WO2002092336A1 - Microbicidal stacked film system - Google Patents

Abstract

The invention relates to the production and use of microbicidal stacked systems based on self-adhesive films.

Description

Microbicidal Foil StacksYstenia

The invention relates to the production and use of microbicidal stack systems based on self-adhesive films.

The use of clinically clean rooms is becoming increasingly important today. With the help of a wide range of disinfection processes, attempts are made to maintain aseptic conditions in appropriately stressed locations.

Rooms that are easily accessible generally represent only a subordinate problem. Rooms that are either very difficult or partially accessible are found to be extremely problematic.

Zones subject to such stress include laminar flows and sterile benches, which are used as standard in particular in microbiological laboratories, operating rooms, isolation stations, incubators, which represent an ideal environment for the growth of cells and bacteria, and interior cladding for air conditioning systems.

The application of protective films for the interior cladding of such rooms has already been described in DE 19806437 AI. The method described is used to line a room with a film as protection against contamination, for. B. during painting or construction work. An antimicrobial effect of the films is not described here.

DE 19730193 AI describes self-adhesive protective films for the outside of painted vehicles as assembly or transport protection. An antimicrobial effect of the protective films is also not disclosed here.

The disadvantage of this method is that a dirty surface can only be replaced by replacing the entire film.

Antimicrobial films, however, are known from DE 10102901.2. These slides serve as Incision foils during operations and are therefore only designed for single use. The films are also equipped with a skin pressure sensitive adhesive that is water-soluble. Use of these films in a humid environment therefore leads to the film becoming detached from the substrate.

From European patent applications 0 862 858 it is known that copolymers of tert-butylaminoethyl methacrylate, a methacrylic acid ester with a secondary amino function, have inherent microbicidal properties. The antimicrobial effectiveness of these polymeric systems is closely related to their three-dimensional structure, conformation and available surface. They are particularly suitable in areas of application where long-lasting, surface-active protection against microbial attack is important.

Antimicrobial polymers that could serve as a film coating are e.g. B. known from the following patent applications: DE 100 24 270, DE 100 22 406, PCT / EP00 / 06501, DE 100 14 726, DE 100 08 177, PCT / EP00 / 06812, PCT / EP00 / 06487, PCT / EP00 / 06506, PCT / EP00 / 02813, PCT / EP00 / 02819, PCT / EP00 / 02818, PCT / EP00 / 02780, PCT / EP00 / 02781, PCT / EP00 / 02783, PCT / EP00 / 02782, PCT / EP00 / O2799, PCT / EP00 / 02798, PCT / EP00 / 00545, PCT / EP00 / 00544.

These polymers do not contain any low molecular weight components; the antimicrobial properties are due to the contact of bacteria with the surface.

In order to effectively counteract undesirable adaptation processes in microbial life forms, especially in view of the development of resistance to germs known from antibiotic research, systems based on novel compositions and improved effectiveness must also be developed in the future. In addition, application technology and economic issues play an equally important role, since on the one hand the antimicrobial polymers are often processed together with other plastics in order to strengthen their resistance to microbiological attacks or, in the ideal case, to render them completely inert, and on the other hand the costs for the antimicrobial finishing of surfaces have to be competitive. In the above-mentioned patent applications, attempts are made to solve the problem by producing antimicrobial polymers which are subsequently applied and fixed on plastic surfaces.

The disadvantage of these systems is that if they are used for a prolonged period of time, they are occupied by killed bacteria and thus lose their contact microbicidal action or are no longer available to a sufficient extent.

The object of the present invention was therefore to provide a system which can ensure an antimicrobial effect over a longer period of time.

It was found that this is possible in an economically attractive and toxicologically harmless manner by using antimicrobial polymers for the production of antimicrobial stack systems based on foils.

The present invention therefore relates to antimicrobial stack systems based on foils, with at least two foils, each having an antimicrobial front and an adhesive back, being glued to one another.

