings or Coatings are used. Here it makes sense to use existing paint systems such as B. Use acrylic paints.

The polymers or polymer blends can also be used as a paint additive in the maritime sector, especially when avoiding barnacle larvae on ship hulls, as an additive in an antifouling paint, especially in saline seawater.

In addition, the antimicrobial polymers or polymer blends according to the invention Use as additives in the formulation of cosmetic products, such as. B. for pastes and ointments. The proportion of polymers according to the invention or  Polymer blends, depending on the effectiveness of the polymer and the formulation down to the bottom Percentage range or alcohol level can be reduced.

Furthermore, the polymers or polymer blends according to the invention are used as biofouling inhibitors, especially in cooling circuits, use. To avoid damage to Cooling circuits caused by algae or bacteria often have to be cleaned or built accordingly oversized. The addition of microbicidal substances like Formalin is used in open cooling systems such as those in power plants or chemical plants are not possible. Other microbicidal substances are often highly corrosive or foaming, which prevents use in such systems.

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

Further objects of the present invention are therefore methods for the disinfection of Cooling water flows in which the cooling water antimicrobial polymers or their Polymer blends can be added in dispersed form. Cooling water in the sense of the present Invention are all process water flows that are used for heating or cooling purposes in closed or open circulatory systems can be used.

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

The following examples are given to further describe the present invention ben, which explain the invention further, but are not intended to limit its scope, as described in the claims are set out.

example 1

65 ml of 2-tert-butylaminoethyl methacrylic acid (Aldrich), 25 ml Methacrylic acid methyl ester (Aldrich) and 180 ml of ethanol are in a three-necked flask submitted and heated to 65 ° C under a stream of argon. Then 0.745 g Azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone was slowly added dropwise with stirring. The The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After expiration During this time, the reaction mixture is stirred into 1 liter of demineralized water, the polymer product fails. After filtering off the product, the filter residue with 100 ml a 10% solution of ethanol rinsed in water to remove any remaining monomers to remove. The product is then dried in vacuo at 50 ° C. for 24 hours. 6 g of the product are dissolved in 32 g of di-isononyl phthalate. Then this Mixture 64 g of polyvinyl chloride granules were added, the mixture being stirred thoroughly until it becomes pasty. 20 g of the paste obtained are so with a doctor on a metal plate spread out that it sets a layer thickness of 0.7 mm thickness. The plate with the the paste on top is then heated to 200 ° C. for 2 minutes, the paste gelling and a soft PVC film is created.

Example 1a

A 3 x 3 cm piece of the soft PVC film from Example 5 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  removed, and the number of bacteria in the test batch determined. After this time there are none Staphylococcus aureus germs more detectable.

Example 1b

A 3 x 3 cm piece of the soft PVC film from Example 5 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 germ suspension removed, and the number of bacteria in the test batch determined. After this time there are none Germs from Pseudomonas aeruginosa more detectable.

Example 2

70 ml 2-tert-butylaminoethyl methacrylic acid (Aldrich) 20 ml Methacrylic acid methyl ester (Aldrich) and 180 ml of ethanol are in a three-necked flask submitted and heated to 65 ° C under a stream of argon. Then 0.745 g Azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone was slowly added dropwise with stirring. The The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After expiration During this time, the reaction mixture is stirred into 1 liter of demineralized water, the polymer product fails. After filtering off the product, the filter residue with 100 ml a 10% solution of ethanol rinsed in water to remove any remaining monomers to remove. The product is then dried in vacuo at 50 ° C. for 24 hours. 2 g of the product are dissolved in 32 g of di-isononyl phthalate. Then this Mixture 64 g of polyvinyl chloride granules were added, the mixture being stirred thoroughly until it becomes pasty. 20 g of the paste obtained are so with a doctor on a metal plate spread out that it sets a layer thickness of 0.7 mm thickness. The plate with the the paste on top is then heated to 200 ° C. for 2 minutes, the paste gelling and a soft PVC film is created.

Example 2a

A 3 x 3 cm piece of the soft PVC film from Example 6 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 removed, and the number of bacteria in the test batch determined. After this time there are none Staphylococcus aureus germs more detectable.

Example 2b

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 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 mixture is determined. After this time, the number of germs has dropped from 10 ⁷ to 10 ³ .

Example 3

75 ml of 2-tert-butylaminoethyl methacrylic acid (Aldrich) 15 ml of tert-methacrylic acid butyl 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. Then 0.745 g of azobisisobutyronitrile are dissolved in 20 ml of ethyl methyl ketone was slowly added dropwise with stirring. The mixture is heated to 70 ° C and stirred for 72 hours at this temperature. After this time the Reaction mixture stirred in 1 l of demineralized water, the polymeric product fails. 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 remaining monomers. in the The product is then dried in vacuo at 50 ° C. for 24 hours. 2 g of Product are dissolved in 32 g di-isononyl phthalate. Then this mixture 64 g of polyvinyl chloride granules were added, the mixture being intimately stirred until it was pasty becomes. 20 g of the paste obtained are spread onto a metal plate using a doctor blade, that she sets a layer thickness of 0.7 mm thickness. The plate with the one on top The paste is then heated to 200 ° C. for 2 minutes, during which the paste gels and a soft PVC film is created.

