Antibacterial medical product and method for producing same

Abstract

The present invention relates to a medical product, comprising an antibacterial hard material coating, which is applied to a main body and which comprises biocide. Said hard material coating includes at least one inner layer and one outer layer, wherein the biocide concentration in the outer layer is substantially constant and greater than the biocide concentration in the inner layer and the biocide concentration in the inner layer is greater than or equal to 0.2 at %.

Claims

1. A method of applying a hard material coating on a main body of a medical product by a physical vapor deposition process, comprising first depositing a biocide-free material applied from a first target via arc ion plating onto the main body, and then depositing a biocide-containing material applied from a second target via magnetron sputter ion plating onto the biocide-free material, wherein the method is conducted at a temperature of less than or equal to 300 C.

2. The method of claim 1, wherein the method is conducted in an atmosphere comprising argon and nitrogen.

3. The method of claim 1, wherein the method is conducted at a pressure of 0.02 mbar.

4. The method of claim 1, further comprising depositing a bonding layer via arc ion plating on the main body prior to deposition of the hard material coating.

5. The method of claim 4, wherein the bonding layer has a thickness of less than or equal to 0.3 m.

6. The method of claim 1, wherein the main body is subjected to mechanical or electro-chemical treatment prior to deposition of the hard material coating.

7. The method of claim 1, wherein the hard material coating comprises an inner layer and an outer layer, wherein the inner layer is between the outer layer and the main body, the outer layer has a biocide concentration (bcI) of 2 at % to 15 at %, and the inner layer has a biocide concentration (bcII) that is greater than or equal to 0.2 at % and less than bcI.

8. The method according to claim 7, wherein bcI and bcII are controlled by varying an arc current of the first target and/or by varying a sputtering power of the second target.

9. The method of claim 7, wherein the outer layer is subjected to polishing, wet blasting, and/or lapping.

10. The method of claim 1, the first target comprising titanium.

11. The method of claim 1, the second target comprising silver.

12. The method according to claim 1, wherein the hard material coating being applied comprises both biocide-free material applied from the first target via arc ion plating and biocide-containing material applied from the second target via magnetron sputter ion plating, wherein a biocide concentration in the hard material coating is controlled by varying an arc current applied to the first target and/or by varying a sputtering power applied to the second target.

13. The method according to claim 12, wherein the biocide in the biocide-containing material applied from the second target is silver.

Description

DESCRIPTION OF THE INVENTION

(1) The invention will hereinafter be explained in more detail on the basis of examples, with reference to the figures shown. The figures show:

(2) FIG. 1a: behavior: adhesive strength vs. concentration of silver of Ag/TiN layer systems without inventive integrated inner layer deposited on polished (Ra: 0.05 m) alloyed cold work steel 1.2842.

(3) FIG. 1b: diagrammatic representation of the classes of adhesive strength

(4) FIG. 2: behavior: Martens hardness vs. concentration of silver of Ag/TiN layer systems deposited on polished (Ra: 0.05 m) alloyed cold work steel 1.2842

(5) FIG. 3: behavior: roughness vs. concentration of silver of Ag/TiN layer systems deposited on polished (Ra: 0.05 m) alloyed cold work steel 1.2842

(6) FIG. 4: behavior: optical properties using the example of color values according to the CIELAB system vs. concentration of silver of Ag/TiN layer systems deposited on polished (Ra: 0.05 m) alloyed cold work steel 1.2842

(7) FIG. 5: design by way of example of a coating resp. of a layer system for the inventive production of antibacterial medical products, with: (1) main body (2) mechanical and/or electrochemical preprocessing to increase the adhesive strength (3) bonding layer and/or anti-wear protection layer (5) inventive inner layer comprising biocide (7) intermediate layer comprising biocide with a higher biocide concentration than that of the outer layer (9) outer layer (10) mechanical post-processing such as e.g. polishing for reducing the roughness

(8) FIG. 6: arrangement by way of example of a coating facility for the inventive production of antibacterial medical products.

