Plasmapolymeric solid, corresponding uses and corresponding methods

Abstract

The present invention relates to a plasmapolymeric solid, in particular a plasmapolymeric layer, having a specified ratio of the sum of monofunctional and difunctional oxygen components of the Si2p peak of the XPS signal relative to the sum of trifunctional and tetrafunctional oxygen components of the Si2p peak of the XPS signal.

Description

[0001] Plasma polymer solid, corresponding uses and corresponding processes

[0002] The present invention relates to a plasma polymer solid, in particular a plasma polymer layer, with a specified ratio of the sum of monofunctional and difunctional oxygen fractions of the Si2p peak of the XPS signal to the sum of trifunctional and tetrafunctional oxygen fractions of the Si2p peak of the XPS signal.

[0003] The present invention also relates to corresponding uses. The present invention also relates to corresponding methods.

[0004] The present invention relates to the technical field of plasma-polymer release and easy-to-clean coatings based on siloxane chemistry. In the prior art, document DE10131156A1 discloses an article comprising a substrate and a plasma-polymer coating comprising oxygen, carbon, and silicon, bonded to the substrate over its entire surface. The molar ratios in the plasma-polymer coating on the side facing away from the substrate are as follows: 1.1:1 < n(O) : n(Si) < 2.6:1 0.6:1 < n(C) : n(Si) < 2.2:1. This describes an easy-to-clean layer with a defined composition. The surface energy is specified as being in the range from 24 mN / m to 30 mN / m, and the Young's modulus is approximately 7.9 GPa. The document describes a wide range of molar ratios. In addition, the coating defined in DE10131156A1 is characterized by a water contact angle of at least 90°; the surfaces described therein are hydrophobic.The document contains no reference to particularly hard layers, i.e., layers with a high modulus of elasticity, or their production. From the examples in the document, gas flow ratios of HMDSO to O2 in the range of < 1:2 are known. These gas flow ratios provide the skilled person with a clearer indication of SiO2-like bonding relationships in the disclosed layer due to the higher oxygen content relative to Si.

[0005] Document WO2015 / 044247 discloses a plasma polymer solid, in particular a plasma polymer layer, wherein the lower limit of the E-modulus of the coating is determined by the following function: E=25-31.5*x+13.5*x2 -1.85*x3 with x = C / O ratio determined by means of XPS, E = E-modulus [GPa] for E > 1.25 GPa and x > 0.5 < 2.0, wherein on the surface of the layer measured by means of XPS for the maximum of the Si 2p peak applies: for E-modulus < 10 GPa: 102.5 - 102.8 eV for E-modulus 10-20 GPa: 102.7 - 103.1 eV and preferably for E-modulus > 20 GPa: > 103.0 eV.

[0006] This paper describes a plasma polymer coating with Young's moduli of up to 30 GPa, as well as a specific relationship between the maximum polar component of the surface energy and the Young's modulus. The document describes a wide range of molar ratios. It also shows that high oxygen fluxes and high plasma powers lead to high Young's moduli, since under these conditions the C / O ratio is less than 1 and the Si2p band lies at values ​​> 103.0 eV.

[0007] Document DE102017131085A1 discloses a plasma polymer solid, in particular a plasma polymer layer, wherein the lower limit of the elastic modulus of the solid is determined by the following function (1): E = 2172.85 - 4716.04 ■ x + 3854.96 ■ x2 - 1405.04 x3+192.54 ■ x4 with x = C / O molar ratio determined by XPS, E = elastic modulus [GPa] for E = 1.5 to 20 GPa and x > 1.3 and < 2.0. The document does not disclose any plasma polymer separating layers with an elastic modulus of more than 20 GPa. For the layers described, a C / O ratio of 1.3 to 2.0 is disclosed, wherein high elastic moduli are linked to small C / O ratios. Document W02010 / 125178A1 discloses a method for coating the surface of a metal substrate, comprising the following steps: A. Providing the metal substrate and, if appropriate, cleaning the substrate surface to be coated, B.Coating the substrate surface, optionally cleaned in step A, in a plasma polymerization reactor by means of plasma polymerization, wherein in step B one or more organosilicon compounds and (a) no further compounds or (b) further compounds are used as precursor(s) for the plasma, and in step B the metal substrate is arranged in the plasma polymerization reactor such that it is connected as a cathode, characterized in that the process is carried out such that the coating produced by the process has an elongation to microcrack of > 1.5%, a yellow index determined according to ASTM D 1925 of < 4, and a hardness to be measured by means of nanoindentation in the range from 2.5 to 10 GPa, with the proviso that the metal substrate is not a light metal substrate and with the proviso that in the case of an elongation to microcrack of the coating of < 2.2%, the hardness to be measured by means of nanoindentation is > 6 GPa.

[0008] Document EP0748259B1 discloses an abrasion-resistant coated substrate product obtainable by a specified process, comprising a substrate and an abrasion-resistant coating material containing carbon, hydrogen, silicon, and oxygen; wherein the abrasion-resistant coating material has the properties of a nano-penetration hardness in the range of approximately 2 to 5 GPa and an elongation to microcrack of greater than approximately 1%.

[0009] The technical article "Effect of self-bias voltage on the wettability, chemical functionality and nanomechanical properties of hexamethyldisiloxane films" by Albuquerque, Santos, Perdone, and Simao, published in "Thin Solid Films," Volume 564, 2014, pp. 73-78, doi: 10.1016 / j.tsf.2O14.05.012, discloses a parallel plate structure in which the anode has a slightly larger surface area than the cathode, allowing self-bias to develop during the plasma process. Details on the type of process control and the system design are not disclosed. O2 is apparently not actively added to the gas flow. According to the technical article, samples were placed on the cathode and the anode for coating, and significant differences were observed between the two coating locations even in the IR spectrum. The resulting surface roughness and the Young's modulus determined using nanoindentation tests also differ significantly depending on the coating location.Values ​​ranging from 44.0 to over 158 GPa were determined on the anode, while values ​​in the range of 1 GPa were determined on the cathode. A conclusive explanation for this different behavior is not given. All surfaces are highly hydrophobic and differ little in this criterion. The scientific article "RF-PACVD of water repellent and protective HMDSO coatings on bell metal surfaces: Correlation between discharge parameters and film properties" by the authors Choudhury, Barve, Chutia, Pal, Kishore, Jagannath, Pande and Patil appeared in "Applied Surface Science", 257, 2011 , 8469 - 8477, doi:10.1016 / j.apsusc.2011 .04.134 discloses a plasma reactor and the relationship between plasma power and self-bias. It was found that the plasma potential decreases with power. A person skilled in the art would expect the opposite behavior. The document discloses investigations of layer compositions with XPS as a function of self-bias.The carbon content of the investigated layers is a maximum of 15 at-% and decreases with higher self-bias.

[0010] The document also discloses a peak fitting of the Si 2p peak in the XPS spectrum. Secondary (D), tertiary (T), and quaternary (Q) Si structures were considered. Primary structures were not fitted. The fitting was performed under varying conditions. Furthermore, it is not clear how and with which device the disclosed XPS measurements were performed. Reference data and information on whether (and if so, how) the energy level was corrected for charging effects are not disclosed. The Young's modulus was determined using nanoindentation and was found to be a maximum of 5 GPa (despite the low carbon content).

[0011] The technical article "Deposition, Characterization, and Application of Plasma-Polymer Layers Based on HMDSO" by Jacoby, Bock, Haupt, Hilgers, Kopnarski, Molter, Oehr, Rühle, and Wahl, published in "Vakuum in Forschung und Praxis" (Vacuum in Research and Practice), doi: 10.1002 / vipr.200600289, discloses a parallel-plate reactor with a symmetrical design (zero-bias condition). Many details regarding the design and procedure, such as information on the plasma potential, are missing.

[0012] HMDSO and O2 are used as working gases. Both gases are used in excess oxygen in ratios ranging from 1:3 to 1:22, with HMDSO always being added at 10 sccm, resulting in varying total flows (40 to 230 sccm). This also significantly changes the residence time in the plasma region, as does the energy supplied per molecule. Information on the Young's modulus or even the hardness is missing.

[0013] The current state of the art shows that no conclusions about the coating properties can be drawn based on the atomic composition of a layer alone, since the interconnection of the layer system is crucial for many properties (e.g., mechanical strength, solubility, refractive index, etc.). Consequently, a layer composition must always be linked to a layer property. Therefore, producing a layer with specific properties requires detailed knowledge of the specific deposition conditions.

[0014] The current state of the art indicates a need for hard and resistant release coatings or easy-to-clean coatings, particularly release coatings and easy-to-clean coatings that eliminate the need for additional release agents. Release coatings or easy-to-clean coatings are particularly suitable for release coatings for thermoplastic processing in injection molding (e.g., to suppress deposit formation) and release coatings for casting processes (e.g., zinc, aluminum, and magnesium die casting).

[0015] In thermoplastic injection molding, the plasticized mass, which may contain fillers, exerts particularly strong shear stresses on the release coatings used. When processing molten metals, however, the metallic liquid is injected turbulently and at high speed and solidifies in the mold. In both cases, temperature-induced volume changes in the respective molded part also create strong local frictional forces, which lead to undesirably high wear in the known release coatings or easy-to-clean coatings.

[0016] There is also a need for release coatings or easy-to-clean coatings that are suitable for use with food, in particular for release coatings or easy-to-clean coatings that are suitable for use in the home. There is also a need for release coatings or easy-to-clean coatings that are free of per- and polyfluorinated chemicals (PFAS), preferably even completely free of fluorine, and that also meet the requirements for stirring and cutting resistance (whisks, knives, or spatulas) in the technical field under consideration. The use of per- and polyfluorinated chemicals (PFAS) is increasingly viewed as problematic in the field of the present invention and is therefore undesirable.

[0017] There is also a need for release coatings or easy-to-clean coatings that exhibit the lowest possible cracking and maintain the best possible adhesion to the substrate when exposed to temperature-related and / or torsional and / or vibration-related movements of the coated substrate. The state of the art also indicates a need for release coatings or easy-to-clean coatings with a hydrophobic surface.

[0018] As many of the aforementioned needs as possible are to be met in whole or in part, preferably in combination with one another. The invention is defined in the appended claims. Preferred aspects of the present invention will become apparent from the following description, including the examples. To the extent that certain embodiments are designated as preferred for an aspect of the invention (plasma polymer solid, use of a plasma polymer solid, in particular a plasma polymer layer, and method for producing a plasma polymer solid, in particular a plasma polymer coating), the corresponding statements also apply to the other aspects of the present invention, mutatis mutandis.Preferred individual features of aspects of the invention (as defined in the claims and / or disclosed in the description) can be combined with one another and are preferably combined with one another, unless otherwise apparent to the person skilled in the art from the present text in the individual case.

[0019] Likewise, the disadvantages of the prior art mentioned above also apply to the other aspects of the present invention; the considerations set out above regarding various tasks apply accordingly.

[0020] According to a primary aspect of the present invention, the above-mentioned tasks and problems are solved in whole or in part by a plasma polymer solid, in particular plasma polymer layer, wherein in the plasma polymer solid, in particular in the plasma polymer layer, a ratio of

[0021] - Sum of monofunctional and difunctional oxygen fractions of the Si2p peak of the XPS signal determined according to Example 2 to the

[0022] Sum of trifunctional and tetrafunctional oxygen components of the

[0023] Si2p peaks of the XPS signal determined according to Example 2 are from 0.25 to 0.70, preferably from 0.35 to 0.65, particularly preferably from 0.45 to 0.65.

[0024] In organosilicon, well-crosslinked, PDMS-like (polydimethylsiloxane-like) plasma polymer solids, particularly plasma polymer layers, crosslinking is controlled by adding oxygen to the plasma discharge and by varying the power coupled into the plasma. Such plasma polymer solids, particularly plasma polymer layers, can in principle crosslink via four structural groups. A high proportion of secondary silicon structural elements, i.e., silicon structural elements in which two oxygen atoms are arranged around one silicon atom, is typically present, whereas quaternary structures, i.e., structures in which silicon is completely surrounded by oxygen atoms, occur only to a very small extent. The corresponding structural elements are known to those skilled in the art from the prior art.

[0025] The sum of monofunctional and difunctional oxygen fractions of the Si2p peak of the XPS signal should be determined according to the procedure given in Example 2; in case of doubt, the prior art documents cited in Example 2 should be consulted.

[0026] The sum of trifunctional and tetrafunctional oxygen fractions of the Si2p peak of the XPS signal should be determined according to the procedure given in Example 2; in case of doubt, the prior art documents cited in Example 2 should be consulted.

