Inorganic fluoride coating compositions

Abstract

A chemically resistant coating composition including a film forming resin, solvent, and filler. The filler may include 5 wt. % of an inorganic fluoride component, based on the total weight of the coating composition. The fluoride component may include at least one of MgF2, CaF2, SrF2, and BaF2. The coating composition may comprise less than 1 wt. % of a phthalate plasticizer, based on the total weight of the coating composition.

Description

INORGANIC FLUORIDE COATING COMPOSITIONSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit under 35 U.S.C. § 119(e) of U.S. Provisional Application No. 63 / 684,088 entitled “INORGANIC FLUORIDE COATING COMPOSITIONS”, filed on August 16, 2024, the entire disclosure of which is incorporated by reference in its entirety.GOVERNMENT LICENSE RIGHTS

[0002] This invention was made with government support under Government Contract No. W91 INF- 14-2-0078 Cooperative Agreement awarded by the U.S. Army Contracting Command on behalf of the U.S. Army Research Laboratory (ARL). The government may have certain rights in the invention.FIELD

[0003] The present disclosure relates to a chemically resistant coating compositions comprising an inorganic fluoride component.BACKGROUND

[0004] Protective surface or exterior coatings are applied to vehicles, such as automobiles and aerospace vehicles, for example, to protect underlying pigmented coatings as well as to provide corrosion protection and / or enhanced performance such as durability and protection from physical damage. Surfaces of vehicles, such as aerospace vehicles, are also exposed to the elements and also possibly to corrosive chemicals such as jet fuels and hydraulic fluids.

[0005] It would be desirable to provide improved coating compositions that demonstrate desired levels of corrosion resistance for use on vehicles such as aerospace vehicles.SUMMARY

[0006] The present disclosure provides a coating composition including a film forming resin; a solvent; and a filler. The filler includes at least one inorganic fluoride component. The coating composition comprises at least 5 wt. % of the filler, based on the total weight of thecoating composition. The coating composition comprises less than 1 wt. % of phthalate plasticizers, based on the total weight of the coating composition.

[0007] The present disclosure further provides a method of coating a substrate with a coating composition, including applying, to a surface of the substrate, a coating composition and curing the coating composition to form a cured coating. The coating composition includes a film forming resin; a solvent; and a filler. The filler includes at least one inorganic fluoride component. The coating composition comprises at least 5 wt. % of the filler, based on the total weight of the coating composition. The coating composition comprises less than 1 wt. % of phthalate plasticizers, based on the total weight of the coating composition.

[0008] The present disclosure also provides an article coated in the coating composition. The method includes applying, to a surface of the article, the coating composition and curing the coating composition to form a cured coating.DETAILED DESCRIPTION

[0009] I. Definitions

[0010] For purposes of the following detailed description, it is to be understood that the disclosure may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about." For example, numerical ranges provided for weight percentages of components or amounts of components added should be construed as being modified by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0011] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherentlycontains certain errors necessarily resulting from the standard variation found in their respective testing measurements.

[0012] Whereas particular examples of this disclosure have been described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the present disclosure may be made without departing from what is defined in the appended claims.

[0013] Also, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges from (and including) the recited minimum value of 1 to the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.

[0014] The use of the singular includes the plural and plural encompasses singular, unless specifically stated otherwise. In addition, the use of "or" means "and / or" unless specifically stated otherwise, even though "and / or" may be explicitly used in certain instances.

[0015] “Wet” coating composition as used herein refers to a liquid, or uncured coating composition which includes water and / or volatile components.

[0016] “Dry” coating composition as used herein refers to a cured coating which essentially lacks water and / or volatile components.

[0017] ‘Substrate” and “article” as used herein refers to an object or other item with a surface onto which a coating composition may be applied.

[0018] II. Chemically Resistant Coating Composition

[0019] A. Film-Forming Resin

[0020] The coating composition may comprise a film-forming resin. A film-forming resin is a resin that can form a self-supporting continuous film on at least a horizontal surface of a substrate upon removal of any diluents or carriers present in the composition or upon curing.

[0021] Additionally, the film-forming resin may be a thermosetting coating composition and can include film-forming polymers or resins having functional groups that are reactive with either themselves (“self-crosslinking”) or a crosslinker, discussed below. Suitable film-forming resins include, for example, acrylic polymers, polyester polymers, polyurethane polymers, and mixtures thereof. Generally, these polymers can be any polymers of these types made by any method known to those skilled in the art. The functional groups on the film-forming resins caninclude, for example, carboxylic acid groups, amine groups, epoxide groups, hydroxyl groups, thiol groups, carbamate groups, amide groups, area groups, isocyanate groups (including blocked isocyanate groups), mercaptan groups, and combinations thereof. Mixtures of film-forming resins can also be used in the preparation of the present film forming component.

[0022] The film forming resin may be present in the coating composition in an amount from about 35 wt. %, 40 wt. %, or 45 wt. % to 50 wt. %, 55 wt. %, or 60 wt. %, or any value encompassed by these endpoints, such as 35 to 60 wt. %, 40 to 55 wt. %, or 45 to 50 wt. %, based on the total weight of the “wet” coating composition.

[0023] The film forming resin may be present in the cured coating composition in an amount from about 60 wt. %, 65 wt. %, or 70 wt. % to 75 wt. %, 80 wt. %, or 90 wt. %, or any value encompassed by these endpoints, such as 60 to 90 wt. %, 65 to 80 wt. %, or 70 to 75 wt. %, based on the total weight of the “dry” coating.

[0024] i. Polyurethane Polymer

[0025] A polyurethane can be prepared by reacting a polyester polyol, polycarbonate polyol, polyether polyol or acrylic polyol with a polyisocyanate and optionally an acid functional polyol (such as dimethylol propionic acid) such that the NCO / OH ratio is greater than 1:1 to generate an NCO functional prepolymer. The terminal isocyanates are then reacted with a non- tertiary aminoalcohol such as diethanolamine or ethanolamine to produce a terminal OH functional polymer. Some or all of the terminal OH groups may then be reacted with anhydrides such as succinic anhydride or methylhexahydrophthalic anhydride to produce a urethane polymer with terminal COOH groups. The acid groups introduced in the first stage of urethane preparation are considered to be internal COOH groups, while the acid groups introduced after reaction of the anhydride with aminoalcohol are considered to be terminal COOH groups.

[0026] Suitable polyisocyanates may be aliphatic, aromatic, cycloaliphatic or heterocyclic isocyanates. Representative examples are the aliphatic isocyanates such as trimethylene, tetramethylene, pentamethylene, hexamethylene, 1 ,2-propylene, 1,2-butylene, 2,3- butylene and 1,3-butylene diisocyanates; the cycloalkylene compounds such as 1,3-cyclopentane, 1,4-cyclohexane, 1,2-cyclohexane diisocyanates and isophorone diisocyanates; the aromatic compounds such as m-phenylene, p-phenylene, 4,4'-diphenyl, 1,5-naphthalene and 1,4- naphthalene diisocyanates; the aliphatic-aromatic compounds such as 4,4'-diphenylene methane diisocyanates, 2,4- or 2,6-tolylene diisocyanates, or mixtures thereof, 4,4'-toluidine, tetramethylxylylene, and xylylene diisocyanates; the nuclear-substituted aromatic compounds such as dianisidinc diisocyanatc, 4,4'-diphcnylcthcr diisocyanatc and chlorodiphcnylcnc diisocyanatc; the triisocyanates such as triphenyl methane-4,4',4"-triisocyanate, 1,3,5-triisocyanato benzene and 2,4,6-triisocyanato toluene; and the tetraisocyanates such as 4,4'-dimethyldiphenyl methane- 2,2',5,5'-tetraisocyanate; the polymerized polyisocyanates such as tolylene diisocyanate dimers and trimers, and the like.

