Solid-state plasma-polymeric siloxane body, preferably plasma-polymeric siloxane layer on a substrate, corresponding methods and corresponding uses

Abstract

The invention relates to a solid-state plasma-polymeric siloxane body, preferably a plasma-polymeric siloxane layer on a substrate, wherein, in the solid-state plasma-polymeric siloxane body, preferably in the plasma-polymeric siloxane layer on a substrate: - the ratio of hydrogen to carbon, preferably determined by means of elemental microanalysis according to example 11, lies in the range from 2.3 to 2.9; and - the atomic proportion of hydrogen, based on the total number of all elements present in the solid-state plasma-polymeric siloxane body, preferably in the plasma-polymeric siloxane layer on a substrate, is greater than 40%, preferably greater than 45%.

Description

[0001] Fraunhofer Society for the Advancement of Applied Research, registered association, Hansastraße 27c, 80686 Munich

[0002] Plasma-polymerized siloxane solids, preferably plasma-polymerized siloxane layers on a substrate, corresponding processes and corresponding uses

[0003] The present invention relates to a plasma-polymerized siloxane solid, preferably a plasma-polymerized siloxane layer on a substrate, with a more precisely defined ratio of hydrogen to carbon and a more precisely defined proportion of hydrogen. The present invention further relates to a method for producing a plasma-polymerized siloxane solid, preferably a plasma-polymerized siloxane layer on a substrate.

[0004] The present invention also relates to corresponding uses.

[0005] The present invention relates to the technical field of plasma-polymer release and easy-to-clean coatings based on siloxane chemistry. The technical article entitled "The Heterogeneous Nature of Deposits from Hexamethyldisiloxane / oxygen Plasmas" by MR Alexander, RD Short, FR Jones, M Stollenwerk, G Mathar, J Zabold, and W Michaeli, published in "Ceramic film and coatings: papers presented at the ceramic films and coatings meeting held at Sheffield University on 19-20 December, 1994"; London: Institute of Materials, 1995 (British Ceramic Proceedings; 54); pages 87 to 99; ISBN 0-901716-79-0, summarizes the effects of adding oxygen to microwave plasmas of hexamethyldisiloxane (HMDSO). Network formation via Si-O bonds is discussed in detail.

[0006] Document DE 101 31 156 A 1 discloses an article comprising a substrate and a plasma-polymer coating comprising oxygen, carbon and silicon, which is bonded over an area to the substrate, wherein the following molar ratios apply in the plasma-polymer coating on the side facing away from the substrate: 1.1 : 1 < n(O) : n(Si) < 2.6 : 1 ; 0.6 : 1 < n(C) : n(Si) < 2.2 : 1 ; preferably: 1.4 : 1 < n(O) : n(Si) < 1.9 : 1 ; 1.2 : 1 < n(C) : n(Si) < 1.7 : 1.

[0007] Document WO 2015 / 044247 discloses a plasma-polymerized solid, in particular a plasma-polymerized layer, wherein the lower limit of the Young's modulus of the coating is determined by the following function (1): E = 25 - 31.5*x + 13.5*x² - 1.85*x³ (1) with x = C / O ratio determined by XPS (X-ray photoelectron spectroscopy) E = Young's modulus [GPa] for E > 1.25 GPa and x > 0.5 and < 2.0; wherein, measured on the surface of the layer by XPS (X-ray photoelectron spectroscopy), the maximum of the Si 2p peak is: for Young's 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.

[0008] Document DE 10 2017 131 085 A1 discloses 1. Plasma-polymer solid, in particular plasma-polymer layer, wherein the lower limit of the Young's 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 (1) with x = C / O molar ratio determined by XPS (X-ray photoelectron spectroscopy) E = Young's modulus [GPa] for E = 1.5 to 20 GPa and x > 1.3 and < 2.0.

[0009] The current state of the art reveals a need for hard and resistant release coatings or easy-to-clean coatings, particularly those that eliminate the need for additional release agents. Release coatings or easy-to-clean coatings are especially suitable for thermoplastic processing in injection molding (e.g., to suppress deposit formation), for casting processes (e.g., zinc, aluminum, and magnesium die casting), and for reactive resins (e.g., unsaturated polyurethane resins with fiberglass fabric).

[0010] In thermoplastic injection molding, the plasticized material, which may contain fillers, exerts particularly strong shear stresses on the release agents used. In contrast, when processing molten metal, the metallic liquid is injected turbulently and at high velocity and solidifies in the mold. In both cases, temperature-related volume changes of the molded part during removal create locally strong frictional forces, which lead to undesirably high wear in conventional release agents or easy-to-clean coatings.

[0011] There is also a need for release coatings or easy-to-clean coatings suitable for use with food, particularly for release coatings or easy-to-clean coatings suitable for household use. Furthermore, there is 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, additives, catalysts, pigments, and residues of the starting materials, and that also meet the requirements for stirring and cutting resistance (whisk, knife, or spatula) in the relevant technical field. The use of per- and polyfluorinated chemicals (PFAS) is increasingly considered problematic in the field of the present invention and is therefore undesirable.

[0012] There is also a need for release coatings or easy-to-clean coatings that exhibit minimal cracking and maintain good adhesion to the substrate under temperature-induced, torsional, and / or vibration-induced movements. A further need exists for easy-to-clean coatings with high optical transparency in the wavelength range of 200 nm to 400 nm, preferably in combination with the aforementioned requirements.

[0013] Furthermore, the current state of the art reveals a need for release coatings or easy-to-clean coatings that have a hydrophobic surface.

[0014] As many of the aforementioned requirements as possible should be met, either wholly or partially. The invention is defined in the accompanying claims. Preferred aspects of the present invention will also become apparent from the following description, including the examples. Where specific embodiments are designated as preferred for an aspect of the invention (plasma polymer siloxane solid, preferably a plasma polymer siloxane layer on a substrate, corresponding methods, and corresponding uses), the corresponding descriptions shall also apply, mutatis mutandis, to the other aspects of the present invention. 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 a person skilled in the art from the present text in a particular case.

[0015] According to a primary aspect of the present invention, the aforementioned tasks and problems are wholly or partially solved by a plasma-polymerized siloxane solid, preferably by a plasma-polymerized siloxane layer on a substrate, wherein in the plasma-polymerized siloxane solid, preferably in the plasma-polymerized siloxane layer on a substrate, the ratio of hydrogen to carbon, preferably determined by microelement analysis according to Example 11 or by secondary ion mass spectrometry (SIMS), particularly preferably by microelement analysis according to Example 11, is in the range of 2.3 to 2.9;and the atomic fraction of hydrogen, based on the total number of all elements contained in the plasma-polymerized siloxane solid, preferably in the plasma-polymerized siloxane layer on a substrate, is greater than 40%, preferably greater than 45%, and wherein the ratio of the sum of monofunctional and difunctional oxygen fractions of the Si2p peak of the X-ray photoelectron spectroscopy signal determined according to Example 2 to the sum of trifunctional and tetrafunctional oxygen fractions of the Si2p peak of the X-ray photoelectron spectroscopy signal determined according to Example 2 is from 0.25 to 1.2.

[0016] In many cases, it is preferred that the ratio of hydrogen to carbon be determined by microelemental analysis according to Example 11 of this text. This is preferred.

[0017] In many cases, it is preferred that the hydrogen-to-carbon ratio be determined by secondary ion mass spectrometry (SIMS). The method of determination is known to those skilled in the art.

[0018] The term "siloxane" is understood, in accordance with the usual understanding of the person skilled in the art, to mean oxygen compounds of silicon of the general formula H3Si-[O-SiH2]nO-SiH3 with n = 0, 1 etc.; the hydrogen atoms can be replaced by organic residues or halogen atoms.

[0019] Accordingly, a “plasma-polymer siloxane solid” is understood to be a solid that can be produced, preferably by means of a plasma process, and which consists predominantly, substantially entirely, or entirely, preferably substantially entirely, of siloxane.

[0020] The term "siloxane" refers, in accordance with the usual understanding of those skilled in the art, to chemical compounds with the general formula R3Si-[O-SiR2]nO-SiR3, where R is preferably selected independently from the group consisting of hydrogen atoms and alkyl groups. Unlike silanes, the silicon atoms in siloxanes are not linked to each other, but rather to their neighboring silicon atom by exactly one oxygen atom: Si-O-Si. Within the scope of the present invention, a siloxane produced by a plasma process is preferred, comprising trifunctional [CHsSiOsc] and tetrafunctional [SiO4 / 2]SiO compounds; such siloxanes often contain a very stable silicon-oxygen-silicon backbone, which leads to mechanical properties that are regularly considered particularly advantageous in the field of the present invention.A “plasma-polymer siloxane layer on a substrate” is understood to be a planar structure (layer) that can be produced, preferably by means of a plasma process, which is bonded to a substrate over a planar area and which consists predominantly, substantially entirely or completely, preferably substantially entirely, of siloxane, preferably a siloxane as described above, particularly preferably a siloxane as designated as preferred above.

[0021] The combination of a hydrogen-to-carbon ratio within the aforementioned defined range with an atomic proportion of hydrogen within the aforementioned defined range yields particularly advantageous crosslinking results, properties, and property combinations. Surprisingly, a correspondingly high proportion of hydrogen within the aforementioned defined range is associated with an advantageously high hardness of the plasma-polymerized siloxane solid according to the invention, preferably of the plasma-polymerized siloxane layer on a substrate according to the invention; the other effects and advantages described in connection with the plasma-polymerized siloxane solid or the plasma-polymerized siloxane layer on a substrate according to the invention are advantageously achieved in combination with the advantageously high hardness.

[0022] Methods for determining hydrogen in a “plasma-polymer siloxane solid” or a “plasma-polymer siloxane layer on a substrate” are known to those skilled in the art from general technical knowledge.

[0023] The determination of hydrogen in a plasma-polymerized siloxane solid or a plasma-polymerized siloxane layer on a substrate is complex and prone to error. Therefore, during the analysis, the person skilled in the art takes precautions to minimize, and preferably substantially eliminate, all known sources of error. In particular, the person skilled in the art will ensure that the results are not distorted by the unintentional inclusion of other substances (e.g., components of the substrate or the plasma-polymerized siloxane layer on a substrate) when determining hydrogen in a plasma-polymerized siloxane solid or a plasma-polymerized siloxane layer on a substrate. The hydrogen content in layers according to the invention (as well as in DLC (diamond-like carbon) layers) can be determined by various methods.The following methods are commonly used in the field of the present invention:

[0024] Secondary ion mass spectrometry (SIMS): This technique allows the analysis of the chemical composition of surfaces and thin films, including the hydrogen content, provided suitable reference substances are available.

[0025] (Micro)elemental analysis: This generally refers to a so-called combustion analysis. In this process, the sample to be analyzed is first weighed precisely using a balance and then catalytically combusted with pure oxygen at high temperatures. Immediately afterward, the combustion gases formed (oxidation products) are passed over a hot copper or tungsten contact using a carrier gas, and any nitrogen oxides (NOx) contained in the gas stream are completely reduced to molecular nitrogen (N2). Subsequently, the defined combustion gases (CO2, H2O, SO2, N2) are separated in specific separation columns (so-called adsorption-desorption columns) or by gas chromatography and successively fed to a thermal conductivity detector (TCD or TCD) and quantified. In case of doubt, the person skilled in the art should follow the procedure described in Example 11 of this text.

[0026] Thermal Desorption Spectroscopy (TDS): In this method, the sample is heated and the released gases are analyzed to determine the hydrogen content.

[0027] Within the scope of the present invention, the hydrogen content is determined by microelemental analysis according to the exemplary embodiment shown in "Example 11" below. This method allows the quantitative determination of the carbon and hydrogen content of a sample. In combination with atomic mass determination using XPS, this enables the determination of the atomic composition of the coating. Even small fluctuations in the hydrogen content can be detected, see Example 11.

[0028] XPS stands for "X-ray photoelectron spectroscopy". XPS is also known to experts as "X-ray photoelectron spectroscopy".

[0029] In well-crosslinked, PDMS-like (polydimethylsiloxane-like) plasma-polymerized siloxane solids, or plasma-polymerized siloxane layers on a substrate, crosslinking is controlled by adding oxygen to the plasma discharge and varying the power coupled into the plasma. Such plasma-polymerized solids, especially plasma-polymerized layers, can, in principle, crosslink via four structural groups. A high proportion of secondary silicon structural elements are regularly found, i.e., silicon structural elements in which two oxygen atoms are arranged on one silicon atom, 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.

[0030] The sum of monofunctional and difunctional oxygen components of the Si2p peak of the XPS signal (X-ray photoelectron spectroscopy signal) is to be determined according to the procedure given in Example 2; in case of doubt, the prior art documents cited in Example 2 are to be consulted.

[0031] The sum of trifunctional and tetrafunctional oxygen fractions of the Si2p peak of the XPS signal (X-ray photoelectron spectroscopy signal) is to be determined according to the procedure given in Example 2; in case of doubt, the prior art documents cited in Example 2 are to be consulted.

[0032] A higher degree of crosslinking in siloxanes produced by the PECVD (Plasma Enhanced Chemical Vapor Deposition) process can be achieved through various measures; these include the following:

[0033] Increased plasma power: By increasing the plasma power, more high-energy ions and radicals can be generated, which promote the cross-linking of siloxanes via oxygen bridges.

[0034] Increasing the self-bias: The self-bias is a voltage that attracts positive ions from the plasma to the sample surface. This results in ion bombardment. This mass and energy input increases the deposition rate and influences the degree of crosslinking. Experts take care not to select excessively high self-bias voltages, as otherwise plasma etching processes will predominate.

