Anionic electrodepositable coating compositions that form resin domains upon cure

Abstract

The present disclosure is directed to an anionic electrodepositable coating composition comprising an anionic salt group-containing, film-forming polymer; a curing agent; a core-shell polymer; and a corrosion inhibitor. The present disclosure is further directed to an anionic electrodepositable coating composition comprising an anionic salt group-containing, film-forming polymer; a curing agent; a latex polymer; and a corrosion inhibitor. Coating layers deposited from the compositions have at least two resin domains having different Tg values. Also disclosed are methods for using the compositions to coat a substrate and substrates coated thereby.

Description

ANIONIC ELECTRODEPOSITABLE COATING COMPOSITIONS THAT FORM RESIN DOMAINS UPON CURECROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 668,834 filed July 9, 2024, which is incorporated herein by reference.FIELD

[0002] The present disclosure is directed towards anionic electrodepositable coating compositions, methods of using these compositions to coat substrates, and substrates coated according to the methods.BACKGROUND

[0003] Electrodeposition as a coating application method involves the deposition of a film- forming composition onto a conductive substrate under the influence of an applied electrical potential. Electrodeposition has gained popularity in the coatings industry because it provides higher paint utilization, outstanding corrosion resistance, and low environmental contamination as compared with non-electrophoretic coating methods. Both cationic and anionic electrodeposition processes are used commercially.SUMMARY

[0004] The present disclosure is directed to an anionic electrodepositable coating composition comprising: an anionic salt group-containing, film-forming polymer; a curing agent; a core-shell polymer; and a corrosion inhibitor; wherein a coating layer deposited from the coating composition will, upon cure, form a first resin domain having a first glass transition temperature of -25 to 30°C and a second resin domain having a second glass transition temperature of 100 to 145 °C.

[0005] The present disclosure is further directed to an anionic electrodepositable coating composition comprising: an anionic salt group-containing, film-forming polymer; a curing agent; a corrosion inhibitor comprising 2,2'-dipyridyl disulfide, tetraethyl thiuram disulfide, thiocarbamyl sulfenamide. or a combination thereof; and a latex polymer; wherein a coating layer deposited from the coating composition will, upon cure, form a first resin domain having a first glass transition temperature of -25 to 30°C and a second domain having a second glass transition temperature of 100 to 145°C.

[0006] The present disclosure also provides a method for coating a substrate comprising electrodepositing a coating deposited from any of the anionic electrodepositablecoating compositions disclosed herein to at least a portion of the substrate, and substrates coated thereby.BRIEF DESCRIPTION OF THE DRAWING

[0007] Fig. 1 is a graph showing DMA traces for Examples 6-9.DETAILED DESCRIPTION

[0008] The present disclosure is directed to an anionic electrodepositable coating composition comprising an anionic salt group-containing film- forming polymer; a curing agent; a core-shell polymer; and a corrosion inhibitor. The present disclosure is further directed to an anionic electrodepositable coating composition comprising an anionic salt group-containing film-forming polymer; a curing agent; a corrosion inhibitor comprising 2,2'- dipyridyl disulfide, tetraethyl thiuram disulfide, thiocarbamyl sulfenamide, or a combination thereof; and a latex polymer. The anionic salt group-containing film-forming polymer and curing agent are sometimes collectively referred to herein as the “film-forming component” or “electrodepositable binder”. The product that results from cure of the film-forming polymer with the curing agent is sometimes referred to herein as the “resin matrix”.

[0009] The present coating may be described herein in terms of a coating composition, which will be understood as referring to an uncured or unhardened mixture of coating components. The coating composition can be deposited and cured to form a “coating” or “coating layer”, which terms may be used interchangeably herein. Upon cure, the coating layers of the present disclosure undergo a phase separation to form at least two separate areas, referred to herein as “resin domain(s)” or just “domain(s)”. One of these domains comprises the resin matrix; another comprises the core-shell polymer and / or the latex polymer. Each domain has a different glass transition temperature as discussed further below.

[0010] As used herein, the term “anionic electrodepositable coating composition” refers to a composition that can be deposited onto an electrically conductive substrate under the influence of an electric potential applied between two electrodes immersed in the electrodepositable coating composition, where the anode is the substrate to be coated.

[0011] An anionic salt group-containing film-forming polymer refers to any filmforming polymer that includes at least partially neutralized anionic functional groups, such as carboxylic acid and / or phosphoric acid groups, that impart a negative charge. The anionic salt group-containing film-forming polymer comprises active hydrogen functional groups, which refers to those functional groups that are reactive with isocyanates, including hydroxylgroups, primary or secondary amine groups, carbamate, and thiol groups. As used herein, the term “film-forming polymer’" may be used interchangeably with “polymer” or “resin”, and refers to one or more polymers, such as homo polymers and / or copolymers, as well as prepolymers, oligomers, and monomers, that, upon hardening and / or curing, such as by reaction with a crosslinker, can form a continuous film on a surface. The terms “crosslinker”, “crosslinking agent”, “curing agent” and variants thereof, may be used interchangeably herein. “Cure”, “harden” and like terms may also be used inter-changeably herein and refer to the ability of at least a portion of the polymerizable and / or crosslinkable components to undergo a reaction.

[0012] The film-forming polymer may be organic or inorganic. An “organic” filmforming polymer is one with a skeletal structure that includes a carbon atom in the backbone, while an “inorganic” film-forming polymer refers to one with a skeletal structure that does not include carbon atoms in the backbone; a suitable example is one that comprises silicone- based materials. It will be understood that the electrodepositable binder may also comprise a mixture of organic and inorganic film-forming and / or curing agent materials.

[0013] Polymers that are suitable for use as the anionic salt group-containing filmforming polymer include drying and / or semi-drying, and / or saturated alkyd polymers, acrylics, polyepoxides, polyamides, polyurethanes, polyureas, polyethers, polyesters, resinous polyols, phosphatized polyepoxides, and phosphatized acrylic polymers, vehicles comprising alkyds and amine- aldehydes, as well as adducts, derivatives and combinations thereof.

[0014] Suitable inorganic electrodepositable film-forming polymers include silicone- based film-forming polymers, such as those described in Int’l Pub. No. WO 2021 / 138384 Al, at paragraphs

[0007] through

[0029] , the cited portion of which is incorporated herein by reference.

[0015] The anionic salt group-containing film-forming polymer may comprise basesolubilized, carboxylic acid group-containing film-forming polymers such as the reaction product or adduct of a drying oil or semi-drying fatty acid ester with a dicarboxylic acid or anhydride, and / or the reaction product of a fatty acid ester, unsaturated acid or anhydride and any additional unsaturated modifying materials that are further reacted with polyol. Also suitable are the at least partially neutralized interpolymers of hydroxy-alkyl esters of unsaturated carboxylic acids, unsaturated carboxylic acid and at least one other ethylenically unsaturated monomer. Still another suitable anionic electrodepositable resin comprises an alkyd-aminoplast vehicle, i.e., a vehicle containing an alkyd resin and an amine-aldehyde resin. Another suitable anionic electrodepositable resin composition comprises mixed estersof a resinous polyol. Other acid functional polymers may also be used such as phosphated epoxide resin or phosphated acrylic polymers. Epoxide includes poly epoxide and so the terms phosphated epoxide and phosphated polyepoxide refer to the same resin and therefore may be used interchangeably herein. Exemplary phosphated polyepoxides are disclosed in U.S. Pat. Application Publication No. 2009-0045071 at

[0004] -

[0015] , and U.S. Pat. Application Ser. No. 13 / 232,093 at

[0014] -

[0040] , the cited portions of which are incorporated herein by reference. Also suitable are addition polymers comprising at least one moiety comprising a phosphorus acid group, wherein the moiety is covalently bound to the addition polymer backbone by a carbon-carbon bond, and at least one carbamate functional group, such as those described in Int’l Pub. No. WO 2020 / 264471 Al, at par.

[0007] to

[0046] , the cited portion of which is incorporated herein by reference. Also suitable are addition polymers comprising at least one moiety comprising a sulfonic acid group, and at least one carbamate functional group, such as those described in Int’l Pub. No. WO 2020 / 264468 Al, at par.

[0007] to

[0046] , the cited portion of which is incorporated herein by reference.

[0016] The anionic salt group-containing film-forming polymer may comprise a phosphated epoxy resin comprising at least one terminal group comprising a phosphorus atom covalently bound to the resin by a carbon-phosphorus bond or by a phosphoester linkage, and at least one carbamate functional group. Suitable phosphated epoxy resins are described in Int’l Pub. No. WO 2020 / 006188 Al, at par.

[0013] to

[0041] , the cited portion of which is incorporated herein by reference.

[0017] As used herein, the terms “phosphated epoxy resin”, “phosphated polyepoxide”, and variants thereof refer to an ungelled epoxy resin resulting from the reaction between at least an epoxy -functional monomer, oligomer, or polymer, and a phosphorus-atom containing compound, such as a phosphorus acid. It will be appreciated that during this reaction, all the epoxy functionality may be consumed and so the phosphated “epoxy” resin may contain only the residue of the epoxy groups. “Ungelled” means the resin is substantially free of crosslinking and has an intrinsic viscosity when dissolved in a suitable solvent, as determined in accordance with ASTM-D1795 or ASTM-D4243. The intrinsic viscosity of this reaction product is an indication of its molecular weight. A gelled reaction product, on the other hand, since it is of essentially infinitely high molecular weight due to substantial crosslinking of the resin molecules, will have an intrinsic viscosity too high to measure (i.e., cannot be dissolved in a solvent). As used herein, a reaction product or resinthat is “substantially free of crosslinking” refers to a reaction product that has a z-average molecular weight (Mz) of less than 500,000 g / mol.

[0018] The anionic salt group-containing film-forming polymer may be present in the anionic electrodepositable coating compositions in an amount such as 30% by weight or greater, such as 40% by weight or greater, such as 45% by weight or greater, such as 50% by weight or greater, or in an amount of 80% by weight or lower, such as 70% by weight or lower, such as 65% by weight or lower, or in an amount of 30% to 80% by weight, such as 40% to 70% by weight, such as 45% to 65% by weight, based on the total weight of the resin solids of the anionic electrodepositable coating composition.

[0019] As used herein, the “resin solids” include the solids from the anionic salt group-containing film-forming polymer, the curing agent, the core-shell polymer and / or the latex polymer, the corrosion inhibitor (if used), and any additional water-dispersible nonpigment component(s) present in the electrodepositable coating composition.

[0020] The anionic electrodepositable coating compositions of the present disclosure further comprise a curing agent. The curing agent reacts with the reactive groups, such as active hydrogen groups, on the anionic salt group-containing film-forming polymer and may also react with reactive groups, if present, on the core-shell or latex polymers, to effectuate cure of the anionic electrodepositable coating composition to form a cured coating. Suitable curing agents include at least partially blocked poly isocyanates, as well as aminoplast resins, and / or phenoplast resins, such as phenolformaldehyde condensates including allyl ether derivatives thereof.

[0021] A “blocked polyisocyanate” will be understood as referring to a polyisocyanate wherein at least a portion of the isocyanato groups is blocked by a blocking group introduced by the reaction of a free isocyanato group of the polyisocyanate with a blocking agent. A “blocking agent” is a compound comprising a functional group reactive with an isocyanato group and a “blocking group” refers to the residual moiety of the blocking agent bound to the isocyanato group. A “blocked polyisocyanate” is therefore one in which the isocyanato groups have been reacted with a blocking agent such that the resultant blocked isocyanate group is stable to active hydrogens at ambient temperature (20°C + / - 5°C). The reaction may be reversed under suitable conditions, such as at elevated temperatures, such as 90°C to 200°C, such that the previously blocked isocyanato groups are unblocked and available to react with the reactive groups; this reaction effectuates cure of the coating composition to form a cured coating. The blocked polyisocyanate may be a fully blocked polyisocyanate wherein essentially 100% of the isocyanato groups of the polyisocyanate areblocked with one or more blocking groups. Optionally, the blocked polyisocyanate curing agent may be a partially blocked polyisocyanate, having fewer than 100% of the isocyanato groups blocked, as long as the coating composition remains stable to active hydrogens at ambient temperature.

[0022] Blocking agents that are disassociated from the blocked polyisocyanate curing agent during cure may be removed from the coating film by volatilization. Alternatively, a portion of or all the blocking agent may remain in the coating film following cure.

[0023] Suitable examples of blocked polyisocyanate curing agents, and amounts thereof, including suitable polyisocyanates, and suitable blocking agents, such as 1,2 polyols, are provided in Int’l Pub. No. WO 2021 / 138583 Al, at paragraphs

[0022] to

[0035] , the cited portion of which is incorporated herein by reference.

[0024] Examples of blocked polyisocyanates comprising a blocking group derived from a blocking agent comprising an alpha-hydroxy amide, ester, or thioester and, optionally, a second blocking agent, are provided in Int’l Pub. No. WO 2018 / 148306 Al, at paragraphs

[0010] to

[0029] , the cited portion of which is incorporated herein by reference.

[0025] The at least partially blocked polyisocyanate may be partially blocked with one or more of the blocking groups discussed above with the remaining isocyanato groups reacted with a compound or polymer, such as described in U.S. Pat. No. 3,947,338, at col. 2, line 65 through col. 5, line 33, the cited portion of which is herein incorporated by reference.

[0026] The blocked polyisocyanate curing agent may comprise a tris(alkoxycarbonylamino)-l,3,5-triazine (TACT). Non-limiting examples of suitable tris(alkoxycarbonylamino)-l ,3,5-triazines include tris(methoxycarbonylamino)-, tris(butoxycarbonylamino)-, and tris(2-ethylhexoxycarbonylamino)-l,3,5-triazines, and any combination thereof.

[0027] The curing agent may comprise an aminoplast or a phenoplast resin. Aminoplast resins are condensation products of an aldehyde with an amino- or amido-group carrying substance. Phenoplast resins are formed by the condensation of an aldehyde and a phenol.

