Polysilazane Composition

Abstract

The present invention relates to a polysilazane composition, in particular to a composition for coating a substrate and its use, as well as to a substrate comprising a coating made from said composition.

Description

[Technical field]

[0001] The present invention relates to a polysilazane composition, in particular to a composition for coating a substrate and its use, as well as to a substrate comprising a coating made from said composition. [Background technology]

[0002] The protection of various surfaces from contamination, such as contamination and contamination, is of great importance in a wide range of technical fields. Surfaces with anti-soiling or self-cleaning properties, such as being resistant to chemical and physical binding of dust particles and other types of contamination, are extremely important not only for photovoltaic modules and solar thermal systems, but also for purposes as mundane as preventing fingerprint marks and dirt on the surface of a smartphone or graffiti on a wall, and making such surfaces easier to clean when dirty. Anti-soiling, anti-stain and anti-corrosion properties are widely required properties of coatings. Due to the different demands on coatings used in widely different fields, there is a constant need for new anti-soiling coatings that combine anti-soiling properties with specific coating features tailored to the specific use.

[0003] The anti-soiling properties of certain inert organic molecules, such as polymers, are related to the coefficient of friction (CoF). The lower the CoF, the more slippery the surface is when loaded. A low CoF makes it easier to brush off any dirt that eventually accumulates on surfaces with no or little mechanical damage to the surface. It can also allow more impactful particles, such as sand particles in a sandstorm, to bounce off the surface without causing significant wear. Additionally, a low CoF can be desirable to enhance human experience, for example for the smooth feel of new smartphone screens. One example of a coating that may have such desirable properties is a fluoropolymer, which can be used to obtain this soft, smooth feel and good anti-fingerprint and anti-soiling properties.

[0004] Furthermore, coatings with low refractive index are needed. The refractive index (the most fundamental quantity in optics and optoelectronics) determines many figures of merit of optical components such as reflectors, filters and resonators. It determines the light gathering power of lenses, the dispersive power of prisms, the reflectivity of lens coatings and the light guiding properties of optical fibers. When entering a medium with a low refractive index, light is refracted away from the normal towards the surface of the medium.

[0005] Polysilazanes, a group of polymers characterized by their Si-N-Si backbone, have been of increasing interest over the last few years due to their use in coatings. Depending on the type and formulation of the coating, polysilazane coatings can exhibit a variety of favorable properties. The high reactivity of polysilazanes allows for example to obtain coatings with high hardness and weathering resistance, excellent adhesion and scratch and abrasion resistance, low surface roughness, and high gloss of the applied surface. Excellent thermal, chemical and UV resistance have been documented. Organic polysilazane coatings have been reported to have a pencil hardness of 5H when cured at room temperature, in contrast to the more widely used (poly)siloxane coatings, which have a pencil hardness of 5B using the same curing conditions. Other polysilazane coatings have a coefficient of friction of 0.03-0.05 as shown in WO2014008443A2, similar to 0.04 for the well-known anti-adhesive Teflon, but even better scratch and abrasion resistance. For inorganic perhydropolysilazane coatings cured under UV light / H2O2 or H2O2 / 80°C (resulting in SiO2), coating hardness as high as 3 Gpa and very high 13 Gpa by curing in air at 700-1000°C have been reported, proving the depth of crosslinking in the functional units of polysilazanes. Apart from other common polymers such as (poly)siloxanes, polyurethanes, epoxy resins, PMMA, which are often used due to their ease of use and / or low reactivity under ambient conditions, polysilazanes have been called the ultimate binders in their class (polymers used in wet chemical formulations) due to their high reactivity. Polysilazane coatings have been used for purposes such as permanent anti-fingerprint coatings for metal surfaces as disclosed in US 2008 / 0131706 A1, but have not yet found widespread use as anti-soiling coatings.

[0006] Coating formulations containing polysilazanes and other components are known in the art. One example is the formulation of siloxane resins, organopolysilazanes and polyhedral oligomeric silsesquioxanes with alkyl or aryl groups in US Pat. No. 9,593,241 B2, which results in coatings with refractive indices of 1.52 to 1.54. Due to the high reactivity of polysilazanes with nucleophilic groups, additives used in coating formulations often do not contain these groups or their concentrations are kept very low. Such nucleophilic groups, including hydroxyl, amine, and unsaturated bonds containing heteroatoms (e.g. carbonyl, S=O), are known to cause fragmentation of polysilazanes. However, these groups can be useful for covalently bonding additives to polysilazanes in coatings. Their exclusion therefore means that polysilazanes and additives are not covalently and strongly bonded to each other, which may result in adverse effects such as leaching of the additives from the coating or phase separation.

[0007] Therefore, there is a need for improved polysilazane coatings. [Brief description of the drawings]

[0008] [Figure 1] 1 shows a high magnification light microscope image of the coating of sample 48T-2. [Diagram 2] 1 shows a high magnification light microscope image of the coating of sample 48T. [Diagram 3] 1 shows a high magnification light microscope image of the coating of sample 48T-40. [Figure 4] 1 shows optical microscope images of the coating of sample 48T-2 illustrating the tribological behavior at loads of 20 MPa (left side of the image) and 250 MPa (right side of the image). [Diagram 5] 1 shows optical microscope images of the coating of sample 48T illustrating the tribological behavior at loads of 20 MPa (left side of the image) and 250 MPa (right side of the image). [Figure 6]1 shows optical microscope images of the coating of sample 48T-40 showing the tribological behavior at loads of 20 MPa (left side of the image) and 250 MPa (right side of the image). [Figure 7] 1 shows optical microscope images of the coating of sample 48R illustrating the tribological behavior at loads of 20 MPa (left side of the image) and 250 MPa (right side of the image). [Figure 8] FT-IR spectra of sample MTDS-1 cured in a humid atmosphere containing H2O2 vapor and a sample cured in ambient atmosphere are shown. Summary of the Invention

[0009] In a first aspect, the present invention provides a method for producing a composition comprising the steps of: i) 0.5 to 30 wt % of a polysilazane component selected from the group consisting of organic polysilazanes, inorganic polysilazanes, and mixtures of any two or more organic and / or inorganic polysilazanes, based on the weight of the composition; ii) 0.1 to 15 wt % of a POSS containing at least one nucleophilic group, based on the weight of the composition; iii) 0.0001 to 2 wt% of a quaternary ammonium salt R based on the weight of the composition 1 R 2 R 3 R 4 N + X - (In the formula, R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of alkyl, aryl, arylalkyl, alkoxysilyl and alkenyl, and X is selected from F, Cl, Br, I, PF6 or BF4 and OH; iv) an inert solvent; The composition of claim 1, comprising:

[0010] In a second aspect, the present invention relates to the use of a composition according to any of the preceding claims for coating a substrate.

[0011] In a third aspect, the present invention relates to a substrate comprising a coating made at least in part from the composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Unless otherwise defined, all technical terms, symbols and other scientific terms used herein are intended to have the meaning commonly understood by those skilled in the art to which this disclosure belongs. In some cases, terms having commonly understood meanings are defined herein for clarity and / or ready reference, and the inclusion of such definitions herein should not necessarily be interpreted as representing a significant difference with respect to the definition commonly understood in the art.

[0013] In one embodiment, the present invention provides a coating composition comprising a polysilazane component, a POSS and a quaternary ammonium salt. When the coating composition of the present invention is coated onto a substrate, the resulting coating after curing has advantageous properties, such as favorable antifouling properties and / or a low refractive index.

[0014] The term "resulting coating" as used herein refers to a coating obtained by applying a particular coating composition, optionally including other components, to a substrate and then curing to obtain a coating. This term is used synonymously with the term "coating" when the intended meaning is clear. The term "coating" as used herein means any layer, covering or covering on a surface of interest, typically also referred to as a "substrate". The coating may be substantially continuous or discontinuous. It may cover the entire surface or only a portion of the surface. It may be a single layer coating or a multi-layer coating. The terms "curing" and "hardening" as used herein refer to any type of strengthening and / or solidification of the coating composition upon application to a substrate, which may or may not be actively induced by heat, plasma, radiation, electron beam and / or chemical additives, etc.

[0015] All of the compositions disclosed and claimed herein can be used for coating purposes, e.g., to form a coating, and therefore the terms "composition" and "coating composition" are used interchangeably.

[0016] The present invention relates to i) 0.5 to 30 wt % of a polysilazane component selected from the group consisting of organic polysilazanes, inorganic polysilazanes, and mixtures of any two or more organic and / or inorganic polysilazanes, based on the weight of the composition; ii) 0.1 to 15 wt % of a POSS containing at least one nucleophilic group, based on the weight of the composition; iii) 0.0001 to 2 wt% of a quaternary ammonium salt R based on the weight of the composition 1 R 2 R 3 R 4 N + X - (In the formula, R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of alkyl, aryl, arylalkyl, alkoxysilyl and alkenyl, and X is selected from F, Cl, Br, I, PF6 or BF4 and OH; iv) an inert solvent; The present invention provides a coating composition comprising:

[0017] The compositions of the present invention include a polysilazane component. The polysilazane component may comprise 0.5-30 wt% of a polysilazane component selected from the group including or consisting of organic polysilazanes, inorganic polysilazanes, and mixtures of any two or more organic and / or inorganic polysilazanes, based on the weight of the composition. Preferably, the polysilazane component is selected from organic polysilazanes, mixtures of two or more organic polysilazanes, or mixtures of one or more organic polysilazanes and one or more perhydropolysilazanes. As used herein, the term "organopolysilazane" ("OPSZ") refers to a polysilazane having the formula [R'R''Si-NR''']n where at least one of R', R'' and R''' is an organic substituent and the remainder are hydrogen, where organic substituent defines any substituent containing carbon. The terms "perhydropolysilazane" ("PHPS") and "inorganic polysilazane" refer to any polysilazane of the formula [HSi-NH] n The terms "polysilazane" and "polysilazanes" are used interchangeably to refer to any polysilazane of the type described above.