[0035] Adjusting the gas composition: The addition of oxygen or other reactive gases can increase the crosslinking density by creating additional crosslinking sites. Temperature control: Precise control of the substrate temperature can influence the mobility of the molecules and thus the crosslinking density. This approach is regularly used, particularly in the semiconductor industry.

[0036] Optimization of process parameters: Parameters such as pressure, total gas flow rate, and plasma density can be adjusted to promote the formation of highly cross-linked structures. A person skilled in the art of the present invention can optimize the process parameters through simple experiments and without undue effort, based on their general expertise.

[0037] The inventors have surprisingly discovered that by selectively varying the hydrogen content in a plasma-polymerized siloxane solid (preferably in a plasma-polymerized siloxane layer on a substrate), a significantly higher Young's modulus, combined with significantly high tensile strength and also with significantly high thermal shock resistance, could be achieved. This is particularly surprising because the prior art (see especially the book chapter "Chapter β - Dynamic effects in siloxane PECVD coatings" by K. Zuber, R. Radjef, and C. Hall in "Nanostructured Thin Films", 2019; ISBN 978-0-08-102572-7; https: / / doi.org / 10.1016 / B978-0-08-102572-7) shows that...00006-4) it was previously assumed that a higher degree of crosslinking in a corresponding plasma-polymerized siloxane solid (preferably in a plasma-polymerized siloxane layer on a substrate) leads to a fracture tendency perceived as disadvantageously high in the field of the present invention; however, such a fracture tendency perceived as disadvantageously high in the field of the present invention does not occur in the layers according to the invention.

[0038] The plasma-polymer siloxane solids or plasma-polymer siloxane layers according to the invention, applied to a substrate, are in many cases designed as release agents or easy-to-clean coatings, preferably without the need for additional release agents. When using the plasma-polymer solids, and in particular the plasma-polymer layers, according to the invention as release agents or easy-to-clean coatings, the use of fluorine, and especially per- and polyfluorinated chemicals (PFAS), is avoided. Furthermore, when using the plasma-polymer solids, and in particular the plasma-polymer layers, according to the invention as release agents or easy-to-clean coatings, the use of cyclic methylsiloxanes is avoided.

[0039] In many cases where the plasma-polymer siloxane solid or the plasma-polymer siloxane layer according to the invention is formed on a substrate as a release coating or easy-to-clean coating, the aforementioned properties, preferably the aforementioned combinations of properties, are also combined with a particularly low tendency to crack formation during temperature-related and / or torsion-related and / or vibration-related movements of the coated substrate and a particularly good adhesion to the surface of a coated substrate during temperature-related and / or torsion-related and / or vibration-related movements of the coated substrate.

[0040] A plasma-polymerized siloxane solid (as described above, preferably referred to as preferred above) is preferred, preferably a plasma-polymerized siloxane layer on a substrate (as described above, preferably referred to as preferred above), wherein the plasma-polymerized siloxane solid, preferably the plasma-polymerized siloxane layer on a substrate, contains the ratio of determinable by XPS (X-ray photoelectron spectroscopy) of

[0041] Oxygen

[0042] silicon

[0043] 0.6 or greater; and / or in the plasma-polymerized siloxane solid, preferably in the plasma-polymerized siloxane layer on a substrate, the proportion of non-carbon atoms determinable by XPS (X-ray photoelectron spectroscopy) is 20 at% or more, preferably more than 20 at%, based on the total number of atoms determinable by XPS (X-ray photoelectron spectroscopy) in the plasma-polymerized siloxane solid, preferably in the plasma-polymerized siloxane layer on a substrate; and / or in the plasma-polymerized siloxane solid, preferably in the plasma-polymerized siloxane layer on a substrate, the total proportion of atoms selected from the group consisting of oxygen atoms and silicon atoms, determinable by XPS (X-ray photoelectron spectroscopy), is 20 at% or more, preferably more than 20 at%.-%; based on the total number of atoms determinable by XPS (X-ray photoelectron spectroscopy) in the plasma-polymerized siloxane solid, preferably in the plasma-polymerized siloxane layer on a substrate; and / or in the plasma-polymerized siloxane solid, preferably in the plasma-polymerized siloxane layer on a substrate, a ratio of the.

[0044] - Sum of monofunctional and difunctional oxygen fractions of the Si2p peak of the XPS signal (X-ray photoelectron spectroscopy signal) determined according to Example 2; to the

[0045] The sum of trifunctional and tetrafunctional oxygen fractions of the Si2p peak of the XPS signal (X-ray photoelectron spectroscopy signal) is determined according to Example 2; the value ranges from 0.6 to 1.0. XPS stands for "X-ray photoelectron spectroscopy." XPS is also known to those skilled in the art as "X-ray photoelectron spectroscopy."

[0046] In well-crosslinked, PDMS-like (polydimethylsiloxane-like) plasma-polymerized siloxane solids, or plasma-polymerized siloxane layers on a substrate, crosslinking is controlled by adding oxygen to the plasma discharge and varying the power coupled into the plasma. Such plasma-polymerized solids, especially plasma-polymerized layers, can, in principle, crosslink via four structural groups. A high proportion of secondary silicon structural elements are regularly found, i.e., silicon structural elements in which two oxygen atoms are arranged on one silicon atom, 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.

[0047] The sum of monofunctional and difunctional oxygen components of the Si2p peak of the XPS signal (X-ray photoelectron spectroscopy signal) is to be determined according to the procedure given in Example 2; in case of doubt, the prior art documents cited in Example 2 are to be consulted.

[0048] The sum of trifunctional and tetrafunctional oxygen fractions of the Si2p peak of the XPS signal (X-ray photoelectron spectroscopy signal) is to be determined according to the procedure given in Example 2; in case of doubt, the prior art documents cited in Example 2 are to be consulted.

[0049] A ratio of oxygen to silicon as defined above leads in many cases to particularly advantageous properties (as described above, preferably as preferred) and combinations of properties (as described above, preferably as preferred) in the plasma-polymer siloxane solid or in the plasma-polymer siloxane layer on a substrate according to the invention.

[0050] A proportion of non-carbon atoms, as defined above, leads in many cases to particularly advantageous properties (as described above, preferably as designated as preferred) and combinations of properties (as described above, preferably as designated as preferred) in the plasma-polymerized siloxane solid or in the plasma-polymerized siloxane layer on a substrate according to the invention. These advantageous properties are not achieved by nitrogen-containing compounds, so-called silazanes.

[0051] A proportion of atoms as defined above, selected from the group consisting of oxygen atoms and silicon atoms, leads in many cases to particularly advantageous properties (as described above, preferably as referred to above as preferred) and combinations of properties (as described above, preferably as referred to above as preferred) in the plasma-polymer siloxane solid or in the plasma-polymer siloxane layer on a substrate according to the invention.

[0052] A forthcoming defined ratio of the sum of monofunctional and difunctional oxygen fractions of the Si2p peak of the X-ray photoelectron spectroscopy signal, determined according to Example 2, to the sum of trifunctional and tetrafunctional oxygen fractions of the Si2p peak of the X-ray photoelectron spectroscopy signal, also determined according to Example 2, is an expression of special properties of the layers according to the invention: These layers have a high proportion of tri- and quaternary functional SiO units, while the proportion of monofunctional and difunctional SiO units in the layers according to the invention is relatively low.

[0053] This distinguishes the layers according to the invention, for example, from the layers disclosed in DE 102020128125 A1 and DE 102017131085 A1. The special feature of the layers according to the invention discussed here leads to surprisingly advantageous properties, such as the possibility of generating a very favorable ratio of high hardness and low surface energy. One measure that is particularly effective in achieving the desired ratio discussed here is the adjustment of a suitable (relatively high) self-bias during the deposition of the plasma-polymer siloxane solid or the plasma-polymer siloxane layer according to the invention.

[0054] A plasma-polymerized siloxane solid, preferably a plasma-polymerized siloxane layer on a substrate, with a ratio of determinable by X-ray photoelectron spectroscopy of

[0055] An oxygen to silicon ratio of 0.6 or greater, preferably 1.0 or greater, is, in the context of this application, a siloxane.

[0056] A plasma-polymerized siloxane solid (as described above, preferably referred to as preferred above) is preferred, preferably a plasma-polymerized siloxane layer on a substrate (as described above, preferably referred to as preferred above), wherein the plasma-polymerized siloxane solid, preferably the plasma-polymerized siloxane layer on a substrate, has a Young's modulus, determined by the surface acoustic waves method according to the procedure in Example 4, in the range of 10 GPa to 45 GPa; and / or a surface energy, determined at the surface of the plasma-polymerized siloxane solid, preferably at the surface of the plasma-polymerized siloxane layer on a substrate facing away from the substrate, by contact angle measurement according to the procedure in Example 3, in the range of 22.5 mN / m to 29.5 mN / m, preferably in the range of 23.5 mN / m to 28.5 mN / m.

[0057] The determination of the modulus of elasticity is carried out within the scope of the present invention using the surface acoustic wave method according to the procedure described in Example 4.

[0058] In many cases, the plasma-polymer siloxane solid according to the invention, preferably the plasma-polymer siloxane layer according to the invention on a substrate, with a Young's modulus in the range defined above, exhibits a particularly advantageously low tendency to crack formation during temperature-induced and / or torsional 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 aforementioned combinations of properties are particularly preferred when the plasma-polymer siloxane solid according to the invention, preferably the plasma-polymer siloxane layer according to the invention on a substrate, is designed as a release coating or easy-to-clean coating.

[0059] In many cases, the plasma-polymer siloxane solid according to the invention, preferably the plasma-polymer siloxane layer according to the invention on a substrate with a Young's modulus in the range defined above, exhibits particularly advantageously good adhesion to the surface of a substrate coated therewith under temperature-induced and / or torsional and / or vibration-induced movements of the coated substrate. This is especially true if the surface to be coated is first finely cleaned (as is known in the prior art in the field of the present invention) and an adhesion promoter layer (as is known in the prior art in the field of the present invention) is used.Gradient layers are particularly preferred as adhesion promoters, 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; such gradient layers and their fabrication are known to those skilled in the art. The further advantageous properties of the plasma-polymerized siloxane solid according to the invention, preferably the plasma-polymerized siloxane layer on a substrate according to the invention, are realized here to a preferred extent in combination with the advantageously good adhesion to the surface of a substrate coated therewith. The aforementioned combinations of properties are particularly preferred when the plasma-polymerized siloxane solid according to the invention, preferably the plasma-polymerized siloxane layer on a substrate according to the invention, is designed as a release coating or an easy-to-clean coating.

[0060] Separating coatings or easy-to-clean coatings are known to those skilled in the art in the field of the present invention.

[0061] The determination of the surface energy is carried out within the scope of the present invention by means of contact angle measurement according to the procedure described in Example 3 of the present text.

[0062] In many cases, the plasma-polymerized siloxane solid according to the invention, preferably the plasma-polymerized siloxane layer on a substrate, with a surface energy in the range defined above, exhibits particularly advantageous hydrophobic (water-repellent) properties. The further advantageous properties of the plasma-polymerized siloxane solid according to the invention, preferably the plasma-polymerized siloxane layer on a substrate, are realized here to a preferred extent in combination with the particularly advantageous hydrophobic properties. The aforementioned combinations of properties are particularly preferred when the plasma-polymerized siloxane solid according to the invention, preferably the plasma-polymerized siloxane layer on a substrate, is designed as a release coating or easy-to-clean coating.

[0063] A plasma-polymerized siloxane solid (as described above, preferably referred to as preferred above), preferably a plasma-polymerized siloxane layer on a substrate (as described above, preferably referred to as preferred above), wherein the plasma-polymerized siloxane solid, preferably the plasma-polymerized siloxane layer on a substrate, has a Mohs hardness, determined according to the procedure in Example 5, in the range of 2.5 to 5.5, preferably in the range of 3.5 to 5.5; and / or a mass density, determined by the surface acoustic waves method according to Example 4, in the range of 1.25 g / cm³ 3 up to 1.80 g / cm³ 3 possesses, preferably in the range of 1.25 g / cm³ 3 up to 1.60 g / cm³ 3 .

[0064] Within the scope 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 on a suitably hard substrate.

[0065] Plasma-polymer siloxane solids or plasma-polymer siloxane layers according to the invention, on a substrate with a Mohs hardness in the range defined above, exhibit stirring and cutting resistance that is considered particularly advantageous in the field of the present invention. Plasma-polymer siloxane solids or plasma-polymer siloxane layers according to the invention, on a substrate with a Mohs hardness in the range defined above, exhibit resistance to the forces acting on a release layer in thermoplastic injection molding, which is considered particularly advantageous in the field of the present invention. The aforementioned combinations of properties are particularly preferred when the plasma-polymer siloxane solid or plasma-polymer siloxane layer according to the invention is designed as a release coating or easy-to-clean coating on a substrate.

[0066] When using plasma-polymerized siloxane solids or plasma-polymerized siloxane layers according to the invention on a substrate with a Mohs hardness in the range defined above as a release layer in thermoplastic injection molding, a particularly advantageously long service life (meaning a high number of injection molding cycles 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-polymerized siloxane solids or, preferably, the plasma-polymerized siloxane layers according to the invention on a substrate. The aforementioned combination of properties is particularly preferred when the plasma-polymerized siloxane solid or, preferably, the plasma-polymerized siloxane layer according to the invention on a substrate is designed as a release coating or easy-to-clean coating.

