Patent Grant
10143196
The present invention relates to a medical product, in particular a tool or instrument comprising an antibacterial hard material coating applied to a main body.
In accordance with council directive 93/42/EEC of 14 Jun. 1993 concerning medical devices, ‘medical device’ means any instrument, apparatus, appliance, software, material or other article, whether used alone or in combination, including the software intended by its manufacturer to be used specifically for diagnostic and/or therapeutic purposes and necessary for its proper application, intended by the manufacturer to be used for human beings for the purpose of:
Furthermore, in accordance with council directive 93/42/EEC of 14 Jun. 1993 concerning medical devices, ‘accessory’ means an article which whilst not being a device is intended specifically by its manufacturer to be used together with a device to enable it to be used in accordance with the use of the device intended by the manufacturer of the device.
For the purpose of this patent, a ‘medical product comprises both a medical device as well as an accessory according to the definitions of medical device and accessory according to council directive 93/42/EEC of 14 Jun. 1993 concerning medical devices, but also for veterinary applications, yet with the exception of:
Hard materials have a great hardness and high wear resistance. These substances are of great technical importance. Due to their manifold properties and different fields of application it is difficult to find a comprehensive definition for hard materials. The following characteristic properties apply to most hard materials: high degree of hardness, high wear resistance, high melting points, chemical stability, further mechanical properties such as e.g. tensile strength, strain or flexural strength, depend strongly on the type of hard material. This is also valid for electrical conductivity. The properties of hard materials generally correlate closely with the electronic structure of these compounds. Depending on whether metallic or covalent compounds are present, clear differences between metallic and non-metallic hard materials will emerge.
In the context of the present invention, designating a coating as hard material coating takes into account in particular the layer hardness or the hardness of the layer system and a characteristic hardness of at least 1500 HV (hardness according to Vickers) or 17 GPa (Martens hardness).
Reported hardness values were measured according to the Martens hardness testing process using a “Fischerscope H100C”. A Vickers diamond was used as indenter. The Martens hardness testing method is standardized in DIN EN ISO 14577 (metallic materials—instrumented indentation test for hardness and materials parameters). According to this method, during the loading and unloading phase, the force and indentation depth are continuously measured. The Martens hardness is defined as the ratio of the maximum force to the respective contact surface and its value is given using the unit Newton per square millimeter. The Martens hardness HM is calculated on the basis of the measurement values of the force/indentation depth curve when the applied test force is increased, preferably after a determined test force has been reached, and in this case, when using a Vickers diamond as indenter, the following definition is true:
where F is the force [N] and h is the indentation depth under test force [mm].
The hardness definition given can in principle be applied also to thin layers. However, some peculiarities must be taken into account. During penetration of the indenter, a deformation of layer and substrate will usually occur simultaneously. A compound hardness Hc is thus determined, for which the following relation applies:
where Hf, Hs are the layer resp. substrate hardness and Vf, Vs are the deformed layer resp. substrate volume
The deformed substrate volume decreases as the indentation depth of the indenter decreases and thus, the smaller the indentation depth and thus the test force, the closer the determined compound hardness is to the effective layer hardness. When measuring the hardness of layer systems, for indentation depths
where df is the layer thickness
it can generally be assumed (according to the Bückle's rule) that the determined hardness is approximately the same as the layer hardness. In the frame of the present invention, the reported layer hardness values were determined taking into account the Bückle's rule.
The class of adhesiveness was determined according to the Rockwell test. When testing the layer bonding by means of the Rockwell test according to the guidelines 3198 “Coating (CVD, PVD) of cold forging tools” and 3824-4 “Quality assurance of PVD and CVD hard coating—Inspection planning of hard coatings” of the VDI (Association of German Engineers), the size and type of the network of cracks as well as the spalling of the coating in the edge area of an HRC (Rockwell value) indentation are assessed and this allows direct conclusions to be made regarding the adhesive strength according to the schema shown in
A 3-range colorimeter MIKRO COLOR II from the company Dr. Lange, which generates diffuse reflections on the sample surface by means of a xenon flash lamp and then measures them according to the norm DIN 5033, was used as a measuring device for measuring the color of the surface of the layer systems. As reference standard for the calibration, a white standard with standard color values X: 84.6, Y: 89.4 and Z: 91.8 was used. After each color measurement, the color values resulting therefrom were displayed in the display of the colorimeter according to the CIELAB three-dimensional coordinate system (L*a*b), where the a* axis describes the green or red ratio of a color with values from −150 to 100 (negative values for green and positive values for red), the b* axis describes the blue or yellow ratio of a color with values from −100 to 150 (negative values for blue and positive values for yellow) and the L* axis describes the brightness (luminance) of the color with values from 0 to 100.
Nowadays, different products are available on the market which claim to have antibacterial or antimicrobial properties. Attempts are made to provide hygiene and medical products with antibacterial resp. antimicrobial properties, in particular in order to prevent infectious diseases. It is known to use silver and its ions as non-organic biocide for treating materials, which then in the course of time release the biocide they contain, so that the colonization or proliferation of microorganisms on these materials and even in their vicinity is reduced or completely prevented. For this purpose, several antimicrobial silver technologies have been researched and developed to date. Other known non-organic biocides are for example also copper and zinc, which for certain reasons such as for example higher toxicity and less efficient biocide efficacy by comparison with silver, are less in demand for medical technology applications.
