WO2002092890A2

WO2002092890A2 - Antimicrobial fibres and fabric

Info

Publication number: WO2002092890A2
Application number: PCT/EP2002/003571
Authority: WO
Inventors: Peter Ottersbach; Beate Kossmann
Original assignee: Creavis Gesellschaft Für Technologie Und Innovation Mbh
Priority date: 2001-05-12
Filing date: 2002-03-30
Publication date: 2002-11-21
Also published as: DE10122753A1; WO2002092890A3; AU2002302482A1

Abstract

The invention relates to the use of antimicrobial polymers for producing fibres and fabric with an antimicrobial action and to the use of said antimicrobial fibres and fabric.

Description

Antimicrobial fibers and fabrics

The invention relates to the use and use of antimicrobial polymers for the production of antimicrobially active fibers and fabrics and the use of the antimicrobial fibers and fabrics.

Colonization and spreading of bacteria on surfaces of pipelines, containers or packaging are highly undesirable. Mucus layers often form, which cause microbial populations to rise extremely, which have a lasting impact on the quality of water, beverages and food, and can even lead to product spoilage and consumer health damage.

Keep bacteria away from old areas of life where hygiene is important. This affects textiles for direct body contact, especially for the intimate area and for nursing and elderly care. In addition, bacteria must be kept away from furniture and device surfaces in care stations, in particular in the area of intensive care and the care of small children, in hospitals, in particular in rooms for medical interventions and in isolation stations for critical infections and in toilets.

In addition, there are also a number of technical systems that are severely restricted in their performance due to microbial growth, or even become completely unusable. In particular systems for material separation, e.g. Membranes or filters are severely affected by microbial deposits and growth. For example, In the case of seawater desalination, the fouling of the systems with seaweed often has considerable run times. In other systems, such as. B. the deep filtration, the filter cake can clog prematurely by grown biofilms. Attempts are being made to counter this in cross-flow filtration by using a defined flow across the filtration level, but this has so far been shown in practice to be insufficient to prevent the growth of biofilms.

Devices, surfaces of furniture and textiles are currently used to fight bacteria in the If necessary, or as a precaution, treated with chemicals or their solutions as well as mixtures that act as a disinfectant, more or less broadly and massively antimicrobially. Such chemical agents have a non-specific effect, are often themselves toxic or irritating or form degradation products which are harmful to health. Often, intolerances also appear in people who are appropriately sensitized.

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

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

In these applications, the copolymer produced with aminomethacrylates is only a matrix or carrier substance for added microbicidal active substances which can diffuse or migrate from the carrier substance. Polymers of this type lose their effect more or less quickly when the necessary “minimal inhibitory concentration” (MIC) is no longer achieved.

From European patent application 0 862 858 it is also known that copolymers of tert-butylaminoethyl methacrylate, a methacrylic acid ester with a secondary amino function, have inherent microbicidal properties. This terpolymer exhibits so-called contact microbicidity without the addition of a microbicidal active ingredient. It is from the following Patent applications a large number of contact microbicidal polymers known: 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 / EPOO / 06506, PCT / EP00 / 02813, PCT / EP00 / 02819, PCT / EP00 / 02818, PCT / EPOO / 02780, PCT EPOO / 02781, PCT / EP00 / 02783, PCT / EP00 / 02782, PCT / EP00 / 02799, 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.

Polymers which have a contact microbicidal action without the addition of low molecular weight biocides are referred to below as antimicrobial polymers.

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 issues play an equally important role, since the antimicrobial polymers are often processed together with other plastics in order to strengthen their resistance to microbiological attacks or, ideally, to render them completely inert.

Separation systems such as filters, membranes or sieves are known from DE 10 11 0885.0, which contain antimicrobial polymers. These separation systems are flat, porous materials and therefore either too fine-meshed / -porous or too inflexible for many application forms.

It was therefore an object of the present invention to find an application form for antimicrobial polymers which, while remaining effective, does not have these disadvantages.

It has been found that antimicrobial fibers, ie fibers which contain antimicrobial polymers, have a high antimicrobial efficiency and can be processed further for a wide range of uses. The present invention therefore relates to antimicrobial fibers containing antimicrobial polymers and fabrics made from these antimicrobial fibers.

These tissues can e.g. B. can be used as textiles for the clothing sector. It is particularly important here to minimize or eliminate the bacteria responsible for the microbiological breakdown of sweat and the associated undesirable odor development. Since textiles often come into contact with the skin, the use of biocides is prohibited.

Since the effect of the antimicrobial polymers described can be attributed to the contact of microorganisms with the surface, an increase in the actively available surface should be reflected in an increased antimicrobial effect. This plays particularly when used in flow systems, i. H. as a filter material in which the contact time of the fluid substances to be cleaned by microorganisms with the surface is relatively short.