[0027] The plasma polymer solids according to the invention, in particular the plasma polymer layers according to the invention, with a ratio of

[0028] - Sum of monofunctional and difunctional oxygen fractions of the Si2p peak of the XPS signal determined according to Example 2 to the

[0029] The sum of trifunctional and tetrafunctional oxygen fractions of the Si2p peak of the XPS signal determined according to Example 2 is from 0.25 to 0.70, preferably from 0.35 to 0.65, particularly preferably from 0.45 to 0.65; have particularly positive combinations of properties that are particularly preferred in the field of the present invention.

[0030] The above-mentioned needs are advantageously met by the properties and combinations of properties of the plasma polymer solids according to the invention, in particular the plasma polymer layers according to the invention.

[0031] The plasma polymer solids according to the invention, in particular the plasma polymer layers according to the invention, also have a particularly advantageous combination of advantageously high resistance and advantageously good hydrophobic properties of the surface.

[0032] The plasma polymer solids according to the invention, in particular the plasma polymer layers according to the invention, are often designed as release coatings or easy-to-clean coatings, preferably as release coatings or easy-to-clean coatings without the use of additional release agents when using these release coatings or easy-to-clean coatings. When using the plasma polymer solids according to the invention, in particular the plasma polymer layers according to the invention as release coatings or easy-to-clean coatings, the use of fluorine, in particular per- and polyfluorinated chemicals (PFAS), is avoided.

[0033] In many cases in which the plasma polymer solids according to the invention, in particular the plasma polymer layers according to the invention, are formed as release coatings or easy-to-clean coatings, the above-mentioned properties, preferably the above-mentioned combinations of properties, are also combined with a particularly low tendency to crack formation in the event of temperature-related and / or torsion-related and / or vibration-related movements of the substrate coated therewith and particularly good adhesion to the surface of a substrate coated therewith, in the event of temperature-related and / or torsion-related and / or vibration-related movements of the substrate coated therewith.

[0034] Preferred is a plasma polymer solid (as described above, preferably as referred to above as preferred), in particular a plasma polymer layer (as described above, preferably as referred to above as preferred), wherein the plasma polymer solid, in particular the plasma polymer layer, has a modulus of elasticity, determined by means of the surface acoustic waves method according to the procedure in Example 4, in the range of 30 GPa to 45 GPa; and / or a surface energy, determined on the surface of the plasma polymer solid or the plasma polymer layer by means of contact angle measurement according to the procedure in Example 3, in the range of 24 mN / m to 38 mN / m.

[0035] In the context of the present invention, the determination of the modulus of elasticity is carried out using the surface acoustic waves method according to the procedure described in Example 4.

[0036] In many cases, plasma polymer solids according to the invention, in particular plasma polymer layers according to the invention, with a modulus of elasticity in the above-defined range, exhibit a particularly advantageously low tendency to crack formation during temperature-induced and / or torsion-induced and / or vibration-induced movements of a substrate coated therewith. The further advantageous properties of the plasma polymer solids according to the invention, in particular plasma polymer layers according to the invention, are realized here to a preferred extent in combination with the advantageously low tendency to crack formation. The above combinations of properties are particularly preferred when the plasma polymer solid according to the invention, in particular the plasma polymer layer according to the invention, is designed as a release coating or easy-to-clean coating.

[0037] In many cases, plasma polymer solids according to the invention, in particular plasma polymer layers according to the invention, with a modulus of elasticity in the above-defined range, exhibit particularly advantageously good adhesion to the surface of a substrate coated therewith during temperature-induced and / or torsion-induced and / or vibration-induced movements of the substrate coated therewith. This is particularly true if a fine cleaning of the surface to be coated takes place beforehand (as is known in the art in the field of the present invention) and an adhesion promoter layer (as is known in the art in the field of the present invention) is used.Gradient layers are particularly preferably constructed as adhesion promoters, which are designed such that the modulus of elasticity on the side of the gradient layer facing the substrate has a higher value than on the functional side; corresponding gradient layers and their production are known to those skilled in the art. The further advantageous properties of the plasma polymer solids according to the invention, in particular plasma polymer layers according to the invention, are realized to a preferred extent here in combination with the advantageously good adhesion to the surface of a substrate coated therewith. The above combinations of properties are particularly preferred when the plasma polymer solid according to the invention, in particular the plasma polymer layer according to the invention, is designed as a release coating or easy-to-clean coating.

[0038] Release coatings or easy-to-clean coatings are known to those skilled in the art in the field of the present invention.

[0039] In the context of the present invention, the surface energy is determined by means of contact angle measurement according to the procedure described in Example 3 of the present text.

[0040] In many cases, plasma polymer solids according to the invention, in particular plasma polymer layers according to the invention, with a surface energy in the above-defined range, exhibit particularly advantageous hydrophobic (water-repellent) properties. The further advantageous properties of the plasma polymer solids according to the invention, in particular plasma polymer layers according to the invention, are realized here to a preferred extent in combination with the particularly advantageous good hydrophobic properties. The above property combinations are particularly preferred when the plasma polymer solid according to the invention, in particular the plasma polymer layer according to the invention, is designed as a release coating or easy-to-clean coating.

[0041] Preferred is a plasma polymer solid (as described above, preferably as referred to above as preferred), in particular a plasma polymer layer (as described above, preferably as referred to above as preferred), wherein the plasma polymer solid, in particular the plasma polymer layer, has a modulus of elasticity, determined by means of the surface acoustic waves method according to the procedure in Example 4, in the range of 30 GPa to 45 GPa; and a surface energy, determined on the surface of the plasma polymer solid or the plasma polymer layer by means of contact angle measurement according to the procedure in Example 3, in the range of 24 mN / m to 38 mN / m.

[0042] The advantageous properties and property combinations described above with regard to the corresponding Young's modulus and with regard to the corresponding surface energy are realized here in combination with one another.

[0043] Preferred is a plasma polymer solid (as described above, preferably as referred to above as preferred), in particular a plasma polymer layer (as described above, preferably as referred to above as preferred), wherein the plasma polymer solid, in particular the plasma polymer layer, has a Mohs hardness, determined according to the procedure in Example 5, of at least 4.5, preferably of at least 5.5; and / or, preferably “and” a mass density, determined by means of the surface acoustic waves method according to Example 4, of at least 1.4 g / cm 3 preferably at least 1.5 g / cm 3 .

[0044] In the context of the present invention, the Mohs hardness is determined using a test kit according to the procedure described in Example 5 of the present text.

[0045] Plasma polymer solids according to the invention, in particular plasma polymer layers according to the invention, with a Mohs hardness in the above-defined range, exhibit a resistance to stirring and cutting that is perceived as particularly advantageous in the field of the present invention. Plasma polymer solids according to the invention, in particular plasma polymer layers according to the invention, with a Mohs hardness in the above-defined range, exhibit a resistance to the forces acting on a release layer in the thermoplastic injection molding sector that is perceived as particularly advantageous in the field of the present invention. The above combinations of properties are particularly preferred when the plasma polymer solid according to the invention, in particular the plasma polymer layer according to the invention, is designed as a release coating or easy-to-clean coating.

[0046] When using plasma polymer solids according to the invention, in particular plasma polymer layers according to the invention, with a Mohs hardness in the above-defined range as a release layer in the thermoplastic injection molding sector, a particularly advantageously long service life (i.e., a high number of injection molding operations without the release layer being damaged to an unacceptable extent) of the corresponding release layer is achieved in combination with the other positive properties of the plasma polymer solids according to the invention, in particular the plasma polymer layers according to the invention. The above property combinations are particularly preferred when the plasma polymer solid according to the invention, in particular the plasma polymer layer according to the invention, is designed as a release coating or easy-to-clean coating.

[0047] In the context of the present invention, the mass density is determined using the surface acoustic waves method according to the procedure described in Example 4 of the present text.

[0048] Plasma polymer solids according to the invention, in particular plasma polymer layers according to the invention, with mass densities in the above-defined range have in many cases particularly advantageous properties, preferably combinations of properties.

[0049] In addition, the other advantageous properties, preferably advantageous combinations of properties, of the plasma polymer solid according to the invention, in particular of the plasma polymer layer according to the invention, are also realized here to a particularly preferred extent.

[0050] Preference is given to a plasma polymer solid body (as described above, preferably as referred to above as preferred), in particular a plasma polymer layer (as described above, preferably as referred to above as preferred), having a polar portion of the surface energy, determined on the surface of the plasma polymer solid body or the plasma polymer layer according to the procedure in Example 3, of less than 4.0 mN / m, preferably of less than 3.0 mN / m, particularly preferably of less than 2.5 mN / m, most particularly preferably of less than 2 mN / m.

[0051] In the context of the present invention, the polar component of the surface energy is determined by means of contact angle measurement according to the procedure described in Example 3 of the present text.

[0052] In many cases, plasma polymer solids according to the invention, in particular plasma polymer layers according to the invention, with a polar component of the surface energy in the above-defined range, very particularly advantageously have good hydrophobic properties, in particular in combination with a surface energy as defined above. The further advantageous properties of the plasma polymer solids according to the invention, in particular plasma polymer layers according to the invention, are realized here to a preferred extent in combination with the very particularly advantageous good hydrophobic properties. The above property combinations are particularly preferred when the plasma polymer solid according to the invention, in particular the plasma polymer layer according to the invention, is designed as a release coating or easy-to-clean coating.

[0053] In addition, the other advantageous properties, preferably advantageous combinations of properties, of the plasma polymer solid according to the invention, in particular of the plasma polymer layer according to the invention, are also realized here to a particularly preferred extent.

[0054] Preferred is a plasma polymer solid (as described above, preferably as referred to above as preferred), in particular a plasma polymer layer (as described above, preferably as referred to above as preferred), wherein in the XPS spectrum the Si 2p photoline lies at an energy of less than 103.0 eV, preferably less than 102.8 eV, particularly preferably less than 102.6 eV; and wherein in the XPS spectrum the Si 2p photoline lies at an energy of more than 102.2 eV; and wherein the half-width of the Si 2p photoline, determined according to Example 2, lies between 1.8 and 2.5 eV, preferably between 2.0 and 2.3 eV.

[0055] A plasma-polymer solid, in particular a plasma-polymer layer, with a silicon 2p photoline in the XPS spectrum (measured according to the procedure described in Example 2 of this text) at an energy in the ranges described above and with a half-width of the Si 2p photoline in the XPS spectrum (measured according to the procedure described in Example 2 of this text) in many cases exhibits a particularly advantageous combination of an advantageous Young's modulus and an advantageous polar component of the surface energy. In particular, the advantageous properties and property combinations described above in connection with an advantageous Young's modulus and an advantageous polar component of the surface energy are also realized here in many cases in a particularly positive manner, preferably in combination with one another.

[0056] Here too, the other advantageous properties, preferably advantageous combinations of properties, of the plasma polymer solid according to the invention, in particular of the plasma polymer layer according to the invention, are realized to a particularly preferred extent.

[0057] Preference is given to a plasma polymer solid (as described above, preferably as referred to above as preferred), in particular a plasma polymer layer (as described above, preferably as referred to above as preferred), wherein the molar ratio of O to Si near the surface of the plasma polymer solid or the plasma polymer layer, measured by means of XPS according to Example 2-1 at a measurement angle to the sample normal of 0°, and / or, preferably “and” measured by means of XPS according to Example 2-2 at a measurement angle to the sample normal of 75°, is in the range from 1.05 to 1.50, preferably in the range from 1.10 to 1.40, particularly preferably in the range from 1.13 to 1.35, very particularly preferably in the range from 1.17 to 1.30; and / or, preferably “and” the molar ratio of C to Si near the surface of the plasma polymer solid orof the plasma polymer layer, measured by means of XPS according to Example 2-1 at a measuring angle to the sample normal of 0°, and / or, preferably “and” measured by means of XPS according to Example 2-2 at a measuring angle to the sample normal of 75°, is in the range from 1.00 to 1.80, preferably in the range from 1.10 to 1.50, particularly preferably in the range from 1.10 to 1.30.

[0058] The molar ratio of O to Si near the surface measured by XPS according to Example 2-1 at a measuring angle to the sample normal of 0° means that the resulting information of the XPS spectrum originates from a range of approximately 0 nm to approximately 10 nm below the examined surface of the examined sample body.

[0059] The molar ratio of O to Si near the surface measured by XPS according to Example 2-2 at a measuring angle to the sample normal of 75° means that the resulting information of the XPS spectrum originates from a range of approximately 0 nm to approximately 2.6 nm below the examined surface of the examined sample body.

