Enhanced non-stick coating system

Abstract

The present invention relates to coating compositions that can be applied to the surface of a substrate to form a durable, non-stick coating. The coating compositions can include a basecoat composition and a topcoat composition for forming a basecoat and a topcoat applied over the basecoat. The basecoat can include one of an organic polymer, a sol-gel composition, and a silicone resin. The basecoat composition and the resulting basecoat can further include reinforcing particles. The topcoat can include a siloxane matrix formed from one of a hydrosilylation reaction, a dehydrocoupling reaction, and a polycondensation reaction. The basecoat and the topcoat can each be substantially free of a fluoropolymer component.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to U.S. Provisional Patent Application Serial No. 63 / 107,033, entitled “Enhanced Non-stick Coating System,” filed May 11, 2021, which is incorporated herein by reference in its entirety. Technical Field

[0003] This disclosure provides a non-stick coating composition that can be applied to the interior or food contact surface and / or exterior or heat contact surface of cookware or baking pan articles. The coating can be formed from the composition to provide a surface having desired properties such as hardness, abrasion resistance, impact resistance, chemical resistance, and non-stick properties. Background Technology

[0004] Heat-resistant coatings are applied to substrates such as cookware or baking pans to cover the substrate and provide additional functions, such as aiding heat transfer, providing a non-stick surface, and / or providing decorative color or aesthetic finish. Existing coating compositions are either based on fluoropolymers or use non-fluoropolymer base resins, but they tend to be brittle and may be prone to crack-based defects, which may limit their service life.

[0005] As an alternative, sol-gel reaction-based siloxane coatings can be used. Typical sol-gel reaction-based siloxane coatings form a highly cross-linked matrix that tends to be very brittle and hard. The non-stick properties of these coatings may result in a limited lifespan, as the coating may separate from the substrate or undercoat.

[0006] We hope to see improvements in the aforementioned areas. Summary of the Invention

[0007] This disclosure provides coating compositions that can be applied to the surface of a substrate to form a durable, non-stick coating. The coating composition may comprise a base coating composition and an outer coating composition for forming a base coating and an outer coating applied over the base coating. The base coating may comprise one of an organic polymer, a sol-gel composition, a silicone resin, and combinations thereof. The base coating composition and the resulting base coating may further comprise reinforcing particles. The outer coating may comprise a siloxane-based material formed by one of a hydrogenation silanization reaction, dehydrogenation coupling, polycondensation reaction, and combinations thereof. Both the base coating and the outer coating may be substantially free of fluoropolymer components. Attached Figure Description

[0008] The above and other features of this disclosure, as well as the manner of obtaining said features, will become clearer and the disclosure itself will be better understood by taking into account the accompanying drawings and reference to various aspects of this disclosure in the following description.

[0009] Figure 1A An exemplary substrate for coating the composition of the present invention is shown.

[0010] Figure 1B An exemplary cross-section of the coating of the composition of the present invention is shown.

[0011] Figure 2A A scratch adhesion image of the silicone elastomer undercoat composition after a scratch test as described in Example 10 is shown.

[0012] Figure 2B A cross-section of the silicone elastomer undercoat composition after a scratch test, as described in Example 10, is shown.

[0013] Figure 3A A scratch adhesion image of the silicone elastomer undercoat composition after a scratch test as described in Example 10 is shown.

[0014] Figure 3B A cross-section of the silicone elastomer undercoat composition after a scratch test, as described in Example 10, is shown.

[0015] Figure 4A Images of the scratch adhesion of the sol-gel undercoat composition after a scratch test, as described in Example 11, are shown.

[0016] Figure 4B A cross-section of the sol-gel undercoat composition after a scratch test, as described in Example 11, is shown.

[0017] Figure 5A Images of the scratch adhesion of the sol-gel undercoat composition after a scratch test, as described in Example 11, are shown.

[0018] Figure 5B A cross-section of the sol-gel undercoat composition after a scratch test, as described in Example 11, is shown.

[0019] Figure 6A Images of the scratch adhesion of the sol-gel undercoat composition after a scratch test, as described in Example 11, are shown.

[0020] Figure 6B A cross-section of the sol-gel undercoat composition after a scratch test, as described in Example 11, is shown.

[0021] Figure 7A Images of the scratch adhesion of the sol-gel undercoat composition after a scratch test, as described in Example 11, are shown.

[0022] Figure 7B A cross-section of the sol-gel undercoat composition after a scratch test, as described in Example 11, is shown.

[0023] Figure 8A A scratch adhesion image of the polyethersulfone / polyamide-imide undercoating composition after a scratch test as described in Example 12 is shown.

[0024] Figure 8B A cross-section of the polyethersulfone / polyamide-imide undercoating composition after a scratch test, as described in Example 12, is shown.

[0025] Figure 9A A scratch adhesion image of the polyethersulfone / polyamide-imide undercoating composition after a scratch test as described in Example 12 is shown.

[0026] Figure 9B A cross-section of the polyethersulfone / polyamide-imide undercoating composition after a scratch test, as described in Example 12, is shown.

[0027] Figure 10A A scratch adhesion image of the polyethersulfone / polyamide-imide undercoating composition after a scratch test as described in Example 12 is shown.

[0028] Figure 10B A cross-section of the polyethersulfone / polyamide-imide undercoating composition after a scratch test, as described in Example 12, is shown.

[0029] Figure 11A Images of the scratch adhesion of the sol-gel undercoat composition after a scratch test, as described in Example 13, are shown.

[0030] Figure 11B A cross-section of the sol-gel undercoat composition after a scratch test, as described in Example 13, is shown.

[0031] Figure 12A A scratch adhesion image of the silicone primer composition after a scratch test as described in Example 13 is shown.

[0032] Figure 12B A cross-section of the silicone primer composition after a scratch test as described in Example 13 is shown.

[0033] Figure 13 A cross-section of the silicone primer composition after a scratch test as described in Example 13 is shown.

[0034] Figure 14A A scratch adhesion image of the polyethersulfone undercoating composition after a scratch test as described in Example 13 is shown.

[0035] Figure 14B A cross-section of the polyethersulfone undercoating composition after a scratch test, as described in Example 13, is shown.

[0036] Figure 15A A scratch adhesion image of the silicone elastomer undercoat composition after a scratch test as described in Example 13 is shown.

[0037] Figure 15B A cross-section of the silicone elastomer undercoat composition after a scratch test, as described in Example 13, is shown.

[0038] Figure 16 A cross-section of the non-uniform coating is shown.

[0039] Figure 17 The mechanical properties of the coating in Example 15 are shown. Detailed Implementation

[0040] I. Introduction

[0041] This disclosure provides compositions that can be applied to the surface of a substrate to form a durable non-stick coating. The coating may comprise a base coat with reinforcing particles and an outer coat disposed on the base coat. Both the base coat and the outer coat may lack the fluoropolymer component used in existing non-stick coating compositions.

[0042] The primer coating can be one of several types. For example, the primer coating may include at least one of the following: (i) a sol-gel composition formed from a siloxane matrix; (ii) an organic polymer, such as at least one of polyphenylene sulfide (PPS), polyethersulfone (PES), polyetheretherketone (PEEK), polyphenylene sulfone (PPSU), polyamide-imide (PAI), polyetherimide (PEI), and polyimide (PI); and (iii) a silicone resin and combinations thereof.

[0043] The primer layer may further include reinforcing particles, such as one or more hard particles embedded in the primer layer composition, such that the primer layer composition can hold the reinforcing particles in place and prevent their displacement. The reinforcing particles can help deflect the mechanical forces applied to the primer layer.

[0044] The coating may further comprise an outer coating including a siloxane. The siloxane can be formed by one or more of a variety of reactions. For example, the siloxane can be formed by a hydrosilylation reaction between a hydrosiloxane and a vinylsiloxane. Alternatively, the siloxane can be formed by a dehydrogenation coupling between a hydrosiloxane and a hydroxysiloxane. Alternatively, the siloxane can be formed by a polycondensation reaction between hydroxysiloxanes or by a polycondensation reaction between a hydroxysiloxane and an alkoxysiloxane, an acetoxysiloxane, or an oxime-modified silane.

[0045] Both the sol-gel undercoat and the siloxane overcoat can be described as being formed from organosiloxane-based solid polymers, which are typically thermosetting systems capable of providing a range of mechanical properties from soft and rubbery to hard and brittle. The hardness of the system is generally proportional to the degree of crosslinking in the system. The degree of crosslinking, in turn, depends on the nature of the organosiloxane units used in the system. As shown in Table 1 below, organosiloxanes can be described based on the degree of oxygen substitution or functionality on the central silicon.

[0046] Table 1

[0047]

[0048] Typically, compositions containing higher-order T (trifunctional) and Q (tetrafunctional) units exhibit higher crosslinking degrees.

[0049] Organosiloxane materials can often be characterized by low surface free energy, thus providing enhanced hydrophobicity and oleophobicity. Hydrophobicity is generally proportional to the amount of organic substituents present in the polymer; in other words, higher-order D (bifunctional) and M (monofunctional) units. Therefore, these properties can be said to be inversely proportional to the degree of crosslinking of the system, and thus inversely proportional to the hardness of the polymer.

[0050] This disclosure provides sol-gel compositions formed from organosiloxanes. The organosiloxanes may have the following formula:

[0051] R x Si(OR') 4-x

[0052] in:

[0053] R is one or more moieties independently selected from straight-chain, branched, or cyclic alkyl and aryl groups;

[0054] R' is methyl, ethyl, propyl, or alkyl; and

[0055] x is 0, 1, 2 or 3.

[0056] In the above formula, R can be a C6 aryl group or a straight-chain or branched alkyl group having as few as 1, 2, 3 or as many as 4, 5, 6 or more carbon atoms, or any number of carbon atoms within any range defined between any two of the above values. Alternatively, R can be selected from methyl, ethyl, propyl and phenyl.

[0057] In the above formula, x is 0, 1, 2, or 3. Alternatively, x can be 1.

[0058] Organoalkoxysilanes can be selected from the group consisting of: methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and combinations thereof.

[0059] Organoalkoxysilanes can be functionalized siloxanes, such as 3-aminopropyltriethoxysilane, (3-glycidoxypropyl)trimethoxysilane, and allyltrimethoxysilane.

[0060] The components of the coating composition will be described in further detail below.

[0061] II. Definition

[0062] For the purposes of the following detailed description, it should be understood that this disclosure may take various alternative variations and sequences of steps, unless the contrary is expressly indicated. Furthermore, except in any operational instance or otherwise specified, all figures representing the quantities of ingredients used, for example, in the specification and claims, should be understood to be modified in all cases by the term “about.” Therefore, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary according to the desired properties to be obtained through this disclosure. At least, and without attempting to limit the application of the equivalence principle to the scope of the claims, each numerical parameter should be interpreted at least according to the number of significant figures reported and by applying ordinary rounding techniques.

[0063] Although the numerical ranges and parameters described in this disclosure are approximate, the values ​​illustrated in specific examples are reported as precisely as possible. However, any numerical value inherently contains some error that is necessarily caused by the standard deviation found in its corresponding test measurement results.

[0064] Furthermore, it should be understood that any numerical range described herein is intended to include all subranges included therein. For example, the range “1 to 10” is intended to include all subranges between (and including) the stated minimum value of 1 and the stated maximum value of 10, that is, a minimum value equal to or greater than 1 and a maximum value equal to or less than 10.

[0065] Unless otherwise specified, the use of the singular includes the plural and the plural encompasses the singular. Additionally, unless otherwise specified, the use of "or" means "and / or," even if "and / or" can be explicitly used in certain situations.

[0066] The term "non-stick" is used in this article to refer to a coating that has non-stick properties, particularly when the coating is applied to cookware and / or baking dishes. When a coating is applied to cookware and / or baking dishes, non-stick can be considered a food non-stick property that includes the ability to prevent food from sticking.

[0067] As used herein, the term "siloxane matrix" is intended to refer to a matrix containing repeating covalent bonds between silicon and oxygen atoms, such as Si-O-Si or Si-O-Si-O.

[0068] III. Substrate

[0069] The coating composition can be applied to the surface of a substrate. Suitable substrates can include metals, ceramic materials, plastics, composites, and minerals. Suitable metals can include, for example, stainless steel, aluminum, and carbon steel. Suitable ceramic materials include, for example, glass such as borosilicate glass, porcelain enamel, various fired clays, and other refractory materials. Suitable plastics and composites include, for example, high-melting-point plastics and composites, such as plastics with melting points higher than the curing temperature of the coating formulation, including, for example, polyester, polypropylene, ABS, polyethylene, carbon fiber epoxy composites, and glass fiber epoxy composites. Suitable minerals include, for example, mica, basalt, alumina, silica and wollastonite, marble, and granite.

[0070] The substrate can be part of a frying pan or other cookware product. (Reference) Figure 1A The cookware 10 is shown in the form of a frying pan, which typically includes a circular bottom wall 12, an annular side wall 14, and a handle 16. The cookware 10 is typically made of metal or metal alloy, such as stainless steel, aluminum, and carbon steel, but may also be made of, for example, ceramic, plastic, or composite materials.

[0071] The bottom wall 12 and side walls 14 include an inner or food contact surface 18 facing the food to be cooked, and an opposing outer or heat contact surface 20, which faces, is adjacent to, or contacts a heat source or heating element 22 during use. Figure 1B As shown, the cookware article 10 may include an internal coating 24 on at least a portion or all of the respective internal surfaces 18 that include the bottom wall 12 and / or side walls 14.

[0072] In this way, the coating composition of the present invention can be used as an internal or external coating. Although cookware article 10 is shown as a frying pan, the coating composition of the present invention can also be used to form coatings for other cookware articles, such as saucepans, frying pans, pots, etc., as well as baking pan articles or other cooking articles exposed to heat during use.

[0073] The coating compositions of the present invention can also be used to coat non-cooking utensils such as rollers, molds, conduits and fasteners, which require non-stick or non-stick properties and / or are exposed to heat during use.

[0074] IV. Coating System

[0075] Coating systems for cookware and baking pans are desired to possess both non-stick properties and abrasion resistance. In the past, perfluoroalkyl and polyfluoroalkyl substances (PFAS) have been used for this capability. However, the demand for PFAS-free coatings is increasing. Organosiloxane-based systems can be used to form non-stick coatings, rather than PFAS-containing compositions. The coating compositions disclosed herein attempt to maintain the non-stick properties of organosiloxane systems by applying them as an outer coating over a more robust undercoat, thereby increasing abrasion and scratch resistance. The coating compositions disclosed herein can be substantially PFAS-free.

[0076] Specifically, this disclosure provides multilayer coating systems and composite material structures. It has been found that the mechanical properties of the system (such as abrasion resistance) can be enhanced by employing a base coat that is harder than the outer coating. The base coat may be filled with a certain amount of hard particles to create texture within the base coat, and optionally allow at least some of the reinforcing particles, or portions thereof, to extend at least partially into the outer coating.

[0077] The reinforcing structure created by the hard particles can help deflect the mechanical forces acting on the outer coating, thus minimizing the effects of scratching and abrasion. As described above, the hard particles are embedded in the undercoating composition, which is harder than the outer coating, allowing the undercoating composition to hold the reinforcing particles in place and prevent their displacement.

[0078] The base coat may include at least one of the following: (i) a sol-gel composition formed from a siloxane matrix; (ii) an organic polymer, such as polyphenylene sulfide (PPS), polyethersulfone (PES), polyetheretherketone (PEEK), polyphenylene sulfone (PPSU), polyamide-imide (PAI), polyetherimide (PEI), polyimide (PI), and combinations thereof; and (iii) a silicone resin. The coating may further include reinforcing particles. Any base coat composition in the base coat composition may then be combined with any outer coat composition in the outer coat composition described below.