[0027] Suitable diisocyanates include aliphatic diisocyanates, aromatic diisocyanates, and mixtures thereof. Suitable diisocyanates are methylene-bis(4-cyclohexylisocyanate), isophorone diisocyanate, 1,4-cyclohexyl diisocyanate, l,3-bis(isocyanatomethyl)cyclohexane, meta-tetramethylxylene diisocyanate (“TMXDI”), toluene diisocyanate, methylene diphenyl diisocyanate and / or a mixture thereof.

[0028] Suitable polyols may include alkylene glycols, such as ethylene glycol; propylene glycol; diethylene glycol; dipropylene glycol; triethylene glycol; tripropylene glycol; hexylene glycol; polyethylene glycol; polypropylene glycol and neopentyl glycol; hydrogenated bisphenol A; cyclohexanediol; propanediols including 1,2-propanediol; 1,3-propanediol; butyl ethyl propanediol; 2-methyl- 1,3-propanediol; and 2-ethyl-2-butyl- 1,3-propanediol; butanediols including 1,4-butanediol; 1,3-butanediol; and 2-ethyl-l,4-butanediol; pentanediols including trimethyl pentanediol and 2-methylpentanediol; cyclohexanedimethanol; hexanediols including 1,6-hexanediol; caprolactonediol (for example, the reaction product of epsilon-capro lactone and ethylene glycol); hydroxy alkylated bisphenols; polyether glycols, for example, poly(oxytetramethylene) glycol; trimethylol propane; pentaerythritol; di-pentaerythritol; trimethylol ethane; trimethylol butane; dimethylol cyclohexane; glycerol and the like or combinations thereof.

[0029] Suitable acid containing polyols may include dimethanol propionic acid, 2,2- bis(hydroxymethyl)butyric acid, tartaric acid, 3,5-dihydroxybenzoic acid, ascorbic acid and its isomers, and any acid derivatives of the polyols listed in the previous paragraph.

[0030] ii. Polyester Polymers

[0031] Polyesters may comprise the reaction product of a polyacid and a polyol. Suitable polyesters may be acid functional polyester generated by a polycondensation reaction, which are then dispersible into water.

[0032] “Polyacid” refers to a compound having two or more carboxylic acid groups, such as two, three or four acid groups, and includes an ester of the polyacid (wherein one or more of the acid groups is esterified) or an anhydride. The polyacid may be an organic polyacid.

[0033] The carboxylic acid groups of the polyacid may be connected by a bridging group selected from: an alkylene group; an alkenylene group; an alkynylene group; an arylalkylene group, an alkylarylene group, or an arylene group.

[0034] The polyester may be formed from any suitable polyacid. Suitable examples of polyacids include, but are not limited to the following: maleic acid; fumaric acid; itaconic acid; adipic acid; azelaic acid; succinic acid; sebacic acid; glutaric acid; decanoic diacid; dodecanoic diacid; phthalic acid; isophthalic acid; 5-tert-butylisophthalic acid; tetrachlorophthalic acid; tetrahydrophthalic acid; trimellitic acid; naphthalene dicarboxylic acid; naphthalene tetracarboxylic acid; terephthalic acid; hexahydrophthalic acid; methylhexahydrophthalic acid; dimethyl terephthalate; cyclohexane dicarboxylic acid; chlorendic anhydride; 1,3 -cyclohexane dicarboxylic acid; 1,4-cyclohexane dicarboxylic acid; tricyclodecane polycarboxylic acid; endomethylene tetrahydrophthalic acid; endoethylene hexahydrophthalic acid; cyclohexanetetra carboxylic acid; cyclobutane tetracarboxylic; esters and anhydrides of all the aforementioned acids and combinations thereof.

[0035] “Polyol” refers to a compound having two or more hydroxyl groups, such as two, three or four hydroxyl groups. The hydroxyl groups of the polyol may be connected by a bridging group selected from: an alkylene group; an alkenylene group; an alkynylene group; an arylalkylene group, an alkylarylene group, or an arylene group. Suitably the polyol is an organic polyol.

[0036] The polyester may be formed from any suitable polyol. Suitable examples of polyols include, but are not limited to the following: alkylene glycols, such as ethylene glycol; propylene glycol; diethylene glycol; dipropylene glycol; triethylene glycol; tripropylene glycol; hexylene glycol; polyethylene glycol; polypropylene glycol and neopentyl glycol; hydrogenated bisphenol A; cyclohexanediol; propanediols including 1,2-propanediol; 1,3-propanediol; butyl ethyl propanediol; 2-methyl- 1,3-propanediol; and 2-ethyl-2-butyl- 1,3-propanediol; butanediols including 1,4-butanediol; 1,3-butanediol; and 2-ethyl-l,4-butanediol; pentanediols including trimethyl pentanediol and 2-methylpentanediol; cyclohexanedimethanol; hexanediols including 1,6-hexanediol; caprolactonediol (for example, the reaction product of epsilon-capro lactone andethylene glycol); hydroxy alkylated bisphenols; polyether glycols, for example, poly(oxytctramcthylcnc) glycol; trimcthylol propane; pcntacrythritol; di-pcntacrythritol; trimethylol ethane; trimethylol butane; dimethylol cyclohexane; glycerol and the like or combinations thereof.

[0037] The polyester may comprise polymers or copolymers formed from the reaction of diols and diacids, where polyols or polyacid components may optionally be used to produce branched polymers.

[0038] The polyester may be formed from a diacid. Suitable examples of diacids include, but are not limited to the following: phthalic acid; isophthalic acid; terephthalic acid; 1,4 cyclohexane dicarboxylic acid; succinic acid; adipic acid; azelaic acid; sebacic acid; fumaric acid; 2,6-naphthalene dicarboxylic acid; orthophthalic acid; phthalic anhydride; tetrahydrophthalic anhydride; maleic anhydride; succinic anhydride; itaconic anhydride; di-ester materials, such as dimethyl ester derivatives for example dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,4-cyclohexane dicarboxylate, dimethyl 2,6-naphthalene di carboxylate, dimethyl fumarate, dimethyl orthophthalate, dimethylsuccinate, dimethyl glutarate, dimethyl adipate; esters and anhydrides of all the aforementioned acids; and mixtures thereof.

[0039] The polyester be formed from a diol. Suitable examples of diols include, but are not limited to the following: ethylene glycol; 1,2-propane diol; 1,3-propane diol; 1,2-butandiol; 1,3-butandiol; 1,4-butandiol; but-2-ene 1,4-diol; 2,3-butane diol; 2-methyl 1,3-propane diol; 2,2'- dimethyl 1 ,3-propanediol (neopentyl glycol); 1,5 pentane diol; 3-methyl 1,5-pentanediol; 2,4- diethyl 1,5-pentane diol; 1,6-hexane diol; 2-ethyl 1,3-hexane diol; diethylene glycol; triethylene glycol; dipropylene glycol; tripropylene glycol; 2,2,4-trimethyl pentane 1,3-diol; 1,4 cyclohexane dimethanol; tricyclodecane dimethanol; 2,2,4,4-tetramethyl cyclobutane 1,3-diol; isosorbide; 1,4-cyclohexane diol; l,T-isopropylidene-bis (4-cyclohexanol); and mixtures thereof.

[0040] Alternatively, suitable polyesters may be acid polyesters generated by anhydride ring opening reactions. Such polyesters are also dispersible into water.

