Polysiloxane coating compositions, methods of forming the coating compositions, and methods of coating articles with the coating compositions

Abstract

There is a coating composition having a base polymer formed from a plurality of monomers, wherein the plurality of monomers comprise 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.

Description

[0001] Polysiloxane coating compositions, methods of forming the coating compositions, and methods of coating articles with the coating compositions

[0002] FIELD

[0003] The present invention relates to coating compositions, methods for making the coating compositions, and methods for coating articles with the coating compositions.

[0004] BACKGROUND

[0005] For many articles, such as touch panel displays, solar panel screens, and windows, it is desirable to provide the articles with suitable properties for hygienic, aesthetic, and functional purposes. In addition, the longevity of such articles may be enhanced by providing such articles with easy-to-claim (E2C) properties, high hardness, and high durability. In this way, the articles may maintain their hygienic, aesthetic, and functional properties, even when subjected to abrasive and undesirable environmental conditions. Further, such coatings should be usable on both smooth and rough substrate surfaces, as well as on different types of substrates such as glass, ceramic, and / or metal. It has been found that one or more of the above objectives may be achieved by the following coating compositions described hereinbelow.

[0006] SUMMARY

[0007] To address the above concerns and in one aspect of the present invention, the present inventors have developed coating compositions that maintain desired hygienic, aesthetic, and functional properties for long durations, such as up to the lifetime of the articles on which the coating compositions are coated. In certain aspects, the coating compositions may be applied by conventional methods and cured at low temperatures. In addition, the coating compositions described herein may provide improved adhesion without the need for using additional adhesion promotion layers for multiple substrate surfaces. Further, the coating compositions desirably have excellent thermal and long-term performance stability. Still further, the coating compositions may provide improved and / or enhanced hydrophobicity, resistance to boiling water, abrasion resistance, stain resistance (e.g., demonstrated by oil pen testing), and / or chemical resistance relative to known coating compositions.

[0008] In accordance with 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 comprise 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.

[0009] In accordance with another aspect, there is provided a substrate comprising a coating on a surface thereof, the coating comprising the coating composition as described herein.

[0010] In accordance with yet another aspect, there is provided a method of forming a coating composition comprising: forming a base polymer from a plurality of monomers, wherein the plurality of monomers comprise at least a plurality of tetraethoxysilane (TEOS) monomers; adding to the base polymer at least:

[0011] - a first additive comprising a fluorinated ether and / or a fluorinated alcohol, and

[0012] - a second additive comprising a perfluorinated polymer to form the coating composition.

[0013] In accordance with 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 comprise at least a plurality of tetraethoxysilane (TEOS) monomers; adding to the base polymer at least:

[0014] - a first additive comprising a fluorinated ether and / or a fluorinated alcohol, and

[0015] - a second additive comprising a perfluorinated polymer to form a coating composition; applying the coating composition on the substrate to form the film; and optionally curing the coating composition.

[0016] EMBODIMENTS

[0017] The description of various embodiments below is merely exemplary and is intended for purposes of illustration only. Although certain embodiments and examples are disclosed below, it will be understood by those in the art that the invention extends beyond the specifically disclosed embodiments and / or uses of the invention and obvious modifications and equivalents thereof. The following description is not intended to limit the scope of the disclosure or the claims. Moreover, recitation of multiple embodiments having indicated features is not intended to exclude other embodiments having additional features or other embodiments incorporating different combinations of the stated features. For example, various embodiments are set forth as exemplary embodiments and may be recited in the dependent claims. Unless otherwise noted, the exemplary embodiments or components thereof may be combined or may be applied separate from each other.

[0018] Unless otherwise stated herein or clear from the context, any percentages referred to herein are expressed as percent by weight, based on a total weight of the respective composition.

[0019] In accordance with one aspect, there is disclosed a method for forming a coating composition as described above. The method comprises step (a) of forming a base polymer from a mixture comprising a plurality of monomers. The plurality of monomers comprise at least a plurality of tetraethoxysilane (TEOS) monomers. In certain embodiments, the base polymer is solely formed from a plurality of TEOS monomers. While not wishing to be bound by theory, it is believed that the TEOS monomers provide the base polymer with desired properties of hardness, scratch resistance, adhesion, alkaline resistance, antimicrobial properties, mechanical stabilization, oxidative stabilization, and the like.