Example 3a

A 3 by 3 cm piece of the soft PVC film from Example 7 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 removed, and the number of bacteria in the test batch determined. After this time there are none Staphylococcus aureus germs more detectable.

Example 3b

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

Example 4

70 ml 2-tert-butylaminoethyl methacrylic acid (Aldrich), 20 ml Methacrylic acid methyl ester (Aldrich) and 180 ml of ethanol are in a three-necked flask submitted and heated to 65 ° C under a stream of argon. Then 0.745 g Azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone was slowly added dropwise with stirring. The The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After expiration During this time, the reaction mixture is stirred into 1 liter of demineralized water, the polymer product fails. After filtering off the product, the filter residue with 100 ml a 10% solution of ethanol rinsed in water to remove any remaining monomers to remove. The product is then dried in vacuo at 50 ° C. for 24 hours. 5 g of the product are in 95 g of an acrylic varnish called Rowacryl G-31293 the company ROWA stirred.

Example 4a

Using a brush, a 5 x 5 cm aluminum plate is treated with the one treated in this way Brush acrylic paint from Example 8 and then in a drying cabinet at 35 ° C for the Dried for 24 hours. This aluminum plate comes with its coated side placed on the bottom of a beaker containing 20 ml of a test microbial suspension of  Contains and shaken Staphylococcus aureus. After a contact time of 2 hours, 1 ml taken from the test microbial suspension, and the number of microbes determined in the test batch. To After this time, no Staphylococcus aureus germs can be detected.

Example 4b

Using a brush, a 5 x 5 cm aluminum plate is treated with the one treated in this way Brush acrylic paint from Example 8 and then in a drying cabinet at 35 ° C for the Dried for 24 hours. This aluminum plate comes with its coated side placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa contains 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 mixture is determined. After this time no more Pseudomonas aeruginosa germs can be detected.

Example 5

75 ml of 2-tert-butylaminoethyl methacrylic acid (Aldrich), 15 ml Butyl methyl acrylate (Aldrich) and 180 ml of ethanol are in a three-necked flask submitted and heated to 65 ° C under a stream of argon. Then 0.745 g Azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone was slowly added dropwise with stirring. The The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After expiration During this time, the reaction mixture is stirred into 1 liter of demineralized water, the polymer product fails. After filtering off the product, the filter residue with 100 ml a 10% solution of ethanol rinsed in water to remove any remaining monomers to remove. The product is then dried in vacuo at 50 ° C. for 24 hours. 2 g of the product are in 98 g of an acrylic varnish called Rowacryl G-31293 the company ROWA stirred.

Example 5a

Using a brush, a 5 x 5 cm aluminum plate is treated with the one treated in this way Brush acrylic paint from Example 9 and then in a drying cabinet at 35 ° C for the Dried for 24 hours. This aluminum plate comes with its coated side  placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Contains and shaken Staphylococcus aureus. After a contact time of 2 hours, 1 ml taken from the test microbial suspension, and the number of microbes determined in the test batch. To After this time, no Staphylococcus aureus germs can be detected.

Example 5b

Using a brush, a 5 x 5 cm aluminum plate is coated with the acrylic lacquer treated in this way from Example 9 and then dried in a drying cabinet at 35 ° C. for 24 hours. This aluminum plate is placed with its coated side up on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 2 hours, 1 ml of the test microbial suspension is removed and the number of microbes in the test mixture is determined. After this time, the number of germs has dropped from 10 ⁷ to 10 ³ .

Example 6

750 ml of 2-tert-butylaminoethyl methacrylic acid (Aldrich), 15 ml Methacrylic acid methyl ester (Aldrich) and 180 ml of ethanol are in a three-necked flask submitted and heated to 65 ° C under a stream of argon. Then 0.745 g Azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone was slowly added dropwise with stirring. The The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After expiration During this time, the reaction mixture is stirred into 1 liter of demineralized water, the polymer product fails. After filtering off the product, the filter residue with 100 ml a 10% solution of ethanol rinsed in water to remove any remaining monomers to remove. The product is then dried in vacuo at 50 ° C. for 24 hours. 5 g of the product are in 95 g of Plextol D 510 from PolymerLatex, an aqueous Dispersion of a methacrylic acid ester / acrylic acid ester copolymer, stirred in.

