Polysiloxane coating compositions, methods of forming the same, and methods of coating articles using the same

Abstract

A coating composition is provided having a base polymer formed from a plurality of monomers wherein the plurality of monomers include at least a plurality of tetraethoxysilane (TEOS) monomers; a first additive including a fluorinated ether and / or a fluorinated alcohol; and a second additive including a perfluorinated polymer.

Description

Technical Field

[0001] The present invention relates to coating compositions, methods of making the coating compositions, and methods of coating articles using the coating compositions. Background Art

[0002] For many articles, such as touch panel displays, solar panel screens and windows, it is necessary to provide the articles with suitable properties for hygienic, aesthetic and functional purposes. In addition, by providing such articles with easy-to-claim (E2C) properties, high hardness and high durability, their service life can be extended. In this way, the articles can maintain their hygienic, aesthetic and functional properties even under abrasive and undesirable environmental conditions. In addition, such coatings should be applicable to smooth and rough substrate surfaces, as well as different types of substrates, such as glass, ceramics and / or metals. It has been found that one or more of the above-mentioned objectives can be achieved by the coating composition described below. Summary of the Invention

[0003] In order to address the above problems, in one aspect of the present invention, the inventors have developed a coating composition, wherein the coating composition keeps required sanitation, attractive in appearance and functional properties over a long duration, such as the longest until the service life of the product coated with the coating composition thereon ends. In some aspects, the coating composition can be applied by conventional methods and solidified at low temperatures. In addition, the coating composition described herein can provide improved adhesion without the need to use an extra adhesion-promoting layer on a plurality of substrate surfaces. In addition, the coating composition desirably has excellent thermal stability and long-term performance stability. Still in addition, relative to known coating composition, the coating composition can provide improved and / or enhanced hydrophobicity, boiling water resistance, wear resistance, stain resistance (for example, demonstrated by an oil pen test) and / or chemical resistance.

[0004] According to one aspect of the present invention, there is provided a coating composition comprising: a base polymer formed from a plurality of monomers, wherein the plurality of monomers comprises at least a plurality of tetraethoxysilane (TEOS) monomers; a first additive comprising a fluorinated ether and / or a fluorinated alcohol; and a second additive comprising a perfluorinated polymer.

[0005] According to another aspect, there is provided a substrate comprising a coating on a surface thereof, the coating comprising the coating composition as described herein.

[0006] According to yet another aspect, there is provided a method for forming the coating composition, comprising: forming a base polymer from a plurality of monomers, wherein the plurality of monomers comprises at least a plurality of tetraethoxysilane (TEOS) monomers; Adding to the base polymer at least: - a first additive comprising a fluorinated ether and / or a fluorinated alcohol, and - A second additive comprising a perfluorinated polymer to form the coating composition.

[0007] According to yet another aspect, there is provided a method of forming a film on a substrate, comprising: forming a base polymer from a plurality of monomers, wherein the plurality of monomers comprises at least a plurality of tetraethoxysilane (TEOS) monomers; Adding to the base polymer at least: - a first additive comprising a fluorinated ether and / or a fluorinated alcohol, and - a second additive comprising a perfluorinated polymer to form a coating composition; applying the coating composition to the substrate to form the film; and The coating composition is optionally cured. DETAILED DESCRIPTION

[0008] The following description of various embodiments is merely exemplary and is intended for illustration purposes only. Although certain embodiments and examples are disclosed below, it will be understood by those skilled in the art that the invention extends beyond the specifically disclosed embodiments and / or uses of the invention and their obvious modifications and equivalents. The following description is not intended to limit the scope of the present disclosure or the claims. Moreover, the listing of multiple embodiments with the features shown is not intended to exclude other embodiments with additional features or other embodiments incorporating different combinations of the features. For example, various embodiments are presented as exemplary embodiments and may be listed in the dependent claims. Unless otherwise stated, the exemplary embodiments or their components may be used in combination or may be applied independently of each other.

[0009] Unless otherwise stated herein or the context clearly indicates otherwise, any percentages mentioned herein are expressed as weight percentages based on the total weight of the corresponding composition.