[0020] In other embodiments, additional monomers may be provided to form the base polymer with enhanced or further desired properties. Such enhanced or further properties also include hardness, scratch resistance, adhesion, alkaline resistance, antimicrobial properties, mechanical stabilization, oxidative stabilization, and the like.

[0021] In certain embodiments, the plurality of monomers comprises one or more second monomers selected from the group consisting of 3 -trimethoxy silylpropyl methacrylate (MEMO), 1 ,4-bis(triethoxysilyl)ethane) (BTESE), 3-glycidoxypropyltrimethoxysilane (GPTMS), and 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane (Fl 7), 1H,1H,2H,2H- perfluorooctyltrimethoxysilane (Fl 3), and combinations thereof.

[0022] In certain embodiments, at least 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 mole % of the plurality of monomers are tetraethoxysilane (TEOS) monomers, based on a total mole % of the plurality of monomers.

[0023] In certain embodiments, the base polymer is present in the coating composition at a concentration of from 0.25 to 50 wt%, for example, 0.30 to 25 wt% or 0.4 to 10, based on dry weight of the solid components in the coating composition.

[0024] The base polymer may be polymerized from a plurality of monomers as described herein via any suitable conditions effective to form the desired base polymer. In an embodiment, the synthesis of the siloxane polymer is carried out in at least two steps (for an example of polysiloxane synthesis using the two steps sol-gel technology, see S. Legrand, M. Hannu-Kuure, A. Karkkainen, J Appl Polym Sci. 2021;138:e49877). In a first step (hydrolysis), the monomers are hydrolyzed, optionally in the presence of water and / or a catalyst, such as an acid or base. When done in the presence of water, the water may be an excess of water, stoichiometric amount of water, or a sub-stoichiometric amount of water. In addition, the water may have a pH of less than 7, preferably less than 6, in particular less than 5.

[0025] In an embodiment, an acid catalyst is provided. In an embodiment, the acid catalyst is selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, acetic acid, citric acid, formic acid, triflic acid, perfluorobutyric acid, and mixtures thereof. In other embodiments, the polymerization is carried out in the presence of a base catalyst. In an embodiment, the base catalyst comprises an amine, such as a Ci to C4 trialkylamine. In an embodiment, heat may be applied during the hydrolysis reaction and refluxing may also be used. In certain embodiments, the hydrolysis is carried out at a temperature of from 50 to 150° C, such as from 80 to 120° C for 0.5 to 10 hours, such as from 1.0 to 5.0 hours.

[0026] In a second step (polymerization), the molecular weight of the forming material is increased by condensation polymerization or other crosslinking, such as by free-radical polymerization (for an example of free-radical polymerization, see S. Legrand; R. Kabir, A. Karkkainen Chemistry Select 2023;e202204271), depending on which monomers are selected. In an 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 comprise any suitable catalyst, such as a catalyst described above for the hydrolysis step. Likewise, heat may be applied during the reaction and refluxing can be used during the polymerization reaction. In certain embodiments, the polymerization is carried out at a temperature of from 50 to 150° C, such as from 80 tol20° C for 0.5 to 10 hours, such as from 1.0 to 5.0 hours.

[0027] The synthesis of the base polymer may be carried out using an inert solvent or inert solvent mixture. It is understood that the selected solvent(s) may affect the final base polymer composition. In particular embodiments, the solvent(s) are selected from the group consisting of: alcohols, e.g., alcohols containing 1 to 6 carbon atoms; ether alcohols, e.g., propylene glycol monomethyl ether; ketones, e.g., acetone; esters, e.g., propylene glycol monomethylether acetate, ethyl acetate, or methylformate; ethers, e.g., diethyl ether or THF; and mixtures thereof.