[0018] The polysilazanes present in the coating composition of the present invention may be linear or branched. They may be cyclic. The polysilazane component advantageously comprises an organic polysilazane, in which one or more, preferably all, of the organic substituents are selected from the group of linear, branched, cyclic and / or aromatic C1-C6 alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, phenyl, vinyl, 3-(triethoxysilyl)propyl and 3-(trimethoxysilylpropyl). Preferably, one or more of the organic substituents are selected from the group of methyl and ethyl. However, in some embodiments, one or more of the organic substituents are linear or branched C5-C6 alkyl. 10 Alkyl, preferably branched C5-C 10 alkyl. Advantageously, the organic substituents do not contain triple bonds or double bonds other than C=C bonds. The organic substituents may contain heteroatoms.

[0019] The polysilazane component may have, for example, a number average molecular weight (Mn) in the range of 150 to 150,000 g / mol. As will be appreciated by those skilled in the art, the polysilazane component can be selected to obtain particular properties of the resulting coating, such as hydrophobicity, refractive index, and soil resistance.

[0020] It has been observed by the inventors that the inclusion of an organopolysilazane known by the trademark Durazane 1800 ("D1800") (Structure I) in a composition containing the organopolysilazane Durazane 1500 Rapid Cure ("D1500 RC") has a favorable effect on the quality of coatings, especially those having a high concentration of nucleophilic groups on the POSS and / or a high concentration of another more reactive polysilazane in the composition. The structure of D1500 RC is shown below (Structure II). a, b and c are proprietary information not known by the inventors. In addition to the propyltriethoxysilane grafted to the backbone of the polymer, D1500 RC may also have 3-aminopropyltriethoxysilane (APTES) added to function as an additional curing agent. According to information provided by the manufacturer Merck, the total amount of propyltriethoxysilane and APTES in D1500 RC is greater than 10% and less than 30% by weight of the total composition. [ka] [ka]

[0021] Visual inspection showed that the coating of Experiment 1 containing D1800 was smoother, more uniform, and had better soil resistance than the corresponding coating without D1800. These effects may be due to the fact that D1800 is more sterically hindered than D1500 RC, which may result in a slower and more controlled reaction, the vinyl groups of D1800, which become ethyl upon curing, are more hydrophobic than the methyl groups of D1800, and the higher amount of organic groups in D1800 may allow it to function as a surfactant, improving the film-forming properties of the composition.

[0022] D1800, D1500 RC and Durazane 1500 Slow Cure ("D1500 SC") all represent examples of preferred polysilazane components. There is no information available regarding the structure of D1500 SC, also manufactured by Merck, but it is believed to contain no grafted triethoxysilane (Z=0) but in the range of more than 3% and less than 10% "free" APTES (hence it cures slower than D1500 RC). The organic groups in D1500 SC are believed to be methyl.

[0023] The polysilazane component is present in an amount of 0.5-30 wt%, such as 1-8 wt%, such as 5-15 wt%, such as 20-30 wt%, based on the weight of the total coating composition. One skilled in the art will appreciate that the amount of polysilazane may be selected based on, for example, the technique used for application of the coating composition to a substrate.

[0024] The compositions of the present invention include POSS, or polyhedral oligomeric silsesquioxanes, which have the chemical formula [RSiO 3 / 2 ] n (R=H, alkyl, aryl, arylalkyl or alkoxyl, fluoroalkyl, perfluoroalkyl, siloxane / (poly)siloxane, ether / polyether) compounds, which may have a cage structure (Figure 1) and whose chemical composition is hybrid, i.e., a mixture of the composition of silicon (SiO2) and silicone (R2SiO) n The composition is intermediate between 1.5 ) n Each POSS molecule may contain covalently attached reactive functional groups suitable for polymerization of POSS monomers or grafting onto polymer chains, and non-reactive organic functional groups for solubility and compatibility of POSS with various polymer systems. A variety of different POSS molecules are available, and many more are in development.

[0025] Advantages of POSS include the fact that their small size of 1-3 nm (Si-O-Si core) allows mixing with polysilazanes at the molecular level, and the fact that POSS behaves like molecules rather than like typical nanoparticles, allowing for very stable concentrated dispersions of POSS in different solvents, thus facilitating the formulation of coating compositions. Furthermore, the Si-O-Si backbone of the POSS molecule means that the light transmittance of a coating is not adversely affected when POSS is included in that coating.

[0026] When used in the coating compositions of the present invention, the ball-like nature of the POSS molecules can contribute to reducing the coefficient of friction of the resulting coating relative to a comparable coating that does not contain POSS; when the rigid Si-O-Si backbone is combined with and surrounded by low friction (slippery) molecules, such as alkyl, fluoroalkyl, from either polysilazanes or POSS itself, the POSS can be considered as a ball that acts like a roller for the slippery components.

[0027] The R groups of POSS may be independently selected from the group consisting of H, alkyl, aryl, arylalkyl, alkoxyl, alkoxysilyl, or alkenyl. In some embodiments, the R groups are H, C1-C 18 Alkyl, C6-C 24 Aryl, C7-C 34 Aryl alkyl, C1-C 18 Alkoxyl, C1-C 12 (C1-C9 alkoxysilyl)alkyl and C2-C 18 Alkenyl, e.g. H, C2-C 12 Alkyl, C6-C 12 Aryl, C7-C 22 Aryl alkyl and C2-C 12 Alkoxyl, C2-C8 (C1-C6 alkoxysilyl) alkyl and C4-C 12Alkenyl, preferably H, C1-C6 alkyl (methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, cyclohexyl, etc.), phenyl, C7-C 18 The R groups are selected from arylalkyl, C1-C6 alkoxyl, C1-C6 (C1-C4 alkoxysilyl) alkyl and C1-C6 alkenyl. The alkyl, arylalkyl, alkoxyl, alkoxysilyl and alkenyl groups may be linear and / or branched. The alkyl, arylalkyl, alkoxyl, alkoxysilyl and alkenyl groups may be cyclic. The R groups may all be the same or one, two, more or all of the R groups may be different from the other R groups.

[0028] Advantageously, the alkenyl or alkoxysilyl groups may be reacted after coating to become covalently bonded to the coating. Such bonding may prevent leaching of unbonded components such as salts. However, the number of such groups should not be too high, and should be limited to a maximum of 5, for example a maximum of 3. The presence of a terminal methyl group somewhere in the POSS, such as a highly branched alkyl group, may result in a coating with favorable antifouling properties.

[0029] POSS useful for the present invention contain at least one group that can react with polysilazanes (covalently bonded to Si) to cause fragmentation. Unsaturated bonds such as C=O and S=O are not normally thought of as nucleophiles, but both can function as nucleophiles in some circumstances. We have found that carbonyls in butyl acetate and S=O in dimethylsulfoxide react with polysilazanes in our coating formulations. Thus, nucleophilic groups are used in the present invention in a broad sense to include unsaturated bonds that can react with polysilazanes to cause fragmentation. Nucleophilic groups include heteroatoms selected from O, N, and S. Nucleophilic groups may be selected from the group including C=O, OH, NH2, NH, S=O, SH, C=N, and C≡N. In some embodiments, nucleophilic groups are selected from NH2, C=O, and OH. Nucleophilic groups may be present as substituents on the R group or may be directly bonded to the Si atom. In some embodiments, the POSS comprises 1-8, preferably 1-5, and more preferably 1-3 nucleophilic groups.

[0030] The Si atoms in polysilazanes (Si-H, and possibly Si-NH-Si) are easy targets for nucleophilic attack. Thus, the nucleophilic groups of the POSS molecules can react with the polysilazanes in the coating composition. A possible mechanism is nucleophilic attack by the nucleophilic groups of the POSS to form an intermediate donor covalent bond with the Si atom, thereby bringing the Si into a penta-coordinated state, followed by bond breakage, which results in fragmentation of the polysilazane chain when the Si-N bond is broken. The degree of fragmentation may depend on the type of nucleophile, the type and / or concentration of the polysilazane.

[0031] The POSS molecules may be open cage or closed cage or random or ladder structures. Closed cage POSS molecules of various cage sizes, such as T8 cage (8 Si atoms, structure III), T10 cage, T12 cage and mixtures of any two or more, may be particularly useful in the coating compositions of the present invention. [ka]

[0032] Advantageously, the POSS further comprises at least one fluoro substituent. The fluoro substituent may be directly bonded to the Si atom. Advantageously, the fluoro substituent is present as a substituent on an R group, making the R group a fluorinated R group. In some embodiments, the fluorinated R group is based on a siloxane, such as a (poly)siloxane. Preferred POSS molecules comprise as an R group at least one group selected from fluoroalkyl, fluoroaryl, fluoroarylalkyl, fluoroalkoxyl, fluoroalkoxysilyl or fluoroalkenyl. In some embodiments, the R group is a C1-C 18 Fluoroalkyl, C6-C 24 Fluoroaryl, C7-C 34 Fluoroarylalkyl, C1-C 18 Fluoroalkoxyl, C1-C 12 Fluoro(C1-C9 alkoxysilyl)alkyl and C2-C 18 Fluoroalkenyl, e.g. C2-C 12 Fluoroalkyl, C6-C 12 Fluoroaryl, C7-C 22 Fluoroarylalkyl and C2-C 12 Fluoroalkoxyl, C2-C8 fluoro(C1-C6 alkoxysilyl)alkyl and C4-C 12 Fluoroalkenyl, for example, C1-C6 fluoroalkyl (fluoromethyl, nonafluorohexyl, fluoroethyl, trifluoropropyl, pentafluorobutyl, isofluorobutyl, heptafluoropentyl, cyclofluorohexyl, etc.), pentafluorophenyl, C7-C 18The R groups may be all the same or one, two, more or all of the R groups may be different from the other R groups. For all of the fluorinated R groups mentioned, the fluorinated R group may contain one or more fluoro substituents, such as 1, 2, 3, 4, 5, 6, 7 or more fluorine substituents. In a preferred embodiment, the POSS comprises at least one C1-C fluoroalkoxyl having 1-15 fluorine substituents as R groups. 10 Contains a fluoroalkyl group.

[0033] In some embodiments, the POSS does not include fluoro substituents. In certain embodiments, the POSS includes 5-7 R groups that are not fluorinated and includes aryl such as phenyl and / or alkyl such as methyl and / or (poly)siloxane and 1-3 R groups that are not fluorinated and includes one or more nucleophilic groups selected from the group including or consisting of C=O, OH, NH2, NH, S=O, SH, C=N or C≡N.