[0079] The outer coating may include a siloxane-based material. The siloxane-based material may be formed by one or more of a variety of reactions. For example, the siloxane-based material may be formed by a hydrosiloxane-vinylsiloxane hydrosilylation reaction. Alternatively, the siloxane-based material may be formed by a dehydrogenation coupling between a hydrosiloxane and a hydroxysiloxane. Alternatively, the siloxane-based material may be formed by a polycondensation reaction between hydroxysiloxanes or by a polycondensation reaction between a hydroxysiloxane and an alkoxysiloxane, acetoxysiloxane, or an oxime-modified silane. The outer coating itself may include a siloxane-based film with a lower hardness than the base coating, which adheres well to the base coating, and may contain any exposed reinforcing particles or portions thereof protruding from the base coating. Any outer coating composition in the outer coating composition may be combined with any base coating composition in the base coating composition described above.

[0080] The coating compositions of the present invention typically comprise a primer and an outer coating, as further described below, which may initially be formulated or provided as separate liquid compositions, followed by sequential application and curing. The primer may be applied directly to the surface of the substrate article, or alternatively, may be applied over one or more undercoats or inner coatings, such as a primer applied directly to the outer surface of the substrate article, wherein the primer is applied over a primer. The outer coating is applied to the primer, or over the primer, or in direct contact with the primer, or over an intermediate coating. The outer coating may be a topcoat, in which case it is the outermost coating of the coating system or the coating exposed to the outside.

[0081] V. Base Coating

[0082] The primer layer of the compositions disclosed herein may comprise at least one of an organosiloxane primer layer, an organic polymer primer layer, and a silicone primer layer. Each of these primer layers will be further described below. Regardless of the chemical properties of the primer layer used to form the composition, certain characteristics may be used to describe the primer layer, such as its hardness and resistance to deformation. For example, as determined by DIN ISO 14577 1-3 and further described below, the primer layer of the present invention may have one of a martens hardness of at least 0.2 GPa and / or an elastic modulus of at least 5 GPa. As determined by DIN ISO 14577 1-3, the primer layer may have both a martens hardness of at least 0.2 GPa and an elastic modulus of at least 5 GPa.

[0083] The base coat may contain reinforcing particles. The reinforcing particles may be partially or completely embedded in the base coat and can enhance the coating composition by helping to deflect mechanical forces acting on the composition.

[0084] a. Organosiloxane base coating

[0085] As discussed above, the organosiloxane primer may comprise a solid polymer based on organosiloxane. Based on wet weight, expressed as a percentage of the total primer composition weight, the organosiloxane may be present in the composition in amounts of about 10 wt.% or more, about 15 wt.% or more, about 20 wt.% or more, about 25 wt.% or more, about 30 wt.% or more, about 35 wt.% or more, about 40 wt.% or more, about 45 wt.% or less, about 50 wt.% or less, about 55 wt.% or less, about 60 wt.% or less, about 65 wt.% or less, or any value encompassed by these endpoints.

[0086] Based on dry (solid) weight, expressed as a percentage of the total weight of the primer composition, the organosiloxane may be present in the composition in amounts of about 20 wt.% or more, about 25 wt.% or more, about 30 wt.% or more, about 35 wt.% or more, about 40 wt.% or more, about 45 wt.% or more, about 50 wt.% or more, about 55 wt.% or more, about 60 wt.% or more, about 65 wt.% or less, about 70 wt.% or less, about 75 wt.% or less, about 80 wt.% or less, about 85 wt.% or less, about 90 wt.% or less, or any value covered by these endpoints.

[0087] The sol-gel undercoat formulation disclosed herein may also include one or more catalysts. Suitable catalysts may include, for example, acid catalysts, such as maleic acid, formic acid, acetic acid, oxalic acid, malic acid, hydrochloric acid, boric acid, nitric acid, sulfuric acid, and phytic acid.

[0088] Based on wet weight, expressed as a percentage of the total weight of the base coat composition, one or more catalysts may be present in the composition in amounts of about 0.01 wt.% or more, about 0.1 wt.% or more, about 0.5 wt.% or more, about 1 wt.% or more, about 2 wt.% or less, about 3 wt.% or less, about 4 wt.% or less, about 5 wt.% or less, or any value covered by these endpoints.

[0089] b. Organic polymer base coating

[0090] The second type of primer composition of the coating system of the present invention is an organic polymer primer. The organic polymer may be at least one of the following: polyphenylene sulfide (PPS), polyethersulfone (PES), polyetheretherketone (PEEK), polyphenylene sulfone (PPSU), polyamide-imide (PAI), polyetherimide (PEI), polyimide (PI), and combinations thereof.

[0091] Properties such as melting point and glass transition temperature (Tg) can be determined by differential scanning calorimetry (DSC), in which the phase transition or glass transition is monitored as the temperature in the sample changes compared to a reference sample.

[0092] Organic polymers can be, for example, crystalline thermoplastic polymers with melting points of about 200°C or higher, about 210°C or higher, about 220°C or higher, or about 250°C or higher, as determined by differential scanning calorimetry (DSC) according to ASTM E794-06 (2018).

[0093] Organic polymers can be, for example, amorphous thermoplastic polymers with a glass transition temperature (Tg) of about 90°C or higher, about 100°C or higher, about 120°C or higher, about 150°C or higher, about 170°C or higher, or about 200°C or higher, as determined by differential scanning calorimetry (DSC) according to ASTM E1356-08 (2014).

[0094] The organic polymer can be a thermosetting polymer with a thermal flexural / deformation temperature (HDT) of about 100°C or higher, about 120°C or higher, about 150°C or higher, about 170°C or higher, or about 200°C or higher as determined by ASTM D648.

[0095] The properties described above (high melting point, high glass transition temperature (Tg) and thermal flexural / heat distortion temperature (HDT)) can individually or in combination contribute to the continuous use of coatings at temperatures above 200°C.

[0096] Based on wet weight, expressed as a percentage of the total weight of the primer composition, the organic polymer may be present in the composition in amounts of about 5 wt.% or more, about 10 wt.% or more, about 15 wt.% or more, about 20 wt.% or more, about 25 wt.% or more, about 30 wt.% or more, about 35 wt.% or more, about 40 wt.% or less, about 45 wt.% or less, about 50 wt.% or less, about 55 wt.% or less, about 60 wt.% or less, or any value covered by these endpoints.

[0097] Based on dry (solid) weight, expressed as a percentage of the total weight of the primer composition, the organic polymer may be present in the composition in amounts of about 10 wt.% or more, about 15 wt.% or more, about 20 wt.% or more, about 25 wt.% or more, about 30 wt.% or more, about 35 wt.% or more, about 40 wt.% or more, about 45 wt.% or more, about 50 wt.% or more, about 55 wt.% or less, about 60 wt.% or less, about 65 wt.% or less, about 70 wt.% or less, about 75 wt.% or less, about 80 wt.% or less, about 85 wt.% or less, about 90 wt.% or less, or any value covered by these endpoints.

[0098] Organic polymers can be provided in solution. Solvents suitable for said solution may include, for example, polar aprotic solvents such as N-methylpyrrolidone, N-ethylpyrrolidone, N-butylpyrrolidone, N,N-dimethylacetamide, caprolactone (ε-lactone), butyrolactone (γ-lactone), 3-methoxy-N,N-dimethylpropionamide, morpholine, and cyclohexanone.

[0099] Alternatively, the organic polymer can be provided as granules. The organic polymer can be ground using, for example, a media mill, such as a ball mill, pot mill, basket mill, or grinder, to produce multiple microparticles, which are then mixed with one or more of the remaining components described herein.

[0100] The particulate particles can be provided in a variety of particle sizes, such as those determined by dynamic light scattering, with a median diameter or D50 of about 0.5 micrometers or greater, about 1 micrometer or greater, about 5 micrometers or greater, about 10 micrometers or greater, about 15 micrometers or greater, about 20 micrometers or greater, about 25 micrometers or less, about 30 micrometers or less, about 35 micrometers or less, about 40 micrometers or less, about 45 micrometers or less, about 50 micrometers or less, or any value covered by these endpoints.

[0101] Organic polymers can be provided as multiple particles having a median diameter, or D50, of about 0.5 micrometers or greater, about 1 micrometer or greater, about 2 micrometers or greater, about 5 micrometers or greater, about 10 micrometers or less, about 20 micrometers or less, about 50 micrometers or less, or any value encompassed by these endpoints. A suitable method for determining the median particle size is described in ISO 13320:2009. This paper discusses additional methods for determining the median particle size in conjunction with reinforced particles.

[0102] Organic polymers can be provided as multiple particles, of which 99% have a particle size or D99 of approximately 100 micrometers, 75 micrometers, 60 micrometers, 50 micrometers, 40 micrometers, 30 micrometers, or smaller, or any range defined between any two of the foregoing values. This article discusses methods for determining particle size in conjunction with reinforced particles.

[0103] c. Silicone resin primer

[0104] The third type of primer composition for the coating system of the present invention is a silicone primer. A suitable silicon-containing portion for the silicone primer of this disclosure may comprise a polymeric silicone resin, which may be linear or branched, end-capped or unend-capped. The resin may contain RSiO2. 3 / 2 unit, R2SiO unit and R3SiO 1 / 2 The polysiloxane polymer or copolymer is a hydroxyl-functionalized and alkoxy-functionalized unit, wherein R is independently alkyl or aryl, and the weight percentage of hydroxyl and / or alkoxy groups is from 0.5 wt.% to 35 wt.%, and the weight percentage of silica residues after complete oxidation is from 45 wt.% to 90 wt.%. Suitable silicone resins may comprise, for example, poly(methylsilsesquioxane), poly(propylsilsesquioxane), poly(phenylsilsesquioxane), polydimethylsiloxane, vinylmethylsiloxane, trimethylsilyl-terminated polydimethylsiloxane, vinyl-terminated polydimethylsiloxane, and trimethylsilyl-terminated polymethylhydrosiloxane.

[0105] Based on wet weight, expressed as a percentage of the total weight of the primer composition, the silicone polymer may be present in the composition in amounts of about 20 wt.% or more, about 25 wt.% or more, about 30 wt.% or more, about 35 wt.% or more, about 40 wt.% or more, about 45 wt.% or more, about 50 wt.% or more, about 55 wt.% or less, about 60 wt.% or less, about 65 wt.% or less, about 70 wt.% or less, about 75 wt.% or less, about 80 wt.% or less, about 85 wt.% or less, about 90 wt.% or less, or any value covered by these endpoints.

[0106] Based on dry (solid) weight, expressed as a percentage of the total weight of the primer composition, the silicone polymer may be present in the composition in amounts of about 20 wt.% or more, about 25 wt.% or more, about 30 wt.% or more, about 35 wt.% or more, about 40 wt.% or more, about 45 wt.% or more, about 50 wt.% or more, about 55 wt.% or less, about 60 wt.% or less, about 65 wt.% or less, about 70 wt.% or less, about 75 wt.% or less, about 80 wt.% or less, about 85 wt.% or less, about 90 wt.% or less, or any value covered by these endpoints.

[0107] The silicone primer formulation disclosed herein may also include one or more catalysts. Suitable catalysts may include, for example, metal catalysts such as platinum-based, tin-based, zinc-based, zirconium-based, and cerium-based catalysts, including platinum-cyclovinylmethylsiloxane complexes, tin ethylhexanoate, zinc ethylhexanoate, zirconium ethylhexanoate, cerium ethylhexanoate, and dibutyltin laurate.

[0108] Based on wet weight, as a percentage of the total weight of the base coat composition, one or more catalysts may be present in the composition in amounts of 0 wt.%, or about 0.01 wt.% or more, about 0.1 wt.% or more, about 0.5 wt.% or more, about 1 wt.% or more, about 2 wt.% or more, about 3 wt.% or more, about 4 wt.% or more, about 5 wt.% or less, about 6 wt.% or less, about 7 wt.% or less, about 8 wt.% or less, about 9 wt.% or less, about 10 wt.% or less, or any value covered by these endpoints.

[0109] Based on dry (solid) weight, expressed as a percentage of the total weight of the base coat composition, one or more catalysts may be present in the composition in amounts of 0 wt.% or about 0.1 wt.% or more, about 0.5 wt.% or more, about 1 wt.% or more, about 2 wt.% or more, about 5 wt.% or more, about 10 wt.% or less, about 15 wt.% or less, about 20 wt.% or less, or any value covered by these endpoints.

[0110] d. Reinforcing particles

[0111] The composition may additionally include one or more reinforcing particles, also known as fillers. Exemplary reinforcing particles include silica, alumina, titanium dioxide, zirconium oxide, wollastonite, quartz, silicon carbide, fluorite, quartz, synthetic diamond, topaz, orthoclase, apatite, and short glass fibers.

[0112] As determined by ASTM E92-17, the Mohs hardness of the reinforcing particles can be 4 or higher. Alternatively, the hardness of the reinforcing particles can be described using Knoop hardness. As determined by ASTM C1326, the Knoop hardness of the reinforcing particles can be 160 kg / m². 2 Or larger.

[0113] Reinforcing particles can also be described by their size. Particle size can be determined by dynamic light scattering. Alternatively, particle size can be determined by scanning electron microscopy (SEM) analysis. Visual inspection of SEM micrographs is performed, where the diameter of the particles in the image can be measured after image magnification, without size correction, such as in cross-section. From these measurements, the average primary particle size can be calculated. Primary particle size is defined herein as the smallest diameter sphere that would completely surround the particle. Therefore, primary particle size refers to the size of an individual particle, not an aggregate of two or more particles. To ensure adequate representation of possible particle sizes, samples of 20 or more particles, 50 or more particles, 70 or more particles, or 100 or more particles can be measured.

[0114] As determined by dynamic light scattering, the average particle size of the reinforcing particles can be about 5 micrometers or larger, about 10 micrometers or larger, about 15 micrometers or larger, about 20 micrometers or larger, about 25 micrometers or larger, about 30 micrometers or larger, about 35 micrometers or larger, about 40 micrometers or larger, about 45 micrometers or larger, about 50 micrometers or larger, 55 micrometers or smaller, 60 micrometers or smaller, 65 micrometers or smaller, 70 micrometers or smaller, 75 micrometers or smaller, 80 micrometers or smaller, 85 micrometers or smaller, 90 micrometers or smaller, 95 micrometers or smaller, 100 micrometers or smaller, or any value covered by these endpoints.

[0115] Reinforcing particles can have various shapes. For example, reinforcing particles can be spherical, elliptical, or lamellar. Reinforcing particles can also be defined by their size ratio. The size ratio is defined herein as the ratio of particle size "p" to the thickness "t" of the undercoat. The size ratio can be determined by cutting a cross-section of the coating and polishing it using an overlapping technique, allowing observation at magnification between 500x and 5000x using a scanning electron microscope (SEM). Dimensional imaging can be performed by measuring the particle size using the smallest circle circumscribed around the particle and by measuring the film thickness of the coating through point-to-point measurements between the observable substrate surface and the coating surface.