[0028] In an embodiment, the shelf-life stability of the formed base polymer is at least 3 months at room temperature, preferably over 6 months at room temperature. If necessary, the base polymer may be stabilized by end-capping the polymer chain, for example, by blocking terminal groups, such as hydroxyl groups. See S. Legrand; A. Karkkainen J Appl Polym Sci. 2021;e50467. Suitable reagents are silyl compounds. These silyl compounds include, but are not limited to, chlorotrimethylsilane, chlorodimethylvinylsilane, ethoxytrimethylsilane, ethoxydimethylvinylsilane, and methoxytrimetylsilane.

[0029] In certain embodiments, prior to the polymerization step, water is removed from the existing reaction mixture, such as by solvent exchange to another solvent. The new solvent may function as the final or one of the final processing solvents for the base polymer.

[0030] In certain embodiments, processing solvent(s) may be added during the polymerization step to form the 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.

[0031] Once the base polymer is formed, the method of forming a coating composition may further comprise step (b) of 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. In certain embodiments, the first and second additive are added under intermittent or continuous mixing conditions.

[0032] First additive

[0033] The first additive comprises a fluorinated ether and / or a fluorinated alcohol. In an embodiment, the first additive comprises a fluorinated ether. In an embodiment, the first additive comprises a fluorinated alcohol. In an embodiment, the fluorinated ether and / or the fluorinated alcohol comprise any suitable fluorinated ether and / or a fluorinated alcohol that provides the base polymer with one or more desired properties or enhances the desired properties of the resulting coating composition. Such enhanced or further properties also include hardness, scratch resistance, adhesion, alkaline resistance, antimicrobial properties, mechanical stabilization, oxidative stabilization, and the like.

[0034] 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 l,l,l,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)pentane, and mixtures thereof.

[0035] In certain embodiments, the first additive is provided from one or more commercially available sources. In particular embodiments, the first additive is commercially available under the trade names: Novec 7100™, Novec 7200™, and Novec 7300™ from 3M™, for example.

[0036] Novec 7100™ is an engineered fluid comprising methoxynonafluorobutane, and specifically two inseparable isomers thereof with essentially identical properties: (CF3)2CFCF2OCH3 (CAS No. 163702-08-7) and CF3CF2CF2CF2OCH3 (CAS No. 163702- 07-6).

[0037] Novec 7200™ is similarly an engineered fluid comprising ethoxynonafluorobutane, and specifically two inseparable isomers thereof with essentially identical properties: (CF3)2CFCF2OC2H5(CAS No. 163702-06-5) and CF3CF2CF2CF2OC2H5 (CAS No. 163702- 05-4).

[0038] Novec 7300™ is an engineered fluid comprising l,l,l,2,2,3,4,5,5,5-decafluoro-3- methoxy-4-(trifluoromethyl)pentane (CAS 132182-92-4).

[0039] In certain embodiments, the first additive is present in the coating composition at a concentration of from 10 to 75 wt%, for example, 25 to 55 wt% or 30 to 40 wt %.

[0040] Second additive

[0041] The second additive is a perfluorinated polymer and may be provided to the base polymer together with or independently of the first additive. In an embodiment, the second additive may comprise any suitable perfluorinated polymer that provides the base polymer with one or more desired properties or enhances the desired properties of the resulting coating composition. In an embodiment, the additional or enhanced properties comprise one or more of: anti-smudge properties; easy-to-clean properties (dirt, fingerprints, etc.); water and oil repellency; scratch-resistance; optical properties; and desired texture(s).

[0042] In an embodiment, the second additive comprises a perfluoropolyether-containing trialkoxy silane. In certain embodiments, the second additive is provided from a commercially available source. It is appreciated that commercially available sources of the second additive may be available without public knowledge of their exact structure. In a particular embodiment, the second additive comprises a composition commercially available under the trade name KY-1901 from Shin-Etsu Chemical Co., Ltd.

[0043] In certain embodiments, the second additive is present in the coating composition at a concentration of from 0.01 to 3.0 wt%, for example, 0.02 to 1.0 wt % or 0.025 to 0.3 wt %, based on a total dry weight of the second additive and the base polymer.

[0044] In certain embodiments, a weight ratio of the combination of the first additive and the second additive (weight of the first and second additive together) to the base polymer in the coating composition is from 1 :1.5 to 325:1, for example 1.5:1 to 100:1 or 2:1 to 25:1.