The use of biocides is automatically prohibited in many filter applications because B. in the filtration of foods such as beer, must not add substances that ultimately contaminate the product and in extreme cases can even poison. In these cases, plant downtime and the associated high costs have so far been unavoidable, since the biofilms can only be removed mechanically and optionally also chemically in a toxicologically harmless manner. Even with purely technical systems that do not come into direct contact with food, the use of low molecular weight biocides is often not possible, since these substances usually have to be disposed of after use.

The antimicrobial fibers according to the invention can consist entirely of antimicrobial polymers, ie they are produced in the form of fibers. It is also possible to coat conventional, ie non-antimicrobial, fibers with antimicrobially active polymers, or conventional, ie non-antimicrobial, polymer fibers by surface grafting of monomers or monomer mixtures from which antimicrobial Polymers can be made to coat while maintaining an antimicrobial surface.

It is also possible to use a polymer blend of antimicrobial and other, i.e. H. antimicrobial and / or non-antimicrobial polymers for the production of the fibers.

In all of the procedures described, the resulting product is an antimicrobial finished fiber without the addition of low molecular weight biocides. The fibers produced in this way can be processed into two- or three-dimensional braids (fabrics). These braids can e.g. are textiles for use in clothing, or textile fabrics for technical and commercial industrial use. In a special embodiment, the braids can be assembled in the form of fabric pieces arranged and fixed one above the other to form modules that can be used for water treatment.

The generally known manufacturing and processing methods can be used to produce the threads and fibers, in particular the various spinning methods, e.g. melt spinning, wet spinning, dry spinning, gel spinning, dispersion spinning and other special processes as described in the relevant literature, e.g. in Hans-Georg Elias, Macromolecules, Volume 2 Technology, Hüthig & Wepf Verlag, 5th edition, p. 508 ff.

For example, antimicrobial fibers can be produced by melt spinning by heating the preheated antimicrobial polymer or a mixture of the antimicrobial polymer with other, non-antimicrobial polymers of commercially used fibers, and by means of a heated spinning pump through nozzles of approx. 50 to 400 Micrometer presses. This corresponds to the thickness of the fibers obtained. The resulting threads are drawn off, drawn and allowed to cool.

A subsequent refinement of commercially available fibers by means of surface grafting takes place, for example, in that radical centers are generated on the surface of the fiber to be refined that can serve as starting points for the grafting process. Appropriate radical centers can be generated, for example, by flame, corona, plasma, UV radiation or initiators, as explained in more detail in US Pat. Nos. 5,967,714 and 6,096,800.

The described procedures result in antimicrobial threads and fibers which combine the mechanical and processing properties required for the tasks as well as the biochemical inhibitory effect on microbial growth in an almost ideal manner. Since the antimicrobial polymer is fixed in the matrix of threads and fibers and consequently no low-molecular components are released into the environment, such threads and fibers can also be used in sensitive areas, e.g. water treatment or direct body contact can be used without the toxicologically questionable transfer of biocides from the product.

Nitrogen- and phosphorus-functionalized monomers are preferably used for the production of the antimicrobial polymers. Monomers functionalized in this way are also suitable for the described refinement by means of surface grafting. In particular, these polymers are prepared from at least one of the following monomers: 2-tert-butylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, 2-diethylaminomethyl methacrylate, 2-tert-butylaminoethyl acrylate, 3-dimethylaminopropyl acrylate, 2-diethylaminoethyl acrylate, 2-dimethylacrylic acid ethyl acrylate, dimethylaminopropyl methacrylamide, diethylamino propyl methacrylamide, 3-dimethylaminopropylamide acrylic acid, 2-methacryloyloxyethyltrimethylammonium methosulfate, methacrylate 2-diethylaminoethyltronyl methylethyl, methacryloylammonylethyl, 2-methacryloylammonylethyl, methacryloylmethyl methoxyethyl, methyl methacrylate 2-methacryloyloxyethyltrimethylammonium chloride, 2-

Acryloyloxyethyl-4-benzoyldimethylammonium bromide, 2-methacryloyloxyethyl-4-benzoyldimethylammonium bromide, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-

Diethylaminoethyl vinyl ether and / or 3-aminopropyl vinyl ether.

The proportion of antimicrobial polymers in the polymer fibers can be 0.01 to 100% by weight, preferably 0.1 to 40, particularly preferably 0.1 to 20% by weight.

The monomers or proportions mentioned also relate to the variant of the invention in which a grafting reaction of monomers is carried out on a polymer.

