UV-curable hybrid organosilicon coating

Abstract

A protective hybrid coating is described. The hybrid coating is a silicon-based coating formed from a multi-stage curing of a single-pot solution containing an epoxy alkoxysilane, an amine alkoxysilane, an alkene alkoxysilane, a thiol alkoxysilane, a solvent, and either (i) a photoinitiator or (ii) a salt, peroxide, or thermal acid generator. An initiator or catalyst may be used as an alternative to initiate curing, and the hybrid coating may contain various additives.

Description

Technical Field

[0001] Related Applications This application claims priority to U.S. Provisional Patent Application No. 63 / 356,197, filed on June 28, 2022, the entire disclosure of which is incorporated herein by reference under 35 U.S.C. § 119(e).

[0002] Description of Research Funded by the Federal Government This invention was made with government support under grant number P20AP00319 awarded by the U.S. National Park Service. The government has certain rights in this invention.

Background Art

[0003] Historically, preferred preservation methods for various materials, including stone, metal, etc., have used a series of surface coatings. Organic polymers such as epoxy resins, acrylates, and fluoropolymers have been used for this purpose due to their hydrophobicity and protective properties, but they are insufficient in some fields when used alone. Epoxy provides very good surface penetration and mechanical strength, but is susceptible to oxidation, discoloration, and biological growth on the surface due to light, and has a short pot life. Acrylic often provides surface strengthening, is light-stable, and may have antifouling properties, but is difficult to remove and tends to take a long time to cure. Fluoropolymers provide highly hydrophobic surfaces with light stability, but their hydrophobicity can make them difficult to handle and may be environmentally unfriendly. There are also coatings that have used polysiloxanes for light and thermal stability and have been successful in other industrial applications, but they deteriorate over time by hydrolysis. Sol-gel systems (i.e., R-alkoxysilanes) have also shown significant success in preventing the oxidation process on metal surfaces. These silicon-based systems utilize components that can be obtained from green chemical sources such as rice husk ash. Each of the systems has advantages, but also has the disadvantage of being difficult to apply for long-term protection.

[0004] There are also coatings designed to overcome the aforementioned limitations by integrating organic and inorganic materials into a hybrid system. The use of organofunctional alkoxysilanes to achieve the characteristics of both systems, including epoxy chains and fluorocarbon chains, has been successful in some cases. Also, to reduce the stress of shrinkage occurring in both organic and inorganic polymers, network-forming side chains such as thiols, alkenes, and alkynes have been incorporated as another option. As another option, surface modification with spacings of less than 0.1 micron in diameter or nanoparticle additives shows an increase in the contact angle of water due to surface roughness, enhancing the overall hydrophobicity. However, in this technical field, new and improved surface coatings are still in demand.

SUMMARY OF THE INVENTION

[0005] A hybrid coating is provided that includes thiol alkoxysilane; alkene alkoxysilane; epoxy alkoxysilane; amine alkoxysilane; and a solvent, and this hybrid coating is in the form of a curable solution.

[0006] In certain embodiments, the hybrid coating further includes a photoinitiator, in which case the hybrid coating is in the form of a photocurable solution. In certain embodiments, the thiol alkoxysilane includes (3-mercaptopropyl)-trimethoxysilane, 2-mercaptoethyltrimethoxysilane, 3-(dimethoxymethylsilyl)-2-methylpropanethiol, or combinations thereof. In certain embodiments, the thiol alkoxysilane is present in an amount up to about 30 volume / volume %.

[0007] In certain embodiments, the alkene alkoxysilane contains a vinyl group. In certain embodiments, the alkene alkoxysilane contains an allyl group. In certain embodiments, the alkene alkoxysilane contains 2,4,6,8-tetramethyl, 2,4,6,8-tetravinylcyclotetrasiloxane, 1,3-divinyltetramethyldisiloxane, vinyltriethoxysilane, N-[2-(vinylbenzylamino)ethyl]-3-aminopropyltrimethoxysilane, vinyltriacetoxysilane, or a combination thereof. In certain embodiments, the alkene alkoxysilane is present in an amount up to about 60 volume / volume %.

[0008] In certain embodiments, the epoxy alkoxysilane contains 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-(2,3-epoxypropoxypropyl)methyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, or a combination thereof. In certain embodiments, the epoxy alkoxysilane is present in an amount up to about 50 volume / volume %.

[0009] In certain embodiments, the amine alkoxysilane contains 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-[2-(vinylbenzylamino)ethyl]-3-aminopropyltrimethoxysilane, or a combination thereof. In certain embodiments, the amine alkoxysilane is present in an amount up to about 50 volume / volume %.

[0010] In certain embodiments, the photoinitiator contains phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylaryl)methane (also known as omnirad 819).

[0011] In certain embodiments, the hybrid coating further contains Norrish type I and II photoinitiators. In certain embodiments, the hybrid coating further comprises a cationic / anionic polymerization initiator.

[0012] In certain embodiments, the hybrid coating further comprises up to about 30 volume / volume % of a fluorocarbon. In certain embodiments, the fluorocarbon comprises triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane or (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane.

[0013] In certain embodiments, the hybrid coating further comprises an aromatic alkoxysilane comprising aryltriethoxysilane, trimethoxy(2-arylethyl)silane, triethoxy-p-tolylsilane, or combinations thereof. In certain embodiments, the arylalkoxysilane is present in an amount up to about 30 volume / volume %.

[0014] In certain embodiments, the alkoxysilane comprises side chains of alkanes, alkenes, or alkynes, or combinations thereof. In certain embodiments, the alkyl-substituted alkoxysilane is present in an amount up to about 30 volume / volume %.

[0015] In certain embodiments, the alkoxysilane comprises siloxane side chains or combinations of siloxane side chains. In certain embodiments, the siloxane-substituted alkoxysilane is present in an amount up to about 30 volume / volume %.

[0016] In certain embodiments, the hybrid coating further comprises a silsesquioxane. In certain embodiments, the hybrid coating further comprises one or more additional siloxanes, silanes, silsesquioxanes, or combinations thereof. In certain embodiments, the additional siloxane, silane, or silsesquioxane comprises D4 octamethylcyclotetrasiloxane, methyltriethoxysilane, vinyl-terminated silsesquioxane, 1,2-bis(triethoxysilyl)ethane, butylpoly(dimethylsiloxanyl)ethyltriethoxysilane, isooctyltriethoxysilane, isobutyltriethoxysilane, or combinations thereof.

[0017] In certain embodiments, the solvent comprises an alcohol. In certain embodiments, the solvent comprises a combination of alcohols. In certain embodiments, the solvent comprises an alcohol that is complementary to one or more of an amine alkoxysilane, an epoxy alkoxysilane, a thiol alkoxysilane, or an alkene alkoxysilane.

[0018] In certain embodiments, the thiol alkoxysilane comprises a di- or tri-alkoxysilane, the alkene alkoxysilane comprises a di- or tri-alkoxysilane, the epoxy alkoxysilane comprises a di- or tri-alkoxysilane, and the amine alkoxysilane comprises a di- or tri-alkoxysilane.

[0019] In certain embodiments, the hybrid coating further comprises a spacer. In certain embodiments, the spacer comprises D4 octamethylcyclotetrasiloxane or polyethylene glycol (PEG).

[0020] In certain embodiments, the hybrid coating further comprises an acid. In certain embodiments, the acid comprises glacial acetic acid, trifluoroacetic acid, or a photoacid generator such as diaryliodonium hexafluorophosphate, or combinations thereof.

[0021] In certain embodiments, the hybrid coating further comprises a hydroxide. In certain embodiments, the hybrid coating further comprises a metal salt. In certain embodiments, the metal salt is zinc chloride.

[0022] In certain embodiments, the hybrid coating further comprises a crosslinking agent. In certain embodiments, the hybrid coating comprises 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane, (3-mercaptopropyl)-trimethoxysilane, vinyltriethoxysilane, omnirad 819, diaryliodonium hexafluorophosphate, methanol, and isopropanol. In certain embodiments, the hybrid coating comprises 3-glycidoxypropyltrimethoxysilane in an amount of about 8.2 volume / volume%; 3-aminopropyltriethoxysilane in an amount of about 7.5 volume / volume%; triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane in an amount of about 1.6 volume / volume%; (3-mercaptopropyl)-trimethoxysilane in an amount of about 2.9 volume / volume%; vinyltriethoxysilane in an amount of about 3.3 volume / volume%; omnirad 819 in an amount of about 0.3 weight / volume%; diaryliodonium hexafluorophosphate in an amount of about 0.1 weight / volume%; methanol in an amount of about 36.1 volume / volume%; and isopropanol in an amount of about 40.1 volume / volume%.

[0023] In certain embodiments, the hybrid coating comprises 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane, (3-mercaptopropyl)-trimethoxysilane, vinyltriethoxysilane, omnirad 819, diaryliodonium hexafluorophosphate, methanol, and isopropanol. In certain embodiments, the hybrid coating comprises 3-glycidoxypropyltrimethoxysilane in an amount of about 13.7 volume / volume %; 3-aminopropyltriethoxysilane in an amount of about 12.3 volume / volume %; (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane in an amount of about 2.8 volume / volume %; (3-mercaptopropyl)-trimethoxysilane in an amount of about 5.0 volume / volume %; vinyltriethoxysilane in an amount of about 5.6 volume / volume %; omnirad 819 in an amount of about 0.5 weight / volume %; diaryliodonium hexafluorophosphate in an amount of about 0.2 weight / volume %; methanol in an amount of about 18.1 volume / volume %; and isopropanol, ethanol, or water in an amount of about 41.8 volume / volume %.

[0024] In certain embodiments, the hybrid coating comprises 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane, (3-mercaptopropyl)-trimethoxysilane, vinyltriethoxysilane, omnirad 819, diaryliodonium hexafluorophosphate, methanol, and 1-butanol. In certain embodiments, the hybrid coating comprises 3-glycidoxypropyltrimethoxysilane in an amount of about 13.6 volume / volume %; 3-aminopropyltriethoxysilane in an amount of about 12.3 volume / volume %; (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane in an amount of about 2.8 volume / volume %; (3-mercaptopropyl)-trimethoxysilane in an amount of about 5.0 volume / volume %; vinyltriethoxysilane in an amount of about 5.5 volume / volume %; omnirad 819 in an amount of about 0.8 weight / volume %; diaryliodonium hexafluorophosphate in an amount of about 0.3 weight / volume %; methanol in an amount of about 18.1 volume / volume %; and 1-butanol in an amount of about 41.7 volume / volume %.

[0025] In certain embodiments, the hybrid coating further comprises a salt, a peroxide, or a thermal acid generator, in which case the hybrid coating is in the form of a thermosetting solution. In certain embodiments, the salt comprises ZnCl2. In certain embodiments, the thermal acid generator comprises p-nitrobenzyl tosylate. In certain embodiments, the hybrid coating comprises 3-glycidoxypropyltrimethoxysilane in an amount of about 13.9 volume / volume %; 3-aminopropyltriethoxysilane in an amount of about 12.5 volume / volume %; (3-mercaptopropyl)-trimethoxysilane in an amount of about 5.1 volume / volume %; vinyltriethoxysilane in an amount of about 5.7 volume / volume %; hydrogen peroxide (30% aqueous solution) in an amount of about 1.0 volume / volume %; ZnCl2 in an amount of about 1.0 weight / volume %; methanol in an amount of about 18.4 volume / volume %; and isopropanol in an amount of about 42.4 volume / volume %.

[0026] In certain embodiments, the hybrid coating further comprises a dye or colorant. In certain embodiments, the hybrid coating comprises a photochromic dye or a combination of photochromic dyes.

[0027] In certain embodiments, the hybrid coating further comprises a metal or carbon fiber. In certain embodiments, the metal or carbon fiber comprises graphene or nanotubes. In certain embodiments, the hybrid coating comprises 3-glycidoxypropyltrimethoxysilane in an amount of about 14.1 volume / volume %; 3-aminopropyltriethoxysilane in an amount of about 12.7 volume / volume %; (3-mercaptopropyl)-trimethoxysilane in an amount of about 5.1 volume / volume %; vinyltriethoxysilane in an amount of about 5.7 volume / volume %; omnirad 819 in an amount of about 0.5 weight / volume %; diaryliodonium hexafluorophosphate in an amount of about 0.2 weight / volume %; methanol in an amount of about 18.6 volume / volume %; and isopropanol in an amount of about 43.0 volume / volume %.

[0028] Further provided is a hybrid coating comprising Formula I:

[0029]

Chemical formula

[0030] The hybrid coating is in the form of a cured solid. In certain embodiments, the hybrid coating is a flame retardant. In certain embodiments, the hybrid coating has a water contact angle greater than 90°. In certain embodiments, the hybrid coating is heat resistant up to a temperature of at least 300 °C. In certain embodiments, the hybrid coating is coated on a substrate comprising stone, brick, wood, glass, metal, plastic, rubber, cloth, leather, glass fiber, carbon fiber composite, polyester gel coat, concrete, steel, aluminum, nitrile, or vinyl.

[0031] Further provided is a hybrid coating comprising a composition formed from (i) the reaction of an amine alkoxysilane and a thiol alkoxysilane, (ii) the reaction of an epoxy alkoxysilane and an alkene alkoxysilane, and (iii) a moisture polymerization that replaces alkoxy groups present from the epoxy alkoxysilane, amine alkoxysilane, thiol alkoxysilane, and alkene alkoxysilane.

[0032] Further provided is a method of protecting a monument from acid rain and graffiti, the method comprising applying the hybrid coating described herein to the monument and curing the hybrid coating to protect the monument from acid rain and graffiti.

[0033] Further provided is a method of protecting a surface from water, the method comprising applying to the surface a hybrid coating comprising a fluorocarbon as described herein and curing the hybrid coating to protect the surface from water.

[0034] Further provided is a method of protecting a surface from scratches, the method comprising applying the hybrid coating described herein to the surface and curing the hybrid coating to protect the surface from scratches.

[0035] Further provided is a method of protecting an article from flame damage, the method comprising applying the hybrid coating described herein to the article and curing the hybrid coating to protect the article from flame damage. In certain embodiments, the article is wood.

[0036] Further provided is a method of protecting a surface or releasing plastic and adhesives from a surface, the method comprising applying the hybrid coating described herein to the surface and curing the hybrid coating to protect the surface from adhesion.

[0037] Furthermore, a method for protecting a surface from biological growth is provided, the method comprising applying a hybrid coating as described herein to a surface that may be exposed to biological contamination, and curing the hybrid coating to protect the surface from biological growth.

[0038] Furthermore, a method for applying a dye to a surface is provided, the method comprising applying a hybrid coating containing the dye to the surface, and curing the hybrid coating.

[0039] Furthermore, a method for reducing cell adhesion to a surface is provided, the method comprising applying a hybrid coating as described herein to the surface, and curing the hybrid coating to reduce cell adhesion to the surface. In certain embodiments, the surface is glass, metal, plastic, or silicone. In certain embodiments, the surface includes a floor or a medical device. In certain embodiments, the surface includes a medical device or an implant.