[0028] Commercially available aminoplast resins are those available under the trademark CYMEL from Allnex Belgium SA / NV, such as CYMEL 1130 and 1156, and RESIMENE from INEOS Melamines, such as RESIMENE 750 and 753. Examples of suitable aminoplast resins, and amounts thereof, also include those described in U.S. Pat. No. 3,937,679 at col. 16, line 3 to col. 17, line 47, this portion of which is hereby incorporated by reference.

[0029] Suitable aminoplast and phenoplast resins also are described in U.S. Pat. No. 4,812,215 at col.6, line 20 to col. 7, line 12, the cited portion of which is incorporated herein by reference.

[0030] The curing agent may comprise or further comprise an inorganic curing agent, such as the silicone-based curing agents described in Int’l Pub. No. WO 2021 / 138384 Al, at paragraphs

[0030] through

[0043] , the cited portion of which is incorporated herein by reference.

[0031] The curing agent may be present in the anionic electrodepositable coating composition, in an amount of 5% by weight or greater, such as 10% by weight or greater, such as 15% by weight or greater, or in an amount of 60% by weight or lower, such as 50% by weight or lower, such as 45% by weight or lower, such as 40% by weight or lower, or in an amount of 5% to 60% by weight, 10% to 50% by weight, 15% to 45% by weight, such as 15% to 40% by weight, based on the total weight of the resin solids of the anionic electrodepositable coating composition.

[0032] The anionic electrodepositable coating composition may further comprise a core-shell polymer. As used herein, the term “core-shell polymer” refers to (1) a polymeric core at least partially encapsulated by (2) a polymeric shell; the polymeric core can be covalently bound to at least a portion of the polymeric shell. The core-shell polymer can be prepared using any method known in the art, such as stepwise polymerization of ethylenically unsaturated monomers or by covalently bonding the polymeric shell to the polymeric core by reacting at least one functional group on the monomers and / or prepolymers that are used to form the polymeric shell with at least one functional group on the monomers and / or prepolymers used to form the polymeric core. Such functionality can comprise unsaturated carbon-carbon bonds.

[0033] The polymeric core may comprise 20% by weight or greater of the core-shell polymer, such as 30% by weight or greater, 40% by weight or greater, 45% by weight or greater, or 80% by weight or lower such as 70% by weight or lower, 60% by weight or lower, or 55% by weight or lower, or 20% to 80% by weight, such as 30% to 70% by weight, such 40% to 60% by weight, or 40% to 55% by weight, where weight is based on the total weight of the core-shell polymer. It will be appreciated that the shell will comprise the remainder of the total weight of the core-shell polymer. The weight ratio of core to shell can therefore range from 20:80 to 80:20.

[0034] The polymeric core and polymeric shell may each independently comprise an acrylic polymer or a polyurethane polymer. The core-shell polymer may comprise an acrylicpolymer core and acrylic polymer shell; an acrylic polymer core and a polyurethane polymer shell; a polyurethane polymer core and an acrylic polymer shell; or a polyurethane polymer core and a polyurethane polymer shell. When either the core or shell comprises acrylic, the core and the shell may be covalently bound through an acrylate linkage.

[0035] As used herein, the term “acrylic polymer” refers to a polymerization product at least partially comprising the residue of unsaturated monomers, including (meth)acrylic monomers, wherein the (meth)acrylic monomers make up more than 50% by weight of the monomers used to make the polymerization product, such as 60% by weight or greater, 70% by weight or greater, or 75% by weight or greater. An unsaturated monomer is a compound having at least one degree of ethylenic unsaturation and a weight average molecular weight (Mw) of less than 1 ,000 g / mol.

[0036] The acrylic polymer may be substantially free, essentially free, or completely free of urethane linkages. As used herein, an acrylic polymer is “substantially free” or “essentially free” of urethane linkages if the acrylic polymer has a urethane linkage equivalent weight of greater than 10,000 g / equivalent of urethane linkage or greater than 25,000 g / equivalent of urethane linkages, respectively. An acrylic polymer is completely free of urethane linkages if urethane linkages are not present in the acrylic polymer.

[0037] The acrylic polymer may be prepared from polymerizable ethylenically unsaturated monomers. Suitable polymerizable ethylenically unsaturated monomers include ethylenically unsaturated hydrocarbons, esters and ethers, such as esters of acrylic and methacrylic acids, and esters of vinyl alcohol and styrene. Specific examples include butadiene, isoprene, styrene, substituted styrenes, the lower alkyl (Ci-Ce) esters of (meth)acrylic and maleic acids such as butyl methacrylate (BMA), vinyl acetate and butyrate, acrylonitrile, vinylmethyl, propyl and butyl ethers, vinyl chloride, vinylidene chloride, and the like. Other suitable polyethylenically unsaturated monomers include allylmethacrylate, diacrylate esters of Ci-Ce diols such as butanediol diacrylate and hexanediol diacrylate, divinyl benzene, divinyl ether, divinyl sulfide, trimethylolpropane triacrylate, and the like.

[0038] Ethylenically unsaturated monomers used to prepare the acrylic polymer may comprise one or more (meth)acrylic monomers and optionally other ethylenically unsaturated monomers. As used herein, the term “(meth)acrylic monomer” refers to acrylic acid, methacrylic acid, and monomers derived therefrom, including alkyl esters of acrylic acid and methacrylic acid, and the like. The ethylenically unsaturated monomers may comprise acid functional monomers such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid and the like; alkyl esters of (meth)acrylic acid, such as aliphatic alkyl esters containing from1 to 30, such as 4 to 18 carbon atoms in the alkyl group, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate, and 2-ethyl hexyl acrylate; monomers having multiple ethylenically unsaturated groups; 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 compounds, such as those having the structure:wherein X is N or O; R is a linear or branched alkyl group having 1 to 18 carbon atoms, or R is bonded to X to form a 5- to 7-member ring. Examples of vinyl esters of alkyl carboxylic acids include vinyl acetate, vinyl pivalate, vinyl laurate, vinyl dodecanoate, and the like. Examples of other suitable vinyl compounds having the above structure include vinyl amides and vinyl lactams such as vinyl pyrrolidone and vinyl caprolactam.

[0039] Examples of monomers having multiple ethylenically unsaturated groups include ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1 ,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6- hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di(meth) acrylate, glycerol allyloxy di(meth)acrylate, 1,1,1 -tris (hydroxymethyl)ethane di(meth)acrylate, 1,1,1- tris(hydroxymethyl)ethane tri(meth)acrylate, 1,1,1 -tris(hydroxymethyl)propane di(meth)acrylate, 1 , 1 , 1 -tris(hydroxymethyl)propane tri(meth)acrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl phthalate, diallyl terephthalte, divinyl benzene, methylol(meth)acrylamide, triallylamine, and methylenebis (meth) acrylamide.

[0040] Amide functional ethylenically unsaturated monomers such as (meth)acrylamide and hydroxyl functional monomers including any of those disclosed below may also be used.

[0041] Amide functionality may be introduced to the acrylic polymer by using suitably functional monomers in the preparation of the polymer, or by converting other functional groups to amido- groups using techniques known to those skilled in the art. Likewise, other functional groups may be incorporated as desired using suitably functional monomers if available or conversion reactions as necessary.

[0042] The acrylic polymer can include hydroxyl functional groups, which may be incorporated into the polymer by including one or more hydroxyl functional monomers in the reactants used to produce the acrylic polymer. Useful hydroxyl functional monomers include hydroxyalkyl (meth)acrylates, such as those having 2 to 4 carbon atoms in the hydroxyalkyl group, such as hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, hydroxy functional adducts of caprolactone and hydroxyalkyl acrylates, and corresponding methacrylates, as well as the beta-hydroxy ester functional monomers.

[0043] Beta-hydroxy ester functional monomers can be prepared from ethylenically unsaturated, epoxy functional monomers and carboxylic acids having, for example, from 13 to 20 carbon atoms, or from ethylenically unsaturated acid functional monomers and epoxy compounds containing 5 carbon atoms that are not polymerizable with the ethylenically unsaturated acid functional monomer.

[0044] Suitable ethylenically unsaturated epoxy functional monomers used to prepare the beta-hydroxy ester functional monomers include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, methallyl glycidyl ether, 1 : 1 (molar) adducts of ethylenically unsaturated monoisocyanates with hydroxy functional monoepoxides such as glycidol, and glycidyl esters of polymerizable polycarboxylic acids such as maleic acid. Examples of carboxylic acids include saturated monocarboxylic acids such as isostearic acid and aromatic unsaturated carboxylic acids.

[0045] Suitable ethylenically unsaturated acid functional monomers used to prepare the beta-hydroxy ester functional monomers include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid; dicarboxylic acids such as itaconic acid, maleic acid and fumaric acid; and monoesters of dicarboxylic acids such as monobutyl maleate and monobutyl itaconate. The ethylenically unsaturated acid functional monomer and epoxy compound are typically reacted in a 1: 1 equivalent ratio. The epoxy compound does not contain ethylenic unsaturation that would participate in free radical-initiated polymerization with the unsaturated acid functional monomer. Useful epoxy compounds include 1,2-pentene oxide, styrene oxide and glycidyl esters or ethers, such as those containing from 8 to 30 carbon atoms, such as butyl glycidyl ether, octyl glycidyl ether, phenyl glycidyl ether and para- (tertiary butyl) phenyl glycidyl ether. Examples of glycidyl esters include those of the structure:where R is a hydrocarbon radical containing from 4 to 26 carbon atoms. R may be a branched hydrocarbon group having from 8 to 10 carbon atoms, such as neopentanoate, neoheptanoate or neodecanoate. Suitable glycidyl esters of carboxylic acids include VERSATIC ACID 911 and CARDURA E, each of which is commercially available from Shell Chemical Co.

[0046] Carbamate functional groups can be included in the acrylic polymer by copolymerizing the acrylic monomers with a carbamate functional vinyl monomer, such as a carbamate functional alkyl ester of methacrylic acid. Alternatively, carbamate functionality may be introduced into the acrylic polymer by reacting a hydroxyl functional acrylic polymer with a low molecular weight carbamate functional material, such as can be derived from an alcohol or glycol ether, via a transcarbamoylation reaction. In this reaction, a low molecular weight carbamate functional material derived from an alcohol or glycol ether is reacted with the hydroxyl groups of the acrylic polyol, yielding a carbamate functional acrylic polymer and the original alcohol or glycol ether. The low molecular weight carbamate functional material derived from an alcohol or glycol ether may be prepared by reacting the alcohol or glycol ether with urea in the presence of a catalyst. Suitable alcohols include lower molecular weight aliphatic, cycloaliphatic, and aromatic alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, 2-ethylhexanol, and 3 -methylbutanol. Suitable glycol ethers include ethylene glycol methyl ether and propylene glycol methyl ether. Propylene glycol methyl ether and methanol are most often used.

[0047] A free radical initiator typically is used in the latex emulsion polymerization process used to form the acrylic polymer. Any suitable free radical initiator may be used, such as thermal initiators, photoinitiators, or oxidation-reduction initiators, all of which may be otherwise categorized as being water-soluble initiators or non-water-soluble initiators. Examples of thermal initiators include azo compounds, peroxides and persulfates. Suitable persulfates include sodium persulfate and ammonium persulfate. Oxidation-reduction initiators include t-hydrogenperoxide and ascorbic acid systems or persulfate-sulfite systems, as well as systems utilizing thermal initiators in combination with appropriate metal ions such as iron or copper.

[0048] Suitable azo compounds include non- water- soluble azo compounds such as 1- 1 '-azobiscyclohexanecarbonitrile, 2-2'-azobisisobutyronitrile, 2-2'-azobis(2- methylbutyronitrile), 2-2'-azobis(propionitrile), 2-2'-azobis(2,4-dimethylvaleronitrile), 2-2'- azobis(valeronitrile), 2-(carbamoylazo)-isobutyronitrile and mixtures thereof; and water- soluble azo compounds such as azobis tertiary alkyl compounds including 4-4'-azobis(4- cyano valeric acid), 2-2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis[2- methyl-N-(2-hydroxyethyl)propionamide], 4,4'-azobis(4-cyanopentanoic acid), 2,2'- azobis(N,N'-dimethyleneisobutyramidine), 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis(N,N'-dimethyleneisobutyramidine) dihydrochloride and mixtures thereof.

[0049] Suitable peroxides include hydrogen peroxide, methyl ethyl ketone peroxides, benzoyl peroxides, di-t-butyl peroxides, di-t-amyl peroxides, dicumyl peroxides, diacyl peroxides, decanoyl peroxide, lauroyl peroxide, peroxydicarbonates, peroxyesters, dialkyl peroxides, hydroperoxides, peroxyketals and mixtures thereof.

[0050] As used herein, the term “polyurethane polymer” refers to a polymer including a urethane linkage.

[0051] The polyurethane polymer may comprise a polymerization product of a polyisocyanate and a hydroxyl functional compound. The hydroxyl functional compound may comprise more than one hydroxyl functional group as well as other functional groups. The polyurethane polymer further comprises an ethylenically unsaturated group. The ethylenically unsaturated groups may be incorporated into the polyurethane polymer by reacting a compound comprising an ethylenically unsaturated group and a hydroxyl functional group with an isocyanato group from the polyisocyanate. Alternatively, ethylenically unsaturated groups may be incorporated into the polyurethane polymer by reacting a compound comprising an ethylenically unsaturated group and an isocyanato functional group with a hydroxyl group from a hydroxyl functional compound. The ethylenically unsaturated group may be used to covalently bond the polyurethane polymer to the polymeric core if the polyurethane polymer is in the polymeric shell or to the polymeric shell if the polyurethane polymer is in the polymeric core.

[0052] The polyurethane polymer may be a water-dispersible carboxy-containing polyurethane prepolymer formed from a reaction mixture including (a) a polyol, (b) a polymerizable ethylenically unsaturated monomer containing at least one acrylic functional group and at least one active hydrogen group, and (c) a polyisocyanate. The water- dispersible polyurethane prepolymer may be prepared by reacting a stoichiometric excess of the isocyanate with the polyols under substantially anhydrous conditions at a temperature of30° to 130°C until the reaction between the isocyanate groups and the active hydrogen (hydroxyl) group is substantially complete (the reaction may be run until the theoretical NCO equivalent weight has been reached). An isocyanate and the active hydrogen containing components are suitably reacted in such proportions that the ratio of number of isocyanate groups to the number of active hydrogen groups is from 1.1:1 to 6:1, such as from 1.5: 1 to 3:1.