[0010] According to one aspect, a method for forming a coating composition as described above is disclosed. The method comprises the step (a) of forming a base polymer from a mixture comprising a plurality of monomers. The plurality of monomers comprises at least a plurality of tetraethoxysilane (TEOS) monomers. In certain embodiments, the base polymer is formed solely from a plurality of TEOS monomers. While not being bound by theory, it is believed that the TEOS monomers provide the base polymer with desired properties such as hardness, scratch resistance, adhesion, alkali resistance, antimicrobial properties, mechanical stability, and oxidative stability.

[0011] In other embodiments, additional monomers may be provided to form a base polymer with enhanced or further desired properties. Such enhanced or further properties also include hardness, scratch resistance, adhesion, alkali resistance, antimicrobial properties, mechanical stability, oxidative stability, etc.

[0012] In certain embodiments, the plurality of monomers includes one or more second monomers selected from the group consisting of 3-trimethoxysilylpropyl methacrylate (MEMO), 1,4-bis(triethoxysilyl)ethane) (BTESE), 3-glycidoxypropyltrimethoxysilane (GPTMS), and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (F17), 1H,1H,2H,2H-perfluorooctyltrimethoxysilane (F13), and combinations thereof.

[0013] In certain embodiments, at least 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 mole percent of the plurality of monomers, based on the total mole percent of the plurality of monomers, are tetraethoxysilane (TEOS) monomers.

[0014] In certain embodiments, the base polymer is present in the coating composition at a concentration of 0.25 to 50 wt %, eg, 0.30 to 25 wt % or 0.4 to 10 wt %, based on the dry weight of solid components in the coating composition.

[0015] The base polymer can be polymerized from a plurality of monomers as described herein via any suitable conditions that effectively form the desired base polymer. In one embodiment, the synthesis of the siloxane polymer is carried out in at least two steps (for example, using a two-step sol-gel technique to synthesize polysiloxanes, see S. Legrand, M. Hannu-Kuure, A. Kärkkäinen, JAppl Polym Sci. 2021; 138: e49877). In the first step (hydrolysis), the monomer is hydrolyzed, optionally in the presence of water and / or a catalyst (such as an acid or a base). When carried out in the presence of water, the water can be excess water, stoichiometric water, or substoichiometric water. In addition, the pH that the water has can be less than 7, preferably less than 6, and particularly less than 5.

[0016] In one embodiment, an acid catalyst is provided. In one embodiment, the acid catalyst is selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, acetic acid, citric acid, formic acid, trifluoromethanesulfonic acid, perfluorobutyric acid and mixtures thereof. In other embodiments, polymerization is carried out in the presence of a base catalyst. In one embodiment, the base catalyst comprises an amine, such as a C1 to C4 trialkylamine. In one embodiment, heat may be applied during the hydrolysis reaction, or reflux may be used. In certain embodiments, hydrolysis is carried out at a temperature of 50 to 150°C (such as 80 to 120°C) for 0.5 to 10 hours (such as 1.0 to 5.0 hours).

[0017] In the second step (polymerization), depending on the selected monomers, the molecular weight of the formed material is increased by polycondensation or other crosslinking, such as free radical polymerization (for examples of free radical polymerization, see S. Legrand; R. Kabir, A. Kärkkäinen Chemistry Select 2023; e202204271). In one embodiment, the polymerization is also carried out in the presence of a suitable catalyst. In this step, the molecular weight is increased to provide the desired properties of the base polymer. The catalyst may include any suitable catalyst, such as the catalyst described above for the hydrolysis step. Similarly, heat may be applied during the reaction, and reflux may be used during the polymerization reaction. In certain embodiments, the polymerization is carried out at a temperature of 50 to 150°C (such as 80 to 120°C) for 0.5 to 10 hours (such as 1.0 to 5.0 hours).

[0018] The synthesis of the base polymer can be carried out using an inert solvent or an inert solvent mixture. It should be understood that the selected one or more solvents may affect the final base polymer composition. In a particular embodiment, the one or more solvents are selected from the group consisting of: alcohols, such as alcohols containing 1 to 6 carbon atoms; ether alcohols, such as propylene glycol monomethyl ether; ketones, such as acetone; esters, such as propylene glycol monomethyl ether acetate, ethyl acetate, or methyl formate; ethers, such as diethyl ether or THF; and mixtures thereof.