Example 6a

Using a brush, a 5 x 5 cm aluminum plate is treated with the one treated in this way Spread dispersion from Example 10 and then in a drying cabinet at 35 ° C for the  Dried for 24 hours. This aluminum plate comes with its coated side placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Contains and shaken Staphylococcus aureus. After a contact time of 2 hours, 1 ml taken from the test microbial suspension, and the number of microbes determined in the test batch. To After this time, no Staphylococcus aureus germs can be detected.

Example 6b

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

Example 7

75 ml of methacrylic acid 2-tert-butylaminoethyl ester (from Aldrich), 15 ml of methacrylic acid tert- Butyl ester and 180 ml of ethanol are placed in a three-necked flask and added under argon current heated to 65 ° C. Then 0.745 g of azobisisobutyronitrile are dissolved in 20 ml of ethylme ethyl ketone slowly added dropwise with stirring. The mixture is heated to 70 ° C and 72 h Stirred for hours at this temperature. After this time, the reaction mixture is in 1 l of demineralized water is stirred in, the polymeric product precipitating. To The product is filtered off with 100 ml of a 10% solution of Rinsed ethanol in water to remove any remaining monomers. In connection the product is dried for 24 hours at 50 ° C in a vacuum. 2 g of the product in 98 g of Plextol D 510 from PolymerLatex, an aqueous dispersion of a Methacrylic acid ester / acrylic acid ester copolymer, stirred.

Example 7a

Using a brush, a 5 x 5 cm aluminum plate is treated with the one treated in this way  Spread dispersion from Example 11 and then in a drying cabinet at 35 ° C for the Dried for 24 hours. This aluminum plate comes with its coated side placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Contains and shaken Staphylococcus aureus. After a contact time of 2 hours, 1 ml taken from the test microbial suspension, and the number of microbes determined in the test batch. To After this time, no Staphylococcus aureus germs can be detected.

Example 7b

Using a brush, a 5 by 5 cm aluminum plate is coated with the dispersion from Example 11 treated in this way and then dried in a drying cabinet at 35 ° C. for a period of 24 hours. This aluminum plate is placed with its coated side up on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 2 hours, 1 ml of the test microbial suspension is removed and the number of microbes in the test mixture is determined. After this time the number of germs has dropped from 10 ⁷ to 10 ² .

Example 8

70 ml 2-tert-butylaminoethyl methacrylic acid (Aldrich), 20 ml Methyl methacrylate (Aldrich) and 180 ml of ethanol are in a three-necked flask submitted and heated to 65 ° C under a stream of argon. Then 0.745 g Azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone was slowly added dropwise with stirring. The The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After expiration During this time, the reaction mixture is stirred into 1 liter of demineralized water, the polymer product fails. After filtering off the product, the filter residue with 100 ml a 10% solution of ethanol rinsed in water to remove any remaining monomers to remove. The product is then dried in vacuo at 50 ° C. for 24 hours. 1 g of the product is dissolved in 99 g of ethanol. In this solution there will be six Cotton pads with a diameter of 3 cm each were immersed for 1 second, removed and 24 Dried for hours at room temperature.  

Example 8a

One coated cotton pad from Example 12 is blended with Chlorella sp., Trentepohlia sp. Gloeocapsa sp. Calothrix sp. and Aspergilus niger. These samples are following spent in an incubator for 3 weeks. In contrast to accompanying control samples no growth can be detected in any of the coated cotton pads.

Claims (26)