[0060] In many cases, it is particularly advantageous to minimize the deviation of the measured molar ratio of O to Si on a plasma-polymer solid, particularly a plasma-polymer layer, at a measurement angle of 0° to the sample normal on the one hand and a measurement angle of 75° to the sample normal on the other. Such layers are particularly homogeneous in composition, particularly with regard to their near-surface chemical composition (composition depending on the distance from the surface), and therefore often exhibit particularly positively homogeneous surface properties. Furthermore, in such layers, the properties are often only altered to a beneficially small extent, even upon mechanical wear of the layer.In the field of the present invention, this leads in many cases to particularly advantageously long-lasting plasma polymer solids, in particular plasma polymer layers, in particular when the plasma polymer solids, in particular plasma polymer layers, are designed as release coatings or easy-to-clean coatings.

[0061] The molar ratio of C to Si near the surface measured by XPS according to Example 2-1 at a measuring angle to the sample normal of 0° means that the resulting information of the XPS spectrum originates from a range of approximately 0 nm to approximately 10 nm below the examined surface of the examined sample body.

[0062] The molar ratio of C to Si near the surface measured by XPS according to Example 2-2 at a measuring angle to the sample normal of 75° means that the resulting information of the XPS spectrum originates from a range of approximately 0 nm to approximately 2.6 nm below the examined surface of the examined sample body.

[0063] In many cases, it is particularly advantageous to minimize the deviation of the C to Si molar ratio measured on a plasma polymer solid, particularly a plasma polymer layer, at a measurement angle of 0° to the sample normal on the one hand and a measurement angle of 75° to the sample normal on the other. Such layers are particularly homogeneous in composition, particularly with regard to their near-surface chemical composition (composition depending on the distance from the surface), and therefore often exhibit particularly positively homogeneous surface properties. Furthermore, in such layers, the properties are often only altered to a beneficially small extent, even upon mechanical wear of the layer.In the field of the present invention, this often leads to particularly advantageously long-lasting plasma polymer solids, in particular plasma polymer layers, especially when the plasma polymer solids, in particular plasma polymer layers, are designed as release coatings or easy-to-clean coatings. With the above-defined molar ratios, the other advantageous properties, preferably advantageous combinations of properties, of the plasma polymer solid according to the invention, in particular of the plasma polymer layer according to the invention, are realized to a particularly preferred extent. In particular, particularly positive combinations of properties of advantageously good elastic modulus and advantageously good polar component of the surface energy are realized in this way.

[0064] Preferred is a plasma polymer solid (as described above, preferably as referred to above as preferred), in particular a plasma polymer layer (as described above, preferably as referred to above as preferred), wherein the molar fraction of O near the surface of the plasma polymer solid or of the plasma polymer layer, measured by means of XPS according to the procedure from Example 2-2, is in the range from 30 at-% to 40 at-%, preferably in the range from 31 at-% to 36 at-%; and / or the molar fraction of Si near the surface of the plasma polymer solid or of the plasma polymer layer, measured by means of XPS according to the procedure from Example 2-2, is in the range from 23 at-% to 28.5 at-%; and / or the molar fraction of C near the surface of the plasma polymer solid orof the plasma polymer layer, measured by XPS according to the procedure of Example 2-2, is in the range of 30 at-% to 45 at-%, preferably in the range of 34 at-% to 44 at-%; and / or the molar fraction of N near the surface of the plasma polymer solid or the plasma polymer layer, measured by XPS according to the procedure of Example 2-2, is 0.1 at-% or less; wherein the percentages are in each case based on the total number of atoms contained in the layer that can be determined by XPS.

[0065] With the above-defined molar ratios, the other advantageous properties, preferably advantageous combinations of properties, of the plasma polymer solid according to the invention, in particular of the plasma polymer layer according to the invention, are realized to a particularly preferred extent.

[0066] Preferred is a plasma polymer solid body (as described above, preferably as referred to above as preferred), in particular a plasma polymer layer (as described above, preferably as referred to above as preferred), wherein the plasma polymer solid body, in particular the plasma polymer layer, has a resistance against

[0067] Fats and oils at temperatures up to 200°C, preferably cooking oils at temperatures up to 200°C, for short periods (< 1 hour) also at temperatures up to 220°C; liquid water up to 100°C;

[0068] Steam up to 120°C; acidic liquids with a pH in the range of pH 2 to pH 4 at 23°C; basic liquids with a pH in the range of pH 11 to pH 12.5 at 23°C;

[0069] Solvents, especially isopropanol, acetone, ethanol, n-heptane, and methyl ethyl ketone at a temperature of 23°C; various blasting processes, such as CO2 cleaning processes and high-pressure water cleaning up to 1000 bar working pressure;

[0070] Cleaning sponges that do not contain particles with a Mohs hardness of more than 3.5, in particular no particles consisting of corundum.

[0071] Preferred is a plasma polymer solid (as described above, preferably as referred to above as preferred), in particular a plasma polymer layer (as described above, preferably as referred to above as preferred), wherein the plasma polymer solid, in particular the plasma polymer layer, has a resistance to liquids with a pH in the range from pH 2 to pH 12.5, in particular also in the range from pH 4 to pH 11.

[0072] Preferred is a plasma polymer solid body according to the invention or a plasma polymer layer according to the invention, wherein the surface energy after contact with a substance (as stated above as preferred and under the above-mentioned specific conditions) does not change to an unacceptable extent, preferably by no more than 25%, based on the respective value before contact with the respective substance, particularly preferably by no more than 20%, based on the respective value before contact with the respective substance, very particularly preferably by no more than 15%, based on the respective value before contact with the respective substance; and / or (preferably “and”) the polar component of the surface energy after contact with a substance (as stated above as preferred and under the above-mentioned specific conditions) is not more than 4.5 mN / m.

[0073] A plasma polymer solid or a plasma polymer layer has a resistance to substances (as stated above) (based on specific conditions such as temperature and exposure time, preferably as described above as preferred) if - the surface energy after contact with a substance (as stated above as preferred and under the above-mentioned specific conditions) does not change to an unacceptable extent, preferably by no more than 25%, based on the respective value before contact with the respective substance, particularly preferably by no more than 20%, based on the respective value before contact with the respective substance, very particularly preferably by no more than 15%, based on the respective value before contact with the respective substance;and / or (preferably "and") the polar component of the surface energy after contact with a substance (as stated above as preferred and under the above-mentioned specific conditions) is not more than 4.5 mN / m. Preferred is a plasma polymer solid (as described above, preferably as referred to above as preferred), in particular a plasma polymer layer (as described above, preferably as referred to above as preferred), wherein the plasma polymer solid, in particular the plasma polymer layer, is dishwasher-safe according to Example 8.;

[0074] The other advantageous properties, preferably advantageous combinations of properties, of the plasma polymer solid according to the invention, in particular of the plasma polymer layer according to the invention, are also realized to a particularly preferred extent in combination with this aspect (dishwasher-resistant in the sense of DIN EN 12875-1:2005-08).

[0075] Preference is given to a plasma polymer solid (as described above, preferably as referred to above as preferred), in particular a plasma polymer layer (as described above, preferably as referred to above as preferred), wherein the plasma polymer solid or the plasma polymer layer has a thickness in the range from 5 nm to 2 pm, preferably a layer thickness in the range from 10 nm to 1 pm, particularly preferably a layer thickness in the range from 20 nm to 0.5 pm; and / or the plasma polymer solid or the plasma polymer layer has hydrophobic groups on its surface, preferably methyl groups; and / or the water contact angle, determined according to the procedure from Example 3, is in the range from 80° to 100°.

[0076] Plasma polymer solids according to the invention, in particular plasma polymer layers according to the invention, with a thickness within the above-defined range are particularly preferred in many cases. Corresponding plasma polymer solids according to the invention, in particular corresponding plasma polymer layers according to the invention, in many cases exhibit particularly positive property combinations of advantageous surface energy and advantageous mechanical properties. A corresponding thickness is particularly preferred when the plasma polymer solid, in particular the plasma polymer layer, is designed as a release coating or easy-to-clean coating.

[0077] Methods for determining the thickness are known to the person skilled in the art from his general technical knowledge.

[0078] In the context of the present invention, the term “hydrophobic groups” refers to chemical groups which, in the field of the present invention, already occur in the prior art on the surfaces of surface coatings known as “hydrophobic”.

[0079] The term “methyl group” refers to a -CH3 group in accordance with the common professional understanding.

[0080] A plasma polymer solid or a plasma polymer layer which has hydrophobic groups on its surface, preferably methyl groups, in many cases has a particularly advantageously low surface energy (determined by contact angle measurement according to the procedure described in Example 3 of the present text) as well as a particularly advantageously low polar component of the surface energy (determined by contact angle measurement according to the procedure described in Example 3 of the present text).

[0081] A water contact angle, determined according to the procedure of Example 3, in the above-defined range of 80° to 100° is particularly preferred in many cases in the field of the present invention, particularly in those cases in which the plasma polymer solid, in particular the plasma polymer layer, is designed as release coatings or easy-to-clean coatings.

[0082] The other advantageous properties, preferably advantageous combinations of properties, of the plasma polymer solid according to the invention, in particular of the plasma polymer layer according to the invention, are also realized here to a particularly preferred extent. The invention also relates to the use of a plasma polymer solid (as described above, preferably as referred to above as preferred), in particular a plasma polymer layer (as described above, preferably as referred to above as preferred), for improving the cleanability, in particular for improving the cleanability of household items such as pans and baking utensils and cooking utensils, of casting molds, in particular casting molds in zinc die-casting, aluminum die-casting, and magnesium die-casting, of injection molds, in particular injection molds in thermoplastic injection molding, of stamps and pressing tools, of dispersing devices,of metal filters for extractor hoods, of cutting tools for gardening, such as pruning shears and lawnmower blades; and / or as a separating layer, in particular as a separating layer for household items such as pans and baking utensils and cooking utensils, for casting molds, in particular zinc die-casting, aluminum die-casting, and magnesium die-casting molds, for injection molds, in particular thermoplastic injection molding, for stamps and pressing tools, and for dispersing devices; and / or to improve scratch resistance, in particular to improve the scratch resistance of household items such as pans and baking utensils and cooking utensils, of casting molds, in particular zinc die-casting, aluminum die-casting, and magnesium die-casting molds, of injection molds, in particular thermoplastic injection molding, of stamps and pressing tools, of dispersing devices, and of cutting tools for gardening,such as pruning shears and lawnmower blades.

[0083] The effects and advantages described above in connection with the plasma polymer solid or the plasma polymer layer are realized to a particularly positive extent when used according to the invention. The invention also relates to a method for producing a plasma polymer solid (as described above, preferably as referred to above as preferred), in particular a plasma polymer coating (as described above, preferably as referred to above as preferred), comprising the steps

[0084] 51) Producing or providing a substrate,

[0085] 52) producing or providing two, three or more gaseous precursors;

[0086] 53) introducing at least partial quantities of the gaseous precursor substances produced or provided in step S2) according to a recipe in a predefined quantity and in predefined proportions into a plasma system so that a plasma system with a continuous inflow of gaseous precursor substances results;

[0087] 54) Depositing a plasma polymer solid, in particular a plasma polymer layer, from the gaseous precursor substances on the substrate produced or provided in step S1), with the plasma system with the continuous inflow of gaseous precursor substances, so that a substrate coated with a plasma polymer solid, in particular a plasma polymer layer, according to one of claims 1 to 8, results.

[0088] The process according to the invention allows the plasma polymer solids or plasma polymer layers according to the invention to be produced in a particularly efficient manner. The effects and advantages described above in connection with the plasma polymer solid or plasma polymer layer are realized in this way to a particularly positive extent.

[0089] Preferred is a process (as described above, preferably as referred to above as preferred), wherein the gaseous precursor substances produced or provided in step S2) and used in step S3) comprise at least: wherein the material of the substrate produced or provided in step S1), preferably at least the material of the surface of the substrate produced or provided in step S1), is selected from the group of materials consisting of:

[0090] tool steel,

[0091] Stainless steel,

[0092] Aluminum,

[0093] ceramics,

[0094] Porcelain and

[0095] Glass, in particular enamel; and / or wherein the gaseous precursor substances produced or provided in step S2) and used in step S3) comprise at least: an organosilicon precursor, preferably comprising methyl groups, particularly preferably the organosilicon precursor is hexamethyldisiloxane; and

[0096] Oxygen.

[0097] In many cases in which the plasma polymer solids according to the invention, in particular the plasma polymer layers according to the invention, are formed as release coatings or easy-to-clean coatings, it is preferred if the plasma polymer solids according to the invention, in particular the plasma polymer layers according to the invention, are formed as a coating on substrates whose material is selected from the group of materials consisting of:

[0098] tool steel,

[0099] Stainless steel,

[0100] Aluminum,

[0101] ceramics,

[0102] Porcelain and glass, especially enamel.