[0019] In one embodiment, the shelf life stability of the formed base polymer at room temperature is at least 3 months, preferably more than 6 months at room temperature. If necessary, the base polymer can be stabilized by end-capping the polymer chain, for example, by blocking the end groups (such as hydroxyl groups). See S. Legrand; A. Kärkkäinen J Appl Polym Sci.2021;e50467. Suitable reagents are silane compounds. These silane compounds include, but are not limited to: trimethylchlorosilane, dimethylvinylchlorosilane, trimethylethoxysilane, dimethylvinylethoxysilane and trimethylmethoxysilane.

[0020] In certain embodiments, water is removed from the existing reaction mixture prior to the polymerization step, such as by solvent exchange with another solvent. The new solvent can serve as the final processing solvent or one of the final processing solvents for the base polymer.

[0021] In certain embodiments, one or more processing solvents may be added during the polymerization step to form a final processing solvent combination.Additives, such as thermal initiators, radiation sensitive initiators, surfactants, and other additives may be added prior to final filtration of the formed base polymer.

[0022] Once the base polymer is formed, the method of forming the coating composition may further include step (b) of adding at least: a first additive comprising a fluorinated ether and / or a fluorinated alcohol, and a second additive comprising a perfluorinated polymer to the base polymer to form the coating composition. In certain embodiments, the first additive and the second additive are added under batch or continuous mixing conditions.

[0023] First additive The first additive comprises a fluorinated ether and / or a fluorinated alcohol. In one embodiment, the first additive comprises a fluorinated ether. In one embodiment, the first additive comprises a fluorinated alcohol. In one embodiment, the fluorinated ether and / or fluorinated alcohol comprises any suitable fluorinated ether and / or fluorinated alcohol that provides one or more desired properties to the base polymer or enhances the desired properties of the resulting coating composition. Such enhanced or further properties also include hardness, scratch resistance, adhesion, alkali resistance, antimicrobial properties, mechanical stability, oxidative stability, and the like.

[0024] In a particular embodiment, the first additive comprises a member selected from the group consisting of methoxynonafluorobutane, ethoxynonafluorobutane, methyl perfluoroisobutyl ether, ethyl perfluoroisobutyl ether, ethyl nonafluorobutyl ether, and 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)pentane, and mixtures thereof.

[0025] In certain embodiments, the first additive is provided by one or more commercial sources. In a specific embodiment, the first additive is commercially available from 3M™ under the trade names Novec 7100™, Novec 7200™, and Novec 7300™.

[0026] Novec 7100™ is an engineered fluid comprising methoxynonafluorobutane, specifically, two inseparable isomers with essentially identical properties: (CF3)2CFCF2OCH3 (CAS No. 163702-08-7) and CF3CF2CF2CF2OCH3 (CAS No. 163702-07-6).

[0027] Novec 7200™ is similarly an engineered fluid comprising ethoxynonafluorobutane, specifically, two inseparable isomers having essentially identical properties: (CF3)2CFCF2OC2H5 (CAS No. 163702-06-5) and CF3CF2CF2CF2OC2H5 (CAS No. 163702-05-4).

[0028] Novec 7300™ is an engineered fluid consisting of 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)pentane (CAS 132182-92-4).

[0029] In certain embodiments, the first additive is present in the coating composition at a concentration of 10 to 75 wt %, eg, 25 to 55 wt % or 30 to 40 wt %.

[0030] Second additive The second additive is a perfluorinated polymer and can be provided to the base polymer together with the first additive or independently. In one embodiment, the second additive can include any suitable perfluorinated polymer that provides one or more desired properties to the base polymer or enhances the desired properties of the resulting coating composition. In one embodiment, the additional or enhanced properties include one or more of the following: anti-fouling properties; easy cleaning properties (stains, fingerprints, etc.); water and oil repellency; scratch resistance; optical properties; and one or more desired textures.

[0031] In one embodiment, the second additive comprises a trialkoxysilane containing a perfluoropolyether. In certain embodiments, the second additive is provided by a commercial source. It should be understood that the commercial source of the second additive may not be publicly known to the public, and its exact structure. In a specific embodiment, the second additive comprises a composition commercially available from Shin-Etsu Chemical Co., Ltd. under the trade name KY-1901.