[0045] In an embodiment, a weight ratio of the first additive to the second additive in the coating composition is from 2:1 to 150:1, such as 10:1 to 100:1, 10:1 to 50:1.

[0046] Solvents In an embodiment, the first additive and / or second additive are provided to the base polymer with or along with one or more solvents. It is appreciated that the type and amount of solvent may be varied as needed to provide desired properties to the coating composition, including but not limited to providing a predetermined thickness of the coating when applied to a substrate. In an embodiment, the solvent is selected from the group consisting of alcohols, ether alcohols, glycols, ketones, esters, ethers, fluorinated hydrocarbons, sulfoxides, and combinations thereof.

[0047] In certain embodiments, the one or more solvents the first additive and / or second additive are selected fr2om the group consisting of dimethyl phthalate (DiMPh), dipropylene glycol methyl ether (DiPGME), dipropylene glycol butyl ether (DiPGBE), diethylene glycol ethyl ether (DiEGEE), 2propylene carbonate (PC), dimethyl sulfoxide (DMSO), 2-propanol (IP A), ethylene glycol (EG), l-methoxy-2-propanol (PGME), di(ethylene glycol) monoethylether, di(ethylene glycol)monobutylether, and combinations thereof.

[0048] In certain embodiments, the one or more solvents are present at a concentration of from 5 to 75 wt%, for example, 10 to 60 wt %, of the total wt % of the coating composition. In an embodiment, the final coating composition comprises a solids content of from 0.1 to 2 wt %, for example, 0.4 to 1 wt%.

[0049] In an embodiment, the coating composition may comprise one or more additional additives (in addition to the first and second additives). In an embodiment, the one or more additional additives (additional additives) may comprise microparticles or nanoparticles (e.g., rods, crystals, spheres, dots, buds, and the like.) In an 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 added functionality for the coating composition.

[0050] Coating process

[0051] In accordance with another aspect, once formed, the coating composition may be applied on a suitable substrate to form a film thereon. Without limitation, the substrate may be formed from ceramic materials, glass, metals, natural and man-made stones, polymeric materials (e.g., poly(meth)acrylate, polycarbonate, polystyrene, styrene copolymers, such as styrene acrylonitrile copolymers, polyesters, or polyethylene terephthalate), or wood and fibrous substrates (e.g., textiles, leather, carpets, or papers). In particular embodiments, the substrate comprises a metal substrate, such as a galvanized steel substrate, a gun metal substrate, a gold substrate, or a copper bronze substrate. The coating composition may be applied on the substrate by any suitable process. In an embodiment, the coating composition is applied by dip coating, slot coating, combined slot and spin coating, spin coating, spray coating, ink-jet printing, curtain coating, roller coating, roll-to-roll coating, screen printing or using a bar or brush, or by rubbing. In certain embodiments, the coating composition is applied by a physical vapor deposition (PVD) technique. In other embodiments, the coating composition is applied by spray coating.

[0052] In an embodiment, the temperature during application of the coating composition is done at a temperature of from 20 to 100° C, such as from 25 to 75° C. In certain embodiments, the substrate is pre-heated to a temperature of from 20 to 100° C, such as from 25 to 50° C.

[0053] In certain embodiments, once the film is formed on the substrate, a pattern can be formed into the film to form surface features and patterns. Such patterns may provide additional optical, physical or chemical properties to the film. Exemplary processes for pattern forming include, but are not limited to, nano-imprinting, embossing, roll-to-roll, gravure, flexo-graphic, roller, ink-jet, screen-printing, spray lithography, and / or UV lithography.

[0054] In certain embodiments, after application of the coating composition on 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 done using temperature and / or by vacuum. In particular embodiments, the removal step is done at a pressure of 50 to 200 kPa at a temperature of 50 to 150° C.

[0055] In certain embodiments, the method further comprises activating the surface prior to applying the coating composition to the substrate. The activating step may be done by any suitable method, such as by the application of ozone, etching, flame, corona discharge, and / or plasma techniques.