[0103] In many cases in which the plasma polymer solids according to the invention, in particular the plasma polymer layers according to the invention, are formed as release coatings or easy-to-clean coatings, it is also preferred if only the surface of the substrate consists of a material selected from:

[0104] tool steel,

[0105] Stainless steel,

[0106] Aluminum,

[0107] ceramics,

[0108] Porcelain and

[0109] Glass, in particular enamel; while parts of the substrate remote from the surface, in particular parts of the substrate which are not in contact with the plasma polymer solid body according to the invention, in particular the plasma polymer layer according to the invention, consist of a different material.

[0110] In this way, in many cases, the above-mentioned properties, preferably the above-mentioned combinations of properties, are also combined with a particularly low tendency to crack formation in the event of temperature-related and / or torsion-related and / or vibration-related movements of the substrate coated therewith and a particularly good adhesion to the surface of a substrate coated therewith, in the event of temperature-related and / or torsion-related and / or vibration-related movements of the substrate coated therewith.

[0111] In this way, in many cases, the aforementioned properties, preferably the aforementioned combinations of properties, are also combined with particularly advantageously good adhesion to the surface of the corresponding substrate in the event of temperature-related and / or torsion-related and / or vibration-related movements of the substrate coated therewith, and particularly good adhesion to the surface of the substrate coated therewith in the event of temperature-related and / or torsion-related and / or vibration-related movements of the substrate coated therewith. When using the specified gaseous precursor substances, the positive properties, in particular the positive combinations of properties, of the plasma polymer solids according to the invention resulting from the process according to the invention, in particular of the plasma polymer layers according to the invention, are realized to a particularly positive extent.

[0112] Preferred is a process (as described above, preferably as referred to above as preferred), wherein in the organosilicon precursor introduced in step S3), a ratio of -CH3 (methyl) to Si of 2.7 or greater is present, preferably a ratio of 3 or greater; and in the organosilicon precursor introduced in step S3), a ratio of O to Si of < 1.5 is present, preferably of < 1.1; and / or the organosilicon precursor introduced in step S3) does not comprise any silazane compounds.

[0113] Silazanes are chemical compounds with the formula R3Si-[NH-SiR2]n-NH-SiR3 (also with n = 0), where R stands for hydrogen atoms and / or hydrocarbon radicals.

[0114] When using the organosilicon precursor substances defined above, the positive properties, in particular the positive combinations of properties, of the plasma polymer solids according to the invention resulting from the process according to the invention, in particular of the plasma polymer layers according to the invention, are realized to a particularly positive extent. In particular, a particularly advantageously good surface energy (determined by contact angle measurement according to the procedure described in Example 3 of the present text) and a particularly advantageously good polar component of the surface energy (determined by contact angle measurement according to the procedure described in Example 3 of the present text) are realized by the plasma polymer solids according to the invention resulting from the process according to the invention, in particular the plasma polymer layers according to the invention.A method is preferred (as described above, preferably as referred to above as preferred), wherein in the deposition of a plasma polymer solid, in particular a plasma polymer layer on the substrate in step S4) a plasma system with a zero-bias electrode structure is used as the plasma system, and preferably the gaseous precursor substances produced or provided in step S2) and used in step S3) at least comprise: an organosilicon precursor, preferably hexamethyldisiloxane and.

[0115] - oxygen and wherein during introduction in step S3) a gas quantity ratio, measured in cm 3 / min, of organosilicon precursor, preferably hexamethyldisiloxane, to oxygen of more than 1.0, preferably more than 1.5, particularly preferably more than 2.0; and / or the plasma system during the deposition in step S4) has a boundary layer potential in the range from 180 V to 300 V, preferably in the range from 190 V to 250 V; and / or the plasma system during the deposition in step S4) has a self-bias amount of less than 50 V, preferably less than 30 V, particularly preferably less than 10 V; and / or during the deposition in step S4) in the plasma system such a high total gas flow is realized that the calculated total residence time of the gases in the plasma chamber is in the range from 0.05 s to 10 s, preferably in the range from 0.08 s to 1 s;or when depositing a plasma polymer solid, in particular a plasma polymer layer on the substrate in step S4), a plasma system with self-bias is used as the plasma system, and preferably the gaseous precursor substances produced or provided in step S2) and used in step S3) comprise at least: an organosilicon precursor, preferably hexamethyldisiloxane and;

[0116] - oxygen and wherein during introduction in step S3) a gas quantity ratio, measured in cm 3 / min, of organosilicon precursor, preferably hexamethyldisiloxane, to oxygen of more than 1.0, preferably of more than 1.5, particularly preferably of more than 2.0; and / or the plasma system during the deposition in step S4) has a boundary layer potential in the range from 250 V to 400 V, preferably in the range from 275 V to 350 V; and / or during the deposition in step S4) in the plasma system such a high total gas flow is realized that the calculated total residence time of the gases in the plasma chamber is in the range from 0.01 s to 1 s, preferably in the range from 0.03 s to 0.6 s.

[0117] In accordance with the common understanding of the expert, plasma systems with “zero bias” are plasma systems for the production of plasma coatings that are designed in such a way that the self-bias amount remains close to zero, i.e. less than 50V.

[0118] The chemical compound “hexamethyldisiloxane” is also known as “2,2,4,4-tetramethyl-3-oxa-2,4-disilapentane” and “HMDSO”.

[0119] In the context of the present invention, the term “oxygen” means gaseous O2, unless otherwise defined in individual cases.

[0120] A method according to the invention, wherein during deposition in step S4) in the plasma system such a high total gas flow is realized that the calculated total residence time of the gases in the plasma chamber is in the range of 0.05 s to 10 s, preferably in the range of 0.08 s to 1 s, is particularly preferred when carrying out the method according to the invention in a zero-bias system.

[0121] Plasma systems with “self-bias” are, in accordance with the usual understanding of the person skilled in the art, plasma systems for producing plasma coatings which are designed in such a way that the self-bias value is more than 150 V, preferably more than 160.

[0122] A method according to the invention, wherein during deposition in step S4) in the plasma system such a high total gas flow is realized that the calculated total residence time of the gases in the plasma chamber is in the range from 0.01 s to 1 s, preferably in the range from 0.03 s to 0.6 s, is in many cases more preferred when carrying out the method according to the invention in a zero-bias system than when carrying out the method according to the invention in a self-bias system. When carrying out the method with the features defined above, in particular combinations of features, the result is plasma polymer solids according to the invention, in particular plasma polymer layers according to the invention, with particularly positive properties (as described above, preferably as referred to above as preferred), in particular particularly positive combinations of properties (as described above, preferably as referred to above as preferred).

[0123] The self-bias is a DC voltage value measured between the RF feed and the grounded reactor. For this purpose, the RF component present at the feed is filtered via a coil. The remaining DC voltage component is related to the grounded reactor wall. The self-bias value, together with the process pressure and the fed-in power, characterizes the plasma process. At a high self-bias value, the fast electrons have migrated to the grounded reactor surfaces. As a result, the ions of the plasma discharge are accelerated toward the electrodes and impact the substrate with increased kinetic energy. This increases the deposition rate but also influences layer formation. The fact that layer deposition occurs even in plasma processes with a self-bias of almost zero volts is due, among other things, to the plasma potential.

[0124] A method is preferred (as described above, preferably as referred to above as preferred), wherein the plasma system used in step S4) has a total leakage rate of less than 0.1 mbar l / s during the deposition in step S4), preferably less than 0.075 mbar l / s; and / or in the plasma system used in step S4) during the deposition in step S4), the ratio of total leakage rate to the inflow of oxygen is in the range of 0.4 or less, preferably 0.2 or less, particularly preferably 0.18 or less; and / or in the plasma system used in step S4) during the deposition in step S4), a working pressure of 0.03 mbar or less is present, preferably 0.02 mbar or less.

[0125] The specialist determines the total leak rate using the pressure increase method over a period of at least one hour. The procedure is familiar to him from his general technical knowledge.

[0126] The above-defined working pressure of 0.03 mbar or, preferably, 0.02 mbar or less refers to the working pressure with plasma discharge.

[0127] When the process is carried out with the features defined above, in particular combinations of features, plasma polymer solids according to the invention, in particular plasma polymer layers according to the invention, result with particularly positive properties (as described above, preferably as designated above as preferred), in particular particularly positive combinations of properties (as described above, preferably as designated above as preferred). The person skilled in the art independently selects the specified parameters depending on the requirements of the individual case, in accordance with the teaching of the present invention and based on his or her general specialist knowledge.

[0128] A method is preferred (as described above, preferably as referred to above as preferred), wherein the electrodes of the plasma system are designed such that no exposed electrode edges are present, at least during the deposition in step S4); and / or the plasma system is operated such that no local plasma secondary discharges occur, at least during the deposition in step S4); and / or the plasma system used in step S4) is designed such that, and the substrate produced or provided in step S1 is selected such that a) the substrate arranged on the electrode is at least 15 cm, preferably at least 20 cm, particularly preferably at least 25 cm away from the nearest wall of the plasma system; and b) the clear distance between the walls delimiting the plasma chamber of the plasma system is at least 50 cm.

[0129] When carrying out the method according to the invention, wherein the electrodes of the plasma system are designed such that no exposed electrode edges are present, at least during the deposition in step S4), a particularly spatially homogeneous plasma discharge is achieved; this results in particularly advantageous results (low spatial fluctuation in the composition of the deposited layer) during deposition. Local, more intense discharges are thus preferably avoided.

[0130] Configuring the plasma system so that no exposed electrode edges are present, at least during deposition in step S4), is achieved, for example, by enclosing the high-frequency electrodes in a suitable insulation layer of at least 50 mm against the chamber wall. Polyethylene (PE) is preferably used as insulation. The use of polytetrafluoroethylene (PTFE) and similar fluorine-containing insulation materials should be avoided for the surfaces exposed to the plasma.

[0131] The formation of the plasma system so that at least during the deposition in step S4) no exposed electrode edges are present can alternatively be realized by using a suitable rectangular vacuum chamber.

[0132] Large-area, flat electrodes (with capacitive coupling) are preferably used, the freely accessible area of ​​which, relative to the plasma, approximately corresponds to the free area of ​​the electrical ground, so that a self-bias close to zero is achieved during operation; in many cases, a preferably geometrically symmetrical discharge is realized.

[0133] A double U-configuration (electrode to ground) is preferred in many cases.

[0134] When the process is carried out with the features defined above, in particular combinations of features, plasma polymer solids according to the invention, in particular plasma polymer layers according to the invention, result with particularly positive properties (as described above, preferably as designated above as preferred), in particular particularly positive combinations of properties (as described above, preferably as designated above as preferred). Here, too, the person skilled in the art independently selects the specified parameters depending on the requirements of the individual case, in accordance with the teaching of the present invention and based on their general specialist knowledge.

[0135] The invention is described in more detail below using examples.

[0136] Examples:

[0137] Example 1: Production of a plasma polymer solid, in particular a plasma polymer layer

[0138] Example 1-1 : Production of a plasma polymer solid, in particular a plasma polymer layer, using a zero-bias plasma reactor

[0139] The plasma polymer solids according to the invention or the plasma polymer layers according to the invention were produced using a plasma reactor with a plasma chamber volume of approximately 1.2 m 3 The basic design of the plasma reactor used is described in the state of the art, for example, in DE 10 2017 131 085 A1 or in the dissertation "Development of a model for the layer formation of highly carbon-containing, organosilicon plasma polymers" by Thorben Brenner, University of Bremen, 2022, https: / / doi.org / 10.26092 / elib / 1921 ; the only deviation from these descriptions for the examples described in this text, unless explicitly stated otherwise, was the following plasma generator and matchbox:

[0140] Plasma generator: TruPlasma RF 3012 (SN 207151790) with a power of P = 12kW

[0141] Matchbox: TruPlasma Match 1024 / 13 (G2 200A) (SN 207083139)

[0142] For the production of plasma polymer solids or plasma polymer layers, plasma densities of more than 3.8E+15 m -3 and worked with plasma potentials of more than 200 V.

[0143] These conditions, especially the high plasma potentials, are particularly suitable for the production of hard release and easy-to-clean coatings. What is particularly surprising is that even at high HMDSO / O2 ratios, a Si crosslinking structure with high proportions of tertiary (T) and quaternary (Q) oxygen bonds is formed, while at the same time, high proportions of secondary (D) and primary (M) oxygen bonds still allow the formation of surfaces with a repellent character.