[0032] In certain embodiments, the second additive is present in the coating composition at a concentration of 0.01 to 3.0 wt%, eg, 0.02 to 1.0 wt% or 0.025 to 0.3 wt%, based on the total dry weight of the second additive and the base polymer.

[0033] In certain embodiments, the weight ratio of the combination of the first additive and the second additive (total weight of the first additive and the second additive) to the base polymer in the coating composition is 1:1.5 to 325:1, e.g., 1.5:1 to 100:1 or 2:1 to 25:1.

[0034] In one embodiment, the weight ratio of the first additive to the second additive in the coating composition is from 2:1 to 150:1, such as from 10:1 to 100:1, or from 10:1 to 50:1.

[0035] solvent In one embodiment, the first additive and / or the second additive are added to the base polymer along with or in conjunction with one or more solvents. It will be appreciated that the type and amount of solvent can be varied as needed to provide the coating composition with desired properties, including, but not limited to, providing a predetermined coating thickness when applied to a substrate. In one embodiment, the solvent is selected from the group consisting of alcohols, ether alcohols, glycols, ketones, esters, ethers, fluorinated hydrocarbons, sulfoxides, and combinations thereof.

[0036] In certain embodiments, one or more solvents in the first additive and / or the second additive are selected from the group consisting of dimethyl phthalate (DiMPh), dipropylene glycol methyl ether (DiPGME), dipropylene glycol butyl ether (DiPGBE), diethylene glycol ethyl ether (DiEGEE), 2-propylene carbonate (PC), dimethyl sulfoxide (DMSO), 2-propanol (IPA), ethylene glycol (EG), 1-methoxy-2-propanol (PGME), di(ethylene glycol) monoethyl ether, di(ethylene glycol) monobutyl ether, and combinations thereof.

[0037] In certain embodiments, the one or more solvents are present in a concentration of 5 to 75 wt %, such as 10 to 60 wt %, of the total wt % of the coating composition. In one embodiment, the final coating composition comprises a solids content of 0.1 to 2 wt %, such as 0.4 to 1 wt %.

[0038] In one embodiment, the coating composition may include one or more additional additives (in addition to the first and second additives). In one embodiment, the one or more additional additives (additional additives) may include microparticles or nanoparticles (e.g., rods, crystals, spheres, dots, buds, etc.). In one embodiment, the additional additives are selected from the group consisting of light scattering pigments, organic and inorganic phosphors, oxides, quantum dots, or metals. The additional additives may enhance desired mechanical, chemical, or physical properties, or provide additional functionality to the coating composition.

[0039] Coating process According to another aspect, once formed, the coating composition can be applied to a suitable substrate to form a film thereon. The substrate can be formed of, but is not limited to, ceramic materials, glass, metal, natural and artificial stone, polymeric materials (e.g., poly(meth)acrylates, polycarbonates, polystyrene, styrene copolymers (such as styrene-acrylonitrile copolymers), polyesters, or polyethylene terephthalate), or wood and fiber substrates (such as textiles, leather, carpet, or paper). In particular embodiments, the substrate comprises a metal substrate, such as a galvanized steel substrate, a gunmetal substrate, a gold substrate, or a copper bronze substrate.

[0040] The coating composition can be applied to the substrate by any suitable process. In one embodiment, the coating composition is applied by dip coating, slot coating, a combination of slot and spin coating, spin coating, spray coating, inkjet printing, curtain coating, roller coating, roll-to-roll coating, screen printing, or using a rod or brush, or by rubbing. In certain embodiments, the coating composition is applied by physical vapor deposition (PVD) techniques.

[0041] In other embodiments, the coating composition is applied by spraying. In one embodiment, the temperature during application of the coating composition is a temperature of 20 to 100° C., such as 25 to 75° C. In certain embodiments, the substrate is preheated to a temperature of 20 to 100° C., such as 25 to 50° C.

[0042] In certain embodiments, once the film is formed on the substrate, a pattern can be formed on the film to form surface features and patterns. Such patterns can provide additional optical, physical, or chemical properties to the film. Exemplary processes for patterning include, but are not limited to, nanoimprinting, embossing, roll-to-roll, gravure printing, flexographic printing, roller coating, inkjet, screen printing, spray lithography, and / or UV lithography.