The HyProtect™ technology for example allows thin (<200 nm) antimicrobial coatings to be applied on, among others, medical products, said coatings consisting of a combination layer of pure silver deposited by means of a PVD (physical vapor deposition) process and of a silicon oxide layer deposited by means of a CVD (chemical vapor deposition) process. This technology makes it possible to generate especially desired optical and antimicrobial properties on different surfaces, but does not allow a true improvement of the anti-wear protection.
It is also known to use physical and/or chemical and/or plasma assisted chemical coating methods under vacuum, i.e. PVD and/or CVD and/or PACVD (plasma assisted CVD) coating of medical products with hard material layers (such as for example with TiN, CrN and DLC). This generally allows desired optical as well as tribological properties to be achieved on the surface of a medical product. However, these do not exhibit sufficient antimicrobial efficacy.
The applicant has in their product portfolio various coatings that have been developed especially for medical products, in order to impart onto the surface of these medical products specific tribological properties as well as defined optical properties. In addition to an increased wear-resistance and improved friction properties, these coatings achieve in particular defined shining or matt colors.
Examples of layer systems and colors are:
Examples of layer systems and tribological and/or desired optical properties for medical devices are:
Several research projects on PVD and/or CVD and/or PACVD deposition of antimicrobial Ag-containing hard layers (such as for example Ag—TiN, Ag—CrN and Ag-a-C:H) for medical purposes, in particular for coating endoprostheses, have also already been published by different research institutions. In these research projects, it was attempted to research antimicrobial and/or tribological properties as well as in some cases also biocompatibility of the thus formed layer systems, however without taking any account of the optical properties such as color and reflection, which play a very important role for some medical-technical tools and instruments.
Own development projects have shown that silver doping of hard layers, using the example of titanium nitride, can negatively affect critical layer parameters such as adhesive strength, hardness and roughness (see
The aim of the present invention is to improve the disadvantages above described of the state of the art. In particular, a suitable coating for medical products should be provided that yields predetermined antibacterial properties and provides an improvement of the tribological properties already exhibited by the substrate such as for example wear resistance and reduction of the friction. For this, the coating must be mainly able to exhibit sufficient adhesiveness to the main body of the medical product. The corrosion resistance should remain intact or at least decrease only within admissible limits. In doing so, the attempt is preferably made to give the medical products those optical properties that lead to acceptance by the user.
It is in particular an aim of the present invention to achieve such properties on surfaces of said medical products, in particular of tools and instruments, by means of coatings, in particular by means of PVD and/or PACVD coatings.
Furthermore, it is necessary to take into account the fact that the substrate temperature during the coating process should be commensurate to the heat resistance of the substrate material, i.e. the maximum admissible temperature with respect to the substrate material should not be exceeded.
In particular, a temperature of 300° C. should as a rule not be exceeded for the coating of medical products such as for example corresponding instruments and tools due to the commonly used types of substrate, such as for example stainless steel 1.4542.
The aim is achieved according to the invention by means of an antibacterial hard material coating, which is applied to a main body (1) and which comprises biocide. The hard material coating includes at least one inner layer (5) with a thickness d1 of at least 0.2 μm and one outer layer (9) with a thickness d2 of at least 0.5 μm. The inner layer (5) is arranged between the outer layer and the main body (1) and the outer layer (9) contains a biocide concentration bcI greater than or equal to 2 at % and that is substantially constant throughout the entire layer thickness. Indications relating to the biocide concentration in the context of this description always refer to an average over at least 20 nm depth. The inner layer (5) has a biocide concentration with a maximum value bcII greater than or equal to 0.2 at %. The biocide concentration of the inner layer (5) over its entire layer thickness is smaller than the substantially constant biocide concentration bcI of the outer layer (9). The silver concentration in the inner layer (5) along its layer thickness can vary and increase especially in the direction from the main body (1) to the outer layer (9). The layer system designed according to the invention thus exhibits an improved adhesiveness to the substrate as compared with a layer system without the inventive inner layer.
The invention will hereinafter be explained in more detail on the basis of examples, with reference to the figures shown. The figures show:
Different PVD coating methods were used for the production of silver doped TiN layers.
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.
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
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.
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.
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.
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
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
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2011/002405 | 5/16/2011 | WO | 00 | 5/17/2013 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2012/003899 | 1/12/2012 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 6333093 | Burrell | Dec 2001 | B1 |
| 8029917 | Spain | Oct 2011 | B2 |
| 20040117007 | Whitbourne et al. | Jun 2004 | A1 |
| 20110104477 | Wagener | May 2011 | A1 |
| Number | Date | Country |
|---|---|---|
| 10 2005 044 361 | Mar 2007 | DE |
| 10 2008 001 014 | Oct 2009 | DE |
| 0217984 | Mar 2002 | WO |
| 2005065603 | Jul 2005 | WO |
| 2007028645 | Mar 2007 | WO |
| Entry |
|---|
| Kelly, P. J. et al. “A study of the antimicrobial and tribological properties of TiN/Ag nanocomposite coatings” Surface & Coatings Technology, 2009, v. 204, 1137-1140. |
| International Search Report for PCT/EP2011/002405 dated Oct. 27, 2011. |
| Number | Date | Country | |
|---|---|---|---|
| 20130224274 A1 | Aug 2013 | US |
| Number | Date | Country | |
|---|---|---|---|
| 61362888 | Jul 2010 | US |