[0040] Furthermore, a method for reducing the gloss of a surface is provided, the method comprising incorporating a salt into a hybrid coating as described herein, applying the salt-containing hybrid coating to the surface, and curing the salt-containing hybrid coating to reduce the gloss of the surface. In certain embodiments, the salt is ZnCl2.

[0041] Furthermore, a method for reducing electrostatic charge accumulation on a surface is provided, the method comprising incorporating a metal or carbon fiber into a hybrid coating as described herein, applying the metal-containing or carbon fiber-containing hybrid coating to the surface, and curing the metal-containing or carbon fiber-containing hybrid coating to reduce electrostatic charge accumulation on the surface. In certain embodiments, the metal or carbon fiber includes copper, zinc, iron, graphene, or nanotubes.

[0042] Furthermore, a method for bonding two surfaces together is provided, which method includes applying the hybrid coating described herein to at least one of the two surfaces, pressing the two surfaces together, and curing the hybrid coating to bond the two surfaces together. In certain embodiments, the two surfaces are glass.

[0043] Furthermore, a method for forming a barrier against oil on a surface is provided, which method includes applying the hybrid coating described herein to the surface and curing the hybrid coating on the surface to form a barrier against oil on the surface. In certain embodiments, the surface includes marble.

[0044] Furthermore, a method for reducing efflorescence on a surface is provided, which method includes applying the hybrid coating described herein to the surface and curing the hybrid coating on the surface to reduce efflorescence on the surface.

[0045] Furthermore, a method for enhancing the fire resistance of a surface is provided, which method includes applying the hybrid coating described herein to the surface and curing the hybrid coating on the surface to enhance the fire resistance of the surface. In certain embodiments, the surface includes wood.

[0046] Furthermore, a method for improving the stain resistance of a surface is provided, which method includes applying the hybrid coating described herein to the surface and curing the hybrid coating on the surface to improve the stain resistance of the surface. In certain embodiments, the surface includes glass.

[0047] Furthermore, a method for making a surface antifungal and anti-corruptive is provided, which method includes applying the hybrid coating described herein to the surface and curing the hybrid coating on the surface to make the surface antifungal and anti-corruptive. In certain embodiments, the surface includes wood.

[0048] Furthermore, a method for preventing wood from cracking at its ends is provided, the method including applying the hybrid coating described herein to a wood piece having ends, and curing the hybrid coating on the wood piece to prevent the wood piece from cracking at the ends.

[0049] Furthermore, a method for curing a hybrid coating is provided, the method including coating a substrate with a hybrid coating solution containing a photoinitiator; causing a first curing process to occur over a first time by exposing the hybrid coating solution to sunlight or artificial UV light to form a coating having a non-impressionable surface on the substrate; causing a second curing process to occur over a second time to improve adhesion between the coating and the substrate; and causing a third curing process to occur over a third time to solidify the non-impressionable surface. In certain embodiments, the hybrid coating solution includes a plurality of alkoxysilanes including epoxy, alkene, amine, and thiol components.

[0050] Furthermore, a coating method for applying a plurality of layers of the hybrid coating described herein onto a substrate is provided, the method including applying a first layer of the hybrid coating described herein to the substrate, completely curing the first layer over a first time, applying a second layer of the hybrid coating to the substrate, and curing the second layer over a second time.

[0051] Furthermore, a method for removing the hybrid coating described herein from a substrate is provided, the method including exposing the substrate having the hybrid coating to a solution containing a fluoride source in a solvent for the purpose of depolymerizing the siloxane polymer to remove the hybrid coating from the substrate.

[0052] Further provided is a coated article comprising a substrate coated with the hybrid coating described herein. In certain embodiments, the article is a monument, gravestone, means of transportation, clothing, tool, industrial mold, or building material.

[0053] Further provided is a method of curing a hybrid coating, the method comprising adding a salt to a hybrid coating solution; adding hydrogen peroxide to the hybrid coating solution; coating a substrate with the hybrid coating solution to form a coated substrate; exposing the coated substrate to a temperature of at least about 65° C. for a first time; and allowing the coated substrate to stand at room temperature for a second time to cure the hybrid coating on the substrate. In certain embodiments, the hybrid coating solution comprises a plurality of alkoxysilanes comprising epoxy, alkene, amine, and thiol components. In certain embodiments, the hybrid coating solution does not contain a photoinitiator. In certain embodiments, the first time is at least about 5 minutes. In certain embodiments, the second time is at least about 45 minutes.

[0054] Further provided is a method of curing a hybrid coating, the method comprising adding a salt to a hybrid coating solution; adding hydrogen peroxide to the hybrid coating solution; coating a substrate with the hybrid coating solution to form a coated substrate; allowing the coated substrate to stand at room temperature for a first time; and exposing the coated substrate to a temperature of at least about 150° C. for a second time to cure the hybrid coating on the substrate. In certain embodiments, the hybrid coating solution comprises a plurality of alkoxysilanes comprising epoxy, alkene, amine, and thiol components. In certain embodiments, the hybrid coating solution does not contain a photoinitiator. In certain embodiments, the first time is at least about 1 hour. In certain embodiments, the second time is less than about 30 seconds.

[0055] Further provided is a hybrid coating comprising a thiolalkoxysilane, an alkenealkoxysilane, an epoxyalkoxysilane, an aminealkoxysilane, a photoinitiator, and a solvent, where the hybrid coating is in the form of a photocurable solution.

[0056] Further provided is a hybrid coating comprising a thiolalkoxysilane; an alkenealkoxysilane; an epoxyalkoxysilane; an aminealkoxysilane; a solvent; and a salt, peroxide, or thermal acid generator, where the hybrid coating is in the form of a thermocurable solution.

[0057] Further provided is a hybrid coating comprising a thiolalkoxysilane; an alkenealkoxysilane; an epoxyalkoxysilane; an aminealkoxysilane; a solvent; and either (i) a photoinitiator (where the hybrid coating is in the form of a photocurable solution), (ii) a salt, peroxide, or thermal acid generator (where the hybrid coating is in the form of a thermocurable solution), or (iii) a cation and / or an anion (where the hybrid coating is in the form of a chemically curable solution).

[0058] This patent or patent application file may contain one or more drawings created in color and / or one or more photographs. Copies of this patent or patent application publication with color drawings and / or photographs are obtained from the United States Patent and Trademark Office by requesting and paying the necessary fees.

Brief Description of the Drawings

[0059]

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Mode for Carrying Out the Invention

[0060] Throughout the present disclosure, various publications, patents, and published patent specifications are referenced by means of identifying citations. The disclosures of these publications, patents, and published patent specifications are hereby incorporated by reference in their entirety to more fully describe the state of the art to which the present invention pertains.

[0061] An ideal protective coating system provides rapid curing, long life, surface hardness, versatile application methods / conditions, exhibits hydrophobicity, and resists photodegradation and acid rain. According to the present disclosure, through the integration of various coating curing methods, a unique hybrid coating system has been created that has a combination of desired individual features and surprisingly advantageous properties. Herein, hybrid coatings made from three orthogonal curing methods in various ratios are provided, which, first, polymerize the surface in a state not subject to rapid influence, second, improve the epoxide-amine surface adhesion, and third, provide long-term sol-gel surface solidification with long life, recoatability, recyclability of components for future use, easy removability, and improved epoxide adhesion. As a result of this curing process, a colorless, transparent, hard, hydrophobic, acid-resistant, photodegradation-resistant, temperature-resistant, UV-stable, fire-resistant, and graffiti-resistant surface coating is obtained that is applicable to any substrate including, but not limited to, stone, glass, brick, wood, cloth, plastic, rubber, glass fiber, plastic (such as polyethylene or polypropylene), concrete, silicone, ceramic, or metal surfaces. This coating can be referred to as a hybrid coating or a tri-cure hybrid organosilicon coating. The hybrid coating substantially exhibits the advantages of conventional silicon-based coatings while its disadvantages are weakened. Among many examples, the hybrid coating can be used, but is not limited to, as a topcoat or finish, a water sealant, a protective coating for monuments or means of transportation, a floor coating, a coating or film for glass products such as glasses, windows, and windshields, an adhesive, a barrier against oil, an efflorescence reducer, a flame-retardant coating, a biomedical coating for floors, equipment, instruments, etc., an antifouling coating, or an antifungal coating.

[0062] Figure 1 shows a non-limiting example of the structure and curing process of the components of a hybrid coating according to the present disclosure. Generally, in some embodiments, the hybrid coating includes a thiolalkoxysilane, an alkenealkoxysilane, an epoxyalkoxysilane, an aminealkoxysilane, a photoinitiator, and a solvent. These components together form a photocurable solution that can be cured by sunlight or artificial light to form a solidified transparent protective coating. In other embodiments that can be cured by a thermal process instead of a photoinitiation process, the photoinitiator is absent. Instead, the hybrid coating may include a salt such as ZnCl2, which is a thermal acid generator, or a peroxide such as hydrogen peroxide, for the purpose of enabling thermal curing, and this hybrid coating solution can be heated instead of using light to initiate three different curing processes. In other embodiments that can be cured by cation / anion curing, the hybrid coating may include a cationic or anionic substance that can initiate the polymerization process. In yet other embodiments, the hybrid coating may not contain an initiator.

[0063] As described below, many additives that are optionally used may also be included in the hybrid coating. Suitable additives include, but are not limited to, dyes; pigments; liquid crystals; microparticles; metals such as copper, zinc, or iron; carbon fibers such as graphene and nanotubes; salts such as NaCl or ZnCl2; and combinations thereof.

[0064] Each of the alkenealkoxysilane, thiolalkoxysilane, epoxyalkoxysilane, and aminoalkoxysilane can be either a di- or tri-alkoxysilane. If present, any other additional alkoxysilane (such as phenylalkoxysilane) can also be a di- or trialkoxysilane. Thus, the hybrid coating herein is a silane-based coating. In one non-limiting example, the hybrid coating may have the structure of Formula I below after the first two curing processes are completed.

[0065]

Chem.

[0066] However, there may be additional reactivity of the alkoxysilane, and thus it is understood that the structure of the final fully cured hybrid coating may be different. Further, since the structure of the final fully cured hybrid coating depends on the types of components used in the solution, many other structures of the cured hybrid coating are possible and are encompassed within the scope of this disclosure.

[0067] As seen in FIG. 1, in this coating system, an oxidation-resistant, thermally stable, and photo-stable siloxane network backbone with functionalized side chains that cause a curing process as an alternative is formed using a sol-gel process. In some embodiments, the hybrid coating incorporates thiol and vinyl photoinitiated curing (thiol-ene) to rapidly form a hard surface, relieve the network stress on the system while imparting additional photo-stability. Additionally, epoxy, amine, and optionally fluorocarbon and aromatic side chains enhance surface adhesion and permeability, mechanical strength, and hydrophobicity (reduction of surface energy). The network as a whole exhibits the advantageous qualities of each type of coating while mitigating the drawbacks commonly seen when using them separately.

[0068] An alkenyl alkoxysilane can contain either a vinyl group or an allyl group bonded to the alkoxysilane. There is no limit to the number of carbon atoms in the chain between the alkene group and the alkoxysilane in the alkenyl alkoxysilane. In some embodiments, there are 1 to 9 carbons in the chain between the alkene group and the alkoxysilane. In the non-limiting example illustrated in Figure 1, there is 1 carbon between the double bond of the alkene group and the alkoxysilane. The alkenyl alkoxysilane can be present in an amount up to about 60 volume / volume %. The alkenyl alkoxysilane may be present in the form of a combination of a plurality of alkenyl alkoxysilanes that together are present in a total amount up to about 60 volume / volume %. The alkoxysilane moiety may be a di- or tri-alkoxysilane, but not a mono-alkoxysilane, because polymerization into the silicon polymer is important for the entire hybrid coating. Non-limiting examples of suitable alkenyl alkoxysilanes include 2,4,6,8-tetramethyl, 2,4,6,8-tetravinylcyclotetrasiloxane, 1,3-divinyltetramethyldisiloxane, vinyltriethoxysilane, N-[2-(vinylbenzylamino)ethyl]-3-aminopropyltrimethoxysilane, vinyltriacetoxysilane, or combinations thereof.

[0069] Thiol alkoxysilane can contain a thiol group and an alkoxysilane, and there is no limitation on the chain length between the two. In some embodiments, the chain between the thiol group and the alkoxysilane has 1 to 9 carbons. In the non-limiting example illustrated in FIG. 1, the chain length between the thiol and the alkoxysilane is 3 carbons in length. The alkoxysilane moiety may be a di- or tri-alkoxysilane, but must not be a mono-alkoxysilane, because polymerization into the silicon polymer is important for the entire hybrid coating. Non-limiting examples of suitable thiol alkoxysilanes include (3-mercaptopropyl)-trimethoxysilane, 2-mercaptoethyltrimethoxysilane, 3-(dimethoxymethylsilyl)-2-methylpropanethiol, or combinations thereof. The thiol alkoxysilane or combination of thioalkoxysilanes can be present in an amount (or total amount) up to about 30 volume / volume %.

[0070] Epoxy alkoxysilane can contain an epoxy group and an alkoxysilane, and there is no limitation on the chain length between the two. In some embodiments, the chain between the epoxy group and the alkoxysilane has 1 to 9 carbons. In the non-limiting example illustrated in FIG. 1, the chain length between the epoxy and the alkoxysilane is 3 carbons in length. The alkoxysilane moiety may be a di- or tri-alkoxysilane, but must not be a mono-alkoxysilane, because polymerization into the silicon polymer is important for the entire hybrid coating. Non-limiting examples of suitable epoxy alkoxysilanes include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-(2,3-epoxypropoxypropyl)methyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and combinations thereof. However, other epoxy alkoxysilanes are possible and are encompassed within the scope of the present disclosure. The epoxy alkoxysilane or combination of epoxy alkoxysilanes can be present in an amount (or total amount) up to about 80 volume / volume %.

[0071] An aminoalkoxysilane can include an amino group and an alkoxysilane, and there is no limitation on the chain length between the two. In some embodiments, there are 1 to 9 carbons in the chain between the amino group and the alkoxysilane. In the non-limiting example illustrated in FIG. 1, the chain length between the amine and the alkoxysilane is 3 carbons in length. The alkoxysilane moiety may be a di- or tri-alkoxysilane, but not a mono-alkoxysilane, because polymerization into the silicon polymer is important for the overall hybrid coating. Non-limiting examples of suitable aminoalkoxysilanes include 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-[2-(vinylbenzylamino)ethyl]-3-aminopropyltrimethoxysilane, or combinations thereof. However, other aminoalkoxysilanes are also possible and are included within the scope of the present disclosure. The aminoalkoxysilane or combination of aminoalkoxysilanes can be present in an amount (or total amount) up to about 80 volume / volume %.

[0072] The amounts of thiolalkoxysilane and alkenealkoxysilane may be less than the amounts of epoxyalkoxysilane and aminoalkoxysilane. The thiol-ene component is provided to make the hybrid coating non-tacky and to prevent debris accumulation. However, the thiol-ene system is susceptible to nucleophilic attack. Therefore, it is advantageous to include more epoxyalkoxysilane and aminoalkoxysilane compared to thiolalkoxysilane and alkenealkoxysilane.