[0041] Suitable polyacids include polyacid half-esters obtained by reaction between a polyol and a 1,2-acid anhydride under conditions sufficient to ring open the anhydride forming the half-ester with substantially no polyesterification occurring. Such reaction products are of relatively low molecular weight, with a narrow weight distribution, and provide lower volatile organic contents in the curable composition while still providing for excellent properties in theresultant coating. By substantially no polyesterification occurring means that the carboxyl groups of the anhydride arc not cstcrificd by the polyol in a recurring manner. By this is meant that less than 10 by weight polyester is formed based on the total weight the polyester resin.

[0042] To form the polyester, a 1, 2-acid anhydride and polyol are contacted together usually by mixing the two together in a reaction vessel. The reaction may be conducted in the presence of an inert atmosphere such as nitrogen and in the presence of a solvent to dissolve the solid ingredients and / or to lower the viscosity of the reaction mixture.

[0043] Suitable solvents include ketones such as methyl amyl ketone, diisobutyl ketone, methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; as well as other organic solvents such as dimethyl formamide and N-methylpyrrolidone.

[0044] For a ring opening reaction and half-ester formation, a 1, 2-acid anhydride may be used. Reaction of a polyol with an acid instead of an anhydride would require esterification by condensation eliminating water which would have to be removed by distillation. These conditions may promote undesired polyesterification. Also, the reaction temperature may be low, that is, less than 135 °C, less than 120 °C, less than 100 °C, or less than 90 °C. Temperatures greater than 135 °C may promote polyesterification, whereas temperatures less than 70 °C may cause a sluggish reaction.

[0045] The time of reaction can vary somewhat depending principally upon the temperature of reaction. Usually, the reaction time will be until a sufficiently constant acid value is obtained and may be from as low as 10 minutes to as high as 24 hours.

[0046] The equivalent ratio of anhydride to hydroxy of the polyol may be at least about 0.8:1 (the anhydride being considered monofunctional) so as to obtain maximum conversion to the desired half-ester.

[0047] Among the anhydrides which can be used in the formation of the polyesters are those which exclusive of the carbon atoms of the anhydride moiety contain from about 2 to 30 carbon atoms. Suitable anhydrides include aliphatic, including cycloaliphatic, olefinic and cycloolefinic anhydrides and aromatic anhydrides. Substituted aliphatic and aromatic anhydrides may also be included within the definition of aliphatic and aromatic provided the substituents do not adversely affect the reactivity of the anhydride or the properties of the resultant polyester.

[0048] Suitable substituents may be chloro, alkyl and alkoxy. Suitable anhydrides may include succinic anhydride, methylsuccinic anhydride, dodecenylsuccinic anhydride,octadecenyl succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, mcthyltctrahydrophthalic anhydride, hcxahydrophthalic anhydride, alkylhcxahydrophthalic anhydrides such as methylhexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylene tetrahydrophthalic anhydride, chlorendic anhydride, itaconic anhydride, citraconic anhydride and maleic anhydride.

[0049] Among the polyols which can be used are simple polyols, that is, those containing from about 2 to 20 carbon atoms as well as polymeric polyols such as polyester polyols, polyurethane polyols and acrylic polyols.

[0050] Among the simple polyols that may be used are diols, triols and mixtures thereof. Suitable polyols may be those containing from 2 to 10 carbon atoms such as aliphatic polyols. Suitable polyols may include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, glycerol, 1 ,2,3-butanetriol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1 ,4-cyclohexanedimethanol, trimethylolpropane, 2,2,4-trimethylpentane-l,3- diol, pentaerythritol and 1,2,3,4-butanetetrol. Aromatic polyols such as bisphenol A and bis(hydroxymethyl) xylene can also be used.

[0051] With regard to polymeric polyols, the polyester polyols are prepared by esterification of an organic polycarboxylic acid or anhydride thereof with organic polyols and / or an epoxide. The polycarboxylic acids and polyols may be aliphatic or aromatic dibasic acids or acid anhydrides and diols.

[0052] The diols that may be employed in forming the polyester include alkylene glycols such as ethylene glycol, neopentyl glycol and other glycols such as hydrogenated bisphenol A, cyclohexanediol, cyclohexanedimethanol, the reaction products of lactones and diols, the reaction product of epsilon-caprolactone and ethylene glycol, hydroxy-alkylated bisphenols, polyester glycols, poly(oxytetramethylene)glycol, and the like. Polymeric polyols of higher functionality can be used.

[0053] The acid component of the polyester may consist of monomeric carboxylic acids or anhydrides having 2 to 18 carbon atoms per molecule. Suitable acids may include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, glutaric acid, chlorendic acid, tetrachlorophthalic acid and other dicarboxylic acids of varying types. Also,there may be employed higher polycarboxylic acids such as trimellitic acid and tricarballylic acid.

[0054] Besides the polyester polyols formed from polybasic acids and polyols, polylactone-type polyesters can also be employed. These products are formed from the reaction of a lactone such as epsilon-caprolactone and a polyol such as ethylene glycol, diethylene glycol and trimethylolpropane.

[0055] The polyester may be neutralized for dispersion in aqueous media by adding a base, such as a tertiary alkylated amine, for example triethyl amine (TEA), N-ethyl-N-(propan-2- yl)propan-2-amine (DIPEA), and 2,2’(methylazanedyl)di(ethan-l-ol).

[0056] iii. Acrylic Polymers

[0057] Acrylic polymers may include copolymers containing carboxylic acid groups and acid groups of sulfur and phosphorus. These acrylic polymers can be synthesized from acid monomers and one or more alkyl esters of (meth)acrylic acid. The acid monomers may include: (meth)acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, 2-sulfo ethyl methacrylate, 2-acrylamido-2-methyl- 1 -propane sulfonic acid, (meth)acrylamido methyl phosphonic acid, and 2-phosphoethyl (meth) acrylate. The presence of these acid groups facilitates dispersing the acrylic polymer in water in the presence of an amine neutralizing compound. Monoalkyl esters of maleic acid, fumaric acid, and itaconic acid can also be used to synthesize the acrylic polymers. As will be appreciated by, and as is conventional to those skilled in the art, (meth)acrylic acid includes both acrylic acid and the coordinating methacrylic acid; the same is true for other compounds with the prefix “(meth)”.

[0058] Alkyl esters of (meth)acrylic acid may include aliphatic or cycloaliphatic alkyl esters containing from 1 to 30 carbon atoms in the alkyl groups, such as from 4 to 18 carbon atoms in the alkyl group. Methyl (meth)acrylate, ethyl (meth)acrylate, butyl(meth)acrylate, 2- ethyl hexyl (meth)acrylate, and hydroxy ethyl (meth) acrylate are all suitable alkyl esters of (meth)acrylic acid.

[0059] The acrylic polymers may further include copolymers synthesized from one of the above-mentioned monomers and one or more of the following polymerizable ethylenically unsaturated monomers: vinyl aromatic compounds such as styrene and vinyl toluene; nitriles such as (meth) acrylonitrile; amides such as (meth)acrylamide; vinyl and vinylidene halides such as vinyl chloride; and vinylidene chloride and vinyl esters such as vinyl acetate.

[0060] iv. Non-isocyanate Resins

[0061] The film forming resin may be a non-isocyanatc resin comprising an anhydride functional compound; at least one of a hydroxyl functional compound having two hydroxyl functional groups, and a carbodiimide functional compound; and a hydrolysable functional group different from anhydride that is present on at least one of the anhydride functional compound, the hydroxyl functional compound, the carbodiimide functional compound, and a separate compound that is different from the anhydride functional compound, the hydroxyl functional compound, and the carbodiimide functional compound. A “non-isocyanate” resin refers to a resin cure chemistry that has no active isocyanate groups in the formulation, such as anhydride, hydroxyl or carbodiimide, and hydroylzable functional groups.