[0144] To verify the plasma system's setup, the self-bias was determined. Since typical commercial matchboxes only indicate the amount of self-bias, control measurements must be performed to ensure that no self-bias voltage exceeding +10 V is generated during the plasma discharge. The self-bias was determined by measuring directly at the electrode using a high-voltage probe and an oscilloscope, observing the usual safety precautions when handling RF transmitters.

[0145] Due to the conductivity of the plasma and its contact with the electrodes, a voltage drop occurs at the electrode surfaces (both at the ground electrode and at the RF electrode), so that a so-called edge layer forms; in English, the formation of this edge layer is also referred to as "sheath formation".

[0146] During the production of the plasma polymer solids or the plasma polymer layers according to the invention, a geometrically symmetrical plasma discharge was ensured. The geometric symmetry of the plasma discharge was monitored by measuring the plasma potential (the plasma potential is a voltage between the plasma and the surface to be coated). The plasma potential was checked using a capacitive measuring probe, as described in the dissertation by Thorben Brenner, University of Bremen, 2022, https: / / doi.org / 10.26092 / elib / 1921). This probe is capable of determining the time-varying plasma potential. If the temporal variability of the plasma potential exhibits a sinusoidal shape, a geometrically symmetrical discharge is present, while deviations from a sinusoidal shape indicate an asymmetrical discharge.The temporal behavior of the boundary layer in front of the RF electrode on the one hand and the boundary layer in front of the ground electrode on the other hand is different.

[0147] Homogenized gas extraction and precursor gas supply were performed as described in the dissertation “Design and evaluation of gas supply systems, electrodes and gas extraction systems for low-pressure plasma chambers” by Gustavo Simiema de Freitas Barbosa (University of Bremen, 2018; http: / / nbn-resolving.de / urn:nbn:de:gbv:46-00106694-13).

[0148] To ensure the most consistent initial conditions in the plasma system, the plasma system was conditioned prior to layer production. This process is carried out at 600 W power under the otherwise selected coating conditions for a period of at least one hour. This conditioning ensures that all surfaces within the plasma system are coated with a plasma polymer coating prior to the actual production of the plasma polymer solid or plasma polymer layer. This prevents uncontrolled contamination of the samples during the actual production of the plasma polymer solid or plasma polymer layers.

[0149] All manufactured samples were placed on the base electrode during coating. To ensure sufficient adhesion of the plasma polymer layer to the test substrates, a 10-minute oxygen activation (400 sccm oxygen, 1500 W, 0.02 mbar) of the test substrates was performed beforehand. Depending on the measurement method, the substrates were silicon wafers, aluminum plates, or glass slides.

[0150] For the production of the inventive coatings, the total gas flow was 145 sccm at a working pressure of 0.012 mbar. Further parameters are listed in Table 1.

[0151] The result was plasma polymer solids according to the invention or plasma polymer layers according to the invention.

[0152] Table 1: Parameters for the production of plasma polymer solids or plasma polymer layers according to the invention using a zero-bias plasma reactor

[0153] [W] [V] [V]

[0154] 1 2.54 2800 203 203 According to the invention Si wafer, glass

[0155] 2 1 ,74 2800 212 212 According to the invention Si wafer, glass

[0156] 3 1 ,23 2800 220 220 According to the invention Si wafer, glass

[0157] 4 1 ,07 2500 224 224 According to the invention Si wafer, glass

[0158] Wherever "Si wafer, glass" is mentioned in this text, Si wafers were used as substrates (each in separate experiments) and, in separate experiments, glass plates (each in separate experiments). For example, this shows that for each layer where "Si wafer, glass" is mentioned, at least two substrates were coated: a "Si wafer" as the substrate on the one hand and a "glass" as the substrate on the other.

[0159] Non-inventive comparative example V-1-1:

[0160] Following the procedure of Example 1-1 above, with only the deviations from the procedure of Example 1-1 above specified below, non-inventive plasma polymer solids or non-inventive plasma polymer layers were produced as non-inventive comparative examples.

[0161] Deviating from the procedure in Example 1-1, the following plasma generator and the following matchbox were used (as already known from the dissertation "Development of a model for the layer formation of highly carbon-containing, silicon-organic plasma polymers" by the author Thorben Brenner, University of Bremen, 2022, https: / / doi.Org / 10 ,26092 / eli b / 1921):

[0162] Plasma generator: PFG 5000 RF (SN 24059493-010-001) with a power of P = 5kW

[0163] Matchbox: PFM 10,000 A (SN 2102 / 001)

[0164] In contrast to the procedure in Example 1-1, the parameters given in Table 2 were used.

[0165] The result was non-inventive plasma polymer solids or non-inventive plasma polymer layers.

[0166] Table 2: Parameters for the production of non-inventive plasma polymer solids or non-inventive plasma polymer layers using a zero-bias plasma reactor

[0167] Non-inventive Si wafer, glass

[0168] 5 2.54 2200 145 145 according

[0169] Non-inventive Si wafer, glass

[0170] 6 1 ,74 2200 148 148 according

[0171] Non-inventive Si wafer, glass

[0172] 7 1 ,01 2200 155 155 according to Example 1-2: Production of a plasma polymer solid, in particular a plasma polymer layer, by means of a self-bias plasma reactor

[0173] Plasma polymer solids according to the invention or plasma polymer layers according to the invention were produced according to the procedure of the above Example 1-1, with only the deviations from the procedure of the above Example 1-1 specified below.

[0174] Deviating from the procedure in Example 1-1, self-bias values ​​according to Table 3 and a chamber size of 50 cm x 50 cm x 60 cm were used.

[0175] The total gas flow was 100 sccm, and the working pressure was controlled at 0.02 mbar. Further parameters are listed in Table 3. The resulting plasma polymer solids and plasma polymer layers were fabricated according to the invention. Table 3: Parameters for the production of plasma polymer solids and plasma polymer layers using a self-bias plasma reactor.

[0176] [V] [V] [V]

[0177] 9 2.33 250 53 303 According to the invention Si wafer, glass

[0178] 10 2.33 275 53 328 According to the invention Si wafer, glass

[0179] 11 2.33 300 53 353 According to the invention Si wafer, glass

[0180] 13 2.80 300 53 353 According to the invention Si wafer, glass

[0181] 14 1 ,78 300 53 353 According to the invention Si wafer, glass Non-inventive comparative example V-1-2:

[0182] Following the procedure of Example 1-1 above, with only the deviations from the procedure of Example 1-1 above specified below, non-inventive plasma polymer solids or non-inventive plasma polymer layers were produced as non-inventive comparative examples.

[0183] Deviating from the procedure in Example 1-1, the following plasma generator and the following matchbox were used (as already known from the dissertation "Development of a model for the layer formation of highly carbon-containing, silicon-organic plasma polymers" by the author Thorben Brenner, University of Bremen, 2022, https: / / doi.org / 10.26092 / elib / 1921):

[0184] Plasma generator: PFG 5000 RF (SN 24059493-010-001) with a power of P = 5kW

[0185] Matchbox: PFM 10,000 A (SN 2102 / 001) Deviating from the procedure in Example 1-1, the parameters given in Table 4 were used.

[0186] The result was non-inventive plasma polymer solids or non-inventive plasma polymer layers.

[0187] Table 4: Parameters for the production of non-inventive plasma polymer solids or non-inventive plasma polymer layers using a self-bias plasma reactor

[0188] M [V] [V]

[0189] 8 2.33 200 50 250 Not according to the invention Si wafer, glass

[0190] 12 2.80 250 53 303 Not according to the invention Si wafer, glass

[0191] Example 2: Determination of monofunctional, difunctional, trifunctional and tetrafunctional oxygen fractions using XPS measurements and subsequent evaluation

[0192] 2-1 : Calibration of the XPS measuring system

[0193] X-ray photoelectron spectroscopy (XPS) is based on the external photoelectric effect; the binding energy relative to the Fermi level can be directly determined from the XPS spectrum. Details of the method are generally known.

[0194] For all measurements, an ESCALAB 250Xi X-ray photoelectron spectrometer (XPS) system from ThermoFisher Scientific with a monochromated Al Ka ​​source was used. The standard electrostatic lens was used, and the X-ray spot had a diameter of 650 pm. Initially, the apparatus was tested using an uncontaminated linear, non-reactive polydimethylsiloxane with a viscosity of approximately 500 mm. 2 / s (Wacker® AK500) as a reference. The known stoichiometry of the sample is: Si: 25 at.%, O: 25 at.%, and C: 50 at.%, based on the total number of atoms selected from Si, O, and C in the sample.

[0195] If the appropriate stoichiometry is not found during the measurement, the relative sensitivity factors (RSF) must be adjusted so that the correct stoichiometry is obtained. The set RSF must be used in subsequent measurements. A suitable pass energy for determining the sample is selected independently by the person skilled in the art according to the requirements of the individual case and on the basis of their general specialist knowledge. A pass energy of 150 eV is used for overview spectra and 20 eV for detailed spectra. It is known from general specialist knowledge that higher resolution can be achieved with a lower pass energy. It must also be noted that an "escape depth correction" according to the TTP2M model must be applied when evaluating the stoichiometry. Otherwise, the signal from the silicon, for example, will be significantly overestimated in the measurement, which in turn leads to incorrect stoichiometry.For the present XPS device, the adjusted RSF values ​​given in Table 5 were determined and used based on a PDMS measurement (polydimethylsiloxane measurement as reference).

[0196] Table 5: Correction of RSF values ​​based on a PDMS measurement (reference)

[0197] OC Si Remark

[0198] O1s C1s Si2p at-% at-% at-%

[0199] Intolerable

[0200] Standard deviation from

[0201] 2.93 1 0.817 21 ,21 48.21 27.86

[0202] RSF of the well-known

[0203] Stoichiometry

[0204] Correct stoichiometry with tolerable

[0205] 3.01 1 0.94 25.02 49.98 25.00

[0206] RSF- possible deviations

[0207] Values

[0208] 2-2: Measurement of inventive layers with 0° measuring angle to the sample standard

[0209] The measurement of the inventive plasma polymer solids or inventive plasma polymer layers produced according to Examples 1-1 and 1-2 above was carried out at a pass energy of 20 eV, unless otherwise specified in individual cases. Measurements were taken at a measurement angle of 0°C. At this measurement angle, photoelectrons can leave the sample surfaces in the measurement direction up to a sample depth of approximately 10 nm, so that the resulting information originates from the top 10 nm of the sample being examined, adjacent to the measurement surface.

[0210] The measurement of the non-inventive plasma polymer solids or non-inventive plasma polymer layers produced according to the above non-inventive comparative examples V-1-1 and V-1-2 was carried out at a pass energy of 20 eV, unless otherwise stated in the individual case.

[0211] Subsequently, a fit of the Si2p peak was performed in each case. The detailed spectrum of the Si2p peak was fitted according to the method described in: O'Hare et al.: "Development of a methodology for XPS curve-fitting of the Si2p core level of siloxane materials" Surf. Interface Anal. 2004; 36: 1427-1434, doi:10.1002 / sia.1917.

[0212] For each oxidation state of silicon, a doublet peak shape was assumed (p-orbital). Four doublet peaks were fitted for each. The ratio of the peak areas of the two individual peaks of a doublet was set to 1:2. These are the p1 / 2 and two p3 / 2 orbitals. The two p3 / 2 orbitals generate a peak of the doublet with twice the peak area compared to the p1 / 2 orbital. The energetic separation of the individual peaks was 0.65 eV within a doublet. All peaks, both the peaks within a doublet and between different doublets, had the same half-width, with the absolute value of the half-width varying in the range from 0.8 to 1.1.

[0213] The energetic position of the Si2p 3 / 2 single peak of the different oxidation states is:

[0214] Monofunctional (M) - [(CH3)3SiO1 / 2] binding energy of 101.34 eV; Difunctional (D) - [(CH3)2SiO2 / 2] binding energy of 101.7 eV; Trifunctional (T) - [CH3SiO3 / 2] binding energy of 102.38 eV; Tetrafunctional (Q) - [SiO4 / 2] binding energy of 103.18 eV.

[0215] The complete fitting conditions can be found in Table 6-1 and Table 6-2. The peak shape according to O'Hare et al. ("Development of a methodology for XPS curve-fitting of the Si 2p core level of siloxane materials" Surf. Interface Anal. 2004; 36: 1427-1434, doi: 10.1002 / sia.1917) as well as all specified constraints must be observed. These may need to be adjusted accordingly depending on the respective analysis software.

