DE102004050462A1 - Substrate material with increased antimicrobial and fungicidal activity and method for surface modification of the substrate material - Google Patents

Abstract

Substrate material (A) with high antimicrobial and fungicidal activity in which the region near the surface includes a predetermined content of bactericidal metal which is present mainly as a non-closed layer and this region is formed by a filtered cathodic vacuum arc method or by ion implantation, especially by introducing ions below the surface into the polymer where they bind to the molecular structure of the substrate. Substrate material (A) with high antimicrobial and fungicidal activity in which (a) the region near the surface includes a predetermined content of bactericidal metal (I); (b) (I) is present mainly as a non-closed layer in the near-surface region; and (c) this region is formed by modifying the polymeric material by a filtered cathodic vacuum arc (FCVA) method or by ion implantation, especially by introducing ions below the surface itself, where they bind to the molecular structure of the substrate. An independent claim is also included for two methods for surface modification to produce (A).

Description

The The invention relates to substrate materials having enhanced antimicrobial and fungicidal Effect, in particular the treatment of substrate materials, the by weaving, knitting, braiding, crocheting, felting, sewing or Gluing or otherwise a variety of filaments, fibers, fiber products or yarns that are made up of a variety of twisted or otherwise connected Threads exist, and materials made of polymeric fiber fabrics consist. The invention further relates to a method for surface modification a substrate material.

The The present invention further relates to clothing, shoes, medical devices, Hygiene articles and the like Things made from FCVA pretreated fibers, fabrics or otherwise processed natural or artificial Raw materials and clothing, Shoes, medical devices, toiletries and similar things.

It It is known that precious metals like silver, gold and platinum and others Metals such as zinc, tin and copper under suitable conditions and in a suitable form an antimicrobial action against a broad Spectrum of bacteria and fungi show. Of these metals is Silver is the most common in antimicrobial applications, such as in creams, ointments and dressings used material. There is a variety of publications that the effect and effectiveness of silver and silver containing compounds in the cleaning of wound infections and in wound healing (for example, N. Gier in "Desinfection, Sterilization and Preservation ", chapter 18, p 375, Seymour Block, 3rd edition Lea & Febiger, Philadelphia, 1983).

One Metal has an antimicrobial (bactericidal or fungicidal) or bacteriostatic effect, when active against pathogenic microorganisms, such as For example, bacteria, fungi, protozoa or viruses, acts. bactericidal Substances destroy microorganisms while bacteriostatic substances that Inhibit growth and multiplication of microorganisms. The bactericidal Effects of silver become major caused by the action of silver ions and can with explained several mechanisms become. The inhibitory effect of silver is due to the strong interaction caused by the thiol groups present in the cell enzymes. additionally it is believed that silver reacts with proteins and preferably with DNA bases binds and thus inhibits cell replication (A.D. Russel and W.B. Hugo, Progr. Med. Chem. 31 (1994) 351. Silver ions are even effective against antibiotic-resistant bacterial and fungal strains. The mode of action of silver is more that of a broadband antiseptic than that of a single-target antibiotic.

These Property represents an important advantage of silver as it thus unlikely to be mutations of microorganisms a resistance to Develop silver. Silver and the metals already mentioned were and are already used in a variety of medical products is used, usually in purely metallic form, in the form of salts or other connections. Recently there has been an increase in one Developed variety of materials, called nanoparticles (Particles with a size of typically 10 to 500 nm) of silver or other metals. These Materials are especially used for the production of dressings, surgical instruments, hygiene products and the like Used things. The materials used are also available partly over special properties such as flexible substrates that adapt to the shape, moisture-absorbing layers as well as moisture and gas-permeable layers. The substrates used and layers made of natural or artificial manufactured fibers are used with antibacterial Substances added to a corresponding therapeutic effect to reach.