[0053] The polyol reacted with the polyisocyanate to form the polyurethane polymer may be a member of any of the chemical class of polymeric polyols such as polyesters, polyesteramides, polyethers, poly thioethers, polycarbonates, polyacetals, polyolefins, polysiloxanes, polyurethanes, or some combination thereof. The polyol may include a polyester polyol, a polycarbonate polyol, or polyester-polycarbonate polyol. The polyol may be a diol, a triol, or higher polyol.

[0054] Polymerizable ethylenically unsaturated monomers containing at least one acrylic functional group and at least one active hydrogen group to react with isocyanate may include ethylenically unsaturated groups such as acrylates or methacrylates. The acrylate and methacrylate functional groups may be represented by the formula, CH2=C(R2) — C(O)O — , wherein R2is hydrogen or methyl. Other monomers may include allyl carbamates and allyl carbonates. The allyl carbamates and carbonates may be represented by the formulae CH2=CH— CTh— NH— C(O)O— and CH2=CH— CTh— O— (C)O— , respectively. The ethylenically unsaturated monomer with an acrylic functional group and an active hydrogen group utilized in preparing the polyurethane prepolymers may comprise a hydroxyalkyl (meth) acrylate. Suitable hydroxyalkyl(meth)acrylates include those having from 1 to 18 carbon atoms in the alkyl radical, the alkyl radical being substituted or unsubstituted. Specific non-limiting examples of such materials include 2-hydroxy ethyl (meth)acrylate (HEMA), 2-hydroxypropyl(meth)acrylate, 2- hydroxybutyl(meth)acrylate, hexane- 1,6-diol mono(meth)acrylate, 4-hydroxybutyl(meth)acrylate, as well as mixtures thereof.

[0055] The core shell polymer may comprise a polymeric shell comprising a polyurethane polymer and a polymeric core comprising an acrylic polymer. Once the polyurethane prepolymer for the polymeric shell is formed, the polyurethane prepolymer may be added to a reaction mixture containing water along with the previously described polymerizable ethylenically unsaturated monomers used to prepare the polymeric acrylic core. A neutralizing amine, a chain extending amine, and / or a chain terminating amine may also be added to the reaction mixture. It should be appreciated that the order of addition of the previously described polymerizable ethylenically unsaturated monomers used to preparethe polymeric acrylic core and the neutralizing amine may be varied. An initiator composition may be added to the reaction mixture in one or more stages to effect and / or continue polymerization.

[0056] The polyisocyanate may be aliphatic or aromatic, and diisocyanates or higher polyisocyanates such as isocyanurates of diisocyanates may be used. Suitable polyisocyanates include, but are not limited to diphenylmethane diisocyanate (MDI), including its 2,4', 2,2' and 4,4' isomers, homopolymers and mixtures thereof, mixtures of diphenylmethane diisocyanates (MDI) and oligomers thereof, and reaction products of polyisocyanates as set out herein with components containing isocyanate-reactive hydrogen atoms forming polymeric polyisocyanates (prepolymers), toluene diisocyanate (TDI), including 2,4 TDI and 2,6 TDI in any suitable isomer mixture, hexamethylene diisocyanate (HMDI or HDI), isophorone diisocyanate (IPDI), butylene diisocyanate, trimethylhexamethylene diisocyanate, di(isocyanatocyclohexyl)methane, including 4,4'- diisocyanatodicyclohexylmethane (H12MDI), isocyanatomethyl-1, 8-octane diisocyanate, tetramethylxylene diisocyanate (TMXDI), 1,5- naphtalenediisocyanate (ND I), p- phenylenediisocyanate (PPDI), 1 ,4-cyclohexanediisocyanate (CD), tolidine diisocyanate (TODD), any suitable mixture of these polyisocyanates, and any suitable mixture of one or more of these polyisocyanates with MDI-type polyisocyanates.

[0057] The ethylenically unsaturated monomers used to form the polyurethane polymer may comprise any of those described above with respect to the acrylic polymer so long as the at least some of the ethylenically unsaturated monomers include a functional group reactive with the isocyanato functional group of the polyisocyanate, such as a hydroxyl functional monomer.

[0058] The polyurethane polymer may have an aliphatic content of 50% by weight or greater, based on the total weight of the polyurethane polymer, such as 60% by weight or greater, 65% by weight or greater, 70% by weight or greater, 75% by weight or greater, 77% by weight or greater, 80% by weight or greater, 83% by weight or greater, 86% by weight or greater, 89% by weight or greater, 92% by weight or greater, or 95% by weight or greater. It will be appreciated that aliphatic content may contribute to resistance to UV degradation, as aromatic moieties are known to be more susceptible to that.

[0059] As used herein, the term “aliphatic content” refers to any organic chemical constituent in which the atoms are connected by single, double, or triple bonds to form nonaromatic structures. The aliphatic content of a resin may be determined based on the mass ofthe atoms comprising aromatic structures in a polymer and the total mass of the polymer, according to the following equation:Total mass of polymer - Mass of atoms in aromatic structures% Aliphatic Content = - x 100Total mass of polymer

[0060] The polyurethane polymer prior to reaction to form the core-shell polymer (i.e., the polyurethane prepolymer) may have a weight average molecular weight (“Mn”) of 2,000 g / mol or greater, such as 5,000 g / mol or greater, or of 50,000 g / mol or lower, such as 15, 000 g / mol or lower, or a weight average molecular weight of 2,000 to 50,000 g / mol, such as 5,000 to 15,000 g / mol.

[0061] The core-shell polymer may have a calculated acid value of 10 mg KOH / g core- shell polymer or greater, such as 13 mg KOH / g core- shell polymer or greater, or 15 mg KOH / g core-shell polymer or greater. The core-shell polymer may have an acid value of 60 mg KOH / g core-shell polymer or lower, such as 48 mg KOH / g core-shell polymer or lower, or 30 mg KOH / g core-shell polymer or lower. The core-shell polymer may have an acid value of 10 to 60 mg KOH / g core-shell polymer, such as 13 to 48 mg KOH / g core-shell polymer, or 15 to 30 mg KOH / g core-shell polymer.

[0062] The core-shell polymer may have a calculated hydroxyl value of 1 mg KOH / g of core-shell polymer or greater, such as 2 mg KOH / g of core-shell polymer or greater, or 180 mg KOH / g core-shell polymer or lower, such as 120 mg KOH / g core-shell polymer or lower, or 60 mg KOH / g core-shell polymer or lower. The core-shell polymer may have a hydroxyl value of 1 to 180 mg KOH / g core-shell polymer, such as 1 to 120 mg KOH / g coreshell polymer, or 2 to 60 mg KOH / g core-shell polymer.

[0063] The core-shell polymer may be present in an amount of 3% by weight or greater, such as 5% by weight or greater, or 7% by weight or greater, based on a total weight of resin solids. The core-shell polymer may be present in an amount of 25% by weight or lower, such as 20% by weight or lower, or 16% by weight or lower, based on a total weight of resin solids. The core-shell polymer may be present in an amount of 3% to 25% by weight, or 5% to 20% by weight, or 7% to 16% by weight, based on a total weight of resin solids.

[0064] Instead of, or in addition to, the core-shell polymer, the present compositions may comprise a latex polymer. The latex polymer may have the same Tgs, acid values, and hydroxyl values, and comprise the same weight percent of the composition as the core-shell particle described above. A latex polymer will be understood by those skilled in the art as a dispersion of polymeric particles in a liquid; the particles form because at least some internalcrosslinking occurs. The latex polymer can be formed, for example, from any monomers known in latex formation. Suitable monomers, for example, may include the monomers described above in conjunction with the acrylic polymer, and the polyurethane polymer. Accordingly, the latex polymer can be an acrylic latex polymer. An “acrylic latex polymer” is one in which more than 50% by weight of the monomers comprise (meth)acrylic functionality, such as 60% by weight or greater, or 70% by weight or greater, or 75% by weight or greater, with % by weight based on the total weight of the monomers used for making the polymer. The latex polymer can also be a polyurethane polymer, which will be understood as a polymer having polyurethane linkages. Any method for making latex polymers known in the art can be used, or the latex can be commercially obtained, such as from Sigma Aldrich.

[0065] The anionic electrodepositable coating compositions of the present disclosure further comprise a corrosion inhibitor. A “corrosion inhibitor” will be understood as referring to a compound that inhibits corrosion of metal as determined according to ASTM Bl 17. The corrosion inhibitor may comprise 2,2’-dipyridyl disulfide, tetraethyl thiuram disulfide, thiocarbamyl sulfenamide, or a combination thereof. The corrosion inhibitor may be incorporated into the anionic electrodepositable coating composition on a pigment, such as silica, as a component of a pigment paste, or combined with the anionic salt group-containing film- forming polymer and / or curing agent.

[0066] The corrosion inhibitor may be present in an amount of 5% by weight or greater, such as 8% by weight or greater, or 10% by weight or greater, based on a total weight of resin solids. The corrosion inhibitor may be present in an amount of 30% by weight or lower, such as 25% by weight or lower, or 20% by weight or lower, or 17% by weight or lower, or 15% by weight or lower, based on a total weight of resin solids. The corrosion inhibitor may be present in an amount of 5% to 30% by weight, such as 8% to 25% by weight, or 10% to 20% by weight, or 10% to 15% by weight, based on a total weight of resin solids.

[0067] The anionic electrodepositable coating composition may further comprise a curing catalyst. As used herein, the term “curing catalyst” may be used interchangeably with “catalyst” and refers to materials that catalyze the curing reaction between components of the anionic electrodepositable coating composition, such as the curing agent and film-forming polymer. For example, the catalyst may catalyze transurethanation reactions, and / or specifically catalyze the deblocking of blocked polyisocyanate blocking groups.

[0068] Examples of curing catalysts include latent acid catalysts. Latent acid catalysts are derivatives of acid catalysts that are generally activated by heating. Suitable examples of latent acid catalysts are identified in WO 2007 / 118024 at paragraph

[0031] . Further examples of suitable latent acid catalysts include derivatives of acid catalysts such as sulfonic acids, such as derivatives of para-toluenesulfonic acid, such as pyridinium paratoluenesulfonate.

[0069] The anionic electrodepositable coating composition may further comprise a pigment component (in addition to any pigment that might be used to introduce the corrosion inhibitor into the composition). The pigment component may include one or more pigments including iron oxides, lead oxides, strontium chromate, carbon black, coal dust, titanium dioxide, talc, barium sulfate, a plate-like pigments, such as inorganic plate-like pigments such as clay, calcined clay, kaolin, and the like, thermally conductive, electrically insulative filler materials, thermally conductive, electrically conductive filler materials, non-thermally conductive, electrically insulative filler materials, fire-retardant pigments, as well as color pigments such as cadmium yellow, cadmium red, chromium yellow and the like. As used herein, the term “plate-like pigments” refers to pigments having a generally platy shape. As used herein, a “fire-retardant pigments” refers to a pigment that slows down or stops the spread of fire and / or reduces its intensity. Examples include inorganic pigments and minerals, such as those described in W02024 / 020483 at

[0060] , hereby incorporated by reference. As used herein, “electrically insulative filler” refers to a pigment, filler, or inorganic powder that has a volume resistivity of at least 10 Q-m (measured according to ASTM D257, C611, or B193). As used herein, “electrically conductive filler” refers to a pigment, filler, or inorganic powder that has a volume resistivity of less than 10 Q-m (measured according to ASTM D257, C611, or B 193). As used herein, “thermally conductive filler” refers to a pigment, filler, or inorganic powder that has a thermal conductivity of at least 5 W / m-K at 25°C (measured according to ASTM D7984). As used herein, “non-thermally conductive filler” refers to a pigment, filler, or inorganic powder that has a thermal conductivity of less than 5 W / m-K at 25°C (measured according to ASTM D7984).

[0070] The pigment-to- electrodepositable binder (P:B) ratio as set forth in this disclosure refers to the weight ratio of the pigment-to- electrodepositable binder in the anionic electrodepositable coating composition, and / or the weight ratio of the pigment-to- electrodepositable binder in the deposited wet film, and / or the weight ratio of the pigment to the binder in the dry, uncured deposited film, and / or the weight ratio of the pigment-to-electrodepositable binder in the cured film. The compositions and coating layers deposited therefrom of the present disclosure may have a high P:B. A “high” P:B may be 0.6: 1 or greater, such as 0.8:1 or greater, such as 1: 1. In determining the P:B, all the pigment in the pigment component is considered, including any pigment used to introduce a corrosion inhibitor to the composition.

[0071] The anionic electrodepositable coating composition may comprise one or more further components in addition to those described above, such as fillers, plasticizers such as those having an Mn of less than 2000, antioxidants, biocides, UV light absorbers and stabilizers, hindered amine light stabilizers, defoamers, fungicides, dispersing aids, flow control agents, surfactants, wetting agents, or combinations thereof. Alternatively, the anionic electrodepositable coating composition may be completely free of any of these optional ingredients, i.e., the optional ingredient is not present in the anionic electrodepositable coating composition. The other additives mentioned above may be present in the anionic electrodepositable coating composition in amounts of 0.01% to 3% by weight, based on total weight of the resin solids of the anionic electrodepositable coating composition.

[0072] According to the present disclosure, the anionic electrodepositable coating compositions may comprise an aqueous medium comprising water and / or one or more organic solvent(s). Water can, for example, be present in amounts of 40% to 90% by weight, such as 50% to 75% by weight, based on total weight of the anionic electrodepositable coating composition. Examples of suitable organic solvents include oxygenated organic solvents, such as monoalkyl ethers of ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol which contain from 1 to 10 carbon atoms in the alkyl group, such as the monoethyl and monobutyl ethers of these glycols. Examples of other at least partially water-miscible solvents include alcohols such as ethanol, isopropanol, butanol and diacetone alcohol. If used, the organic solvents may typically be present in an amount of less than 10% by weight, such as less than 5% by weight, based on total weight of the anionic electrodepositable coating composition. The anionic electrodepositable coating composition may be provided in the form of a dispersion, such as an aqueous dispersion.