[0116] The thickness ratio of the base coating to the particles is about 0.5:1.0 or greater, about 0.6:1.0 or greater, about 0.7:1.0 or greater, about 0.8:1.0 or greater, about 0.9:1.0 or greater, about 1.0:1.0 or greater, about 1.1:1.0 or greater, about 1.2:1.0 or greater, about 1.3:1.0 or less, about 1.4:1.0 or less, about 1.5:1.0 or less, about 1.7:1.0 or less, about 1.8:1.0 or less, about 1.9:1.0 or less, about 2.0:1.0 or less, about 2.1:1.0 or less, about 2.2:1.0 or less, or any value covered by these endpoints as determined by cross-sectional analysis by scanning electron microscopy.

[0117] If determined by cross-sectional analysis by scanning electron microscopy, the number of reinforcing particles present in the base coat is approximately 3 or more, approximately 4 or more, approximately 5 or more, approximately 6 or less, approximately 7 or less, approximately 8 or less, approximately 9 or less, or approximately 10 or less per 1 cm length of the base coat cross-section.

[0118] Based on wet weight, expressed as a percentage of the total weight of the base coat composition, one or more reinforcing particles may be present in the composition in amounts of about 3 wt.% or more, about 4 wt.% or more, about 5 wt.% or more, about 6 wt.% or less, about 7 wt.% or less, about 8 wt.% or less, about 9 wt.% or less, about 10 wt.% or less, or any value covered by these endpoints.

[0119] Based on dry (solid) weight, expressed as a percentage of the total weight of the base coat composition, one or more reinforcing particles may be present in the composition in amounts of about 5 wt.% or more, about 10 wt.% or more, about 15 wt.% or more, about 20 wt.% or less, about 25 wt.% or less, about 30 wt.%, or any value covered by these endpoints.

[0120] e. Additives

[0121] The base coating of this disclosure may further include, for example, one or more nanoparticle additives, such as silica, titanium dioxide, zirconium oxide, and alumina. Not wishing to be bound by theory, nanoparticles can act as seeds for gel growth during the sol-gel process. Nanoparticles can also help increase both the hardness and cohesiveness of the sol-gel composition while maintaining transparency and gloss. When used in combination with other base coating compositions, such as the organic polymer and silicone base coatings of this disclosure, the nanoparticle additives can act as co-adhesives. In these cases, nanoparticles can impart adhesion and cohesiveness and increase the critical film thickness in the coating.

[0122] The particle size of the nanoparticle additive is about 10 nm or larger, about 20 nm or larger, about 50 nm or larger, about 75 nm or larger, about 100 nm or larger, about 150 nm or larger, about 200 nm or smaller, about 250 nm or smaller, about 300 nm or smaller, about 350 nm or smaller, about 400 nm or smaller, about 450 nm or smaller, about 500 nm or smaller, or any value covered by these endpoints.

[0123] Based on wet weight, as a percentage of the total weight of the base coat composition, the nanoparticle additive may be present in the composition in amounts of about 0 wt.% or more, about 1 wt.% or more, about 5 wt.% or more, about 10 wt.% or more, about 15 wt.% or more, about 20 wt.% or less, about 25 wt.% or less, about 30 wt.% or less, about 35 wt.% or less, or any value covered by these endpoints.

[0124] The nanoparticle additive may be present in the composition in amounts of about 0 wt.% or more, about 1 wt.% or more, about 5 wt.% or more, about 10 wt.% or more, about 15 wt.% or more, about 20 wt.% or more, about 25 wt.% or more, about 30 wt.% or more, about 35 wt.% or more, about 40 wt.% or less, about 45 wt.% or less, about 50 wt.% or less, about 55 wt.% or less, about 60 wt.% or less, or any value covered by these endpoints, expressed as a percentage of the total composition weight based on dry (solid) weight.

[0125] The primer layer of this disclosure may further include one or more additives, such as thickeners, surfactants, diluents, extenders, and pigments. Suitable additives may include talc, mica, barium sulfate, associative polyurethane thickeners, alkali-swellable acrylic thickeners, bentonite, nonionic surfactants such as alkyl ethoxylates, alkyne surfactants, siloxane-based polyether surfactants, fatty acid-based, silica-based, and siloxane-based defoamers, etc. These additives may be present in the primer layer in amounts of about 0.1 wt.% or more, about 1 wt.% or more, about 5 wt.% or more, about 10 wt.% or more, about 20 wt.% or more, about 30 wt.% or less, about 40 wt.% or less, about 50 wt.% or less, about 60 wt.% or less, or any value covered by these endpoints, expressed as a percentage of the total primer layer composition on a wet weight basis.

[0126] Based on dry (solid) weight, expressed as a percentage of the total weight of the primer composition, these additives may be present in the primer in amounts of about 2 wt.% or more, about 5 wt.% or more, about 10 wt.% or more, about 20 wt.% or more, about 30 wt.% or more, about 40 wt.% or more, about 50 wt.% or less, about 60 wt.% or less, about 70 wt.% or less, about 80 wt.% or less, or any value covered by these endpoints.

[0127] Any of the primers described above may be used together with any of the outer coating compositions described below in the coating compositions disclosed herein.

[0128] VI. Outer Coating

[0129] As discussed above, the outer coating provides the desired non-stick properties to the coating of this disclosure, while the undercoat provides mechanical strength. The outer coating of this disclosure may include a siloxane film. The siloxane film may be formed by at least one of a hydrogenation silanization reaction, a dehydrogenation coupling reaction, or a polycondensation reaction.

[0130] Some known coatings may have non-stick properties due to the presence of silicone oil. This type of coating may be uneven because the silicone oil may separate from the rest of the coating. Figure 16 An example of this type of coating is shown, wherein the coating is applied to a substrate, the coating having a main phase and a thin surface layer separated from or non-uniform to the main phase. In this way, more than one morphology is observed in a scanning electron microscope (SEM) cross section, or in other words, significant changes in chemical composition and / or compositional gradients are observed in the cross section.

[0131] and Figure 16 In contrast to the coatings depicted herein, the siloxane film outer coating of this disclosure can be homogeneous, meaning that the chemical composition of the outer coating can be substantially the same across the entire cross-section of the outer coating. In other words, when observed at a microscopic level, the siloxane film of the outer coating may not exhibit a compositional gradient across the entire cross-section of the outer coating. For example, only one morphology may be observed in a scanning electron microscope (SEM) cross-section. As used herein, morphology refers to the phase distribution within a given system.

[0132] a. Hydrosilanization

[0133] Silicone elastomers have been used in non-stick coatings for industrial baking pans due to their excellent non-stick properties and high film build-up. However, silicone elastomers in existing coatings tend to have weaker scratch resistance and lower hardness, and therefore often contain particulate fillers. However, since elastomers themselves lack cohesion, the use of fillers may not lead to an increase in mechanical properties. Alternatively, increasing the crosslinking density of the elastomer can provide a harder film, but at the cost of reduced non-stick properties and stress cracking.

[0134] The first type of outer coating composition of the coating system of the present invention is a siloxane film formed by a hydrogenation silanization reaction of a silicone elastomer film composition, which maximizes non-stick properties, allows for high film build-up, and also provides good hardness and scratch resistance in the clear coating. Furthermore, as described below and in examples, the superior mechanical properties of these outer coatings are not compromised by a reduction in the initial non-stick properties of the coating, and the outer coatings also have improved resistance to stress cracking, resulting in better film integrity in the clear coating.

[0135] Hydrosilylation reactions can occur between vinyl-substituted organosiloxanes and hydride-substituted organosiloxanes, as shown in Scheme 1 below:

[0136] Option 1

[0137]

[0138] R and R' can each be alkyl, aryl, or siloxy.

[0139] These outer coatings typically consist of a base adhesive resin, co-adhesive, and inorganic filler in the form of a silicone elastomer characterized by aspect ratios such as needle-like or lamellar.

[0140] The base adhesive resin is formed by a hydrosilylation reaction between vinyl-terminated polydimethylsiloxane and polydimethylsiloxane containing hydride groups, as shown in Scheme 1 above, the reaction optionally being catalyzed by a catalyst.

[0141] The precursor for the hydrosilylation reaction may contain a polymer component. Suitable polymer components can be linear or branched. The polymer component may be end-capped and / or substituted. Examples of suitable precursors include polymethylhydrosiloxanes, vinylmethylsiloxanes, polydiphenylsiloxanes, vinyl-terminated polydimethylsiloxanes, vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymers, hydride-terminated polydimethylsiloxanes, hydride-terminated polyphenylmethylsiloxanes, cyclic vinylmethylsiloxanes, vinyl MQ resins, trimethylsilyl-terminated polymethylhydrosiloxanes, trimethylsiloxane-terminated methylhydrosiloxane-dimethylsiloxane copolymers, hydride MQ resins, and combinations thereof.

[0142] A suitable precursor is linear vinyl-terminated polydimethylsiloxane (PDMS), such as those shown in the table below.

[0143] Product Name Chemical description CAS number Viscosity (cSt) Molecular weight (g / mol) DMS-V-31 Vinyl-terminated PDMS 68083-19-2 1000 12000 DMS-V35 Vinyl-terminated PDMS 68083-19-2 5000 49500 Silmer VIN10000 Vinyl-terminated PDMS 68083-19-2 10000 5400

[0144] In these vinyl-terminated polydimethylsiloxanes, the molecular weight is proportional to the viscosity.

[0145] The viscosity of vinyl-terminated polydimethylsiloxanes can be 500 cSt, 1,000 cSt, 2,000 cSt, or 3,500 cSt to 5,000 cSt, 8,000 cSt, 10,000 cSt, 12,000 cSt, 20,000 cSt, or 50,000 cSt, or any value covered by any two of the foregoing as endpoints. Viscosity can be determined by ASTM D445-21e1, measured directly with a Brookfield viscometer according to methods such as ISO 3219.

[0146] The molecular weight of vinyl-terminated polydimethylsiloxanes can be 10,000 g / mol, 20,000 g / mol, or 30,000 g / mol up to 40,000 g / mol, 50,000 g / mol, 60,000 g / mol, or 100 g / mol, or any value encompassed by any two of the foregoing as endpoints. Molecular weight, expressed herein as weight-average molecular weight, can be determined by gel permeation chromatography (GPC).

[0147] Based on the total solid weight of the outer coating composition, the vinyl-terminated polydimethylsiloxane may be present in amounts of 35 wt.%, 40 wt.%, 45 wt.% to 55 wt.%, 60 wt.%, 65%, or any of the values ​​covered by any two of the foregoing as endpoints.

[0148] Vinyl-terminated polydimethylsiloxanes can react with polydimethylsiloxanes containing hydride groups.

[0149] The hydride content of the polydimethylsiloxane containing the hydride group can be 15 mol%, 30 mol%, or 35 mol% to 45 mol%, 50 mol%, or 60 mol%, or any value covered by any two of the foregoing as endpoints.

[0150] The viscosity of polydimethylsiloxanes containing hydride groups can be from 20 cSt or 25 cSt to 35 cSt or 40 cSt, or any value covered by any two of the foregoing endpoints. Viscosity can be determined by a Brookfield viscometer according to a method such as ISO 3219.

[0151] The molecular weight of polydimethylsiloxanes containing hydride groups can be from 1,500 g / mol, 1,750 g / mol, or 1,900 g / mol to 2,000 g / mol, 2,250 g / mol, or 2,500 g / mol, or any value encompassed by any two of the foregoing as endpoints. Molecular weight, expressed herein as weight-average molecular weight, can be determined by gel permeation chromatography (GPC).

[0152] A suitable polydimethylsiloxane containing hydride groups is a methylhydrosiloxane-dimethylsiloxane copolymer (catalog number 68037-59-2) with a viscosity of 25-35 cSt, a molecular weight of 1900-2000, and 25-35 mol% of hydride groups, and terminated with trimethylsiloxane groups. Based on the total solid weight of the outer coating composition, the polydimethylsiloxane containing hydride groups may be present in amounts of 2 wt.%, 5 wt.%, 10 wt.%, 20 wt.%, 25 wt.%, or 27.5 wt.% to 32.5 wt.%, 35 wt.%, or 40%, or any of the values ​​covered by any two of the foregoing as endpoints.

[0153] The molar equivalent ratio of the vinyl-substituted precursor to the hydride-substituted precursor can be about 0.5:1.0 or greater, about 0.8:1.0 or greater, about 0.9:1.0 or greater, about 1.0:1.0 or greater, about 1.1:1.0 or greater, about 1.2:1.0 or less, about 1.3:1.0 or less, about 1.4:1.0 or less, about 1.5:1.0 or less, or any value covered by these endpoints.

[0154] Based on wet weight, the precursor may be present in the base coat composition in an amount of about 40 wt.% or more, about 45 wt.% or more, about 50 wt.% or more, about 55 wt.% or more, about 60 wt.% or more, about 65 wt.% or more, about 70 wt.% or less, about 75 wt.% or less, about 80 wt.% or less, about 85 wt.% or less, about 90 wt.% or less, about 95 wt.% or less, about 100 wt.% or less, or any value covered by these endpoints, based on the total weight of the base coat composition.

[0155] Hydrosilylation reactions can be catalyzed using suitable catalysts such as platinum, and suitable platinum-based catalysts include Karstedt catalysts and Ashby catalysts, as shown below.

[0156]

[0157] These catalysts can be provided in solution and are highly stable, thus providing a long pot life under conditions of rapid curing at high temperatures. The catalysts can be present in relatively small amounts, such as 1 ppm to 50 ppm.

[0158] The coating may further include an oligomeric co-binder to increase crosslinking between the aforementioned vinyl-substituted precursor and the hydride-substituted precursor, and it has been found that said crosslinking increases the scratch resistance of the coating.

[0159] Co-binders can be linear PDMS with vinyl functional groups along the chain, cyclic siloxane rings with vinyl functional groups, MQ resins or VQ resins with vinyl functional groups. Suitable co-binders are shown below.

[0160]

[0161] The viscosity of the co-adhesive can be 50 cSt, 100 cSt, 000 cSt, or 350 cSt, up to 500 cSt, 800 cSt, 1000 cSt, or 1200 cSt, or 2500 cSt, or 5000 cSt, or any value covered by any two of the foregoing as endpoints. Viscosity can be determined by ASTM D445-21.

[0162] Molecular weight can be 5,000 g / mol, 10,000 g / mol, or 15,000 g / mol up to 20,000 g / mol, 30,000 g / mol, or 40,000 g / mol, or any value encompassed by any two of the foregoing as endpoints. Molecular weight, expressed herein as weight-average molecular weight, can be determined by gel permeation chromatography (GPC).

[0163] Advantageously, the co-adhesive can be a vinyl "Q" resin or VQ resin of an organopolysiloxane represented by an average unit formula:

[0164] [(CH2=CH)(R)2SiO 0.5 ] u [(R)3SiO 0.5 ] v [SiO2] w

[0165] Where R represents methyl, and u, v, and w are the mole fractions of the corresponding siloxane units, and (u+v) / w is between 0.5 and 2.

[0166] Based on the total solid weight of the outer coating composition, the co-adhesive may be present in amounts of 0.5 wt.%, 5 wt.%, 12 wt.%, 15 wt.%, or 17.5 wt.% to 22.5 wt.%, 25 wt.%, or 30%, or any value covered by any two of the foregoing as endpoints.

[0167] Suitable fillers for coatings can include fillers with an elongation-to-width ratio, such as lamellar crystals or short fibers. It has been found that fillers with an elongation-to-width ratio help maintain the mechanical integrity of the coating and increase the indentation modulus without affecting surface properties, food stain resistance, or gloss.

[0168] Based on the total solid weight of the outer coating composition, the filler may be present in amounts of 1 wt.%, 2 wt.%, 3 wt.% to 4 wt.%, 5 wt.%, 7.5%, or any of the values ​​covered by any two of the foregoing as endpoints.