[0043] In certain embodiments, after the coating composition is applied to the substrate, one or more solvents may be partially or completely removed from the coating composition by any suitable process. In certain embodiments, the removal step may be performed using temperature and / or by vacuum. In a specific embodiment, the removal step is performed at a pressure of 50 to 200 kPa and a temperature of 50 to 150° C.

[0044] In certain embodiments, the method further comprises activating the surface prior to applying the coating composition to the substrate. The activation step can be accomplished by any suitable method, such as by application of ozone, etching, flame, corona discharge, and / or plasma techniques.

[0045] Curing In one embodiment, the coating composition applied is optionally cured on substrate during film formation. Curing is completed by applying heating, such as by hot air stove, hot plate or by electromagnetic radiation. In some embodiments, curing is completed by heating and applying a combination of UV energy. The temperature of the curing step can be any suitable one or more values, such as 25 to 300 ℃, and can be lower than 150 ℃ or 80 ℃. Curing time can be any suitable duration, such as 10 min to 5.0 hours, such as 20 min to 3.0 hours, for example 5 min to 1.0 hour.

[0046] The formed film can have any suitable thickness, such as 1 nm to 10 μm, such as 100 nm to 1 μm or 10 to 100 nm. Exemplary methods of producing thin films are described in US Patent No. 7,094,709, the contents of which are incorporated herein by reference.

[0047] characteristic In one embodiment, the film has a water contact angle of at least 110°, at least 115°, or at least 120°.

[0048] In one embodiment, the film has a pencil hardness (PEHA) of at least 7H, at least 8H, or at least 9H.

[0049] In one embodiment, the film has a refractive index (at 632 nm) of 1.1 to 1.50, such as 1.25 to 1.45 (at 632 nm).

[0050] In one embodiment, the film has an RMS surface roughness of less than 5.0 nm, less than 3.5 nm, or less than 2.5 nm.

[0051] In one embodiment, when the film is formed on a metal substrate, the film has a water contact angle of at least 85°, at least 95°, or at least 105° after 2000 cycles of steel wool abrasion.

[0052] It should be understood that the configurations and / or methods described herein are merely exemplary in nature, and that these specific embodiments or examples should not be considered restrictive, as many variations are possible. The specific routines or methods described herein may represent one or more processing strategies in any number of ways. Thus, the various operations shown may be performed in the order shown, in other orders, or omitted in some cases.

[0053] The subject matter of the present disclosure includes all novel and nonobvious combinations and subcombinations of the various compositions and processes, and other features, functions, acts and / or properties disclosed herein, as well as any and all equivalents thereof.

[0054] Example Preparation of coating composition 1 Synthetic base (root) polymer: In a 10 L reactor, tetraethoxysilane (510.72 g) and acetone (1600 g) were mixed. HNO₃ (0.1 M; 353.28 g) was added dropwise, and the reaction mixture was refluxed for 1 hour. After cooling to room temperature, 1-methoxy-2-propanol (1600 g) was added, and a solvent exchange from EtOH / acetone / H₂O to PGME was performed under reduced pressure. After moisture analysis, the solids content was adjusted to 10% by adding 1-methoxy-2-propanol.

[0055] preparation The base polymer (10% solids in 1-methoxy-2-propanol; 6000 g) was mixed with Novec 7200™ (39480 g), KY-1901 (280 g; 0.4% in Novec 7200™), 2-propanol (32312 g), and ethylene glycol (1984 g).

[0056] Preparation of coating composition 2 Synthetic base (root) polymer: In a 10 L reactor, tetraethoxysilane (510.72 g) and acetone (1600 g) were mixed. HNO₃ (0.1 M; 353.28 g) was added dropwise, and the reaction mixture was refluxed for 1 hour. After cooling to room temperature, 1-methoxy-2-propanol (1600 g) was added, and a solvent exchange from EtOH / acetone / H₂O to PGME was performed under reduced pressure. After moisture analysis, the solids content was adjusted to 10% by adding 1-methoxy-2-propanol.

[0057] preparation: The base polymer (10% solids in 1-methoxy-2-propanol; 525 g) was mixed with Novec 7100™ (3454.5 g), KY-1901 (24.5 g; 0.4% in Novec 7100™), 2-propanol (2827.3 g), and ethylene glycol (3.72 g).