[0062] The anhydride functional compound may comprise a “small molecule” (i.e., a compound having a molecular weight less than 1000 g / mol, such as less than 700 g / mol, or less than 500 g / mol, and at least 98 g / mol, or at least 125 g / mol, or at least 200 g / mol, as determined by mass spectroscopy). The anhydride functional compound may comprise an anhydride- containing polymer. Such polymers are typically not prepared from alkoxy vinyl silanes. In other words, the polymers are not prepared using any vinyl monomers that contain silane functional groups (as opposed to (meth)acrylic monomers that contain silane functional or other hydrolyzable groups as discussed below, which may be used). By “polymer” is meant a polymer including homopolymers and copolymers, and oligomers. For example, the anhydride functional compound may comprise an addition polymer, prepared from ethylenically unsaturated monomers or polymeric compounds such as anhydride functional polymers having number average molecular weights up to 1,000,000 g / mol, such as in the range of at least 1,000 g / mol, or at least 50,000 g / mol, or at least 100,000 g / mol, to at most 1,000,000 g / mol, or at most 500,000 g / mol, or at most 250,000 g / mol, as measured using gel permeation chromatography with a polystyrene standard.

[0063] Suitable hydroxyl functional compounds include polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, 1 ,6-hexylene glycol, neopentyl glycol, diethylene glycol, glycerol, trimethylol propane, and pentaerythritol. More often the hydroxyl functional compounds are polymers, such as acrylic polyols, polyester polyols, and / or polyurethane polyols. Suitable acrylic polyols include copolymers of one or more alkyl esters of acrylic acid or methacrylic acid, optionally together with one or more other polymerizableethylenically unsaturated monomers. Useful alkyl esters of acrylic acid or methacrylic acid include aliphatic alkyl esters containing from 1 to 30, and often 4 to 18 carbon atoms in the alkyl group. Non-limiting examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate, and 2-ethyl hexyl acrylate. Suitable copolymerizable ethylenically unsaturated monomers include vinyl aromatic compounds such as styrene and vinyl toluene; nitriles such as acrylonitrile and methacrylonitrile; vinyl and vinylidene halides such as vinyl chloride and vinylidene fluoride and vinyl esters such as vinyl acetate. The polyester polyol hydroxyl functional compounds may be prepared in a known manner by condensation of polyhydric alcohols and polycarboxylic acids, while using the polyhydric alcohols in stoichiometric excess. Polyurethanes may additionally or alternatively be used as the hydroxyl functional compound in the non-isocyanate film-forming resin. Among the polyurethanes which can be used are polymeric polyols which generally are prepared by reacting a polyol such as those mentioned above, or a different polyol such as a polyether polyol with a polyisocyanate such that the OH / NCO equivalent ratio is greater than 1:1 and free hydroxyl groups are present in the product. The organic polyisocyanate which is used to prepare the polyurethane polyol can be an aliphatic or an aromatic polyisocyanate or a mixture of the two.

[0064] A carbodiimide functional compound may have at least two carbodiimide functional groups, or when the carbodiimide functional compound further includes hydrolyzable functional groups, compounds that are monofunctional with respect to carbodiimide groups are suitable. Suitable polycarbodiimides may be prepared by reacting a polyisocyanate such as any of those disclosed above in the presence of an appropriate catalyst to form carbodiimides with the release of carbon dioxide, followed by reacting residual isocyanate with an active hydrogen functional material. Any suitable organic compound containing active hydrogens may be used. The term “active hydrogen” refers to hydrogens which, because of their position in a molecule, display activity according to the Zerewitinoff test. Accordingly, active hydrogens include hydrogen atoms attached to oxygen, sulfur or nitrogen, and thus useful compounds will include those having at least one of these groups (in any combination) such as primary amine, secondary amine, alcohol, and / or thiol.

[0065] The non-isocyanate film-forming resin further comprises hydrolyzable functional groups different from anhydride. By “hydrolyzable” is meant functional groups that may undergo hydrolysis in the presence of water molecules and subsequently condense, such as byselfcondensation, to form crosslinks. The hydrolyzable functional groups typically comprise one or more of alkoxy silane (such as methoxy silane, ethoxy silane, and the like); acetoxy silane, ketoxime silane, silicates, including orthosilicates such as alkylorthosilicates; titanates such as tetraalkyl titanates; and zirconates such as tetraalkyl zirconates. Chelates of titanium, zirconium, and / or silicon are also suitable. The hydrolyzable functional groups may be present on the anhydride functional compound, the hydroxyl functional compound, the carbodiimide functional compound, and / or on a separate compound that is different from the anhydride functional compound, the hydroxyl functional compound, and the carbodiimide functional compound. For example, the hydrolyzable groups may be present only on the anhydride functional compound, only on the hydroxyl functional compound, only on the carbodiimide functional compound, only on the separate compound, or on two or more of the compounds. Examples of anhydride functional compounds that further comprise hydrolyzable functional groups include 3- (trialkoxysilyl)propyl succinic anhydrides, such as 3-(triethoxysilyl)propyl succinic anhydride and 3-(trimethoxysilyl)propyl succinic anhydride. When the anhydride functional compound a) comprises a polymer, hydrolyzable functional groups may be incorporated, for example, by including (meth)acrylic monomers that contain hydrolyzable functional groups in the reaction mixture used to prepare the polymer. Examples of suitable silane functional monomers include methacryloxyethoxytris(trimethoxy) silane, 3-methacryloxypropyl tris-(2-methoxyethoxy) silane, and 3-(trimethoxysilyl)propyl methacrylate, available as SILQUEST A- 174 from Momentive Performance Chemicals. The hydrolyzable functional groups may be present additionally or alternatively on a separate compound that is different from the anhydride functional compound, the hydroxyl functional compound, and the carbodiimide functional compound. One skilled in the art would appreciate that one or more of the afore-mentioned or other polyisocyanates would be suitable for reaction with one or more polyols and active hydrogen functional materials having hydrolyzable functional groups in a similar fashion to prepare a compound having hydrolyzable functional groups.

[0066] B. Inorganic Fluoride Components

[0067] The coating composition may comprise a filler, such as an inorganic fluoride component, which may be present in particulate form in the coating composition. Such components may include ionic fluorine-containing compounds, such as fluoride salts of group II metals. Suitable compounds may include calcium fluoride (CaF2). Suitable such ionic fluorine-containing compounds may also include magnesium fluoride (MgF2), barium fluoride (BaF ), or strontium fluoride (SrFi).

[0068] The fluoride component may also be distinct from filler particles, discussed below. The fluoride component may enhance the chemical resistance of the coating composition over traditional coating compositions.

[0069] The fluoride component may be present in the coating composition in an amount from about 1 wt. %, 5 wt. %, or 10 wt. % to 15 wt. %, 20 wt. %, or 25 wt. %, or any value encompassed by these endpoints, such as 1 to 25 wt. %, 5 to 20 wt. %, or 10 to 15 wt. %, based on the total weight of the “wet” coating composition.

[0070] The fluoride component may be present in the cured coating in an amount from about 10 wt. %, 15 wt. %, or 20 wt. % to 25 wt. %, 30 wt. %, or 40 wt. %, or any value encompassed by these endpoints, such as 10 to 40 wt. %, 15 to 30 wt. %, or 20 to 25 wt. %, based on the total weight of the “dry” coating.