(9) Different PVD coating methods were used for the production of silver doped TiN layers.

Example 1

(10) By means of a combined arc/sputter process resp. of a hybrid AIP+MSIP process, silver doped TiN layer systems resp. Ag/TiN layer systems were produced. FIG. 6 illustrates diagrammatically an arrangement of a vacuum coating facility 701, wherein the layer systems with biocide effect were deposited onto the main body of medical products and/or test bodies. Separate titanium targets 703, 703, 703, 703 and silver targets 705, 705 were used as material source. Layer systems with different silver concentrations were produced by varying the arc current at the Ti targets 703, 703, 703, 703, the sputter performance at the Ag targets 705, 705 and the bias voltage at the substrate. It would furthermore be possible to vary the silver concentration by varying the number of the active titanium and/or silver targets. The Ag/TiN layers were deposited under controlled pressure in Ar/N.sub.2 atmosphere at a process pressure of 0.02 mbar. The substrates were placed during the coating in a carrousel arrangement 707 with double and triple rotation. The speed of rotation of the substrates was maintained constant. After corresponding heating and etching processes in the vacuum coating chamber, a very thin bonding layer of TiN (thickness 0.3 m) was deposited by means of the AIP technique onto the surface of the test bodies or medical products of different steel grades and also of hard metal and then the Ag/TiN layer was deposited by means of a combination of AIP and MSIP techniques with constant process parameters, as described above. FIGS. 1 to 4 illustrate the influence of the silver concentration on the hardness, roughness and optical properties that were deposited with different Ag sputter performances and otherwise identical process parameters. It could be established (as represented in FIG. 1a) that at increased silver concentrations, the adhesiveness deteriorates considerably.

(11) The inventors have observed that by including an inner layer 5 between the main body 1 and the outer layer 9 provided with an increased concentration of silver, as represented in FIG. 5, the adhesive strength of Ag/Ti layer systems with increased silver content can be significantly improved.

(12) This also applies when an intermediate layer 7 is provided between the inner layer 5 and the outer layer 9 and which has an increased concentration as compared with the outer layer 9 and can serve as a reservoir of silver for the outer layer 9.

(13) Additionally, a bonding layer 3 or anti-wear protection layer 3 can be provided between the main body 1 and the inner layer 5, which increases the adhesiveness even more.

(14) As the above example shows, it was possible by means of the inventive sequence of layers and of the method to clearly improve the adhesive strength of the layers with increased silver content. A further possibility according to the following example 2 consists in integrating the biocide in DLC layers. Starting from the substrate, for example a bonding layer, for example chromium, is applied. Subsequently a DLC layer is deposited by means of PACVD and simultaneously the silver target is activated. Here too, only little silver is first incorporated for example by means of a low sputter performance. The concentration is then increased, for example by increasing the sputter power whilst the coating parameters otherwise remain the same. At the end, the silver concentration is kept constantly high during the coating, in order to produce the outer layer with constant biocide concentration. Again, an inventive layer was generated with improved adhesive properties as compared with the state of the art.

(15) The question then arises as to how the concentration value of the biocide can be limited. One would actually expect that the higher the biocide concentration is, the better the effect would be. However, surprisingly, the measurements performed by the inventors contradict this. Additionally, from a concentration greater than 15a5%, the hardness of the layer, as represented in FIG. 2, decreases drastically and, as illustrated in FIG. 4, the color appearance varies greatly. It is thus proposed to use biocide concentrations of up to 15a5%, preferably of up to 13 at %.

(16) It can happen that when incorporating silver, the surface of the coated product, in particular medical product, will exhibit increased roughness, as represented for example in FIG. 3. The inventors have observed that increased roughness leads to a reduction of the biocide effect. This can be prevented in that the surface is subjected to a post-processing, in particular a mechanical post-processing such as polishing, wet blasting or lapping or a suitable chemical polishing. Due to the constancy of the biocide concentration in the outer layer, this post-processing will essentially no affect the biocide effect when the medical product is used.