[0067] The determination of the mass density is carried out within the scope of the present invention using the Surface-Acoustic-Waves method according to the procedure described in Example 4 of the present text.

[0068] Plasma-polymer siloxane solids according to the invention, preferably plasma-polymer siloxane layers according to the invention on a substrate, with mass densities in the above-defined range, exhibit in many cases particularly advantageous properties, preferably combinations of properties.

[0069] Furthermore, the other advantageous properties, preferably advantageous combinations of properties, of the plasma-polymer siloxane solid according to the invention, preferably of the plasma-polymer siloxane layer according to the invention on a substrate, are also realized here to a particularly preferred extent.

[0070] A plasma-polymerized siloxane solid (as described above, preferably referred to as preferred above), preferably a plasma-polymerized siloxane layer on a substrate (as described above, preferably referred to as preferred above), having a polar component of the surface energy, determined at the surface of the plasma-polymerized siloxane solid, preferably at the side facing away from the substrate or of the plasma-polymerized siloxane layer on a substrate, according to the procedure in Example 3, of less than 1.8 mN / m, preferably of less than 1.5 mN / m.

[0071] The other effects and advantages described in connection with the plasma-polymer siloxane solid according to the invention, preferably the plasma-polymer siloxane layer on a substrate, are also realized here to a preferred extent.

[0072] A plasma-polymerized siloxane solid (as described above, preferably referred to as preferred above) is preferred, preferably a plasma-polymerized siloxane layer on a substrate (as described above, preferably referred to as preferred above), wherein in the XPS (X-ray photoelectron spectroscopy) spectrum the Si 2p photoline is at an energy of less than 102.8 eV, preferably less than 102.5 eV; and wherein in the XPS (X-ray photoelectron spectroscopy) spectrum the Si 2p photoline is at an energy of more than 101.8 eV.

[0073] A plasma-polymerized siloxane solid according to the invention, preferably a plasma-polymerized siloxane layer according to the invention on a substrate, with a silicon 2p photoline in the XPS spectrum (measured according to the procedure described in Example 2 of this document) at an energy in the ranges described above and with a full width at half maximum (FWHM) of the Si 2p photoline in the XPS spectrum (measured according to the procedure described in Example 2 of this document) as defined above, exhibits in many cases 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 combinations of properties 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.The other effects and advantages described in connection with the plasma-polymer siloxane solid according to the invention, preferably the plasma-polymer siloxane layer on a substrate, are also realized here to a preferred extent.

[0074] A plasma-polymerized siloxane solid (as described above, preferably referred to as preferred above), preferably a plasma-polymerized siloxane layer on a substrate (as described above, preferably referred to as preferred above), wherein the molar ratio of O to Si near the surface of the plasma-polymerized siloxane solid, preferably near the surface of the plasma-polymerized siloxane layer on a substrate facing away from the substrate, measured by XPS (X-ray photoelectron spectroscopy) according to Example 2-1 at a measurement angle to the sample normal of 0°, and / or measured by XPS (X-ray photoelectron spectroscopy) according to Example 2-2 at a measurement angle to the sample normal of 75°, is in the range of 1.05 to 1.50, preferably in the range of 1.08 to 1.25; and / or the molar ratio of C to Si near the surface of the plasma-polymerized siloxane solid,preferably near the surface of the plasma-polymerized siloxane layer facing away from the substrate, as measured by XPS (X-ray photoelectron spectroscopy) according to Example 2-1 at a measurement angle to the sample normal of 0°, and / or as measured by XPS (X-ray photoelectron spectroscopy) according to Example 2-2 at a measurement angle to the sample normal of 75°, in the range of 1.05 to 1.65, and / or the molar ratio of C to O is near the surface of the plasma-polymerized siloxane solid, preferably near the surface of the plasma-polymerized siloxane layer facing away from the substrate, as measured by XPS (X-ray photoelectron spectroscopy) according to Example 2-1 at a measurement angle to the sample normal of 0°, and / or as measured by XPS (X-ray photoelectron spectroscopy) according to Example 2-2 at a measurement angle to the sample normal of 75°, in the range from 0.85 to 1.60, preferably between 1.1 and 1.5.

[0075] The stoichiometric ratio of O to Si near the surface, measured by XPS (X-ray photoelectron spectroscopy) according to Example 2-1 at a measurement angle to the sample normal of 0°, means that the resulting information of the XPS spectrum originates from a region of approximately 0 nm to approximately 10 nm below the investigated surface of the investigated sample.

[0076] The stoichiometric ratio of O to Si near the surface, measured by XPS (X-ray photoelectron spectroscopy) according to Example 2-2 at a measurement 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 investigated surface of the investigated sample.

[0077] In many cases, minimizing the deviation of the O₂ to Si stoichiometric ratio measured on a plasma-polymerized siloxane solid, preferably a plasma-polymerized siloxane layer on a substrate, at both a measurement angle of 0° and a measurement angle of 75° to the sample normal is particularly advantageous. Such plasma-polymerized siloxane solids, preferably plasma-polymerized siloxane layers on a substrate, are particularly homogeneous, especially with regard to their near-surface chemical composition (composition as a function of distance from the surface), and therefore often exhibit exceptionally homogeneous surface properties.Furthermore, in such plasma-polymerized siloxane solids, preferably in such plasma-polymerized siloxane layers on a substrate, the properties are often only minimally altered by mechanical wear. In the field of the present invention, this often leads to particularly advantageously durable plasma-polymerized siloxane solids, preferably plasma-polymerized siloxane layers on a substrate, especially when the plasma-polymerized siloxane solids, preferably the plasma-polymerized siloxane layers on a substrate, are designed as release coatings or easy-to-clean coatings.

[0078] The molar ratio of C to Si near the surface, measured by XPS (X-ray photoelectron spectroscopy) according to Example 2-1 at a measurement angle to the sample normal of 0°, means that the resulting information of the XPS spectrum originates from a region of approximately 0 nm to approximately 10 nm below the investigated surface of the investigated sample.

[0079] The molar ratio of C to Si near the surface, measured by XPS according to Example 2-2 at a measurement 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 investigated surface of the investigated sample.

[0080] In many cases, minimizing the deviation of the C to Si stoichiometric ratio measured on a plasma-polymerized siloxane solid, preferably a plasma-polymerized siloxane layer on a substrate, at both a measurement angle of 0° and a measurement angle of 75° to the sample normal is particularly advantageous. Such plasma-polymerized siloxane solids, preferably plasma-polymerized siloxane layers on a substrate, are particularly homogeneous, especially with regard to their near-surface chemical composition (composition as a function of distance from the surface), and therefore often exhibit particularly homogeneous surface properties.Furthermore, in such plasma-polymerized siloxane solids, preferably in such plasma-polymerized siloxane layers on a substrate, the properties are often only altered to a beneficially small extent even under mechanical wear. In the field of the present invention, this often leads to particularly advantageously durable plasma-polymerized solids, especially plasma-polymerized layers, particularly when the plasma-polymerized solids, especially plasma-polymerized layers, are designed as release coatings or easy-to-clean coatings.

[0081] With the above-defined stoichiometric ratios, the other advantageous properties, preferably advantageous combinations of properties, of the plasma-polymer siloxane solid according to the invention, preferably of the plasma-polymer siloxane layer according to the invention on a substrate, are realized to a particularly preferred extent. In particular, especially positive combinations of properties with an advantageously good Young's modulus and an advantageously low polar component of the surface energy are realized in this way.

[0082] A plasma-polymerized siloxane solid (as described above, preferably referred to as preferred above) is preferred, preferably a plasma-polymerized siloxane layer on a substrate (as described above, preferably referred to as preferred above), wherein the mole fraction of O near the surface of the plasma-polymerized siloxane solid, preferably near the surface of the plasma-polymerized siloxane layer on a substrate facing away from the substrate, as measured by XPS (X-ray photoelectron spectroscopy) according to the procedure of Example 2-2, is in the range of 28 at-% to 44 at-%, preferably in the range of 28 at-% to 35 at-%, particularly preferably between 28 at-% and 32.5 at-%;and / or the mole fraction of Si near the surface of the plasma-polymerized siloxane solid, preferably near the surface of the plasma-polymerized siloxane layer on a substrate facing away from the substrate, as measured by XPS (X-ray photoelectron spectroscopy) according to the procedure of Example 2-2, is in the range of 24 at-% to 30 at-%; and / or the mole fraction of C near the surface of the plasma-polymerized siloxane solid, preferably near the surface of the plasma-polymerized siloxane layer on a substrate facing away from the substrate, as measured by XPS (X-ray photoelectron spectroscopy) according to the procedure of Example 2-2, is in the range of 30 at-% to 45 at-%, preferably in the range of 38 at-% to 45 at-%;and / or the mole fraction of N near the surface of the plasma-polymerized siloxane solid, preferably near the surface of the plasma-polymerized siloxane layer on a substrate facing away from the substrate, measured by XPS (X-ray photoelectron spectroscopy) according to the procedure in Example 2-2, is in the range of 0 at-% to 2 at-%, preferably in the range of 1 at-% and less; wherein the percentages are in each case based on the total number of atoms contained in the plasma-polymerized siloxane solid, preferably the plasma-polymerized siloxane layer on a substrate, that can be determined by XPS (X-ray photoelectron spectroscopy).

[0083] With the above-defined amount-of-substance ratios, the other advantageous properties (as described above, preferably as designated above as preferred), preferably advantageous combinations of properties (as described above, preferably as designated above as preferred), of the plasma-polymerized siloxane solid according to the invention, preferably of the plasma-polymerized siloxane layer according to the invention on a substrate, are realized to a particularly preferred extent. A plasma-polymerized siloxane solid (as described above, preferably as designated above as preferred), preferably a plasma-polymerized siloxane layer on a substrate (as described above, preferably as designated above as preferred), is preferred, wherein the plasma-polymerized siloxane solid, preferably the plasma-polymerized siloxane layer on a substrate, possesses resistance to

[0084] Fats and oils at temperatures up to 200 °C for an exposure time of at least 60 minutes, preferably edible oils at temperatures up to 200 °C for a duration of at least 60 minutes; and / or, preferably “and”

[0085] Fats and oils at temperatures in the range of 200 °C to 250 °C for an exposure time of at least 10 minutes, preferably edible oils at temperatures in the range of 200 °C to 250 °C for an exposure time of at least 10 minutes; and / or, preferably, liquid water up to 100 °C; and / or, preferably,

[0086] Water vapor at temperatures up to 121 °C for an exposure time of at least 60 minutes; and / or, preferably, acidic liquids with a pH in the range of pH 2 to pH 4 at a temperature of 23 °C for an exposure time of at least 4 hours; and / or, preferably, basic liquids with a pH in the range of pH 11 to pH 12.5 at a temperature of 23 °C for an exposure time of at least 4 hours; and / or, preferably,

[0087] Solvents, preferably isopropanol, acetone, ethanol, n-heptane and methyl ethyl ketone at a temperature of 23°C for an exposure time of at least 4 hours; and / or, preferably, various cleaning processes, such as CO2 jet cleaning and high-pressure water cleaning up to 1000 bar working pressure; and / or, preferably,

[0088] Cleaning sponges that do not contain particles with a Mohs hardness of more than 3.5, preferably no particles consisting of corundum; preferably possessing resistance to:

[0089] Fats and oils at temperatures up to 200 °C for an exposure time of at least 60 minutes, preferably edible oils at temperatures up to 200 °C for an exposure time of at least 60 minutes; and / or, preferably “and”

[0090] Fats and oils at temperatures in the range of 200°C to 250°C for an exposure time of at least 10 minutes, preferably edible oils at temperatures in the range of 200°C to 250°C for an exposure time of at least 10 minutes; liquid water up to 100°C; and / or, preferably, acidic liquids with a pH in the range of pH 2 to pH 4 at a temperature of 23°C for an exposure time of at least 4 hours; and / or, preferably, basic liquids with a pH in the range of pH 11 to pH 12.5 at a temperature of 23°C for an exposure time of at least 4 hours; and / or, preferably,

[0091] Solvents, preferably isopropanol, acetone, ethanol, n-heptane and methyl ethyl ketone, at a temperature of 23°C for an exposure time of at least 4 hours; and / or, preferably “and”

[0092] Cleaning sponges that do not contain particles with a Mohs hardness of more than 3.5, preferably no particles consisting of corundum; and / or, preferably “and”, wherein the plasma-polymer siloxane solid is present as a plasma-polymer siloxane layer on a substrate and wherein the substrate material is preferably a metal and / or an alloy, particularly preferably stainless steel.

[0093] A plasma-polymerized siloxane solid, preferably a plasma-polymerized siloxane layer on a substrate, possesses resistance to substances (with respect to specific conditions such as temperature and exposure duration, preferably as defined above, preferably as referred to above as preferred) if the surface energy does not change to an unacceptable extent after contact with a substance (as preferably specified above and under the aforementioned specific conditions), preferably by no more than 25%, relative to the respective value before contact with the respective substance, particularly preferably by no more than 20%, relative to the respective value before contact with the respective substance, and most preferably by no more than 15%, relative to the respective value before contact with the respective substance;and / or (preferably “and”) if the polar component of the surface energy after contact with a substance (as preferably specified above and under the specific conditions mentioned above) is at a value of 2.5 mN / m or less, preferably at a value of 2.0 mN / m or less.