[0073] When present in the hybrid coating solution, the photoinitiator is present to catalyze the thiol-ene reaction (i.e., the reaction between an alkene alkoxysilane and a thiol alkoxysilane). Any radical initiator or photoacid initiator, including Norrish type I and II, may be used. Non-limiting examples of suitable photoinitiators include aryl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylaryl)methane (also known as omnirad 819), diaryliodonium hexafluorophosphate, or combinations thereof. However, many other photoinitiators are possible and are encompassed within the scope of the present disclosure. Further, as described above, in some embodiments, the hybrid coating solution does not contain a photoinitiator. Instead, the hybrid coating solution may be configured for a thermosetting process and may include a salt such as ZnCl2, a peroxide such as hydrogen peroxide, or a thermal acid generator. Examples of thermal acid generators include, but are not limited to, p-nitrobenzyl tosylate. As another option, the hybrid coating may include a cationic or ionic substance capable of initiating cation / anion curing.

[0074] The hybrid coating may further contain one or more fluorocarbons in an amount up to about 30 volume / volume %, if desired. The presence of fluorocarbons in the hybrid coating increases the hydrophobicity of the hybrid coating. Suitable fluorocarbons include fluorosiloxanes or long-chain fluoro-containing alkyls. Non-limiting examples of fluorocarbons include triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane, (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane, or combinations thereof. However, many other fluorocarbons are possible and are included within the scope of the present disclosure. Advantageously, the hybrid coating does not release fluorocarbons. Further, one or more coats of the hybrid coating containing fluorocarbons can be applied after 48 hours over one or more coats of the hybrid coating not containing fluorocarbons, or after one month over one or more coats of the hybrid coating containing fluorocarbons. By using a combination of coating formulations, the surface can be kept out of contact with the fluorinated coating, if necessary, to comply with any applicable laws, regulations, or preferences, while still providing the hydrophobic advantages of the fluorinated coating.

[0075] The hybrid coating may further contain one or more aromatic, alkane, alkene, or alkyne alkoxysilanes in an amount up to about 30 volume / volume %, if desired. For example, the hybrid coating may contain one or more arylalkoxysilanes and one or more perfluoroalkoxysilanes. The presence of hydrocarbon groups in the hybrid coating increases the hydrophobicity of the hybrid coating. Suitable hydrocarbon alkoxysilanes include short-chain and long-chain saturated and unsaturated hydrocarbon-containing alkyls. Non-limiting examples of hydrocarbon alkoxysilanes include aryltriethoxysilane, trimethoxy(2-arylethyl)silane, triethoxy-p-tolylsilane, isooctyltriethoxysilane, isobutyltriethoxysilane, (alkyl)n - Triethoxysilane, or combinations thereof, may be mentioned. However, many other aryl, alkane, alkene, and alkyne silanes are possible and are encompassed within the scope of the present disclosure.

[0076] The hybrid coating may further optionally include one or more aromatic, alkane, alkene, or alkyne siloxane alkoxysilanes in an amount up to about 30 volume / volume %. The presence of siloxane side chains in the hybrid coating increases the hydrophobicity and crosslinkability of the hybrid coating and relieves stress. Suitable hydrocarbon alkoxysilanes include short-chain and long-chain saturated and unsaturated siloxane-containing side chains. Non-limiting examples of siloxane side chains are butylpoly(dimethylsilanilyl)ethyltriethoxysilane. However, many other siloxane-containing side chain alkoxysilanes are possible and are encompassed within the scope of the present disclosure.

[0077] The hybrid coating may further optionally include a spacer, which is an unreacted diluent that delays the curing process. The advantage of including a spacer is to reduce the possibility of cracks caused by the curing process being too fast. The spacer may be, for example, a non-reactive siloxane (i.e., a siloxane that does not contain reactive groups such as epoxy, amine, thiol, or alkene) or a polyethylene glycol (PEG) compound. Non-limiting examples of suitable spacers include D4 octamethylcyclotetrasiloxane, poly(ethylene glycol) 400, and combinations thereof. However, many other spacers are possible and are encompassed within the scope of the present disclosure.

[0078] The hybrid coating may further include a crosslinking agent, if desired, for the purpose of enhancing the flexibility of the hybrid coating, which may cause a decrease in the hardness of the hybrid coating. The crosslinking agent softens the hybrid coating, which is particularly useful when the hybrid coating is used for coating flexible articles such as gloves. Suitable crosslinking agents include, but are not limited to, compounds having amine-reactive groups such as esters or imidoesters; and compounds having sulfhydryl-reactive groups such as maleimides, haloacetyl compounds, pyridyldisulfides, thiosulfonates, or vinylsulfonates. Non-limiting examples of crosslinking agents include dimethyl suberimidate, ethylene dimethacrylate, ethylene glycol dimethacrylate, polymethyl (ketoxime) siloxane, or combinations thereof. However, other crosslinking agents are possible and are encompassed within the scope of the present disclosure.

[0079] If desired, the hybrid coating may further optionally include a thickening agent such as anthraquinone siloxane. The presence of the thickening agent may assist in spreading or applying the hybrid coating onto the substrate prior to curing.

[0080] The hybrid coating solution can be prepared by combining the components in a suitable solvent in an amount sufficient to dissolve the solids. The solvent can be any liquid other than water that dissolves the components of the hybrid coating. Water cannot be used as a solvent because it interferes with the third coating process. Alcohol is a particularly advantageous solvent because it is environmentally friendly. Further, an alcohol that is complementary to the groups on the reactants (i.e., alkene alkoxysilane, amine alkoxysilane, thiol alkoxysilane, and epoxy alkoxysilane) may be selected, thereby enabling the exchange of these groups without forming a polymer. This complementarity between the reactant and the solvent improves the shelf life of the hybrid coating. However, any intermediate polar solvent or combinations thereof (excluding water) may be used. Further, in some embodiments, the solvent is a mixture of solvents. For example, when methanol is used alone as a solvent, evaporation may be too fast at high temperatures (such as in certain outdoor environments where the hybrid coating is applied to monuments), so a high-boiling solvent such as butanol can be used in combination with methanol.

[0081] The solvent may be present in an amount up to about 80 volume / volume %, and typically is present in an amount of at least about 20 volume / volume %. The high solvent loading (relatively low solids content) of the hybrid coating enables the hybrid coating to be aerosolized for application by a suitable aerosol spray system, if desired. The solvent can be, for example, water, ethanol, isopropanol, methanol, 1-butanol, or combinations thereof. However, many other solvents are possible and are encompassed within the scope of the present disclosure.

[0082] One non-limiting example of a hybrid coating referred to herein as Example 11 comprises, in amounts (prior to curing), about 8.2 volume / volume % of 3-glycidyloxypropyltrimethoxysilane, about 7.5 volume / volume % of 3-aminopropyltriethoxysilane, about 1.6 volume / volume % of triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane, about 2.9 volume / volume % of (3-mercaptopropyl)-trimethoxysilane, about 3.3 volume / volume % of vinyltriethoxysilane, about 0.3 weight / volume % of omnirad 819, about 0.1 weight / volume % of diaryliodonium hexafluorophosphate, about 36.1 volume / volume % of methanol, and about 40.1 volume / volume % of isopropanol.

[0083] Another non-limiting example of a hybrid coating referred to herein as Example 12 comprises, in amounts (prior to curing), about 13.7 volume / volume % of 3-glycidyloxypropyltrimethoxysilane, about 12.3 volume / volume % of 3-aminopropyltriethoxysilane, about 2.8 volume / volume % of (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane, about 5.0 volume / volume % of (3-mercaptopropyl)-trimethoxysilane, about 5.6 volume / volume % of vinyltriethoxysilane, about 0.5 weight / volume % of omnirad 819, about 0.2 weight / volume % of diaryliodonium hexafluorophosphate, about 18.1 volume / volume % of methanol, and about 41.8 volume / volume % of isopropanol. Example 12 is an example of a fluorinated hybrid coating.

[0084] In a version as another option of Example 12 using ethanol as a solvent (referred to herein as Example 12E), the hybrid coating contains, prior to curing, about 13.7 volume / volume% of 3-glycidoxypropyltrimethoxysilane, about 12.3 volume / volume% of 3-aminopropyltriethoxysilane, about 2.8 volume / volume% of (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane, about 5.0 volume / volume% of (3-mercaptopropyl)-trimethoxysilane, about 5.6 volume / volume% of vinyltriethoxysilane, about 0.5 weight / volume% of omnirad 819, about 0.2 weight / volume% of diaryliodonium hexafluorophosphate, about 18.1 volume / volume% of methanol, and about 41.8 volume / volume% of ethanol.

[0085] In a version as yet another option of Example 12 using water as a solvent (referred to herein as Example 12W), the hybrid coating contains, prior to curing, about 13.7 volume / volume% of 3-glycidoxypropyltrimethoxysilane, about 12.3 volume / volume% of 3-aminopropyltriethoxysilane, about 2.8 volume / volume% of (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane, about 5.0 volume / volume% of (3-mercaptopropyl)-trimethoxysilane, about 5.6 volume / volume% of vinyltriethoxysilane, about 0.5 weight / volume% of omnirad 819, about 0.2 weight / volume% of diaryliodonium hexafluorophosphate, about 18.1 volume / volume% of methanol, and about 41.8 volume / volume% of water.

[0086] Another non-limiting example of a hybrid coating, referred to herein as Example 13, contains, prior to curing, about 13.6 volume / volume % of 3-glycidoxypropyltrimethoxysilane, about 12.3 volume / volume % of 3-aminopropyltriethoxysilane, about 2.8 volume / volume % of (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane, about 5.0 volume / volume % of (3-mercaptopropyl)-trimethoxysilane, about 5.5 volume / volume % of vinyltriethoxysilane, about 0.8 weight / volume % of omnirad 819, about 0.3 weight / volume % of diaryliodonium hexafluorophosphate, about 18.1 volume / volume % of methanol, and about 41.7 volume / volume % of 1-butanol.

[0087] Another non-limiting example of a hybrid coating, referred to herein as Example 14, contains, prior to curing, about 14.1 volume / volume % of 3-glycidoxypropyltrimethoxysilane, about 12.7 volume / volume % of 3-aminopropyltriethoxysilane, about 5.1 volume / volume % of (3-mercaptopropyl)-trimethoxysilane, about 5.7 volume / volume % of vinyltriethoxysilane, about 0.5 weight / volume % of omnirad 819, about 0.2 weight / volume % of diaryliodonium hexafluorophosphate, about 18.6 volume / volume % of methanol, and about 43.0 volume / volume % of isopropanol. Example 14 is an example of a non-fluorinated hybrid coating.

[0088] Another non-limiting example of a hybrid coating suitable for thermosetting, designated as Example 15, contains about 13.9 volume / volume % of 3-glycidoxypropyltrimethoxysilane, about 12.5 volume / volume % of 3-aminopropyltriethoxysilane, about 5.1 volume / volume % of (3-mercaptopropyl)-trimethoxysilane, about 5.7 volume / volume % of vinyltriethoxysilane, about 1.0 volume / volume % of hydrogen peroxide (30% aqueous solution), about 1.0 weight / volume % of ZnCl2, about 18.4 volume / volume % of methanol, and about 42.4 volume / volume % of isopropanol (before curing).

[0089] Many other specific formulations of the hybrid coating are possible and are encompassed within the scope of the present disclosure. Further, while the above specific formulations are given as non-limiting examples, it is understood that adding additives (such as dyes or pigments, silver for antibacterial properties, or salts, etc.) to these formulation examples will change the concentrations of the components in the formulation from the specific concentrations given above.

[0090] The hybrid coating can be applied to the substrate in a wide variety of ways before the hybrid coating is cured. The hybrid coating solution may be sprayed onto the desired substrate, or the substrate may be immersed in the hybrid coating solution, or the hybrid coating solution may be spread or brushed onto the substrate. The method of applying the hybrid coating to the substrate before curing is not particularly limited. Further, there is no limitation on the type of substrate to which the hybrid coating is useful. The substrate may be porous or non-porous, hard or soft, flexible or rigid. Non-limiting examples of the substrate include stone, brick, wood, glass, metal, plastic, cloth, glass fiber, concrete, ceramic, steel, aluminum, and polymeric materials such as nitrile or vinyl. In the case of a stone substrate, it is beneficial to slightly etch the stone with acid before coating. However, this is not strictly essential.

[0091] The curing of the hybrid coating can be carried out step by step. Referring to FIG. 1, in some embodiments, there is a first fast curing process (1) from the thiol-ene reaction, which takes about 10 to 30 minutes after exposure to light, and after that time, the hybrid coating is soft but unaffected. In this first curing process (1), a photoinitiator, which can be any radical initiator, is involved. The thiol-ene reaction is generated with the assistance of the initiator. The ideal wavelength of light for curing varies depending on the type of photoinitiator, but generally, UV light can be used to complete the first curing process. In fact, the first curing process (1) works well under sunlight. When curing indoors, a UV lamp can be used. There is a second curing process (2) for the curing of epoxy and amine to improve the adhesion of the hybrid coating to the substrate, and this curing takes several hours. The second curing process (2) makes the hybrid coating adhere better to the substrate and makes the hybrid coating somewhat harder. There is a third curing process (3) for producing a silicon polymer so as to improve the long-term stability of the hybrid coating and obtain the final hardness of the hybrid coating, and this curing process takes several days to complete. The third curing process (3) is moisture curing, which occurs by drawing in water to replace the alkoxy groups and solidify the coating to its final hardness. When an acid is present in the hybrid coating, the acid can increase the rate of the second curing process (2) and the third curing process (3) to some extent. Therefore, in some embodiments, the hybrid coating further contains an acid such as a photoacid generator, which is any photo-responsive group capable of emitting photons. Non-limiting examples of acids are glacial acetic acid, diaryliodonium hexafluorophosphate of the photoacid generator, and combinations thereof. However, other acids and photoacid generators are also possible and are included within the scope of the present disclosure.

[0092] Even when the hybrid coating is fully cured by three different curing processes, the hybrid coating can be formulated as a one - pot composition, i.e., a single solution. This provides the advantage that the storage, transportation, and application of the hybrid coating become easier and more convenient.

[0093] As described above, the hybrid coating can be cured by various alternative curing processes. The formulation of the hybrid coating solution can be divided into one or more containers that cure by a non - photoinitiated process. For example, a cationic and / or anionic initiated polymerization process can be used. Another example is that thermosetting including, but not limited to, peroxides, thermal acid generators, or thermal activation by general heating is possible. This includes thermosetting methods that are stable at room temperature.

[0094] Upon curing, the components become interdispersed to form a homogeneous coating, which, as described above, can be a siloxane and can have the formula of Formula I.

[0095]

Chemical formula

[0096] In some embodiments, the cured hybrid coating can have a thickness in the range of about 1.3 microns to about 10.3 microns. However, the thickness of the cured hybrid coating can be adjusted according to the method by which the hybrid coating is applied to the substrate and can be adjusted as desired.