[0058] Preparation of coating composition 3 Synthetic base (root) polymer:In a round-bottom flask, tetraethoxysilane (43 g), 3-trimethoxysilylpropyl methacrylate (5.7 g), and ZrO2 (9.74 g) were combined in acetone (136 g). HNO3 (0.1 M; 32.23 g) was added dropwise, and the reaction mixture was refluxed for 2 hours. After cooling to room temperature, 1-methoxy-2-propanol (116 g) was added, and a solvent exchange from EtOH / MeOH / acetone / H2O to PGME was performed under reduced pressure. After moisture analysis, the solids content was adjusted to 10% by adding 1-methoxy-2-propanol.

[0059] preparation: The base polymer (10% solids in 1-methoxy-2-propanol; 15 g) was mixed with Novec 7200™ (64.4 g), KY-1901 (37.5 g; 0.4% in Novec 7200™), 2-propanol (80.79 g), and ethylene glycol (4.96 g).

[0060] Table 1 Properties of coatings on metal substrates:

[0061] As can be seen in Table 1, the compositions exhibited similar properties, but one (Composition 1) passed the boiling water test.

[0062] Table 2 Another coating property on a metal substrate:

[0063] It can be seen from Table 2 that composition 1 has the best wear resistance among the three compositions and passes the boiling water test.

[0064] Table 3 Another coating property on a metal substrate:

[0065] As can be seen from Table 3, Composition 1 provides the best water contact angle.

[0066] Table 4 PVD maximum wear resistance research:

[0067] As can be seen in Table 4, all compositions (1-3) deposited by PVD on the listed substrates passed the specific tests.

[0068] The coating method is automated spray coating. The coating parameters are adjusted to obtain a film thickness of approximately 50-80 nm. Abrasion testing is performed using a linear abrader (1 kg load, 1 x 1 cm abrasive head, wet cotton cloth, 2-inch stroke length, and a speed of 60 cycles / min). Boiling tests are performed using tap water. After coating, wait up to one week to evaluate the properties of the coated substrate. The film thickness needs to be at least 65 nm. Plasma treatment and cleaning conditions are crucial to obtaining high-quality films.

[0069] Industrial Applicability Aspects of the present invention can be used, for example, as films on articles such as display devices, touch screen devices, photovoltaic devices (cells, panels, and modules), lamps, metal surfaces, and equipment. The films can provide excellent properties including, but not limited to, mechanical stability, oxidative stability, adhesion, hardness, and wear resistance.

Claims

1. A coating composition comprising: a base polymer formed from a plurality of monomers, wherein the plurality of monomers comprises at least a plurality of tetraethoxysilane (TEOS) monomers; a first additive comprising a fluorinated ether and / or a fluorinated alcohol; and A second additive includes a perfluorinated polymer.

2. The coating composition according to claim 1, wherein The plurality of monomers include one or more second monomers selected from the group consisting of 3-trimethoxysilylpropyl methacrylate (MEMO), 1,4-bis(triethoxysilyl)ethane) (BTESE), 3-glycidoxypropyltrimethoxysilane (GPTMS) and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (F17), 1H,1H,2H,2H-perfluorooctyltrimethoxysilane (F13), and combinations thereof.

3. A coating composition according to any one of the preceding claims, wherein At least 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 mole percent of the plurality of monomers, based on the total mole percent of the plurality of monomers, are tetraethoxysilane (TEOS) monomers.

4. A coating composition according to any one of the preceding claims, wherein The first additive includes methoxynonafluorobutane, ethoxynonafluorobutane, methyl perfluoroisobutyl ether, ethyl perfluoroisobutyl ether, ethyl nonafluorobutyl ether and 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)pentane, and a mixture of two or more thereof.

5. A coating composition according to any one of the preceding claims, wherein The second additive includes a perfluoropolyether-containing alkoxysilane, such as a perfluoropolyether-containing trialkoxysilane.

6. A coating composition according to any one of the preceding claims, wherein The weight ratio of the first additive to the second additive in the coating composition is 1:1 to 100:1, for example, 2:1 to 50:1, or 5:1 to 25:

1.

7. A coating composition according to any one of the preceding claims, wherein The coating composition includes a solid content of 0.1 to 2 wt %, for example 0.4 to 1 wt %.