[0034] POSS molecules that contain fluoro substituents can improve the antifouling effect of the resulting coating compared to POSS that does not contain fluoro substituents. POSS molecules that contain fluoro substituents can reduce the refractive index of the resulting coating compared to POSS that does not contain fluoro substituents. In addition, fluorinated POSS can also produce a lower coefficient of friction, as shown in the following example using CO-POSS.

[0035] The 8, 10 or 12 Si centers of the T8, T10, T12 cage-type POSS make it possible to optimize the surface chemistry of the coating composition and the resulting coating. For example, if low surface energy (soiling resistance) and low coefficient of friction are required, the majority of the centers can have fluoroalkyl groups, with only one or two having reactive nucleophilic groups. Advantageously, the POSS structure allows the surface of the coating to be rich in CF2 and CF3 groups without introducing too many reactive groups, unlike most common molecules where each fluoroalkyl chain or other chain of interest has its own reactive and / or functional group.

[0036] POSS may additionally or alternatively contain other substituents not mentioned above, such as at least one chloro substituent. POSS molecules may also contain as or within the R group groups or substituents selected specifically for their properties, such as antimicrobial agents, UV absorbers / stabilizers, IR absorbers and / or upconversion phosphors.

[0037] In some embodiments, the preferred POSS is CO-POSS. CO-POSS has isobutyl groups attached to all but one of the Si centers, and a mixture of propyl methacrylate and perfluorododecyl (-CH2CH2(CF2)7CF3) at the last Si center. This combination of R groups in CO-POSS results in a POSS with the favorable properties associated with fluoro substituents, which are fairly hydrophobic, can form stable solutions with polysilazane, and results in a fairly uniform distribution of POSS in the polysilazane matrix as observed by microscopy.

[0038] Further preferred POSS are those with a greater number of fluorinated R groups on the T8 POSS than CO-POSS, for example up to 7 fluorinated groups, for example up to 6 fluorinated groups. The inclusion of these POSS molecules in the coating composition of the present invention is expected to result in coatings with lower coefficients of friction and / or better stain resistance / cleanability relative to other comparable coatings. An example of such a preferred POSS is CH2CH2(CF2) n T8 POSS with fluorinated chains such as CF3 (wherein 0≦n≦8, more preferably 0≦n≦7). POSS with larger cage size may have a correspondingly larger number of fluorinated chains. Some non-limiting examples of useful POSS are shown below (structures IV-VI). [ka]

[0039] In some embodiments, (CF2) n POSS having fluorinated chains such as CF3, where 0≦n≦8 (assuming T8 cage type) may be used. These POSS molecules may further optionally contain more nucleophilic and / or polar functional groups. This may help to increase the solubility in the solvent, especially with longer fluoroalkyl chains (e.g., n≧3). In these embodiments, the coating composition may contain a fluorinated solvent, e.g., as the only solvent or, e.g., in combination with another solvent, to further increase the solubility of such POSS. Those skilled in the art have knowledge of various fluorinated solvents and compatible solvents for solvent mixtures. Compound VII is an example of a useful POSS of such structure. [ka]

[0040] All POSS molecules containing fluoro substituents may further contain any other type of fluorinated and / or non-fluorinated R group, such as, but not limited to, linear or branched alkyl, aryl (e.g., phenyl), (poly)siloxane and alkoxysilyl (alkyl-O-Si). The combination of fluorinated and non-fluorinated substituents may help to increase the solubility of the POSS, especially in non-fluorinated solvents. It may also reduce the tendency of fluorinated molecules, such as compounds containing CF2 and / or CF3 groups, to stick to each other or to phase separate, a phenomenon that can result in high surface roughness, hazy coatings and even an increased coefficient of friction. Alkoxysilyls, such as methoxysilyl and ethoxysilyl, hydrolyze very quickly in the presence of moisture to form silanols, which contribute to the fast curing of polysilazanes. POSS molecules with only alkoxysilyl groups or a majority of alkoxysilyl groups may also be used with / without one R group containing a reactive functional group.

[0041] Examples of POSS molecules with fluorinated (trifluoropropyl) and non-fluorinated R (phenyl and isobutyl) groups for use in the present invention include the following: [ka]

[0042] The inventors have discovered that combinations of phenyl or alkyl (such as isobutyl, isooctyl, etc.) with fluoroalkyl (such as trifluoropropyl, heptafluoropentyl, etc.) result in POSS with better solubility in solvents and / or better dispersion in the polymer matrix, thereby eliminating the coating haze commonly seen in structures IV and V, and resulting in overall improved coating quality based, for example, on visual observation. For example, structure VIII has been tested up to 40 wt % for polysilazane concentrations that do not exhibit haze, unlike VI. The theoretical ratios shown in structures VII-XI are merely exemplary, as are the R group combinations.

[0043] The inclusion of one or more phenyl groups in the POSS molecules used in the compositions of the present invention may enhance the toughness of the resulting coating, such as mechanical toughness as measured by tensile strength, and may further enhance resistance to space electrons, protons, and / or harmful radiation, such as UV. Thus, in some embodiments, at least one R group comprises a phenyl group.

[0044] Furthermore, when the POSS contains naturally slippery R groups, the resulting coating appears to have a relatively low coefficient of friction. Examples of such naturally slippery R groups are polyethers, (poly)siloxanes and fluorinated chains.

[0045] Another POSS investigated by the inventors is N-POSS, in which three of the eight R groups are 3-aminopropyl groups. A molecule of N-POSS with three amino groups (assuming a T8 cage type) can react 3 to 6 times more with polysilazanes than a molecule of POSS with only one OH or C=O group. Thus, N-POSS reacts more vigorously with polysilazanes than CO-POSS.

[0046] Furthermore, the POSS of the present invention may not be fluorinated, but have R groups that are inert or contain inert groups. Examples of such inert groups include phenyl, alkyl, alkene, siloxane and ether. Non-fluorinated POSS may have a combination of two or more R groups. Such combinations, such as phenyl and vinyl, alkyl and vinyl or alkyl and phenyl, may enhance dispersion and compatibility in solvents and coating matrices. Examples of non-fluorinated POSS include aminopropyl isobutyl POSS (structure IV where trifluoropropyl is replaced by isobutyl) and trisilanol isobutyl POSS (open cage type). The latter has been found to be too reactive and requires reduction of the silanol concentration by reaction with an appropriate silane to form a silyl ether.

[0047] The POSS present in the compositions of the present invention typically have a T8 cage type (8 Si atoms), a T10 cage type or a T12 cage type or a mixture of any two or more. POSS with larger cage structures such as T14 or T18 may also be useful in the coating compositions of the present invention. In some embodiments, T8 is preferred. In other embodiments, T10 and / or T12 are preferred as they can impart greater mechanical strength to the coating. Furthermore, they may provide slightly higher nanoporosity than their T8 counterparts due to less close packing compared to the smaller T8. So-called dumbbell and / or star-shaped POSS may also be useful. In some embodiments, the POSS has a dumbbell shape in which two POSS cages are linked to each other. In some embodiments, the POSS has an "extended dumbbell" shape in which three, four or more POSS cages are linked to each other. Such structures may advantageously contain only 1-3 nucleophilic groups, for example 2 nucleophilic groups, preferably 1 nucleophilic group. The low number of nucleophilic groups per POSS structure may reduce reactivity, thus increasing reaction control. The use of dumbbell-shaped POSS may increase the distribution of POSS cages throughout the composition, such as by providing a more uniform distribution of POSS cages in the composition. This effect may improve the transmittance of the resulting coating. Examples of useful POSS with dumbbell shapes are shown below. [ka] JPEG2024529311000008.jpg208159

[0048] All dumbbell structures have a secondary amine as the reactive nucleophile depending on the synthetic approach employed. Other nucleophiles may be used. Furthermore, the ratio of R groups is exemplary. The R group on one ball of the dumbbell structure may be different from that on the other ball.

[0049] The POSS is present in the coating composition of the present invention in an amount of 0.1-15 wt%, such as 0.2-15 wt%, for example 0.5-10 wt%, such as 1-5 wt%, based on the weight of the coating composition.

[0050] Combinations of two or more POSS types may be used. For example, a POSS containing primarily fluorinated groups and an R group containing one or two nucleophiles may be combined with another POSS containing an alkoxysilyl and fluorinated R group. Combinations of different POSS structures (T8, T10, T12, open or closed cage) may be used. POSS structures VIII, IX, and X were synthesized by a method designed to obtain the T8 structure and the closed cage. However, nuclear magnetic resonance (NMR) analysis showed that for VIII and IX (phenyl and trifluoropropyl combinations), about 2-4% of the product was open cage, and for X, about 9% was open cage. Furthermore, the ratio of trifluoropropyl:non-fluorinated R groups differed slightly from the theoretical value, with the phenyl:trifluoropropyl POSS structure having a slightly higher trifluoropropyl content than the theoretical value, and vice versa for the isobutyl:trifluoropropyl combination. These variations in structure and R groups naturally apply to their derivative dumbbell structures.

[0051] In some embodiments, the composition of the present invention further comprises 0.005-5 wt%, such as 0.05-5 wt%, such as 1-3 wt%, of POSS that does not contain reactive nucleophilic groups, based on the total weight of the composition.

[0052] The composition of the present invention comprises a compound that can promote the reaction of the POSS with the polysilazane component and / or cause defragmentation of the polysilazane. The compound comprises a nucleophilic component, such as an anion. Preferably, the compound is a salt. More preferably, the salt is a quaternary ammonium salt R 1 R 2 R 3 R 4 N + X -As used herein, the term "quaternary ammonium salt" refers to a monovalent, positively charged group R having a tetravalent nitrogen and a negative counterion (anion). 1 R 2 R 3 R 4 Anion X - may be selected from fluoride, chloride, bromide and iodide. Alternatively, X - PF6 - Or BF4 - or polyatomic anions such as OH - In some embodiments, X is selected from F, Cl, Br, I, PF6 or BF4 and OH. In some embodiments, X is selected from F, Cl and Br. R 1 , R 2 , R 3 and R 4 are independent of each other, C1~C 10 It is selected from the group including or consisting of alkyl, aryl, arylalkyl, alkoxysilyl and alkenyl. Advantageously, the alkoxysilyl group of the alkoxysilyl can be hydrolyzed to a silanol, which can polycondense with other silanols from the polysilazane hydrolysis to give a covalent bond after coating. Other groups that can react with the polysilazane or additive after coating to establish a covalent bond, such as an alkenyl group with an activated C=C double bond, can also be advantageous.