[0097] The cured hybrid coating is a coating that is not affected and has resistance to water, acids, impact, scratches, fire, and graffiti, and by providing a multi-purpose protective coating, extends the life of the substrate to which the coating is applied. The hybrid coating has very good hardness, stain resistance, and washable performance. The graffiti resistance makes it easy to remove permanent markers and paints that would otherwise be costly to remove, and it is advantageous to use the hybrid coating on public monuments. The hybrid coating has good heat resistance and is stable up to at least about 300 °C. The hybrid coating is also a flame retardant, preventing fire damage to the substrate coated with the hybrid coating and self-extinguishing flames. The hybrid coating has water stain resistance, exhibits performance in suppressing corrosion over time (see Figure 25B), and adheres to oxidation. The hybrid coating is unlikely to undergo any significant degradation due to exposure to wind and rain. The hybrid coating achieves these benefits by combining the use of three different orthogonal curing processes, and because it is made in a one-pot method, it is easy and convenient to use. The hybrid coating solution (i.e., before curing) has a very good shelf life of at least three years if stored sealed in the dark. Frequent exposure to light can cause some discoloration after about six months, but this discoloration does not affect the properties of the coating obtained after curing.

[0098] Since hybrid coatings are generally transparent, they can be used on monuments or other structures without the observer noticing the coating or even being aware that the monument or structure contains the coating. However, hybrid coatings are reflective on glass substrates. Additionally, if color or opacity is desired for a particular application, one or more dyes or pigments may be added to the hybrid coating prior to curing. Photochromic dyes and compounds may be incorporated into the hybrid coating to obtain a transitional effect. A non-limiting example of such a dye is spiropyran. The hybrid coating may be substantially tinted, if desired.

[0099] Hybrid coatings are stable when immersed in water up to pH 3. Thus, hybrid coatings can be applied to substrates placed in water after curing or to dry floating surfaces. As non-limiting examples, hybrid coatings can be applied to boat hulls above the waterline and then cured with sunlight to form a protective coating on the boat hull. As another non-limiting example of an alternative, hybrid coatings can be applied to the surface of an oil drilling rig above the waterline and then cured with sunlight to form a protective coating on the structure.

[0100] The surface adhesion of the cured hybrid coating is very good. In fact, in some embodiments, the hybrid coating can be used as an adhesive to bond two substrates together, such as a glass substrate. Once fully cured, the hybrid coating cannot be easily peeled off from the substrate or removed with common detergents. Epoxyalkoxysilane aids in the surface adhesion of the hybrid coating. Conversely, the hybrid coating can be removed from the substrate by a method that depolymerizes the siloxane polymer. The hybrid coating can be easily removed using the process for depolymerizing the siloxane polymer described in International Patent Application PCT / US2022 / 014500 (published as International Publication No. WO 2022 / 165305 (A1), the entire contents of which are incorporated herein by reference). In particular, the hybrid coating can be removed using a solution containing a solvent (such as THF) that dissolves the alkoxysiloxane bonds of the cured hybrid coating and a fluoride source. However, other methods of depolymerizing the alkoxysiloxane polymer and thus removing the hybrid coating from the substrate are possible and are encompassed within the scope of the present disclosure.

[0101] The hybrid coatings described herein are advantageous compared to conventional coatings in that they can provide a long pot life, various applications, rapid photoinitiated curing, and enhanced hardness. Further, the hybrid coatings provide resistance to oxidation and hydrolysis, which are common problems in most current technologies. The rapid curing prevents surface contamination from external sources, which is not seen at present. The hybrid coatings can be easily removed without damaging or harming the original surface, which is an issue with acrylates. Most prior art based on siloxanes do not provide a method of rapid photo-curing and non-thermal post-curing. The siloxane-based systems described herein utilize three independent curing methods to simultaneously form a colorless, transparent, and hard coating. Photoinduced rapid curing using UV and / or visible light enables a hard, non-penetrating cure in less than 30 minutes upon touch and prevents contamination by debris. In the second and third stages, curing continues over time under ambient conditions, strengthening the surface adhesion and hardness over several days. Specific heat conditions are not required, and ambient conditions are desirable for obtaining the best coating performance. Solutions for these hybrid coatings have been confirmed to have a pot life of one year when stored in the dark at ambient temperature and are applicable by spraying, dipping, rolling, etc. The hybrid coatings are environmentally friendly, composed of non-toxic materials, and applicable by variable means.

[0102] Advantageously, the hybrid coating is an easy, simple, and potentially inexpensive one-pot system. The hybrid coating can be made from only commercially available components. There are numerous applications contemplated for the hybrid coating. The hybrid coating can be used to protect monuments, such as outdoor monuments in parks, from graffiti and acid rain. The hybrid coating can be used to protect the surfaces of means of transportation from scratches or other abrasions. The hybrid coating can be used to reduce the flame damage of structures. The hybrid coating can be used to protect boat hulls from scratches or other damages. The hybrid coating is particularly useful for the outdoor / indoor preservation of objects exposed to the elements in the architecture, construction, and cultural heritage protection industries where stone, concrete, metal, and glass are widely used. The hybrid coating can protect from acid rain, water erosion, and graffiti while extending the lifespan of cultural resources. Furthermore, the hybrid coating can also be used for the protection of stone, glass, and metal objects in marine and aerospace environments. The hybrid coating can also be useful in the automotive industry to protect automotive surfaces, impart hydrophobicity (e.g., for windows so that rain runs off), and enable photochromic coloring. The hybrid coating is similarly useful for the protection of marine, recreational vehicle (RV), aviation, and aerospace means of transportation or other surfaces. The hybrid coating can be used for biomaterials for surgical implants or devices. The hybrid coating can also be useful in production facilities to coat molds or presses of high-temperature materials and facilitate the release of materials such as the release of plastics or rubber from aluminum or steel molds. Acid rain is particularly important in the future due to, in particular, the increase in the concentration of CO2 and H2SO4 in the atmosphere resulting in a decrease in the pH of rainfall and furthermore the increasing tendency of severe storms. Such situations, and also vandalism, can potentially damage expensive buildings and monuments left unprotected. The hybrid coating is a suitable solution to this problem.Hybrid coatings are also useful in HVAC applications that protect HVAC systems from the elements or any environment. By coating HVAC units or components (e.g., blowers, doors, enclosures, fans, louvers, exposed piping, and coils), functionality can be improved and the life of the unit extended. Hybrid coatings can be used to carry or encapsulate pigments, dyes, liquid crystals, or particulates, thereby providing a changed surface color or appearance after curing on the surface. This can be used, for example, to change the appearance of a painted surface such as unwanted scribbles. Thus, hybrid coatings are particularly useful for the protection of buildings and cultural resources, but have many other valuable applications in addition to the protection of buildings and cultural resources.

[0103] Examples To protect a range of materials including, but not limited to, stone, concrete, polymers, metals, and glass, a coating system was developed that integrates three different chemistries. Initial curing is achieved using a UV-initiated thiol-ene / vinyl reaction to form a non-affected surface. Second, an amine / epoxy reaction forms strong surface adhesion and imparts mechanical strength. Third, sol-gel curing of alkoxysilanes integrates a silicon network while imparting thermal stability, hydrophobicity, surface hardening, and abrasion resistance. Curing can be accelerated by incorporating one or more photoinitiators including radical and cationic (i.e., photoacid generator) initiators to increase reaction efficiency. The coating composition can be applied by spray, dip, or spread methods. This coating quickly presents a non-affected surface that is resistant to scribbles and environmental conditions (moisture, sunlight, acids) (as fast as 10 minutes) and is used and stored as a single-component system with a pot life of over one year. A series of examples are provided to show the properties and life of the coating, including field tests and accelerated weathering.

[0104] The base formulations of the coatings in these examples contained components of vinylalkoxysilane, thiolalkoxysilane, epoxyalkoxysilane, aminoalkoxysilane, and fluorocarbon (optionally) alkoxysilane, which were detailed in these examples and shown schematically in Table 1 in ratios. The initial formulations also contained components in various ratios, along with a relatively low percentage of solvent (10 - 15% methanol) and D4 octamethylcyclotetrasiloxane as a spacer. These were designed to examine the effects of varying the ratios of the components in relation to different curing methods. This was achieved by increasing one set of components while decreasing another over a range of volume percentages and repeating this process for multiple combinations of adjustments (i.e., increase in thiol - ene / decrease in adhesion component, increase in adhesion component / decrease in fluorocarbon).

[0105] The obtained coating was examined for hydrophobicity, and the systems that did not peel off after curing were selected for further study and provided throughout. This included Example 1 prepared using 3-glycidoxypropyltrimethoxysilane (28.0%), 3-aminopropyltriethoxysilane (28.0%), triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane (5.5%), (3-mercaptopropyl)-trimethoxysilane (9.0%), vinyltriethoxysilane (9.0%), omnirad 819 (0.5%), D4 octamethylcyclotetrasiloxane (8.0%), and methanol (12.0%), and applied by spraying. Using Example 1 as the base system, a set of solutions was designed to investigate the adjustments. Although the adhesion was good, the system of Example 1 peeled over time. Therefore, a series of formulations were designed to see the effect when the solvent ratio was increased to 25%, 50%, and 70%. From these tests, the peeling that occurred during curing was eliminated, and Example 2 [3-glycidoxypropyltrimethoxysilane (13.8%), 3-aminopropyltriethoxysilane (12.4%), triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane (2.8%), (3-mercaptopropyl)-trimethoxysilane (4.8%), vinyltriethoxysilane (5.6%), omnirad 819 (0.3%), and methanol (60.3%), applied by spraying] was found to have the highest water contact angle when examined on glass (to ensure equivalent surface roughness).

[0106] Next, as a method to enhance the hydrophobicity of the system and ensure the survival of the samples through long-term water exposure tests, the introduction of different vinyl-containing compounds, the effect of acetic acid addition to increase the reaction rate, and the surface modification by nanoparticle formation were investigated. Based on the contact angle, adhesiveness, and removability of the permanent marker, the best samples were selected from all the formulations so far. Among these, 3-glycidyloxypropyltrimethoxysilane (13.8%), 3-aminopropyltriethoxysilane (12.3%), triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane (2.7%), (3-mercaptopropyl)-trimethoxysilane (4.9%), vinyltriethoxysilane (5.6%), Omnirad 819 (0.6%), and methanol (60.2%) of Example 3, as well as spray coating, were selected for detailed description because they contain no toxic components and have a low overall manufacturing cost resulting from their use. To solve the peeling caused by dipping, several sets of this formulation were investigated, including the change in coating thickness, UV exposure time, solvent as an alternative option, thickness vs. curing time, annealing, and the effect of the addition of tetrabutylammonium fluoride as a co-catalyst. From these tests, it was found that when spraying the solution, applying approximately 1.2 mL (70.8 cm 2 per 1 mL) of the solution on an 8.5×10 cm marble surface gives an advantageous thickness (about 10 microns). In Example 4, these results were obtained from a mixture of 3-glycidyloxypropyltrimethoxysilane (13.8%), 3-aminopropyltriethoxysilane (12.3%), triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane (2.7%), (3-mercaptopropyl)-trimethoxysilane (4.9%), vinyltriethoxysilane (5.6%), Omnirad 819 (0.4%), and methanol (60.3%). Extending the curing time and annealing at 45°C for 24 hours resulted in an increase in the contact angle, indicating high suitability for outdoor applications. However, by maintaining a 2-minute UV exposure indoors, a wide range of end-user applications become possible.

[0107] Example 5 [3-glycidyloxypropyltrimethoxysilane (13.7%), 3-aminopropyltriethoxysilane (12.3%), triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane (2.7%), (3-mercaptopropyl)-trimethoxysilane (4.9%), vinyltriethoxysilane (5.6%), omnirad 819 (0.7%), and ethanol (60.1%), and spray application] was obtained by using ethanol as a solvent. Example 4 survived well in the water immersion test and subsequent tests with acid rain and base solution, but Example 5 peeled off after long-term exposure to water.

[0108] Using Example 4 that survived long-term exposure, the effects of coating method and surface preparation were investigated. As a result, it was shown that the application method has little effect on the resulting coating. However, when comparing stones pretreated with water, vinegar (5%), or 0.11 M nitric acid, an improvement in contact angle was observed with the latter. From the results so far, it was shown that for indoor use coatings, thinner coatings and surfaces prepared with nitric acid (mimicking the state of being exposed to acid rain for a long time) should be used, and outdoor surfaces exposed to rain are suitable for use.

[0109] Next, Example 6 [3-glycidyloxypropyltrimethoxysilane (14.1%), 3-aminopropyltriethoxysilane (12.7%), (3-mercaptopropyl)-trimethoxysilane (5.0%), vinyltriethoxysilane (5.7%), omnirad 819 (0.7%), and methanol (61.8%), applied by spraying] and Example 7 [3-glycidyloxypropyltrimethoxysilane (12.7%), 3-aminopropyltriethoxysilane (11.3%), triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane (10.5%), (3-mercaptopropyl)-trimethoxysilane (4.5%), vinyltriethoxysilane (5.1%), omnirad 819 (0.5%), and methanol (55.4%), spray applied] were used to confirm the additive effect that fluorocarbon species have on hydrophobicity. Similarly, a set of examples without the thiol-ene component was prepared under the same conditions, but these peeled off, indicating that thiol is most likely to relieve the tension in the alkoxysilane network.

[0110] As a measure to increase the overall hydrophobicity and reaction rate, a small amount of a photoacid generator (e.g., diaryliodonium hexafluorophosphate) was added, and the influence on the contact angle was compared between sprayed Example 8 [3-glycidyloxypropyltrimethoxysilane (13.3%), 3-aminopropyltriethoxysilane (11.9%), triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane (2.6%), (3-mercaptopropyl)-trimethoxysilane (4.7%), vinyltriethoxysilane (5.4%), omnirad 819 (5.5%), diaryliodonium hexafluorophosphate (3.4%), and methanol (58.2%)] and Example 9 [3-glycidyloxypropyltrimethoxysilane (13.7%), 3-aminopropyltriethoxysilane (12.3%), triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane (2.7%), (3-mercaptopropyl)-trimethoxysilane (4.9%), vinyltriethoxysilane (5.6%), omnirad 819 (0.5%), diaryliodonium hexafluorophosphate (0.1%), and methanol (60.1%)]. These samples were used in the initial outdoor test, but in the first sample, the solvent evaporated before curing could be achieved. In response to this, the formulation was diluted with isopropanol, and the diluted Example 8 is still in the field test and has shown stability after exposure to the weather for over 250 days.

[0111] Example 10, which is a modification of Example 9, was prepared using only isopropanol, subjected to various analyses, spray-applied, and used 3-glycidyloxypropyltrimethoxysilane (13.7%), 3-aminopropyltriethoxysilane (12.3%), triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane (2.7%), (3-mercaptopropyl)-trimethoxysilane (4.9%), vinyltriethoxysilane (5.6%), omnirad 819 (0.6%), diaryliodonium hexafluorophosphate (0.2%), and isopropanol (60.1%).