[0073] According to the present disclosure, the total solids content of the anionic electrodepositable coating composition may be 1% by weight or greater, such as 5% by weight or greater, and may be 50% by weight or lower, such as 40% by weight or lower, or 20% by weight or lower, based on the total weight of the anionic electrodepositable coating composition. The total solids content of the anionic electrodepositable coating compositionmay be from 1% to 50% by weight, such as 5% to 40% by weight, or 5% to 20% by weight, based on the total weight of the anionic electrodepositable coating composition. As used herein, “total solids” refers to the non-volatile content of the anionic electrodepositable coating composition, i.e., materials which will not volatilize when heated to 110°C for one hour.

[0074] The present disclosure is further directed to methods for using any of the anionic electrodepositable coating compositions described above to coat a substrate comprising electrophoretically applying the coating composition to a portion of the substrate and curing the composition to form a cured coating layer. The electrodepositable coating composition may be electrocoated onto an electroconductive substrate and cured using application conditions, times, and temperatures, known to those skilled in the art.

[0075] For example, the anionic electrodepositable coating composition of the present disclosure may be deposited upon an electrically conductive substrate by placing the composition in contact with an electrically conductive cathode and an electrically conductive anode, with the surface to be coated being the anode. Following contact with the composition, an adherent coating of the coating composition may be deposited on the anode when a sufficient voltage is impressed between the electrodes. The applied voltage in the electrophoretic application of the electrodepositable coating compositions of the present disclosure may be varied and may be, for example, as low as one volt to as high as several thousand volts, such as 50 to 500 volts. The current density may, for example, be 0.5 ampere to 15 amperes per square foot.

[0076] Following application of the electrodepositable coating composition, the substrate may be heated to a temperature and for a time sufficient to at least partially cure the electrodeposited coating on the substrate. As used herein, the term “at least partially cure” refers to subjecting the coating composition to curing conditions such that at least a portion of the reactive groups of the components of the coating composition cure or crosslink to form a coating. In general, the substrate may be heated to a temperature ranging from 250°F to 450°F (121.1°C to 232.2°C), such as from 275°F to 400°F (135°C to 204.4°C), or from 300°F to 360°F (149°C to 180°C). For purposes of the present disclosure, all that is necessary is that the time be sufficient to effect cure of the coating on the substrate. The curing time may, for example, range from 10 minutes to 60 minutes, such as 20 to 40 minutes. The thickness of the resultant cured electrodeposited coating is not limited and may range from 15 to 50 microns.

[0077] The substrate may be pretreated with a pretreatment composition prior to applying the electrodeposited coating. Any suitable pretreatment can be used. The pretreatment solution may be a non-metal phosphate pretreatment composition, such as a zirconium-containing pretreatment composition. Suitable zirconium-containing pretreatment compositions include those described in U.S. Pat. No. 7,749,368, at col. 3, line 24 through col. 6, line 48, and U.S. Pat. No. 8,673,091, at col. 3, line 18 through col. 8, line 55, the cited portion of which from each are incorporated herein by reference.

[0078] A “pretreatment composition” refers to a composition that can react with and chemically alter the substrate surface and bind to it to form a layer that affords corrosion protection. A “non-metal phosphate pretreatment composition” refers to pretreatment compositions wherein a metal phosphate compound, such as zinc phosphate or iron phosphate, is not the primary active compound in the pretreatment composition. Alternatively, zinc phosphate pretreatment compositions can be used, such as those described in U.S. Pat. No. 4,793,867, at col. 3, line 5 through col. 5, line 8 and col. 5, line 64 through col. 11, line 50, and U.S. Pat. No. 5,588,989, at col. 2, line 20 through col. 4, line 47, the cited portion of which for each is incorporated herein by reference.

[0079] The non-metal phosphate pretreatment composition, such as the zirconium- containing pretreatment composition, may be substantially free, essentially free, or completely free of phosphate. As used herein, a non-metal phosphate pretreatment composition is “substantially free” or “essentially free” of phosphate if it comprises less than 1% by weight or less than 0.5% by weight of phosphate, respectively, based on the total weight of the non-metal phosphate pretreatment composition. As used herein, a non-metal phosphate pretreatment composition is “completely free” of phosphate if phosphate is not present, that is, 0% by weight phosphate, based on the total weight of the non-metal phosphate pretreatment composition.

[0080] Suitable substrates coated according to the present methods include metal substrates, metal alloy substrates, and / or substrates that have been metallized, such as nickel- plated plastic. Additionally, substrates may comprise non-metal conductive materials including composite materials such as, for example, materials comprising carbon fibers or conductive carbon. The metal or metal alloy can comprise or be steel, aluminum, zinc, nickel, and / or magnesium. For example, the steel substrate could be cold rolled steel, hot rolled steel, electrogalvanized steel, and / or hot dipped galvanized steel. Aluminum alloys of the 1XXX, 2XXX, 3XXX, 4XXX, 5XXX, 6XXX, or 7XXX series as well as clad aluminum alloys also may be used as the substrate. Aluminum alloys may comprise, for example,0.01% by weight copper to 10% by weight copper. Aluminum alloys that are treated may also include castings, such as 1XX.X, 2XX.X, 3XX.X, 4XX.X, 5XX.X, 6XX.X, 7XX.X, 8XX.X, or 9XX.X (e.g., A356.0). Magnesium alloys of the AZXX (including Eform Plus), AMXX, EVXX, ZEXX, ZCXX, HKXX, HZXX, QEXX, QHXX, WEXX, ZEK100, or Elektron 21 series also may be used as the substrate. The substrate used may also comprise titanium and / or titanium alloys, zinc and / or zinc alloys, and / or nickel and / or nickel alloys. Suitable substrates for use in the present disclosure include those that are often used in the assembly of vehicular bodies (e.g., without limitation, door, body panel, trunk deck lid, roof panel, hood, roof and / or stringers, rivets, landing gear components, and / or skins used on an aircraft), a vehicular frame, vehicular parts, motorcycles, wheels, industrial structures and components such as appliances, including washers, dryers, refrigerators, stoves, dishwashers, and the like, personal electronics, agricultural equipment, lawn and garden equipment, metal fencing, guard rails, air conditioning units, heat pump units, heat exchangers, lawn furniture, and other articles. As used herein, “vehicle” or variations thereof include civilian, commercial and military aircraft, and / or land vehicles such as cars, motorcycles, trucks, and / or bicycles including electric bicycles and includes the vehicle parts listed above and any other vehicle part that can be electrophoretically coated. The metal substrate also may be in the form of, for example, a sheet of metal or a fabricated part. Particularly suitable substrates comprise aircraft parts, which refer to any part that is used in the fabrication of any type of aircraft, on the inside and / or outside of the aircraft.

[0081] The substrate may be a multi-metal article. As used herein, the term “multimetal article” refers to (1) an article that has one surface comprised of a first metal and one surface comprised of a second metal that is different from the first metal, (2) a first article that has at least one surface comprised of a first metal and a second article that has at least one surface comprised of a second metal that is different from the first metal, or (3) both (1) and (2). The substrate may comprise surfaces or parts of different substrate materials that are adjacent or joined together, such as a galvanic assembly.

[0082] The anionic electrodepositable coating compositions of the present disclosure may comprise part of a multi-layer coating system. The coating layer deposited from the present composition may have one or more additional coating layers deposited under and / or over the layer. The coating system may comprise a pretreatment layer, such as a phosphate layer (e.g., zinc phosphate layer), and the anionic electrodepositable coating composition described in the present disclosure may be deposited over at least a portion of the pretreated layer; one or more additional coating layers may be applied over at least a portion of theelectrodeposited coating layer. This includes one or more additional coating layers comprising primers, basecoats, color coats, monocoats, clear coats and / or topcoats. Suitable additional coating layers include any of those known in the art, and each independently may be waterborne, solventbome, in solid particulate form (i.e., a powder coating composition), or in the form of a powder slurry. The additional coating layers may each be cured independently or optionally applied “wet-on-wet” and cured simultaneously. As used herein, “wet-on-wet” refers to a process, wherein a coating, for example a clear coat, is applied over a substantially uncured different coating, for example a color coat, and both coatings are then cured simultaneously. When one or more additional coating layers are used with the coating layer deposited from the present compositions, the coating layers may be collectively referred to as a “coating stack”.

[0083] The electrodeposited coating layer resulting from electrodepositing the anionic electrodepositable coating composition of the present disclosure may have two or more resin domains, such as a first resin domain and a second resin domain.

[0084] As used herein, the term “resin domain” in first resin domain or second resin domain refers to a visible disruption in the homogeneity of the cured coating layer. The visible disruption may be visible using TEM and / or SEM. For example, the second resin domain may be the resin matrix, and the first resin domain may be the core-shell polymer and / or the latex polymer, present as resinous areas that are phase separated from the resin matrix. For example, the first resin domain may comprise pockets of core-shell / latex polymer dispersed throughout the resin matrix of the second resin domain. The dispersed pockets of resin may have any geometric shape or morphology, such as spherical, lamellar, cylindrical, etc. The dispersed pockets may be generally uniformly dispersed or may be inconsistently dispersed. The dispersed pockets may also be stratified throughout the resin matrix. Alternatively, the first resin domain and second resin domain may phase separate into a bi-layer configuration wherein one of the resin domains is present on the substrate surface and the other resin domain is present on top of that domain. The first resin domain may be generally free of the pigment.

[0085] The first resin domain has a first glass transition temperature, and the second resin domain has a second glass transition temperature. The first glass transition temperature may be -25°C to 30°C, such as -KFC, to KFC, or 0 + / - 2°C. The second glass transition temperature may be lOCFCto 145°C, such as 100°C to 120°C. Tg of the first and second domains was measured as described below. The delta between the first and second glasstransition temperatures may be greater than 50°C, such as greater than 80°C or greater than 90°C, such as 90°C to 110°C.

[0086] The glass transition temperatures as reported herein were measured according to the following procedure: A conductive electrocoat was first used to generate free films of the example electrocoats. The conductive electrocoat was made using commercially available PPG products under product codes CR756 and CP639. Deionized water (1959 g) was added to 2093 g of CR756 and 220 g of CP639 paste under agitation for one hour. This material was then used to electrocoat panels using the technical bulletin specifications.

[0087] CRS panels pretreated with zinc phosphate (C700 / DI; item number 28630 available from ACT, Hillsdale, MI.) were cut in half to yield a 4” by 6” panel. These panels were submerged in the conductive electrocoat and electrodeposition was carried out using a rectifier (Xantrax Model XFR 600-2, Elkhart, Indiana, or Sorensen XZG 300-5.6, Ameteck, Berwyn, Pennsylvania) which was DC-power supplied. The target film build was 0.5 - 0.7 mils (12.7 - 17.8 microns) on the vertical face of the panel. To achieve the target film-build per panel, the electrocoat bath was maintained at 80°F and used 115 volts with a 0.75-amp limit set. Coating continued until 40 coulombs were generated. After panels were electrocoated, these panels were rinsed with deionized water and baked at 219°C for 90 minutes in an electric oven (Despatch Model LFD-1-42).

[0088] The panels coated in the conductive electrocoat were then submerged in the example electrocoats and electrodeposition was carried out using a rectifier (Xantrax Model XFR600-2, Elkhart, Indiana, or Sorensen XZG 300-5.6, Ameteck, Berwyn, Pennsylvania), which was DC-power supplied. The target film build was 15-25 microns on the vertical face of the panel. After panels were electrocoated, the panels were rinsed with deionized water and baked at 107°C for 30 minutes in an electric oven (Despatch Model LFD-1-42). The example electrocoat was then peeled off from the conductive electrocoat panel and used to measure glass transition temperature.

[0089] Glass transition temperatures (Tg) were measured using a dynamic mechanical analyzer (DMA). A TA Instruments DMA Q800 apparatus was employed in tensile mode with a preload force of 10 mN, amplitude of 15 pm (tensile strain < 0.3%), static stress / dynamic stress amplitude ratio (“force tracking”) of 125%, and an oscillation frequency of 1 Hz. The samples were first cut into a rectangular shape, featuring a width of 7 mm, gauge length of 15 mm, and thickness of 25 pm. After loading each film specimen at ambient temperature under tensile stress, they were cooled to -50°C, thermally equilibrated,and ramped to 250°C at 3°C / min. The glass transition temperatures were determined by peak temperature value of loss tangent (tan 5).

[0090] The electrodeposited cured coating layer may have a corrosion inhibitor leaching, such as a DPDS leaching, of 0 ppb or greater, such as 20 ppb or greater, such as 50 ppb or greater, such as 75 ppb or greater, such as 100 ppb or greater, such as 120 ppb or greater, such as 140 ppb or greater, such as 200 ppb or greater, such as 400 ppb or greater, as measured according to the CORROSION INHIBITOR LEACHING TEST METHOD described in the Examples section.

[0091] The electrodeposited coating layer may have 30% or lower scribe corrosion following 1,000 hours of salt spray exposure tested according to ASTM B-117, such as 25% or lower, such as 15% or lower, such as 10% or lower.

[0092] The electrodeposited coating layer may have 50% scribe corrosion or lower following 3,000 hours of salt spray exposure tested according to ASTM B-117, such as 40% or lower, such as 30% or lower, such as 25% or lower.

[0093] The electrodeposited coating layer may have Skydrol resistance of 1 ,000 g or higher, such as 1,200 g, as tested according to ISO 1518 at 1000 hours of exposure.