[0053] The salt may facilitate the reaction of the polysilazane with nucleophilic groups on the POSS and / or other components of the coating composition. This activation may involve X coordination, etc. - with the silicon atoms of the polysilazane, resulting in activation of the silicon atoms for nucleophilic attack.

[0054] The salt may also function as a catalyst for defragmentation. As discussed above, the presence of nucleophilic (reactive) centers in the POSS in the coating composition results in fragmentation of the polysilazane chain. Fragmentation may begin immediately upon mixing of the polysilazane component with the POSS. The resulting fragments may be volatile, less reactive than the original polysilazane, or even non-reactive. Due to their smaller size, they may be lost by evaporation. They may also leave unreacted polar groups in the cured coating, reducing the soil resistance of the coating.

[0055] Without wishing to be bound by any theory regarding their mechanism of action, a possible explanation for the observed positive effect of the presence of quaternary ammonium salts in the experiments discussed below may relate to the fact that polysilazane fragments contain NH2 and NH functional units, and that quaternary ammonium salts may facilitate the reaction of electrophilic Si atoms in Si-H with nucleophiles such as NH2 and NH. These properties may allow for the reincorporation of the fragments into the larger polymer network. Importantly, the anion of the salt is a stronger nucleophile than the nucleophiles (NH2 and NH) in the reaction, and "Fragment" -N-H + "Chain" -Si-H → "Fragment" -N-Si- "Chain" + H2(g) (where "chain" refers to the chain of polysilazane polymer backbones). The observation of foaming (i.e., evolved gas) upon mixing of polysilazane with catalyst supports this theory. When two different polymer backbones are linked together (as can happen), this phenomenon is called solution crosslinking. Solution crosslinking can occur in the absence of POSS (or polysilazane fragments), since the NH group of polysilazane (Si-NH-Si) can react with Si-H in the presence of a catalyst, resulting in the formation of Si-N bonds.

[0056] Preferred quaternary ammonium salts are the commercially available tetra-n-butylammonium fluoride (TBAF), tetra-n-butylammonium bromide (TBAB), tetra-n-butylammonium chloride (TBAC), and tetra-n-butylammonium hydroxide.

[0057] The salt may be present in the coating composition in an amount of 0.0001 to 2 wt%, such as 0.001 to 1 wt%, for example 0.1 to 0.5 wt%, based on the weight of the composition.

[0058] The composition of the present invention may include a curing agent. The term "curing agent" as used herein refers to any compound known by a person skilled in the art to promote the curing of a polymer by crosslinking the polymer chains. Examples of preferred curing agents are 3-aminopropyltriethoxysilane (APTES), tetraethyl orthosilicate (TEOS), alkyltriethoxysilane (e.g. ethyltriethoxysilane) and alkyltrimethoxysilane. APTES can react with polysilazane through its amino group and therefore can be considered a reactive additive, which means that the use of a defragmentation catalyst may be required. The less sterically hindered alkoxysilyl group can be rapidly hydrolyzed, which results in the formation of silanols, thus promoting the curing of the polysilazane.

[0059] The curing agent may be grafted onto the polymer chain as in D1500 RC.

[0060] The curing agent may be present in the coating composition in an amount of 1-30 wt%, such as 3-30 wt%, such as 3-10 wt%, such as 10-20 wt%, based on the weight of the polysilazane component.

[0061] The composition of the present invention includes an inert solvent. As used herein, the term "solvent" refers to a liquid substance in which a compound is sufficiently soluble or partially soluble at a given concentration to dissolve or partially dissolve the compound. The term refers to both solvent mixtures (i.e., solvents consisting of multiple components) and pure compounds (i.e., solvents consisting of a single component) unless the context indicates otherwise. As used herein, the term "inert solvent" refers to a solvent known by those skilled in the art to not react with other components of the coating composition. The solvent should be present in an amount of 20-99 wt% based on the total weight of the composition. The solvent may be selected from the list including or consisting of aromatic solvents such as tetrahydrofuran (THF), 2-methyltetrahydrofuran (MTHF), dibutyl ether (DBE), methoxyperfluorobutane (MPB), cyclopentyl methyl ether, xylene, and toluene, as well as other polar aprotic and non-polar solvents that do not contain functional groups that can react with polysilazanes. It is typically an ether or a hydrocarbon. In some embodiments, the solvent is selected from the list including or consisting of THF, DBE, MTHF, MPB, and xylene. THF, MTHF and dibutyl ether are examples of preferred solvents. The solvents DMSO and butyl acetate can react with polysilazanes in the presence of TBAF or other catalysts and therefore should preferably be avoided, as should other solvents containing unsaturated bonds containing heteroatoms, since TBAF and other quaternary ammonium fluorides or catalysts may promote the reaction of such double or triple bonds containing Si-H.

[0062] In some embodiments, the compositions of the present invention further comprise one or more components selected from the group including or consisting of flow and leveling agents, photoinitiators, fibers, polymer stabilizers, fillers, and pigments.

[0063] The composition of the present invention may further comprise a flow leveling agent. As used herein, the term "flow leveling agent" refers to one or more compounds known by those skilled in the art to be capable of enhancing coating uniformity and eliminating defects such as pinholes, "fish eyes", "orange peel", high roughness, etc. The flow leveling agent may be present in an amount of 0.01 to 1.5 wt%, such as 0.1 to 0.8 wt%, such as 0.3 to 0.5 wt%, based on the weight of the coating composition. The flow leveling agent may not have a reactive nucleophilic group selected from the group C=O, OH, NH2, NH, S=O, SH, C=N or C≡N. One example of a flow leveling agent is a polyether siloxane copolymer commercially available as "TEGO® Glide 410" (TG4). In some embodiments, leveling agents containing organic fluorine groups are preferred, such as to achieve coating formulations with lower surface tension, especially when using additives or polysilazanes containing fluoro substituents. A non-limiting example of a leveling agent containing an organic fluorine group is a derivative of the leveling agent reported in US Patent Application Publication No. 20110319581A1 having the structure shown below (Structure XVII). [ka]

[0064] The flow leveling agent should not react with the polysilazane, and therefore in structure XVII, Rf may represent a linear or branched perfluoroalkyl group containing 1 to 10 carbon atoms, X represents a trifluoromethyl group, Q may represent an ether containing 1 to 12 carbon atoms, R is an alkyl or acyl group containing 1 to 6 carbon atoms, and R 1 and R 2 are independently an alkyl group, an aryl group, or an aralkyl group containing 1 to 10 carbon atoms.

[0065] The composition of the present invention may further comprise a photoinitiator, such as 1-hydroxycyclohexyl phenyl ketone. The photoinitiator may further assist in curing the coating when the cure is assisted by UV or visible light. The photoinitiator may be present in an amount of 0.05 to 5 wt%, such as 0.1 to 4 wt%, for example 0.3 to 1 wt%, based on the weight of the coating composition.

[0066] The composition of the invention may further comprise fibers, such as nanofibers, such as cellulose nanofibers. The fibers may have one or more alkyl and / or fluoroalkyl groups and groups that include a nucleophile capable of covalently bonding to the polysilazane. The inclusion of fibers may reduce the refractive index of the resulting coating, such as by forming air pockets in the coating. The fibers may also enhance the mechanical properties of the coating, such as impact toughness and tensile strength. The fibers may be present in an amount of 0.01-10 wt %, such as 0.1-7 wt %, such as 1-3 wt %, based on the weight of the composition.

[0067] The composition may further comprise one or more linear, branched or cyclic (poly)siloxanes, an example of which is 1,3,5,7-tetramethylcyclotetrasiloxane is shown below (Structure XVIII). [ka]

[0068] Modifications of structure X in which one or more hydrogen atoms are replaced with alkyl, aryl, (poly)siloxane, organic fluoro, such as fluoroalkyl, reactive groups, such as 3-aminopropyl or 6-hydroxyhexyl, and / or alkoxysilyl groups may be preferred. The groups mentioned may have similar functions as present in polysilazanes and / or POSS, for example reactive groups may be covalently bonded to polysilazanes, inert organic and organic fluoro groups may improve coating formulation stability and antifouling properties of the resulting coating, and alkoxysilyl groups may enhance the curing of polysilazanes. The (poly)siloxane-based additive may be present in the coating formulation in an amount of 0.05-15 wt%, such as 0.08-10 wt%, such as 1-3 wt%, based on the weight of the composition. A particular advantage of the (poly)siloxane-based additive is that it does not have to be as crystalline and hard as POSS, and therefore may increase the flexibility of the resulting coating. Other advantages include improved light transmission.

[0069] The composition of the present invention may further comprise a polymer stabilizer. The term "polymer stabilizer" as used herein refers to any compound or composition that can inhibit or delay any degradation of the polysilazane component and / or the present coating. Common polymer degradation processes include combinations thereof such as oxidation, UV damage, thermal decomposition, ozonolysis, photooxidation, and the like, as well as reactions with catalyst residues, dyes, or impurities. The polymer stabilizer may be selected from the group including or consisting of antioxidants such as radical scavengers, hydroperoxide scavengers, antiozonants; light stabilizers such as UV stabilizers, quenchers, hindered amine light stabilizers; acid scavengers; metal deactivators; thermal stabilizers; flame retardants; biocides, and any combination thereof. Preferably, the polymer stabilizer is a UV stabilizer, i.e., a compound or composition that prevents photodegradation of the polysilazane component or the present coating, such as by absorbing ultraviolet light.

[0070] The coating composition may further comprise one or more additional fillers and / or pigments, such as wollastonite, carbon black, micaceous iron oxide, and / or thixotropic agents.

[0071] The compositions of the present invention may be coated and cured onto a substrate to obtain a coating. Thus, in another aspect, the present invention relates to the use of any of the compositions disclosed herein for coating a substrate.