[0112] Example 9 diluted with isopropanol was applied to a stone monument and remained stable even after 300 days. This Example 11 [3-glycidyloxypropyltrimethoxysilane (8.2%), 3-aminopropyltriethoxysilane (7.5%), triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane (1.6%), (3-mercaptopropyl)-trimethoxysilane (2.9%), vinyltriethoxysilane (3.3%), omnirad 819 (0.3%), diaryliodonium hexafluorophosphate (0.1%), methanol (36.1), and isopropanol (40.1%)] was further diluted and sprayed with a pressure garden spray. As another option, two additional systems were designed using the longer and less expensive fluorocarbon (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane. First, Example 12 [3-glycidyloxypropyltrimethoxysilane (13.7%), 3-aminopropyltriethoxysilane (12.3%), (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane (2.8%), (3-mercaptopropyl)-trimethoxysilane (5.0%), vinyltriethoxysilane (5.6%), omnirad 819 (0.5%), diaryliodonium hexafluorophosphate (.2%), methanol (18.1), and isopropanol (41.8%)] when used as an isopropanol dilution and sprayed or dip-coated has properties equivalent to Example 11.As another option, Example 13 was designed to extend the pot life of the solution, using the dilution of butanol, and depending on the application method and thickness, extended the time to an unaffected state from 30 minutes in the aforementioned system to 60 - 100 minutes [3 - glycidyloxypropyltrimethoxysilane (13.6%), 3 - aminopropyltriethoxysilane (12.3%), (tridecafluoro - 1,1,2,2 - tetrahydrooctyl)triethoxysilane (2.8%), (3 - mercaptopropyl)-trimethoxysilane (5.0%), vinyltriethoxysilane (5.5%), omnirad 819 (0.8%), diaryliodonium hexafluorophosphate (0.3%), methanol (18.1), and 1 - butanol (41.7%)]. The final collection of systems includes a plurality of formulations including Examples 4 - 13, all of which share similar properties. A partial range of the materials used in different formulation Examples 1 - 13 is shown in Table 1. These are non - limiting examples, and other thiols, allyls, epoxies, amines, initiators, alkoxysilanes that may be present as desired, and additives can be readily substituted within these ranges.

[0113] Table 1 - Ranges included in the set of Examples 4 - 13. Minimum and maximum values in volume percent are shown. Omnirad 819 and diaryliodonium hexafluorophosphate are solids and are calculated as weight / volume %.

[0114]

Table 1

[0115] Curing process The formulations were developed with several shelf-life targets in mind. The solutions were made in a single container as a no-mix system, and the final formulations achieved a pot life of over three years. The formulations are usable even after three years, and the cured hybrid coatings are stable after two years of environmental exposure and two years of simulated marine exposure. A series of formulations were designed with rapid curing in mind, but by using long-chain alcohols in the base solvent, the rate at which the coating dries can be adjusted, extending the time required for the network to settle on the surface. This system was good with spray, dip, and spread application methods, but was designed to be easily used with an outdoor pressure pump spray system or an industrial spray system. One example of use is for monument preservation, and for this reason, most of the tests focused on spray and dip applications using marble samples.

[0116] A tri-curing system was developed using three different chemistries shown in Figure 1. The composition of the system was designed to integrate thiol-ene, epoxy / amine, and optionally fluorocarbon chemistry onto an alkoxysilane sol-gel backbone. The thiol-ene reaction provides a photoinitiated rapid-curing surface, which achieved a surface that was consistently soft and unaffected within 30 minutes. To drive the initial thiol-ene curing, the omnirad 819 photoinitiator was used in the presence of either a UV-C mercury lamp or sunlight. This was initially adjusted to occur within 10 minutes. However, this can be too fast in some cases to allow for proper settling and rearrangement of the other components. For this reason, it was adjusted to a 30-minute cure after 2 minutes of irradiation.

[0117] The amine-epoxy component is designed to further penetrate the surface and add adhesion and mechanical strength to the coating as a secondary curing process. The initial formulation did not contain specific activators for this process, but a promoter was found to assist in driving the ring-opening. Therefore, a common photoacid generator (PAG) (e.g., diaryliodonium hexafluorophosphate) was used to increase the reaction rates of the secondary reaction and the tertiary reaction discussed later. When used at high concentrations as in Example 8, the system became unaffected within 9 minutes, and at lower amounts, it maintained the surface hardness achieved so far at 30 minutes. Finally, due to the observed decrease in contact angle when the addition amount was too high, a small amount of PAG was used, with a higher concentration in Example 8 and a lower amount in Example 9 (95.9° - 101.5°). This made it possible to simultaneously drive both the radical curing and acid curing processes in the same UV process. The first two curing processes form macromonomers for the third sol-gel curing process.

[0118] In the third curing process, by taking advantage of the slower and more time-consuming sol-gel reaction of alkoxysilane, while integrating the polymer network, thermal stability and photo-stability are provided. Through alkoxysilane cross-linking, other functionalities are imparted to the system. The fluorocarbon component, which may be included as desired, was used in a low ratio to enhance hydrophobicity and for its chemical and biological resistance. Depending on the formulation, triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane and (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane were used, with the latter being a much lower-cost option. The overall difference in their properties was negligible. The fluorocarbon was used in a minimal amount due to cost, but completely removing it resulted in a decrease in the contact angle to 92.5° as shown in Example 6. Tests showed that increasing the amount slightly increased the contact angle observed in Examples 4 and 7 from 97.1° (about 3%) to 101.5° (about 10%), but further considering a ratio higher than 5% for the protective system was an unnecessary additional cost. The combination of the above components was examined through the analysis of various chemical and physical properties as detailed below.

[0119] Chemical property evaluation To examine the reaction mechanism of the system in detail, chemical analysis using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and thermogravimetric analysis (TGA) was performed. ATR-FTIR of the solution and the coated glass surface was taken to observe the changes occurring during the curing process (Figure 2). The spectrum of the solution mainly showed O-H stretching at 3300 cm -1 C-H peak at 2900 cm -1 C-O stretching at 1085 cm -1 C-O stretching at 1033 cm -1 C-O stretching at 1033 cm, and C-O stretching at 950 cm -1The presence and disappearance of methanol and isopropanol are indicated by the O-H bending angle of [[ID=]], which are hardly seen in the cured samples. In addition, the absence of peaks of amines and alcohols in the final product indicates that the reaction process between the second epoxy and the amine has occurred. However, there is a possibility that some by-products still exist in the system. In the coated spectrum, the absence of the S-H peak near 2600 cm -1 or the C=C-H peak near 3000 cm -1 indicates that only a minimal amount of vinyl remains in the system, confirming that the thiol-ene reaction is approaching completion. Furthermore, the peaks at 1012 cm -1 and 875 cm -1 in the cured product spectrum indicate the presence of a combination of Si-O, C-O, and Si-O-C bonds derived from alkoxysilanes and partially reacted species, confirming that the third sol-gel reaction has occurred over a longer period of time. The formation of siloxane is further confirmed by TGA analysis (Figures 3-5). When dried before analysis, these coatings remain stable at T d5% of 308 °C, 275 °C, and 262 °C in Examples 10, 11, and 12, respectively, which is within the expected range for the siloxane network. This information supports the reaction mechanism described in this specification.

[0120] Physical Property Evaluation Surface inspection was performed by scanning electron microscope (SEM) images to investigate how the coating adheres to various substrates. The initial images were focused on the marble samples coated in Example 11. In both the 50x and 300x images, there is a significant difference in the surface after the solution has settled in the defect areas, resulting in a much smoother appearance (Figure 6). In the coated areas, the electron beam interacts with the transparent coating, reducing the resolution, and as a result, a dark translucent feature that becomes darker as the coating gets thicker is observed. In the 1000x image of the coated part, there are traces of micron-sized protrusions, indicating that a thin secondary application may be useful for protecting rough stone. The removal of the stone's surface layer by using sandpaper is evident from the tracts seen in Figure 7, and the transition from the untreated surface to the protected surface is easily distinguishable. Since air pockets are trapped under the coating, imaging a thicker surface results in cracks forming in these areas upon exposure to ultra-high vacuum. This issue is eliminated because there are no surface dips on glass where air could be trapped. Images of the untreated glass surface show spots from oil, but the difference on the coated surface is minimal. The areas of the surface that wrap debris to form defects were selected because the remaining areas have no features, and both sides are essentially smooth (Figure 8). Despite being cleaned with dry air on both sides before imaging, the untreated glass appears dirtier. For the inspection of stainless steel, a dip-coated tissue examination razor blade with an ultra-thin edge less than 1 micron thick was used (Figure 9). On the coated surface where the system closely wraps the honing part, a slight slope is visible, but the overall edge is clearly maintained. Small depressions are seen in the final magnified image, but there are no traces of system defects, and the entire blade edge remains smooth and in a usable state (Figure 10). This indicates that the surfaces investigated in the oxidation experiment (see below) had appropriate adhesion from a similar application method, and this system can be used to coat sharp corners on different substrates.Finally, the surface interaction between the nitrile glove and the spread coating was investigated. The detailed images show that the coating covers and fills many of the recessed parts on the surface (Figure 11). At a magnification of 1000 times, the recessed parts of the surface show how thin plates are formed by this application method. Although the entire surface is not covered, this may provide additional protection against chemicals that conventionally penetrate nitrile gloves, because, as detailed below, the coating did not show any change even when exposed to some of such reagents.

[0121] Surface evaluations were performed to examine the hardness and abrasion resistance of the coating. Pencil hardness tests were conducted on samples on various surfaces (marble, glass, steel), and all samples evaluated achieved a hardness of 9H each, which was the highest score by this method. The abrasion resistance was quantified by measuring the mass lost from each marble sample using a method combining sandpaper and sandblasting. In the initial tests using coated small stone pieces (average 3.5×4 cm), after both smooth sandpaper (400 grit) and then coarse sandpaper (220 grit), the maximum mass loss was 3 mg. Two larger samples (average 8.5×10 cm) showed total mass losses of 4 mg and 7 mg after exposure tests to both sandpapers. Overall, with direct abrasive force, surface changes can be considered minimal (from 207.768 g to 207.764 g in Example 8 and from 197.445 g to 197.438 g in Example 9). Scratches on these stone samples were observable under a microscope but not visible to the naked eye for these grits of sandpaper. Next, when the same samples were sandblasted for 30 seconds, 15 mg and 5 mg were lost respectively, and the scratches were clearly visible (Figure 12). This is reinforced by the loss of surface hydrophobicity of Example 9, the second sample, which decreased from 101.5° to 80.3° after sandblasting, indicating significant loss of the coating (Figure 13). This shows that while this coating system is rigid and shows some resistance to weak abrasion, it may not be ideal for surface protection in dry and extreme sand environments that cause extreme sandstorms.

[0122] For samples by spraying and dipping, the coating thickness was analyzed. Using a Keyence 3D laser confocal microscope, Example 1 was applied to stone and steel samples to conduct an initial investigation of surface topography and coating thickness. From the topographic mapping of the uncoated side and the coated side of a single stone sample, a denser and more consistent surface was shown across the entire area, indicating that the coating was fixed in the concave parts of the surface (Figure 14). The deposition of the coating on the brick surface is supported by the fact that the solution coats the surface, fills many defects, and appears to be absorbed into the substrate (Figure 15). The film thickness was also evaluated using an optical profilometer with stainless steel, and the distance between the upper and lower scan surfaces was measured to obtain an estimated thickness measurement of 0.013 mm (Figure 16). Next, 10 measurements were taken for Examples 11 and 12 applied to glass slides, and the average thickness was calculated using them (Figure 17, Table 2). The spray samples had an average thickness of 2.76 μm (Example 11) and 10.28 μm (Example 12), while the thickness of the dip coating samples was 1.35 μm (Example 12), indicating that this is an ideal application method for thinner coatings. When intentionally applied to the surface of stone or glass, the resulting coating will have a thickness similar to that of the second analysis due to surface differences.

[0123] The interactions with water and other solutions were investigated by various methods. The stability of the coating was examined by the immersion tests detailed in the method. Starting with Example 4, the system showed no change on the surface when immersed in water, synthetic acid rain, and sodium hydroxide solution. Prior to this, peeling was observed upon exposure to water. Chemical resistance was observed in Examples 8 - 12, and no change in the size, shape, color, or state of the samples was found when cured coating pieces were exposed to small amounts of tetrahydrofuran, hexane, dichloromethane, ethanol, isopropanol, 0.1 M nitric acid, 0.1 M sodium hydroxide, and acetone. Due to the stability of this coating, the resistance to scribbling / ease of scribbling removal on the finished surface is also ensured. Both Sharpie percent marker and Rust - oleum outdoor paint can be removed from the coated surface without leaving scratches on the coating surface by using a dry Kimwipe (or tissue paper) with a light force (Figs. 18 - 19). The implications this suggests are broad and very beneficial for coatings on surfaces that are targets of vandalism.

[0124] Recyclability and recoatability were investigated to determine whether the system could be recovered, reused, or enhanced. When exposed to a siloxane depolymerization solution containing a fluoride source described in International Patent Application PCT / US2022 / 014500 (incorporated herein by reference) for four weeks, partial removal of the coating was observed in the sample of Example 10, but the solid remained partially intact, which is presumably due to thiol - ene and epoxy / amine crosslinking (Fig. 20). This technique decomposes the siloxane chains to form recyclable cyclic monomers and provides a second purpose for any siloxane after its initial use. Although incomplete, partial decomposition can improve recoating by reopening siloxane bonds to improve adhesion of the next layer.

[0125] The initial recoating test was conducted within 2 days after curing using the spray method. As a result, the two layers self-repelled, the second coat peeled off, but the first layer was maintained without change (due to complete curing and fluorocarbon interaction). In the follow-up test, samples that had been exposed for more than one month from both outdoor and indoor environments were used. In both cases, the adhesion of the second layer was successful, but in some samples where the second application was thick, some peeling was observed. However, most of the second layer remained intact. This demonstrates the recoatability of the system, but it shows that it is advantageous to increase the time elapsed between applications or use the chemical decomposition of the first application described above to ensure the complete reactivity of the initial layer. Further tests showed that the second coat can be applied to the non-fluorinated base coat after 48 hours. When the base coat contains fluorocarbon, an application interval of one month may be important. When applying multiple layers, any combination of formulations may be used. The non-fluorinated base coat can be overcoated when curing is complete, and the second coat can be applied on top of it after 48 hours (one month later in the case of a fluorinated formulation). Furthermore, a combination of coating formulations may be used during recoating.

[0126] Hydrophobicity is important for the design of this system and was evaluated by static contact angle measurement in addition to the immersion test described above. As previously mentioned, the introduction of fluorocarbons increases the overall hydrophobicity observed, and for this reason, it was incorporated into this modification. Table 3 (Figure 21) shows the range of static contact angles observed in Examples 1 to 13 of this series. Not only the ones shown, but all the coated marble samples of the modifications of this system were in the range of 85.0° to 103.4°, and many ideal samples were measured to be 96° to 101°. When applied to a slide glass as a smooth and consistent surface, a maximum contact angle of 105.5° and a minimum contact angle of 95.6° were obtained, and this series consistently had measured values exceeding 100°. Examples 8 to 12 were tested on several different substrates to confirm their effectiveness on other materials. Nitrile gloves were examined to see if additional hydrophobicity could be imparted. The solution was spread on the surface, and after curing, the surface was made in a strongly stretched state. The contact angle was estimated from the elastic properties of the substrate, and the untreated surface was about 88.1°, and the coated samples were about 88.8° to 93.4°. The difference in contact angle was not surprising, but water droplets flowed off the surface more easily than on the uncoated gloves, indicating that this system can be used on vinyl surfaces. Regarding bricks and steel, these are used in building construction and have similar environmental erosion problems as stone, so they were investigated. Since bricks are porous, the contact angle was measured before curing, after curing, and several days later. The untreated surface completely absorbs water droplets within 30 seconds. In the first brick 2 days after curing, a contact angle of 103.9° was exhibited 10 minutes after adhesion and was measured to be 94.4° on the 39th day. When the second brick was coated and inspected 4 days after curing, the contact angle was measured 10 minutes after adhesion, and 129.1° was achieved, which was a very high angle compared to other substrates of the present applicants (Figure 22). Wood samples were also tested in this way. In this case, the uncoated samples absorbed water droplets within 30 seconds, and the dip-coated samples 3 days after curing exhibited a static contact angle of 131.7° 10 minutes after passing. Stainless steel also showed a significant difference in hydrophobicity after dip coating.The initial contact angles of the uncoated samples were 58.8° (A.1) and 53.5° (B.1) on the untreated surfaces, but after coating, they were measured to be 103.7° (A.2) and 103.5° (B.2) respectively (Figure 23). This indicates that the coating is very effective in enhancing the hydrophobicity of the steel surface and can impart oxidation resistance.