[0094] Any numerical range recited herein is intended to include all sub-ranges subsumed therein. Singular encompasses plural and vice versa. For example, although reference is made herein to “an” anionic salt group-containing film-forming polymer, “a” curing agent, “a” core-shell polymer, “an” acrylic polymer, and “a” corrosion inhibitor, a combination (i.e., a plurality) of these components may be used. Also, as used herein, the term “polymer” refers to prepolymers, oligomers and both homopolymers and copolymers; the prefix “poly” refers to two or more. Amine includes polyamine, epoxy includes polyepoxy, and isocyanate includes di- and tri-isocyanates, isocyanurates and dimers of isocyanate. When ranges are given, any endpoints of those ranges and / or numbers within those ranges can be combined with the scope of the present disclosure. “Including”, “such as”, “for example” and like terms means “including / such as / for example but not limited to”. The term “(meth)acrylic” means methacrylic and / or acrylic, and the terms “acrylic” and “acrylate” are used interchangeably (unless to do so would alter the intended meaning) and include acrylic acids, anhydrides, and derivatives thereof, lower alkyl-substituted acrylic acids, e.g., C1-C2 substituted acrylic acids, such as methacrylic acid, methacrylic acid, etc., and their C1-C6 alkyl esters and hydroxyalkyl esters, unless clearly indicated otherwise. As used herein, the transitional term “comprising” (and other comparable terms, e.g., “containing” and “including”) is “open-ended” and open to the inclusion of unspecifiedmatter. Although described in terms of “comprising”, the terms “consisting essentially of’ and “consisting of’ are also within the scope of the disclosure. As used herein, the terms “on,” “onto,” “applied on,” “applied onto,” “formed on,” “deposited on,” “deposited onto,” “injected on,” “injected onto” and the like mean formed, overlaid, deposited, or provided on, but not necessarily in contact with, a substrate surface. For example, a composition “applied onto” a substrate surface does not preclude the presence of one or more other intervening coating layers or films of the same or different composition located between the composition and the substrate surface. Mn and Mw as reported herein were as measured by Gel Permeation Chromatography using polystyrene standards.Aspects

[0095] Aspect 1. An anionic electrodepositable coating composition comprising: an anionic salt group-containing film-forming polymer; a curing agent; and a core-shell polymer; wherein a coating layer deposited from the coating composition will, upon cure, form a first resin domain having a first glass transition temperature of -25 to 30°C and a second resin domain having a second glass transition temperature of 100 to 145°C.

[0096] Aspect 2. An anionic electrodepositable coating composition comprising: an anionic salt group-containing, film-forming polymer; a curing agent; and a latex polymer; wherein a coating layer deposited from the coating composition will, upon cure, form a first resin domain having a first glass transition temperature of -25 to 30°C and a second resin domain having a second glass transition temperature of 100 to 145°C.

[0097] Aspect 3. The anionic electrodepositable coating composition of aspect 1 or 2, wherein the film-forming polymer comprises hydroxyl groups.

[0098] Aspect 4. The anionic electrodepositable coating composition of any preceding aspect, wherein the film-forming polymer comprises amine groups.

[0099] Aspect 5. The anionic electrodepositable coating composition of any preceding aspect, wherein the film- forming polymer comprises carbamate groups.

[0100] Aspect 6. The anionic electrodepositable coating composition of any preceding aspect, wherein the film-forming polymer comprises thiol groups.

[0101] Aspect 7. The anionic electrodepositable coating composition of any preceding aspect, wherein the film- forming polymer comprises phosphated epoxy resin.

[0102] Aspect 8. The anionic electrodepositable coating composition of any preceding aspect, wherein the film-forming polymer comprises phosphated acrylic.

[0103] Aspect 9. The anionic electrodepositable coating composition of any preceding aspect, wherein the film- forming polymer comprises a carbamate- functional phosphated epoxy resin.

[0104] Aspect 10. The anionic electrodepositable coating composition of any preceding aspect, wherein the film forming polymer comprises 30% by weight or greater of the composition, based on total resin solids weight.

[0105] Aspect 11. The anionic electrodepositable coating composition of any preceding aspect, wherein the film forming polymer comprises 40% by weight or greater of the composition, based on total resin solids weight.

[0106] Aspect 12. The anionic electrodepositable coating composition of any preceding aspect, wherein the film forming polymer comprises 45% by weight or greater of the composition, based on total resin solids weight.

[0107] Aspect 13 The anionic electrodepositable coating composition of any preceding aspect, wherein the film forming polymer comprises 80% by weight or lower of the composition, based on total resin solids weight.

[0108] Aspect 14. The anionic electrodepositable coating composition of any preceding aspect, wherein the film forming polymer comprises 70% by weight or lower of the composition, based on total resin solids weight.

[0109] Aspect 15. The anionic electrodepositable coating composition of any preceding aspect, wherein the film forming polymer comprises 65% by weight or lower of the composition, based on total resin solids weight.

[0110] Aspect 16. The anionic electrodepositable coating composition of any preceding aspect, wherein the film forming polymer comprises 30% to 80% by weight of the composition, based on total resin solids weight.

[0111] Aspect 17. The anionic electrodepositable coating composition of any preceding aspect, wherein the film forming polymer comprises 40% to 70% by weight of the composition, based on total resin solids weight.

[0112] Aspect 18. The anionic electrodepositable coating composition of any preceding aspect, wherein the film forming polymer comprises 45% to 65% by weight of the composition, based on total resin solids weight.

[0113] Aspect 19. The anionic electrodepositable coating composition of any preceding aspect, wherein the curing agent comprises a blocked polyisocyanate.

[0114] Aspect 20. The anionic electrodepositable coating composition of any preceding aspect, wherein the curing agent comprises a fully blocked polyisocyanate.

[0115] Aspect 21. The anionic electrodepositable coating composition of any preceding aspect, wherein the curing agent comprises a partially blocked polyisocyanate.

[0116] Aspect 22. The anionic electrodepositable coating composition of any preceding aspect, wherein the curing agent comprises a blocked polyisocyanate and at least 30% of the blocking groups comprise the residue of a 1,2-polyol.

[0117] Aspect 23. The anionic electrodepositable coating composition of any preceding aspect, wherein the curing agent comprises an aminoplast resin.

[0118] Aspect 24. The anionic electrodepositable coating composition of any preceding aspect, wherein the curing agent comprises a phenoplast resin.

[0119] Aspect 25. The anionic electrodepositable coating composition of any preceding aspect, wherein the curing agent comprises 5% by weight or greater of the composition, based on total resin solids weight.

[0120] Aspect 26. The anionic electrodepositable coating composition of any preceding aspect, wherein the curing agent comprises 10% by weight or greater of the composition, based on total resin solids weight.

[0121] Aspect 27. The anionic electrodepositable coating composition of any preceding aspect, wherein the curing agent comprises 15% by weight or greater of the composition, based on total resin solids weight.

[0122] Aspect 28. The anionic electrodepositable coating composition of any preceding aspect, wherein the curing agent comprises 60% by weight or lower of the composition, based on total resin solids weight.

[0123] Aspect 29. The anionic electrodepositable coating composition of any preceding aspect, wherein the curing agent comprises 50% by weight or lower of the composition, based on total resin solids weight.

[0124] Aspect 30. The anionic electrodepositable coating composition of any preceding aspect, wherein the curing agent comprises 45% by weight or lower of the composition, based on total resin solids weight.

[0125] Aspect 31. The anionic electrodepositable coating composition of any preceding aspect, wherein the curing agent comprises 5% to 60% by weight of the composition, based on total resin solids weight.

[0126] Aspect 32. The anionic electrodepositable coating composition of any preceding aspect, wherein the curing agent comprises 10% to 50% by weight of the composition, based on total resin solids weight.

[0127] Aspect 33. The anionic electrodepositable coating composition of any preceding aspect, wherein the curing agent comprises 15% to 45% by weight of the composition, based on total resin solids weight.

[0128] Aspect 34. The anionic electrodepositable coating composition of any preceding aspect, wherein the curing agent comprises 15% to 40% by weight of the composition, based on total resin solids weight.

[0129] Aspect 35. The anionic electrodepositable coating composition of aspect 2, further comprising a core-shell polymer.

[0130] Aspect 36. The anionic electrodepositable coating composition of any preceding aspect that comprises a core- shell polymer, wherein the core and shell are covalently bound.

[0131] Aspect 37. The anionic electrodepositable coating composition of any preceding aspect that comprises a core- shell polymer, wherein the weight ratio of core to shell is 20:80 to 80:20.

[0132] Aspect 38. The anionic electrodepositable coating composition of any preceding aspect that comprises a core- shell polymer, wherein the core and shell each independently comprise an acrylic polymer and / or a polyurethane polymer.

[0133] Aspect 39. The anionic electrodepositable coating composition of aspect 38, wherein at least one of the core or shell comprises an acrylic polymer and the core and shell are covalently bound through an acrylate linkage.

[0134] Aspect 40. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core comprises an acrylic polymer and the shell comprises a polyurethane polymer.

[0135] Aspect 41. The anionic electrodepositable coating composition of any of aspects 35 to 40, wherein the core-shell polymer comprises an acrylic polymer comprising a diacrylate ester of a C1-C6 diol, and / or an alkylester of (meth)acrylic acid.

[0136] Aspect 42. The anionic electrodepositable coating composition of any of aspects 35 to 41, wherein the core-shell polymer comprises a polyuerethane prepolymer formed from a reaction mixture including a polyol, a polymerizable ethylenically unsaturated monomer containing at least one acrylic functional group and at least one active hydrogen group, and a polyisocyanate.

[0137] Aspect 43. The anionic electrodepositable coating composition of any of aspects 35 to 42, wherein the core-shell polymer comprises a polyuerethane prepolymer formed from a reaction mixture including a polyol, a polymerizable ethylenically unsaturatedmonomer containing at least one acrylic functional group and at least one hydroxy group, and a polyisocyanate.

[0138] Aspect 44. The anionic electrodepositable coating composition of aspect 43, wherein the polyisocyanate comprises isophorone diisocyanate.

[0139] Aspect 45. The anionic electrodepositable coating composition of aspect 43 or 44, wherein the polyurethane polymer has an aliphatic content of 50% by weight, or greater, based on the total weight of the polyurethane polymer.

[0140] Aspect 46. The anionic electrodepositable coating composition of any of aspects 43 to 45, wherein the polyurethane prepolymer has an Mn of 2,000 g / mol or greater.

[0141] Aspect 47. The anionic electrodepositable coating composition of any of aspects 43 to 46, wherein the polyurethane prepolymer has an Mn of 5,000 g / mol or greater.

[0142] Aspect 48. The anionic electrodepositable coating composition of any of aspects 43 to 47, wherein the polyurethane prepolymer has an Mn of 50,000 g / mol or lower.

[0143] Aspect 49. The anionic electrodepositable coating composition of any of aspects 43 to 48, wherein the polyurethane prepolymer has an Mn of 15,000 g / mol or lower.

[0144] Aspect 50. The anionic electrodepositable coating composition of any of aspects 43 to 49, wherein the polyurethane prepolymer has an Mn of 2,000 g / mol to 50,000 g / mol.

[0145] Aspect 51. The anionic electrodepositable coating composition of any of aspects 43 to 50, wherein the polyurethane prepolymer has an Mn of 5,000 g / mol to 15,000 g / mol.

[0146] Aspect 52. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer has a calculated Tg of -15°C to 15°C, as determined according to the Fox equation.

[0147] Aspect 53. The anionic electrodepositable coating composition of any preceding aspect wherein the first resin domain has a first glass transition temperature of -10 to 10°C and the second resin domain has a second glass transition temperature of 100 to 120°C.

[0148] Aspect 54. The anionic electrodepositable coating composition of any preceding aspect wherein the first resin domain has a first glass transition temperature of 0°C + / - 2°C.

[0149] Aspect 55. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer has an acid value of 10 mg KOH / g core- shell polymer or greater.

[0150] Aspect 56. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer has an acid value of 13 mg KOH / g core- shell polymer or greater.

[0151] Aspect 57. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer has an acid value of 15 mg KOH / g core-shell polymer or greater.

[0152] Aspect 58. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer has an acid value of 60 mg KOH / g core- shell polymer or lower.

[0153] Aspect 59. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer has an acid value of 48 mg KOH / g core-shell polymer or lower.

[0154] Aspect 60. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer has an acid value of 30 mg KOH / g core-shell polymer or lower.

[0155] Aspect 61. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer has an acid value of 10 to 60 mg KOH / g core-shell polymer.

[0156] Aspect 62. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer has an acid value of 13 to 48 mg KOH / g core-shell polymer.

[0157] Aspect 63. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer has an acid value of 15 to 30 mg KOH / g core-shell polymer.

[0158] Aspect 64. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer has a hydroxyl value of 1 mg KOH / g core-shell polymer or greater.

[0159] Aspect 65. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer has a hydroxyl value of 2 mg KOH / g core-shell polymer or greater.

[0160] Aspect 66. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer has a hydroxyl value of 180 mg KOH / g core-shell polymer or lower.

[0161] Aspect 67. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer has a hydroxyl value of 120 mg KOH / g core-shell polymer or lower.

[0162] Aspect 68. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer has a hydroxyl value of 60 mg KOH / g core-shell polymer or lower.

[0163] Aspect 69. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer has a hydroxyl value of 1 to 180 mg KOH / g core-shell polymer.

[0164] Aspect 70. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer has a hydroxyl value of 2 to 120 mg KOH / g core-shell polymer.

[0165] Aspect 71. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer has a hydroxyl value of 2 to 60 mg KOH / g core-shell polymer.

[0166] Aspect 72. The anionic electrodepositable coating composition of any of preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer comprises 3% by weight or greater of the composition, based on total resin solids.

[0167] Aspect 73. The anionic electrodepositable coating composition of any of preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer comprises 5% by weight or greater of the composition, based on total resin solids.

[0168] Aspect 74. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer comprises 7% by weight or greater of the composition, based on total resin solids.

[0169] Aspect 75. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer comprises 25% by weight or lower of the composition, based on total resin solids.

[0170] Aspect 76. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer comprises 20% by weight or lower of the composition, based on total resin solids.

[0171] Aspect 77. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer comprises 16% by weight or lower of the composition, based on total resin solids.

[0172] Aspect 78. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer comprises 3% to 25% by weight of the composition, based on a total weight of resin solids.

[0173] Aspect 79. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer comprises 3% to 20% by weight of the composition, based on a total weight of resin solids.