In addition to the mixing of the antimicrobial polymers with microbiologically neutral polymers before the spinning process, it is also possible to carry out the mixing only at the thread or fiber level. This happens e.g. in that antimicrobial threads / fibers are woven together with microbiologically neutral threads / fibers. Here the proportion of antimicrobial fibers should be up to 50% by weight, in particular up to 10% by weight.

In principle, all macromolecules used for the production of polymer filaments fibers can be used as further non-antimicrobial polymers, in particular silk, rayon, cotton, wool, flax, ramie, aramid, polyamides, polyesters, polyacrylic derivatives, polyethylene, polypropylene, PTFE, polymethacrylates, polysulfones, Polyacrylonitrile, cellulose, cellulose acetate, cellulose derivatives or their blends. Like all other hydrophilic polymer threads / fibers, the cellulose derivatives have the advantage that no formation of microdomains with the often likewise hydrophilic antimicrobial polymers is to be expected, as a result of which a uniform surface availability of the antimicrobial polymers is facilitated.

These polymers can be used as a base fiber for coating, as a blend component or as a further fiber in a blended fabric.

The present invention therefore also relates to antimicrobial fabrics which contain the aforementioned antimicrobial fibers. In addition to the antimicrobial fibers, the tissues can also contain other non-antimicrobial fibers, e.g. B. from the polymers mentioned.

Use of the fibers or fabrics according to the invention Further objects of the present invention are the use of the antimicrobial threads / fibers / fabric produced according to the invention as part of filters, nets, filter systems or filter modules and for the production of fabrics or textiles.

The fabrics according to the invention can be used for the filtration and disinfection of beer, wine, fruit juices, milk, drinking water, in air conditioning systems or as a liquid / gas separation system (oxygenator module).

The fabrics are also used in clothing, bedding, masking varnishes, floor or wall coverings, cleaning cloths, hygiene material, handkerchiefs or seat covers.

The fabrics can e.g. B. as surgical clothing or surgical textiles, bed linen in hospitals or as seat covers in car, train or airplane seats.

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

Example 1;

50 ml of dimethylaminopropyl methacrylamide (from Aldrich) and 250 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.5 g of azobisisobutyronitrile dissolved in 20 ml of ethanol are slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 6 hours. After this time, the solvent is removed from the reaction mixture by distillation and dried for 24 hours at 50 ° C in a vacuum. The product is then dissolved in 200 ml of acetone, after which the solvent is removed from the reaction mixture by distillation and dried in vacuo at 50 ° C. for 24 hours. The reaction product is then ground up finely.

Example la: 50 g of polypropylene are heated to 180 ° C. and mixed intimately with 10 g of the product from Example 1. The still hot polymer mixture is pressed through a nozzle with a diameter of 400 micrometers and allowed to cool.

Example lb:

20 fibers, each 5 cm long, from Example 1 are fixed on the bottom of a beaker containing 10 mL of a test microbial suspension of Pseudomonas aeruginosa. The system prepared in this way is now shaken for a period of 4 hours. Then 1 mL of the test microbial suspension is removed. After this time the number of germs has dropped from 10 ⁷ to 10 "germs per mL.

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 0.5 g of azobisisobutyronitrile dissolved in 20 ml of ethanol are slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 6 hours. After this time, the solvent is removed from the reaction mixture by distillation. The product is then dried in vacuo at 50 ° C. for 24 hours. The product is then dissolved in 200 ml of acetone, after which the solvent is removed from the reaction mixture by distillation and dried in vacuo at 50 ° C. for 24 hours.

Example 2a:

50 g of polypropylene are heated to 180 ° C. and mixed intimately with 10 g of the product from Example 2. The still hot polymer mixture is pressed through a nozzle with a diameter of 400 micrometers and allowed to cool.

Example 2b

20 fibers, each 5 cm long, from Example 2a are fixed on the bottom of a beaker containing 10 mL of a test microbial suspension of Pseudomonas aeruginosa. The so prepared

System is now shaken for 4 hours. Then 1 mL of Test microbial suspension removed. After this time, the number of germs dropped from 10 ⁷ to 10 ° germs per mL.

Example 2c

15 g of polyacrylonitrile and 4 g of the product from Example 2 are dissolved in 90 g of dimethylformamide (DMF). 10 mL of this solution are drawn into a medical syringe and then the contents of the syringe are injected evenly and continuously into a precipitation bath consisting of 10 percent by weight DMF and 90 percent by weight demineralized water. The threads thus obtained are shortened to a length of approximately 5 cm.