[0127] Oxidation stress was applied to the stainless steel samples using a corrosive solution. After dip coating, the samples were sprayed and immersed according to the method, and both the untreated surface and the coated surface were observed. When sprayed, the solution immediately corroded the untreated surface, but the coated surface was properly protected, as seen in Figure 24 which shows the difference in effect with the upper half of the sample left untreated. This indicates that the coating system can appropriately prevent oxidation when regularly exposed (Figure 25A). As a comparison, similar samples were suspended at a height of approximately 6 feet and exposed to ambient conditions in the laboratory to show an example of less severe long-term oxidation stress. Figure 25B shows that the unprotected part of the sample gradually oxidizes after 200 days of exposure. The second corrosion test was carried out by directly immersing the dip-coated stainless steel posts in a corrosive solution (Figures 26A - 26F). Figure 26B shows that bubbles are formed on the coated surface but not on the untreated material. After 14 days, significant oxidation occurred on the uncoated surface, but only a little corrosion and discoloration were observed on the coated section, indicating that the process was delayed (Figure 26F).

[0128] Water stains become an obstacle on the surface and cause discoloration and calcification over time. The resistance to ion attachment was tested by partially coating a slide glass and using a concentrated synthetic hard aqueous solution. As a result of rapid heating, a hard residue was formed and an attempt was made to remove it using a Kimwipe. With the same force, the calcification was easily wiped off from the coated surface and fragmented, but remained attached to the untreated surface. The same experiment was conducted, but when heated slowly and dried, the resulting deposit was soft. Spots on the uncoated side and the coated side were removed using a Kimwipe. The deposit was removed immediately, but there was dirt on both sides. It was easily wiped off from the coating but remained on the glass. These results indicate that this coating system has resistance to calcification and helps prevent the accumulation of hard water.

[0129] The final set of physical properties investigated was environmental stability. Initial tests were conducted indoors to test the general thermal stability when exposed to various situations. In both methods, exposure to high and low temperatures had no significant effect on the surface appearance and the persistence in the immersion test, and the effect on the contact angle after exposure was also negligible (±3°). As described above, an immersion test was also conducted using a synthetic acidic rain solution with a pH of 4.3 that simulated outdoor meteorological phenomena, but there was no effect on the system. The long-term stability test was conducted on a flat rooftop, providing a stable outdoor environment with restricted access to reduce artificial effects. Since the start of these tests, the daily weather and atmospheric conditions were recorded, and samples were inspected regularly to confirm continuous success and to be aware of any abnormal events that could affect the test. The UV index was recorded and monitored to determine the optimal conditions for coating application. This is an estimate of the amount of ultraviolet exposure that a specific area is expected to receive [(mW / m 2 / s) / 25mW]. The samples were applied from summer to early autumn when the UV index exceeded 7.2 (about 180mW / m 2 / s), which is 18.7mW / cm at the distance used. 2It is lower in energy than a 200W UVA lamp used indoors, which is measured in / second. When coated during peak exposure times when the UV index exceeds 7.2 and the temperature exceeds 21°C, the sample surface, as intended, remained unaffected within 30 minutes after application. The sample with the longest lifespan was placed over 252 days and is ongoing, using a diluted variant of Example 8 (Figs. 27A - 27D). Up until nearly 250 days, no changes were visible on the surface, but as seen in Fig. 27D, the previously shiny appearance was lost. However, the coating was still intact and recognizable by touch due to its leathery texture. For scale-up, the tombstone was cleaned, sanded to remove all existing protective surfaces, then coated using a pressure pump spray, resulting in a slightly increased thickness but a uniform finish. This monument was subjected to a field test over 300 days and was exposed to various environmental conditions, but there were no notable changes in the surface condition. This may be attributed to the hydrophobicity of the surface, and small-scale samples applied in the same way exhibited contact angles of 100.1° on stone and 105.5° on glass (Table 3, Fig. 21 - Example 11). Before application, the tombstone had a dull gray appearance (Fig. 27A), but after application, as seen in Figs. 28A - 28F, the color of the stone became more vivid (Fig. 27B). This change in appearance with a shiny gloss and leathery texture continues to indicate the presence and long lifespan of this coating. Looking closely at the details of the edges and etching, the difference between the uncoated surface and the protected surface can be clearly seen (Figs. 29A - 29D). Similarly, an initial improvement in surface color was also seen in the two brick samples, but this became clearly duller over time under outdoor conditions and became a lighter color than the original substrate, as is common with brick materials (Figs. 30A - 30C, Figs. 31A - 31C).

[0130] Conclusion We have successfully synthesized a three - crosslinking - process - utilizing triple - curing hybrid organic silicone coating system. Formulation examples designed for outdoor use on stone substrates were applied to various material surfaces, and the material properties of the resulting layers were investigated. Analysis shows that the coating exhibits hydrophobicity with consistent contact angle measurements around 100°. In addition, the coating provides a hard surface that is stable against light and heat. The unique performance of resisting permanent markers and spray paints and repelling them offers further possibilities for end - uses and provides a way to maintain at low cost surfaces that are often targeted by vandalism. The scope of application extends beyond flat surfaces and has also been successful for coating glass cylinders and tubes, as well as metal blades and hand tools, all of which retained the properties detailed above. Ideal application parameters were established as follows, but it should be understood that while these parameters are useful, they are not strictly essential. When applying to outdoor surfaces, the system should be exposed to sunlight when the UV index exceeds 7 and the air temperature is higher than 21°C. To ensure complete curing, use should be limited to days when no precipitation is forecast. For indoor application, a UVA lamp with an output of 200 watts should be used, and the system should be exposed to the lamp for 2 minutes after application. In the case of dip - coating, excess solution should be removed from the bottom edge of the item. The solution should be placed in an airtight amber - colored light - blocking bottle and stored in a cool, dark place. This system can form a surface that is not affected within 30 minutes after initial UV exposure and can be stored for over a year while being repeatedly used as a one - pot solution. However, it is understood that coatings can be formed, cured, and provide advantageous properties even under conditions that do not meet the ideal conditions described herein.

[0131] Throughout the development process, various potential uses have been found. This system has shown success in coating many types of materials, including stone, brick, glass, and steel used in buildings, monuments, sculptures, and architectural designs. And it has also been successful in use on materials such as nitrile, vinyl, and leather. The properties on some of these materials may not be the same as those described above (nitrile and leather have much lower contact angles, and on these surfaces, the coating solution should be spread and applied in multiple coats), yet still provide unique functionality. When applied to the rails of a bass fishing boat, the hybrid coating provided a smooth and shiny finish that protected against scratches (Figure 39). Glass can be dyed by immersing a coated sample containing food coloring in water for a long period (e.g., 1 month), and then a second coating can be applied to lock in the color (Figure 32). To impart the desired color or effect, a dye may be incorporated into the system or applied between the layers of the coating. For example, a photochromic dye can be incorporated into the hybrid coating applied to glasses (Figure 40). As another example, a hybrid coating containing a dye or pigment may be applied over a painted substrate and provide a different color or appearance to the substrate upon curing. When the inside or outside of a glass vial is coated, the aqueous solution is easier to remove, and the container dries quickly after removal. In addition, the coated slide glass floats on the water surface due to the additional hydrophobicity imparted to the surface tension effect (Figures 33 - 34). In SEM images, the steel blade showed strong adhesion at the edge, and when coated, a hydrophobicity similar to that seen in glass was also imparted to the metal tool (Figures 35 - 36). Initial tests on the release of PET plastic were conducted using molten PET and a coated blade, and this system showed some promise, but the metal samples used were too thin to be quantified.In secondary tests using samples of untreated and coated aluminum, molten PET adhered to the untreated samples, while in the case of coated aluminum, it was shown that the material easily released. These findings indicate the potential for a wide range of uses in one-pot systems, including items that require the imparting of properties such as architecture, preservation, graffiti resistance, art, textiles, tools, industrial mold processes, flame retardancy, automobiles, water transportation means, marine tools, antifouling properties, corrosion resistance, water stain prevention, protection of hard water systems, anti-fog / stain resistance, and chemical resistance.

[0132] Integrating three orthogonal polymer chemistries led to the formation of a single coating system that combined the favorable properties of each chemical species. By using complementary systems, many of the negative properties of the individual polymer groups were prevented or canceled out. When fluoropolymers are added, if done in reasonable amounts, additional desired properties are imparted, but if too much, the opposite effect occurs. By providing a UV-initiated reaction, a base network is formed for forming the underlying systems together, resulting in a unique set of properties with rapid formation and long pot life.

[0133] substance All chemicals were obtained from reliable commercial sources and used without further purification, unless otherwise specified. The following chemicals were used in the formation of Examples 1 - 13 and the test methods detailed above. Hexane and sodium chloride were obtained from VWR International. Calcium chloride dihydrate, dichloromethane, glacial acetic acid, magnesium chloride, nitric acid, sodium hydroxide, sulfuric acid, and 1 - butanol were purchased from Fisher Chemicals. 3 - Aminopropyltriethoxysilane, (3 - glycidoxypropyl)trimethoxysilane, 3 - mercaptopropyltrimethoxysilane, (tridecafluoro - 1,1,2,2 - tetrahydrooctyl)triethoxysilane, and vinyltriethoxysilane were obtained from Gelest Inc. Isopropyl alcohol and methanol were purchased from EMD Millipore Corporation. 1,3 - Divinyltetramethyldisiloxane, poly(ethylene glycol) 400, and tetrahydrofuran were obtained from Sigma - Aldrich, and triethoxy(1H,1H,2H,2H - nonafluorohexyl)silane was obtained from AmBeed. Diaryliodonium hexafluorophosphate and 1M tetrabutylammonium fluoride in THF were obtained from Acros Organics, omnirad 819 was obtained from IGM Resins USA, Inc. 1,2 - Bis(triethoxysilyl)ethane was obtained from Accela, methyltriethoxysilane was obtained from Alfa Aesar. Octamethylcyclotetrasiloxane, 2,4,6,8 - tetramethyl and 2,4,6,8 - tetravinylcyclotetrasiloxane were purchased from TCI. Ethanol (200 proof) was purchased from Pharmco. Microflex powder - free nitrile gloves were purchased from Ansell Healthcare Products LLC. Vivosun handheld garden pressure - pump sprayers were purchased from Amazon Inc. Great Value distilled white vinegar (5%) was purchased locally from Wal - mart Stores, Inc. Mixed vinylsilsesquioxane cages (T8, T10, T12) were synthesized according to known methods.The siloxane depolymerization solution was prepared according to International Patent Application No. PCT / US2022 / 014500.

[0134] Experimental method Test solution The corrosive solution was prepared by diluting 350 mL of white vinegar to 1 L with distilled water and adding 3.048 g of NaCl.

[0135] The simulated hard water was prepared by adding 1.4729 g of NaCl, 2.8143 g of CaCl₂·2H₂O, and 5.0883 g of MgCl₂ to 250 mL of distilled water. The synthetic rain was prepared using 1 L of distilled water with a soda stream carbonated water system until the pH reached 5. Next, while stirring, 5 drops of nitric acid were added, and then sulfuric acid was added dropwise until the same pH as acid rain (4.31) was reached.

[0136] Sample preparation To remove existing films or coatings, the stone surface was removed using 120-grit sandpaper (Ryobi 4-inch × 36-inch belt sander). The stone and glass samples were rinsed with distilled water, dried, sprayed with 0.1 M nitric acid, dried, and then rinsed to simulate accelerated exposure to acid rain. The stainless steel surface was sandblasted to expose the untreated surface and used as is. The brick samples were washed by rubbing with a brush and water and then dried for several weeks. The nitrile gloves were used as is.

[0137] Coating synthesis General coating synthesis was performed in a one-pot manner by volume percentage. Solids were calculated by mass volume percentage to obtain the final formulation. The components of each formulation were placed in a 500 mL bottle, and the resulting solution was then vortexed and stored in the dark at room temperature. Before subsequent use, the bottle was always shaken and vortexed. In all formulations, ratios within the ranges shown in Table 1 were used for their related variants (i.e., thiol, allyl, epoxy, amine, initiator, and additives as desired). Examples are shown below the formulation.

[0138] Application of Coating Indoor method: Three application methods were used. The samples were sprayed until the surface appeared wet, dipped in the solution and then hung / suspended to dry, or spread using a tissue and the solution. After coating, the samples were exposed to a UVA light (200-watt mercury arc lamp with a 320 - 390 nm filter, OmniCure Series 1500, Excelitas Technologies, Lumen Dynmaics Group Inc.) for 2 minutes and left for 30 minutes.

[0139] Outdoor method: The samples were spray-coated outdoors under sunny conditions where the UV index was over 7 (> 175 mW / m 2 / s), the temperature was over 21 °C, and there was a sunny forecast 12 hours after application. The application was performed with a sweeping motion back and forth, like the method of aerosol paint. For small samples, a disposable perfume bottle was used. For larger samples, a handheld pressurized spray was used.

[0140] Analysis Method Thermogravimetric Analysis (TGA) The ceramic yield and thermal stability of the samples were measured by a Hitachi STA7200 thermal analysis system (SN: 19112035C1 - 01) using Software for NEXTA (Hitachi High - Tech Science Corporation, 2018, 2019). Samples of 3.11 mg, 4.44 mg, and 9.60 mg were placed in a ceramic crucible and heated from 25 °C to 1000 °C at a rate of 10 °C per minute and an air flow of 60 mL / min. Before the thermal stability test, the pre - dried samples were fired at 45 °C for 24 hours to remove all solvents.

[0141] Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR - FTIR) Spectra were collected using the attenuated total reflection (ATR) method with OMNIC Spectra (Thermo Scientific, 2017). The spectra were obtained with a Thermo Scientific ATR-FTIR (Nicolet iS5 Fourier transform infrared spectrometer iD7 attenuated total reflection, SN: ASB1817610). Liquid samples were placed on a ZnSe crystal, and cured samples were coated on a slide glass and placed on top of the detector with the coated side down after curing. Cured samples were obtained by coating on a slide glass and placing on a ZnSe crystal with the coated side down, and liquid samples were placed directly on the ZnSe crystal and scanned. All samples were scanned 16 times with a data interval of 0.121 cm from 4000 to 400 cm -1 to -1 .