[0174] Aspect 80. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer comprises 5% to 20% by weight of the composition, based on a total weight of resin solids.

[0175] Aspect 81. The anionic electrodepositable coating composition of any preceding aspect that comprises a core-shell polymer, wherein the core-shell polymer comprises 7% to 16% by weight of the composition, based on a total weight of resin solids.

[0176] Aspect 82. The anionic electrodepositable coating composition of any preceding aspect, wherein the core-shell polymer and / or the latex polymer comprise an acrylic polymer comprising more than 50% by weight (meth)acrylic monomers, where % by weight is based on the total weight of the monomers used to make the acrylic polymer.

[0177] Aspect 83. The anionic electrodepositable coating composition of any preceding aspect, wherein the core-shell polymer and / or the latex polymer comprise an acrylic polymer comprising 60% by weight or greater (meth)acrylic monomers, where % by weight is based on the total weight of the monomers used to make the acrylic polymer.

[0178] Aspect 84. The anionic electrodepositable coating composition of any preceding aspect, wherein the core-shell polymer and / or the latex polymer comprise an acrylic polymer comprising 70% by weight or greater (meth)acrylic monomers, where % by weight is based on the total weight of the monomers used to make the acrylic polymer.

[0179] Aspect 85. The anionic electrodepositable coating composition of any preceding aspect, wherein the core-shell polymer and / or the latex polymer comprise an acrylic polymer comprising 75% by weight or greater (meth)acrylic monomers, where % by weight is based on the total weight of the monomers used to make the acrylic polymer.

[0180] Aspect 86. The anionic electrodepositable coating composition of any preceding aspect, wherein the core-shell polymer and / or the latex polymer comprise an acrylic polymer that is substantially free, essentially free or completely free of urethane linkages.

[0181] Aspect 87. The anionic electrodepositable coating composition of any preceding aspect, further comprising a corrosion inhibitor.

[0182] Aspect 88. The anionic electrodepositable coating composition of aspect 87, wherein the corrosion inhibitor comprises 2,2’-dipyridyl disulfide.

[0183] Aspect 89. The anionic electrodepositable coating composition of aspect 87 or 88, wherein the corrosion inhibitor is introduced to the coating composition on a pigment.

[0184] Aspect 90. The anionic electrodepositable coating composition of aspect 89, wherein the corrosion inhibitor is introduced to the coating composition on silica.

[0185] Aspect 91. The anionic electrodepositable coating composition of any of aspects 87 to 90, wherein the corrosion inhibitor is introduced to the coating composition as a component of a pigment paste.

[0186] Aspect 92. The anionic electrodepositable coating composition of any of aspects 87 to 91, wherein the corrosion inhibitor is introduced to the coating composition by combining it with the film-forming polymer and / or the curing agent.

[0187] Aspect 93. The anionic electrodepositable coating composition of any of aspects 87 to 92, wherein the corrosion inhibitor comprises 5% by weight or greater of the coating composition, based on total weight of the resin solids.

[0188] Aspect 94. The anionic electrodepositable coating composition of any of aspects 87 to 93, wherein the corrosion inhibitor comprises 8% by weight or greater of the coating composition, based on total weight of the resin solids.

[0189] Aspect 95. The anionic electrodepositable coating composition of any of aspects 87 to 94, wherein the corrosion inhibitor comprises 10% by weight or greater of the coating composition, based on total weight of the resin solids.

[0190] Aspect 96. The anionic electrodepositable coating composition of any of aspects 87 to 95, wherein the corrosion inhibitor comprises 30% by weight or lower of the coating composition, based on total weight of the resin solids.

[0191] Aspect 97. The anionic electrodepositable coating composition of any of aspects 87 to 96, wherein the corrosion inhibitor comprises 25% by weight or lower of the coating composition, based on total weight of the resin solids.

[0192] Aspect 98. The anionic electrodepositable coating composition of any of aspects 87 to 97, wherein the corrosion inhibitor comprises 20% by weight or lower of the coating composition, based on total weight of the resin solids.

[0193] Aspect 99. The anionic electrodepositable coating composition of any of aspects 87 to 98, wherein the corrosion inhibitor comprises 17% by weight or lower of the coating composition, based on total weight of the resin solids.

[0194] Aspect 100. The anionic electrodepositable coating composition of any of aspects 87 to 99, wherein the corrosion inhibitor comprises 15% by weight or lower of the coating composition, based on total weight of the resin solids.

[0195] Aspect 101. The anionic electrodepositable coating composition of any of aspects 87 to 100, wherein the corrosion inhibitor comprises from 5% to 30% by weight, based on total weight of the resin solids.

[0196] Aspect 102. The anionic electrodepositable coating composition of any of aspects 87 to 101 , wherein the corrosion inhibitor comprises from 8% to 25% by weight, based on total weight of the resin solids.

[0197] Aspect 103. The anionic electrodepositable coating composition of any of aspects 87 to 102, wherein the corrosion inhibitor comprises from 10% to 20% by weight, based on total weight of the resin solids.

[0198] Aspect 104. The anionic electrodepositable coating composition of any of aspects 87 to 103, wherein the corrosion inhibitor comprises from 10% to 15% by weight, based on total weight of the resin solids.

[0199] Aspect 105. The anionic electrodepositable coating composition of any preceding aspect, further comprising a pigment component.

[0200] Aspect 106. The anionic electrodepositable coating composition of aspect 105, wherein the pigment component comprises TiC) .

[0201] Aspect 107. The anionic electrodepositable coating composition of aspect 105 or 106, wherein the pigment component comprises clay.

[0202] Aspect 108. The anionic electrodepositable coating composition of any of aspects 105 to 107, wherein the pigment component comprises calcined clay.

[0203] Aspect 109. The anionic electrodepositable coating composition of any of aspects 105 to 108, wherein the pigment component comprises kaolin.

[0204] Aspect 110. The anionic electrodepositable coating composition of any of aspects 105 to 109, wherein the pigment component comprises TiO2 and calcined clay in a weight ratio of 40:60 to 60:40.

[0205] Aspect 111. The anionic electrodepositable coating composition of any preceding aspect, further comprising water.

[0206] Aspect 112. The anionic electrodepositable coating composition of any preceding aspect, further comprising water in an amount of 40% to 90% by weight, based on total weight of the composition.

[0207] Aspect 113. The anionic electrodepositable coating composition of any preceding aspect, further comprising water in an amount of 50% to 75% by weight, based on total weight of the composition.

[0208] Aspect 114. The anionic electrodepositable coating composition of any preceding aspect, further comprising organic solvent.

[0209] Aspect 115. The anionic electrodepositable coating composition of any preceding aspect, further comprising organic solvent in an amount of less than 10% by weight, based on total weight of the composition.

[0210] Aspect 116. The anionic electrodepositable coating composition of any preceding aspect, wherein the composition has a total solids content of 1 % by weight or greater, based on the total weight of the composition.

[0211] Aspect 117. The anionic electrodepositable coating composition of any preceding aspect, wherein the composition has a total solids content of 5% by weight or greater, based on the total weight of the composition.

[0212] Aspect 118. The anionic electrodepositable coating composition of any preceding aspect, wherein the composition has a total solids content of 50% by weight or lower, based on the total weight of the composition.

[0213] Aspect 119. The anionic electrodepositable coating composition of any preceding aspect, wherein the composition has a total solids content of 40% by weight or lower, based on the total weight of the composition.

[0214] Aspect 120. The anionic electrodepositable coating composition of any preceding aspect, wherein the composition has a total solids content of 20% by weight or lower, based on the total weight of the composition.

[0215] Aspect 121. The anionic electrodepositable coating composition of any preceding aspect, wherein the composition has a total solids content of 1% to 50% by weight, based on the total weight of the composition.

[0216] Aspect 122. The anionic electrodepositable coating composition of any preceding aspect, wherein the composition has a total solids content of 5% to 40% by weight, based on the total weight of the composition.

[0217] Aspect 123. The anionic electrodepositable coating composition of any preceding aspect, wherein the composition has a total solids content of 5% to 20% by weight, based on the total weight of the composition.

[0218] Aspect 124. A method for using the anionic electrodepositable coating composition of any preceding aspect to coat a substrate, comprising electrophoreticallyapplying the coating composition to a portion of the substrate and curing the composition to form a cured coating layer.

[0219] Aspect 125. A substrate coated according to the method of aspect 124.

[0220] Aspect 126. The substrate of aspect 125, wherein the coating layer comprises a first resin domain and a second resin domain.

[0221] Aspect 127. The substrate of aspect 126, wherein the first resin domain has a Tg of -25 to 30°C.

[0222] Aspect 128. The substrate of aspect 126 or 127, wherein the first resin domain has a Tg of -10 to 10°C.

[0223] Aspect 129. The substrate of any of aspects 126 to 128, wherein the first resin domain has a Tg of 0°C + / - 2°C.

[0224] Aspect 130. The substrate of any of aspects 126 to 129, wherein the second resin domain has a Tg of 100 to 145°C.

[0225] Aspect 131. The substrate of any of aspects 126 to 130, wherein the second resin domain has a Tg of 100 to 120°C.

[0226] Aspect 132. The substrate of any of aspects 125 to 131, wherein the coating layer has a dry film thickness of 0.7 to 0.9 mils and a corrosion inhibitor leaching amount of 10 ppb or greater, as measured according to the CORROSION INHIBITOR LEACHING TEST METHOD.

[0227] Aspect 133. The substrate of any of aspects 125 to 132, wherein the coating layer has a dry film thickness of 0.7 to 0.9 mils and 30% or lower scribe corrosion following 1,000 hours of salt spray exposure tested according to ASTM B-117.

[0228] Aspect 134. The substrate of any of aspects 125 to 133, wherein the coating layer has a dry film thickness of 0.7 to 0.9 mils and 50% or lower scribe corrosion following 3,000 hours of salt spray exposure tested according to ASTM B-117.

[0229] Aspect 135. The substrate of any of aspects 125 to 134, wherein the coating layer has a dry film thickness of 0.7 to 0.9 mils and Skydrol resistance of 1 ,000 g or greater, as tested according to ISO 1518 at 1000 hours of exposure.

[0230] Aspect 136. The substrate of any of aspects 125 to 135, wherein the coating layer has a dry film thickness of 0.7 to 0.9 mils and Skydrol resistance of 1 ,200 g, as tested according to ISO 1518 at 1000 hours of exposure.

[0231] Aspect 137. The substrate of any of aspects 125 to 136, wherein the substrate comprises metal and / or, metal alloys.

[0232] Aspect 138. The substrate of any of aspects 125 to 137, wherein the substrate comprises substrates that have been metallized.

[0233] Aspect 139. The substrate of any of aspects 125 to 138, wherein the substrate comprises nickel plated plastic.

[0234] Aspect 140. The substrate of any of aspects 125 to 139, wherein the substrate comprises non-metal conductive materials.

[0235] Aspect 141. The substrate of any of aspects 125 to 140, wherein the substrate comprises composite materials.

[0236] Aspect 142. The substrate of aspect 141, wherein the substrate comprises composite material comprising conductive carbon and / or carbon fibers.

[0237] Aspect 143. The substrate of any of aspects 125 to 142, wherein the substrate comprises steel.

[0238] Aspect 144. The substrate of any of aspects 125 to 143, wherein the substrate comprises aluminum.

[0239] Aspect 145. The substrate of any of aspects 125 to 144, wherein the substrate comprises aluminum alloy.

[0240] Aspect 146. The substrate of aspect 145, wherein the substrate comprises aluminum alloy in the 2000, 6000, and / or 7000 series.

[0241] Aspect 147. The substrate of aspect 145 or 146, wherein the substrate comprises aluminum alloy in the 2024 series.

[0242] Aspect 148. The substrate of aspect 143, wherein the steel comprises cold rolled steel.

[0243] Aspect 149. The substrate of any of aspects 125 to 148, wherein the substrate comprises a vehicle.

[0244] Aspect 150. The substrate of any of aspects 125 to 149, wherein the substrate comprises an aircraft.

[0245] Aspect 151. The substrate of any of aspects 125 to 148, wherein the substrate comprises an aircraft part.

[0246] Aspect 152. An aircraft comprising the substrate of any of aspects 126 to 148.

[0247] The following examples are intended to illustrate the disclosure and should not be construed as limiting the disclosure in any way.EXAMPLES

[0248] Example 1 : Preparation of Hydroxypropylcarbamate Half-CappedIsophoronediisocyanate (IPDI) Reactant.

[0249] A hydroxypropylcarbamate half-capped isophoronediisocyanate was prepared using the materials in Table 1.Table 1: Hydroxypropylcarbamate isophoronediisocyanateHydroxypropylcarbamate. Available commercially from Huntsman

[0250] Charges 1-3 were added to a flask set up for total reflux with stirring under nitrogen. The mixture was heated to a temperature of 60 °C. Charge 4 was added over 2 hours through an addition funnel while the resulting exotherm was maintained under 70°C. After 2 hours, the mixture was titrated for isocyanate (NCO) equivalent weight and found to have a value of 463 g / eq of NCO (theoretical of 456 g / eq). The mixture was then cooled to 40°C. Final solids were 75.6%. The solids content was determined by adding a quantity of the dispersion to a tared aluminum dish, recording the weight of the dispersion and dish, heating the test specimen in the dish for 60 minutes at 110°C in an oven, allowing the dish to cool, reweighing the dish to determine the amount of non-volatile content remaining, and determining the solids content by dividing the weight of the non-volatile content by the total sample weight and multiplying by 100. This procedure was used to determine the solids content in each of the examples below.

[0251] Final z-average molecular weight (Mz) of the resin was determined to be 674 g / mol. The molecular weight was determined by Gel Permeation Chromatography using Waters 2695 separation module with a Waters 410 differential refractometer (RI detector), polystyrene standards having molecular weights of from approximately 500 g / mol to 900,000 g / mol, tetrahydrofuran (THF) with lithium bromide (LiBr) as the eluent at a flow rate of 0.5 mL / min, and one Asahipak GF-510 HQ column for separation.