[0094] A plasma-polymerized siloxane solid (as described above, preferably referred to as preferred above) is preferred, preferably a plasma-polymerized siloxane layer on a substrate (as described above, preferably referred to as preferred above), wherein the plasma-polymerized siloxane solid, preferably the plasma-polymerized siloxane layer on a substrate, has resistance to liquids with a pH value in the range of pH 2 to pH 12.5, in particular also in the range of pH 4 to pH 11, preferably with an exposure time of 4 hours.

[0095] A plasma-polymerized siloxane solid (as described above, preferably referred to as preferred above) is preferred, preferably a plasma-polymerized siloxane layer on a substrate (as described above, preferably referred to as preferred above), wherein the plasma-polymerized siloxane solid, preferably the plasma-polymerized siloxane layer on a substrate, is dishwasher-safe - in accordance with DIN EN 12875-1 :2005-08 - as determined according to Example 8.

[0096] The other advantageous properties (as described above, preferably as referred to above as preferred), preferably advantageous combinations of properties (as described above, preferably as referred to above as preferred), of the plasma-polymerized siloxane solid according to the invention, preferably of the plasma-polymerized siloxane layer according to the invention on a substrate, are also realized to a particularly preferred extent in combination with this aspect (dishwasher-safe in accordance with DIN EN 12875-1 :2005-08).

[0097] A plasma-polymerized siloxane solid (as described above, preferably referred to as preferred above), preferably a plasma-polymerized siloxane layer on a substrate (as described above, preferably referred to as preferred above), wherein the plasma-polymerized siloxane solid, preferably the plasma-polymerized siloxane layer on a substrate, 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-polymerized siloxane solid, preferably the plasma-polymerized siloxane layer on a substrate, has hydrophobic groups, preferably methyl groups, on the surface of the plasma-polymerized siloxane solid, preferably on the surface of the plasma-polymerized siloxane layer on a substrate facing away from the substrate;and / or the water surface angle, determined according to the procedure in Example 3, is in the range of 85° to 110°, preferably in the range of 90° to 105°.

[0098] Plasma-polymerized siloxane solids according to the invention, preferably plasma-polymerized siloxane layers on a substrate, with a thickness in the range defined above, are particularly preferred in many cases. Such plasma-polymerized siloxane solids, preferably plasma-polymerized siloxane layers on a substrate, often exhibit particularly favorable combinations of advantageous surface energy and advantageous mechanical properties. A corresponding thickness is particularly preferred when the plasma-polymerized siloxane solid, preferably the plasma-polymerized siloxane layer on a substrate, is designed as a release coating or an easy-to-clean coating. Methods for determining the thickness are known to those skilled in the art from their general technical knowledge.

[0099] A plasma-polymerized siloxane solid (as described above, preferably referred to as preferred above) is preferred, preferably a plasma-polymerized siloxane layer on a substrate (as described above, preferably referred to as preferred above), wherein the plasma-polymerized siloxane solid, preferably the plasma-polymerized siloxane layer on a substrate, 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 wherein the plasma-polymerized siloxane solid, preferably the plasma-polymerized siloxane layer on a substrate, has a Young's modulus, determined by the surface acoustic waves method according to the procedure in Example 4, in the range of 10 GPa to 45 GPa;and / or a surface energy, determined at the surface of the plasma-polymerized siloxane solid, preferably at the surface of the plasma-polymerized siloxane layer on a substrate facing away from the substrate, by means of contact angle measurement according to the procedure in Example 3, in the range of 22.5 mN / m to 29.5 mN / m, preferably in the range of 23.5 mN / m to 28.5 mN / m.;

[0100] In many cases, the plasma-polymer siloxane solid according to the invention, with a thickness as defined above, preferably the plasma-polymer siloxane layer according to the invention with a thickness as defined above, on a substrate with a Young's modulus in the range defined above, exhibits a particularly advantageously low tendency to crack formation during temperature-induced and / or torsional 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 siloxane solid according to the invention, preferably the plasma-polymer siloxane layer according to the invention, is designed on a substrate as a release coating or easy-to-clean coating and has a layer thickness as defined above.

[0101] Within the scope of the present invention, the term “hydrophobic groups” refers to chemical groups that already occur in the prior art on the surfaces of surface coatings known as “hydrophobic”.

[0102] The term "methyl group" refers, in accordance with the usual professional understanding, to a -CH3 group.

[0103] A plasma-polymerized siloxane solid, preferably a plasma-polymerized siloxane layer on a substrate, 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 this 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 this text).

[0104] A water edge angle, determined according to the procedure from Example 3 (of the present text), in the above-defined range of 85° to 100° is particularly preferred in many cases in the field of the present invention, especially in cases where the plasma-polymer siloxane solid, preferably the plasma-polymer siloxane layer on a substrate, is designed as a release coating or easy-to-clean coating.

[0105] The other advantageous properties (as described above, preferably as referred to above as preferred), preferably advantageous combinations of properties (as described above, preferably as referred to above as preferred), of the plasma-polymer siloxane solid according to the invention, preferably of the plasma-polymer siloxane layer according to the invention on a substrate, are also realized here to a particularly preferred extent.

[0106] A plasma-polymerized siloxane solid (as described above, preferably referred to as preferred above) is preferred, preferably a plasma-polymerized siloxane layer on a substrate (as described above, preferably referred to as preferred above), wherein the plasma-polymerized siloxane solid is a plasma-polymerized siloxane-

[0107] The layer on a substrate is, particularly preferably, a plasma-polymer siloxane layer on a substrate, wherein the material of the substrate is selected from the group of materials consisting of:

[0108] Steel preferably selected from the group consisting of tool steel and stainless steel

[0109] Aluminum,

[0110] Magnesium,

[0111] Zinc,

[0112] Chrome,

[0113] ceramics

[0114] porcelain and

[0115] Glass, preferably enamel.

[0116] In many cases where the plasma-polymer siloxane solid according to the invention, preferably the plasma-polymer siloxane layer according to the invention, is formed on a substrate as a release coating and / or easy-to-clean coating, it is preferred if the plasma-polymer siloxane solid according to the invention, preferably the plasma-polymer siloxane layer according to the invention, is formed as a coating on a substrate whose material is selected from the group of materials consisting of: steel, preferably selected from the group consisting of tool steel and stainless steel, aluminum, magnesium,

[0117] ceramics

[0118] porcelain and

[0119] Glass, especially enamel.

[0120] In many cases where the plasma-polymerized siloxane solid according to the invention, preferably the plasma-polymerized siloxane layer according to the invention, is formed on a substrate as release coatings or easy-to-clean coatings, it is equally preferred if only the surface of the substrate consists of a material selected from:

[0121] Tool steel

[0122] Stainless steel,

[0123] Aluminum,

[0124] Magnesium,

[0125] ceramics

[0126] porcelain and

[0127] Glass, in particular enamel; while portions of the substrate far from the surface, in particular portions of the substrate that are not in contact with the plasma-polymer siloxane solid according to the invention, preferably with the plasma-polymer siloxane layer according to the invention on a substrate, consist of a different material.

[0128] In this way, in many cases the properties (as described above, preferably as referred to above as preferred), preferably the combinations of properties (as described above, preferably as referred to above as preferred), of the plasma-polymer siloxane solid according to the invention, preferably of the plasma-polymer siloxane layer according to the invention on a substrate, are combined with a particularly low tendency to crack formation during temperature-related and / or twisting-related and / or vibration-related movements of the substrate coated therewith and a particularly good adhesion to the surface of a substrate coated therewith, during temperature-related and / or twisting-related and / or vibration-related movements of the substrate coated therewith.

[0129] In this way, in many cases the properties (as described above, preferably as referred to above as preferred), preferably the combinations of properties (as described above, preferably as referred to above as preferred), of the plasma-polymer siloxane solid according to the invention, preferably of the plasma-polymer siloxane layer according to the invention on a substrate, are combined with a particularly advantageously good adhesion to the surface of the corresponding substrate during temperature-related and / or twisting-related and / or vibration-related movements of the substrate coated therewith and a particularly good adhesion to the surface of the substrate coated therewith, during temperature-related and / or twisting-related and / or vibration-related movements of the substrate coated therewith.

[0130] The present invention further relates in particular and preferably to a method for producing a plasma-polymerized siloxane solid (preferably as described above, preferably as referred to above as preferred), preferably a plasma-polymerized siloxane layer on a substrate (preferably as described above, preferably as referred to above as preferred), comprising the steps

[0131] 51) Producing or providing a substrate,

[0132] 52) Manufacturing or supplying two, three or more gaseous precursor substances;

[0133] 53) Introducing at least partial quantities of the gaseous precursor substances produced or provided in step S2) according to a formulation in predefined quantities and ratios into a plasma system, resulting in a plasma system with a continuous inflow of gaseous precursor substances; S4) Deposition of a plasma-polymerized siloxane solid, in particular a plasma-polymerized siloxane layer, from the gaseous precursor substances onto the substrate produced or provided in step S1) using the plasma system with the continuous inflow of gaseous precursor substances, resulting in a plasma-polymerized siloxane solid (preferably as described above, preferably as referred to above as preferred), preferably a plasma-polymerized siloxane layer on a substrate (preferably as described above, preferably as referred to above as preferred).

[0134] Within the scope of the present invention, it is preferred that the substrate is a suitably pre-purified substrate; methods for suitable pre-purification of substrates are known to those skilled in the art.

[0135] The deposition in step S4) is preferably carried out by means of a continuous, uninterrupted plasma discharge.

[0136] Within the scope of the present invention, it is preferred that a plasma-polymer siloxane layer on a substrate is a plasma-polymer siloxane coating on a substrate, wherein preferably the plasma-polymer siloxane coating on a substrate or the plasma-polymer siloxane layer on a substrate is contacted with the substrate in a planar, preferably planar and adhesive, manner.

[0137] The process according to the invention produces the plasma-polymerized siloxane solids, preferably the plasma-polymerized siloxane layers on a substrate, in a particularly efficient manner. The effects and advantages described above in connection with the plasma-polymerized siloxane solid and / or the plasma-polymerized siloxane layer on a substrate are realized in a particularly advantageous manner and to a particularly positive extent with the process according to the invention.

[0138] A preferred method is one for producing a plasma-polymerized siloxane solid (preferably as described above, particularly preferably as referred to above as preferred), preferably a plasma-polymerized siloxane layer on a substrate (preferably as described above, particularly preferably as referred to above as preferred), wherein the roughness values ​​Sa and Sq of the substrate before the deposition of a plasma-polymerized siloxane solid, in particular a plasma-polymerized siloxane layer in step S4), are smaller than Sa = 0.4 nm and Sq = 0.5 nm, determined according to Example 10, and the roughness values ​​Sa and Sq of the plasma-polymerized siloxane solid, in particular a plasma-polymerized siloxane layer, on this substrate after coating in step S4), are smaller than Sa = 0.45 nm and Sq = 0.55 nm, determined according to Example 10.

[0139] A preferred method is (as described above, preferably referred to as preferred above), wherein the material of the substrate produced or provided in step S1), preferably at least the surface material of the substrate produced or provided in step S1), is selected from the group of materials consisting of:

[0140] Steel preferably selected from the group consisting of tool steel and stainless steel

[0141] Aluminum,

[0142] Magnesium,

[0143] Zinc,

[0144] Chrome,

[0145] ceramics

[0146] porcelain and

[0147] 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, the organosilicon precursor hexamethyldisiloxane being particularly preferred; and

[0148] Oxygen.

[0149] Using the materials defined above as substrates in step S1, the inventive method often yields particularly advantageous results. This is especially true in cases where

[0150] The chemical compound “hexamethyldisiloxane” is also known as “2,2,4,4-tetramethyl-3-oxa-2,4-disilapentane” and “HMDSO”.

[0151] In the context of the present invention, the term "oxygen" is understood to mean gaseous O2, unless otherwise defined in individual cases.

[0152] When using the specified gaseous precursor substances, the positive properties (as described above, preferably referred to as preferred above), in particular the positive combinations of properties (as described above, preferably referred to as preferred above), of the plasma polymer solids resulting from the process according to the invention, in particular the plasma polymer layers according to the invention, are realized to a particularly positive extent.

[0153] By using an organosilicon precursor, preferably comprising an organosilicon precursor comprising methyl groups, particularly preferably with hexamethyldisiloxane as the organosilicon precursor, together with oxygen, plasma-polymer siloxane solids according to the invention, preferably plasma-polymer siloxane layers on a substrate, are obtained in many cases in a particularly advantageous and efficient manner using the process according to the invention.A preferred method (as described above, preferably referred to as preferred above) is wherein the organosilicon precursor introduced in step S3) has a ratio of -CH3 to Si of 2.7 or greater, preferably a ratio of 3 or greater, and / or the organosilicon precursor introduced in step S3) has a ratio of O to Si of 1.5 or less, preferably a ratio of 1.1 or less; and / or the organosilicon precursor introduced in step S3) does not comprise any cyclic siloxanes and / or any cyclic silazane compounds.

[0154] Silazanes are chemical compounds with the formula R3Si-[NH-SiR2]n-NH-SiR3 (also with n = 0), where R represents hydrogen atoms and / or hydrocarbon residues. This understanding is consistent with the usual understanding of a person skilled in the art.

[0155] Cyclic siloxanes are ring-shaped organic compounds in which silicon and oxygen are bonded alternately.

[0156] When using the silicon-organic precursor substances defined above, the positive properties (as described above, preferably referred to as preferred above), in particular the combinations of positive properties (as described above, preferably referred to as preferred above), of the plasma-polymer siloxane solids resulting from the process according to the invention, preferably of the plasma-polymer siloxane layers on a substrate, 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 achieved by the plasma-polymer siloxane solid resulting from the inventive process, preferably a plasma-polymer siloxane layer on a substrate.