8. A coating composition according to any one of the preceding claims, wherein The base polymer is present in a concentration of 0.25 to 50 wt%, eg, 0.30 to 25 wt% or 0.40 to 10 wt%, based on the dry weight of solid components in the coating composition.

9. A coating composition according to any one of the preceding claims, wherein The first additive is present in a concentration of 10 to 75 wt%, eg, 25 to 55 wt%, or 30 to 50 wt%.

10. A coating composition according to any one of the preceding claims, wherein The second additive is present in a concentration of 0.01 to 3 wt%, eg, 0.02 to 1.0 wt% or 0.025 to 0.3 wt%, based on the total dry weight of the second additive and the base polymer.

11. A coating composition according to any one of the preceding claims, wherein The weight ratio of the sum of the first additive and the second additive to the base polymer in the coating composition is 1:1.5 to 325:1, for example, 1.5:1 to 100:1 or 2:1 to 50:

1.

12. A coating composition according to any one of the preceding claims, wherein The coating composition further includes one or more solvents selected from the group consisting of alcohols, ether alcohols, glycols, ketones, esters, ethers, fluorinated hydrocarbons, sulfoxides, and combinations thereof.

13. The coating composition according to claim 12, wherein The one or more solvents are selected from the group consisting of dimethyl phthalate (DiMPh), dipropylene glycol methyl ether (DiPGME), dipropylene glycol butyl ether (DiPGBE), diethylene glycol ethyl ether (DiEGEE), propylene carbonate (PC), dimethyl sulfoxide (DMSO), 2-propanol (IPA), ethylene glycol (EG), 1-methoxy-2-propanol (PGME), di(ethylene glycol) monoethyl ether, di(ethylene glycol) monobutyl ether, and combinations thereof.

14. The coating composition according to claim 12, wherein The one or more solvents are present in a concentration of 5 to 75 wt %, such as 10 to 60 wt %, of the total wt % of the coating composition. 15 . A substrate comprising a film on a surface thereof, the film being formed from the coating composition of claim 1 .

16. The substrate according to claim 15, wherein The substrate includes a metal substrate such as galvanized steel, gunmetal, gold substrate, copper bronze substrate.

17. The substrate according to any one of claims 15 to 16, wherein The film has a water contact angle of at least 110°, such as at least 115° or at least 120°.

18. A method of forming a coating composition, comprising: forming a base polymer from a plurality of monomers, wherein the plurality of monomers comprises at least a plurality of tetraethoxysilane (TEOS) monomers; Adding to the base polymer at least: - a first additive comprising a fluorinated ether and / or a fluorinated alcohol, and - A second additive comprising a perfluorinated polymer to form the coating composition.

19. A method for forming a film on a substrate, comprising: forming a base polymer from a plurality of monomers, wherein the plurality of monomers comprises at least a plurality of tetraethoxysilane (TEOS) monomers; Adding to the base polymer at least: - a first additive comprising a fluorinated ether and / or a fluorinated alcohol; and - a second additive comprising a perfluorinated polymer to form a coating composition; applying the coating composition to the substrate; and The coating composition is optionally cured.

20. The process of claim 19, wherein The plurality of monomers include one or more second monomers selected from the group consisting of 3-trimethoxysilylpropyl methacrylate (MEMO), 1,4-bis(triethoxysilyl)ethane) (BTESE), 3-glycidoxypropyltrimethoxysilane (GPTMS) and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (F17), 1H,1H,2H,2H-perfluorooctyltrimethoxysilane, and combinations thereof.

21. The process according to any one of claims 19 to 20, wherein The first additive includes a mixture of two or more of methoxynonafluorobutane, ethoxynonafluorobutane, methyl perfluoroisobutyl ether, ethyl perfluoroisobutyl ether, ethyl nonafluorobutyl ether and 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)pentane and mixtures thereof.

22. A process according to any one of claims 19 to 21, wherein The second additive includes a perfluoropolyether-containing alkoxysilane, such as a perfluoropolyether-containing trialkoxysilane.

23. A process according to any one of claims 19 to 22, wherein Application of the coating composition is accomplished by spraying or physical vapor deposition (PVD).

24. The process of any one of claims 19 to 23, further comprising activating the surface prior to applying the coating composition to the substrate.

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