[0216] Table 6-1 : Fit conditions (part 1) component D3 / 2 D1 / 2 T3 / 2 T1 / 2

[0217] (A) (B) (C) (D)

[0218] LineShape GL(30)T(2.3) GL(30)T(2.3) GL(30)T(2.3) GL(30)T(2.3) area constraint - A*0.5 - C*0.5 fwhm constraint 0.8 - 1 .1 A*1 A*1 A*1 position constraint 101 .7 A+0.65 A+0.68 A+1 .33

[0219] Table 6-2: Fit conditions (part 2) component M3 / 2 M1 / 2 Q3 / 2 Q1 / 2

[0220] (E) (F) (G) (H)

[0221] LineShape GL(30)T(2.3) GL(30)T(2.3) GL(30)T(2.3) GL(30)T(2.3) area constraint - E*0.5 - G*0.5 fwhm constraint A*1 A*1 A*1 A*1 position constraint A-0.36 A+0.29 A+1 .48 A+2.13

[0222] For the background, i.e. the baseline of the fit data, a sufficiently large “region” is created to describe the data background with a “U 2 Tougaard”.

[0223] The necessary calibration of the binding energy scale (BE scale) is performed iteratively. First, the aliphatic CC / CH peak of the C1s peak is set to 285 eV. Then, a peak fitting of the Si2p peak is performed as described above. From the fit result, the carbon content is calculated according to Formula 1, which is derived from the fit of the Si2p peak.

[0224] Formula 1 : The values ​​M^, MI , D3 , DJ_ , T3 , TI are the percentage area from the fit of the Si2p peak. The quantity C si denotes the atomic concentration of silicon (in at%) determined from the overview spectrum. This value is compared with the measured carbon concentration. The oxygen content is calculated and compared accordingly. Formula 2 applies.

[0225] The naming of the variables is analogous to Equation 1. For the coatings in question, this is a reliable way to exclude faulty fits. Particular attention should be paid to a small deviation in the oxygen content; the deviation according to Equation 3 must be ±2% or less. The deviation for the carbon content, which is calculated analogously, must be less than 20%. Equation 3: 100

[0226] If the values ​​differ from each other, the binding energy scale is adjusted in small steps until the 2% interval is reached.

[0227] The resulting band position of the Si2p peak was subsequently determined.

[0228] For the plasma polymer solids or plasma polymer layers according to the invention produced according to Example 1-1 above (see also Table 1 above), the values ​​summarized in Table 7 are obtained:

[0229] Table 7: Values ​​for the plasma polymer solids according to the invention or plasma polymer layers according to the invention produced according to Example 1-1 above

[0230] [eV] [%] [%] [%] [%]

[0231] 1 2.54 1 102.65 1 .29 1 .73 33 67 According to the invention

[0232] 2 1 ,74 1 102,54 1 ,33 1 ,69 33 67 According to the invention

[0233] 3 1 ,23 1 102,62 1 ,38 1 ,64 28 72 According to the invention

[0234] 4 1 ,07 1 102,80 1 ,47 1 ,61 24 76 According to the invention

[0235] Refe- PDMS 1 101 ,85 1 ,00 2,01 99 1 XPS reference rence (AK 500)

[0236] For the non-inventive plasma polymer solids or non-inventive plasma polymer layers produced according to the above non-inventive comparative example V-1-1 (cf. also Table 2 above), the values ​​summarized in Table 8 are obtained.

[0237] Table 8: Values ​​for the non-inventive plasma polymer solids or non-inventive plasma polymer layers produced according to the above non-inventive comparative example V-1 -1

[0238] [eV] [%] [%] [%] [%]

[0239] 5 2.54 1 102.80 0.92 1 ,84 82 18 Not according to the invention

[0240] 6 1 ,74 1 102,86 0,97 1 ,77 77 23 Not according to the invention

[0241] 7 1 ,01 1 102,90 1 ,11 1 ,60 71 29 Not according to the invention

[0242] Refe- PDMS 1 101 ,85 1 ,00 2,01 99 1 XPS reference rence (AK 500) The values ​​summarized in Table 9 result for the plasma polymer solids according to the invention or the plasma polymer layers according to the invention produced according to Example 1-2 above (cf. also Table 3 above).

[0243] Table 9: Values ​​for the plasma polymer solids according to the invention or plasma polymer layers according to the invention produced according to Example 1 -2 above

[0244] [eV] [%] [%] [%] [%]

[0245] 9 2,33 1 102,60 1 ,30 1 ,28 32 68 According to the invention

[0246] 10 2.33 1 102.53 1 .29 1 .29 33 67 According to the invention

[0247] 11 2.33 1 102.51 1 ,30 1 ,26 34 66 According to the invention

[0248] 13 2.80 1 102.48 1 .22 1 .32 36 64 According to the invention

[0249] 14 1 ,78 1 102,63 1 ,34 1 ,21 29 71 According to the invention

[0250] Refe- PDMS 1 101 ,85 1 ,00 2,01 99 1 XPS reference rence (AK 500)

[0251] For the non-inventive plasma polymer solids or non-inventive plasma polymer layers produced according to the above non-inventive comparative example V-1-2 (cf. also Table 4 above), the values ​​summarized in Table 10 are obtained.

[0252] Table 10: Values ​​for the non-inventive plasma polymer solids or non-inventive plasma polymer layers produced according to the above non-inventive comparative example V-1 -2

[0253] [eV] [%] [%] [%] [%]

[0254] 8 2.33 1 102.52 1 ,34 1 ,27 30 70 Not according to the invention

[0255] 12 2.80 1 102.45 1 .24 1 .32 35 65 Not according to the invention

[0256] Refe- PDMS 1 101 ,85 1 ,00 2,01 99 1 XPS reference rence (AK 500)

[0257] 2-3: Measurement of inventive layers with 75° measuring angle to the sample standard

[0258] Additionally, investigations were conducted according to the procedure described in Example 2-2, with a measurement angle of 75° being used as the only deviation from the procedure described in Example 2-2. At this measurement angle, photoelectrons can leave the sample surface in the measurement direction up to a sample depth of approximately 2.6 nm, so that the resulting information originates from the top 2.6 nm of the sample being investigated, adjacent to the measurement surface.

[0259] Table 11 : Values ​​for layer no. 13

[0260] [eV] [%] [%] [%] [%]

[0261] 13 2.80 1 102.55 1 .16 1 .23 31 69 75° to the surface normal

[0262] From these results in Table 11, in comparison with the results from Table 9 above, it is clear that the layer composition and the degree of cross-linking in the upper approximately 2.6 nm of the sample body examined do not differ from the layer composition in the upper 10 nm of the sample body examined within the limits of the measurement accuracy.

[0263] Our own investigations on other plasma polymer solids or plasma polymer layers according to the invention have shown that this behavior occurs regularly. This aspect is important because it is not a "grafted" top molecular layer, but rather the XPS results show a homogeneous solid.

[0264] Example 3: Determination of surface energy

[0265] The surface free energy (SFE) of a solid is calculated here from the measurable three-phase contact angle. The measurement of the contact angle and its mathematical description dates back to Thomas Young. According to Thomas Young, the measurable contact angle 0 is described by the following formula 4:

[0266] Formula 4: 0050=^^ ei

[0267] In formula 4, a s the surface energy of the solid and cr ; the surface energy of the test liquid used. The surface energy in formula 4 is defined as a s; The interaction referred to is described in the present invention following the Owens-Wendt-Rabel-Kaelble approach according to Formula 5. Formula 5:

[0268] This approach to solving the surface free energy of a solid assumes that the interaction between the solid and the liquid phase is <7 slcan be described by the geometric mean of the disperse fractions o , of and polar fractions of , of . Furthermore, within the scope of the present invention, Formula 6 applies to the surface energies or tensions of the solid and liquid.

[0269] Formula 6: o s I = of + of

[0270] To solve the system of equations formed by Formulas 5 and 6, contact angle measurements must be performed with at least two liquids with known polar and disperse fractions. For the purposes of the present invention, at least one liquid must have a polar fraction greater than zero.

[0271] The static measurement method was used to experimentally determine the contact angle. The surface energy of coatings was determined using the "Mobil Surface Analyzer MSA" from "Krüss." For this purpose, one drop of water (ROTISOLV® HPLC Gradient Grade, 99.9%) and one drop of diiodomethane (99%) with a volume of 1 pl ± 0.3 pl were deposited onto the coated sample surface (glass slide), and the respective contact angles were measured. In the case of a water drop, the contact angle is also referred to as the "water edge angle" in the field of the present invention. Six pairs of drops were used for the evaluation, and average values ​​were calculated. The surface energy was determined from the average values ​​of the measured contact angles according to Owens-Wendt-Rabel-Kaelble. In case of doubt, DIN 55660-2 is used. The determination was carried out at room temperature.

[0272] Even if the Mobil Surface Analyzer MSA performs the measurement independently, the measurements must still be checked. For example, the baseline may not always be positioned correctly for optical reasons. Manual adjustments are necessary in these cases. In the case of dirt, etc., a supplementary measurement may be necessary.

[0273] For the plasma polymer solids according to the invention or the plasma polymer layers according to the invention produced according to Example 1-1 above (see also Table 1 above), the values ​​summarized in Table 12 are obtained: Table 12: Values ​​for surface energy (Owens-Wendt-Rabel-Kaelble) for the plasma polymer solids according to the invention or the plasma polymer layers according to the invention produced according to Example 1-1 above _

[0274] Layer- HMDSO / O2 polar

[0275] OFE Remark

[0276] No. Ratio Share

[0277] [mN / m] [mN / m]

[0278] 1 2.54 29.4 2.0 According to the invention

[0279] 2 1 ,74 30,2 2,8 According to the invention

[0280] 3 1 ,23 32,2 3,0 According to the invention

[0281] 4 1 ,07 32,0 3,5 According to the invention For the non-inventive plasma polymer solids or non-inventive plasma polymer layers produced according to the above non-inventive comparative example V-1-1 (cf. also Table 2 above), the values ​​summarized in Table 13 are obtained.

[0282] Table 13: Surface energy values ​​(Owens-Wendt-Rabel-Kaelble) for the non-inventive plasma polymer solids or non-inventive plasma polymer layers produced according to the above non-inventive comparative example V-1-1

[0283] Layer- HMDSO / O2 polar

[0284] OFE Remark

[0285] No. Ratio Share

[0286] [mN / m] [mN / m]

[0287] 5 2.54 24.1 0.9 Not according to the invention

[0288] 6 1 ,74 24,1 0,9 Not according to the invention

[0289] 7 1 ,01 25,9 1 ,3 Not according to the invention

[0290] For the plasma polymer solids according to the invention or the plasma polymer layers according to the invention produced according to Example 1-2 above (see also Table 3 above), the values ​​summarized in Table 14 are obtained. Table 14: Surface energy values ​​(Owens-Wendt-Rabel-Kaelble) for the plasma polymer solids according to the invention or the plasma polymer layers according to the invention produced according to Example 1-2 above.

[0291] Layer- HMDSO / O2 polar

[0292] OFE Remark

[0293] No. Ratio Share

[0294] [mN / m] [mN / m]

[0295] 9 2.33 28.5 2.4 According to the invention

[0296] 10 2.33 28.3 2.9 According to the invention

[0297] 11 2.33 28.4 3.0 According to the invention

[0298] 13 2.80 27.2 1.6 According to the invention

[0299] 14 1 ,78 30,5 2,6 According to the invention For the non-inventive plasma polymer solids or non-inventive plasma polymer layers produced according to the above non-inventive comparative example V-1-2 (cf. also Table 4 above), the values ​​summarized in Table 15 are obtained.

[0300] Table 15: Surface energy values ​​(Owens-Wendt-Rabel-Kaelble) for the non-inventive plasma polymer solids or non-inventive plasma polymer layers produced according to the above non-inventive comparative example V-1-2

[0301] Layer- HMDSO / O2 polar

[0302] OFE Remark

[0303] No. Ratio Share

[0304] [mN / m] [mN / m]

[0305] 8 2.33 26.0 2.0 Not according to the invention

[0306] 12 2.80 28.0 2.8 Not according to the invention

[0307] Checking the measuring fluids The fluids used were checked for contamination prior to measurements. For this purpose, glass slides were thoroughly cleaned with acetone. They were then measured 10 times, using a drop volume of 2 μl each. The following values ​​were obtained as the mean values ​​in Table 16. Table 16: Mean values ​​for layer 13

[0308] liquid

[0309] Contact angle (°) Standard deviation (°)

[0310] (measured on glass slide)

[0311] Water 35.3 2

[0312] Diiodomethane 50.9 2

[0313] Example 4: Determination of Young's modulus and mass density

[0314] The Young's modulus and the mass density of plasma polymer solids, in particular thin plasma polymer layers, were determined by measuring the dispersion of surface acoustic waves (SAW) in coated media (Si wafer 100).