[0071] Alternatively, the fluoride component may be present in the coating composition in relatively low amounts, such as from about 0.0001 wt. %, 0.0005 wt. %, or 0.001 wt. % to 0.005 wt. %, 0.01 wt. %, or 0.1 wt. %, or any value encompassed by these endpoints, such as 0.0001 to 0.1 wt. %, 0.0005 to 0.01 wt. %, or 0.001 to 0.005 wt. %, based on the total weight of the “wet” coating composition.

[0072] The low amount of fluoride component may be present in the cured coating in an amount from about 0.00015 wt. %, 0.0007 wt. %, or 0.0015 wt. % to 0.007 wt. %, 0.015 wt. %, or 0.15 wt. %, or any value encompassed by these endpoints, such as 0.00015 to 0.15 wt. %, 0.0007 to 0.015 wt. %, or 0.0015 to 0.007 wt. %, based on the total weight of the “dry” coating.

[0073] The fluoride component may have an average number particle size (D50) of about 5 micrometers or larger, about 10 micrometers or larger, about 15 micrometers or larger, about 20 micrometers or larger, about 25 micrometers or later, about 30 micrometers or larger, about 35 micrometers or larger, about 40 micrometers or larger, about 45 micrometers or larger, about 50 micrometers or larger, 55 micrometers or smaller, 60 micrometers or smaller, 65 micrometers or smaller, 70 micrometers or smaller, 75 micrometers or smaller, 80 micrometers or smaller, 85 micrometers or smaller, 90 micrometers or smaller, 95 micrometers or smaller, 100 micrometers or smaller, or any value encompassed by these endpoints, such as 10 micrometers to 100 micrometers, 15 micrometers to 95 micrometers, 20 micrometers to 85 micrometers, 25micrometers to 80 micrometers, 30 micrometers to 75 micrometers, 35 micrometers to 70 micrometers, 40 micrometers to 65 micrometers, 45 micrometers to 60 micrometers, or 50 micrometers to 55 micrometers, as determined by dynamic light scattering.

[0074] C. Solvents

[0075] The coating composition may include one or more solvents. Suitable solvents include hydrocarbon solvents such as xylene; alcohols such as methanol, ethanol, isopropanol, and t-butanol; ketones such as acetone; esters such as Ethyl 3-ethoxypropionate (EEP), N-butyl acetate; ethers such as dipropylene glycol methyl ether; and other protic or non-protic solvents like dimethylsulfoxide or N-methylpyrrolidone. The coating composition of the present disclosure may be solvent-borne.

[0076] Solvent may be present in the coating composition in an amount from about 15 wt. %, 20 wt. %, or 25 wt. % to 30 wt. %, 35 wt. %, or 40 wt. %, or any value encompassed by these endpoints, such as 15 to 40 wt. %, 20 to 35 wt. %, or 25 to 30 wt. %, based on the total weight of the “wet” coating composition.

[0077] D. Additional Fillers

[0078] The coating composition may further comprise additional fillers. Additional fillers may include pigments, such as carbon black, and finely divided minerals such as barium sulfate, silica, including fumed silica and colloidal silica, alumina, colloidal alumina, titanium dioxide, zirconia, colloidal zirconia, clay, mica, dolomite, talc, magnesium carbonate, calcium carbonate, calcium sulfate, calcium silicate, and / or calcium metasilicate.

[0079] Filler may be present in the coating composition in an amount from about 0 wt. %, 5 wt. %, or 10 wt. % to 15 wt. %, 20 wt. %, or 30 wt. %,or any value encompassed by these endpoints, such as 0 to 30 wt. %, 5 to 20 wt. %, or 10 to 15 wt. %, based on the total weight of the “wet” coating composition.

[0080] Filler may be present in the cured coating in an amount from about 0 wt. %, 2 wt. %, or 5 wt. % to 10 wt. % %, 20 wt. %, or 40 wt.%, or any value encompassed by these endpoints, such as 0 to 40 wt. %, 2 to 20 wt. %, or 5 to 10 wt. %, based on the total weight of the “dry” coating composition.

[0081] E. Additives

[0082] Additives may be present in the coating composition of the present disclosure in addition to the components described above. These additives may comprise components toimprove stability, applicability and aesthetics. Additives that may be included in the present coating composition may include wetting agents, surface agents, catalysts, dispersing aids, defoamers, thickeners, surface agents, and tinting paste.

[0083] Additives may be present in the coating composition in an amount from about 0.05 wt. %, 0.5 wt. %, or 1 wt. % to 1.5 wt. %, 2 wt. %, or 3 wt. %, or any value encompassed by these endpoints, such as 0.05 wt. % to 3 wt. %, 0.5 wt. % to 2 wt. %, or 1 wt. % to 1.5 wt. %, based on the total weight of the “wet” coating composition.

[0084] Additives may be present in the cured coating in an amount from about 0.1 wt. %, 0.5 wt. %, or 1 wt. % to 2 wt. %, 3 wt. %, or 5 wt. %, or any value encompassed by these endpoints, such as 0.1 wt. % to 5 wt. %, 0.5 wt. % to 3 wt. %, or 1 wt. % to 2 wt. %, based on the total weight of the “dry” coating.

[0085] F. Phthalate Plasticizers and Maleic Imide

[0086] The coating composition may be completely free, essentially free, or substantially free of phthalate plasticizers. “Phthalate plasticizers” as used herein refer to any non-polymeric compound derived from the esterification of phthalic acid with one or more alkyl alcohols. Further, a phthalate compound, as used herein, may be a phthalate with two alkyl substituents associated with carboxyl groups, such as dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, and their esters. By completely free of phthalate plasticizers, it is meant that the coating composition / cured coating comprises less than 0.1 wt. % of phthalate plasticizers, based on the total weight of the coating composition / cured coating. By essentially free of phthalate plasticizers, it is meant that the coating composition / cured coating comprises less than 0.5 wt. % of phthalate plasticizers, based on the total weight of the coating composition / cured coating. By substantially free of phthalate plasticizers, it is mean that the coating composition / cured coating comprises less than 1 wt. % of phthalate plasticizers, based on the total weight of the coating composition / cured coating.

[0087] Further, the coating composition may be completely free, essentially free, or substantially free of maleic imide. “Maleic imide” or “maleimide” as used herein refer to any compound that comprises a maleic acid or maleimide group. By completely free of maleic imide, it is meant that the coating composition / cured coating comprises less than 0.1 wt. % of maleic imide, based on the total weight of the coating composition / cured coating. By essentially free of maleic imide, it is meant that the coating composition / cured coating comprises less than 0.5 wt.% of maleic imide, based on the total weight of the coating composition / cured coating. By substantially free of maleic imide, it is mean that the coating composition / cured coating comprises less than 1 wt. % of maleic imide, based on the total weight of the coating composition / cured coating.

[0088] G. Fluoropolymers

[0089] With mounting regulation of fluoropolymers, including per- and polyfluoroalkyl substances (PFAS) such as perfluoroalkyl acids (PFAAs), perfluorooctanoic acid (PFOA), and / or perfluorooctane sulfonate (PFOS), there is a draw to have fluoropolymer free coating compositions. The coating compositions of the present disclosure may be essentially, substantially, or completely free of fluoropolymers.

[0090] By essentially fluoropolymer free it is meant that the coating compositions of the present disclosure comprises a total amount of perfluorinated and polyfluorinated alkyl compounds of 5 wt. % or less, based on a total weight of the coating composition / cured coating. By substantially fluoropolymer free it is meant that the coating compositions of the present disclosure comprises a total amount of perfluorinated and polyfluorinated alkyl compounds of 2.5 wt. % or less, based on a total weight of the coating composition / cured coating. By completely fluoropolymer free it is meant that the coating compositions of the present disclosure comprises a total amount of perfluorinated and polyfluorinated alkyl compounds of 1 wt. % or less, based on a total weight of the coating composition / cured coating.