[0252] Example 2a: Preparation of a Carbamate-Functional Phosphated Epoxy Resin without Corrosion Inhibitor:

[0253] A carbamate-functional phosphated epoxy resin without corrosion inhibitor was prepared using the materials in Table 2.Table 2: Carbamate-functional phosphated epoxy resin without inhibitor'2- Butoxyethanol available from the Dow Chemical Company2Ethylene glycol 2-ethylhexyl ether available from Eastman Chemical Company 3Methylated / n-butylated melamine-formaldehyde crosslinker available from Allnex

[0254] Charges 1-4 were added to a flask set up for total reflux with stirring under nitrogen and heated to 130°C and allowed to exotherm to 160°C. The mixture was held at 160°C for 1 hour. After 1 hour, charge 5 was added while cooling to 80°C. When 80°C was reached, charge 6 was added, rinsed with charge 7 and followed by charge 8, over 1 hour. After, addition charge 8 was rinsed with charge 9. After 1 hour, residual NCO was checked by IR and none was detected. The mixture was then warmed to 90°C and charges 10-11 were added followed by charges 12- 14 (predissolved at ambient temperature). The mixture was allowed to exotherm, and the temperature was adjusted to 120°C. The mixture was held at that temperature for 30 minutes, then cooled to 100°C. Charge 15 was added slowly, rinsed with charge 16 and the mixture was held at 100°C for 1 hour, then cooled to 90°C. Charge 17 was added followed by charge 18. The mixture was stirred for 30 minutes as the temperature was readjusted to 90°C. The resulting mixture was then reverse thinned into charge 19, which was at ambient temperature, and held for 30 minutes. Charge 20 was then added and held for 30 minutes. Charge 21 was then added and held for 30 min. Following the final hold time, the flask set-up was switched to total distillation and the mixture was placed under 21-22 inches of vacuum. The temperature was increased to 55 °C and themixture was stripped until the amount of residual methyl isobutyl ketone was less than 0.1% as determined by gas chromatography. Final solids were 29.8%. Final z-average molecular weight of the resin was 253896 g / mol.

[0255] Example 2b: Preparation of a Carbamate-Functional Phosphated Epoxy Resin with 2,2'-Dipyridyldisulfide Corrosion Inhibitor:

[0256] A Carbamate-Functional Phosphated Epoxy Resin with 2,2'-Dipyridyldisulfide Corrosion Inhibitor was prepared using the materials in Table 3.Table 3: Carbamate-functional phosphated epoxy resin with inhibitor4Available from Highfine Import & Export

[0257] Charges 1-4 were added to a flask set up for total reflux with stirring under nitrogen and heated to 130°C and allowed to exotherm to 160°C. The mixture was held at 160°C for 1 hour. After 1 hour, charge 5 was added while cooling to 80°C. When 80°C was reached, charge 6 was added, rinsed with charge 7 and followed by charge 8, over 1 hour. After, addition charge 8 was rinsed with charge 9. After 1 hour, residual NCO was checked by IR and none was detected. The mixture was then warmed to 90°C and charges 10-11 were added followed by charges 12- 14 (predissolved at ambient temperature). The mixture wasallowed to exotherm and the temperature was adjusted to 120°C. The mixture was held at that temperature for 30 minutes, then cooled to 100°C. Charge 15 was added slowly, rinsed with charge 16 and the mixture was held at 100°C for 1 hour, then cooled to 90°C. Charge 17 was added followed by charge 18-19. The mixture was stirred for 30 minutes as the temperature was readjusted to 90°C. The resulting mixture was then reverse thinned into charge 20, which was at ambient temperature, and held for 30 minutes. Charge 21 was then added and held for 30 minutes. Charge 22 was then added and held for 30 min. Following the final hold time, the flask set-up was switched to total distillation and the mixture was placed under 21-22 inches of vacuum. The temperature was increased to 55 °C and the mixture was stripped until the amount of residual methyl isobutyl ketone was less than 0.1% as determined by gas chromatography. Final solids were 29.8%. Final z-average molecular weight of the resin was 253896 g / mol.

[0258] Example 3A / 3B: Preparation of Solventbome Carbamate-Functional Phosphated Epoxy Resin with and without 2,2'-Dipyridyldisulfide Corrosion Inhibitor, respectively.

[0259] Solventbome Carbamate-Functional Phosphated Epoxy Resin with and without 2,2'-Dipyridyldisulfide Corrosion Inhibitor was prepared using the materials inTable 4.Table 4: Solventbome Carbamate-functional phosphated epoxy resin with and without inhibitor

[0260] Charges 1-4 were added to a flask set up for total reflux with stirring under nitrogen and heated to 130°C and allowed to exotherm to 160°C. The mixture was held at 160°C for 1 hour. After 1 hour, charge 5 was added while cooling to 80°C. When 80°C was reached, charge 6 was added, rinsed with charge 7 and followed by charge 8, over 1 hour. After, addition charge 8 was rinsed with charge 9. After 1 hour, residual NCO was checked by IR and none was detected. The mixture was then warmed to 90°C and charges 10-11 were added followed by charges 12- 14 (predissolved at ambient temperature). The mixture was allowed to exotherm, and the temperature was adjusted to 120°C. The mixture was held at that temperature for 30 minutes, then cooled to 100°C. Charge 15 was added slowly, rinsed with charge 16 and the mixture was held at 100°C for 1 hour, then cooled to 90°C. Charge 17 was added followed by charge 18-20. The mixture was stirred for 30 minutes as the temperature was readjusted to 90°C. Then, the mixture was allowed to cool to ambient temperature.

[0261] Example 4: Preparation of Corrosion-inhibitor loaded Pigment.

[0262] Corrosion-inhibitor loaded pigment was prepared using the materials in table 5. Charge 1 was added to a stainless-steel kettle and charge 2 was added under stirring until all of the powder dissolved into a solution. Charge 3 was added slowly to ensure mixing of silica into the inhibitor solution. Charge 4 was then added. Next, the solution was mixed for 30 minutes. The sample was then transferred to an open container to dry over 48 to 72 hours in a fume hood at ambient temperature.Table 5: Corrosion- inhibitor loaded Pigment Composition

[0263] Example 5A / 5B: Preparation of Corrosion-Inhibitor Paste.

[0264] Corrosion Inhibitor-loaded paste was made using the materials in table 6.Table 6: High Pigment-to-Binder (High P:B) Corrosion-Inhibitor Pastes6Anionic Acrylic resin described in W00202850A2, Formerly POWERCRON 290 from PPG Available from PPG8TiO2 available from Tronox9Kaolin available from BASF

[0265] A paste was formulated by mixing Charges 1 -5 together. Under stirring, Charges 6-8 were added slowly to incorporate into the mixture. Charge 9 was added slowly. Spherical and cylindrical dispersing media (2mm 92% alumina balls available from Fox Industries) were then added to each jar at a level equal to approximately 50% of the total weight of the materials. The jars were sealed with lids and then placed on a Lau DAS 200 Dispersing Unit (Lau GmbH) with a dispersion time of 3 hours. After dispersion, media was strained from the mixed solution.

[0266] Example 6-17: Formulation of Electrodepositable Coating Compositions.

[0267] The uninhibited carbamate-functional epoxy polymer (Example 2a) was formulated into primer paints at 20% non-volatile compositions with a pigment to binder ratio of 0.20 using the charge amounts in Table 7.Table 7: Electrodepositable Coating Composition10ACPP2122 Gray pigment paste available from PPG Aerospace.

[0268] Inhibited coating compositions were created using example 2b, as well as core-shell polymers as indicated. The corresponding core-shell polymers for each example are shown in Table 8.Table 8: Core-Shell (C-S) Polymers Corresponding to Inhibited Examples

[0269] Core-shell polymer 1 : Core-shell polymer 1 was prepared by a two-stage polymerization process comprising a first polyurethane polymerization stage (Stage- 1) followed by a second radical polymerization stage (Stage-2) as described below.

[0270] Stage- 1: A polyurethane polymer having ethylenically unsaturated functionality and carboxylic functionality was prepared using the materials in Table 9A.Table 9A: Polyurethane polymer preparation.

[0271] Charges 1-7 were added to a four necked round bottom flask equipped with a mechanical stirrer, condenser, and a thermocouple. This charge mixture was stirred and heated in the flask to 90°C to produce a homogeneous mixture. Charge 8 was then added to the homogeneous mixture in the flask. The resulting mixture was stirred and heated in the flask to 90°C. Charge 9 was then metered into the flask over a period of 90 minutes to form a reaction mixture. The container that held Charge 9 was rinsed with Charge 10 and the rinse liquid added to the reaction mixture in the flask. The reaction mixture was maintained at 90°C with stirring until no unreacted isocyanate groups remined in the reaction mixture.Charges 11 and 12 were then added to the resulting product mixture in the flask, which was then cooled to ambient temperature. The resulting product mixture was comprised of unreacted 2-ethylhexylprop-2-enoate and a polyurethane polymer having ethylenically unsaturated functionality and carboxylic functionality. The resulting product mixture had a non-volatile content of 53.65% (remaining weight after 60 minutes at 110°C).

[0272] Stage-2: The core-shell polymer 1 was prepared using the materials in Table 9B.Table 9B: Core-shell polymer 1 preparation.nDiethylhexyl sodium sulfosuccinate in ethanol, available from Syensqo as AEROSOL OT-7512ACTICIDE MBS, a waterborne mixture of methylisothiazolinone and benzisothiazolinone available from Thor Specialties, Inc.13FOAMKILL 649, a non-silicone defoamer available from Crucible Chemical Company

[0273] Charges 1 -6 were added to a four necked round bottom flask equipped with a mechanical stirrer, condenser, and a thermocouple. This charge mixture was stirred and heated in the flask to 33 °C to produce a homogeneous mixture. Charges 7 and 8 were then added to the flask and stirred into the mixture. A mixture of Charges 9-11 was then metered into the flask over a period of 90 minutes to form a reaction mixture. The reaction mixture was maintained at 65 °C for 60 minutes after reaching peak exotherm. The resulting product mixture was then cooled to 45 °C and Charges 12-14 were mixed into the product mixture in the flask and stirred for 15 minutes. The final product mixture comprised a core- shell polymer comprising an acrylic core and a poly ether- polyurethane shell. The final product mixture had a pH of 8.48, a nonvolatile solids content of 38.1% (remaining weight after 60minutes at 110°C), a Brookfield viscosity of 165 cps (spindle #1, 50 rpm), and a z-average particle size of 92.2 nanometers as determined by dynamic light scattering.

[0274] Core-shell polymer 2: Core-shell polymer 2 was prepared by an identical two- stage polymerization process comprising a first polyurethane polymerization stage followed by a second radical polymerization stage as described above for the preparation of core-shell polymer 1, except that during the polyurethane polymerization reaction, the 405.5 grams of the poly(tetramethylene ether) glycol was replaced with a diol mixture of 202.8 grams of the same poly(tetramethylene ether) glycol and 94.08 grams of an ethoxylated bisphenol-A diol (BPA-6EO, supplied as MACOL 98 B from BASF). This mixture constitutes a substitution of the ethoxylated bisphenol-A diol for approximately 50% of the poly (tetramethylene ether) glycol on a hydroxyl equivalent basis compared to core-shell polymer 1.Table 10: Inhibited Electrodepositable Coating Compositions1437.62% resin solids, C-S polymer 11537.95% resin solids, C-S polymer 2

[0275] Coating compositions with varying inhibitor and core-shell polymer loading concentrations were prepared. Inhibitor loading concentrations were varied by mixing resin examples 2a and 2b. Concentration ranges are shown in Table 11 and charge amounts are shown in Table 12.Table 11: Inhibitor and core- shell polymer compositions.Table 12: Electrodepositable compositions varying inhibitor and core-shell polymer loading.

[0276] Example 15-23: Formulation of High P:B Electrodepositable Coating Compositions.

[0277] High P:B formulations (0.6- 1.0 P:B) were made using the IK Cowles method or the 2K Paste method (both described below), with inhibitor introduced through the resin (Example 3b) or by silica (Example 4 or Examples 5a or 5b, both of which contained the corrosion inhibitor loaded pigment of Example 4) as shown below in Table 13.Table 13: High P:B Electrocoat Formulations

[0278] For Examples 15-19, a IK Cowles method was used. The carbamate- functional uninhibited epoxy polymer (Example 3a) was formulated into primer paints at 20% non-volatile compositions using the charge amounts in Table 14. Charges 1-3 were added to a stainless-steel vessel and stirred with a Cowles blade for 15 minutes. Next, Charges 4 and 5 were incorporated into the mixture and mixed for 1 hour. Charge 6 was added with an additional 30 minutes of mixing. Charge 7 was added to Examples 15, 16, and17 with an additional 30-minute mixing time. The degree of dispersion was determined by a BYK Grind Gauge No. 64 until a minimal reading of 5.5 was achieved. The sample was then thinned using charges 8 and 9.Table 14: Formulation of Example 15-19 Inhibited IK Cowles primer paints.

[0279] For Examples 20-21 , a 1 K Cowles method was used. The carbamate- functional epoxy inhibited resin (Example 3b) was formulated into primer paints at 20% nonvolatile components using the charge amounts in Table 15. Charges 1-3 were added to a stainless-steel vessel and stirred with a Cowles blade for 15 minutes. Charge 4 was also added to the initial Cowles mixture of Example 21 and stirred. Next, Charges 5 and 6 were incorporated into the mixture and mixed for 1 hour. Charge 7 was added with an additional 30 minutes of mixing. Charge 8 was added to Example 20 with an additional 30-minute mixing time. The degree of dispersion was determined by a BYK Grind Gauge No. 65 until a minimal reading of 5.5 was achieved. The sample was then thinned using Charges 9 and 10.Table 15: Formulation of Inhibited resin High P:B primer paints17available from Dow

[0280] To formulate 2K Paste High P:B formulations (example 22 / 23), the Example 5A / 5B pastes (Charge 1 / 1 a) were mixed with dispersed resin, core-shell polymer and water to formulate at 20% non-volatile compositions using the charge amounts in Table 16. The paste was thoroughly mixed with Charges 2 and 3 and then Charge 4 was added.Table 16: Formulation of 2K Paste High P:B primer paints

[0281] Pretreatment: Test specimens were prepared by applying coatings onto test coupons of 0.032” x 3” x 4” 2024 T3 bare and clad aluminum alloy panels. The panels were first cleaned using an acetone wipe. Panels were then immersed in SOCOSURF A 1806 ALKALINE CLEANER available from Socomore for 10 minutes at 140°F followed by a 3- minute immersion in DI water and a spray rinse of DI water. The panels were then immersed in a deoxidizing bath of SOCOSURF A1858 acid etchant available from Socomore for 5 minutes (bare) or 10 minutes (clad) at 122°F; followed by a 3-minute immersion in DI water and finally a spray rinse of deionized water. The panels were allowed to dry under ambient conditions for 15 minutes prior to electrocoat application.