[0142] Scanning electron microscope (SEM) Samples were prepared using a Hummer VI-A sputter coater. Images were obtained using a Hitachi S-2700 scanning electron microscope. A series of images were obtained using magnifications of 50 - 1000 times, working distances within the range of 13 - 25, 15 - 20 KV, and an aperture of 3 or 4. Coatings were applied to different materials, and images of the coated and uncoated areas were taken using the same settings.

[0143] Pencil hardness evaluation The hardness test was performed using an Elcometer 501 pencil hardness tester (7.5 Newtons, Elcometer Instruments Ltd., Manchester, England). Coated glass and stone samples were evaluated while increasing the hardness.

[0144] Quantitative abrasion resistance The coated stone samples were weighed, and sandpaper was placed on the surface with a weight (50.004 g) on top and moved across the surface (100 times). Then, the samples were blown with air for cleaning (airflow at 45 psi) and weighed again. This was done successively using smooth sandpaper (400 grit), followed by coarse sandpaper (220 grit). Subsequently, the samples were sandblasted (for 30 seconds at 45 psi), weighed again, and calculated. The mass loss percentage was calculated and observations were made during each test.

[0145] Coating surface analysis Initial coating thickness measurements and topography mapping were obtained using a 3D laser confocal microscope (Keyence, VK-X1000 series). The average coating thickness was obtained using an Alpha-Step IQ surface profiler (KLA Tencor). Slide glasses were prepared using the dip-coating method, and measurements were taken 5 times in opposite directions across the entire interface, and the average value was obtained from a total of 10 thickness values. The step analysis was performed with a needle pressure of 24.2 - 25.7 mg, a scan length of 2000 μm, a scan speed of 50 μm / second, a sampling rate of 50 Hz, a scan time of 40 seconds, a sensor range of 400 μm / 23.8 pm, center bias adjustment, a resolution of 1 μm, a contact speed of 5, and a required radius of 5.0 μm.

[0146] Immersion test Before drying, the coated stone samples were immersed in various solutions for 24 hours to examine water stability and pH stability. Distilled water, tap water, synthetic acid rain (pH 4.31), and 0.1 M NaOH solution were used. The samples were inspected for peeling, cracking, and discoloration.

[0147] Chemical resistance The hardened coating pieces were placed on a watch glass and subsequently immersed in various solvents for 24 hours to confirm reactivity and solubility. Tetrahydrofuran, hexane, dichloromethane, acetone, methanol, ethanol, isopropanol, 0.1 M nitric acid, 0.1 M sodium hydroxide, and water were used. Additional coating pieces were placed in a vial with a siloxane depolymerization solution and stirred in the solution for one month.

[0148] Anti-graffiti property To investigate the effect of common vandalism tools on the final product, two tests were conducted. First, a line was drawn on the sample using a Sharpie (Newell Brands). Subsequently, the permanent marker was gently wiped off the surface using a tissue. Next, spray paint (Rust-Oleum Painters touch 2x Ultracover paint+primer) was applied to the surface and allowed to dry. Subsequently, the paint was removed using a tissue.

[0149] Contact angle measurement Water was dropped onto the surface using a syringe, and images were acquired using a Zeiss Stemi 2000-C optical microscope equipped with an AxioCam ERc5s camera. Contact angle analysis was performed using ImageJ software (1.53e, National Institutes of Health, USA), and a manual point procedure using a contact angle plugin. The numerical values were obtained by taking the average of the left and right angles.

[0150] Corrosion resistance The occurrence of oxidation was promoted using a corrosive solution. Steel samples were dip-coated and two test methods were performed. The samples were suspended and the solution was sprayed on both sides daily for one week, and the samples were immersed in the solution for two weeks, exposing the same length of the coated and uncoated samples to the solution.

[0151] Anti-stain property A mixture of 0.1 M NaCl, 0.1 M CaCl2, and 0.1 M MgCl2 was prepared and applied dropwise to both regions of a slide glass (half coated by the dip-coating method). Two heating methods were used. The solution was quickly dried using a heat gun to leave a salt residue, and then the residue was wiped from the surface using a clean tissue. The oven was set to 45 °C, and the slide glass was baked for 24 hours. After cooling, the residue was wiped from the surface using a tissue. For both, stains, dirt, and adhesion were observed.

[0152] Environmental stability test Indoor method: The samples were placed in an oven at 45 °C for 24 hours. After cooling for 24 hours, two cycles of reheating were performed to examine the heat resistance. The samples were placed in a freezer for 24 hours and then warmed to room temperature, which was repeated after the samples were immersed in water for 24 hours, simulating a weather condition with a mixture of rain and snow.

[0153] Outdoor method: The samples were prepared outdoors, and the initial meteorological conditions including air temperature, forecast, precipitation probability, wind, humidity, dew point, atmospheric pressure, UV index, air quality, ozone, nitrogen dioxide, sulfur dioxide, carbon monoxide, and particulate matter (μg / m 3 ) were recorded. The meteorological data were recorded daily throughout the life of the samples and continued as long as the samples remained intact. Cases where data were not recorded on the day were described, using past records. All special phenomena including local wildfires, floods, and nearby activities such as construction that could change the air quality of the test site were described.

[0154] Flammability test A performance test on the flammability of the hybrid coating was conducted. Example 12 was coated on wood chips and cured, and the coated wood chips were ignited side by side with the same uncoated wood chips. Figure 37 shows a photograph of the result. The wood on the right of the photograph is coated with the cured hybrid coating, and the wood on the left of the photograph is uncoated. As can be seen from Figure 37, the hybrid coating is effective as a flame retardant.

[0155] Material Release Test A performance test of a hybrid coating that facilitates the release of materials used in industrial molds was conducted. In the initial test, a tissue inspection blade partially coated with Example 11 was used. A PET #1 plastic bottle was heated with a heat gun until it reached the viscosity of the liquid and then deposited on both sides. Additional tests were conducted using a stock aluminum plate and a welded steel plate coated with Example 12 according to the same method. The results are shown in Figure 38.

[0156] Test of Marine Transport Means The hybrid coating was tested on a boat. Figure 39 shows photos of the rails of a bass boat before and after coating with Example 12. From Figure 39, the transparency and protective properties of the hybrid coating can be clearly seen. The hybrid coating provided a smooth and shiny finish that protected the boat's rails from scratches.

[0157] Thermosetting Test The test of the curing performance of the hybrid coating by heat initiation was carried out in a 20 mL vial. 2 mL of the hybrid coating, 0.22 g of ZnCl2, and 4 drops of hydrogen peroxide (30% aqueous solution) were mixed and then divided into two samples. Sample 1 was exposed to 65 °C for 5 minutes and then left to stand at room temperature. After 30 minutes, the hybrid coating became hard and non-flowing, and the material solidified within 45 minutes. This material was in a spongy state like a hard gel and was not affected. Sample 2 was left to stand at room temperature for 1 hour to observe its stability at room temperature. No change was observed (no observable thickening or curing occurred), and then when the sample was exposed to over 150 °C, it solidified within 30 seconds. Further verification was carried out with the formulation shown in Table 4 (Example 15) to confirm that the process was indeed occurring by a thermal process and that there was no activation of the photoinitiator by the thermal process. In this version, the coating was exposed to 65 °C for 5 minutes and solidified within 45 minutes. This indicates that thermosetting can increase the speed by raising the temperature and results in stability at room temperature.

[0158]

Table 2

[0159] Encapsulant Hybrid coatings can be used to carry or encapsulate pigments, dyes, liquid crystals, or microparticles. Hybrid coatings can be applied as a topcoat over a paint or coating. Applying a hybrid coating containing a dye over a painted surface can change the surface color of the painted surface using one or more reactive dyes. FIG. 41 shows a still-frame image (22 seconds) of a camouflage-painted surface coated with a hybrid coating filled with an active agent (specifically, Example 12).

[0160] Reactive pigment The reactive pigment on the slide glass produces a photo transitioning effect. FIG. 42 shows a square glass coated with a hybrid coating containing a reactive dye (Example 12) before exposure to sunlight (top) and after 5 seconds of exposure (bottom). The color disappears several seconds after being removed from sunlight.

[0161] Pigments and dyes Adding pigments and dyes to the hybrid coating before applying it to the surface can result in a colored finish. FIG. 43 shows a still-frame image of a slide glass coated with the hybrid coating of Example 14, which further contains two dyes.

[0162] Luster reduction by salt in a semi-gloss matte finish When a ZnCl2 concentration exceeding 0.9 M is used in the UV-curable hybrid coating formulation, a matte finish can be obtained. Figure 44 shows fluorocarbon-containing coatings containing 0.95 M (left) and 1.84 M (right) of ZnCl2, which exhibit an off-white color and show a loss of gloss and reflectivity (notably, these amounts of ZnCl2 are approximately 10 times more than the amount of ZnCl2 used in Example 15 for thermal curing).

[0163] Impregnation of the coating For the purpose of reducing electrostatic charge accumulation on the coating surface, metals such as copper, zinc, and iron, as well as carbon fibers such as graphene and nanotubes, can be added to the hybrid coating. For example, copper powder can be suspended in the coating. Figure 45 shows encapsulated copper powder suspended in the hybrid coating of Example 12.

[0164] Coating / film for glass The hybrid coating can be used as a coating or film for glass products such as windows and windshields. The hybrid coating can also be used as an adhesive for glass products. Figure 46 shows a slide glass adhered to a larger glass sheet using the hybrid coating (specifically Example 14).

[0165] Barrier for oil Used motor oil was applied onto marble chips and left for one month. Figure 47 shows the result. The marble on the left side of the line in Figure 47 was coated with the hybrid coating of Example 12 and prevented oil absorption. On the right side of Figure 47, the marble was not coated and the oil was absorbed.

[0166] Efflorescence Granite tombstones were coated with a hybrid coating (Example 12) and exposed to 100% humidity and 5% NaCl salt smoke for 240 hours. Figure 48 shows the results. The uncoated surface (top of Figure 48) exhibits efflorescence or salt accumulation, and it can be seen that there is white powder in the cracks of the stone. The coated surface (bottom of Figure 48) showed a significant reduction in efflorescence.

[0167] Flame retardancy Hybrid coatings provide self-extinguishing performance to wooden structures, reduce flammability, and reduce structural damage after a fire (either natural or man-made). Figure 49 shows a comparison of untreated pine wood (left) and coated pine wood (right) burned at over 1000 °C for 4 minutes. The coated pine wood was coated in Example 12.

[0168] Biomedical applications Hybrid coatings can be used for coating floors, equipment, instruments, etc. for biomedical applications. Cells show a decrease in adhesion on the coated surface, but the hybrid coating is non-toxic in that it does not inhibit proliferation. Figure 50 shows a photograph of a square glass coated in Example 14 and inoculated with HEK293 mammalian adherent cells. The hybrid coating did not prevent proliferation but decreased cell adhesion to the glass.

[0169] Antibacterial property Silver can be filled in the non-fluorinated formulation for antibacterial coatings in medical or biotechnology applications in hybrid coatings. Side chain functional groups can be used for biomedical purposes. For example, silver chloride can be added to the hybrid coating to impart antibacterial properties in addition to the above-mentioned reduction in adhesion.

[0170] Antifouling property Hybrid coatings prevent the adhesion of microorganisms or, alternatively, weaken the strength of adhesion of microorganisms to the coated surface. As a result, the removal of bacteria from the coated surface becomes easier. In an aqueous environment, for example, the hybrid coating prevents barnacles or mussels from adhering to the coated surface or, alternatively, weakens the adhesion force of barnacles or mussels to make it easier to remove barnacles or mussels from the coated surface. Figure 51 shows a glass vial with an internal coating and immersed in water. Zebra mussels were placed in the glass vial, their adhesion force was examined, and it was determined whether they would move out of the container. From left to right in Figure 51, two glass vials are uncoated, three glass vials are coated in Example 14, and three glass vials are coated in Example 12. Adhesion was minimal, indicating that it was difficult for the mussels to climb inside the vial.

[0171] Antifungal Hybrid coatings prevent the growth of black mold and white mold on the coated wood surface. Figure 52 shows the differences in the growth and discoloration of mold and white mold when untreated pine wood, wood coated with a non-fluorinated coating (coated in Example 14), and wood coated with a fluorinated coating (coated in Example 12) were saturated with 100% humidity and 5% NaCl salt smoke for 240 hours. In the photo, the samples are still wet.

[0172] Decay and color loss Figure 53 shows the same blocks as shown in Figure 52 after drying for 6 months. The uncoated sample (left) still maintained mold and white mold, but had lost its color and the ends were starting to crack. Samples coated with non-fluorinated (center; coated in Example 14) and fluorinated (right; coated in Example 12) hybrid coatings retained their original color and no cracking had started at the ends.

[0173] Certain embodiments of the compositions and methods disclosed herein are illustrated in the above examples. It should be understood that while these examples show specific embodiments of the invention, they are given by way of illustration only. From the foregoing discussion and these examples, one skilled in the art can ascertain the essential characteristics of this disclosure and make various changes and modifications to the compositions and methods described herein to adapt them to various uses and conditions without departing from the spirit and scope of this disclosure. Various changes may be made and equivalents may be substituted for elements of this disclosure without departing from the essential scope thereof. In addition, many modifications may be made to adapt a particular situation or material to the teachings of this disclosure without departing from the essential scope thereof.

Claims

1. A hybrid coating comprising: a thiol alkoxysilane, an alkene alkoxysilane, an epoxy alkoxysilane, an amine alkoxysilane, and a solvent, wherein the hybrid coating is in the form of a curable solution.

2. The hybrid coating according to claim 1, further comprising a photoinitiator, wherein the hybrid coating is in the form of a photocurable solution.

3. The hybrid coating according to claim 1, wherein the thiol alkoxysilane comprises (3-mercaptopropyl)-trimethoxysilane, 2-mercaptoethyltrimethoxysilane, 3-(dimethoxymethylsilyl)-2-methylpropanethiol, or combinations thereof.

4. The hybrid coating according to claim 1, wherein the thiol alkoxysilane is present in an amount up to about 30 volume / volume %.

5. The hybrid coating according to claim 1, wherein the alkene alkoxysilane comprises a vinyl group.

6. The hybrid coating according to claim 1, wherein the alkene alkoxysilane comprises an allyl group.

7. The hybrid coating according to claim 1, wherein the alkene alkoxysilane comprises 2,4,6,8-tetramethyl, 2,4,6,8-tetravinylcyclotetrasiloxane, 1,3-divinyltetramethyldisiloxane, vinyltriethoxysilane, N-[2-(vinylbenzylamino)ethyl]-3-aminopropyltrimethoxysilane, vinyltriacetoxysilane, or combinations thereof.

8. The hybrid coating according to claim 1, wherein the alkene alkoxysilane is present in an amount up to about 60 volume / volume %.

9. The hybrid coating according to claim 1, wherein the epoxy alkoxysilane comprises 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-(2,3-epoxypropoxypropyl)methyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, or combinations thereof.

10. The hybrid coating according to claim 1, wherein the epoxy alkoxysilane is present in an amount up to about 50 volume / volume %.