The Adding silver or other metals to a corresponding one Material can be different physical or chemical Processes take place. The following references give an overview of the current State of the art for the production of silver-containing materials.

in the Patent WO 0160 559 describes B.G. Kania and R.O. Becker an antimicrobial Multilayer system consisting of a polymer layer and a silver-containing layer. The silver is hereby vapor-deposited, spraying, Sputtering, magnetron sputtering, vacuum evaporation, chemical deposition or metallization in concentrations of typically 2 to 20 weight applied.

in the US Pat. 4 728 323 describes C. Matson antimicrobials, in which the base material with a film of silver chloride or Silver sulfate is provided by vapor deposition or sputtering.

H. Stowasser describes in US Pat. 2,934,066 a metallized dressing material consisting of a non-woven fabric, which was provided by vacuum coating with metallic silver. Wound dressings containing silver or silver containing compounds are described in a variety of patents, eg, Weaver et al. in US Pat. 5,218,973, to Fabo in US Pat. 5,340,363 and McKnight et al. in US Pat. 3,800,792.

Acticoat (Westaim Biomedical Inc., Alberta, Canada) is a fabric composed of two layers of polyethylene fabric separated by an absorbent inner core. The fabric is provided by sputtering with nanocrystalline silver, allowing a quick water contact and the subsequent exchange of silver ions. Silberlon ^® (Argentum Medical, LLC, Georgia, USA) consists of a three-dimensional silver-plated polyamide fabric which is prepared by an autocatalytic electroless silver-plating process was used.

Actisorb ^® Silver 220 (Johnson and Johnson Medical Ltd., UK) containing halted activated carbon which is impregnated with metallic silver. The preparation is carried out by the controlled heating of a specially pretreated viscose fabric.

One another product of this type, SPI-Argent (Spire Corporation, USA), uses an anti-infective silver coating based on polymer, metal, and ceramic surfaces of medical devices by means of ion beam Deposition is applied. This coating is supposed to be a risk Reduce bacterial infection without causing unwanted Side effects is coming.

antimicrobial Coatings by vapor deposition of silver and others Metals on medical devices are described in US Pat. 6,017,553 to S.P. Apte described. Various experiments [E.g. Marino, M., et al., Journal of Biological Physics 12 (1984) 93; J. Haynes and J. Mansour, US Patent 4,886,505] have also been made for the antimicrobial efficacy of metallic silver coatings by increasing electrical activation or galvanic processes.

One general disadvantage of metallic silver coatings is the low Diffusion rate of silver ions from the layer surface to Wound area. Electrical and Galvanic activation usually leads not for the controlled and continuous release of silver ions in sufficient quantity and over longer periods time. Such coatings are therefore unsuitable for outpatient treatments.

Farther has been discovered lately that many medical products, do not contain the silver salts or colloidal silver compounds can generally be considered safe and efficient, since They may have unwanted side effects cause [e.g. M. C. Fung and D.L. Bowen, J. Toxicol. Clin. Toxicol. 34 (1996) 119].

One general feature of the state-of-the-art produced Standard coatings is that on the surface of a carrier substrate an additional silver-containing layer is applied. This forms as a new phase a heterolayer over the substrate and is not compatible with the substrate in general. This results in poor adhesive properties, and silver can also not be released in therapeutically meaningful amounts. In some cases the efficiency of such coatings, especially in multilayer systems, through the complexity and the cost of manufacturing compensated. The atoms of such Heterolayers tend to easily detach from the substrate, especially when the coating process is carried out in a mold, the a discontinuous layer (rather than a continuous one) Layer).

It Care should therefore be taken with the antimicrobial and healing properties of silver, as silver may be harmful under certain circumstances can. It is difficult to guarantee a certain positive effect and exclude, that this is not compensated by an undesirable side effect becomes.

The Properties and the associated uses hanging from silver strongly depends on the state in which the silver in the material located.

In a recent study, the anti-microbial efficacy of the aforementioned dressings Acticoat and Silverlon ^® was compared [JW Richard III et al, Journal of Burns, 1 (2002) 11]. The results of the study suggest that Acticoat efficiently acts as Silverlon ^® due to structural differences in the tissue. Although the entire silver-coated surface of Silverlon ^® up to 50 times greater than that of Acticoat, the latter is due to the nano-crystalline state form of silver this much more efficiently released. This evidence underscores the primary importance of the state form of silver for its antimicrobial and healing properties.