[0157] A preferred method (as described above, preferably referred to as preferred above) is wherein, in the deposition of a plasma-polymerized siloxane solid, in particular a plasma-polymerized siloxane layer, onto a substrate in step S4), a plasma system is used which can form and preferably control a self-bias, and preferably comprises the gaseous precursor substances produced or provided in step S2) and used in step S3) at least: an organosilicon precursor, preferably hexamethyldisiloxane and

[0158] oxygen and wherein, when introduced in step S3) a gas quantity ratio, measured in standard cm 3 / min, of a silicon-organic precursor, preferably hexamethyldisiloxane, to oxygen in a ratio of 1.5:1 to 7:1, preferably 2.5:1 to 5.5:1; and / or the plasma system during deposition in step S4) has a boundary layer potential (self-bias) in the range of 80 V to 400 V, preferably in the range of 100 V to 350 V, particularly preferably in the range of 125 to 325 V; and / or during deposition in step S4) a total gas flow is realized in the plasma system so that the calculated total residence time of the gases in the plasma chamber is in the range of 0.5 s to 20 s, preferably in the range of 1 s to 10 s, particularly preferably in the range of 2 s to 6 s.

[0159] The plasma-polymerized siloxane solids according to the invention, preferably the plasma-polymerized siloxane layers according to the invention on a substrate,

[0160] 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, with particularly positive properties (as described above, preferably as referred to above as preferred), in particular combinations of particularly positive properties (as described above, preferably as referred to above as preferred), are obtained.

[0161] The self-bias is a DC voltage value measured between the RF input and the grounded reactor. For this purpose, the RF component present at the input is filtered via a coil. The remaining DC voltage is then measured relative to the grounded reactor wall. The self-bias value, together with the process pressure and the input power, characterizes the plasma process. With a high self-bias value, the faster electrons migrate towards the reactor surfaces. As a result, the ions of the plasma discharge are accelerated towards the electrodes and strike the substrate with increased kinetic energy. This increases the deposition rate but also affects the 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.

[0162] A preferred method (as described above, preferably referred to as preferred above) is wherein the plasma system used in step S4) has a total leakage rate of less than 0.01 mbar l / s, preferably less than 0.0075 mbar l / s, during the deposition in step S4); and / or the ratio of total leakage rate to oxygen inflow in the plasma system used in step S4) during the deposition in step S4) is in the range of 0.005 or less, preferably 0.003 or less, particularly preferably 0.0025 or less; and / or the operating pressure in the plasma system used in step S4) during the deposition in step S4) is 0.03 mbar or less, preferably 0.02 mbar or less.

[0163] The person skilled in the art determines the total leakage rate using the pressure rise method over a period of at least one hour. The procedure is familiar to them from their general technical knowledge.

[0164] The above-defined working pressure of 0.03 mbar or, preferably, 0.02 mbar or less refers to the working pressure with plasma discharge.

[0165] When the process is carried out with the features defined above, in particular combinations of features, plasma-polymer siloxane solids according to the invention, in particular plasma-polymer siloxane layers according to the invention, are obtained on a substrate, exhibiting particularly positive properties (as described above, preferably as referred to above as preferred), in particular combinations of particularly positive properties (as described above, preferably as referred to above as preferred). The person skilled in the art selects the specified parameters independently, according to the requirements of the individual case, in accordance with the teachings of the present invention and based on their general technical knowledge.

[0166] A preferred method (as described above, preferably as referred to above as preferred) is one in which the electrodes are covered as completely as possible by the product during deposition in step S4). This requirement applies particularly to enamel, porcelain, glass, and other non-conductors, and / or the plasma system is operated, at least during deposition in step S4), in such a way that no local plasma surface discharges occur; and / or the plasma system is operated, at least during deposition in step S4), in such a way that no plasma discharges occur in the suction flange; and / or the plasma system used in step S4) is designed, and the substrate produced or provided in step S1 is selected, such that a) the substrate arranged on the electrode is at least 5 cm, preferably at least 10 cm, particularly preferably at least 15 cm away from the nearest wall of the plasma system;

[0167] In carrying out the method according to the invention, wherein the electrodes of the plasma system are designed, at least during deposition in step S4), such that no exposed electrode edges are present, a particularly spatially homogeneous plasma discharge is achieved; this results in particularly advantageous outcomes (low spatial variation in the composition of the deposited layer) during deposition. Local, more intense discharges are thus preferably avoided.

[0168] The design of the plasma system, such that no electrode edges are exposed at least during deposition in step S4), is achieved, for example, by embedding the high-frequency electrodes in suitable insulation 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 insulating materials should be avoided for the surfaces exposed to the plasma.

[0169] Alternatively, the design of the plasma system so that no exposed electrode edges are present, at least during deposition in step S4), can be achieved by using a suitable rectangular vacuum chamber. When the process is carried out with the features defined above, in particular combinations of features, plasma-polymer siloxane solids according to the invention result, preferably plasma-polymer siloxane layers according to the invention on a substrate, with particularly positive properties (as described above, preferably as referred to above as preferred), in particular combinations of particularly positive properties (as described above, preferably as referred to above as preferred). Here, too, the person skilled in the art selects the specified parameters independently according to the requirements of the individual case, in accordance with the teachings of the present invention and based on their general technical knowledge.

[0170] The present invention relates in particular and preferably to the

[0171] Use of a plasma-polymerized siloxane solid (preferably as described above, particularly preferably as referred to above as preferred), preferably a plasma-polymerized siloxane layer on a substrate (preferably as described above, particularly preferably as referred to above as preferred), to improve the cleanability of an uncoated solid (easy-to-clean applications).

[0172] In many cases, the advantageous properties (as described above, preferably as referred to above as preferred) and / or the advantageous combinations of properties (as described above, preferably as referred to above as preferred) of the plasma-polymer siloxane solids according to the invention, preferably of the plasma-polymer siloxane layer according to the invention on a substrate, are particularly beneficial when used to improve the cleanability of an uncoated solid (easy-to-clean applications). The advantages (as described above, preferably as referred to above as preferred) and effects (as described above, preferably as referred to above as preferred) associated with the present invention are thereby realized to a particularly positive extent.

[0173] Easy-to-clean applications are known to those skilled in the art in the field of the present invention from their general knowledge.

[0174] An improved cleanability can be determined by a person skilled in the art in simple tests and without unreasonable effort, based on their expertise. The present invention also relates in particular and preferably to the use of a plasma-polymerized siloxane solid (preferably as described above, particularly preferably as designated as preferred above), preferably a plasma-polymerized siloxane layer on a substrate (preferably as described above, particularly preferably as designated as preferred above), as a coating of a permanent mold in a primary forming process from the plastic state according to DIN 8580:2003-09, preferably selected from the group of primary forming processes from the plastic state consisting of:

[0175] - Pressing dies,

[0176] - Injection molding, preferably injection molding of thermoplastics,

[0177] - Injection molds, and

[0178] - Extrusion; and / or as a coating of a permanent mold in a primary forming process from the liquid state according to DIN 8580:2003-09, preferably selected from the group of primary forming processes from the liquid state consisting of:

[0179] - Gravity casting,

[0180] - Die casting,

[0181] - Low-pressure casting,

[0182] centrifugal casting,

[0183] Continuous casting, foaming,

[0184] - Diving forms, and

[0185] - Primary forming of fiber-reinforced plastics (low-pressure process), and / or as an internal coating of pipes, and / or as a coating of conveying equipment, preferably screw conveyors.

[0186] In many cases, the advantageous properties (as described above, preferably as referred to above as preferred) and / or the advantageous combinations of properties (as described above, preferably as referred to above as preferred) of the plasma-polymer siloxane solids according to the invention, preferably the plasma-polymer siloxane layer according to the invention on a substrate, are realized in a particularly positive and advantageous manner in one or all of the uses defined above. The advantages (as described above, preferably as referred to above as preferred) and effects (as described above, preferably as referred to above as preferred) associated with the present invention are thereby realized to a particularly positive extent.

[0187] The present invention further relates in particular and preferably to the use of a plasma-polymerized siloxane solid (preferably as described above, particularly preferably as referred to above as preferred), preferably a plasma-polymerized siloxane layer on a substrate (preferably as described above, particularly preferably as referred to above as preferred), as a coating for components and / or workpieces that come into contact with liquids, wherein the coating preferably has a water surface angle on the side facing away from the respective component and / or workpiece, determined according to the procedure in Example 3, in the range of 85° to 110°, preferably in the range of 90° to 105°. Rough surfaces significantly alter the water surface angle. In the preferred range, higher water surface angles, in some cases considerably larger angles up to superhydrophobicity, are then observed.A comparison of contact angles is therefore only meaningful on mirror-smooth surfaces (Example 10) or in a direct comparison of similar surface structures.

[0188] The present invention will be explained in more detail below using examples.

[0189] Examples:

[0190] Example 1: Production of a plasma-polymer solid, in particular a plasma-polymer layer, using a self-bias plasma reactor

[0191] The production of plasma-polymerized siloxane solids or plasma-polymerized siloxane layers on a substrate was carried out using a plasma reactor with a chamber size of 50 cm x 50 cm x 60 cm. An RF electrode (300 mm x 300 mm) was mounted on suitable insulation on the reactor's base plate. The exhaust system was positioned opposite the electrode. Gas was supplied via two inlet nozzles next to the electrode.

[0192] To verify the plasma system's design, the formation of a dark area (sheath layer) with a rim width exceeding 10 mm (300 V) around a conductive substrate or product was visually verified. Such a sheath layer arises from the plasma's conductivity and its contact with the electrodes as a result of a voltage drop across the RF electrode surfaces. In English, the formation of such a sheath layer in the context of the present invention is also referred to as "sheath formation." This is caused by the geometrically asymmetrical design of the plasma system (positive ratio of ground plane to electrode surface area).

[0193] To ensure the most consistent initial conditions possible in the plasma system, the system was conditioned prior to the production of the siloxane layers. This conditioning involved performing the coating process without a substrate, but otherwise in exactly the same manner as the subsequent substrate coating, before each coating step. This conditioning ensures that all surfaces forming the interior of the plasma system are coated with a plasma polymer before the actual production of the respective plasma-polymerized siloxane solid or layer on a substrate. This prevents unwanted contamination of the samples during the actual production of the plasma-polymerized siloxane solid or layer on a substrate.For the production of the layers according to the invention, the total gas flow was 150 sccm at a working pressure of 0.03 mbar. Further parameters are given in Table 1.

[0194] All substrates were placed directly on the reactor's base electrode during the coating process. To ensure sufficient adhesion of the plasma polymer layer to the test substrates, each substrate underwent a 4-minute oxygen activation (100 sccm oxygen, 300 V, 0.03 mbar) beforehand.

[0195] This resulted in plasma-polymer solids or plasma-polymer layers according to the invention.

[0196] Table 1: Parameters for the production of plasma-polymerized solids or plasma-polymerized layers using a self-bias plasma reactor

[0197] [sccm] [V]

[0198] 1 a 2 150 300 Si-Wafer according to the invention

[0199] 1 b 2 150 300 Glass according to the invention

[0200] 1 c 2 150 300 Aluminium according to the invention

[0201] 2a 3 150 300 Si-Wafer according to the invention

[0202] 2b 3 150 300 Glass according to the invention

[0203] 2c 3 150 300 Aluminium according to the invention

[0204] 3a 4 150 300 Si-Wafer according to the invention

[0205] 3b 4 150 300 Glass according to the invention

[0206] 3c 4 150 300 Aluminium according to the invention

[0207] 4a 4 150 200 Si wafers according to the invention

[0208] 4b 4 150 200 Glass according to the invention

[0209] 4c 4 150 200 Aluminium according to the invention 5a 5 175 100 Si-Wafer according to the invention

[0210] 5b 5 175 100 Glass according to the invention

[0211] 5c 5 175 100 Aluminium according to the invention

[0212] 6a 5 150 100 Si-Wafer according to the invention

[0213] 6b 5 150 100 Glass according to the invention

[0214] 6c 5 150 100 Aluminium according to the invention

[0215] 7a 5 150 200 Si-Wafer according to the invention

[0216] 7b 5 150 200 Glass according to the invention

[0217] 7c 5 150 200 Aluminium according to the invention

[0218] 8a 5 150 300 Si-Wafer according to the invention

[0219] 8b 5 150 300 Glass according to the invention

[0220] 8c 5 150 300 Aluminium according to the invention

[0221] 9a 1 150 300 Si wafer not according to the invention

[0222] 9b 1 150 300 Glass not according to the invention

[0223] 9c 1 150 300 Aluminium not according to the invention

[0224] 10a 4 150 175 Si wafer according to the invention

[0225] 10b 4 150 175 Glass according to the invention

[0226] 10c 4 150 175 Aluminium according to the invention

[0227] Example 2: Determination of the monofunctional, difunctional, trifunctional and tetrafunctional oxygen fractions using XPS (X-ray photoelectron spectroscopy) measurements and subsequent evaluation 2-1: Calibration of the XPS (X-ray photoelectron spectroscopy) measuring system

[0228] X-ray photoelectron spectroscopy (XPS) is based on the external photoelectric effect; the binding energy, referenced to the Fermin level, can be directly determined from the XPS spectrum. Details of the method are known from general scientific knowledge. For all measurements, an ESCALAB 250Xi X-ray photoelectron spectrometer (XPS) system from Thermo Fisher Scientific with a monochromatized AI Ka source was used. The standard electrostatic lens was employed, and the X-ray spot had a diameter of 650 pm. The apparatus was initially calibrated using an uncontaminated linear, non-reactive polydimethylsiloxane with a viscosity of approximately 500 mmol / L.2 / s (Wacker® AK500) to be calibrated 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.