[0072] In yet another aspect, the invention relates to a substrate comprising a coating made at least in part from any of the compositions disclosed herein, in some embodiments, the coating is made from the compositions disclosed herein.

[0073] The substrate may be made of any material. For materials with low surface energy (high water contact angle), surface activation prior to coating may be required. Such activation typically involves coating the coating composition and generating nucleophilic functional groups that promote wettability, such as by covalently bonding the coating to the substrate, which can be achieved, for example, using atmospheric plasma, UV, or chemical treatment. Atmospheric plasma treatment may be preferred, as it may be faster and safer. For example, the surface of polyethylene may be treated with atmospheric plasma within 30 seconds to generate functional groups such as hydroxyl, carbonyl, and carboxyl. Other substrates, such as glass, may also be treated to increase the concentration of nucleophilic functional groups and thereby enhance wettability and coating adhesion. These nucleophilic groups can be covalently bonded to the polysilazane via Si-H to obtain strong coating adhesion. If the substrate is glass, covalent bonding can be achieved based on the reaction of silanols on the glass surface with silanols generated by hydrolysis of the polysilazane, thereby obtaining Si-O-Si bonds. Atmospheric plasma activation of the glass may increase the concentration of surface silanol groups, thus resulting in stronger coating adhesion.

[0074] For the preparation and / or application of the coating composition, the coating methods disclosed in Norwegian Patent Application No. 20200778, any patent or patent application issuing therefrom or claiming priority therefrom may be used. Thus, in order to limit the fragmentation of the polysilazane, i) preparing a coating composition, a. introducing component A into a coating composition container; b. introducing component B into the coating composition container and mixing component B with component A; and c. introducing component C into the coating composition container and mixing component C with components A and B; Including sub-processes, Components A, B and C are each selected from the group of polysilazanes, the group of quaternary ammonium salts or the group of reactive nanomaterials and / or reactive molecules such as POSS that can spontaneously react with the polysilazane polymer backbone to cause fragmentation; Components A, B and C are all selected from different groups, the selection of groups for each of components A, B and C is predetermined based on the known reactivities of the components relative to one another; ii) applying the coating composition to a substrate, Step ii) is a process for determining the time period t based on the known reactivities of the components with respect to each other. ii Start with For a given period t ii is 1≦t ii may be selected to be ≦1200 seconds; The introduction of component C in sub-step ic) occurs at a given time t after the introduction of component B in sub-step ib). c Starts with t c is 0≦t c selecting the time to be < 900 seconds; Polysilazane coating methods including:

[0075] Alternatively, two or more, such as all, of the components of the coating composition may be mixed together at the same time, prior to applying the coating composition to a substrate. c = 0, where application of the coating composition to a substrate is performed after the mixing at t ii Starts at a given time period between 1 and 1200 seconds, and ii is predetermined based on the known reactivities of the components relative to one another.

[0076] In some embodiments, the polysilazane is mixed with any additive that does not react with the polysilazane (e.g., TG4), and a reactive additive (e.g., POSS) and a quaternary ammonium salt are mixed together separately. Depending on their compatibility with the contents of such solutions, other additives such as antimicrobial agents, UV stabilizers, etc. may be added to the solution containing the polysilazane or the solution containing the POSS. The two mixtures are combined and mixed. The two mixtures are then allowed to stand for a predetermined period of time, such as 1 to 1200 seconds after mixing. ii Application of the coating composition to the substrate may commence at this point.

[0077] In some embodiments, polysilazane is mixed with any additives that do not react with polysilazane (Solution A), and separately reactive additives (e.g., POSS) and quaternary ammonium salts are mixed together (Solution B), and a third mixture contains additives that can react with polysilazane, such as UV absorbers, photoinitiators, radical curing agents, antimicrobial agents, etc. (Solution C). A and B are mixed together first, and C is introduced 1-1000 seconds later. Then, after a predetermined period t, such as 1-1200 seconds after mixing of A and B, ii The application of the coating composition to a substrate may commence at 100° C. The definition of reactive additive may be in terms of the concentration and type of such additive. The reactive component may be present in such small amounts, for example as an impurity or as part of an additive, but does not have a significant fragmentation effect on the polysilazane. It may then be combined with the polysilazane in solution A.

[0078] The duration of solution C in the coating formulation prior to coating application (i.e., the time between the introduction of solution C and its application by spray coating) may be selected such that there is a time sufficient to uniformly mix its contents in the coating formulation, but short enough to limit reaction of its contents with the polysilazane. This is to ensure that this set of additives remains active (e.g., as a UV absorber) since their activity is related to the presence of functional groups thereon, e.g., hydroxyl, carbonyl. Such functional groups are reactive towards polysilazane. To further reduce the probability of reaction of the components of solution C with polysilazane, the solution may be diluted, for example, by adding an appropriate amount of solvent in solution C, or by diluting the mixture of A and B prior to the introduction of solution C.

[0079] The coating formulation may be diluted with / without an additional reactive component (Solution C) before coating.

[0080] Other coating, mixing and / or preparation methods known to those skilled in the art may also be used.

[0081] The coating composition may be applied to a substrate using any technique known to those skilled in the art, such as, but not limited to, a method selected from the list including spraying, such as ultrasonic spray coating, spray painting or pneumatic spraying; spin coating; die casting; inkjet printing; doctor blading, electrospinning, and other processes known in the art for converting solution-processed chemical compositions into coatings or films. The advantage of using spray application is that a more dilute coating composition can be used, resulting in a thinner coating.

[0082] The thickness of the applied coating is typically in the range of 0.1 to 10 μm.

[0083] Curing may be assisted by one or more of plasma, heat and UV or visible light, all in the presence of water and / or ammonia and / or H2O2 vapor. UV and plasma curing is fast due to the presence of radicals (e.g., hydroxyl radicals) and ozone or excited molecules, e.g., water. These energetic molecules may cause rapid hydrolysis to form Si-OH and may further affect their energy on silanols for faster polycondensation. When exposed to moisture, Si-H and Si-NH-Si groups hydrolyze to give silanols, which then crosslink to obtain Si-O-Si bonds. These reactions can also be enhanced by curing agents, e.g., APTES, that easily become hydrolyzed on exposure to air. The use of such curing agents is important, especially for organopolysilazanes, since their reactivity is limited by steric hindrance. Alkoxy groups present in the polysilazane molecules may accelerate the hydrolysis and crosslinking.

[0084] Fast curing may allow roll-to-roll coating. Complete curing may enhance abrasion and / or rub resistance and / or promote better stain resistance since all or most of the nucleophilic groups have been consumed. Fast curing may advantageously be obtained by using atmospheric plasma and / or UV as curing means, in an environment that may be air (standard conditions), nitrogen, forming gas with an appropriate level of relative humidity (RH), such as RH above 30%, above 60%. Humidity in the environment may be controlled. Other preferred methods that may shorten the curing period compared to curing under standard atmospheric conditions include infrared heating in a humidified atmosphere.

[0085] For example, with respect to aspects relating to the present composition, embodiments and features described in the context of one aspect also apply to other aspects of the invention, such as uses of the present composition, substrates including coatings, etc.

[0086] The present invention is not limited to the illustrated embodiments and examples. Although various embodiments of the present disclosure are described herein, it will be apparent to those skilled in the art that such embodiments are provided by way of example only. Numerous modifications and changes to the embodiments described herein, as well as variations and replacements thereof, will be apparent to those skilled in the art without departing from the present disclosure. It will be appreciated that various alternatives to the embodiments described herein can be used in implementing the present disclosure.

[0087] It should be understood that all embodiments of the present disclosure may be optionally combined with any one or more of the other embodiments described herein.

[0088] It should be understood that each component, compound or parameter disclosed herein should be construed as being disclosed alone or in combination with one or more of each and every other component, compound or parameter disclosed herein. Each amount / value or amount / value range of each component, compound or parameter disclosed herein should also be construed as being disclosed in combination with each amount / value or amount / value range disclosed for any other component, compound or parameter disclosed herein, and thus it should be further understood that any combination of amount / values ​​or amount / value ranges of two or more components, compounds or parameters disclosed herein is also disclosed in combination with each other for the purposes of this specification. Any and all features and combinations of such features described herein are included within the scope of the present invention, unless those features are mutually inconsistent.

[0089] It should be understood that each lower limit of each range disclosed herein should be interpreted as being disclosed in combination with each upper limit of each range disclosed herein for the same component, compound or parameter. Thus, a disclosure of two ranges should be interpreted as a disclosure of four ranges obtained by combining each lower limit of each range with each upper limit of each range. A disclosure of three ranges should be interpreted as a disclosure of nine ranges obtained by combining each lower limit of each range with each upper limit of each range, and so on. Furthermore, a specific amount / value of a component, compound or parameter disclosed in the specification or examples should be interpreted as a disclosure of either the lower or upper limit of a range, and thus can be combined with any other lower or upper limit or range or specific amount / value of the same component, compound or parameter disclosed anywhere in this application to form a range of that component, compound or parameter. EXAMPLES

[0090] Coating Composition (Experiment 1) [Table 1]

[0091] In Table 1, PS refers to polysilazanes D1500, D1500 SC, and D1500 RC, TG4 is as defined above, and PI refers to the photoinitiator 1-hydroxycyclohexyl phenyl ketone. The concentration of D1500 RC may have been up to 30-40% lower than that shown in the table due to decomposition of the stock solution.

[0092] method Preparation of the Coating Composition Unless otherwise stated, the coating compositions were prepared by mixing the polysilazane and TG4, if present, in one container and separately mixing the other components (POSS, TBAF and PI) in another container (both containers containing additional solvent (THF)) and then combining the two mixtures and mixing for 5 minutes.

[0093] coating The coating composition was applied to a glass substrate by drop casting and spread with a glass rod.

[0094] hardening Curing was achieved by treatment with UV light (405 and 360 nm lamps) for 10 minutes followed by heating for 50-60 minutes on a hot plate maintained at 150° C. with a relative humidity of 40% or higher.

[0095] Surface roughness Surface roughness was measured with a Mitutoyo Surftest SJ 301 surface profilometer. The reported roughness value, Ra (average roughness), is the arithmetic mean of the absolute values ​​of the roughness profile coordinates.