[0091] III. Application of the Chemically Resistant Coating Composition

[0092] A. Substrates

[0093] Substrates to which the coating composition can be applied include a wide range of substrates. The coating compositions of the present invention can be applied to vehicle substrates, industrial substrates, aerospace substrates, and the like.

[0094] The vehicle substrate may comprise a component of a vehicle. In the present disclosure, the term "vehicle" is used in its broadest sense and includes all types of aircraft, spacecraft, watercraft and land vehicles. For example, the vehicle may include, but is not limited to, an aerospace substrate (a component of an aerospace vehicle, such as an aircraft, such as, for example, an airplane (e.g., private airplanes and small, medium, or large commercial airliners, cargo planes, and military planes), a helicopter (e.g., private, commercial, and military helicopters), an aerospace vehicle (e.g., rockets and other spacecraft), and the like). The vehiclemay also include a land based vehicle such as, for example, an animal trailer (e.g., horse trailer), an All Terrain Vehicle (ATV), an automobile, a truck, a bus, a minibus, heavy equipment, a tractor, a golf cart, a motorcycle, a bicycle, a snowmobile, a train, a tram, or the like. The vehicle may also include a watercraft such as, for example, a ship, a boat, a hovercraft, and the like. The vehicle substrate may comprise a component of a vehicle body, such as an automobile hood, door, trunk, roof, etc.; such as aircraft or spacecraft wings, fuselages, etc.; such as a watercraft hull or the like.

[0095] B. Application and Curing

[0096] The coating composition may be applied to the substrate using, spray coating, drawdown coating, vapor deposition, roller coating, air-over-knife, or any other suitable coating method. Once applied to a substrate, the coating composition may be cured at ambient temperatures for a period of greater than 1 day, greater than 3 days, greater than 5 days, greater than 7 days, greater than 9 days, or greater than 10 days. Ambient temperature usually ranges from 60 to 90° F. (15.6 to 32.2° C.), such as a typical room temperature, 72° F. (22.2° C.).

[0097] IV. Properties of the Chemically Resistant Coating Composition

[0098] Aerospace vehicles in particular’ benefit from coatings with excellent chemical resistance and durability due to the hard conditions the exteriors of the aerospace vehicles may be exposed to. The exterior of aerospace vehicles may experience extreme temperature, weather, and exposure to hydraulic fluid, such as Skydrol. The cured coating of the present application may exhibit excellent chemical resistance, harness, durability, and weather resistance as compared to known coatings.

[0099] A. Pendulum Hardness

[0100] The pendulum hardness test, or Kbnig test, is a method used to measure the hardness or resistance to indentation of coatings. The test involves a pendulum-like instrument with a weighted arm that swings freely. At the end of the weighted arm is a indenter or hammer. The pendulum is held in a fixed position from the coated surface. The pendulum is released such that the indenter strikes the surface of the coating with a defined force. The hardness of the coating is measured by the oscillation time made by the pendulum. A higher time indicates higher hardness of the coating.

[0101] The coating composition of the present disclosure may have a pendulum hardness from 90 sec, 100 sec, or 130 sec to 150 sec, 170 sec, or 190 sec, or any range using any two ofthe foregoing values as endpoints, such as 90 sec to 190 sec, 100 sec to 170 sec, or 130 sec to 150 see, as measured according to ASTM D4366-16 (2021).

[0102] B. Pencil Hardness

[0103] Pencil hardness was determined in accordance with ASTM D3363 (2022) before and after a 24 hour immersion in hydraulic fluid at 72°F. Hardness was determined relative to a standard set of pencil leads by scratching the leads across the coating film at a 45 degree angle and for about *4 inch stroke. The process was repeated until a lead was identified that did not scratch the film. The number of the lead was recorded as the hardness.

[0104] The coating composition may have a pencil hardness of at least 5H, at least 4H, at least 4H, at least 2H, at least H, at least F, at least HB, or at least B, as determined by ASTM D3363 (2022).

[0105] The coating composition after exposure to hydraulic fluid may have a pencil hardness of at least 2H, at least H, at least F, at least HB, at least B, at least 2B, at least 3B, at least 4B, or at least 5B, as determined by ASTM D3363 (2022).

[0106] C. Chemical Resistance and Weight Gain

[0107] The coating may exhibit chemical resistance such as resistance to fuels, hydraulic fluids, solvents, greases, lubricants, salt spray, gases, oils, and / or cleaning fluids.

[0108] The coatings were evaluated and weighted before and after a 24-hour immersion in hydraulic fluid at 72°F of 2.5” x 2.5” panels. The amount of weight gain the coating experienced due to the immersion was recorded after blotting the coating with isopropanol and letting the coating dry for 10 minutes.

[0109] The coating may have a weight gain of less than 50g, less than 40g, less than 30g, less than 20g, less than 10g, or less than 5g, or any range using any two of the foregoing values as endpoints, such as 5 g to 50 g, 10 g to 40 g, or 20 g to 30 g, according to the method described above.

[0110] D. Scribe Corrosion and Shine

[0111] The fully coated test panels coated with coating Examples 1 through 4 were allowed to age under ambient conditions for a minimum of 7 days, after which the panels were inscribed with a 10 cm by 10 cm “X” that was scribed into the panel surface to a sufficient depth to penetrate any surface coating and to expose the underlying metal. The scribed coated test panels were then placed into a 5% sodium chloride neutral salt spray cabinet according to ASTMBl 17 (2019) (exception: pH & salt concentration checked weekly as opposed to daily). The ratings of each test arc taken at 504 hours of exposure.

[0112] i. Corrosion

[0113] Corrosion resistance describes the ability for a coating composition to resist tarnish and corrosion. Rating is 0 to 100 and number represents percent of scribe area showing visible corrosion. The value is the average of two replicates. The lower the number, the less visible corrosion and better corrosion performance.

[0114] The coating composition may have a corrosion resistance from 5, 20, or 40 to 60, 80, or 100, or any range using any two of the foregoing values as endpoints, such as 5 to 100, 20 to 80, or 40 to 60, as measured according to the method described above.

[0115] ii. Shine

[0116] Rating is 0 - 100 and number represents percent of scribe which is dark / tamished scribe. The value is the average of two replicates. The lower the number, the better the performance.

[0117] The coating composition may have a scribe shine from 20, 40, or 60 to 80, 90, or 100, or any range using any two of the foregoing values as endpoints, such as 20 to 100, 40 to 90, or 60 to 80, as measured according to the method described above.

[0118] F. Color Shift / Delta E

[0119] The cured coating on a substrate or article may exhibit improved durability after exposure to weathering over traditional coatings, as evidenced by the Delta E of the coating after accelerated weathering.

[0120] Delta E is used to quantify the difference between two colors. In the context of coating compositions, Delta E describes the shift of color from the uncoated substrate to the coated substrate. The smaller the Delta E, the more similar the colors.

[0121] To test Delta E, coated panels (2.25” x 1.75”) may be put into a Xenon-arc WEATHEROMETER according to ASTM G155 (2021), cycling between 102 minutes light only, and 18 minutes of light and water spray.