In another study (DW Brett et al., Proc. 15th Annual Regional Burn Conference, December 6-8, 2002, Louisville, Kentucky, USA (published March 11, 2003)), a nanocrystalline silver film deposited by Chemical Vapor Deposition This study also demonstrates the antimicrobial effect of nanocrystalline silver-coated fabrics with the silver-containing products Arglaes Film Dressing, Actisorb Plus, Avance Antimicrobial Polyurethane Foam Dressing, SilverIon Contact Wound Dressing , Silver nitrate and silver sulfadiazine cream compared Antimicrobial activity was determined by measuring the logarithmic reduction in the number of living cells of 17 clinically relevant microorganisms. Nanocrystalline silver achieved a reduction in the number of all microbes by 3 orders of magnitude after 30 minutes, and by 4 orders of magnitude after 2 hours, while the other silver-based products either showed only a slight effect after 2 hours or there, the reaction did not appear as fast as in the fabric coated with nanocrystalline silver.

These Findings clearly show that the shape and condition in the silver in a corresponding substance or similar Material is present, of crucial importance for the antimicrobial Effect of such a system is. It is proven that the effectiveness of silver from bulk material to nanoscale systems is increasing significantly. One can therefore assume that this trend is in another Miniaturization in the sub-nanometer range down to atomistic Dimensions increase again.

Of the The term "standard coating" is used here for coating processes by evaporation (by inductive heating, resistance heating and with the help of an electron beam) and using magnetron sputtering, both belong to a group of techniques called physical Deposition from the vapor phase (PVD) can be called. The evaporation provides a metal vapor with particles whose kinetic energies lie in the thermal range and simply on a substrate condense.

At the Sputtering becomes a particle flow with an average energy of few electron volts (eV) and a large proportion of neutral, low-energy Generated particles. Coatings made with such processes are for many applications are sufficient. Increasingly, however, there are cases in those produced by PVD metal layers an insufficient Adhesion, coverage or density. This is especially true for complex constructed substrate materials.

It is therefore necessary to consider alternative techniques. The usefulness of silver and other elements can be increased tremendously, though in the treatment of materials processes are used which allow, by means of energetic ion beams or energetic, high ionized plasma rays silver and other elements in layer depths below the surface too incorporate.

Especially when the energy of the incident ions exceeds about 30 eV, can this deeper than the outer atomic layer penetrate and become part of the near-surface layer.

by virtue of the just mentioned embodiments appears It is advantageous to have an energetic vacuum process for making using silver-containing materials, not just silver in atomic dimension is deposited on the surface but also by the energetic process atomic silver directly under the surface of the base material is incorporated.

by virtue of of the big one Proportion of low-energy particles with an energy less than 5 eV can this effect with PVD techniques not be implemented, because the silver does not have any material layers below the surface reached. Applying a bias voltage would not solve this problem, because a lot the particle is electrically neutral and not in the electric field can be accelerated.

Even though the ones just mentioned Methods different problems when using silver-containing Materials arise, solved there is still a demand for efficient and cost effective Dressing materials with improved antimicrobial and healing Properties.

The Ion implantation is a known method for surface treatment of materials. A stream of positively charged atoms or molecules (ions) passes an analyzer magnet, the ions of a particular element, selected from a certain mass and a certain charge. The Ions are then exposed to an energy of typically 5 to 200 KeV is accelerated and implanted in the substrate material where it the properties nearer to the surface Change areas significantly can.

The surface modification of polymers by ion implantation is a relatively recent branch of research. A big part Work in this area is related to the change a certain material property such as conductivity, hardness, wear, coefficient of friction, chemical stability etc. (e.g., R.D. Day et al., U.S. Patent 4,491,605; R. C. Tennyson et al. U.S. Patent 5,683,757; G.R. Rao, K. Monar, E.H. Lee and J. Treglio, Surface and Coatings Technology, 64 (1994) 69].