The number of foils glued onto one another is expediently 2-10, preferably 3-8. In principle, an antimicrobial film stack is an application of several film layers one above the other. Each individual film in this stack has two very different sides. On the top is the active component, in this case the antimicrobial polymer, which characterizes the functionality of the film from a microbiological point of view. On the back there is an adhesive adhesive that on the one hand securely connects the back of the film with the film underneath, but on the other hand can be separated from the top of the film underneath when the top film is peeled off, which makes the fresh surface a natively effective antimicrobial Represents surface. Corresponding adhesive adhesives are widely available commercially, e.g. B. appropriate adhesives for the Neschen company, such as the Neschen product Gudy 804. The application is generally carried out by peeling, spraying or knife application. The application of the stack systems according to the invention on the one hand prevents bacteria or fungi from settling in the edges and cracks and continues to grow there unhindered, and on the other hand the colonization of such surfaces is actively prevented. The film stack also offers the advantage of being able to replace contaminated surfaces elegantly and efficiently at any time by simply pulling off the top film.

The proportion of the antimicrobial polymer in the individual films can vary within wide limits without the antimicrobial effect becoming too small, e.g. from 0.5 to 95% by weight, preferably 1 to 20% by weight.

The antimicrobial polymer can either be used directly in the manufacture of the films, e.g. in the extrusion or blow molding, with incorporated or subsequently in the form of a coating, for. B. as part of a varnish or resin. The result is a surface of the film impregnated with an antimicrobial polymer.

It is also possible that the films consist of a polymer blend, of antimicrobial polymers with at least one further polymer or of a copolymer of the respective monomers.

In the case of coating, metal foils, e.g. for applications at elevated temperatures, applicable.

The surfaces treated in this way show an antimicrobial effectiveness that is permanent and resistant to physical stress. These coatings do not contain any low molecular weight biocides, which effectively rules out the migration of toxicologically problematic substances over the entire period of use.

Nitrogen and phosphorus functionalized monomers are preferably used for the preparation of the antimicrobial polymers, in particular one or more of the following monomers: 2-tert-butylaminoethyl methacrylic acid, 2-diethylaminoethyl methacrylate, 2-diethylaminomethacrylate, 2-tert-butylaminoethyl acrylate, 3-dimethylaminopropyl acrylate, 2-diethylaminoethyl acrylate, 2-dimethylamino acrylate ethyl ester, dimethylaminopropyl methacrylamide, diethylaminopropyl methacrylamide, acrylic acid-3-dimethylaminopropylamide, 2-methacryloyloxyethyltrimethylammonium methosulfate, methacrylic acid-2-diethylaminoethyl ester, 2-methacryloyloxyethyltrimethylammoniumchloride, 3-methacryloylaminopropylchloromethyloxyethylammoylmethyldimethylammoylmethylmethyloxyethylmethylmethyloxyethylmethylmethyloxyethylmethyloxyethylmethyloxyethylmethylmethylimidoylmethylimidoylmethylmethylimidoylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmoyl Meth-acryloyloxyethyl-4-benzoyldimethylammonium bromide, allyltriphenylphosphonium bromide, allyltriphenylphosphonium chloride, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-diethylaminoethyl vinyl ether and / or 3-aminopropyl vinyl ether.

If the film consists or contains polymers, these can be polypropylene, polyamides, polysulfoxides, polysiloxanes, polyurethanes, polystyrene, polyvinyl chloride, polymethyl methacrylate, polyethylene, polyethylene terephthalate, cellulose, cellulose derivatives, polyacrylic acid, polysilicones or polyurethanes whose blends or copolymers.

If a copolymer of the monomers of the antimicrobial polymers and monomers of one or more other polymers is used as the film, preference is given to monomers or oligomers of the abovementioned. Polymers used.