[0229] If the corresponding stoichiometry is not found during the measurement, the relative sensitivity factors (RSF) must be adjusted to obtain the correct stoichiometry. The set RSFs are to be used in subsequent measurements. A suitable pass energy for determining the sample is selected independently by a person skilled in the art, based on their general technical knowledge and requirements. A pass energy of 150 eV is used for overview spectra and 20 eV for detailed spectra. It is known from general technical knowledge that a lower pass energy yields higher resolution. Furthermore, it must be noted that an escape depth correction according to the TTP2M model must be applied when evaluating the stoichiometry. Otherwise, for example, the signal from silicon will be significantly overemphasized in the measurement, which in turn leads to incorrect stoichiometry.For the XPS device in question, the adjusted RSF values ​​shown in Table 5 were determined and used based on a PDMS measurement (polydimethylsiloxane measurement as reference).

[0230] Table 2: Correction of RSF values ​​based on a PDMS measurement (reference)

[0231] OC Si Remark

[0232] O1s C1s Si2p at-% at-% at-%

[0233] Unacceptable

[0234] Deviation from

[0235] standard

[0236] 2.93 1 0.817 21 ,21 48.21 27.86 of the known

[0237] RSF Stoichiometry

[0238] Correct stoichiometry adapted with tolerable-

[0239] 3.01 1 0.94 25.02 49.98 25.00

[0240] RSF- bare deviations-

[0241] Values ​​gen 2-2: Measurement of layers with a 0° measuring angle to the sample normal

[0242] Unless otherwise specified in individual cases, the measurement of the plasma-polymer solids and non-inventive layers produced according to Example 1-1 above was carried out at a pass energy of 20 eV. Measurements were taken at a measuring angle of 0°C. At this measuring angle, photoelectrons can leave the sample surfaces in the measuring direction up to a sample depth of approximately 10 nm, so that the resulting information originates from the uppermost 10 nm of the sample adjacent to the measuring surface.

[0243] Subsequently, a fit of the Si2p peak was performed in each case. The fitting of the detailed spectrum of the Si2p peak was carried out according to the method described in: 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.

[0244] For each oxidation state of silicon, a doublet was assumed as the peak shape (p-orbital). Four doublets were fitted for each state. The ratio of the peak areas of the two individual peaks within a doublet was set to 1:2. These consist of the p1 / 2 orbital and two p3 / 2 orbitals. The two p3 / 2 orbitals together produce one peak of the doublet with twice the peak area of ​​the p1 / 2 orbital. The energy difference between the individual peaks within a doublet was 0.65 eV. All peaks, both within a doublet and between different doublets, had the same full width at half maximum (FWHM), with the absolute value of the FWHM varying from 0.8 to 1.1 eV.

[0245] The energy position of the Si2p 3 / 2 single peaks of the different oxidation states is:

[0246] 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.

[0247] The complete fitting conditions are listed in Table 3-1 and Table 3-2. 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) and all specified constraints must be observed. These may need to be adjusted according to the specific evaluation software used.

[0248] Table 3-1: Fit conditions (Part 1) component D3 / 2 D1 / 2 T3 / 2 T1 / 2

[0249] (A) (B) (C) (D)

[0250] 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

[0251] Table 3-2: Fit conditions (Part 2) component M3 / 2 M1 / 2 Q3 / 2 Q1 / 2

[0252] (E) (F) (G) (H)

[0253] 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

[0254] 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”.

[0255] 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 carried out as previously described. From the fitting result, the carbon content is calculated according to Formula 1, which is derived from the Si2p peak fit.

[0256] Formula 1 : The values ​​M^, MI, D3, DJ_, T3, TI represent the percentage of the area resulting from the fit of the Si2p peak. The quantity C si This 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. Formula 2:

[0257] The variable names are defined analogously to Equation 1. For the coatings in question, this is a reliable way to rule out faulty fits. Particular attention must be paid to a small deviation in the oxygen content; the deviation according to Formula 3 must be ±2% or less. The deviation in the carbon content, calculated analogously, must be less than 20%. Formula 3: 100

[0258] If the values ​​differ significantly, the binding energy scale is adjusted in small steps until the 2% interval is reached.

[0259] The resulting band position of the Si2p peak was then determined.

[0260] For the plasma polymer solids or plasma polymer layers produced according to the invention in accordance with the preceding Example 1-1 (see also Table 1 above), the values ​​summarized in Table 7 (each mean value from duplicate determinations) are obtained:

[0261] Table 4: Values ​​for the plasma polymers produced according to the preceding Example 1-1

[0262] solid or plasma-polymer layers _

[0263] [eV] [at-%] [%] [%] [%] [%]

[0264] 1 a 2 102.27 36.3 1 ,26 1 ,29 38 62 0.62 according to the invention

[0265] 2a 3 102.38 38.5 1 .17 1 .36 44 56 0.79 according to the invention

[0266] 3a 4 102.12 39.7 1 ,12 1 ,40 47 53 0.89 according to the invention

[0267] 4a 4 102.37 39.7 1 ,16 1 ,42 43 57 0.75 according to the invention

[0268] 5a 5 102.25 40.7 1 .14 1 .47 44 56 0.79 according to the invention

[0269] 6a 5 102.31 40.8 1 .14 1 .46 45 55 0.82 according to the invention

[0270] 7a 5 102.15 40.8 1 ,12 1 ,40 46 54 0.85 according to the invention

[0271] 8a 5 102.27 40.9 1 0.08 1 0.44 49 51 0.96 according to the invention not according to the invention

[0272] 9a 1 102.83 30.6 1 .45 1 .08 24 76 0.32

[0273] XPS Reference PDMS

[0274] 101.85 1.00 2.01 99 1.99 (not inventive)

[0275] (AK 500); moderate) reference

[0276] Example 3: Determination of Surface Energy The surface free energy (SFE) of a solid is calculated here from the measurable three-phase contact angle. The measurement of the contact angle (water surface angle) and its mathematical description are based on the work of Thomas Young. According to Young, the measurable contact angle 0 is described by the following formula 4: Formula 4: cos √=^ : ^- oi In Formula 4 means <J S the surface energy of the solid and at the surface energy of the test liquid used. The energy shown in formula 4 as a sl The interaction described is described in the present invention according to the approach of Owens-Wendt-Rabel-Kaelble in accordance with formula 5.

[0277] Formula 5:

[0278] This approach to solving the free surface energy of a solid assumes that the interaction between the solid and liquid phases a sl about the geometric mean of the dispersed components , oP and polar components of , can be described. Furthermore, within the scope of the present invention, formula 6 applies to the surface energies or stresses of solids and liquids.

[0279] Formula 6: o s l = o s D ; + of ;

[0280] To solve the system of equations formed from formulas 5 and 6, measurements of the contact angle must be carried out with at least two liquids having known polar and dispersive components. Within the scope of the present invention, at least one liquid must have a polar component greater than zero.

[0281] The static measurement method was used to experimentally determine the contact angle (water surface 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 the water droplet, the contact angle is also referred to as the "water surface angle" in the context of the present invention. Six pairs of drops were used for evaluation, and average values ​​were calculated. The surface energy was then determined from the average values ​​of the measured contact angles according to Owens-Wendt-Rabel-Kaelble. In case of doubt, DIN 55660-2 was consulted. The determination was carried out at room temperature.

[0282] Even though the "Mobile Surface Analyzer MSA" performs the measurements automatically, they still need to be checked. For example, the baseline is not always correctly positioned for optical reasons. Manual corrections are necessary in these cases. If dirt or other imperfections are present, a supplementary measurement may be required.

[0283] For the plasma-polymer solids or plasma-polymer layers produced according to the invention in accordance with the preceding Example 1-1 (see also Table 1 above), the values ​​summarized in Table 12 (each a mean value from three determinations) are obtained:

[0284] Table 5: Surface energy (Owens-Wendt-Rabel-Kaelble) values ​​for the plasma-polymerized solids or plasma-polymerized layers produced according to the preceding Example 1-1

[0285] Layer-HMDSO / O2 polar

[0286] OFE remark

[0287] No. Ratio Share

[0288] [mN / m] [mN / m]

[0289] 1 b 2 26.4 1 ,5 according to the invention

[0290] 2b 3 26.5 1 ,4 according to the invention

[0291] 3b 4 26.8 1 ,1 according to the invention

[0292] 4b 4 26.6 1 ,6 according to the invention

[0293] 5b 5 24.3 0.5 according to the invention

[0294] 6b 5 24.6 0.8 according to the invention

[0295] 7b 5 25.7 1 ,0 according to the invention

[0296] 8b 5 26.7 1 ,1 according to the invention

[0297] 9b 1 29.8 2.1 not according to the invention

[0298] 10b 4 25.5 1 ,2 according to the invention

[0299] Checking the measuring fluids

[0300] The liquids used were checked for impurities before the measurements. For this purpose, glass slides were thoroughly cleaned with acetone. These were then measured 10 times, using a drop volume of 2 pl each time. The mean values ​​obtained are shown in Table 6. Table 6: Mean values ​​for one glass slide

[0301] liquid

[0302] (measured at bearing angle (°) standard deviation (°)

[0303] (Glass slide)

[0304] Water 35.3 2

[0305] Diiodomethane 50.9 2

[0306] Example 4: Determination of Young's modulus and mass density

[0307] The modulus of elasticity and the mass density of plasma-polymer solids, especially thin plasma-polymer layers, were determined by measuring the dispersion of surface acoustic waves (SAW) in coated media (Si-Wafer 100).

[0308] The measurements were performed using a LaWave®, a development of the Fraunhofer IWS. The high-frequency sensor (15-250 MHz) was used. (https: / / www.iws.fraunhofer.de / de / technologiefelder / pvd_nanotechnik / schichtcharakterisierung / lawave.html; accessed on September 18, 2023).

[0309] Three measurements were performed for each sample. Care was taken to ensure the wafers were correctly aligned along the crystal axis. Correct alignment was verified by comparing the dispersion curves. If a significant offset was found in the dispersion curve propagation velocities, the samples were incorrectly aligned, and a corresponding correction was made.

[0310] For the plasma-polymerized siloxane solids or plasma-polymerized siloxane layers produced according to the preceding Example 1-1 (see also Table 1 above), the values ​​summarized in Table 7 are obtained (each a mean value from three determinations). Table 7: Values ​​for Young's modulus and mass density for the plasma-polymerized solids or plasma-polymerized layers produced according to the invention according to the preceding Example 1-1.

[0311] [GPa] [g / cm 3 ]

[0312] 1 a 2 42 1 ,72 according to the invention

[0313] 2a 3 40 1 ,72 according to the invention

[0314] 3a 4 39 1 ,66 according to the invention

[0315] 4a 4 25 1 ,52 according to the invention

[0316] 5a 5 12 1 ,32 according to the invention

[0317] 6a 5 15 1 ,38 according to the invention

[0318] 7a 5 23 1 ,48 according to the invention

[0319] 8a 5 30 1 ,52 according to the invention

[0320] 9a 1 48 1 ,80 not according to the invention

[0321] Example 5: Determining Mohs hardness

[0322] The Mohs hardness was determined using a Mohs' Hardness Kit from Mineral Lab. This kit contains pen-like "hardness picks." These picks have tips of varying hardness and are drawn across the surface at a 70° angle, similar to a writing pen, applying moderate pressure. The hardness principle of this simple hand test is based on the fact that hard materials scratch soft ones. Accordingly, it is a comparative test. The pressure is calibrated using the reference materials included in the Mohs' Hardness Kit (brass with a known Mohs hardness and glass with a known Mohs hardness). Care was taken to ensure that the test force was not applied abruptly upon releasing the pick, but rather gradually increased until the required test force was reached.

[0323] To determine the Mohs hardness of thin films, it has proven effective to test surfaces that are as smooth as possible, since the force is applied evenly and any defects are easily visible. Furthermore, to determine the film hardness, it must be ensured that the substrate is harder than the coating, or at least equally hard. Silicon wafers were used in this application. Before determining the Mohs hardness, the surface of the sample was carefully wiped dry with a paper towel (e.g., Cleanex). If scratches occur during wiping—as is the case with softer films—only light wiping is necessary, or wiping may even be omitted entirely.

[0324] For example, if a material or coating leaves a scratch with a hardness of 5 but not with a hardness of 4, then the Mohs hardness is 4.5. The values ​​summarized in Table 8 are obtained for the plasma-polymerized solids or plasma-polymerized siloxane layers on a substrate produced according to the preceding Example 1-1 (see also Table 1 above).