US Pat. 4,452,827 discloses a process for surface treatment of synthetic and natural polymers by ion implantation of metals, non-metals and gases. The term "polymer" as used by the authors of the above mentioned patent includes synthetic polymers made by polycondensation, polyaddition or polymerization; artificial fiber fabrics; natural polymers such as Cotton, wool, cellulose, leather etc. and materials made therefrom, as well as resins and varnishes.

One There is a significant problem with the process of ion implantation However, in the technologically related relatively high cost of Process, which is particularly problematic in the treatment of large areas is.

It However, it is known that the use of a highly ionized plasma jet the same advantages in the surface modification of materials offers, like, the ion implantation. This is especially true when the ions are extracted from the plasma jet and into the near-surface Implanted region of the material to be treated.

Filtered Cathodic Vacuum Arc (FCVA) is a relatively new process of this kind. At the FCVA, an arc between cathode and Anode ignited, the former consisting of a specific conductive material, the allows the generation of a high-energy plasma. This will passed after passing a magnetic filter on the substrate. The plasma is almost 100% ionized, and the ions of the plasma jet have a kinetic energy in the range 10 to 100 eV. The energy of Ions can be increased in a controlled manner to a few keV by the treatment to be treated Substrate or the substrate holder are biased negative. This makes it possible Procedure of FCVA treatment the introduction of ions into a near-surface layer.

Of the physical background, previous developments and current Advances in the use of vacuum arcs are in a series of Works shown [e.g. in D.M. Sanders et al, IEEE Trans. Plasma Sci. 18 (1990); also P.J. Martin, Surface Coating Technol. 54/55 (1992) 136; S. et al., IEEE Trans. Plasma Sci. 25 (1997) 670 and I. G. Brown, Ann. Rev. Mat. Sci. 28 (1998) 243]. Examples of patents open the FCVA process and the necessary equipment are US Patent no. 6,663,755 to V.I. Gorokhovsky, US Patent No. 5,902,462 to A.R. Kraus and US Pat. 5 480 527 of R.P. Welty.

at FCVA treatment, the target material, e.g. Silver, that simultaneously acts as a cathode, by the action of the arc gradually evaporated. A typical FCVA system consists of one Vacuum chamber, a cathode, a power supply for the arc, an ignition device, an anode, a magnetic filter system and a substrate holder with power supply.

Of the Arc is by applying a high voltage pulse to a Electrode in the immediate vicinity the cathode (i.e., by gas discharge) or mechanically ignited. Of the Arc of the arc moves randomly over the surface the cathode and evaporates the cathode material there. The arc is maintained by the formation of a high-energy plasma, the ionized atoms and molecules, one certain proportion of neutral particles and microparticles. Latter have a size in the range of 1 μm and arise at ignition of the arc. The expanding plasma enters the area of the annular curved Magnetic filter, where the neutral particles and microparticles sorted out become. Due to the axial magnetic field of the filter, the electrons of the plasma to a tight spiral motion around the magnetic field lines and along the curvature forced the filter. The electrons generate a negative electrical Potential that attracts the positively charged ions, which thus the Movement of the electrons follow. The neutral particles and microparticles However, they move on a straight trajectory and can use it the curved one Magnetic filter does not happen. The plasma leaves the magnetic filter almost 100% ionizes and then strikes the substrate surface.

Of the FCVA process offers many advantages over the PVD techniques such as higher vapor deposition rate, better Adhesion and homogeneity the coating and low process temperatures. The FCVA is especially in areas where less stringent control the process parameter is sufficient as with the PVD and high Process temperatures are not mandatory. The latter allows the coating of low melting point materials, e.g. Polymer substrates.

Of the Main advantage of the FCVA ion implantation is the ability size surfaces in shorter Time to process and the possibility of this Method easily in the large industrial scale apply.

FCVA has recently been particularly focused on applications in the field used for the treatment of metals and metallic surfaces. So far are not applications of FCVA fiber treatment technology, Tissues or fabrics or products thereof derived in the following Silver which has an antimicrobial or fungicidal action, known.