[0169] The median diameter or d50 of the packing can be about 1 micrometer or larger, about 2 micrometers or larger, about 5 micrometers or larger, about 10 micrometers or larger, about 20 micrometers or smaller, about 30 micrometers or smaller, about 40 micrometers or smaller, about 50 micrometers or smaller, 60 micrometers or smaller, or any range or value covered by these endpoints.

[0170] The aspect ratio of the filler particles can be 3:1 or greater, 5:1 or greater, 10:1 or greater, 20:1 or greater, 50:1 or greater, 100:1 or greater, 200:1 or greater, 500:1 or greater, 1000:1 or greater, 2000:1 or greater, 5000:1 or greater, or 10,000:1 or greater.

[0171] The filler can be wollastonite (calcium silicate, CaSiO3), such as Imerys Nyglos 4W, Nyglos 8, Nyglos 9000 or muscovite mica.

[0172] Other inorganic fillers include kaolin, potassium titanate, talc, plasmon, perlescent mica, glass flakes, hexagonal boron nitride, graphite, graphene, graphene oxide, molybdenum disulfide, basalt short fibers, alumina whiskers, glass short fibers, and hydroxyapatite whiskers.

[0173] b. Dehydrogenation coupling

[0174] The second type of external coating composition of the coating system of the present invention is a siloxane film formed by dehydrogenation coupling. Dehydrogenation coupling can occur between hydride-substituted organosiloxanes and hydroxyl-substituted organosiloxanes, as shown in Scheme 2 below:

[0175] Option 2

[0176]

[0177] R can be alkyl, aryl, or alkoxy, and R' can be alkyl, aryl, alkoxy, or silyloxy.

[0178] The precursor for the dehydrogenation coupling reaction may contain a polymer component. Suitable polymer components may be linear or branched. The polymer component may be end-capped and / or substituted. Examples of suitable precursors may include polymethylhydrosiloxanes, hydride-terminated polydimethylsiloxanes, hydride-terminated polyphenylmethylsiloxanes, hydroxyl-terminated polydimethylsiloxanes, silanol-terminated polydimethylsiloxanes, silanol-terminated polyphenylsiloxanes, silanol-terminated diphenylsiloxane-dimethylsiloxane copolymers, trimethylsilyl-terminated polymethylhydrosiloxanes, trimethylsiloxane-terminated methylhydrosiloxane-dimethylsiloxane copolymers, hydride MQ resins, hydroxide MQ resins, and combinations thereof.

[0179] The molar equivalent ratio of the hydride-substituted precursor to the hydroxyl-substituted precursor can be about 0.8:1.0 or greater, about 0.9:1.0 or greater, about 1.0:1.0 or greater, about 1.1:1.0 or greater, about 1.2:1.0 or less, about 1.3:1.0 or less, about 1.4:1.0 or less, about 1.5:1.0 or less, or any value covered by these endpoints.

[0180] Based on wet weight, based on the total weight of the primer composition, the precursor may be present in the primer composition in amounts of about 40 wt.% or more, about 45 wt.% or more, about 50 wt.% or more, about 55 wt.% or more, about 60 wt.% or more, about 65 wt.% or more, about 70 wt.% or more, about 75 wt.% or less, about 80 wt.% or less, about 85 wt.% or less, about 90 wt.% or less, about 95 wt.% or less, about 100 wt.% or less, or any value covered by these endpoints.

[0181] c. Condensation

[0182] The third type of external coating composition of the coating system of the present invention is a siloxane film formed by polycondensation. The polycondensation reaction can occur between two silanols, as shown in Scheme 3 below:

[0183] Option 3

[0184]

[0185] Where R can be alkyl, aryl, or siloxy, and R' can be alkyl, aryl, or siloxy. Alternatively, the polycondensation reaction can occur between a silanol and an alkoxysilane, as shown in Scheme 4 below:

[0186] Option 4

[0187]

[0188] R and R' can be alkyl, acetoxy, aryl, alkynyl or siloxy, and R” can be alkyl.

[0189] The precursor for the polycondensation reaction may contain a polymer component. Suitable polymer components may be linear or branched. The polymer component may be end-capped and / or substituted. Suitable precursors for the polycondensation reaction of this disclosure may include hydroxyl-terminated polydimethylsiloxanes, silanol-terminated polydimethylsiloxanes, silanol-terminated polyphenylsiloxanes, silanol-terminated diphenylsiloxane-dimethylsiloxane copolymers, poly(methylsilsesquioxane), poly(propylsilsesquioxane), poly(phenylsilsesquioxane), poly(2-acetoxyethylsilsesquioxane), organically modified alkoxysilanes, and oligomers thereof, including combinations thereof.

[0190] d. Catalyst

[0191] One or more catalysts can be used in the hydrosilylation reaction. Suitable catalysts for hydrosilylation may include, for example, transition metal-based catalysts, such as tin-based, titanium-based, platinum-based, palladium-based, rhodium-based, and ruthenium-based catalysts, and organic peroxides, such as dicumyl peroxide.

[0192] One or more catalysts can be used in the dehydrogenation coupling reaction. Suitable catalysts may include, for example, transition metal-based catalysts, such as tin-based, rhodium-based, ruthenium-based, gold-based, copper-based, zinc-based, zirconium-based, titanium-based, platinum-based, and palladium-based catalysts.

[0193] One or more catalysts can be used in the polycondensation reaction. Suitable catalysts may include protic acids, Lewis acids, or bases. Suitable catalysts may also include transition metal catalysts, such as zinc-based, zirconium-based, tin-based, and titanium-based catalysts.

[0194] Based on wet weight, expressed as a percentage of the total weight of the outer coating composition, the catalyst may be present in the composition in amounts of about 0.005 wt.% or more, about 0.05 wt.% or more, about 0.1 wt.% or more, about 0.5 wt.% or more, about 1 wt.% or more, about 2 wt.% or more, about 3 wt.% or more, about 4 wt.% or less, about 5 wt.% or less, about 6 wt.% or less, about 7 wt.% or less, about 8 wt.% or less, about 9 wt.% or less, about 10 wt.% or less, or any value covered by these endpoints.

[0195] Based on dry (solid) weight, expressed as a percentage of the total weight of the outer coating composition, the catalyst may be present in the composition in amounts of about 0.005 wt.% or more, about 0.05 wt.% or more, about 0.1 wt.% or more, about 0.5 wt.% or more, about 1 wt.% or more, about 2 wt.% or more, about 3 wt.% or less, about 4 wt.% or less, about 5 wt.% or less, about 6 wt.% or less, about 7 wt.% or less, about 8 wt.% or less, about 9 wt.% or less, about 10 wt.% or less, or any value covered by these endpoints.

[0196] Any of these outer coating compositions can be used together with any of the base coating compositions described above in the coating compositions disclosed herein.

[0197] VII. Solvent

[0198] The composition may contain one or more solvents. Exemplary solvents include water, alcohols such as C1-C8 alcohols including methanol, ethanol, isopropanol, and tert-butanol, C2-C8 ketones including acetone, and C2-C... 20 Ethers, including dipropylene glycol methyl ether and other protic or aprotic solvents, such as dimethyl sulfoxide or N-methylpyrrolidone.

[0199] Based on wet weight, expressed as a percentage of the total weight of the coating composition, the solvent may be present in the composition in amounts of about 0 wt.% or more, about 1 wt.% or more, about 5 wt.% or more, about 10 wt.% or more, about 15 wt.% or more, about 20 wt.% or more, about 25 wt.% or more, about 30 wt.% or more, about 35 wt.% or less, about 40 wt.% or less, about 45 wt.% or less, about 50 wt.% or less, about 55 wt.% or less, about 60 wt.% or less, about 65 wt.% or less, about 70 wt.% or less, or any value covered by these endpoints.

[0200] After the coating is applied and cured, the total coating composition may be substantially solvent-free. In other words, based on dry (solid) weight, solvent may be present in the composition in an amount of about 1 wt.% or less, about 0.5 wt.% or less, or about 0.1 wt.% or less of the total coating composition weight.

[0201] VIII. Methods for Forming Coatings

[0202] a. Mixing of components

[0203] The coating composition is formed by separately formulating the primer composition and the top coat composition. Each of these can be formulated by mixing their respective components. Once the primer and top coat compositions have been mixed, the composition can be applied separately to the substrate to ultimately form the coating composition.

[0204] On the one hand, the components can be mixed together before the resulting coating composition is applied to the substrate, and those skilled in the art can determine the point at which mixing occurs before application based on the desired degree of hydrolysis and condensation of the silane reactants before applying the coating composition to the substrate. On the other hand, subsets of components can be prepared, wherein each subset contains components that do not react with other components within each subset, wherein subsets of two or more components are combined before the resulting composition is applied to the substrate.

[0205] b. Flash evaporation

[0206] After the primer composition is applied to the substrate, the resulting coating can be rapidly heated. The coating can be rapidly heated at a temperature of about 80°C or higher, about 100°C or higher, about 120°C or higher, about 140°C or higher, about 150°C or lower, about 170°C or lower, about 190°C or lower, about 200°C or lower, or any value covered by these endpoints.

[0207] The coating can be rapidly heated for a period of time of approximately 1 minute or longer, approximately 2 minutes or longer, approximately 5 minutes or longer, approximately 8 minutes or longer, approximately 10 minutes or less, approximately 12 minutes or less, approximately 15 minutes or less, approximately 18 minutes or less, approximately 20 minutes or less, or any value covered by these endpoints.

[0208] After rapidly heating the primer layer and before applying the top coat, the primer layer can be cured as described below. After applying the top coat, the resulting coating can be rapidly heated at a temperature of about 80°C or higher, about 100°C or higher, about 120°C or higher, about 140°C or higher, about 150°C or lower, about 170°C or lower, about 190°C or lower, about 200°C or lower, or any value covered by these endpoints.

[0209] The coating can be rapidly heated for a period of time of approximately 1 minute or longer, approximately 2 minutes or longer, approximately 5 minutes or longer, approximately 8 minutes or longer, approximately 10 minutes or less, approximately 12 minutes or less, approximately 15 minutes or less, approximately 18 minutes or less, approximately 20 minutes or less, or any value covered by these endpoints.

[0210] Alternatively, the outer coating can be applied to the base coating before curing. In this case, after the outer coating is applied, the resulting coating can be rapidly heated to a temperature of about 80°C or higher, about 100°C or higher, about 120°C or higher, about 140°C or higher, about 150°C or lower, about 170°C or lower, about 190°C or lower, about 200°C or lower, or any value covered by these endpoints.

[0211] The coating can be rapidly heated for a period of time of approximately 1 minute or longer, approximately 2 minutes or longer, approximately 5 minutes or longer, approximately 8 minutes or longer, approximately 10 minutes or less, approximately 12 minutes or less, approximately 15 minutes or less, approximately 18 minutes or less, approximately 20 minutes or less, or any value covered by these endpoints.

[0212] Alternatively, the outer coating can be applied to the primer before the primer is rapidly heated and cured. Then, both the outer and primer coatings can be rapidly heated and cured simultaneously. In this case, after applying the outer and primer coatings, the resulting coating can be rapidly heated to a temperature of about 80°C or higher, about 100°C or higher, about 120°C or higher, about 140°C or higher, about 150°C or lower, about 170°C or lower, about 190°C or lower, about 200°C or lower, or any value encompassed by these endpoints.

[0213] The coating can be rapidly heated for a period of time of approximately 1 minute or longer, approximately 2 minutes or longer, approximately 5 minutes or longer, approximately 8 minutes or longer, approximately 10 minutes or less, approximately 12 minutes or less, approximately 15 minutes or less, approximately 18 minutes or less, approximately 20 minutes or less, or any value covered by these endpoints.

[0214] c. Curing

[0215] Curing may occur very slowly at room temperature, but it is usually completed at high temperatures, such as in a box oven or tunnel oven.

[0216] The primer can be cured before the top coat is applied. After the primer is applied, the coating can be cured at a temperature of about 200°C or higher, about 225°C or higher, 250°C or higher, about 275°C or higher, about 300°C or lower, about 325°C or lower, about 350°C or lower, about 400°C or lower, or any value covered by these endpoints.

[0217] The coating can cure for about 5 minutes or longer, about 10 minutes or longer, about 15 minutes or longer, about 20 minutes or longer, about 25 minutes or longer, about 30 minutes or less, about 45 minutes or less, about 60 minutes or less, or any value covered by these endpoints.

[0218] After the outer coating is applied and rapidly heated, the entire coating composition can then be cured. The coating can be cured at temperatures of about 200°C or higher, about 225°C or higher, about 250°C or higher, about 275°C or higher, about 300°C or lower, about 325°C or lower, about 350°C or lower, about 400°C or lower, or any value covered by these endpoints.

[0219] The coating can cure for about 5 minutes or longer, about 10 minutes or longer, about 15 minutes or longer, about 20 minutes or longer, about 25 minutes or longer, about 30 minutes or less, about 45 minutes or less, about 60 minutes or less, or any value covered by these endpoints.

[0220] Alternatively, the outer coating can be applied to the base coat before curing the primer. In this case, the primer can be applied and rapidly heated, followed by the outer coating and rapid heating. Once both the primer and outer coating have been applied and rapidly heated, the entire coating composition can be cured.

[0221] The coating can be cured at temperatures of about 200°C or higher, about 225°C or higher, 250°C or higher, about 275°C or higher, about 300°C or lower, about 325°C or lower, about 350°C or lower, about 400°C or lower, or any value covered by these endpoints.

[0222] The coating can cure for about 5 minutes or longer, about 10 minutes or longer, about 15 minutes or longer, about 20 minutes or longer, about 25 minutes or longer, about 30 minutes or less, about 45 minutes or less, about 60 minutes or less, or any value covered by these endpoints.

[0223] Alternatively, the outer coating can be applied to the base coating before the base coating is rapidly heated and cured. The coating can then be cured after rapid heating of both the outer and base coatings.

[0224] The coating can be cured at temperatures of about 200°C or higher, about 225°C or higher, 250°C or higher, about 275°C or higher, about 300°C or lower, about 325°C or lower, about 350°C or lower, about 400°C or lower, or any value covered by these endpoints.

[0225] The coating can cure for about 5 minutes or longer, about 10 minutes or longer, about 15 minutes or longer, about 20 minutes or longer, about 25 minutes or longer, about 30 minutes or less, about 45 minutes or less, about 60 minutes or less, or any value covered by these endpoints.

[0226] IX. Coating Characteristics

[0227] As discussed below, for example, the base coat, top coat, or the entire coating can be characterized by hardness, resistance to deformation, abrasion and scratch resistance, impact resistance, chemical resistance, and resistance to thermal degradation. Each of these characteristics is described in further detail below.

[0228] a. Characteristics of the base coating

[0229] The minimum effective martensitic hardness of the base coating of this disclosure can be 0.2 GPa or higher, 0.3 GPa or higher, 0.4 GPa or higher, 0.5 GPa or higher, or 0.6 GPa or higher, as determined by nanoindentation according to DIN ISO 14577 1-3.

[0230] The elastic modulus of the base coating of this disclosure may be 5 GPa or higher, 7 GPa or higher, 9 GPa or higher, 10 GPa or higher, or 12 GPa or higher, as determined by the method described in ISO 14577-1:2015.

[0231] The coating may contain siloxane-based materials, organic polymers, and inorganic reinforcing particles, illustratively such as hard inorganic reinforcing particles of silicon carbide. Without being bound by theory, the inclusion of hard inorganic reinforcing particles may increase wear resistance by applying deflecting forces to the outer coating.