[0122] The coating composition may have a Delta E of less than 1, less than 0.9, less than 0.8, less than 0.7, less than 0.6, or less than 0.5, or any range using any of the foregoing values as endpoints, such as 0.5 to 1, 0.6 to 0.9, or 0.7 to 0.8, as measured according to ASTM G155 (2021).EXAMPLES

[0123] Aspects of the present disclosure are further illustrated by reference to the following examples. It will be apparent to those skilled in the art that many modifications, both to materials, and methods, may be practiced without departing from the scope of the disclosure.EXAMPLE 1: CHEMICALLY RESISTANT COATING COMPOSITIONS - POLYURETHANE FILM FORMING RESIN

[0124] Coating compositions 1A-1H were formulated according to Table 1. For chemical resistance measurements, coating compositions were prepared according to the formulations shown in Table 1. A set amount of paint was transferred to a 2.5 oz. glass jar along with corresponding charges of acrylic polyol, n-butyl acetate, EastmanTM EEP (Ethyl 3- Ethoxypropionate) solvent, and calcium fluoride. Milling media at approximately half the weight of the component materials was added to the mixture. The jars were sealed with lids and placed on a Lau Dispersing Unit for 3 hours. After the dispersion process was complete, the paints were passed through 125 micron filters to remove the media. Next, Dibutyltin dilaurate catalyst (10% solution in xylene) and BYKO-306 were added. Finally, CA 8200B was added under stirring.Samples were then drawn down over electrocoated steel panels that had been wet-sanded with 240 grit sand paper. The panels were purchased from ACT Test Panel Technologies, item #44049. Panels were cured at ambient temperature for 1 week before testing.Table 1: Coating Composition 1A-1H Formulation’63% solids acrylic polyol containing 4-hydroxylbutylacrylate, methyl methacrylate, styrene, butyl methacrylate and butyl acrylate.Available from Fisher ScientificAvailable from Strem Chemicals, Inc.Available from Omya.’available from PPG Aerospace.

[0125] Chemical Resistance

[0126] Skydrol® LD-4 immersion was used to assess chemical resistance of the coating formulations as a representative aerospace hydraulic fluid for which coatings must exhibit resistance in numerous specifications. 1 inch x 3 inch pre- weighed panels coated with formulations 1A-1H were immersed completely in Skydrol LD4 for 24 hours based on a modified version of 4.6.16 (Shorter time; full immersion, rather than dipping panels) for MIL- PRF-32239. Weight gain was assessed 10-15 minutes after removal of the panels followed by thorough rinsing with isopropyl alcohol and blotting with absorbent paper (Table 2). A significant reduction in weight gain (63%-87%) in comparison to the control is observed for formulations B and C containing 10, and 20 weight percent calcium fluoride and ID, IE containing 10, and 20 percent magnesium fluoride respectively. At lower levels (5 weight percent) of calcium fluoride (1A) and with calcium carbonate (IF, 1G) limited reduction (<40%) is seen.Table 2: Weight Gain of Cured Coating Compositions per 1 mil coating thickness after Skydrol LD4 Immersion

[0127] Pencil Hardness

[0128] Formulations A-H were also tested for pencil hardness before and after immersion to test if the coating softened from the Skydrol® LD-4. As seen in Table 3, formulations IB, 1C, ID, IE all show less than 2 units of hardness drop after immersion, including no change for formulation 1C. Formulations 1 A, IF, 1G, and 1H range from a drop of 2-5 units, consistent with increased weight gain observed in Table 2.Table 3: Pencil Hardness After Skydol Immersion

[0129] Pendulum Hardness

[0130] Formulations 1 A-1H were also investigated for changes in pendulum hardness (Konig method) as a function of chemical composition. The majority of formulations (1A-1F) show increases in pendulum hardness compared to the control (formulation 1H). Formulation 1C with 20 weight percent calcium fluoride showed a 73% increase in hardness while magnesium fluoride (as seen in formulation IE) and calcium carbonate (as seen in formulation IF) showed a 30% increase and less than 1% increase respectively.Table 4: Pendulum HardnessEXAMPLE 2: NON-ISOCYANATE FORMULATIONS

[0131] Non-isocyanate coating compositions were created according to the formulations shown in Table 5. A silane functional resin, anhydride resin, and polyol resin was used inaccordance with US 2023 / 0287173 Al Composition IX. In addition, inorganic fluoride and other fillers were added. Charges 1- 13 were added to a 16oz. glass jar with Milling media at approximately half the weight of the component materials was added to the mixture. The jars were sealed with lids and placed on a Lau Dispersing Unit for 3 hours. After the dispersion process was complete, the paints were passed through 125 micron filters to remove the media. Next charges 14-18 were added under stirring. Finally, charges 1-18 were then mixed with Charges 19-20, and charge 21 under stirring. Samples were then sprayed-applied using a SATA HVLP spray gun with a 1.4 um orifice at an application pressure of ca. 30 psi over Desothane® CA7502 Primer applied over abraded pre-Kote aluminum 2024-T3 panels with a primer thickness of and a topcoat dry film thickness of 1.9 mil to 2.5 mils. The panels were purchased from ACT Test Panel Technologies, item #26241. Panels were cured at ambient temperature for 1 week before testing.Table 5: Non-Isocyanate Coating Compositions 4A-4C’available from PPG Aerospace Available from AGC Chemicals, inc.3available from Ingevity, UK, LTD4available from King Industries, inc. 'available from Chemours6available from Birla Carbon ’available from Omya.Available from Fisher Scientific ’available from Strem Chemicals, Inc10available from PQ corporation ’’available from BASF’’available from Momentive14available from Wacker, inc.

[0132] Coated panels (2.25” x 1.75”) were put into Xenon-arc WEATHEROMETER according to ASTM G155 (2021) cycling between 102 minutes light only, and 18 minutes of light and water spray. Table 6 shows Color shift (Delta E) calculated after 500, 1000, and 1500 hours for formulations 4A-4C.Table 6: Delta-E of Non-Isocyanate Coating Compositions 4A-4C

[0133] The sample with calcium fluoride (4B) shows greatly decreased Delta E compared to other fillers (4A,4C).

[0134] Coated bare panels were scribed with a 10 cm by 10 cm “X” that was scribed into the panel surface to a sufficient depth to penetrate any surface coating and to expose the underlying metal. Scribed test panels were then placed into a 5% sodium chloride neutral salt spray cabinet according to ASTM Bl 17 (2019) (with the exception that the pH & salt concentration checked weekly as opposed to daily). The panels were rated according to the following scale for scribe corrosion with a rating scale of 0 to 100 and the number represents the percent of scribe area showing visible corrosion with lower numbers indicating less corrosion and better corrosion resistance. The lower the number, the better the performance. Values are the average of two replicates.

[0135] Scribe shine was also evaluated from a scale from 0 to 100 where the number represents percent of scribe which is dark / tarnished scribe. Lower rating number is better. The value is the average of two replicates on. Table 7 shows the corrosion and scribe shine for formulations 4A-4C.Table 7: Properties of Non-Isocyanate Coating Compositions 4A-4CEXAMPLE 3: LOW INCORPORATION OF CaF IN POLYURETHANE SILICONE- MODIFIED ACRYLIC ADDITIVE

[0136] Low incorporation of commercial grade CaF2 in silicone modified acrylic resin media was achieved by sonicating a mixture of CaFi particles in silicone resin at a concentration (g CaF2 / g resin) ranging from 6 x 10-3 to 3 x 10-2. Once a stable solution was achieved, the mixture was kept at room temperature for 72 hours. After which the supernatant was isolated via decantation and analyzed for CaF2 content via HX204 moisture analyzer and ICP OES.Table 8: Quantifying CaF2in Silicone Resin*determined from HX204 moisture analyzer** determined from ICPOES

[0137] The silicone containing CaF2containing resin prepared in Table 8 were then used as additive in a polyurethane clearcoat formulation as shown in Table 9.Table 9: Inventive Coating Compositions and Properties

[0138] Wherein particular examples of this invention have been described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the present invention may be made without departing from the invention as defined in the appended claims. This application is therefore intended to cover any variations, uses, or adaptations of the disclosure using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this disclosure pertains and which fall within the limits of the appended claims.ASPECTS

[0139] Aspect 1 is a coating composition, comprising: a film forming resin; a solvent; and a filler, the filler comprising at least one inorganic fluoride component; wherein the coating composition comprises at least 5 wt. % of the filler, based on the total weight of the coating composition; and wherein the coating composition comprises less than 1 wt. % of phthalate plasticizers .