Despite the variety of medical products currently available on the market, such as dressings, antimicrobials, etc., there is a demonstrable need for more simple, versatile and cost-effective antimicrobial materials used to make medical, hygienic, and medical devices or everyday clothing and equipment of industry and household can be used.

Of the Invention is based on the object, easy to produce, versatile and inexpensive materials and semi-finished products with particular antimicrobial effect, for further processing and manufacturing of products in the fields of medicine, hygiene and everyday clothing as well as packaging and equipment of industry and household can be used.

The The object underlying the invention is characterized by the characterizing Characteristics of claim 1 solved. Further embodiments of Invention go from the associated dependent claims out.

Of the Invention is also the object of a cost-effective and effective method for surface modification corresponding To create materials.

These The object is achieved by the characterizing features of independent patent claim 11 or 14 solved. Further embodiments of the invention will become apparent from the accompanying dependent claims.

With of the invention are those described in the prior art Fields of application by providing a surface modification of materials using FCVA and the wideband ones thus available expanded antimicrobial effects. Mainly focuses the invention on improving the antimicrobial properties of tissues, Fibers and threads by near-surface material modifications using FCVA with silver.

The surface modification by means of FCVA is generally advantageous over standard coatings, since the introduction of the silver into a near-surface layer does not cause any adhesion problems and also the previously existing material properties of the substrate remain virtually unchanged. The silver or possibly another element is incorporated by the process in atomic form in the near-surface region of the substrate material and there strongly bound by internal structural bonds to the substrate material. Furthermore, the concentration of incorporated silver is relatively low, preferably in the range 20 to 200 mg / m ² . The combination of these two properties can ensure that the correspondingly modified fabric material has virtually no toxicity and thus lasting adverse effects caused by unwanted silver overloading are avoided, and not problems as usual in long-term applications of other silver-containing material systems with significantly higher silver concentration.

Other Metals as silver can also alone or in combination with silver or in combination various metals to modify the near-surface Layer can be used.

It It is also advantageous that treatment by FCVA the original bulk material properties of the substrate fabric or substrate material, and only the near-surface Layer changed becomes.

Of the in the invention named manufacturing process additionally has the Advantage of good controllability, short treatment times and he needs in principle, no upstream processes. That through the treatment obtained material can be applied directly to human skin it can be over longer periods be used and it also loses after the execution of Washing or cleaning procedures do not have its antimicrobial properties.

The Invention will now be more detailed in the following embodiment described, with the concrete process steps and equipment only to be understood as illustrative examples. The invention is therefore not on the process parameters mentioned here, equipment and limited materials.

Of the inventive process for surface modification includes a single surface modification step, namely the direct modification of a suitable substrate by the near-surface Incorporation of a bactericidal metal by FCVA. in principle is not an additional treatment of the substrate before or after the FCVA necessary. The FCVA process changes physically the surface properties the substrate material, in particular by the incorporation of Silver or other suitable metals such as gold, platinum, palladium, Zinc, tin and copper, and forms an active near-surface Layer with antibacterial and fungicidal properties.

According to the invention Preferably, the substrate material to be modified by means of FCVA a textile fabric of any kind and any manufacturing method.

The Alternatively, substrate material can also consist of any polymer fabric, that in area or foil-like form. This restriction is due to the nature of the Given the FCVA process, the caused by the plasma jet a line-of-sight arrangement.

These line-of-sight restriction can by suitable linear or rotational movements (or combinations both movements or several such movement in different Axes) of the substrate are bypassed against the plasma jet. Thereby can also individual fibers, threads, yarns or other raw materials, such as granules or so said batches of plastics and later to a Tissue or other semi-finished products are processed.

In dependence from the particular application, the tissue may be complete or partially made of FCVA-treated fibers. In detail, that can Substrate material both from natural fiber fabric like cotton, linen, jute, silk, wool, flax etc. as well made of synthetic materials such as polyethylene, polycarbonate, fluorocarbonate, polyester, Acrylic and others and consist of appropriate combinations thereof. The substrate material may further comprise stretchable tissue of natural or synthetic rubber. The to be treated by FCVA Fabric can be made in any way.

in the In general, the substrate material should have some flexibility and biological Possess inertness.