[0096] Abrasion Test Tribological studies were carried out using a unidirectional ball-on-disk tribometer (Phoenix Tribology, Newbury, UK).

number

[0097] Permanent Marker Test As a measure of stain resistance, a permanent marker test was used, which is applicable to anti-fingerprint, anti-smudge, anti-graffiti, etc. A permanent marker was applied onto the coating and its effect was observed. The stain resistance effect was considered to be present if the marker formed a beaded drop (dashed line) or significantly shrunk compared to uncoated glass. The ease of stain removal was determined by wiping the permanent marker line with tissue after 10-60 seconds. The marker could not be wiped off from uncoated glass and only rarely spread at the edges (stain formation) if too much force was applied during wiping.

[0098] CoF Test A stationary ball made of alumina or Teflon

number

[0099] Results and Findings Pure polysilazanes, N-POSS and TBAF The coating of Sample 61, which did not contain POSS, did not exhibit any stain release in the permanent marker test, and exhibited the limited stain release of a pure polysilazane coating without the additive enhancing properties. Additionally, the marker was only slightly wiped off.

[0100] Coating 62 with N-POSS performed poorer than 61, neither showing any smudge resistance nor any indication that the permanent marker was wiped off. These observations can be explained by reactive N-POSS generating many polysilazane fragments resulting in unreacted polar groups (e.g. NH2, NH and Si-H) that cause strong binding of the marker to the coating. This indicates the importance of the presence of quaternary ammonium salts as discussed above. Note that by visual inspection 62 appeared to be comparable in appearance to the smooth 48 coating and significantly better than 46, 50 and 48R (below). However, its surface roughness ranged from a Ra of 0.03±0.01 indicating the effect of fragmentation to as high as a Ra of 0.1±0.01 nm. However, its upper limit of surface roughness is similar to 50. Thus, 50 showed clear water repellency and wipeability to the permanent marker, so its limited / poor smudge resistance was not related to high surface roughness.

[0101] In the coating composition of Sample 50, larger particles were formed in the solution compared to Samples 61 and 62. A possible explanation for this observation is the fact that the composition of Sample 50 contained TBAF, and therefore it can be expected that a certain level of solution cross-linking and defragmentation occurred. Furthermore, N-POSS is highly reactive, which may also affect the formation of precipitates. The presence of precipitates may be the cause of the high surface roughness of the coating. Interestingly, even though the coating of Sample 50 showed significantly higher surface roughness and poorer coating quality than Samples 61 and 62, it showed obvious water repellency to permanent markers, which was easily wiped off.

[0102] The coating of Sample 46 differs from Sample 50 by the presence of polysilazane D1800 in addition to D1500 RC. This coating had an even higher surface roughness, but was still water repellent to permanent marker, although less than that of 50. This further indicates that the absence of water repellency of the coating of Sample 62 to permanent marker is not related to surface roughness.

[0103] The addition of photoinitiator to sample 50 or type 46 did not show any effect on surface roughness or water repellency to permanent marker. The intended role of the photoinitiator was to enhance the cure of the coating under UV, but further experiments did not show any noticeable benefits. This may be related to the fact that the photoinitiator itself can react with the polysilazane through its carbonyl and / or hydroxyl groups, a process that may make it insensitive to UV light. It may be that direct UV heating (thermal cure with or without moisture) masks the impact of the photocuring effect of the photoinitiator.

[0104] CO-POSS In these experiments, the highly reactive N-POSS was replaced by CO-POSS, which represents a rather different class of POSS due to its many inactive R groups.

[0105] The coating of Sample 48T, which mirrors Sample 50 except for the selection of POSS, was observed to be smoother and of higher optical quality than 46 and 50 by visual inspection while also providing better stain resistance / cleanability in the permanent marker test than 50. Therefore, the 48 series was examined in more detail for surface roughness, coefficient of friction and abrasion resistance.

[0106] For sample 48T-2, the coating composition identical to 48T was coated onto a glass substrate after mixing for only 2 minutes, and the resulting coating exhibited a very smooth coating surface as evidenced by a surface roughness Ra of 20±10 nm, similar to that of the bare glass substrate.

[0107] To evaluate the effect of mixing time, sample 48T-40 was prepared again using the same coating composition as 48T, where the composition was coated on a glass substrate after 40 minutes. Figures 1, 2 and 3 show high magnification light microscope images of the coatings of samples 48T-2, 48T and 48T-40, respectively. They show how for 48T the coating consists of dendrite-like particles that are not evident in 48T-2. In 48T-40, these dendrites had grown large enough to produce optical inhomogeneities (color patterns) under the light microscope. Upon visual inspection, the coating of 48T-40 still appeared transparent.

[0108] In the abrasion tests, the coating of sample 48-T2 showed slight abrasion, which is understood to be merely an abrasive action at both 20 and 250 MPa. 48T showed no abrasion at 20 MPa, but slight abrasion at 250 MPa. Under Hertzian contact pressures of 20 and 250 MPa, 48T-40 was completely abraded, revealing bare glass indicating poor coating adhesion and hardening. Figures 4, 5 and 6 show the tribological behavior of the coatings of samples 48T-2, 48T and 48T-40, respectively.

[0109] A possible explanation for the poor abrasion resistance of the 48T-40 coating could be that too much solution crosslinking occurred prior to application, reducing the ideal concentration of Si-H and Si-NH-Si functional groups, which are necessary for post-coating curing, and the Si-H groups are also crucial for covalent bonding to glass substrates or any other substrates containing nucleophilic groups such as hydroxyl, carbonyl, carboxyl, etc.

[0110] The reason for the better tribological properties of 48T compared to 48T-2 could be that solution crosslinking resulted in higher molecular weight polysilazanes, but not too much as in 48T-40. This hypothesis is supported by the higher surface roughness of 48T compared to 48T-2. 48T is predicted to have fewer available functional groups than 48T-2, so adhesion or curing is predicted to play no role. It can be argued that the concentration of functional groups in 48T-5 is sufficient for curing and adhesion after coating. This then indicates a balance between higher molecular weight polymers or polymer-POSS and post-application treatment, which is achieved by optimal mixing time before application.

[0111] It should be noted that anti-fingerprint and anti-soiling coatings that are typically applied to glass in smart screens, eyewear, solar panels, etc., are typically prepared from fluorinated polymer chains with silicon alkoxy or acrylate end groups for adhesion and curing. Typical applied loads for abrasion testing are, for example, about 0.1 MPa (1 kg / cm) for SUBELYN™ (perfluoropolyether with Si-alkoxy end groups) from Shin-Etsu and OPTOOL DSX-E (fluoropolymer containing Si-alkoxy end groups) from Daikin Chemicals. 2 ). There are also examples in the literature of lower applied loads. The much higher applied loads for the abrasion tests of coatings made from the coating compositions according to the present invention indicate stronger and significantly more durable coatings for antifouling applications.

[0112] A variant of 48T was prepared in which D1500 RC was replaced with the more "reactive" D1500 SC (designated 48R). D1500 SC exhibited higher solution reactivity than 1500RC, which may be due to a higher concentration of Si-H groups at the same molecular weight. During coating application, D1500 RC was more reactive (cured faster) due to the higher concentration of APTES.

[0113] Even with the presence and stabilizing effect of CO-POSS, the reactivity of the coating solution became as vigorous as that of 50 and other similar samples, resulting in a coating consisting of a smooth surface interspersed with large and agglomerated particles, as is evident from Figure 7. Although transparent and exhibiting as good stain resistance (permanent marker adhesion and wipeability) as the 48 series, the visual roughness of the coating makes it less useful for ecstatic applications. Interestingly, sample 48R showed no signs of wear (abrasion or deep wear) at 250 MPa.

[0114] Solvent effects Some pre-made formulations of the OPSZ brand are made with butyl acetate as the primary or only solvent. Certain manufacturers also recommend the use of dibutyl ether to dilute PHPS. Butyl acetate is likely to react with PHPS, which explains why it is not in the list of recommended solvents for PHPS. The inventors have found that n-butyl acetate is reactive with OPSZ in coating compositions in the presence of TBAF, resulting in a completely worn coating at a Hertzian contact pressure of 20 MPa. The presence of large particles and color patterns seen in 48T-40 were also observed in coating compositions containing butyl acetate. This may indicate excessive consumption of Si-H functionality by the carbonyl groups of the solvent (a process enhanced by the catalyst TBAF), which confirms that Si-H can react with unsaturated bonds in the presence of a catalyst. Thus, solvents containing heteroatom-containing unsaturated bonds are not preferred for use in polysilazane compositions when TBAF or a catalyst that behaves similarly is used.

[0115] Coefficient of Friction (CoF) Sample 48T-2 was compared to polished Teflon in CoF testing. With a Teflon counterface (40 MPa) and an alumina counterface (500 MPa), the pure and well-polished Teflon sheets exhibited CoFs of 0.05-0.06 and 0.07-0.08, respectively, while sample 48T-2 exhibited CoFs of 0.01-0.015 on both counterfaces. Further testing at a lower Hertzian contact pressure of 250 MPa (alumina ball) on 48T-2 showed a CoF of 0.03-0.04. 48T-2 was selected due to its smoother surface and abrasive nature. However, further testing at 20 MPa (Teflon ball) and 250 MPa (alumina ball) on 48T showed CoF values ​​of 0-.02-0.03, slightly lower than 48T-2. These results indicate a very low CoF for the 48 series coatings.

[0116] Typically, the CoF and applied load are expected to be correlated such that a higher CoF is expected to be measured when a higher load is used. The opposite trend was observed with the 48T-2 coating. An explanation for this observation could be that the ball-like POSS additives can transform sliding friction into rolling friction at the contact / interface, as the lubrication mechanism is in nanobearings.

[0117] Further Experiments (Part of Planned Experiments Below) Experiment 2 Compared to fully fluorinated POSS (e.g., Structure IV), POSS samples with mixed fluorinated and non-fluorinated R groups gave better coating properties, mostly clean and non-uniform appearance, and better appearance especially with ultrasonic spray coating. Dumbbell-shaped POSS were overall better, e.g., in terms of coating hardness, lower refractive index, and appearance.