[0282] Electrodeposition: The coating compositions from Tables 7, 10 and 12 were electrodeposited onto the 2024 T3 aluminum alloy test panels at 85 °F, with a current of 0.3 amps. The voltages for each composition were adjusted to achieve the desired dry film thickness ranging from 0.7-0.9 mils, measured using a Positector 6000 permascope. Afterelectrodeposition, the panels were dried for 15 minutes to 1 hour. The panels were then baked in an electric oven at 225 °F for 30 minutes.

[0283] The coating compositions from Tables 14-16 were electrodeposited onto the 2024 T3 aluminum alloy test panels at 75°F, with a current of 0.3 amps. The voltages for each composition were adjusted to achieve the desired dry film thickness ranging from 0.7- 0.9 mils, measured using a Positector 6000 permascope. After electrodeposition, the panels were dried for 15 minutes to 1 hour. The panels were then baked in an electric oven at 225 °F for 30 minutes.

[0284] To obtain the glass transition temperatures, a conductive electrocoat was first used to generate free films of the example electrocoats. The formulation and use of the conductive electrocoat is detailed in the following. The conductive electrocoat is made using commercially available PPG products under product codes CR756 and CP639. Deionized water (1959 g) was added to 2093 g of CR756 and 220 g of CP639 paste under agitation for one hour. This material was then used to electrocoat panels using the technical bulletin specifications. CRS panels pretreated with zinc phosphate (C700 / DI; item number 28630 available from ACT, Hillsdale, Ml.) were cut in half to yield a 4” by 6” panel. These panels were submerged in the conductive electrocoat, and electrodeposition was carried out using a rectifier (Xantrax Model XFR600-2, Elkhart, Indiana, or Sorensen XZG 300-5.6, Ameteck, Berwyn, Pennsylvania) which was DC-power supplied. The target film build was 0.5 - 0.7 mils (12.7 - 17.8 microns) on the vertical face of the panel. To achieve the target film-build per panel, the electrocoat bath was maintained at 80°F and used 1 15 volts with a 0.75 amp limit set. Coating continued until 60 coulombs were generated. After panels were electrocoated, these panels were rinsed with deionized water and baked at 219°C for 90 minutes in an electric oven (Despatch Model LFD-1-42).

[0285] The coating compositions were then electrodeposited onto the cured, conductive electrocoat panels. The coating compositions from Table 7, 10 and 12 were electrodeposited 85°F, with a current of 0.3 amps. Coating compositions from Tables 14-16 were deposited at 75 °F, with a current of 0.3 amps. The voltages for each composition were adjusted to achieve the desired dry film thickness ranging from 0.7-0.9 mils, measured using a Positector 6000 permascope. After electrodeposition, the panels were dried for 15 minutes to 1 hour. The panels were then baked in an electric oven at 225 °F for 30 minutes. Free films were generated by cutting the outer electrodeposited layer in dimensions of 15-16 mm x 8-12 mm and delaminating from the conductive electrocoat.TESTING

[0286] 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 (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 inhibition. Values are the average of two replicates. The lower the number, the better the performance. The panels were evaluated after either 1,000 or 3,000 hours of exposure. Results are shown in the tables below.

[0287] For DPDS Leaching, a scribed 2024 clad panel was cut into 2 2” x 3” pieces and taped together. Panels were immersed in 300 mL water for 24 hours. The resulting liquid / supematant was then tested for DPDS Concentration using HPLC-MS.

[0288] DPDS within the water extracts were quantified by an ultra-high performance liquid chromatography (UHPLC) hyphenated to a quadrupole orbitrap mass spectrometer (MS) equipped with a heated electrospray ionization (HESI) source. The UHPLC was equipped with a C18 column (2.1 m, 2.1 x 100 mm) and the mobile phase was comprised of deionized water and acetonitrile (MeCN), where MeCN acted as eluent in a gradient elution profile with a constant 0.4 mL / min flow rate. Each standard and sample solution were injected at 2 pL volume and column temperature was kept at 40°C throughout the analysis. The HESI source parameters of the MS instrument were set as follows: spray voltage: 3.5 kV; polarity: positive; auxiliary gas flow rate: 7.50 a. u.; sheath gas pressure: 22.50 a. u.; inner capillary temperature: 300°C; probe heater temperature: 300°C; S-lens radio frequency (RF) level: 75.0.

[0289] An external calibration approach was used to carry out the quantification of DPDS. The external calibration curve was generated by using standard DPDS solution prepared at 0.2, 0.4, 0.6, 0.8, and 1 ppb concentration. The extracted ion chromatograms (EICs) for mass-to-charge (m / z) value of 221.0202 ([DPDS + H]+) was generated from the total ion chromatograms (TIC) obtained for each standard solution. The integrated peak areas of these EICs were used to generate the external calibration curve for quantification. Sample water extracts were initially injected after lOx volumetric dilution in deionized water to understand where they would fit within the DPDS working calibration range. Based on the preliminary signal response, each sample was reinjected with adjusted dilution factor indeionized water to accurately measure DPDS concentration within the working calibration range. This test method is referred to herein as the CORROSION INHIBITOR LEACHING TEST METHOD.

[0290] Coated clad panels were immersed in the hydraulic fluid SKYDROL 5 (available from Solutia, Inc.) at a temperature of 160°F (71 °C) for 1,000 hours. The surfaces of the coatings were checked for paint peeling, blistering, and significant color change. Within 30 min after removing the panels from the hot Skydrol 5, a scratch resistance test was performed according to ISO 1518-1 :2023. (Paints and varnishes — Determination of scratch resistance). ISO 1518-1:2023 specifies a test method for determining under defined conditions the resistance of a single coating or a multicoat system to penetration by scratching with a scratch stylus loaded with a specified load. Testing was done at a range of 400-1200 g by placing weights on the apparatus above the tip to apply a normal force. Fluid resistance was taken as the highest weight where scratching did not penetrate to the metal below the coating.

[0291] The free films were measured by Dynamic Mechanical Analysis (DMA) using a TA Instruments Q800 Unit in tension mode from -50 to 250°C with a ramp rate of 3°C / min and a frequency of 1 Hz. The peaks of the tan delta versus temperature thermograms were taken as glass transition temperatures.

[0292] DMA traces for Examples 6-9 are shown in Fig. 1. Glass transition temperatures and test results are shown in Table 17.Table 17: Test results for Examples 6-9.

[0293] In all cases, Tg2 represents the glass transition of the resin matrix. It appears the inhibitor slightly lowers Tg2 by ~15°C. Regardless, the resin matrix glass transition remains >100°C. The core-shell polymers do not appear to lower Tg2 by any appreciableamount, but rather show distinct, lower glass transition temperatures, Tgl, depending on the architecture of the core-shell polymer. For example, core-shell polymer 1, which contains a polyol-based polyurethane shell (Example 9) demonstrates aTgl value of ~0°C. The coreshell polymer in example 9 demonstrates a Tgl of 20°C. The presence of two different Tg peaks for the coating layers confirms the core-shell polymers from these examples are phase separating from the resin matrix to form distinct domains.

[0294] The salt spray % corroded results at 3,000 hours show minimal differences between the uninhibited and inhibited control (70-80%), and there was a significant reduction in salt spray % corroded when core-shell polymers were included in the composition. The best performance was observed when a core shell particle having a Tg of ~0°C was used. Skydrol resistance was maintained at 1200 g in all the examples.

[0295] Results for examples with varying inhibitor and core-shell polymer amounts in compositions are shown in Table 18.Table 18: Inhibitor and Core-Shell Polymer 1 composition ranges.

[0296] At a constant loading of Core-Shell Polymer 1 (10.71% on resin solids), increasing DPDS concentration from 0-12.61% on resin solids also decreased % corroded and increased leaching. There also appeared to be a step-change in leaching and % corroded at 1000 hours from 5.66-10.71% of Core-Shell Polymer 1. Moreover, increasing the composition of both core-shell polymer and DPDS did not appear to negatively impact fluid resistance, as all examples display scratch resistance of 1100-1200g following hot Skydrol exposure.Table 19: Performance properties for Examples 15-23

[0297] As can be seen in Table 19, Example 15, 16, and 17 which contain the coreshell particle show significant improvements in salt spray % compared to controls without (Examples 18 and 19). In addition, they show an order of magnitude increase in DPDS leaching. These coatings maintain Skydrol resistance while improving leaching. Example 20, with a different inhibitor incorporation, also shows a significant reduction in salt spray corrosion. Example 21, a comparative example with no phase separation, does not show a reduction of salt spray corrosion or any increase in leaching. Finally, Examples 22 and 23 (2K Paste method) show significant reduction in salt spray corrosion (%) and improvement in leaching with no softening from hot Skydrol seen with Example 23.

[0298] Whereas particular features of the present 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 coating composition, coating, and methods disclosed herein may be made without departing from the scope in the appended claims.

Claims

1. What is claimed is:

1. An anionic electrodepositable coating composition comprising: an anionic salt group-containing, film-forming polymer; a curing agent; a core- shell polymer; and a corrosion inhibitor; wherein a coating layer deposited from the coating composition will, upon cure, form a first resin domain having a first glass transition temperature range of -25 to 30°C and a second resin domain having a second glass transition temperature range of 100 to 145°C.

2. The anionic electrodepositable coating composition of claim 1 , wherein the shell comprises polyurethane linkages.

3. An anionic electrodepositable coating composition comprising: an anionic salt group-containing, film-forming polymer; a curing agent; a corrosion inhibitor comprising 2,2'-dipyridyl disulfide, tetraethyl thiuram disulfide, thiocarbamyl sulfenamide, or a combination thereof; and a latex polymer; wherein a coating layer deposited from the coating composition will, upon cure, form a first resin domain having a first glass transition temperature range of -25 to 30°C and a second domain having a second glass transition temperature range of 100 to 145°C.

4. The anionic electrodepositable coating composition of claim 3, wherein the latex polymer comprises an acrylic latex polymer and / or a polyurethane polymer.

5. The anionic electrodepositable coating of any preceding claim, wherein the anionic salt group-containing film-forming polymer comprises a phosphated epoxy resin and / or the curing agent comprises an at least partially blocked isocyanate.

6. The anionic electrodepositable coating composition of any of claims 1, 2, or 5, wherein the core comprises an acrylic polymer and the shell comprises a polyurethane polymer.

7. The anionic electrodepositable coating composition of any of claims 1, 2, 5, or 6, wherein the core comprises an acrylic polymer and the shell comprises a polyurethane polymer, and the polyurethane polymer is formed from an acrylic functional polyurethane pre-polymer having a weight average molecular weight of 2,000 to 50,000 g / mol.

8. The anionic electrodepositable coating composition of any of claims 1, 2 or 5 to 7, wherein the corrosion inhibitor comprises 2,2'-dipyridyl disulfide, tetraethyl thiuram disulfide, thiocarbamyl sulfenamide, or a combination thereof.

9. The anionic electrodepositable coating composition of any of claims 3, 4, or 5 to 8, wherein the corrosion inhibitor is incorporated into the anionic electrodepositable coating composition on silica, in a pigment paste, and / or with the film-forming polymer and / or curing agent.

10. The anionic electrodepositable coating composition of claim 1 , wherein the composition comprises:40% to 82% by weight of the anionic salt group-containing, film-forming polymer; 10% to 52% by weight of the curing agent;3% to 25% by weight of the core-shell polymer; and5% to 25% by weight of the corrosion inhibitor, the % by weight based on a total weight of resin solids.

11. The anionic electrodepositable coating composition of any preceding claim, wherein a coating layer deposited from the coating composition will, upon cure, form a first resin domain having a first glass transition temperature and a second domain having a second glass transition temperature and the delta between the first and second glass transition temperatures is 90°C to 110°C.

12. The anionic electrodepositable coating composition of any preceding claim, wherein the composition further comprises a pigment component and has a pigment-to-binder ratio of 0.6:1 to 1:1.

13. A method for using the anionic electrodepositable coating composition of any preceding claim to coat a substrate comprising electrophoretically applying the composition to at least a portion of the substrate and curing the composition to form a cured coating layer.

14. A substrate prepared according to the method of claim 13.

15. The substrate of claim 14, wherein the coating layer has a dry film thickness of 0.7 to 0.9 mils, and a Skydrol resistance of 1 ,000 g or greater, when tested according to ISO 1518 at 1 ,000 hours of exposure.

16. The substrate of claim 14 or 15, wherein the coating layer has a dry film thickness of 0.7 to 0.9 mils and a 2,2'-dipyridyl disulfide corrosion inhibitor, and has a corrosion inhibitor leaching rate of 10 ppb or greater, as measured according to the CORROSION INHIBITOR LEACHING TEST METHOD; less than 30% scribe corrosion following 1000 hours of salt spray exposure tested according to ASTM B-117, and / or less than 50% scribe corrosion following 3,000 hours of salt spray exposure tested according to ASTM B-117.

17. The substrate of any of claims 14 to 16, wherein the substrate comprises aluminum and / or aluminum alloy.

18. The substrate of claim 17, wherein the substrate comprises aluminum alloy in the 2000, 6000, or 7000 series.

19. The substrate of any of claims 14 to 18, wherein the substrate comprises an aircraft part.

20. An aircraft comprising the substrate of any of claims 14 to 19.

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