[0325] Table 8: Values ​​for Young's modulus and mass density for the plasma-polymerized siloxane solids or plasma-polymerized siloxane layers produced according to the preceding Example 1-1

[0326] Layer HMDSO / O2

[0327] Mohs hardness remark

[0328] No. Ratio

[0329] 1 a 2 5.5 according to the invention

[0330] 1 b 2 5.5 according to the invention

[0331] 2a 3 5,5 according to the invention

[0332] 2b 3 5.5 according to the invention

[0333] 3a 4 5,5 according to the invention

[0334] 3b 4 5,5 according to the invention

[0335] 4a 4 4,5 according to the invention

[0336] 4b 4 4,5 according to the invention

[0337] 5a 5 3.5 according to the invention

[0338] 5b 5 3.5 according to the invention

[0339] 6a 5 3.5 according to the invention

[0340] 6b 5 3.5 according to the invention

[0341] 7a 5 4,5 according to the invention

[0342] 7b 5 4,5 according to the invention

[0343] 8a 5 5.5 according to the invention

[0344] 8b 5 5.5 according to the invention not

[0345] 9a 1 5,5 according to the invention

[0346] 9b 1 5.5 not according to the invention

[0347] 10a 4 4,5 according to the invention

[0348] 10b 4 4,5 according to the invention Example 6: Resistance to liquid substances

[0349] Resistance to liquid substances always depends on specific conditions such as the duration of exposure and the corresponding temperature.

[0350] In accordance with the procedure in the preceding Example 1, the plasma polymer solids or plasma polymer layers according to the invention used in the following resistance tests were produced as test specimens.

[0351] The surface energy and the polar component of the surface energy were determined on these layers according to the procedure described in Example 3 above. The resistance of each specimen to the test liquids (substances) listed in Table 9 was then tested. The procedure followed DIN EN ISO 175:2011-03, meaning each specimen was completely immersed in the respective test liquid. Testing was carried out according to sections 4.2ff of the standard at 23 °C for 24 hours, unless otherwise specified. No sample conditioning was performed. Each specimen was used in only one resistance test.

[0352] Table 9: Test fluids and test conditions

[0353] Test fluid, test temperature, immersion time

[0354] Acetic acid 23 2

[0355] (0.17 mol / L; pH 2.75)

[0356] Sulfuric acid 23 1

[0357] (0.5 mol / L; pH 1.0)

[0358] Acetone 23 24

[0359] (analytically pure)

[0360] Ethanol 23 24

[0361] (Purity: 96 vol%) n-Hexane 23 24

[0362] (Purity >98%) The samples were then cleaned to prevent contamination by the respective test liquid for the subsequent investigations (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 and then dried in ambient air.

[0363] 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 the preceding example 3.

[0364] In all cases, a deviation of 20% or less was observed in the surface energy, relative to the corresponding value before contact with the test fluid (as described above). In many cases, a deviation of 15% or less was observed in the surface energy, relative to the corresponding value before contact with the test fluid (as described above).

[0365] 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 fluid (as described above) and after contact with the test fluid (as described above).

[0366] The plasma-polymer solids or plasma-polymer layers according to the invention, as investigated above, each possess resistance to the respective substances (test liquids) defined above under the conditions defined above.

[0367] Additional in-house tests have shown that plasma polymer solids or plasma polymer layers according to the invention also possess resistance to other substances and under other conditions described as preferred in the present text.

[0368] Example 7: Water vapor resistance

[0369] Following the procedure described in Example 1 above, plasma-polymer solids or plasma-polymer layers according to the invention were produced as test specimens. Subsequently, the surface energy and the polar component of the surface energy of the plasma-polymer solids or plasma-polymer layers on the test specimens were determined according to the procedure described in Example 3 above.

[0370] The steam resistance test was performed according to DIN EN ISO 17665-1:2006-1, using a steam sterilizer according to DIN EN 285-2021-12. The aim of the test was not to achieve sterilization, but solely to investigate the steam resistance. The procedure according to DIN 17665 E2 (method with air-steam mixtures) was applied, using distilled water and orienting the samples vertically. A temperature of 121 °C was reached during the 15-minute heating phase. This temperature was then held constant at 121 °C for 1440 minutes. A cooling phase of 15 minutes followed, after which pressure equalization was carried out. Three measurements were taken in each case.

[0371] In all cases, a deviation of 15% or less was observed in the surface energy, compared to the corresponding value before vapor deposition (as described above). In many cases, a deviation of 5% or less was observed in the surface energy, compared to the corresponding value before vapor deposition (as described above).

[0372] 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 vapor deposition (as described above).

[0373] The plasma-polymer solids or plasma-polymer layers according to the invention that were investigated each possess resistance to water vapor under the conditions defined above.

[0374] Example 8: Dishwasher resistance

[0375] Following the procedure described in Example 1 above, plasma-polymer solids or plasma-polymer layers according to the invention were produced as test specimens. Subsequently, the surface energy and the polar component of the surface energy of the plasma-polymer solids or plasma-polymer layers on the test specimens were determined according to the procedure described in Example 3 above.

[0376] The dishwasher resistance of the prepared specimens was determined according to DIN EN 12875-1:2005-08 as described below. 125 test cycles were performed in accordance with sections 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). Afterwards, the samples were removed and dried by rinsing with acetone (analytically pure).

[0377] 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 the preceding example 3.

[0378] In all cases, a deviation of 15% or less was found in the surface energy, compared to the corresponding value before the 125 test cycles (as described above). In many cases, a deviation of 5% or less was found in the surface energy, compared to the corresponding value before the 125 test cycles (as described above).

[0379] 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 the 125 test cycles (as described above).

[0380] Furthermore, our own practical tests showed that the non-stick and easy-to-clean properties have been retained in very good quality.

[0381] The plasma-polymer solids or plasma-polymer layers according to the invention that were investigated each possess dishwasher resistance.

[0382] Example 9: Temperature resistance

[0383] Following the procedure described in Example 1 above, plasma-polymer solids or plasma-polymer layers according to the invention were produced as test specimens. Subsequently, the surface energy and the polar component of the surface energy of the plasma-polymer solids or plasma-polymer layers on the test specimens (glass) were determined according to the procedure described in Example 3 above.

[0384] Subsequently, the temperature resistance of the plasma-polymerized solid or plasma-polymerized layers on the test specimens was tested by storing them in a clean oven at 200°C, 230°C, or 250°C for 24 hours each, whereby the test specimens were carefully wrapped in fresh aluminum foil to protect them from cross-contamination by the oven, without the foil touching the test surface.

[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 the preceding example 3.

[0386] In all cases, a deviation of 15% or less was observed in the surface energy, compared to the corresponding value before storage in the furnace (as described above). In many cases, a deviation of 10% or less was observed in the surface energy, compared to the corresponding value before storage in the furnace (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 storage in the furnace (as described above) and after storage in the furnace (as described above).

[0388] The plasma-polymer solids or plasma-polymer layers according to the invention, as investigated, each possess temperature resistance.

[0389] Table 10: Temperature resistance - Resistance of surface energy (OFE) and its polar component after oven aging for 24 hours.

[0390] Layer-pol.pol.pol.pol.pol.

[0391] OFE OFE OFE OFE No. Share Share Share Share

[0392] 20°C 200°C 230°C 250°C 20°C 200°C 230°C 250°C

[0393] 1 26.3 28.0 27.8 1.58 2.00 1.93

[0394] 2 27.5 29.6 30.1 1 0.67 2.63 2.45

[0395] 3 27.1 28.6 29.2 1.61 1.89 2.20

[0396] 5 24.1 26.1 24.9 1 0.03 1 0.32 0.80

[0397] 8 27.5 29.0 30.5 1.40 2.09 2.79

[0398] 9 29.8 30.7 33.2 2.09 2.82 4.44

[0399] 10 25.7 28.0 28.9 28.0 1.60 1.84 1.62 1.67

[0400] Example 10: Determining roughness

[0401] Roughness is a measurement scale-dependent quantity. The magnitude of the measured roughness depends significantly on the measured area or line. Depending on the measurement area, appropriate filtering must be performed to differentiate waviness and roughness according to DIN EN ISO 25178 Parts 1 to 3, as amended on October 18, 2024. For example, a small lateral area (e.g., 90 x 90 pm) measured using AFM (atomic force microscope) will likely yield low roughness values, while a larger measurement area of ​​150 x 250 pm, measured using optical profilometry, will likely show higher roughness. Therefore, the measurement conditions are crucial for ensuring comparability.

[0402] Measurements were performed on a Bruker Dimension Icon3 with a NanoScope V SPM control unit and NanoScope V9.40R1 software. The cantilever used was selected based on its very smooth surface properties (SNL-10 C, Bruker, 0.24 nN / nm, tip radius 2-12 nm). The force constant and sensitivity were calibrated by analyzing thermal noise in combination with the Sader method.

[0403] The QNM mode was used to measure the topography. For this, the cantilever was excited non-resonantly at 1 kHz with amplitudes of 30 nm. The image area was 1 x 1 pm. 2 The image was scanned at 512x512 pixels and a scan rate of 0.3 Hz per line. Image processing and roughness determination were performed in Gwyddion 2.63. Line correction was applied using the trimmed means of differences scheme. A first-order polynomial was subtracted as the background.

[0404] The roughness was evaluated area-based (averaging the individual measured rows) without filtering, and the mean and RMS roughness values ​​Sa and Sq were determined. In the case of the glass surface, a sub-area without particulate structures was evaluated.

[0405] For comparison, the roughness of the substrates under consideration was also examined. These must be thoroughly cleaned beforehand, e.g. with acetone.

[0406] Table 11: Roughness - Sa and Sq.

[0407] Example 11: Microelemental analysis

[0408] Following the procedure described in Example 1 above, plasma-polymer solids or plasma-polymer layers according to the invention were produced as test specimens. However, in contrast to Example 1, oxygen activation of the substrates was omitted or carried out for a very short time. The aim of this measure was to achieve the lowest possible adhesion of the plasma-polymer solid to the glass slides used.

[0409] The material for analysis of microelements can be obtained from the glass slides prepared in this way.

[0410] Microelemental analysis is a combustion analysis that is gravimetrically normalized. Different combustion conditions are selected depending on the type of atom being detected. To ensure that the results are free from contamination or distortion, the plasma-polymer solid is used in powder form for analysis. For this purpose, the coating is scraped off the glass slides with a suitable tool, such as a clean scalpel, and collected on a fresh sheet of aluminum foil. Extremely clean work is essential. Furthermore, care must be taken not to scrape off any parts of the glass, for example, at the edges. Otherwise, an inaccurate result with excessively high levels of inorganic components will be obtained.

[0411] An alternative approach is to apply the coating to a substrate. It is important to ensure that the gravimetric accuracy is sufficient and that the substrate does not distort the results. When determining the carbon and hydrogen content, this primarily means that substrates containing these components must not be used.

[0412] The atomic weights in wt% are obtained from the measurement. These can be converted into a ratio of atomic concentrations using the atomic mass. This ratio can be considered directly, or the overall stoichiometry of the

[0413] Coatings are determined.

[0414] The sample (weighed weight) was burned in a pure oxygen stream. The carbon dioxide (CO2) produced during combustion was used to determine the carbon content, as it causes a change in conductivity in sodium hydroxide solution. The carbon dioxide dissolves in the sodium hydroxide solution. The combustion temperature was 1200°C.

[0415] To determine the hydrogen content, the sample is burned at 1050°C and the resulting combustion water is analyzed by IR spectroscopy. From these two results, the H / C ratio is then calculated via the atomic mass, as described.

[0416] Table 12: Elemental ratio of the overall composition from microelemental analysis and XPS analysis (substrate is glass slide for microelemental analysis and Si for XPS)

[0417] [seem] [V]

[0418] 6 5 150 100 2.62 1.13 1.47 3.85

[0419] 7 5 150 200 2.45 1 ,11 1 ,45 3.56

[0420] 8 5 150 300 2.32 1 .07 1 .44 3.33 Further experiments have shown that in all layers 1 a, 1 b, 2a, 2b, 2c, 3a, 3b, 3c, 4a, 4b, 4c, 5a, 5b, 5c, 10a, 10a and 10c, the ratio of hydrogen to carbon (H / C ratio) was in the range of 2.3 to 2.9.

Claims

Patent claims:

1. Plasma-polymerized siloxane solid, preferably a plasma-polymerized siloxane layer on a substrate, wherein in the plasma-polymerized siloxane solid, preferably in the plasma-polymerized siloxane layer on a substrate, the ratio of hydrogen to carbon, preferably determined by microelement analysis according to Example 11, is in the range of 2.3 to 2.9;and the atomic fraction of hydrogen, based on the total number of all elements contained in the plasma-polymerized siloxane solid, preferably in the plasma-polymerized siloxane layer on a substrate, is greater than 40%, preferably greater than 45%, and wherein the ratio of the sum of monofunctional and difunctional oxygen fractions of the Si2p peak of the X-ray photoelectron spectroscopy signal determined according to Example 2 to the sum of trifunctional and tetrafunctional oxygen fractions of the Si2p peak of the X-ray photoelectron spectroscopy signal determined according to Example 2 is from 0.25 to 1.

2.

2. Plasma-polymerized siloxane solid, preferably a plasma-polymerized siloxane layer on a substrate, according to the preceding claim 1, wherein in the plasma-polymerized siloxane solid, preferably in the plasma-polymerized siloxane layer on a substrate, the ratio of which can be determined by X-ray photoelectron spectroscopy Oxygen silicon 0.6 or greater; and / or in the plasma-polymerized siloxane solid, preferably in the plasma-polymerized siloxane layer on a substrate, the proportion of non-carbon atoms determinable by X-ray photoelectron spectroscopy is 20 at% or more, preferably more than 20 at%, based on the total number of atoms determinable by X-ray photoelectron spectroscopy in the plasma-polymerized siloxane solid, preferably in the plasma-polymerized siloxane layer on a substrate; and / or in the plasma-polymerized siloxane solid, preferably in the plasma-polymerized siloxane layer on a substrate, the total proportion of atoms selected from the group consisting of oxygen atoms and silicon atoms, determinable by X-ray photoelectron spectroscopy, is 20 at% or more, preferably more than 20 at%.-%; based on the total number of atoms determinable by X-ray photoelectron spectroscopy in the plasma-polymerized siloxane solid, preferably in the plasma-polymerized siloxane layer on a substrate; and / or. in the plasma-polymerized siloxane solid, preferably in the plasma-polymerized siloxane layer on a substrate, a ratio of the sum of monofunctional and difunctional oxygen fractions of the Si2p peak of the X-ray photoelectron spectroscopy signal determined according to Example 2 to the The sum of trifunctional and tetrafunctional oxygen fractions of the Si2p peak of the X-ray photoelectron spectroscopy signal, determined according to Example 2, is between 0.6 and 1.