[0118] Table 2 below summarizes the effect of POSS XIII concentration on coating hydrophobicity and surface roughness. To prepare the coatings, D1500 RC (200 μl) and TG4 were mixed in an Eppendorf tube (solution A, 0.5 ml total volume). Solution B (0.5 ml total volume) contained different concentrations of POSS XIII relative to polysilazane and TBAF. Both solutions were mixed by vortexing and combined to obtain a composition containing 22 wt% polysilazane, 0.03 wt% TBAF, and 0.6 wt% TG4. As mentioned earlier, the percentage of hardener in D1500 RC is reported to be 10-30 wt% relative to polysilazane molecules. After mixing solutions A and B for 5 minutes, 200 ul of the resulting solution was dropped onto a glass slide and spread with a glass rod. The coatings were dried on a hot plate maintained at 100°C for 10 minutes. The coating was then cured in a humid atmosphere containing H2O2 vapor.

[0119] The WDRV (Water Droplet Rolling Volume), which is the amount of water (in μl) that rolls off the surface of the coating when tilted at 45 degrees, and the sliding angle (SA), which is the angle at which 12 μl of water starts to slide off the surface of the coating, were measured using a setup made on site.

[0120] All coatings exhibited resistance to permanent markers (no beading and easy wiping).

[0121] Only 1500RC was used to minimize the effect of the more hydrophobic D1800. For coatings without POSS or catalyst, (PS+TG4)WDRV and slip angle were significantly higher, indicating easier cleaning and less tendency for water repellency. FT-IR data also indicates lower cure levels compared to coatings containing POSS.

[0122] The lowest WDRV and SA were recorded for the coating containing 3 wt% XIII, with 1.5 wt% having roughly similar values. Further increasing the POSS concentration to 4.5 wt% resulted in higher WDRV and SA compared to the coating with lower POSS concentration. This may be due to the effect of higher fragmentation with increased amounts of POSS, an effect that can be countered by increased amounts of TBAF. The latter is not without its limitations: increasing the amount of catalyst results in higher reactivity (evidenced by stronger foaming), which increases the difficulty of controlling the coating process. However, the hydrophobicity of the 4.5 wt% POSS coating is still better than that of PS+TG4. [Table 2]

[0123] The higher surface roughness of the coatings containing POSS and TBAF may be due to reactions in the coating formulation, namely solution crosslinking and incorporation of POSS into the polymer chains.

[0124] Experiment 3 D1500 RC (360 μl), D1800 (40 μl), MTHF (800 μl) and TG4 were mixed in an Eppendorf tube (solution A, 1.4 ml total volume). Solution B (2.6 ml total volume) contained dibutyl ether (1600 μl), TBAF and POSS XIV. Both solutions were mixed by vortexing and combined to obtain a composition containing approximately 12 wt% polysilazane, 0.012 wt% TBAF and 0.3 wt% TG4. After mixing for 5 minutes, 200 μl of the resulting solution was dropped onto a glass slide and spread with a glass rod. The volume ratio of MTHF:DBE in the coating formulation was 1.5:1. In the coating formulation, TG4, POSS XIV and TBAF were dissolved in MTHF only before obtaining the appropriate volume.

[0125] The coatings were dried in an oven maintained at 80°C for 10 minutes. MTDS-1 and MTDP-1 were further cured in a humid atmosphere containing H2O2 vapor. After the drying process, MTDS-4 was left in an ambient environment. The pencil hardness of these coatings was analyzed after 14 days to allow sufficient time for MTDS-4. The results are shown in Table 3. [Table 3]

[0126] The difference in hardness between MTDS-1 and MTDP-1 indicates the importance of the optimal POSS concentration for coating hardness.

[0127] The poor pencil hardness of MTDS-4 is due to suboptimal curing of polysilazane (hydrolysis of Si-NH-Si and Si-H to form Si-OH and subsequent condensation to form Si-O-Si). This is confirmed by the FT-IR spectrum (Figure 8), which shows peaks at around 900 and 1260 cm belonging to Si-NH-Si and Si-H, respectively. -1 It can be seen that the peak position at is still stronger in MTDS-4 compared to the other coatings. We also found that for the reference samples (lacking either POSS or TBAF or both), hydrolysis and polycondensation of these functional groups, especially Si-NH-Si, is also limited.

[0128] The presence of uncured polar groups (Si-NH-Si and Si-H) can limit the application of the coatings in environments with humidity and contaminants, especially those capable of hydrogen or covalent or chemical interactions with them. As an example, the inventors have discovered that coatings that have been cured under ambient conditions or with water vapor only can be damaged by wiping them with a cloth soaked in acetone or isopropanol less than 24 hours after coating preparation.

[0129] All coatings in Table 3, including MTDS-4, exhibited water repellency to permanent markers. Glass slide substrates were plasma activated (after cleaning) for 15 seconds using a diffuse coplanar surface barrier discharge (DCSBD) atmospheric plasma system.

[0130] Experiment 4 D1033 (80 μl), D1800 (20 μl), THF:MPB (1:1) (300 μl) and TG4 were mixed in an Eppendorf tube (Solution A, 500 μl total volume). Solution B (500 μl total volume) contained THF, MPB, TBAF and POSS X. Both solutions were mixed by vortexing and combined to obtain a composition containing about 10 wt% polysilazane, 0.5 wt% TG4 and 2.7 wt% POSS X. After mixing solutions A and B for 5 minutes, 200 μl of the resulting solution was dropped onto a glass slide and spread with a glass rod. The volume ratio of THF:MPB was about 3.5:1. In the coating formulation, TG4, POSS X and TBAF were dissolved in THF only before obtaining the appropriate volume.

[0131] The coating was dried in an oven maintained at 80° C. for 10 minutes and cured in a humid atmosphere containing H2O2 vapor. [Table 4]

[0132] Depending on the amount of reactive POSS, there is an optimum concentration of catalyst (TBAF) that gives the lowest refractive index. The high refractive index of the reference coating with 0 wt% TBAF may be due to non-uniformity of the surface roughness as seen by infrared spectroscopy and / or a relatively high concentration of polar groups from the polysilazane (insufficient or limited hydrolysis and polycondensation). The slight increase in refractive index after 0.22 wt% TBAF may be an indication of excessive solution crosslinking, which may result in larger particulates in the coating, as already shown in 48-T40.

[0133] Experiment 5 D1500 RC (720 μl), D1800 (80 μl), THF (1600 μl) and TG4 were mixed in an Eppendorf tube (Solution A, 2.800 ml total volume). Solution B (5.200 ml total volume) contained dibutyl ether (3200 μl), TBAF and POSS VIII. Both solutions were mixed by vortexing and combined to obtain a composition containing 11.4 wt% polysilazane, 0.013 wt% TBAF, 0.3 wt% TG4 and 2.3 wt% POSS VIII. The volume ratio of THF:DBE was 1.5:1. In the coating formulation, POSS VII, TG4 and TBAF were dissolved in THF only before obtaining the appropriate volume.

[0134] After mixing solutions A and B for 5 min, 4 mL of the resulting solution was placed in a syringe and mounted on an ultrasonic spray coater from LRS AS. The nozzle frequency was 45 Hz, operated at 50% power output, and the syringe speed (liquid flow rate) was 35 mm / s. Plasma activated (15 s) and non-activated glass slides were used as substrates. The coatings were dried for 10 min in an oven maintained at 80 °C and cured in a humid atmosphere containing H2O2 vapor. For the plasma activated substrates, the coating pencil hardness was F and 2H after 48 h and 7 days, respectively. For the coatings on non-activated substrates, the values ​​were B and HB after 48 h and 7 days, respectively. Thus, plasma activation increased the coating adhesion due to better wetting.

[0135] Test 6 The coating preparation process, composition, drying and curing are the same as in Experiment 5, except that THF was replaced with MTHF and POSS XV was used instead of POSS VIII.

[0136] Uncoated or hard-coated flat polythiourethane (PTU) lens material was cleaned and plasma activated for 15 seconds before coating application by ultrasonic spray coating. For transmission studies, the coatings were applied to both sides of the flat substrate.

[0137] Application of the coating to both sides of the PTU substrate recorded an increase in transmission of about 4 to about 5% for hard-coated or uncoated PTU substrates, respectively, which is a result of the lower refractive index of the coating. Thus, the transmission increased to about 93% at 500 nm. This is close to the transmission of CR39, a mainstream eyewear material that is neither scratch-resistant nor smudge-resistant. Coating hardness of 4B and HB was recorded for uncoated or hard-coated PTU, respectively. Application of the coating of the present invention increased the hardness of uncoated or hard-coated PTU lenses to HB and F, respectively. Additionally, coatings including those from well-known eyewear manufacturers showed very good to excellent water repellency and wipeability against permanent markers. Using the same procedure as above, the coating was successfully applied, dried, and cured on curved PTU lenses. The same permanent marker test results were obtained as on flat substrates. In fact, it was much easier to wipe the permanent marker off the coating of the present invention compared to lenses (curved) containing a commercial anti-soiling coating, which were received from a local eyewear company with the anti-soiling coating already applied. Thus, the coating of the present invention has the ability to function as both a scratch resistant layer and an anti-soiling layer on eyewear and related products, with the added benefit of increasing the light transmission of high refractive index materials.

[0138] Planned Experiments The following experiments are planned (Table 5). [Table 5]

[0139] In Table 5, the components are defined as follows:

[0140] POSS: (Based on the T8 closed cage structure, structure III, but applicable to other cage and non-cage structures with the same ratio of R groups).

[0141] NA1: 0-7 R groups are Y(CF2) n CF3, where 0-7 R groups are non-fluorinated and contain aryl (e.g., phenyl) and / or alkyl (e.g., methyl, propyl, isobutyl, isooctyl) and / or (poly)siloxane (e.g., low molecular weight siloxanes of 180-800 g / mol), and 1-3 R groups are non-fluorinated and contain one or more nucleophilic groups that can react with polysilazanes and cause fragmentation, such as 3-propylamine (NH2 reactive units), 3-propyl methacrylate (C=O reactive units), 2-propoxyethanol (OH reactive units). Y can be alkyl, aryl, ether, siloxane or any combination thereof, or it can be a bond in which case the fluorinated group is directly attached to the Si of the POSS cage. n is an integer from 0 to 7.