Example 2d:

20 fibers, each 5 cm long, from Example 2c are fixed on the bottom of a beaker containing 10 mL of a test microbial suspension of Pseudomonas aeruginosa. The system prepared in this way is now shaken for a period of 4 hours. Then 1 mL of the test microbial suspension is removed. After this time the number of germs dropped from 10 ⁷ to 10 "germs per mL.

Example 2e:

20 fibers, each 5 cm long, from Example 2c are fixed on the bottom of a beaker containing 10 mL of a test germ suspension of Staphylococcus aureus. The system prepared in this way is now shaken for a period of 4 hours. Then 1 mL of the test germ suspension is removed. After this time, the number of germs dropped from 10 ⁷ to 10 ² germs per mL.

Claims

claims:

1. Antimicrobial fibers containing antimicrobial polymers.

2. Antimicrobial fibers according to claim 1, characterized in that the fibers consist of a polymer blend of at least one antimicrobial polymer and at least one further non-antimicrobial polymer.

3. Antimicrobial fibers according to claim 1, characterized in that the fibers consist of a non-antimicrobial polymer which is coated with at least one antimicrobial polymer.

4. Antimicrobial fibers according to claim 1, characterized in that the fibers consist of a non-antimicrobial polymer which is coated by graft polymerization with monomers to obtain an antimicrobial, polymeric surface.

5. Antimicrobial fibers according to one of claims 1 to 4, characterized in that the antimicrobial polymers or the antimicrobial surface have been produced from at least one of the following monomers: 2-tert-butylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, 2-methacrylic acid - Diethylaminomethylester, acrylic acid-2-tert. butylaminoethyl ester, acrylic acid 3-dimethylaminopropyl ester, acrylic acid 2-diethylaminoethyl ester, acrylic acid 2-dimethylaminoethyl ester, dimethylaminopropyl methacrylamide,

Diethylaminopropyln ethacrylamide, acrylic acid-3-dimethylaminopropylamide, 2-methacryloyloxyethyltrimethylammonium methosulfate, methacrylic acid-2-diethylaminoethyl ester, 2-methacryloyloxyethyltrimethylammonium chloride, 3 - Methacryloylaminopropyltrimethylammonium chloride, 2-methacryloyloxyethyltrimethylammonium chloride, 2-acryloyloxyethyl-4-benzoyldimethylammoniumbiOmid, 2-

Methacryloyloxyethyl-4-benzoyldimethylammonium bromide, allyltriphenylphosphonium bromide, allyltriphenylphosphonium chloride, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-diethylaminoethyl vinyl ether and / or 3-aminopropyl vinyl ether.

6. Antimicrobial fibers according to claim 2, 3 or 4, characterized in that as non-antimicrobial polymer silk, rayon, cotton, wool, flax, ramie, aramid, polyamides, polyesters, polyacrylic derivatives, polyethylene, polypropylene,

PTFE, polymethacrylates, polysulfones, polyacrylonitriles, cellulose, cellulose acetate, cellulose derivatives or their blends are used.

7. Antimicrobial fibers according to one of claims 1 to 6, characterized in that the fibers contain 0.01-25% by weight of antimicrobial polymers.

8. Antimicrobial tissue containing the antimicrobial fibers according to claims 1 to 7.

9. Antimicrobial tissue according to claim 8, characterized in that the tissue contains non-antimicrobial fibers in addition to the antimicrobial fibers.

10. Antimicrobial fabric according to claim 9, characterized in that the non-antimicrobial fibers made of silk, rayon, cotton, wool, flax, ramie, aramid, polyamides, polyesters, polyacrylic derivatives, polyethylene, polypropylene, PTFE, polymethacrylates, polysulfones, polyacrylonitriles, Cellulose, cellulose acetate,

Cellulose derivatives or their blends exist.

1 1. Antimicrobial tissue according to one of claims 8 or 9, characterized in that the tissue contains up to 50 wt .-% of antimicrobial fibers.

12. Use of the antimicrobial fibers according to one of claims 1 to 7 for the production of antimicrobial fabrics or textiles.

13. Use of the antimicrobial fibers according to one of claims 1 to 7 in nets or filters.

14. Use of the antimicrobial tissue according to one of claims 8 to 11 as part of filler systems or filter modules.

15. Use of the antimicrobial tissue according to one of claims 8 to 1 1 for the filtration of beer, wine, fruit juices, milk or drinking water.

16. Use of the antimicrobial tissue according to one of claims 8 to 11 as a liquid / gas separation system (oxygenator module).

17. Use of the antimicrobial fabric according to one of claims 8 to 1 1 in clothing, bedding, masking lacquers, floor or wall coverings, cleaning wipes, hygiene material, handkerchiefs, seat covers or in air conditioning systems.