[0315] The measurements were conducted using a LaWave®, a development of the Fraunhofer IWS, using a high-frequency sensor (15-250 MHz). (https: / / www.iws.fraunhofer.de / de / technologiefelder / pvd_nanotechnik / schichtcharakteri- sierung / lawave.html; accessed on September 18, 2023).

[0316] Three measurements were performed for each sample. Care was taken to ensure the correct alignment of the wafers along the crystal axis. Correct alignment was verified by comparing the dispersion curves. Any significant offset in the propagation velocities of the dispersion curves indicated a poor alignment of the samples, and the appropriate correction was made.

[0317] For the plasma polymer solids according to the invention or the plasma polymer layers according to the invention produced according to Example 1-1 above (see also Table 1 above), the values ​​summarized in Table 17 are obtained.

[0318] Table 17: Values ​​for Young's modulus and mass density for the plasma polymer solids according to the invention or plasma polymer layers according to the invention produced according to Example 1-1 above

[0319] 1 2.54 32.2 1 .52 According to the invention

[0320] 2 1 ,74 32,2 1 ,52 According to the invention

[0321] 3 1 ,23 35,0 1 ,55 According to the invention

[0322] 4 1 ,07 30,3 1 ,53 According to the invention For the non-inventive plasma polymer solids or non-inventive plasma polymer layers produced according to the above non-inventive comparative example V-1-1 (cf. also Table 2 above), the values ​​summarized in Table 18 are obtained.

[0323] Table 18: Values ​​for Young's modulus and mass density for the non-inventive plasma polymer solids or non-inventive plasma polymer layers produced according to the above non-inventive comparative example V-1-1

[0324] 5 2.54 6.0 1.19 Not according to the invention

[0325] 6 1 ,74 7,3 1 ,25 Not according to the invention

[0326] 7 1 ,01 9,7 1 ,35 Not according to the invention

[0327] For the plasma polymer solids according to the invention or the plasma polymer layers according to the invention produced according to the above examples 1-2 (see also Table 3 above), the values ​​summarized in Table 19 are obtained. Table 19: Values ​​for the modulus of elasticity and mass density for the plasma polymer solids according to the invention or the plasma polymer layers according to the invention produced according to the above examples 1-2

[0328] 9 2.33 31 .3 1 .55 According to the invention

[0329] 10 2.33 32.5 1.54 According to the invention

[0330] 11 2.33 35.6 1.58 According to the invention

[0331] 13 2.80 35.5 1.60 According to the invention

[0332] 14 1 ,78 35,9 1 ,62 According to the invention For the non-inventive plasma polymer solids or non-inventive plasma polymer layers produced according to the above non-inventive comparative example V-1-2 (cf. also Table 4 above), the values ​​summarized in Table 20 are obtained.

[0333] Table 20: Values ​​for Young's modulus and mass density for the non-inventive plasma polymer solids or non-inventive plasma polymer layers produced according to the above non-inventive comparative example V-1-2

[0334] 8 2.33 26.8 1.54 Not according to the invention

[0335] 12 2.80 26.4 1.49 Not according to the invention

[0336] Example 5: Determination of Mohs hardness

[0337] Mohs hardness was determined using a Mohs' Hardness Kit from Mineral Lab. This kit contains pen-like "hardness picks." These are equipped with tips of varying hardness and are moved across the surface at a 70° angle, similar to a writing pen, with a medium pressure. The hardness principle of this simple hand test is based on the fact that hard materials scratch soft materials. Accordingly, it is a comparative test. The contact pressure is calibrated using the reference materials included in the Mohs' Hardness Kit (brass of known Mohs hardness and glass of known Mohs hardness). Care was taken to ensure that the test force was not applied suddenly upon placing the test pin down, but rather the force was increased until the required test force was reached.

[0338] To determine the Mohs hardness of thin coatings, it has proven useful to test surfaces that are as smooth as possible, as the force is applied evenly and any defect traces are easily detectable. Furthermore, when testing the coating hardness, it is important to ensure that the substrate is harder than the coating, at least as hard. Silicon wafers were used in this application. Before determining the Mohs hardness, the surface of the sample was vigorously and carefully wiped dry with a paper towel (e.g., Cleanex). If scratches are caused by wiping – with softer coatings – wiping can be omitted.

[0339] For example, if a material or coating with a hardness rating of 5 leaves a scratch and a coating with a hardness rating of 4 does not, the Mohs hardness is 4.5.

[0340] For the plasma polymer solids according to the invention or the plasma polymer layers according to the invention produced according to Example 1-1 above (see also Table 1 above), the values ​​summarized in Table 21 are obtained.

[0341] Table 21: Values ​​for Young's modulus and mass density for the plasma polymer solids according to the invention or plasma polymer layers according to the invention produced according to Example 1-1 above

[0342] Layer HMDSO / O2 Mohs hardness Remark No. Ratio

[0343] 1 2.54 5.5 According to the invention

[0344] 2 1 ,74 5,5 According to the invention

[0345] 3 1 ,23 5,5 According to the invention

[0346] 4 1 ,07 5,5 According to the invention

[0347] For the non-inventive plasma polymer solids or non-inventive plasma polymer layers produced according to the above non-inventive comparative example V-1-1 (see also Table 2 above), the values ​​summarized in Table 22 are obtained. Table 22: Values ​​for Young's modulus and mass density for the non-inventive plasma polymer solids or non-inventive plasma polymer layers produced according to the above non-inventive comparative example V-1-1

[0348] Layer- HMDSO / O2

[0349] Mohs hardness Remark

[0350] No. Ratio

[0351] 5 2.54 2.5 Not according to the invention

[0352] 6 1 ,74 2,5 Not according to the invention

[0353] 7 1 ,01 2,5 Not according to the invention For the plasma polymer solids according to the invention or the plasma polymer layers according to the invention produced according to Example 1-2 above (cf. also Table 3 above), the values ​​summarized in Table 23 are obtained.

[0354] Table 23: Values ​​for Young’s modulus and mass density for the 1-

[0355] 2 manufactured plasma polymer solids according to the invention or plasma polymer layers according to the invention _

[0356] Layer HMDSO / O2 Mohs hardness Remark

[0357] No. Ratio

[0358] 9 2.33 5.5 According to the invention

[0359] 10 2.33 5.5 According to the invention

[0360] 11 2.33 5.5 According to the invention

[0361] 13 2.80 5.5 According to the invention

[0362] 14 1 ,78 5,5 According to the invention

[0363] For the non-inventive plasma polymer solids or non-inventive plasma polymer layers produced according to the above non-inventive comparative example V-1-2 (see also Table 4 above), the values ​​summarized in Table 24 are obtained. Table 24: Values ​​for Young's modulus and mass density for the non-inventive plasma polymer solids or non-inventive plasma polymer layers produced according to the above non-inventive comparative example V-1-2

[0364] Layer- HMDSO / O2

[0365] Mohs hardness Remark

[0366] No. Ratio

[0367] 8 2.33 5.5 Not according to the invention

[0368] 12 2.80 5.5 Not according to the invention

[0369] Example 6: Resistance to liquid substances

[0370] Resistance to liquid substances always depends on specific conditions such as the period of exposure and the corresponding temperature.

[0371] According to the procedure in Example 1 above, the plasma polymer solids according to the invention or the plasma polymer layers according to the invention used in the following resistance tests were produced as test specimens.

[0372] The surface energy and the polar component of the surface energy were determined on these layers according to the procedure from Example 3 above.

[0373] The resistance of the specimens to the test liquids (substances) listed in Table 25 was then tested. The procedure was in accordance with DIN EN ISO 175:2011-03, meaning the respective specimen was completely immersed in the respective test liquid. Testing was carried out according to points 4.2ff of the standard at 23 °C for 24 hours, unless otherwise specified in individual cases. Sample conditioning was not performed. Each specimen was used in only one resistance test. Table 25: Test liquids and test conditions

[0374] Test liquid Test temperature Immersion time

[0375] Acetic acid 23 2

[0376] (0.17 mol / L; pH 2.75)

[0377] Sulfuric acid 23 1

[0378] (0.5 mol / L; pH 1.0)

[0379] Acetone 23 24

[0380] (analytically pure)

[0381] Ethanol 23 24

[0382] (Purity: 96 vol%) n-Hexane 23 24

[0383] (Purity >98%)

[0384] The specimens were then cleaned to exclude contamination by the respective test fluid for subsequent tests (as described below). For cleaning, acetone (analytical grade) was applied to a fresh paper towel, and the respective surface was carefully cleaned in one direction, then dried in ambient air.

[0385] Subsequently, the surface energy and the polar component of the surface energy were determined again for the plasma polymer solids or plasma polymer layers on the test specimens according to the procedure from Example 3 above.

[0386] In all cases, a surface energy deviation of 20% or less was observed compared to the corresponding value before contact with the test fluid (as described above). In many cases, a surface energy deviation of 15% or less was observed compared to the corresponding value before contact with the test fluid (as described above).

[0387] In all cases, the polar component of the surface energy was in the range of 4.5 mN / m or less both before contact with the test liquid (as described above) and after contact with the test liquid (as described above).

[0388] The plasma polymer solids or plasma polymer layers according to the invention investigated each have resistance to the respective substances defined above (test liquids) under the conditions defined above.

[0389] Additional tests of our own have shown that plasma polymer solids according to the invention or plasma polymer layers according to the invention also have resistance to other substances described as preferred in the present text and under other conditions described as preferred in the present text.

[0390] Example 7: Water vapor resistance

[0391] According to the procedure in Example 1 above, plasma polymer solids according to the invention or plasma polymer layers according to the invention were produced as test specimens.

[0392] Subsequently, the surface energy and the polar component of the surface energy were determined for the plasma polymer solids or plasma polymer layers on the test specimens according to the procedure from Example 3 above.

[0393] The water vapor resistance test was carried out according to DIN EN ISO 17665-1:2006-11, using a steam sterilizer according to DIN EN 285 - 2021-12. The aim of the test was not to achieve sterilization, but simply to investigate the water vapor resistance. The method according to DIN 17665 E2 (method using air-steam mixtures) was applied, using distilled water in each case and orientating the samples vertically. A temperature of 121 °C was reached during the 15-minute heating phase. The temperature was then held constant at 121 °C for 1440 minutes. This was followed by a 15-minute cooling phase, after which pressure equalization was achieved. In each case, a triplicate determination was carried out.

[0394] In all cases, a surface energy deviation of 15% or less was observed compared to the corresponding value before vapor deposition (as described above). In many cases, a surface energy deviation of 5% or less was observed compared to the corresponding value before vapor deposition (as described above). In all cases, the polar component of the surface energy was in the range of 4.5 mN / m or less both before vapor deposition (as described above) and after vapor deposition (as described above).

[0395] The plasma polymer solids or plasma polymer layers according to the invention investigated each have resistance to water vapor under the conditions defined above.

[0396] Example 8: Dishwasher resistance

[0397] According to the procedure in Example 1 above, plasma polymer solids according to the invention or plasma polymer layers according to the invention were produced as test specimens.

[0398] Subsequently, the surface energy and the polar component of the surface energy were determined for the plasma polymer solids or plasma polymer layers on the test specimens according to the procedure from Example 3 above.

[0399] The dishwasher resistance of the thus produced specimens was determined according to DIN EN 12875-1:2005-08 as described below. 125 test cycles were carried out according to points 8.1 to 8.5 of DIN EN 12875-1:2005-08. The specimens were then cleaned in a commercially available ultrasonic bath filled with distilled water to remove surfactant and rinse aid residues (10 min, 45°C). The samples were then removed and dried by rinsing with acetone (analytical grade).

[0400] Subsequently, the surface energy and the polar component of the surface energy were determined again for the plasma polymer solids or plasma polymer layers on the test specimens according to the procedure from Example 3 above.

[0401] In all cases, the surface energy was found to be 15% or less than the corresponding value before the 125 test cycles (as described above). In many cases, the surface energy was found to be 5% or less than the corresponding value before the 125 test cycles (as described above). In all cases, the polar component of the surface energy was in the range of 4.5 mN / m or less both before the 125 test cycles (as described above) and after the 125 test cycles (as described above).

[0402] The plasma polymer solids and plasma polymer layers according to the invention investigated are each dishwasher-resistant.

[0403] Example 9: Temperature resistance

[0404] According to the procedure in Example 1 above, plasma polymer solids according to the invention or plasma polymer layers according to the invention were produced as test specimens.

[0405] Subsequently, the surface energy and the polar component of the surface energy were determined for the plasma polymer solids or plasma polymer layers on the test specimens according to the procedure from Example 3 above.