All the previously mentioned Materials and products are hereinafter referred to as "substrate" Designations "material", "polymer material", "substrate material", "product", "article" and modified thereof Terms are used in the sense of the word "substrate".

The materials to be treated by FCVA can be conveniently obtained from individual small sizes up towards big ones Rolls are provided. The FCVA fabric is especially for use in the manufacture of clothing, dressings, packaging, Disguises or curtains or carpets of any kind.

alternative silver can also be added to the finished product by means of FCVA. Furthermore, silver or other metal may be incorporated into any suitable product incorporated, e.g. medical devices or containers for limited-life goods such as blood Etc.

preferred Elements for surface modification are silver, gold, platinum, palladium, zinc, tin and copper, where Silver is preferred.

The Invention allowed - in particular in the production of textile u.a. hygienic articles - the production a material with pronounced antibacterial and fungicidal properties in which the active Component in a near-surface layer is localized.

The FCVA treatment of a suitable substrate involves incorporation of at least one item from the list mentioned above in the substrate and the formation of a near-surface layer, this Contains element.

There the FCVA is an almost 100% ionized plasma with particle energies generated in the range of 10 to 100 eV, can be a considerable Proportion of incident ions penetrate the outer atomic layer and just below the surface come to rest where they are in the internal structure of the substrate material be involved. The penetration depth of these ions can additionally by a bias increases Since these are the energy of the ions and thus their average Range determined in the material. For example, the penetration depth is for silver ions at an energy of 1.2 or 5 keV after a SRIM calculation 6, 8 and 13 nm, respectively (www.srim.org). The FCVA treatment creates a material with modified surface properties, the based on the presence of metals at the atomic level.

The Thickness of the total modified layer including the near-surface, Metal-rich layer hangs on the type of polymer material used and the energy of the Ions and is typically in the range 1 to 500 nm.

The preferred process parameters of the FCVA are according to the invention the following:
The FCVA treatment can be either continuous or pulsed. The latter is preferred according to the invention, since in particular in high-current operation, the process parameters such as shape, amplitude, duration and number of pulses can be controlled with higher reproducibility with simultaneous high throughput. The pressure in the vicinity of the substrate is usually 10 ^-6 to 10 ^-4 Torr and increases to 10 ^-4 to 10 ^-2 Torr during the treatment. Generally, the pressure must be low enough to minimize impact between the ions and the remaining neutral particles. On the other hand, the pressure should not be lower than necessary as this slows down the FCVA process and reduces throughput.

The substrate exposed to the plasma is usually set to negative potential by applying a negative voltage to the substrate holder, which leads to an additional acceleration of positively charged ions towards the substrate. This increases the proportion of energetic ions, which gelan in a near-surface layer of the substrate can. For the treatment of rolls or foils, the plasma chamber is equipped with a metal plate behind or under the material to be unrolled. While the front side of the material to be unrolled faces the plasma, a voltage - preferably pulsed and in the range of -100 eV to -50 keV - is applied to the metal plate facing the rear side. Alternatively, a pulsed negative voltage may be applied to a metal grid surrounding the substrate such that the ions of the plasma are accelerated toward the metal grid. The majority of the ions fly through the metal grid and reach the substrate. Another way to bias an electrically nonconductive substrate is to use a bipolar high frequency voltage pulse. FCVA treatment without prestressing is also possible; however, the ability to incorporate ions in layers below the surface is significantly limited.

The ion dosage to achieve useful silver concentrations is in the range of 10 ¹⁶ to 10 ¹⁸ ions / cm ² , with the range between 5 × 10 ¹⁶ to 7 × 10 ¹⁷ ions / cm ^{2 being} preferred. For such an optimal dose, the silver content is in the range of 90 to 1000 mg / m ² .

Under The above conditions of FCVA can not be closed Form metal layer in the substrate. The so-called clustering and others Processes leading to the agglomeration of silver or other metals or lead to the formation of nanoclusters are due to the unfavorable Conditions for nucleation and growth are very unlikely. Therefore, silver is essentially in atomic form. Under certain Process conditions and for but sufficiently high doses can also be used to form nanoscale Cluster or even a closed metal layer come.