Use of the antimicrobial stack systems Further objects of the present invention are the use of the stack systems according to the invention as antimicrobial protective films in laminar flows, sterile benches, operating rooms, isolation stations, incubators, flooring and interior linings of air conditioning systems. To further describe the present invention, the following examples are given, which illustrate the invention further, but are not intended to limit the scope thereof, as set out in the patent claims. Example 1:

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. Then 0.6 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 at this temperature for 72 hours. After this time, the reaction mixture is stirred into 1.5 l of deionized water, the polymeric product precipitating. After filtering off the product, the filter residue is rinsed with 100 ml of a mixture of ethanol / demineralized water in a ratio of 1: 1 in order to remove any remaining monomers. The product is then dried in vacuo at 50 ° C. for 24 hours. 2 g of the product are dissolved in 10 g of ethanol and applied to a 4 by 6 cm polyethylene film using a 100 micrometer doctor blade. The film is then dried at 50 ° C for 24 hours.

Example la: The backs of four films from Example 1 are coated with the Gudy 804 film adhesive from Neschen. Subsequently, the film backs coated with adhesive in this way are placed on the respective film front sides, so that ultimately a stack of four films connected to one another results. The back of the adhesive that is still free is now glued to the bottom of a Petri dish. A drop of a germ suspension of Pseudomonas aeruginosa, which contains a germ count of 10 ⁷ germs per mL, is applied to this film stack. The mixture is then incubated at 37 ° C. for 1 hour. After the time has elapsed, the original drop is taken up with water of standardized hardness and subjected to a bacterial count determination. As a result of the determination, no more Pseudomonas aeruginosa germs could be detected.

Example lb:

The top film is removed from the film stack from Example 1a. This fresh one

The surface is coated with a mixture of 100 millimolar magnesium sulfate solution and 10% soapy water. A drop of one is placed on this prepared stack

Germ suspension of Pseudomonas aeruginosa, which has a germ count of 10 ⁷ germs per mL contains, applied. The mixture is then incubated at 37 ° C. for 1 hour. After the time has elapsed, the original drop is taken up with water of standardized hardness and subjected to a bacterial count determination. The result of the determination was a germ count of 10 ⁶ germs per ml.

Example lc:

The top film is removed from the film stack from Example 1b. A drop of a germ suspension of Pseudomonas aeruginosa, which contains a germ count of 10 ⁷ germs per ml, is applied to this fresh surface. The mixture is then incubated at 37 ° C. for 1 hour. After the time has elapsed, the original drop is taken up with water of standardized hardness and subjected to a bacterial count determination. As a result of the determination, no more Pseudomonas aeruginosa germs could be detected.

Example 2:

50 ml of tert-butylaminoethyl 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 0.6 g of azobisisobiityronitrile dissolved in 20 ml of ethyl methyl ketone are slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After this time, the reaction mixture is stirred into 1.5 l of deionized water, the polymeric product precipitating. After filtering off the product, the filter residue is rinsed with 100 ml of a mixture of ethanol / demineralized water in a ratio of 1: 1 in order to remove any remaining monomers. The product is then dried in vacuo at 50 ° C. for 24 hours. 2 g of the product are dissolved in 10 g of ethanol and applied to a 4 by 6 cm polyethylene film using a 100 micrometer doctor blade. The film is then dried at 50 ° C for 24 hours.

Example 2a:

The backs of four films from Example 2 are coated with the Gudy 804 film adhesive from Neschen. Then they are coated with glue

Foil backs placed on the respective foil front sides, so that ultimately one Stack of four interconnected foils results. The back of the adhesive that is still free is now glued to the bottom of a Petri dish.

A drop of a germ suspension of Pseudomonas aeruginosa, which contains a germ count of 10 ⁷ germs per mL, is applied to this film stack. The mixture is then incubated at 37 ° C. for 1 hour. After the time has elapsed, the original drop is taken up with water of standardized hardness and subjected to a bacterial count determination. As a result of the determination, no more Pseudomonas aeruginosa germs could be detected.