0.

3. A plasma-polymerized siloxane solid, preferably a plasma-polymerized siloxane layer on a substrate, according to any of the preceding claims, wherein the plasma-polymerized siloxane solid, preferably the plasma-polymerized siloxane layer on a substrate, has a Young's modulus, determined by the surface acoustic waves method according to the procedure in Example 4, in the range of 10 GPa to 45 GPa; and / or a surface energy, determined at the surface of the plasma-polymerized siloxane solid, preferably at the surface of the plasma-polymerized siloxane layer on a substrate facing away from the substrate, by contact angle measurement according to the procedure in Example 3, in the range of 22.5 mN / m to 29.5 mN / m, preferably in the range of 23.5 mN / m to 28.5 mN / m.

4. A plasma-polymerized siloxane solid, preferably a plasma-polymerized siloxane layer on a substrate, according to any one of the preceding claims, wherein the plasma-polymerized siloxane solid, preferably the plasma-polymerized siloxane layer on a substrate, has a Mohs hardness, determined according to the procedure in Example 5, in the range of 2.5 to 5.5, preferably in the range of 3.5 to 5.5; and / or a mass density, determined by the surface acoustic wave method according to Example 4, in the range of 1.25 g / cm³ 3 up to 1.80 g / cm³ 3 owns.

5. Plasma-polymerized siloxane solid, preferably a plasma-polymerized siloxane layer on a substrate, according to one of the preceding claims, having a polar component of the surface energy, determined at the surface of the plasma-polymerized siloxane solid, preferably at the side facing away from the substrate or of the plasma-polymerized siloxane layer on a substrate, according to the procedure in Example 3, of less than 1.8 mN / m, preferably less than 1.5 mN / m.

6. Plasma-polymerized siloxane solid, preferably a plasma-polymerized siloxane layer on a substrate, according to one of the preceding claims, wherein in the X-ray photoelectron spectroscopy spectrum the Si 2p photoline is located at an energy of less than 102.8 eV, preferably less than 102.5 eV; and wherein in the X-ray photoelectron spectroscopy spectrum the Si 2p photoline is located at an energy of more than 101.8 eV.

7. Plasma-polymerized siloxane solid, preferably a plasma-polymerized siloxane layer on a substrate, according to any one of the preceding claims, wherein the mole fraction of O near the surface of the plasma-polymerized siloxane solid, preferably near the surface of the plasma-polymerized siloxane layer on a substrate facing away from the substrate, as measured by X-ray photoelectron spectroscopy according to the procedure of Example 2-2, is in the range of 28 at-% to 44 at-%, preferably in the range of 28 at-% to 35 at-%, particularly preferably between 28 at-% and 32.5 at-%; and / or the mole fraction of Si near the surface of the plasma-polymerized siloxane solid, preferably near the surface of the plasma-polymerized siloxane layer on a substrate facing away from the substrate, as measured by X-ray photoelectron spectroscopy according to the procedure of Example 2-2, is in the range of 24 at-% to 30 at-%;and / or the mole fraction of C near the surface of the plasma-polymerized siloxane solid, preferably near the surface of the plasma-polymerized siloxane layer on a substrate facing away from the substrate, as measured by X-ray photoelectron spectroscopy according to the procedure of Example 2-2, is in the range of 30 at-% to 45 at-%, preferably in the range of 38 at-% to 45 at-%; and / or the mole fraction of N near the surface of the plasma-polymerized siloxane solid, preferably near the surface of the plasma-polymerized siloxane layer on a substrate facing away from the substrate, as measured by X-ray photoelectron spectroscopy according to the procedure; from Example 2-2, in the range of 0 at-% to 2 at-%, preferably in the range of 1 at-% and less; wherein the percentages are in each case based on the total number of atoms contained in the plasma-polymerized siloxane solid, preferably the plasma-polymerized siloxane layer on a substrate, which can be determined by X-ray photoelectron spectroscopy.

8. Plasma-polymerized siloxane solid, preferably a plasma-polymerized siloxane layer on a substrate, according to any of the preceding claims, wherein the plasma-polymerized siloxane solid, preferably the plasma-polymerized siloxane layer on a substrate, possesses resistance to Fats and oils at temperatures up to 200 °C for an exposure time of at least 60 minutes, preferably edible oils at temperatures up to 200 °C for an exposure time of at least 60 minutes; and / or Fats and oils at temperatures in the range of 200 °C to 250 °C for an exposure time of at least 10 minutes, preferably edible oils at temperatures in the range of 200 °C to 250 °C for an exposure time of at least 10 minutes; and / or liquid water up to 100 °C; and / or Water vapor at temperatures up to 121 °C for an exposure time of at least 60 minutes; and / or acidic liquids with a pH in the range of pH 2 to pH 4 at a temperature of 23°C for an exposure time of at least 4 hours; basic liquids with a pH in the range of pH 11 to pH 12.5 at a temperature of 23°C for an exposure time of at least 4 hours; and / or Solvents, preferably isopropanol, acetone, ethanol, n-heptane and methyl ethyl ketone at a temperature of 23°C for an exposure time of at least 4 hours; and / or various cleaning processes, such as CO2 jet cleaning and high-pressure water cleaning up to 1000 bar working pressure; and / or Cleaning sponges that do not contain particles with a Mohs hardness of more than 3.5, preferably no particles consisting of corundum and / or, wherein the plasma-polymerized siloxane solid is present as a plasma-polymerized siloxane layer on a substrate and wherein the material of the substrate is preferably a metal and / or an alloy, particularly preferably stainless steel.

9. Plasma-polymerized siloxane solid, preferably a plasma-polymerized siloxane layer on a substrate, according to any of the preceding claims, wherein the plasma-polymer siloxane solid, preferably the plasma-polymer siloxane layer on a substrate, is dishwasher-safe, as determined according to Example 8.

10. Plasma-polymerized siloxane solid, preferably a plasma-polymerized siloxane layer on a substrate, according to any one of the preceding claims, wherein the plasma-polymerized siloxane solid, preferably the plasma-polymerized siloxane layer on a substrate, 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-polymerized siloxane solid, preferably the plasma-polymerized siloxane layer on a substrate, has hydrophobic groups, preferably methyl groups, on the surface of the plasma-polymerized siloxane solid, preferably on the surface of the plasma-polymerized siloxane layer on a substrate facing away from the substrate; and / or the surface angle, determined according to the procedure in Example 3, is in the range of 85° to 110°, preferably in the range of 90° to 105°.

11. Plasma-polymerized siloxane solid, preferably a plasma-polymerized siloxane layer on a substrate, according to any of the preceding claims, wherein the plasma-polymerized siloxane solid is a plasma-polymerized siloxane layer on a substrate, particularly preferably a plasma-polymerized siloxane layer on a substrate, wherein the material of the substrate is selected from the group of materials consisting of: Tool steel Stainless steel, Aluminum, Magnesium, Zinc, Chrome, ceramics porcelain and Glass, preferably enamel.

12. Method for producing a plasma-polymerized siloxane solid according to any one of the preceding claims 1 to 11, preferably a plasma-polymerized siloxane layer on a substrate according to any one of claims 1 to 11, comprising the steps 51) Producing or providing a substrate, 52) Manufacturing or supplying two, three or more gaseous precursor substances; 53) Introducing at least partial quantities of the gaseous precursor substances produced or provided in step S2) according to a recipe in predefined quantities and in predefined ratios into a plasma system, so that a plasma system with a continuous inflow of gaseous precursor substances results; S4) Deposition of a plasma-polymerized siloxane solid, in particular a plasma-polymerized siloxane layer, from the gaseous precursor substances on the substrate produced or provided in step S1), using the plasma system with the continuous inflow of gaseous precursor substances, such that a plasma-polymerized siloxane solid results, preferably a plasma-polymerized siloxane solid as defined in any one of claims 1 to 11, preferably a plasma-polymerized siloxane layer on a substrate, preferably a plasma-polymerized siloxane layer on a substrate as defined in any one of claims 1 to 11.

13. A method for producing a plasma-polymerized siloxane solid according to the preceding claim 12, preferably a plasma-polymerized siloxane layer on a substrate according to the preceding claim 12, wherein the roughness values ​​Sa and Sq of the substrate before the deposition of a plasma-polymerized siloxane solid, in particular a plasma-polymerized siloxane layer in step S4) are less than Sa = 0.4 nm and Sq = 0.5 nm, determined according to Example 10, and the roughness values ​​Sa and Sq of the plasma-polymerized siloxane solid, in particular a plasma-polymerized siloxane layer, on this substrate after coating in step S4) are less than Sa = 0.45 nm and Sq = 0.55 nm, determined according to Example 10.

14. Method according to any one of the preceding claims 12 to 13, 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, Magnesium, chrome zinc 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, the organosilicon precursor hexamethyldisiloxane being particularly preferred; and Oxygen.

15. The method of claim 14, wherein the silicon-organic precursor introduced in step S3) has a ratio of -CH3 to Si of 2.7 or greater, preferably a ratio of 3 or greater and / or in the organosilicon precursor introduced in step S3), the ratio of O to Si is 1.5 or less, preferably a ratio of 1.1 or less; and / or the organosilicon precursor introduced in step S3) does not comprise cyclic siloxanes and / or cyclic silazane compounds.

16. A method according to any one of the preceding claims 12 to 15, wherein, in the deposition of a plasma-polymerized siloxane solid, in particular a plasma-polymerized siloxane layer, onto a substrate in step S4), a self-biasing plasma system is used, 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, when introduced in step S3), a gas quantity ratio, measured in cm 3 / min, of a silicon-organic precursor, preferably hexamethyldisiloxane, to oxygen in a ratio of 3:1 to 7:1; and / or the plasma system during deposition in step S4) has a surface potential in the range of 80 V to 400 V, preferably in the range of 100 V to 350 V, particularly preferably in the range of 125 to 325 V; and / or during deposition in step S4) the plasma system achieves such a high total gas flow that the calculated total residence time of the gases in the plasma chamber is in the range of 0.05 seconds to 20 seconds, preferably in the range of 1 second to 10 seconds, particularly preferably in the range of 2 seconds to 6 seconds.

17. A method according to any one of the preceding claims 12 to 16, wherein the plasma system used in step S4) has a total leakage rate of less than 0.01 mbar l / s, preferably less than 0.0075 mbar l / s, during the deposition in step S4); and / or the ratio of total leakage rate to oxygen inflow in the plasma system used in step S4) during the deposition in step S4) is in the range of 0.005 or less, preferably 0.003 or less, particularly preferably 0.0025 or less; and / or the operating pressure in the plasma system used in step S4) during the deposition in step S4) is 0.03 mbar or less, preferably 0.02 mbar or less.

18. A method according to any one of the preceding claims 12 to 17, wherein the electrodes of the plasma system are designed, at least during deposition in step S4), such that no exposed electrode edges are present; and / or the plasma system is operated, at least during deposition in step S4), such that no local plasma plane discharges occur; and / or the plasma system is operated, at least during deposition in step S4), such that no plasma discharges occur in the intake flange; and / or the plasma system used in step S4) is designed, 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 bounding the plasma chamber of the plasma system is at least 50 cm.

19. Use of a plasma-polymerized siloxane solid according to any one of the preceding claims 1 to 11, preferably a plasma-polymerized siloxane layer on a substrate according to any one of the preceding claims 1 to 11, to improve the cleanability of an uncoated solid (easy-to-clean applications).

20. Uses: Use of a plasma-polymerized siloxane solid according to any one of the preceding claims 1 to 11, preferably a plasma-polymerized siloxane layer on a substrate according to any one of the preceding claims 1 to 11, as a coating of a permanent mold in a primary forming process from the plastic state according to DIN 8580:2003-09, preferably selected from the group of primary forming processes from the plastic state consisting of: - Pressing dies, - Injection molding, preferably injection molding of thermoplastics, - Injection molds, and - Extrusion; and / or as a coating of a permanent mold in a primary forming process from the liquid state according to DIN 8580:2003-09, preferably selected from the group of primary forming processes from the liquid state consisting of: - Gravity casting, - Die casting, - Low-pressure casting, centrifugal casting, - Continuous casting, - Foaming, - Dip molding, and - primary forming of fiber-reinforced plastics (low-pressure process), and / or as an internal coating of pipes, and / or as a coating of conveying equipment, preferably screw conveyors.

21. Use of a plasma-polymerized siloxane solid according to any one of the preceding claims 1 to 11, preferably a plasma-polymerized siloxane layer on a substrate according to any one of the preceding claims 1 to 11, as a coating for components and / or workpieces which come into contact with liquids, wherein the coating preferably has a water surface angle on the side facing away from the respective component and / or workpiece, determined according to the procedure from Example 3, in the range of 85° to 110°, preferably in the range of 90° to 105°.

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