[0142] NA2: 0-6 R groups are Y(CF2) n CF3, wherein 1-6 R groups are non-fluorinated and include aryl and / or alkyl and / or siloxane, and 1-6 R groups are non-fluorinated and include alkoxysilyl, such as methoxysilyl and ethoxysilyl, and n is an integer from 0 to 7.

[0143] NA3: 1-6 R groups are Y(CF2) n CF3, where 1-6 R groups are non-fluorinated and contain alkoxysilyl such as methoxysilyl, ethoxysilyl, and 1-2 R groups are non-fluorinated and contain one or more nucleophilic groups that can react with polysilazane to cause fragmentation, and n is an integer from 0 to 7.

[0144] NA4: 1-6 R groups contain alkoxysilyl and 1-2 R groups contain one or more nucleophilic groups that can react with polysilazane to cause fragmentation.

[0145] NA5: All R groups contain alkoxysilyl groups and no other groups specified above.

[0146] NA6: 5-7 R groups are non-fluorinated and contain aryl (e.g., phenyl) and / or alkyl (e.g., methyl) and / or siloxane, and 1-3 R groups are non-fluorinated and contain one or more nucleophilic groups that can react with polysilazane and cause fragmentation.

[0147] Polysiloxane: Linear, branched or cyclic, structure X being an example.

[0148] NA7: 1 to 3.5 R groups are Y(CF2) n CF3, wherein 0.5 to 3 R groups are non-fluorinated and comprise aryl or alkyl, and 0.5 to 3 R groups are non-fluorinated and comprise alkoxysilyl, and n is an integer from 0 to 7.

[0149] NA8: 1 to 3.5 R groups are Y(CF2) n CF3, 0.5-3 R groups are non-fluorinated and contain alkoxysilyl, and 0.5-1 R group are non-fluorinated and contain one or more nucleophilic groups capable of reacting with polysilazane to cause fragmentation. n is an integer from 0 to 7. R may be hydrogen or contain Si-H, such as 0.5-1 hydrogen atom or 0.5-1 Si-H group in NA7-NA8.

[0150] NA9: For example, cellulose nanofibers in which some of the hydroxyl groups are substituted with organofluorine groups or molecules containing them, and / or some of the hydroxyl groups are substituted with alkyl or aryl groups or molecules containing them, and some of the hydroxyl groups remain unsubstituted.

[0151] NA10: Same as NA9 except that some or the remaining hydroxyl groups are replaced with molecules bearing functional groups that can react with polysilazanes causing fragmentation, e.g. 2-propoxyethanol, 3-aminopropyl.

[0152] D1033: refers to a polysilazane of structure XI where X and Y are reported to be 0.33 and 0.67, respectively. [ka]

[0153] Additional components included in the experiment but not listed in the table: 1. A nucleophilic catalyst such as a quaternary ammonium salt added in an amount of 0.001-2 wt%. 2. A leveling agent such as TG4 or a fluorinated leveling agent (e.g., TG4 modified with perfluoropolyether) added in an amount of 0.001-2 wt% of the coating composition. 3. Solvents which may be ethers such as tetrahydrofuran, dibutyl ether or methoxyperfluorobutane, aromatic solvents such as xylene or other polar aprotic and non-polar solvents that do not contain functional groups capable of reacting with polysilazanes. The solvents may be mixed or alone and comprise 20-99% of the coating composition. 4. Fluorinated analogs may be used to partially or completely replace one or all of the polysilazanes in a given coating composition to obtain modified forms of the coatings shown in the table.

[0154] The various additives are designed to perform the same functions already described.

[0155] This table represents a guide to experiments designed with the present compositions designed to address typical problems already identified. For example, 1. Since the additives contain reactive groups, the reduction in the amount of NA1 and NA3 as well as the absence of NA10 in coating B compared to A can help provide better control of solution reactivity in the presence of the more reactive PHPS. Control of solution reactivity can also benefit from a lower PS+P concentration relative to the solvent. The same is true for coatings E and F. 2. Because NA1 and NA3 have been restored to their earlier concentrations in Coating A, the significant presence of the bulkier D1800 in Coating C may help control solution reactivity in the presence of PHPS. Similarly, the use of NA9 in Coating E or the absence of the more reactive NA10 in all compositions containing PHPS may help control solution reactivity. 3. Increasing the concentration of reactive POSS in coating G (sum of NA1, NA4, NA8 and NA10) allows for more flexibility in controlling solution reactivity by increasing the concentration of the bulkier, more slowly reacting D1800. 4. The use of D1800 may result in a softer coating due to its longer R groups compared to, for example, D1500 RC. The same effect may be achieved by selection of the type and length of the R groups, for example using softer (poly)siloxane and polyether groups. 5. The nucleophilic functional (reactive) groups present in NA1, NA3, NA4, NA6, NA8, NA9 and NA10 covalently bond them to the polysilazane backbone, ensuring uniform distribution of the additive in the polysilazane matrix, which is why they can be used at higher concentrations compared to NA2, which does not have reactive nucleophilic groups. 6. The alkoxysilyl groups immobilized on NA2-NA5 and NA7-NA8 ensure faster hydrolysis and hardening in the presence of moisture. As some of these additives also contain reactive groups, the distribution of alkoxysilyl groups in the coating matrix is ​​optimized. 7. For example, fluoro groups or substituents on NA1 and NA8 may enhance anti-soiling and low friction properties. 8. The selection of aryl and alkyl groups, optionally in combination with organic fluoro groups, may enhance the stability and dispersion of nano additives in the coating formulation, which is the first step towards uniformity of the coating composition. This is achieved by matching their polarity with that of the polysilazane and the solvent. 9. When NA2 contains a reactive group that is fluorinated, it usually floats on the coating composition. This may enhance antifouling and refractive index properties within a certain concentration limit. The limit may be a concentration of less than 3% in the coating composition, preferably 1% or less. The upper limit of NA2 is intentionally kept lower than, for example, fluorinated POSS containing reactive groups. If the determined upper concentration limit is exceeded, the fluoro groups in NA2 and other fluorinated additives will attach to each other and begin to cause coating turbidity. 10. Coating I, which may have a high concentration of fluorinated NA2, is intended to provide anti-soiling and / or low friction properties, but not necessarily high clarity. 11. The presence of alkoxysilyl groups in NA2 ensures that the additive is covalently bonded to the coating matrix via the silanols generated by hydrolysis, thereby obviating any issues with leaching.

[0156] Coating application and curing: The coating may be applied by ultrasonic spray coating, pneumatic spray coating, roller coating or any other process known in the art.

[0157] Curing is accomplished by one or more of thermal (e.g. infrared heating), plasma, UV and other methods known to promote hydrolysis leading to silanol formation and polycondensation. Humidity during cure is optimized.

[0158] Coating characterization The coatings are characterized for: 1. Refractive index, for example using an ellipsometer or an Abbey 5 refractometer 2. Transparent 3. Chemical analysis to identify functional groups and degree of cure, surface species and failure mechanisms under UV, moist heat or chemical and environmental attack. FT-IR, XPS, EDS and other known techniques may be used. 4. Hardness, abrasion resistance and scratch resistance by known processes such as tribometer, pencil hardness, abrasion tester, etc. 5. Anti-fouling and easy to clean 6.Water contact angle 7. CoF 8. Other known methods for quantifying and optimizing coatings for use in low friction, anti-fouling, self-cleaning and easy to wash clear coatings may be utilized.

Claims

1. i) a polysilazane component of 0.5 to 30 wt% based on the weight of a composition selected from the group consisting of an organic polysilazane, an inorganic polysilazane, and a mixture of any two or more organic and / or inorganic polysilazanes, ii) a POSS containing at least one nucleophilic group of 0.1 to 15 wt% based on the weight of the composition, iii) a quaternary ammonium salt R in an amount of 0.0001 to 2 wt% based on the weight of the composition １ R ２ R ３ R ４ N ＋ X － (wherein R １ , R ２ , R ３ and R ４ are each independently selected from the group consisting of alkyl, aryl, arylalkyl, alkoxysilyl and alkenyl, and X is selected from F, Cl, Br, I, PF ６ or BF ４ and OH) and iv) an inert solvent and a composition.

2. The composition according to claim 1, further comprising a curing agent of 1 to 30 wt% based on the weight of the polysilazane component.

3. The composition according to claim 1, further comprising a POSS not containing a nucleophilic group of 0.005 to 5 wt% based on the weight of the composition.

4. The composition according to claim 2, further comprising a POSS not containing a nucleophilic group of 0.005 to 5 wt% based on the weight of the composition.

5. The composition according to claim 1, further comprising a flow leveling agent of 0.01 to 1.5 wt% based on the weight of the composition.

6. The composition according to claim 1, further comprising a photoinitiator of 0.05 to 5 wt% based on the weight of the composition.

7. The composition according to claim 1, further comprising nanofibers of 0.01 to 10 wt% based on the weight of the composition.

8. The at least one nucleophilic group is selected from C=O, OH, NH ２ , NH, S=O, SH, C=N, epoxy or C≡N, the composition according to claim 1.

9. The composition according to claim 1, wherein the POSS further comprises a fluoro substituent.

10. The POSS has a C having 1 to 10 fluoro substituents １ ~C ５ The composition according to claim 9, comprising a fluoroalkyl group.

11. The composition according to claim 3, wherein the POSS further comprises a fluoro substituent, and the POSS not containing a nucleophilic group comprises at least one alkoxysilyl group.

12. The composition according to claim 4, wherein the POSS comprises a C1-C5 fluoroalkyl group having 1 to 10 fluoro substituents, and the POSS not containing a nucleophilic group comprises at least one alkoxysilyl group.

13. The composition according to claim 1, wherein the POSS does not contain a fluoro substituent.

14. The composition according to claim 1, wherein the POSS has a combination of fluoro and non-fluoro substituents.

15. The composition according to claim 1, wherein the POSS contains a dumbbell structure.

16. R １ 、 R ２ 、 R ３ 、 R ４ is the composition according to claim 1, each being a tert-butyl group.

17. Use of the composition according to any one of claims 1 to 16 for coating a substrate.

18. A substrate comprising a coating made at least in part from the composition according to any one of claims 1 to 16.

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