[0232] The primer coating of this disclosure may be free of fluoropolymers. In other words, based on wet weight, based on the total weight of the primer coating, the primer coating of this disclosure contains 1 wt.% or less, 0.5 wt.% or less, or 0.1 wt.% or less of fluoropolymers. Based on dry (solid) weight, based on the total weight of the primer coating, the primer coating of this disclosure contains 1 wt.% or less, 0.5 wt.% or less, or 0.1 wt.% or less of fluoropolymers.

[0233] b. External coating characteristics

[0234] The outer coating of this disclosure can be described by its martensitic hardness. Specifically, the martensitic hardness of the outer coating of this disclosure can be less than that of the base coating. For example, as determined by nanoindentation according to DIN ISO 14577 1-3, the martensitic hardness of the outer coating of this disclosure can be 0.2 GPa or less, 0.1 GPa or less, or 0.05 GPa or less.

[0235] The siloxane film coating of this disclosure can be uniform, meaning that the chemical composition of the coating can be substantially the same across the entire cross-section of the coating. In other words, the siloxane film coating of this disclosure can have no compositional gradient across the entire cross-section of the coating.

[0236] The siloxane film coating disclosed herein provides high hydrophobicity and good non-stick properties. Hydrophobicity can be determined using contact angle measurements. For example, a contact angle goniometer can be used with ethylene glycol as a test fluid of moderate polarity. The receding contact angle of a 30 μL ethylene glycol droplet is measured on the test surface. Satisfactory non-stick properties may include a receding contact angle greater than 60 degrees. Satisfactory non-stick properties may further include a roll-off angle less than 20 degrees (plane tilt to cause droplet displacement). Other satisfactory non-stick properties may include sufficient cohesion, lack of surface cracking, thermal inertia at cooking temperatures, and lack of reactivity with food (as demonstrated in tests with burnt milk and fried eggs).

[0237] The outer coating of this disclosure may be free of fluoropolymers. In other words, based on wet weight, based on the total weight of the outer coating, the outer coating of this disclosure contains 1 wt.% or less, 0.5 wt.% or less, or 0.1 wt.% or less of fluoropolymers. Based on dry (solid) weight, based on the total weight of the outer coating, the outer coating of this disclosure contains 1 wt.% or less, 0.5 wt.% or less, or 0.1 wt.% or less of fluoropolymers.

[0238] The outer coating based on the hydrogen silanization reaction described in Section VI(a) above can have the desired properties, such as non-stick or anti-stick, that combine scratch resistance with hardness.

[0239] The martensitic hardness of these outer coatings can be 0.003 GPa, 0.005 GPa, or 0.01 GPa to 0.015 GPa, 0.02 GPa, 0.04 GPa, 0.07 GPa, 0.1 GPa, or 0.15 GPa, or any value encompassed by any two of these values ​​as endpoints. The hardness is determined according to DIN ISO 14577 1-3 using the nanoindentation hardness parameters reported in Table 19 of Example 14 herein.

[0240] As for non-stick or anti-stick properties, these coatings exhibit good initial non-stick properties when tested according to Examples 10-12 in this article.

[0241] c. Characteristics of the entire coating

[0242] The entire coating can be tested to determine its abrasion and scratch resistance, as well as its chemical and thermal degradation resistance. These properties can be used to describe the overall performance of the coating.

[0243] Abrasion resistance can be determined using standards such as British Standard 7069-1988, EN 12983-1:2004, and Taber abrasion tests. As used herein, abrasion resistance is determined using the Dry Reciprocating Abrasion Test (DRAT). This test measures the abrasion resistance of the coating using a reciprocating Scotch-Brite pad. The Scotch-Brite pad is manufactured by 3M Company, Abrasive Systems Division, St Paul, MN 55144-1000. The pads are available in different grades with the following abrasion levels: Lowest – 7445, 7448, 6448, 7447, 6444, 7446, 7440, 5440 – Highest. Using the Scotch-Brite 7447 pad, it should be replaced every 1000 cycles.

[0244] The test subjectes the coating to abrasion through back-and-forth motion. The test is a measure of the coating's service life after it has been subjected to washing-induced erosion and other similar forms of damage, as shown in British Standard 7069-1988 and EN12983-1:2004.

[0245] The testing machine is capable of holding a 2-inch Scotch-Brite abrasive pad of a specific size onto the test surface with a fixed force of 3 kg, and can move the pad back and forth (reciprocating) over a distance of 10-15 cm (4 to 6 inches). The force and motion are applied by a freely falling weighted stylus. The machine is equipped with a counter. The coated substrate is secured under the reciprocating pad by bolts, clamps, or tape. This section should be as flat as possible and long enough to prevent the pad from slipping off the edges.

[0246] The abrasive pad is then circulated back and forth (one round trip is defined as one cycle), and the machine is allowed to run for 1000 cycles. After 1000 cycles, the pad is replaced with a new one. Testing continues until 10% of the worn area is exposed to the bare metal. Abrasion resistance is reported as the number of cycles per thousand inches of coating (cycles / mil).

[0247] Scratch resistance can be determined using the scratch adhesion "Happy Flower" Test (HFT). The test is conducted using a pen tip fixed to a balance arm calibrated with a specific weight, with the sample placed on a rotating heated turntable (150°C, oil-filled). After two hours, the test is stopped, and the sample is scored based on the degree of surface damage.

[0248] The inclusion of hard reinforcing particles in the composition increases the scratch resistance of the coating composition. Specifically, as shown in the following example, the Knoop hardness is 160 kg / m. 2 Higher particle size or higher particle size improves both the abrasion resistance and scratch resistance of the coating. It appears that harder particle size provides more resistance improvement than softer particle size.

[0249] As further illustrated in the following examples, it was surprisingly found that smaller reinforcing particles appeared to be just as effective as larger ones in increasing the scratch and abrasion resistance of the coating. Without being bound by theory, it is likely that the ability of the undercoat to at least partially or completely immobilize the reinforcing particles plays a greater role than particle size in imparting scratch and abrasion resistance.

[0250] As further described in the following examples, a strong correlation was found between the abrasion resistance of the coating and the hardness of the adhesive resin, along with a strong correlation between the scratch resistance of the coating and the elastic modulus of the adhesive resin.

[0251] As mentioned above, chemical resistance can also be measured. As used herein, chemical resistance is determined by exposure to hydrochloric acid, such as a 10 wt.% or 30 wt.% hydrochloric acid solution, or exposure to sodium hydroxide, such as a 10 wt.% sodium hydroxide solution, for 24 hours.

[0252] The coating of this disclosure is considered satisfactory when the scratch resistance measured using the HFT technique has a presence level of greater than 80% of the test surface, as observed when the modulus of the base coat is greater than 5 GPa. In other words, the elastic recovery work of the base coat is less than 60 nJ.

[0253] The coating is considered to perform satisfactorily when it exhibits at least 200 cycles / micron of wear resistance, as observed when the base coat exhibits a martensitic hardness greater than 0.2 GPa or an equivalent measurement (e.g., a Vickers hardness greater than 20).

[0254] Typically, a synergistic effect is observed between the hardness of the primer adhesive and the presence of hard reinforcing particles within the primer. Specifically, softer adhesives are less effective at holding the reinforcing particles in place; therefore, their contribution to mechanical resistance remains negligible even when their size and hardness vary. Conversely, according to DIN ISO 145771-3, when the hardness of the primer is greater than about 0.2 GPa, the presence of hard reinforcing particles significantly and synergistically improves abrasion resistance by one or two orders of magnitude compared to compositions without reinforcing particles.

[0255] The coating disclosed herein may be entirely free of fluoropolymers. In other words, based on wet weight, based on the total weight of the entire coating, the entire coating of this disclosure contains 1 wt.% or less, 0.5 wt.% or less, or 0.1 wt.% or less of fluoropolymers. Based on dry (solid) weight, based on the total weight of the entire coating, the entire coating of this disclosure contains 1 wt.% or less, 0.5 wt.% or less, or 0.1 wt.% or less of fluoropolymers.

[0256] Example

[0257] The following non-limiting examples illustrate various features and characteristics of this disclosure, but should not be construed as limiting thereto. Throughout the examples and elsewhere herein, percentages are by weight unless otherwise stated.

[0258] Example 1: Sol-gel base coating

[0259] Four sol-gel undercoat formulations were prepared according to Table 2 below. In these formulations, the binder was gradually enriched with inorganic reinforcing particles; specifically, flaky mica SG and acicular wollastonite, Nyglos 4W grade.

[0260] Table 2

[0261]

[0262] The formulation was prepared as follows: In each test, the thickener was milled in colloidal silica, and the mixture was diluted with deionized water. Maleic acid and isopropanol were then added, followed by methyltrimethoxysilane (MTMS). The reaction was stirred for two hours. Once the sol-gel reaction had occurred, the milled alumina reinforcing particles, along with isopropanol and any desired additives such as pigments, matting agents, and wetting agents, were added to the mixture, as shown in Table 2. Finally, the desired reinforcing particles were added and dispersed in the base coat composition by high-speed mixing.

[0263] The primer is then applied to the sandblasted aluminum substrate and flash-coated at 100-150°C for 5-10 minutes, followed by an exterior coating with a siloxane topcoat formulation, as reported in the examples below. The coated part is then cured at 300°C for 20 minutes. Dry coating compositions are reported in Table 3 below.

[0264] Table 3

[0265]

[0266]

[0267] Example 2: Polyamide-imide / polyethersulfone undercoating

[0268] Three organic polymer primer formulations were prepared according to Table 4 below. The binder was gradually enriched with ceramic particle reinforcing particles of various sizes and compositions; in particular, silicon carbide with a particle size range of 5.6 to 55 μm D50.

[0269] Table 4

[0270]

[0271] The formulation was prepared as follows: The polymer was added to ammonium benzoate, and the mixture was transferred to a ball mill. The mixture was ground, and water and additives, such as reinforcing particles, thickeners, pigments, and surfactants, were gradually added. The mixture was ground for 48 hours. Then, black pigment was added and stirred until the mixture was uniformly colored. Hydroxyethyl cellulose thickener was stirred into water and added to the mixture along with any desired diluent. Finally, silicon carbide was added and dispersed throughout the mixture by high-speed mixing.

[0272] The primer is then applied to the aluminum substrate and flash-coated at 100-150°C for 5-10 minutes, followed by an exterior coating with a siloxane topcoat formulation, as reported in the examples below. The coated part is then cured at 300°C for 20 minutes. Dry coating compositions are reported in Table 5 below.

[0273] Table 5

[0274]

[0275] Example 3: Polyphenylene sulfide primer coating

[0276] Formulas for organic polymer base coatings were prepared using polyphenylene sulfide as the organic polymer, according to Table 6 below. The compositions are suitable for use with the outer coatings described below to form the multi-coat compositions of this disclosure.

[0277] Table 6

[0278]

[0279]

[0280] Example 4: Polyetheretherketone (PEEK) primer coating

[0281] Formulas for organic polymer base coatings were prepared using polyetheretherketone (PEEK) as the organic polymer, according to Table 7 below. Compositions were prepared using silicon carbide reinforcing particles. The compositions are suitable for use with the outer coatings described below to form the multi-coat compositions of this disclosure.

[0282] Table 7

[0283] Components Function wet composition (%) Dry film weight % silicon carbide Reinforcing Particles 4.25 14.80 Defoaming additives Defoaming additives 0.95 1.66 surfactants surfactants 4.88 - Alkali-soluble associative thickeners Thickener 0.36 0.35 Monopropylene glycol solvent 20.13 - PEEK resin Main adhesive 21.35 74.39 Deionized water 45.49 - Black pigment Black pigment 2.52 8.80 2-Amino-2-methyl-2-propanol 95% pH adjuster, solvent 0.05 - Defoaming additives Defoaming additives 0.01 0.00 total 100.00 100.00

[0284] Example 5: Silicon Elastomer Primer Coating

[0285] Two base coat formulations comprising silicone elastomers were prepared according to Table 8 below. In one experiment, 30 and 70 micrometer silicon carbide particles were added to the compositions by high-speed mixing.

[0286] Table 8

[0287]

[0288]

[0289] The composition is rapidly applied to a metal substrate and then coated with a siloxane composition, such as those described below. The substrate is dried at 100-150°C for 5-10 minutes and then cured at 300°C for 20 minutes. The composition of the dry coating is expected to be substantially unchanged from that provided in Table 6, as the composition does not contain volatile components.

[0290] Example 6: Adhesive

[0291] Five different adhesives were formulated into various primer coating compositions. The adhesives were selected within a range of hardness and modulus. Table 9 below describes the different adhesives.

[0292] Table 9

[0293]

[0294] Different adhesives were compared among formulations with the same reinforcing particle type and filler factor. The compositions of different primer formulations are shown in Table 10 below.

[0295] Table 10

[0296]

[0297]

[0298] The formulations were designed such that the type and amount of reinforcing particles were identical for each composition when the dry weight of the polymer was normalized, as shown in Table 11 below. The dry coating compositions were determined by applying a base coat to a sandblasted aluminum substrate, flash-coating at 100–150°C for 5–10 minutes, followed by an overcoating with a siloxane topcoat formulation, as reported in the examples below. The coated parts were cured at 300°C for 20 minutes. The dry coating compositions are shown in Table 11.

[0299] Table 11

[0300]

[0301]

[0302] Example 7: Hydrogenated Silanized Outer Coating

[0303] Representative compositions suitable for forming external coatings through a hydrosilanization reaction between hydrosiloxane and vinylsiloxane moieties are shown in Table 12 below. The compositions are mixed in a container until homogeneous, and then applied directly and rapidly to a metal substrate or a primer of varying chemical composition via air-mixing spraying. After application, the compositions are dried at 100-150°C for 5-10 minutes and cured at 300°C for 20 minutes.

[0304] Table 12

[0305]

[0306]

[0307] The dry coating composition is expected to be substantially unchanged from the wet coating composition reported in the error! Reference source 2 was not found because all components are non-volatile. The degree of crosslinking in the coating is between 50% and 60%.

[0308] The films obtained from the compositions in Table 12 were characterized by high hydrophobicity, good non-stick properties for non-stick foods, and low hardness.

[0309] Example 8: Dehydrogenation Coupling External Coating

[0310] Representative compositions suitable for forming external coatings via the dehydrogenation coupling reaction between hydrosiloxane and hydroxysiloxane moieties are shown in Table 13 below. The compositions are mixed in a container until homogeneous, and then applied directly and rapidly to a metal substrate or a primer of varying chemical composition via air-mixing spraying. After application, the compositions are dried at 100-150°C for 5-10 minutes and cured at 300°C for 20 minutes.

[0311] Table 13

[0312]

[0313] The dry coating composition is expected to be substantially the same as the wet coating composition reported in Table 13, as all components are non-volatile. The degree of crosslinking in the coating is between 50% and 60%.

[0314] The films obtained from the compositions in Table 13 were characterized by high hydrophobicity, good non-stick properties for non-stick foods, and low hardness.

[0315] Example 9: Polycondensation outer coating

[0316] Representative compositions suitable for forming external coatings through polycondensation reactions between hydroxysiloxane or alkoxysiloxane moieties are shown in Table 14 below. The compositions are mixed in a container until homogeneous, and then applied directly and rapidly to a metal substrate or a primer of varying chemical composition via air-mixing spraying. After application, the compositions are dried at 100-150°C for 5-10 minutes and cured at 300°C for 20 minutes.