[0140] Aspect 2 is the coating composition of Aspect 1, wherein the at least one inorganic fluoride component comprises at least one of MgF , CaF2, SrF2, and BaF2.

[0141] Aspect s is the coating composition of either Aspect 1 or Aspect 2, wherein the coating composition comprises less than 1 wt. % of a compound comprising a maleic acid or maleic imide, based on the total weight of the coating composition.

[0142] Aspect 4 is the coating composition of any one of Aspects 1-3, further comprising a catalyst.

[0143] Aspect 5 is the coating composition of any one of Aspects 1-4, further comprising a wetting agent.

[0144] Aspect 6 is the coating composition of any one of Aspects 1-5, wherein the coating composition comprises a total content of per- and polyfluoroalkyl substances (PFAS) of less than 1 ppm, based in a total weight of the coating composition, as determined by liquid chromatography-tandem mass spectrometry (LC-MS / MS).

[0145] Aspect 7 is the coating composition of any one of Aspects 1-6, wherein film forming resin comprises at least one of a polyurethane resin, a polyester resin, a polyurethane resin, a non-isocyanate resin, and an acrylic resin.

[0146] Aspect 8 is the coating composition of any one of Aspects 1-7, wherein the coating composition comprises from 1 to 30 wt. % of filler, based on the total weight of the coating composition.

[0147] Aspect 9 is the coating composition of any one of Aspects 1-8, wherein the at least one inorganic fluoride component is CaFz.

[0148] Aspect 10 is the coating composition of Aspect 9, wherein the coating composition comprises from 1 to 25 wt. % of CaFz, based on the total weight of the coating composition.

[0149] Aspect 11 is the coating composition of any one of Aspects 1-10, wherein the coating composition comprises from 35 to 60 wt. % of film forming resin, based on the total weight of the coating composition.

[0150] Aspect 12 is a method of coating a substrate with a coating composition, comprising: applying, to a surface of the substrate, a coating composition comprising the composition of any one of claims 1-11; and curing the coating composition to form a cured coating.

[0151] Aspect 13 is an article coated according to the method of Aspect 12.

[0152] Aspect 14 is the article of Aspect 13, wherein the cured coating comprises at least one of the following: from 60 to 90 wt. % film forming resin; and from 15 to 30 wt. % filler, wherein wt. % is based on a total weight of the cured coating.

[0153] Aspect 15 is the article of either Aspect 13 or Aspect 14, wherein the cured coating comprises less than 1 wt. % of a phthalate plasticizer, wherein wt. % is based on a total weight of the cured coating.

[0154] Aspect 16 is the article of any one of Aspects 13-15, wherein the cured coating comprises from 0.01 to 4 wt. % catalyst, wherein wt. % is based on a total weight of the cured coating.

[0155] Aspect 17 is the article of any one of Aspects 13-16, wherein the cured coating comprises from 0.01 to 4 wt. % wetting agent, wherein wt. % is based on a total weight of the cured coating.

[0156] Aspect 18 is the article of any one of Aspects 13-17 wherein the cured coating has a pencil hardness of at least B, according to ASTM D3363 (2022).

[0157] Aspect 19 is the article of any one of Aspects 13-18, wherein the cured coating resists hydraulic fluid.

[0158] Aspect 20 is the article of any one of Aspects 13-19, wherein the cured coating gains less than 20g when immersed in hydraulic fluid for 24 hours.

[0159] Aspect 21 is the article of any one of Aspects 13-20, wherein the cured coating has a pencil hardness of at least H after being immersed in hydraulic fluid for 24 hours, according to ASTM D3363 (2022).

[0160] Aspect 22 is the article of any one of Aspects 13-21, wherein the cured coating has a Delta E less than 0.7 after 1500 hours.

[0161] Aspect 24 is the article of any one of Aspects 14-22, wherein the cured coating exhibits improved durability after exposure to accelerated weathering.

Claims

CLAIMSWhat is claimed is:

1. A coating composition, comprising: a film forming resin; a solvent; and a filler, the filler comprising at least one inorganic fluoride component; wherein the coating composition comprises at least 5 wt. % of the filler, based on the total weight of the coating composition; and wherein the coating composition comprises less than 1 wt. % of a phthalate plasticizers, based on the total weight of the coating composition.

2. The coating composition of claim 1, wherein the at least one inorganic fluoride component comprises at least one of MgFi, CaF , SrF . and BaF .

3. The coating composition of either claim 1 or claim 2, wherein the coating composition comprises less than 1 wt. % of a compound comprising a maleic acid or maleic imide, based on the total weight of the coating composition.

4. The coating composition of any one of claims 1-3, further comprising a catalyst.

5. The coating composition of any one of claims 1-4, further comprising a wetting agent.

6. The coating composition of any one of claims 1-5, wherein the coating composition comprises a total content of per- and polyfluoroalkyl substances (PFAS) of less than 1 ppm, based in a total weight of the coating composition, as determined by liquid chromatographytandem mass spectrometry (LC-MS / MS).

7. The coating composition of any one of claims 1-6, wherein film forming resin comprises at least one of a polyurethane resin, a polyester resin, a polyurethane resin, a non-isocyanate resin, and an acrylic resin.

8. The coating composition of any one of claims 1-7, wherein the coating composition comprises from 1 to 30 wt. % of filler, based on the total weight of the coating composition.

9. The coating composition of any one of claims 1-8, wherein the at least one inorganic fluoride component is CaFi; and wherein the coating composition comprises from 1 to 25 wt. % of CaF2, based on the total weight of the coating composition.

10. The coating composition of any one of claims 1-9, wherein the coating composition comprises from 35 to 60 wt. % of film forming resin, based on the total weight of the coating composition.

11. A method of coating a substrate with a coating composition, comprising: applying, to a surface of the substrate, a coating composition comprising the composition of any one of claims 1-10; and curing the coating composition to form a cured coating.

12. An article coated according to the method of claim 11.

13. The article of claim 12, wherein the cured coating comprises at least one of the following: from 60 to 90 wt. % film forming resin; and from 15 to 30 wt. % filler, wherein wt. % is based on a total weight of the cured coating.

14. The article of either claim 12 or claim 13, wherein the cured coating comprises less than 1 wt. % of a phthalate plasticizer, wherein wt. % is based on a total weight of the cured coating.

15. The article of any one of claims 12-14, wherein the cured coating comprises from 0.01 to 4 wt. % catalyst, wherein wt. % is based on a total weight of the cured coating.

16. The article of any one of claims 12-15, wherein the cured coating comprises from 0.01 to 4 wt. % wetting agent, wherein wt. % is based on a total weight of the cured coating.

17. The article of any one of claims 12-16, wherein the cured coating has at least one of: a pencil hardness of at least B, according to ASTM D3363 (2022); and a pencil hardness of at least H after being immersed in hydraulic fluid for 24 hours, according to ASTM D3363 (2022).

18. The article of anyone of claims 12-17, wherein the cured coating resists hydraulic fluid.

19. The article of any one of claims 12-18, wherein the cured coating gains less than 20g when immersed in hydraulic fluid for 24 hours.

20. The article of any one of claims 12-19, wherein the cured coating has a Delta E less than1 after 1500 hours.

Images