[0406] Subsequently, the temperature resistance of the plasma polymer solid or the plasma polymer layers on the test specimens was tested by storage in a clean oven at 200°C for 24 hours, with the specimens carefully wrapped in fresh aluminum foil to protect against cross-contamination.

[0407] Subsequently, the surface energy and the polar component of the surface energy were determined again for the plasma polymer solids or plasma polymer layers on the test specimens according to the procedure from Example 3 above.

[0408] In all cases, a surface energy deviation of 15% or less was observed compared to the corresponding value before oven storage (as described above). In many cases, a surface energy deviation of 10% or less was observed compared to the corresponding value before oven storage (as described above).

[0409] In all cases, the polar component of the surface energy was in the range of 4.5 mN / m or less, both before and after storage in the furnace (as described above). The plasma polymer solids and plasma polymer layers of the invention investigated each possess temperature stability.

Claims

Patent claims 1. Plasma polymer solid body, in particular plasma polymer layer, wherein in the plasma polymer solid body, in particular in the plasma polymer layer, a ratio of - Sum of monofunctional and difunctional oxygen fractions of the Si2p peak of the XPS signal determined according to Example 2 to the The sum of trifunctional and tetrafunctional oxygen fractions of the Si2p peak of the XPS signal determined according to Example 2 is from 0.25 to 0.70, preferably from 0.35 to 0.65, particularly preferably from 0.45 to 0.65, wherein the plasma polymer solid, in particular the plasma polymer layer, has an E-modulus, determined by means of the surface acoustic waves method according to the procedure in Example 4, in the range 30 GPa to 45 GPa.

2. Plasma polymer solid body, in particular plasma polymer layer, according to claim 1, wherein the plasma polymer solid body, in particular the plasma polymer layer, has a surface energy, determined on the surface of the plasma polymer solid body or the plasma polymer layer by means of contact angle measurement according to the procedure in Example 3, in the range from 24 mN / m to 38 mN / m.

3. Plasma polymer solid, in particular plasma polymer layer, according to one of the preceding claims, wherein the plasma polymer solid, in particular the plasma polymer layer, has a Mohs hardness, determined according to the procedure in Example 5, of at least 4.5, preferably of at least 5.5; and / or a mass density, determined by means of the surface acoustic waves method according to Example 4, of at least 1.4 g / cm 3 preferably at least 1.5 g / cm 3 .

4. Plasma polymer solid body, in particular plasma polymer layer, according to one of the preceding claims, having a polar component of the surface energy, determined on the surface of the plasma polymer solid body or the plasma polymer layer according to the procedure in Example 3, of less than 4.0 mN / m, preferably of less than 3.0 mN / m, particularly preferably of less than 2.5 mN / m, most particularly preferably of less than 2 mN / m.

5. Plasma polymer solid, in particular plasma polymer layer, according to one of the preceding claims, wherein in the XPS spectrum the Si 2p photo line lies at an energy of less than 103.0 eV, preferably less than 102.8 eV, particularly preferably less than 102.6 eV; and wherein in the XPS spectrum the Si 2p photo line lies at an energy of more than 102.2 eV; and wherein the half-width of the Si 2p photoline, determined according to Example 2, is between 1.8 and 2.5 eV, preferably between 2.0 and 2.3 eV.

6. Plasma polymer solid, in particular plasma polymer layer, according to one of the preceding claims, wherein the molar ratio of O to Si near the surface of the plasma polymer solid or the plasma polymer layer, measured by means of XPS according to example 2-1 at a measuring angle to the sample normal of 0°, and / or measured by means of XPS according to example 2-2 at a measuring angle to the sample normal of 75°, is in the range from 1.05 to 1.50, preferably in the range from 1.10 to 1.40, particularly preferably in the range from 1.13 to 1.35, very particularly preferably in the range from 1.17 to 1.30; and / or the molar ratio of C to Si near the surface of the plasma polymer solid or the plasma polymer layer, measured by XPS according to Example 2-1 at a measurement angle to the sample normal of 0°, and / or measured by XPS according to Example 2-2 at a measurement angle to the sample normal of 75°, in the range from 1.00 to 1.80, preferably in the range from 1.10 to 1.50, particularly preferably in the range from 1.10 to 1.

30.

7. Plasma polymer solid, in particular plasma polymer layer, according to one of the preceding claims, wherein the molar fraction of O near the surface of the plasma polymer solid or the plasma polymer layer, measured by XPS according to the procedure from Example 2-2, is in the range from 30 at-% to 40 at-%, preferably in the range from 31 at-% to 36 at-%; and / or the molar fraction of Si near the surface of the plasma polymer solid or the plasma polymer layer, measured by XPS according to the procedure from Example 2-2, is in the range from 23 at-% to 28.5 at-%; and / or the molar fraction of C near the surface of the plasma polymer solid or the plasma polymer layer, measured by XPS according to the procedure from Example 2-2, is in the range from 30 at-% to 45 at-%, preferably in the range from 34 at-% to 44 at-%; and / or the molar fraction of N near the surface of the plasma polymer solid orof the plasma polymer layer, measured by XPS according to the procedure of Example 2-2, is 0.1 at-% or less; the percentages being based on the total number of atoms contained in the layer that can be determined by XPS.

8. Plasma polymer solid body, in particular plasma polymer layer according to one of the preceding claims, wherein the plasma polymer solid body, in particular the plasma polymer layer, has a resistance against Fats and oils at temperatures up to 200°C, preferably edible oils at temperatures up to 200°C; liquid water up to 100°C; Steam up to 140°C; acidic liquids with a pH in the range of pH 2 to pH 4 at 23°C; basic liquids with a pH in the range of pH 11 to pH 12.5 at 23°C; Solvents, especially isopropanol, acetone, ethanol, n-heptane, and methyl ethyl ketone at a temperature of 23°C; various cleaning processes, such as CO2 jet cleaning and high-pressure water cleaning up to 1000 bar working pressure; Cleaning sponges that do not contain particles with a Mohs hardness of more than 3.5, in particular no particles consisting of corundum.

9. Plasma polymer solid, in particular plasma polymer layer according to one of the preceding claims, wherein the plasma polymer solid, in particular the plasma polymer layer, is dishwasher-resistant, determined according to Example 8.

10. Plasma polymer solid body, in particular plasma polymer layer according to one of the preceding claims, wherein the plasma polymer solid or the plasma polymer layer has a thickness in the range of 5 nm to 2 pm, preferably a layer thickness in the range of 10 nm to 1 pm, particularly preferably a layer thickness in the range of 20 nm to 0.5 pm; and / or the plasma polymer solid or the plasma polymer layer has hydrophobic groups on its surface, preferably methyl groups and / or the water contact angle, determined according to the procedure from Example 3, is in the range of 80° to 100°.

11. Use of a plasma polymer solid, in particular a plasma polymer layer, as defined in any one of claims 1 to 10 for improving the cleanability, in particular for improving the cleanability of household items such as pans and baking utensils and cooking utensils, of casting molds, in particular casting molds in zinc die casting, aluminum die casting and magnesium die casting, of injection molds, in particular injection molds in thermoplastic injection molding, of stamps and pressing tools, of dispersing devices of metal filters for extractor hoods, of cutting tools for gardening, such as pruning shears and blades for lawnmowers;and / or as a separating layer, in particular as a separating layer for household items such as pans and baking utensils and cooking utensils, for casting moulds, in particular casting moulds for zinc die-casting, aluminium die-casting and magnesium die-casting, for injection moulds, in particular for injection moulds for thermoplastic injection moulding, for stamps and pressing tools and for dispersing devices; and / or to improve the scratch resistance, in particular to improve the scratch resistance of household items such as pans and baking utensils and cooking utensils, of casting moulds, in particular casting moulds in zinc die-casting, aluminium die-casting and magnesium die-casting, of injection moulds, in particular injection moulds in thermoplastic injection moulding, of stamps and pressing tools, of dispersing devices and of cutting tools for gardening, such as pruning shears and blades for lawn mowers.

12. A method for producing a plasma polymer solid, in particular a plasma polymer coating according to one of claims 1 to 10, comprising the steps 51) Producing or providing a substrate, 52) producing or providing two, three or more gaseous precursors; 53) introducing at least partial quantities of the gaseous precursor substances produced or provided in step S2) according to a recipe in a predefined quantity and in predefined proportions into a plasma system so that a plasma system with a continuous inflow of gaseous precursor substances results; 54) Depositing a plasma polymer solid, in particular a plasma polymer layer, from the gaseous precursor substances on the substrate produced or provided in step S1), with the plasma system with the continuous inflow of gaseous precursor substances, so that a substrate coated with a plasma polymer solid, in particular a plasma polymer layer, according to one of claims 1 to 8, results.

13. The method according to claim 12, wherein the material of the substrate produced or provided in step S1), preferably at least the material of the surface of the substrate produced or provided in step S1), is selected from the group of materials consisting of: tool steel, Stainless steel, Aluminum, ceramics, Porcelain and Glass, in particular enamel; and / or wherein the gaseous precursor substances produced or provided in step S2) and used in step S3) comprise at least: an organosilicon precursor, preferably comprising methyl groups, particularly preferably the organosilicon precursor is hexamethyldisiloxane; and Oxygen.

14. The process according to claim 13, wherein in the organosilicon precursor introduced in step S3), a ratio of -CH3 to Si of 2.7 or greater is present, preferably a ratio of 3 or greater; and / or the organosilicon precursor introduced in step S3) does not comprise any silazane compounds.

15. Method according to one of the preceding claims 12 to 14, wherein in the deposition of a plasma polymer solid, in particular a plasma polymer layer on the substrate in step S4) a plasma system with zero-bias electrode structure is used as the plasma system, and preferably the gaseous precursor substances produced or provided in step S2) and used in step S3) comprise at least: an organosilicon precursor, preferably hexamethyldisiloxane and - oxygen and wherein during introduction in step S3) a gas quantity ratio, measured in cm 3 / min, of organosilicon precursor, preferably hexamethyldisiloxane, to oxygen of more than 1.0, preferably more than 1.5, particularly preferably more than 2.0; and / or the plasma system during deposition in step S4) has a boundary layer potential in the range of 180 V to 300 V, preferably in the range of 190 V to 250 V; and / or the plasma system during deposition in step S4) has a self-bias value of less than 50 V, preferably less than 30 V, particularly preferably less than 10 V; and / or during deposition in step S4) in the plasma system such a high total gas flow is realized that the calculated total residence time of the gases in the plasma chamber is in the range from 0.05 s to 10 s, preferably in the range from 0.08 s to 1 s; or when depositing a plasma polymer solid, in particular a plasma polymer layer on the substrate in step S4), a plasma system with self-bias is used as the plasma system, and preferably the gaseous precursor substances produced or provided in step S2) and used in step S3) at least comprise: an organosilicon precursor, preferably hexamethyldisiloxane and - oxygen and wherein during introduction in step S3) a gas quantity ratio, measured in cm 3 / min, of organosilicon precursor, preferably hexamethyldisiloxane, to oxygen of more than 1.0, preferably more than 1.5, particularly preferably more than 2.0; and / or the plasma system has a boundary layer potential in the range of 250 V to 400 V during deposition in step S4), preferably in the range of 275 V to 350 V; and / or during deposition in step S4), such a high total gas flow is realized in the plasma system that the calculated total residence time of the gases in the plasma chamber is in the range of 0.01 s to 1 s, preferably in the range of 0.03 s to 0.6 s.

16. The method according to any one of the preceding claims 12 to 15, wherein the plasma system used in step S4) has a total leakage rate of less than 0.1 mbar l / s during the deposition in step S4), preferably less than 0.075 mbar l / s; and / or in the plasma system used in step S4) during the deposition in step S4), the ratio of total leakage rate to the inflow of oxygen is in the range of 0.4 or less, preferably 0.2 or less, particularly preferably 0.18 or less; and / or in the plasma system used in step S4) during the deposition in step S4), a working pressure of 0.03 mbar or less is present, preferably 0.02 mbar or less.

17. The method according to any one of the preceding claims 12 to 16, wherein the electrodes of the plasma system are designed such that no exposed electrode edges are present, at least during the deposition in step S4); and / or the plasma system is operated such that no local plasma secondary discharges occur, at least during the deposition in step S4); and / or the plasma system used in step S4) is designed such that, and the substrate produced or provided in step S1 is selected such that a) the substrate arranged on the electrode is at least 15 cm, preferably at least 20 cm, particularly preferably at least 25 cm, away from the nearest wall of the plasma system; and b) the clear distance between the walls delimiting the plasma chamber of the plasma system is at least 50 cm.

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