[0317] Table 14

[0318]

[0319] Example 10: Abrasion and scratch resistance of silicone elastomer undercoating

[0320] The abrasion resistance of the coating described above is tested using a reciprocating abrasion test (RAT). The motion performed by the RAT machine simulates the abrasion experienced during cleaning with a household scrubbing pad. RAT machines typically have variable settings for speed and application load. The grade is the number of cycles that the coating remains intact until 10% of the substrate is exposed; 1 cycle = 2 strokes.

[0321] The scratch resistance of the coating was further tested using the HFT (Happiness Flower) scratch adhesion test. The test was conducted using a pen tip fixed to a balance arm calibrated with a specific weight, in which the article was placed on a rotating heated turntable (150°C, oil-filled). After two hours, the test was stopped, and the results were scored according to the degree of surface damage. Results were categorized as follows: 10: No effect; 9: No abrasion; 8: Minimal abrasion; 7: Some abrasion; 6: Minor damage; 5: Moderate damage; 4: Quite significant damage; 3: Severe damage; 2: Extensive damage; 1: General failure; 0: Utter failure.

[0322] Test the scratch and abrasion resistance of the formulations shown in Table 15 below. As described in the example above, base coat 9 is a silicon base coat without reinforcing particles, while base coat 10, as described in the example above, contains silicon carbide reinforcing particles.

[0323] Table 15

[0324]

[0325] Figure 2A Images of the coating from Test 1 after scratch adhesion are shown, and Figure 2B An image of the cross-section of the same coating after testing is shown. Figure 3A Images of the coating in Test 2 after scratch adhesion are shown, and Figure 2B Images of the same coating after testing are shown. These tests demonstrate the extreme mechanical weaknesses of a system based solely on the chemistry of silicone elastomers. The coating is easily peeled off the substrate and can be easily polished with an abrasive pad. Figure 3B The cross-section shows large reinforcing particles across the coating, but the weakness of the undercoat renders it almost ineffective in providing mechanical toughening, and the gain in wear cycles is negligible.

[0326] Example 11: Abrasion and scratch resistance of sol-gel undercoat

[0327] Using the tests described in the examples above, the abrasion and scratch resistance of the formulations shown in Table 16 below were tested. In the cases without reinforcing particles and with different reinforcing particles, a sol-gel undercoat was used, as described in the examples above. In each case, the outer coating was a siloxane film formed by dehydrogenation coupling, as described in the examples above.

[0328] Table 16

[0329]

[0330] Figure 4A and 4B Images and cross-sections of the coating from Test 3 are shown. Figure 5A and 5B Images and cross-sections of the coating from Test 4 are shown. Figure 6A and 6B Images and cross-sections of the coating from Test 5 are shown. Figure 7A and 7B Images and cross-sections of the coating from Test 6 are shown.

[0331] As can be seen from both Table 16 and the figures mentioned above, these coatings demonstrate a significant improvement in imparting mechanical resistance to the system when using sol-gel undercoats. In particular, abrasion resistance is improved by two and three orders of magnitude compared to the examples above using silicone elastomer undercoats.

[0332] Compared to the silicone elastomer base coat, the scratch resistance of the coating was also improved. Specifically, the presence of the coating was observed on up to 84% of the test surfaces.

[0333] It is noteworthy that, based on RAT data, tests 5 and 6 show significantly superior abrasion resistance compared to the coatings in tests 3 and 4. This performance improvement can be attributed to the increased hardness of the reinforcing particles in tests 5 and 6, which in turn contributes to the overall hardness of the coating system. The coating in test 3 did not contain reinforcing particles. The muscovite reinforcing particles in test 4 have a Mohs hardness of approximately 2.5, while the wollastonite reinforcing particles in test 5 have a Mohs hardness of 6, and the silicon carbide reinforcing particles in test 6 have a Mohs hardness of 9. Therefore, it appears that reinforcing particles with a Mohs hardness greater than 4 can significantly increase the abrasion resistance of the coating system.

[0334] Example 12: Abrasion and scratch resistance of polyethersulfone / polyamide-imide undercoating

[0335] The abrasion and scratch resistance of the formulations shown in Table 17 were tested using the tests described in the examples above. The formulations used an organic polymer undercoat as described in the examples above. As shown in Table 17, the outer coating was a siloxane film formed by dehydrogenation coupling or hydrogenation silanization.

[0336] Table 17

[0337]

[0338] Figure 8A and 8B Images and cross-sections of the coating from Test 7 are shown, respectively, showing the scratch adhesion. Figure 9A and 9B Images and cross-sections of the coating from Test 8 are shown. Figure 10A and 10B Images and cross-sections of the coating from test 9 are shown.

[0339] This set of experiments demonstrates the synergistic effect of reinforcing particles and a tougher primer based on the aPAI / PES polymer composition. Although the composition in Test 7 showed an increase in the system's scratch resistance, the absence of hard reinforcing particles in the composition provided only a negligible benefit to overall abrasion resistance. Tests 8 and 9, in which the primer layer contained silicon carbide reinforcing particles (Mohs hardness 9), collaborated with the tough primer composition to produce a structure that reinforced the entire system and made it abrasion and scratch resistant.

[0340] Surprisingly, particle size did not appear to significantly affect abrasion resistance; relatively small reinforcing particles provided the same improvement as larger particles. However, there was a clear synergistic effect between the hardness of the reinforcing particles and the hardness of the polymer, resulting in abrasion resistance cycles increasing from 9 to 140 per micrometer when silicon carbide was introduced into the system.

[0341] Example 13: Comparison of the abrasion resistance and scratch resistance of various primer coatings

[0342] Using the tests described in the examples above, the abrasion and scratch resistance of the formulations shown in Table 18 were tested. In each case, the outer coating was a siloxane film formed by hydrogenation silanization. The same type and amount of reinforcing particles were used in each test. The undercoat composition was different for each test; the formulation used the silicone resin, polyethersulfone, or silicone elastomer described in the examples above.

[0343] Table 18

[0344]

[0345] Figure 11A and 11BScratch adhesion images and cross-sections of the coating in Test 10 are shown. Figure 12A and 12B Scratch adhesion images and cross-sections of the coating in Test 11 are shown. Figure 13 A cross-section of the coating in test 12 is shown. Figure 14A and 14B Scratch adhesion images and cross-sections of the coating in test 13 are shown. Figure 15A and 15B Scratch adhesion images and cross-sections of the coating in test 14 are shown.

[0346] Example 14: Nano-indentation hardness of various primer coatings

[0347] The nanoindentation hardness of the coating compositions in tests 10-14 (as described above) was tested using the parameters described in Table 19 below.

[0348] Table 19

[0349] Instrument PB1000 unit micro-module Feeding speed micrometers per minute 50 Contact load mN 10 Target load N 0.1 Load rate Newtons per minute 0.2 Non-load rate Newtons per minute 0.2 pressure head --- Vickers hardness tester Material --- diamond

[0350] The test results are shown in Table 20 below.

[0351] Table 20

[0352]

[0353] Example 15: Outer coating prepared by hydrosilylation reaction .

[0354] In this example, an outer coating was prepared from the components listed in Table 21 below to demonstrate the synergistic effect of aspect ratio co-adhesives such as VQ resin and inorganic fillers on the mechanical properties of a silicone elastomer outer coating prepared by a hydrosilylation reaction between a linear vinyl-terminated polydimethylsiloxane and a polydimethylsiloxane containing hydride groups, catalyzed by an Ashby catalyst.

[0355] The components were blended until homogeneous through high-speed dispersion, and the resulting composition was then sprayed onto a metal substrate made of aluminum 3003 alloy on the same day of preparation. The composition was then cured in a box oven at 300°C for 20 minutes. The composition and test results are shown in Tables 21A and 21B below.

[0356] Table 21A

[0357]

[0358]

[0359] Table 21B

[0360]

[0361]

[0362] The above results also Figure 17 As shown in the image.

[0363] Martens hardness (GPa) was determined according to DIN ISO 14577 1-3 and using the parameters reported in Table 19 of this document.

[0364] The normalized maximum force (N) for releasing a whole egg was determined using a Nanovea PB1000 mechanical testing instrument. Specifically, prior to analysis, 0.4 g of freshly beaten eggs were cooked on a coated surface at 120°C for 5 minutes, followed by cooking in a ventilated oven at 200°C for 10 minutes. Afterward, a stainless steel probe was inserted through the food adhering to the coated surface at a speed of 60 mm / s while applying a force of 5 N over a length of 25 mm. During its passage, the beaten egg was removed, and the frictional force curve was recorded. The normalized maximum release force corresponds to the recorded maximum frictional force.

[0365] Adhesive work of whole egg (J / m) 2 The adhesion work is determined mathematically from the friction curve. Specifically, before the probe contacts the beaten egg, a baseline friction force is first calculated within a probe travel range of 1-4 mm. This baseline is then subtracted from each subsequent friction force value to obtain a normalized friction curve. The adhesion work is then calculated by averaging the values ​​of two subsequent friction force values ​​and multiplying the result by the corresponding δ value. The sum of the adhesion work values ​​is finally divided by the area of ​​the Teflon containing the beaten egg to obtain the specific adhesion work.

[0366] Comparative Examples 1, 2, and 4 show that mechanical properties gradually decrease as the vinyl chain extends from 1000 cSt to 10000 cSt. Similarly, Examples 1 and 2 show that the films applied to the aluminum substrate lack film integrity and exhibit significant stress cracking.

[0367] Comparative Example 3 shows a strong gain in mechanical properties provided by another crosslinking agent such as VDT 731, but at the cost of an equally large increase in the effort required to remove food stains.

[0368] Example 5 shows that when wollastonite filler is introduced into a linear mixture of vinyl PDMS with 10,000 cSt, only a negligible gain in mechanical properties is obtained.

[0369] Example 1 illustrates the beneficial effects of introducing VQ resin into the system on hardness and scratch resistance without affecting non-stick properties.

[0370] Examples 2 and 3 illustrate the synergistic effect of wollastonite, a filler with a needle-like aspect ratio, which increases the scratch resistance and indentation hardness of the resulting coating.

[0371] Examples 4, 5, and 6 demonstrate that inorganic fillers with different aspect ratios, namely different grades of wollastonite and muscovite, provide considerable enhancements in mechanical properties without affecting non-stick properties. Comparative Example 6 shows that although silicon carbide filler has a greater specific hardness compared to wollastonite or muscovite, it does not contribute positively to the increase in mechanical properties compared to the control, possibly due to the absence of aspect ratio.

[0372] Example 8 shows that reducing the amount of VQ resin in the formulation to less than 0.5% without affecting non-stickiness still largely preserves the mechanical properties of the blend.

[0373] Example 9 shows that different grades of VQ resin, namely BRB MQ339 polymer supplied by BRB silicone, have properties almost as good as VQ20 supplied by Gelest. Example 10 shows that when the amount of VQ20 is set at 10%, increased hardness is also obtained without loss of non-stickiness.

[0374] When the coating is applied at a dry film thickness of 50 μm, all the examples mentioned above demonstrate an optical transparency of at least 50% transmittance at a wavelength of 550 nm.

[0375] Example 16: Coating consisting of a base coat and an outer coat

[0376] Prepared via hydrosilylation reaction .

[0377] A complete coating system is obtained by combining the primer layer of composition 13 in Table 8 with the outer coating layer of invention 3 in Table 21B. The primer layer is applied by spraying onto a metal substrate such as an aluminum alloy or stainless steel alloy. The primer layer is rapidly dried at a temperature of 80-120°C for 2-10 minutes, followed by spraying the outer coating layer onto the dried primer layer. After applying the outer coating layer, the part is gradually heated to 300°C and cured at that temperature for 20 minutes. The resulting multilayer coating system exhibits superior mechanical properties as well as good non-stick and optical properties.

[0378] Specific examples of the invention have been described above for illustrative purposes; however, it will be apparent to those skilled in the art that many detailed changes can be made to the invention without departing from the invention as defined in the appended claims. Therefore, this application is intended to cover any variations, uses, or adaptations of this disclosure using its general principles. Furthermore, this application is intended to cover any such departures from this disclosure within the known or conventional practice in the field to which this disclosure pertains, and which fall within the limitations of the appended claims.

[0379] aspect

[0380] One aspect 1 is a coated article comprising: a substrate having a surface; and a coating disposed on the surface, the coating comprising: a primer having at least one of the following: a martensitic hardness of 0.2 GPa or higher as determined by nanoindentation according to DIN ISO 14577 1-3; and

[0381] If the elastic modulus is 5 GPa or higher as determined by DIN ISO 14577 1-3, the undercoat comprises at least one of the following: (i) a sol-gel matrix formed from at least one siloxane of formula (I):

[0382] R x Si(OR') 4-x (I)

[0383] Wherein R is one or more moieties independently selected from linear, branched, or cyclic alkyl and aryl groups; R' is methyl, ethyl, propyl, or alkyl; and x is 0, 1, 2, or 3; (ii) an organic polymer having at least one of the following: a melting point of 200°C or higher as determined by differential scanning calorimetry (DSC); a glass transition temperature of 90°C or higher as determined by differential scanning calorimetry (DSC); and a thermal flexure / deformation temperature of 100°C or higher as determined by ASTM D648; and (iii) a silicone resin, wherein the base coating comprises at least one type of reinforcing particles, wherein the at least one type of reinforcing particles has a Knoop hardness of at least 160 kg / m² as determined by ASTM C1326. 2 ; and an outer coating layer disposed on the base coating layer and comprising a siloxane-based material, wherein the martensitic hardness of the outer coating layer is less than that of the base coating layer.

[0384] Aspect 2 is a coated article according to aspect 1, wherein the organic polymer comprises at least one of the following: polyphenylene sulfide (PPS), polyethersulfone (PES), polyetheretherketone (PEEK), polyphenylene sulfone (PPSU), polyamide imide (PAI), polyetherimide (PEI), polyimide (PI), and combinations thereof.

[0385] Aspect 3 is the coated article according to aspect 1 or aspect 2, wherein, as determined by scanning electron microscopy (SEM) analysis, the average particle size (D50) of the reinforcing particles is from 5 micrometers to 100 micrometers.

[0386] Aspect 4 is a coated article according to any one of Aspects 1 to 3, wherein the reinforcing particles are present in an amount of 3 wt.% to 10 wt.% based on the total weight of the base coating.

[0387] Aspect 5 is a coated article according to any one of Aspects 1 to 4, wherein the number of reinforcing particles present in the base coating is at least 3 per 1 cm of the transverse cross-section of the base coating.

[0388] Aspect 6 is a coated article according to any one of Aspects 1 to 5, wherein the outer coating comprises a siloxane, and the siloxane has a martensitic hardness of less than 0.2 GPa as determined by nanoindentation according to DIN ISO 14577 1-3.

[0389] Aspect 7 is a coated article according to any one of aspects 1 to 6, wherein the outer coating comprises a siloxane-based material formed from at least one siloxane.

[0390] Aspect 8 is a coated article according to any one of Aspects 1 to 7, wherein the siloxane is formed from at least one of the following: a hydrosilylation reaction between a siloxane and at least one of a hydride-substituted organosiloxane and a vinyl-substituted organosiloxane; a dehydrogenation coupling reaction between a hydride-substituted organosiloxane and a hydroxyl-substituted organosiloxane; a polycondensation reaction between two hydroxyl-substituted organosiloxanes; a polycondensation reaction between an alkoxy-substituted organosiloxane and a hydroxyl-substituted organosiloxane; or a polycondensation reaction between an acetoxy-substituted organosiloxane and a hydroxyl-substituted organosiloxane.