Example 2b

The top film is removed from the film stack from Example 2a. This fresh surface is coated with a mixture of 100 millimolar magnesium sulfate solution and 10% soapy water. A drop of a germ suspension of Pseudomonas aeruginosa, which contains a germ count of 10 ⁷ germs per mL, is applied to this stack prepared in this way. The mixture is then incubated at 37 ° C. for 1 hour. After the time has elapsed, the original drop is taken up with water of standardized hardness and subjected to a bacterial count determination. The result of the determination was a germ count of 10 ⁵ germs per ml.

Example 2c

The top film is removed from the film stack from Example 2b. A drop of a germ suspension of Pseudomonas aeruginosa, which contains a germ count of 10 ⁷ germs per ml, is applied to this fresh surface. The mixture is then incubated at 37 ° C. for 1 hour. After the time has elapsed, the original drop is taken up with water of standardized hardness and subjected to a bacterial count determination. As a result of the determination, no more Pseudomonas aeruginosa germs could be detected.

Example 3: 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. After that 0.745 g of azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone was slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After this time, the reaction mixture is stirred into 1 liter of demineralized water, the polymeric 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 remaining monomers. The product is then dried in vacuo at 50 ° C. for 24 hours. 4 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, the mixture being stirred intimately until it becomes pasty. 20 g of the paste obtained are spread onto a metal plate using a doctor blade in such a way that a layer thickness of 0.7 mm is obtained. The plate with the paste on it is then heated to 200 ° C. for 2 minutes, during which the paste gels and a soft PVC film is formed.

Example 3a: The backs of four films from Example 3 are coated with the Gudy 804 film adhesive from Neschen. Subsequently, the film backs coated with adhesive in this way are placed on the respective film front sides, so that ultimately a stack of four films connected to one another results. The back of the adhesive that is still free is now glued to the bottom of a Petri dish. A drop of a germ suspension of Pseudomonas aeruginosa, which contains a germ count of 10 ⁷ germs per mL, is applied to this film stack. The mixture is then incubated at 37 ° C. for 1 hour. After the time has elapsed, the original drop is taken up with water of standardized hardness and subjected to a bacterial count determination. As a result of the determination, no more Pseudomonas aeruginosa germs could be detected.

Example 3b

The top film is removed from the film stack from Example 3a. This fresh one

The surface is coated with a mixture of 100 millimolar magnesium sulfate solution and 10% soapy water. A drop of one is placed on this prepared stack

Germ suspension of Pseudomonas aeruginosa, which has a germ count of 10 ⁷ germs per mL contains, applied. The mixture is then incubated at 37 ° C. for 1 hour. After the time has elapsed, the original drop is taken up with water of standardized hardness and subjected to a bacterial count determination. The result of the determination was a germ count of 10 ⁷ germs per ml.

Example 3c

The top film is removed from the film stack from Example 3b. A drop of a germ suspension of Pseudomonas aeruginosa, which contains a germ count of 10 ⁷ germs per ml, is applied to this fresh surface. The mixture is then incubated at 37 ° C. for 1 hour. After the time has elapsed, the original drop is taken up with water of standardized hardness and subjected to a bacterial count determination. As a result of the determination, no more Pseudomonas aeruginosa germs could be detected.

Example 4:

50 ml of tert-butylaminoethyl 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 0.6 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 at this temperature for 72 hours. After this time, the reaction mixture is stirred into 1.5 l of deionized water, the polymeric product precipitating. After filtering off the product, the filter residue is rinsed with 100 ml of a mixture of ethanol / demineralized water in a ratio of 1: 1 in order to remove any remaining monomers. The product is then dried in vacuo at 50 ° C. for 24 hours. 30 g of the product are compounded together with 1000 g of PVC granulate. The compound is then extruded into a 4 cm wide film using a laboratory extruder.

Example 4a

The backs of four films from Example 4 are coated with the Gudy 804 film adhesive from Neschen. Then they are coated with glue

Foil backs placed on the respective foil front sides, so that ultimately one Stack of four interconnected foils results. The back of the adhesive that is still free is now glued to the bottom of a Petri dish.