1. Antimicrobial copolymers, obtainable by copolymerization of monomers of the formulas I and II
With
R ¹ , R ⁶ = -H or -CH ₃ ,
R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ = substituted or unsubstituted, branched or unbranched aliphatic or aromatic hydrocarbon radical with 1 to 50 carbon atoms, in each case the same or different,
X = Q, NR, NR ⁵ ,
Y = O, NH, NR ⁸ . 2. Copolymer according to claim 1, characterized, that the copolymerization of the monomers of the formulas I and II with additionally at least  another aliphatic unsaturated monomer is carried out. 3. Antimicrobial copolymers according to claim 2, characterized, that the aliphatic unsaturated monomers are methacrylic acid compounds. 4. Antimicrobial copolymers according to claim 2, characterized, that the aliphatic unsaturated monomers are acrylic acid compounds. 5. Antimicrobial copolymers according to one of claims 1 to 4, characterized, that as the monomer of formula I methacrylic acid 2-tert-butylaminoethyl ester, 2-diethylaminoethyl methacrylate, 2-diethylaminomethyl methacrylate, 2-tert.-butylaminoethyl acrylate, 3-dimethylaminopropyl acrylate, acrylic Acid-2-diethylaminoethyl ester, acrylic acid-2-dimethylaminoethyl ester, methacrylic acid-3- dimethylaminopropylamide, acrylic acid-3-dimethylaminopropylamide, methacrylic acid-2- dimethylaminoethyl ester or N-3-dimethylaminopropyl methacrylamide can be used. 6. Antimicrobial copolymers according to one of claims 1 to 4, characterized, that as a monomer of formula II methacrylic acid isopropylamide, acrylic acid 3- diethylamino-propylamide, acrylic acid-tert-butylamide, N, N-dimethylacrylamide, N- Isopropyl acrylamide, methyl methacrylate, methyl acrylate, methacrylic acid tert-butyl ester, Tert-butyl acrylate, butyl methacrylate, butyl acrylate, Ethyl methacrylate, ethyl acrylate, propyl methacrylate, isopropyl methacrylate, Propyl methacrylic acid, propyl acrylate or isopropyl acrylate is used. 7. Antimicrobial copolymers according to one of claims 1 to 6, characterized,  that the copolymerization is carried out as a graft polymerization of a substrate. 8. Antimicrobial copolymers according to claim 6, characterized, that the substrate before the graft polymerization by UV radiation, plasma treatment, Corona treatment, flame treatment, ozonization, electrical discharge or γ-radiation is activated. 9. Antimicrobial polymer blends containing an antimicrobial copolymer, obtainable by copolymerizing monomers of the formulas I and II
With
R ¹ , R ⁶ = -H or -CH ₃ ,
R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ = substituted or unsubstituted, branched or unbranched aliphatic or aromatic hydrocarbon radical with 1 to 50 carbon atoms, in each case the same or different,
X = Q, NH, NR ⁵ ,
Y = O, NH, NR ⁸
and at least one other polymer. 10. Antimicrobial polymer blends according to claim 9, characterized, that the copolymerization of the monomers of the formulas I and II with additionally at least another aliphatic unsaturated monomer is carried out. 11. Antimicrobial polymer blends according to claim 9 or 10, characterized, that the antimicrobial copolymer has a proportion of 0.2 to 70% by weight in the polymer blend having. 12. Antimicrobial polymer blends according to one of claims 9 to 11, characterized, that as another polymer, polyurethanes, polyamides, polyesters and ethers, Polyether block amides, polystyrene, polyvinyl chloride, polycarbonates, polyorganosiloxanes, Polyolefins, polysulfones, polyisoprene, poly-chloroprene, polytetrafluoroethylene (PTFE) or polyterephthalates and / or their copolymers is used. 13. A process for the preparation of antimicrobial copolymers, characterized in that a radical copolymerization of monomers of the formula I and II
With
R ¹ , R ⁶ = -H or -CH ₃ ,
R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ = substituted or unsubstituted, branched or unbranched aliphatic or aromatic hydrocarbon radical with 1 to 50 carbon atoms, in each case the same or different,
X = Q, NH, NR ⁵ ,
Y = O, NH, NR ⁸
is chemically, thermally or radiation-chemically induced. 14. The method according to claim 13, characterized, that the copolymerization of the monomers of the formulas I and II with additionally at least another aliphatic unsaturated monomer is carried out. 15. The method according to claim 13 or 14, characterized, that the copolymerization is carried out as a graft copolymerization of a substrate. 16. The method according to claim 15, characterized,  that the substrate before the graft polymerization by UV radiation, plasma treatment, Corona treatment, flame treatment, ozonization, electrical discharge or γ-radiation is activated. 17. Use of the antimicrobial copolymers according to one of claims 1 to 8 for Manufacture of products with an antimicrobial coating from the polymer. 18. Use of the antimicrobial copolymers according to one of claims 1 to 8 for Manufacture of medical articles with an antimicrobial coating from the Polymer. 19. Use of the antimicrobial copolymers according to one of claims 1 to 8 for Manufacture of hygiene articles with an antimicrobial coating from the Polymer. 20. Use of the antimicrobial copolymers according to one of claims 1 to 8 in Varnishes, protective coatings and coatings. 21. Use of the antimicrobial polymer blends according to one of claims 9 to 12 for Manufacture of products with an antimicrobial coating from the polymer. 22. Use of the antimicrobial polymer blends according to one of claims 9 to 12 for Manufacture of medical articles with an antimicrobial coating from the Polymer. 23. Use of the antimicrobial polymer blends according to one of claims 9 to 12 for Manufacture of hygiene articles with an antimicrobial coating from the Polymer. 24. Use of the antimicrobial polymer blends according to one of claims 9 to 12 in Varnishes, protective coatings and coatings.   25. Processes for the disinfection of cooling water flows, characterized, that the cooling water antimicrobial copolymers according to claims 1 to 6 in dispersed form can be added. 26. Processes for the disinfection of cooling water flows, characterized, that the cooling water antimicrobial polymer blends according to claims 9 to 12 in dispersed form can be added.