[0391] Aspect 9 is a coated article according to any one of Aspects 1 to 8, wherein the coating comprises less than 0.1 wt.% of a fluoropolymer based on the total weight of the coating.

[0392] Aspect 10 is a coating system comprising: a base coating composition comprising at least one of the following: (i) at least one siloxane of formula (I).

[0393] R x Si(OR') 4-x (I)

[0394] Wherein R is one or more moieties independently selected from linear, branched, or cyclic alkyl and aryl groups; R' is methyl, ethyl, propyl, or alkyl; and x is 0, 1, 2, or 3; and (ii) an organic polymer having at least one of the following: a melting point of 200°C or higher as determined by differential scanning calorimetry (DSC); a glass transition temperature of 90°C or higher as determined by differential scanning calorimetry (DSC); and a thermal flexural / deformation temperature of 100°C or higher as determined by ASTM D648; and (iii) a silicone resin; and at least one type of reinforcing particles having a Knoop hardness of 160 kg / m as determined by ASTM C1326. 2 The average particle size (D50) of the reinforcing particles is 5 micrometers to 100 micrometers, as determined by dynamic light scattering; and the outer coating composition comprises at least one organosiloxane and at least one catalyst.

[0395] Aspect 11 is a coating system according to aspect 10, wherein the organic polymer comprises at least one of the following: polyphenylene sulfide (PPS), polyethersulfone (PES), polyetheretherketone (PEEK), polyphenylene sulfone (PPSU), polyamide-imide (PAI), polyetherimide (PEI), polyimide (PI), and combinations thereof.

[0396] Aspect 12 is a coating system according to aspect 10 or aspect 11, wherein the at least one type of reinforcing particles are present in an amount of 3 wt.% to 10 wt.% based on the total weight of the base coating composition.

[0397] Aspect 13 is a coating system according to any one of Aspects 10 to 12, wherein the Knoop hardness of the at least one type of reinforcing particles, as determined by ASTM C1326, is at least 160 kg / m. 2 .

[0398] Aspect 14 is a coating system according to any one of aspects 10 to 13, wherein the outer coating composition further comprises at least one of the following: an organosiloxane and at least one of the following: hydride-substituted organosiloxanes, vinyl-substituted organosiloxanes, acetoxy-substituted organosiloxanes, hydroxyl-substituted organosiloxanes and alkoxy-substituted organosiloxanes; hydride-substituted organosiloxanes and hydroxyl-substituted organosiloxanes; and at least one of hydroxyl-substituted organosiloxanes, acetoxy-substituted organosiloxanes and alkoxy-substituted organosiloxanes.

[0399] Aspect 15 is a coating system according to any one of Aspects 10 to 14, wherein the catalyst comprises tin, titanium, platinum, palladium, ruthenium, gold, copper, zinc or zirconium.

[0400] Aspect 16 is a coating system according to any one of aspects 10 to 15, wherein the catalyst comprises an organic peroxide.

[0401] Aspect 17 is a coating system according to any one of aspects 10 to 16, wherein the catalyst comprises a protic acid, a Lewis acid, or a base.

[0402] Aspect 18 is a coating system according to any one of Aspects 10 to 17, wherein the coating system comprises less than 0.1 wt.% of a fluoropolymer based on the total weight of the base coating composition and the outer coating composition.

[0403] Aspect 19 is a coated article according to any one of aspects 1 to 9, wherein the base coating comprises a sol-gel matrix formed of at least one siloxane of formula (I).

[0404] R x Si(OR') 4-x (I)

[0405] Where R is one or more moieties independently selected from straight-chain, branched, or cyclic alkyl and aryl groups; R' is methyl, ethyl, propyl, or alkyl; and x is 0, 1, 2, or 3.

[0406] Aspect 20 is a coated article according to any one of Aspects 1 to 9, wherein the base coating comprises an organic polymer having at least one of the following: a melting point of 200°C or higher as determined by differential scanning calorimetry (DSC); a glass transition temperature of 90°C or higher as determined by differential scanning calorimetry (DSC); and a thermal flexural / deformation temperature of 100°C or higher as determined by ASTM D648.

[0407] Aspect 21 is a coated article according to any one of aspects 1 to 9 or aspect 20, wherein the base coating comprises an organic polymer having a melting point of 200°C or higher, as determined by differential scanning calorimetry (DSC).

[0408] Aspect 22 is a coated article according to any one of aspects 1 to 9 or aspect 20, wherein the base coating comprises an organic polymer having a glass transition temperature of 90°C or higher, as determined by differential scanning calorimetry (DSC).

[0409] Aspect 23 is a coated article according to any one of aspects 1 to 9 or aspect 20, wherein the base coating comprises an organic polymer having a thermal flexural / deformation temperature of 100°C or higher as determined by ASTM D648.

[0410] Aspect 24 is a coated article according to any one of aspects 1 to 9 or aspect 20, wherein the base coating comprises an organic polymer having a melting point of 200°C or higher as determined by differential scanning calorimetry (DSC) and a glass transition temperature of 90°C or higher as determined by differential scanning calorimetry (DSC).

[0411] Aspect 25 is a coated article according to any one of aspects 1 to 9 or aspect 20, wherein the base coating comprises an organic polymer having a melting point of 200°C or higher as determined by differential scanning calorimetry (DSC) and a thermal flexural / deformation temperature of 100°C or higher as determined by ASTM D648.

[0412] Aspect 26 is a coated article according to any one of aspects 1 to 9 or aspect 20, wherein the base coating comprises an organic polymer having a glass transition temperature of 90°C or higher as determined by differential scanning calorimetry (DSC) and a thermal flexural / deformation temperature of 100°C or higher as determined by ASTM D648.

[0413] Aspect 27 is a coated article according to any one of aspects 1 to 9 or aspect 20, wherein the base coating comprises an organic polymer having a melting point of 200°C or higher as determined by differential scanning calorimetry (DSC), a glass transition temperature of 90°C or higher as determined by differential scanning calorimetry (DSC), and a thermal flexural / deformation temperature of 100°C or higher as determined by ASTM D648.

[0414] Aspect 28 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 27, wherein the organic polymer comprises at least one of the following: polyphenylene sulfide (PPS), polyethersulfone (PES), polyether ether ketone (PEEK), polyphenylene sulfone (PPSU), polyamide imide (PAI), polyether imide (PEI), polyimide (PI), and combinations thereof.

[0415] Aspect 29 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 28, wherein the organic polymer comprises polyphenylene sulfide (PPS).

[0416] Aspect 30 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 28, wherein the organic polymer comprises polyethersulfone (PES).

[0417] Aspect 31 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 28, wherein the organic polymer comprises polyether ether ketone (PEEK).

[0418] Aspect 32 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 28, wherein the organic polymer comprises polyphenylsulfone (PPSU).

[0419] Aspect 33 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 28, wherein the organic polymer comprises polyamide-imide (PAI).

[0420] Aspect 34 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 28, wherein the organic polymer comprises polyetherimide (PEI).

[0421] Aspect 35 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 28, wherein the organic polymer comprises polyimide (PI).

[0422] Aspect 36 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 28, wherein the organic polymer comprises polyphenylene sulfide (PPS) and polyethersulfone (PES).

[0423] Aspect 37 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 28, wherein the organic polymer comprises polyphenylene sulfide (PPS) and polyether ether ketone (PEEK).

[0424] Aspect 38 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 28, wherein the organic polymer comprises polyphenylene sulfide (PPS) and polyphenylene sulfone (PPSU).

[0425] Aspect 39 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 28, wherein the organic polymer comprises polyphenylene sulfide (PPS) and polyamide imide (PAI).

[0426] Aspect 40 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 28, wherein the organic polymer comprises polyphenylene sulfide (PPS) and polyetherimide (PEI).

[0427] Aspect 41 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 28, wherein the organic polymer comprises polyphenylene sulfide (PPS) and polyimide (PI).

[0428] Aspect 42 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 28, wherein the organic polymer comprises polyethersulfone (PES) and polyetheretherketone (PEEK).

[0429] Aspect 43 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 28, wherein the organic polymer comprises polyethersulfone (PES) and polyphenylsulfone (PPSU).

[0430] Aspect 44 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 28, wherein the organic polymer comprises polyethersulfone (PES) and polyamide-imide (PAI).

[0431] Aspect 45 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 28, wherein the organic polymer comprises polyethersulfone (PES) and polyetherimide (PEI).

[0432] Aspect 46 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 28, wherein the organic polymer comprises polyethersulfone (PES) and polyimide (PI).

[0433] Aspect 47 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 27, wherein the organic polymer comprises polyetheretherketone (PEEK) and polyphenylsulfone (PPSU).

[0434] Aspect 48 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 27, wherein the organic polymer comprises polyether ether ketone (PEEK) and polyamide imide (PAI).

[0435] Aspect 49 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 27, wherein the organic polymer comprises polyether ether ketone (PEEK) and polyether imide (PEI).

[0436] Aspect 50 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 27, wherein the organic polymer comprises polyether ether ketone (PEEK) and polyimide (PI).

[0437] Aspect 51 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 27, wherein the organic polymer comprises polyphenylsulfone (PPSU) and polyamide-imide (PAI).

[0438] Aspect 52 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 27, wherein the organic polymer comprises polyphenylsulfone (PPSU) and polyetherimide (PEI).

[0439] Aspect 53 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 27, wherein the organic polymer comprises polyphenylsulfone (PPSU) and polyimide (PI).

[0440] Aspect 54 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 27, wherein the organic polymer comprises polyamide-imide (PAI) and polyether-imide (PEI).

[0441] Aspect 55 is a coated article according to any one of aspects 1 to 9 or aspects 20 to 27, wherein the organic polymer comprises polyamide-imide (PAI) and polyimide (PI).

[0442] Aspect 56 is a coated article according to any one of Aspects 1 to 9, wherein the base coating comprises a silicone resin containing at least one type of Knoop hardness of at least 160 kg / m as determined by ASTM C1326. 2 The base coating having reinforcing particles; and an outer coating having the outer coating disposed on the base coating and comprising a siloxane material, the outer coating having a martensitic hardness less than that of the base coating.

[0443] Aspect 57 is a coated article according to any one of aspects 1 to 9 or aspects 19 to 56, wherein the outer coating comprises a siloxane material formed by a hydrosilylation reaction between a siloxane and at least one of a hydride-substituted organosiloxane and a vinyl-substituted organosiloxane.

[0444] Aspect 58 is a coated article according to any one of aspects 1 to 9 or aspects 19 to 56, wherein the outer coating comprises a siloxane material formed by a dehydrogenation coupling reaction between a hydride-substituted organosiloxane and a hydroxyl-substituted organosiloxane.

[0445] Aspect 59 is a coated article according to any one of aspects 1 to 9 or aspects 19 to 56, wherein the outer coating comprises a siloxane material formed by a polycondensation reaction between two hydroxyl-substituted organosiloxanes.

[0446] Aspect 60 is a coated article according to any one of aspects 1 to 9 or aspects 19 to 56, wherein the outer coating comprises a siloxane material formed by a polycondensation reaction between an alkoxy-substituted organosiloxane and a hydroxy-substituted organosiloxane.

[0447] Aspect 61 is a coated article according to any one of aspects 1 to 9 or aspects 19 to 56, wherein the outer coating comprises a siloxane material formed by a polycondensation reaction between an acetoxy-substituted organosiloxane and a hydroxy-substituted organosiloxane.

[0448] Aspect 62 is a coated article according to any one of aspects 19 to 61, wherein the coating comprises less than 0.1 wt.% of a fluoropolymer based on the total weight of the coating.

[0449] Aspect 63 is a coating system according to any one of aspects 10 to 18, wherein the base coating comprises a siloxane of formula (I).

[0450] R x Si(OR') 4-x (I)

[0451] Where R is one or more moieties independently selected from straight-chain, branched, or cyclic alkyl and aryl groups; R' is methyl, ethyl, propyl, or alkyl; and x is 0, 1, 2, or 3.

[0452] Aspect 64 is a coating system according to any one of Aspects 10 to 18, wherein the base coating comprises an organic polymer having at least one of the following: a melting point of 200°C or higher as determined by differential scanning calorimetry (DSC); a glass transition temperature of 90°C or higher as determined by differential scanning calorimetry (DSC); and a thermal flexural / deformation temperature of 100°C or higher as determined by ASTM D648.

[0453] Aspect 65 is a coating system according to any one of aspects 10 to 18 or aspect 64, wherein the base coating comprises an organic polymer having a melting point of 200°C or higher, as determined by differential scanning calorimetry (DSC).

[0454] Aspect 66 is a coating system according to any one of aspects 10 to 18 or aspect 64, wherein the base coating comprises an organic polymer having a glass transition temperature of 90°C or higher, as determined by differential scanning calorimetry (DSC).

[0455] Aspect 67 is a coating system according to any one of aspects 10 to 18 or aspect 64, wherein the base coating comprises an organic polymer having a thermal flexural / deformation temperature of 100°C or higher as determined by ASTM D648.

[0456] Aspect 68 is a coating system according to any one of aspects 10 to 18 or aspect 64, wherein the base coating comprises an organic polymer having a melting point of 200°C or higher as determined by differential scanning calorimetry (DSC) and a glass transition temperature of 90°C or higher as determined by differential scanning calorimetry (DSC).

[0457] Aspect 69 is a coating system according to any one of aspects 10 to 18 or aspect 64, wherein the base coating comprises an organic polymer having a melting point of 200°C or higher as determined by differential scanning calorimetry (DSC) and a thermal flexural / deformation temperature of 100°C or higher as determined by ASTM D648.

[0458] Aspect 70 is a coating system according to any one of aspects 10 to 18 or aspect 64, wherein the base coating comprises an organic polymer having a glass transition temperature of 90°C or higher as determined by differential scanning calorimetry (DSC) and a thermal flexural / deformation temperature of 100°C or higher as determined by ASTM D648.

[0459] Aspect 71 is a coating system according to any one of aspects 10 to 18 or aspect 64, wherein the base coating comprises an organic polymer having a melting point of 200°C or higher as determined by differential scanning calorimetry (DSC), a glass transition temperature of 90°C or higher as determined by differential scanning calorimetry (DSC), and a thermal flexural / deformation temperature of 100°C or higher as determined by ASTM D648.

[0460] Aspect 72 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises at least one of the following: polyphenylene sulfide (PPS), polyethersulfone (PES), polyether ether ketone (PEEK), polyphenylene sulfone (PPSU), polyamide imide (PAI), polyether imide (PEI), polyimide (PI), and combinations thereof.

[0461] Aspect 73 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyphenylene sulfide (PPS).

[0462] Aspect 74 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyethersulfone (PES).

[0463] Aspect 75 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyetheretherketone (PEEK).

[0464] Aspect 76 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyphenylsulfone (PPSU).

[0465] Aspect 77 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyamide-imide (PAI).

[0466] Aspect 78 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyetherimide (PEI).

[0467] Aspect 79 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyimide (PI).

[0468] Aspect 80 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyphenylene sulfide (PPS) and polyethersulfone (PES).

[0469] Aspect 81 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyphenylene sulfide (PPS) and polyether ether ketone (PEEK).

[0470] Aspect 82 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyphenylene sulfide (PPS) and polyphenylene sulfone (PPSU).

[0471] Aspect 83 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyphenylene sulfide (PPS) and polyamide imide (PAI).

[0472] Aspect 84 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyphenylene sulfide (PPS) and polyetherimide (PEI).

[0473] Aspect 85 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyphenylene sulfide (PPS) and polyimide (PI).