A drop of a germ suspension of Pseudomonas aeruginosa, which contains a germ count of 10 ⁷ germs per mL, is applied to this film stack. The mixture is then incubated at 37 ° C. for 1 hour. After the time has elapsed, the original drop is taken up with water of standardized hardness and subjected to a bacterial count determination. As a result of the determination, no more Pseudomonas aeruginosa germs could be detected.

Example 4b

The top film is removed from the film stack from Example 4 a. This fresh surface is coated with a mixture of 100 millimolar magnesium sulfate solution and 10% soapy water. A drop of a germ suspension of Pseudomonas aeruginosa, which contains a germ count of 10 ⁷ germs per mL, is applied to this stack prepared in this way. The mixture is then incubated at 37 ° C. for 1 hour. After the time has elapsed, the original drop is taken up with water of standardized hardness and subjected to a bacterial count determination. The result of the determination was a germ count of 10 ⁶ germs per ml.

Example 4c

The top film is removed from the film stack from Example 4b. A drop of a germ suspension of Pseudomonas aeruginosa, which contains a germ count of 10 ⁷ germs per ml, is applied to this fresh surface. The mixture is then incubated at 37 ° C. for 1 hour. After the time has elapsed, the original drop is taken up with water of standardized hardness and subjected to a bacterial count determination. As a result of the determination, no more Pseudomonas aeruginosa germs could be detected.

Claims

claims: 1. Antimicrobial stack systems based on foils, characterized in that at least two foils, each having an antimicrobial front and an adhesive back, are glued to one another. 2. Antimicrobial stack systems according to claim 1, characterized in that the films consist of 0.5 to 95 wt .-% of antimicrobial polymers. 3. Antimicrobial stack systems according to claim 1 and 2, characterized in that the films are coated with the antimicrobial polymers. 4. Antimicrobial stack systems according to claim 1 or 2, characterized in that the films consist of a polymer blend of the antimicrobial polymers and at least one further polymer. 5. Antimicrobial stack systems according to claim 1 or 2, characterized in that the films consist of a copolymer of the monomers of the antimicrobial polymers and the monomers of at least one further polymer. 6. Antimicrobial stack systems according to claims 1 to 5, characterized in that the antimicrobial polymers are made from nitrogen and phosphorus functionalized monomers. 7. Antimicrobial stack systems according to claims 1 to 6, characterized in that the antimicrobial polymers from one or more monomers from the group: 2-tert-butylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, 2-diethylaminomethyl methacrylate, 2-tert-butylaminoethyl acrylate, 3-acrylate acrylic acid, 3-acrylate dimethylaminopropyl ester, 2-diethylaminoethyl acrylate, acrylic acid 2-dimethylaminoethyl ester, dimethylaminopropylniethacrylamide, diethylaminopropyl-methacrylamide, acrylic acid-3-dimethylaminopropylamide, 2-methacryloyloxyethyltrimethyl-ammonium methoxy sulfate, 2-methacrylo-oyloxyethyltrimethylammonyl chloride, 3-methacrylate benzoyldimethylammonium bromide, 2-methacryloyloxyethyl-4-benzoyldimethylammonium bromide, allyltriphenylphosphonium bromide, allyltriphenylphosphonium chloride, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-diethylaminoethyl vinyl ether and / or 3 - aminopropyl were prepared. 8. Antimicrobial stack systems according to claims 1 to 7, characterized in that the further polymers from the group polypropylene, polyamides, polysulfoxides, polysiloxanes, polyurethanes, polystyrene, polyvinyl chloride, polymethyl methacrylate, polyethylene, polyethylene terephthalate, cellulose, cellulose derivatives, polyacrylic acid, Polysilicones, or polyurethanes whose blends or copolymers are selected. 9. Use of the antimicrobial stack systems according to claim 1 to 8 in laminar flows, sterile benches, operating rooms, isolation stations, incubators, as flooring and as interior cladding for air conditioning systems.