The Process temperature must be chosen so that excludes combustion or melting of the substrate becomes. The substrate temperature depends primary From the ionic current, which is typically between 0.1 and 50 A. emotional. This ion streams preferred, which bring the required ion dose in a very short time, without to burn or thermally damage the substrate.

The Presence of macroparticles in the modified layer that a disadvantage of the FCVA in the manufacture of precision layers for optical and electrical applications is within the scope of the applications not critical to this invention. Nevertheless, it is desirable that these particles are at least partially removed because their Number is difficult to control and their presence fluctuates lead in the metal concentration can. The use of a simple, 60 ° or 90 ° bent tube with an axial Magnetic field is sufficient according to the invention. With the possibility, to remove the macroparticles in this or similar way it is not necessary to increase the pressure in the vacuum chamber, which affect the properties of the modified layer could.

One according to the description of the invention surface modified material with a silver FCVA process has self-sterilizing properties and can be stored for long periods of time be applied. Even after performing washing or cleaning procedures the antimicrobial properties are retained.

One according to the description of the invention surface modified material with a silver FCVA process offers prophylactic and therapeutic effects to avoid from infections, it shows anti-inflammatory and anti-allergic effects and promotes healing processes. Corresponding Modified materials are easy in clinical or everyday processes adaptable and safe in the application.

The The present invention can be used in addition to the use for the treatment of soft, flexible and elastic fabrics, yarns, threads or other polymer materials also for surface modification of hard, stiff or other non-flexible structures, fibers or other Polymer materials are used.

The The present invention can also be used for the generation of different biocompatible surface modifications by the combination of suitable, preferably noble, metals also for the generation of intermediate layers can be used. Latter can for example, to improve the interface or the adhesion between substrate material and medical facilities, systems and equipment.

Without the theory of the exact antimicrobial mode of action of the Restrict the invention by silver modified Materi aloberflächen to want, the inventors suspect a complex mechanism of antimicrobial Effect not alone by a simple release of silver ions is caused. Rather, there should also be effects caused by a bond of the silver to polymer chains in the near-surface Area of the material caused to be taken into account become.

It should also be noted that other energetic processes besides FCVA can be applied to similar surface / sub-surface modifications of materia to carry out. An essential feature of the processes is that ions are introduced below the actual surface and thus a near-surface region is modified. Examples of other such processes are beamline ion implantation, plasma immersion ion implantation (PIII), ion beam assisted film deposition (IBAD), etc.

Claims (22)