[0474] Aspect 86 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyethersulfone (PES) and polyetheretherketone (PEEK).

[0475] Aspect 87 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyethersulfone (PES) and polyphenylsulfone (PPSU).

[0476] Aspect 88 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyethersulfone (PES) and polyamide-imide (PAI).

[0477] Aspect 89 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyethersulfone (PES) and polyetherimide (PEI).

[0478] Aspect 90 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyethersulfone (PES) and polyimide (PI).

[0479] Aspect 91 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyetheretherketone (PEEK) and polyphenylsulfone (PPSU).

[0480] Aspect 92 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyether ether ketone (PEEK) and polyamide imide (PAI).

[0481] Aspect 93 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyether ether ketone (PEEK) and polyether imide (PEI).

[0482] Aspect 94 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyetheretherketone (PEEK) and polyimide (PI).

[0483] Aspect 95 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyphenylsulfone (PPSU) and polyamide-imide (PAI).

[0484] Aspect 96 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyphenylsulfone (PPSU) and polyetherimide (PEI).

[0485] Aspect 97 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyphenylsulfone (PPSU) and polyimide (PI).

[0486] Aspect 98 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyamide-imide (PAI) and polyether-imide (PEI).

[0487] Aspect 99 is a coating system according to any one of aspects 10 to 18 or aspects 64 to 71, wherein the organic polymer comprises polyamide-imide (PAI) and polyimide (PI).

[0488] Aspect 100 is a coating system according to any one of Aspects 10 to 18, wherein the base coat comprises a silicone resin having a Knoop hardness of at least 160 kg / m as determined by ASTM C1326.2 The base coating of reinforcing particles; and the outer coating disposed on the base coating and comprising an organosiloxane.

[0489] Aspect 101 is a coating system according to any one of aspects 10 to 18 or aspects 63 to 100, wherein the outer coating is formed by a hydrosilylation reaction between a siloxane and at least one of a hydride-substituted organosiloxane and a vinyl-substituted organosiloxane.

[0490] Aspect 102 is a coating system according to any one of aspects 10 to 18 or aspects 63 to 100, wherein the outer coating is formed by a dehydrogenation coupling reaction between a hydride-substituted organosiloxane and a hydroxyl-substituted organosiloxane.

[0491] Aspect 103 is a coating system according to any one of aspects 10 to 18 or aspects 63 to 100, wherein the outer coating is formed by a polycondensation reaction between two hydroxyl-substituted organosiloxanes.

[0492] Aspect 104 is a coating system according to any one of aspects 10 to 18 or aspects 63 to 100, wherein the outer coating is formed by a polycondensation reaction between an alkoxy-substituted organosiloxane and a hydroxy-substituted organosiloxane.

[0493] Aspect 105 is a coating system according to any one of aspects 10 to 18 or aspects 63 to 100, wherein the outer coating is formed by a polycondensation reaction between an acetoxy-substituted organosiloxane and a hydroxy-substituted organosiloxane.

[0494] Aspect 106 is a coating system according to any one of aspects 63 to 105, wherein the coating system comprises less than 0.1 wt.% of a fluoropolymer based on the total weight of the base coating composition and the outer coating composition.

[0495] Aspect 107 is a coated article according to any one of aspects 1 to 9, wherein the base coating comprises a sol-gel matrix and an organic polymer according to any one of aspects 20 to 55.

[0496] Aspect 108 is a coated article according to any one of aspects 1 to 9, wherein the base coating comprises a sol-gel matrix and a silicone resin.

[0497] Aspect 109 is a coated article according to any one of aspects 1 to 9, wherein the base coating comprises a silicone resin and an organic polymer according to any one of aspects 20 to 55.

[0498] Aspect 110 is a coating system according to any one of aspects 10 to 18, wherein the base coating comprises a sol-gel matrix and an organic polymer according to any one of aspects 64 to 99.

[0499] Aspect 111 is a coating system according to any one of aspects 10 to 18, wherein the base coating comprises a sol-gel matrix and a silicone resin.

[0500] Aspect 112 is a coating system according to any one of aspects 10 to 18, wherein the base coating comprises a silicone resin or an organic polymer according to any one of aspects 64 to 99.

[0501] Aspect 113 is a coated article according to any one of aspects 1 to 63 or a coating system according to any one of aspects 64 to 112, wherein the outer coating composition comprises: a vinyl-terminated polydimethylsiloxane; a polydimethylsiloxane containing hydride groups; a co-binder containing vinyl Q resin; and filler particles having a length-to-width ratio of at least 3:1.

[0502] Aspect 114 is a coating composition comprising a vinyl-terminated polydimethylsiloxane; a polydimethylsiloxane containing hydride groups; a co-binder containing vinyl Q resin; and filler particles having a length-to-width ratio of at least 3:1.

[0503] Aspect 115 is the coating system according to aspect 114, wherein the viscosity of the vinyl-terminated polydimethylsiloxane is 1,000 cSt and 50,000 cSt, as determined by ASTM D445-21e1.

[0504] Aspect 116 is a coating system according to aspect 114 or aspect 115, wherein the polydimethylsiloxane containing hydride groups has 30 mol% to 50 mol% hydride groups.

[0505] Aspect 117 is a coated article comprising: a substrate having a surface; and a coating disposed on the surface, the coating comprising a base coat having at least one of the following: a martensitic hardness of 0.2 GPa or higher as determined by nanoindentation according to DIN ISO 14577 1-3; and an elastic modulus of 5 GPa or higher as determined by DIN ISO 14577 1-3; and the base coat comprising at least one of a sol-gel matrix, an organic polymer, and a silicone resin, the base coat containing reinforcing particles having a Knoop hardness of at least 160 kg / m² as determined by ASTM C1326. 2; and an outer coating layer disposed on the base coating layer and comprising a siloxane compound, the outer coating layer having a Marlowan hardness less than that of the base coating layer, and further comprising: a vinyl-terminated polydimethylsiloxane; a polydimethylsiloxane containing hydride groups; a co-binder containing vinyl Q resin; and filler particles having a length-to-width ratio of at least 3:1.

[0506] Aspect 118 is the coating system according to aspect 117, wherein the viscosity of the vinyl-terminated polydimethylsiloxane is 1,000 cSt and 50,000 cSt, as determined by ASTM D445-21e1.

[0507] Aspect 119 is a coating system according to aspect 117 or aspect 118, wherein the polydimethylsiloxane containing hydride groups has 30 mol% to 50 mol% hydride groups.

[0508] Aspect 120 is a coated article according to any one of aspects 117 to 119, wherein the outer coating further comprises at least one of the following: the vinyl-terminated polydimethylsiloxane is present in an amount of 40 wt.% to 60 wt.% based on the total solid weight of the coating; the polydimethylsiloxane containing hydride groups is present in an amount of 25 wt.% to 40 wt.% based on the total solid weight of the coating; the co-adhesive is present in an amount of 15 wt.% to 25 wt.% based on the total solid weight of the coating; and the filler is present in an amount of 2 wt.% to 7.5 wt.% based on the total solid weight of the coating.

Claims

1. A coated article comprising: Substrate, the substrate having a surface; as well as A coating, wherein the coating is disposed on the surface, the coating comprising: The base coating has at least one of the following: For example, a martensitic hardness of 0.2 GPa or higher as determined by nanoindentation according to DIN ISO 14577 1-3; and If the elastic modulus is 5 GPa or higher as determined by DIN ISO 14577 1-3, the undercoat comprises an organic polymer having at least one of the following: Such as a melting point of 200°C or higher as determined by differential scanning calorimetry (DSC); Such as a glass transition temperature of 90°C or higher as determined by differential scanning calorimetry (DSC); and The undercoat contains reinforcing particles with a heat flexure / deformation temperature of 100°C or higher as determined by ASTM D648, and the Knoop hardness of the reinforcing particles is at least 160 kg / m² as determined by ASTM C1326. 2 ;as well as An outer coating layer, wherein the outer coating layer is disposed on the base coating layer and comprises a siloxane-based material, The martensitic hardness of the outer coating is less than that of the base coating. The coating comprises less than 0.1 wt.% of a fluoropolymer, based on the total weight of the coating.

2. The coated article according to claim 1, wherein the organic polymer comprises at least one of the following: polyphenylene sulfide (PPS), polyethersulfone (PES), polyether ether ketone (PEEK), polyphenylene sulfone (PPSU), polyamide imide (PAI), polyether imide (PEI), polyimide (PI), and combinations thereof.

3. The coated article according to claim 1 or claim 2, wherein the average particle size D50 of the reinforcing particles is 5 micrometers to 100 micrometers, as determined by scanning electron microscopy (SEM).

4. The coated article according to claim 1 or claim 2, wherein the reinforcing particles are present in an amount of 3 wt.% to 10 wt.% based on the total weight of the base coating.

5. The coated article according to claim 1 or claim 2, wherein the number of reinforcing particles present in the base coating is at least 3 per 1 cm of the transverse cross-section of the base coating.

6. The coated article according to claim 1 or claim 2, wherein the outer coating comprises a siloxane, and the martensitic hardness of the siloxane is less than 0.2 GPa, as determined by nanoindentation according to DIN ISO 14577 1-3.

7. The coated article according to claim 1 or claim 2, wherein the outer coating comprises a siloxane-based material formed from at least one siloxane.

8. The coated article according to claim 1 or claim 2, wherein the outer coating comprises a siloxane-based material formed from at least one of the following: Hydrosilylation reaction between a siloxane and at least one of a hydride-substituted organosiloxane and a vinyl-substituted organosiloxane; Dehydrogenation coupling reactions between hydride-substituted and hydroxyl-substituted organosiloxanes; and Polycondensation reaction between two hydroxyl-substituted organosiloxanes; polycondensation reaction between an alkoxy-substituted organosiloxane and a hydroxyl-substituted organosiloxane; or polycondensation reaction between an acetoxy-substituted organosiloxane and a hydroxyl-substituted organosiloxane.

9. The coated article according to claim 1 or claim 2, wherein the outer coating is substantially uniform.

10. A coating system comprising: A primer coating composition comprising an organic polymer having at least one of the following: Such as a melting point of 200°C or higher as determined by differential scanning calorimetry (DSC); Such as a glass transition temperature of 90°C or higher as determined by differential scanning calorimetry (DSC); as well as Such as a thermal flexure / deformation temperature of 100°C or higher as determined by ASTM D648; as well as The reinforcing particles, as determined by ASTM C1326, have a Knoop hardness of 160 kg / m. 2 ; Furthermore, as determined by dynamic light scattering, the average particle size D50 of the reinforcing particles is from 5 micrometers to 100 micrometers; as well as An external coating composition comprising at least one organosiloxane, and At least one catalyst, The martensitic hardness of the outer coating is less than that of the base coating. The coating system comprises less than 0.1 wt.% of a fluoropolymer, based on the total weight of the base coating composition and the outer coating composition.

11. The coating system of claim 10, wherein the organic polymer comprises at least one of the following: polyphenylene sulfide (PPS), polyethersulfone (PES), polyetheretherketone (PEEK), polyphenylene sulfone (PPSU), polyamide-imide (PAI), polyetherimide (PEI), polyimide (PI), and combinations thereof.

12. The coating system of claim 10 or claim 11, wherein the reinforcing particles are present in an amount of 3 wt.% to 10 wt.% based on the total weight of the base coating composition.

13. The coating system of claim 10 or claim 11, wherein the Knoop hardness of the reinforcing particles is at least 160 kg / m², as determined by ASTM C1326. 2 .

14. The coating system of claim 10 or claim 11, wherein the outer coating composition further comprises at least one of the following: Organosiloxanes and at least one of the following: hydride-substituted organosiloxanes, vinyl-substituted organosiloxanes, acetoxy-substituted organosiloxanes, hydroxyl-substituted organosiloxanes and alkoxy-substituted organosiloxanes; Hydrogenated organosiloxanes and hydroxyl-substituted organosiloxanes; and At least one of hydroxyl-substituted organosiloxanes, acetoxy-substituted organosiloxanes, and alkoxy-substituted organosiloxanes.

15. The coating system according to claim 10 or claim 11, wherein the catalyst comprises tin, titanium, platinum, palladium, ruthenium, gold, copper, zinc or zirconium.

16. The coating system of claim 10 or claim 11, wherein the catalyst comprises an organic peroxide.

17. The coating system according to claim 10 or claim 11, wherein the catalyst comprises a protic acid, a Lewis acid, or a base.

18. The coating system of claim 10 or claim 11, wherein the average particle size D50 of the reinforcing particles is from 5 micrometers to 100 micrometers, as determined by scanning electron microscopy (SEM).

19. The coating system of claim 10 or claim 11, wherein the number of reinforcing particles present in the base coating is at least 3 per 1 cm of the transverse cross-section of the base coating.

20. A coated article comprising: Substrate, the substrate having a surface; as well as A coating, wherein the coating is disposed on the surface, the coating comprising: The base coating has at least one of the following: For example, a martensitic hardness of 0.2 GPa or higher as determined by nanoindentation according to DIN ISO 14577 1-3; and For example, an elastic modulus of 5 GPa or higher as determined by DIN ISO 14577 1-3; and The base coating comprises an organic polymer and includes reinforcing particles, wherein the Knoop hardness of the reinforcing particles is at least 160 kg / m² as determined by ASTM C1326. 2 ;as well as An outer coating layer, wherein the outer coating layer is disposed on the base coating layer and comprises a siloxane-based material, The outer coating has a lower Martens hardness than the undercoat coating, and further includes: Vinyl-terminated polydimethylsiloxane; Polydimethylsiloxanes containing hydride groups; Co-adhesives containing vinyl Q resin; and Filler particles with a length-to-width ratio of at least 3:

1. The coating comprises less than 0.1 wt.% of a fluoropolymer, based on the total weight of the coating.

21. The coated article of claim 20, wherein the viscosity of the vinyl-terminated polydimethylsiloxane is 1,000 cSt and 50,000 cSt, as determined by ASTM D445-21e1.

22. The coated article according to claim 20 or claim 21, wherein the polydimethylsiloxane containing hydride groups has 30 mol% to 50 mol% of hydride groups.

23. The coated article according to claim 20 or claim 21, wherein the outer coating further comprises at least one of the following: Based on the total solid weight of the coating, the vinyl-terminated polydimethylsiloxane is present in an amount of 40 wt.% to 60 wt.%. Based on the total solid weight of the coating, the polydimethylsiloxane containing hydride groups is present in an amount of 25 wt.% to 40 wt.%. Based on the total solid weight of the coating, the co-adhesive is present in an amount of 15 wt.% to 25 wt.%; and Based on the total solid weight of the coating, the filler is present in an amount of 2 wt.% to 7.5 wt.%.

24. The coating system of claim 20 or claim 21, wherein the organic polymer comprises at least one of the following: polyphenylene sulfide (PPS), polyethersulfone (PES), polyether ether ketone (PEEK), polyphenylene sulfone (PPSU), polyamide imide (PAI), polyether imide (PEI), polyimide (PI), and combinations thereof.

25. The coating system of claim 20 or claim 21, wherein the average particle size D50 of the reinforcing particles is from 5 micrometers to 100 micrometers, as determined by scanning electron microscopy (SEM).

26. The coating system of claim 20 or claim 21, wherein the reinforcing particles are present in an amount of 3 wt.% to 10 wt.% based on the total weight of the base coating.

27. The coating system of claim 20 or claim 21, wherein the number of reinforcing particles present in the base coating is at least 3 per 1 cm of the transverse cross-section of the base coating.

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