[0056] Curing

[0057] In an embodiment, the applied coating composition is optionally cured on the substrate in the process of forming the film. The curing is done by the application of heat, such as by a convection oven, a hot plate, or by electromagnetic irradiation. In certain embodiments, the curing is done by a combination of heat and the application of UV energy. The temperature for the curing step may be any suitable value(s), such as 25 to 300° C, and may be less than 150° C or 80° C. The curing time may be any suitable duration, such as from 10 min. to 5.0 hours, such as 20 min. to 3.0 hours, e.g., 5 min. to 1.0 hour. The formed film may comprise any suitable thickness, such as from 1 nm to 10 pm, such as from 100 nm to 1 pm 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 herewith incorporated by reference.

[0058] Properties

[0059] In an embodiment, the film comprises a water contact angle of at least 110°, at least 115°, or at least 120°.

[0060] In an embodiment, the film comprises a pencil hardness (PEHA) of at least 7H, at least 8H, or at least 9H.

[0061] In an embodiment, the film comprises a refractive index (at 632 nm) from 1.1 to 1.50, such as 1.25 to 1.45 (at 632 nm).

[0062] In an embodiment, the film comprises an RMS surface roughness of below 5.0 nm, below 3.5 nm, or below 2.5 nm.

[0063] In an embodiment, the film has a water contact angle after a 2000 cycle steel wool abrasion of at least 85°, at least 95°, or at least 105°, when the film is formed on a metal substrate.

[0064] It is to be understood that the configurations and / or approaches described herein are exemplary in nature, and that these specific embodiments or examples are not to be considered in a limiting sense, because numerous variations are possible. The specific routines or methods described herein may represent one or more of any number of processing strategies. Thus, the various acts illustrated may be performed in the sequence illustrated, in other sequences, or omitted in some cases.

[0065] The subject matter of the present disclosure includes all novel and nonobvious combinations and sub-combinations of the various compositions and processes, and other features, functions, acts, and / or properties disclosed herein, as well as any and all equivalents thereof.

[0066] Examples n a 10L reactor, tetraethoxy silane (510.72 g) is mixed with acetone (1600 g). HNCh (0.1M; 353.28 g) is added dropwise and the reaction mixture is refluxed for Ih. After cooling to room temperature, l-methoxy-2 -propanol (1600 g) is added and solvent exchange from EtOH / acetone / H2O to PGME is performed under reduced pressure. After moisture analysis, the solids content is adjusted to 10% by addition of l-methoxy-2-propanol. Formulation The base polymer (10% solids content in l-methoxy-2-propanol; 6000 g) is mixed with Novec 7200™ (39480 g), KY-1901 (280 g; 0.4% in Novec 7200™), 2-propanol (32312 g) and ethylene glycol (1984 g). n a 10L reactor, tetraethoxy silane (510.72 g) is mixed with acetone (1600 g). HNO3 (0.1M; 353.28 g) is added dropwise and the reaction mixture is refluxed for Ih. After cooling to room temperature, l-methoxy-2 -propanol (1600 g) is added and solvent exchange from EtOH / acetone / H2O to PGME is performed under reduced pressure. After moisture analysis, the solids content is adjusted to 10% by addition of l-methoxy-2-propanol.

[0067] Formulation The base polymer (10% solid content in l-methoxy-2-propanol; 525 g) is mixed with Novec 7100™ (3454.5 g), KY-1901 (24.5 g; 0.4% inNovec 7100™), 2-propanol (2827.3 g) and ethylene glycol (3.72 g).

[0068] Synthesis of the base (root) In a round bottom flask, tetraethoxysilane (43 g), 3-

[0069] Trimethoxysilylpropyl methacrylate 3 -Trimethoxy silylpropyl methacrylate (5.7 g) and ZrCh (9.74 g) are mixed in acetone (136 g). HNO3 (0.1M; 32.23 g) is added dropwise and the reaction mixture is refluxed for 2h. After cooling to room temperature, 1 -methoxylpropanol (116 g) is added and solvent exchange from EtOH / MeOH / acetone / H2O to

[0070] PGME is performed under reduced pressure. After moisture analysis, the solid content is adjusted to 10% by addition of l-methoxy-2 -propanol.