Substrate material with increased antimicrobial and fungicidal activity, characterized in that (a) the surface area of the substrate material includes a predetermined content of a bactericidal metal which is the active component for realizing the antimicrobial effect; that (b) this bactericidal metal is present mainly in the form of a non-closed layer in the near-surface region of the substrate material; in that (c) the near-surface region of the substrate material enriched in the bactericidal metal is modified by a Filtered Cathodic Vacuum Arc (FCVA) method or alternatively by a method of ion implantation, in particular ions below the actual surface ("sub-surface"). Surface ") are introduced into the polymer material and bound to the molecular structure of the substrate material. Substrate material according to claim 1, characterized that it comes from the group of materials that are woven, knitted or other tissues are for further processing into fabrics, articles of clothing or Packaging materials are used. Substrate material according to claim 1, characterized that it is the shape of a flat substrate having. Substrate material according to claim 1, characterized that it is the form of fibers, threads or yarn or the compound of several individual ones Structures, e.g. twisted, glued or braided. Substrate material according to Claims 1 to 4, characterized that it is woven from natural fibers such as cotton, linen, jute, Silk, sheep's wool, flax and combinations of these materials. Substrate material according to Claims 1 to 4, characterized that it is fabric made of synthetic fibers such as polyethylene, Polycarbonate, Fluorocarbon, Polyester, Acrylics, Modacrylics, Nylon and Combinations of these materials is. Substrate material according to claim 1, characterized that it is plastic additive granules, referred to as so-called biocidal masterbatches in the further production of semi-finished products be used. Substrate material according to Claims 1 to 7, characterized that it is a mixture of natural and synthetic fibers is. Substrate material according to claim 1, characterized that the modified surface layer includes a range of 1 to 500 nm in depth. Substrate material according to claim 1, characterized that the bactericidal metal is a metal the group silver, gold, platinum, palladium, zinc, tin, copper or Combinations of metals of this group is. Method for surface modification of a substrate material according to one of the claims 1 to 10, characterized in that an ion implantation of Silver, gold, platinum, palladium, zinc, tin, copper, antimony or Iodine enters the substrate by following these steps: a) Placing the substrate material in a vacuum chamber; b) evacuation the vacuum chamber; c) providing a jet of mass-selected, accelerated and positively charged ions of the desired element; d) Leading of the ion beam onto the substrate material and suitable scanning of the beam, so that the ionic species in the near-surface layer of the substrate material is incorporated and there forms an implanted layer, the contains at least one of said elements, which to the polymer chains the substrate material is bound. Method according to claim 11, characterized in that the ion beam is a particle energy from 0.5 keV to 100 keV. A method according to claim 11 and 12, characterized in that the necessary for achieving a correspondingly high concentrations of the element ion dose in the range 1 × 10 ¹⁶ to 1 × 10 ¹⁸ cm ² . A method for surface modification of a polymer material according to any one of claims 1 to 10, characterized in that a FCVA treatment with silver, gold, platinum, palladium, zinc, tin, copper, antimony or iodine in the substrate material by carrying out the following steps a) placing the substrate material in a vacuum chamber; b) evacuation of the vacuum chamber; c) providing a plasma jet of accelerated and positively charged ions of the desired element; d) filtering and guiding the plasma jet onto the substrate material and optionally additionally applying a negative potential to the substrate or to a device which serves to hold the substrate, so that the ion species is incorporated into the near-surface layer of the substrate material and forms a modified layer there containing at least one of said elements in atomic form, which is bound to the poly merketten of the substrate material. Method according to claim 14, characterized in that the plasma jet contains ions which have an average kinetic energy of 10 eV to 100 eV. A method according to claim 14 and 15, characterized in that the necessary for achieving a correspondingly high concentrations of the element ion dose in the range 1 × 10 ¹⁶ to 1 × 10 ¹⁸ cm ^-2 . Method according to claim 14, characterized in that the bias voltage is negative and in the range -500 V and -50000 V is. Method according to one of claims 11 to 17, characterized that the substrate material is moved mechanically. Method according to one of claims 14 to 17, characterized that the substrate material is tissue or cloth, which are moved from roll to roll, whereby roll-to-roll, which can also run from air-to-air, bypassing the plasma jet and so will the even treatment the tissue or substances is reached and thus at a possible air-to-air procedure a continuous operation for treatment greater surfaces guaranteed becomes. Method according to one of claims 14 to 17, characterized that it is the substrate material to yarns, threads or Fiber is handled by a roller guide (roll-to-roll), which also from air-to-air, can be guided past the plasma jet and in which by suitable deflection mechanisms, the uniform treatment of Yarns, threads or fibers is achieved and thus in a possible air-to-air process a continuous operation can be realized. Method according to one of claims 14 to 17, characterized in that the substrate material is a plastic additive granulate (so-called biocidal masterbatches), which is characterized by a mechanical Device with appropriate shaking on the plasma jet is passed to achieve a uniform treatment. Method according to one of claims 11 to 17, characterized in that the substrate material is molded parts (preferably from the field of medical technology, hygiene, packaging) or already prefabricated semi-finished products (such as filter materials) or also finished products or parts thereof (such as clothing, toothbrushes, other brushes, Dental floss, surgical instruments, catheters, condoms, feminine hygiene articles) treated by a suitable mechanical device on the ionic or plasma jet are passed to a uniform treatment to reach the operating mode dis continuous (single piece treatment) or in semicontinuous batch mode.