11. The hybrid coating according to claim 1, wherein the aminoalkoxysilane comprises 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-[2-(vinylbenzylamino)ethyl]-3-aminopropyltrimethoxysilane, or a combination thereof.

12. The hybrid coating according to claim 1, wherein the aminoalkoxysilane is present in an amount up to about 50% volume / volume.

13. The hybrid coating according to claim 2, wherein the photoinitiator comprises aryl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylaryl)methane (omnirad 819).

14. The hybrid coating according to claim 1, further comprising up to about 30% volume / volume of a fluorocarbon.

15. The hybrid coating according to claim 14, wherein the fluorocarbon comprises triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane or (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane.

16. The hybrid coating according to claim 1, further comprising silsesquioxane.

17. The hybrid coating according to claim 1, further comprising one or more additional siloxanes, silanes, silsesquioxanes, or combinations thereof.

18. The hybrid coating according to claim 17, wherein the additional siloxane, silane, or silsesquioxane comprises D4 octamethylcyclotetrasiloxane, alkyltriethoxysilane, vinyl-terminated silsesquioxane, aryltriethoxysilane, alkynyltriethoxysilane, 1,2-bis(triethoxysilyl)ethane, or combinations thereof.

19. The hybrid coating according to claim 1, wherein the solvent comprises an alcohol.

20. The hybrid coating according to claim 1, wherein the solvent comprises a combination of alcohols.

21. The hybrid coating according to claim 1, wherein the solvent comprises an alcohol that is complementary to one or more of the aminoalkoxysilane, epoxyalkoxysilane, thioalcoholoxysilane, or alkenealkoxysilane.

22. The thioalkoxysilane includes di- or tri-alkoxysilane, The alkenylalkoxysilane includes di- or tri-alkoxysilane, The epoxyalkoxysilane includes di- or tri-alkoxysilane, and The aminoalkoxysilane includes di- or tri-alkoxysilane, The hybrid coating according to claim 1.

23. The hybrid coating according to claim 22, wherein any additional alkoxysilane present is a di- or tri-alkoxysilane.

24. The hybrid coating according to claim 1, further comprising a spacer.

25. wherein the spacer is D ４ The hybrid coating according to claim 24, comprising octamethylcyclotetrasiloxane or polyethylene glycol (PEG).

26. The hybrid coating according to claim 1, further comprising an acid.

27. The hybrid coating according to claim 26, wherein the acid includes glacial acetic acid, or a photoacid generator, or a combination thereof.

28. The hybrid coating according to claim 27, wherein the photoacid generator is diaryliodonium hexafluorophosphate.

29. The hybrid coating according to claim 1, further comprising a crosslinking agent.

30. The hybrid coating according to claim 1, comprising 3-glycidyloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane, (3-mercaptopropyl)-trimethoxysilane, vinyltriethoxysilane, omnirad 819, diaryliodonium hexafluorophosphate, methanol, and isopropanol.

31. 3-glycidyloxypropyltrimethoxysilane in an amount of about 8.2 volume / volume %, 3-aminopropyltriethoxysilane in an amount of about 7.5 volume / volume %, triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane in an amount of about 1.6 volume / volume %, (3-mercaptopropyl)-trimethoxysilane in an amount of about 2.9 volume / volume %, vinyltriethoxysilane in an amount of about 3.3 volume / volume %, omnirad 819 in an amount of about 0.3 weight / volume %, diaryliodonium hexafluorophosphate in an amount of about 0.1 weight / volume %, methanol in an amount of about 36.1 volume / volume %, and isopropanol in an amount of about 40.1 volume / volume %, The hybrid coating according to claim 1.

32. The hybrid coating according to claim 1, comprising 3-glycidyloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane, (3-mercaptopropyl)-trimethoxysilane, vinyltriethoxysilane, omnirad 819, diaryliodonium hexafluorophosphate, methanol, and isopropanol.

33. 3-glycidyloxypropyltrimethoxysilane in an amount of about 13.7 volume / volume %, 3-aminopropyltriethoxysilane in an amount of about 12.3 volume / volume %, (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane in an amount of about 2.8 volume / volume %, (3-mercaptopropyl)-trimethoxysilane in an amount of about 5.0 volume / volume %, vinyltriethoxysilane in an amount of about 5.6 volume / volume %, omnirad 819 in an amount of about 0.5 weight / volume %, diaryliodonium hexafluorophosphate in an amount of about 0.2 weight / volume %, methanol in an amount of about 18.1 volume / volume %, and isopropanol, ethanol, or water in an amount of about 41.8 volume / volume %, The hybrid coating according to claim 1.

34. The hybrid coating according to claim 1, comprising 3-glycidyloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane, (3-mercaptopropyl)-trimethoxysilane, vinyltriethoxysilane, omnirad 819, diaryliodonium hexafluorophosphate, methanol, and 1-butanol.

35. 3-glycidyloxypropyltrimethoxysilane in an amount of about 13.6 volume / volume %, 3-aminopropyltriethoxysilane in an amount of about 12.3 volume / volume %, (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane in an amount of about 2.8 volume / volume %, (3-mercaptopropyl)-trimethoxysilane in an amount of about 5.0 volume / volume %, vinyltriethoxysilane in an amount of about 5.5 volume / volume %, omnirad 819 in an amount of about 0.8 weight / volume %, diaryliodonium hexafluorophosphate in an amount of about 0.3 weight / volume %, Methanol in an amount of about 18.1 volume / volume %, and 1-butanol in an amount of about 41.7 volume / volume %, The hybrid coating according to claim 1, comprising the same.

36. The hybrid coating according to claim 1, further comprising a salt, a peroxide, or a thermal acid generator, wherein the hybrid coating is in the form of a thermosetting solution.

37. wherein the salt is ZnCl ２ The hybrid coating according to claim 36, comprising

38. The hybrid coating according to claim 36, wherein the thermal acid generator comprises p-nitrobenzyl tosylate.

39. 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (3-mercaptopropyl)-trimethoxysilane, vinyltriethoxysilane, ZnCl ２ The hybrid coating according to claim 36, comprising methanol, isopropanol, and hydrogen peroxide.

40. 3-glycidyloxypropyltrimethoxysilane in an amount of about 13.9 volume / volume %, 3-aminopropyltriethoxysilane in an amount of about 12.5 volume / volume %, (3-mercaptopropyl)-trimethoxysilane in an amount of about 5.1 volume / volume %, Vinyltriethoxysilane in an amount of about 5.7 volume / volume %, Hydrogen peroxide (30% aqueous solution) in an amount of about 1.0 volume / volume %, ZnCl in an amount of about 1.0% by weight / volume ２ , Methanol in an amount of about 18.4 volume / volume %, and Isopropanol in an amount of about 42.4 volume / volume %, The hybrid coating according to claim 36, comprising the same.

41. 3-glycidyloxypropyltrimethoxysilane in an amount of about 14.1 volume / volume %, 3-aminopropyltriethoxysilane in an amount of about 12.7 volume / volume %, (3-mercaptopropyl)-trimethoxysilane in an amount of about 5.1 volume / volume %, Vinyltriethoxysilane in an amount of about 5.7 volume / volume %, Omnirad 819 in an amount of about 0.5 weight / volume %, Diaryliodonium hexafluorophosphate in an amount of about 0.2 weight / volume %, Methanol in an amount of about 18.6 volume / volume %, And isopropanol in an amount of about 43.0 volume / volume %, The hybrid coating according to claim 1, comprising the same.

42. The hybrid coating according to claim 1, further comprising a dye or a colorant.

43. Formula I: 【Chemical 1】 The hybrid coating, comprising the same and being in the form of a cured solid.

44. The hybrid coating according to claim 43, which is a flame retardant.

45. The hybrid coating according to claim 43, which is a coating for industrial molds.

46. The hybrid coating according to claim 43, which is a surface colorant.

47. The hybrid coating according to claim 43, having a water contact angle greater than 90°.

48. The hybrid coating according to claim 43, which is coated on a substrate containing stone, brick, wood, glass, metal, plastic, rubber, cloth, glass fiber, concrete, steel, aluminum, nitrile, or vinyl.

49. A hybrid coating comprising a composition formed from (i) the reaction of an amine alkoxysilane and a thiol alkoxysilane, (ii) the reaction of an epoxy alkoxysilane and an alkene alkoxysilane, and (iii) a moisture polymerization that replaces the alkoxy groups present and derived from the epoxy alkoxysilane, the amine alkoxysilane, the thiol alkoxysilane, and the alkene alkoxysilane.

50. A method for protecting a monument from acid rain and graffiti, comprising applying the hybrid coating according to claim 1 to the monument and curing the hybrid coating to protect the monument from acid rain and graffiti.

51. A method for protecting a surface from water, comprising applying the hybrid coating according to claim 14 to the surface and curing the hybrid coating to protect the surface from water.

52. A method for protecting a surface from scratches, comprising applying the hybrid coating according to claim 1 to the surface and curing the hybrid coating to protect the surface from scratches.

53. A method for protecting an article from flame damage, comprising applying the hybrid coating according to claim 1 to the article and curing the hybrid coating to protect the article from flame damage.

54. The method according to claim 53, wherein the article is wood.

55. A method for facilitating the release of a material in an industrial mold, comprising applying the hybrid coating according to claim 1 to the industrial mold and curing the hybrid coating to facilitate the release of the material after a thermoforming process.

56. A method for coloring a surface, comprising applying the hybrid coating according to claim 35 to the surface and curing the hybrid coating to encapsulate a dye or colorant on the surface.

57. A method for reducing cell adhesion to a surface, comprising applying the hybrid coating according to claim 1 to the surface and curing the hybrid coating to reduce cell adhesion to the surface.

58. The method according to claim 57, wherein the surface is glass, metal, plastic, or silicone.

59. The method according to claim 57, wherein the surface includes a floor or a medical device.

60. The method according to claim 57, wherein the surface includes a medical device or an implant.

61. A method for reducing the gloss of a surface, comprising incorporating a salt into the hybrid coating according to claim 1, applying the salt-containing hybrid coating to the surface, and curing the salt-containing hybrid coating to reduce the gloss of the surface.

62. wherein the salt is ZnCl ２ The method according to claim 61, wherein the salt is ZnCl ２ .

63. A method for reducing electrostatic charge accumulation on a surface, comprising incorporating a metal or carbon fiber into the hybrid coating according to claim 1, applying the metal-containing or carbon fiber-containing hybrid coating to the surface, and curing the metal-containing or carbon fiber-containing hybrid coating to reduce electrostatic charge accumulation on the surface.

64. The method according to claim 63, wherein the metal or carbon fiber includes copper, zinc, iron, graphene, or nanotubes.

65. A method for bonding two surfaces together, comprising applying the hybrid coating according to claim 1 to at least one of the two surfaces, pressing the two surfaces together, and curing the hybrid coating to bond the two surfaces together.

66. The method according to claim 65, wherein the two surfaces are glass.

67. A method for forming a barrier against oil on a surface, comprising applying the hybrid coating according to claim 1 to the surface and curing the hybrid coating on the surface to form a barrier against oil on the surface.

68. The method according to claim 67, wherein the surface includes marble.

69. A method for reducing efflorescence on a surface, comprising applying the hybrid coating according to claim 1 to the surface and curing the hybrid coating on the surface to reduce efflorescence on the surface.

70. Applying the hybrid coating according to claim 1 to a surface and curing the hybrid coating on the surface to enhance the fire resistance of the surface, a method for enhancing the fire resistance of a surface.

71. The method according to claim 70, wherein the surface includes wood.

72. Applying the hybrid coating according to claim 1 to a surface and curing the hybrid coating on the surface to improve the antifouling property of the surface, a method for improving the antifouling property of a surface.

73. The method according to claim 72, wherein the surface includes glass.

74. Applying the hybrid coating according to claim 1 to a surface and curing the hybrid coating on the surface to make the surface antifungal and anti-corruptive, a method for making a surface antifungal and anti-corruptive.

75. The method according to claim 74, wherein the surface includes wood.

76. Applying the hybrid coating according to claim 1 to a wood piece having an end and curing the hybrid coating on the wood piece to prevent the wood piece from cracking at the end, a method for preventing wood from cracking at its end.

77. A method for curing a hybrid coating, the method comprising: Coating a substrate with a hybrid coating solution containing a photoinitiator; Exposing the hybrid coating solution to sunlight or artificial UV light for a first period of time to cause a first curing process to form a coating having a surface unaffected on the substrate; Causing a second curing process for a second period of time to improve the adhesion between the coating and the substrate; and Causing a third curing process for a third period of time to solidify the unaffected surface. Including, a method.

78. The method according to claim 77, wherein the hybrid coating solution includes a plurality of alkoxysilanes containing epoxy, alkene, amine, and thiol components.

79. A method of removing a hybrid coating according to claim 43 or claim 49 from a substrate, the method comprising depolymerizing a siloxane polymer and exposing the substrate having the hybrid coating to a solution containing a fluoride source in a solvent for the purpose of removing the hybrid coating from the substrate.

80. A coated article comprising a substrate coated with a hybrid coating according to claim 42 or claim 48.

81. The coated article according to claim 80, wherein the article is a monument, gravestone, means of transportation, clothing, tool, industrial machining part, or building material.

82. A method of curing a hybrid coating, the method comprising: adding a salt to a hybrid coating solution; adding hydrogen peroxide to the hybrid coating solution; coating a substrate with the hybrid coating solution to form a coated substrate; exposing the coated substrate to a temperature of at least about 65°C for a first time; and allowing the coated substrate to stand at room temperature for a second time to cure the hybrid coating on the substrate. The method comprising.

83. The method according to claim 82, wherein the hybrid coating solution comprises a plurality of alkoxysilanes comprising epoxy, alkene, amine, and thiol components.

84. The method according to claim 83, wherein the hybrid coating solution does not contain a photoinitiator.

85. The method according to claim 82, wherein the first time is at least about 5 minutes.

86. The method according to claim 82, wherein the second time is at least about 45 minutes.

87. A method of curing a hybrid coating, the method comprising: adding a salt to a hybrid coating solution; adding hydrogen peroxide to the hybrid coating solution; coating a substrate with the hybrid coating solution to form a coated substrate; allowing the coated substrate to stand at room temperature for a first time; and exposing the coated substrate to a temperature of at least about 150°C for a second time to cure the hybrid coating on the substrate. A method comprising...

88. The method according to claim 87, wherein the hybrid coating solution comprises a plurality of alkoxysilanes comprising epoxy, alkene, amine, and thiol components.

89. The method according to claim 87, wherein the hybrid coating solution does not contain a photoinitiator.

90. The method according to claim 87, wherein the first time is at least about 1 hour.

91. The method according to claim 87, wherein the second time is less than about 30 seconds.

92. A hybrid coating comprising: thiol alkoxysilane, alkene alkoxysilane, epoxy alkoxysilane, amine alkoxysilane, a solvent, and either (i) a photoinitiator (in which case the hybrid coating is in the form of a photocurable solution), (ii) a salt, peroxide, or thermal acid generator (in which case the hybrid coating is in the form of a thermosetting solution), or (iii) a cation and / or an anion (in which case the hybrid coating is in the form of a chemically curable solution). A hybrid coating.

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