[0071] Formulation The base polymer (10% solid content in 1 methoxy-2 -propanol; 15 g) is 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). Table 1

[0072] Properties of the coatings on a metal substrate:

[0073] As can be seen from Table 1, the compositions showed similar properties, but one (Composition 1) passed the boiling water test. Table 2

[0074] Properties of the coatings on another metal substrate:

[0075] As can be seen from Table 2, Composition 1 has the best abrasion resistance of the 3 compositions and passed the boiling water test. Table 3

[0076] Properties of the coatings on another metal substrate:

[0077] As can be seen from Table 3, Composition 1 provides the best water contact angle.

[0078] Table 4 PVD maximum abrasion resistance studies:

[0079] As can be seen from Table 4, all compositions (1-3) deposited by PVD on the listed substrates passed the subject tests. The coating method is automatic spray. The coating parameters were adjusted to obtain a film thickness of about 50 - 80 nm. The abrasion tests were performed with a linear abraser (1 kg load, 1 x 1 cm head, a wet cotton cloth, 2 inches stroke length and with a speed of 60 cycles / min). Boiling test was conducted with tape water. After coating, the properties of the coated-substrates are evaluated after a waiting time up to one week. The thickness of the film needs to be at least 65 nm. Plasma treatment and washing conditions are important to obtain good quality films.

[0080] Industrial Applicability

[0081] Aspects of the present invention may be used, for example, as films on articles, such as display devices, touch screen devices, photovoltaic devices (cells, panels, and modules), luminaires, metal surfaces, and apparatuses. The film may provide excellent properties, including but not limited to: mechanical stabilization, oxidation stabilization, adhesion, hardness, and abrasion resistance.

Claims

CLAIMS1. A coating composition comprising: a base polymer formed from a plurality of monomers, wherein the plurality of monomers comprise 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.

2. The coating composition of claim 1 , wherein the plurality of monomers comprises 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 (Fl 7), 1H,1H,2H,2H-Perfluorooctyltrimethoxysilane (Fl 3), and combinations thereof.

3. The coating composition of any one of the preceding claims, wherein at least 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 mole % of the plurality of monomers are tetraethoxysilane (TEOS) monomers, based on a total mole % of the plurality of monomers.

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

5. The coating composition of any one of the preceding claims, wherein the second additive comprises a perfluoropolyether-containing alkoxysilane, such as a perfluoropolyether-containing trialkoxy silane.

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

7. The coating composition of any one of the preceding claims, wherein the coating composition comprises a solids content of from 0.1 to 2 wt %, for example, 0.4 to 1 wt%.

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

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

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

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

12. The coating composition of any one of the preceding claims, wherein the coating composition further comprises 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 of 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), l-methoxy-2-propanol (PGME), di(ethylene glycol) monoethylether, di(ethylene glycol)monobutylether, and combinations thereof.

14. The coating composition of claim 12, wherein the one or more solvents are present at a concentration of from 5 to 75 wt%, for example, 10 to 60 wt %, of the total wt % of the coating composition.

15. A substrate comprising a film on a surface thereof, the film formed from the coating composition of claim 1.

16. The substrate of claim 15, wherein the substrate comprises a metal substrate, such as a galvanized steel, gun metal, gold substrate, copper bronze substrate.

17. The substrate of any one of claims 15 to 16, wherein the film comprises 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 comprise 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 of forming a film on a substrate comprising: forming a base polymer from a plurality of monomers, wherein the plurality of monomers comprise 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 on the substrate; and optionally curing the coating composition.

20. The process of claim 19, wherein the plurality of monomers comprises 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 (Fl 7), 1H,1H,2H,2H-Perfluorooctyltrimethoxysilane, and combinations thereof.

21. The process of any one of claims 19 to 20, wherein the first additive comprises a mixture of two or more of methoxynonafluorobutane, ethoxynonafluorobutane, methyl perfluoroisobutyl ether, ethyl perfluoroisobutyl ether, ethyl nonafluorobutyl ether, and l,l,l,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)pentane, and mixtures thereof22. The process of any one of claims 19 to 21, wherein the second additive comprises a perfluoropolyether-containing alkoxysilane, such as a perfluoropolyether-containing trialkoxy silane.

23. The process of any one of claims 19 to 22, wherein the applying of the coating composition is done by spray coating 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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